US3045047A - 6-acetyl-1, 1, 2, 4, 4, 7-hexamethyl-1, 2, 3, 4, tetrahydronaphthalene - Google Patents
6-acetyl-1, 1, 2, 4, 4, 7-hexamethyl-1, 2, 3, 4, tetrahydronaphthalene Download PDFInfo
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- US3045047A US3045047A US453428A US45342854A US3045047A US 3045047 A US3045047 A US 3045047A US 453428 A US453428 A US 453428A US 45342854 A US45342854 A US 45342854A US 3045047 A US3045047 A US 3045047A
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- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 description 24
- 235000019645 odor Nutrition 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 241000402754 Erythranthe moschata Species 0.000 description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 125000002723 alicyclic group Chemical group 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- -1 alkyl radicals Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000000834 fixative Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- HSTAGCWQAIXJQM-UHFFFAOYSA-N 2,5-dichloro-2,5-dimethylhexane Chemical compound CC(C)(Cl)CCC(C)(C)Cl HSTAGCWQAIXJQM-UHFFFAOYSA-N 0.000 description 2
- DNRJTBAOUJJKDY-UHFFFAOYSA-N 2-Acetyl-3,5,5,6,8,8-hexamethyl-5,6,7,8- tetrahydronaphthalene Chemical compound CC(=O)C1=C(C)C=C2C(C)(C)C(C)CC(C)(C)C2=C1 DNRJTBAOUJJKDY-UHFFFAOYSA-N 0.000 description 2
- FKUPPRZPSYCDRS-UHFFFAOYSA-N Cyclopentadecanolide Chemical compound O=C1CCCCCCCCCCCCCCO1 FKUPPRZPSYCDRS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000006210 cyclodehydration reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000002678 macrocyclic compounds Chemical class 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000012437 perfumed product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000005329 tetralinyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 2
- JIVANURAWUCQIG-UHFFFAOYSA-N 1,1,2,4,4,7-hexamethyl-2,3-dihydronaphthalene Chemical compound C1=C(C)C=C2C(C)(C)C(C)CC(C)(C)C2=C1 JIVANURAWUCQIG-UHFFFAOYSA-N 0.000 description 1
- AISXBZVAYNUAKB-UHFFFAOYSA-N 1,1,4,4,6-pentamethyl-2,3-dihydronaphthalene Chemical compound CC1(C)CCC(C)(C)C=2C1=CC(C)=CC=2 AISXBZVAYNUAKB-UHFFFAOYSA-N 0.000 description 1
- DGMOBVGABMBZSB-UHFFFAOYSA-N 2-methylpropanoyl chloride Chemical compound CC(C)C(Cl)=O DGMOBVGABMBZSB-UHFFFAOYSA-N 0.000 description 1
- SLIOAQVQWDNBNB-UHFFFAOYSA-N 6-ethyl-1,1,4,4-tetramethyl-2,3-dihydronaphthalene Chemical compound CC1(C)CCC(C)(C)C=2C1=CC(CC)=CC=2 SLIOAQVQWDNBNB-UHFFFAOYSA-N 0.000 description 1
- ZKVZSBSZTMPBQR-UHFFFAOYSA-N Civetone Natural products O=C1CCCCCCCC=CCCCCCCC1 ZKVZSBSZTMPBQR-UHFFFAOYSA-N 0.000 description 1
- XRHCAGNSDHCHFJ-UHFFFAOYSA-N Ethylene brassylate Chemical compound O=C1CCCCCCCCCCCC(=O)OCCO1 XRHCAGNSDHCHFJ-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- ALHUZKCOMYUFRB-OAHLLOKOSA-N Muscone Chemical compound C[C@@H]1CCCCCCCCCCCCC(=O)C1 ALHUZKCOMYUFRB-OAHLLOKOSA-N 0.000 description 1
- 150000003855 acyl compounds Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ZKVZSBSZTMPBQR-UPHRSURJSA-N civetone Chemical compound O=C1CCCCCCC\C=C/CCCCCCC1 ZKVZSBSZTMPBQR-UPHRSURJSA-N 0.000 description 1
- 229940093468 ethylene brassylate Drugs 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ALHUZKCOMYUFRB-UHFFFAOYSA-N muskone Natural products CC1CCCCCCCCCCCCC(=O)C1 ALHUZKCOMYUFRB-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- LVECZGHBXXYWBO-UHFFFAOYSA-N pentadecanolide Natural products CC1CCCCCCCCCCCCC(=O)O1 LVECZGHBXXYWBO-UHFFFAOYSA-N 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings
- C11B9/0046—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings
- C11B9/0049—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings the condensed rings sharing two common C atoms
- C11B9/0053—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings the condensed rings sharing two common C atoms both rings being six-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
- C07C49/792—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic containing rings other than six-membered aromatic rings
Definitions
- This invention relates to a new class of chemical com pounds adapted for use as fixatives and ,blending agents in the manufacture of perfumes and perfumed products. These compounds are acylpolyalkyl-l,2,3,4-tetrahydronaphthalenes and most of them have a pronounced musklike odor.
