JPS62270571A - 6-ethyl-5-oxatricyclo(4,2,1,03.7)nonane-3-carboxylic acid ester and perfume composition containing same - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R is lower alkyl). EXAMPLE:6-Ethyl-5-oxatricyclo[4,2,1,0<3.7>]nonane-4-carboxylic acid methyl ester. USE:Perfume. Showing tasty ester-like fruity aroma when R is methyl, showing fruity and spicy aroma when R is ethyl and showing mugwort-like green, floral and fruity aroma when R is n-propyl. PREPARATION:For example, 2-ethylidenebicyclo[2,2,1]heptane-5(or 6)-car boaldehyde shown by formula II and formaldehyde are subjected to Cannizzaro reaction to give a compound shown by formula III, which is subjected to ring formation to give a compound shown by formula IV, which oxidized to give a compound shown by formula V, which is further esterified to give a compound shown by formula I.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to 6-ethyl-5-oxatricyclo[4 ，
2,1,0) Nonane-3-carporic acid ester and a fragrance composition containing the same.

[Conventional technology and its problems]

Conventionally, bicyclo[2,2,1)heptanecarbaldehyde was subjected to Canitzaro reaction to obtain the following formula (I) [JP-A-5'
No. 1-45179] or formula (2) [JP-A-57-823
No. 30] is known to obtain a compound having a gem-bis(hydroxymethyl) structure.

However, there have been no reports to date that have investigated the usefulness of these compounds as tricyclic compounds.

[Failure to solve the problem]

Under such circumstances, the present inventor discovered that 2,2-bis(hydroxymethyl)-6-ethylidenebicyclo[2,2,1
The present invention was completed based on the discovery that a novel compound having a trinomial skeleton represented by formula (I) derived from heptane has an excellent aroma.

That is, the present invention provides a 6-ethyl-5-oxatrinculo[4,2,1°3.70]]nonane-3-carboxylic acid ester represented by the formula (■). The present invention further provides a fragrance composition containing the same.

The compound (I) of the present invention can be prepared, for example, according to the following reaction formula:
2-ethylidenebicyclo[2,2,1)butane-5(
The father is methylolated by subjecting 6)-rubaldehyde (II) to Canitzaro reaction with formaldehyde to produce 2,
2-bis(hydroxymethyl)-6-ethylidenebicyclo(2,2,1]hebutane (Ill), which was then cyclized under acidic conditions to give 6-ethyl-3-hydroxymethyl-5-oxatri cyclo[4,2,1,0)nonane (transformation), which is then oxidized to 6-ethyl-5
-oxatricyclo[4,2,1,0E nonane-3-carboxylic acid (V), and is produced by further esterifying this.

(II) (III) (
Vl) (IV) In formula 1, R represents the same as above) In addition, in the Canitzaro reaction between the compound of (I) and formaldehyde, in addition to the 6-ethylidene of formula (III), the compound of formula (M) However, in the next cyclization reaction, under the cyclization conditions for 6-ethylidene, 5-ethylidene is also produced.
Since cyclization of the ethylidene compound does not occur, there is no need to separate the two prior to the cyclization reaction, and the compound can be directly subjected to the reaction.

The reaction for obtaining (lft) from compound (II) is known and carried out according to this method. From compound (III) to (IV
) in the presence of an acid such as sulfuric acid or phosphoric acid,
It may be heated under reflux in a solvent such as isopropyl alcohol. Examples of the oxidizing agent used to obtain (V) from compound (fV) include chromic acid and potassium permanganate, and the reaction is carried out under oxidizing conditions known per se. compound m
The esterification of is carried out by a conventional method.

[Effect]

The compound (I) of the present invention has a fruit-like aroma; for example, the methyl ester C(I), R-methyl] has an astringent, ester-like fruity aroma; the ethyl ester C(I), R-methyl has a fruity aroma. = Eech] Ha fruity, spicy scent, n-propyl ester C (I), R = n
-Propyl] has a wormwood-like butane, floral, fruity aroma.

〔Effect of the invention〕

The compound (I) of the present invention can be widely used in products that require fragrance, such as high-grade fragrance compositions, perfumes, soaps, shampoos, hair rinses, detergents, cosmetics, sprays, and fragrances.

〔Example〕

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

Reference Example 1 2.2-bis(hydroxymethyl)-6-ethylidenebicyclo[2,2,1)heptane and 2,2-bis(hydroxymethyl)-5-ethylidenebicyclo[2,2,1
) Synthesis of hebutane: 2-ethylidenebicyclo[2,2,
1) Hebutane-5 (or 6)-rubaldehyde 300
．． 4y (2mot) and 37% formalin water bath solution 405
．． 5 r (5mat) and 480 g of methanol were stirred under a water bath, and 20% aqueous sodium hydroxide solution 16F was added. When the temperature was gradually returned to room temperature, the system became cloudy. 1
After 40 minutes, add 20% sodium hydroxide aqueous solution 1
84? was added dropwise at 10 minutes for 1 hour.

