JPS59157289A - Manufacture of cyclic terpene hydrocarbon - Google Patents

Abstract

PURPOSE:To manufacture easily a cyclic terpene hydrocarbon represented by a specified general expression by bringing an acylic terpene alcohol represented by a specified general expression into an electrolytic reaction. CONSTITUTION:An acyclic terpene alcohol represented by general expression I and/or II such as geraniol is brought into an electrolytic reaction to manufacture a cyclic terpene represented by general formula III such as limonene. In the expression, n is integer ''0'' or ''1'', one between Z<1> and Z<2> is H, the other forms a single bond together with Z, two among X<1>, X<2> and X<3> are H, and the residual one forms a single bond together with X. In the electrolytic reaction, it is preferable to use a suitable electrolyte such as an alkali metallic perchlorate by about 0.1-10mol per 1mol acyclic terpene alcohol as starting material, and the reaction is desirably carried out in a solvent such as tetrahydrofuran so as to increase the reaction rate and to improve the selectivity coefficient in the reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a cyclic terpene hydrocarbon, and more specifically, the present invention relates to a method for producing a cyclic terpene hydrocarbon, and more specifically, it has the general formula (IT-1) CH3CH3CH3 H-(CH2C-CHCH2, CH2C=CHCH
2CH2C=CHCHz-OR...(II-1) (wherein, n means an integer of O or 1) and/or a chain terpene alcohol and/or general formula (II-2) CH
3CH3CH3 HICH2C=CHCH2幇CH2C=CHCFI2C
General formula (1) characterized by electrolytically reacting a chain terpene alcohol represented by H2C-CH=CH2...(II-2), OH (in the formula, n is as defined above) (In the formula, n is as defined above, and % Z' and z
One of 2 is a hydrogen atom and the other together with 2 represents a single bond, two of XI, X2 and X3 are hydrogen atoms, and the remaining one together with X represents a single bond. represents. ) The present invention relates to a method for producing a cyclic terpene hydrocarbon shown in the following.

The cyclic terpene hydrocarbon represented by the general formula (1) is not only used as an aroma component of perfumes, but also useful as a synthetic intermediate for aroma components of other perfumes, cosmetic base materials, pharmaceuticals, and the like. For example, limonene, terpinolene, and pisabolene are known as active ingredients in deodorants and soap fragrances.

Conventionally, methods for producing cyclic terpene hydrocarbons from chain terpene alcohols include, for example, a method for obtaining limonene by treating nerol or geraniol with a 2-fluoropyridinium salt in the presence of tri-n-butylamine; It is known that bisabolene is obtained by treating dol with 2-fluorobenzothiazolium salt in the presence of trijn-bunalamine [Free et al., Chemistry Letters, 1137].
1976) and Chemistry Letters
.

1169 (1977)], 2 used in these methods.
- Preparation of onium salts such as fluorohyricinium salts and 2-fluorobenzothiazolium salts is not easy.

As a result of research on the cyclization reaction of chain terpene alcohols, the present inventors found that the chain terpene alcohol represented by the general formula (II-1) or the chain tilbene alcohol represented by the general formula (II-2) It has been discovered that the cyclic terpene hydrocarbon represented by the general formula (1) can be easily obtained by carrying out a lamination reaction, and the present invention has been achieved.

In the electrolytic reaction of the present invention, it is preferable to use a suitable electrolyte, such as perchlorates of alkali metals or alkaline earth metals such as lithium, sodium, potassium, calcium, paris, and rum. Examples include boron tetrafluoride salt; quaternary ammonium salts such as tetraethylammonium salt and tetrabutylammonium salt of perchloric acid. The amount of electrolyte used varies depending on the electrolyte employed, but for example, when lithium perchlorate is used as the electrolyte, it is approximately 0.1 to 10 times the mole per mole of chain terpene alcohol as the raw material.
Preferably it is about 1 to 5 times the molar amount.