- musks Compounds possessing an odor of musk are valuable in perfumery for their marked fixative and blending properties.
- the mostvaluable are the macrocyclic musks, that is organic compounds containing 15 to 18 atoms in an alicyclic ring. Examples of such compounds are muscone, civetone, pentadecanolide, and ethylene brassylate.
- these macrocyclic compounds are not readily available because either they must be extracted from diflicultly accessible natural sources or they must be synthesized by complicated chemical processes.
- nitro musks are polynitrated aromatic compounds, and also possess musklike odors.
- the manufacture of nitro musks is relatively uncomplicated. Consequently, they are inexpensive, but the quality of their odor is harsh and therefore they are not as desirable as the macrocyclic musks.
- These compounds are acyl derivatives of 1,2,3,4-tetrahydronaphtha'lene in which at least two carbon atoms in the alicyclic ring of the nucleus are quaternary carbon atoms in that they have two alkyl groups attached thereto. Those compounds which have been found to possess the most pronounced musk-like odor have two methyl groups attached to the carbon atoms located in the positions 1 and 4 of the alicyclic ring. Further, the preferred compounds have the acyl group attached to the carbon atom in position 6 in the aromatic ring of the nucleus, although because of the isomeric and sometimes symmetrical nature of many of these compounds, the positions 6 and 7 are generally equivalent. In addition, both the alicyclic and aromatic rings may be further substituted by alkyl groups containing one to three carbon atoms. This class of compounds may therefore be represented by the following general formula moo 6 R0 l R2 8 1 2 R:
- a further object of the invention is to provide acylpolyalkyl-1,2,3,4-tetrahydronaphthalene derivatives containing two quarternary carbon atoms and possessing musk-like odors.
- a specific object of the invention is to provide a new class of compounds consisting of acylpolyalkyl-1,2,3,4- tetrahydronaphthalenes containing two quaternary carbon atoms in the positions 1 and 4 of the alicyclic ring of the nucleus and in which the alkyl groups of the compound contain from one to three carbon atoms.
- the compounds of the present invention may be prepared in any suitable way, as, for example, by acylating the alkyl-1,2,3,4-tetrahydronaphthalenes by means of a suitable catalyst and thereafter isolating and purifying the alkylated acyl compounds. Typical procedures for this acylation are given in the examples below.
- the polyalkyl l,2,3,4 -tetrahydronaphthalenes employed for the acylation may be represented by formula wherein R,,, R,,, R R are alkyl radicals selected from the group consisting of methyl and ethyl; R R R R R and R are selected from the group consisting of hydrogen, methyl, ethyl, propyl, and isopropyl.-
- T-hese polyalkyl l,'2,3,4 tetrahydronaphthalenes may be prepared from appropriately substituted monocyclic hydrocarbons such as a 2,5-dichloro-2,5-dialkylhexane derivative, and particularly, 2,5-dichloro-2,5-dimethylhexane when R,,, R R R are methyl.
- a typical method which may be used is that wherein aluminum chloride is employed as a catalyst in accordance with the procedure described by Bruson and Kroeger in the Journal of the American Chemical Society, vol. 62, pp. 36-44 1940).
