NL8302289A - PHENYL DERIVATIVES OF 2,4-DIMETHYL-2-HEXENE. - Google Patents

Description

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# I

NO 31914 1 APPLICANT AS INVENTORS: 1. Kolt Vladimirovich LEETS.

2. Heino Antonovich GRADE, 3. Sirie Ottovna VIITMAA and

4. Toomas Kaljuvich VYALIMYAE

Phenyl derivatives of 2,4-dimethyl-2-hexene

The invention relates to new chemical compounds, in particular phenyl derivatives of 2,4-dimethyl-2-hexene, which can be used as perfumes in the perfume preparation or as intermediates for their synthesis · These compounds can be used in fragrant compositions for perfumes and cosmetics (perfumes, lotions, spreads and the like) and as fragrant additives for household chemical products (soaps, washing powders, shampoo, cleaning agents, aerosols and the like).

Substances with a related structure are known, such as 3-methyl-1-phenyl (or 1-methylphenyl) -4-hexenols and their acetates of the general formula 1, in which R represents a hydrogen atom or the group -0 (0) 0¾ t and R 'represents a hydrogen atom or a methyl group (see Russian inventor certificate 685658).

These substances can be used as fragrances. They have a green fragrance with a greasy note or a bird cherry fruit fragrance with a grassy note.

There are also known compounds such as 3-methyl-1-phenyl-4-hexen-1-one of the general formula 2, wherein R represents a hydrogen atom or a methyl group.

These compounds can be used as fragrances. They have an odor of bitter vegetables (cf. Russian inventor certificate 721.402).

Aromatic ketones of the general formula 3 are known, in which R represents a hydrogen atom or a methyl group and R 'represents a methyl group.

These compounds have a geranium scent (cf. Russian inventor certificate 574.434).

All of these prior art compounds do not have a sufficiently stable and intensive odor and exhibit a limited variety of odors, which limits their use in the perfume preparation.

The present invention is directed to the provision of new compounds, namely phenyl derivatives of 2,4-dimethyl-2-hexene, which can be used as fragrances and which have more intensive and stable natural scents of various nuances, which enhances the area of fragrant ingredients.

The compounds of the present invention are new and hitherto unknown in the literature.

According to the present invention, the new compounds, ie the phenyl derivatives of 2,4-dimethyl-2-hexene, have the general formula 4, in which R represents a hydrogen or a methyl group and A has the group> CHCl, .i »CHOH or> * Represents C = 0.

The compounds of the present invention include colorless or yellowish liquids with a stable intensive odor, which are readily soluble in ethanol. The compounds of formula IV, wherein A represents the group> CHOH or> C = 0, are resistant to both alkaline and acid medium.

The compounds of the present invention are prepared in the following manner.

Methyl chloropentenes are reacted with styrene or methyl styrene in the presence of a catalyst, e.g. tin (IV) chloride. The conversion can be carried out in an environment of an organic solvent or without a solvent at a temperature in the range from 0 to 100 ° C. After the completion of the reaction, the catalyst is separated from the reaction mixture, the unreacted compounds are distilled off and the desired product, for example 2,4-dimethyl-6-phenyl (or methylphenyl) -6-chloro-2-hexene of the residue distilled.

These compounds can be used as intermediates for the synthesis of fragrances.

Saponification of 2,4-dimethyl-6-phenyl (or methylphenyl) -chloro-2-hexene gives the desired product, ie 3,5-dimethyl-1-phenyl (or methylphenyl) -4-hexen-1-ol ·

These substances have the following fragrance: notes of bergamot, linalyl-35 acetate, a faint green note or bird cherry fruit scent, and are used as fragrant ingredients in the preparation of perfumes.

From 3,5-dimethyl-1-phenyl (or methylphenyl) -4-hexen-1-ol the desired product, ie 3,5-dimethyl-1-phenyl (or methylphenyl) -4-hexen-1-one is obtained by oxidation obtained.

40 These compounds have a green odor or bitter green odor with a hue of iris or dill roots with 83022Θ9 * »3 and can be used as fragrances in the perfume industry.

