Separation of reaction products containing phosphoro-organic complexes

FIELD: processes catalyzed by metal-phosphoro-organic ligand complexes when target product may be selectively extracted and separated from liquid product.

SUBSTANCE: Specification gives description of methods of separation of one or several products of decomposition of phosphoro-organic ligand, one or several reaction byproducts and one or several products from liquid reaction product synthesized continuously and containing one or several non-consumed reagents, catalyst in form of complex of metal-phosphoro-organic ligands, not obligatory free phosphoro-organic ligand, one or several said decomposition products of phosphoro-organic ligand, one or several said reaction byproducts, one or several said products, one or several non-polar solvents and one or several polar solvents by separation of phases where (i) is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several products expressed by ratio of distribution coefficient Ef1 whose magnitudes exceeds about 2.5; (ii)is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several decomposition products expressed by ratio of distribution coefficients Ef2 whose magnitude exceeds proximately 2.5; and (iii) is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several reaction byproducts expressed by ratio of distribution coefficients Ef3 whose magnitude exceeds approximately 2.5 (versions). Description is also given of continuous methods of obtaining one or several products (versions) and reaction mixture containing one or several aldehyde products.

EFFECT: increased conversion of initial materials and selectivity by product; avoidance or exclusion of deactivation of catalyst.

20 cl, 2 tbl

 

Technical area

This invention relates to improved processes catalyzed by complexes of a metal-organophosphorus ligand. More specifically, this invention relates to processes catalyzed by complexes of a metal-organophosphorus ligand, in which the target product, together with any decomposition products of organophosphorus ligand and side reaction products, can be selectively extracted and separated from the liquid reaction product by separation of the phases.

Background of the invention

It is known that the interaction of one or more reactants in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, one can get a variety of foods. However, stabilization of the catalyst and organophosphorus ligand remains of paramount importance. It is obvious that the stability of the catalyst is a key issue when using any catalyst. The loss of catalyst or catalytic activity due to adverse reactions very expensive metal catalysts can be harmful for the production of the desired product. Moreover, it is obvious that the production costs of the product increases when the performance of the catalyst is reduced.

For example, the cause decomposition of the FOSFA organicheskoi ligand and deactivation of the catalyst, representing a complex of a metal-organophosphorus ligand, catalytic process hydroformylation, partly due to the conditions existing in the evaporator, during, for example, evaporation, used in the separation and removal of the aldehyde product from the mixture of reaction products. When using an evaporator to facilitate separation of the aldehyde product of this process created severe conditions of high temperature and low partial pressure of carbon monoxide compared with applicable during hydroformylation, and it was found that when promoted organophosphorus compound rhodium catalyst is placed in such conditions the evaporator, it is deactivated with accelerated speed over time. Further, it is believed that this deactivation is likely caused by the formation of inactive or less active compounds of rhodium. This is especially apparent when the partial pressure of carbon monoxide is very low or absent. It was also observed that the rhodium is susceptible to precipitation by prolonged exposure to conditions of the evaporator.

For example, it is theoretically predicted that under severe conditions, such as conditions in the evaporator, the active catalyst under the conditions of hydroformylation, as I believe, includes a complex of rhodium, phospho the organic ligand, carbon monoxide and hydrogen, loses at least some amount of coordinated carbon monoxide, thus providing a path for the formation of such catalytically inactive or less active rhodium. Accordingly, a successful method of preventing and/or reducing such destruction of organophosphorus ligand and deactivation of the catalyst, which take place in the harsh conditions of separation in the evaporator, would be highly desirable.

The destruction of organophosphorus ligand or deactivation of a catalyst comprising a complex of a metal-organophosphorus ligand, catalytic process hydroformylation can occur when process conditions different from the conditions of the evaporator. Increase the decomposition products of organophosphorus ligand, as well as side reaction products in the liquid reaction product can have an adverse effect on the process, for example to reduce the efficiency of the catalyst, the conversion of raw materials and the selectivity for the product. Accordingly, a successful method to prevent and/or reduce such increase of the decomposition products of organophosphorus ligand and side reaction products in the liquid reaction product would be highly desirable.

Description of the invention

It was found that in the process, ka is elizerbeth complex metal-organophosphorus ligand, target product, together with any decomposition products of organophosphorus ligand and side reaction products, can be selectively extracted and separated from the liquid reaction product by separation of the phases. On the basis of the practice of this invention it is now possible to separate the target product, together with any decomposition products of organophosphorus ligand and by-products of the reaction, the liquid reaction product without the use of separation by evaporation and the associated hard conditions. This invention provides a very desirable method of separation that prevents and/or reduces the decomposition of organophosphorus ligand and deactivation of the catalyst, which happen under the harsh conditions of separation by evaporation. This invention also offers a highly desirable method of separation that prevents and/or reduces the buildup of decomposition products of organophosphorus ligand and side reaction products in the liquid reaction product.

This invention partially relates to a method for separating one or more products of the decomposition of organophosphorus ligand, one or more by-products of the reaction and one or more products from a continuously synthesized liquid reaction product comprising one or not is how many unspent during the reaction reagents, a catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand, one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products, one or more of these products, one or more nonpolar solvents and one or more polar solvents, where the method includes (1) the filing of specified liquid reaction product from the reaction zone into a separation zone, (2) mixing the specified liquid reaction product in said separation zone to obtain phase separation of non-polar phase comprising one or more of these unspent during the reaction of the reagents specified a catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents and a polar phase comprising one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products, one or more of these products and one or more of these polar solvents, (3) removing from the specified zone dividing such amount of one or more specified the s decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education in the specified liquid reaction product in a specified reaction zone whereby the amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, (4) flow from the zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more specified unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents, (5) the selection of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products from one or more of these polar solvents and (6) submission of a specified area of the section is of the specified reaction zone and/or the specified separation zone one or more recycle streams, includes one or more of these polar solvents, where (i) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more products is expressed by the following ratio of the distribution coefficients Ef1:

where the specified distribution coefficient KR1 is the ratio of the concentration of organophosphorus ligand in the nonpolar phase after extraction to concentration of organophosphorus ligand in the polar phase after extraction, the specified distribution coefficient Kr represents the ratio of the concentration of products in the nonpolar phase after extraction to product concentration in the polar phase after extraction and specified Ef1 is set to a value greater than about 2.5, (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand expressed as the ratio of the distribution coefficients Ef2:

where the specified distribution coefficient KR1 is like is definitely above the specified distribution coefficient WP3 is the ratio of the concentration of decomposition products of organophosphorus ligand in the nonpolar phase after extraction to concentration of decomposition products phospho the organic ligand in the polar phase after extraction and the specified Ef2 is set to a value greater than about 2.5, and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more secondary products of the reaction expressed by the following ratio of the distribution coefficients Ef3:

where the specified distribution coefficient KR1 is like is definitely above the specified distribution coefficient Kr represents the ratio of the concentration of by-products of the reaction in the nonpolar phase after extraction to concentration of by-products of the reaction in the polar phase after extraction, and the specified Ef3 is set to a value greater than about 2.5.

This invention also partially relates to a method for separating one or more products of the decomposition of organophosphorus ligand, one or more by-products of the reaction and one or more products from a continuously synthesized liquid reaction product comprising one or more unspent during the reaction of the reactants, the catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand, one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products, one or bore is only specified products and one or more nonpolar solvents, where the method includes (1) the filing of specified liquid reaction product from the reaction zone into a separation zone, (2) mixing the specified liquid reaction product in said separation zone one or more polar solvents to obtain phase separation of non-polar phase comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents and a polar phase comprising one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products one or more of these products and one or more of these polar solvents, (3) removing from the specified zone dividing such amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education in the specified liquid reaction product in a specified reaction zone whereby the amount of one or more of these products is s decomposition of organophosphorus ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, (4) flow from the zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents, (5) the selection of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products from one or more of these polar solvents and (6) the filing of a given zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these polar solvents, where (i) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more products is expressed by the ratio of the coefficients of the races is to determine Ef1, defined above, the value of which exceeds about 2.5; (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand expressed by the ratio of distribution coefficients Ef2 defined above, the value of which exceeds about 2.5, and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more secondary products of the reaction expressed by the ratio of distribution coefficients Ef3 defined above, the value of which exceeds about 2.5.

The invention further partially relates to a continuous method for producing one or more products, including (1) the interaction in the reaction zone one or more reactants in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand, one or more nonpolar solvents and one or more polar solvents to obtain a liquid reaction product comprising one or more unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one Il the several products of the decomposition of organophosphorus ligand, one or more by-products of the reaction, one or more of these products, one or more of these non-polar solvents and one or more of these polar solvents, (2) submission of specified liquid reaction product from the reaction zone into a separation zone, (3) mixing the specified liquid reaction product in said separation zone to obtain phase separation of non-polar phase comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents and a polar phase, includes one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products, one or more of these products and one or more of these polar solvents, (4) removal from the zone of separation such amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education in the specified liquid d is cconom the product in the specified reaction zone, whereby the amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, (5) the filing of a given zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents (6) selection of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products from one or more of these polar solvents and (7) submission of a specified area of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these polar solvents, where (i) the selectivity of the nonpolar phase for the FOSFA organicheskoi ligand with respect to one or more products is expressed by the ratio of distribution coefficients Ef1, defined above, the value of which exceeds about 2.5; (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand expressed by the ratio of distribution coefficients Ef2 defined above, the value of which exceeds about 2.5, and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more secondary products of the reaction expressed by the ratio of distribution coefficients Ef3 defined above, the value of which exceeds about 2.5.

Additionally, this invention is due in part to a continuous method for producing one or more products, including (1) the interaction in the reaction zone one or more reactants in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand and one or more nonpolar solvents, to obtain a liquid reaction product comprising one or more unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the decomposition products of the FOSFA organicheskoi ligand, one or more by-products of the reaction, one or more of these products and one or more of these nonpolar solvents, (2) submission of specified liquid reaction product from the reaction zone into a separation zone, (3) mixing the specified liquid reaction product in said separation zone one or more polar solvents to obtain phase separation of non-polar phase comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents and a polar phase comprising one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products, one or more of these products and one or more of these polar solvents, (4) removal from the zone of separation such amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education in the specified liquid reacts the main objective of the product in the specified reaction zone, whereby the amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, (5) the filing of a given zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents (6) selection of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products from one or more of these polar solvents and (7) submission of a specified area of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these polar solvents, where (i) the selectivity of the nonpolar phase for the FOSFA organicheskoi ligand with respect to one or more products is expressed by the ratio of distribution coefficients Ef1, defined above, the value of which exceeds about 2.5; (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand expressed by the ratio of distribution coefficients Ef2 defined above, the value of which exceeds about 2.5, and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more secondary products of the reaction expressed by the ratio of distribution coefficients Ef3 defined above, the value of which exceeds about 2.5.

This invention partially relates to a method for separating one or more products of the decomposition of organophosphorus ligand, one or more by-products of the reaction and one or more products from a continuously synthesized liquid reaction product comprising one or more unspent during the reaction of the reactants, the catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand, one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products, one or more of these products, one or more first nonpolar solvents and Odie is or more second nonpolar solvents, where the method includes (1) the filing of specified liquid reaction product from the reaction zone into a separation zone, (2) mixing the specified liquid reaction product in said separation zone to obtain phase separation of non-polar phase comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the specified first nonpolar solvents and one or more specified second nonpolar solvents and a polar phase comprising one or more of these decomposition products of organophosphorus ligand, one or more specified side reaction products and one or more of these products, (3) removing from the specified zone dividing such amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education in the specified liquid reaction product in a specified reaction zone whereby the amount of one or more of these decomposition products of organophosphorus what about the ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, and (4) the filing of a given zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the specified first nonpolar solvents and one or more specified second nonpolar solvents, where (i) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more products is expressed by the ratio of distribution coefficients Ef1 defined above, the value of which exceeds about 2.5; (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand expressed by the ratio of distribution coefficients Ef2 defined above, the value of which exceeds about 2.5, and (iii) the selectivity of the nonpolar phase for fosfororganicheskikh in relation to one or more secondary products of the reaction expressed by the ratio of distribution coefficients Ef3, defined above, the value of which exceeds about 2.5.

This invention also partially relates to a method for separating one or more products of the decomposition of organophosphorus ligand, one or more by-products of the reaction and one or more products from a continuously synthesized liquid reaction product comprising one or more unspent during the reaction of the reactants, the catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand, one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products, one or more of these products and one or more first nonpolar solvents, where the method includes (1) the filing of specified liquid reaction product from the reaction zone into a separation zone, (2) mixing the specified liquid reaction product in said separation zone one or more second nonpolar solvents to obtain phase separation of non-polar phase comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified long is Ino free organophosphorus ligand, one or more of the specified first nonpolar solvents and one or more specified second nonpolar solvents and a polar phase comprising one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, (3) removing from the specified zone dividing such amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education in the specified liquid reaction product in a specified reaction zone whereby the amount of one or more these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, (4) flow from the zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these unspent during the reaction of the reagents specified catalyst, p is establishe a complex of a metal-organophosphorus ligand, specified optionally free organophosphorus ligand, one or more of the specified first nonpolar solvents and one or more specified second nonpolar solvents, where (i) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more products is expressed by the ratio of distribution coefficients Ef1 defined above, the value of which is greater than about 2.5, (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand expressed by the ratio of distribution coefficients Ef2 defined above, the value of which exceeds about 2.5, and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more secondary products of the reaction expressed by the ratio of distribution coefficients Ef3 defined above, the value of which exceeds about 2.5.

