JPH0649685B2 - 1-benzylpyridinium salt derivative and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a 1-benzylpyridinium salt derivative and a method for producing the same.

DISCLOSURE OF THE INVENTION The 1-benzylpyridinium salt derivative of the present invention is a novel compound which has not been described in the literature and is represented by the following general formula (I).

[In the formula, R represents an alkyl group and X represents a halogen atom. The 1-benzylpyridinium salt derivative represented by the above general formula (I) has the following general formula (II) [In the formula, R is the same as above. ] It is useful as a manufacturing raw material of 4-pyridyl pimelic acid ester shown by these. General formula (I
The 4-pyridylpimelic acid ester represented by I) is a compound useful as a raw material for a functional polymer (functional polyester, functional polyamide, etc.) and as an intermediate for agricultural medicine.

Conventionally, as a method for producing a pimelic acid ester having a substituent at the 4-position, for example, a method of sequentially extending an alkyl chain of ethyl phenylmalonate to obtain a 4-phenylpimelic acid ester is known (RH Manske, J. Am. Chem. .Soc., 193
1, 53 , 1104). However, applying this method
-When trying to synthesize pyridyl pimelic acid ester,
Starting from pyridyl malonic acid ester, a reaction operation of at least 8 steps is required, the reaction process is complicated, and the yield of the target 4-pyridyl pimelic acid ester is extremely low.

An object of the present invention is to provide 4-pyridyl pimelic acid ester with 1
The present invention provides a 1-benzylpyridinium salt derivative represented by the above general formula (I) that can be a raw material that can be produced in a step and in a high yield, and a production method thereof.

In the present specification, examples of the alkyl group represented by R include methyl, ethyl, propyl, isopropyl,
Examples thereof include alkyl groups such as butyl, isobutyl, tert-butyl, pentyl, hexyl and 2-ethylhexyl groups. Examples of the halogen atom include chlorine atom, bromine atom, iodine atom and the like.

The 1-benzylpyridinium salt derivative of the present invention has the general formula [In the formula, X is the same as above. 1-benzylpicolinium halide represented by the formula) and a general formula CH ₂ ═CHCOOR (IV) [wherein R is the same as defined above]. ] It is easily manufactured by reacting with an acrylic acid ester represented by the following in the presence of a basic catalyst.

The compound represented by the general formula (III) and the compound represented by the general formula (IV) used as starting materials are known and available compounds.

In the reaction of the compound of the general formula (III) with the compound of the general formula (IV), examples of the basic catalyst used include triethylamine, pyridine bases, 1,8-diazabicyclo (5,4,0) -7. Examples include amines such as undecene and 1,5-diazabicyclo (4,3,0) -5-nonene, and metal alkoxides such as sodium methoxide and sodium ethoxide. The amount of the basic catalyst used varies depending on the type of the basic catalyst used and the like and cannot be generally specified, but it is usually at least about 0.01 times the molar amount of the compound of the general formula (III). Is good. For example, in the case of triethylamine, the general formula (II
It is particularly preferable to use it in an amount of 0.1 times to equimolar to the compound of I).

The reaction between the compound of general formula (III) and the compound of general formula (IV) is usually carried out in a suitable reaction solvent. Examples of the solvent used include alcohols such as water, methanol, ethanol, propanol and butanol, aprotic solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, ethyl acetate, methyl acetate and triethyl phosphate. And the like, and mixed solvents thereof.

In the reaction of the compound of the general formula (III) with the compound of the general formula (IV), there is no particular limitation on the usage ratio of the two and they can be appropriately selected from a wide range. The molar ratio is about 10 to 10 times, preferably about 1 to 3 times.

In carrying out the method of the present invention, for example, the compound represented by the general formula (II
It is preferred that the compound of I) is dissolved or suspended in the above solvent and then the basic catalyst and the compound of general formula (IV) are added thereto to carry out the reaction. The reaction proceeds at either room temperature or under heating, but it is usually preferable to set the temperature at room temperature to around 150 ° C.

The 1-benzylpyridinium salt derivative of the present invention thus obtained is isolated and purified by a conventional separation means, for example, a method in which a solvent, a catalyst and unreacted raw materials are removed from the reaction solution after completion of the reaction, and then column separation is performed. It

From the 1-benzylpyridinium salt derivative of the present invention, 4-pyridylpimelic acid ester represented by the general formula (II) can be easily debenzylated by hydrogen reduction in the presence of a catalyst such as palladium-carbon to give 1 It can be obtained in steps and in high yield (see Reference Examples 1 and 2 below).