All compounds of the present invention have a more intensive, stable (stability of more than 1 week on paper), natural, vibrant and interesting scent compared to known fragrances, allowing them to be used to formulate very high-quality formulations . The variety of the fragrances provides an opportunity for a more extensive use of the fragrant ingredients of the present invention in various fragrance formulations.

The invention is further elucidated in the following examples. Example I

208.4 g of styrene, 118.5 g of methyl chloropentenes and 327 g of dichloroethane are placed in a flask and, with stirring under an atmosphere of argon, 2 ml of a 2% by weight solution of tin (IV) are made over 1 hour. ) chloride in dichloroethane. The reaction temperature is kept in the range from 0 to 20 ° C. At the end of the reaction, carbamide is added, the mixture is stirred, it is allowed to settle and carbamide is filtered off with the catalyst complex. The unreacted substances are distilled off. The residue is distilled under reduced pressure, removing 2,4-dimethyl-6-phenyl-6-chloro-2-hexene at a temperature of 105-108 ° C / 4 mm Hg; the product is obtained in an amount of 140.4 g (yield 69%), its melting point is 105-108 ° C / 4 mm Hg; 20 20 25 = 1.5158, d * - 0.981, purity 93%,

Cl 15.75 wt% (calculated 15.94 wt%); molecular mass 223.5 (calculated 222.7).

Chemical shifts of the NMR spectrum: compound of the formula 5 30 Cl C-2 C-3 C-4 C-5 C-6 C-7 treo 25.8 132.1 129.6 30.5 48.0 62 .5 18.1 erythro 25.7 131.1 129.6 30.3 47.8 61.5 17.9 C-8 C-9 C-10 C-11 C-12 C-13 C-14 35 treo 21.3 142.7 126.9 128.5 126.9 128.5 126.9 erythro 20.9 141.7 127.3 128.0 126.9 128.0 127.3

Example II

70 g of methyl chloropentenes, 70 g of m-methyl styrene 8302289% 4 and 140 g of dichloroethane are placed in a flask. 1 ml of a 2% by weight solution of tin (IV) chloride in dichloroethane is added with stirring under an atmosphere of argon. The reaction temperature is kept at 0 ° C. At the end of the reaction, carbamide is added, the mixture is stirred, allowed to settle and filtered. The solvent and unreacted compounds are distilled off. 2,4-Dimethyl-6- (3-methylphenyl) -6-chloro-2-hexene is distilled from the residue; the product is obtained in an amount of 71.6 g, yield 51%, boiling point 118-120 ° C / 1 mm Hg; n * = 1.5139; 20 D 10 d ^ = 0.9726, purity 92%, Cl 14.0 wt% (calculated 14.19 wt%), molecular mass 236.5 (calculated 236.78).

Chemical shifts of the C NMR spectrum: compound of the formula 6 15 Cl C-2 C-3 C-4 C-5 C-6 C-7 C-8 treo 25.9 132.2 129.5 30.4 47.7 62.7 18.1 21.5 erythro 25.8 131.1 129.6 47.6 61.6 C-9 C-10 C-11 C-12 C-13 C-14 C-15 20 treo 142.5 127.5 138.2 128.8 123.9 128.5 21.1 erythro 141.5 128.0 138.1 128.9 124.3

Example III

53.5 g of methyl chloropentenes, 53.5 g of p-methylstyrene (90 wt%) and 107.0 g of dichloroethane are stirred under an atmosphere of argon for 55 minutes, whereby a 2 wt% solution of tin (IV) chloride in dichloroethane is added thereto. The temperature of the mixture is kept in the range from 0 to 10 ° C. At the end of the reaction, carbamide is added, the mixture is stirred, it is allowed to settle and it is filtered. The unreacted compounds are distilled off. From the residue, 2,4-dimethyl-6- (4-methylphenyl) -6-chloro-2-hexene is distilled off under reduced pressure in an amount of 45.7 g with a purity of 89%. The yield of the product thus obtained is 42.4%. Boiling point 120-124 ° C / 1 mm Hg; n ^ 1.5188, d ^ 0.9699, Cl 14.3 wt% (calculated 14.19 wt%), molecular weight 237.1 (calculated 236.78).

