GB1577646A - Camphene addition products and perfumed compostions containing the same - Google Patents

Description

(54) CAMPHENE ADDITION PRODUCTS AND PERFUMED COMPOSITIONS CONTAINING THE SAME (71) We, INTERNATIONAL FLAVORS & FRAGRANCES INC., a corporation of the State of New York in the United States of America of 521 West 57th Street, New York N.Y. 10019, United States of America, do hereby declare the invention for which we pray that a Patent may be granted to us and the method by which it is to be performed, to be particularly described by the following statement: The present invention relates to novel mixtures having an intense sandalwood aroma, and precursors thereof which are intermediate diols, prepared by a process which comprises first reacting catechol having the structure:

with camphene having the structure::

in the presence of a Friedel Crafts Catalyst and then hydrogenating the resulting mixture to first produce the intermediate nonodiferous diol composition of our invention which is a mixture of compounds represented by the structures:

and then, on continued hydrogenation to produce the composition of our invention which has the intense sandalwood aroma, which odoriferous composition is a mixture of compounds including compounds having the structures:

wherein the R group is isocamphanyl and isobornyl.

The above-stated reaction sequence is summarized as follows:

OH OH OH OH (QI OH OH OH OH FREtEL CRMS +OH j t CA[ALYsT OH OH OH (C21 t + X+ f ZH2 R CATALYST (IN VARIOUS SSEREOCONFIGURATIONS ) Insofar as the reaction between camphene and catechol under the influence of the Friedel Crafts Catalyst is concerned, the following Friedel Crafts Catalysts may be employed: Boron trifluoride etherate; Sulfuric acid; Acid Clay (e.g.Filtrol); Molecular Sieve Catalysts (e.g. "SK-500" manufactured by the Union Carbide Company of New York, New York; a type of "Y" molecular sieve crystalline aluminosilicate catalyst); Aluminum trichloride; Boron trifluoride; Boron trifluoride-acetic acid; Boron trifluoride-phosphoric acid; Ferric chloride; and Zinc chloride. Preferred catalysts are: Acid Clay; and Sulfuric acid.

The reaction temperature range for the reaction of catechol with camphene is from 75"C up to about 220"C with a preferred temperature of 120-175"C.

The mole ratio range of catechol to camphene is generally from 0.5:1 up to 4:1 with a preferred mole ratio range of catechol to camphene being from about 0.8:1 up to about 1.2:1.

The ratio of Friedel Crafts Catalyst:catechol is dependent upon the particular catalyst used. Thus, when using a boron trifluoride-etherate catalyst the range used is from 2 up to 25 g of catalyst per mole of catechol, with a preferred range of from about 8 up to about 12 g catalyst per mole of catechol. When using sulfuric acid thc range is from 0.05 up to about 5 g of sulfuric acid per mole of catechol with a preferred range of from about 0.1 up to about 0.5 g of sulfuric acid per mole of catechol (based upon 100% sulfuric acid). When using an acid clay such as Filtrol a range of from about 2.5 up to about 50 g of catalyst per mole of catechol is used with a preferred range of from about 8 g of acid clay up to about 15 g of acid clay per mole of catechol.

An inert solvent (that is, not reactive with either of camphene or catechol or the Friedel Crafts Catalyst) may be used for the step of reacting catechol with camphene, but it is not necessary to use such inert solvent. When it is desired to utilize the inert solvent, particularly when using a boron trifluoride-etherate catalyst, a convenient solvent is toluene; but other ' inert" solvents may also be used, e.g. o-xylene, m-xylene, p-xylene and halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride.

The reaction between catechol and camphene in the presence of a Friedel Crafts Catalyst may be carried out at either atmospheric pressure, super atmospheric pressures or pressures lower than atmospheric; however, for the purposes of convenience and economy, it is preferred to carry out the reaction at atmospheric pressure.

The time of reaction of catechol with camphene is inversely proportional to the temperature of reaction. Thus, at the higher range of temperatures of reaction, shorter times of reaction are required and at the lower temperatures of reaction, longer times of reaction are required. Accordingly, the time of reaction varies from about 2 up to about 25 hours with the usual time of reaction being between 5 and 12 hours.

Insofar as the hydrogenation reaction is concerned, it may be conducted as a one stage reaction or a two stage reaction. When carrying out the two stage reaction, the first stage reaction temperature is 100"C up to 2000C; preferably 125-165"C and the second stage reaction temperature is from 200"C to 300"C; with a preferred second stage reaction temperature range of 225-250"C. At the end of the first stage, a nonodoriferous diol intermediate mixture is produced having the structures: (A1/A2)

This is exemplified in Example XIII, infra. The odoriferous sandalwood composition of our invention is produced at the higher temperature range during the carrying out of the second stage.When the process of our invention is carried out in one stage, the intermediate diol composition of our invention is apparently still produced in situ and as the hydrogenation proceeds this intermediate diol is converted into the odoriferous sandalwood aroma composition of our invention at the higher temperature range.

