2,815,382 United States Patent Office Patented Dec. 3, 1957 2 A solution of 56.4 g. of 1,1,4,7-tetramethyl 1,2,3,4- 2,815,382 tetrahydronaphthalene and 40.5 g. of 3-chloropropionyl chloride was added with agitation to a suspension of 48 ALKYTL-SUBSTITUTED TETRAHYDRONAPH. g. of anhydrous aluminum chloride in 250 g. of ethylene THNDANONES dichloride, keeping, the temperature at 25-30° C. When Marion S. Carpenter, Nutley, William M. Easter, Jr., hydrogen chloride evolution had ceased the reaction mix Hasbrouck Heights, and Thomas F. Wood, Little Falls, ture was quenched on ice and the ethylene dichloride so N. J., assignors to The Givaudan Corporation, New lution was, washed to neutrality and the solvent was York, N. Y., a corporation of New Jersey evaporated, leaving 81 g. of crude 3-chloroethyl 1, 1,4,7- No Drawing. Application May 10, 1955, 10 tetramethyl 1,2,3,4-tetrahydronaphthyl-6-ketone as a dark Serial No. 507,505 colored oil. The latter was added to 1,200 g. of 93% sulfuric acid and the mixture was agitated while heating 6. Claims. (Cl. 260-590) to 70° C. When hydrogen chloride evolution had sub sided the reaction mixture was quenched on ice, ex This invention relates to novel chemical compounds tracted with benzene and the benzene solution was washed and more especially to alkyl-substituted tetrahydro to neutrality and the solvent was evaporated, leaving naphthindanones having musk-like odors. 60 g. of oil. After crystallization from alcohol there was Most of the known synthetic musk-like compounds obtained 10 g. of 4,6,6,9-tetramethyl 6,7,8,9-tetrahydro fall into two classes: (1) nitrated aromatic hydrocarbons, ce-naphthindan-3-one as practically colorless crystals Such as musk xylene, and (2) macrocyclic ketones, lac 20 melting at 153-154 C. and having a musk-like odor. tones or esters such as cyclopentadecanone, cyclopenta decanolide and ethylene brassylate. While members in EXAMPLE 2 the first group are inexpensive to manufacture, they suf Preparation of 5,5,8,8-tetramethyl 5,6,7,8-tetrahydro B fer from the disadvantage that they are not light-stable naphthindan-1-one or alkali-stable, frequently causing discoloration in prod 25 ucts Such as Soap. Members of the second group, while A solution of 37.6 g. of 1,1,4,4-tetramethyl 1,2,3,4- reasonably stable to light and alkali, are difficult to tetrahydronaphthalene and 27 g. of 3-chloropropionyl manufacture and are relatively costly. chloride was added with agitation to a suspension of 32 We have found that alkyl-substituted tetrahydronaph g. of anhydrous aluminum chloride in 200 g. of ethylene thindanones possess musk-like odors, are light-stable and dichloride, keeping the temperature at 25-30° C. When alkali-stable and are relatively inexpensive to manufac hydrogen chloride evolution had ceased the reaction mix ture. ture was quenched on ice and the ethylene, dichloride In general, our novel musk-like compounds are pre solution was washed to. neutrality and the solvent was pared in three steps: (1) preparation of suitable alkyl evaporated, leaving 54 g, of crude (3-chloroethyl, 1,1,4,4- substituted tetrahydronaphthalenes, (2) condensation of 35 tetramethyl 1,2,3,4-tetrahydronaphthyl-6 ketone as a the latter with 6-chloropropionyl chloride to the corre dark-colored oil. The latter was added to 800 g. of 93% sponding (3-chloroethyl ketones and (3) cyclization of sulfuric acid and the mixture was agitated while heating the latter with elimination of hydrogen chloride to pro to 80° C. When hydrogen chloride evolution had sub duce the desired alkyl-substituted tetrahydronaphthin sided the reaction mixture was quenched on ice, ex danones. 40 tracted with benzene and the benzene solution was washed Examples of specific compounds we have prepared in to neutrality and the solvent was evaporated, leaving clude 4,6,6,9-tetramethyl 6,7,8,9-tetrahydro ov-naphthin 40 g. of crude crystalline material. After crystallization dan-3-one, 5,5,8,8-tetramethyl 5,6,7,8-tetrahydro 3-naph from alcohol there was obtained 15 g. of 5,5,8,8-tetra thindan-1-one, 4,6,6,9,9-pentamethyl. 