Integrated chemical methods of industrial application of seed oils

FIELD: chemistry.

SUBSTANCE: raw material composition based on fatty acids or esters of fatty acids, obtained by hydrolysis of oil from seeds or by re-etherification of oil from seeds with C1-8-alkanol, contains more than 70 wt % of unsaturated fatty oleic acid, and less than 1.5 milliequivalents of admixture(s), poisoning methathesis catalyst, per kilogram of composition, after purification with adsorbent. Admixture contains one or more organic hydroperoxides. Method of olefin methathesis lies in contacting of raw composition, obtained from seed oil and containing one or more unsaturated fatty acids or esters of unsaturated fatty acids, with lower olefin in presence of catalyst based on phosphororganic transition metal complex. Used raw material composition contains less than 25 milliequivalents of admixture(s), poisoning methathesis catalyst, per kilogram of raw material composition, able to inhibit methathesis catalyst. As a result of reaction olefin with shortened chain and unsaturated acid or unsaturated ester with shortened chain is obtained. Method of obtaining complex polyether polyepoxide lies in carrying out the following stages. At the first stage raw material compositiojn, obtained from seed oil, containing one or more unsaturated fatty acids or esters of fatty acids, contacts with lower olefin in presence of olefin methathesis catalyst. Used raw material composition contains less than 25 milliequivalents of admixture(s), poisoning methathesis catalyst, per kilogram of composition. At the second stage (re)etherification of obtained unsaturated acid with shortened chain or unsaturated ester with shortened chain with polyol is carried out. At the third stage epoxidation of obtained complex polyether polyolefin is carried out with epoxidising agent optionally in presence of catalyst. Method of obtaining α,ω-oxoacid, complex α,ω-oxyester and/or α,ω-diol with shortened chain lies in carrying out the following stages. At the first stage raw material composition, obtained from seed oil, containing one or more unsaturated fatty acids or esters of fatty acids contacts with lower olefin in presence of olefin methathesis catalyst. Used raw material composition contains less than 25 milliequivalents of admixture(s), poisoning methathesis catalyst, per kilogram of composition. At the second stage hydroformilation is carried out with hydrating of obtained unsaturated acid or ester with shortened chain in presence of hydroformiolation/hydration catalyst.

EFFECT: increase of catalyst serviceability and obtaining chemical compounds with high productivity.

25 cl, 3 tbl, 12 ex

 

Background of the invention

In one aspect the present invention relates to a raw material composition for olefin metathesis and to the manner of exercise of metathesis. In particular the present invention relates to a raw material compositions based on unsaturated fatty acids or esters of fatty acids and its metathesis with a lower olefin, particularly ethylene, in the presence of a metathesis catalyst to obtain olefin with a short chain and unsaturated acid, or a complex ester with a short chain, preferably α-olefin with a short chain and α,ω-unsaturated acid, or a complex ester with a short chain.

In another aspect the present invention relates to integrated way, including the first metathesis raw material compositions based on unsaturated fatty acids or esters of fatty acids with olefin, preferably ethylene, with the formation of the unsaturated acid or a complex ester with a short circuit, and then the conversion of the unsaturated acid or a complex ester with a short chain α,ω-hydroxy acid, a complex of α,ω-oxivir and/or α,ω-diol. Alternative unsaturated acid or ester with a short circuit can be converted into the α,ω-amino acid, a complex of α,ω-aminoethyl and/or α,ω-amerosport.

In yet another aspect, the present invention relates to the integration of the new method, including a first metathesis raw material compositions based on unsaturated fatty acids or esters of fatty acids with olefin, preferably ethylene, with the formation of the unsaturated acid or a complex ester with a short circuit, and then the conversion of the unsaturated acid or a complex ester with a short circuit in epoxysilane or complex epoxyether.

In yet another aspect the present invention relates to compositions based on complex polyether polyols complex politicalization and complex politicalised.

Using a known organic chemistry methods olefinic (unsaturated) functional group can be converted into alcohol, amine or epoxy functional groups. In addition, monobasic acids and complex monetary can be turned into polyesters respectively by esterification or interesterification with a polyol. In line with this, there is the potential conversion of unsaturated monobasic acids and complex monoamino in applied industrial complex polyether polyols complex politically or complex politicalised, preferably a complex of α,ω-polyether polyols complex α,ω-politically or complex α,ω-politicalised. The polyols and polyamine find application in the production of polymers on oneveryone. Polyepoxide find application in the production of epoxy resins. Yourself α-olefins are used in the production of polyolefin polymers.

Recently, when searching for renewable chemicals for the oil industry of origin attention was paid to the various vegetable oils from seeds, in particular vegetable oils from seeds with a high content of esters of unsaturated fatty acids, such as glycerides of oleic acid. For example, sunflower oil, canola oil and some soy oils contain esters of oleic acid in concentrations of more than 70 wt.%. Known, for example, transesterification of esters of fatty acids contained in vegetable oils from seeds with a lower alcohol, for example, C1-8-alcohol, such as methanol, esters of unsaturated fatty acids and lower alcohol. The latter can be subjected to metathesis with ethylene in the presence of a metathesis catalyst with the formation of α-olefin with a short chain and a complex of α,ω-unsaturated ester with a short chain. For example, to obtain 1-mission and methyl-9-decenoate the methyl oleate can be subjected to metathesis with ethylene.

In WO 96/04289 described by way of metathesis in which to obtain 1-mission and methyl-9-decenoate the methyl oleate and ethylene in contact presets the catalyst under metathesis, containing carboxylic compound of ruthenium or osmium, such as dichloro-3,3-diphenylvinylene)ruthenium(II). In the patent reports the number of revolutions of the catalyst (hereinafter "rpm"), equal to 143 in cases where the method is performed at room temperature and pressure of ethylene at 100 psi (689 kPa). In the context of the present invention, the term "speed" will be defined as the number of moles of the unsaturated acid or of ester, which undergoes metathesis, for example, the number of moles obtained by metathesis of methyl oleate per mole of catalyst.

In the publication of D. Mandelli et al. Journal of American Oil Chemical Society, 73, No. 2 (1996), 229-232 also described atenais esters of vegetable oils, such as methyl oleate and ethylene on rhenium catalysts, and reported speed 112. Before applying the methyl oleate treated aluminum oxide.

For the commercial implementation of these methods metathesis disadvantageous when the above speed is too low.

In the publication M.D. Refvik et al., Journal of American Oil Chemical Society, 76, No. 1 (1999), 93-98 reported that vegetable oils can be summitatis in the presence of ruthenium catalyst Rough (Grubb) - dichloride bis(tricyclohexylphosphine)benzyladenine. Revealed that oil before use purify on silica gel. Dopolnitelnoye, revealing Simonetti esters of unsaturated fatty acids, includes cleaning unsaturated esters on silica or alumina before use, as reported, for example, in the publications W.Buchowicz et al., Journal of Molecular Catalysis A: Chemical, 148(1999), 97-103, and P.O.Nubel et al., Journal of Molecular Catalysis A:Chemical, 145 (1999), 323-327. It is reported that for methyl oleate speed is in the range between 650 and 2500. Disadvantageously, if the metathesis of esters of unsaturated fatty acids with ethylene is more problematic than Simonetti esters of unsaturated fatty acids. Accordingly, if coreagent applied ethylene or other olefin with a low molecular weight, is expected to be much lower speed.

In the publication C.Demes, Chemosphere, 43 (2001), 39 describes the metathesis of methyl oleate with ethylene in the presence of ruthenium metathesis catalyst. It is reported that at 50°C and a pressure of 145 psi method is characterized by the total numbers of revolutions of the catalyst, in the interval between 2320 and 2960.

Implementation of integrated chemical ways to get from renewable raw materials based on vegetable oils from seeds may vary depending on the performance on stage metathesis, where the feedstock unsaturated fatty acid or a complex ester of unsaturated fatty sour is s, derived from vegetable oils from seeds subjected to metathesis with a lower olefin such as ethylene. Performance can be defined, for example, the activity of the catalyst (for example, for converting unsaturated fatty acids or of ester) and the number of revolutions. How metathesis prior art are characterized by unacceptable performance that is unprofitable. Despite the fact that unsaturated fatty acids and esters derived from vegetable oils from seeds can be converted into olefins with a short chain and unsaturated acids or esters with short circuit with higher performance in comparison with the methods of the prior art, the integration method metathesis with other subsequent applied industrial continuous production methods can be difficult to achieve from a commercial point of view.

Given the above, there is a need to develop improved ways in which to obtain olefin with a short chain and unsaturated acid, or a complex ester with a short chain with acceptable performance raw material composition on the basis of unsaturated fatty acids or esters of fatty acids derived from vegetable oils from seeds subjected to metathesis with a lower olefin, such as ethyl is N. To implement this method requires a catalyst with higher activity and number of turns compared with the catalysts of the prior art. In addition, such improved results in any superior way should be achieved at acceptable conditions (in particular, at moderate temperature and pressure and a minimum amount of diluent or solvent) and with acceptable selectivity for the desired products of metathesis. The way metathesis with the above characteristics can be advantageously used for the conversion of unsaturated fatty acids and esters of fatty acids derived from renewable vegetable oils from seeds, olefins with a short chain and unsaturated acids and esters with short-chain, preferably α-olefins with a short chain and α,ω-unsaturated acids and esters with shorter chain. Olefins with a shortened chain of these types can be integrated in the subsequent continuous way to obtain industrial application of chemical compounds, such as complex polyether polyols complex politically, complex politicalised and poly(olefins).

Brief description of the invention

In the first aspect of the present invention relates to a new method of olefin metathesis for the conversion of the two source (participants who coexist in the reaction of olefins, one of which is obtained from vegetable oils from seeds, in two target (result) of the olefin, which is different from participating in the reaction of olefins. A new way of metathesis involves contacting the raw material composition based on fatty acids or complex fatty acid ester, depending on the circumstances containing one or more unsaturated fatty acids or esters of unsaturated fatty acids, with a lower olefin in the presence of a metathesis catalyst under conditions of the method of metathesis, sufficient to obtain, respectively, of the olefin with a short chain and unsaturated acid, or a complex ester with a short chain. In an important aspect of the present invention the raw material composition based on fatty acids or esters of fatty acids characterized by the fact that essentially does not contain poisons admixture(s), able to inhibit the metathesis catalyst, as described in further. It is established that such toxic impurities inherent in the raw raw materials used for the specified metathesis, and are formed due to normal atmospheric conditions. In the context of the present invention, the term "short chain" means that the chain length of the resulting olefin is shorter than the chain length of the original olefin, from which we obtain the olefin p is otvoditsya.

In a related aspect, the present invention relates to a new composition based on fatty acids or esters of fatty acids derived from vegetable oils from seeds and containing one or more unsaturated fatty acids or esters of unsaturated fatty acids, characterized in that it contains less than 3.0 milliequivalents admixture(s), poisons the catalyst for metathesis, per kilogram of the composition based on fatty acids or esters of fatty acids.

Mostly in the way of metathesis according to the present invention is applied commodity composition based on fatty acids or esters of fatty acids derived from vegetable oils from seeds, raw composition based on fatty acids or esters of fatty acids derived from vegetable oils from seeds, and in purified form, in order to ensure increased efficiency of the metathesis catalyst. Mainly the way metathesis according to the present invention is characterized by improved performance in comparison with the methods metathesis of the prior art. Advantageously, in the preferred embodiment of the method of metathesis according to the present invention in comparison with the methods of the prior art are achieved by a higher degree of transformation of Olaf the new and higher turnover. Moreover, such improvements are achieved in terms of implementation of the method at moderate temperature and pressure and with a minimum amount of diluent or solvent, if any. The above superior characteristics make the method of metathesis according to the present invention is highly desirable for the conversion of unsaturated fatty acids and esters of unsaturated fatty acids derived from vegetable oils from seeds, products with higher performance, including olefins with a short chain and unsaturated acids and esters with shorter chain.

The aforementioned method of metathesis according to the present invention gives the opportunity for a useful application of vegetable oils from seeds as a renewable source of industrial chemical products non-petroleum origin by integrating the method of metathesis and subsequent continuous chemical methods. For example, a new way of metathesis according to the present invention finds application in obtaining olefins with a short chain, preferably α-olefins, unsaturated acids and esters with short-chain, preferably α,ω-unsaturated acids and esters. α-Olefins are valuable starting monomers for obtaining polyolefin polymers. When about is EDINENIE (re)esterification with other known chemical methods, such as epoxidation or hydroformylation with recovery, or rehabilitation amination of α,ω-unsaturated acids and esters can be transformed into a complex politicalised, complex polyether polyols, diols, complex politically and aminoalcohols. Complex politicalised used in the manufacture of thermosetting epoxy resins. Complex polyether polyols, diols, complex politically and aminoalcohols are used in the production of polyurethanes.

In a second aspect the present invention relates to a new method of obtaining complex politicalised. In the mentioned second aspect, the method includes: (1) contacting the raw material composition based on fatty acids or esters of fatty acids containing one or more unsaturated fatty acids or esters of unsaturated fatty acids, with a lower olefin in the presence of a catalyst for the metathesis of olefins in terms of the way metathesis sufficient to obtain unsaturated acid, or a complex ester with a short circuit; the raw material composition based on fatty acids or esters of fatty acids characterized by the fact that it essentially does not contain poisons admixture(s), able to inhibit the metathesis catalyst; (2) (re)esterification unsaturated acid, or a complex ester with UCO is ocenol chain with a polyol under conditions of (re)esterification, sufficient to obtain the unsaturated complex of the polyester; and (3) epoxidation of unsaturated complex polyester epoxidised agent, optionally in the presence of an epoxidation catalyst in the epoxidation conditions sufficient to produce complex politicalised.

In connection with the above-described method of metathesis-(re)the esterification of the present invention also relates to a new composition of complex politicalarena represented by the following formula(I):

where each R1independently selected from a hydrogen atom and Cl-8-alkyl radicals; R2selected from a hydrogen atom, methyl, ethyl, and vinyl radicals; x is an integer from about 3 to about 7; and n is an integer from 2 to about 15.

