JPS6010006B2 - New fragrance composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to novel perfume compositions.

More specifically, the present invention relates to a fragrance composition containing a novel aldehyde. The novel aldehydes of the present invention have the following general formula (wherein R, R2 and R3 each represent a hydrogen atom or a methyl group)*.

Among the aldehydes of general formula 1, particularly preferred are the aldehydes of general formula (wherein R and R2 have the above meanings).

The aldehydes of general formula 1 have the general formula (wherein R and R2 have the above meanings, and R is 1 to 6
acetals of the general formula (representing an alkyl group having 5 carbon atoms) or phenol ethers of the general formula (in which R, R. and R2 have the meanings given above), It can be produced by reacting alkenol with an acidic catalyst.

C, ~C6 denoted by R in general formulas D and m
The alkyl group may be a straight or branched alkyl group such as a methyl, ethyl, propyl, isobropyl or hexyl group.

R preferably represents an ethyl group. Particularly preferred aldehydes of formula la from the fragrance point of view are alkenols of formula W (i.e., 2-methyl-3-buten-2-ol) in which R3 represents a hydrogen atom, and aldehydes of formula 0 in which R2 represents a hydrogen atom or a methyl group. acetanol or formula m
or b an alkenol of formula W in which R3 represents a methyl group (i.e. 3-
Methyl-1-penten-3-ol can be converted into an acetal of formula 0 or a phenol of formula m, where R2 represents a hydrogen atom.
It can be produced either by reacting with tel.

Acetal of formula D or phenol of formula m and formula N
The reaction of with alkenol can be carried out in a manner known per se (for example Swiss Patent Specification No. 416,596). Thus, as acidic catalyst it is possible to use, for example, sulfuric acid or mineral acids such as, in particular, phosphoric acid. However, strong organic acids such as oxalic acid, trichloroacetic acid, p-toluenesulfonic acid, acid salts such as potassium bisulfite, or Lewis acids such as boron trichloride, boron trifluoride or zinc chloride may also be used. I can do it. According to a particularly preferred embodiment, the aldehydes of formula 1 are obtained in particularly good yields when pyridine hydrohalides, especially pyridine hydrochloride, are used as acidic catalysts. The concentration of this catalyst in the reaction mixture conveniently amounts to about 2-5% by weight, in particular about 3-4% by weight, which corresponds to about 1/10 molar equivalent of the catalyst relative to the amount of acetal or phenol ether starting material used. corresponds to Reactions using this catalyst are preferably carried out in the presence of a solvent.

Particularly suitable solvents are aromatic hydrocarbons, such as benzene, toluene or xylene. however,
High-boiling petroleum ethers or chlorinated aliphatic hydrocarbons such as methylene chloride, ethylene chloride or trichloroethylene can also be used. A particularly preferred solvent is toluene. As for a suitable solvent, this reaction is preferably carried out under atmospheric pressure.

An acetal of formula 0 or a phenol ether of formula m or a mixture thereof is heated to the reflux temperature of the reaction mixture, e.g. in the presence of an alkenol of formula W in one of the aforementioned solvents and a catalyst, and the alcohol ROH formed during the reaction is added to the reaction mixture. (e.g. as an azeotrope with the solvent used). Preferably, the total volume of the reaction mixture and the initial proportions of the reactants are approximately maintained by the addition of a solvent and/or an alkenol (the alkenol is distilled off in small quantities at the same time as the alkanol ROH formed during the reaction is stripped off). Ru. The optimum molar ratio of acetal of formula B or phenol ether of formula rainbow to alkenol of formula W is 1:
It becomes 1.5. The amount of solvent should be used, for example, in an amount equivalent to about twice the amount of acetal (or phenol ether) and alkenol by weight. To obtain the highest yield,
It is best to locate a sample for analysis (e.g. gas chromatography) and allow the reaction to proceed, discontinuing heating as soon as 95% of the acetal or enol ether reactant has reacted; in this case the yield of the aldehyde of formula 1 is 70% or reach more than that.

