JPS62167738A - 2,2,7,7-tetramethylcycloheptan-1-ol and perfume composition containing the same - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R is H, 1-4C alkyl). EXAMPLE:1-Ethyl-2,2,7,7-tetramethylcycloheptan-1-ol. USE:A component of perfume. PREPARATION:2,2,7,7-Tetramethylcycloheptanone of formula II is reduced to give 2,2,7,7-tetramethylcycloheptan-1-ol of formula I where R is H. Or the com pound of formula II is allowed to react with a compound of the formula: R'M [R' is 1-4C alkyl; M is MgX (X is halogen), Li] to give the compound of formula I where R is a 1-4C alkyl.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a novel general formula ([
) (wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) 2,2.7.7-titramethylcyclohebutan-1-ols represented by the following and fragrance compositions containing the same. Regarding.

[Conventional technology]

Conventionally, many useful fragrance compounds have been known to exist in saturated or unsaturated alcohols [Osamu Okuda, [Fragrance Chemistry Comprehensive Review (n) J, Koyo Shoten, Nos. 482-681]
1980)].

[Problem that the invention seeks to solve]

However, the aromas of compounds are generally completely different due to slight differences in structure, so it is extremely important to synthesize various compounds and study their aromas in order to obtain new fragrances.

[Means for solving problems]

The present inventors conducted intensive research to obtain a compound useful as a fragrance, and as a result, we newly found a compound with the general formula (1), which has not been described in any literature (wherein, R is a hydrogen atom or has a carbon number of 1 to 4 The inventors synthesized 2,2,7,7-titramethelcyclohebutan-1-ols represented by the following alkyl groups, and found that the compounds had a useful aroma, and completed the present invention.

That is, the present invention provides a novel compound 2,2.7°7-titramethylcyclohebutan-1-ol (1) and a fragrance composition containing the same.

The compound (1) of the present invention is prepared, for example, by any of the following methods.

Method 1: In formula (1), R is a hydrogen atom 2,2°7.7
-Titramethelcyclohebutane-1-oak (Ia)
can be obtained by reducing 2,2,7,7-titramethylcycloheptanone ([) according to the following reaction formula.

(1) (Ia) For this reduction reaction, any method generally used for reduction of keto/groups can be used.

Typical methods include reduction reaction with metal hydrides such as lithium aluminum hydride or boron hydride; platinum oxide, ruthenium/activated carbon, Cu
Examples include hydrogenation reactions using transition metal catalysts such as -Cr catalysts.

The reduction reaction using a metal hydride can be carried out by conventional methods described in the literature [for example, L.F.
ser & M, Fieser), “Reagen for Organic Synthesis”
tafor Organic 5 synthesis)
J Shore Willey & Sons Inc. (
John Wiley & 5ons Inc.) (1
967)').

On the other hand, the hydrogenation reaction using a metal catalyst can be carried out without using a solvent, and includes, for example, saturated olohydrocarbons such as n-hexane; alcohols such as methanol and ethanol; diethyl ether, Tl(F).

It can also be carried out using a solvent such as ethers such as dioxane. The reaction temperature may be 100°C or higher and 250°C, more preferably 150°C to 250°C.
It is.

Method 2: 2,2,7.7-titramethylcyclopebutane-1- in formula (I), where R is an alkyl group having 1 to 4 carbon atoms.
Ols (To) are 2, 2, 7. according to the following reaction formula.
It is obtained by reacting 7-titramethylcycloheptanone (I) with compound M represented by the formula (■).

(1) (u) (Ib) (wherein, R' represents an alkyl group having 1 to 4 carbon atoms, and M is MgX
or represents a lithium atom, where X represents a ).rogen atom) The compound of formula (n) which is the raw material for this method has 1 to 4 carbon atoms.
It can be easily prepared by reacting an alkylnoride with metal magnesium or lithium.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R' include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 5ec-butyl group, inbutyl group, and the like. The amount of the compound of formula (I[) to be used is at least 1 equivalent, preferably at least 1.2 equivalents, relative to the compound of formula (1).

As the solvent used in this reaction, solvents commonly used in the reaction of ketone bodies with Grignard reagents or lithium reagents can be used, but ether-based solvents such as diethyl ether, tetrahydrofuran, and diglyme (dimethyl selonup) can be used. Solvents are preferred.

