The method of obtaining ala-4z-enes

 

The invention relates to the field of organic chemistry, namely, the method of production of Ala-4Z-ENES. Essence: Ala-4Z-ENES General formulawhere R = n-C6H13; n8H17; n9H19receive interaction of terminal allenes General formula R-CH= C= CH2where R is n-C6H13; n8H17; n9H19with triethylaluminium in the presence of a catalyst of zirconatetitanate in the amount of 2-6 mol.% with respect to the terminal Allen in an argon atmosphere at room temperature and atmospheric pressure in the environment of methylene chloride, for 8-12 h with subsequent acid hydrolysis of the reaction mass. The molar ratio of terminal allene: triethylaluminium is 10: (10-14). Effect: simplified method. table 1.

The invention relates to the field of organic chemistry, specifically to a method for Ala-4Z-ENES General formula (1)where R= n-C6H13; n-C8H17the h9H19Z-Olefins and their derivatives can be used in thin organic synthesis, and also to obtain epoxides, alcohols, ketones, interest in production a method of obtaining the Z-olefin (Tolstikov, A., Dzhemilev, U. M., Vostrikova O. S. , Gimaev A. R., Uman L. I. a method of obtaining a Z-olefins. Auth. mon. 1657479 from 22.02.1991) gidrometeorologia disubstituted acetylenes (R--R) using triisobutylaluminum (VI3iAl) and isobutylamine (BuiMgBr), taken in a molar ratio BuiMgBr:Bu3iAl:R--R=l:(2.53.75): 2.5, in the presence of a catalyst Cp2TiCl2at room temperature (~20oS, 0.5 h) in sulphuric ether as solvent followed by acid hydrolysis of the reaction mass schemeThere is a method allows to obtain Ala-4Z-ENES with the condition of their involvement in the response of hard-Ala-4-ENES with a fixed position of the triple bond exclusively in the 4mposition.

The known method (M. M. Bhagwat, D. Devaprabhakara. Selextive hydrogenation of allenes with chlorotris(tripnenylphosphine)rhodium catalyst. Tetrahedron Lett. , N 15, 1391-1392, 1972) receiving Ala-4Z-ENES by hydrogenation of 1,3-disubstituted 1,2-dienes (internal allenes) with hydrogen at atmospheric pressure in benzene at a temperature of 60oC for 24 h in the presence of 0.5 mol.% Tris(triphenylphosphine)radioid as a catalyst scheme

Offers an improved method of obtaining Ala-4Z-ENES.

The method consists in the interaction of terminal allenes General formula R-CH=C=CH2where R = n-C6H13; n8H17; n9H19with triethylaluminium (1t3), taken in a molar ratio of terminal allene: AlEt310:(1014), preferably 10:12, in the presence of a catalyst of zirconatetitanate (CpZrCl2) in an amount of 2 to 6 mol.% with respect to the terminal Allen, preferably 4 mol.%, in an argon atmosphere at room temperature (~ 20oC) and normal Dawley in methylene chloride (CH2CL2as the solvent for 8-12 hours, preferably 10 hours with subsequent acid (~ 10% model HC1) by hydrolysis of the reaction mass. The total yield of Ala-4Z-ENES (1) is 82-96%.

The reaction proceeds according to the schemewhere R = n-C6H13; n-C8H17; n-C9H19
Ala-4Z-ENES (1) are formed only with the participation 1t3, terminal allenes and zirconium catalyst Cp2ZrCl2. In the presence of other aluminum compounds (e.g., Bu2iAlCl, VI3iA1,RA (for example, Zr(acac)4, ZrCl4Cp2TiCl2Pd(acac)2, Ni(acac)2, NiCl2, Fe(acac)2target products (1) are not formed.

The conduct of a specified reaction in the presence of zirconium catalyst Cp2ZrCl2more than 6 mol.% does not lead to a significant increase in the yield of the target products (1). The use of the catalyst is less than 2 mol.% reduces the output of the Z-olefin (1), which is connected, possibly, with a reduction of catalytically active sites in the reaction mass. The reaction was carried out at a temperature of ~20oC. At a higher temperature (e.g., ~40o(C) has not been a significant increase in the yield of the target product, and at a lower temperature (for example, 0oC) decreases the reaction rate.

Changing the ratio of initial reagents in the direction of increasing the content 1t3in relation to the original 1-substituted Allen does not lead to a significant increase in the yield of target products (1).

The reaction was performed using methylene chloride as solvent. In other solvents (for example, aliphatic or aromatic) decreases the regiospecificity of the reaction and, along with Ala-4Z-s (1), we observed the formation of significant amounts of 1-atill-1-ENES.

Su is on the more accessible terminal allene (R-==), triethylaluminium (1t3), which is produced in the country on an industrial scale, the reaction proceeds at room temperature (~20o(C) in methylene chloride (CH2CL2in the presence of a catalyst Cp2ZrCl2.

In the known method are used less accessible 1,3-disubstituted 1,2-diene (the internal alleni), gaseous hydrogen, the reaction proceeds at elevated (60oC) temperature in benzene (C6H6in the presence of a rhodium catalyst (RhCl(PPh3)3).

The proposed method has the following advantages.

The method allows to obtain with high Regio - and stereoselectivity Ala-4Z-ENES (1), on the basis of available reagents (terminal allene and 1t3in mild conditions (~ 20o(C) in the presence of available catalyst Cp2ZrCl2.

The method is illustrated by the following examples:
Example 1. In a glass reactor with a volume of 50 ml, mounted on a magnetic stirrer, an argon atmosphere was placed 5 ml of methylene chloride (CH2Cl2), 10 mmol of 1,2-nonadiene, 0.4 mmol Cp2ZrCl2at a temperature of ~0oWith 12 mmol AlEt3, stirred for 10 hours at room temperature (~20oC) hydrolyzing -10% model HC1. And the 81-82o(20 Torr), IR spectrum (cm-1): 3080, 2920, 2850, 2300, 1640, 1460, 910, 720. An NMR spectrum1With (, M. D.): 0.77-0.92 (m, 6N, CH3), 1.06-1.55 (m, 10H, CH2), 1.76-1.99 (m, 4H, CH2-C=C), 5.26-5.36 (m, 2H, CH=CH). An NMR spectrum13With (CDCl3,, M. D.): 13.89 (K1), 23.00 (t2), 29.11 (t3), 129.71 (d4), 130.17 (With D.5), 27.35 (t6), 29.89 (t7), 29.43 (t8), 31.90 (t9), 22.74 (t10), 14.15 (K11). M+154.

Other examples of the method shown in the table.

The reaction was carried out at room temperature (~20o(C) in methylene chloride.


Claims

The method of obtaining Ala-4Z-ENES General formula

where R is n-C6H13; n8H17; n9H19,
characterized in that the terminal allene General formula
R-CH= C= CH2,
where R is n-C6H13; n8H17; n9H19,
interact with triethylaluminium A1Et3in a molar ratio of terminal allene: AlEt310: (10-14), in the presence of a catalyst zircon-candalaria (Cf2SrCl2) in an amount of 2-6 mol. % the e methylene chloride as solvent followed by acid hydrolysis of the reaction mass.

 

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