In connection with the above-described method of metathesis-(re)esterification-epoxidation present invention also relates to a new composition of complex politicalised represented by the following formula (II)

where each R1independently selected from a hydrogen atom and C1-8-alkyl radicals; R2selected from a hydrogen atom, methyl, ethyl, and vinyl radicals; x is an integer from about 3 to about 7; and n is an integer from 2 to bring the LNA 15.

In the third aspect of the present invention relates to a method for producing α,ω-hydroxy acid, a complex of α,ω-oxyethira and/or α,ω-diol with a short chain. In the specified third aspect, the method includes: (1) contacting the raw material composition based on fatty acids or esters of fatty acids containing one or more unsaturated fatty acids or esters of fatty acids with a lower olefin in the presence of a catalyst for the metathesis of olefins in the conditions sufficient to obtain an unsaturated acid, or a complex ester with a short circuit, depending on the circumstances; the raw material composition based on fatty acids or esters of fatty acids characterized by the fact that it essentially does not contain poisons admixture(s), able to inhibit the metathesis catalyst; and (2) hydroformylation with the restoration of the unsaturated acid or a complex ester with a short circuit in the presence of a catalyst of hydroformylation/recovery conditions hydroformylation/restore sufficient to obtain α,ω-hydroxy acid, a complex of α,ω-oxyethira and/or α,ω-diol. Not necessarily at the third stage (3) method of an α,ω-hydroxy acids, complex oxivir and/or diol can (re)atrificial in terms of (re)esterification enough for complex α,ω-polyetherpolyols.

In connection with op the toboggan above metathesis-hydroformylation-(re)esterification according to the invention the present invention relates to a new composition of complex α,ω-polyetherpolyols, the following formula (III):

where each R1independently selected from a hydrogen atom and C1-8-alkyl radicals; R2selected from a hydrogen atom, methyl, ethyl, and vinyl radicals; x is an integer from about 3 to about 7; and n is an integer from 2 to about 15.

In the fourth aspect of the present invention relates to a method for producing α,ω-amino acids, complex α,ω-aminoether and/or α,ω-amerosport with a short chain. In the mentioned fourth aspect, the method includes: (1) contacting the raw material composition based on fatty acids or esters of fatty acids containing one or more unsaturated fatty acids or esters of fatty acids, depending on the circumstances, with a lower olefin in the presence of a catalyst for the metathesis of olefins in the conditions sufficient to obtain an unsaturated acid, or a complex ester with a short circuit; the raw material composition based on fatty acids or esters of fatty acids characterized by the fact that it essentially does not contain poisons admixture(s), able to inhibit the metathesis catalyst; and then (2) hydroformylation by reductive amination with an unsaturated acid or a complex ester with a short circuit in the presence of a catalyst is hydroformylation in terms of hydroformylation/reductive amination, sufficient to obtain α,ω-amino acids, complex α,ω-aminoether and/or α,ω-amerosport. Not necessarily at the third stage (3) method of an α,ω-amino acid, complex aminoether and/or aminoplast can (re)atrificial in terms of (re)esterification enough for complex α,ω-politicalarena.

In connection with the above-described method of metathesis-hydroformylation-reductive amination-(re)esterification according to the invention the present invention also relates to a new composition of complex α,ω-politicalarena represented by the following formula (IV):

where each R1independently selected from a hydrogen atom and Cl-8-alkyl radicals; R2selected from a hydrogen atom, methyl, ethyl, and vinyl radicals; x is an integer from 3 to about 7; and n is an integer from 2 to about 15.

Detailed description of the invention

As described above, the new integrated ways are getting new complex politicalised, complex α,ω-polyether polyols and complex α,ω-politicalarena from purified raw material compositions based on unsaturated fatty acids or esters of fatty acids derived from renewable raw materials based on vegetable oil from the seeds.

In the first aspect of the proposed the fast new way metathesis of olefins for the conversion of the two source olefins, one of which is obtained from vegetable oils from seeds, in two of the resulting olefin, preferably α-olefin, which is different from the original olefin. A new way of metathesis involves contacting the raw material composition based on fatty acids or esters of fatty acids containing one or more unsaturated fatty acids or esters of unsaturated fatty acids, preferably esters of oleic acid, with a lower olefin, preferably ethylene, in the presence of a catalyst for the metathesis of olefins in terms of the way metathesis sufficient to obtain olefin with a short chain and unsaturated acid, or a complex ester with a short chain. Preferably the resulting products contain α-olefin with a short chain and α,ω-unsaturated acid or ester with a short chain. The term "short circuit" is to be understood that the chain length of the resulting olefin, as described, is shorter than the chain length of the original olefin from which the resulting olefin is produced. In an important aspect of the present invention features a raw material composition for the method of metathesis in a form that essentially does not contain poisons admixture(s), able to inhibit the metathesis catalyst, especially organic hydropeaking poisonous note is this. For the purposes of the present invention the phrase "essentially does not contain poisons admixture(s), able to inhibit the metathesis catalyst" is to be understood that the raw material composition based on fatty acids or esters of fatty acids contains less than approximately 100 milliequivalents poison metathesis admixture(s), preferably organic hydroperoxides, per kilogram of raw material composition (mEq./kg). By reducing the content poisoning impurities in the raw material composition to below 100 mEq./kg and preferably to the lower levels, as noted below, in the method of metathesis achieved improved performance, which makes the method more suitable for commercial applications.

In the preferred embodiment of the present invention the raw material composition based on fatty acid contains more than about 70 wt.% oleic acid. In another preferred embodiment of the raw material composition based on esters of fatty acids contains more than about 70 wt.% of methyl oleate.

In yet another preferred embodiment of the present invention, the olefin with a short chain is an α-olefin, more preferably 1 to the mission. In an additional preferred aspect of the present invention the unsaturated acid or ester shortened the second chain is an α,ω-unsaturated acid or ester; more preferably dezenove acid or methyl-9-decenoate.

In a related aspect the present invention relates to new raw material composition based on fatty acids or esters of fatty acids containing one or more unsaturated fatty acids or esters of fatty acids (depending on circumstances), further characterized in that it contains less than 3.0 mEq. admixture(s), poisons the catalyst for metathesis, per kg of composition based on fatty acids or esters of fatty acids. Preferably the raw material composition based on fatty acids or esters of fatty acids contains less than about 2.5, more preferably less than approximately 2.0, even more preferably less than about 1.5, and most preferably less than about 1.0 mEq. admixture(s), poisons the catalyst for metathesis/kg of raw material.

In a second aspect the present invention relates to a new method of obtaining complex politicalised, preferably a complex of α,ω-politicalised. In the mentioned second aspect, the method comprises (1) contacting the raw material composition based on fatty acids or esters of fatty acids containing one or more unsaturated fatty acids or esters of unsaturated fatty acids, preferably oleic gislature esters of oleic acid, with a lower olefin, preferably ethylene, in the presence of a catalyst for the metathesis of olefins in the metathesis conditions sufficient to obtain an unsaturated acid, or a complex ester with a short circuit; the raw material composition is characterized by the fact that it essentially does not contain poisons admixture(s), able to inhibit the metathesis catalyst; (2) (re)the esterification of unsaturated acid, or a complex ester with a short chain with a polyol under conditions of (re)esterification sufficient to produce complex politicalarena; and (3) epoxidation of complex politicalarena using epoxidised agent, optionally in the presence of an epoxidation catalyst in the epoxidation conditions sufficient to produce complex politicalised. Preferably the unsaturated acid or ester with a short chain is an α,ω-unsaturated acid or ester with a short chain. Preferably complex politicalisation is a complex of α,ω-politicalisation; and preferably a complex politicalised is a complex of α,ω-politicalised.

In connection with the above-described method of metathesis-(re)the esterification of the present invention relates to a new composition of complex politicalarena represented by the following formula (I)

where each Rlindependently selected from a hydrogen atom and Cl-8- alkyl radicals, preferably hydrogen atom; R2selected from a hydrogen atom, methyl, ethyl and vinyl radicals, preferably hydrogen atom; x is an integer from about 3 to about 7, preferably about 7; and n is an integer from 2 to about 15, preferably about 3.

In connection with the above-described method of metathesis-(re)esterification-epoxidation present invention also relates to a new composition of complex politicalised represented by the following formula (II):

where each R1independently selected from a hydrogen atom and C1-8- alkyl radicals, preferably hydrogen atom; R2selected from a hydrogen atom, methyl, ethyl and vinyl radicals, preferably hydrogen atom; x is an integer from about 3 to about 7, preferably about 7; and n is an integer from 2 to about 15, preferably about 3. More preferably each Rland R2represents a hydrogen atom; x is equal to 7; n is 3; and complex politicalised is a triglyceride 9,10-epoxydecane acid.

The third is the SPECTA present invention relates to a method for producing α,ω-hydroxy acid, complex α,ω-oxyethira and/or α,ω-diol. In the specified third aspect, the method comprises (1) contacting the raw material composition based on fatty acids or esters of fatty acids containing one or more unsaturated fatty acids or esters of fatty acids, preferably oleic acid or esters of oleic acid, with a lower olefin, preferably ethylene, in the presence of a catalyst for the metathesis of olefins in the conditions sufficient to obtain an unsaturated acid, or a complex ester with a short circuit; the raw material composition is characterized by the fact that it essentially does not contain poisons admixture(s), able to inhibit the metathesis catalyst; and (2) with hydroformylation the recovery of the unsaturated acid or a complex ester with a short circuit in the presence of a catalyst of hydroformylation/recovery conditions of hydroformylation/restore sufficient to obtain α,ω-hydroxy acid, a complex of α,ω-oxyethira, and/or α,ω-diol. Preferably the unsaturated acid or ester with a short circuit are α,ω-unsaturated acid or ester with a short chain. In a more preferred embodiment of the present invention the complex of α,ω-exifer is a methyl-11-hydroxyalkanoate; α,ω-hydroxy acid present is employed, an 11-hydroxyureabuy acid; and α,ω-diol is a 1,11-dihydroxyindole. Not necessarily at the third stage (3) α,ω-hydroxy acids, ester and/or diol can be (re)esterification in terms of (re)esterification sufficient to produce complex polyetherpolyols, preferably a complex of α,ω-polyetherpolyols.

Complex α,ω-polyetherpolyols obtained using the above method metathesis-hydroformylation-(re)esterification can be represented by the formula (III):

where each Rlindependently selected from a hydrogen atom and Cl-8- alkyl radicals, preferably hydrogen atom; R2selected from a hydrogen atom, methyl, ethyl and vinyl radicals, preferably hydrogen atom; x is an integer from about 3 to about 7, preferably about 7; and n is an integer from 2 to about 15, preferably about 3. Thus, in the preferred embodiment each Rland R2represents a hydrogen atom; x is equal to 7; n is 3; and complex polyetherpolyols is a complex triglyceride ester 11-hydroxyoctanoic acid.

In the fourth aspect proposes a method of obtaining α,ω-amino acids, complex α,ω-aminoether and/or α,ω-amerosport. In the mentioned fourth aspect, the method includes the (1) contacting the raw material composition based on fatty acids or esters of fatty acids, containing one or more unsaturated fatty acids or esters of fatty acids, preferably oleic acid or esters of oleic acid, with a lower olefin, preferably ethylene, in the presence of a catalyst for the metathesis of olefins in the conditions sufficient to obtain an unsaturated acid, or a complex ester with a short circuit; the raw material composition is characterized by the fact that it essentially does not contain poisons admixture(s), able to inhibit the metathesis catalyst; and then (2) hydroformylation by reductive amination with an unsaturated acid or a complex ester with a short circuit in the presence of a catalyst of hydroformylation/recovery conditions hydroformylation/recovery amination sufficient to obtain α,ω-amino acids, complex α,ω-aminoether and/or α,ω-amerosport. In the preferred embodiment the unsaturated acid or ester with a short circuit are α,ω-unsaturated acid or ester with a short chain. In the preferred embodiment of the complex of α,ω-aminoethyl represents methyl 11-aminoundecanoic. Similarly, the preferred α,ω-amino acid is an 11-aminoundecanoic acid, and the preferred α,ω-amerosport is an 11-aminoundecanoic. Optional is the third stage (3) method of an α,ω-amino acid, complex aminoether and/or aminoplast can (re)atrificial in terms of (re)esterification enough for complex α,ω-politicalarena.

In connection with the above-described method of metathesis-hydroformylation-amination-(re)esterification according to the invention the present invention also relates to a new composition of complex α,ω-politicalarena following formula (IV):

where each R1independently selected from a hydrogen atom and Cl-8-alkyl radicals, preferably hydrogen atom; R2independently selected from a hydrogen atom, methyl, ethyl and vinyl radicals, preferably hydrogen atom; x is an integer from about 3 to about 7, preferably about 7; and n is an integer from 2 to about 15, preferably about 3. Thus, in the preferred embodiment, the complex politically is a complex of α,ω-politically. More preferably each R1and R2represents a hydrogen atom; x is equal to 7; n is 3; and complex politically is a triglyceride of 11 aminoundecanoic acid.

In the most preferred embodiment of the present invention relates to a new method of olefin metathesis include is he contacting ethylene with a raw material composition on the basis of complex fatty acid ester, which is obtained from vegetable oil from seeds and which contains more than about 80 wt.% of methyl oleate; raw material composition on the basis of ester fatty acid contains less than about 100 mEq. organic hydroperoxides per kg of raw material, in the presence of a metathesis catalyst under conditions of the method of metathesis, sufficient to get 1-mission and methyl-9-decenoate.

In another most preferred embodiment of the present invention relates to a new method of obtaining complex α,ω-politicalised, including complex triglyceride ester of 9,10-epoxydecane acid. The preferred method comprises (1) contacting ethylene with a raw material composition on the basis of complex fatty acid ester, which is obtained from vegetable oils from seeds, which contains more than about 80 wt.% of methyl oleate, which further comprises less than about 100 mEq. organic hydroperoxides per kg of raw material composition on the basis of complex fatty acid ester, in the presence of a catalyst for the metathesis of olefins in the conditions of the method of metathesis, sufficient to obtain methyl-9-decenoate; (2) the transesterification of methyl 9-decenoate with glycerol in the interesterification conditions sufficient to produce complex triglyceride ester 9-decanoas acid; and (3) epoxitiolan the e complex triglyceride ester 9-decanoas acid epoxidised agent, optionally in the presence of an epoxidation catalyst in the epoxidation conditions sufficient to produce complex triglyceride ester 9,10-epoxydecane acid.

