JPH0341453B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION The present invention relates to novel aromatic substances. These substances have the formula (In the formula, R, R ¹ and R ² are hydrogen or C _1-3
-represents alkyl, and X is

【formula】

[Formula] or

Represents [formula]. If both symbols R ¹ are hydrogen, all three symbols R ² represent C _1-3 -alkyl and the total number of carbon atoms in the molecule does not exceed 15). The formula encompasses stereoisomers that can be formed as a result of cis or trans configurations at the C=C and C=N double bonds. The individual notations R, R ¹ and R ² may be the same or different. _C1-3 -alkyl radicals are methyl, ethyl, n-propyl or isopropyl. Methyl is preferred. The present invention also relates to a method for preparing compounds of formula. This method uses the formula Formula the compound of (wherein R, R ¹ and R ² have the above meanings,
and Y represents halogen) in the presence of a base, and if desired, the resulting ketone of formula is reduced to obtain a secondary alcohol of formula (a),
or (b) converted into a tertiary alcohol of the formula by reacting with a compound of the formula RMgY, or (c) converted into an oxime of the formula by reacting with hydroxylamine. The reaction of the compound with a compound of the formula can be carried out essentially according to known methods. Chloride, bromide or iodide can be used as the halide in the formula. Chlorides are preferred. The reaction is preferably performed with an alkali metal hydroxide (e.g. potassium hydroxide), an alkaline earth metal hydroxide (e.g. calcium hydroxide), an alkali metal amide (e.g. sodium amide) or an alkali metal halide (e.g.
It is carried out in the presence of a strong inorganic base such as sodium halide) or an organic base such as potassium tert butoxide, for example. The reaction can be carried out in the presence or absence of a solvent. Particularly suitable solvents are neutral or slightly polar solvents, such as dimethoxymethane,
Dimethoxyethane, diethyl ether or tetrahydrofuran, but also toluene or benzene. The reaction is carried out at approximately -20 to +50°C, preferably -10 to +20°C.
It is advantageously carried out at a temperature of .degree. Lower temperatures are not commercially practical, and higher temperatures readily result in the formation of undesirable polymer by-products. The reaction of the initially obtained ketone of the formula with the compound of the formula RMgY is advantageously carried out essentially according to known methods for Grignard reactions. for example,
Organikum, Organisch−chemisches
Grundprakti¨kum, co-author, 7th edition, VEB
Dentscher Verlag der Wlssenschaftem,
See Berlin 1967, pp. 486 et seq. The reaction was carried out in diethyl ether as a solvent at 0°C.
- Advantageously carried out at the boiling point temperature of the ether. Although the customary halides are considered halides, bromide is preferred. The ketone of the initially obtained formula is preferably sodium, borohalide, lithium aluminum.
Reducing agents such as halides, triisopropylaluminate, etc. can be used to reduce to the secondary alcohol. (LFFieser and M.Fieser,
Reagents for Organic Synthesis, John Wiley
& Sons (1967), 581, 582, 584, 1049 and
Organikum, cited above, pp. 475-476). Particularly considered solvents are therefore ethanol or water when sodium borohalide is used, diethyl ether when lithium aluminum halide is used, and isopropanol when triisopropylaluminate is used. On the other hand, the ketones of the formula initially obtained can be converted into the corresponding oximes by reaction with hydroxylamine. The reaction is advantageously carried out essentially according to known methods. For example, Organikum,
Organische-chemisches Grund praktikum,
Co-author, 7th edition, VEB Dentscher Verlag der
See Wissenschaftem, Berlin, 1967, 375. The hydroxylamine is advantageously used in the form of a salt (eg hydrochloride or sulfate) and is reacted with the ketone of the formula in a pyridine-containing alkaline solution or an aqueous alkaline solution. In this case, the reaction is preferably carried out at the reflux temperature of the reaction mixture. The compounds of the formula have a special functionality and are therefore particularly suitable as fragrances. The invention therefore also relates to the use of compounds of the formula as fragrance substances. The compound of the formula is bergamot oil, lavender,
