A method for simultaneous obtaining of tree-5,6-disubstituted hept-1 - enes, tree-5,6-disubstituted deca-1,9-dienes
(57) Abstract:A method for simultaneous obtaining of tree-5,6-disubstituted hept-1-ENES, tree-5,6-disubstituted DECA-1,9-dienes of the General formula CH2=CH-CH2-CH2-CH (R')-CH(R')-CH3(I) and (CH2= CH-CH2-CH2-CH (R')-CH(R')-CH2-CH2-CH=CH2(II) where R' is n-butyl or benzyl, which may find application in thin organic synthesis, synthesis of biologically active drugs, special polymers. A mixture containing R22AlCl, where R2- ethyl or isobutyl, metal Mg, alpha-olefin R1-CH= CH2where R1- n-butyl or benzyl, and the catalyst ZrCl4in a molar ratio of(20:22):10:(20:22):(0,2-0,4) accordingly, in a solution of tetrahydrofuran, maintained under stirring at room temperature for 8 h, the resulting reaction mixture BuZi at 0oWith, CuCl and allylchloride in a molar ratio of(20-22):(0,1-0,3):(60-66) respectively and incubated under stirring at room temperature 7 - 9 PM Method has a high stereo - and regiospecificity. table 1. The invention relates to the field of petrochemical synthesis, in particular to a method for simultaneous obtaining of tree-5,6-disubstituted hept-1-ENES, tree-5,6-disubstituted DECA-ze, as well as in the synthesis of biologically active preparations containing substituents exclusively threo-configuration, special polymers.The known method (patent Belgium N 630046, 1963) get replaced by decatriene, such as 1-phenyl-1,4 E, 9-decatriene together with 4-phenyl-1,7-cyclodecane, which consists in the interaction of butadiene (350g) with styrene (butadiene:styrene 2:1) in the presence of a three-component catalyst consisting of Ni(acac)2(6,18 g), Et2Aloet (6.3 g) and tri-O-hydroxyphenylacetate (12.9 g) in 100 ml of cyclooctadiene. The reaction is carried out in a steel autoclave at a temperature of 80oC under a pressure of 60 ATM. The result is a 1,4 E,9-decatriene (73,1%) and 4-phenyl-1,7-cyclodecane (4,3%). The disadvantage of this method is the necessity of working with flammable and explosive gaseous source reagent (butadiene) under pressure (60 bar) at a relatively high temperature ( 80oC), low selectivity and inability to obtain by this method Treo-substituted of decatriene.A method of obtaining substituted decatriene, such as 1-phenyl-1,4 E, 9-decatriene (U.S. patent N 3390195, 1968), together with 1,4,9-decatriene and cyclic oligomers of butadiene (4 vinylcyclohexane, cyclooctadiene, CIII 3.9 mmol CO-and two-component catalyst, consisting of Ni (acac)2(3.9 mmol) and AlEt3by 19.5 mmol) in 25 ml of benzene. The reaction is carried out in a steel autoclave under pressure at a temperature of approximately 80oC. the result is a complex mixture of hydrocarbons consisting of 1,4,9-decatriene, 1-phenyl-1,4 E,9-decatriene and cyclic oligomers (4 vinylcyclohexane, cyclooctadiene, cyclododecatriene).The process has a high fire risk, because you must work with a gaseous source reagent (butadiene) under pressure at a temperature of approximately 80oC. in Addition, the known method does not allow you to get three-5,6-disubstituted hept-1-ENES, tree-5,6-disubstituted DECA-1,9-diene.We propose a new method stereoselective synthesis of threo-5,6-disubstituted hept-1-ENES, tree-5,6-disubstituted DECA-1,9-dienes.The essence of the method lies in the interaction-olefins, such as 1-hexene of allylbenzene with metallic magnesium (powder) and diisobutylaluminium (i-Bu2AlCl) or diethylaluminium (Et2AlCl), taken in a molar ratio of Mg: 10: (20-22): (20-22), mostly 10 : 21 : 21, in the presence of a catalyst zirconium tetrachloride (ZrCl4) 2-4 mol.