JPH0637410B2 - 7,7-Dimethyl-9-hydroxymethylbicyclo [4.3.0] nonane and fragrance composition containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides the following formula (I): The present invention relates to 7,7-dimethyl-9-hydroxymethylbicyclo [4.3.0] nonane represented by and a perfume composition containing the same.

[Conventional technology]

Conventionally, some aroma compounds are known as compounds having a bicyclo [4.3.0] nonane skeleton. For example, 2-hydroxy-7,7,8,9,9-pentamethylbicyclo [4.3.0] non-1 (6) -ene is earth-like,
Having a woody odor (US Pat. No. 3,636,165), 1-hydroxy-7,7,8,9,9-pentamethylbicyclo [4.3.0] nonane is a patchouli-like, camphor-like Has a fragrance, 1-hydroxy-7,7,8,9,9-
Pentamethylbicyclo [4.3.0] non-5-ene is known to have a musk-like, patchouli-like, and earthy aroma.

[Problems to be Solved by the Invention]

However, since the aroma of a compound is generally completely different due to a slight difference in structure, it is extremely important to synthesize various compounds and study their aroma in order to obtain a new perfume.

[Means for Solving the Problems]

Under such circumstances, the present inventors have synthesized various compounds having a bicyclo [4.3.0] nonane skeleton, evaluated the aroma and examined the use of the perfume, and the compound represented by the above formula (I) was obtained. 7,7-Dimethyl-9
The present invention has been completed by finding that -hydroxymethylbicyclo [4.3.0] nonane has an excellent fragrance and is useful as a perfuming ingredient for perfumes.

That is, the present invention is 7,7-represented by the above formula (I).
Dimethyl-9-hydroxymethylbicyclo [4.3.
0] to provide nonane. 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:
1,1-dimethyl-3-hydroxymethylindane (I
I) can be easily synthesized by catalytic hydrogenation using a metal catalyst in the presence or absence of a solvent.

The compound (II) as a starting material can be produced according to the following reaction formula, for example, by the method described in Japanese Patent Application No. 63-265017 filed by the present applicant.

(In the formula, R represents an alkyl group) First, phenylacetonitrile (III) and methallyl chloride (IV) are reacted in the presence of a phase transfer catalyst to give 4-methyl-2-phenyl-4-pentenenitrile (V ) Is synthesized. Examples of the phase transfer catalyst include triethylbenzylammonium chloride, tetra-n-butylammonium bromide and the like. Phenylacetonitrile used (III)
Is preferably 1 to 10 equivalents, especially 2 to 10 equivalents based on methallyl chloride (IV), and the amount of the phase transfer catalyst is 0.001 to 0.1 equivalents based on methallyl chloride (IV), particularly 0.005 to 0.0 equivalents.
5 equivalents are preferred. The reaction is preferably carried out in the presence of water and caustic in the temperature range of 5 to 50 ° C, particularly 5 to 30 ° C.

Next, an acid such as dilute hydrochloric acid or dilute sulfuric acid is caused to act on the nitrile (V) to carry out hydrolysis and cyclization reaction all at once in a single operation to obtain 4,4-dimethyl-2-phenyl-4-butanolide. (VII) is synthesized. The reaction can be carried out without using a solvent, but may be carried out using, for example, alcohols such as methanol and ethanol, organic acids such as acetic acid and formic acid, and the like.

Next, lactone (VII) is reacted with a Lewis acid such as aluminum chloride or aluminum bromide to synthesize 3-carboxy-1,1-dimethylindane (VIII). The amount of Lewis acid used is preferably 0.1 to 3.0 equivalents, particularly 1.0 to 3.0 equivalents, relative to the intermediate lactone (VII).
As the organic solvent used in the above reaction, dichloromethane, 1,2-dichloroethane, chloroform and the like can be preferably mentioned. The reaction temperature is preferably 0 to 50 ° C, particularly preferably 0 to 40 ° C.

To obtain (II) from carboxylic acid (VIII), for example, it is produced by reducing carboxylic acid (VIII) with a reducing agent in an ether solution such as diethyl ether or tetrahydrofuran, preferably lithium aluminum hydride or the like. it can.

As another method for obtaining (II) from carboxylic acid (VIII), for example, carboxylic acid (VIII) and alcohols such as methanol and ethanol are heated under reflux in the presence of an acid such as sulfuric acid and p-toluenesulfonic acid. , 3-alkoxycarbonyl-1,1-dimethylindane (IX), and then subjecting this to catalytic hydrogenation reaction in the presence of a copper-chromium or copper-zinc catalyst. Although the hydrogenation reaction can be carried out without using a solvent, for example, saturated hydrocarbons such as n-hexane and alcohols such as methanol and ethanol may be used.