Both stages of the hydrogenation reaction may be carried out at pressures between 200 and 2500 pounds per square inch of hydrogen. When the reaction is conducted in one stage, heating is carried out whereby the reaction mass is heated directly to 200-300"C, preferably to 225-2500C.

The hydrogenation reaction may be carried out in the presence of inert solvents, (e.g.

isopropyl alcohol and diisobutyl carbinol).

The ratio of solvent to camphene-catechol reaction product will thus vary from about 0 up to about 4:1 (wt/wt).

The hydrogenation is carried out in the presence of a hydrogenation catalyst, for example: (i) Nickel catalysts such as Raney Nickel and Nickel-on-Kieselguhr; (ii) Palladium containing catalysts such as Palladium-on-carbon (iii) Rhodium catalysts such as Rhodium-on-carbon or Rhodium-on-Alumina; (iv) Platinum catalysts; and (v) Mixed Rhodium and Platinum.

More specifically, the catalysts preferred are Raney Nickel, 5% Palladium-on-carbon and 5% Rhodium-on-carbon. With regard to the use of Raney Nickel catalysts, the percent of catalyst in the camphene-catechol reaction product may vary from about 3% up to about 20% (based on weight of camphene-catechol reaction product) with a preferred percent of hydrogenation catalyst in the camphene-catechol reaction product being from about 5% up to about 10% by weight. With regard to the Palladium-on-carbon and Rhodium-on-carbon catalysts, the percent of catalyst in the reaction product may vary from about 0.1% up to about 5% (based on the total weight of camphene-catechol reaction product).

The production of the mono-hydroxy derivatives from the dihydroxy or diol derivative using this hydrogenation technique is surprising, unobvious and commercially advantageous. The prior art discloses hydrogenation of phenols at high temperatures, but indicates that cyclohexyl alcohols do not form as a result of such hydrogenation. This is exemplified by the following articles: 1. Chem Abstracts 44: 3445b ("Catalytic Hydrogenation of Phenols at Higher Temperatures. II. Reduction of the isomeric di- and triphenols") Abstract of Article by Fujita, Mem. Coll. Sci. Kyoto-Imp. Univ. 23A, pp 405-20 (1942) (Shows production only of the cyclohexane diol isomers using Nickel catalyst); 2.Chem Abstracts 47: 11239b ("Alicyclic Diols"); Abstract of German Patent 857,962, issued on December 4, 1952 (Discloses an improved process for preparing alicyclic diols by hydrogenating isocyclic ortho-di-hydroxy compounds in the presence of hydrogenation catalysts at elevated temperatures); 3. Chem Abstracts 52: 2912c ("Partial Dehydroxylation of Divalent Phenols by Hydrogenation"); Abstract of Czech Patent 86160 issued on January 15, 1957 (Discloses the reduction of catechol using molybdenum trioxide-aluminum oxide catalyst to form phenol); 4. Chem Abstracts 53: 14058a ("Monohydric Phenols"); Abstract of German Patent 849,557 issued on September 15, 1952 (Discloses production of monohydric phenols from polyhydric phenols by hydrogenation of polyhydric phenols over a zinc oxide chrome oxide catalyst); 5.Chem Abstracts 54; 22456f ("Selective Hydrogenation of the Pyrocatechols and Higher Alkyl Phenols"); Abstract of Article by Kubieka et al in Freiberger Forschungsh A131, (1960) (Discloses hydrogenation of polyhydric phenolic compositions to yield phenols using nickel sulfide, iron sulfide, copper sulfide or cobalt sulfide catalysts on alumina or silica carriers); 6. Chem Abstracts 55: 2496e ("Catalytic Hydrogenation of Hydroxybenzenes over Pt and Rh Catalysts"); Abstract by Smith et al, J. Am. Chem. Soc. 83, 2739-43 (1961) (Discloses hydrogenation of catechol over rhodium on alumina catalysts to produce 2-hydroxy-cyclohexanone); 7. Chem Abstracts 58: 5432f ("Coke Formation During High Temperature Hydrogenation on an Alumina-Molybdena Catalyst"); Abstract of article by Lozovoi et al in Tr. Inst.