It has an odor generally reminiscent of notes of sage and lemon peel. Owing to their natural olfactory notes and their perfuming properties (with respect to lasting effects, especially freshness), the compounds of the formula are particularly suitable for modification. For example (α) known floral compositions, for example citrus notes will be emphasized (e.g. cologne type, essences ("extraits")), (β) known fruity compositions, for example of currant type. (γ) known compositions with green notes, especially producing the desired natural effect, and finally (δ) known compositions of the rusted type (i.e. Compositions with "inside notes"). Compounds of particular interest are: 2,4,4-trimethyl-6,8-nonadien-3-one: This compound has a very natural lavender note. Additionally, the odor is reminiscent of black currants, cut stinging nettles and mebokki. This compound produces a surprising effect on the composition. That is, it enhances the natural harmonious roundness on the one hand and the pleasant floral notes on the other. 2,2-dimethyl-6,8-nonadiene-3-
All: The odor of this compound is fruity (particularly citrus), earthy and floral in the direction of sage flowers. The aldehydic odor properties of this alcohol are surprising. In the composition the citrus-sage complex imparts a novel note that is particularly valuable in male perfumes. 2,4,4,7-Tetramethyl-6,8-nonadien-3-one: The odor of this compound is fresh, natural and reminiscent of black currant and bergamot oil. 3-Ethyl-4,7-dimethyl-6,8-nonadien-3-ol: This tertiary alcohol is particularly characterized by its diffusivity. The olfactory note is lavender-like and very natural. The surprising effect is that this alcohol imparts more volume to it and the composition is produced in a harmonious manner into a rounded composition. 2,3,4,4,7-pentamethyl-6,8-
Nonadien-3-ol: The olfactory notes are fruity, somewhat earthy, reminiscent of grapefruit, with pine room and woody bottom notes. 2,4,4,,7-Tetramethyl-6,8-nonadien-3-one oxime: This compound has a very natural note after black currant and is very persistent. Other preferred compounds of the formula are: 2,2,7-trimethyl-6,8-nonadien-3-one, 2,2,7-trimethyl-6,8-nonadien-3-ol, 2,2,3, 7-tetramethyl-6,8-nonadien-3-ol, 3,6-dimethyl-5,7-octadiene-2
-ol, 5-isopropyl-2,9-dimethyl-7,9
-decadien-4-one, 2,4,4,7,8-pentamethyl-6,8-
Nonadien-3-one, 2,4,4,8-tetramethyl-6,8-nonadien-3-ol, 2,3,6-trimethyl-5,7-octadien-2-one, 5-ethyl-8 -methyl-7,9-decadien-4-one, 3,3,6-trimethyl-5,7-octadien-2-one oxime and 5-ethyl-8-methyl-7,9-decadien-4-one oxime. The compounds of the formula can be combined with a large number of known natural or synthetic fragrance composition ingredients, whereby the range of natural ingredients can include not only readily volatile, but also semi-volatile and refractory substances, and The range of synthetic ingredients can include representatives from almost all types of materials, as is evident from the following compositions. - Natural products, such as Trimos absolute,
mebouki oil, bergamot oil, acetylated cedar wood oil (e.g. Vertofix IFF or
Cedartone Givaudan), oakmoss, chamomile oil, galbanum oil, geranium oil, diasmine absolute and its substitutes, lavender oil, lavandan oil, mastix absolute, coriander oil, neroli oil, pachy lily oil, petigrain oil Paraguay, elemi oil,
Sandalwood oil, vetiver oil, ylang-ylang oil,
Lemon oil, mugwort oil, angelica seed oil, rosemary oil, mandarin oil, hyssop oil. -Alcohols, such as linalool, citronellol, geraniol, natural rhodinol, alpha-terpineol, phenylethyl alcohol, phenylpropyl alcohol, cinnamic alcohol, 3-methyl-5-(2',2',3'-trimethyl-
Cyclopent-3'-en-1'-yl)-pentan-2-ol (Sandalore Givaudan), dimethylbenzylcarbinol, terpineol, menthol, 2,2,8-trimethyl-7-nonen-3-ol. -Aldehydes, such as 3,5-dimethyl-cyclohex-3-ene-carboxaldehyde, decanal, methylnonylacetaldehyde, hydroxycitronellal, α-hexylcinnamaldehyde, cyclamenaldehyde, p-t.butyl-α-methyl-dihydro - cinnamaldehyde (e.g. Lilial Givaudan), citral, alpha
-amylcinnamaldehyde, n-undecene-
10-A, n-dodecanal. - Ketones, such as α-ionone, acetylcedrene, p-methyl-acetophenone, methylionone, allylionone, p-hydroxybenzylacetone. -Esters, such as cedryl acetate, cis-3-hexenyl acetate, cis-3-hexenyl benzoate, ethyl acetoacetate, linalyl acetate, geranyl acetate, terpenyl acetate, phenylethyl acetate, styralyl acetate, p-t. Butylcyclohexyl acetate, 4-[4-methyl-3-pentenyl]-cyclohex-3-en-1-yl-carbinyl acetate (e.g. Myraldylacetate
Givaudan), cinnamyl formate, benzyl acetate, benzyl salicylate, amyl salicylate, isobutyl salicylate, hexyl salicylate, methyl dihydrodiasmonate, 3
-ethyl-1,1-dimethyl-cyclohexe-3
-ene-2carboxylic acid ethyl ester (Givescone Givaudan), linalyl anthranilate, 3-ethyl-1,1,4-trimethyl-
Cyclohex-3-ene-2-carboxylic acid ethyl ester (Myrascone Givaudan). -Lactones, such as γ-nonalactone, γ-decalactone, γ-undecalactone, γ-dodecalactone, coumarin. - various additional ingredients often used in fragrances, such as musk compounds [musk ketones, 12-oxahexadecanolides (e.g. Musk 174)]
Naarden), 1,1-dimethyl-4-acetyl-
6-t.butylindane], indole, p-methane-8-thiol-3-one, eugenol, acetaldehyde propyl phenyl-ethyl acetal, methyl 1-methyl-cyclododecyl ether (e.g. Madrox Givaudan), phenyl acetaldehyde dimethyl acetal (Viridine),
Cyclocytrilidene-acetonitrile, 8α,12
-Oxide-13,14,15,16-tetranorhabdane (Fixateur404). Compounds of formula can be used within wide limits. For example, it can range from 0.1% in detergents to 50% in alcohol solutions.