6,7,8,9-tetrahydro co methyl 5,6,7,8-tetrahydro 6-naphthindan-1-one as prac naphthindan-3-one, 4-ethyl 6,6,9,9-tetramethyl 6,7,8,9- tically colorless crystals. melting at about 140 C. and tetrahydro ox-naphthindan-3-one, and 4-isopropyl-6,6,9,9- having a musk-like odor. tetramethyl 6,7,8,9-tetrahydro ox-naphthindan-3-one. The following examples are given in order more fully EXAMPLE 3 to illustrate the invention without, however, limiting the Preparation of 4,6,6,9,9-pentamethyl 6,7,8,9-tetrahydro same to them. 50 or-naphthindan-3-one EXAMPLE 1. Preparation of 4,6,6,9-tetramethyl 6,7,8,9-tetrahydro cy A solution of 40.5 g. of 1,1,4,4,6-pentamethyl 1,2,3,4- naphthindan-3-one tetrahydronaphthalene and 27 g. of 3-chloropropionyl chloride was added with agitation to a suspension of 32 An ether solution of 142 g. of 5-p-toly hexan-2-one 55 g. of anhydrous aluminum chloride in 200 g. of ethylene was added with agitation to an ether solution of methyl dichloride, keeping the temperature at 25-30 C. When magnesium iodide prepared from 116 g. of methyl iodide hydrogen chloride evolution had ceased the reaction mix and 20 g. of magnesium shavings. The reaction mixture ture was quenched on ice and the ethylene dichloride was quenched on iced dilute hydrochloric acid and the solution was washed to neutrality and the solvent was ether solution was washed to neutrality and distilled to 60 evaporated, leaving 58 g. of crude 3-chloroethyl 1, 14,4,6- yield 141 g. of 2-methyl 5-p-tolyl hexan-2-ol as a color pentamethyl 1,2,3,4-tetrahydronaphthyl-7 ketone as a less oil boiling at 102 C./1 mm. Hg and having Sp. Gr. brown-colored oil. The latter was added to 865 g. of (25 C.) 0.9466 and n20 1.5155. 93% sulfuric acid and the mixture was agitated while To 260 g. of 93% sulfuric acid previously cooled to heating to 80° C. When hydrogen chloride evolution 0° C. there was added with agitation during 40 minutes 65 had subsided the reaction mixture was quenched on ice, 140 g. of 2-methyl 5-p-tolyl hexan-2-ol, maintaining the extracted with benzene and the benzene solution was temperature at 0° C. by cooling. The reaction mixture washed to neutrality and the solvent was evaporated, was quenched on ice and the oil layer was separated, leaving 38 g. of crude crystalline material. After crystal washed to neutrality and distilled to yield 113 g. of lization from alcohol there was obtained 26 g. of 4,6,6,99 1,1,4,7-tetramethyl 1,2,3,4-tetrahydronaphthalene as a 70 pentamethyl 6,7,8,9-tetrahydro o-naphthindan-3-one as colorless oil boiling at 86 C./2 mm. Hg and having Sp. practically colorless crystals melting at 116-117° C. and Gr, (25 C.) 0.94.10 and n20 1.5300. having a musk-like odor, - 2,815,882 5 4. EXAMPLE 4 propyl. 1,2,3,4-tetrahydronaphthalene and 50 grams off chloropropionyl chloride was added with agitation to a Preparation of 4-ethyl 6,6,99-tetramethyl 6,7,8,9-tetra suspension of 60 grams of anhydrous aluminum chloride hydro a-naphthindan-3-one in 400 grams of ethylene dichloride, keeping the tem A solution of 183 g. of 2,5-dichloro-2,5-dimethyl hex perature at 25-30° C. When hydrogen chloride evolu ane in 249 g. of ethyl benzene was added with agitation tion had ceased the reaction mixture was quenched on during one hour to a mixture of 6 g. of anhydrous ferric ice and the ethylene dichloride solution was washed to chloride and 279 g. of ethyl benzene, keeping the tem neutrality and the solvent was evaporated, leaving 115 perature at 0° C. to 5 C., by cooling. When hydrogen grams of crude g-chloroethyl 1, 1,4,4-tetramethyl 6-iso chloride evolution had ceased the reaction mixture was propyl. 