% with respect to the metal magnesium, preposterone (THF) with stirring for 8 h followed by addition of BuLi in equimolar amounts with respect to R22AlCl (BuLi: R22AlCl = 1:1) and at a temperature of about 0oC odnoklasniki copper (CuCl) in the amount of 1-3 mol.% with respect to the metal magnesium, preferably 2 mol.%, and allylchloride in three-fold excess with respect to R22AlCl, followed by stirring at room temperature (22-23oC) for 7-9 hours Get Treo-5,6-disubstituted hept-1-ENES, tree-5,6-disubstituted DECA-1,9-diene in the ratio of 1:1 with a total yield 82-96%. The reaction proceeds according to the scheme
< / BR>The conduct of a specified reaction in the presence of a catalyst ZrCl4or CuCl more respectively 4 or 3 mol.% does not lead to a significant increase in the yield of the target products. The use of catalyst ZrCl4or CuCl less than 2 or 1 mol.% with respect to the metal magnesium reduces the yield of unsaturated compounds, due to the decrease in reaction centers. Experiments were performed at room temperature (22-23oC). At a higher temperature (for example, 50oC) increases the amount of seal products, at a lower temperature, for example 0oC, decreases the reaction rate.Without dialkylaminoalkyl (R22AlCl) reaction is not. Unable to carry out the reactions of the Sabbath. 3Al, i-Bu2AlH.Thus, the proposed method differs from the known fact that in the known method are used as initial reagents butadiene, styrene and gaseous carbon monoxide, the reaction proceeds under pressure at elevated temperature in the presence of a phosphine complex of Nickel. With the proposed method, the reaction proceeds in the presence of metallic Mg - olefins, dialkylaminoalkyl (R22AlCl) , zirconium and copper catalyst without pressure at room temperature.The proposed method in contrast to the known allows to obtain with high Regio - and stereoselectivity of tree-5,6-disubstituted hept-1-ENES, tree-5,6-disubstituted DECA-1,9-diene.Example 1. In a glass reactor with a volume of 100 ml, mounted on a magnetic stirrer, an argon atmosphere was placed 21 mmol i-Bu2AlCl in 20 ml of THF, 10 mmol magnesium (powder), 21 mmol of 1-hexene and 0.3 mmole ZrCl4, stirred for 8 h at room temperature 22-23oC add at a temperature of 0oC 21 mmol BuLi, then 0.2 mmol CuCl and 63 mmol of allylchloride. The temperature slowly raised to room temperature and stirred for 8 h, the reaction mass is treated with water, emit tree-5,6-di(n-butyl)-hept-1 the-butyl)-hept-1-ene:
IR spectrum (cm-1): 3080, 2930, 1640, 1460, 1375, 990, 910. Range of the MRP , M. D.): 0,74-of 0.95 (m, 9H, CH3), 1,24 (m, 16H, CH, CH2), a 1.88-to 2.18 (m, 2H, CH2), 4,88-5,08 (M, 3H, CH = CH2).An NMR spectrum13C , M. D.): 113,9 t (C1), 139,6 d (C2), 30,9 t (C3), 32,4 (C4), 41,8 d (C5), 34,3 d (C6), 15,5 to (C7), 34,3 t (C7), 34,3 t (C8), 30,2 t (C9), 23.1 (C10), 14,2 (C11), 33,7 t (C12), 29.3 t (C13), 22,1 t (C14), 14,2 (C15), M+210.Spectral characteristics of three-5,6-di(n-butyl)-DECA-1,9-diene:
IR spectrum (cm-1): 3095, 2985, 2940, 2870, 1640, 1470, 1010, 930. Range of the MRP , M. D.): to 0.89 (t,6H,CH3), of 1.23 (m, 18H, CH, CH2), 1,84 -2,18 (m, 4H, CH2), 4,88-of 6.02 (m, 6H, CH=CH2)
An NMR spectrum13C , M. D.): 114,08 t (C1), 139,48 d(C2), 32,37 t (C3), 30,38 t (C4), 38,96 d(C5), 30,21 t (C6), 30,08 t (C7), 23,14 t (C8), 14,17 (C10), M+250.Other examples of the method shown in the table.All experiments were performed at room temperature (22-23oC) in THF. In other solvents (dioxane, ether, hexane, benzene, cyclohexane), the yield of the target products is sharply reduced. A method for simultaneous obtaining of tree-5,6-disubstituted hept-1-ENES, tree-5,6-disubstituted DECA-1,9 the decomposing those the mixture containing in solution of tetrahydrofuran dialkylaminoalkyl General formula