The invention further partially relates to a continuous method for producing one or more products, including (1) the interaction in the reaction zone one or more reactants in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand, one or bore the channels at the first nonpolar solvents and one or more second nonpolar solvents to obtain a liquid reaction product, includes one or more unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the decomposition products of organophosphorus ligand, one or more by-products of the reaction, one or more of these products, one or more of the specified first nonpolar solvents and one or more specified second nonpolar solvents, (2) submission of specified liquid reaction product from the reaction zone into a separation zone, (3) mixing the specified liquid reaction product in said separation zone to obtain phase separation of nonpolar phase comprising one or more specified unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the specified first nonpolar solvents and one or more specified second nonpolar solvents and a polar phase comprising one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these is Reducto, (4) removal from the zone of separation such amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education in the specified liquid reaction product in a specified reaction zone whereby the amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, (5) the filing of a given zone of separation specified in reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the specified first nonpolar solvents and one or more specified second nonpolar solvents, where (i) the selectivity of the nonpolar phase for the organophosphorus ligand referred by the Yu to one or more products is expressed by the ratio of distribution coefficients Ef1, defined above, the value of which exceeds about 2.5; (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand expressed by the ratio of distribution coefficients Ef2 defined above, the value of which exceeds about 2.5, and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more secondary products of the reaction expressed by the ratio of distribution coefficients Ef3 defined above, the value of which exceeds about 2.5.

In addition, this invention is due in part to a continuous method for producing one or more products, including (1) the interaction in the reaction zone one or more reactants in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand and one or more first nonpolar solvents to obtain a liquid reaction product comprising one or more unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the decomposition products is astrologicheskogo ligand, one or more by-products of the reaction, one or more of these products and one or more of the specified first nonpolar solvents, (2) submission of specified liquid reaction product from the reaction zone into a separation zone, (3) mixing the specified liquid reaction product in said separation zone one or more second nonpolar solvents to obtain phase separation of non-polar phase comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the specified first nonpolar solvents and one or several of these second nonpolar solvents and a polar phase comprising one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, (4) removal from the zone of separation such amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education is education in the specified liquid reaction product in a specified reaction zone, whereby the amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, and (5) the filing of a given zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the specified first nonpolar solvents and one or more specified second nonpolar solvents, where (i) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more products is expressed by the ratio of distribution coefficients Ef1 defined above, the value of which exceeds about 2.5; (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand expressed by the ratio of distribution coefficients Ef2 defined the military above, value which is greater than about 2.5, and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more secondary products of the reaction expressed by the ratio of distribution coefficients Ef3 defined above, the value of which exceeds about 2.5.

This invention partially relates to a method for separating one or more products of the decomposition of organophosphorus ligand, one or more by-products of the reaction and one or more products from a continuously synthesized liquid reaction product comprising one or more unspent during the reaction of the reactants, the catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand, one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products, one or more of these products and one or more nonpolar solvents, where the method includes (1) the filing of specified liquid reaction product of the reaction zone into a separation zone, (2) mixing the specified liquid reaction product in said separation zone to obtain phase separation of non-polar phase comprising one or more specified the unspent during the reaction reagents, the specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents and a polar phase comprising one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, (3) removing from the specified zone dividing such amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education in the specified liquid reaction product in a specified reaction zone, whereby the number of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, (4) flow from the zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more which of these unspent during the reaction reagents, the specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these non-polar solvents, where (i) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more products is expressed by the ratio of distribution coefficients Ef1 defined above, the value of which exceeds about 2.5; (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand expressed by the ratio of distribution coefficients Ef2 defined above, the value of which exceeds about 2.5, and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand in relation to one or more secondary products of the reaction expressed by the ratio of distribution coefficients Ef3 defined above, the value of which exceeds about 2.5.

Also, this invention is due in part to a continuous method for producing one or more products, including (1) the interaction in the reaction zone one or more reactants in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus League is Yes and one or more nonpolar solvents, to obtain a liquid reaction product, includes one or more unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the decomposition products of organophosphorus ligand, one or more by-products of the reaction, one or more of these products and one or more of these nonpolar solvents, (2) submission of specified liquid reaction product from the reaction zone into a separation zone, (3) mixing the specified liquid reaction product in said separation zone to obtain phase separation of non-polar phase comprising one or more of these unspent during the reaction reagents, the specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents and a polar phase comprising one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, (4) removal from the zone of separation such amount of one or more specified products of decomposition of phosphororganic the one ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education in the specified liquid reaction product in a specified reaction zone whereby the amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, (5) the filing of a given zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more specified unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these non-polar solvents, where (i) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more products is expressed by the ratio of distribution coefficients Ef1 defined above, the value of which exceeds about 2.5; (ii) the selectivity of the nonpolar phase for the organophosphorus leagues the NDA in relation to one or more degradation products of organophosphorus ligand expressed by the ratio of distribution coefficients Ef2, defined above, the value of which exceeds about 2.5, and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more side products of the reaction expressed by the ratio of distribution coefficients Ef3 defined above, the value of which exceeds about 2.5.

A detailed description of the invention

Processes according to this invention can be asymmetric or nesimmetrichnymi, and nesimmetrichnye processes are preferred and may be held in any continuous or semi-continuous manner. Extraction and separation are critical features of this invention and can be carried out, as described here. Processing technologies used in this invention may be any known processing technology, first used in conventional processes. Similarly, the method and order of adding the ingredients of the reaction and the catalyst are not critical and can be performed in any conventional way. It is assumed that when used herein, the term "liquid reaction product" includes, but is not limited to this, the reaction mixture containing the following one or several components: (a) a catalyst comprising a complex of a metal-organophosphorus ligand, (b) free organophosphorus League is d, (C) the product(s), product(s) decomposition of organophosphorus ligand and by-product(s)formed in the reaction, (d) unspent(s) during the reaction of the reagent(s) and (e) solvent(s). It is assumed that when used herein, the term "decomposition of organophosphorus ligand" includes, but is not limited to, any and all products resulting from the decomposition of the free organophosphorus ligand and organophosphorus ligand in the form of a complex with a metal, such as phosphorus-containing acid, allegedely and similar compounds. It is assumed that when used herein, the term "the reaction by-products" includes, but is not limited to, any and all by-products resulting from the reaction of one or more reagents for producing one or more products, such as dimers product, trimers product, products, isomerization, hydrogenation products and similar.

This invention covers the known conventional syntheses in the traditional way and carrying out processes of extraction and separation of the present invention. In the implementation in practice of the present invention it is now possible to extract and separate the one or more products, decomposition products of organophosphorus ligand and the reaction by-products from kata is Isadora, representing a complex of a metal-organophosphorus ligand, and unspent during the reaction of the reagents without the need for separation by evaporation and the associated hard conditions.

Examples of processes include, for example, hydroformylation, gidroalkilirovanie (intramolecular and intermolecular), hidrotsianova, gidrogenizirovanii, hydroesterification, aminals, alcoholysis, hydrocarbonylation, rehabilitation hydroformylation, hydrogenation, oligomerization of olefins, hydroxycarbonylmethyl, carbonylation, isomerization of olefins, hydrogenation with hydrogen transport and similar. Preferred processes involve the reaction of organic compounds with carbon monoxide or carbon monoxide and a third component, for example with hydrogen or with hydrogen cyanide, in the presence of catalytic amounts of a catalyst comprising a complex of a metal-organophosphorus ligand. The most preferred processes include hydroformylation, hidrotsianova, hydrocarbonylation, hydroxycarbonylmethyl and carbonylation.

Hydroformylation can be performed in accordance with conventional methods known from the prior art. For example, the aldehydes can be obtained by reaction of olefinic compound, carbon monoxide and water is kind of under the conditions of hydroformylation in the presence of a catalyst, representing a complex of a metal-organophosphorus ligand, which is described here. Alternatively, hydroxyaldehyde can be obtained by reaction of the epoxide, carbon monoxide and hydrogen under conditions of hydroformylation in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, which is described here. Hydroxyaldehyde you can gidrirovanii to diol, such as hydroxypropylmethyl you can gidrirovanii to propane diol. How hydroformylation more fully described below.

Intramolecular gidroalkilirovanie can be performed by conventional procedures known from the prior art. For example, aldehydes containing deleted olefinic groups in which from 3 to 7 carbon atoms, can be converted into cyclic ketones under the conditions of gidroalkilirovaniya in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, which is described here.

Intermolecular gidroalkilirovanie can be performed by conventional procedures known from the prior art.

For example, the ketones can be obtained by the reaction of olefin and aldehyde under the conditions of gidroalkilirovaniya in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, which is described here.

Hidrotsianova you can perform p the traditional procedures, known from the prior art. For example, compounds NITRILES can be obtained by reaction of olefinic compounds and hydrogen cyanide under conditions of hydrocyanide in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, which is described here. The preferred method of hydrocyanide involves the reaction of unpaired acyclic aliphatic monoolefins, monoolefins associated with the ester group, for example methylpent-2-enoate, or monoolefins paired with a nitrile group, such as 2-pentenenitrile, with a source of hydrogen cyanide in the presence of the composition of the catalyst precursor, comprising a Nickel zero-valent state and bidentate fosfatnyi ligand, to obtain organonitriles with the terminal nitrile group, such as adiponitrile, alkyl-5-cyanovaleric or 3-(perfluoroalkyl)propionitrile. Preferably the reaction is carried out in the presence of a promoter, which is a Lewis acid. Examples of methods hydrocyanide are described in U.S. patent No. 5523453 and WO 95/14659, the description of which is included here by reference.

Gidrogenizirovanii can be performed by conventional procedures known from the prior art. For example, the amides can be obtained by reaction of olefins, carbon monoxide and a primary or secondary amine or ammonia when y is s gidrolizirovanny in the presence of a catalyst, representing a complex of a metal-organophosphorus ligand, which is described here.

Hydroesterification can be performed by conventional procedures known from the prior art. For example, esters can be obtained by reaction of olefins, carbon monoxide and alcohol under conditions of hydroesterification in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, which is described here.

Aminals can be performed by conventional procedures known from the prior art. For example, amines can be obtained by reaction of olefins with primary or secondary amines under the conditions of aminolysis in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, which is described here.

The alcoholysis can be performed according to conventional procedures known from the prior art. For example, the esters can be obtained by reaction of an olefin with an alcohol under conditions of alcoholysis in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, which is described here.

Hydrocarbonylation can be performed by conventional procedures known from the prior art. For example, alcohols can be obtained by reaction of olefinic compounds, carbon monoxide, hydrogen and promoter under conditions of hydrocarbonylation in prisutstvie and catalyst, representing a complex of a metal-organophosphorus ligand, which is described here.

Restorative hydroformylation can be performed by conventional procedures known from the prior art. For example, alcohols can be obtained by reaction of olefinic compound, carbon monoxide and hydrogen under conditions of reductive hydroformylation in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, which is described here.

The hydrogenation can be performed according to conventional procedures known from the prior art. For example, alcohols can be obtained by reaction of the aldehyde under the conditions of hydrogenation in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, which is described here.

The oligomerization of olefins can be performed according to conventional procedures known from the prior art. For example, higher olefins can be obtained by reaction of olefins under oligomerization conditions in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, which is described here.

Hydroxycarbonylmethyl can be obtained by conventional procedures known from the prior art. For example, acids can be obtained by reaction of olefinic compounds, carbon monoxide, water and promoter with us what the conditions of hydroxycarbonate in the presence of a catalyst, representing a complex of a metal-organophosphorus ligand, which is described here.

Carbonylation can be performed according to conventional procedures known from the prior art. For example, lactones can be obtained by processing allyl alcohols and carbon monoxide under carbonylation conditions in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, which is described here.

The isomerization can be performed according to conventional procedures known from the prior art. For example, allyl alcohols can be isomerizate at isomerization conditions to obtain an aldehyde, in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, which is described here.

Hydrogenation with hydrogen transport can be done in accordance with conventional procedures known from the prior art. For example, alcohols can be obtained by reaction of the ketone and alcohol under the conditions of transfer hydrogenation with hydrogen in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand.

Valid source reagents covered by the methods of the present invention, of course, chosen depending on the particular process. Such starting materials are well known in the art and can be used with t the ion quantities using traditional methods. Examples of reagents include, for example, substituted and unsubstituted aldehydes (intramolecular gidroalkilirovanie), olefins (hydroformylation, carbonylation, hydrocarbonylation, rehabilitation hydroformylation, intermolecular gidroalkilirovanie, hidrotsianova, gidrogenizirovanii, hydroesterification, aminals, alcoholysis), ketones (hydrogenation with hydrogen transport), epoxides (hydroformylation, hidrotsianova), alcohols (carbonylation) and similar compounds. Examples of suitable reagents for performing the methods of the present invention is described in detail in Kirk-Othmer, Encyclopedia of Chemical Technology, Fourth Edition, 1996, the relevant portions of which are incorporated here by reference.

Examples of catalysts consisting of a complex of a metal-organophosphorus ligand, which can be employed in the processes covered by this invention and methods for their preparation, are well known in the art and include those that are described in the following patents. In General, such catalysts can be made or obtained in situ, as described in these links, and they consist essentially of metal in the form of a complex with an organophosphorus ligand. Active compounds may also contain carbon monoxide and/or hydrogen directly related to the metal.

The catalyst useful in the processes, includes a catalyst comprising a complex of a metal-organophosphorus ligand, which may be optically active or optically inactive. Acceptable metals, which form complexes with metal-organophosphorus ligand, include the metals of groups 8, 9 and 10, selected from rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), Nickel (Ni), palladium (Pd), platinum (Pt), osmium (Os) and mixtures thereof, with the preferred metals are rhodium, cobalt, iridium and ruthenium, more preferred are rhodium, cobalt and ruthenium and especially rhodium. Other acceptable metals include metals 11 group selected from copper (Cu), silver (Ag), gold (Au) and their mixtures, as well as metals of group 6, selected from chromium (Cr), molybdenum (Mo), tungsten (W) and mixtures thereof. In this invention it is also possible to use mixtures of metals from 6, 8, 9, 10 and 11 groups. Valid organophosphorus ligands, which are part of complexes the metal-organophosphorus ligand and free organophosphorus ligands include organophosphine, for example bisphosphines and triorganotin, and organophosphites, for example mono-, di-, tri - and polygonoffset. Other valid organophosphorus ligands include, for example, organophosphonate, organophosphonate, phosphorus amides and similar compounds. If desired, the catalyst comprising Soboh the complex metal-organophosphorus ligand, and/or in the free ligand, it is possible to use mixtures of such ligands, and such mixtures may be the same or different. There is no intention to limit the invention in any way a valid organophosphorus ligands or mixtures thereof. It should be noted that the successful practice of this invention does not depend and is not claimed, the exact structure of compounds representing a complex of a metal-organophosphorus ligand, which may be present in maneadero, dual-core and/or more vysokogornyh forms. Indeed, the exact structure is not known. Although there is no intention to build not any theory or mechanistic discourse, it is obvious that the catalytic compounds can in its simplest form consist essentially of metal in the form of a complex with organophosphorus ligand, carbon monoxide and/or hydrogen, in the case of their use.

