DE2445649A1 - USE OF ARALIPHATIC KETONS AS FRAGRANCE AND FLAVOR - Google Patents

Description

Case 1250

FIRMENICH SA, Geneva

Use of araliphatic ketones as olfactory and

Flavors

The invention relates to the use of araliphatic ketones as fragrances and flavorings.

The araliphatic ketones which the invention relates to use correspond to the general one

formula

, 5

1 in which each of the symbols R to R is hydrogen or is a lower alkyl group having 1 to 6 carbon atoms and X is a group of the formula

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OR ⁶ R ⁷ R ⁶ R ⁷ O

Nile 8 I I Ii 8

-CCC-CH ₂ -R or -CC-C-CH-R ⁰

AWAY

fi Q

denote, wherein each of the symbols R to R is hydrogen or a lower alkyl group having 1 to 6 carbon atoms

• 7

represents, with the proviso that when R is in group B

6 8
Is methyl and R and R denote hydrogen, at least one of the symbols R to R represents a lower alkyl group,

ο fi 7

and when R is methyl and the symbols R and R denote hydrogen, at least one of the symbols R to R represents a lower alkyl group.

It has been found that the compounds of the formula _# I have interesting organoleptic properties and can therefore be used as fragrances and flavorings. They can be used as fragrance components or odor-modifying additives in the production of perfume compositions or as perfuming agents in products such as soaps, detergents and cleaning agents, cosmetic products, etc. The compounds of the formula I can also be used as flavorings or flavor-changing additives in the production of artificial flavors and as additives for improving, enhancing or otherwise changing the taste and aroma of foods for humans and animals, beverages, pharmaceutical products and tobacco products

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be used.

The invention relates to the use of the compounds of the formula I as fragrances or fragrance additives in fragrance compositions, the composition of which is outside the composition of the substances of formula I. Natural products or their concentrates.

The invention also relates to the use of the compounds of the formula I as flavorings or flavor additives in flavorings whose composition is outside the composition of those containing the substances of formula I. Natural products or their concentrates. ,

The compounds of the formula I are partly known and partly new. In the literature are found for the well-known Compounds, however, do not indicate any organoleptic properties. The fact that this is known Compounds can be used as fragrances and flavorings, was first established on the basis of the invention.

The 1- (2,3,6-trimethylphenyl) -but-l-en-3-one (formula IB, R ¹ = R * ~ R ⁵ = CH ^{1, R 2} , R ³ and R ⁶ to R ⁸ = Hydrogen) is a particularly interesting substance. It was first found in the urine of pregnant mares. See V. PRELOG et al., HeIv. Chim. Acta 31, 1799, 1807, 18ll (19 * 17) 7 isolated. However, the authors of this publication say nothing at all about the organoleptic properties of this compound. The same substance could now also be obtained from a flavor concentrate

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the yellow passion fruit (Passiflora edulis f. flavicarpa) can be isolated. The mentioned ketone is a trace substance that occurs in extremely low concentrations, namely of 3 ppm based on the weight of the flavor concentrate or 0.03 ppb (parts per billion) _t based on the weight of the whole fruit. The amounts of l- (2,3,6-trimethylphenyl) -but-l-en-3-one (hereinafter referred to as "passion fruit ketone") obtained from the aroma concentrate were too small to .because of the extremely low concentration enable a reliable assessment of the organoleptic properties. Therefore, larger amounts of passion fruit ketone were used according to the method of G. LOWE et al. (J. Chem. Soc. 1958 , 1855). It has now been found for the first time that this ketone has surprisingly interesting organoleptic properties and can be used not only as a flavoring but also as a fragrance. The breadth of its area of application is very large. The passion fruit ketone develops green, fruity and slightly precious wood-like smells and flavors.

When the compounds of formula I serve as a fragrance components or odor modifying additives in perfume compositions, they may be present in amounts of about 5 JO ^1?, Based on the total weight of the perfume compositions used.