Chemical shifts of the ^ C NMR spectrum: compound of the formula 7 8302289 φ,.

5 Cl C-2 C-3 G-4 C-5 C-6 C-7 C-8 treo 25.9 132.2 129.5 47.7 62.6 30.4 18.1 21.5 erytro 25 , 8 '131.1 129.6 47.6 61.7 5 C-9 C-10 C-11 C-12 C-13 C-14 C-15 treo 139.6 126.8 137.8 126.8 129.2 129.2 20.9 erythro 139.9 127.2 137.9 127.2 10

Example IV

20.8 g of styrene, 23.7 g of methyl chloropentenes, 0.001 g of hydroquinone, and 0.02 g of anhydrous zinc chloride are placed in a flask and stirred under an atmosphere of argon. The reaction temperature is kept in the range from 0 to 80 ° C. At the end of the reaction, water is added, the reaction mixture is stirred, it is allowed to settle and the layers are separated. The product is dried over anhydrous sodium sulfate, distilled under reduced pressure at 105-108 ° C / 4 mm Hg to give 32.9 g (74% yield) of 2,4-dimethyl-6-phenyl-6-chloro-2- hexene 20 20 20; Πρ * 1.5158; d ^ 0.981; purity 93%, Cl 15.75 wt% (calculated 15.94 wt%), molecular mass 223.5 (calculated 222.7).

55 g of water, 14 g of sodium hydrogen carbonate and 25 g of 2,4-dimethyl-6-phenyl-chloro-2-hexene are placed in a flask. The mixture is stirred at a temperature of 95-100 ° C under an atmosphere of argon until all chlorine in the organic layer has disappeared.

Then the layers are separated. The organic layer is dried over anhydrous sodium sulfate and distilled under reduced pressure to give 18.6 3,5-dimethyl-1-phenyl-4-hexen-1-ol (yield 81% of theory).

30 20

Boiling point 96-97 ° C / l mm Hg; n »1.5143; 20 D d * 0.9510, molecular mass 203 (calculated 2 04.31), purity 95.2%. Characteristic fragrance properties: notes of bergamot, linalyl acetate, a weak green note.

2 ^ Chemical shifts of the ^ 3C NMR spectrum: compound of the formula 8 8302 289 6 Cl C-2 C-3 G-4 05 06 07 erythro 130.9 29.3 47.3 72.5 25.8 130.6 17 .9 treo 131.0 29.8 47.0 73.3 5 08 09 Cl O Oil 012 013 014 erytro 21.7 145.7 125.7 128.2 127.1 128.2 127.1 treo 21.4 144.8 126.2 128.6 127.3 128.6 127.3

10 Example V

150 ml of water, Hg sodium hydrogen carbonate and 27.5 g of 2,4-dimethyl-6- (3-methylphenyl) -6-chloro-2-hexene, prepared as in Example 2 above, are placed in a flask. 0.03 g of hydroquinone are added to the mixture. The reaction material is stirred at a temperature of 100 ° C under an atmosphere of argon until chlorine disappears into the organic layer. The organic layer is separated and distilled under reduced pressure to give 21.5 g of 3,5-dimethyl-1- (3-methylphenyl) -4-hexen-1-ol (yield 84%). Boiling point 115-120 ° C / 1 mm Hg, n = 1.5141;

20 D

2p d * 0.9405, purity 91.3%, molecular mass 216.0 (calculated 218.34). Characteristic fragrance properties: floral-fruity with an almond nut.