Used herein and in the claims, the term "complex" means a coordination compound formed by combining one or more electrondonating (donors) of molecules or atoms capable of independent existence, with one or more electronmomentum (acceptors) molecules or atoms, each of which can independently exist. For example, the use of what has been created here organophosphorus ligands may have one or more donor atoms of phosphorus, each of which has one free or unshared pair of electrons, each of which is capable of forming coordination covalent bond independently or perhaps together (for example, through helatoobrazutee) with metals. Carbon monoxide (which is also, strictly speaking, is classified as a ligand) may also be present and form a complex with the metal. The ultimate composition of a catalyst comprising a complex may also contain additional ligand, such as hydrogen or an anion, satisfying focal points or nuclear charge of the metal. Examples of additional ligands include, for example, halogen (Cl, Br, I), alkyl, aryl, substituted aryl, acyl, CF3C2F5CN, (R)2PO and RP(O)(OH)OH (where each R is the same or different and represents a substituted or unsubstituted hydrocarbon radical, for example alkyl or aryl), acetate, acetylacetonate, SO4PF4PF6, NO2, NO3CH3O, CH2=CHCH2CH3SN=SNSN2With6H5CN, CH3CN, NO, NH3, pyridine, (C2H5)3N, monoolefinic, diolefine and triolein, tetrahydrofuran and similar. Of course, you need to understand that complex compounds preferably do not contain any additional organic ligand or anion,which can poison the catalyst or to have undue adverse effects on the operational characteristics of the catalyst. In the process, catalyzed by a complex of a metal-organophosphorus ligand, such as hydroformylation, it is preferable that the active catalysts do not contain halogen or sulfur directly related to the metal, although it may not be absolutely necessary. The preferred catalysts, consisting of a complex of the metal-ligand include catalysts are complexes of rhodium-organophosphine ligands, and catalysts are complexes of rhodium-organophosphine ligand.

The number of available focal points on these metals is well known. Thus, the catalytic compounds can include a mixture of catalytic complexes, in their Monomeric, dimeric or higher forms of adereti, which are preferably characterized by at least one molecule containing organophosphorus group, in the form of a complex with one molecule of metal, such as rhodium. For example, it is believed that the catalytic compounds of the preferred catalyst used in the reaction of hydroformylation, can be complex with carbon monoxide and hydrogen in addition to the organophosphorus ligand, whereas carbon monoxide and hydrogen gas used in the reaction of hydroformylation.

Organophosphine and organophosphate is, which can serve as ligands in catalyst comprising a complex of a metal-organophosphorus ligand, and/or free ligand, in the methods according to this invention, can be achiral (optically inactive) or chiral (optically active) type and are well known in the prior art. Under "free ligand" means a ligand that is not in the form of a complex (associated or connected with metal, for example metal atom, the catalytic complex. As noted here, the method according to this invention, and especially the way hydroformylation, can be carried out in the presence of free organophosphorus ligand.

The achiral organophosphine and organophosphate are preferred.

Among organophosphines that can serve as ligands in catalyst comprising a complex of a metal-organophosphine, and/or free organophosphine ligand reaction mixture starting materials, are triorganotin, trialkylphosphine, alkyldiphenylamine, dialkylacrylamide, dicyclohexylphenylphosphine, cycloalkylcarbonyl, trialkylphosphine, trialkylphosphine, tricyclohexylphosphine and triarylphosphine, alkyl - and/or kivipostid and monooxide bisphosphines and similar compounds. Of course, any hydrocarbon radical such third is different nonionic organophosphines may be substituted, if desired, any suitable substitute, which does not impact unduly adversely on the desired reaction of hydroformylation. Phosphinotricine ligands that can be used in the reactions and/or methods for their preparation, are known from the prior art.

Examples trehzameshchenny organophosphine ligands can be represented by the formula

where each R1is the same or different and is a substituted or unsubstituted monovalent hydrocarbon radical, for example alkyl or aryl radical. Suitable hydrocarbon radicals can contain from 1 to 24 carbon atoms or more. Illustrative of the group of substituents that may be present in the aryl radicals include, for example, alkyl radicals, CNS radicals, silyl radicals such as -- Si(R2)3; aminosalicylic, such as-N(R2)2; acyl radicals such as-C(O)R2; carboxyl radicals such as-C(O)OR2; aryloxyalkyl, such as-OC(O)R2; emidiately, such as-C(O)N(R2)2and-N(R2)C(O)R2; sulfonylurea radicals, such as-SO2R2; ether radicals such as-OR2; sulfinyl radicals, such as-SOR2; sulfanilimide radicals, such as-SR2and halogen, is itagroup, the cyano, triptoreline, hydroxyl radicals and similar, where each R2individually represents the same or different substituted or unsubstituted monovalent hydrocarbon radicals, with the proviso that the substituents representing the amino group, such as-N(R2)2each of R2taken together can also represent a divalent bridging group that forms a heterocyclic radical with the nitrogen atom and the substituents representing aminogroup, such as-C(O)N(R2)2and-N(R2)C(O)R2each R2associated with N can also be hydrogen. Illustrative alkyl radicals include, for example, methyl, ethyl, propyl, butyl and similar. Illustrative aryl radicals include, for example, phenyl, naphthyl, diphenyl, forfinal, differenl, benzyloxyphenyl, carbamaxepine, acetylphenyl, ethoxyphenyl, phenoxyphenyl, hydroxyphenyl, carboxyphenyl, triptoreline, methoxyethanol, acetamidophenyl, dimethylcarbamoyl, tolyl, xylyl and similar.

Illustrative typical organophosphine include, for example, tributylphosphine, though, triphenylphosphine, Tris-p-tolylphosphino, Tris-p-methoxyphenylacetyl, Tris-p-forperforming, Tris-p-chlorphenesin, Tris-dimethylaminopropoxy, propylpiperazine, tert-butyl is Ivanishin, n-butyldiethanolamine, n-hexylbiphenyl, cyclohexylpiperazine, dicyclohexylphenylphosphine, tricyclohexylphosphine, tribenzylphosphine, as well as salts of alkali and alkaline earth metals from sulphonated triphenylphosphine, for example (three-m-sulfophenyl)phosphine, (m-sulfophenyl)diphenylphosphine and similar.

More specifically, examples of the catalysts, which is a complex metal-organophosphine, and examples of free organophosphine ligands include, for example, compounds described in U.S. patents№3527809, 4148830, 4247486, 4283562, 4400548, 4482749 and 4861918, the description of which is included here by reference.

Among organophosphates, which can serve as a ligand in the catalyst comprising a complex of a metal-organophosphate, and/or free organophosphine ligand in the reaction mixture of original substances, are monoethanolamide, diorganotin, triorganotin and organophosphate. Organophosphine ligands that can be used in this invention, and/or methods for their preparation are known from the prior art.

Typical representatives of monoethanolamide may include compounds having the formula

where R3represents a substituted or unsubstituted trivalent hydrocarbon radical containing from 4 to 40 carbon atoms or more, Taco is as trivalent acyclic or trivalent cyclic radicals, for example trivalent alkylene radicals, such as radicals derived from 1,2,2-trimethylolpropane, and the like, or trivalent cycloalkene radicals, such as radicals derived from 1,3,5-trihydroxychalcone, and similar. A more detailed description of such monoethanolamide can be found, for example, in U.S. patent No. 4567306, the description of which is included here by reference.

Typical diorganotin may include compounds having the formula

where R4represents a substituted or unsubstituted divalent hydrocarbon radical containing from 4 to 40 carbon atoms or more, and W represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 18 carbon atoms or more.

Typical substituted or unsubstituted monovalent hydrocarbon radicals represented by W in the above formula (III)include alkyl and aryl radicals, while typical substituted or unsubstituted divalent hydrocarbon radicals represented by R4include divalent acyclic radicals and divalent aromatic radicals. Examples of the divalent acyclic radicals include, for example, alkylene, alkylene-hydroxy-alkylene, alkylene-NX-alkylene, where X represents hydrogen or substituted for the first or unsubstituted monovalent hydrocarbon radical, alkylen-S-alkylene, cycloalkene radicals and similar. Preferred divalent acyclic radicals are divalent alkylene radicals, such as more fully described in, for example, U.S. patent No. 3415906 and 4567302 and similar, the description of which is included here by reference. Examples of divalent aromatic radicals include, for example, allenbyi, bizarrerie, Allen-alkylene, Allen-alkylen-allenbyi, Allen-hydroxy-allenbyi, Allen-NX-allenbyi, where X is as defined above, Allen-S-allenbyi, Allen-S-alkylene and similar. More preferably R4represents a divalent aromatic radical, such as more fully described in, for example, in U.S. patent No. 4599206 and 4717775 and similar, the description of which is included here by reference.

Typical representatives of more preferred class of georganopoulou are the compounds of formula

where W is as defined above, each Ar is the same or different and represents a substituted or unsubstituted aryl radical, each y is the same or different and is 0 or 1, Q represents a divalent bridging group selected from-C(R5)2-, -O-, -S-, -NR6-, Si(R7)2- CO-, where each R5it is the same or different and represents hydrogen, alkyl radicals having from 1 to 12 carbon atoms, phenyl, tolyl and anisyl, R6represents hydrogen or a methyl radical, each R7is the same or different and represents hydrogen or a methyl radical, and m is 0 or 1. Such diorganotin more detail, for example, in U.S. patent No. 4599206, 4717775 and 4835299, the description of which is included here by reference.

Typical triorganotin may include compounds having the formula

where each R8is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical, for example alkyl, cycloalkyl, aryl, alkalline or Uralkaliy radical, which may contain from 1 to 24 carbon atoms. Suitable hydrocarbon radicals can contain from 1 to 24 carbon atoms or more and may include radicals described above for R1in the formula (I). Examples of triorganotin include, for example, trialkylphosphine, dialkylacrylamide, alkylarylphosphites, triarylphosphite and similar compounds such as, for example, trimethylphosphite, triethylphosphite, butylmethylether, tri-n-propylphosphine, tri-n-butylphosphate, three 2-ethylhexyloxy, tri-n-octylphosphine, tri-n-dodecylphenyl, tri-o-tolylphosphino, dimethylphenylphosphine, diethylphenylphosphine, merdiven ltopic, ethyldiphenylphosphine, triphenylphosphite, trinatriumfosphate, bis(3,6,8-tri-tert-butyl-2-naphthyl)methylphosphate, bis(3,6,8-tri-tert-butyl-2-naphthyl)cyclohexyloxy, Tris-(3,6-di-tert-butyl-2-naphthyl)FOSFA, bis(3,6,8-tri-tert-butyl-2-naphthyl)(4-diphenyl)FOSFA, bis(3,6,8-tri-tert-butyl-2-naphthyl)phenylphosphate, bis(3,6,8 three-tert-butyl-2-naphthyl)(4-benzoylphenyl)FOSFA, bis(3,6,8-tri-tert-butyl-2-naphthyl)(4 - sulfanilyl)FOSFA and similar. The preferred reorganistion is triphenylphosphite. Such triorganotin more detail, for example, in U.S. patent No. 3527809 and 5277532, descriptions of which are incorporated here by reference.

Typical organophosphate contain two or more tertiary (trivalent) phosphorus atom, and may include compounds having the formula

where X1represents a substituted or unsubstituted n-valent hydrocarbon bridging radical containing from 2 to 40 carbon atoms, each R9is the same or different and represents a divalent hydrocarbon radical containing from 4 to 40 carbon atoms, each R10is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms, a and b may be the same or different, and each has a value from 0 to 6 when is slowiy, that the sum a + b is equal to from 2 to 6 and n equals a + b. Of course, you need to understand that when a is 2 or more, each R9the organic radical can be the same or different, and when b is 1 or more, each R10the radical may be the same or different.

Typical representatives of the n-valent (preferably divalent) hydrocarbon bridging radicals represented by X1as well as typical representatives of the divalent hydrocarbon radicals represented by the above R9include both acyclic radicals and aromatic radicals, such as alkylene, alkylene-Qm-alkylene, cycloalkene, allenbyi, bizarrerie, Allen-alkylene, Allen-(CH2)y-Qm-(CH2)y-allenbyi radicals and similar, where Q, m and y are as defined above for formula (IV). More preferred acyclic radicals represented by the above X1and R9are divalent alkylene radicals, while the more preferred aromatic radicals represented by the above X1and R9are divalent allenbyi and bizarrerie radicals, such as described more fully, for example, in U.S. patents№4769498; 4774361; 4885401; 5179055; 5113022; 5202297; 5235113; 5264616 and 5364950 and in the publication of the European States and in patent No. 662 468 and similar, the description of which is included here by reference. Typical representatives of the monovalent hydrocarbon radicals represented by each of the above radical R10include alkyl and aromatic radicals.

Illustrative preferred organophosphate may include bisphosphite, such as the compounds described by formulas (VII)to(IX) below

where each R9, R10and X1from formulas (VII)to(IX) is the same as defined above for formula (VI). Preferably each R9and X1represents a divalent hydrocarbon radical selected from alkilinity, arenovich, Allen-alkylen-arenovich and bizarrely, while each R10represents a monovalent hydrocarbon radical selected from alkyl or aryl radicals. Description organophosphine ligands such formulas (VI)to(IX) can be found, for example, in U.S. patents№4668651; 4748261; 4769498; 4774361; 4885401; 5113022; 5179055; 5202297; 5235113; 5254741; 5264616; 5312996; 5364950 and 5391801, the description of which is included here by reference.

