The way to obtain 1-ethyl-2-aza-3-methyl-4 - alcaligenaceae-2-enes

 

Describes how to obtain 1-ethyl-2-Aza-3-methyl-4-alcaligenaceae-2-ENES General formula where R is n-C6H13n-C8H17, characterized in that 1-alkylarene General formula R-CH=C=CH2where R is n-C6H13n-C8H17expose interaction with triethylaluminium (AlEt3in the presence of catalyst zirconatetitanate (Cp2ZrCl2where Cf=5-C5H5), in a molar ratio of R-CH= C= CH2: AlEt3: Cp2ZrCl2equal 10:(10-14):(0,2-0,6), at room temperature in the environment of methylene chloride for 5 h followed by adding to the reaction mass acetonitrile CH3CN, taken in a threefold excess in relation to triethylaluminium, and stirring for 4-8 hours at a temperature of approximately 40oC. the compounds may find application in ORGANOMETALLIC and fine organic synthesis. 1 PL.

The invention relates to methods for new alyuminiiorganicheskikh compounds, specifically to a method for producing 1-ethyl-2-Aza-3-methyl-4-alcaligenaceae-2-ENES General formula (1):where R=n-Sogut to find application in ORGANOMETALLIC and fine organic synthesis ([1] Tolstikov, A. , George B. N. Alyuminiiorganicheskikh synthesis. M.: Nauka, 1979, S. 131).

The known method ([2] Takahashi T., Kageyama M., Denissov V., Nagy R., Negishi E. Facile Cleavage of the C-CBond of Zirconacyclopentenes. Convenient Method for Selectively Coupling Alkynes, Nitriles and Aldehydes. Tetrahedron Lett. , 1993, 34, 687) obtain the N-containing unsaturated metallocycles, in particular 2-azacyclopentadecan (2) the interaction of circoncision-2-ENES with NITRILES schemeThe known method does not allow to obtain 1-ethyl-2-Aza-3-methyl-4-alcaligenaceae-2-ENES (1).

The known method ([3] Zakharkin L. I., Savin L. A. Synthesis of some cyclic alkylamidoamines and alkylamidoamines. WPI. An SSSR, Series chem. , 1962, 824) to obtain 1-(isobutyl)-2-ethyl-2-analyticity (3) the interaction of Diisobutyl(N-ethyl-N-allylamino)aluminium diisobutylaluminium at a temperature of 120-130oWith 6 hours schemeThe known method cannot be obtained 1-ethyl-2-Aza-3-methyl-4-alcaligenaceae-2-ENES (1).

Offers a way to generate new alyuminiiorganicheskikh compounds, specifically 1-ethyl-2-Aza-3-methyl-4-alcaligenaceae-2-b>13the h8H17with triethylaluminium (lt3in the presence of catalyst zirconatetitanate (Cp2ZrCl2where Cf=5-C5H5), taken in a molar ratio of R-CH=C=CH2:AlEt3:Cp2ZrCl2=10:(10-14):(0,2-0,6), preferably 10: 12: 0,4, at a temperature of ~20oWith in methylene chloride for 5 h followed by adding to the reaction mass acetonitrile (CH3SP) 3xfold excess relative to lt3(one mole of acetonitrile per Al-connection) with stirring 4-8 hours, preferably 6 hours, at a temperature of ~40oC. In these conditions, the yield of 1-ethyl-2-Aza-3-methyl-4-alcaligenaceae-2-ENES (1) is 42-58%.

The reaction proceeds according to the schemeThe catalyst Cp2ZrCl2in the amount of more than 6 mol.% in relation to 1-alkylamino not lead to a significant increase of the yield of the target product (1). Use Cp2ZrCl2in less than 2 mol.% in relation to 1-alkylamino reduces output 1-ethyl-2-Aza-3-methyl-4-alcaligenaceae-2-ENES (1), which is connected, possibly, with a reduction of catalytically active sites in the reaction mixture.

Fundamental differences predlovennogo compounds are amide and hydride of aluminium at a temperature of 120-130oSince, then, the proposed method uses 1-alkylamine, acetonitrile (CH3JV), triethylaluminium (lt3) and catalytic amounts Cp2ZrCl2at a temperature of ~ 40oC. in Addition, the proposed method allows you to get an individual 1-ethyl-2-Aza-3-methyl-4-alcaligenaceae-2-ENES (1), which cannot be obtained by known methods.

The method is illustrated by examples.

Example 1. In a glass reactor with a volume of 50 ml in an argon atmosphere was placed at a temperature of ~0oWith 10 mmol of 1-(n-hexyl)Allen, 12 mmol lt3in 10 ml of methylene chloride and 0.4 mmol Cp2ZrCl2, stirred for 5 hours at room temperature (~20oC). Add 36 mmol of acetonitrile (CH3JV) and stirred for 6 hours under heating (~40oC). Get an individual 1-ethyl-2-Aza-3-methyl-4-(n-reptilian)-lumicycle-2-ene (1) in 51% yield. The yield of the target product (1) was determined by the product of acid hydrolysis (4).


An NMR spectrum13(4) (M. D., CDCl3, TMC): 27,55 to (1), 199,75 C (2), 142,20 C (3), 144,28 d (4), 25,79 t (5), 29,04 t (6), 29,04 t (7), 31,77 t (8), 22,61 t (9), 14,15 (With10), 29,04 to (oC) followed by heating to ~40oC. At a lower temperature (for example, 0oC) and other solvents (e.g. ether, THF) decreases the yield of the target products.


Claims

The way to obtain 1-ethyl-2-Aza-3-methyl-4-alcaligenaceae-2-ENES General formula

where R is n-C6H13n-C8H17,
characterized in that 1-alkylarene General formula
R-CH= C= CH2,
where R is n-C6H13n-C8H17,
subjected to interaction with triethylaluminium (lt3in the presence of catalyst zirconatetitanate (Cp2ZrCl2where Cf5-C5H5), in a molar ratio of R-CH= C= CH2: lt3: Cp2ZrCl2equal 10: (10-14): (0,2-0,6), at room temperature in the environment of methylene chloride for 5 h followed by adding to the reaction mass acetonitrile CH3CN, taken in a threefold excess in relation to triethylaluminium, and stirring for 4-8 hours at a temperature of approximately 40oC.

 

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R=n-C6H13n-C8H17n-C9H19< / BR>
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where R=n-C6H13the h8H17< / BR>
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