JPS5910542A - Tricyclic aliphatic compound and preparation thereof - Google Patents

Abstract

NEW MATERIAL:6-Ethyltricyclo[2.2.1.0<2>,<6>]heptyl-3-aldehyde of formula I . USE:Useful as a synthetic intermediate for medicines, agricultural chemicals, and perfumes, etc. PROCESS:A glycidic acid ester of formula II (R is ethyl or 1-6C hydrocarbon group) is hydrolyzed and decarbonated to give the aimed compound of formula I . The above-mentioned hydrolysis is preferably carried out in a basic aqueous solution, and water and an alcohol, e.g. methanol, or an aqueous solution of ethanol is preferably used as the solvent. Sodium hydroxide, etc. is used as the base, and the hydrolysis is carried out at 0-100 deg.C. Hydrochloric acid is added thereto to acidify the reaction mixture and give glycidic acid because the hydrolysis under basic conditions gives the glycidic acid in the form of a salt. The reaction mixture is then decarbonated at 0-250 deg.C. The compound of formula II is synthesized by reacting a compound of formula III with an alkyl monohalogenoacetate in the presence of a basic catalyst, and dehydrohalogenating the resultant product.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel ternary aliphatic compound and a method for producing the same.

Trinculo L 2.2.1.0', a bicyclic compound
1-heptane compounds are important synthetic raw materials for medicines, fragrances, etc. 7, it cannot be said that sufficient research has been conducted in the past.

The present inventors have completed the present invention by discovering a novel triadic aliphatic compound useful as an intermediate for the synthesis of pharmaceuticals, agricultural chemicals, fragrances, and the like.

That is, the present invention relates to a ternary aliphatic compound represented by the F formula (1) and a method for producing the same.

The ternary aliphatic compound described in item 2 is produced by hydrolyzing and decarboxylating a grid acid ester represented by the F formula (■) at 0 to 250'C.

In the formula, It represents an ethyl group or other hydrocarbon group having 1 to 6 carbon atoms.

The above-mentioned glycidic acid ester is hydrolyzed in an acidic or basic aqueous solution, but decomposition is usually faster in a basic environment, and the solvents used include water and -r alcohol,
For example, it is preferable to use methanol or an aqueous ethanol solution. As a base, sodium hydroxide,
An alkali metal hydroxide such as potassium hydroxide, a metal alcoholade or alkaline carbonate such as sodium methylate, or an anion exchange resin is used.

The temperature during hydrolysis is 0 to 1000C.

When hydrolyzed in basic conditions, glycidic acid is usually obtained in the form of 111 salt, which is then acidified by adding a mineral acid such as hydrochloric acid to form glycidic acid, and then decarboxylated at a temperature of 0 to 250°C. Do this. When the reaction temperature is lower than 0°C, the decarboxylation reaction is difficult to proceed, and when the reaction temperature is higher than 250°C, decomposition reactions other than decarboxylation and polymerization reactions are likely to occur. A more preferable decarboxylation temperature is 10.degree. to 150.degree. Adjust the heating time so that it continues until the generation of carbon dioxide gas stops.
However, it is usually about 0.5 to 5 hours. Note that it is not preferable that the hydrocarbon group R of the glycidic acid ester of formula (II) is a hydrocarbon group having more than 6 carbon atoms, since decarboxylation becomes difficult.

After the above reaction is completed, the bicyclic aliphatic compound represented by formula (1) can be separated from the reaction mixture by an appropriate means such as extraction or distillation.

In addition, the glinodoic acid ester represented by the above formula (II) is a ketone which is a bicyclic aliphatic compound represented by the formula (III) -C, and for example, alkyl motupromacetate, alkyl monochloroacetate, etc. It can be produced by reacting with an alkyl monohalocynoacetate in the presence of a completely basic catalyst and collecting dehalogenated water.

The alkyl group in monohaloketa-alkyl acetate includes methyl, ethyl, propyl, inglovil, butyl, see'-butyl, -amyl, isoamyl, \
Examples include gyl/yl and chlorohexyl groups.