In the third preferred aspect of the present invention relates to a method for producing a complex of α,ω-oxyethira or α,ω-diol, including methyl 11-hydroxyalkanoate or 1,11-undecanol (1,11-dihydroxyindole), respectively. In the specified third most preferred aspect, the method comprises (1) contacting ethylene with a raw material composition on the basis of complex fatty acid ester, which is obtained from vegetable oils from seeds, which contains more than about 80 wt.% of methyl oleate, which further comprises less than about 100 mEq. organic hydroperoxides per kg of composition on the basis of complex fatty acid ester, in the presence of a catalyst for the metathesis of olefins in terms of the way enough to obtain methyl-9-decenoate; and (2) hydroformylation recovery methyl-9-decenoate in the presence of a rhodium catalyst hydroformylation and catalyst recovery in terms of hydroformylation/restore sufficient to obtain methyl 11-hydroxyalkanoate and/or 1,11-undecanedioic. Not necessarily at the third stage (3) ways methyl 11-hydroxyalkanoate preterition the t by contact with glycerol under conditions of interesterification, sufficient to produce complex triglyceride ester 11-hydroxyoctanoic acid.

In a fourth preferred aspect, the present invention relates to a method for producing a complex of α,ω-aminoether with a short chain, most preferably methyl-11-aminoundecanoic. In the specified fourth most preferred aspect, the method comprises (1) contacting ethylene with a raw material composition on the basis of complex fatty acid ester, which is obtained from vegetable oil from seeds and which contains more than about 80 wt.% of methyl oleate and which additionally contains less than about 100 mEq. organic hydroperoxides per kg of composition on the basis of complex fatty acid ester, in the presence of a metathesis catalyst at conditions sufficient to obtain methyl-9-decenoate; and then (2) hydroformylation with by reductive amination of methyl-9-decenoate in the presence of a catalyst of hydroformylation in terms of hydroformylation/reductive amination sufficient to obtain methyl-11-aminoundecanoic. Not necessarily at the third stage (3) ways methyl-11-aminoundecanoic praeteritorum contacts with glycerol in the interesterification conditions sufficient to produce complex triglyceride ester 11-aminoundecanoic to the slots.

Commodity composition based on fatty acids and esters of fatty acids suitable for use in the method according to the present invention, contains a high concentration of unsaturated fatty acids (acids), complex ether (ether) unsaturated fatty acids or mixtures thereof. Used in the present method, the raw material composition will typically contain more than about 60 wt.% unsaturated fatty acids (acids) and/or of ester (esters) of unsaturated fatty acids, more preferably more than about 70 wt.%, and even more preferably more than about 80 wt.% unsaturated fatty acids (acids) and/or of ester (esters) unsaturated fatty acids. Commodity composition, meeting such criteria can be obtained from the oil crops and vegetable oils, including castor, olive, peanut, rapeseed, corn, sesame, cottonseed, soybean, sunflower, canola, safflower, linseed and other oils. Preferably the raw material composition is obtained from sunflower, canola and certain genetically modified oils, including genetically modified soybean oil.

Usually the raw material composition on the basis of complex fatty acid ester used in the present invention, can be obtained by transesterification of vegetable oil from which eman with the lowest alkanols. In this context, the lower alkanols usually is Cl-10-alkanol, preferably C1-8-alkanol, more preferably C1-4-alkanol, such as methanol, ethanol, isopropanol or butanol, and most preferably methanol. Vegetable oil from the seeds contain a mixture of glycerides of both saturated and unsaturated fatty acids. When interesterification of vegetable oil from seeds with the lowest alkanols get the appropriate mixture of esters of saturated and unsaturated fatty acids lower alkanol. Because of the mixture of glycerides can be difficult to handle and divide by the transesterification of vegetable oil from seeds with the lowest alkanols receive a mixture of esters of fatty acids, more suitable for chemical reactions and separation. Any interesterification conditions are suitable, provided that achieves ester products of lower alkanol. Transesterification (e.g., methanolysis, ethanolic) vegetable oils from seeds in the art described adequately; for example, see WO2001/012581, DE 19908978, BR953081 included in the description by reference.

In a General way interesterification lower alcohol, preferably C1-10-alkanol, such as methanol or ethanol, interacts with an alkaline metal, preferably sodium, at a temperature between PR is around 30°C and about 100°C with the formation of the corresponding metal alcoholate. Then add vegetable oil from seeds and the resulting reaction mixture is heated further at a temperature of between approximately 30°C and about 100°C until until you are transesterification. Raw preterition composition can be distinguished well-known in this field of ways, including, for example, methods of phase separation, extraction and distillation. The crude product may be discolored coal and separated from other unwanted side products column chromatography, for example on silica gel. Variants of the above-described General methods well known in the field.

If instead of raw materials based on esters of fatty acids is desirable to use raw materials on the basis of fatty acids, to obtain the appropriate mixture of fatty acids selected vegetable oil from the seeds can be subjected to hydrolysis. Methods of hydrolysis of vegetable oils from seeds prior to entering into their composition of fatty acids is also well known in this field.

For the method of metathesis any commodity composition based on fatty acids or esters of fatty acids may be used, provided that it contains unsaturated fatty acids or esters of unsaturated fatty acids can be subjected to metathesis with the formation of olefins with a short circuit and nenasi the military acids or esters with shorter chain. As is well known in this field, ester of unsaturated fatty acid is a product of ester condensation of unsaturated fatty acids and alcohol. Unsaturated fatty acid contains a long chain of carbon atoms containing at least one double carbon-carbon bond and a terminal carboxylic acid group. Typical unsaturated fatty acid will contain more than about 6 carbon atoms, preferably more than about 10 carbon atoms, and more preferably more than about 12 carbon atoms. Typical unsaturated fatty acid will contain less than about 50 carbon atoms, preferably less than about 36 carbon atoms and more preferably less than about 26 carbon atoms. At least one double carbon-carbon bond is present in the carbon chain, such double bond, as a rule, is located approximately in the middle of the chain, but not necessarily in the same position. Unsaturated fatty acids containing two or more double carbon-carbon links, can also be appropriately applied in the method according to the present invention. Since the metathesis can be carried out by any of the double carbon-carbon bonds of fatty acids with more than one double bond can get the various products of metathesis, which can then require more effort-sharing. Accordingly, the preferred unsaturated fatty acid with one double carbon-carbon bond. Unsaturated fatty acid may be straight or branched chain and may be substituted by one or more substituents chain fatty acids, provided that one or more of the substituents with respect to the method of metathesis are essentially inert. Non-limiting examples of suitable substituents include alkyl groups, preferably C1-10is an alkyl group, including, for example, methyl, ethyl, propyl, butyl and the like; cycloalkyl group, preferably C4-8-cycloalkyl group, including, for example, cyclopentyl and cyclohexyl; monocyclic aromatic group, preferably C6-aromatic groups such as phenyl; arylalkyl group, preferably C7-16-arylalkyl group, including, for example, benzyl; and alcylaryl group, preferably C7-16-alcylaryl group, including, for example, tolyl, ethylphenyl, xylyl and the like; and hydroxyl, ether, ketone, aldehyde, halide, preferably chlorine and bromine, the functional group.

Non-limiting examples of unsaturated fatty acids, which can be respectively used in raw materials on the basis of fatty KIS is from or fatty acid raw materials on the basis of esters, include 3-hexenoic (hydrocarbonous), TRANS-2-heptanoyl, 2-Ortenovo, 2-nonnovel, CIS - and TRANS-4-dezenove, 9-dezenove (carolinabuy), 10-undecenol (undecylenate), TRANS-3-dodecanoyl (linderberg(linderic)), tridecanol, CIS-9-tetradecenoic (myristoleic), pentadecanol, CIS-9-hexadecanol (CIS-9-palmitoleic), TRANS-9-hexadecanol (TRANS-9-palmitoleic), 9-heptadecanol, CIS-6-octadecenoyl (Petroselinum), TRANS-6-octadecenoyl (Petroselinum), CIS-9-octadecenoyl (oleic acid), TRANS-9-octadecenoyl (elaidic), CIS-11-octadecenoyl, TRANS-11-octadecenoyl (vaccinology), CIS-5-Aksenova, CIS-9-Aksenova (gadolinium), CIS-11-docosanol (carolinabuy), CIS-13-docosanol (erucic), TRANS-13-docosanol (brassicicola), CIS-15-tetracosane (selfrenewal), CIS-17-hexacosanol (semenovoy) and CIS-21-triacontanol (lumequeic) acid, and 2,4-hexadienoic (sorbic), CIS-9-CIS-12-octadecadienoic (linoleic acid), CIS-9-CIS-12-CIS-15-octadecatrienoic (linolenic), oleostearin, 12-hydroxy-CIS-9-octadecenoyl (ricinoleic), CIS-5-docosanol, CIS-5,13-dokozagexaenovu and the like acids. The most preferred unsaturated fatty acid is oleic acid, containing a chain of eighteen carbon atoms with one double bond at the carbon atom in position 9.

Sportova is part of esters of fatty acids, present in the raw material composition may be any monatomic, diatomic or polyatomic alcohol, capable of condensation with an unsaturated fatty acid with the formation of ester. In vegetable oils from seeds of alcohol is glycerin, a trivalent alcohol. By transesterification of the glycerides can be converted into esters of fatty acids and lower alkanols, which are more easily separated or suitable for subsequent chemical processing. Typically the alcohol contains at least one carbon atom. Typically the alcohol contains less than about 15 carbon atoms, preferably less than about 12 carbon atoms, more preferably less than about 10 carbon atoms and even more preferably less than about 8 carbon atoms. The carbon atoms in the alcohol portion may be in the form of straight or branched structure and may be substituted by various substituents, such as deputies, previously described in connection with the fatty acid part, including the aforementioned alkyl, cycloalkyl, an aromatic monocyclic, arylalkyl, alcylaryl, hydroxyl, halogen, ether (common), ester, aldehyde and ketone substituents. The alcohol preferably represents Cl-8-alkanol with direct or rasvet the feudal chain. Most preferably the alcohol is a Cl-4-alkanol, suitable examples of which include methanol, ethanol, propanol and butanol. Most preferably the raw material composition based on esters of fatty acids comprises a mixture of methyl esters of unsaturated fatty acids, mainly oleic acid.

Under the terms of the present invention the raw material composition based on fatty acids or esters of fatty acids, usually obtained by hydrolysis or transesterification of vegetable oil from seeds is in a purified form, in substance not containing one or more toxic impurities that inhibit the operation of the metathesis catalyst. Inhibition of poisoning impurity is expressed in reduced activity of the catalyst, including a reduction in the number of revolutions and the reduction of the service life of the catalyst, as compared with catalyst operating in an environment that is essentially not containing poisoning impurities. Usually toxic impurities include organic gidroperekisi and decomposition of peroxides, such as water, alcohols (e.g. allyl alcohols), ketones and aldehydes (for example, Denali). Present in the raw material compounds, but not necessarily derived hydroperoxides, can also act as toxic impurities, including water, alcohols (for example the EP, allyl alcohols), ketones and aldehydes (for example, Denali). It is believed that organic gidroperekisi are more common and cause more damage. It is known that usually organic gidroperekisi can appear as a result of free radical oxidation in air of double bonds present in unsaturated fatty acid. Using cleaning materials to remove toxic impurities, preferably organic hydropeaking toxic impurities, it is possible to achieve a considerable increase in the activity of the metathesis catalyst, which is determined by the number of revolutions.

You can buy either unmodified or modified with the hydrolysis or transesterification of vegetable oil from seeds of acceptable purity or alternative can be cleaned to a higher level of cleanliness described method. The purity of commercial raw materials, based on fatty acids or esters of fatty acids usually varies from sample to sample; therefore, in order to achieve consistently low levels of impurities, chemical catalyst, such raw material is preferably subjected to purification. If the sample is to be subjected to cleaning, the preferred cleaning immediately before use in the method of metathesis; however, it may be acceptable storage of purified raw materials in an inert atmosphere, t is coy as a nitrogen atmosphere, over a period of time. By itself, the cleaning method is easy to implement when contacting the raw material composition based on fatty acids or esters of fatty acids with adsorbent designed to remove poisons the catalyst admixture(s) to these low concentrations. Typical adsorbents include alumina, silica, activated carbon, clay, magnesia, silicates, molecular sieves, titanosilicates and their mixtures. Preferred adsorbents include alumina, clays and silicates; even more preferred are clays and activated aluminum oxide. The most preferred adsorbent is activated alumina.