It will be appreciated that these values are not limiting. This is because skilled perfumers can produce effects at even lower concentrations or synthesize new compounds at even higher concentrations. Preferred concentrations vary from 0.5 to 25%. Compositions prepared with the compound of the formula can be used in scented consumable products such as eau de cologne, eau de toilette, essence ("extrait"), lotions, creams, shampoos, soaps, ointments, cosmetic powders, deodorants, detergents,
Can be used for all types of tobacco (e.g. cigarettes). Compounds of the formula can therefore be used in the production of fragrances and, as is clear from the collected material above, a wide range of known fragrances can be used. In the preparation of such compositions, the above-mentioned specific known fragrances may be used, for example, WAPoucher, Perfumes,
Cosmetics and Soaps, 2nd , 7th edition, Chapman
and Hall, London, 1974. In the preparation of the compounds, it is further advantageous to use phase change agents, such as tri-caprylylmethylammonium chloride (eg "Alignaf 336", Henkel), when reacting compound with compound. The following examples illustrate the invention. Example 1 2,4,4-Trimethyl-6,8-nonadien-3-one 60 g of caustic potash powder and 180 ml of anhydrous toluene are placed in a round flask equipped with a stirrer, thermometer, condenser and addition funnel. The mixture was cooled to -10°C and 30 g of 1-chloro-2,4-
A mixture of pentadiene and 33 g of diisopropyl ketone is added dropwise with stirring within 35 minutes. The temperature was kept below 0°C during the addition, then raised to 20°C,
The reaction mixture is then stirred for a further 7 hours. The mixture was allowed to stand for 12 hours, then the flask contents were reduced to 200 g.
Pour over crushed ice. The forming layer is separated and the organic layer is washed to neutrality with water. The solvent is evaporated off, leaving 40 g of crude product, which is subjected to fractional distillation. Boiling point of pure 2,4,4-trimethyl-6,8-nonadien-3-one: 54°C/0.75mmHg, n ²⁰ _D =
1.4711, d ²⁰ ₄ = 0.8623. Aroma: Lavender-like, natural, reminiscent of cut pungent nettle and black currant. Example 2 2,2-dimethyl-6,8-nonadiene-3-
A mixture of 34 g of 1-chloro-2,4-pentadiene and 34.7 g of 3,3-dimethyl-butan-2-one (pinacolin) was dissolved in caustic potassium in 230 ml of anhydrous toluene with stirring at a temperature of 40-45°C. powder
Add dropwise to 76g within 80 minutes. The mixture is cooled to room temperature and the flask contents are poured onto 200 g of crushed ice. The forming layer is separated and the organic layer is washed to neutrality. The solvent is distilled off and 56 g of crude product is obtained which is subjected to fractional distillation. Pure 2,2-dimethyl-6,8-nonadiene-
Boiling point of 3-one: 57℃/1.2mmHg, n ²⁰ _D = 1.4700,
^d204 ₌ 0.8618. Aroma: rose-like, somewhat camphorous,
Reminds me of phenylethyl isobutyrate. Example 3 2,2-dimethyl-6,8-nonadiene-3-
All 6.8 g of lithium aluminum hydride and 150 ml of anhydrous ether are placed in a circular flask equipped with a stirrer, thermometer, condenser and addition funnel. A solution of 30 g of 2,2-dimethyl-6,8-nonadien-3-one in 300 ml of dry ether is added dropwise to the resulting suspension with stirring at a temperature of 0 DEG C. within 2 hours. After addition, the mixture is kept at reflux temperature for 4 hours. After cooling, excess lithium aluminum hydride is destroyed with 30 ml of ethyl acetate. The flask contents are poured into ice-cold 10% sulfuric acid, the layers are separated and the organic layer is washed successively with water, 8% sodium bicarbonate solution and water again until neutral. After drying over sodium sulfate, the ether is evaporated off and the residue (35 g) is distilled. Pure 2,2-dimethyl-6,8-nonadiene-
Boiling point of 3-ol: 78℃/2.5mmHg, n ²⁰ _D =
1.4809, d ²⁰ ₄ = 0.8654. Aroma: Fruity, post-lavender, somewhat pine room-like. Example 4 2,2-dimethyl-6,8-decadiene-3-
19.4 g of 1-chloro-
30 g of crude 2,2-hexadiene and 17.4 g of 3,3-dimethyl-butan-2-one
Dimethyl-6,8-decadien-3-one is obtained,