where R2- ethyl or isobutyl, metallic magnesium, alpha-olefin of General formula
R1- CH = CH2,
where R1- n-butyl or benzyl,
and the catalyst is zirconium tetrachloride in a molar ratio of 20 - 22 : 10 : 20 - 22 : 0,2 - 0,4 accordingly stand under stirring for 8 h at room temperature and then adding to the resulting reaction mixture at 0oWith utility, odnoklasniki copper and allylchloride in a molar ratio of 20 - 22 : 0,1 - 0,3 : 60 - 66 accordingly, by keeping the reaction mixture under stirring at room temperature for 7 to 9 hours
R = C4H9C6H13C9H19
FIELD: regeneration of heat and extraction of impurities.
SUBSTANCE: the invention is pertaining to the method of regeneration of heat and extraction of impurities from the area of the heat-producing reaction in the fluidized flow, conducted for conversion into light olefins of oxygenates present in the flow of the oxygenate (oxygen-containing) raw. raw. The offered method includes the new system of a two-stage quick chilling intended for extraction at the first stage of water from the outgoing from the reactor flow and regeneration of heat of this flow for the purpose, at least, of the partial evaporation of the raw flow due to indirect heat-exchange between the oxygenated raw and the flow of the upper product of the first stage or the flow of recirculation of the first stage. The flow of purification being withdrawn from the first stage, contains the large share of impurities and the high-boiling oxygenates. In the second stage besides conduct extraction of water from the products flow containing light olefins, and produce the flow of the purified water, which requires only the minimum evaporation of the water for production of the water flow of the high degree purification. The method allows to concentrate the impurities in a rather small flow and ensures the significant saving of power and money resources at production of a flow of the vaporous raw guided into the area of realization of the heat-exchange reaction in the fluidized flow.
EFFECT: the invention ensures concentration of the impurities in a rather small flow and the significant saving of power and money at production of the flow of the vaporous raw directed into the area of realization of the heat-exchange reaction in the fluidized flow.
19 cl, 3 tbl, 4 dwg, 5 ex
FIELD: petrochemical processes.
SUBSTANCE: narrow-range hydrocarbon stock is fed into reaction-distillation tower at a level located between lower and upper tower parts to perform isomerization and disproportionation of hydrocarbons. Reaction mixture is maintained in vapor-liquid equilibrium state to concentrate lighter reaction products in vapor phase and higher ones in liquid phase by means of controlling temperature profile and in-tower pressure. Higher olefins are withdrawn as bottom product and lighter olefins from the top of tower.
EFFECT: increased yield of desired product.
41 cl, 4 dwg, 5 ex
FIELD: petroleum chemistry.
SUBSTANCE: claimed method includes oligomerization of one or more alpha-olefins with ethylene in presence of metal-containing catalytic system, using one or more bisaryl pyrimidine-MXa complex and/or one or more [bisaryl pyrimidine-MYpLb+]q- complex. Process is carried out at ethylene pressure less than 2.5 MPa.
EFFECT: method for production of target product of increased yield.
10 cl, 1 tbl, 3 dwg, 17 ex
FIELD: industrial organic synthesis catalysts.