More specifically, the cleaning method includes contacting the raw material composition based on fatty acids or esters of fatty acids with an adsorbent under conditions sufficient to obtain the purified raw material composition, total concentration of poisons the catalyst admixture(s), preferably organic hydroperoxides, less than approximately 100 milliequivalents per kilogram (mEq./kg) of raw materials. Preferably the total concentration of poisons the catalyst admixture(s), preferably organic hydroperoxides, is less than about 25, more preferably less than approx is Ino 15, even more preferably less than about 10 and most preferably less than 3.0 mEq. poisoning impurities(s)/kg of raw material. Within the most preferred range being less than 3.0 mEq./kg, it is preferable to use a raw material composition based on fatty acids or esters of fatty acids containing less than about 2.5, more preferably less than approximately 2.0, even more preferably containing less than about 1.5, and most preferably less than about 1.0 mEq. poisoning impurities(s)/kg of raw material. Methods of analysis of hydroperoxides is well known in this field, for example described in the publication R. Johnson and I.W. Siddiqi, The Determination of Organic Peroxides, Pergamon Press, New York, NY, 1970, and in the publication of American Oil Chemical Society Official Methods Cd 8-53 and Cd 8b-90; relevant sections of these publications is incorporated herein by reference. In the General case, the various metathesis catalysts exhibit varying degrees of sensitivity to impurities, and poison the metathesis. For the method of metathesis suitable for practical implementation, it is now known that the maximum concentration of poisoning impurities in raw materials for the metathesis is preferably less than about 100 mEq./kg

The adsorbent can be suspended from the raw commodity composition, or preferably once is estate column with a fixed layer, through which is passed the raw commodity composition. Usually the number of the used adsorbent is more than about 1 wt.% and less than about 100 wt.% relative to the mass of the raw material composition. You can apply any temperature at which the raw material composition is chemically and thermally stable and has a suitable viscosity to flow through the adsorbent. The temperature is usually more than approximately 10°C and preferably equal to or greater than approximately than ambient temperature, taken as 21°C. Usually the temperature is below approximately 100°C, preferably below about 50°C. the External pressure exerted by the column of adsorbent, is typically in the range from atmospheric pressure to about 100 psig (690 kPa). In order to achieve a high degree of cleaning, we can provide multiple passes of the raw material through a column of adsorbent or repeated contact with the adsorbent. Typically, cleaning is performed, as a rule, in the atmosphere of inert gas, which essentially does not contain oxygen. Appropriately it is possible to apply nitrogen, helium, argon, neon and other inert gases and their mixtures. The term "essentially does not contain oxygen" will mean oxygen concentration less than about 1% and preferably less than CA is approximately 0,1%, calculated on the total amount present of the gas phase.

The above description includes the purification stage separation is carried out before stage metathesis, i.e. before the raw material is based on fatty acids or esters of fatty acids will come in contact with a metathesis catalyst; however, the person skilled in the art will identify other technology implementation stage of purification. For example, you can schedule the cleaning stage was carried out in situ in the reactor unit for metathesis during the implementation of the method of metathesis. In addition, it should be noted that impurities, toxic metathesis catalyst, usually can poison the catalysts hydroformylation and epoxidation catalysts. Accordingly arising after metathesis stream was polluted with poisonous impurities, or raw materials should be re-contaminated with harmful impurities, for example, in contact with trace amounts or accidental seepages air during storage or transporting by pipeline, so if necessary purification step can be repeated before further catalytic processing, for example, before metathesis, hydroformylation and epoxydecane.

As briefly noted above, the analysis of toxic impurities in the raw material composition both before and after cleaning the can is about to carry out using any suitable analytical method. For example, the concentration of hydroperoxides can be performed using standard iodide-thiosulfate titration methods known to the person skilled in the art. After cleaning, the raw material composition is usually directly subjected to metathesis or stored in a protective layer of inert gas in order to avoid re-oxidation of unsaturated fatty acids or esters of fatty acids with oxygen.

In addition, for the method of metathesis in addition to the raw material composition based on fatty acids or esters of fatty acids according to the present invention also requires a lower olefin. The term "lower olefin" in this case means C2-5-olefin, such as ethylene, propylene, 1-butene, 2-butene, butadiene, pentene and mixtures thereof. The lower olefin and a raw material composition can be served in the way of metathesis in any operational quantities. Specifically, the applied amount can vary depending on the concentration of unsaturated fatty acids or esters in raw materials and specific design of the reactor. Usually it is desirable to keep the number of lower olefin, sufficient to minimize Simonetti unsaturated fatty acids or esters, i.e. metathesis between two molecules of unsaturated fatty acids or complex average it is desirable to minimize Simonetti lower olefin. (In the preferred embodiment, when the lower olefin is an ethylene, Simonetti is not problematic, as this just again produces ethylene.) Specialist in this field must be known, as without conducting unnecessary experiments to choose the relative amount of lower olefin and raw materials in order to minimize reaction of sometathesysis. The following molar ratios established as a General guide, however, the present invention should not be limited to ratios described here. Usually the molar ratio of lower olefin to the total number of unsaturated fatty acids or esters of fatty acids in the raw material is more than about 0,1/1,0, more preferably approximately 0,9/1,0. Usually the molar ratio of lower olefin to the total number of unsaturated fatty acids or esters of fatty acids in the raw material is less than about 5/1, and preferably less than about 3/1. In the preferred case, where the lower olefin is an ethylene, the upper limit of the molar ratio of ethylene to the total number of unsaturated fatty acids or esters of fatty acids may be in the range up to about 20/1,0. When using ethylene, the molar ratio is preferably less than CA is approximately 20/1,0, and more preferably less than about 15/1,0.

Usually raw materials based on fatty acids or esters of fatty acids used for the method of metathesis in the form of pure (undiluted) of the liquid phase, i.e. without a diluent or solvent. The solvent may increase requirements for recycling and costs. If you want, though not necessarily, you can apply the solvent. Non-limiting examples of suitable solvents include aromatic hydrocarbons such as benzene, toluene, xylenes and the like; chlorinated aromatic hydrocarbons, preferably chlorinated benzenes, such as chlorobenzene and dichlorobenzene; alkanes, such as pentane, hexane, cyclohexane and the like; and chlorinated alkanes, such as methylenechloride and chloroform. If used, the solvent can be any amount, provided that the method of metathesis occurs as described. Typically, the concentration of raw materials based on fatty acids or esters of fatty acids in the solvent is more than about 0.05 M, preferably more than about 0.5 M, usually about less than the concentration at saturation, and preferably less than approximately 5,0 M.

Usually the lower olefin used for the reaction is supplied in the form of essentially pure gas or, optionally, diluted gaseous p is zbavitel. As gaseous diluent can be applied to any essentially inert gas, suitable examples of which include, without limitation, helium, neon, argon, nitrogen and mixtures thereof. If you're using a gaseous diluent, the concentration of the lower olefin in the diluent may accordingly be in the range of from more than about 5 molar percent, preferably more than about 10 mole percent, up to typically less than about 90 mole percent of the lower olefin in the calculation of the total number of moles of a lower olefin and a gaseous diluent. It is advisable method of metathesis to exclude oxygen, to avoid unwanted interactions of oxygen with the metathesis catalyst and the unsaturated fatty acids and/or esters.

As an additional alternative in the way of metathesis you can add a stabilizing ligand. Stabilizing the ligand can be any molecule or ion, promoting the stability of the catalyst in the method of metathesis, which is determined, for example, increased activity and increased service life of the catalyst. Non-limiting examples of stabilizing ligands include three(alkyl)phosphines, such as tricyclohexylphosphine, tricyclohexylphosphine and tributylphosphine; three(aryl)phosphines, such as tri(phenyl)phosphine and three(meth shall fenil)phosphine; alkyldiphenylamine, such as cyclohexylpiperazine; dialkylacrylamide, such as dicyclohexylphenylphosphine; and ethers, such as anisole; phosphine oxides such as triphenylphosphine oxide; and phosphinite, phosphonites, phosphoramidite, pyridine and combinations thereof. The stabilizing ligand is preferably selected from the above-mentioned phosphines and more preferably from three(cyclohexyl)phosphine and three(phenyl)phosphine. The amount of stabilizing ligand may vary depending on the specific catalyst and components specific ligand. Usually the molar ratio of the stabilizing ligand and catalyst is more than about 0.05/1 and preferably is more than about 0.5/1. Usually the molar ratio of the stabilizing ligand and catalyst is less than approximately 4,0/1 and preferably less than about 1.5/1.

The metathesis catalyst may be any catalyst capable of promoting the reaction between unsaturated fatty acids or esters of unsaturated fatty acids with a lower olefin. In this area there are a large number of catalysts for metathesis, representative examples are described in WO 93/20111, US 5312940, WO 96/04289; and J. Kingsbury and others, Journal of American Chemical Society, 121 (1999), 791-799; and are simultaneouslythe pending international patent application no PCT/US 02/05894 (Attorney Docket No. 61071A), filed on February 27, 2002 in the name of Thomas E.Newman, Cynthia Rand, Robert Maughon, Kenneth Burdett, Donald Morrison, and Eric Wasserman; the above publication is incorporated herein by reference. The preferred metathesis catalyst is a ruthenium or OSMANY the metathesis catalyst, more preferably ruthenium metathesis catalyst. Non-limiting examples of suitable ruthenium catalysts include

dichloro-3,3-diphenylvinylene-bis(tricyclohexylphosphine)ruthenium(II)

dichloride, bis(tricyclohexylphosphine)benzyladenine,

dibromide bis(tricyclohexylphosphine)benzyladenine,

the dichloride tricyclohexylphosphine-[1,3-bis-(2,4,6-trimetilfenil)-4,5-dihydroimidazole-2-ilidene][benzylidene]ruthenium,

dibromide tricyclohexylphosphine-[1,3-bis-(2,4,6-trimetilfenil)-4,5-dihydroimidazole-2-ilidene][benzylidene]ruthenium and

the diiodide tricyclohexylphosphine-[1,3-bis-(2,4,6-trimetilfenil)-4,5-dihydroimidazole-2-ilidene][benzylidene]ruthenium.

Most preferably ruthenium metathesis catalyst selected from the group including dichloro-3,3-diphenylvinylene-bis(tricyclohexylphosphine)ruthenium(II)

dichloride, bis(tricyclohexylphosphine)benzyladenine and chelate complexes of ruthenium represented by the following formula (V):

In the formula (V) M is Ru; each L is independently selected from neutral and the anion is s ligands in any combination, where is the balance maintained between the chemical bond and the charge of M; a is an integer, preferably from 1 to about 4, representing the total number of ligands L; R' is selected from a hydrogen atom, an alkyl radical with a straight or branched chain, cycloalkyl, aryl and substituted aryl radicals; Y represents an electron-donating group element 15 or 16 groups of the Periodic system (according to the Nomenclature of inorganic chemistry IUPAC: Recommendations 1990, G.J. Leigh, Editor, Blackwell Scientific Publications, 1990); more preferably Y is O, S, N or P; each R" is independently selected from a hydrogen atom, alkyl, cycloalkyl, aryl and substituted aryl radicals, corresponding to the valency of Y, preferably so that Y was formally neutral; b is an integer, preferably from 0 to about 2, representing the total number of R ' radicals; and Z is an organic diradical that is associated with Y, and with the carbene carbon atom (C) forming a bidentate ligand, which when connected to an atom of M forms a loop containing from about 4 to about 8 atoms. More preferably, each L in the formula V is independently selected from the group consisting of halides, most preferably fluoride, chloride, bromide and iodide, cyanide, ticia the ATA, phosphines of the formula PR3, amines of the formula NR3, water and ethers of the formula OR2simple thioethers of the formula SR2and ligands having formula VI and VII, below:

where each of R in any of the above formulas is independently selected from the group consisting of hydrogen atom, alkyl, preferably Cl-l5-alkyl; cycloalkyl, preferably3-8-cycloalkyl; aryl, preferably C6-l5-aryl, and substituted aryl, preferably substituted C6-15-aryl radicals. In any of the following formulas V you can use a combination of any of the above ligands L. More preferably R' is selected from the group consisting of a hydrogen atom, a C1-15-alkyl, C3-8-cycloalkyl and C6-l5-aryl radicals. More preferably, each R" is independently selected from the group consisting of C1-15-alkyl, C3-8-cycloalkyl and C6-15-aryl radicals. Z is preferably selected from the following diradical: ethylene (VIII), vinylene (IX), phenylene (X), substituted vinylene (XI), substituted fenelonov (XII), naphthylene (XIII), substituted naphthalenol (XIV), piperazinyl (XV), piperidine (XVI):

where each R is, as noted above, to choose from a hydrogen atom, al the ilen, preferably C1-15-alkyl; cycloalkyl, preferably C3-8-cycloalkyl; and aryl, preferably C6-15-aryl radicals; and where each n is an integer from 1 to about 4. In the most preferred embodiment of formula V represents the formula XVII:

where each T is independently selected from Cl and Br, and PCy3is tricyclohexylphosphine.

Despite the fact that the metathesis catalyst is preferably a homogeneous catalyst, i.e. dissolved in the liquid reaction mixture, the catalyst may be associated with or caused by any of the traditional media catalyst known to the person skilled in the art, such as silicon dioxide, aluminum oxide, silica - alumina, aluminosilicates, titanium dioxide, titanosilicates, coal, net cross-linked polystyrene, etc. When you use the carrier for the catalyst, the catalyst can be loaded on the catalyst carrier in any quantity, provided that the method of metathesis proceeds with the formation of the desired metathesis products. Typically, the catalyst loading on the media more than about 0.01 wt.%. the catalytic metal, and preferably more than about 0.05 % wt. the catalytic metal per total weight of the cat who lyst and media. Typically, the catalyst loading on the carrier in amounts less than about 20 % wt. the catalytic metal, and preferably less than about 10 % wt. the catalytic metal per total weight of catalyst and carrier.

Typically, the reactor and the conditions of the method of metathesis traditional, remember, though, that the high performance of this method can be achieved under relatively mild conditions metathesis. Respectively, can be used reactors, batch, flow-through reactor with a stirrer, a flow-through reactors continuous fixed bed catalyst, slurry reactors, fluidized-bed catalyst reactors continuous reciprocating flow and catalytic distillation reactors. Typically, the temperature of the method is above approximately 0°C, preferably above about 15°C and more preferably above about 25°C. Typically, the temperature of the method is below about 80°C, preferably below about 50°C and more preferably below about 35°C. the Pressure of the lower olefin is typically above about 5 psig (34,5 kPa), preferably above about 10 psig (68,9 kPa) and more preferably above about 45 psig (310 kPa). Oba is but the pressure of the lower olefin is less than about 500 psig (3450 kPa), preferably less than about 250 psig (1723 kPa), and more preferably less than about 100 psi (690 kPa).

If the method is carried out in a batch reactor, the, the ratio of the number of moles of the raw material based on unsaturated fatty acids or esters of fatty acids to the number of moles of metathesis catalyst will usually be more than about 10:1, more preferably about 50:1 and more preferably more than about 100:1. Under these conditions the molar ratio of raw materials based on unsaturated fatty acids or esters of fatty acids and metathesis catalyst will usually be less than approximately 10000000:1, preferably less than approximately 1000000:1 and more preferably less than about 500000:1. The time of contact in the reactor periodic action is usually more than approximately 5 minutes, and more preferably approximately 10 minutes. Typically, the time of contact in the batch reactor is less than about 25 hours, preferably less than about 15 hours, and more preferably less than about 10 hours.