Typical representatives of the more preferred classes of organobentonites are compounds of the following formulas (X) -(XII):

where Ar, Q, R9, R10X1, m and y are as defined above. Most preferably X1p is ecstasy a divalent aryl-(CH 2)y-Qm-(CH2)y-arrowy radical, where each y individually has a value of 0 or 1; m is 0 or 1 and Q is-O-, -S - or-C(R5)2-, where each R5is the same or different and represents hydrogen or a methyl radical. More preferably, each alkyl radical of the defined above, R10groups can contain from 1 to 24 carbon atoms and each aryl radical videopreteen Ar, X1, R9, R10groups of the above formulas (VI)-(XII) may contain from 6 to 18 carbon atoms, these radicals can be identical or different, while the preferred alkylene radicals X1can contain from 2 to 18 carbon atoms and preferred alkylene radicals R9can contain from 5 to 18 carbon atoms. In addition, preferably the divalent Ar radicals and divalent aryl radicals X1of the above formulas are phenylanaline radicals, where the bridging group represented by -(CH2)y-Qm-(CH2)y-associated with the specified phenylanaline radicals in positions that are ortho-position to the oxygen atoms that connect phenylenebis radicals on the phosphorus atoms in formulas. Also is preferred that any radical, which batch is ielem, when it is present in such filinovich the radicals, would be connected in the para and/or ortho-position filinovich radicals relative to the oxygen atoms that connect this substituted phenylenebis radical with the phosphorus atom.

Of course any of the radicals R3, R4, R8, R9, R10X1X2, W, Q and Ar such organophosphites formulas (II)-(XII)above, may be substituted, if desired, any suitable Deputy containing from 1 to 30 carbon atoms, which is not affected unduly adversely on the desired reaction of hydroformylation. The substituents that may be present in the above radicals, of course, in addition to corresponding hydrocarbon radicals such as alkyl, aryl, kalkilya, alkaline and tsiklogeksilnogo substituents may include for example silyl radicals such as -- Si(R12)3; amino radicals such as-N(R12)2; phosphine radicals, such as aryl-P(R12)2; acyl radicals such as-CO(R12)2; Allexinno radicals, such as-OC(O)R12; emidiately, such as-CON(R12)2and-N(R12)COR12; sulfonylurea radicals, such as-SO2R; CNS radicals, such as-OR12; sulfinyl radicals, such as-SOR12; sulfanilimide R is dicale, such as-SR12; postonline radicals such as -- P(O)(R12)2and halogen, the nitro-group, a cyano, triptorelin, hydroxyl radicals and similar, where each R12the radical is the same or different and represents a monovalent hydrocarbon radical having from 1 to 18 carbon atoms (for example, alkyl, aryl, kalkilya, alkaline and tsiklogeksilnogo radicals), provided that in aminosalicylates, such as-N(R12)2each R12taken together can also represent a divalent bridging group that forms a heterocyclic radical with the nitrogen atom, and in imidazolides, such as C(O)N(R12)2and N(R12)COR12each R12associated with N can also be hydrogen. Of course you must understand that any group that represents a substituted or unsubstituted hydrocarbon radical, which make this specific organophosphate, may be the same or different.

More specifically, illustrative substituents include primary, secondary and tertiary alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, amyl, sec-amyl, tert-amyl, isooctyl, decyl, octadecyl and similar; aryl radicals such as phenyl, naphthyl and similar is; kalkilya radicals, such as benzyl, phenylethyl, triphenylmethyl and similar; alkaline radicals, such as tolyl, xylyl and similar; alicyclic radicals such as cyclopentyl, cyclohexyl, 1-methylcyclohexyl, cyclooctyl, cyclohexylethyl and similar; CNS radicals, such as methoxy, ethoxy, propoxy, tert-butoxy, -och2CH2Och3, -(Och2CH2)2OCH3, -(Och2CH2)3Och3and similar; aryloxyalkyl, such as phenoxy and similar, as well as silyl radicals such as -- Si(CH3)3, -Si(och3)3, -Si(C3H7)3and similar; aminosalicylic, such as-NH2-, -N(CH3)2, -NHCH3, -NH(C2H5and similar; arylphosphine radicals such as-P(C6H5)2and similar; acyl radicals such as-C(O)CH3-C(O)2H5-C(O)6H5and similar; carboniteservice, such as-C(O)och3and similar; oxycarbonyl radicals, such as-O(CO)6H5and similar; emidiately, such as-CONH2, -CON(CH3)2, -NHC(O)CH3and similar; sulfonylurea radicals, such as-S(O)2C2H5and similar; sulfinyl radicals, such as-S(O)CH3and similar; sulfanilimide Radik the crystals, such as-SCH3, -SC2H5, -SC6H5and similar; postonline radicals such as -- P(O)(C6H5)2, -P(O)(CH3)2, -P(O)(C2H5)2, -P(O)(C3H7)2, -P(O)(C4H9)2, -P(O)(C6H13)2, -P(O)CH3(C6H5), -P(O)(N)(C6H5and similar.

Specific illustrative examples of organophosphorus ligands are described in simultaneously considering U.S. patent No. 5786517, the description of which is included here by reference.

Catalysts, consisting of a complex of a metal-organophosphorus ligand, preferably located in a homogeneous form. For example, pre-molded catalysts redigitization-organophosphorus ligand can be prepared and put in the reaction mixture the particular process. More preferably, the catalysts, consisting of a complex of a metal-organophosphorus ligand, can be obtained from the original substances for rhodium catalyst, which can be introduced into the reaction environment at the place of formation of the active catalyst. For example, the starting materials for the rhodium catalyst, such as decarbonylation rhodium, Rh2O3Rh4(CO)12Rh6(CO)16Rh(NO3)3and similarly, you can enter in the reaction mixture the place with organophosphorus ligand to obtain in situ active catalyst.

As noted above, the organophosphorus ligands can be used in the form of a ligand of a catalyst comprising a complex of a metal-organophosphorus ligand and free organophosphorus ligand, which may be present in the reaction medium of the method according to the present invention. In addition, you must understand that while organophosphorus ligands of the catalyst comprising a complex of a metal-organophosphorus ligand, and abundant free organophosphorus ligand, preferably present in the process of the present invention, typically are of one type of ligand for each target in any given way, if you prefer, you can use different types of organophosphorus ligands, as well as a mixture of two or more different organophosphorus ligands.

It is necessary that the amount of catalyst comprising a complex of a metal-organophosphorus ligand present in the reaction medium of this method according to this invention, it is only the minimum number necessary to ensure the concentration of the metal desired for use, and which will supply a basis, at least for that amount of metal necessary to catalyze the particular desired process. In General, it is ncentratio metal in the range of from about 1 part per million to 10,000 parts per million, calculated free metal, and the molar ratios of ligand to metal in the catalyst solution being in the range of from about 1:1 or less to about 200:1 or greater, should be sufficient for most processes.

As noted above, in addition to catalysts, consisting of a complex of a metal-organophosphorus ligand, methods according to this invention, and in particular the process of hydroformylation, can be carried out in the presence of free organophosphorus ligand. While the methods of this invention can be held in any desired excess amount of free organophosphorus ligand, the free organophosphorus ligand may not be absolutely necessary. Accordingly, in General, the number of ligand from about 1.1 or less up to 200 or higher moles per 1 mole of metal (e.g., rhodium), present in the reaction medium, if desired, should be suitable for most purposes, particularly with regard to hydroformylation catalyzed by rhodium, and the specified number of ligand are the sum of the amount of ligand that is bound (complex) to the presence of metal, and the amount of free (not included in package) available ligand. Of course, if desired, to the reaction medium of the process m which can be used for more number of ligand at any time and in any appropriate manner to maintain a predetermined level of free ligand in the reaction medium.

Valid reaction conditions that can be used in the methods according to this invention, of course, chosen depending on the specific desired synthesis. Such process conditions are well known in the prior art. All the methods of this invention can be carried out according to conventional procedures known from the prior art. Examples of the reaction conditions for the implementation of the methods of the present invention are described, for example, in Kirk-Othmer, Encyclopedia of Chemical Technology, Fourth Edition, 1996, the relevant portions of which are incorporated here by reference. Depending on the specific process operating temperatures can be in the range of from about -80°or less up to 500°s or greater and operating pressures can be in the range of from about 1 pound per square inch(wt.) or less to 10,000 pounds/square inch(wt.) or more.

Methods according to this invention is carried out in a period of time sufficient to obtain the desired products. Accurate used, the reaction time depends in part on factors such as temperature, pressure, nature and proportions of the starting materials, and similar. The reaction time will normally be within the range from about half an hour to 200 hours or more, preferably about less than one hour to 10 hours.

Methods according to this invention is useful for obtaining substituted or unsubstituted is optically active s and optically inactive compounds. Examples of compounds obtained by the methods according to this invention include, for example, substituted and unsubstituted alcohols or phenols; amines; amides; ethers or epoxides; esters; ketones; aldehydes and NITRILES. Examples of suitable optically active and optically inactive compounds, which can be obtained by the methods according to this invention (including compounds of source materials, as described above) include a valid connection, which are described in Kirk-Othmer, Encyclopedia of Chemical Technology, Fourth Edition, 1996, the relevant portions of which are incorporated here by reference and The Merck Index, An Encyclopedia of Chemicals, Drugs and Biologicals, Eleventh Edition, 1989, relevant portions of which are incorporated here by reference.

As indicated above, the methods according to this invention is carried out in the reaction zone in the presence of a nonpolar solvent and a polar solvent or in the presence of a nonpolar solvent, followed by mixing with a polar solvent to the separation zone, or in the presence of a nonpolar solvent, followed by mixing with a second non-polar solvent to the separation zone. Depending on the specific of the used catalyst and reagents suitable nonpolar solvents include, for example, alkanes, cycloalkanes, alkenes, alkadienes, aldehydes, ketones, ethers, esters, amines, aromatics, silanes, silicone is, carbon dioxide and similar. Examples of inappropriate non-polar solvents include fluorocarbons and fluorinated hydrocarbons. They are undesirable because of their high cost, risk of environmental pollution and potential formation of multiple phases. In one embodiment, the implementation in practice of the invention one or more of the reactants, the catalyst comprising a complex of a metal - organophosphorus ligand, and optionally free organophosphorus ligand show a sufficient solubility in non-polar solvent so that the agents for the phase transfer or surfactants are not required.

If you prefer, you can use a mixture of one or more different non-polar solvents. The amount of nonpolar solvent is not critical to the subject invention and need only be that amount sufficient to provide the reaction medium with the concentration of the metal desired for this process. In General, the number of non-polar solvent can be in the range of from about 5-99 wt.% or more of the total mass of the reaction mixture.

Examples of nonpolar solvents useful in this invention include, for example, propane, 2,2-DIMETHYLPROPANE, butane, 2,2-Dimethylbutane, pentane, isopr pillowy ether, hexane, triethylamine, heptane, octane, Noonan, Dean, isobutylester, tributylamine, undecane, 2,2,4-trimethylpentane, isobutylacetate, butadiene, Diisobutylene, cyclopentane, cyclohexane, isobutylbenzene, n-nonylbenzene, n-octylbenzoic, n-butylbenzoyl, p-xylene, ethylbenzene, 1,3,5-trimethylbenzene, m-xylene, toluene, o-xylene, the mission dodecen, tetradecene and heptadecanol. The solubility parameters illustrative non-polar solvents are given in table 1.

Table 1

The solubility parameters illustrative non-polar solvents

Non-polar solventδsolvent - < / br>
(cal/cm3)1/2
δsolvent - < / br>
(kJ/m3)1/2
Propane5,76373
2,2-DIMETHYLPROPANE6,10395
Bhutanto 6.58426
2.2-Dimethylbutan6,69433
Pentane7,02454
Isopropyl ether7,06457
Hexane7,27470
The triethylamine7,42480
Heptane7,5045
Octane7,54488
Noonanof 7.64494
Dean7,72499
Isobutylester7,74501
Tributylamine7,76502
Undecane7,80505
2,2,4-Trimethylpentaneto 7.93513
Isobutylketone ketone7,95514
Diisobutyrateof 8.06521
The cyclopentane8,08523
Cyclohexane8,19530
n-Nonylbenzene8,49549
n-Octylbenzoic8,56554
n-Butylbenzoyl8,57554
p-Xylene8,83571
Ethylbenzene8,84572
1,3,5-Trimethylbenzene8,84572
m-Xylene8,88574
Toluene8,93578
o-Xylene9,06586

The desired products filed with the invention can be selectively removed by extraction or separation of phases in polar solvent. As shown above, the polar solvent may be present together with a nonpolar solvent for the reaction or the liquid reaction product can be contacted with a polar solvent after the reaction. The desired reaction product is preferably extracted from the liquid reaction product, using the appropriate polar solvent so that the extraction of one or more of the reactants, the catalyst comprising a complex of a metal-organophosphorus ligand, and optionally free organophosphorus ligand from the liquid reaction product is minimal or eliminated. In one embodiment, in practice, the polar solvent is an aqueous mixture, preferably containing up to about 8 wt.% water, more preferably less than approximately 6 wt.% water and most preferably less than approximately 4 wt.% water. It is believed that in this embodiment, in practice the methods of the present invention are essentially "not water" means, in other words present in the reaction medium, water is not in quantities sufficient to cause a specific reaction or a specified environment is seen as including a separate aqueous phase or water phase or layer in addition to the organic phase. Depending on the specific W the products being suitable polar solvents include, for example, NITRILES, lactones, alkanols, cyclic acetals, water, pyrrolidone, formamide, sulfoxidov and similar compounds. In another embodiment, in practice, the polar solvent is a different combination than the combination of the primary alkanol and water.

If you prefer, you can use a mixture of one or more different polar solvents. The solubility parameter of Hildenbrand for polar solvent or mixtures of one or more different polar solvents should be approximately less than 13.5 (cal/cm3)1/2or 873 (kJ/m3)1/2preferably less than approximately 13,0 (cal/cm3)1/2or 841 (kJ/m3)1/2and more preferably about less than 12.5 (cal/cm3)1/2or 809 (kJ/m3)1/2. The amount of the polar solvent is not critical to the subject invention, it is only necessary that the amount would be sufficient for the extraction of one or more products from the liquid reaction product for any given process. In General, the amount of polar solvent can be in the range of from about 5 to 50 wt.% or more of the total weight of the liquid reaction product.

