The way to obtain 1-ethyl-3-methyl-3-phenyl-(ethyl-, cyclopropyl- )-4-alcaligenaceae-2-arslanov

 

The invention relates to a method of obtaining a new alyuminiiorganicheskikh connection, which can be applied in thin organic synthesis, and as acetalization in oligo - and polymerization of olefins and conjugated dienes. Describes how to obtain 1-ethyl-3-methyl-3-phenyl-(ethyl-, cyclopropyl-)-4-alcaligenaceae-2-oxolane interaction terminal Allen with triethylaluminium in the presence of a catalyst CpZrCl2in argon, CH2Cl2c CuCl and CH3RCO, where R=Ph, C2H5and cyclo-C3H5. The technical result is to obtain new compounds with high regiospecificity. table 1.

The present invention relates to methods for new alyuminiiorganicheskikh compounds (AOC), specifically to a method for producing 1-ethyl-3-methyl-3-phenyl-(ethyl-, cyclopropyl-)-4-alcaligenaceae-2-Arslanov General formula (1):where R=Ph, C2H5, cyclo-C3H9; R1=n-C6H13n-C8H17.

The proposed compounds may find application in thin organic and ORGANOMETALLIC synthesis, as well as socialization in the processes of oligo - and polymerize is which chelate alyuminiiorganicheskikh compounds. WPI. An SSSR, Ser. chem. , 1960, 6, 1039-1043) obtain chelate alyuminiiorganicheskikh compounds (2) interaction Bu2iAlH-functionally substituted-olefins schemeX=OC2H5NEt2The known method does not allow to obtain 1-ethyl-3-methyl-3-phenyl-(ethyl-, cyclopropyl-)-4-alcaligenaceae-2-oxolane (1).

The known method ([2] , L. I. the Zakharkin, L. A. Savin. Synthesis of some cyclic alkylamidoamines and alkylamidoamines. WPI. An SSSR, OHP, 1962, 5, 824-827) get 1 isobutyltrimethoxysilane (3) the interaction of allyl alcohol with triisobutylaluminum (AlBu3i) when -5-10oWith the subsequent addition of diisobutylaluminium (Bu2iAlH) and heated for 6 hours at 125-130oWith the schema:The known method cannot be obtained 1-ethyl-3-methyl-3-phenyl-(ethyl-, cyclopropyl-)-4-alcaligenaceae-2-oxolane (1).

Thus, the literature contains no information on the selective reception of 1-ethyl-3-methyl-3-phenyl-(ethyl-, cyclopropyl-)-4-alcaligenaceae-2-Arslanov (1).

We propose a new method for the synthesis of 1-SEEIT interaction of terminal allenes General formulawhere R1=n-C6H13the h8H17with triethylaluminium (1t3), taken in the ratio (mmol)in the presence of a catalyst of zirconatetitanate (Cp2ZrCl2) in an amount of 0.2-0.6 mmol, in an argon atmosphere at room temperature (~20oC) and atmospheric pressure in methylene chloride (CH2CL2as the solvent for 5 hours followed by the addition at a temperature of -15oWith catalyst odnoklasniki copper (CuCl) in an amount of 0.2-0.6 mmol and a ketone of General formula CH3RCO, where R= Ph, C2H5, cyclo-C3H5in equimolar towards AlEt3number of stirring the reaction mixture for 6-8 hours at room temperature (~ 20oC). The reaction proceeds with the formation of 1-ethyl-3-methyl-3-phenyl(ethyl-, cyclopropyl-)-4-alcaligenaceae-2-Arslanov(1) with output 62-81% schemeR1=na6H13n-C8H17; R=Ph, Et, cyclo-C3H5
1-Ethyl-3-methyl-3-phenyl(ethyl-, cyclopropyl-)-4-alcaligenaceae-2-oxolane (1) are formed only with the participation of AlEt3, terminal allenes, ketones and zirconium catalyst Cp2ZrCl2. In the presence of D. the ub>2AlCl), other allenes (e.g., internal), other carbonyl compounds (e.g. aldehydes) or other catalysts (e.g., 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 catalysts Cp2ZrCl2or CuCl more than 0.6 mmol does not lead to a significant increase in the yield of the target products (1). The use of catalysts Cp2ZrCl2or CuCl less than 0.2 mmol reduces output 1-ethyl-3-methyl-3-phenyl-(ethyl-, cyclopropyl-)-4-alcaligenaceae-2-Arslanov (1), which is connected, possibly, with a reduction of catalytically active sites in the reaction mass. The reaction was carried out at room temperature (~20oC). At a higher temperature (for example, 40o(C) has not been a significant increase in the yield of the target products (1), 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 of AlEt3in 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 chloritoid the regiospecificity of the reaction.

Significant differences of the proposed method.

1. In the proposed method for obtaining cyclic Al-organic compounds are used as starting compounds terminal allenetriethylaluminum (AlEt3), ketones (CH3R), the reaction proceeds in the presence of catalysts Cp2ZrCl2and CuCl.

In the known method as the initial reagents are applied allyl alcohol, triisobutylaluminum (lu3iand diisobutylaluminium (Bu2iAlH). The reaction proceeds at elevated temperatures (120-130oC).

The proposed method has the following advantages.

1. The method allows to obtain high regiospecificity individual 1-ethyl-3-methyl-3-phenyl-(ethyl-, cyclopropyl-)-4-alcaligenaceae-2-oxolane (1), the synthesis of which are not described in literature.

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 10 ml of methylene chloride (CH2Cl2), 10 mmol of 1,2-nonadiene, 0.4 mmol of catalyst Cp2ZrCl2at a temperature of ~0oWith 12 mmol 1t3, stirred for 5 hours at room temp>PhCO, stirred for 7 hours at room temperature (~20oC). Get 1-ethyl-3-methyl-3-phenyl-4-getElementsByTagName-2-oxolane (1) with 71% yield. The yield of the target product identified by the product of the hydrolysis.

The spectral characteristics of 1-ethyl-3-methyl-3-phenyl-4-getElementsByTagName-2-oxolane (1):

An NMR spectrum13With(, M. D.): 81.31(1), 151.20(2), 33.19(3), 30.99(4), 18.36(5), 2.76(6), 8.73(7), 141.98(8), 129.50(9, 13), 128.72(10, 12), 126.70(11), 25.51(14), 129.76(15), 29.68(16), 29.87(17, 18), AT 32.28 WITH(19), 22.98(20), 14.26(21).

Other examples of the method shown in the table.

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


Claims

The way to obtain 1-ethyl-3-methyl-3-phenyl-(ethyl-, cyclopropyl-)-4-alcaligenaceae-2-Arslanov General formula (1)

where R=Ph, C2H5, cyclo-C3H5;
R1=n-C6H13the h8H17,
characterized in that the terminal allene General formula R1-CH=C= CH2where R1= n-C6H13the h8H17interact with triethylaluminium AlEt3in the ratio of R1-CH= C= CH2ZrCl2), taken in an amount of 0.2-0.6 mmole relative to the 1-substituted Allen, in an argon atmosphere at room temperature and atmospheric pressure in methylene chloride as the solvent for 5 h, followed by the addition at a temperature of -15oWith catalyst odnoklasniki copper (CuCl), taken in an amount of 0.2-0.6 mmole in relation to the original Allen, and a ketone of the formula CH3RCO, where R=Ph, C2H5, cyclo-C3H5in equimolar towards AlEt3the number and stirring the reaction mixture for 6-8 h at room temperature.

 

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