JPH0256339B2 - - Google Patents

Description

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

Although tricyclo[2.2.1.0 ^2,6 ]heptane compounds, which are tricyclic compounds, can be used as important synthetic raw materials for medicines, fragrances, etc., sufficient research has not been conducted to date.

The present inventors have completed the present invention by discovering a novel tricyclic 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 tricyclic aliphatic compound represented by the following formula (I) and a method for producing the same.

The above tricyclic aliphatic compound is produced by hydrolyzing and decarboxylating a glycidic acid ester represented by the following formula () at 0 to 250°C.

In the formula, R 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 water and alcohol, such as methanol or ethanol aqueous solution, can be used as the solvent. suitable. As the base, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, a metal alcoholate such as sodium methylate, an alkaline carbonate, or an anion exchange resin is used. The temperature during hydrolysis is 0 to 100°C.

When hydrolyzed with basicity, glycidic acid is usually obtained in the form of a salt, and then a mineral acid such as hydrochloric acid is added to acidify it to give glycidic acid, and then 0.
Decarboxylation is carried out at a temperature of ~250°C. If the reaction temperature is lower than 0°C, the decarboxylation reaction will be difficult to proceed;
When the 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 to 150°C. The heating time may be continued until the generation of carbon dioxide gas stops, but it is usually about 0.5 to 5 hours. In addition, the above formula ()
The hydrocarbon group R of the glycidic acid ester has 6 carbon atoms.
If the number of hydrocarbon groups exceeds 1,000,000 or more, decarboxylation becomes difficult, which is not preferable.

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

In addition, the glycidic acid ester represented by the above formula () is the following formula () Manufactured by dehydrohalogenation by reacting a ketone, which is a tricyclic aliphatic compound represented by can do. Examples of the alkyl group in the monohalogen alkyl acetate include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, amyl, isoamyl, hexyl, and cyclohexyl groups.

In addition, in the above dehydrohalogenation, the number of carbon atoms in the alkyl group of the alkyl monohalogenoacetate is 1.
- 6, the reaction is completed relatively quickly, and as a result, the hydrolysis and subsequent decarboxylation of the obtained glycidic acid ester are easy;
When the number of carbon atoms in the alkyl group is 7 or more, reactions such as dehydrohalogenation, 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 monohalogenoacetate having an alkyl group having 1 to 6 carbon atoms. Industrially advantageous alkyl monohalogenoacetates include methyl chloroacetate, ethyl chloroacetate, isopropyl chloroacetate and ethylene bis(chloroacetate).

Further, the basic catalyst used in the reaction with the alkyl monohalogenoacetate is, for example, an alkali hydroxide, an alkali carbonate, an alkali fluoride, an alkali metal alcoholate, an alkali metal amide, an alkali metal hydride, or the like.

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

Example (a) Synthesis of glycidic acid ester 6-ethyltricyclo[2.2.1.0 ^2,6 ]heptan-3-one, a ketone of tricyclic aliphatic compounds
62g (0.46 mol) and ethyl chloroacetate 61.8g (0.50
51.1 g (0.46 mol) of potassium t-butoxide was added while stirring the mixture of
- Butanol solution (750 ml) was slowly added dropwise.
Subsequently, after stirring at room temperature, t-butanol was distilled off under reduced pressure, and the residue was extracted with ether. After washing the ether extract with water and drying, the ether was distilled off and distilled under reduced pressure to obtain spiro{3-ethoxycarbonyloxirane-2,3'-(6'-ethyltricyclo[2.2.1.0 ² ′ ^,6 ′]heptane)}64g (yield, 62.7%;
boiling point, 92-93°C/0.6mmHg).

(b) Synthesis of tricyclic aliphatic compound 22.6 g (0.33 mol) of sodium ethylate was added to 300 ml of ethanol, and while stirring while keeping the temperature below 20°C, 61.5 g of the glycidic acid ester obtained in the above step (a) was added. g (0.28 mol) was added dropwise, and then 7.2 ml of water was added, followed by stirring at about 70°C for 3 hours.
Ethanol was distilled off from the reaction mixture, water and benzene were added to the residue, and an aqueous hydrochloric acid solution was added dropwise to the mixture while stirring at room temperature. The mixture was heated to about 50° C. and stirred until the generation of carbon dioxide gas ceased, then cooled, made slightly alkaline by adding an aqueous sodium bicarbonate solution, and extracted with ether-benzene. After washing the extract with water and drying, the solvent was distilled off, followed by distillation under reduced pressure to obtain 6-ethyltricyclo[2.2.1.0 ^2,6 ]heptyl-3-aldehyde.
20.7g (yield, 49.8%; boiling point 54°C/1.0mmHg) was obtained.

Elemental analysis and IR of this tricyclic aliphatic aldehyde
(neat) spectrum and NMR ( _CCl4 ) spectrum, it was confirmed that it had the structure of formula (I).

Elemental analysis (C ₁₀ H ₁₄ O) C (%) H (%) Calculated value 80.0 9.3 Actual value 80.3 9.1 IR (neat): 2880 cm ^-1 and 2720 cm ^-1 (C-H of aldehyde
Stretching vibration), 1720cm ^-1 (C=O stretching vibration of aldehyde) NMR (CCl ₄ ): 0.85-1.10δ (triplet, 3H) 1.35-1.70δ (quartet, 2H) 0.90-2.00δ (multiplet , 6H) 2.30-2.40δ (broad singlet, 2H) 9.70-9.85δ (quartet, 1H)

Claims (1)

[Claims] 1. A tricyclic aliphatic compound represented by the following formula (I). 2. A method for producing a tricyclic aliphatic compound represented by the following formula (I), which comprises hydrolyzing and decarboxylating a glycidic acid ester represented by the following formula () at 0 to 250°C; In the formula, R represents a hydrocarbon group having 1 to 6 carbon atoms.