The reaction time and reaction temperature vary depending on the solvent used, but are preferably from room temperature to 100°C for 1 to 5 hours.

After the reaction is completed, 2°2.7. of the present invention is extracted from the reaction mixture.
7-Titramethylcyclohebutan-1-ols ([)
For isolation and purification, conventional methods such as extraction, washing, and distillation are used.

Method 3: In the formula (lI[), the compound in which R is perpropyl can be obtained by hydrogenating 1-allyl-2,2,7,7-titramethylcyclohebutan-1-ol in the presence of a metal catalyst. Prepared by

The hydrogenation catalyst at this time may be any catalyst that is normally used in the hydrogenation reaction of olefins, and for example, Raney nickel, palladium/activated carbon, platinum oxide, etc. can be used. The hydrogenation reaction using a metal catalyst can be carried out without using a solvent; for example, saturated hydrocarbons such as n-hexane; aromatic hydrocarbons such as benzene and toluene; alcohols such as methanol and ethanol; It can also be carried out using a solvent such as ethers such as diethyl ether, THF, and dioxane. The reaction temperature may range from room temperature to 250°C, more preferably from room temperature to 100°C.

The compound (1) of the present invention obtained as described above has a woody, earthy, camphor-like, and herbal-like aroma, so it can be used as it is, but other It can also be combined with various perfume bases to form perfume compositions.

To prepare a fragrance composition, the compound (1) of the present invention is added in an amount of 0.1
~20% by weight (hereinafter simply indicated by H), preferably 0.5
Although it is sufficient to mix up to 5 ml, there is no particular restriction on this amount.

Furthermore, it is particularly preferable that the compound (1) of the present invention is combined with other fragrances having a fougere-like, wood-like, animal-like, or amber-like aroma, such as methyl ionone, oakmoss, absolute, lavender, etc., to form a mixed fragrance. .

〔effect〕

As described above, the compound of the present invention is excellent as a compounding material for various fragrances, and can be used as a flavoring agent for high-grade fragrance compositions, perfumes, soaps, shampoos, hair rinses, detergents, cosmetics, hair sprays, fragrances, etc. It can be used in a wide range of applications where

〔Example〕

Next, the present invention will be explained with reference to reference examples and examples.

Reference example 1 2.2.7.7-titramethelcycloheptanone (I)
Synthesis of Sodium amide (39,01?, t, Omon) and toluene (4,000 t, Omon) in a 14-four flask equipped with a stirrer, a dropping funnel, a thermometer, a reflux condenser, and a nitrogen gas inlet tube.
oomg), and the mandible was heated under nitrogen atmosphere. Add diimpropyl ketone (
A mixed solution consisting of 45,687, 0.4 mop)/1°4-dichlorobutane (50,80?, 0.4 mop:) was added dropwise over a period of 3.5 hours. The mixture was stirred under heating under reflux for 5 hours. After cooling, add water (
200at) was added for 1 minute, and the organic layer was neutralized and washed with a 10% aqueous solution of sulfuric acid (5Q+++/), then washed with a 10% aqueous sodium carbonate solution (5Qml), and then twice with saturated brine (toomg). Washed. The organic layer was dried over anhydrous magnesium sulfate, separated from F, and then subjected to fractional distillation to obtain the above compound 34.4351-(yield 51.2%).

Boiling point: 98°C/20mtxHP Elemental analysis (C,,1 (as 200) Elbow numbness value (%): C7B, 51 t-111,98 Actual value (%): C78,32Hll, 89 [(Liquid film * 1
'? ff! -')? 2960, 2920.2860
('C1i)1690(νC,O) lH-NMR (CDC also solvent, TMS internal criterion, δ):
1.60 (-CH,+, 8H,s) 1.16 (
-CH,,12H,s) MS (Relative Intensity) The results of gas mass measurement using a capillary column [Methyl silicon, column length 25 m, manufactured by Hewlett-Paracard] are shown below.

