JPH02282339A - Ketones and alcohols - Google Patents

Abstract

NEW MATERIAL:The compound of formula 1 (dotted line is none or single bond: Y is O or OH; R1 is H or 1-6C alkyl; R2 is 1-6C alkyl; R1 and R2 may together form tri- or tetra-methylene group) EXAMPLE:3,6,8,8-Tetramethylnon-3-en-2-one. USE:A formulation raw material for a perfumery substance or lasting perfumery composition emitting lasting ionone-like, woody, floral, olive-like, sandal-like, amber-like, sweety or powdery fragrance, etc. PREPARATION:The compound of formula (2)-2 which is one of the compound of formula 1 can be produced by condensing a compound of formula 4 with a compound of formula 3 in the presence of a catalyst in a solvent. The product can be converted to the compound of formula (2)-1, (1)-2 or (1)-1 belonging to the compound of formula 1 by the catalytic reduction in the presence of a catalyst or reduction with a metal hydride in a solvent or catalytic reduction with hydrogen in the presence of a catalyst.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention is a fragrance substance that has not been described in conventional literature. or represents a hydroxyl group (OH), R1 represents a hydrogen atom or an 01-C6 alkyl group, R2 represents a C2-C6 alkyl group, and R1 and R2 together represent a trimethylene group or a tetramethylene group. Relating to ketones and alcohols represented by

More specifically, the present invention is included in the above formula (A), and in the following formula (2) having an ionone-like aroma, the broken line, R3, and R2 have the same meanings as described above.

Included in the ketones represented by and the above formula (A),
In the following formula (1) having a sandal-like fragrance, the broken line, R
1 and R2 have the same meanings as described above.

Regarding alcohols represented by

(Prior Art) Ketones or alcohols are important components of mixed fragrances, and a large number of these compounds have been used as fragrances.

Among these compounds, compounds similar to the above formula (2) included in the formula (A) of the present invention include, for example, 2.
5, which can be obtained by condensation reaction of 2.5-trimedel-4-hexene l-al with acetone in the presence of a base.
, 5.8-) dimethyl-3, founonadien-2-one (see JP-A-62178539), and the like are known.

In addition, as a compound similar to the formula (1) included in the formula (A) of the present invention, for example, 4-methylundecane which can be obtained by reacting 2-methyl 2-pentenal and hexyl magnesium halide. -3-en-5-ol (see JP-A-58-128332) and the like are known.

(Problems to be Solved by the Invention) However, the above-mentioned conventionally proposed ketones and alcohols are not necessarily satisfactory in terms of fragrance or fragrance sustainability, and there are problems to be solved.

Therefore, as a result of intensive research to solve the above problems, the present inventors have provided a compound of the formula (A) that has excellent fragrance or fragrance persistence and has not been published in any conventional literature. What can be done, and the above formula (A) included in the above formula (A)
The compound of 2) has a long-lasting ionone-like odor, and the compound of formula (1) included in the above formula (A) has a long-lasting sandal-like odor, and is extremely useful as a fragrance substance. They discovered this and completed the present invention.

It is therefore an object of the present invention to provide compounds of formula (2) and formula (1) above, which have not been described in the prior literature and are useful as long-lasting ionone-like and sandal-like perfume substances.

(Means for Solving the Problems) According to the present invention, the compounds of formula (2) and formula (1) included in formula (A) are represented by R1 and R2 in the following formula (4).
has the same meaning as described above.

After obtaining the unsaturated ketones represented by the formula (2), the compound represented by the formula (2) 2 is subjected to a catalytic reduction reaction in the presence of a catalyst to obtain the unsaturated ketones represented by the following formula (2) included in the formula (2). 3, 5.
5-Trimethylhexanal is represented by the following formula (3) % formula % In the formula, R1 and R2 have the same meanings as described above.

A condensation reaction is carried out in the presence of a carbonyl compound represented by the following formula (2), which is included in the above formula (2), and R1 and R2 have the same meanings as described above.

