JPH0212934B2 - - Google Patents

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention provides a novel formula () useful as a compounding agent for fragrances. The present invention relates to 1-allyl-2,2,7,7-tetramethylcycloheptan-1-ol represented by and a fragrance composition containing the same. [Prior Art] Conventionally, many useful fragrance compounds have been known in saturated or unsaturated alcohols [Osamu Okuda, "Fragrance Chemistry Overview ()", Hirokawa Shoten, No. 482-
681 pages (1980)]. [Problem to be solved by the invention] However, since the aromas of compounds are generally completely different due to slight differences in structure, it is difficult to synthesize various compounds and study their aromas. It is extremely important for obtaining new fragrances. [Means for Solving the Problems] As a result of intensive research to obtain a compound useful as a fragrance, the present inventors have newly synthesized a compound, 1-allyl-2, which has not been described in any literature.
2,7,7-tetramethylcycloheptane-1-
The present invention was completed based on the discovery that all () has a useful aroma. That is, the present invention provides a novel compound 1-allyl-
2,2,7,7-tetramethylcycloheptane-
The present invention provides 1-ol () and a fragrance composition containing the same. For example, 1-allyl-2,2,7,7-tetramethylcycloheptan-1-ol () of the present invention can be prepared using 2,2,7,7-tetramethylcycloheptanone according to the following reaction formula. It is produced by reacting () with a compound of formula (). (In the formula, M represents MgX or a lithium atom,
Here, X represents a halogen atom) The compound of formula (), which is a raw material for this method, can be easily prepared by reacting an allyl halide such as allyl bromide or allyl chloride with metal magnesium or lithium. Therefore, the reaction to obtain the compound () of the present invention can be carried out by preparing a compound of formula () and then adding the compound of formula () to it. The reaction can also be carried out by adding a solution of the compound and allyl halide to a reaction system containing metal magnesium or lithium, while producing the compound of formula () in the reaction mixture. The amount of the compound of formula () or allyl halide used is 1 equivalent or more relative to the compound of formula (),
Preferably it is 1.2 equivalents or more. As the solvent used in these reactions, solvents commonly used in reactions between ketone bodies and Grignard reagents or lithium reagents can be used, but ether-based solvents such as diethyl ether, tetrahydrofuran, and diglyme (dimethyl cellosolve) can be used. Solvents are preferred. The reaction time and reaction temperature vary depending on the solvent used, but are preferably 1 to 5 at room temperature to 100°C.
It's time. After the reaction is completed, 1- of the present invention is extracted from the reaction mixture.
In order to isolate and purify allyl-2,2,7,7-tetramethylcycloheptan-1-ol, conventional methods such as extraction, washing, and distillation are employed. Since the compound of the present invention obtained as described above has a woody, grassy, earthy, pachylily-like aroma, it can be blended into various bases to form useful fragrance compositions. be able to. [Function] The compound of the present invention obtained as described above has a woody, grassy, and earthy odor, especially a scent reminiscent of norpatiyulenol, which is an important aromatic component in pachylily oil. A perfume composition containing also has a similar odor. [Effect] Therefore, the compound of the present invention is excellent as a compounding material for various fragrances, and can be used in high-grade fragrance compositions, perfumes, soaps, shampoos, hair rinses, detergents, cosmetics, hair sprays, air fresheners, etc. It can be used in a wide range of applications where fragrance is required. [Example] Next, the present invention will be described with reference to Reference Examples and Examples. Reference Example 2 Synthesis of 2,2,7,7-tetramethylcycloheptanone (): Sodium amide (39.0% g, 1.0 mol) and toluene (400 ml) were added in this order, and the mixture was heated to reflux under a nitrogen atmosphere. A mixed solution of diisopropyl ketone (45.68 g, 0.4 mol)/1,4-dichlorobutane (50.80 g, 0.4 mol) was added