The internal temperature rose to 28°C. 50℃ for 20 hours after completion of dropping
The mixture was heated and stirred. Heating was stopped and the mixture was stirred again in an ice water bath.

Sodium borohydride 7,56 F (0,2 mol
) in 20% aqueous sodium hydroxide solution at 400 liters was added dropwise over 1 hour, and the mixture was stirred at room temperature for 1 hour. Extracted with ether three times. The ether layer was made acidic with 4N hydrochloric acid, washed with a saturated aqueous sodium bicarbonate solution and water, and then dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain crude product 3639 (yield 99.7%).

Boiling point: 101-118℃ 70.1 mHy Elemental analysis CI
IHII (calculated value as h (ch): c; 72.49, H; 9
．． 95 Actual value (%): C; 72.42, H:
10.00IR (NaCt, cm): 3305 (
OH), 3040 (vinyl group), 2950, 1450.
1375 (methyl group).

"H-NMR (δppm): 5.57-4.9 (I
H, m).

3.57 (4H, br, m), 3.17 (2H, br,
s, OH).

1.55 (3H, d, J-6Hz), 2.77-1.
0 (8H, m) MS (relative intensity): 182 (M”, 31
%), 151 (M-CH!OH, 24%), 79 (54
%), 57 (I00%) Reference Example 2 Synthesis of 6-nity-3-(hydroxymethyl)-5-oxatricyclo[4,2,1,0E nonane: 2.2-bis(hydroxymethyl)-5( or 6)-ethylidenebicyclo[2,2,1)hebutane 5'I (
27.4 mmot) was heated under reflux for 1 hour in 15-m water, 15-m isopropyl alcohol, and 5 v concentrated sulfuric acid.

It was poured into ice water and extracted with ether. The ether layer was washed with water, saturated aqueous sodium bicarbonate solution and water, and dried over anhydrous sodium sulfate. After distilling off the solvent, the title alcohol was isolated by silica gel column chromatography using hexane-ethyl acetate (2:1) as a solvent.

Yield: 1.58F (yield: 32%) Boiling point: 110°C/0.06 IJHy Elemental analysis: Calculated value as C1IH1aOt (c%): C: 72.49, H; 9.
95 actual value c%): C near 2.55, H; 9.80I
R (NaCt, CF++): 3400 (OH), 2
955°2875.1460.1375 (methyl group),
1020"H-NMR (δppm): 3.80 (IH,
d, J=8Hz) t3-62 (I H, d*J
-8H2) s 3-48 (2Hs broad s
s), 0.92 (3H, t, J-6H2), 3-0.5
(IIH.

m) MS (relative strength): 182 (M+, 100 chi), 1
51 (M-CHaOH, 63%), 57 (80%) Reference Example 3 6-ethyl-5-oxatricyclo[4,2,1°o3
．． 7) Synthesis of nonane-3-carboxylic acid: 200 t (2 mot) of chromic anhydride was added to 160 t of chromic anhydride while stirring on ice.
0 ml of acetic acid and 200 ml of water. Alcohol 90% obtained in Reference Example 2 was secreted in 200H acetic acid. (0.5 mot) was added dropwise while keeping the temperature below 5°C. After stirring for 2 hours at room temperature, it was stored overnight. 1.5 t of saturated saline was added and extracted with chloroform. The chloroform layer was extracted with a strongly alkaline sodium hydroxide water bath. The aqueous layer was made strongly acidic with hydrochloric acid and extracted with ether.

Etherno was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off and the residue was distilled under reduced pressure to obtain the title carboxylic acid.

Yield 52.77f (yield 55%) Boiling point 116-138°C/0.04 maHy Elemental analysis Calculated value as IH 603 c%): C: 67.32, H; 8.
22 actual measurement value (standard: C; 67.40, H; 8.
10IR (NaC1, cm): 2960, 2880
, 1700°3500-2150 1H-NMR (δppm): 9.42 (IH,s)
, 4.10 (I,H.

d, J-8H2), 3.78 (IH, d, J-8H2)
+1.58 (2H, Q, J=7H2), 093 (3H,
t, J=7 H2) + 2.7~o, 5 (8H+
m) MS (relative intensity): 196 (M+, 68%),
165 (33 chi).

151 (M -C0OH, 36chi), 81 (34chi)
, 79 (43chi), 77 (39%), 57 (I00%)
, 55 (37%), 41 (37%) Example 1 6-ethyl-5-oxatricyclo[: 4 , 2 ,
1゜3.7 03Methyl nonane-3-carboxylate (I,R=methyl)
Synthesis of: Carboxylic acid (I, R=H) obtained in Reference Example 3 15? (0
,077 mol) in 50-methanol of 0782 Tl! 4 sulfuric acid (0,008 mot) was added as a catalyst, and the mixture was heated under reflux for 10 hours. The solvent was concentrated, a small amount of water was added, and the mixture was extracted with ether. It was washed with saturated aqueous solution and water, and dried over anhydrous magnesium sulfate. The solvent was distilled off and the residue was distilled under reduced pressure to obtain the title compound.