168 (M, 24), 83 (19), 81 (24)
, 70(22), 69(92), 57(31), 56(
100), 55(35), 43(20), 41(43) Reference example 2 1-allyl-2,2,7,7-titramethylcyclohebutan-1-ol 0-=formation: Stirrer, dropwise addition Magnesium (5,37 t, 0.221 mol) was added to a SOOMZ four-way flask equipped with a funnel, a thermometer, a reflux condenser, and a -4 gas inlet tube, and after removing moisture inside the flask through nitrogen gas, the mixture was stirred. A small amount of allyl bromide (1,5P, 0.0124 rn
o))/dry diethyl ether (7,5d) was added dropwise, and allyl bromide (21,297,0,176m0A)/2.
2,7,7-titramethylcycloheptanone (24,6
A mixed solution consisting of a t, o, t 47 moa)/dry diethyl ether (75 mJ) was added dropwise over a period of 2 hours. While keeping this mixture below 15℃,
Stir for hours. The reaction mixture was poured into ice water and made weakly acidic with an IN aqueous solution of hydrochloric acid.Then, the organic layer was washed with a saturated aqueous solution of sodium bicarbonate (59 mJ), and then washed with water (50 ml) three times.

The organic layer was dried over anhydrous magnesium sulfate, filtered and fractionated to obtain the above compound 23.037 (yield 74.5t).
s) was obtained. This product was a colorless and transparent liquid.

Boiling point: 115℃/5 am H5' Elemental analysis (C34 bird.O) Calculated value (chi): C79,941 (12,,46 actual value ((trans)20 79,75 f(12,,63IR)
(Liquid film + cWI″″′): 3580 (ν0H) 3080CI/CM (=CH-, -CH,)) 2950
, 2920.2870 (1'cH) 1635 (νc, c
) 980.920 (δcH (-CH, CH, out-of-plane bending angle)
[1H-NMR (CDC solvent, TMS internal standard, δ)
:6.31~5.61 (-CH2-CH-cu,,t
H, m) 5, 15-4.88 (-CH2-CH-CH
,,2H,m)2,. 43 (-CH, -CH-CH
,,2H,d,J-8,0Hz)2.02~1.2
0 [: −(C3)4+, 8 H,m”]1.0
5 and 0.98 (-CH,, 12H, s) MS (relative intensity) The results of gas mass measurements using a capillary column [Methyl silicon, Co., Ltd., Hewlett-Paracard, column length 25 m] are shown below.

210 (M, 4), 111 (64), 95 (78)
, 82(63), 81(89), 71(64), 69(
99), 55(79), 43(100), 41(83) Example 1 Synthesis of 2.2.7.7-titramethylcyclohebutan-1-ol: Stirrer, dropping funnel, thermometer, reflux Add ether to a 1 to 4 flask equipped with a condenser and calcium chloride tube (
1/ was added and stirred at room temperature. 2,2,7,7-titramethylcyclohebutanone 33.
A mixed solution consisting of 69 ml of 66 P (0.2 moA)/dry ether was added dropwise over a period of 1 hour. This mixture was stirred at room temperature for 1 hour.

To the reaction mixture, 40 d of water and 250 d of an aqueous 10-thiosulfuric acid solution were added in this order to separate the layers, and the organic layer was washed twice with 100 at of saturated brine. The organic layer was dried over anhydrous magnesium sulfate;
After the separation, the mixture was concentrated and fractionated to obtain 33.45p of the above compound (yield: 98.2g). This thing is wood-like, earth-like, camphor-like,
It was a white solid with a hay-like odor.

Boiling point: 105°C/16 H% Melting point (in a pair of tubes): 47.7-48.6°C Elemental analysis (C
1, H220) Calculated value (chi): C77,58H13,02 actual value (%
): C77,32H12,92IR (thin film, α-1)
: 3460(νO)I) 2950.2920.2860(νCH)l H-NM
R (C1χ, solvent, TMS internal standard, δ): 3.02
(〉C!:0H0IH,d, J a=6.0Hz )
1.70 (CH-OH, IH, d, J-6,0Hz
)1.47 [-(CI(,), +, 8H,s
) 1.00 and 0.97 (Peyo, 12H, 8) MS (
Relative Intensity) The results of gas mass measurement using a capillary column (Methyl silicon, Column length 25 m, manufactured by Hewlett-Paracard) are shown below.

