The way to obtain 1-ethyl-trans-3,4-dialkylanilines

 

(57) Abstract:

The invention relates to methods of producing a cyclic boron compounds which may find application in the synthesis of TRANS-2,3-dialkyl-1,4-butandiol, substituted cyclic ketones, alcohols, esters, and other practically important compounds used in thin organic and ORGANOMETALLIC synthesis. The method consists in the interaction of olefins with ethylaminoethanol and magnesium in the presence of two-component catalyst consisting of zirconatetitanate and diisobutylaluminium in an argon atmosphere under normal conditions for 8 h, followed by addition of boron TRIFLUORIDE and stirring for 2 to 6 hours the solvent is tetrahydrofuran. The yield of the target products is 64 - 79%. table 1.

The invention relates to methods for cyclic Bioorganicheskaya compounds, specifically, to a method for producing 1-ethyl-TRANS-3,4-dialkylanilines General formula (1):

< / BR>
Offer Bioorganicheskaya compounds may find application in the synthesis of threo-2,3-dialkyl-1,4-butandiolov, substituted cyclic ketones, alcohols, esters, and other practically important"Organoboron compounds in organic synthesis", M., "Nauka", 1977, S. 331].

The known method [B. M. Mikhailov, V. A. Dorokhov, DAN SSSR, 133, 119, (1960)] obtain 1-ethyl-C-methylrosaniline reaction of isoprene with 1,2-dereviana broadcast scheme

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By a known method cannot be obtained 1-ethyl-TRANS-3,4-dialkylanilines (1).

The known method [R. Koster, G. Schomburg, Angew. Chem., 72. 567 (I960)] for 1-ethyl-3-methylrosanilinium reaction of isoprene with trialkylamine in the presence trialkylborane at a temperature of 140oC scheme

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The known method does not allow to obtain 1-ethyl-TRANS-3,4-dialkylanilines (1).

Thus, in the literature there are no data on Regio - and stereoselective synthesis of 1-ethyl-TRANS-3,4-dialkyl - braziliano.

We propose a new method Regio - and stereoselective synthesis of 1-ethyl-TRANS-3,4-dialkylanilines.

The essence of the method lies in the interaction - olefins such as 1-hexene, 1-octene, 1-mission with ethylaminoethanol (Et-AlCl2) and metallic magnesium (powder), taken in a molar ratio of Mg : Et - AlCl2= (20-22) : 10 : (10-14), preferably 21:10:12, in the presence of two-component catalyst consisting of circoncision is igeria (i - Bu2AlH), taken in a molar ratio Cp2ZrCl2: Bui2AlH = 1 : (1-3), preferably 1:2, in an argon atmosphere at room temperature (22-23oC) and normal pressure for 8 hours, in tetrahydrofuran as a solvent, and then adding epirate boron TRIFLUORIDE (BF3Et2O) in equimolar number relative to Et - AlCl2and stirring for 2 to 6 hours, preferably 4 hours. The yield of the target products 64-79%. The reaction proceeds according to the scheme

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The reaction is accompanied by the release of MgCl2and AlF3as by-products.

1-ethyl-TRANS-3,4-dialkylanilines are formed only with the involvement of Et - AlCl2and the catalytic system (Cp2ZrCl2+ i - Bu2AlH). In the presence of other aluminum compounds (e.g., i - Bu3Al, Et3Al, AlH3i - Bu2AlCl) or other catalysts (e.g., TiCl4, Zr(OBnu)4, Zr(ACAC)4, Zr(OPir)4, Ti(OBnu)4target products (1) are not formed.

The conduct of a specified reaction in the presence of catalyst is more than 5 mol.% in relation to the magnesium does not lead to a significant increase in the yield of the target product. And reduced catalytically active sites in the reaction mass. Experiments were performed at room temperature (22-23oC). At a higher temperature (for example, 60oC) increases the amount of seal products, at a lower temperature (for example, 0oC) decreases the reaction rate. Changing the ratio of initial reagents in the direction of increasing the content of the olefin or EtAlCl2in relation to the magnesium does not lead to a significant increase in the yield of the target product. Reduction of the olefin or Et-AlCl2in relation to the magnesium reduces the yield of the target products.

Significant differences of the proposed method:

1. The proposed method is based on the use of a - olefins, metal magnesium, Et - AlCl2and BF3OEt2in the presence of zirconium bearing catalyst. The reaction proceeds at room temperature (22-23oC). In the known method are used trialkylamines, isoprene and trialkylborane. The reaction proceeds at 140oC.

The proposed method allows to obtain with high Regio - and stereoselectivity individual 1-ethyl-TRANS-3,4-dialkylanilines under mild conditions from available reagents.

The method is illustrated by the following examples:

Example 1. In steklyannoj), 20 ml of dry THF, 21 mmol of 1-hexene, 12 mmol Et - AlCl2and a catalyst consisting of 0.3 mmol Cp2ZrCl2and 0.6 mmol i-Bu2AlH in 2 ml of dry THF, stirred for 8 hours at room temperature (22-23oC) add 12 mmol BF3Et2O, stirred for 4 hours. Get an individual 1-ethyl-TRANS-3,4-dialkylanilines. The yield of the target product was determined by oxidation of (1) known method [I] using alkaline hydrogen peroxide. In the oxidation of 1-ethyl-TRANS-3,4-dialkylanilines formed threo-2,3-di(n-butyl)-1,4-butanediol (2) according to the scheme:

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An NMR spectrum13C , M. D.) threo-2,3-di(n-butyl)-1,4-butanediol (2): 60.86 t (C1), 42.52 d (C2), 29.39 t (C3), 30.08 t (C4), 23.10 t (C5), 14.17 (C6).

Other examples of the method shown in the table.

The reaction was carried out at room temperature (22-23oC) in THF. In other solvents (ether, dioxane), the yield of the target products and the selectivity of the reaction are plummeting. In the aromatic (benzene, toluene) and aliphatic (hexane, cyclohexane) solvents the reaction is not. The temperature rise is impractical because it does not increase the yield of the target products. At lower temperatures snijaetsa-olefins interact with ethylaminoethanol (Et-AlCl2) and metallic magnesium, taken in a molar ratio of Mg : Et - AlCl2= (20 - 22) : 10 : (10 - 14), in the presence of two-component catalyst consisting of zirconatetitanate (Cp2ZrCl2), in the amount of 2 to 5 mol. % relative to magnesium, and diisobutylaluminium (i-Bu2AlH), taken in a molar ratio Cp2ZrCl2: i-Bu2AlH = 1 : (1 - 3), in an argon atmosphere under normal conditions in the presence of tetrahydrofuran as a solvent and then adding epirate boron TRIFLUORIDE (BF3Et2O) in equimolar number relative to Et-AlCl2and stirred for 2 to 6 hours

 

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