The electrolytic reaction is preferably carried out in a solvent in order to increase the reaction rate and reaction selectivity. Examples of solvents include chain or cyclic ethers such as diethyl ether, dimethoxyethane, jetoxyethane, and tetrahydrofuran; lower fatty acid esters such as ethyl formate, methyl acetate, ethyl acetate, methyl propionate, and methyl valerate; acetone, methyl ethyl ketone, and methyl imbutyl. Lower aliphatic ketones such as ketones; carbonic acid esters of lower aliphatic alcohols such as dimethyl carbonate and diethyl carbonate; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, and carbon tetrachloride, etc. can be used; Tetrahydrofuran is particularly preferred. In addition, in these solvents and in the presence of the above electrolyte, in a system where strong acids are generated, for example, in an ether solvent such as tetrahydrofuran, or an alkali metal perchlorate such as lithium perchlorate, or an alkali metal perchlorate such as lithium perchlorate. When the electrolytic reaction of the present invention is carried out in the presence of an electrolyte such as a quaternary ammonium salt of perchloric acid such as tetraethylammonium chlorate (( is represented by the general formula (
The dehydration cyclization reaction of the chain terpene alcohol represented by It-1) or the chain terpene alcohol represented by the general formula (n-2) becomes more likely to occur, and the desired electrolyzed product can be obtained in good yield. Further, the electrolytic reaction of the present invention is easily affected by temperature, and the yield of the electrolyzed product decreases as the temperature decreases. The reaction is preferably carried out at a temperature range from room temperature to about 80°C.The electrodes are gold, platinum, gold or platinum plated titanium, carbon; or nickel, titanium/nickel, stainless steel, lead, copper or acids thereof. Although it is possible to use electrodes commonly used in electrolytic reactions, such as oxides, platinum, carbon, nickel, stainless steel, and lead electrodes give good results in terms of reaction yield and jl, 4J< ratio. . The current density is in the range of ~500 mA/crl, and a small amount of electricity, such as about 0.01 ~ IF/mol, is sufficient, but the current required for the electrolytic reaction of the present invention is Density and charge will vary depending on the reaction conditions employed. For example, the necessary current density for cyclodehydration of (E) nerolidol at 58°C in tetrahydrofuran solvent using lithium perchlorate as an electrolyte is 3.3 mA/c.
trl, and the amount of electricity is 0.28 F”/mol.

Examples of the chain terpene alcohol represented by the general formula (II-1,) or the chain terpene alcohol represented by the general formula (II-2) used as a raw material in the present invention include hakelaniol, nerol, 'J narol, (E , E) farnesol, (E,Z) farnesol, and (E) nerolidol.

After the electrolytic reaction is complete, pour the reaction mixture into water, sodium bicarbonate solution, etc.
Then, by extracting with an organic solvent such as hexane and distilling off the solvent from the extract, the target cyclic terpene-based carbonized limescale represented by the general formula (1) can be separated and obtained. Note that cyclic terpene hydrocarbons are usually recovered as a mixture of positional isomers regarding double bonds. Each isomer can be easily obtained by subjecting this mixture to a separation operation such as distillation.

The present invention will be specifically explained below using examples.

Example 1 (1-1) (1-2) (I-3) 30d
(E) Nerolidol 100 tons (0,4
5 mmol) and lithium perchlorate 350 TQ (3
, 28 mmol) was weighed out, and the sheath part tetrahydrofuran/8 td was added to it and stirred to make a homogeneous solution.

A platinum electrode (1.5 x 2 ca) was attached to this corrugated test tube, and while the reaction temperature was maintained at 58°C, 3.3 rrLI
VC, i constant current for 20 minutes (amount of electricity: 0°28
F/mol). After the electrolytic reaction was completed, saturated sodium bicarbonate solution was added to the reaction mixture. Concentrate the organic layer under reduced pressure 1~
Combine this with the n-hexane extract (extracted twice) from the aqueous layer, wash this mixture once with saturated brine, dry over anhydrous sodium sulfate, and distill the solvent from this under reduced pressure. A 1'lE-like proboscis 108.3+++2'tc was obtained.

This oily substance was purified by Nori-Gel-Ryram to obtain a colorless oily substance with 84. I got Onq. As a result of analyzing this product by gas chromatography (SE-30, 6m 1160°C), α-bisabolene represented by formula (1-1), β-bisabolene represented by formula (1-2), and formula (1 -3
), yields of γ-bisabore/are 36% and 18%, respectively.
, 18%. In addition, compounds corresponding to peaks indicating these products were separated by gas chromatography, and each compound was confirmed by IR analysis and NMR% analysis.

α-Bisabolene IR (Neat): 2960 (CHa), 2910 (C
f(2), 2840°1600.1440,1376.
-1'H-NMR (CDCIs) δ of 1100°875: 1.56-1.8
0(m, 13H, CH3゜)CM-); 1.88□
~2.36 (m, 6H.

-CH2-)i2.71(t, J=7.7Hz.

2H, -CH2-); 5.00-5.28 (m.

2H, -CH=C:); 5.34-5.52 (m, I
H, -C)l=C,) β-bisabolene IR (solv, CHCl5): 2960 (CHs),
2920 (CH2).