170 (M, 4), 109 (25), 96 (24),
85 (27), 82 (100), 81 (20), 69 (
21), 55(21), 43(20), 41(18) Example 2 1.2.2.7.7-pentamethylcyclohebutane-1
-Synthesis of all: Magnesium Z90? Add 23.90 S' (0,16 rnoA ) of methyl iodide to a mixture of (0,12 mo, e)/20 m of dry ether while stirring under water cooling.
A mixed solution consisting of /dry ether lQ+uJ was added dropwise over a period of 1 hour. After stirring this mixture at room temperature for 48 hours, it was separated and added to this p solution at room temperature with stirring at 2°2.7.
7-Titramethylcycloheptanone 16,80 S'
(0,10mo, 13) / Dry Aete A, 30
A mixed solution consisting of M was added dropwise over 30 minutes. This mixture was stirred at room temperature for 48 hours. Thereafter, the reaction mixture was treated in the same manner as in Example 1 to obtain the above compounds 10 and 20 t (yield: 55.3%). It was a white solid.

Boiling point: 102℃/10℃ Melting point (in a sealed tube): 8℃7℃ Elemental analysis (Ctt) as 1mO) Calculated value (ch): C7 & 20 Hlfu12 actual value (→
, C77,921 (13,011R (thin film, 100-1)
: 3650, 3550 (+10H) 2950, 2920.2860 (νCH) 1) 1-NM
R (CDCB, solvent, TMS internal standard, δ): 2.03
~1.35 (Becliri 44-l8H1) 1.20 (
→ IFL, s) 1.00 and 0.98 (-CH,, 12H, s) M
S (Relative Intensity) The results of gas mass measurement using a capillary column (same as in Example 1) are shown below.

184 (M, 2), 99 (33), 95 (22), 8
6 (27), 83 (16), 82 (100), 69 (2
0), 55(20), 43(25), 41(16) Example 3 Synthesis of 1-ethyl-2,2,7,7-titramethylcyclohebutan-1-ol: Lithium 4.30? (0,62 moA) / ethyl bromide a 3.30 ? (0,4omo-6)
A mixed solution of 4 Qit/dry ether was added dropwise over a period of 2 hours. 40IILt of dry ether was added and the temperature was raised to 0°C. This mixture was distributed from house to house, and this P solution was poured into 2, 2,
7゜7-titramethylcyclohebutanone 15.00p (
The mixture was added dropwise to a mixed solution of 0.0,09 mob)/dry ether 40- over a period of 30 minutes while stirring at 0°C. This mixture was stirred at 0°C for 2 hours. Thereafter, the reaction mixture was treated in the same manner as in Example 1 to obtain the above compound t 3.50 ? (
A yield of 7664 cm) was obtained. This substance was a colorless and transparent liquid with a woody, earthy, and patchouli-like aroma.

Boiling point: 108℃/5++ua HS' elemental analysis (C
, 3H, 8O) Measurement value (%): C7B, 72 i (13, 21
Actual measurement value t%): C78,401 (13,32ILL
(Liquid film + Cfn-'): 3650, 3600 (ν01() 2950, 2920.2860 (&'cH) + 14-N
MR (CDC4g medium, fle4 quasi in TMS, δ): 2.
00-1.38 (-cljs-, 10H, m)1.
26 (-0 IH, s) 1.15-0.77 (-CH,, 15H, m) MS
(Relative intensity) The results of gas mass measurement using a capillary column (same as in Example 1) are shown below.

198 (M, 0.4), 113 (42), 100 (
92), 95 (49), 85 (28), 82 (100)
, 69(45), 55(42), 43(31), 41(
27) Example 4 Synthesis of 1-n'-propyl-2,2,7,7-titramethylcyclohebutan-1-ol: 1-allyl-2,2
,7,7-tetramethylcycloheptan-l-ol 1
5.00? (0,09moJ3), 5wt%Pd
/C1,0O5' (0,33 wt% Pd), 20 rnl of n-hexane are added into the autoclave. After replacing the air in the autoclave with nitrogen, the autoclave is pressurized to 50 atmospheres, and then the autoclave is heated to 50° C. and stirred. The reaction ends when gas absorption stops. During this time,
It took about 2 hours. Cool the autoclave to room temperature,
After returning to normal pressure, remove the contents. This was concentrated and fractionated to give the above compound 11.90% (yield 77.6%)
I got it. This substance was a colorless and transparent liquid with a woody, earthy, and patchouli-like aroma.