- 1,2,3,4 tetrahydronaphthalenes not previously described, but which have now been prepared using the general process either of Bruson and Kroeger or of Rob lin, Davidson and Bogert, are the following:
- Acylated compounds of the present invention may be derived from the foregoing or other similar polyalkyl- 1,2,3,4-tetrahydronaphthalenes by methods such as those employed in the following typical examples.
- Example I 6-Acetyl-1,1,2,4,4,7-Hexamethyl- 1,2,3,4-Tetrahydranaphthalene
- a solution of 12.0 g. (0.055 M) 1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene and 5.5 g. (0.070 M) acetyl chloride were added'in minutes at 0-5 C., 12.0 gms. (0.07 M) anhydrous ferric chloride.
- the temperature was raised slowly to 25 C., then mixed 1 hour at 25.
- One hundred cubic centimeters of cold water and 100 cc. benzene were added.
- the oil layer was first washed with aqueous salt solution then aqueous sodium carbonate solution. After removing the benzene by distillation, the crude product was fractionated to obtain 6.9 g. (43%) of 6-acetyl-1,1,2,4,4,7-hexamethyl-1,2,3,4- tetrahydronaphthalene with a powerful odor of musk reminiscent of the macrocyclie musks.
- the boiling point of the product was 150 at 2 mm. and the refractive index was 1.5350 at C.
- Example 2 .6-Pr0pi0ny l-] ,1 ,4,4-Tetramethyl-7- Ethyl-1,2,3,4-Tetrahydronaphzhalene
- a solution of 43.2 g. (0.2 M) 1,1,4,4-tetrarnethyl- 6-ethyl-1,2,3,4tetrahydronaphthalene, 50.0 g. ethylene dichloride, and 19.9 g. (0.215 M) propionyl chloride were added 30.2 g. (0.226 M) aluminum chloride over a period of two hours at 05 C. The temperature was raised slowly to and then the reaction was mixed 1% hours at 25.
- Example 3 6-A cetyl-1,1,4,4-Tetramethyl-7-Ethyl- 1,2,3,4-Tetrahydronaphthalene
- a solution of 400 g. (1.85 M) 1,1,4,4-tetramethyl- 6-ethyl-1,2,3,4-tetrahydronaphthalene and 167 g. (2.13 M) acetyl chloride were added 295 g. (2.24 M) aluminum chloride powder in 3 hours.
- the reaction mixture was allowed to rise to room temperature overnight and then benzene and dilute hydrochloric acid were added.
- the oil layer was washed with 500 cc. portions of aqueous salt solution and sodium carbonate solution. After the crude product was fractionated at at 2 mm.
- Example 4-6-Isobutyryl-1,1,4,4-Tetramethyl-7- Etltyl-1,2,3,4-Tetrahydr0naphthalene The procedure of Example 3 was followed with 43.2 g. 1,1,4,4 tetramethyl 6 ethyl-1,2,3,4-tetrahydronaphrtbalene, 24.5 g. isobutyroyl chloride, and 32 g. aluminum chloride.
- the purified fi-isobutyryl-l,1,4,4tetramethyl-7-ethyl-1,2,3,4-tetrahydronaphthalene melted at 61 and had a pleasant odor resembling that of musk.
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States Patent 3,045,047 6-ACETYL-1,1,2,4,4,7-HEXAlVlETHYL-1,2,3,4, TETRAHYDRONAPHTHALENE David Davidson, New York, N.Y., and Robert M. Lusskin, Haworth, N.J., assignors, by mesne assignments, to The Truhek Laboratories, 1110., East Rutherford,
N .J., a corporation of Delaware No Drawing. Filed Aug. 31, 1954, Ser. No. 453,428 1 Claim. (Cl. 260592) This invention relates to a new class of chemical com pounds adapted for use as fixatives and ,blending agents in the manufacture of perfumes and perfumed products. These compounds are acylpolyalkyl-l,2,3,4-tetrahydronaphthalenes and most of them have a pronounced musklike odor.