It is possible to easily synthesize saturated carbons represented by:

By adopting another embodiment method, the above formula (2)
Formula (1) is obtained by reducing the compound of -2 with a metal hydride.
In the following formula (1) included in formula (1), R1 and R2 have the same meanings as described above.

It is possible to synthesize unsaturated alcohols represented by

Furthermore, by adopting another embodiment method, the above formula (
2) The compound of formula (2) which can be obtained by the present invention by subjecting the compound of -2 to a catalytic reduction reaction in the presence of a catalyst to obtain the following formula (1)-1% formula% included in the above formula (1) Compounds of formula (2)-2 and formula (2)-1 included, and further compounds of formula (
Formula (1)2 and formula (1)- included in the compound of 1)
The method for synthesizing compound 1 can be expressed, for example, as follows using a reaction formula.

In the formula, R1 and R2 have the same meanings as described above.

To easily synthesize saturated alcohols represented by the formula,
R1 and R2 have the same meanings as described above.

The method for synthesizing the compounds of formulas (2) and (1) of the present invention will be explained in detail below according to the above reaction formula.

The compound of formula (4), which is the starting material of the present invention, is a known compound and can be easily obtained on the market.

In the above reaction formula, from the compound of formula (4) to the compound of formula (2)-
Compound 2 can be easily synthesized by subjecting the compound of formula (4) to a condensation reaction with the compound of formula (3) in a solvent in the presence of a base.

The above condensation reaction can be carried out, for example, at a temperature range of about 10° C. to about 80° C. for about 1 hour to about 10 hours.

Specific examples of the alkyl group represented by R and R2 of the carbonyl group of formula (3) used in this reaction include methyl, ethyl, propyl, isopropyl, butyl,
Preferred examples include groups such as isobutyl, pentyl, impentyl, and hexyl. The amount of the compound of formula (3) to be used may range from about 1 mol to about 5 mol per 1 mol of the compound of formula (4).

Examples of the base used in the above reaction include potassium hydroxide, sodium hydroxide, barium hydroxide, lithium hydroxide, sodium methylate, and sodium ethylate. ) About 0.1 mol to about 2 mol is sufficient for 1 mol of the compound.

Furthermore, examples of the solvent used in the above reaction include methanol, ethanol, and water. A more preferable example of the amount of these solvents used is about 1 to about 20 times the weight of the compound of formula (4).

After completion of the reaction, the compound of formula (2) 2 can be obtained in good yield and purity by washing, drying, concentrating and, if necessary, purifying by means such as distillation, according to conventional methods.

Specific examples of the compound of formula (2) 2 that can be obtained as described above include, for example, 3,6°8.8-tetramethylnonan-3-en-2-one, 7,9.9- 1-limethyldecane-4-en-3-one, 4,7.9,9. −
Tetramethyldecane-4-en-3-one, 8,10.
10-trimethyl-5-undecen-4-one, 3,5
．． 5-trimethylhexylidenecyclopentanone, 3゜5.5-trimethylhexylidenecyclohexanone, 3
-Ethyl-6,8,8-1-rifthylnonane-3-ene-
2-one, 3-propyl-6,8゜8-trimethylnonan-3-en-2-one, 3-pentyl-6.8.8-
Trimethylnonan-3en-2-one, 5-ethyl-8
,10,10=trimethylundecane-5-ene-4-
More preferred examples include 9.11.11-trimethyldodecane-6-en-5-one, 11.13,134-trimethyltetradecan-8-en-7-one, and the like.

In the above reaction formula, to synthesize the compound of formula (2)=■ from the compound of formula (2)-2 which can be obtained as described above, for example, the compound of formula (2)=2 is mixed with a catalyst. This can be easily carried out by carrying out a catalytic reduction reaction in the presence of catalytic reduction.

=11 The catalytic reduction reaction can be carried out, for example, at a temperature range of about 0°C to about 1000°C, more preferably at about 0°C.
A range of about 80° C. is often employed. There is no particular restriction on the reaction time, and the end point of the reaction may be the point at which the theoretical amount of hydrogen has been absorbed. The hydrogen pressure can be, for example, in a range of about 5 kg/cm2 to about 50 kg/cm2, preferably about 10 kg/cm2 to about 30 kg/cm2.
Ranges of the order of kg/cm2 are often adopted.