When the compounds of formula I are used as flavor components or flavor-changing additives in flavorings

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serve, they can be used in amounts of about 1-10 % ₉ based on the total weight of the flavoring agent. If the compounds of the formula I are used as taste-changing additives in foods for humans and animals, beverages,
pharmaceutical products or luxury goods, such as tobacco, are incorporated, their concentration can be between about 1 ppm and 0.1 wt.

The compounds listed below that fall under the definition of formula I are new:

1- (2,3,6-trimethylphenyl) -l-methyl-but-l-en-3-one, l- (2,3,6-trimethylphenyl) -4-methyl-pent-l-en-3- one, l- (2,3,6-trimethylphenyl) -2-methyl-pent-l-en-3-one, 1- (2,3,6-trimethylphenyl) -non-l-en-3-one, 1- (2,3,6-Trimethylphenyl) -2-pentyl-but-1-en-3-one, 1- (2-methyl - ^ - isopropylphenyl) -but-1-en-3-one, 1- (2,3,5-Trimethylphenyl) -but-2-en-l-one, 1- (2, ⁱ l, 5-trimethylphenyl) -but-2-en-l-one, 1- (2,3, 6-trimethylphenyl) -but-2-en-l-one and 1- (* J, 5-dimethylphenyl) -but-2-en-l-one.

The compounds of the formula IA can be prepared by acylating a compound of the formula

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II

in the presence of a Friedl-Crafts catalyst with an acid chloride of the formula

0 it ⁶ R ⁷

1 I I

Hal-C-CC-CH ₂ -R

III

in which Hal denotes a halogen, e.g. chlorine or bromine, or with an acid anhydride of the formula

0 (C-

R ⁶ Η?
II

,8th.

IV

getting produced.

The acylation of the compounds II can be carried out according to methods known per se, e.g. according to the method described in "Organikum", VEB Deutscher Verlag der Wissenschaften, Berlin, 1968, page 306, described method.

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As Friedl-Crafts-Katälysator one can e.g. aluminum chloride, zinc chloride, tin chloride, iron trichloride, etc., use. The solvents which can be used as the acylation medium are, for example, halogenated hydrocarbons such as Methylene chloride, dichloroethane and chlorobenzene, hydrocarbons such as petroleum ether, or carbon disulfide, or nitrobenzene.

By acylation of compounds of the formula II with 2-methyl-but-2-ene-carboxylic acid chloride, 3-methyl-but-2-ene-carboxylic acid chloride or pent-2-ene-carboxylic acid chloride for example, get the following connections:

1- (2,3> 6-trimethylphenyl) -2 ~ methyl-but-2-en-l-one, 1- (2,3,6-trimethylphenyl) -3-methyl-but-2-en-l-one and 1- (2,3,6-trimethylphenyl) pent-2-en-1-one.

The compounds of the formula IB in which R in the side chain B is hydrogen can be obtained by condensation a compound of the formula

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1 5
in which R to R have the same meaning as in formula I, with a ketone of the formula

CH-CO-CH ₂ R VI

in which R is a lower alkyl group having 1 to 6 carbon atoms in an alkaline or acidic medium getting produced.

The condensation can be carried out according to methods known per se, for example according to the methods described by D.S. NOYCE et al. in J. Am. Chem. Soc. 81 62Ί (1959) and by M. STYLES et al. in J. Am. Chem. Soc. £ l, 628 (1959) described methods.

If methyl ethyl ketone as a compound of formula VI is used and the condensation is carried out in an alkaline medium, one obtains, for example, l- (2,3,6-trimethylphenyl) pent-l-en-3-one. However, if the same condensation is carried out in an acidic medium, one obtains, for example 1- (2,3> 6-trimethylphenyl) -2-methyl-but-l-en-3-one.

The compounds of the formula IB in which R in the side chain B is a lower alkyl group can by an aldol condensation of a ketone of the formula

CO-R

VII

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in which R ¹ to R ^{5 have} the same meaning as in formula I and R denotes a lower alkyl group having 1 to 6 carbon atoms, prepared with an aldehyde

will.