Subject to fractional distillation. Boiling point of pure product: 49℃/0.1mmHg, n ²⁰ _D =
1.4755, d ²⁰ ₄ = 0.8613. Aroma: Fruity, pear-like, reminiscent of geranyl formate, rose-like. Example 5 2,2-dimethyl-6,8-decadiene-3-
All 17 g of crude product were obtained by reducing 16.2 g of 2,2-dimethyl-6,8-decadien-3-one with 3.4 g of lithium aluminum hydride in 250 ml of anhydrous ether according to the method described in Example 3. and then by fractional distillation 7.8 g of pure 2,2
-dimethyl-6,8-decadien-3-ol is obtained. Boiling point: 62℃/0.2mmHg, n ²⁰ _D = 1.4861, d ²⁰ ₄ =
0.8703. Scent: Reminiscent of lavender, pine tree room, and unripe mandarin. Example 6 2,4,4,8-tetramethyl-6,8-nonadien-3-one 58 g of 1-chloro-
57 g crude 2,4,4,8-tetramethyl-6,8-nonadien-3-one from 4-methyl-2,4-pentadiene and 59 g diisopropyl ketone
and subjected to fractional distillation. Boiling point of pure product: 53℃/0.25mmHg, n ²⁰ _D =
1.4770, d ²⁰ ₄ = 0.8701, Scent: Lavender, bergamot, similar to linalyl acetate. Example 7 2,4,4,7-tetramethyl-6,8-nonadien-3-one 264 g of caustic potash powder and 800 ml of dry toluene are placed in a 2-round flask equipped with a stirrer, thermometer, condenser and addition funnel. . The mixture was cooled to -10 °C and a mixture of 153.5 g 1-chloro-3-methyl-2,4-pentadiene and 151 g diisopropyl ketone was added thereto with stirring for 2 hours, the temperature was kept at 0 °C by external cooling. Keep below. After the addition, the mixture is stirred for a further 6 hours at room temperature. The mixture is allowed to stand for 12 hours, then the flask contents are poured onto 500 g of crushed ice. The forming layer is separated and the organic layer is washed with water until neutral. The solvent is distilled off, leaving behind 160 g of crude product which is subjected to fractional distillation. Pure 2,4,4,7-tetramethyl-6,8-
Boiling point of nonadien-3-one: 64℃/0.3mmHg,
n ²⁰ _D = 1.4790, d ²⁰ ₄ = 0.8733, aroma: fruity, post-bergamot, ocimene, very natural. Example 8 2,2,7-Trimethyl-6,8-nonadien-3-one 116 g of 1-chloro-3-methyl-2,4-pentadiene and 100
g of 3,3-dimethyl-butan-2-one
In the presence of 200 g of caustic potash powder in 600 ml of toluene, 141 g of crude 2,2,7-trimethyl-6,8-nonadien-3-one are obtained and subjected to fractional distillation. Boiling point of pure product: 50℃/0.1mmHg, n ²⁰ _D =
1.4763, d ²⁰ ₄ = 0.8699, Scent: Lavender-like, ocimene, but much better adhesion than ocimene. Example 9 4,7-dimethyl-6,8-nonadiene-3-
On Following the method described in Example 1, 58 g of 1-chloro-
200 from 3-methyl-2,4-pentadiene and 43 g of pentan-3-one (dimethylketone)
Crude 4,7-dimethyl-6,8-nonadiene-3- in the presence of 50 g of caustic potash powder in ml of dry pentane.
51 g of onion was obtained and subjected to fractional distillation. Boiling point of pure product: 86°C/6mmHg, n ²⁰ _D =
1.4788, d ²⁰ ₄ = 0.8782, Aroma: Lavender-like, fruity, allyl-like, reminiscent of grapefruit. Example 10 3-Ethyl-4,7-dimethyl-6,8-nonadien-3-ol Ethylmagnesium bromide 9.4 g (0.39 g atoms) magnesium and 44.6 g (0.41 mol) ethyl bromide in 210 ml dry ether in a round flask equipped with a thermometer, stirrer, condenser and addition funnel. There, 64.5 g (0.39 mol) of 4,7-dimethyl-6,
Add 200 ml of a solution of 8-nonadien-3-one in dry ether. After the addition is complete, the mixture is kept at reflux temperature for 3 hours and then cooled in an ice bath. The magnesium complex formed was mixed with 30 g of ammonium chloride.
Decompose by adding 300ml aqueous solution. The organic layer is separated and the aqueous layer is extracted three times with 50 ml of ether each time. The combined organic layers are washed with 5% tartaric acid, water, 8% sodium bicarbonate solution and more water until neutral. The ether is distilled off and the crude product (72 g) is distilled off. Pure 3-ethyl-4,7-dimethyl-6,8-
Boiling point of nonadien-3-ol: 65℃/0.2mm
Hg, n ²⁰ _D = 1.4947, d ²⁰ ₄ = 0.8935, aroma: very natural, post-lavender, sticky and diffusive. Example 11 5-isopropyl-2,9-dimethyl-7,9
-Decadien-4-one Following the method described in Example 1, the above ketone is obtained from 1-chloro-4-methyl-2,4-pentadiene and 2,6-dimethylheptan-4-one.