Generally, the reaction time required for this is about 2 field hours.
The resulting aldehyde of formula 1 can be isolated from the mixed reaction product by known methods, conveniently by fractional distillation.

Advantageously, the catalyst used is neutralized before the distillation by addition of an inorganic or organic base such as sodium acetate, caustic soda, sodium carbonate, ammonia, a tertiary amine such as triethylamine or pyridine, and then optionally added to the reaction mixture. remove from Acetals of the formula m and phenol ethers of the formula m of Z unknown can be prepared essentially according to known methods (see, for example, Belgian Patent Specification No. 650,657). Aldehydes of formula 1, especially aldehydes of formula la, have interesting aromatic properties.

As will be clear from the description below, its properties can generally be described as hesveridin-like, green. This totally surprising and fresh property is also important. This fragrance characteristic is unique to aldehydes of formula 1, and in particular to aldehydes of formula la, as shown by the tests below with lower and higher congeners of formula la.
2,5-dimethyl-2-[3-methyl-2'-butene]
Iru 4-hexenal: Hesveridine (lemon),
Green, spicy, fruity and floral.

The aldehydes are suitable as modifiers of the top notes of flora and/or green compositions. For example, it increases the diffusibility of woody and chypre compositions. 5-Methyl-2-[3'-methyl-2'-butyn]yl-hexenal: Hesveridine-like, very fresh, natural-green, floral (rose-like), anise and lavender-like.

This aldehyde is particularly pervasive in floral compositions such as musier, lilac, and gardenia, giving them a
Gives a lightness and pronounced diffusivity. However, the properties of fusier and animal compositions are also improved by this aldehyde. 5-Methyl-2-[3'-methyl-2'-butene]yl-4-hepteol: Similar to the aldehydes above, but with stronger fruity and green properties.

2,5-dimethyl-2-[3'-methyl-2-butene]
Il-4-heptenal: Hesveridine, green,
Somewhat woozy.

Owing to their interesting odor properties, which distinguish them from structurally related aldehydes, the aldehydes of formula 1 can be used as perfumes.

For the production of fragrance compositions according to the invention, such as perfumes, or for the fragrance of perfumed products of all kinds, such as soaps, detergents, bleaching detergents, aerosols or ointments, face wipes, cosmetics, such as make-up, bath salts, etc. Can be used for The concentration of the aldehyde of formula 1 used can vary over a wide range, for example from about 0.1 to about 20% by weight, depending on the application.

For use in fragrance compositions, preferred concentrations range from about 1 to about 5% by weight. Representative fragrance compositions containing the aldehyde of Formula 1 as the aroma-imparting component are shown below.

Reference Example 1 3209 g of 2-methyl-3-buten-2-ol, 2 g of crystalline phosphoric acid, and 500 g of 2,5-dimethyl-4-hexenal jethylacetal are sequentially poured into a suitable reaction vessel.

The mixture is then heated under reflux for 5 hours while passing nitrogen through it. In this way, the temperature will go from 107℃ to 102qo
down to. The reflux condenser is then replaced by a column with a distillation head, and the ethanol produced is gradually removed over a period of 6 to 8 hours. In this way the temperature rises continuously to 140 oo. At this temperature, with the same rate of heating, the distillation begins to proceed more rapidly and the temperature at the top decreases (formation of isoprene from methylbutenol)
. A total of 425 ml of distillate is recovered. After the reaction is complete, the reaction product is cooled, diethyl ether is added, and the ethereal solution is washed with sodium bicarbonate solution and water and then dried. After distilling off the catalyst, the composition product is subjected to vacuum fractional distillation. Boiling point 115-117℃/20 side sun/evening, n
2,5-dimethyl-2-[3'-methyl-2'-butene]il-4-hexenal 240 with color o = 1.4688
(49% of the theoretical amount) is obtained. Reference example 2 2-methyl-3-butene-2-ol 8.6 hours, 85%
0.1 parts of phosphoric acid and 30.8 parts of 1-ethoxy-2,5-dimethyl-1,4-hexadiene are mixed in a suitable autoclave.