If the method is carried out in the reactor of continuous operation, the average hourly feed rate expressed in units: grams raw materials for the missile, the Zisa per gram of catalyst per hour (h -1)determines the relative amount of unsaturated fatty acids (acids) and/or of ester (esters) fatty acids (acids) to the amount of the used catalyst and the residence time of the feedstock in the reactor. Accordingly, the average hourly feed rate is usually more than approximately 0.04 g of raw materials on g catalyst per hour (h-l), and more preferably approximately 0.1 h-1. Average hourly feed rate is usually less than about 100 h-land preferably less than approximately 20 h-l. The flow rate of the lower olefin is usually adjusted to obtain the desired ratio of lower olefin to unsaturated fatty acid (acids) and/or complex ether (ether) unsaturated fatty acids.

When the method of metathesis according to the present invention is carried out as described above, the raw material composition on the basis of unsaturated fatty acids or esters of fatty acid and a lower olefin, preferably ethylene, is subjected to co-metathesis with the formation of at least two olefinic products, which differ from the original (participating in the reaction) of olefins, in particular, with the formation of the olefin with a short chain and unsaturated acid, or a complex ester with a short chain. The term "short circuit" razumeetsa shorter chain length, than the length of the chain involved in the reaction of fatty acids or of ester fatty acids. Preferably two olefinic product contain α-olefin with a short chain and α,ω-unsaturated acid or ester with a short chain. As a more preferred example, the metathesis of raw materials with high concentrations of methyl oleate and ethylene will develop joint products of the metathesis of 1-mission and methyl-9-decenoate. A mixture of metathesis products containing olefin with a short chain unsaturated acid or ester with a short circuit, the metathesis catalyst and optionally unconverted raw materials for the metathesis can be separated using conventional methods known to the person skilled in the art, including for example, distillation, extraction, precipitation, crystallization, membrane separation, etc. α-olefin, obtained according to the method of metathesis, preferably 1-the mission can be used as a monomer in the production of polyolefin polymers.

Unsaturated ester with a short circuit obtained according to the method of metathesis, preferably represented by the following formula:

CHR2=CH-(CH2)x-C(O)OR3,

where R2selected from a hydrogen atom and monovalent C1-5-hydrocarbon radicals, such as methyl, ethyl and vinyl, R is dicale, preferably the hydrogen atom; R3represents a monovalent C1-8is an alkyl radical, and x is an integer from 3 to about 7. Preferred embodiments include α,ω-unsaturated esters, more preferably methyl-9-decenoate, ethyl-9-decenoate, propyl-9-decenoate and butyl-9-decenoate. Most preferably, R2represents a hydrogen atom, R3represents methyl, x is equal to 7, and α,ω-unsaturated ester is a methyl-9-decenoate. Similarly, the most preferred α,ω-unsaturated acid is a 9-dezenove acid.

In the method of metathesis according to the present invention, the degree of conversion of unsaturated fatty acid or a complex ester of the fatty acid may vary considerably depending on the particular raw material composition of the catalyst and the applied conditions. In the context of the present invention under the "degree of transformation" refers to the mol.% unsaturated fatty acids (acids) or of ester (esters) unsaturated fatty acid, which reacted to the formation of products. Usually the degree of transformation of unsaturated fatty acids (acids) or of ester (esters) is more than about 10 mol.%, preferably more than about 20 mol.% and more preferably more than CA is approximately 40 mol.%.

For the method of metathesis according to the present invention is also characterized by an increased number of revolutions of the catalyst, which represents the number of converted moles of unsaturated fatty acids (acids) or of ester (esters) unsaturated fatty acid per mole of catalyst. Usually achieved a speed of more than about 900. Preferably achieved a speed of more than about 1500, more preferably more than about 2000 and most preferably more than about 3500.

In one implementation unsaturated acid or ester with a short chain, preferably the lower complex alkalemia esters of 9-decanoas acid can (re)atrificial with a polyol under conditions of (re)esterification sufficient to produce complex politicalarena formula (I)described above. The person skilled in the art it is obvious that the unsaturated acid with a short chain atrificial, while unsaturated ester with a short chain preterition. The polyol used to (re)esterification may be any polyhydric alcohol, allowing this way, and preferably is a polyatomic C2-15-alcohol. Glycerin is a preferred polyol. The interesterification conditions similar to the conditions the m interesterification, described above, except that efforts should be made to remove the lower alkanol, preferably methanol from the reaction mixture. More specifically, the unsaturated ester is usually in contact with the polyol at elevated temperature in the presence of a catalyst, such as an oxide n-butyrophenone, with simultaneous distillation of the reaction mixture or in conditions of reduced pressure to remove volatile lower alkanol that comes back. Typically on an equivalent basis apply at least about 1 equivalent of ester per 1 equivalent of OH groups in the polyol. Preferably ester relative to the HE-groups used in excess. As a maximum, preferably used is about 2.5 equivalents of ester to 1 equivalent of OH. The most preferred range is from about 1.1 to about 1.5 equivalents of ester per equivalent of OH. Temperature interesterification is usually above approximately 100°C, but below about 250°C. Further description and representative ways interesterification see JP-A2-01093558 and A.Gros and others, Journal of American Oil Chemical Society, 26 (1949), 704-709, incorporated herein by reference. Similar methods known in the field for the esterification of acids with polyols.

Obtained by (re)esterification complex is olivecolored (I) can be epoxidizing epoxidised agent, such as peroxycarbonates acid without catalyst in the epoxidation conditions sufficient to produce complex politicalised. Alternative epoxidation can be performed with the use of hydrogen peroxide or organic gidroperekisi in the presence of an epoxidation catalyst. Preferred epoxygenase agents include hydrogen peroxide, peracetic acid, naturalyou acid, adventurou acid, m-chlormadinone acid, CRYPTOMAGAZINE acid, Gidropress tert-butyl, Gidropress of isopentyl, Gidropress of cyclohexyl, Gidropress ethylbenzene and Gidropress cumene. To effect the epoxidation known various ORGANOMETALLIC catalysts, including, for example, titanosilicates, such as Ti-Beta, Ti-MCM-41 and Ti-ZSM-5; an alcoholate of titanium, such as Ti-isopropylate; wolframite, such as H2WO4; aluminium oxide coated with molybdenum oxide (MoO3); and methyltrioxorhenium. Standard epoxidation conditions include a temperature above about ambient temperature and preferably above about 30°C; however, below approximately 130°C, and preferably below about 100°C. the Pressure is generally equal to ambient pressure, however, if you want or require, you can apply a higher or more than the izkuyu pressure. Description of epoxidation conditions, including temperature, pressure, relative amount involved in the reactions of substances, the design of the reactor and the amount used of the catalyst, in the General case can be found in the following publications, incorporated herein by reference: WO00/18751, ES 2126485, WO01/000605, DE 2009047; Recent Developments in Synthesis of Fatty Acid Derivatives, G.Knothe and J.T.P Derksen, Eds., American Oil Chemical Society: Champaign, IL, 1999, p.157-195; and Handbook of Epoxy Resins, H.Lee and K.Neville, McGraw-Hill, NY, 1982, Chapter 3, p.5-12.

Obtained by the method of epoxidation product preferably contains a complex politicalised above formula (II). More preferably complex politicalised is a complex of α,ω-politicalised. Most preferably complex politicalised is a triglyceride 9,10-epoxydecane acid. Complex politicalised are used as reactive diluents, plasticizers and coatings when using epoxy resins and as components of stabilizers in the pictures.

Alternative unsaturated acid or ester with a short circuit obtained according to the method of metathesis can be hydroformylating recovery to obtain α,ω-hydroxy acid, a complex of α,ω-oxyethira and/or α,ω-diol. In the preferred method, for example, an ester of 9-dice the OIC acid can be hydroformylating to obtain the corresponding complex of α,ω-formirovala ether, for example methyl-11-formylanhalanine, which can be restored to the corresponding complex of α,ω-oxyethira, for example methyl-11-hydroxyalkanoate, or the corresponding α,ω-diol, for example 1,11-undecanedioic. How hydroformylation typically include contacting the olefinic part with a mixture of carbon monoxide and hydrogen in the presence of a catalyst of hydroformylation and optionally in the presence of free organophosphorus ligand under conditions of hydroformylation sufficient to obtain the aldehyde. In the context of the present invention a method of hydroformylation will include contacting an unsaturated acid, or a complex ester with a short chain with carbon monoxide and hydrogen in the presence of a catalyst based on a complex of the transition metal and organophosphorus ligand and optionally free organophosphorus ligand under conditions of hydroformylation sufficient to obtain Foresteria acid or complex formirovala ether, preferably α,ω-Foresteria acid or a complex of α,ω-formirovala ether. Catalysts and conditions hydroformylation described in detail in this area. See, for example, US-B1-6307108, incorporated herein by reference.

Used in the method of hydroformylation according to the present invention catalysts include Liu the nd-based catalyst complex of a transition metal and an organophosphorus ligand, active in the way of hydroformylation. Suitable metals included in the composition of the metal complexes and organophosphorus ligand include metals 8, 9 and 10 groups selected from rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), Nickel (Ni), palladium (Pd), platinum (Pt), osmium (Os) and mixtures thereof; preferably rhodium, cobalt, iridium and ruthenium; more preferably rhodium, cobalt and ruthenium; and most preferred is ruthenium. Other suitable metals include the metals of the 11th group selected from copper (Cu), silver (Ag), gold (Au) and their mixtures, as well as metals of the 6th group selected from chromium (Cr), molybdenum (Mo), tungsten (W) and mixtures thereof. Also suitable metals 8, 9, 10 groups.

Suitable organophosphorus ligands, which form the free ligands and are part of the catalyst on the basis of a complex of a transition metal-ligand include, without limitation, organophosphine, such as triorganotin; and organophosphites, for example mono-, di - and triorganotin and bisphosphite. Other suitable organophosphorus ligands include, for example, organophosphonate, organophosphonate, phosphorus amides, and mixtures of any of the above-mentioned ligands. This area is known for a wide range of phosphorus ligands, such as, for example, illustrated in US-B1-6307108, incorporated herein by reference.

Reaction conditions, the method of hydroformylation, covered by the present invention include any conventional conditions method hydroformylation. For example, the total pressure of the gases hydrogen, carbon monoxide and the source of the olefin may be in the range from about 1 psig (6.9 kPa) or above to below approximately 10,000 psi (68950 kPa). Preferably the total pressure of the gas is below about 2000 psig (13800 kPa) and more preferably below about 1000 psig (6850 kPa). More specifically, the partial pressure of carbon monoxide in the process of hydroformylation according to the present invention is preferably above about 1 psi (6.9 kPa), and preferably above about 3 psi (20.7 kPa). The partial pressure of carbon monoxide is usually below about 1000 psig (6895 kPa) and preferably below about 800 psig (5516 kPa). The partial pressure of hydrogen is usually above about 5 psig (34,5 kPa), preferably above about 10 psig (68,9 kPa). The partial pressure of hydrogen is usually below about 500 psig (3448 kPa), and preferably below about 300 psig (2069 kPa). In General the molar ratio of H2:CO gas in the of Arada and gaseous carbon monoxide is in the range from about 1:10 to about 10:1. How hydroformylation usually carried out at a reaction temperature above about -25°C and preferably above about 50°C. the Method of hydroformylation usually carried out at a reaction temperature below about 150°C and preferably below about 120°C. the Exact time of the reaction will depend on the specific compounds involved in the reaction, and the catalyst; although in the General case, the reaction time is usually in the range from about 30 minutes to about 200 hours. How hydroformylation can be carried out in the presence of a solvent, suitable examples of which include, without limitation, alkanes, cycloalkanes, aldehydes, ketones, ethers, esters, aromatic compounds, etc.

As noted above, the α,ω-formuladoras acid or a complex of α,ω-formally ether, obtained by the method of hydroformylation, you can gidrirovanii in the presence of a hydrogenating agent, usually hydrogen, and usually in the presence of a hydrogenation catalyst to obtain the corresponding α,ω-hydroxy acid, a complex of α,ω-oxyethira and/or α,ω-diol. The specific conditions of the method of hydrogenation of α,ω-Foresteria acid or a complex of α,ω-formirovala ether are not strictly critical and can be any conditions effective hydrogenation, sufficient is to obtain a desired product recovery. Suitable hydrogenation conditions described P.N. Rylander, Hydrogenation Methods, Academic Press, New York, 1985, Chapter 5, incorporated herein by reference. Typically, the hydrogenation is carried out at a temperature above about 0°C and below about 400°C over a period of time of more than about 1 minute and less than about 10 hours. The total pressure during the hydrogenation may vary in a wide range from above about 10 psig (68,9 kPa) to below about 2000 psig (13790 kPa). The partial pressure of hydrogen may vary within a specified range. On stage hydrogenation is normally required catalytic hydrogenation. Such catalysts are known in this field, as described P.N. Rylander, ibid. Preferred catalysts include Raney Nickel, Raney cobalt, Nickel on silica/alumina, palladium on charcoal, platinum on charcoal, rhodium on aluminum oxide and the like, the Catalyst can be used in conventional amounts, which usually implies a concentration of more than about 5 wt.%, but less than approximately 50 wt.%, in the calculation of the mass supplied Foresteria acid or complex formirovala ether. If you want, you can apply a solvent.

Obtained at the stage of hydrogenation of α,ω-hydroxy acid, a complex of α,ω-oxivir and/or α,ω-diol can be distinguished using conventional techniques, such as the filter, crystallization, distillation, extraction, precipitation, membrane separation, or by using other suitable methods of separation. When conducting stage hydrogenation can be applied reactive distillation. The preferred complex of α,ω-oxyethira (esters of hydroxy acids), illustrating the esters obtained according to the method of the present invention include methyl-11-hydroxyalkanoate, ethyl-11-hydroxyalkanoate, propyl-11-hydroxyalkanoate and butyl-11-hydroxyalkanoate, including mixtures thereof; most preferably methyl-11-hydroxyalkanoate. Similarly, the preferred α,ω-hydroxy acid which is a 1,11-hydroxyureabuy acid. Preferred α,ω-diol includes 1,11-dihydroxyindole.