1 s

Chemical shifts of the C NMR spectrum; compound of the formula 9 25 Cl C-2 C-3 C-4 C-5 C-6 C-7 C-8 erythro 130.5 131.2 29.5 47.1 73.6 21.4 25.8 17, 9 treo 131.0 130.8 30.0 47.4 72.7 21.7 30 C-9 C-10 C-ll C-12 C-13 C-14 C-15 erythro 144.9 126.9 128 , 123.2 137.8 128.3 21.4 treo 145.7 126.5 128.0 122.8

Example VI 35 150 g of water, 11 g of sodium hydrogen carbonate and 28.4 g of 2,4-dimethyl-6- (4-methylphenyl) -6-chloro-2-hexene, prepared as described in Example III above, are prepared in a flask and 0.03 g of hydroquinone are added thereto. The mixture is stirred at a temperature of 95-100 ° C under an atmosphere of argon, after which the 8302289 7 layers are separated. The organic layer is dried over anhydrous sodium sulfate and distilled under reduced pressure.

20.7 g of 3,5-dimethyl-1- (4-methylphenyl) -4-hexen-1-ol are obtained (yield 79%), boiling point 117 ° C / 1 mm Hg, n * 1.5151 ; 20 D 5 d * 0.9359, purity 89.6%, molecular mass 217.1 (calculated 218.34). Characteristic properties of the odor: the odor is identical to that of 3,5-dimethyl-1- (3-methylphenyl) -4-hexen-1-ol.

Chemical shifts of the C NMR spectrum: compound of the formula 10 10 Cl C-2 C-3 C-4 C-5 C-6 C-7 C-8 erythro 130.5 131.2 47.2 73.7 21.4 25.8 29.5 17.9 treo 130.9 130.8 47.4 72.5 21.7 15 C-9 C-10 C-11 C-12 C-13 C-14 C-15 erytro 142.0 126.2 129.0 136.9 126.2 129.0 21.0 treo 142.7 125.7 129.0 136.7 125.7

2Q Example VII

10.4 g styrene, 11.8 g methyl chloropentenes, 0.001 g tert. butyl pyrocatechol and 0.01 g anhydrous zinc chloride are placed in a flask and stirred under an atmosphere of argon. The temperature during the conversion is kept in the range of 0-100 ° C. At the end of the reaction, a cooled aqueous glycol solution is added, stirred, allowed to settle and the layers are separated. The product is dried over anhydrous sodium sulfate. The product, ie 2,4-dimethyl-6-phenyl-6-chloro-2-hexene, is removed under reduced pressure at a temperature of 105-108 ° C / 4 mm Hg in an amount of 17.2 g. Distilled (yield 77.6%), n * 1.5158;

JU 20 D

d ^ 0.981, purity 93%, Cl 15.75 wt% (calculated 15.95 wt%), molecular mass 223.5 (calculated 222.7). Then 33 g of water, 9 g of sodium hydrogen carbonate and 15 g of 2,4-dimethyl-6-phenyl-6-chloro-2-hexene are introduced into the flask and the atmosphere is argon 22 at 100 ° C. stirred intensively until chlorine has disappeared in the organic layer. Then the layers are separated. The organic layer is dried over anhydrous sodium sulfate and distilled under reduced pressure to give 11 g (80% yield) of 3,5-dimethyl-1-phenyl-4-hexen-1-ol. Boiling point 96-97 ° C / l mm Hg, 20 20 n ^ 1.5143; d ^ = 0.9510, molecular mass 203 8302289 V * 8 (calculated 204.3), purity 95.2%. Then 50 g of water, 9 g of potassium dichromate and 5.5 ml of concentrated sulfuric acid are introduced into the flask. While stirring, 7 g of 3,5-dimethyl-1-phenyl-4-hexen-1-ol are added dropwise at 0 ° C, then the mixture is stirred at a temperature of 40 ° G for 1 hour. The product obtained is poured into ice-cold water. The organic layer is extracted with petroleum ether, washed with a 1 wt.% Solution of sodium carbonate and then with a saturated solution of sodium chloride until the washings react neutral. The product obtained is dried over anhydrous sodium sulfate and the solvent is distilled off. The product is distilled under reduced pressure. 5.8 g of 3,5-dimethyl-1-phenyl-4-hexen-1-one are obtained (yield 75%). Boiling point 101-102 ° C / 2 mm Hg, il »1.5202; 20 D d * 0.9581, molecular mass 201.6 (calculated 202.3), purity 90.1%. Characteristic scent properties: from dill root and green nuts.