Examples of polar solvents useful in this invention include, for example, propionitrile, 1,3-di is Xalan, 3-methoxypropionitrile, N-methylpyrrolidinone, N,N-dimethylformamide, 2-methyl-2-oxazoline, adiponitrile, acetonitrile, Epsilon-caprolactone, glutaronitrile, 3-methyl-2-oxazolidinone, water, dimethylsulfoxide and sulfolane. For the purposes of the present invention one or more products can serve as a polar reaction solvent. The solubility parameters illustrative polar solvents are given in table 2.

Table 2

The solubility parameters illustrative polar solvents

The polar solventδsolvent - < / br>
(cal/cm3)1/2
δsolvent - < / br>
(kJ/m3)1/2
Propionitrileof 10.73694
1,3-Dioxolane11,33733
3-Methoxypropionitrile11,37735
N-Organic11,57748
N,N-Dimethylformamide11,76761
2-Methyl-2-oxazoline12,00776
Adiponitrile12,05779
Acetonitrile12,21790
ε-Caprolacton12,6 819
Sulfolan12,80828
Glutaronitrile13,10847
The sulfoxide13,10847
3-Methyl-2-oxazolidinone13,33862
Water23,531522

Extraction with in order to obtain one phase comprising one or more reactants, the catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand and non-polar solvent, and at least one other phase comprising one or more products and the polar solvent is an equilibrium process. The relative amounts of polar solvent (or solvent extraction solution) and non-polar solvent or liquid reaction product in this activity, the extraction is partially determined by the solubility of one or more of the reactants, the catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand and one or more products in the used solvent, and the amount of the desired product, which should be extracted. For example, when the extraction of the desired product, if the desired product is CT, which is to be extracted, shows high solubility in polar solvent and is present in relatively low concentrations in the liquid reaction product, it is possible to extract the desired product using a polar solvent in a relatively small volume ratio of the liquid reaction product. Polar and non-polar solvents described above can be used as extraction solvents.

Further, as the concentration of the desired product becomes high, it is usually necessary to increase the ratio of polar solvent to the liquid reaction product for extraction of the desired product from the liquid reaction product. When the desired product shows a relatively low solubility in the polar solvent, the relative amount of polar solvent or extraction solution should be increased. In General, the volume ratio of the polar solvent or extraction solution to the liquid reaction product can vary in the range of from about 20:1 to 1:20.

In one embodiment, in practice, the products obtained according to the method of this invention can have sufficient polarity to make the products is not miscible with non-polar solvent. Phase separation can occur which resolved spontaneously before the separation zone or may be caused by changes in temperature or pressure, or the introduction of additives such as salt or by evaporating the solvent, or combination thereof. Adding external polar solvent, to cause separation of the phases may not be required for certain methods according to this invention.

Except that the above-noted relative to the temperature of extraction, there is no advantage in using a temperature higher than the reaction temperature of the specific process, and the desired results can be obtained using the temperature of extraction is lower than the reaction temperature of the process. Depending on the specific process temperature of extraction may be in the range of from about -80°or less than about 200°s or greater.

Mixing time of the liquid reaction product with a polar solvent, i.e. the time before phase separation depends on the speed at which the two phases reach equilibrium. Typically, such time may vary from a minute or less before a longer period of one hour or more.

The method of extraction according to this invention is partly equilibrium process organophosphorus ligand dissolved in two separate liquid phases. The efficiency of this extraction process can be measured by the distribution coefficient organophosphorus ligand KR1, which is determined by the t in the following way:

When one or more desired products are distributed between the polar phase and the nonpolar phase of the extraction process of the present invention, the value of Kp1 organophosphorus ligand can be maintained at greater than about 5, more preferably about 7.5, and more preferably more than about 10, depending on the efficiency of the extraction process. If this value Kp1 is high, the organophosphorus ligand is preferably dispersed in the nonpolar phase. Used in Kp1 concentration of organophosphorus ligand includes free organophosphorus ligand and organophosphorus ligand in the form of a complex with the metal.

The method of extraction according to this invention is also partly equilibrium process one or more products, dissolved in two separate liquid phases. The efficiency of this extraction process can be measured by the distribution coefficient Kr one or more products, which is determined as follows:

When one or more desired products are distributed between the polar phase and the nonpolar phase of the extraction process of the present invention, the value CR products can be maintained at less than about 2, predpochtitelno less than about 1.5, and more preferably less than about 1, depending on the efficiency of the extraction process. If this value CR is low, the products are preferably will be distributed in the polar phase.

The method of extraction according to this invention further is partly equilibrium process one or more decomposition products of organophosphorus ligand dissolved in two separate liquid phases. The efficiency of this extraction process can be measured by the distribution coefficient WP3 one or more decomposition products of organophosphorus ligand, which is determined as follows:

When one or more of the decomposition products of organophosphorus ligand is distributed between the polar phase and the nonpolar phase of the extraction process of the present invention, the value of WP3 decomposition products of organophosphorus ligand can be maintained at less than about 2, preferably less than about 1.5, and more preferably less than about 1, depending on the efficiency of the extraction process. If this value WP3 is low, the decomposition products of organophosphorus ligand preferably will be distributed in the polar phase.

Additionally, the method of extraction according to this invention is partly equilibrium process one renesola side reaction products, dissolved in two separate liquid phases. The efficiency of this extraction process can be measured by the distribution coefficient Kr one or more by-products of the reaction, which is determined as follows:

When one or more by-products of the reaction are distributed between the polar phase and the nonpolar phase of the extraction process of the present invention, the value CR side reaction products can be maintained at less than about 2, preferably less than about 1.5, and more preferably less than about 1, depending on the efficiency of the extraction process. If this value CR is low, by-products preferably will be distributed in the polar phase.

The method of extraction according to this invention is conducted in such a way as to meet three specific criteria. Three criteria are referred to here as the coefficients of extraction based on the ratio of distribution coefficients defined above. Relationship, ohvatyvajushee coefficients extraction include the selectivity of the nonpolar phase for the organophosphorus ligand with respect to the product, the selectivity of the nonpolar phase for the organophosphorus ligand with respect to the decomposition products of organophosphorus ligand and the village of the effectiveness of the nonpolar phase for the organophosphorus ligand with respect to side-reaction products. Three factor extraction is shown below.

Factor extraction, which determines the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more products is the following ratio of the distribution coefficients:

The value for Ef1 above the support ratio greater than about 2.5, more preferably about 3.0, and more preferably more than about 3.5, depending on the efficiency of the extraction process. If this value Ef1 is high, the selectivity of extraction is high.

Factor extraction, which determines the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand, is the following ratio of the distribution coefficients:

The value Ef2 for the above ratio is maintained at greater than about 2.5, more preferably about 3.0, and more preferably more than about 3.5, depending on the efficiency of the extraction process. If this value Ef2 is high, the selectivity of extraction is high.

Factor extraction, which determines the selectivity of the nonpolar phase for the organophosphorus ligand in the RH is increased by one or more side-reaction products, is the following ratio of the distribution coefficients:

Is Ef3 for the above ratio is maintained at greater than about 2.5, more preferably about 3.0, and more preferably more than about 3.5, depending on the efficiency of the extraction process. If this value Ef3 is high, the selectivity of extraction is high.

The method of extraction according to this invention can be carried out in one or several stages. The exact number of reaction stages will be governed by the best compromise between capital costs and high efficiency of extraction and ease of use, and stability of raw materials and the desired reaction product in relation to the conditions of extraction. Furthermore, the method of extraction according to this invention can be carried out in batch or continuous mode. In the case of continuous mode, the extraction can be performed in parallel or countercurrent manner or can be used fractionated by countercurrent extraction. Suitable methods of fractional countercurrent extraction methods are described in simultaneously considering applications for U.S. patent (serial No. D-18040 and D-18041), which is filed herewith by the same number, the description of which is included in the estuaries and the ü link. In one embodiment, in practice, the liquid reaction product is fed from the reaction zone into a separation zone, preferably contains at least 5 wt.%, preferably, at least 10 wt.%, one or more products.

In a preferred embodiment, in practice, when the liquid reaction product is fed from the reaction zone into a separation zone, the liquid reaction product first passes through the evaporator or distillation column, or other device to separate, to remove at least some part of the product, side products of the reaction and/or are not consumed during the reaction substances. At least part of the resulting liquid reaction product, depleted product, side reaction products and/or unreacted reagents, and then served in the fractional countercurrent extractor. Split up fractional countercurrent extractor can remove essentially all of the products and the main byproducts of the reaction and is not consumed during the reaction reagents. In another embodiment, in practice the division to fractionation extractor you can remove the main byproducts of the reaction and is not consumed during the reaction reagents, and essentially all products come in fractio yuushi countercurrent extractor. The liquid reaction product can represent a single liquid phase or may form two partially immiscible phase. The liquid reaction product may contain one or more solid phases. For the purposes of this invention, the separation zone includes, but is not limited to, one or more fractionation countercurrent extractors, one or more evaporators, one or more distillation columns, one or more other apparatus for the separation and valid serial or parallel combination. Preferably from the separation zone to remove this amount of one or more degradation products of organophosphorus ligand, one or more by-products of the reaction and one or more products, which is essentially equal to their rate of formation in the liquid reaction product in the reaction zone whereby the amount of one or more degradation products of organophosphorus ligand, one or more by-products of the reaction and one or more products in the liquid reaction product in the reaction zone is maintained at a predefined level. In variants of the practice, including intermediate division evaporator or distillation column, or other devices for the section is to be placed, subsequent separation of the phases, it is possible to perform liquid-liquid separation of the phases, countercurrent extraction or fractionation countercurrent extraction.

Typical examples of extractors that can be used in this invention include, for example, columns, centrifuges, mixers-settlers and mixed devices. Extractors that can be used include columns without stirring, for example irrigated column, a column with pneumatic partitions and the Packed column, the column with stirring, for example, pulsation, with stirring by rotating and vibrating plates, mixer-settlers, such as the pump-separator, a static mixer-settler and mix mixer-settler, dewatering centrifuges, such as the devices manufactured Robatel, Luwesta, deLaval, Dorr Oliver, Bird and Podbielniak, a mixed extractors, such as a mixer with emulational phase and the membrane of the hollow fibers. A description of these devices can be found in Handbook of Solvent Extraction, Krieger Publishing Company, Mallabar, Florida, 1991, the disclosure of which is included here by reference. Used in this invention various types of extractors can be combined in any combination to implement the desired extraction.

After extraction of the desired products of this invention can be distinguished by the separation of the phases, in which the polar phase, Lucaya one or more products, together with any decomposition products of organophosphorus ligand and by-products of the reaction, is separated from the nonpolar phase. Methods of separation of the phases may correspond to the methods used previously in conventional processes, and can be held in the extractor or in a separate liquid-liquid separating device. Suitable liquid-liquid separating devices include, but are not limited to, coalescers, cyclones and centrifuges. Typical equipment used for liquid-liquid separating device, is described in Handbook of Separation Process Technology, ISBN 0-471-89558-X, John Wiley & Sons, Inc., 1987, the description of which is included here by reference. After separation of the phases, in which the layer of extraction fluid, for example a polar solvent, and one or more decomposition products of organophosphorus ligand, one or more by-products of the reaction and one or more products, the layer is separated from the remaining liquid reaction product, the desired products can then be separated from the undesirable decomposition products of organophosphorus ligand and side reaction products by traditional methods, such as distillation.

From the point of view of free energy, in order to achieve dissolution or Miscibility of phosphorus-containing ligand in a particular solvent, enthalpy with the right must be so small, to the extent possible. The enthalpy of mixing (ΔNm) can be approximated by the equation of Hildenbrand (1)

using the solubility parameters of the solvent (δsolvent - ) and ligand (δligand), where V is the molar volume of the mixture, and fpand flare the volume fractions of solvent and ligand, respectively. Based on equation (1) is an ideal solvent for the ligand would have the same solubility parameter as the ligand, so that ΔNm=0. However, for each ligand, there is the characteristic range, resulting from its solubility parameter, which limits all liquids which are solvents for the ligand. In General, the solvent or mixture of solvents having a solubility parameter that is within two units of the solubility parameter of the ligand, will dissolve the ligand; however, it can sometimes appear relatively large deviations from this value, especially if there is a strong interaction due to hydrogen bonding. Therefore, equation (2)

can be used semi-quantitatively to determine whether the fluid is a good solvent for the ligand. In equation (2) (δsolvent - and (δ ligandrepresent the solubility parameters of solvent and ligand, respectively.

For the purposes of this invention, the solubility parameters for solvents can be calculated from equation (3)

in which ΔNvis the heat of vaporization, R is the gas constant, T is temperature in Kelvin, d is the density of the solvent and MW is the molecular weight of the solvent. The solubility parameters for a wide range of solvents are given K.L. Hoy, "New Values of the Solubility Parameters from Vapor Pressure Data", Journal of Paint Technology, 42, (1970), 76.

The heat of vaporization of phosphorus-containing compounds cannot be easily measured, since many of these compounds decompose at higher temperatures. Moreover, since many phosphorus-containing compounds are solid at room temperature, and density measurements are not easy. The solubility parameters, in units of (cal/cm3)1/2for phosphorus-containing ligands can be calculated using equation (4)

from theory of the contributions of groups, developed (1) K.L. Hoy, "New Values of the Solubility Parameters from Vapor Pressure Data", Journal of Paint Technology, 42, (1970), 76, and (2) L. Constantinou, R. Gani, J.P. O′Connell, "Estimation of the Acentric Factor and the Liquid Molar Volume at 298 K Using a New Group Contribution Method", Fluid Phase Equilibria, 103, (199), 11. In equation (4) ΣFTrepresents the sum of all molar constants of attraction for all groups, a ΣNiV1irepresents the sum of all molar volume constant of the liquid of the first order V1ioccurring Nitime. These methods have been expanded to include the molar constant of gravity of the group, which is equal 79,4 (cal/cm3)1/2/mol, and the molar volume constant of the liquid of the first order, which is equal to 0,0124 m3/KMOL (>R), obtained from the data for triphenylphosphine found in ..Daubret, R.P.Danner, H.M.Sibul and ..Stebbins, "DIPPR Data Compilation of Pure Compound Properties" Project 801, Sponsor Release, July 1995, Design Institute for Physical Property Data, 'alche, New York, NY.