Specific examples of catalysts used in the above reaction include Raney nickel, palladium-carbon, and Raney cobalt. The amount of these catalysts used can be changed as appropriate, but is preferably about 1 to about 30% by weight, more preferably about 5 to about 20% by weight, based on the compound of formula (2)-2.
It is about % by weight.

Further, the above reaction can be carried out in the presence of an organic solvent, and specific examples of the organic solvent used include methanol, ethanol, hexane, and toluene. There is no particular restriction on the amount of these organic solvents used, but the formula (2
)-2 in an amount of about 1 to about 50 times by weight.

After the reaction, the used catalyst was filtered off, the solvent was distilled off, and distillation was performed under reduced pressure to obtain the compound of formula (2)-1 in good yield.
It can be obtained with good purity.

Specific examples of the compound of formula (2) 1 that can be obtained as described above include 3,68.8-tetramethylnonan-2-one, 7,9°9-trimethyldecane-
3-one, 4,7.9°9-tetramethyldecane-3-
on, 8.10゜IO-trimethylundecan-4-one, 3,5゜5-trimethylhexylcyclopentanone, 3゜5.5-1-limethylhexylcyclopentanone, 3-ethyl-6,8 , 1-triphthylnonane-2one, 3-propyl-6,8,8-triphthylnonane-2-
on, 3-pentyl-6,8,8-trinotylnonane-2
-one, 5-ethyl-8゜10.10-trimethylundecane-4-one, 9.11,11-trimethyldodecane-5-one, 11.13.13-)limethyltetradecan-7one, etc. are preferably mentioned. be able to.

In the above reaction formula, the compound of formula (1)-2 can be synthesized from the compound of formula (2)-2 by employing another method.

The synthesis of the compound of formula (1)-2 can be carried out, for example, by synthesis of the compound of formula (2)-
Compound 2 may be subjected to a reduction reaction with a metal hydride in a solvent.

The above reaction can be carried out, for example, at a temperature range of about -30°C to about 100°C, preferably about O'C to about 50°C, for about 1 hour to about IO hours, preferably about 2 to about 5 hours. It can be carried out.

The types of metal hydrides used in the above reduction reaction are:
For example, sodium borohydride can be mentioned. The amount of the metal hydride to be used is in the range of about 0.25 mol to about 1 mol, preferably about 0.3 mol to about 0.5 mol, per 1 mol of the compound of formula (2)-2. be able to.

Furthermore, examples of the solvent used in this reaction include ethanol, methanol, water, diglyme, and the like. There is no particular restriction on the amount of these solvents used, but for example, about 1 to about 5
The amount may be about 0 times by weight, preferably about 5 to about 20 times by weight.

After the reaction is completed, the compound of formula (1)-2 can be obtained in good yield by washing, drying, concentrating, and distilling according to conventional methods.
It can be obtained with good purity.

Specific examples of the compound of formula (1)-2 that can be obtained as described above include, for example, 3,6°8.8-tetramethylnonan-3-en-2-ol, 7,9.9 −)
Riftyldecane-4-en-3-ol, 4,7.9.9
-tetramethyldecane-4-en-3-ol, 8.1
0.10 trimethyl-5-undecen-4-ol, 3
5.5-1-lymethylhexylidenecyclopentanol,
3,5.5-trimethylhexylidenecyclopentanol, 3-ethyl-6,8,8-1-dimethylnonan-3-en-2-ol, :l propyl-6,8,8-
Trimethylnonan-3-en-2-ol, 3-pentyl-6,8,8-tri]5 Methylnonan-3-en-2-ol, 5-ethyl-8
,10,IO-trimethylundecane-5en-4-ol,9. Preferred examples include 11-trimethyldodecane-6-en-5-ol, 11.13°13-trimethyltetradecan-8-en-7-ol, and the like.