Yield 12.96 f/ (yield 80%) Boiling point 136°C/
14 MHf Elemental analysis Calculated value as CIIH11108: c; 6 s, 55%, H: 8.6
3% actual value: c; 68.64%, H; 8.5
1% IR (NaCt, crn): 2970, 2880
,1725°1435.1360,1275,1220
, 1120°"H-NMR (δppm): 4.00 (I
H, d, J-8H2).

3.70 (IH, d, J=7H2), 3.65 (3H,
s).

1.55 (2H, Q, J-7Hz), 0.93 (3H,
t, J=7H2), 2.6~0.7 (8H, m
) MS (relative intensity): 210 (M+, 39%), 179
(31%).

151 (36 tai), 150 (51 tchi), 79 (45%)
.

77 (33), 57 (I00%) Example 2 6-ethyl-5-oxatricyclo (4,2,1°83
．． 7) Ethyl nonane-3-carboxylate +1. Synthesis of the ethyl ester (■) in the same manner as in Example 1.

R=ethyl) was synthesized.

Yield 84% Boiling point 136-137℃/14yHy Elemental analysis C13
Calculated value as H200a: C: 69.61%, H: 8.99% Actual value: c: 69.55%, H: 9.02%I
R(NaCt, cln): 2975.2890,17
30°1365.1280,1220,1120.10
40"H-NMR (δpI)m): 4.08 (2HtQ
, J-7Hz).

4.00 (IH, d, J-8Hz), 3.70 (IH,
d, J-8Hz), 1.55 (2H,q, J
=7Hz), 1.23(3)1°t, J-7H
z), 0.93 (3H, t, J=7Hz) +2.6~
0.5 (8H, m) MS (relative intensity): 224 (M+, 36%), 15
1 (49 chi).

150 (57%), 79 (50chi), 77 (33%).

57 (I00%) Example 3 6-ethyl-5-oxatricyclo[4,2,l].

3.7 0]]Nonane-3-carboxylic acid n-propyl I.

Synthesis of R=n-propyl): An n-propyl compound (I, R=n-propyl) was synthesized in the same manner as in Example 1.

Yield 82 cm Boiling point 148~b Elemental analysis Calculated value as Cx1HzOs: C: 70.56%, H; 9.30% Actual value: c; 70.51%, H; 9.30%I
R(NaCt, cyy+-”): 2970.288
0.1725.

1460.1375,1275,1220,1120°'H-NMR (δppm): 4.00 (2H, t, J=
6Hz).

4.03 (IH, d, J=7Hz), 3.72 (IH,
d, J=7H2), 0.93(6H,t, J-6Hz
), 2.6-1.2 (I2H, m) MS (relative intensity): 238 (M, 29%), 151
(59%).

150 (56%), 79 (51%), 77 (28%).

57 (I00%), 43 (36%), 41 (42%) Example 4 Bergamot base fragrance for fruity type shampoo 80 (parts by weight) Lemon base 100 Allyl heptanoate 10 Benzyl acetate 40 Citronellol 40 Citronellyl acetate 20 Geraniol 60 Phenylethyl Alcohol 100 Lilial (I
) 30 (parts by weight) Lyral (2) 40 Hexylcinnamic aldehyde 150 Methyl dihydrodiasmonate 40 γ-Methyl ionone 25 Acetyl cedrene 50 Bornylmethoxycyclohexanol 30 Galacturide (3
) 1o.

(50% diethyl phthalate solution) γ-undecalactone 5p-hydroxyphenylbutanone 20 benzoin resinoid 40 To 980 parts of the above blended fragrance, ethyl 6
-ethyl-5-oxatricycloC4,2,1,0'''
By adding 20 parts of E-nonane-3-carboxylate, a fruity-type shampoo fragrance with an increased fresh fruity feeling was obtained.

Note (I): Givaudan product name pt-butyl-a-methylhydrocinnamic aldehyde (2): IFFFF company name product name (4-hydroxy-4-methylhentyl)-3-cyclohexene-1-carboxaldehyde (3) a IFF company fishing product name 1.3,4,6,7.8-hexahydro-4,6,6
, 7,8,8-hexamethylcyclopenta-γ-2-benzopyran Written amendment (voluntary) June 17, 1985

Claims (1)

[Claims] 1. 6-ethyl-5-oxatricyclo represented by the following formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R represents a lower alkyl group) [4,
2,1,0^3^,^7] Nonane-3-carboxylic acid ester. 2. 6-ethyl-5-oxatricyclo[4,
2,1,0^3^,^7] A fragrance composition characterized by containing nonane-3-carboxylic acid ester.