Goryuch. Isokop., Akad. Nauk. SSSR 17, pp 23-45 (1962) (Discloses hydrogenation of catechol over a molybdenum oxide-alumina catalyst at very high temperatures [515 C]); 8. Chem Abstracts 62: 5120f ("High-Pressure Hydrogenation of Catechols in the Liquid Phase-Influence of the Quality of the Diluent and the Circulation of Products"); Abstract of article by Svajgl. Sb. Praci Vyzkumu Chem. Vyuzili Uhli. Dehtu Ropy, No. 2, pp 21-35 (1962) (Discloses hydrogenation of catechol using ferrous hydroxide on activated charcoal catalyst to yield phenol); 9. Chem Abstracts 63: 16188b ("Stereochemistry of the Catalytic Hydrogenation of Dihydroxybenzene Derivatives"); Abstract of article by Zymalkowski et al, Arch. Pharm.

298(9), pp 604-12 (1965) (Discloses the formation of cis and trans cyclohexane diols by hydrogenation of divalent phenols using rhodium on alumina and rhodium-platinum mixed catalysts).

The odoriferous mixtures thus produced as disclosed herein can be incorporated into a wide variety of finished perfume compounds and components for finished perfume compounds. It has been found that the novel materials of this invention have persistent fragrances as more fully described below which adapts them for incorporation into perfume compositions where a distinct sandalwood, woody musky aroma is required. To make a sandalwood type of perfume, the materials produced according to this invention can be combined with many types of odor materials, such as alcohols, hydrocarbons (e.g.

sesquiterpenes), aldehydes nitriles, esters, lactones and natural essential oils. These materials may be admixed with the product produced according to the process of our invention so that the combined odors of the individual components produce a pleasant and desired fragrance, particularly and preferably in sandalwood fragrances. Such perfume compositions usually contain (a) the main note or the bouquet or foundation stone of the compositions; (b) modifiers which round off and accompany the main notes; (c) fixatives which include (i) odorous substances which lend a particular note to the perfume throughout all stages of the evaporation and (ii) substances which retard evaporation; and (d) top notes which are usually low boiling fresh smelling materials.

In perfume compositions, it is the individual components which contribute to a particular olfactory characteristic, however, the over-all sensory effect created by the perfume composition will be at least the sum total of the effects of each of the ingredients. Thus, the product produced according to the process of our invention can be used to alter, modify or enhance the aroma characteristics of a perfume composition, for example, by utilizing or moderating the olfactory reaction contributed by another ingredient in the composition.

The amount of composition produced by means of hydrogenation of the camphene catechol reaction product of our invention which will be effective in perfume compositions as well as in perfume articles and colognes depends on many factors including the other ingredients, their amounts and the effects which are desired. It has been found that perfume compositions containing as little as 0.01% of reaction product produced according to the proccss of our invention or even less (e.g. 0.005%) can be used to impart an intense sandalwood, musky, woody aroma to perfumes, soaps, cosmeties, colognes, detergents or other products. The amount cmployed can range up to 100% of the fragrance components and will depend on consideration of costs, nature of the end product. the effeet desired en the finished product and the particular fragrance sought.The perfumed compositions of the present invention comprise a perfume adjuvant selected from alcohols, aldehydes.

hydrocarbons, nitriles, esters, lactones, natural essential oils and mixtures of two or more alochols. aldchydes. hydrocarbons. nitriles, esters, lactones and natural essential oils.

The composition produced by means of hydrogenation of the reaction product of camphene and catechol, produced according to our invention, is useful, taken alone or in perfume compositions as an olfactory component for use in detergents and soaps ; sapce odorants and deodorants ; perfume ; colognes ; toilet water ; bath preparations, such as bath oils, and bath solids ; hair prcparations, such as lacquers, brilliantines, pomades and shampoos ; cosmetic preparation, such as creams, deodorants, hand lotions and sun sereens ; powders, such as tales, dusting powders and face powders. When used as an olfactory component, as little as 1% of the composition produccd by means of hydrogenation of the reaction product of catcchol and camphene will suffice to impart an intense sandalwood note to sandalwood and woody type formulations.Generally, no more than 3% of the composition produced by means of hydrogenation of the reaction product of catechol and camphene (based on the ultimate end product) is required in the perfume composition.

In addition, the perfume composition or fragrance composition of our invention can contain a vehicle, or carrier for the composition produced by means of hydrogenation of the reaction product of catechol and camphene. The vehicle can be a liquid such as an alcohol, (necessarily a non-toxic alcohol) or a non-toxic glycol. The carrier can also be absorbent solid, such as a gum (e.g. gum arabic) or components for encapsulating the composition (such as gelatin).

It will thus be apparent that the composition produceed by means of hydrogenation of the reaction product of camphene and catechol of our invention ean be utilized to alter, modify or enhance the aroma of perfume compositions, perfumed artieles and colognes. In addition to the reaction product, a cologne in accordance with the invention comprises ethanol and water.