Examples The present invention will be further clarified below with reference to Examples and Reference Examples.

Example 1 Preparation of 4- [bis [2-methoxycarbonyl) ethyl] methyl] -1-benzylpyridinium chloride 1-benzyl-4-picolinium chloride 43.9 g
100 g of N, N-dimethylformamide and 5 g of triethylamine were added to, and the temperature was raised to 100 ° C. with stirring. While maintaining this temperature, methyl acrylate 34.4
g was added dropwise. After the dropping was completed, the mixture was further stirred for 1 hour. After completion of the reaction, the solvent, catalyst and unreacted methyl acrylate were distilled off from the resulting reaction solution under reduced pressure, and the remaining oily matter was developed with methanol using a column packed with activated alumina, and 4- [ Bis [2-methoxycarbonyl) ethyl] methyl] -1-benzylpyridinium chloride 4
2.7 g was obtained. The analysis results of the IR spectrum and the NMR spectrum were as follows.

IR spectrum: 3400, 2950, 1725, 1640, 1460,
1440, 1180, 700 cm ^{-1 1} H-NMR spectrum: (CD ₃ OD, TMS) δ 2.1 (m, 8H), 3.6 (s, 6H), 6.3.
(M, 2H), 7.3 (m, 5H), 7.75 (m, 2)
H), 9.7 (m, 2H) ppm Example 2 Preparation of 4- [bis [2-ethoxycarbonyl) ethyl] methyl] -1-benzylpyridinium chloride Ethyl acrylate 40.0 g instead of methyl acrylate
4- [bis [2-ethoxycarbonyl) ethyl] methyl] -1-in the same manner as in Example 1 except that is used.
43.6 g of benzylpyridinium chloride was obtained. I
The analysis results of the R spectrum and the NMR spectrum were as follows.

IR spectrum: 3400, 2950, 1730, 1630, 1460,
1250, 1180, 700 cm ^{-1 1} H-NMR spectrum: (CD ₃ OD, TMS) δ 1.2 (t, 6H), 2.1 (m, 8H), 4.1
(Q, 4H), 6.2 (m, 2H), 7.1 (m, 5)
H), 7.5 (m, 2H), 9.5 (m, 2H) ppm Reference Example 1 Preparation of methyl 4- (4′-pyridyl) pimelate 4- [bis [obtained from Example 1 above] 2-methoxycarbonyl) ethyl] methyl] -1-benzylpyridinium chloride (39.2 g) was dissolved in methanol (100 g),
After adding 2.0 g of palladium-carbon, the debenzylation reaction was carried out in an autoclave at room temperature under a hydrogen pressure of 3.0 kg. The reaction solution was neutralized with an aqueous potassium carbonate solution and then distilled to give methyl 4- (4'-pyridyl) pimelate 24.
2 g was obtained.

IR spectrum: 2950, 1740, 1600, 1435, 1250,
1200,1170 cm ^{-1 1} H-NMR spectrum: (CCl ₄ , TMS) δ 1.7-2.2 (m, 8H), 2.55 (m, 1)
H), 3.58 (s, 6H), 7.4 (m, 2H),
8.6 (m, 2H) ppm Reference Example 2 Production of ethyl 4- (4′-pyridyl) pimelate Palladium-containing 145 g of the reaction solution obtained in Example 2 above.
After adding 2.0 g of carbon, in an autoclave at room temperature,
The debenzylation reaction was carried out under a hydrogen pressure of 3.0 kg.
Then, the same treatment as in Reference Example 1 was carried out to obtain 26.7 g of ethyl 4- (4'-pyridyl) pimelate.

IR spectrum: 3000, 1740, 1600, 1460, 1420,
1250,1180 cm ^{-1 1} H-NMR spectrum: (CCl ₄ , TMS) δ1.12 (t, 6H), 1.7-2.3 (m, 8)
H), 2.6 (m, 1H), 4.0 (q, 4H), 7.
05 (m, 2H), 8.45 (m, 2H) ppm

Claims (2)

[Claims] 1. A general formula [In the formula, R represents an alkyl group and X represents a halogen atom. ] The 1-benzyl pyridinium salt derivative shown by these. 2. General formula [In the formula, X represents a halogen atom. ] 1-Benzyl picolinium halide represented by the following formula and general formula CH ₂ = CHCOOR [wherein R represents an alkyl group. ] Acrylic ester represented by the following general formula characterized by reacting in the presence of a basic catalyst [In the formula, R and X are the same as above. ] The manufacturing method of the 1-benzyl pyridinium salt derivative shown by these.