Furthermore, by adopting another embodiment method, formula (2)
The compound of formula (1)-1 can be obtained from the compound of -2. The compound of formula (1)-1 can be synthesized by bringing the compound of formula (2)-2 into contact with hydrogen to perform a reduction reaction in the presence of a catalyst.

The above reaction can be carried out, for example, at a temperature range of about 50°C to about 250°C. Regarding the reaction time, the end point of the reaction may be the point at which the theoretical amount of hydrogen has been absorbed.

The hydrogen pressure can be, for example, in a range of about 20 to about 100 kg/cm 2 .

Specific examples of the catalyst used in the above-mentioned catalytic reaction include copper-chromium and Raney nickel. The amount of these catalysts used can be changed as appropriate, but
The amount is about 1 to about 30 times the weight of the compound of formula (2)-2.

In addition, examples of the types of solvents used in this reaction include Eva,
methanol, ethanol/lz, fi-7” lovanol,
Examples include improvisational tools. The amount of these solvents to be used is about 1 to
An example is about 50 times the weight.

After the reaction is completed, the used catalyst is filtered off, and then a compound of formula (1)-1 can be obtained using conventional separation means.

Specific examples of the compound of formula (1) 1 that can be obtained as described above include 3,6,8,8-tetramethylnonane-2-oat-7.9.9-)dimethyldecane-3-ol. ,4. ．． 7.9.9 Tetramethyldecane-3-oat 8,1010-trimethylundecane-4-o/
L-,'3,5゜5-trimethylhexylcyclopentanonomutsu 3゜5.5-to'J methylhexylcyclo, xanol, 3-ethyl-6,8,8-trimethylnonan-2=ol, 3-propyl-6,8,8-triphthylnonan-2-ol, 3-benzene 6.8°8-
Trimethylnonan-2-ol, 5-ethyl 8.10.
IO-trimethylundecane-4ol, 9,11.1
1-1 Limethyldodecane-5-ol, 11.13. l'
Examples include 3-trimethyltetradecan-7-ol.

In another embodiment, the compound of formula (2)-1 and the compound of formula (1)-2 can be easily reduced by reducing the compound of formula (1)-2, such as metal hydride reduction or catalytic reduction. 1 compound can be synthesized.

The compound of formula (2) of the present invention has an ionone-like, odor-like, floral-like, orris-like odor, and the compound of formula (1) has an odor such as sandal-like, amber-like, odor-like, sweet, border-like, etc. It retains aroma and has extremely long-lasting properties, and can be used by being added to various fragrance compositions. The amount of the compound of formula (A) to be added varies depending on the purpose or the type of fragrance composition, but for example, for boat fishing, approximately 0.001% of the total amount is added.
An example of the range is about 30% by weight.

Thus, according to the present invention, it is possible to provide an aroma and flavor imparting composition containing the compound of the formula (A) as an active ingredient, and using the composition, the compound of formula (A) can be used as an aroma and flavor component. Food and drink products characterized by containing the compound of formula (A), cosmetics and cosmetics characterized by containing the compound of formula (A) as an aroma component, and health care products characterized by containing the compound of formula (A) as an aroma component.・Can provide hygiene, medicine, etc.

For example, beverages such as fruit juice drinks, fruit alcoholic drinks, milk drinks, carbonated drinks, ice creams, sherbet, etc.
Frozen desserts such as popsicles; Japanese and Western sweets, jams, chewing gums, breads, coffee, cocoa,
Black tea, luxury goods such as tea; soups such as Japanese-style soups and Western-style soups; flavor seasonings, various instant beverages and foods, and various snack foods, etc., with appropriate amounts added to impart their unique aroma and flavor. We can provide products. In addition, it is suitable for imparting its unique fragrance to, for example, shampoos, hair creams, pomades, other hair cosmetic bases, hair creams, lipsticks, other cosmetic bases, and cosmetic detergent bases. We can provide cosmetics with added amounts. Furthermore, laundry detergents, disinfectant detergents, room air fresheners, and various other health and hygiene materials;
We can provide health, hygiene, and pharmaceutical products such as flavorings and flavoring agents to make it easier to take medicines.