2845, 1640 (C=C), 1450°1435
, C376,895 box-1 1H-NMR (CDC1a) δ: 4.58-1.76
(m, 11 H, CH13°CH2) + 1.8
4-2.16 ("y9Hr-CH2-,';c
) I-), ; J,, 80 (sr 2I'LH2C
=(,: );s,oo ~5.28(rq, IH.

-CH=C: ) i5.32~5.52 (m, I
H.

-CH=Cte) IR (solv, Cj (C13): 2960, 2910
, 2840, 1525. ．． 1510, 1450.143
('), 1375°1225.1195 礪-1'H-N M, R, (CDC13) δ: 1.58-1.
134 (m, 12H, CHs); 1.8! :i ~
2.16 (r+1,6H, -CH2-); 2.32 (t
, J=6.6H2,21(,-CH2-); 2.64~
2.88 (nl, 2n, -CH2-); 5.00
~5.28 (rrl, IH, -CH,,,CC);5
30-5.56 (rrl, ], ]H, -CFf
= Example 2 (1-1) (1-2) (1-3) (E, E) Farnesol 100"i in a 30-capacity suction test tube
7 (0,45 mrnol) and lithium perchlorate 3
50~(3.28 rrunol) was weighed out, 8 mg of Japanese tetrahydrofuran was added thereto, and the mixture was stirred to form a homogeneous solution. Platinum electrodes (1, 5X, 2
d) was installed, and while keeping the reaction temperature at 60°C,
Electrify for 10 minutes at a constant current of 3 mA/c++t (amount of electricity: Q
, 14F/mo 1). After the electrolytic reaction was completed, saturated sodium bicarbonate solution was added to the reaction mixture. The organic +iu was concentrated under reduced pressure, and this and the n-hexane extract from the aqueous layer (
The mixture was washed once with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 94.4rr4 of an oil. This oily substance was purified using a silica gel column to obtain a colorless oily substance 91.173F.As a result of analyzing this substance by gas chromatography, it was found that α-bi-ybo1/one (I-1), β- It was observed that bisabolene (I-2) and γ-bisabolene (1-3) were obtained in yields of 37%, 18%, and 17%, respectively.

(E, Z) farnesol 10 in a 30d suction test tube
0-(0,45 mmol) and lithium perchlorate 35
0'n? (3.28 mmol) was weighed out and weighed t1.
．． Fc4'fgaUf Door Hydrofuran 8me was added and stirred to form a homogeneous solution.

A platinum electrode (1.5 x 2 cJ) was attached to this adsorption test tube, and while keeping the reactive group IW at 58°C, 3.31 nA/
Electrify for 15 minutes with CD constant current (amount of electricity: 0.21 i
'/mol) was performed. After the electrolytic reaction was completed, the reaction mixture was treated in the same manner as in Example 1, and a colorless oil was obtained.
86 mg was obtained. As a result of analyzing this product by gas chromatography, α-bisabolene (1-1),
β-bisabolene (1-2) and γ-bisabolene (1-3
) were obtained in yields of 40%, 18%, and 19%, respectively.

Example 4 (1-4) (1-5) Geraniol 100・■(0
, 65 mmol) and lithium perchlorate 346 mr (3
, 25m tool) was weighed, 8 tall of purified tetrahydrofuran was added thereto, and the mixture was stirred to form a homogeneous solution. Place a platinum electrode (1,5X2C+4
) while maintaining the reaction temperature at 60°C. 3.
31TIA/cr! Electrify for 15 minutes at a constant current (electricity,
jt: 0.21 F/rnol).

After the electrolytic reaction was completed, the reaction mixture was concentrated under reduced pressure, washed once with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to form a yellow oil.
．． 31nf was obtained. This oil was purified by a very short gel ram to give a colorless oil with a yield of 64.5. As a result of analyzing this substance by gas chromatography,
It was observed that limonene represented by formula (1-4') and terpinolene represented by C1-5) were obtained in a yield of 23φ and 41 cracks, respectively. In addition, chemical fractions corresponding to peaks indicating these products were separated by gas chromatography, and each compound was confirmed by its physical property values matching those of existing limonene and terpinolene.

Claims (1)

[Claims] 1. A chain terpene alcohol represented by the general formula (wherein n means an integer of 0 or 1) and/or a chain terpene alcohol represented by the general formula The general formula is characterized by electrolytically reacting a chain terpene alcohol represented by The other, together with 2, represents a single bond, two of Xl, X2, and X3 are hydrogen atoms, and the remaining one, together with X, represents a ton bond.) Method 02 for producing a terpene-based hydrocarbon scale, the method for producing a cyclic terpene-based hydrocarbon according to claim 1, wherein in the general formula, 11 is 1.