This condensation can be carried out using the method of WITTIG £ see G. WITTIG et al., Angew. Chemistry §0, 8 (1968) 7 be performed. This method was used to prepare, for example, 1- (2,3,6-trimethylphenyl) -l-methyl-but-l-en-3-one.

1- (2,3,6-Trimethylphenyl) -but-2-en-l-one can according to the method shown by the reaction scheme below getting produced:

By-product

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In the following exemplary embodiments, the temperatures are given in degrees Celsius.

A series of compounds of the formula I, in which X is the group -CO-CH = CH-CH, was named after the "Organikum", VEB Deutscher Verlag der Wissenschaften, Berlin 1968, page 306, described method. It became the following rule used:

A three-necked round bottom flask equipped with a stirrer, a dropping funnel, a reflux condenser and a calcium chloride tube was charged with ¹ JOO ml of dichloroethane. First 1.2 mol of powdered aluminum chloride and then 1.05 mol of but-2-ene-carboxylic acid chloride were added dropwise with stirring and cooling (5 °) with ice water. Afterward

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2U5649

became one mole of the starting aromatic compound of formula II dropwise while cooling with water at such a rate admitted that the contents of the flask were kept at about 20 °. The reaction mixture was refluxed for 1 hour and then left to their own devices overnight. The ketone aluminum chloride complex was made by carefully pouring out the Reaction mixture decomposes on ice * The organic layer was separated from the aqueous phase in a dropping funnel. The aqueous phase was extracted twice with dichloroethane. The combined organic phases were washed with water, 2- / Sigem aqueous sodium hydroxide and washed again with water. The washed solution was dried and freed from the solvent, whereupon the residue was distilled in vacuo.

The compounds prepared according to this procedure are summarized in the table below.

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TABEL

example cn Aromatic starting
links End product Physical Properties CCl ₁₁ ): \
t NJ 1 098 ' O f ^^ V "CO-CHsCH-CH- (3H, s), I. tn Ξ 2
«Ο toluene l- (p-methylphenyl) -but-2-en- = 1.5, (Ji
jr- co
ta 1-on ! CO (known connection, see I600, Literature 1) r * ^ N— CO-CH = CH-CH, KRS (60 MHz, solution in (53), 133 XJ 6.6-7.7 (5H, m), 2.08 T T 1.88 (3H, d of d, J ₁ : o-xylene l- (3,4-dimethylphenyl) -but- J ₂ = 4 Hz); 2-en-l-on IR: 1700, 1665, I63O, (new connection) 1570 cjn "¹; MS: 174 (M ⁺ , 46), 159 (100), 105 (42).

example

TABLE (port setting)

Aromatic starting compounds

End product

Physical Properties

m-xylene

p-xylene

CO-CH = Ch-CH, '

1- (2,4-Dimethylphenyl) but-2-en-l-one

(known compound, see reference 2)

CO-CH = CH-CH.

1- (2,5-dimethylphenyl) -but-2-en-1-one

(known compound, see reference 3)

TAB ELLE (port setting)

example

Aromatic starting compounds

End product

Physical Properties

^ 6

1,3,5-trimethylbenzene

1,3,4-trimethyl benzene

CO-CH = CH-CH.

1- (2,4,6-trimethylphenyl) -but-2-en-1-one

(known compound, see reference 4)

CO-CH = CH-CH.

l- (2,4,5-trimethylphenyl) -

but-2-en-l-one

(new connection)

KRS (60 MHz, solution in CCl ^): 7.08 (IH, s), 6.82 (IH, s), 6.1-6.7 (2H, m), 2.36 (3H, s) , 2.14 (6H, s), 1.84 (3H, d, J = 5 Hz); IR: 1660, 1650, 1620, 1550 cm "¹; MS: 188 (M ⁺ , 18), 173 (100), 158 (26), 147 (26), 146 (17), 119 (22), 41 ( 18).

TAB ELLE (continued)

For example

Aromatic starting compounds

Final product physical properties

(a)

1,3,4-trimethylbenzene

CO-CH = CH-CH.