The Examples serve to illustrate processes for producing the products useful in our invention as well as uses of the odiferous products of our invention in the perfume compositions, perfumed artieles and colognes of our invention. lixamples I, VIII and XI relating to the preparation of intermediates.

It will be understood that these Examples arre illustrative and the invention is to be considered to be restricted thereto only as indicated in the appended claims.

All parts and perentages given herein are by weight untess otherwise speeified The words "Filtrol" and Carbowax" are Trade Marks, as is the word "Primol" EXAMPLE 1 Reaction of camphene and cutechol (Bf,-etherate catalyst) Into a 1 liter reaction flash equippen with stirrer, thermometer, reflux condenser, dropping funel, and heating mantle are placed: Catechol 188 g Toluene 110 g Boron trifluoroide 16 g etherate The resulting mixture is heated to 45 C Placed in a dropping funnel are the following ingredients: : Camphene 1.36 g Toluene 1.50 g The camphene-toluene solution is added to the catechol-toluene-boron trifluoride-etherate mixture over a period of two hours while maintaining the reaction mass at 45 C The reaction mass is then heated to 95 C and maintamed at that temperature with stirring for an additional 12 hour period. 100 g of 5% sodium hydroxide are then added to the reaction mass followed by the stirring of the reaction mass for a period of 1. minutes. The reaction mass is then separated and the organie layer is washed neutral. Solvent is then stripped off yielding 34.3 g of an oil.

The resulting oil is rushed-over yielding the following fractions: Fraction Vapor Temp- Liquid Temp- Pressure Weight of Number erature ("C) erature ("C) mm Hg Fraction 1 110-170 164-200 2.3 10.7 gm 2 210 214 2.3 10.2 3 210 215 2.3 9.8 4 215 215 2.3 12.0 5 215 215 2.3 23.0 6 215 220 2.3 20.3 7 214 225 2.7 21.9 8 240 250 2.3 30.0 9 245 250 27.2 10 245 280 2.3 2.5 Fractions 2-7 are bulked.

EXAMPLE II Hydrogenation of reaction product of catechol and camphene Into à 1 liter autoclave is placed the following materials: Reaction product of 250 g catechol and camphene produced according to Ex. I (fractions 2-7) Isopropyl alcohol 100 ml Raney nickel 15 g After sealing, the autoclave is then purged with nitrogen followed by hydrogen. and heated to 2200C under 450 psi hydrogen pressure. While maintaining the autoclave pressure between 450 and 500 psig and stirring at a rate of 1200 rpm, the autoclave is periodically repressurized with hydrogen over a period of 16 hours. At the end of the 16 hour period, the reaction mass is removed from the autoclave and filtered. The autoclave is rinsed with two 200 g portions of isopropyl alcohol.The isopropyl alcohol is then stripped from the reaction mass and the resulting material (240 g) is distilled on an 8" vigreaux column yielding the following fractions: Fraction Vapor Temp- Liquid Temp- Pressure Weight of Number erature ("C) erature (OC) mm Hg Fraction 1 95-120 151-174 2.5 16.2 gm 2 156 186 2.5 11.3 3 175 196 2.5 17.0 4 175 194 2.5 19.7 5 182 197 2.5 19.6 6 184 197 2.5 30.7 7 187 200 2.5 29.9 8 167 197 2.5 24.7 9 172 207 2.5 26.6 10 170 250 2.5 17.3 Fractions 2-9 are bulked and the resulting product has a strong sandalwood aroma; about five-ten times as strong as that product produced according to Example II or Example V of U.S. Patent 3.499.937.

The resulting product is a mixture of several chemical compounds.

EXAMPLE III Floral-woody formulation The following mixture is produced: Ingredients Parts by Weight Rhodinol 40 Phenylethyl alcohol 60 Linalol 20 Bergamot oil 30 Hydroxycitronellal 110 Alpha-amylcinnamic aldehyde 30 p-isopropyl-alpha-methyl 45 phenyl-propyl-aldehyde (10% in ethyl alcohol) Undecylaldehyde 45 (10% in ethyl alcohol) Benzyl acetate 75 Indol (10% in ethyl alcohol) 15 Undecalactone (1% in ethyl 30 alcohol) Ylang 20 Eugenol 10 Methylionone 90 Vetiver acetate 30 Product produced according to 6 Ex.II Musk ketone 60 Heliotropin 40 Coumarin 20 Natural Civet (10% in 25 ethyl alcohol) Orange absolute 30 Jasmin absolute 35 Rose absolute 30 The product produced according to Example II adds an intense sandalwood note to this floral woody formulation using a concentration of the product of Example II which is 1/5 to 1/10 that required when using the product of Example II or Example V of U.S. Patent 3,499,937.