The amount of the catalyst used is preferably 1 to 20% by weight with respect to the ester (IX), and the reaction hydrogen pressure is preferably 20 to 150 atm. The reaction temperature may be usually in the range of 80 to 300 ° C., but particularly 150 to 2 from the viewpoint of reaction time and formation of by-products.
50 ° C is preferred.

Next, examples of the metal catalyst used in the catalytic hydrogenation reaction from the compound (II) to the compound (I) of the present invention include transition metal catalysts such as platinum oxide, Raney nickel and ruthenium carbon. The amount of the metal catalyst is preferably 1 to 20% by weight based on the aromatic alcohol (II). When an organic solvent is used, for example, n
-Saturated hydrocarbons such as hexane and alcohols such as methanol and ethanol are used. The hydrogenation reaction is
For example, reaction temperature 80 to 200 ° C., reaction hydrogen pressure 20 to 15
It can be easily carried out under a reaction condition of 0 atm.

After completion of the reaction, the compound of the present invention can be easily purified by, for example, distillation or column chromatography.
-Dimethyl-9-hydroxymethylbicyclo [4.3.
0] Nonane (I) is obtained.

The compound (I) of the present invention obtained as described above exists as a mixture of stereoisomers based on the hydrogenation reaction. Usually, the odor characteristics between isomers are considered to be slightly different, but if necessary, the isomer mixture can be separated into each isomer by a customary method such as precision distillation or high performance liquid chromatography. . However, when the compound (I) of the present invention is used as a fragrance, it is usually unnecessary to carry out this separation.

[Operation and effect of the invention]

The novel 7,7-dimethyl-9-hydroxymethylbicyclo [4.3.0] nonane (I) of the present invention has a flower-like, wood-like, mint-like persistent aroma, and therefore it is used alone. Can be used in or in combination with conventional perfume ingredients to prepare perfume compositions.

The perfume composition containing the compound of formula (I) thus obtained can be widely used as a perfume material for perfumes, soaps, shampoos, indoor air fresheners, detergents and the like.

〔Example〕

Next, the present invention will be described with reference to examples. Further, a method for producing a synthetic intermediate of the compound of the present invention will be shown as a reference example.

Reference Example 1 Synthesis of 4-methyl-2-phenyl-4-pentenenitrile (V): Mixed solution of 1580 g (13.5 mol) of phenylacetonitrile, 11.3 g (5.0 mmol) of triethylbenzylammonium chloride and 1200 m of 50% aqueous sodium hydroxide solution. While stirring vigorously, 410 g (4.5 mol) of methallyl chloride was added dropwise over 2 hours while maintaining the temperature range of 20 to 30 ° C. After completion of dropping, the mixture was stirred at the same temperature for 1 hour.
Water (1700 m) was added to this reaction mixture, and then the mixture was separated into an organic layer and an aqueous layer. The organic layer was washed twice with saturated saline (300 m), once with 10% aqueous hydrochloric acid (50 m), twice with saturated saline (100 m), and then dried over anhydrous sodium sulfate. Next, the solvent was removed from the organic layer, and 670 g (3.9 mol) of the desired product (V) was obtained by vacuum distillation.
(Yield 87% based on charged methallyl chloride).

Boiling point: 126-130 ° C / 10 mmHg MS (relative intensity) 171 (M ⁺ , 24), 154 (6), 143 (26), 129 (13),
116 (58), 103 (11), 89 (12), 77 (11), 55 (1
00), 39 (29) IR (neat, cm ^-1 ) 3084, 2924, 2244, 1652, 1498,
1456,902,754,700 ¹ H-NMR (CDCl ₃ solvent, TMS internal standard, δ) 7.32 (5H, s), 5.0 to 4.7 (2H, m), 3.92 (1H, t, 8), 2.55 (2H ,
d), 1.77 (3H, s) Reference Example 2 4,4-Dimethyl-2-phenyl-4-butanolide (VI
Synthesis of I): 385 g (2.2 mol) of 4-methyl-2-phenyl-4-pentenenitrile (V) in 530 m of water, and 3
The mixture was heated under reflux in 90 m of concentrated sulfuric acid for 3 hours. Return to room temperature,
After water (900 m) was added, the generated white crystals were filtered by suction. This crystal was washed twice with hexane (500 m),
After washing twice with warm water (500 m), the solvent was removed to obtain 300 g (1.6 mol) of the desired product (VII). Yield 7
0%.