CO-CH = CH-CH, Cb)

1- (2,3,5-trimethylphenyl) -but

2-en-l-on

(new connection)

-. / ** WM Γ * ΐί _ Π tJ

1- (2,3,6-trimethylphenyl) -but

2-en-l-on

(new connection)

b) KRS (60 MHz, solution in CCl ₁₁ ): 5.90-6.90 (4H, m), 2.21 (3H, s), 2, Ο4. (6H, s), 1.81 (3H , d, J = 5 Hz);

IR: 1700, 1670, 1650, 1620 cm "¹; MS: 188 (M ⁺ , 30), 173 (100), 159 (26), 158 (22), 147 (44), 119 (30), 91 ( 20).

c) KRS (60 MHz, solution in CCl ₄ ): 6.60-7.10 (2H, m), 6.0-6.5 (2H, m), 2.13, 2.02, 1.97 (3 x 3 H ₄ s), 1.74 (3H, d, J = 5 Hz);

IR: 1760, 1720 cm " ¹
MS: 188 (M ⁺ , 40), 173 (100), 159 (42), 158 (27), 147 (3D, 119 (37),. 91 (24).

a) The acetylation mixture was heated at 60 ° for 4 hours. References:

1. J.U. Lowe et al., J. Org. Chem. ^ O, 3001 (1965)

2. Chemical Abstracts 6-7, 32422 ρ

3. DV Hertzler et al., J. Org. Chem. 33, 2008 (1968) ¹ JRC Fuson, J. Am. Chem. Soc. £ 5, 2 ^ 50 (1936).

Example 8

~ 1- (2,3,6-Trimethylphenyl) -but-2-en-l-one

50 g (0.36 mol) of 2,5,6-cyclohex-2-en-l-one dissolved in 250 ml of methanol were at 23 ° in the presence of 500 mg platinum-carbon catalyst (10 Jiig) catalytically hydrogenated. The hydrogenation mixture was filtered, the solvent was evaporated from the filtrate and the residue was distilled. Ί2 g of 2,3,6-trimethyl-cyclohexanone were obtained.

A solution of 29.5 g (0.17 mol) of 2,3,6-trimethylcyclohexanone in 30 ml of dimethylsulfoxide was treated of the complex formed from sodium acetylide ethylenediamine and at 7 with stirring, with 2 ¹ J g (0.26 mol). The reaction mixture was stirred at 23 ° for 20 hours and then poured into a mixture of water and ice. After the usual work-up of the mixture and distillation of the residue, 27 g (0.16 mol) of 1-ethynyl-2,3,6-trimethyl-cyclohexan-1-ol were obtained.

A solution of 22 g of l-ethynyl-2,3,6-trimethyl-cyclo-

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hexan-l-ol in a mixture of 90 ml of acetic acid and 13 ml of water was added to 15 g of the ion exchanger "Dowex" in its acid form (50 WX 2200, 400 mesh). The mixture was stirred at 60 ° for 10 days. The ion exchanger was removed by filtration on a "Celite" filter, after which water was added to the filtrate. After extraction with ether, washing the extract with water and aqueous sodium bicarbonate, removing the solvent and fractional distillation of the residue, 11 g of a mixture distilling at 91-98 ° were obtained, the l-acetyl-2,5 _> 6-trimethyl-cyclohex- l-ene and l-acetyl-2,3 »6-trimethyl-cyclohex-l-ene as main components and 1,3,4-trimethyl-2-ethyl-benzene as a by-product. This mixture was used for the next reaction stage without further work-up,

3.63 g of the mixture mentioned and 1.58 g of sulfur were heated in a sealed tube for 20 hours at 240 °. The tube was then opened to allow the hydrogen sulfide formed to escape, whereupon the reaction mixture was taken up in ether. The ethereal solution was chromatographed on a column of 20 ml of aluminum oxide (Woelm). The combined eluates were concentrated and subjected to fractional distillation. This gave 627mg of an at 75-92 ° / 12 torr and boiling mainly of l, 3, ¹ * -trimethyl-2-ethyl-benzene existing fraction and a 903 mg at 1O5-11O ° / 12 torr and boiling mainly of 2, 3,6-trimethylphenyl-methyl-ketone existing fraction. A sample of the latter fraction was chromatographed

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tography purified in the gas phase. The cleaned sample had the following physical properties:

KRS: 6.79 (2H, m), 2.24, 2.10, 2.05, 1.98 (4 3H, s); IR: 1700 cm "¹;

MS: 162 (M ⁺ , 42), 147 (100), 119 (79), 91 (20).