Compounds possessing an odor of musk are valuable in perfumery for their marked fixative and blending properties. Among these, the mostvaluable are the macrocyclic musks, that is organic compounds containing 15 to 18 atoms in an alicyclic ring. Examples of such compounds are muscone, civetone, pentadecanolide, and ethylene brassylate. However, these macrocyclic compounds :are not readily available because either they must be extracted from diflicultly accessible natural sources or they must be synthesized by complicated chemical processes.
Other products which are known as nitro musks are polynitrated aromatic compounds, and also possess musklike odors. The manufacture of nitro musks is relatively uncomplicated. Consequently, they are inexpensive, but the quality of their odor is harsh and therefore they are not as desirable as the macrocyclic musks.
We have discovered a class of non-nitrated compounds which are not macrocyclic but which possess valuable musk-like odors quite as line as those of the macrocyclic compounds themselves. It is surprising that compounds unrelated chemically to the macrocyclic musks should possess odors so similar to them. Moreover, these new compounds are synthesized readily from commercially available, inexpensive raw materials.
These compounds are acyl derivatives of 1,2,3,4-tetrahydronaphtha'lene in which at least two carbon atoms in the alicyclic ring of the nucleus are quaternary carbon atoms in that they have two alkyl groups attached thereto. Those compounds which have been found to possess the most pronounced musk-like odor have two methyl groups attached to the carbon atoms located in the positions 1 and 4 of the alicyclic ring. Further, the preferred compounds have the acyl group attached to the carbon atom in position 6 in the aromatic ring of the nucleus, although because of the isomeric and sometimes symmetrical nature of many of these compounds, the positions 6 and 7 are generally equivalent. In addition, both the alicyclic and aromatic rings may be further substituted by alkyl groups containing one to three carbon atoms. This class of compounds may therefore be represented by the following general formula moo 6 R0 l R2 8 1 2 R:
3,045,047. Patented July 17, 1962 The presence of two quaternary carbons in the alicyclic portion of the molecule appears to be necessary for the production of a musk-like odor. Thus the acetyl-1,1-di-- nitrated compounds which possess musk-like odors similar to the macrocyclic musks.
A further object of the invention is to provide acylpolyalkyl-1,2,3,4-tetrahydronaphthalene derivatives containing two quarternary carbon atoms and possessing musk-like odors.
A specific object of the invention is to provide a new class of compounds consisting of acylpolyalkyl-1,2,3,4- tetrahydronaphthalenes containing two quaternary carbon atoms in the positions 1 and 4 of the alicyclic ring of the nucleus and in which the alkyl groups of the compound contain from one to three carbon atoms.
These and other objects and features of the present invention will appear from the following description thereof wherein reference is made to specific compounds of the class of acylpoly-alkyl-1,2,3,4-tetrahydronaphthalenes which possess musk-like odors, a suflicient number of compounds being particularly described to indicate the common characteristics of the compounds embraced within the class to which this invention relates.
The compounds of the present invention may be prepared in any suitable way, as, for example, by acylating the alkyl-1,2,3,4-tetrahydronaphthalenes by means of a suitable catalyst and thereafter isolating and purifying the alkylated acyl compounds. Typical procedures for this acylation are given in the examples below.
The polyalkyl l,2,3,4 -tetrahydronaphthalenes employed for the acylation may be represented by formula wherein R,,, R,,, R R are alkyl radicals selected from the group consisting of methyl and ethyl; R R R R R and R are selected from the group consisting of hydrogen, methyl, ethyl, propyl, and isopropyl.-
T-hese polyalkyl l,'2,3,4 tetrahydronaphthalenes may be prepared from appropriately substituted monocyclic hydrocarbons such as a 2,5-dichloro-2,5-dialkylhexane derivative, and particularly, 2,5-dichloro-2,5-dimethylhexane when R,,, R R R are methyl. A typical method which may be used is that wherein aluminum chloride is employed as a catalyst in accordance with the procedure described by Bruson and Kroeger in the Journal of the American Chemical Society, vol. 62, pp. 36-44 1940).