The methods of this invention can perform the periodic or continuous method with recirculation of the unused raw materials, if required. The reaction can be performed in multiple reaction zones, in series or in parallel, or you can spend intermittently or continuously in an elongated tubular zone or series of such zones. For example, a reactor with back-mixing can be applied consistently with the multi-stage reactor, and the reactor with a back-mixing is the first. Used materials of construction must be inert with respect to the starting materials for the reaction, and Assembly of the equipment should is and to be able to withstand the reaction temperature and pressure. For convenience, the ways you can use the device for writing and/or regulate the amount of starting materials or ingredients, periodically or continuously introduced into the reaction zone during the course of the reaction, especially to maintain the desired molar ratio of starting materials. The reaction stage can be done growing by adding one raw material to another. In addition, the reaction stage can be combined joint addition of raw materials. When complete conversion is not desired or is not reachable, the source materials can optionally be separated from the product by separation of the phases and the raw materials then return to recirculated to the reaction zone.

At the end of (or during) the method according to this invention, the desired products are obtained in the method according to this invention, can be separated from the reaction mixture. For example, in method with continuous recirculation of liquid catalyst portion of the liquid reaction mixture (containing the product, catalyst, etc), remote from the reaction zone can be fed to a separation zone where the desired product can be extracted or separated by the separation of the phases from the liquid reaction mixture and additionally clear if this is desirable. The remaining containing catalyst in the liquid reaction mixture may then life is again returned to the reaction zone, like any other material, if this is desirable, for example, unspent in the reaction reagents together with hydrogen and carbon monoxide dissolved in the liquid reaction mixture, after its separation from the product.

The process can be carried out either in a lined glass, stainless steel or similar type of reaction equipment. The reaction zone can be equipped with one or more internal and/or external heat exchangers(and) in order to control unwanted temperature fluctuations, or to prevent a possible exit from under the control of the reaction temperature.

Methods according to this invention can be one or more reaction steps, or more than one of the reaction stages. The exact number of reaction steps and reaction stages will be governed by the best compromise between capital costs and achieving high catalyst selectivity, activity, durability and ease of use, and the inherent reactivity of the source material in question, and the stability of the starting materials and the desired product of the reaction with respect to the reaction conditions.

In the preferred embodiment to practice the method of hydrocarbonylation includes the conversion of one or more substituted is whether unsubstituted olefins in one or more substituted or unsubstituted alcohols. In the preferred embodiment to practice the method of hydrocarbonylation includes the conversion of one or more substituted or unsubstituted alkadienes in one or more substituted or unsubstituted unsaturated alcohols, and/or converting one or more substituted or unsubstituted penttala in one or more substituted or unsubstituted hydroxyaldehyde and/or diols. Methods hydrocarbonylation can be performed by one or more steps or stages, preferably one-step method. It is assumed that when used herein, the term "hydrocarbonylation" includes all valid ways of hydrocarbonylation, which include the conversion of one or more substituted or unsubstituted olefins in one or more substituted or unsubstituted alcohols and/or conversion of one or more substituted or unsubstituted penttala in one or more substituted or unsubstituted hydroxyaldehyde and/or diols. In the preferred embodiment to practice the method of hydrocarbonylation involves the reaction of one or more substituted or unsubstituted alkadienes, for example butadiene, with carbon monoxide and hydrogen in the presence of a catalyst comprising a complex of a metal-ligand, such as a catalyst, PR is stableuser a complex of a metal-organophosphorus ligand, promoter and optionally free ligand to produce one or more substituted or unsubstituted unsaturated alcohols, such as pentan-1-tins, and/or reaction of one or more substituted or unsubstituted penttala with carbon monoxide and hydrogen in the presence of a catalyst comprising a complex of a metal-ligand, for example a catalyst comprising a complex of a metal-organophosphorus ligand, a promoter and optionally free ligand to produce one or more substituted or unsubstituted hydroxyaldehyde, for example 6-hydroxyhexane. Alcohol product then you can select the separation method according to this invention. Preferred methods of hydroxycarbonate, useful in the present invention, described below, in U.S. patent No. 5817883.

In another preferred embodiment, in practice, the methods of recovery hydroformylation include the conversion of one or more substituted or unsubstituted olefins in one or more substituted or unsubstituted alcohols. In the preferred embodiment to practice the method of recovery hydroformylation includes the conversion of one or more substituted or unsubstituted alkadienes in one or more substituted or unsubstituted of nenasi the military alcohols, and/or converting one or more substituted or unsubstituted penttala in one or more substituted or unsubstituted hydroxyaldehyde and/or diols. The ways of recovery hydroformylation can be performed by one or more steps or stages, preferably one-step method. It is assumed that when used herein, the term "recovery hydroformylation" includes, but is not limited to, all permissible ways of hydroformylation, hydrogenation and isomerization, which include the conversion of one or more substituted or unsubstituted olefins in one or more substituted or unsubstituted alcohols and/or conversion of one or more substituted or unsubstituted penttala in one or more substituted or unsubstituted hydroxyaldehyde and/or diols. In the preferred embodiment to practice the method of recovery hydroformylation involves the reaction of one or more substituted or unsubstituted alkadienes, for example butadiene, with carbon monoxide and hydrogen in the presence of a catalyst comprising a complex of a metal-ligand, for example a catalyst comprising a complex of a metal-organophosphorus ligand, and optionally free ligand to produce one or several the x substituted or unsubstituted unsaturated alcohols, for example penten-1-tins, and/or reaction of one or more substituted or unsubstituted penttala with carbon monoxide and hydrogen in the presence of a catalyst comprising a complex of a metal-ligand, for example a catalyst comprising a complex of a metal-organophosphorus ligand, and optionally free ligand to produce one or more substituted or unsubstituted hydroxyaldehyde, for example 6-hydroxyhexane. Alcohol product then you can select the separation method according to this invention. The preferred methods of rehabilitation hydroformylation, useful in the present invention, described below, in U.S. patent No. 5821389.

In another preferred embodiment, in practice the ways of hydroformylation include the conversion of one or more substituted or unsubstituted olefins in one or more substituted or unsubstituted aldehyde. In the preferred embodiment to practice the methods of hydroformylation include the conversion of one or more substituted or unsubstituted unsaturated alcohols with one or more substituted or unsubstituted hydroxyaldehyde and/or conversion of one or more substituted or unsubstituted unsaturated esters in one or more substituted or nezam the seal formulation. How hydroformylation can be performed in one or more steps or stages, preferably one-step process. It is assumed that when used herein, the term "hydroformylation" includes all valid processes hydroformylation, which include the conversion of one or more substituted or unsubstituted olefins in one or more substituted or unsubstituted aldehyde. In the preferred embodiment to practice the method of hydroformylation involves the reaction of one or more substituted or unsubstituted alcohols, such as pentan-1-tin, carbon monoxide and hydrogen in the presence of a catalyst comprising a complex metallised, such as a catalyst comprising a complex of a metal-organophosphorus ligand, and optionally free ligand to obtain one or more substituted or unsubstituted hydroxyaldehyde, for example 6-hydroxyaldehyde. Then aldehyde product can be distinguished by the method of separation according to this invention. Preferred ways of hydroformylation, useful in this invention are described in U.S. patents№4148830, 4593127, 4769498, 4717775, 4774361, 4885401, 5264616, 5288918, 5360938, 5364950, 5491266, 5731472, 5741942, 5763679, 5817883 and 5821389, descriptions of which are included here by reference. Other preferred ways hydroforming the Finance, useful in this invention are described in simultaneously considering applications for U.S. patent (serial No. D-17977, D-17978 and D-17979), descriptions of which are included here by reference.

Products such as aldehydes, obtained by the method according to this invention, can be subjected to further reaction(s)to give the desired derivatives. These possible reactions obtain the derivatives can hold traditional procedures known from the prior art. Examples of reactions obtain derivatives include, for example, hydrogenation, esterification, etherification, amination, alkylation, dehydrogenation, reduction, acylation, condensation, carboxylation, carbonylation, oxidation, cyclization, similarobama and similar, including their valid combinations. There is no intention in any way to limit the invention by means of valid reactions obtain derivatives or permitted derivative works.

It is assumed that for the purposes of this invention, the term "hydrocarbon" includes all permissible compounds having at least one hydrogen atom and one carbon atom. Such valid connection can also have one or more heteroatoms. In a broad aspect, the permissible hydrocarbons include acyclic (with or without heteroatoms) and cyclic, razwell is installed and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic organic compounds, which may be substituted or unsubstituted.

It is assumed that when used herein, the term "substituted" includes all permissible substituents of organic compounds, if not specified otherwise. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Examples of substituents include, for example, alkyl, alkyloxy, aryl, alloctype, the hydroxy-group, hydroxyalkyl, amino group, aminoalkyl, halogen and similar, in which the number of carbon atoms can be in the range of from 1 to about 20 or more, preferably from 1 to about 12. Permissible substituents may be one or more, they may be the same or different for the respective organic compounds. There is no intention to limit the invention in any manner by the permissible substituents of organic compounds.

1. A way of separating one or more products of the decomposition of organophosphorus ligand, one or more by-products of the reaction and one or more products from the continuous what about the synthesized liquid reaction product, includes one or more unspent during the reaction of the reactants, the catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand, one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products, one or more of these products, one or more nonpolar solvents and one or more polar solvents, where the method includes (1) the filing of specified liquid reaction product from the reaction zone into a separation zone, (2) mixing the specified liquid reaction product in said separation zone to obtain by phase separation of the nonpolar phase comprising these one or more unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents and a polar phase comprising one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products, one or more of these products and one or more of these polar solvents, (3) removing the C specified the separation zone such amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education in the specified liquid reaction product in a specified reaction zone whereby the amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, (4) flow from the zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more designated unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents, (5) the selection of one or more degradation products of organophosphorus ligand, one or more of these side reaction products and one or more of these products from one or more of these polar solvents, and (6) the filing of a given zone of separation in the shown reaction zone and/or the specified separation zone one or more recycle streams, includes one or more of these polar solvents, where (i) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more products is expressed by the following ratio of the distribution coefficients Ef1:

where the specified distribution coefficient KR1 is the ratio of the concentration of organophosphorus ligand in the nonpolar phase after extraction to concentration of organophosphorus ligand in the polar phase after extraction, the specified distribution coefficient Kr represents the ratio of the concentration of products in the nonpolar phase after extraction to product concentration in the polar phase after extraction, and the specified Efl value greater than about 2.5;

(ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand expressed as the ratio of the distribution coefficients Ef2:

where the specified distribution coefficient KR1 is like is definitely above the specified distribution coefficient WP3 is the ratio of the concentration of decomposition products of organophosphorus ligand in the nonpolar phase after extraction to concentration is produktov decomposition of organophosphorus ligand in the polar phase after extraction and specified Ef2 value, greater than about 2.5 and

(iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more secondary products of the reaction expressed by the following ratio of the distribution coefficients Ef3:

where the specified distribution coefficient KR1 is like is definitely above the specified distribution coefficient Kr represents the ratio of the concentration of by-products of the reaction in the nonpolar phase after extraction to concentration of by-products of the reaction in the polar phase after extraction and specified Ef3 value greater than about 2.5.

2. A way of separating one or more products of the decomposition of organophosphorus ligand, one or more by-products of the reaction and one or more products from a continuously synthesized liquid reaction product comprising one or more unspent during the reaction of the reactants, the catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand, one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products, one or more of these products and one or more nonpolar dissolve is Italy, where the method includes (1) the filing of specified liquid reaction product from the reaction zone into a separation zone, (2) mixing the specified liquid reaction product in said separation zone one or more polar solvents to obtain by phase separation of the nonpolar phase comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents and a polar phase comprising one or more of these decomposition products of organophosphorus ligand, one or more of these products reaction, one or more of these products and one or more of these polar solvents, (3) removing from the specified zone dividing such amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education in the specified liquid reaction product in a specified reaction zone whereby the amount of one or more of these products is s decomposition of organophosphorus ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, (4) flow from the zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents, (5) the selection of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products from one or more of these polar solvents, and (6) the filing of a given zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these polar solvents; where (i) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more products is expressed by the ratio of RA the distribution Ef1, defined in claim 1, the value of which exceeds about 2.5; (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand expressed by the ratio of distribution coefficients Ef2 defined in claim 1, the value of which exceeds about 2.5; and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more secondary products of the reaction expressed by the ratio of distribution coefficients Ef3 defined in claim 1, the value of which exceeds about 2.5.

3. A continuous method of obtaining one or more products comprising: (1) interaction in the reaction zone one or more reactants in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand, one or more nonpolar solvents and one or more polar solvents to obtain a liquid reaction product comprising one or more unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more decomposition products phosphororganic the one ligand, one or more by-products of the reaction, one or more of these products, one or more of these non-polar solvents and one or more of these polar solvents; (2) submission of specified liquid reaction product from this reaction zone into a separation zone, (3) mixing the specified liquid reaction product in said separation zone to obtain by phase separation of the nonpolar phase comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these non-polar solvents and polar phase comprising one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products, one or more of these products and one or more of these polar solvents, (4) removal from the zone of separation such amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their formation shown in the liquid reaction product in a specified reaction zone, whereby a specified number of one or more degradation products of organophosphorus ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, (5) the filing of a given zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents (6) selection of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products from one or more of these polar solvents, and (7) submission of a specified area of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these polar solvents; where (i) the selectivity of the nonpolar phase for FOS is organicheskoi ligand with respect to one or more products is expressed by the ratio of distribution coefficients Ef1, defined in claim 1, the value of which exceeds about 2.5; (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand expressed by the ratio of distribution coefficients Ef2 defined in claim 1, the value of which exceeds about 2.5; and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more secondary products of the reaction expressed by the ratio of distribution coefficients Ef3 defined in claim 1, the value of which exceeds about 2.5.