By reacting .0.24 g (10 mmol) of magnesium and 1.87 g (10 mmol) of 1,2-dibromoethane in 13 ml of ether was a essential solution made from magnesium bromide. To this Solution were first 6.2 ml of a 1-N solution at 5 with stirring of butyllithium (10 mmol) in hexane and then a solution of 1.05 g (10 mmol) N-Methylanilih in 7 ml benzene added » The reaction mixture was stirred for a further 15 minutes at 5 ° and then within 10 minutes at 5 ° dropwise with a Solution of 860 mg (5.3 mmol) 2,3,6-trimethylphenyl-methyl-ketone added in 7 ml of benzene. The solution was stirred at 23 for 20 min and then cooled to 5. The cooled solution was A solution of 1.17 g of acetaldehyde (26 mmol) in 7 ml of benzene was added dropwise over the course of 15 minutes. The reaction mixture was Stirred for 75 min. At 23 ° and mixed with water. The aqueous phase was acidified with 1N sulfuric acid and with ether extracted, whereupon the extract with 2% aqueous sulfuric acid and then washed with water, with MgSO. dried and freed from solvent. 2.0 g of one was obtained Crude product containing l- (2,3,6-trimethylphenyl) butan-3-ol-l-one

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This product was dissolved in 10 ml of benzene and 170 mg (2.8 mmol) of boric acid were added to the solution. The reaction mixture was subjected to azeotropic distillation. After 2 hours the benzene was distilled off. The residue was subjected to thermolysis at 90-160 ° / 0.05 torr. 1.09 g of a product boiling at about 85 ° / _{0.05 torr and containing 1- (2.3 S} 6-trimethylphenyl) but-2-en-1-one were obtained. The product would be redistilled at 71-78 ° / 0.05 torr. The distillate was subjected to preparative gas phase chromatography. Finally the product was subjected to molecular distillation. The purified substance had the physical properties given in Example 7. The l- (2,3,6-trimethylphenyl) -but-2-en-l-one develops interesting fruity, woody and slightly oily odor and taste notes that are reminiscent of dried fruits, especially dried figs and dried grapes.

Example 9

1- (2,3> 6-trimethylphenyl) but-l-en-3-one

One with a stirrer, one dropping funnel, one Thermometer, an inlet tube for the introduction of an inert gas and an outlet tube equipped with a three-neck flask was with 35 g (0.25 mol) 2,3,6-trimethylbenzaldehyde and 150 g

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(2.6 moles) of acetone charged. Nitrogen was now introduced into the flask. A solution of 3.4 g NaOH (0.085 mol) in 20 ml Water was added to the contents of the flask with stirring while maintaining the temperature at 20. The reaction mixture Was stirred for a further 20 hours, then acidified with 400 ml of 2-55% sulfuric acid and extracted with ether. The extract was washed neutral and concentrated. 49 g of crude product were obtained which were subjected to fractional distillation in a Vigreux column was subjected. 32 g of at 75-76 ° / 0.100 torr were obtained boiling 1- (2,3 »6 ^ trimethylphenyl) -but-l-en-3-one.