Melting point: 66.0 to 66.8 ° C MS (relative intensity) 190 (M ⁺ , 2), 175 (6), 146 (M ⁺ -CO ₂ , 54), 131
(100), 116 (6), 104 (16), 91 (34), 77 (12),
51 (12), 43 (83) IR (KBr tablet, cm ^-1 ) 2984, 1776, 1378, 1264, 1142
958,706,692 ¹ H-NMR (CDCl ₃ solvent, TMS internal standard, δ) 7.35 to 7.20 (5H, m), 4.00 (1H, dd, 9,12), 2.53 (1H, dd, 9,1)
3), 2.18 (1H, dd, 12,13), 1.49 (3H, s), 1.44 (3H, s) ¹³ C-NMR (CDCl ₃ , TMS, δ) 176.2 (s), 137.3 (s), 128.6 (d), 128.0 (d), 127.2 (d),
81.8 (s), 46.7 (d), 43.7 (t), 28.7 (q), 26.7 (q) Reference Example 3 Synthesis of 3-carboxy-1,1-dimethylindane (VIII): 164 g of anhydrous aluminum chloride (1.23 mol) ) 1,2-
117 g of 4,4-dimethyl-2-phenyl-4-butanolide (VII) was added to a dichloroethane (200 m) solution.
(0.615 mol) of 1,2-dichloroethane (200m
) The solution was added over 1 hour under ice cooling. After stirring for an additional 2 hours, pour into ice water (1000 m) and add chloroform (50 m).
0 m). The organic layer was washed twice with water (500 m) and then dried over anhydrous sodium sulfate. Then, the solvent is removed from the organic layer, and the target product (VIII) 96 is obtained by vacuum distillation.
g (yield 82% based on the charged lactone) was obtained.

Boiling point: 152-153 ° C / 3 mmHg MS (relative intensity) 190 (M ⁺ , 44), 175 (100), 145 (26), 129 (7)
0), 115 (15), 91 (11), 77 (7), 63 (5), 51
(7), 39 (6) IR (liquid film, cm ^-1 ) 3028, 2960, 1710, 1482, 1418,
1306, 1228, 928, 762 ¹ H-NMR (CDCl ₃ solvent, TMS internal standard, δ) 12.07 (1H, br s), 7.40 (1H, d, 7), 7.3 to 7.1 (3H, m), 4.13
(1H, t, 8), 2.32 (1H, dd, 8,13), 2.23 (1H, dd, 8,13), 1.38
(3H, s) 1.23 (3H, s) ¹³ C-NMR (CDCl ₃ solution, TMS, δ) 180.9 (s), 152.4 (s), 138.4 (s), 128.0 (d), 126.8 (d),
125.0 (d), 122.3 (d), 47.8 (d), 44.1 (t), 43.5 (s), 29.
5 (q), 29.0 (q) Reference Example 4 1,1-Dimethyl-3-hydroxymethylindane (I
Synthesis of I): [A] 25 g (0.66 mol) of lithium aluminum hydride
In an ether (300 m) solution of 3-carboxy-1,
A mixed solution of 100 g (0.53 mol) of 1-dimethylindane (VIII) and ether (300 m) was added dropwise over 1 hour under ice cooling. After the dropping was completed, the mixture was gently heated to reflux for 1 hour. Next, 25 m of water, 25 m of a 15% aqueous sodium hydroxide solution and 75 m of water were sequentially added to this reaction mixture to crush the excess lithium aluminum hydride. The white precipitate that had formed was removed by suction filtration, and the filtrate was distilled under reduced pressure to obtain 89 g (0.51 mol) of the desired product (II). Yield 96%.

Boiling point: 108 ° C / 2.5 mmHg MS (relative intensity) 176 (M ⁺ , 28), 161 (12), 145 (100), 143 (2
9), 128 (23), 117 (13), 105 (6), 91 (11),
77 (5) IR (liquid film, cm ^-1 ) 3370, 2956, 2866, 1482, 1026
759,744 ¹ H-NMR (CDCl ₃ , TMS, δ) 7.3 to 7.1 (4H, m), 4.0 to 3.8 (2H, m), 3.41 (1H, m), 2.13 (1
H, dd, 7,12), 1.78 (1H, dd, 7,12), 1.54 (1H, br, s), 1.36
(3H, s) 1.21 (3H, s) ¹³ C-NMR (CDCl ₃ , TMS, δ) 153.2 (s), 142.4 (s), 127.2 (d), 126.4 (d), 123.8 (d),
122.3 (d), 66.1 (t), 44.9 (d), 44.9 (t), 43.0 (s), 29.9
(q), 29.3 (q) [B] (1) 3-carboxy-1,1-dimethylindane (VIII) 100 g (0.53 mol) was added to methanol (60 m
) And dichloroethane (500 m) were added with sulfuric acid (1.5 m) as a catalyst, and the mixture was heated under reflux for 10 hours. After allowing to cool, it was diluted with water and the organic layer was separated.
This was washed with an aqueous solution of sodium hydrogen carbonate, dried to remove the solvent, and distilled under reduced pressure to obtain 1,1-dimethyl-3-methoxycarbonylindane (IX) 103 g (0.50 mol).
Got

Yield 95%.

