Method for synthesis of 1-aminomethyl-2-phenylacetylenes

FIELD: chemistry.

SUBSTANCE: present invention relates to a method for synthesis of 1-aminomethyl-2-phenylacetylenes of formula (1), where is characterised by that, phenylacetylene (Ph-C≡CH) is reacted with gem-diamines R2NCH2NR2, where R2N is as defined above, in the presence of a Sm(NO3)2*6H2O catalyst in molar ratio phenylacetylene: gem-diamine: Sm(NO3)2*6H2O=10:(8-12):(0.2-0.6) at 80°C and atmospheric pressure for 3-5 hours.

EFFECT: new method is designed for synthesis of 1-aminomethyl-2-phenylacetylenes, which can be used in fine organic synthesis, particularly for synthesis of scarce polycyclic compounds.

1 tbl, 1 ex

 

The present invention relates to organic chemistry, in particular to a method for producing 1-aminomethyl-2-phenylacetylenes General formula (1):

where

Propargylamine formula (1) can be applied in thin organic synthesis, in particular in the synthesis of hard-to-reach polycyclic compounds (A.T. Babayan. Intramolecular rearrangement salts chetyrehjadernogo ammonium. Yerevan: Publishing House. Academy of Sciences of the Armenian SSR, 1976, s-348).

The known method (Ahogan, Areworking, So the Chukhajyan, Cgean. Synthesis of dialkyl(4-hydroxy-2-butynyl)amines. Zhur.org.chem., 2000, T.36, 9, s-1305) obtain propargylamines, in particular, dialkyl(4-hydroxy-2-butynyl)amines of General formula (2) interaction of propanol with dipropyl, dibutylamine, morpholine and formaldehyde in the environment dioxane in the presence of ferric chloride and copper acetate when heated (90-92°C) for 60 h under the scheme:

The known method cannot be obtained 1-aminomethyl-2-phenylacetylene General formula (1).

The known method (Air, Aceraceae, Ass, Illangovan, Caspersen. Improved methods of aminomethylpyridine acetylenes. Zhur.org.chem., 2006, t, VIP, s) obtain aminomethylating acetylenes (3) the interaction is 1 EQ. acetylene compounds with an excess of paraformaldehyde and a secondary amine, which are selected: diethylamine, piperidine and morpholine (1.1 to 1.3 mol per 1 mol of acetylene compounds) in the presence of several drops of the suspension supersaturated solution of copper chloride in DMF (1 g of salt in 3.5 ml of solvent) at a temperature of 95-105°C for 4-6 h under the scheme:

A known method can be obtained 1-aminomethyl-2-phenylacetylene General formula (1), provided the inclusion in the reaction as a source of compounds phenylacetylene and the corresponding secondary amines (piperidine, morpholine, N-methylpiperazine).

We propose a new method of obtaining 1-aminomethyl-2-phenylacetylenes General formula (1).

The method consists in the interaction of phenylacetylene with gem-diamines of the formula R2N-CH2-NR2where R2N=piperidyl, morpholyl, N-methylpiperazin, in the presence of a catalyst Sm(NO3)2*6H2O, taken in the ratio of phenylacetylene: gem-diamine: Sm(NO3)2*6N2O=10:(8-12):(0.2-0.6), preferably 10:10:0.4 mmol, at a temperature of 80°C and atmospheric pressure within 3-5 hours-Output 1-aminomethyl-2-phenylacetylene (1) is 72-84%. The reaction proceeds according to the scheme:

where R2N = piperidyl, morpholyl, N-methylpiperazin.

the spruce products 1-aminomethyl-2-phenylacetylene (1) are formed only with the participation of phenylacetylene and the corresponding gem-diamines of General formula R 2N-CH2-NR2where R2N = piperidyl, morpholyl, N-methylpiperazin. In the presence of 1-alkynes or other diamines target product (1) is not formed.

The conduct of a specified reaction in the presence of a catalyst Sm(NO3)2*6H2O more than 0.6 mmol does not lead to a significant increase in the yield of the target product (1). The use of catalyst Sm(NO3)2*6H2O less than 0.2 mmol reduces output (1), which is connected, possibly, with a reduction of catalytically active sites in the reaction mass. The reaction was carried out at a temperature of 80°C without solvent. At a higher temperature (e.g. 90°C) increase energy costs, and at a lower temperature (e.g. 70°C) decreases the reaction rate.

The change in the ratio of the original gem-diamine in the direction of increasing its content in relation to the original phenylacetylene does not lead to a significant increase in the yield of the target product (1).

Significant differences of the proposed method

In the known method uses a three-component mixture of reagents consisting of alkylation, paraformaldehyde and secondary amines, which are selected: diethylamine, piperidine and morpholine. The reaction is carried out at a temperature of 95-105°C in a solution of DMF using as catalyst CuCl.

In the proposed method is used on componenta mixture of initial reagents, consisting of phenylacetylene and gem-diamine. The reaction proceeds at a temperature of 80°C without solvent using as a catalyst Sm(NO3)2*6H2O.

The method is illustrated by the following examples.

Example 1. In a glass reactor, mounted on a magnetic stirrer, placed 10 mmol of phenylacetylene, 10 mmol of 1-(piperidinomethyl)piperidine, 0.4 mmol of catalyst Sm(NO3)2*6H2O, stirred for 4 hours at a temperature of 80°C. From the reaction mass produce 1-(3-phenyl-2-PROPYNYL)-piperidine with a yield of 78%.

The spectral characteristics of 1-(3-phenyl-2-PROPYNYL)-piperidine (1).

An NMR spectrum13C (CDCl3, δ, ppm) 1-(3-phenyl-2-PROPYNYL)-piperidine (1): 24.70, 25.65, 48.08, 53.00, 77.00, 82.44, 123.50, 127.92, 128.31, 131.77.

Other examples of the method shown in the table.

Table
№№ p/pThe original gem-diamineThe ratio of phenylacetylene: 1-(piperidinomethyl)piperidine: Sm(NO3)2*6H2O mmolReaction time, hOutput (1),%
11-(piperidinomethyl)-piperidine10:10:0.4 41-(3-phenyl-2-PROPYNYL)-piperidine,
78
2-//-10:12:0.44-//-, 80
3-//-10:8:0.44-//-, 77
4-//-10:10:0.64-//-, 84
5-//-10:10:0.24-//-, 72
6-//-10:10:0.45-//-, 81
7-//-10:10:0.43-//-, 73
84-(morpholinomethyl)-morpholine10:10:0.4479,
4-(2-phenylethenyl)-morpholine
91-methyl-4-[(4-methyl-piperazine derivatives)methyl]-piperazine 10:10:0.4476,
1-methyl-4-(2-phenylethyl)piperazine

The reaction was carried out at a temperature of 80°C without solvent.

A method of obtaining a 1-aminomethyl-2-phenylacetylenes General formula (1)
,
where
,,
characterized in that phenylacetylene (Ph-C≡CH), subject to interaction with the heme-diamines R2NCH2NR2where R2N is the same as defined above, in the presence of a catalyst Sm(NO3)2·6H2O, when the molar ratio phenylacetylene:gem-diamine:Sm(NO3)2·6H2O=10:(8-12):(0,2-0,6) at a temperature of 80°C and atmospheric pressure for 3-5 hours



 

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1 tbl, 1 ex

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