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

R22AlCl,

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

 

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