Obtained by the method of hydroformylation α,ω-hydroxy acids or complex α,ω-oxivir can (re)atrificial in contact with a polyol under conditions of (re)esterification enough for complex α,ω-polyetherpolyols above formula (III). The preferred complex of α,ω-polyetherpolyols is a triglyceride of 11 hydroxyoctanoic acid. Conditions (re)esterification again similar to the conditions described and cited above. Complex α,ω-polyetherpolyols is used in the production of urethane polymers and epoxy resins.

On the other hand, unsaturated acid or with whom you can broadcast with a short circuit can podvegnut hydroformylation in the presence of a catalyst of hydroformylation in terms of hydroformylation, sufficient to obtain the corresponding α,ω-Foresteria acid or a complex of α,ω-formirovala ether; and then α,ω-formuladoras acid or ester can be subjected to reductive aminating under conditions of reductive amination, sufficient to obtain the corresponding α,ω-amino acids, complex α,ω-aminoether and/or α,ω-amerosport. Stage hydroformylation described and referenced above. Specific conditions for reductive amination are not strictly critical and can be any conditions effective rehabilitation amination sufficient to obtain the desired α,ω-amino acids, α,ω-complex aminoether or α,ω-amerosport. Used reactor may be a tubular reactor, a reactor with a stirrer or other conventional reactor, suitable for implementing the method. Illustrative conditions for reductive amination described in this area, for example, in U.S. patents 2777873, 4766237, 5068398 and 5007934, the description of which is incorporated herein by reference.

More specifically, the reaction of reductive amination can be carried out at temperatures above about 0°C and below about 400°C over a period of time from about 1 minute to less than about 10 hours. You can apply a wide range of giving the response. Usually the pressure is above about 10 psig (68,9 kPa) and preferably above about 100 psig (689,5 kPa), however, below approximately 4500 psi (31028 kPa) and preferably below about 2000 psig (13790 kPa). The reaction of reductive amination is preferably carried out in the liquid or vapor phase or in their mixtures. As amineralo means preferably used ammonia, which usually comes for implementing the method in the conventional quantities, preferably in excess amounts relative to the α,ω-Foresteria acid or a complex of α,ω-formirovala ether. For implementing the method, the ammonia can be supplied in various ways, including ammonia in liquid or gaseous state, or in the form of, for example, solution in water, or in the form of ammonium salts such as urea. After reductive amination is complete, any excess ammonia is preferably emit. α,ω-formuladoras acid or a complex of α,ω-formally ether serves on stage reductive amination in any convenient way, such as in the form of a solution or in the form of undiluted liquid.

Stage reductive amination is usually carried out in the presence of a catalyst reductive amination. Suitable catalysts of the s for this stage include, for example, Raney Nickel, Raney cobalt, Nickel on silica/alumina, palladium on charcoal, platinum on charcoal, rhodium on aluminum oxide and the like, and mixtures thereof. The amount used of the catalyst will depend on the specific compounds involved in the reaction, and the applicable conditions of reductive amination. The quantity should be sufficient to obtain the desired product selectivity and degree of conversion Foresteria acid or complex formirovala ether. Usually the amount of catalyst is more than about 5 wt.%, preferably more than about 10 wt.%, and preferably less than about 20 wt.%, in calculating the masses Foresteria acid or complex formirovala ether. Obtained at the stage of reductive amination of α,ω-amino acid, complex aminoether and/or aminoplast can be separated using conventional methods, including filtration, distillation, extraction, precipitation, crystallization, membrane separation, etc. When conducting stage of the regenerative amination can also be applied reactive distillation.

Examples to illustrate complex α,ω-amino esters that can be obtained using the method according to the present invention include methyl 11-aminoundecanoic, ethyl 11-aminoundecanoic, propyl 11 undecanoate libutil 11 undecanoate etc. The preferred complex of α,ω-aminoethyl represents methyl 11-aminoundecanoic. Similarly, the α,ω-amino acid is an 11-aminoundecanoic acid; and the preferred α,ω-amerosport is an 11-aminoundecanoic.

α,ω-Amino acid or a complex of α,ω-aminoethyl obtained by the method of hydroformylation/reductive amination, you can (re)atrificial by contact with a polyol under conditions of (re)esterification enough for complex α,ω-politicalarena above formula (IV). Conditions of esterification and interesterification again similar to that described and cited above conditions. Preferred complex politically is a triglyceride of 11 aminoundecanoic acid. Complex α,ω-politicalamity used in the manufacture of urethane and as hardeners of epoxy resins. The last application is discussed in the publication H.Lee and K.Neville, Epoxy Resins, McGraw-Hill, NY, 1982, Chapter 7, incorporated herein by reference.

The following examples are an illustration of the method according to the present invention, but should not be construed as limiting the scope of invention in any way. In the light described here, the person skilled in the art will determine the modification of the reactants, the catalyst and the conditions of the method, which is displayed within the scope of the present invention.

General methods of analysis of peroxides

Esters fatty acids derived from vegetable oils from seeds, in particular methyl oleate, were analyzed for the content of peroxides in the following way. In Erlenmeyer flask (100 ml) with a side branch were combined with stirring glacial acetic acid (40 ml) and deionized water (10 ml), using a magnetic stirrer. In the solution through the side branch through syringe was purged nitrogen and continued the stirring for five minutes. To purged with nitrogen, the solution was added potassium iodide (5 g). The mixture under stirring was re-purged with nitrogen for an additional 5 minutes to form a homogeneous solution. To the resulting solution was added a sample of 20 g of methyl oleate and about 5 minutes to put the solution in an oil bath at 110°C until until he started education phlegmy. Then the flask was removed from the oil bath and returned on the magnetic stirrer, which was added deionized water (40 ml). Then, the resulting yellow-orange solution was titrated 0.01 n sodium thiosulfate (water.), until the discoloration at the endpoint, which was defined by the concentration of hydrogen peroxide according to the following calculation:

[ROOH]=[(X)/(g of methyl oleate)]×(N)×1000

where [ROOH] represents the concentration of peroxide in units of milliequivalents peroxide per kilogram of ester of ironicaly (mEq./kg); X is equal to the volume of sodium thiosulfate solution for titration, in ml; and N is the normality of sodium thiosulfate solution for titration, in units of mEq. of thiosulfate per ml of solution for titration.

Example 1

Example 1 illustrates the cleaning compositions based on esters of fatty acids for the removal of peroxides and subsequent metathesis purified composition based on fatty acids with ethylene to obtain α-olefin with a short chain and α,ω-unsaturated complex ester with a short chain.

Activated alumina (160 ml, Brockmann I, basic, 150 mesh.) load into a separating funnel of fused glass (350 ml, medium caliber). A funnel attached to the Erlenmeyer flask to filter in the vacuum. The methyl oleate (Witco Kemester 205 VEG, 200 ml)containing 305 mEq. peroxide per kg oleate, poured on alumina and enable methyl oleate pass through the alumina in the next ten minutes, applying a vacuum to speed up the process. As determined in the way described above iodide-thiosulfate titration, the concentration of the peroxide after processing is 0.7 mEq./kg

In a clean 2-liter Parr reactor of stainless steel, equipped broskovoy mixer (Mono Mold, the blade with the holes 3"×3/4") add purified methyl oleate (1400 g of 4.44 mol, 91%purity) with a concentration per the TRC 0.7 mEq./kg The reactor is hermetically closed and pumped for about 20 min at a pressure of 30 inches of Hg (rtsora). Rolled back the reactor is connected with the compartment and attached to the reactor, a gas-feeding system. The system is rinsed three times with nitrogen and release (300 psi) (2069 kPa), then rinsed with ethylene. In the reactor, creating pressure ethylene (60 psi) (414 kPa) and stirred for approximately 10 minutes, after which stirring is stopped and the pressure in the reactor to release the pressure of the environment. The valve opening of the syringe immediately open and using a gas tight syringe with a catalyst of verification (Grubbs)dichloride bis(tricyclohexylphosphine)benzyladenine (24.6 ml of 0.04 M of the catalyst of verification, dissolved in toluene) serves the catalyst in the reactor. Hole close and open the valve to ethylene. Operating pressure is 60 psi (414 kPa). Magnetic stirrer high power set at full speed to work within 3 hours of reaction at ambient temperature. The results are presented below in table 1.

Table 1
The effect of the concentration of the peroxide (ROOH) on the degree of conversion of methyl oleate (MO) and the number of revolutions of the catalyst (CTN)1
Example[ROOH]
(mEq./kg)
MO/cat.
Molar
ratio
Rxn
Time
(min)
The conversion of MO (mol.%)CTN (number of moles reacted MO per mole of catalyst)
CE-130545009600%0
E-33,1450024922%990
E-10,70450027448%2160
E-20,30450024957%2565
1Conditions method: room temperature (~22°C) at a pressure of 60 psi.

The table shows that in the sample of methyl oleate containing 0.70 mEq. peroxide/kg, the duration of the reaction 274 minutes achieved the degree is not the stop of methyl oleate 48 mol.% when the number of revolutions 2160.

Example 2

Repeat the experiment of example 1 except that the methyl oleate (Witco) is treated with aluminum oxide and the set content of the peroxide is only 0.3 mEq. peroxides/kg Results metathesis presented in table 1, which shows that the number of revolutions 2565 and the degree of conversion of methyl oleate 57 mol.% achieved when the duration of the reaction 249 minutes If example 2 compared to example 1, it is found that the concentration of peroxide from example 1 to example 2 leads to a significant increase in the speed and degree of conversion at shorter reaction.

Example 3

Repeat the experiment of example 1 except that the obtained methyl oleate (Witco) contains only 3.1 mEq. peroxides/kg and this methyl oleate is used directly for the method of metathesis without processing aluminum oxide. The results of metathesis are shown in table 1, which shows that the number of revolutions of the 990 and the degree of conversion of methyl oleate 22 mol.% achieved when the duration of the reaction 249 minutes If example 3 compared with examples 1 and 2, it is found that at lower concentration of peroxide, the speed and degree of conversion of methyl oleate increased at a comparable or lower the duration of the reaction.

Experiment 1 to compare

Repeat the experimental the NT in example 2 except the obtained methyl oleate (Witco) with a concentration of peroxide 305 mEq./kg and this methyl oleate is used directly for the method of metathesis without processing aluminum oxide. The results are shown in table 1. No conversion of methyl oleate was not observed until the duration of the reaction 960 minutes. Accordingly, the number of revolutions equal to 0. If experiment 1 to compare to compare with the examples 1, 2 and 3, we can conclude that if the concentration of peroxides in the methyl oleate is reduced, the number of revolutions of the catalyst and the degree of conversion of oleate increases with reduced duration of response.

Example 4

Example 4 illustrates the large-scale purification method of composition based on a complex ester of fatty acid and its subsequent metathesis with ethylene to α-olefin with a short chain and α,ω-unsaturated complex ester with a short chain.

Mount the capacity of the reactor, including a reactor Pfaulder (Pfaulder) 316 stainless steel (50 gallons)equipped with two partitions and a mechanism for mixing using a top drive with dual 12" diameter impeller stainless steel, with four slanted blades operating in isolation (~20") with a speed of 337 rpm Original methyl oleate (methyl oleate brand Witco) is cleaned by passing it through a stainless steel column [diameter 14 DUI is s (35.6 cm)×8 feet (2.5 m)], containing aluminum oxide (alumina brand UOP A2, 12×32 mesh.). The concentration of peroxide in a purified source product is 0.2 mEq./kg Cleaned the original product serves in the capacity of the reactor. Filled reactor (300 pounds, 136,1 kg 1.1 lb-mol of methyl oleate) with stirring (60-100 rpm) bubbled with gaseous nitrogen at atmospheric pressure during the night using a bubbler line 1/4 inch and vent lines. The valve is closed and vacuum (2.5 psi) (17,2 kPa) for 2 hours, yet still bubbling. Bubbling nitrogen is stopped and the vacuum reactor to 1.5 psi (10.3 kPa) for 5 minutes Pumping cease; fill the reactor with ethylene to achieve saturation with ethylene at a pressure of 75 psi (517 kPa) at full mixing. During the metathesis reaction of ethylene served on demand to maintain the reaction pressure of ethylene 74-75 psi (510-517 kPa).

Three tanks to enter the catalyst, each of which contains the catalyst of verification (Grubbs) [dichloride, bis(tricyclohexylphosphine)benzyladenine(IV)] in anhydrous toluene (Aldrich, 1 liter, 300 hours/million by weight of water), prepared in a dry box and one of them immediately attached to the hole of the reactor for feeding catalyst. In fixed tanks for feeding catalyst to create the excess nitrogen pressure 80 psi) (552 kPa) and open the inlet valve, to enable the solution of catalyst to get in the reactor. The inlet valve is closed. The empty container is removed and instead attach the following filled balloon. This procedure is repeated with each of the three cylinders for filing. Between additions of catalyst passes approximately 35 minutes reaction time. The molar ratio of the methyl oleate:the total number of catalyst 4500:1.

The reaction mixture after the first submission of the catalyst is stirred for 4 hours at 25-26°C, keeping the temperature by cooling water jacket. At the end of 4 hours of interaction the resulting mixture is pumped from the reactor at atmospheric pressure in a container in an inert atmosphere of nitrogen. Gas chromatographic analysis of samples taken from the mixture, showed a degree of conversion of methyl oleate to 39.5 mol.% with 95%selectivity for each of the compounds: 1-mission and methyl-9-decenoate. Set the number of revolutions of the catalyst was 1689.