The present invention will be described in more detail below with reference to Examples and Reference Examples (Example) Example 1 3.6,8.8-Tetramethylnonan-3-ene-2-
85% in the synthesis flask of [compound of formula (2)-2]
33 g (0.5 mol) of potassium hydroxide and 355 g of methanol were charged and stirred to dissolve. 180 g (2-5 mol) of methyl ethyl ketone are added to this at room temperature.

After the addition, 3.5.5-1-limethylhexanal is added dropwise for about 2 hours while stirring to react. After the reaction is complete,
The reaction was completed by further stirring for 1 hour. After the reaction was completed, the reaction product was neutralized with a 50% aqueous sulfuric acid solution, and then extracted.
After washing, drying, concentrating, and further purifying means such as distillation, 78 g of pure compound of formula (2) 2 was obtained.

Boiling point = 100°C ~ 105°O/lmmHg Yield: 80
% Examples 2 to 12 According to the method of Example 1, various carbonyls [formula (3
) with 3.5.5-trimethylhexanal to form the corresponding unsaturated ketones [formula (2:l-2
The compound] was synthesized. The results are shown in Table-1.

Table-1 Example 13 3.6,8.8-tetramethylnonazine [Synthesis of compound 1 of formula (2)-1] 3.6,8.8-tetramethylnonane-3 -en-2-one 20g (0,1
mol), 2.0 g of Raney nickel catalyst, and 80 ml of methanol. After replacing the inside of the autoclave with nitrogen gas, the initial pressure of hydrogen was 30 kg/cm 2.50
The reduction reaction is carried out by contacting at °C for 5 hours. After the reaction is complete,
Cool, drain, filter, and concentrate. The resulting residue was distilled to obtain 18 g of pure compound of formula (2)=1.

Boiling point = 85°0-88°O/lmmHg Yield: 90% Examples 14-24 According to the method of Example 13, various compounds of formula (2) 2 were subjected to catalytic reduction reaction to obtain the corresponding formula ( 2)-1 saturated ketones were synthesized. The results are shown in Table 2.

Table Example 25 3.6,8.8-Tetramethylnonan-3-ene-2-
Synthesis of All [compound of formula (1)-2] 2.0 g of sodium borohydride (0.05
molar) and 50 ml of 95% ethanol. 3.6, 8.8 in 30 minutes under ice water cooling (5 to JO'C)
-Tetramethylnonan-3-en-2-one 20g (o
, 1 mol) of ethanol solution is added dropwise. After the dropwise addition is completed, the mixture is stirred for an additional 2 hours to react. After the reaction is complete,
Pour the reaction into water and extract with ether. The ether layer was washed, dried and concentrated, and the residue was distilled to obtain pure formula (1)-
17 g of compound No. 2 was obtained.

Boiling point = 100 ° C ~ 103 ° O / l mmHg yield:
85% Examples 26 to 36 According to the method of Example 25, the compound of formula (2)-2 was reduced with a metal hydride to synthesize the corresponding unsaturated alcohol of formula (1)-2. The results are shown in Table-3.

Table 3 Example 37 Synthesis of 3.6,8.8-tetramethylnonan-2-ol [compound of formula (1)-1] 3.6,8.8-tetramethylnonane-3 was placed in a 300 ml autoclave. -en-2-one 20 g (0.1 mol), copper-chromium catalyst 2.0 g 585% potassium hydroxide 4
0 mg and 40 ml of isopropyl alcohol. Thereafter, the inside of the autoclave was replaced with nitrogen gas, and a contact reaction was carried out at 180° C. for 4 hours at an initial pressure of hydrogen gas of 50 kg/cm 2 . After the reaction is completed, it is cooled, drained, filtered, and concentrated.

The obtained residue was distilled to obtain 1.8 g of pure compound of formula (1)-1.

Point: 92°0-94°C/lmmHg Yield: 88% Examples 38 to 48 According to the method of Example 37, various compounds of formula (2) 2 were subjected to a catalytic reduction reaction to obtain the corresponding formula (1)-1 saturated alcohols were synthesized. The results are shown in Table 4.