EXAMPLE IV Preparation of a cosmetic and powder composition A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcum powder with 0.25 g of the composition produced by means of hydrogenation of the reaction product of camphene and catechol prepared according to Example II. It has an excellent sandalwood aroma with woody and musky notes. By the same process a cosmetic powder is prepared by mixing in a ball mill, 100 g of talcum powder with 1 g of the perfume composition prepared according to Example III. It, too, has an excellent sandalwood aroma with woody and musky nuances.

EXAMPLE V Perfumed liquid detergent Concentrated liquid detergents with intense sandalwood aromas are prepared containing 0.10%, 0.15% and 0.20% of the composition produced by means of the hydrogenation of the reaction product of camphene and catechol prepared according to Example II. The detergents are prepared by adding and homogeneously mixing the appropriate quantity of hydrogenation product (of reaction product of catechol and camphene) in the liquid detergent. The detergents all possess intense sandalwood aromas, with the intensity increasing with greater concentrations of hydrogenation product.

EXAMPLE VI Preparation of a cologne and handkerchief perfume The composition produced by means of hydrogenation of the reaction product of camphene and catechol prepared according to the process of Example II is incorporated into a cologne at a concentration of 2.5% in 85% aqueous ethanol; and into a handkerchief perfume at a concentration of 20% (in 95% aqueous ethanol). A distinct and definite sandalwood fragrance with musky and woody nuances is imparted to the cologne and to the handkerchief perfume.

EXAMPLE VII Preparation of a soap composition One hundred grams of soap chips are mixed with one gram of the composition produced by means of hydrogenation of the reaction product of catechol and camphene produced according to Example II until a substantially homogenous composition is obtained. The perfumed soap composition manifests an excellent sandalwood, woody, musky aroma. A similar aroma is created by adding three grams of the perfume composition to Example III to the soap chips and mixing until a homogenous composition is obtained. The resulting perfumed soap composition manifests an excellent sandalwood aroma.

EXAMPLE VIII Reaction of camphene and catechol (using H2504 catalyst) Into a 1 liter reaction flask equipped with stirrer, thermometer, reflux condenser, dropping funnel and heating mantle are placed: Catechol 330 g Concentrated Sulfuric 0.4 g Acid (95%) The resulting mixture is heated to 120 C. Placed in a dropping funnel fitted with a heating tape is 375 g of molten camphene. The molten camphene is added to the catechol-sulfuric acid mixture over a period of six (6) hours while maintaining the reaction mass at 1200C. At the end of the six 06) hour period, the reaction mass is stirred at 1200C for another two hours. 0.5 g of sodium hydroxide dissolved in 1 gm water is then added, followed by the stirring of the reaction mass for a period of 15 minutes.

The resulting crude product is then rushed-over yielding the following fractions: Fraction Vapor Temp- Liquid Temp- Pressure Weight of Number erature ( C) erature (OC) mm Hg Fraction 1 120-140 147-160 3.0 23.3 gm 2 140 165 3.0 45.7 3 175 204 3.0 40.2 4 210 215 3.0 51.8 5 210 215 3.0 38.8 6 212 220 3.0 47.2 7 215 224 3.0 41.2 8 222 230 3.0 45.6 9 236 254 3.0 39.9 10 230 260 6.0 29.8 Fractions 4-9 are bulked.

EXAMPLE IX Hydrogenation of reaction product of catechol and camphene of Example VIII Into a 1 liter autoclave is placed the following materials: Reaction product of 350 g catechol and camphene produced according to Ex. VIII (fractions 4-9) Isopropyl alcohol 100 ml Raney nickel 30 g After sealing, the autoclave is purged with nitrogen followed by hydrogen, and then heated to a temperature in the range of 225-230"C at a pressure of 500 psig. The autoclave is operated at this set of conditions for three hours. After the three hour period the autoclave pressure rises to about 850 psig and the autoclave is periodically vented back to 500 psig for a period of 12 hours.

At the end of the 12 hour period, the reaction mass is removed from the autoclave and and filtered. The autoclave is then rinsed with two 200 g portions of isopropyl alcohol. The isopropyl alcohol is then stripped from the reaction mass and the resulting material is distilled on an 10" vigreaux column yielding the following fractions: Fraction Vapor Temp- Liquid Temp- Pressure Weight of Number erature ("C) erature ("C) mm Hg Fraction 1 80-116 148-150 2.5 4.4 gm 2 135 155 2.5 10.1 3 140 156 2.5 12.3 4 145 160 2.5 12.2 5 148 160 2.5 24.5 6 150 164 2.5 31.1 7 154 167 2.5 30.0 8 157 173 2.5 31.3 9 162 181 2.5 31.6 10 168 189 2.5 26.5 11 181 215 2.5 29.4 12 182 224 2.5 17.8 13 194 257 2.5 29.5 14 231 274 2.5 32.6 15 239 290 2.5 8.4 Fractions 6-10 are bulked. The resulting product has a strong sandalwood aroma, with woody nuances; approximately 5-10 times the strength of the product produced according to the processes of Example 11 or Example V of U.S. Patent 3,499,937.

