The way to obtain (z)-1,2-dialkyl-1,2-diethylethylene

 

(57) Abstract:

The invention relates to a method for producing (Z)-1,2-dialkylanilines General formula 1, where R=n-C3H7n-C4H9. These hydrocarbons can be used as monomers in the process of oligomerization, polymerization and intermediates used in paint industry. The proposed method lies in the interaction dialkylamides acetylenes of the formula R-CC-R triethylaluminium (Et3A1) in the presence of zirconatetitanate (Cp2ZrC12) as a catalyst in their molar ratio, respectively, 10: (10:20): (0,1-0,5). The interaction is carried out at normal conditions in the environment of hexane with stirring for 8 hours Then to the reaction mass at 0oTo add atylosia (EtTs), taken in a molar ratio RCCR:EtTs = 10:(40-60) and the reaction mass is stirred for 16-20 h at room temperature with subsequent hydrolysis of the reaction mixture with hydrochloric acid. Effect: increase of the compounds of formula 1 of disubstituted acetylenes with high Regio - and stereoselectivity. 1 PL.

The present invention relates to the field of organic chemistry, specifically to the way the

Unsaturated hydrocarbons and their derivatives can be used as starting monomers in the processes of oligomerization, polymerization, as well as intermediates used in paint industry.

The known method (R. D. Gardner, M. Narayana, J. Org. Chem., 1961, V. 26, P. 3518) obtain Tetra-substituted olefins interaction getdialogwindow with metallic magnesium in ether scheme

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The known method does not allow to obtain (Z)-1,2-dialkyl-1,2-diethylethylene.

The known method (E. Negishi, N. Okukado, A. O. King, D. E. Van Horn, C. J. Spiegel, J. Am. Chem. Soc., 1978, V. 100, p. 2254) obtain Tetra-substituted olefins interaction disubstituted acetylenes with equimolar number of trimethylaluminum (Me3Al) in the presence of catalytic amounts of zirconatetitanate (Cp2ZrCl2) at room temperature and then adding to the reaction mass of alkenyl-, aryl - or alkylhalogenide, equimolar amount of zinc chloride (ZnCl2), catalytic amounts of palladium acetylacetonate or Nickel (Pd(acac)2or Ni(acac)2) and triphenylphosphine (PH3P) using the pattern

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The known method does not allow to obtain (Z)-1,2-dialkyl-1,2-diethylethylene.

We propose a new way to obtain (Z)-1,2-dia is ENES RCCR (octene-4, decina-5) with triethylaluminium (Et3Al) in the presence of catalytic amounts of zirconatetitanate (Cp2ZrCl2), taken in a molar ratio 10:(10-20):(0,1-0,5) accordingly, predominantly 10:15:0,3, at room temperature (23-25oC) and atmospheric pressure in hexane with stirring for 8 hours, followed by adding to the reaction mass at a temperature of ~ 0oWith tiltability (EtTs), taken in a molar ratio RCCR:EtTs = 10:(40-60), mostly 10:50, with stirring the reaction mass for 16-20 hours, preferably 18 hours, at room temperature (23-25o(C) with subsequent hydrolysis of the reaction mixture model HC1 solution. Get (Z)-1,2-dialkyl-1,2-diethylethylene 1 output 45-66%.

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Use the specified reaction smaller quantities of E3Al and tiltability (EtTs) reduces the yield of the target product 1. Use in the reaction of large quantities of tiltability (EtTs) does not lead to a significant increase in the yield of the target product 1. At a higher temperature (for example, 60oC) the yield of the target products is not increased, and at a lower temperature (for example, 0oC) decreases the reaction rate.

Without triethylaluminum and tiltability (EtTs) Southsea.

Significant differences of the proposed method:

1. In the known method used by alkenyl-, aryl - or alkylhalogenide, while the proposed use atylosia (EtTs).

2. In the known method as catalysts zirconatetitanate (Cp2ZrCl2), acetylacetonate, palladium or Nickel (Pd(acac)2or Ni(acac)2in the presence of socializaton of zinc chloride, while the proposed uses only the catalyst zirconatetitanate (Cp2ZrCl2).

4. The proposed method allows to obtain (Z)-1,2-dialkyl-1,2-diethylethylene, whereas according to the method are formed 1,2,2-trialkyl-1 alkenyl(aryl, quinil)ethylene.

The advantages of the proposed method:

1. In contrast to known methods proposed allows to obtain (Z)-1,2-dialkyl-1,2-diethylethylene 1 of disubstituted acetylenes with high Regio - and stereoselectivity.

The method is illustrated by examples:

EXAMPLE 1. In a glass reactor with a volume of 50 ml, mounted on a magnetic stirrer, inert gas load 10 ml of hexane, 10 mmol decina-5, 15 mmol Et3Al and 0.3 mmol Cp2ZrCl2, stirred for 8 hours at room temperature) and stirred the reaction mass for 18 hours at room temperature (23-25oC). The reaction mass hydrolyzing model HC1 solution, the organic layer is separated from the water. From the organic layer emit (Z)-1,2-di(n-butyl)-1,2-diethylethylene with yield 59%.

The spectral characteristics of the (Z)-1,2-dialkyl-1,2-diethylethylene

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An NMR spectrum13With (, m D.): 14,15 (Cl), 24,43 (C2), 31,06 (C3), 31,64 (C4), 134,46 (C5), 23,19 (C6), 13,89 (C7). M+196.

Other examples of the method shown in the table.

All experiments were performed at room temperature (23-25oC). As a solvent used hexane at 10 ml

The way to obtain (Z)-1,2-dialkyl-1,2-diethylethylene General formula

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where R=n-C3H7n-C4H9,

characterized in that dialkylamino acetylene formula RCCR interact with triethylaluminium (Et3Al) in the presence of a catalyst of zirconatetitanate (Cp2ZrCl2) in a molar ratio RCCR:Et3Al:Cp2ZrCl2= 10:(10:20):(0,1-0,5) under normal conditions in the environment of hexane with stirring for 8 h and then adding to the reaction mass at a temperature of 0oWith tiltability (EtTs), taken in a molar ratio RCCR:EtTs = 10:(40-60) with stirring the reaction mass for 16-20 h at room those who

 

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