Boiling point: 72℃/0.3mmHg, n ²⁰ _D = 1.4728, Aroma: Linalool-like with a musky note, very natural. Example 12 2,4,4,7,8-pentamethyl-6,8-
Nonadien-3-one 1-chloro-3,4 according to the method described in Example 1
The above ketone is obtained from -dimethyl-2,4-pentadiene and diisopropyl ketone. Boiling point: 74
°C/0.22mmHg, ^n20D = _1.4795 . Fragrance: Lavender-like, amber-like, pine room-like, somewhat depressing. Example 13 2,2,7-trimethyl-6,8-nonadien-3-ol 41.8 g of 2,2,7-trimethyl-6,8-nonadien-3-one, 20 ml of water and 54 ml of ethanol are mixed with a stirrer. and a round flask equipped with a thermometer. 6.1 g of sodium borohydride are added in portions to this mixture with stirring. The temperature is maintained at 25°C by external cooling. After the addition, the mixture is stirred for a further 3 hours at 25°C. The mixture is neutralized with tartaric acid solution while cooling and then slightly acidified. The mixture was taken up in ether and
Wash with water until neutral and dry the ether solution over sodium sulfate. The ether is distilled off and the residue (41.4 g) is distilled. Boiling point of pure 2,2,7-trimethyl-6,8-nonadien-3-ol: 59-60℃/0.2mmHg,
^n20D ₌ 1.4863. Scent: Fruit-like, post-lavender flower-like,
Extremely natural. Example 14 2,4,4,8-tetramethyl-6,8-nonadien-3-ol 2,4,4,8,-
By reducing tetramethyl-6,8-nonadien-3-one with lithium aluminum hydride in dimethyl ether, a boiling point of 89°C/0.8
The corresponding secondary alcohol with mmHg, n ²⁰ _D =1.4910 is obtained. Scent: Lavender, somewhat balsamic. Example 15 2,2,3,7-tetramethyl-6,8-nonadien-3-ol 2,2,3,7-tetramethyl-6,8-nonadiene-3-ol Boiling point from on and methylmagnesium iodide: 62
C/0.05 mmHg, the above alcohol having n ²⁰ _D =1.4910 is obtained. Aroma: Reminiscent of lavender seeds. Very natural and good adhesion. Example 16 Following the method described in Example 10, 58.3 g of 2,4,
4,7-tetramethyl-6,8-nonadiene-3
-one and methylmagnesium iodide (7.2 g of magnesium) to crude 2,3,4,4,
7-Pentamentyl-6,8-nonadiene-3-
57.9 g of oar was obtained and subjected to fractional distillation. Boiling point of pure product: 79℃/0.3mmHg, n ²⁰ _D =
1.4983, d ²⁰ ₄ = 0.9011. Aroma: Fruity, reminiscent of grapefruit, somewhat muddy, powdery, and dull. Example 17 127 g of 2,4,4,7-tetramethyl-6,
8-nonadien-3-one and 127 g of hydroxylamine hydrochloride in 127 ml of pyridine and 1.27
The ethanol solution is kept at reflux temperature for 2 hours in a circular flask equipped with a stirrer, thermometer and condenser. Next, most of the ethanol is immediately distilled off. After cooling, the mixture is poured into ice/water and taken up in ether. The ether solution is first mixed with water,
Then with 5% hydrochloric acid (to remove excess pyridine),
Then, wash again with water until it becomes neutral. After evaporation of the ether, a crude product containing 86 g of unreacted ketone was obtained.
Obtain 109g. Ketones are distilled off. The residue consists of the oxime as a mixture of isomers and can be used in perfumery in the form of a 10% alcohol solution. A portion of the residue is separated by column chromatography. 17.8g of the residue was dissolved in toluene,
Chromatograph on 500 g of silica gel. 12
fractions are obtained, whereby fractions 2 and 3 and 10 and 11 on the other hand obtain crystals.
Fractions 2 and 3 from methanol and water
After recrystallization of , one of the oxime isomers with a melting point of 68-70 °C is obtained. Example 18 According to the method described in Example 1, crude 3,3,6-trimethyl was prepared from 58.1 g of 1-chloro-2,4-pentadiene and 45.2 g of isopropyl methyl ketone in the presence of 100 g of caustic potash powder in 300 ml of toluene. 49.9 g of -5,7-octadien-2-one are obtained and subjected to fractional distillation. Boiling point of pure product: 83°C/6mmHg, n ²⁰ _D =
1.4815, d ²⁰ ₄ = 0.8913. Scent: Oshimen-sama, reminiscent of heated rhubarb. Example 19 From 116.6 g of 1-chloro-2,4-pentadiene and 114.2 g of dipropyl ketone (heptan-4-one), 600 ml of
In the presence of 200 g of caustic potash powder in toluene of
-ethyl-8-methyl-7,9-decadiene-4
91.9 g of -on were obtained and subjected to fractional distillation. Boiling point of pure product: 61℃/0.2mmHg, n ²⁰ _D =
1.4770, d ²⁰ ₄ = 0.8713. Aroma: Fruit-like, cooked pear, plum-like. Example 20 33.2g of 3,3,6 according to the method described in Example 17
33.9 g of crude oxime are obtained from -trimethyl-5,7-octadien-2-one which is subjected to fractional distillation. Boiling point of pure product: 73℃/0.15mmHg, n ²⁰ _D =
1.5072, d ²⁰ ₄ = 0.9339. Aroma: Green, natural, reminiscent of grapefruit and celery. Example 21 26.3 g of hydroxylamine sulfate was added using a stirrer,