The resulting product is a mixture of several chemical compounds. The GLC profile thereof is set forth in Figure 1. (Conditions: 2% Carbowax-coated 18' x 1/4" column, programmed at 80-220 C).

EXAMPLE X Floral-woody formulation The following mixture is prepared: Ingredients Parts by Weight Rhodinol 4() Phenylethyl alcohol 60 Linalol 20 Bergomot oil 3() Hydroxycitronellal 110 Alpha-amylcinnamic aldehyde 30 p-isopropyl-alpha-methyl 45 phenyl-propyl-aldehy(ic (100/o in ethyl alcohol) Undecylaldehyd@ 45 (10% in ethyl alcohlo) Benzyl acetate 75 Indol (10% in ethyl alcohol) 15 Undecalactone (1% in ethyl 30 alcohol) Ylang 2() Eugenol 10 Methylionone ()() Vetiver acetate 3() Product produced according to 6 Ex.IX Musk ketone 6() Heliotropin 4() Coumarin 2() Natural Civet (10% in 25 ethyl alcohol ) Orange absolute 3() Jasmin absolute 35 Rose absolute 3() The product produced according to Example IX adtls the intense sandalwood note to this floral woody formulation using a concentration of the product of Example IX which is 1/5-1/10 that of the product produced according to the processes of Example II or Example V of U.S. Patent 3,499,937.

EXAMPLE XI Reaction of camphene and catechol (using a "Filtrol" catalyst) Into a 1 liter reaction flask equipped with stirrer, thermometer, reflux condenser, dropping funnel and heating mantle are placed: Catechol 330 g Filtrol 24 33 g (A 20-60 mesh acid clay manufactured by the Filtrol Corporation of Los Angeles, California and having the following properties: Particle-Size Analysis by Tyler Standard Sieve Through 20 Mesh, Wt.% 100 Through 60 Mesh, Wt.% 5 Free Moisture, Wt.% 10 Free & Combined Moisture, Wt.% (Loss at 1700 F) 15 (max.) Bulk Density, Ibs.cu.ft. 47 Particle Density 1.3 Surface Area, N2 adsorption (BET Method) sq.M/gm. 280-300) The resulting mixture is heated to 1500C. 408 Grams of molten camphene are then placed in a dropping funnel fitted with a heating tape. The molten camphene is added to the catechol-Filtrol mixture over a period of six (6) hours while maintaining the reaction mass at 150-155"C. At the end of the six (6) hour period, the reaction mass is stirred for an additional four (4) hours at 1500C. The reaction mass is rushed-over yielding the following fractions:: Fraction Vapor Temp- Liquid Temp- Pressure Weight of Number erature ("C) erature ("C) mm Hg Fraction 1 100-150 150-170 3.0 46.2 gm 2 175 204 21.4 3 186 215 3.5 42.2 4 198 205 2.5 49.5 5 205 209 2.5 53.2 6 208 212 2.5 51.6 7 210 215 2.5 50.5 8 211 217 2.5 45.1 9 211 218 2.5 51.7 10 215 218 2.5 54.0 11 218 230 2.5 49.3 12 223 240 2.5 39.3 13 210 245 3.8 28.9 14 230 280 5.0 27.1 15 250 320 3.8 28.7 Fractions 3-13 are bulked.