After pressurizing with nitrogen (5k9/v), place the autoclave in an oil tank (preheated to 1660°C) and bring the internal temperature to 165°C.
1. at 5°C. Heat for an hour. In this way the pressure reaches a maximum of 10.4k9/h. After cooling the autoclave, excess pressure is vented and the reaction mixture is treated with about 1 portion of triethylamine and fractionally distilled in vacuo. Boiling point 112~
113qo/13 skin days, n effect 0 = 1.4680 2.
10.6 units (54% of theory) of 5-dimethyl-2-[3'-methyl-2'-butene]yl-4-hexenal are obtained. Purity by gas chromatography is approximately 85%
It is. Z Reference Example 3 400 tons of 2,5-dimethyl-4-hexenal diethyl acetal, 2 tons of 2-methyl-3-pten-2-ol, 1000 tons of toluene and 24 tons of pyridine hydrochloride were mixed with a thermometer, a dropping furnace, and The distillation solution is then placed in a reaction solution equipped with a 40-skin Vigreux column.

The mixture is heated to boiling point and the toluene/ethanol azeotrope containing some 2-methyl-3-buten-2-ol is slowly distilled off through a Pigraw column. Fresh toluene (total amount 3k9) is poured from the dropping furnace at the same rate as the catalyst is distilled off. After 7 hours, an additional 43 hours of 2-methyl-3-buten-2-ol is added and distillation is continued until the total process time is 2 hours.

After this time approximately 90% of the starting material had reacted. Stop the addition of fresh toluene and distill off as much of the solvent remaining in the reaction flask as possible. The reaction mixture is treated with sodium acetate for 16 hours and fractionally distilled in vacuo. boiling point 112
290 g (74% of theory) of 2,5-dimethyl-2-[3-methyl-2-butene]yl-4-hexenal of 0/12 ml is obtained. Reference Example 4 2-Methyl-
3-butene...2-ol 171 units, crystalline phosphoric acid 2 units, and 5-methyl-4-hexenal diethyl acetal 39 units
The mixture was heated under reflux for 5 hours under a stream of nitrogen gas.

After pouring the generated ethanol, the internal temperature of the flask was 133-1.
Distill slowly through the column until 35 qo is reached. This temperature is reached after about 6 hours and 285 g of distillate is obtained. Post-processing is carried out using a method similar to that described in Reference Example 1. Boiling point 102-114 qo/10 side sun/evening, n=color. =
1.4661 of 5-methyl-2-[3-methyl-2'-butene]yl-4-hexener (28% of theory) lo
5 evenings are obtained. Reference Example 5 Using a method similar to that described in Reference Example 3, 400 g of 3-methyl-4-hexenal diethyl acetal, 275 g of 2-methyl-3-buten-2-ol, and 1000 g of toluene were prepared.
25 hours of reaction with pyridine hydrochloride and pyridine hydrochloride for 7 hours.

Further, 50 ml of 2-methyl-3-buten-2-ol is added and the reaction is stopped after 2 hours (total reaction time). Workup is carried out by adding 20 ml of sodium acetate to the crude product before vacuum distillation. , in the same manner as described in Reference Example 3. 180 g of 5-methyl-2-[3-methyl-2'-butene]yl-4-hexenal (40% of the theoretical amount) is obtained.

Reference Example 6 Using a method similar to that described in Reference Example 3, 300 g of 2,5-dimethyl-4-hexenal diethyl acetal was converted into 3-
225 ml of methyl-1-penten-3-ol is reacted in the presence of 17.4 ml of pyridine hydrochloric acids and 1000 ml of toluene.

After 1 hour, an additional 75 hours of 3-methyl-1-benten-3-ol is added.

The reaction is complete after 30 hours (all steps).