Table 4 (Reference example) Reference example 1 The following ingredients were used as a 0-'s type blended fragrance composition (
parts by weight) were mixed.

Phenylethyl alcohol 200 Geraniol 50 Heli No. 1 Lopine 20 Citronellol
10 nerol
100 hydroxy citronellol
30 Methyl phenyl carbinyl acetate 25 Geranium oil 10 Linalool 30 Benzyl acetate 35 Benzyl alcohol
20 Rose Phenon
10 rhodinol
280 rose oil I
Oβ-Ionone 50 Benzyl Salidilate 40 Cyclobentadecatulide 30 Guayaud
50 Total 1000 A new rose formulation composition was prepared by mixing 4 g of 3.6,8.8-tetramethylnonan-3-en-2-one with 96 g of the above composition. This new blended composition and the above-mentioned rose blended fragrance composition to which the compound was not added were compared by 10 expert panelists. As a result, all 10 expert panelists agreed that the newly formulated fragrance composition to which the compound was added had the characteristics of natural rose with an emphasized ionone-like aroma, and was significantly superior in terms of sustainability.

Reference Example 2 According to the method of Reference Example 1, various formulas (2
) were added to compare the changes in aroma. As a result, 8.10 10trimethyl-5-undecene-
4-one is Utsuday-like; 3, 5, 5. -Trimethylhexylidenecyclohexanone is floral-like; 3. a,
a, 8-tetramethylnonan-2-one had an ionone-like aroma with a 70-ral feel; 4,7,9.9-tetramethyldecan-3-one had an accentuated orris-like aroma with a 70-ral feel. A new long-lasting perfume composition was obtained.

Reference Example 3 The following components (parts by weight) were mixed as a Lira type blended fragrance composition.

phenylethyl acetate cinnamic alcohol terpineol cyclamen aldehyde heli otrobin cinnamyl acetate carnation linalool indole stylax resinoid ylang ylang hydroxycitronellal benzyl acetate anisaldehyde absolute jasmine phenylethyl alcohol anis alcohol bulk 3.6 to 93 g of the above composition; A novel perfume composition was prepared by mixing 7 g of 8.8-tetra7thylnonan-3-en-2-ol. This novel blended fragrance composition and the above-mentioned Lila blended fragrance composition to which the compound was not added were compared by a panel of 10 experts. As a result, all 10 expert panelists agreed that the newly formulated fragrance composition to which the compound had been added had an accentuated amber-like aroma, captured the characteristics of natural lyra, and was extremely long-lasting.

Reference Example 4 According to the method of Reference Example 3, various formulas (
Compound 1) was added and the change in aroma was compared and studied.

As a result, 4,7.9.9-tetramethyldecane-4-en-3-ol is sandal-like; 3.5.5-trimethylhexylidenecyclohexanol is wood-like; 3,
6゜8.8-Tetramethylnonan-2-ol is powder soy-like; 8,10.1O-t-riftylundecane-
4-All is sweet Ude-sama; 3,5.
5-1-limethylhexylcyclohexanol was used to obtain a novel blended fragrance composition with an accentuated and long-lasting amber-like aroma accompanied by a dull feeling.

(Effects of the Invention) The present invention provides ketones and alcohols represented by the formula (A) that have not been described in conventional literature.

The compound of the formula (2) included in the formula (A) has a long-lasting ionone-like, odor-like, 70-ral-like or oris-like aroma, or the compound of the formula (2) included in the formula (A) The compound (1) has a long-lasting sandal-like, amber-like, morning-like, sweet-like, or borderline-like odor, and is useful as a fragrance substance, and as a compounding material for a long-lasting fragrance composition. can be used.

Patent applicant: Hasegawa Fragrance Co., Ltd.

Claims (1)

[Claims] 1. The following formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (A) In the formula, a broken line indicates no bond or a single bond, and Y is a keto group (=O) or a hydroxyl group. (-OH), R_
1 represents a hydrogen atom or a C_1 to C_5 alkyl group, R_2 represents a C_1 to C_6 alkyl group, and R_1 and R_2 together represent a trimethylene group or a tetramethylene group. and alcohol.