EXAMPLE XII Hydrogenation of reaction product of catechol and camphene Into a 1 liter autoclave is placed the following materials: Reaction product of 400 g catechol and camphene produced according to Ex. XI (fractions 3-13) Isopropyl alcohol 100 ml Raney nickel 30 g After sealing. the autoclave is then purged with nitrogen followed by hydrogen. The autoclave is then heated to 155"C under 500 psig hydrogen pressure and kept at 155-197"C for about 1 hour at which time the hydrogen uptake diminishes considerably. The reaction mass is then heated to between 2200C and 235"C and the autoclave pressure builds up to about 900 psig.The autoclave is periodically vented down to 500 psig over a period of 11 hours while maintaining the temperature at 220 C-235 C. At the end of the 11 hour period the reaction mixture is cooled to llO"C at which temperature it is stirred for a period of about 5 hours during which time significant hydrogen uptake is observed. The reaction mass is then removed from the autoclave. filtered and the isopropanol is recovered at atmospheric pressure to 100"C. then at 20 mm Hg at 100 C. 11 Grams of Primol is added to the resulting oil.The resulting oil is then distilled on an 8" Vigreux column yielding the following fractions: Fraction Vapor Temp- Liquid Temp- Pressure Weight of Number erature ("C) erature ("C) mm Hg Fraction 1 44-100 120-155 2.5 8.0 gm 2 140 160 2.5 16.0 3 146 163 2.5 17.8 4 150 165 2.5 22.0 5 155 165 2.5 25.0 6 157 167 2.5 26.8 7 159 169 2.5 7.5 8 160 171 2.5 31.2 9 165 177 2.5 28.0 10 170 185 2.5 32.5 11 172 190 2.5 23.2 12 187 207 2.5 19.7 13 195 214 2.5 26.0 14 203 219 2.5 24.9 15 225 308 2.5 12.3 Fractions 5-10 are bulked and the resulting product has a strong sandalwood aroma with woody nuances;; approximatelv 5-10 times the strength of the product which is produced according to the processes of Example II or Example IV of U.S. Patent 3,499,937.

The resulting product is a mixture of several chemical compounds. The GLC profile thereof is set forth in Figure 2.

EXAMPLE XIII Hydrogenation of reaction product of catechol and camphene in two stages: (A) Stage 1 product: diol mixture; (B) Stage 2 product: odiferous monohydroxy compound mixture Stage 1: Into a 1 liter autoclave is placed the following materials: Reaction product of 397 g catechol and camphene produced according to Ex. XI (Fractions 3-13) (GLC Profile of this mixture is set forth in Figure 3) Isopropyl Alcohol 100 ml Raney Nickel 30 g After sealing, the autoclave is then purged with nitrogen followed by hydrogen. The autoclave is pressurized with hydrogen to 500 psig and heated to 1000C, at which temperature stirring is commenced. The autoclave is then heated up to a temperature of less than 1600C for the major portion of the time of the 1st stage of hydrogenation.

However, as the uptake of hydrogen diminishes, the autoclave is heated to a temperature of 205"C. A table showing the time, temperature of hydrogenation, autoclave pressure, reservoir pressure, pressure drop and total pressure drop is set forth below: Total Temp- Auto- Reservoir Pressure Pressure erature crave Pressure Drop Drop Time ( C) (psig) (psig): (psig) (psig) 0920 75 500 2010 0947 110 540 2010 0952 125 340 2010 1017 110 500 850 1160 1160 1030 125 500 580 170 1430 1030 125 500 2010 - 1045 145 - - 1055 180 500 600 1410- 2840 1055 180 480 2010 - 1205 160 500 680 1330 4170 1205 160 480 2000 - 1240 170 480 1620 380 4550 1317 195 480 1430 - 1533 205 500 1130 - 1616 205 480 1120 500 5050 1920 90 150 - - At the end of the period of 10 hours as is set forth in the above table, the autoclave is opened and the reaction mass is filtered. The autoclave is then rinsed twice with isopropyl alcohol. The solvent is stripped off at 110"C and atmospheric pressure, then at 25 mm Hg at 110 C. At this point IR and GLC analysis indicates that the reaction mass is a mixture of compounds represented by the structures:

The GLC profile for the reaction mass existing at the end of Stage 1 is set forth in Figure 4.

The Infrared spectrum for the compounds having the structures as above is set forth in Figure 4a.

The resulting material at the end of Stage 1 has no odor.

Stage 2: The solvent-stripped reaction product of the first stage of hydrogenation is admixed with 30 g of Raney nickel and 100 g of isopropyl alcohol and replaced into the 1 liter autoclave.

After sealing, the autoclave is purged with nitrogen followed by hydrogen. The autoclave is then heated to 217"C and held at 225-230"C and 500 psig for a period of eight hours. At the end of the eight hour period, the reaction mixture is cooled, the autoclave is opened and the reaction mass is removed from the autoclave, filtered and the isopropanol recovered at atmospheric at 100"C, then at 25 mm Hg at 1100C. 19.5 g of Primol is added to the resulting oil which is then distilled on a 6" Vigreux column yielding the following fractions:: Fraction Vapor Temp- Liquid Temp- Pressure Weight of Number erature (OC) erature ("C) mm Hg Fraction 1 113 148 2.3 4.9 2 146 165 3.5 17.4 3 139 165 2.7 12.4 4 145 170 2.7 11.6 5 147 175 2.7 14.0 6 154 175 2.7 15.5 7 158 178 2.7 16.7 8 165 178 2.5 22.7 9 165 185 2.8 15.8 10 156 183 2.4 21.4 11 162 187 2.4 22.1 12 172 192 2.4 26.0 13 187 204 2.3 18.2 14 209 236 2.5 21.9 15 235 250 2.7 20.5 16 241 250 2.7 8.6 Fractions 6-14 are bulked and the resulting product has a strong sandalwood aroma with woody nuances; approximately 5-10 times the strength of the product which is produced according to the products of Example II and Example V of U.S. Patent 3,499,937.