Example 5

Example 5 illustrates the cleaning compositions based on esters of fatty acids and its subsequent metathesis with ethylene. The metathesis of methyl oleate is carried out in accordance with the method of example 1 with the following differences: (a) the original methyl oleate contains 99 % wt. esters of oleic acid (Aldrich), instead of 85 % wt. esters oleine the first acid; (b) the concentration of peroxide in a purified source product is 0.40 mEq./kg; (c) the molar ratio of methyl oleate to the catalyst of 18000:1. Under the conditions of the method similar to example 1, the observed number of revolutions of the catalyst is 8100.

Experiment 2 to compare

The metathesis of methyl oleate (Aldrich) is carried out in accordance with the method of example 5 with the following differences: (a) the concentration of peroxide is 26.3 mEq./kg; (b) the molar ratio of methyl oleate to the catalyst 4500:1. Under the conditions of the method similar to example 5, no activity of the catalyst is not observed. When comparing example 5 with experiment 2 for comparison, the concentration of peroxide in the original methyl oleate from 26.3 mEq./kg to 0.4 mEq./kg gives an active catalyst with a higher number of revolutions (8100) with a higher molar ratio oleate:catalyst (18001). In contrast, in the method for comparison, which uses a higher concentration of peroxide, found no activity, even despite the presence of larger quantities of catalyst (ratio of oleate to the catalyst 4500:1). The "experiment for comparison also illustrates the sensitivity of the metathesis catalyst, representing dichloride, bis(tricyclohexylphosphine)be slidermenu, 26 maquirriain/kg. This example can be compared with example 9, below, uses a different catalyst for metathesis: dichloride {tricyclohexylphosphine-[1,3-bis-(2,4,6-trimetilfenil)-4,5-dihydroimidazole-2-ilidene][benzylidene]ruthenium}, which shows activity at approximately 100 maquirriain/kg of raw material.

Example 6

Example 6 illustrates hydroformylation/recovery of α,ω-unsaturated complex ester, particularly methyl-9-decenoate, obtaining a complex of α,ω-oxyethira, in particular methyl-11-hydroxyalkanoate. Methyl-9-decenoate receive in accordance with the method described above in any of examples 1-5.

The reaction hydroformylation carried out in a Parr reactor (capacity 300 ml), equipped with a mechanical stirrer, a pipe for supplying a gas, a heating jacket, a pressure sensor and a thermocouple. Charged to the reactor methyl-9-decenoate (100 g, 0.54 mol), acetylacetonate(dicarbonyl)-rhodium(II) [Rh(CO)2ACAC.] (32 mg, 0.12 mmol) and 2,7-di-tert-butyl-9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (342 mg, 0.49 mmol) under nitrogen atmosphere and then sealed reactor. The reactor is connected with the line of delivery of synthesis gas (CO/H2, 1:1). The system is washed twice synthesis gas and then create excessive pressure 450 psig (3103 kPa). The reactor is heated to 85°C for 16 hours while maintaining the providing synthesis gas 450 psig (3103 kPa). After 16 hours the temperature was raised to 100°C and continue heating for an additional 4 hours. The reactor is cooled to ambient temperature and unreacted gas release. After flushing the reactor with nitrogen to remove any remaining traces of the synthesis gas in the reactor is injected dioxane (50 ml) and 1 g of 5% Pt/SiO2. The system is washed twice with hydrogen and create the excess hydrogen pressure of 500 psig (3448 kPa). The mixture is then heated to 150°C for 20 hours while maintaining the hydrogen pressure of 500 psig (3448 kPa). After cooling, the contents filtered to remove the solid catalyst and using a rotary evaporator to remove the solvent. The liquid phase is subjected to distillation under reduced pressure. Take boiling at 140-150°C at a pressure of 1.5 mm) fraction and dissolved in 1200 ml of hexane. Then the solution is allowed the opportunity to crystallize in the freezer apparatus for 18 hours. By filtering on the cold away crystals in white and washed once with cold hexane. Drying under reduced pressure to obtain methyl 11-hydroxyalkanoate in the form of a white solid (77 g; total yield 65%). The conversion of methyl-11-hydroxyalkanoate by interesterification with a polyol, such as glycerol, in the corresponding complex polyetherpolyols, such as triglyceride 11-hydroxyoctanoic is islote, can be accomplished using methods interesterification known in this field.

Example 7

Example 7 illustrates the obtaining of complex triglyceride ester 9,10-epoxydecane acid. In chetyrehosnuju 500-ml round bottom flask add glycerine (to 73.65 g, 2.4 equiv.) methyl-9-decenoate (540,1 g, 2,93 EQ.) and sodium methylate (25% in methanol, to 3.89 g, 0,0182 EQ.). The flask is fitted is fixed to the side of the condenser flask for collecting the samples, followed by a cooled trap and drying column. The mixture is heated to 200°C under stirring and purging with nitrogen. The distillate methanol selected. After a total duration of heating for approximately 22 hours the reaction is completed, which is determined by gas chromatography. The reaction mixture is cooled to room temperature. The basic catalyst is neutralized by adding glacial acetic acid (0.84 g; 0,014 EQ.). The mixture is then filtered and washed with water until until the pH of the aqueous layer becomes equal to approximately 7-8. The excess methyl-9-decenoate removed by vacuum distillation. The final distillation conditions correspond to 200°C and 1 mm Hg Final product, triglyceride 9-decanoas acid has an iodine value of 127 (theoretical=139). (Iodine value characterizes the degree of unsaturation present in the sample).

The above triglyceride 9-dezenove the acid (100 g, 0,493) placed in a three-neck round bottom flask, equipped broskovoy a magnetic stir bar, separating funnel, thermocouple, and vacuum reflux condenser cooled with circulating at 0°C glycol. In a separating funnel, add peracetic acid (23% in ethyl acetate; 200 g, 0,591 EQ.). The reaction flask is heated to 50°C, then start adding peracetic acid. When added to a sufficient quantity of a solution of peracetic acid, the capacitor slightly vaccum through the upper end to support the boil under reflux at 55°C. the Addition of peracetic acid finish within 40 minutes. The mixture is optionally heated at 55°C for 4 hours, then cooled to room temperature. The product distinguish by removing the greater part of the volatile components on a rotary evaporator under reduced pressure (approximately 25°C with a light bubbling nitrogen). Conditions final distillation light ends meet 80°C and 0.1 mm Hg for approximately 20 minutes. The final product is identified as triglyceride 9,10-epoxydecane acid has an epoxy equivalent weight of approximately 227 g/EQ. (theoretical: 199 g/EQ.).

Example 8

Example 8 illustrates the metathesis of the pure raw material of methyl oleate and ethylene depending on m is polar ratio of methyl oleate and catalyst (MO/Cat). The metathesis was carried out according to the methods of example 1 with the following differences: (1) the original methyl oleate contained 99 % wt. esters of oleic acid (Aldrich) instead of 85 % wt. esters of oleic acid; (b) the concentration of peroxides in the purified raw materials accounted for less than 0.2 mEq./kg (limit of determination); (c) the molar ratio of methyl oleate and catalyst ranged from 4633:1 to 103000:1. The method was carried out in conditions similar to the conditions of example 1 with the results presented in table 2.

Table 2
The number of revolutions of the catalyst (CTN) as a function of molar
the ratio of methyl oleate and catalyst (MO/Cat)1
The molar ratio of MO/CatCTN
46333125
71234548
1710010700
5159312833
10300016069
1Conditions of implementation method: room temperature (~22°C), pressure 60 psi.

Table 2 shows that the number of s is s catalyst increases with increasing molar ratio of methyl oleate to the catalyst.

Example 9

In example 9 illustrates the effect of the concentration of gidroperekisi on the metathesis catalyst, consisting of the dichloride tricyclohexylphosphine-[1,3-bis-(2,4,6-trimetilfenil)-4,5-dihydroimidazole-2-ilidene][benzylidene]ruthenium. The metathesis of methyl oleate was carried out in accordance with the methods of example 1 with the following differences: (a) the original methyl oleate contained 99 % wt. esters of oleic acid (Aldrich) instead of 85 % wt. esters of oleic acid; (b) the peroxide concentration in the purified raw materials accounted for less than 0.2 mEq./kg (limit of determination); (c) the molar ratio of methyl oleate to the catalyst (MO/Cat) was maintained equal to 4,500:1; (d) to methyl oleate in controlled concentrations was added Gidropress cumene and evaluate its impact on the number of revolutions of the catalyst. The metathesis was performed under conditions similar to example 1, with results shown in table 3.

Table 3
The number of revolutions of the catalyst (CTN) as a function of the concentration of peroxide1
The mEq. ROOH per kgCTN
<0,2450
26330
52243
104176
1Conditions of implementation method: room temperature (~22°C), pressure 60 psi.

Thus, the catalyst consisting of the dichloride tricyclohexylphosphine-[1,3-bis-(2,4,6-trimetilfenil)-4,5-dihydroimidazole-2-ilidene][benzylidene]ruthenium, active (CTN) at a concentration of peroxide 104 mEq./kg; however, the catalyst activity increases significantly with decreasing concentration of peroxide.

The following experiment was carried out in accordance with the present invention to obtain a complex of α,ω-oxyethira and α,ω-diol via via (1) metathesis of ester of unsaturated fatty acids, namely methyl oleate, with the formation of α,ω-unsaturated ester with a short chain, namely methyl-9-decenoate; followed by (2) hydroformylation α,ω-unsaturated complex ester with a short chain, namely methyl-9-decenoate, when CO and H2subsequent reduction with the formation of α,ω-oxyethira with a short chain, namely methyl-11-hydroxyalkanoate; then (3) recovering the α,ω-oxyethira with a short chain, namely methyl-11-hydroxyalkanoate, with hydrogen in the presence of a hydrogenation catalyst with the formation of 1,11-dihydroxyindoline.

Example 10. The metathesis of methyl oleate about what adowanie methyl-9-decenoate

Activated alumina (160 ml, Brockmann I, basic, 150 mesh.) loaded into a separating funnel of fused glass (350 ml, medium caliber). The funnel was attached to the Erlenmeyer flask to filter in the vacuum. The methyl oleate (Witco Kemester 205 VEG, 200 ml)containing 305 mEq. peroxide per kg oleate, then poured into aluminum oxide and gave the opportunity methyl oleate pass through the alumina in the next ten minutes, applying a vacuum to speed up the process. The peroxide concentration after treatment was 0.7 mEq./kg, as determined in the standard way iodide-thiosulfate titration.

In a clean 2-liter Parr reactor of stainless steel, equipped broskovoy mixer (Mono Mold, the blade with the holes 3“×3/4”) was added to the purified methyl oleate (1400 g of 4.44 mol, 91%purity) with a peroxide concentration of 0.7 mEq./kg Reactor is hermetically closed and pumped for about 20 minutes under pressure to 101.6 kPa (30 inches Od (RT. post)). Rolled back the reactor was connected with the compartment and attached to the reactor, a gas-feeding system. The system blew three times with nitrogen and stravovali (2069 kPa/300 psi), then purged with ethylene. In the reactor has created pressure ethylene (414 kPa/60 psi) and stirred for approximately 10 minutes, after which stirring was stopped and the pressure in the reactor was stravovali to pressure the he environment. The valve opening of the syringe immediately opened and using a gas tight syringe with a catalyst of verification (Grubbs)dichloride bis(tricyclohexylphosphine)benzyladenine (24.6 ml of 0.04 M of the catalyst of verification, dissolved in toluene) was applied to the catalyst in the reactor. The molar ratio of methyl oleate to the catalyst was 4500/1. The hole closed and opened the valve to ethylene. Working pressure amounted to 414 kPa (60 psi). Magnetic stirrer great power was set at full speed for over 274 min of reaction at a temperature of 22°C. One metathesis product identified as 1-the mission by gas chromatography by comparison with authentic commercial sample and through NMR spectroscopy by comparison with the published spectrum. Another product of the metathesis identified as unsaturated ester methyl-9-decenoate with a short chain.

Chemical formula: CH3O-C(O)-(CH2)7-CH2=CH2

GC-mass spectroscopy MW 184,27 (tiora. 185,3)

1H NMR (d6benzene) δ 5 0,85-2,1 (multiple multiplet, 14 H, CH2), 3,29 (s, 3H CH3), 4,99 (m, 2H), 5,79 (m, 1H)

13With NMR (d6benzene) δ 173, 47, 139, 21, 114, 43, 50, 94, 34, 18-34, 07, 32, 24, 29, 85-29, 33, 25, 20, 23, 04, 14, 29

IR-spectrum (nerdball.) 2930, 2860, 1740, 1640, 1440, 1170, 992, and 910 cm-1

Example 11. Hydroformylation ethyl-9-decenoate and subsequent reduction with the formation of methyl-11-hydroxyalkanoate

The reaction hydroformylation was performed in a Parr reactor (capacity 300 ml), equipped with a mechanical stirrer, a pipe for supplying a gas, a heating jacket, a pressure sensor and a thermocouple. The reactor was loaded methyl-9-decenoate (100 g, 0.54 mol), acetylacetonate(dicarbonyl)-rhodium (II) [Rh(CO)2ACAC.] (32 mg, 0.12 mmol) and 2,7-di-tert-butyl-9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (342 mg, 0.49 mmol) under nitrogen atmosphere and then hermetically closed reactor. The reactor was connected with the line of delivery of synthesis gas (CO/H2, 1:1). The system was twice washed synthesis gas and then created excessive pressure 450 psig (3103 kPa). The reactor was heated to 85°C. for 16 hours while maintaining the pressure of the synthesis gas 3103 kPa (450 psig). After 16 hours the temperature was raised to 100°C and continued heating for an additional 4 hours. The reactor was cooled to ambient temperature and unreacted gas release. After flushing the reactor with nitrogen to remove any remaining traces of the synthesis gas into the reactor was introduced dioxane (50 ml) and 1 g of 5% Pt/SiO2. The system was twice washed with hydrogen and create excess pressure of hydrogen 3448 kPa (500 psig). Then the mixture was heated to 150°C for 20 hours while maintaining the hydrogen pressure 3448 kPa (500 psig). After cooling, the contents were filtered to removed the I of the solid catalyst, and using a rotary evaporator solvent was removed. The liquid phase was subjected to distillation under reduced pressure. Was collected boiling at 140-150°C. (at a pressure of 1.5 mm) fraction was dissolved in 1200 ml of hexane. Then the solution given the opportunity to crystallize in the freezer apparatus for 18 hours. By filtering on the cold was selected crystals white and washed once with cold hexane. Drying under reduced pressure was obtained α,ω-oxivir with short circuit, identified as methyl-11-hydroxyalkanoate in the form of a white solid (77 g; total yield 65%). The conversion of methyl-11-hydroxyalkanoate.