4. A continuous method of obtaining one or more products comprising: (1) interaction in the reaction zone one or more reactants in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand and one or more nonpolar solvents, to obtain a liquid reaction product comprising one or more unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the decomposition products of organophosphorus ligand, one or more side cont the mswb reaction, one or more of these products and one or more of these non-polar solvents; (2) submission of specified liquid reaction product from this reaction zone into a separation zone, (3) mixing the specified liquid reaction product in said separation zone one or more polar solvents to obtain by phase separation of the nonpolar phase comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents and a polar phase comprising one or more of these products decomposition of organophosphorus ligand, one or more of these side reaction products, one or more of these products and one or more of these polar solvents, (4) removal from the zone of separation such amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education in the specified liquid reaction product in this reaction is Oh area whereby the amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, (5) the filing of a given zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents (6) selection of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products from one or more of these polar solvents, and (7) submission of a specified area of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these polar solvents; where (i) the selectivity of the nonpolar phase for FOS is organicheskoi ligand with respect to one or more products is expressed by the ratio of distribution coefficients Ef1, defined in claim 1, the value of which exceeds about 2.5; (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand expressed by the ratio of distribution coefficients Ef2 defined in claim 1, the value of which exceeds about 2.5; and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more secondary products of the reaction expressed by the ratio of distribution coefficients Ef3 defined in claim 1, the value of which exceeds about 2.5.

5. A way of separating one or more products of the decomposition of organophosphorus ligand, one or more by-products of the reaction and one or more products from a continuously synthesized liquid reaction product comprising one or more unspent during the reaction of the reactants, the catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand, one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products, one or more of these products, one or more first nonpolar solvents and one or more second nonpolar solution of the residents, where the method includes (1) the filing of specified liquid reaction product from the reaction zone into a separation zone, (2) mixing the specified liquid reaction product in said separation zone to obtain by phase separation of the nonpolar phase comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the specified first nonpolar solvents and one or more specified second nonpolar solvents and a polar phase comprising one or more of these decomposition products of organophosphorus ligand, one or more these side reaction products and one or more of these products, (3) removing from the specified zone dividing such amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education in the specified liquid reaction product in a specified reaction zone whereby the amount of one or more of these decomposition products of organophosphorus what about the ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, and (4) the filing of a given zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the specified first nonpolar solvents and one or more specified second nonpolar solvents; where (i) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more products is expressed by the ratio of distribution coefficients Ef1 defined in claim 1, the value of which exceeds about 2.5; (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand expressed by the ratio of distribution coefficients Ef2 defined in claim 1, the value of which exceeds about 2.5; and (iii) the selectivity of the nonpolar phase for the organophosphorus is Uganda in relation to one or more secondary products of the reaction expressed by the ratio of distribution coefficients Ef3, defined in claim 1, the value of which exceeds about 2.5.

6. A way of separating one or more products of the decomposition of organophosphorus ligand, one or more by-products of the reaction and one or more products from a continuously synthesized liquid reaction product comprising one or more unspent during the reaction of the reactants, the catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand, one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products, one or more of these products and one or more first nonpolar solvents, where the method includes (1) the filing of specified liquid reaction product from the reaction zone to zone separation, (2) mixing the specified liquid reaction product in said separation zone one or more second nonpolar solvents to obtain by phase separation of the nonpolar phase comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, Odie is or more specified first nonpolar solvents and one or more specified second nonpolar solvents, and a polar phase comprising one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, (3) removing from the specified zone dividing such amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education in the specified liquid reaction product in a specified reaction zone whereby the amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or several of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, and (4) the filing of a given zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus Li gang is, one or more of the specified first nonpolar solvents and one or more specified second nonpolar solvents; where (i) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more products is expressed by the ratio of distribution coefficients Ef1 defined in claim 1, the value of which exceeds about 2.5; (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand expressed by the ratio of distribution coefficients Ef2 defined in claim 1, the value of which exceeds about 2.5; and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more side products of the reaction expressed by the ratio of distribution coefficients Ef3 defined in claim 1, the value of which exceeds about 2.5.

7. A continuous method of obtaining one or more products comprising: (1) interaction in the reaction zone one or more reactants in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand, one or more first nonpolar solvents and one or more second nonpolar solvents to obtain Idaho reaction product, includes one or more unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the decomposition products of organophosphorus ligand, one or more by-products of the reaction, one or more of these products, one or more of the specified first nonpolar solvents and one or more specified second nonpolar solvents; (2) submission of specified liquid reaction product from this reaction zone into a separation zone, (3) mixing the specified liquid reaction product in said separation zone to obtain by phase separation of the nonpolar phase, includes one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the specified first nonpolar solvents and one or more specified second nonpolar solvents and a polar phase comprising one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or nickelcontaining products (4) removal from the zone of separation such amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education in the specified liquid reaction product in a specified reaction zone whereby the amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, and (5) the filing of a given zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the specified first nonpolar solvents and one or more specified second nonpolar solvents; where (i) the selectivity of the nonpolar phase for the organophosphorus ligand to the tion to one or more products is expressed by the ratio of distribution coefficients Ef1, defined in claim 1, the value of which exceeds about 2.5; (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand expressed by the ratio of distribution coefficients Ef2 defined in claim 1, the value of which exceeds about 2.5; and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more secondary products of the reaction expressed by the ratio of distribution coefficients Ef3 defined in claim 1, the value of which exceeds about 2.5.

8. A continuous method of obtaining one or more products comprising: (1) interaction in the reaction zone one or more reactants in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand and one or more first nonpolar solvents to obtain a liquid reaction product comprising one or more unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the decomposition products of organophosphorus ligand, one or more poboon the x reaction products, one or more of these products and one or more of the specified first nonpolar solvents; (2) submission of specified liquid reaction product from this reaction zone into a separation zone, (3) mixing the specified liquid reaction product in said separation zone one or more second nonpolar solvents to obtain by phase separation of the nonpolar phase comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the specified first nonpolar solvents and one or more specified second nonpolar solvents and a polar phase comprising one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, (4) removal from the zone of separation such amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education in the specified liquid reaction is the first product in the specified reaction zone, whereby the amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, (5) the filing of a given zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more of these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the specified first nonpolar solvents and one or more specified second nonpolar solvents; where (i) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more products is expressed by the ratio of distribution coefficients Ef1 defined in claim 1, the value of which exceeds about 2.5; (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand expressed by the ratio of distribution coefficients Ef2, identifying the major in claim 1, the value of which exceeds about 2.5; and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more side products of the reaction expressed by the ratio of distribution coefficients Ef3 defined in claim 1, the value of which exceeds about 2.5.

9. A way of separating one or more products of the decomposition of organophosphorus ligand, one or more by-products of the reaction and one or more products from a continuously synthesized liquid reaction product comprising one or more unspent during the reaction of the reactants, the catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand, one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products, one or more of these products, and one or more nonpolar solvents, where the method includes (1) the filing of specified liquid reaction product from the reaction zone to zone separation, (2) mixing the specified liquid reaction product in said separation zone to obtain phase separation of non-polar phase comprising one or more of these unspent during the reaction of real now, the specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents and a polar phase comprising one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, (3) removing from the specified zone dividing such amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education in the specified liquid reaction product in a specified reaction zone, whereby the number of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, and (4) the filing of a given zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or a few is to these unspent during the reaction reagents, the specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these non-polar solvents; where (i) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more products is expressed by the ratio of distribution coefficients Ef1 defined in claim 1, the value of which exceeds about 2.5; (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more degradation products of organophosphorus ligand expressed by the ratio of distribution coefficients Ef2 defined in claim 1, the value of which exceeds about 2.5; and (iii) the selectivity of the nonpolar phase for organophosphorus ligand with respect to one or more secondary products of the reaction expressed by the ratio of distribution coefficients Ef3 defined in claim 1, the value of which exceeds about 2.5.

10. A continuous method of obtaining one or more products comprising: (1) interaction in the reaction zone one or more reactants in the presence of a catalyst comprising a complex of a metal-organophosphorus ligand, optionally free organophosphorus ligand and one or more non-polar will dissolve the lei to obtain a liquid reaction product, includes one or more unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand, one or more of the decomposition products of organophosphorus ligand, one or more by-products of the reaction, one or more of these products and one or more of these non-polar solvents; (2) submission of specified liquid reaction product from the reaction zone into a separation zone, (3) mixing the specified liquid reaction product in said separation zone to obtain phase separation of non-polar phase comprising one or more of these unspent during the reaction reagents, the specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these nonpolar solvents and a polar phase comprising one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products; (4) removal from the zone of separation such amount of one or more specified products of decomposition of phosphororganic the one ligand, one or more of these side reaction products and one or more of these products, which is essentially equal to the speed of their education in the specified liquid reaction product in a specified reaction zone whereby the amount of one or more of these decomposition products of organophosphorus ligand, one or more of these side reaction products and one or more of these products in the specified liquid reaction product in a specified reaction zone is maintained at a predefined level, and (5) the filing of a given zone of separation in the specified reaction zone and/or the specified separation zone one or more recycle streams comprising one or more these unspent during the reaction of the reagents specified catalyst comprising a complex of a metal-organophosphorus ligand specified optionally free organophosphorus ligand and one or more of these non-polar solvents; where (i) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more products is expressed by the ratio of distribution coefficients Ef1 defined in claim 1, the value of which exceeds about 2.5; (ii) the selectivity of the nonpolar phase for the organophosphorus whether the Anda with respect to one or more degradation products of organophosphorus ligand expressed by the ratio of distribution coefficients Ef2, defined in claim 1, the value of which exceeds about 2.5; and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to one or more secondary products of the reaction expressed by the ratio of distribution coefficients Ef3 defined in claim 1, the value of which exceeds about 2.5.

11. The method according to claim 1, where the value Ef1 has a value greater than approximately 3,0, value Ef2 has a value greater than about 3.0 and the value Ef3 has a value greater than approximately 3,0.

12. The method according to claim 3, which includes the processes of hydroformylation, gidroalkilirovaniya (intramolecular and intermolecular), hydrocyanide, gidrolizirovanny, hydroesterification, aminolysis, alcoholysis, hydrocarbonylation, recovery hydroformylation, hydrogenation, oligomerization of olefins, hydroxycarbonylmethyl, carbonylation, isomerization or hydrogenation with hydrogen transport.

13. The method according to claim 1, where one or more specified non-polar solvent is selected from alkanes, alkadienes, cycloalkanes, alkenes, aldehydes, ketones, ethers, esters, amines, aromatic compounds, silanes, silicones, carbon dioxide and mixtures thereof, and one or more of these polar solvents selected from NITRILES, lactones, alkanols, cyclic acetals, water, pyrrolidone, formamide is in, the sulfoxidov and mixtures thereof.

14. The method according to item 13, where one or more of these non-polar solvents selected from propane, 2,2-DIMETHYLPROPANE, butane, 2,2-Dimethylbutane, pentane, isopropyl ether, hexane, triethylamine, heptane, octane, nonane, decane, isobutylacetate, tributylamine, undecane, 2,2,4-trimethylpentane, isobutylketone, Diisobutyl ketone, cyclopentane, cyclohexane, isobutylbenzene, n-nonylbenzene, n-octylbenzene, n-butylbenzene, p-xylene, ethylbenzene, 1,3,5-trimethylbenzene, m-xylene, toluene, o-xylene, mission, dodecene, tetradecene, butadiene, heptadecanol and mixtures thereof, and one or more of these polar solvents selected from propionitrile, 1,3-dioxolane, 3-methoxypropionitrile, 1-methyl-2-pyrrolidinone, N,N-dimethylformamide, 2-methyl-2-oxazoline, adiponitrile, acetonitrile, Epsilon-caprolactone, water, glutaronitrile, 3-methyl-2-oxazolidinone, dimethyl sulfoxide, sulfolane and mixtures thereof.

15. The method according to claim 1, where the specified catalyst comprising a complex of a metal-organophosphorus ligand includes a complex of rhodium with the organophosphorus ligand represented by the formula:

(i) translesanas fosfororganicheskikh ligand represented by the formula:

where R1is the same or different represent a substituted or unsubstituted monovalent hydrocarbon radical, containing from 1 to 24 carbon atoms or more;

(ii) monoethanolamine represented by the formula:

where R3represents a substituted or unsubstituted trivalent hydrocarbon radical containing from 4 to 40 carbon atoms or more;

(iii) diorganotin represented by the formula:

where R4represents a substituted or unsubstituted divalent hydrocarbon radical containing from 4 to 40 carbon atoms or more, and W represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 18 carbon atoms or more;

(iv) triorganotin represented by the formula:

where each R8is odinakovym or different and represents a substituted or unsubstituted monovalent hydrocarbon radical; and

(v) organophosphate containing two or more tertiary (trivalent) phosphorus atoms represented by the formula:

where X1represents a substituted or unsubstituted n-valent hydrocarbon bridging radical containing from 2 to 40 carbon atoms, each R9is the same or different and represents LW is valenty hydrocarbon radical, containing from 4 to 40 carbon atoms, each R10is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms, a and b may be the same or different and each has a value from 0 to 6, provided that the sum a + b is equal to from 2 to 6 and n equals a + b.

16. The method according to claim 3, where the specified separation zone includes one or more evaporators, one or more distillation columns, one or more fractionation countercurrent extractors or a valid serial or parallel combination.

17. The method according to clause 16, where a specified liquid reaction product first passes through the evaporator or distillation column to remove at least a certain number of products, by-products of the reaction and/or unspent during the reaction reagent, and the resulting liquid reaction product depleted in products, by-products of the reaction and/or unspent during the reaction reagents, and then served in the fractionation countercurrent extractor.

18. The method according to clause 16, where a specified liquid reaction product first passes through the evaporator or distillation column to remove at least some amount of side reaction products and/or Nisroch is published during the reaction reagents, and the resulting liquid reaction product, depleted side reaction products and/or unspent during the reaction reagents, and then served in the fractionation countercurrent extractor.