Bruson and Kroegerhave described the preparation and properties of l,1,4,4-ttetramethyl-1,2,3,4-tetuahydronaphthalene and 1,1,4,4, 6-pentamethyl 1,2,3,4 tetrahydronaphthalene. The compound 1,1,4,4-tetramet.hyl-6- ethyl-1,2,3,4-tetrahydronaphthalene was prepared from ethylbenzene, 2,5 dichloro 2,5 dimethyl-hexane, and aluminum chloride.
The 1,1,4,4-tetraalkyl 1,2,3,4 tetrahydronaphthalenes substituted with alkyl groups at position 2 or 3 of the alicyclic ring, as well as on the aromatic ring, were prepared by the cyclodehydration of the appropriately substituted alcohols where the R groups have the same significance as in the preceding formula.
These alcohols themselves may be prepared by any suitable method, as, for example, by a Grignard reaction. The procedure employed for the cyclodehydration was that described by Roblin, Davidson and Bogert, in the Journal of the American Chemical Society, vol. 57, pp.
1,2,3,4 tetrahydronaphthalenes not previously described, but which have now been prepared using the general process either of Bruson and Kroeger or of Rob lin, Davidson and Bogert, are the following:
Acylated compounds of the present invention may be derived from the foregoing or other similar polyalkyl- 1,2,3,4-tetrahydronaphthalenes by methods such as those employed in the following typical examples.
Example I .6-Acetyl-1,1,2,4,4,7-Hexamethyl- 1,2,3,4-Tetrahydranaphthalene To a solution of 12.0 g. (0.055 M) 1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene and 5.5 g. (0.070 M) acetyl chloride were added'in minutes at 0-5 C., 12.0 gms. (0.07 M) anhydrous ferric chloride. The temperature was raised slowly to 25 C., then mixed 1 hour at 25. One hundred cubic centimeters of cold water and 100 cc. benzene were added. The oil layer was first washed with aqueous salt solution then aqueous sodium carbonate solution. After removing the benzene by distillation, the crude product was fractionated to obtain 6.9 g. (43%) of 6-acetyl-1,1,2,4,4,7-hexamethyl-1,2,3,4- tetrahydronaphthalene with a powerful odor of musk reminiscent of the macrocyclie musks. The boiling point of the product was 150 at 2 mm. and the refractive index was 1.5350 at C.
Example 2 .6-Pr0pi0ny l-] ,1 ,4,4-Tetramethyl-7- Ethyl-1,2,3,4-Tetrahydronaphzhalene To a solution of 43.2 g. (0.2 M) 1,1,4,4-tetrarnethyl- 6-ethyl-1,2,3,4tetrahydronaphthalene, 50.0 g. ethylene dichloride, and 19.9 g. (0.215 M) propionyl chloride, were added 30.2 g. (0.226 M) aluminum chloride over a period of two hours at 05 C. The temperature was raised slowly to and then the reaction was mixed 1% hours at 25. Dilute hydrochloric acid was added and the oil layer was washed first with aqueous salt solution, then with aqueous salt solution containing sodium carbonate. The ethylene dichloride was removed by distillation and the distilled product, which boiled at 160 at 5 mm. was crystallized from aqueous methanol. The recrystallized 6 propionyl 1,1,4,4 tetramethyl-7-ethyl- 1,2,3,4-tetrahydronaphthalene melted at 46-48" and had a fine odor of musk.
Example 3 .6-A cetyl-1,1,4,4-Tetramethyl-7-Ethyl- 1,2,3,4-Tetrahydronaphthalene To a solution of 400 g. (1.85 M) 1,1,4,4-tetramethyl- 6-ethyl-1,2,3,4-tetrahydronaphthalene and 167 g. (2.13 M) acetyl chloride were added 295 g. (2.24 M) aluminum chloride powder in 3 hours. The reaction mixture was allowed to rise to room temperature overnight and then benzene and dilute hydrochloric acid were added. The oil layer was washed with 500 cc. portions of aqueous salt solution and sodium carbonate solution. After the crude product was fractionated at at 2 mm. it was crystallized from aqueous methanol to obtain purified 6-acety1-1,1,4,4-tetramethyl-7-ethyl 1,2,3,4 tetrahydronaphthalene (M.P.=46.5), with a fine, persistent musklike odor.
