JPS63227548A - Novel formic acid ester - Google Patents

Abstract

NEW MATERIAL:8-Acetoxy-2,6-dimethyl-1-formyloxy-2,6-octadiene expressed by formula I. USE:A perfume having green notelike aroma and synthetic intermediate for pro ducing various terpene compounds having polyprenyl units in the molecule, such as medicines, e.g. vitamin A, perfumes or pheromones. PREPARATION:8-Acetoxy-2,6-dimethyl-3-chloro-1,6-octadiene expressed by formu la III is reacted with sodium formate and a catalytic amount of a tetraalkylammonium iodide in toluene while refluxing and heating to afford the aimed compound expressed by formula I, which is then reacted with a catalytic amount of sodium carbonate in methanol solution at room temperature to provide a compound expressed by formula II (useful as vitamin A, perfume, pheromone, etc.).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a novel formic acid ester, 8-7 setoxy 2.
．． It relates to 6-dimethyl-1-formyloxy-2°6-octadiene (hereinafter, this compound may be simply referred to as formate ester).

[Conventional technology]

The formic acid ester of the present invention is a new compound, and the thermal properties and synthesis method of this compound are unknown.

[Problem that the invention seeks to solve]

An object of the present invention is to provide novel formic acid esters.

[Means for solving problems]

The present inventors have now discovered that HCOCH2-C=CH-CH2-CH2C=CH-0
M20CCH.

8-acetoxy-2,6-dimethyl- having the structure
We succeeded in newly synthesizing 1-formyloxy-2,6-octadiene.

The formic acid ester of can be used as a fragrance because it has a green note-like aroma. This compound can also be used with weakly basic substances such as aqueous ammonia, hydrogen chloride, carbonate, sulfuric acid,
The formyl group is easily selectively hydrolyzed under conditions catalyzed by acidic substances such as hydrochloric acid and p-toluenesulfonic acid.
8-acetoxy-2,6-dimethyl-1-hydroxy-
This can lead to 2,6-octadiene. This 8-
Acetoxy-2,6-dimethyl-1-hydroxy-2,
6-Octadiene is a compound widely used for producing various terpene compounds having a polybrenyl unit in the molecule, such as medicines such as vitamin A, perfumes, and pheromones. An example of synthesis of vitamin A and a terpene compound from 8-acetoxy-2,6-dimethyl-1-hydroxy-2,6-octadiene is shown below.

1) Synthesis of vitamin A (J, Drg, Chem, 5
1 t2) African monarch but
terfly hairpenc11 secretion (E
)-3,7-dimethyl-2-octene-1,8-diol synthesis (Tetrahedron Lett*p 34
85 (1971)) 3) Synthesis of C17 juvenile hormone (J
, C.S., Chem.

Comm, 486 (1972)) 8-acetoxy-2,6-dimethyl-1-hydroxy-
As a method for synthesizing 2,6-octadiene, dimethylamine, acetic anhydride, 8-acetoxy-2,6-dimethyl-3-chloro-1,6-octadiene obtained by reacting hypochlorous acid etc. with geranyl acetate, A method is known in which peracetic acid, zinc, etc. are applied sequentially (Litt, Inoue et al., Chetm, Lett, 1999).

2035 (1986)), this method requires a long reaction step;
There are also other problems, such as the use of peroxide, which poses a risk of explosion.

8-acetoxy-2,6-dimethyl-1-formyloxy-2,6-octadiene (I) of the present invention is 8-acetoxy-2,6-dimethyl-3-chloro-1,6-octadiene (2) It can be synthesized in high yield by reacting sodium formate with a catalytic amount of a tetraalkylammonium iodide salt under heating under reflux in toluene. Furthermore, as shown in the reference example below, this product can be produced in good yield by simply reacting with a catalytic amount of sodium carbonate in a methanol solution at room temperature. - can be derived from octadiene (n).

That is, the formate ester (11) of the present invention is not useful as a fragrance per se, but 8-acetoxy 2 is not important as a synthetic intermediate for vitamin A, juvenile phorphone, etc.
, 6-dimethyl-1-hydroxy-2°6-octadiene (If).

Double lower margin (II) Raw material compound 8-acetoxy-2,6-dimethyl-3-
Chlor-1,6-octadiene (2) can be obtained by a known method, for example, a method in which hypochlorous acid or bleaching powder is applied to r-ranyl acetate (Tetrahedron Lett-+
21 #4.4.1 (1980)) and the method of reacting r-ranyl acetate with chlorinated isocyanuric acid (Japanese Unexamined Patent Publication No. 58-52231).

