NL7809557A - PARA-C10-TERPENYLBENZOIC ACID AND ITS SALTS, ESTERS AND ANHYDRIDES, THE PREPARATION OF THESE COMPOUNDS AND THEIR USE IN THE PREPARATION OF 3-C10-TERPE-NYLCYCLOHEXANOL. - Google Patents

Description

^. -t

K 348 NET

Applicant; Shell International Research Society B.V.

Short designation: "Para-C 6 -terpenylbenzoic acid and its salts, esters and anhydrides, the preparation of these compounds and their use in the preparation of 3-C 6 -terpenylcyclohexanol"

The invention relates to para-C 1 -T-terpenyl-benzoic acid and its salts, esters and anhydrides, to the preparation of these compounds and to their use in the preparation of the fragrance 3-C 1 -T-terpenyl-cyclohexanol.

In the article "Investigating the composition of Santalydol by I.S.Aulchenko and L.A. Kheifits in" American Perfumer and Cosmetics "Vol. 85, July 1970 p.

37-45, 3-terpenylcyclohexanols such as 10-cis- and trans-3-isokamphylcyclohexanol and cis- and trans-3-isobornylcyclohexanol have an intensive sandalwood scent, while 2 and 4-terpenyl cyclohexanols are practically odorless.

C10-Terpenylcyclohexanols can generally be prepared by catalytic hydrogenation of C-terpenylphenols obtained by reaction of camphene with phenol in the presence of a Friedel-Crafts catalyst. However, the preparation of meta-C 1 -t-terpenylphenol, from which the 3-C 1 -t-terpenylcyclohexanol desired for its fragrance properties is formed by hydrogenation, is less simple because the product of the Friedel-Crafts reaction mainly consists of para -penylphenol exists. According to U.S. Pat. 3,920,758, however, by heating this reaction product in the presence of aluminum chloride at a temperature between 100 and 150 ° C in the presence of aluminum chloride, one can obtain an equilibrium mixture with a higher content of meta-terpenylphenol. . Since it is very difficult to separate meta-terpenylphenol therefrom, this mixture is hydrogenated after distillation to remove unreacted phenol without further purification to yield meta-terpenylphenol which is contaminated with ortho and para-terpenylphenol.

In Dutch patent application no. No. 7708060, to obtain a higher yield of the desired meta isomer, the reaction of phenol with camphene is carried out in the presence of anhydrous hydrogen fluoride. In this method too, in addition to the meta isomer, a considerable amount (about 50% by weight of the total reaction product) of the undesired para and ortho isomers is formed.

The known methods therefore have the drawback that in the preparation of 3-terpenylcyclohexanol one can only have meta-terpenylphenol which is highly contaminated by ortho and para-terpenylphenol.

It has now surprisingly been found that meta-C10 terpenylphenol which is not contaminated with said isomers can be prepared in a simple manner and in good yield by para-C 1 -T-terpenyl benzoic acid or its salts, esters or anhydrides, in the presence oxidize and decarboxylate a copper compound. Hydrogenation of the obtained meta-C 1 -T-terpenylphenol gives 3-C-Q-ter-penylcyclohexanol with good odor properties.

Para-CjQ-terpenylbenzoic acid and its salts, esters and anhydrides are new compounds and the invention therefore relates to these compounds, to their preparation and to their use as starting material in the preparation of 3-CjQ-terpenylcyclohexanol. The terpenyl group can be, for example, an isokamphyl group or an isomer thereof, for example an isobornyl or an isophenchyl group. The preparation methods described below generally result in mixtures of para-C10 terpenyl benzoic acids with different isomeric C10 terpenyl groups.

780 95 57 "*" "" · "· ·; -. Ν ^ ν ^ 9 * + -3-

For example, para-C8-terpenylbenzoic acid can be prepared by (1) converting a bicyclic terpene of the formula C 1 -H 2 H or a hydrogen halide addition product thereof by reaction with benzene in the presence of a Friedel-Crafts 5 catalyst to C 1 -H 4 terpenylbenzene, (2) acetylating the C 1 -Tetpenylbenzene to para-C 1 -T-terpenyl-acetophenone and (3) oxidizing the para-C 1 -G-terpenylacetophenone to para-C 1 -G-terpenylbenzoic acid.

Preferred bicyclic terpenes or hydrogen halide addition products are camphene and alpha and beta pinene and their HCl addition products (bornyl chloride, isobornyl chloride).

The preparation of C18 terpenylbenzene (step 1) is also referred to hereinafter as "alkylation." Examples of Friedel-Crafts catalysts useful in this step are HFSO 2, H 2 SO 2, HF, TiCl 2, BF 2, SbF 2 and AlCl 3 Very good results are obtained with HF or an AlCl 2 nitroalkane complex.