Example 4.-6-Isobutyryl-1,1,4,4-Tetramethyl-7- Etltyl-1,2,3,4-Tetrahydr0naphthalene The procedure of Example 3 was followed with 43.2 g. 1,1,4,4 tetramethyl 6 ethyl-1,2,3,4-tetrahydronaphrtbalene, 24.5 g. isobutyroyl chloride, and 32 g. aluminum chloride. The purified fi-isobutyryl-l,1,4,4tetramethyl-7-ethyl-1,2,3,4-tetrahydronaphthalene melted at 61 and had a pleasant odor resembling that of musk.
Other acylpolyalkyltetralins prepared by the general procedures of Examples 1, 2 and 3 are as follows:
The quality, intensity and persistency of the odors of the present compounds cited by way of example above varies considerably although all appear to have valuable properties as fixatives and blending agents in the manufacture of perfumes and perfumed products.
While numerous compounds have been mentioned above and typical methods of procedure for their production have been described, it will be apparent that other membersof the class of acylpolyalkyl-1,2,3,4-tetrahydronaphthalenes may be produced and other methods for their production may be employed. In view thereof, it should be understood that the particular compounds and methods of procedure described should be understood to be illustrative only and are not intended to limit the scope of the invention.
What we claim is:
6-acetyl-1,1,2,4,4,7-hexamethyl 1,2,3,4 tetrahydronaphthalene.
References Cited in the file of this patent UNITED STATES PATENTS 2,897,237 Carpenter et al. July 28, 1 959
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US453428A US3045047A (en) | 1954-08-31 | 1954-08-31 | 6-acetyl-1, 1, 2, 4, 4, 7-hexamethyl-1, 2, 3, 4, tetrahydronaphthalene |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US453428A US3045047A (en) | 1954-08-31 | 1954-08-31 | 6-acetyl-1, 1, 2, 4, 4, 7-hexamethyl-1, 2, 3, 4, tetrahydronaphthalene |
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US3045047A true US3045047A (en) | 1962-07-17 |
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US453428A Expired - Lifetime US3045047A (en) | 1954-08-31 | 1954-08-31 | 6-acetyl-1, 1, 2, 4, 4, 7-hexamethyl-1, 2, 3, 4, tetrahydronaphthalene |
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3246044A (en) * | 1963-06-10 | 1966-04-12 | Givaudan Corp | Process for making 1, 1, 3, 4, 4, 6-hexamethyl-1, 2, 3, 4-tetrahydronaphthalene |
US3499751A (en) * | 1966-07-05 | 1970-03-10 | Givaudan Corp | Method and composition for controlling weeds with acylated tetrahydronaphthalene |
US4406828A (en) * | 1979-08-10 | 1983-09-27 | Givaudan Corporation | Odorant and/or flavorant substances |
EP0405427A2 (en) * | 1989-06-30 | 1991-01-02 | Firmenich Sa | Aromatic compounds, process for their preparation and their use as perfuming ingredients |
US5084440A (en) * | 1989-01-27 | 1992-01-28 | Givaudan Corporation | Acetals and ketals of oxo-tetralins and oxo-indanes |
US5087770A (en) * | 1990-12-03 | 1992-02-11 | Union Camp Corporation | Isopropyl tetramethyl and pentamethyl indane musks |
US5185318A (en) * | 1989-06-30 | 1993-02-09 | Firmenich S.A. | Aromatic compounds, a process for preparation thereof and use of same as perfuming ingredients |
US5354737A (en) * | 1993-08-13 | 1994-10-11 | The Mennen Company | Fragrance composition containing substantial amounts of acetyl hexamethyl tetralin, and deodorant composition containing the fragrance composition |
US5362715A (en) * | 1992-04-16 | 1994-11-08 | Pfw Aroma Chemicals B.V. | Mixtures of acetylpolyalkylindanes and acetylpolyalkyltetralines |
US5442124A (en) * | 1989-06-30 | 1995-08-15 | Firmenich Sa | Process for the preparation of novel aromatic compounds |
US20110000483A1 (en) * | 2009-05-01 | 2011-01-06 | Matthias Joseph A | External nasal dilator |