19. The reaction mixture comprising one or more aldehyde products obtained by the process of hydroformylating olefins with carbon monoxide and hydrogen, where specified, the reaction mixture obtained by the method according to claim 3.

20. The method according to claim 3, further comprising deriving one or more products, where the reaction of obtaining derivatives include hydrogenation, esterification, etherification, amination, alkylation, dehydrogenation, reduction, acylation, condensation, carboxylation, carbonylation, oxidation, cyclization, reductive amination, similarobama, hydrolysis, polymerization, copolymerization and their valid combinations.



 

Same patents:

FIELD: improved processes catalyzed by complexes of a metal- organophosphorous ligand.

SUBSTANCE: the invention presents the improved processes catalyzed by complexes of metal-organophosphorous ligand. The method of extraction includes: feeding of the indicated liquid reactionary product in the zone of separation, stirring of the indicated liquid reactionary product with production by separation of phases of a polar phase containing one or several unreacted reactants, a complex catalyst metal- organophosphorous ligand, not obligatory free organophosphorous ligand and one or several polar dissolvents; and a nonpolar phase containing one or several products of decomposition of the organophosphorous ligand, one or several by-products of the reaction and one or several products. Further the method provides for the stages of withdrawal from the zone of separation and feeding into the reaction zone and-or into the zone of separation. In the given method selectivity of the polar phase for the organophosphorous ligand concerning one or several products is expressed by a ratio of distribution coefficients Efl, which has a value more than approximately 2.5; (ii) the selectivity of the polar phase for the organophosphorous ligand concerning one or several decomposition products of the organophosphorous ligand is expressed by a ratio of distribution coefficients Ef2, which has a value more than approximately 2.5; and (iii)the selectivity of the polar phase for the organophosphorous ligand concerning one or several by-products of reaction is expressed by a ratio of distribution coefficients Ef3, which value is more, than approximately 2.5. The method allows to reduce a negative effect on the process, for example, on prevention of a decrease of efficiency of the catalyst, conversion of the initial material and selectivity by a product.

EFFECT: the invention ensures reduction of a negative effect on the process, on efficiency of the catalyst, on conversion of the initial material and selectivity by a product.

20 cl, 2 tbl

The invention relates to an improved method of separating one or more products from the liquid reaction product containing the catalyst in the form of complex compounds of a metal with an organophosphorus ligand, optionally free organophosphorus ligand, a non-polar solvent, the polar solvent is selected from the group comprising NITRILES, lactones, pyrrolidone, formamide and sulfoxidov, and named one or more products, the method comprises (1) mixing named liquid reaction product to obtain phase separation a nonpolar phase containing the above catalyst, optionally free organophosphorus ligand and called nonpolar solvent and a polar phase, contains named one or more products and a polar solvent, and (2) the Department called the polar phase from the named non-polar phase, and named the organophosphorus ligand has a distribution coefficient between the nonpolar solvent and the polar solvent of greater than about 5, and named one or more products is the distribution coefficient between the polar solvent and the nonpolar rastvorimo of the reaction product, containing the catalyst in the form of complex compounds with metal-phosphorus metal, optionally free organophosphorus ligand, a non-polar solvent and one or more products, the method comprises (1) mixing named liquid reaction product with a polar solvent selected from the group comprising NITRILES, lactones, pyrrolidone, formamide and sulfoxidov, to obtain phase separation a nonpolar phase containing the above-mentioned catalyst, optionally free organophosphorus ligand and called nonpolar solvent and a polar phase containing named one or more products and a polar solvent, and (2) the Department called the polar phase from the named non-polar phase, and named the organophosphorus ligand and named one or more products have the distribution coefficient between the nonpolar solvent and the polar solvent of greater than about 5, and named one or more products is the distribution coefficient between the polar solvent and the nonpolar solvent of greater than about 0.5

The invention relates to an improved method of separating one or more products from the liquid reaction product containing the catalyst in the form of complex compounds of a metal with an organophosphorus ligand, optionally free organophosphorus ligand, a non-polar solvent, the polar solvent is selected from the group comprising NITRILES, lactones, pyrrolidone, formamide and sulfoxidov, and named one or more products, the method comprises (1) mixing named liquid reaction product to obtain phase separation a nonpolar phase containing the above catalyst, optionally free organophosphorus ligand and called nonpolar solvent and a polar phase, contains named one or more products and a polar solvent, and (2) the Department called the polar phase from the named non-polar phase, and named the organophosphorus ligand has a distribution coefficient between the nonpolar solvent and the polar solvent of greater than about 5, and named one or more products is the distribution coefficient between the polar solvent and the nonpolar rastvorimo of the reaction product, containing the catalyst in the form of complex compounds with metal-phosphorus metal, optionally free organophosphorus ligand, a non-polar solvent and one or more products, the method comprises (1) mixing named liquid reaction product with a polar solvent selected from the group comprising NITRILES, lactones, pyrrolidone, formamide and sulfoxidov, to obtain phase separation a nonpolar phase containing the above-mentioned catalyst, optionally free organophosphorus ligand and called nonpolar solvent and a polar phase containing named one or more products and a polar solvent, and (2) the Department called the polar phase from the named non-polar phase, and named the organophosphorus ligand and named one or more products have the distribution coefficient between the nonpolar solvent and the polar solvent of greater than about 5, and named one or more products is the distribution coefficient between the polar solvent and the nonpolar solvent of greater than about 0.5

The invention relates to a method for producing 1,3-alkanediols and 3-hydroxyaldehyde through hydroformylation of oxirane (1,2-epoxide)

The invention relates to chemical processing of lignin, and in particular to methods selection of vanilla, which finds wide application in the production of medical drugs in the food and perfume industry
The invention relates to a thin organic synthesis, and is intended to improve existing processes of obtaining vanillin (4-hydroxy-3-methoxybenzaldehyde) from lignin products of wood processing, such as lignosulfonates

FIELD: methods of production of 1.3 alkandiol.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to production of 1.3 alkandiol by hydrogenation of the raw material, containing 3-hydroxyaldehyde at presence of a catalyst and a source of hydrogen, where as a source of hydrogen use a synthesis gas, and the catalyst represents a heterogeneous catalyst containing copper on the carrier; and also to the method of production of 1.3-alkandiol by conversion of an oxide in the process including a hydroformylation and hydrogenation. At that it is not obligatory to realize the indicated phases simultaneously in one reaction vessel. The reached technical result consists in essential reduction of the fixed value of equipment and in bringing to a "single-phase" production of 1.3-propandiol (or a similar 3-alcandil) from ethylene oxide (or a corresponding oxide).

EFFECT: the invention ensures essential reduction of the fixed value of equipment and reduction to a "single-phase" process of the propandiol or alkandiol production.

9 cl, 2 tbl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing concentrate of butyric aldehydes by oxonation. Method is carried out by the hydroformylation reaction of propylene with synthesis-gas in two in-line connected reactors at temperature 120-150°C, under pressure 250-300 kgf/cm2 and with heat removing by circulation of cooling agent through Field's tubes installed in hydroformylation reactors followed by separation of reaction products. The hydroformylation process in the first reactor is carried out in regimen when the ratio of volume consumptions of cooling agent circulating in Field's tubes and propylene feeding into reactor is (18-28):1. Invention provides enhancing yield of end products, improving energetic indices due to effective heat transfer in the hydroformylation reactor.

EFFECT: improved preparing method.

1 tbl, 4 ex

FIELD: improved processes catalyzed by complexes of a metal- organophosphorous ligand.

SUBSTANCE: the invention presents the improved processes catalyzed by complexes of metal-organophosphorous ligand. The method of extraction includes: feeding of the indicated liquid reactionary product in the zone of separation, stirring of the indicated liquid reactionary product with production by separation of phases of a polar phase containing one or several unreacted reactants, a complex catalyst metal- organophosphorous ligand, not obligatory free organophosphorous ligand and one or several polar dissolvents; and a nonpolar phase containing one or several products of decomposition of the organophosphorous ligand, one or several by-products of the reaction and one or several products. Further the method provides for the stages of withdrawal from the zone of separation and feeding into the reaction zone and-or into the zone of separation. In the given method selectivity of the polar phase for the organophosphorous ligand concerning one or several products is expressed by a ratio of distribution coefficients Efl, which has a value more than approximately 2.5; (ii) the selectivity of the polar phase for the organophosphorous ligand concerning one or several decomposition products of the organophosphorous ligand is expressed by a ratio of distribution coefficients Ef2, which has a value more than approximately 2.5; and (iii)the selectivity of the polar phase for the organophosphorous ligand concerning one or several by-products of reaction is expressed by a ratio of distribution coefficients Ef3, which value is more, than approximately 2.5. The method allows to reduce a negative effect on the process, for example, on prevention of a decrease of efficiency of the catalyst, conversion of the initial material and selectivity by a product.

EFFECT: the invention ensures reduction of a negative effect on the process, on efficiency of the catalyst, on conversion of the initial material and selectivity by a product.

20 cl, 2 tbl

The invention relates to an improved method of separating one or more products from the liquid reaction product containing the catalyst in the form of complex compounds of a metal with an organophosphorus ligand, optionally free organophosphorus ligand, a non-polar solvent, the polar solvent is selected from the group comprising NITRILES, lactones, pyrrolidone, formamide and sulfoxidov, and named one or more products, the method comprises (1) mixing named liquid reaction product to obtain phase separation a nonpolar phase containing the above catalyst, optionally free organophosphorus ligand and called nonpolar solvent and a polar phase, contains named one or more products and a polar solvent, and (2) the Department called the polar phase from the named non-polar phase, and named the organophosphorus ligand has a distribution coefficient between the nonpolar solvent and the polar solvent of greater than about 5, and named one or more products is the distribution coefficient between the polar solvent and the nonpolar rastvorimo of the reaction product, containing the catalyst in the form of complex compounds with metal-phosphorus metal, optionally free organophosphorus ligand, a non-polar solvent and one or more products, the method comprises (1) mixing named liquid reaction product with a polar solvent selected from the group comprising NITRILES, lactones, pyrrolidone, formamide and sulfoxidov, to obtain phase separation a nonpolar phase containing the above-mentioned catalyst, optionally free organophosphorus ligand and called nonpolar solvent and a polar phase containing named one or more products and a polar solvent, and (2) the Department called the polar phase from the named non-polar phase, and named the organophosphorus ligand and named one or more products have the distribution coefficient between the nonpolar solvent and the polar solvent of greater than about 5, and named one or more products is the distribution coefficient between the polar solvent and the nonpolar solvent of greater than about 0.5

The invention relates to new furifosmin formula I

< / BR>
where n denotes an integer of 1 or 2; R1denotes a hydrophilic group selected from the following groups: -SO2M, -SO3M, -CO2M, -PO3M, where M represents inorganic or organic cationic residue selected from a proton, cations, alkaline or alkaline earth metals, ammonium cations -- N(R)4where R denotes hydrogen or C1-C14alkyl, and the other cations are based on metals, salts with acids: fullsleeve, fullcarbon, fullsleeve or furylphosphonous soluble in water; m denotes an integer of 1; R2denotes a hydrophilic group,- SO2M, -SO3M, -CO2M, RHO3M, where M denotes hydrogen or an alkaline metal salt with the acid fullsleeve, fullcarbon, fullsleeve or fullfactorial soluble in water, R denotes an integer from 0 to 2

The invention relates to a mixture of branched primary alcohols from C11to C36and to mix them sulfates, alkoxylated, alkoxylates and carboxylates, which have high washing ability in cold water and good biological degradability
The invention relates to a method for producing alcohols from 7-18 carbon atoms by hydroformylation corresponding olefins with synthesis gas in the presence containing cobalt catalyst of the organic phase with 50 - 220oC and a pressure of 100 to 400 bar, with subsequent hydrogenation of the thus obtained aldehyde

The invention relates to processes for the oxidized products, namely the processes of obtaining the oxidized products enriched in olefins feedstock

The invention relates to petrochemistry, namely the method of production of isovalerianic aldehyde, which is used in the pharmaceutical industry (drugs cardiology appointment)

FIELD: improved processes catalyzed by complexes of a metal- organophosphorous ligand.

SUBSTANCE: the invention presents the improved processes catalyzed by complexes of metal-organophosphorous ligand. The method of extraction includes: feeding of the indicated liquid reactionary product in the zone of separation, stirring of the indicated liquid reactionary product with production by separation of phases of a polar phase containing one or several unreacted reactants, a complex catalyst metal- organophosphorous ligand, not obligatory free organophosphorous ligand and one or several polar dissolvents; and a nonpolar phase containing one or several products of decomposition of the organophosphorous ligand, one or several by-products of the reaction and one or several products. Further the method provides for the stages of withdrawal from the zone of separation and feeding into the reaction zone and-or into the zone of separation. In the given method selectivity of the polar phase for the organophosphorous ligand concerning one or several products is expressed by a ratio of distribution coefficients Efl, which has a value more than approximately 2.5; (ii) the selectivity of the polar phase for the organophosphorous ligand concerning one or several decomposition products of the organophosphorous ligand is expressed by a ratio of distribution coefficients Ef2, which has a value more than approximately 2.5; and (iii)the selectivity of the polar phase for the organophosphorous ligand concerning one or several by-products of reaction is expressed by a ratio of distribution coefficients Ef3, which value is more, than approximately 2.5. The method allows to reduce a negative effect on the process, for example, on prevention of a decrease of efficiency of the catalyst, conversion of the initial material and selectivity by a product.

EFFECT: the invention ensures reduction of a negative effect on the process, on efficiency of the catalyst, on conversion of the initial material and selectivity by a product.

20 cl, 2 tbl

The invention relates to the chemical industry for the production of chlorobenzene method of chlorination of benzene, and can be used in the production of phenyltrichlorosilane (FTHS), where on the one hand, the chlorobenzene is used as a raw material, and on the other hand in the production FTHS as a by-product is formed benzene, chlorine - and organochlorosilane
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