Boiling point: 118 ° C / 5 mmHg MS (relative intensity) 204 (M ⁺ , 40), 189 (71), 157 (12), 145 (7
6), 130 (21), 129 (100), 128 (17), 115 (1
2), 91 (8) IR (liquid film, cm ⁻¹ ) 2956, 1743, 1482, 1167, 762 ¹ H-NMR (CDCl ₃ solvent, TMS, δ) 7.4 to 7.1 (4H, m), 4.10 (1H , t, 8), 3.75 (3H, s), 2.31 (1H,
dd, 8,13), 2.19 (1H, dd, 8,13), 1.37 (3H, s), 1.21 (3H, s) ¹³ C-NMR (CDCl ₃ , TMS, δ) 174 (s), 152 ( s), 139 (s), 128 (d), 127 (d), 125 (d), 12
2 (d), 52 (q), 48 (d), 44 (t), 43 (s), 29.5 (q), 29 (q) (2) This 1,1-dimethyl-3-methoxycarbonylindane ( IX) 50 g (0.24 mol) and copper-chromium catalyst 5 g
The mixture was charged into a 100 m autoclave. After replacement with hydrogen, the initial hydrogen pressure was set to 100 kg / cm ² and the temperature rise was started. Thirty minutes after the start of heating, the reaction temperature reached 230 ° C.
The absorption of hydrogen ceased after 8 hours at the same temperature. After cooling, the pressure was returned to normal pressure and the catalyst was filtered off. By distilling this filtrate under reduced pressure, 35 g (0.20 mol) of the desired product (II) was obtained. Hydrogenation reaction yield 82%.

Example 1 Synthesis of 7,7-dimethyl-9-hydroxymethylbicyclo [4.3.0] nonane (I): 1,1-Dimethyl-3-hydroxymethylindan (I
I) 11.3 g (64 mmol), catalyst 5% ruthenium carbon hydrous product 3 g (manufactured by Engelhard) and ethanol 30 m were charged in a 100 m autoclave. After replacement with hydrogen, the initial hydrogen pressure was set to 100 kg / cm ² and the temperature rise was started. One hour after the start of heating, the reaction temperature reached 140 ° C. The absorption of hydrogen ceased after 7 hours at the same temperature. After cooling
The pressure was returned to normal pressure, and the catalyst was filtered off. The filtrate was distilled under reduced pressure to obtain 9.7 g (53 mmol) of the desired product (I). (Yield 83%). As a result of capillary gas chromatography analysis, this compound was a mixture containing two peaks with an area ratio of 59:41 as a main component.

Boiling point: 97 ° C / 0.9 mmHg Elemental analysis (as C ₁₂ H ₂₂ O): Analytical value (%) C 79.10 H12.18 Calculated value (%) C 79.06 H12.16 MS (relative intensity): [59% peak of main component] ] 167 (2), 164 (3), 149 (100), 123 (41), 1
08 (92), 95 (55), 81 (50), 69 (56), 55 (37),
41 (51) [Principal component 41% peak] 167 (10), 164 (3), 151 (37), 126 (35), 1
08 (100), 95 (57), 82 (69), 67 (60), 55 (3
9), 41 (54) IR (liquid film, cm ⁻¹ ): [mixture] 3340, 2940, 2873, 1460, 1369,
1021 ¹ H-NMR (CDCl ₃ , TMS, δ): [mixture] 3.7 to 3.4 (2H, m), 2.35 to 2.0 (3H, m), 1.85 to 1.15 (11H,
m), 0.98 (3H, s), 0.92 (3H, s) Example 2 Rose type compounded fragrance: (parts by weight) Hexanol 40 Rose oxide 5 Citral 5 l-Mentone 10 Stellalyl acetate 30 Geraniol 100 Citronellol 200 Phenylethyl alcohol 390 Eugenol 20 γ-Methylionone 50 Guiac Wood Oil 50 Total 900 By adding 100 parts of the compound (I) of the present invention to 900 parts of the above-prepared perfume, a fresh and natural sweetened rose-type perfume is obtained. Was given.

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Claims (2)

[Claims] 1. The following formula (I) 7,7-Dimethyl-9-hydroxymethylbicyclo [4.3.0] nonane represented by 2. A fragrance composition containing 7,7-dimethyl-9-hydroxymethylbicyclo [4.3.0] nonane according to claim 1.