The alkylation temperature is generally between -20 and 80 ° C, preferably between -20 and 30 ° C. The reaction may very suitably be carried out by passing the amount of HCl calculated for the formation of camphene hydrochloride into a mixture of camphene and benzene and then gradually adding a complex of AlClg with nitro-methane or 2-nitropropane as catalyst.

The alkylation can, if desired, be carried out in a solvent such as, for example, cyclohexane, dioxane or tetrahydrofuran and / or in excess of benzene.

The acetylation of the obtained C10 terpenylbenzene 30 (step 2) can be carried out in the usual manner, for example with acetyl chloride or acetic anhydride in the presence of a catalyst, preferably AlCl 2.

The reaction temperature is generally between -20 and 80 ° C, preferably between 20 and 60 ° C. The acetylation can conveniently be carried out in a solvent, for example dichloroethane or monochlorobenzene. By working up the reaction mixture in the usual manner, 780 95 57 -4-para-C 12 -terpenylacetophenone which is not contaminated with the ortho isomer is obtained in good yield.

If AICl3 is used as a catalyst in the alkylation, the acetylation can, if desired, be carried out in the same reactor 5 as the alkylation. It is then not necessary to completely work up the reaction mixture obtained in the alkylation. It is sufficient to distill off the excess of benzene and / or the solvent and to add fresh AlCl 2, solvent and acetyl chloride to the residue obtained.

The oxidation of para-C 1 -T-terpenylacetophenone (step 3) preferably takes place by passing oxygen or an oxygen-containing gas at elevated temperature in a solution of para-C 1 -T-terpenylacetophenone 15 in an alkane carboxylic acid, for example propionic acid, to which a catalytic amount of manganese acetate is added. The oxidation is preferably carried out at a temperature between 100 and 250 ° C.

Para-CjQ-terpenylbenzoic acid can also be prepared by reacting CjQ-terpenylbenzene, preferably at a temperature between -20 and 50 ° C, in the presence of AlCl 2 with oxalyl chloride (COCl 2, Ce. This reaction is preferably in a solvent preferably cyclohexane, dichloroethane or chlorobenzene.

Another suitable process for the preparation of para-C 12 terpenyl benzoic acid is to react terpenyl benzene in anhydrous HF with an alkali cyanate, preferably at a temperature between -30 and 0 ° C. The product obtained, which consists of about 90% para-terpenylbenzamide and 10% ortho-terpenylbenzamide, is converted by hydrolysis with an acid or a base into a mixture of the corresponding benzoic acids. This mixture is a suitable starting material for the conversion of para-C10-terpenylbenzoic acid into meta-C10-terpenylphenol described below, because in this process, also raetterpenylphenol is formed from the ortho-terpenylbenzoic acid present.

780 9 5 57 o- -5-

Para-C18 terpenyl benzoic acid can be converted into its salts, esters or anhydrides in any conventional manner.

The process for the preparation of SCG-terpenyl cyclo-hexanol according to the invention consists in the oxidation and decarboxylation of para-C-terpenyl benzoic acid or its salts, esters or anhydrides in the presence of a copper compound and the resulting meta-C 4 -g- terpenylphenol hydrogenates.

The oxidation and decarboxylation of benzoic acid or substituted benzoic acids in the presence of a copper compound is generally known from, for example, Dutch patent 90,684. According to this patent, instead of benzoic acid or a substituted benzoic acid, a salt, ester or anhydride of such an acid can also be used as starting material. However, it was not obvious that starting from para-C18-terpenylbenzoic acid, which compound is substituted in the para-position with an oxidisable group, meta-C18-terpenylphenol could be used in a practically useful manner in good yield. can prepare. From an article by W.G. Toland in J.Am.Chem.Soc.Vol. 83, pp. 2507-2512 (1961), it appears that, for example, the reaction with p-methylbenzoic acid proceeds in considerably lower yield than with benz-25oic acid.

The oxidation and decarboxylation can be carried out by the para-terpenyl benzoic acid or its salt, ester or anhydride in the molten state or in an inert reaction medium in the presence of a copper compound 30 at a temperature between 200 and 400 ° C, preferably between 220 and heating at 300 ° C. The amount of copper compound is generally between 0.001 and 1 mole, preferably between 0.01 and 0.20 mole per mole of starting material. As a copper compound, for example, a salt or an oxide of copper can be used. Both cupro and cupri compounds are suitable; however, cupriver compounds are preferred. Examples of suitable cupric compounds are cupric acetate, cupric benzoate, cupric para-C 12 terpenyl benzoate, cuprisalicylate, cupricarbonate, cupric chloride and cupric sulfate. Optionally, the copper compound can be created in situ by adding elemental copper to the reaction mixture. It is likely that during the oxidation and decarboxylation process, part of the copper is always present as cuprous salt of the terpenyl benzoic acid to be converted.