Example 10

1- (2,3,6-trimethylphenyl) -2-methyl-pent-1-en-3-one

The apparatus used was similar to the apparatus described in Example 9, but instead of the Dropping funnel an inlet tube for the introduction of hydrogen chloride gas on. The flask was filled with 8 grams (0.054 moles) of 2,3,6-trimethylbenzaldehyde and 14.75 grams (0.17 moles) of diethyl ketone loaded. The mixture was cooled to 10 °, whereupon dry hydrogen chloride gas was introduced. The temperature of the Reaction mixture was kept between 10-15 by cooling. After 67.4 ml (0.027 mol) of hydrogen chloride gas had been passed in the reaction mixture was left on its own for 24 hours at room temperature. Then the reaction

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Mixture diluted 30 ml of water and extracted with ether. The extract was washed neutral and concentrated. By fractional distillation of the residue in a Vigreux column 3.5 g of 1- (2,3,6-trimethylphenyl) -2-methyl-pentl-en-3-one were obtained. This product had the following physical Features on:

99-103 ° / 0.01 torr; n ^ ⁰ = 1.5 * 35; dj ° = 1,0008 MS: M ⁺ 216 (1); m / e: 201 (100), 187 (32), 159 (20), 129 (16),

1 ** (15), 29 (9).

KRS. (60 MHz, CCl ₁₁ ) PPm: 1.15 (3H), 1.55 (3H), 2.05-2.23 (9H),

2.8 (2H, q), 6.9 (2H, s), 7, * (IH, s).

Example 11

2,3,6-Trimethylbenzaldehyde was reacted with methyl-ethyl-ketone according to the method described in Example 9. 1- (2,3,6-Trimethylphenyl) pent-1-en-3-one was obtained, which had the following physical properties: bp 81 ° / 0.01 torr; n ^ ° = 1.55 * 1; d ^ ° = 0.99 * 1 MS: M ⁺ 202 (12); m / e: 187 (100), 173 (84), 1 * 5 (* 5), 130 (36),

115 (27), 29 (24).

Example 12

2,3,6-Trimethylbenzaldehyde was reacted with methyl-ethyl-ketone according to the method described in the example. One received

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1- (2,3,6-Trimethylphenyl) -2-methyl-but-l-en-3-one, which had the following physical properties: bp 77 ° / o, ol torr; n ^ ⁰ = 1.5462; d ^ ° = 0.9910 MS: M ⁺ 202 (2); m / e: 187 (100), 43 (26), 129 (16), 144 (12),

172 (11), 159 (H).

Example 13

'2,3,6-Trimethylbenzaldehyde was reacted with methyl isopropyl ketone according to the method described in Example 9. 1- (2,3,6-Trimethylphenyl) -4-methyl-pent-l-en-3-one was obtained, which had the following physical properties: bp 100-103 ° / 0.01 torr; η £ ° = 1.5499; djj ° = 0.9787 MS: M ⁺ 216 (6); m / e: 173 (100), 201 (42), 145 (39), 130 (22),

115 (13), 43 (8). KRS (60 MHz, CCl ₁₁ ) ppm: 1.18 (6H, d); 2.23 (9H); 2.78 (IH, q);

6.23 (IH, d, J = 17 Hz); 6.87 (2H, s);

7.67 (IH, d, J = 17 Hz).

Example 14

2, -3,6-trimethylbenzaldehyde was according to the example 9 described method reacted with methyl hexyl ketone. Man obtained l- (2,3,6-trimethylphenyl) ~ non-l-en-3-one, which has the following physical properties:

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MS: M ⁺ 258 (4); m / e: 173 (100), 243 (68), 145 (20), 130 (14),

43 (10), 115 (9). KRS (60 MHz, CCl ₁₁ ) ppm: 0.9 (3H, t); 1.3 (8H, m, broad); 3.13

(3H, s); 2.19 (6H, s); 2.54 (2H, t);

6.12 (IH, d, J = 17 Hz); 6.87 (2H, s);

7.58 (IH, d, J = 17 Hz),

Example 15

2,3,6-Trimethylbenzaldehyde was reacted with methyl-hexyl-ketone according to the method described in the example. 1- (2,3,6-Trimethylphenyl) -2-pentyl-but-l-en-3-one was obtained, which had the following physical properties: bp 103-105 ° / 0.001 torr
MS: M ⁺ 258 (I) V m / e: 2 ^ 3 (100), 43 (38), 187 (18), 173 (11),

145 (6), 153 (5).