SUBSTANCE: catalyst contains following active components: Pd (0.001-1%), Bi (0.001-5%), at least of Ag, Cu, Zn, K, Na, Mg, Ca, Be, Sn, Pb, Cd, Sr, Ba, Ra, Mn, Zr, Mo, and Ge (0.001-10%), and at least one of rare-earth metals deposited on porous inorganic carrier (the balance.). Catalyst is capable of selectively and rapidly hydrogenating strongly unsaturated hydrocarbons such as alkynes. Catalyst is suitable for industrial cracking process and is characterized by favorable long regeneration period, long service time, and low cost.
EFFECT: improved performance characteristics of catalyst at low cost.
23 cl, 5 tbl, 22 ex
FIELD: petroleum chemistry.
SUBSTANCE: 1,3-butadiene is exposed to telomerization with telogene of general formula H-X-Y-H, wherein X represents oxygen, sulfur, nitrogen or phosphorus; Y represents carbon, nitrogen or silicium; and X and Y optionally may have substituents according to valence thereof to form telomer of general formula H2C=CH-CH2-CH2-CH2-CH=CH-CH2-X-Y-H. Said telomer is hydrolyzed to 1-substituted 2-octene of formula H3C-CH-CH2-CH2-CH2-CH=CH-CH2-X-Y-H. Substituted 2-octene is splitted to produce 1-octene.
EFFECT: improved method for production of 1-octene.
28 cl, 4 ex
FIELD: organic chemistry.
SUBSTANCE: claimed method includes a) reaction of carbon monoxide and hydrogen in presence of effective amount of Fischer-Tropsch catalyst; b) separation of at least one hydrocarbon cut containing 95 % of C15+-hydrocarbons from obtained hydrocarbon mixture; c) contacting separated cut with hydrogen in presence of effective amount of hydration catalyst under hydration conditions; d) treatment of hydrated hydrocarbon cut by medium thermal cracking; and e) separation of mixture, including linear C5+-olefins from obtained cracking-product. Method for production of linear alcohols by oxidative synthesis of abovementioned olefins also is disclosed.
EFFECT: improved method for production of linear olefins.
12 cl, 3 tbl, 1 dwg, 2 ex
FIELD: industrial organic synthesis.
SUBSTANCE: before olefin-containing raw material is brought into contact with isomerization catalyst, one or several components of the raw material are subjected to preliminary treatment coming into contact with preliminary treatment material containing zeolite with pore size at least 0.35 nm. Initial olefin is, in particular, vinylidene olefin of general formula CH2=C(R1)R2, wherein R1 and R2 independently represent alkyl groups having at least 2 carbon atoms so that molecular structure includes at least one allyl hydrogen atom.
EFFECT: increased selectivity.
10 cl, 1 tbl, 11 ex
FIELD: organic synthesis catalysts.
SUBSTANCE: vinylidene olefin-containing starting material is brought into contact with isomerization catalyst consisting of molecule sieve in H form, which contains pore larger than 0.6 nm.
EFFECT: increased selectivity of catalyst.
12 cl, 1 tbl, 11 ex
FIELD: petrochemical processes.
SUBSTANCE: liquid olefin-containing feed stream is brought into contact with activated catalyst composed of basic metal oxides or essentially basic metal oxides under olefin isomerization conditions. Catalyst has original olefin isomerization activity and contains activity affecting admixture in amount not exceeding that which would lead to reduction in catalytic activity with a rate of about 0.075% of hourly conversion loss as measured under 1-butene-to-2-butene isomerization process conditions, said activity affecting admixture being on including sulfur, phosphorus, at least one transition metal, or combination thereof.
EFFECT: increased catalytic activity.
34 cl, 5 dwg, 3 tbl, 2 ex
FIELD: petrochemical processes.