After adding 139% of sodium acetate to the crude mixture, the reaction product is fractionally distilled in vacuo. Boiling point 157-158
C/6W, 160 g of 2,5-dimethyl-2-[3-methyl-2-butene]yl-4-heptenal with n volume = 1.4690 is obtained. Reference Example 7 Using a method similar to that described in Reference Example 3, 5-methyl-4-
150 ml of hexenal diethyl acetal was reacted with 130 ml of 3-methyl-1-bewaten-3-ol in the presence of 10.5 ml of pyridine hydrochloride and 450 ml of toluene for 3 feeding hours, followed by 3-methyl-1-benten-3-ol. Add all 25 hours after the first 15 hours.

Post-treatment was carried out according to Reference Example 3, and the boiling point was 125-12, 0/15, n color. =1.4675 of 5-methyl-
75.7 g of 2-[3'-methyl-2'-butene]yl-4-heptenal were obtained. The intermediate for producing the novel aldehyde of the present invention can be produced as follows. Reference Example 8 1-Ethoxy-2,5-dimethyl-1,4-hexadiene (Reference Example 2) a Stirrer, thermometer, manometer and heating mantle (glass containing circulating oil)
3-Methyl-1-butene-3-ol Satoshi. 8 days, ethyl-1-probenyl ether (cisnotrans mixture) 145 days and 85 days
% ratio P040.4 was introduced.

The mixture was evaporated and the autochnope purged with nitrogen. A pressure of 5 atm N2 was applied. Close the valve, 150
The autoclave was heated to an internal temperature of °C. 1 hour later
Heating was removed, the mixture was cooled to room temperature, and the pressure was reduced.

Zb 2,5-dimethyl-4-hexenal (see step a)) 126, triethyl orthoformic acid 155, C2 & OH 95 and BFI3.Et
20 2 screams were added slowly. The mixture was allowed to stand for 30 minutes at room temperature. Add a small amount of triethylamine and Z
Neutralized with 5% sodium bicarbonate. The sexual layer was separated and removed. The organic layer was vacuum distilled. 2,5-dimethyl-4-hexenal diethylacetal, b. p97-9800/
15 legs Hg, n color 0 = 1.4318143 days were obtained.

2b. p. 73～7yo/
The entire precursor of the above acetal distillation showing 14 Hadayagi Hg includes:
cis and trans 1-ethoxy 2,5-dimethyl m1,
It contains a mixture of 30% and 60% respectively of 4-hexadiene, 2% of 2,5-dimethyl-4-hexenal and 8% of 2,5-dimethyl-hexenal diethyl acetal. Careful rectification using a spin band yielded a pure enol ether mixture. Towards the end of the distillation, the trans isomer content reached 89%. Each crab portion showed the following properties. Initial fraction: b. p. 7.1-7
．． 20/14 skin Hg, n group: 1.451 to cis 48.8
%, trans 51.2%, 3-terminal crab content:
b. p. 75-7 is ○/16 rib Hg, n force = 1.453
0 cis: 11.0%, trans: 89.0%, c2,5-dimethyl-4-hexenal diethyl acetal (see step b)) was added dropwise through the heating column of a pyrolysis apparatus under nitrogen.

The column is packed with clay chips. The operation took 30 minutes and the pyrolysis temperature used was 350 qo. (metal case). The receiving container contains 0.5 liters of crucian sodium hydroxide. The reaction mixture was washed neutral with 10% NaCI solution, dried and distilled. 1-Ethoxy2,5-dimethyl-1,4-hexadiene (cisnotrans=2/3
4.7 hours of a 60% mixture of ) was obtained.

The mixture contained many volatile impurities. Pure 1-ethoxy-2,5-dimethyl-1,4-hexadiene can be obtained from sperm crabs (see step b) above). Reference example 9 5-methyl-4-hexanal-diethyl acetal (
Reference examples 4, 5, 7) a 400 [in an autoclave,
3-methyl-1-buten-3-ol 86 units, vinyl ethyl ether 7 units 151 units and ratio P04 (85%) 6.5
Added evening.