US8506996B2 (en) | 1997-01-29 | 2013-08-13 | Peter J. Cronk | Therapeutic delivery system |
US8834514B2 (en) | 2006-08-30 | 2014-09-16 | Xennovate Medical Llc | Resilient band medical device |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US2897237A (en) * | 1953-12-14 | 1959-07-28 | Givaudan Corp | Substituted tetrahydronaphthalenes |
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1954
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Patent Citations (1)
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US2897237A (en) * | 1953-12-14 | 1959-07-28 | Givaudan Corp | Substituted tetrahydronaphthalenes |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3246044A (en) * | 1963-06-10 | 1966-04-12 | Givaudan Corp | Process for making 1, 1, 3, 4, 4, 6-hexamethyl-1, 2, 3, 4-tetrahydronaphthalene |
US3499751A (en) * | 1966-07-05 | 1970-03-10 | Givaudan Corp | Method and composition for controlling weeds with acylated tetrahydronaphthalene |
US4406828A (en) * | 1979-08-10 | 1983-09-27 | Givaudan Corporation | Odorant and/or flavorant substances |
US5084440A (en) * | 1989-01-27 | 1992-01-28 | Givaudan Corporation | Acetals and ketals of oxo-tetralins and oxo-indanes |
US5324875A (en) * | 1989-06-30 | 1994-06-28 | Firmenich Sa | Aromatic compounds, a process for preparation thereof and use of same as perfuming ingredients |
US5559272A (en) * | 1989-06-30 | 1996-09-24 | Firmenich S.A. | Aromatic compounds |
JPH0344348A (en) * | 1989-06-30 | 1991-02-26 | Firmenich Sa | Aromatic compounds or arbitrary mixture of at least two structural isomers thereof, their preparation, intermediates therefor, method for improving, strengthening or modifying aromatizing characteristics of aromatizing composition or aromatized article and aromatized articles |
JP2690387B2 (en) | 1989-06-30 | 1997-12-10 | フイルメニツヒ・ソシエテ・アノニム | NOVEL AROMATIC COMPOUND, PROCESS FOR PRODUCING THE SAME, fragrance composition or fragranced product containing the compound, and method for improving, enhancing or changing aroma characteristics and intermediate for the compound |
US5162588A (en) * | 1989-06-30 | 1992-11-10 | Firmenich S.A. | Aromatic compounds, a process for preparation thereof and use of same as perfuming ingredients |
US5185318A (en) * | 1989-06-30 | 1993-02-09 | Firmenich S.A. | Aromatic compounds, a process for preparation thereof and use of same as perfuming ingredients |
EP0405427A2 (en) * | 1989-06-30 | 1991-01-02 | Firmenich Sa | Aromatic compounds, process for their preparation and their use as perfuming ingredients |
EP0405427A3 (en) * | 1989-06-30 | 1991-12-11 | Firmenich & Cie | Aromatic compounds, process for their preparation and their use as perfuming ingredients |
US5442124A (en) * | 1989-06-30 | 1995-08-15 | Firmenich Sa | Process for the preparation of novel aromatic compounds |
US5087770A (en) * | 1990-12-03 | 1992-02-11 | Union Camp Corporation | Isopropyl tetramethyl and pentamethyl indane musks |
US5362715A (en) * | 1992-04-16 | 1994-11-08 | Pfw Aroma Chemicals B.V. | Mixtures of acetylpolyalkylindanes and acetylpolyalkyltetralines |
US5354737A (en) * | 1993-08-13 | 1994-10-11 | The Mennen Company | Fragrance composition containing substantial amounts of acetyl hexamethyl tetralin, and deodorant composition containing the fragrance composition |
US8506996B2 (en) | 1997-01-29 | 2013-08-13 | Peter J. Cronk | Therapeutic delivery system |
US8852224B2 (en) | 1997-01-29 | 2014-10-07 | Peter J. Cronk | Therapeutic delivery system |
US8834514B2 (en) | 2006-08-30 | 2014-09-16 | Xennovate Medical Llc | Resilient band medical device |
US20110000483A1 (en) * | 2009-05-01 | 2011-01-06 | Matthias Joseph A | External nasal dilator |
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