1,2,3,4-tetrahydronaphthyl-7 ketone as a brown quenched in water, the ethylbenzene solution was washed colored oil. The latter was added to 1,684 grams of to neutrality and distilled. There was obtained, in 93% sulfuric acid and the mixture was agitated while addition to the excess of ethyl benzene, 205 g. of 1,1,4,4- heating to 55° C. When hydrogen chloride evolution tetramethyl 6-ethyl 1,2,3,4-tetrahydronaphthalene as a had subsided the reaction mixture was quenched on ice, colorless oil boiling at 88-89 C./1.5 mm. Hg. 15 extracted with benzene, the benzene solution was washed A solution of 43.2 g. of 1,1,4,4-tetramethyl 6-ethyl to neutrality and the solvent was evaporated leaving 77 1,2,3,4-tetrahydronaphthalene and 27 g. of 3-chloropro grams of crude crystalline material. After crystallaztion pionyl chloride was added with agitation to a suspension from alcohol there was obtained 37 grams of 4-isopropyl of 32 g. of anhydrous aluminum chloride in 200 g. of 6,6,9,9-tetramethyl 6,7,8,9-tetrahydro a-naphthindan-3- ethylene dichloride, keeping the temperature at 25-30 20 one as colorless crystals melting at 88.5-90.5 C. and C. When hydrogen chloride evolution had ceased the re having a musk-like odor. action mixture was quenched on ice and the ethylene di The foregoing illustrates the practice of the invention, chloride solution was washed to neutrality and the sol which however is to be construed as broadly as permis vent was evaporated, leaving 61 g. of crude 6-chloroethyl sible in view of the prior art and limited solely by the 1,1,4,4-tetramethyl 6-ethyl 1,2,3,4-tetrahydronaphthyl-7 25 appended claims. ketone as a brown-colored oil. The latter was added to We claim: 900 g. of 93% sulfuric acid and the mixture was agitated 1. Alkyl-substituted tetrahydronaphthindanones select while heating to 80 C. When hydrogen chloride evolu ed from the group consisting of tetrahydronaphthindan tion had subsided the reaction mixture was quenched on 1-ones and tetrahydronaphthindan-3-ones having lower ice, extracted with benzene, the benzene solution was 30 alkyl substituents in the tetrahydronaphthalene portion washed to neutrality and the solvent was evaporated, so as to yield at least one quaternary carbon atom in said leaving 40 g. of crude crystalline material. After crystal portion. lization from alcohol there was obtained 22 g. of 4-ethyl 2. 4,6,6,9 - tetramethyl - 6,7,8,9 - tetrahydro - c. - naph 6,6,9,9-tetramethyl 6,7,8,9-tetrahydro ox-naphthindan-3- thindan-3-one. one as colorless crystals melting at 64-65 C. and having 35 3. 5,5,8,8-tetramethyl - 5,6,7,8-tetrahydro - B - naph a musk-like odor. thindan-1-one. EXAMPLE 5 4. 4,6,6,9.9 - pentamethyl - 6,7,8,9 - tetrahydro - a Preparation of 4-isopropyl 6,6,99-tetramethyl 6,7,8,9- naphthindan-3-one. tetrahydro o-naphthindan-3-one 5. 4-ethyl- 6,699 - tetramethyl- 6,7,8,9 - tetrahydro 40 or-naphthindan-3-one. A mixture of 200 grams of cumene and 10 grams of 6. 4 - isopropyl - 6,6,9,9 - tetramethyl - 6,7,8,9 - tetra anhydrous ferric chloride was cooled to 10 C. and to it hydro-or-naphthindan-3-one. was added a solution of 366 grams of 2,5-dichloro 2,5- dimethylhexane in 520 grams of cumene during 1 hour, References Cited in the file of this patent keeping the temperature at 10-15 C. and agitating con 45 tinuously. After the evolution of hydrogen chloride had UNITED STATES PATENTS ceased the solution was quenched in water, washed to 1,754,031 Mayer et al. ------Apr. 8, 1930 neutrality and distilled to yield, in addition to 408 grams of recovered cumene, 392 grams of a colorless, practically OTHER REFERENCES odorless oil boiling at 94-95 C./1 mm. Hg which con 50 Cauquil et al.: Chem. Abstracts, vol. 41, page 1649 gealed upon cooling and melted at 28 C., and which (1947). is 1,1,4,4-tetramethyl 6-isopropyl. 1,2,3,4-tetrahydronaph Arnold et al.; J. Am. Chem. Soc., vol. 68, pgs. 2176-8 thalene. (1946), A solution of 85 grams of 1,1,4,4-tetramethyl 6-iso