In addition, in the dehydrohalocenation described in "-,"
When the number of carbon atoms in the alkyl group of the J-phenoacetate ester is 1 to 6, the reaction is completed relatively quickly, and as a result, the hydrolysis and subsequent decarboxylation of the obtained glycidate ester are easy. However, when the number of carbon atoms in the alkyl group is 7 or more, reactions such as dehydrogenation, hydrolysis and decarboxylation take too much time and are also disadvantageous from an economical point of view.

Therefore, it is preferable to use an alkyl monohaloketaacetate having an alkyl group having 1 to 6 carbon atoms.

Industrially advantageous monohalogenoalkyl acetates are methyl chloroacetate, ethyl chloroacetate, inofurovir chloroacetate and ethylene bis(chloroacetate).

In addition, the 1-st basic catalyst used in the reaction with monohalocarbonyl acetate is, for example, hydroxide-alkali,
These include alkali carbonate, alkali hepta-oxide, 1' alkali metal alcoholade, -r alkali metal amide, r alkali metal hydride, and the like.

Next, the present invention will be explained in detail with reference to Examples.

Example (a) Synthesis of glinodoic acid ester A ketone of a bicyclic aliphatic compound, 6-ethrintho(2,2,1,0"61hebutane-3-ono62y)
(0,46 mol) and ethyl chloroacetate 61.8F (0,
While stirring the mixture of
Dry t-7 linole solution (750 m(?)) of 1-gutkind 51.1 F (0.46 mol) was gradually added dropwise. Subsequently, after stirring at room temperature, t-butanol was distilled off using a vacuum knife. The residue was subjected to needle extraction. The ether extract was washed with water, dried, the ether was distilled off, distilled under reduced pressure, and the glinodoic acid ester spiro(3-ethoginecarbonyl oxifuran-2,3 '-(6'-ethyltri/chloro 2.2.1.02'/6']hebutane)
164'f (yield, 62.7%; boiling point, 92-93°C
/0.6 mmHg) k was obtained.

(B) Synthesis of bicyclic aliphatic compound] Add 22.67 (0.33 mol) of lium edilate to 300 ml of ethanol, and while keeping it below 20°C and stirring 1i' 1~, carry out the above steps. Glycidic acid ester 61.51i' (0.28 mol) obtained in (a)
was added dropwise, and then 7.2 ml of water was added, followed by stirring at about 70°C for 3 hours. Distilling off ethanol from the reaction mixture,
Water and benzene were added to the residue, and an aqueous hydrochloric acid solution was added dropwise thereto while stirring at room temperature. The mixture was heated to about 50° C., stirred until the generation of carbon dioxide ceased, and then cooled, made slightly alkaline by adding an aqueous sodium bicarbonate solution, and extracted with needle-benzene. After washing the extract with water and drying, the solvent was distilled off, followed by distillation under reduced pressure to obtain 6-ethyltricycloC2,2,1,02.6]butyl-3-fuldehyde 20.77 (yield, 49 .8chi; boiling point 54°c/
1.0 pharyngeal Hg) was obtained.

This bicyclic aliphatic ``I'' was subjected to elemental analysis, IR (ne
It was confirmed that the compound had the structure of the above formula (1) by conducting a sample test and NMR (CCI4) sample test.

Elemental analysis (Cl0H] 40) C (ri H (chi) word 1 calculation value so, o q, 3 real...11 value 80.3 9.11R (neat): 2880cm and 2720c+++-' (C-H expansion and contraction of aldehyde Vibration), 1720cm-' (c=o stretching vibration of aldehyde) NMR (CCI4): 0.85-1.10δ (Triple line, 3■1) 1.35
~1.70δ (quartet, 2H) 0.90~2.00
δ (multiplet, 6) ■) 2.30~2.40δ
(broad singlet, 21■) 9.70-9.85δ (
Quadruple line, 1■]) Patent applicant: Japan Petrochemical Co., Ltd.

Claims (1)

[Scope of Claims] ('') 1. A ternary aliphatic compound represented by formula (1). (2) When the glycidic acid ester represented by the following formula (n) is hydrolyzed and decarboxylated at 0 to 250°C, t
A method for producing a ternary aliphatic compound represented by the following formula (, ■), which has a W character, where R represents a hydrocarbon group having 1 to 6 carbon atoms.