Equipped with thermometer, condenser and dropping funnel
Dissolve in 55 ml of water in a 500 ml round flask. 52g
of 33% caustic soda is added thereto and the temperature is maintained at 25°C with cooling during the addition. Next, 61 g of 5-ethyl-8-methyl-7,9-decadien-4-one
120 ml of ethanol solution is slowly added dropwise thereto at room temperature. The mixture is then kept at reflux temperature for 4 hours. After cooling, the mixture is poured onto ice/water, taken up in ether and washed to neutrality. The solvent is distilled off. 64.3 g of crude oxime are obtained, which is subjected to fractional distillation. Boiling point of pure product: 95℃/0.2mmHg, n ²⁰ _D =
1.4997, d ²⁰ ₄ = 0.9141. Aroma: after celery pods, very natural, some after grapefruit, good adhesion. Example 22 50 parts by weight of 2,4,4-trimethyl-6,8-
Nonadien-3-one (Example 1) was dissolved in parts by weight of hydroxycitronellal 150 linalool 150 α-ionene 100 Lilial (pt.butyl-α-methylhydrocinnamaldehyde) 100 phenylethyl alcohol 100 hexyl salicylate 50 Linalyl anthranilate 50 Galbanum (synthetic) (10% DPG) (dipropylene glycol) 20 Roman chamomile oil (1% DPG) 10 Eugenol 5 Coumarin 5 DPG Added in the direction of linden flowers to a fragrance base containing 210 950 . In this way the pleasant floral, sweet notes that give the composition a round powdery character are intensified in a welcome way. Due to its long-lasting properties, the new base is particularly suitable for soap fragrances. Example 23 50 parts by weight of 2,2-dimethyl-6,8-nonadien-3-ol (Example 3) were added to 150 parts by weight of 2-ethyl-3,6,6-trimethyl-2-cyclohexenecarboxylic acid ethyl ester. Aldehydes [3-(p-isopropylphenyl-2-methyl)-propionaldehyde 100 linalyl acetate 80 geraniol 80 benzyl acetate 70 hydroxycitronellal 50 α-hexylcinnamaldehyde 50 linal 50 linal 50 C ₁₂ -aldehyde (10%DPG) ) 20 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylic acid ethyl ester 20 DPG 230 950 is added to the perfume base in the direction of the cyclamen. Some raw benzyl acetate notes predominate in the initial base. It becomes more floral, soft and warm after addition. The new compositions are substantially more polyurethane and more diffusive. Example 24 50 parts by weight of 2,2-dimethyl-6,8-nonadien-3-ol (Example 3) were mixed with 50 parts by weight of methyl 1-methyl-cyclododecyl ether.
150 2,2,8-trimethyl-7-nonen-3-ol 150 Bergamot oil 80 Mask 174 (12-oxahexadecanolide)
70 Hydroxycitronellal 70 Coriander oil 50 Pachuli oil 50 Trimos (50%DPG) 30 Galbanum oil 30 Rhodinol 30 Isoraldeine (isomethyl-α-ionone) 30 Pettigrain oil 20 Allylionone 20 Elemi oil 15 Angelica seed oil 10 Geranium oil (Synthetic) 10 Added to the fragrance base containing DPG 85 900 in the direction of the fuguet. After addition, the composition becomes even stronger and fresher, with citrus notes in the direction of sage. The addition of new compounds is
The composition is enriched with a citrus-sage complex which gives the composition a surprisingly novel note. The new composition is very well suited for modern men. Example 25 50 parts by weight of 2,2-dimethyl-6,8-decadien-3-ol (Example 5) are added to the perfume base of Example 16 (linden flower direction). Thereby an aldehydic character is imparted to the composition, which makes it very well suited for the fragrance of cosmetics. Example 26 150 parts by weight of 2,4,4,8-tetramethyl-
6,8-nonadien-3-one (Example 6) in parts by weight Lemon oil 300 Bergamotu oil 200 Neroli oil 70 Rosemary oil 70 Pettigrain oil 50 Ketone moscus (4-t.butyl-3,5-
2,6-Dimethylacetophenone) 20 Mandarin Oil 15 Hydroxycitronellal 10 Eugenol 10 Linalyl Anthranilate 5 DPG 100 850 is added in the direction of the colon. After the addition, the composition becomes substantially "stronger" in citrus notes and changes noticeably in the direction of grapefruit. In addition, it produces a green note, which imparts a vetiver character to the composition, and with which it can appear very precious. Example 27 A fragrance complex in the direction of sage consists of parts by weight 2,2,8-trimethyl-7-nonen-3-ol 200 methyl dihydrdiasmonate 100 oil of bergamot 100 methyl 1-methylcyclododecyl ether
100 Hyssoh oil 80 Allylionene 30 Corpse Cassis (p-menthane-8-thiol-3-one) 1% 5 Fixateur 404 (8α,12-oxide-
13, 14, 15, 16-tetranorabden) 5 Contains DPG 280 900. This base is reminiscent of a sage tree. 100 parts by weight of 2,4,4,7-tetramethyl-6,8-
The addition of nonadien-3-one (Example 7) produces a new compound reminiscent of sage flowers, fresher and more potent than the original base. Example 28 The pleasant morning notes of the following "chypre" composition in the direction of vetiver are 100 parts by weight of 3-ethyl-4,
