The method of obtaining trans-3,4-tetrahydrothiophene

 

The invention relates to a method for producing TRANS-3,4-dialkylacrylamide. TRANS-3,4-dialkylacrylamide produced by interaction of 1-ethyl-TRANS-3,4-dialkylaminomethyl (ADC) with thionyl chloride (SOCl2) in a molar ratio ADC: SOCl2=10:(1014) in hexane solution at -40oC for 6-8 hours the Invention allows the reaction at a low temperature using thionyl chloride instead of toxic benzene. table 1.

The invention relates to the field of organic chemistry, in particular to a method for producing TRANS-3,4-dialkylacrylamide General formula (1)where R=n-C4H9the h5H11the h7H15.

These compounds can be used as accelerators in the vulcanization of rubber, additives for lubricating oils and fuels.

The known method ([1] . Dzhemilev, U. M., A. Ibragimov,, Ergaliev M. N., Muslumov P. P. Synthesis and transformations of metallocycles. Message 16. Synthesis of a new class of acyclic alyuminiiorganicheskikh connections - threo-2,3-disubstituted 1,4-volumebutton using zirconium catalysts. WPI. An. Ser. chem., 1995, 8, S. 1561-15 the butane with a threefold excess of elemental sulfur (S8) in boiling benzene (~ 80o(C) in argon atmosphere for 8 hours. The target products are formed from the outputs 62-78% schemewhere R=alkyl.

The disadvantage of this method is the increased fire hazards of the process, because the reaction takes place in boiling benzene. In addition, benzene is a toxic solvent with mutagenic properties.

The known method ([2]. Dzhemilev, U. M., A. Ibragimov,, Ergaliev M. N., Muslumov P. P. Synthesis and transformations of metallocycles. Message 14. Stereoselective synthesis of TRANS-3,4-disubstituted dialkylacrylamide Izv. An. The series of chem. , 1994, 2, S. 276-278) to obtain TRANS-3,4-disubstituted dialkylacrylamide (1) the interaction of 1-ethyl-TRANS-3,4 - dialkylaminomethyl with a threefold excess of elemental sulfur (S8) in solution in dry benzene in an argon atmosphere at a temperature of ~80oC for 6-8 hours with outputs 65-80% schemewhere R=alkyl.

The disadvantages of this method: 1. Increased fire hazards of the process, because the reaction is carried out in boiling benzene.

2. Carrying out the reaction using toxic benzene, which has mutagenic properties.

3. Increased consumption of one of the C-3,4-dialkylanilines.

We propose a new method for production of TRANS-3,4-dialkylacrylamide.

The method consists in the interaction of 1-ethyl-TRANS-3,4-dialkylaminomethyl (ADC) with thionyl chloride (SOCl2), taken in a molar ratio ADC:SOCl2=10:(1014), preferably 10:12, in hexane solution at -40oC for 6-8 hours, preferably 7 hours. The output of TRANS-3,4-dialkylacrylamide is 73-82%. The reaction takes place according to the schemewhere R=n-C4H9the h5H11n-C7H15.

Conducting the process at a higher temperature (for example, 0oC) reduces the selectivity of the reaction. Carrying out the process at lower temperatures (e.g. -50oC) reduces the reaction rate. Changing the ratio of initial reagents in the direction of increasing the content of SOCl2with respect to the ADC does not lead to a significant increase in the yield of target products (1).

Significant differences of the proposed method.

If in the known method for the sulfonation used a three-fold excess of elemental sulfur (S8), the reaction proceeds at elevated temperatures (~80o(C) in boiling benzene. In the proposed spooney temperature (-40o(C) in hexane.

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 mmol 1-ethyl-TRANS-3,4-di(n-butyl)aromaticity in 10 ml of hexane at a temperature of -40oWith added 12 mmol of thionyl chloride (SOCl2) and stirred for 7 hours at this temperature. Upon completion of the reaction the reaction mass is treated with 5% Hcl, allocate TRANS-3,4-di(n-butyl)tetrahydrothiophene with the release of 78%.

Spectral characteristics of TRANS-3,4-di(n-butyl)-tetrahydrothiophene (1):

An NMR spectrum1N (, M. D.): 0,92 (t, 6N, CH3), 1,12-at 1.91 (m, 14N, CH, CH2), 2,33-2,64, 2,86-3,06 (m, 4H, CH2S).

An NMR spectrum13With (, M. D.): 36,51 t (1), 48,77 d (2), 32,73 t (3), 30,21 t (4), 22,94 t (5), 14,06 to (5). M+200.

Other examples of the method shown in the table.

Add thionyl chloride and subsequent reaction of sulfonation was carried out at -40oWith in hexane.


Claims

The method of obtaining TRANS-3,4-dialkylacrylamide General formula
14) in hexane solution at -40oC for 6-8 hours

 

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