SUBSTANCE: branched olefins from isomerization feedstock in the form of linear olefin/paraffin mixture containing 5 to 50% of linear olefins having 7 to 28 carbon atoms are obtained in the first isomerization stage, wherein carbon backbone of linear olefins in the isomerization feedstock is isomerized when in contact with isomerization catalyst, which is effective to isomerize carbon backbone in linear olefin blend to convert the latter into olefin blend, wherein average number of branches in molecule chain is at least 0.7, followed by second stage, wherein branched and linear molecules are separated, the former being essentially olefinic molecules and the latter olefinic and/or paraffin molecules. Resulting branched olefins are served as starting material for production of alcohols and alkylbenzenes.
EFFECT: enabled olefin branching control.
6 cl, 4 tbl, 3 ex
FIELD: organic chemistry.
SUBSTANCE: alkyl(benzyl)allene of general formula (R-= =), wherein R is n-C2H11, n-C6H13,CH2Ph is reacts with EtMgBr, Mg, Cp2TiCl2, methyl iodide and CuCl in argon atmosphere in tetrahydrofuran medium for 18-22 hours. Total yield of target products is 69-86 %.
EFFECT: selective method for production of 3,6-dimethyl-4,7-dialkyl(phenyl)-2,6-octadiens.
1 tbl, 1 ex
FIELD: obtaining of unsaturated hydrocarbons.
SUBSTANCE: method involves obtaining a mixture, containing one or more cyclic unsaturated hydrocarbons and surplus from one or more non-cyclic unsaturated hydrocarbons, where the molar ratio of the non-cyclic unsaturated hydrocarbons to the cyclic unsaturated hydrocarbons ranges from 5:1 to 3:1. The indicated cyclic unsaturated hydrocarbons have ΔG less than 0 at 25°C and have a ring structure, containing "x" atoms of carbon. The method also involves reaction of a cross-metathesis mixture of one or more cyclic unsaturated hydrocarbons and one or more non-cyclic unsaturated hydrocarbons. The method is characterised by that, the cross-metathesis stage is carried out under effective conditions with formation of a mainly non-cyclic unsaturated hydrocarbon product, containing one molecule of the indicated cyclic unsaturated hydrocarbon and more than "x" carbon atoms. The indicated unsaturated hydrocarbon products contain 10-16 atoms of carbon.
EFFECT: cheap method, with high selectivity of obtaining non-cyclic unsaturated compounds, containing from ten to sixteen carbon atoms.
24 cl, 10 ex, 9 tbl, 4 dwg
SUBSTANCE: invention relates to a method for synthesis of 1-aminomethyl-α,ω-alkadiines of general formula (1): , where R2N = piperidyl, morpholyl, N-methylpiperazyl, characterised by that α,ω-diacetylenes HC≡C-(CH2)n-C≡CH, where n=4, 6, 8, react with gem-diamines R2NCH2NR2, where R2N is as defined above, in the presence of a copper (I) chloride catalyst (CuCl), taken in molar ratio α,ω-diacetylene: gem-diamine: CuCl=10:10: (0.3-0.7),preferably 10:10:0.5 mmol without a solvent at temperature of 80°C and atmospheric pressure for 4-5 hours. 1-aminomethyl-α,ω-alkadiines can be used in fine organic synthesis and particularly in synthesis of scarce polycyclic compounds, as well as in synthesis of biologically active substances.
EFFECT: method increases output of the desired products.
1 cl, 1 ex, 1 tbl
SUBSTANCE: invention relates to a method of separating isopentane-isoamylene-isoprene-containing hydrocarbon fractions or butane-butylene-divinyl hydrocarbon fractions obtained at the first step of two-step dehydrogenation of corresponding paraffin hydrocarbons, involving separation of paraffin-olefin-diene fraction obtained at the first dehydrogenation step through extraction rectification, and is characterised by that a vapour stream is extracted from a desorber via lateral collection, where the said vapour stream contains large amount of diene, and after condensation, said stream is taken for extraction of the diene end product at the second extraction rectification step, and an olefin fraction which does not contain diene is collected from the top of the desorber and taken to the second dehydrogenation step.
EFFECT: use of said method increases output of the end product.
1 cl, 2 ex, 1 dwg