The resulting product is a mixture of several chemical compounds. The GLC profile thereof is set forth in Figure 5.

EXAMPLE XIV Preparation of a cosmetic and powder composition A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcum powder with 0.25 g of the composition produced by means of hydrogenation of the reaction product of camphene and catechol prepared according to Example XIII, second stage. It has an excellent sandalwood aroma with woody and musky nuances.

EXAMPLE XV Perfumed liquid detergent Concentrated liquid detergents with intense sandalwood aromas are prepared containing 0.10%, 0.15% and 0.20% of the composition produced by means of the hydrogenation of the reaction product of camphene and catechol prepared according to Example XIII, second stage. The detergents are prepared by adding and homogeneously mixing the appropriate quantity of second stage hydrogenation product (of reaction product of catechol and camphene) in the liquid detergent. The detergents all possess intense sandalwood aromas, with the intensity increasing with greater concentrations of hydrogena tion product.

Claims (22)

WHAT WE CLAIM IS:

1. The process comprising reacting catechol having the structure: (1)

with camphene having the structure (2)

in the presence of a Friedel Crafts Catalyst to form a catechol-camphene alkylation product and hydrogenating the said catechol-camphene alkylation product in the presence of a hydrogenation catalyst to form a hydrogenated catechol-camphene addition product.

2. A process according to Claim 1, wherein the Friedel Crafts Catalyst is selected from boron trifluoride etherate, sulfuric acid, acid clay, aluminum trichloride, boron trifluoride, boron trifluoride-acetic acid, boron trifluoride-phosphoric acid, zinc chloride, aluminosilicate molecular sieve and ferric chloride.

3. A process according to Claim 1 or 2, wherein the reaction between catechol and camphene is carried out at a temperature in the range of from 1200C up to 1750C and the mole ratio of catechol to camphene is in the range of from 0.5:1 up to 4:1.

4. A process according to Claim 1, 2 or 3, wherein the hydrogenation is carried out within a temperature range of 100"C up to 3000C, the latter portion of the reaction time being at from 200 up to 300"C.

5. A product whenever produced by the process of any one of Claims 1 - 4.

6. A perfumed composition comprising the product of Claim 5 in a perfuming amount, and a perfume adjuvant selected from alcohols, aldehydes, hydrocarbons, nitriles, esters, lactones, natural essential oils and mixtures of two or more alcohols, aldehydes, nitriles, esters, hydrocarbons, lactones and natural essential oils.

7. A perfumed article comprising the product of Claim 5 and a material selected from a soap, a powder and a detergent.

8. A cologne comprising ethanol, water and the product of Claim 5.

9. A process according to Claim 1, wherein the hydrogenation is carried out in the presence of an inert solvent.

10. A process according td Claim 1, wherein the hydrogenation is carried out in two consecutive stages: (1) A first stage carried out at a temperature of from 100" up to 200"C; and (2) A second stage carried out at a temperature of from 200 up to 300"C.

11. A process according to Claims 1, 4, 9 and 10, wherein the hydrogenation catalyst is selected from Raney nickel, Palladium-on-carbon and Rhodium-on-carbon.

12. A product whenever produced by the process of any one of Claims 9 to 11.

13. A diol composition comprising a mixture of compounds represented by the structures:

14. A process in accordance with Claim 1, substantially as herein described with reference to any one of Examples II, IX, XII or XIII.

15. A process in accordance with Claim 2, substantially as herein described with reference to any one of Examples II, IX, XII or XIII.

16. A process in accordance with Claim 3, substantially as herein described with reference to any one of Examples IX, XII or XIII.

17. A process in accordance with Claim 4, substantially as herein described with reference to any one of Examples XII or XIII.

18. A product in accordance with Claim 5, substantially as herein described with reference to any one of Examples II, IX, XII or XIII.

19. A perfumed composition in accordance with Claim 6, substantially as herein described with reference to any one of Examples III, VI or X.

20. A perfumed article in accordance with Claim 7, substantially as herein described with reference to any one of Examples IV, V, VII, XIV or XV.

21. A cologne in accordance with Claim 8, substantially as herein described with reference to Example VI.

22. A process in accordance with Claim 10 substantially as herein described with reference to Example XIII.