I · 3

Chemical shifts of the C NMR spectrum: compound of the formula 11 20 Cl C-2 C-3 C-4 C-5 C-6 C-7 25.7 130.8 129.8 29.5 46.3 199 , 8 17.8 C-8 C-9 C-10 C-11 C-12 C-13 C-14 21.2 137.6 128.1 128.5 132.8 128.5 128.1 25

Example VIII

150 ml of water, 11 g of sodium hydrogen carbonate and 27 g of 2,4-dimethyl-6- (3-methylphenyl) -6-chloro-2-hexene, prepared as described in Example 2 above, are placed in a flask. 0.3 g of hydroquinone are added to the mixture. The mixture is stirred at a temperature of 100 ° C until chlorine disappears in the organic layer. The organic layer is separated and distilled under reduced pressure to give 21.5 g of 3,5-dimethyl-1- (3-methylphenyl) -4-hexen-1-ol (86% yield). Boiling point 115-120 ° C / 1 mm Hg, 35 n = 1.5141; d * = 0.9405, purity 91.3%, molecular mass 216.0 (calculated 218.34). 73 g of water, 14 g of potassium dichromate and 9 g of concentrated sulfuric acid are stirred and cooled to a temperature of 0 ° C. 13 g of 3,5-Dimethyl-1- (3-methylphenyl) -4-hexen-1-ol are added with stirring at a temperature of 40 ° C, with 40 being stirred for 1 hour. Then it becomes 8302289

J

9 reaction material poured into ice-cold water and extracted with petroleum ether. The organic layer is first washed with a 10 wt% solution of sodium carbonate, then with a 10 wt% solution of sodium chloride, until washing liquid reacts neutral, and dried over anhydrous sodium sulfate. The solvent is distilled off and 10.8 g of 3,5-dimethyl-1- (3-methylphenyl) -4-hexen-1-one are obtained from the residue after fractionation under reduced pressure (yield 77.7%), boiling point 124-130 ° C / 2 mm Hg, n = 1.52 03; 20 D d ^ = 0.9643, molecular mass 217.0 (calculated 216.33). Purity 93.0%. The characteristic odor properties: green, floral, iris, vetiver acetate.

Chemical shifts of the C MR spectrum. compound of the formula 12 15 Cl C-2 C-3 C-4 C-5 C-6 C-7 C-8 25.7 130.5 129.9 29.4 46.2 199.6 17.9 21 , 2 C-9 C-10 C-11 C-12 C-13 C-14 C-15 137.5 129.1 138.1 133.5 128.4 125.4 20.5 20

Example IX

150 g of water, 11 g of sodium hydrogen carbonate and 28.4 g of 2,4-dimethyl-6- (4-methylphenyl) -6-chloro-2-hexene prepared as in Example III above are placed in a flask and 0.03 g of hydroquinone is added thereto. The mixture is stirred at a temperature of 95-100 ° C until chlorine disappears in the organic layer, after which the layers are separated. The organic layer is dried over anhydrous sodium sulfate and distilled under reduced pressure to give 20.7 g of 3,5-dimethyl-1- (4-methylphenyl) -4-hexen-1-ol (yield 79%). Boiling point 117 ° C / 1 mm Hg, n 1.5151; 20 D d * 0.9359, purity 89.6%, molecular mass 217.1 (calculated 218.34).

To a mixture of 53 ml of water, 10.4 g of potassium dichromate and 6.64 ml of concentrated sulfuric acid, 9.5 g of 80% by weight of 3,5-dimethyl-35 1- (4-methylphenyl) -4-hexene- are added. 1-ol at a temperature of 40 ° C and stirred for 1 hour. The reaction material is then poured into ice-cold water and extracted with petroleum ether. The organic layer is first washed with a 10 wt% sodium carbonate solution, then with a 10 wt% sodium 40 chloride solution until the washings react neutral, and dried over anhydrous sodium sulfate. The solvent is distilled off and the residue is fractionated under reduced pressure to give 5 g of 3,5-dimethyl-1- (4-methylphenyl) -4-hexen-1-one in 61% yield of theory. . Boiling point 115-117 ° C / 1 mm Hg, 20 20 5 ηβ a 1.5223; d ^ 0.9616, purity 90%.