KRS (60 MHz, CCl ₁₄ ) ppm: 0.75 (3H, t), 0.87-1.1 (6H, m, broad),

2.07-2.37 (12H, 4s), 6.9 (2H, s), 7.33 (IH, s).

Example 16

2-Methyl-4-isopropyl-benzaldehyde was according to the im Example 9 implemented method described with acetone. One received

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l- (2-Methyl-4-isopropyl-phenyl) -but-l-en-3-one, which has the following

physical properties:

110-114 ° / 0.01 torr

MS: M ⁺ 202 (23); m / e: 187 (100), 43 (71), 159 (65), 1 ^ 5 (61),

202 (23), 1 ^ 5 (18), 115 (18).

KRS (60 MHz, CCl ₁₁ ) ppm: 1.16 (3H, s), 1.27 (3H, s), 2.25 (3H, s),

2.3 ¹ I (3H, s), 2.7 (IH, m), 6.57 (IH, d, J = 17 Hz), 7.06 (2H, s); 7.38 (IH, s), 7.71 (IH, d, J = 17 Hz).

Example 17

A flavor base would be made according to the following formula:

Weight-g

Methylcyclopentenolone 6.0

Vanillin 4.0

Tolu balm 50 % * 0.5

Sumatran Benzoin 50 % * 3.0

Furfural 0.3

Clary sage oil 0.5

2-methyl-butyric acid 2.0

Isovaleric acid 2.0

Acetaldehyde 2.0

Anise alcohol 20.0

Propylene glycol 59.7

100.0 509814/1233

5% 1- (2,3 »6-trimethylphenyl) -but-2-en-l-one were added to this flavor base. The flavoring agent and the flavoring base thus obtained were subjected to a taste test at a concentration of 0.01% in an aqueous 10% sugar solution. The taste testers found that the aroma was fruity and fig-like compared to the aroma base and also had a taste note reminiscent of dried figs.

Example 18

A base for a peach flavor was made according to the following formula:

Weight -%

Maltol 2.0

Vanillin 4.0

Linalyl caproate 1.0

Bergamot oil 1.0

Isovaleric acid 2.5

n-hexanal 1.5

Benzyl acetate "3 * 0

Ethyl butyrate 3.5

γ-undecalactone 4.0

Ethyl aproate k _t 0

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Ethyl acetate 7.5

Benzyl alcohol 15.0

. Propylene glycol 51.0

100.0

5% 1- (2,3,6-trimethylphenyl) -but-1-en-3-one were added to this flavor base. The aroma composition obtained and the aroma base were subjected to a taste test at a concentration of 0.01 % in a 10% aqueous sugar solution. The taste testers found that the flavoring agent had a greener taste note than the flavoring base and tasted more juicy and fruity.

Example 19

It rde w a perfume base according to the following formula was prepared:

Parts by weight

Artificial bergamot oil 120

Artificial lime oil 45

Nerol 170

Neroli bigarade 45 Oak moss absolute 50 Jf * 45 Rosemary oil 45

Thyme oil 45

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Olibanum Oil 30

Origanum Oil 30

Artificial jasmine oil 30

a-Damascone 10 % * 80

Rose oxide (counterclockwise) 10 % * 30

Labdanum ice. 80

Pentadecanolide 10 % * ■ 80

Muscon 10 % * 80

Allspice leaf oil "JJ5.

1000 * in diethyl phthalate

This perfume base had a characteristic citrus-like appearance Scent note on.

350 parts by weight of 1- (2,3,6-trimethylphenyl) but-1-en-3-one were added to 650 parts by weight of this base. the Compared to the base, the perfume composition obtained had a more original and spicy fragrance note and, moreover, one of the fragrance nuance reminiscent of algae.