There is a clear strengthening by adding 7-dimethyl-6,8-nonadien-3-ol (Example 10). Part by weight 2-ethyl-3,6,6-trimethyl-2-cyclohexenecarboxylic acid ethyl ester 100 Isoraldeine 100 Geranoyl 60 Methyl dihydrodiasmonate 60 Bergamot oil 50 Ketone moscus 35 2,2,8-trimethyl-7-nonene- 3-ol 30 linalool 30 benzyl acetate 20 methyl 1-methyl-cyclododecyl ether
20 Pachuli oil 15 Sandalole (3-methyl-5-(2,2,
3-trimethylcyclopent-3-ene-1-
yl) pentan-2-ol) 10 Cyclocytrilidene-acetonitrile 5 Styralyl acetate 5 C ₁₁ -aldehyde (10%DPG) 5 Undecalactone 3 p-Hydroxybenzylacetone 2 DPG 350 900 Effective for fixing active substances This strengthens the base in an amazing way. The base can be used as a final perfume extract without any further modification. Example 29 Parts by weight of fragrance base in the dark direction Methyl 1-methylcyclododecyl ether
150 Vetivenyl acetate 100 Sandella Gibb [3-isocanhyel-(5)-cyclohexanol] 100 Linalool 100 Pachuli oil 50 Iron 50 Linalyl acetate 50 Citronellol 50 Benzyl acetate 30 Trimos (colorless, absolute) 30 α-amyl cinnamaldehyde 20 Methylnonylacetaldehyde (10%DPG)
20 Eugenol 20 C ₁₁ -Aldehyde (10%DPG) 10 Cyste oil (France) 10 Sandalore Gibb 10 800 200 parts of 2,3,4,4,7-pentamethyl-
When 6,8-nonadien-3-ol is added to this cloudy perfume base, it becomes very pleasantly rounded. The vetybenyl acetate note, which was strongly predominant before addition, is suppressed by a pleasant fresh green note, which is still predominant even after 24 hours. Example 30 Parts by weight of perfumed cologne Bergamot oil 80 2-ethyl-3,6,6-trimethyl-2-cyclohexen-1-yl-carboxylic acid ethyl ester 80 Galaxolide IFF (1,3,4,6,7,
8-hexahydro-4,6,6,7,8,8-
Hexamethyl-cyclopenta-γ-2-benzopyran) 60 Hydroxycitronellal 60 Methyl 1-methylcyclododecyl ether 60 Bornyl acetate 40 Muskketone 40 Gibbescone Gibb 20 Pettigrain oil 20 Sandalore Gibb 30 Corpse Cassis Gibb (p-methane-8 -Thiol-3-one) 5 Tri-Mos (absolute) 5 Dipropylene glycol 450 950 This is a classic cologne base, with 100 parts of 2,
The addition of 3,4,4,7-pentamethyl-6,8-nonadien-2-ol greatly enhances the organoleptic properties. Colon changes completely. Lina,
Rule - Enhancing the cassis note makes it even more powerful, fresh and voluminous in character. If an equal volume of a 10% alcoholic solution of the oxime of 2,4,4,7-tetramethyl-6,8-nonadien-3-one (crude product of Example 17) is added thereto, the effect is the same. Moreover, in this case a surprisingly natural coriander character is established. Example 31 Parts by weight of flower complex Hydroxycitronellal 700 2,4,4,7-tetramethyl-6,8-nonadien-3-one 60 Hexyl salicylate 40 800 200 parts 5-ethyl-8-methyl By adding -7,9-decadien-4-one oxime, this floral complex is modified in the direction of linden flowers. The previously green-floral complex, quite surprisingly, now also exhibits a powdery note. However, 2,4,4,7-tetramethyl-6,8
Addition of an equal volume of a 10% alcoholic solution of the oxime of -nonadien-3-one (crude product of Example 17) to this complex results in a very effective correction in the direction of spice. The composition is particularly suitable for soap and detergent bases. Example 32 Parts by weight on an animal basis Sandera Gibb 100 Methyl 1-methylcyclododecyl ether
100 Acetyl Cedrene 100 Pachyuli Oil 50 Benzyl Salicylate 40 Linalyl Acetate 40 Myrrh Oil 30 Benzoin Resinoid (Syam) 30 Ethylene Brassylate 30 Castoliyum (Synthetic) 30 ω-Undecenal 20 Dodecanal 20 β-Ionone 20 p-Cresyl -phenylacetate 5 indole 5 DPG In addition, 1000 parts of 5-ethyl-8-methyl-7,9-decadien-4-one oxime (Example 21) are added to this base with animal characteristics, which is highly effective. will be strengthened. That fact is surprising regarding the odor of the oxime itself. The bass is now much warmer and exhibits even more volume. Example 33 Spice base parts by weight Benzyl acetate 100 Hydroxycitronellal 100 Phenylethyl alcohol 100 Amyl salicylate 100 Pachu lily oil 80 Ylang oil 50 Eugenol 50 Linalyl acetate 60 Musk ketone 50 Cedryl acetate 30 Epoxycedrene 30 Acetyl-cedrene 30 Coumarin 30 spearmint oil 15 sage oil 15 lemon oil 5 DPG plus 1000 50 parts of a 10% solution of the oxime of 2,4,4,7-tetramethyl-6,8-nonadien-3-one (Example 17) This initially introduces a fleeting spice note with a heavy sweet orientation into this base. The overall notes stand out in an impressive way from the initial base notes. The spearmint-lemon-sage of the compound is accentuated. The addition of 100 parts of 3,3,6-trimethyl-5,7-octadien-2-one oxime (Example 20) also gives the base more longevity and freshness. The lavender-like notes of the oxime itself combine very favorably with the spice-floral elements of the base, creating a fuguet,
Gives a compound effect.