Molecular mass 217.7 (calculated 216.33). The odor is similar to that of 3,5-dimethyl-1- (3-methylphenyl) -4-hexen-1-one.

Chemical shifts of the NMR spectrum compound of the formula 13 10 Cl C-2 C-3 C-4 C-5 C-6 C-7 C-8 25.7 130.5 129.9 29.5 46.0 199.1 17.9 21.2 C-9 C-10 C-11 C-12 C-13 C-14 C-15 15 135.0 128.3 128.6 143.3 128.6 128.8 21.2 8302289

Claims (6)

Phenyl derivatives of 2,4-dimethyl-2-hexene of the general formula 4, wherein R represents a hydrogen atom or a methyl group and A represents the group> CHCl,> CHOH or> C 0 O. 2. Perfume compositions or products perfumed with these compositions, characterized by a content of at least one phenyl derivative of 2,4-dimethyl-2-hexene of the general formula 4, wherein R and A have the meaning as defined in claim 1, as fragrance. Η Ι ·· Η I 1 III Μ I I I 8302289 -Λβ- B. y. 1 I. E 1 fc + r- * · 11 i ιΊι · ΙΜ · ΤΠΓ A 1 1 23 DEC j i l Improvement of errata in the description associated with Me J Patent Application No. 83.02289 proposed by the applicant, dated 21 December 1983. Page 26. 2, line 31: 5 change "(or methylphenyl) -chloro-2-" to "(or methylphenyl) -6-chloro-2-" 3, line 23: Change "melting point" to "boiling point". 5, line 24 ·: Change "2,4-dimethyl-6-phenyl-chloro-2-hexene" to 10 "2,4-dimethyl-6-phenyl-6-chloro-2-hexene". 5, line 29: Change "18.6" to "18.6 g" 8, line 37: Change "9 g" to "9 ml" 15 Change formula 11 of the formula sheet "6" above "Q ^" to "5" 8302289 V.- _L R 'R' - <^> - CH - CH2 - CH - CH = CH - CH ^ OS GH ^ 2 ((3) -C - 0¾ - CH - CH = CH - CH3 H __......._ _ CH3 E—— | - CHa - 0¾ - C - C - CHj SSO RH ', 4. - CH2 - CH (CH3) - CH = C (CH3) - CH3 R JL '6 5 ^ 5- 2 I i2 / QV— CHCI - CH2 -CH - CH = C - CH3 u ~ io I ch3 CH3 6. 8 7 6 5 4 3 2 1 ft / ^ _ CHCI - CH2 - CH - CH = C - CH3 H | f0 CHa CH. CH. 4 R 3 J j JL 8 7 45 5 5 432I -CHCI - CH2 - CH - CH = G - CH3 44 10 | j CH- CH 3 3 8-7 8302289 · »w JL -1¾ ih 6 5 4 3 2 1 ^ (0 / ° CH0H - CH2 - CH - CH = C - CH ^ hV / h 11 10 CH3 CH ^ 8 7 * 3 «6 5. 4 3 2 1 fQ, —CHOI - CH ^ - CH - CH = G - CEL pré J CH * L · CH- 15 3 3 10. 0 J - - 8 7 is / ^ \ 6 5 4321 H3c— (O) rCH0H "C12 - CH - CH = C - CH3 I5« To ƒ CH3 CH3 8 7 JJL o 9-4 "I 6 4 3 2 1« © J- 0 - 0¾ - CH - CH = C - CH3, 2 11 <0 6 ch3 ch3 o 8 7 isj ^ j 5 4 3 2 1 —CH2— CH - CH = C - CH3 V ° 6 II CH * CH- CH- 15 15 3 3 8. A. O 15 & _ * li 5 4 3 2 1 (Ι, Ο-Λ-C - CHg-CH-CH = C - CH3 (H * 6 ch3 ch3 8 7 8302289