Example 20

A perfume base was prepared according to the following formula:

Parts by weight

Decanal IO % * 20

Undecylenealdehyde 10 % * 90

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Methylnonylacetaldehyde 10? * 2445649
10 Artificial jasmine oil 180 Artificial rose oil 80 Methyl dihydrojasmonate 10 % * ' 60 Ylang 20th Hydroxycitronellal 80 Artificial bergamot oil 120 Labdanum ice 10 % * 35 Phenylmethylcarbinylacetate 20th Citronellol - 60 Phenylethyl alcohol 60 Pentadecanolide 10 % * 60 Coumarin 35 Oriental sandalwood oil 20th Eugenol 20th Isobutyl salicylate 20th Neroli bigarade 10 1000

* in diethyl phthalate

130 parts by weight of 1- (2,3,6-trimethylphenyl) but-2-en-1-one were added to 870 parts by weight of this perfume base. The perfume composition obtained had a more original fragrance than the base and also had a more fruity one and more woody character.

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example

l- (2,3> 6-Trimethylphenyl) -but-l-en-3-one was used as Flavor-changing additive in those listed below Food and Beverage Used: Food Concentration.

or drink of the additive

1. Raspberry syrup (to dilute 1: 4)

2. Strawberry juice (natural)

3. Passion fruit juice (natural)

4. Mushroom soup (commercial product)

5. Carbonated drinks

Sugar syrup 65 ° Brix 30 cc.

Citric acid, 50- ies

Solution 0.4 cc.

Passion fruit juice (natural) 25 cc.

1-liter alcoholic solution of the additive carbonated water

up to 200 cc.

10 ppm 3 ppm 2 ppm 3 - 5th
Λ ppm drink 1 Drink 2

30 cc.

0.4 cc. 25 cc.

0.02 cc. cc '.

The following taste effects were observed: 1. The syrup containing the additive had a fuller, more rounded and fruity taste than the added syrup.

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2. The juice containing the additive had a greener and more fruity flavor and a less pronounced "cook" flavor than the juice without additive.

3. The juice containing the additive had a fresher and more distinctive head note and a more fruity taste than the juice without the additive.

4. The soup containing the additive had a fuller and fresher taste reminiscent of "Champignons de Paris" on as the additive soup.

5. Drink 2 was judged to be fresher and fruity than drink 1.

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Claims (4)

PATENT CLAIMS in which each of the symbols R to R is hydrogen or a lower alkyl group having 1 to 6 carbon atoms and X is a group of the formula -C R ⁶ R ⁷ II CH ₂ -R ' or R ⁶ R ⁷ II -CC - C- CH ₂ -R he ρ denote, wherein each of the symbols R to R represents hydrogen or a lower alkyl group having 1 to 6 carbon atoms with the proviso that when R in group B is methyl and C Q R and R denote hydrogen, at least one of the symbols R to R represents a lower alkyl group, and when R denotes methyl fi 7 and the symbols R and R denote hydrogen, at least one of the symbols R to R represents a lower alkyl group, as fragrances or fragrance additives in fragrance compositions, 509814/1233 2. Use of the compounds of the formula given in claim 1 as flavorings or flavor additives in flavorings whose composition is outside the composition of those containing the substances of formula I. Natural products or whose concentrates lies. 3. Execution according to claim 2, characterized in that the compounds of formula I or these compounds containing flavorings for flavoring food for humans and animals, beverages and pharmaceutical products be used. 4. The connections: l- (2 ₉ 3,6-trimethylphenyl) -l-methyl-but-l-en-3-one, l- (2,3,6-trimethylphenyl) -ll-methyl-pent-l-en-3- one, l- (2,3,6-trimethylphenyl) -2-methyl-pent-l-en-3-one, l- (2,3,6-trimethylphenyl) -non-l-en-3-one, 1- (2,3,6-Trimethylphenyl) -2-pentyl-but-1-en-3-one, 1- (2-methyl- * J-isopropylphenyl) -but-1-en-3-one, l - (2,3,5-Trimethylphenyl) -but-2-en-l-one, 1- (2, l \ , 5-trimethylphenyl) -but-2-en-l-one, 1- (2,3 , 6-trimethylphenyl) but-2-en-1-one and 1- ( ¹ I, 5-dimethylphenyl) -but-2-en-1-one. 509814/1233