Boiling point: 117°C75=, Hy Elemental analysis (CI41 (as 280) Calculated value (%): C79,18) I 13.29 Actual H Direct (%): C78,85i (13, LIIR (liquid film, cm -' ): 3650, 3600 (Si0l-1) 2960, 2920.2860 (νCH)' H-NM
R (CDCQ s solvent, TMS internal standard, δ).

zo 5~1.4 a (-Ck3.-, 12H, m
)1.32 (-〇!L 1 kl, s )1.13
~0.80(-C4,15)L, m) The results of gas mass measurement are shown in the following 4c.

+ 212 (M, 0.5), 127 (41), 114 (
82), 95 (50), 82 (100), 71 (47)
, 69 (47), 55 (37), 43 (41), 41 (
29) Example 5 Synthesis of l-n-butyl-2,2,7,7-titramethylcyclohebutan-1-ol: 2.2,7.7-titramethylcyclohebutanone 16.80 ? (0,10m
ot3)/100 ml of dry ether at a concentration of 1.6 man/1 while stirring at -5°C.
3 n-butyllithium/n-hexane solution 7 Q m
l (Q, l l moJ3 n -BuLi) was added dropwise over a period of 30 minutes. The mixture was stirred at -5°C for 1 hour. Thereafter, the reaction mixture t was treated in the same manner as in Example 1 to obtain the above compounds xs and oot (yield 70.7).

This substance was a colorless and transparent liquid with a woody, earthy, and grassy aroma.

Boiling point: 128℃/4-day elemental analysis (as C+sHy+0) Calculated value (chi): C79,58H13,36 actual value (
%): C79,63)113.28IRC liquid film 1
/'FF+-'): 3650, 3600 (ν0)1
) 2960, 2920.2860 (1/CH) 1) (-N
MR (CDC (3, solvent, TMS internal standard, δ): 2.
05-1.42 (-CH, +, 14H, m) 1.32
(-CHJ, 15 H, m) 1.20~0.80
MS (Relative Intensity) The results of gas mass measurement using a capillary column (same as in Example 1) are shown below.

226 (M, 0.4), 141 (37), 128 (6
7), 95 (49), 85 (39), 82 (100),
69 (49), 57 (46), 55 (34), 41 (3
0) Example 6 +l) Pine type mixed fragrance: Jubube lemon oil California 40
Pine needle oil 100
In-bornyl acetate 4
0 Lavender oil Mont Blanc 40/42
50 benzyl acetate
40 citronellol
60 geraniol
40 phenylethyl alcohol
100p-tert-butyl α-methyl
50 Hydrocinnamic Qualdehyde Ionone 100% 50
Hexyl cinnamic aldehyde 60
Acetyl cedrene 150
Pachylily oil 10 Cuyuline 30 Musk ketone 60
900 parts of the compound of the present invention 1,2°2.7.
7-pentamethylcyclohebutan-1-ol 100
By adding this amount, a research fragrance was obtained that had a stronger pine-like aroma, increased freshness, and had a patchouli-like euphoric effect.

(2) Preparation ingredients for cream: Chokeibu Bergamotu Oil Italy 60
Ylang-ylang oil 1 40
miyuge base 200
Phenylethyl alcohol 40
rose base 100
Methyl dihydrdiasmonate 80
Hexyl cinnamic aldehyde 100
jasmine base 4
0 Shibres oil 2
0γ-methylionone
60 Vetiveryl Acetate 94 Acetyl Cedrene 4
0 Sandal Oil Mineol 2
0 Oris concrete 8%
5 musk ketones
40 pentalides
10 Add the compound of the present invention l-ethyl-2,2,7,7-titramethylcyclohebutane-1 to 950 parts of the above blended fragrance.
- By adding 50 parts of all, a blended fragrance was obtained in which the elegant Utsuddy tone of Nokuturi was enhanced.

that's all Procedural amendment (voluntary) February 25, 1986

Claims (1)

[Claims] 1. General formula (III) ▲There are numerical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) 2 , 2,7,7-tetramethylcycloheptan-1-ols. 2. General formula (III) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (III) (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) 2,2,7,7 represented by - A fragrance composition containing tetramethylcycloheptan-1-ols.