Chemical formula: CH3O-C(O)-(CH2)9-CH2OH

TPL 27°C

IR-spectrum (nerdball.) 3589, 3000, 2854, 1747, 1441, 1048 cm-1

1H NMR (CDCl3) δ 3,66 (s, 3H)and 3.59 (m, J=6,7 Hz, 2H), 2.88 (user. S., 1H), 2,3 (m, J=7.5 Hz, 2H), 1,55 of 1.28 (m, N)

13With NMR (CDCl3) δ 174, 15, 62, 36, 51, 16, 33, 79, 32, 46, 29, 27, 29, 17, 29, 11, 28, 96, 28, 85, 25, 53 and to 24.66

Example 12. Hydrogenation, methyl-11-hydroxyalkanoate education 1.11-dihydroxyindoline

In the Parr reactor was loaded methyl-11-hydroxyalkanoate (75 g), dioxane as solvent (75 ml) and the catalyst chromite copper (8 g). The reactor was closed and the pressure is brought up to 1200 psi (8,273 kPa) with hydrogen and heated at 210°C for 48 hours. Then the reaction mixture was cooled and filtered to remove chromate is ediu. The dioxane was removed with a rotary evaporator. The analysis of the obtained product by means of gas-phase chromatography indicated the conversion of methyl-11-hydroxyalkanoate about 93,6%. The mixture of products was washed with hexane to remove unmodified methyl-11-hydroxyalkanoate and the residue was dissolved in hot toluene. When cooling was obtained crystals of α,ω-diol, identified as 1,11-digitoxigenin (or 1,11-undecanol), output: 55 grams (84%)

Chemical formula: NACN2CH2-(CH2)9-CH2HE

TPL 63°C

1H NMR (CDCl3) δ of 3.60 (m, J=6.59 Hz, 4H), 1,6-of 1.18 (m, 20N)

13With NMR (CDCl3) δ 62, 98, 32, 74, 29, 52, 29, 43, 29, 36 and 25, 68

MC m/e 206,1 (M+NH4)+

1. Commodity composition based on fatty acids or esters of fatty acids obtained by hydrolysis of vegetable oil from seeds or by transesterification of vegetable oil from seeds with C1-8alkanols, containing more than 70 wt.% unsaturated fatty oleic acid, or a complex ester of unsaturated fatty oleic acid, and additives(s), poisons the metathesis catalyst, characterized in that after cleaning the adsorbent contains less than 1.5 milliequivalents admixture(s), poisons the catalyst for metathesis, per kilogram of the composition, and the mixture contains one or more organic hydroperoxides.

2. The composition is based on the false fatty acid ester according to claim 1, characterized in that it is produced by transesterification of vegetable oil from seeds with C1-8-alkanols with formation of a mixture of esters of unsaturated fatty acids (C1-8-alkanol and then contacting the mixture of esters of unsaturated fatty acids With1-8-alkanol with the adsorbent at adsorption conditions sufficient to remove organic hydroperoxides to a concentration of less than 1.5 mEq./kg

3. Composition based on fatty acids according to claim 1, characterized in that it is obtained by hydrolysis of vegetable oil from seeds with a mixture of one or more unsaturated fatty acid, and then contacting a mixture of one or more unsaturated fatty acids with an adsorbent to remove organic hydroperoxides to a concentration of less than 1.5 mEq./kg

4. Composition based on fatty acids or esters of fatty acids according to claim 2 or 3, characterized in that the adsorbent is selected from the group consisting of alumina, silica, activated carbon, clays, oxides of magnesium, silicates, molecular sieves, titanosilicates and their mixtures.

5. Method of olefin metathesis, comprising contacting the raw material composition, obtained from vegetable oil from seeds and containing one or more unsaturated fatty acids or esters of unsaturated fatty acids, with a lower olefin in the presence of the tvii catalyst based on organophosphorus complex transition metal with obtaining the olefin with a short chain and unsaturated acid or unsaturated complex ester with a short circuit, where the raw material composition is characterized in that it contains less than 25 mEq. admixture(s), poisons the catalyst for metathesis, per kilogram of raw material composition capable of inhibiting catalyst for metathesis.

6. The method according to claim 5, characterized in that the raw material composition contains less than 15 mEq. impurities, poisons the catalyst for metathesis, per kg of raw material composition, where the admixture, poisonous metathesis catalyst is an organic hydropeaking.

7. The method according to claim 6, characterized in that the raw material composition contains less than 3.0 mEq. impurities, poisons the catalyst for metathesis, per kg of raw material composition, where the admixture, poisonous metathesis catalyst is an organic hydropeaking.

8. The method according to claim 7, characterized in that the raw material composition contains less than 1.0 mEq. impurities, poisons the catalyst for metathesis, per kg of raw material composition, where the admixture, poisonous metathesis catalyst is an organic hydropeaking.

9. The method according to claim 5, characterized in that the raw material composition contains more than 70 wt.% unsaturated fatty acids (acids) or of ester (esters) unsaturated fatty acids.

10. The method according to claim 9, characterized in that the raw material composition contains more than 70 wt.% oleic acid, or a complex ester (esters) of oleic acid.

11. The way is about to claim 5, characterized in that the raw material composition is produced by transesterification of vegetable oil from seeds with C1-8-alkanol with a mixture of esters of fatty acids (C1-8-alkanol, and optional purification of the mixture of esters of fatty acids (C1-8-alkanol by contacting the mixture with an adsorbent to remove impurities, poisons the catalyst for metathesis, to a concentration of less than 25 mEq./kg, where the admixture, poisonous metathesis catalyst is an organic hydropeaking.

12. The method according to claim 5, characterized in that the raw material composition is obtained by hydrolysis of vegetable oil from seeds with water to form a mixture of fatty acids, and need not be contacting the mixture of fatty acids with an adsorbent to remove impurities, poisons the catalyst for metathesis, to a concentration of less than 25 mEq./kg, where the admixture, poisonous metathesis catalyst is an organic hydropeaking.

13. The method according to claim 5, characterized in that the catalyst based on organophosphorus complex of the transition metal is a complex catalyst containing ruthenium (Ru) or osmium (Os), forming a complex with an organophosphorus ligand.

14. The method according to item 13, wherein the catalyst is selected from the group consisting of
dichloro-3,3-diphenylvinylene-bis(tricyclohexylphosphine)is Utena (II)
dichloride bis(tricyclohexylphosphine)benzyladenine,
dibromide bis(tricyclohexylphosphine)benzyladenine,
dichloride tricyclohexylphosphine-[1,3-bis-(2,4,6-trimetilfenil)-4,5-dihydroimidazole-2-ilidene][benzylidene]ruthenium,
dibromide tricyclohexylphosphine-[1,3-bis-(2,4,6-trimetilfenil)-4,5-dihydroimidazole-2-ilidene][benzylidene]ruthenium,
the diiodide tricyclohexylphosphine-[1,3-bis-(2,4,6-trimetilfenil)-4,5-dihydroimidazole-2-ilidene][benzylidene]ruthenium and chelate complexes of ruthenium represented by the following formula:

where M represents Ru; each L is independently selected from neutral and anionic ligands in any combination, in which is supported a balance between the chemical bond and the charge of M; and a is an integer from 1 to 4; R' is selected from a hydrogen atom, an alkyl radical with a straight or branched chain, cycloalkyl, aryl and substituted aryl radicals; Y represents an electron-donating group elements of group 15 and 16 of the Periodic table; each R" is independently selected from a hydrogen atom, alkyl, cycloalkyl, aryl and substituted aryl radicals corresponding to the valence of Y; b is integer from 0 to 2; and Z is an organic diradical that is associated with Y, and with the carbene carbon atom (S) with the formation of bidentate the second ligand, which when connected to an atom of M forms a cycle of 4 to 8 atoms.

15. The method according to claim 5, wherein the lower olefin is selected from C2-5-olefins.

16. The method according to claim 5, characterized in that the olefin with a short chain is an α-olefin with a short chain and unsaturated esters with short-chain is an α,ω-unsaturated ester with a short chain.

17. The method according to item 16, wherein the α-olefin with a short chain is a 1-mission and α,ω-unsaturated ester with a short chain is a methyl-9-decenoate.

18. The method of obtaining complex politicalised comprising (1) contacting the raw material composition, obtained from vegetable oil from seeds containing one or more unsaturated fatty acids or esters of fatty acids with a lower olefin in the presence of a catalyst for the metathesis of olefins with obtaining unsaturated acid with a short chain or unsaturated complex ester with a short chain or olefin with a short circuit, where the raw material composition is characterized in that it contains less than 25 mEq. admixture(s), poisons the catalyst for metathesis, per kilogram of the composition; (2) (re)the esterification of unsaturated acid, or a complex ester with a short chain polyol with obtaining complex politicalarena; and () epoxidation of complex politicalarena epoxidised agent, optionally in the presence of a catalyst for the epoxidation of obtaining complex politicalised.

19. The method according to p, characterized in that a raw material composition based on esters of fatty acids produced by transesterification of vegetable oil from seeds with1-8-alkanols with formation of a mixture of esters of fatty acids (C1-8-alkanol and need not be contacting the mixture of esters of fatty acids with an adsorbent to remove impurities, poisons the catalyst for metathesis, to a concentration of less than 25 mEq./kg, where the admixture, poisonous metathesis catalyst is an organic hydropeaking.

20. The method according to p, characterized in that a raw material composition based on fatty acids obtained by hydrolysis of vegetable oil from seeds with water to form a mixture of fatty acids and need not be contacting the mixture of fatty acids with an adsorbent to remove impurities, poisons the catalyst for metathesis, to a concentration of less than 25 mEq./kg, where the admixture, poisonous metathesis catalyst is an organic hydropeaking.

21. The method according to p, wherein the lower olefin is an ethylene.

22. The method according to p, characterized in that the olefin with a short chain is an α-olefin and the unsaturated ester is an α,ω-Genaside the hydrated ester.

23. The method of obtaining α,ω-hydroxy acid, a complex of α,ω-oxyethira and/or α,ω-diol with a short chain comprising (1) contacting the raw material composition, obtained from vegetable oil from seeds containing one or more unsaturated fatty acids or esters of fatty acids with a lower olefin in the presence of a catalyst for the metathesis of olefins with obtaining unsaturated acid, or a complex ester with a short circuit, where the raw material composition is characterized in that it contains less than 25 mEq. admixture(s), poisons the catalyst for metathesis, per kilogram of the composition; and (2) hydroformylation with hydrogenation of the unsaturated acid or a complex ester with a short circuit in the presence of a catalyst of hydroformylation/hydrogenation to obtain α,ω-hydroxy acid, a complex of α,ω-oxyethira and/or α,ω-diol.

24. The method according to item 23, wherein the raw material composition on the basis of esters of fatty acids produced by transesterification of vegetable oil from seeds with1-8-alkanols with formation of a mixture of esters of fatty acids (C1-8-alkanol, and not necessarily by contacting a mixture of esters of fatty acids with an adsorbent to remove impurities, poisons the catalyst for metathesis, to a concentration of less than 25 mEq./kg, where the admixture, poisonous metathesis catalyst is organizes the Yu hydropeaking.

25. The method according to item 23, wherein the lower olefin is an ethylene.



 

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47 cl, 1 tbl, 93 ex

FIELD: medicine, pharmaceutics.

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3 cl, 4 tbl, 6 ex

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7 cl, 1 tbl, 10 ex

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21 cl, 2 tbl, 4 ex

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15 cl, 7 ex

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10 cl, 6 ex

FIELD: organic chemistry, chemical technology.

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1 tbl, 1 ex

FIELD: organic chemistry.

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EFFECT: method of increased yield.

1 tbl, 12 ex

FIELD: mining; chemical industry; methods of production of a reactant-foamer.

SUBSTANCE: the invention is pertaining to the improved method of production of a reactant-foamer used for flotation of the ores and representing a mixture of 2.2.4-trimethylpentadiol - 1.3-monoisobutyrate (a synonym - 2.2.4-trimethyl-3-pentanol-1-isobutyrate) and 2.2.4- trimethylpentadiol -1.3 with the share of the latter from 6 up to 45 mass %. The given mixture is produced by a method of an esters condensation of an isobutyric aldehyde at presence of a water solution of sodium hydrate in the tubular reactor at heating with the subsequent fragmentation of the reaction mixture into a hydrocarbon part and a water solution of sodium hydrate, the water flushing a hydrocarbon part and extraction from it by a method of a rectification of a target product and the unreacted isobutyric aldehyde. At that and the recyculation factor of the reaction mixture lays within the limits of 0.6-10. The technical result is an increased speed of the synthesis, decreased power input of the process, decreased (by 20-30 %) consumption of isobutyric aldehyde per a pass per one ton of the target product, a possibility of production of the reactant-foamer with a broad range of the share of diol in it, application of the produced product as the reactant-foamer increases extraction of the floatable material in a flotation concentrate.

EFFECT: the invention ensures an increased speed of the synthesis, a decreased power input and consumption of isobutyric aldehyde, production of the reactant-foamer with a different share of diol in it, increases extraction of the floatable material in the flotation concentrate.

1 tbl, 3 ex

The invention relates to a method of producing methylformate used as an intermediate product when receiving the organic acid is formic, acetic, propionic and their esters, as well as formamido, and to a method of preparation of the catalyst to obtain methylformate

The invention relates to the production of catalysts on the basis of ateleta aluminum used in the production of ethyl acetate from acetaldehyde

The invention relates to the production of catalysts on the basis of ateleta aluminum used in the production of ethyl acetate from acetaldehyde
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