dropwise to this mixture over 3.5 hours while stirring under heating under reflux. The mixture was stirred under heating under reflux for 5 hours. After cooling, water (200 ml) was added to the reaction mixture to separate the layers, and the organic layer was neutralized and washed with a 10% aqueous sulfuric acid solution (50 ml), then washed with a 10% aqueous sodium carbonate solution (50 ml), and further washed with a saturated brine solution ( 100ml) twice. The organic layer was dried over anhydrous magnesium sulfate, separated, concentrated, and fractionally distilled to obtain 34.43 g (yield 51.2%) of the above compound. Boiling point: 98℃/20mmHg Elemental analysis (as C ₁₁ H ₂₀ O) Calculated value (%): C78.51 H11.98 Actual value (%): C78.32 H11.89 IR (liquid film, cm ^-1 ): 2960, 2920, 2860 (ν _CH ) 1690 (ν _C=O ) ¹ H-NMR (CDCl ₃ solvent, TMS internal standard, δ): 1.60 ( -CH ₂ --, 8H, s) 1.16 ( -CH ₃ , 12H, s) MS (relative intensity) The results of Galamas measurement using a capillary column [Methyl silicon, column length 25 m, manufactured by Hewlett-Packard Co., Ltd.] are shown below. 168 (M ⁺ , 24), 83 (19), 81 (24), 70 (22), 69
(92), 57 (31), 56 (100), 55 (35), 43 (20), 4
1
(43) Example 1 Synthesis of 1-allyl-2,2,7,7-tetramethylcycloheptan-1-ol (): Equipped with a stirrer, dropping funnel, thermometer, reflux condenser, and nitrogen gas introduction tube Magnesium (5.37 g, 0.221 mol) was added to a 500 ml four-necked flask, and the moisture inside the vessel was removed by passing nitrogen gas. While stirring, a small amount of allyl bromide (1.5 g, 0.0124 mol)/dry diethyl ether (7.5 g) was added to the flask. ml) was added dropwise, and allyl bromide (21.29g, 0.176mol)/2,2,7,7- was added dropwise while cooling to below 15°C in an ice water bath.
Tetramethylcycloheptanone (24.68g,
A mixed solution of 0.147 mol)/dry diethyl ether (75 ml) was added dropwise over 2 hours. The mixture was stirred for 1 hour while maintaining the temperature below 15°C. The reaction mixture was poured into ice water, made weakly acidic with 1N aqueous hydrochloric acid solution, separated into layers, and the organic layer was washed with saturated aqueous sodium bicarbonate solution (50 ml), and then diluted with water (50 ml).
ml) three times. The organic layer was dried over anhydrous magnesium sulfate, separated, concentrated, and fractionally distilled to obtain 23.03 g (yield 74.5%) of the above compound. This substance was a colorless, transparent liquid with a woody, grassy, earthy, pachylily-like aroma. Boiling point: 115℃/5mmHg Elemental analysis (as C ₁₄ H ₂₆ O) Calculated value (%): C79.94 H12.46 Actual value (%): C79.75 H12.63 IR (liquid film, cm ^-1 ): 3580 (ν _OH ) 3080 [ν _CH (=CH-,=CH ₂ )] 2950, 2920, 2870 (ν _CH ) 1635 (ν _C=C ) 980, 920 [δ _CH (-CH=out-of-plane of CH ₂ ¹ H-NMR (CDCl ₃ solvent, TMS internal standard,
δ ): 6.31~5.61 ( _-CH2 - CH = _CH2,1H ,m) 5.15-4.88(-CH2 _- CH=CH2,2H,m) 2.43( -CH2 _- CH _{= CH2} ,2H,d,J=8.0
Hz) 2.02 _~ 1.20 [-( CH2 ) _4- , 8H, m and -O
H, 9H, m] 1.05 and 0.98 (-C H ₃ , 12H, s) MS (relative intensity) The results of gas mass measurements using a capillary column [Methylsilicon, Column length 25 m, Heuretz-Packard] are shown below. show. 210 (M ⁺ , 4), 111 (64), 95 (78), 82 (63), 81
(89), 71 (64), 69 (99), 55 (79), 43 (100), 4
1
(83) Example 2 Men's cologne fragrance composition: (parts by weight) 1-allyl-2,2,7,7-tetramethylcycloheptan-1-ol 150 cedryl acetate 150 acetylcedrene 150 vetiver oil 10 clove oil 20 Trimos absolute 40 Amber base 30 Castorium absolute 5 Calaxolide 50 ¹ ) 50 Celestride ²⁾ 50 Coumarin 30 Amyl salicylate 20 Diasmine absolute 20 Isobutylquinoline 1 Lavender oil 50 Undecylenic aldehyde 2 Ligustral3 ⁾ 3 Galbanum oil 2 Laurel oil 40 Gamma undecalactone 1 Nutmeg oil 10 Pine oil 30 Dipropylene glycol 96 850 1 Galaxolide 50: 1,3,4,6,7,8-hexahydro-
4,6,6,7,8,8-hexamethylcyclopent-γ-2-benzopyran2 Celestride: 4-acetyl-6-tert-butyl-1,1-dimethylindan3 Ligustral: 3,5 (or 2,4)-Dimethyl-3-cyclohexene-1-carbaldehyde The 1-allyl of the present invention is used as a fragrance for men's cologne.
2,2,7,7-tetramethylcycloheptane-
By adding 1-ol, it was possible to impart freshness, warmth and volume to the preparation.

Claims (1)

[Claims] 1 1-allyl-2,2,7,7-tetramethylcycloheptan-1-ol. 2. A fragrance composition containing 1-allyl-2,2,7,7-tetramethylcycloheptan-1-ol.