The amount of formic acid and thorium used is based on the raw material allyl chloride (
Although it is sufficient to use an amount equal to or more than 1 molar amount of the amount of 20% of the total amount of the compound, it is preferable to use about 2 times the molar amount in order to carry out the reaction efficiently. The halog/tetraalkylammonium salt used as a catalyst preferably has a total number of carbon atoms of four alkyl groups in the range of 8 to 20, and a typical example is iodinated tetra-n-
An example is butylammonium. The amount used is usually 0.1 to 20 mol% based on allyl chloride.
Particularly preferred is 1 to 5 mol%.

This reaction requires an inert solvent such as hexane, benzene,
Aliphatic and aromatic hydrocarbons such as toluene, chlorinated hydrocarbons such as chloroform, ethers such as dioxane, isopropyl ether, and esters such as ethyl acetate can be used. A particularly preferred solvent is toluene. The reaction can be carried out at a temperature within the range of 30°C to 180°C, but is preferably carried out at a temperature within the range of 70°C to 140°C while heating the reaction solution under reflux.

The method of the present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Example t 8-acetoxy-2,6-dimethyl-3-chloro-1,
6-octadiene 30II (90.9% purity, 118m
moL), sodium formate 16.32g (240mm
ot), iodinated tetra-n-butylammonium 0.
A mixture of 9II (2.4 mmot) and Torzy 100 mJ was heated under reflux for 9 hours with vigorous stirring. After cooling, the solid matter was separated in a suction oven, and the filtrate was washed with 50-g water.

Furthermore, the organic layer was treated with 50ml of 5% sodium thiosulfate aqueous solution.
After washing with 50 ml of 5% sodium bicarbonate solution and 50 ml of 5% saline solution, the solvent was distilled off under reduced pressure to obtain an oily substance 32.
441S' was obtained. Analysis by gas chromatography revealed that the target 8-acetoxy-2,6
The purity of -dimethyl-1-formyloxy-2,6-octadiene was 76.5%, and the yield was 24.821 (1
03.4 mmot), yield was 87.6%. The cis to trans ratio of the double bond at position 2 is 58.2 to 41.
．． It was 8. This crude formate ester can be distilled using a distiller equipped with a packed column (boiling point 115-1
18°C 10.2 wHg).

The results of instrumental analysis of 8-acetoxy-2,6-dimethyl-1-formyloxy-2,6-octadiene are shown below.

NMR (tetramethylsilane/carbon tetrachloride) δ: 1.
71 (broad, 6H), 1.96 (s, 3H),
2.09 (broad*4I(), 4.40~4.7
0 (m, 4H), 5.28 (t.

J=10Hz, 2H), 7.5(a, IH)I R(
K B r plate) ν: 1720cm-' (C=O)M
8 m/e (relative intensity): 195 (10, M+-H
C0□), 134 (62), 84 (100), 43 (1
00) Reference example As a reference example, 8-acetoxy-2,6-dimethyl-1-
Formyloxy-2,6-octareninekara 8-acetoxy-2,6--,'methy/l/Φ1-hydroxy-2
, 6-octane.

8-acetoxy-2,6-dimethyl-1-formyloxy-2,6-octadiene 100.9 (96% purity, 4
00 mmot) of methanol/I 1500 m solution was added 318 μm (3 mmol) of soda carbonate, and the mixture was stirred at room temperature for 1 hour. After terminating the reaction by adding 300 g of concentrated sulfuric acid, 30 g of methanol and pyridine O and Ig, the solvent was distilled off under reduced pressure to obtain 113 g of an oily substance. Analysis by gas chromatography revealed that the purity Fi of the target 8-acetoxy-2,6-dimethyl-1-hydroxy-2,6-octadiene was 72.7%, and the yield was 82.1! [1(387,71TirnoL
>, yield was 96.9%. Note that the cis to trans ratio of the double bond at the 2nd position is 54.7 to 45.3. 8-
Acetoxy-2,6-dimethyl-1-hydroxy-2,
The results of the instrumental analysis of 6-octadiene are shown below.

NMR (tetramethylsilane/carbon tetrachloride) δ: 1.
71 (broad, 6 H), 1.96 (m, 3
H), 2.05 (broads 4H), 3.20 (b
road, IH), 3.87, 4.00 (a, total IH), 4.00 (d, J=6Hz, 2H), 5.1
5-5.60 (m, 2H) IR: 1720m-' (C=O), 3400crn-'
(OH)MS wind/・(relative strength): 134(21),
84(90), 68(100), [Effects of the Invention] According to the present invention, 8-acetoxy-2,6-dimethyl-1-formyloxy-2,6 which is a novel formate ester
- Octadiene is provided. This compound is expected to be used as a fragrance, and the 8
-acetoxy-'2,6-dimethyl-1-hydroxy-
Vitamin A and woodcutter terpene compounds can be synthesized from 2,6-octadiene.

Claims (1)

[Claims] 8-acetoxy-2,6-dimethyl-1-formyloxy-2,6-octadiene