The pressurized vessel was closed and 5 atmospheres of N2 was applied. The autoclave was placed in a 170q0 oil bath. The internal temperature of the autoclave was maintained at 150±2° C. for 2 hours. The autoclave pressure was initially raised to 11k9/kg and then slowly lowered. At the end of the reaction, place the autoclave into an ice cube;
The reaction was stopped at the aldehyde level. When the contents of the autoclave reached room temperature, the autoclave was opened and the contents were neutralized with 4-triethylamine, washed, dehydrated, and distilled. 5-methyl-4-hexenal, b. p. 61～
620028 skin Hg, n color 0 = 1.4360.327 m were obtained. b 5-methyl-4-hexanal (step a)
112 ml of triethyl orthoformic acid, 95 ml of ethanol, and 2 ml of polytrifluoride etherate were added to a mixture of 155.5 ml of triethylorthoformic acid, 95 ml of ethanol, and 2 ml of polytrifluoride etherate, resulting in a slight exothermic reaction that caused a temperature rise, i.e., 35-40°C.

Finally, the mixture was heated under pressure at 50° C. for 1 hour, then cooled and processed as usual. By distillation, 5-methyl-4-hexenal diethyl acetal, b. p5400/2
Yanagi Hg, n color 0=1.4300, 13 was obtained. The following examples illustrate typical fragrance compositions containing the aldehydes of the present invention.

Example A Hyacinth type composition: Parts by weight 5-Methyl-2-[3'-methyl-2'-butene]yl-4-hexenal 20 Phenylacetaldehyde (50%) 5 Indole (10%) 5 Skatole (
1%) 5 galbanum euthanasia
10 hydrato/aldehyde dimethyl acetal 10 eugenol 20 ethyl phenylmofurate 30 ethyl phenylformate 30 phenylf.

Lopyl Alcohol 30Z Penzyl Acetate 30 Citronellol
30 Ethyl phenylsalicylate 50 Ethyl phenylisobutyrate
50 cinnamon alcohol (synthetic product)
50Z Hydroxycitronellal
70 phenylethyl alcohol
1806255-Methyl-2-[3'-methyl-2'-butene]yl-4-hexenal imparts excellent elegance and natural freshness to the composition.

Example B Composition of the chypre type: Parts by weight 2,5-dimethyl-2-[3'-methyl-2'-butene]yl-4-hexenal 60 frankincense (resinoid) 10 nightshade oil (10%)* 10** methylnonylacetaldehyde (1%)*
202,6,10-trimethyl-9-undecen-1-al (10%) 1
0 usodecylenaldehyde (10%) *lo
y-Undecalactone (1%)* 10 Vetiver oil (Pourbon) 20 Sandalwood oil (East India) 40 Patchouli oil
401,1,4,4-tetramethyl-6-ethyl-7-acetyl-1,2,3,4-tetrahydronaphthalene 4
0 Pure bleached oak moss 40 Linalool 40 Bergamot oil 80 Hydroxycitronellal 140 Q-ionone
100 citronellol (
levorotatory) 80 phenylethyl alcohol
100 Jasmine (Absolute, Synthetic)
15010〇〇* Phthalate Jetyl Ester Solution This 2,5-dimethyl-2-[3-methyl-2'butene]yl-4-hexenal imparts freshness and fruit-like properties to this chypre composition, while increasing its diffusibility. .

An aromatic composition containing an aldehyde having the general formula (wherein R and R2 each represent a hydrogen atom or a methyl group).

An aromatic composition containing 2,5-dimethyl-2-[3'-methyl-2'-butene]yl-4-hexenal.

5-methyl-2-[3-methyl-2'butene]yl-4
-Fragrance composition containing hexenal.

Claims (1)

[Claims] 1. Contains a compound having the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (in the formula, R, R_2, and R_3 each represent a hydrogen atom or a methyl group) as an essential scent-imparting component, Aromatic composition.