Claims (1)

[Claims] 1 formula (In the formula, R, R ¹ and R ² are hydrogen or C _1-3
- represents alkyl, and X represents [Formula] [Formula] or [Formula], provided that when both symbols R ¹ are hydrogen, all 3
R ² represents C _1-3 alkyl and the total number of carbon atoms in the molecule does not exceed 15). 2 2,2-dimethyl-6,8-nonadiene-3
-ol according to claim 1. 3. The compound according to claim 1, which is 3-ethyl-4,7-dimethyl-6,8-nonadien-3-ol. 4. The compound according to claim 1, which is 2,2,4-trimethyl-6,8-nonadien-3-one. 5. The compound according to claim 1, which is 2,2,7-trimethyl-6,8-nonadien-3-ol. 6. The compound according to claim 1, which is 2,2,7-trimethyl-6,8-nonadien-3-one. 7. The compound according to claim 1, which is 2,3,3,7-tetramethyl-6,8-nonadien-3-ol. 8. The compound according to claim 1, which is 2,4,4,7-tetramethyl-6,8-nonadien-3-one. 9. The compound according to claim 1, which is 5-ethyl-8-methyl-7,9-decadien-4-one. The compound according to claim 1, which is 10 5-ethyl-8-methyl-7,9-decadien-4-one oxime. 11 The compound according to claim 1, which is 3,3,6-trimethyl-5,7-octadien-2-one. 12 The compound according to claim 1, which is 3,3,6-trimethyl-5,7-octadien-2-one oxime. 13 2,3,4,4,7-pentamethyl-6,
The compound according to claim 1, which is 8-nonadien-3-ol. 14 2,4,4,7-tetramethyl-6,8-
A compound according to claim 1 which is a nonadien-3-one oxime. 15 2,2-dimethyl-6,8-nonadiene-
3-one, 2,2-dimethyl-6,8-decadien-3-ol, 2,2-dimethyl-6,8-decadien-3-one, 4,7-dimethyl-6,8
-nonadien-3-one, 2,4,4,8-tetramethyl-6,8-nonadien-3-one, 5-
Isopropyl-2,9-dimethyl-7,9-decadien-4-one, 2,4,4,8-tetramethyl-6,8-nonadien-3-ol and 2,
A compound according to claim 1 selected from 4,4,7,8-pentamethyl-6,8-nonadien-3-one. 16 formula (In the formula, R, R ¹ and R ² are hydrogen or C _1-3
^{-alkyl ;} _{_} A fragrance composition characterized in that it comprises a compound having a total number of carbon atoms in the molecule (the total number of carbon atoms in the molecule does not exceed 15). 17. The fragrance composition according to claim 16, comprising 2,4,4-trimethyl-6,8-nonadien-3-one. 18 2,4,4,7-tetramethyl-6,8-
17. A fragrance composition according to claim 16, comprising nonadien-3-one. 19. The fragrance composition according to claim 16, comprising 2,2,7-trimethyl-6,8-nonadien-3-one. 20 2,2-dimethyl-6,8-nonadiene-
17. A fragrance composition according to claim 16, comprising 3-ol. 21 3-ethyl-4,7-dimethyl-6,8-
17. A fragrance composition according to claim 16, comprising nonadien-3-ol. 22 Claim 16 containing 2,2,7-trimethyl-6,8-nonadien-3-ol
The aromatic substance composition described in Section 1. 23 2,2,3,7-tetramethyl-6,8-
17. A fragrance composition according to claim 16, comprising nonadien-3-ol. 24. A fragrance composition according to claim 16, comprising 5-ethyl-8-methyl-7,9-decadien-4-one. 25. A fragrance composition according to claim 16, comprising 5-ethyl-8-methyl-7,9-decadien-4-one oxime. 26 Claim 16 containing 3,3,6-trimethyl-5,7-octadien-2-one
The aromatic substance composition described in Section 1. 27. The fragrance composition according to claim 16, comprising 3,3,6-trimethyl-5,7-octadien-2-one oxime. 28 2,3,4,4,7-pentamethyl-6,
17. A fragrance composition according to claim 16, comprising 8-nonadien-3-ol. 29 2,4,4,7-tetramethyl-6,8-
17. A fragrance composition according to claim 16, comprising a nonadien-3-one oxime. 30 formula (In the formula, R, R ¹ and R ² are hydrogen or C _1-3
^{-alkyl ;} _{_} The total number of carbon atoms in the molecule does not exceed 15), with the formula A compound with the formula (wherein R, R ¹ and R ² have the above meanings,
Y represents halogen) in the presence of a base and, if desired, the resulting ketone of the formula:
(a) reduction to form a secondary alcohol of formula; or (b) reaction with a compound of formula RMgY to convert it to a tertiary alcohol of formula; or (c) reaction with hydroxylamine to form an oxime of formula. The above-mentioned manufacturing method is characterized by converting.