Suitable solvents in which the reaction can be carried out are, for example, benzene, toluene, xylene and biphenyl. Since esters of para-C 1 -g-terpenylbenzoic acid and the formed meta-C 2 -g-terpenylphenol are formed as a by-product, the oxidation and decarboxylation is preferably carried out in the presence of steam. Optionally, water can also be used as the solvent and the reaction can take place in a pressure vessel. The esters formed are hydrolysed by the presence of water or steam.

Preferably, the reaction is carried out in the presence of oxygen, which can be done, for example, by passing oxygen or an oxygen-containing gas, for example air, through the reaction mixture. Cupro compounds formed are hereby converted back into cupri compounds.

Oxygen or the oxygen-containing gas and steam can be passed through the reaction mixture simultaneously or alternately. Preferably, for example, for 1-6 hours, an oxygen-containing gas is passed through the reaction mixture and then, for example, for 0.5-3 hours, a mixture of this gas and steam.

The reaction can be carried out batchwise or continuously. To promote the catalytic activity, salts or oxides of lithium, sodium, potassium, barium, magnesium, manganese, rare earth metals or cobalt can be added as promoter, preferably in an amount between 0.04 and 0.17 gram equivalent per gram equivalent of acid .

For example, the reaction mixture can be upgraded by diluting it with a water-immiscible solvent, for example toluene, and after filtration, diluting the resulting solution with a dilute mineral acid, for example sulfuric or hydrochloric acid. 5 to hydrolyze any remaining esters and extract the copper compounds from the solution. After the solution has been washed acid-free, unreacted para-C-terpenyl benzoic acid can be dissolved with an aqueous solution of NaOH or KOH at a concentration of between 4 and 15 wt. % 10 are extracted. The meta-Cgg-terpenylphenol can be recovered from the solution by extraction with Claisen's alkali (35 g KOH, 25 ml HjO and 100 ml methanol).

The hydrogenation of meta-C18-terpenylphenol can be carried out in a manner known per se in the presence of a catalyst, for example rhodium or platinum, which is optionally provided on a support.

EXAMPLE 1

200 ml of anhydrous HF (10 mol) were placed in a 400 ml Hastelloy B autoclave equipped with a stirrer. While stirring and cooling, a solution of 45 g of camphene (0.33 mole) in 78 g of benzene (1 mole) was added over 20 minutes at 0 ° C.

The mixture was stirred for an additional hour at which the temperature rose to 10 ° C and was then cooled to about -30 ° C, then carefully at this temperature 27 g (0.33 mol.) Of powdered dry potassium cyanate under good stirring was added portionwise.

The autoclave was closed and brought to 30 ° C. After 4 hours, the excess HF was distilled off and the HF still present was neutralized with a concentrated solution of 10 COg in water. The resulting emulsion was extracted several times with cyclohexane and the extract washed with water and dried over Na 2 SO 4. The residue consisted of a mixture of 10% ortho-C ^ Q-terpenylbenzamide and 90% para-C ^ Q-terpenylbenzamide.

35 I.R. spectrum: 3450, 2980, 1660, 1620, 1610, 1480, 1450, 800 and 750 cm "1.

78 0 9 5 57 -8-

The residue was boiled with a 15% aqueous solution for 1 hour to obtain the corresponding terpenyl benzoic acids. The hydrolyzed product was taken up in cyclohexane and after washing with water treated with a 10% aqueous solution of potassium hydroxide to extract the terpenyl benzoic acids. 33 g (0.13 mol) of ortho and para-penyl benzoic acid were obtained from the lye extract by neutralization and extraction. For analysis purposes, a small portion was converted into the methyl esters by reaction with methanol in the presence of followed by distilling off the esters, bp 169 ° C - 175 ° C / 26 Pa. I.R. spectrum: 3010, 2910, 1660, 1440, 1410, 1350, 1260, 1180, 1020, 860, 730 cm ”1.

After extraction of the acids, a further 38 g (0.18 mol.) Of C 1 -T-terpenylbenzene was isolated from the cyclohexane solution. It was shown by gas chromatography to be a mixture of 5 isomers. The terpenylbenzene had a boiling point of 114 ° C - 116 ° C / 39 Pa.

20 I.R. spectrum: 3060, 3020, 2950, 2880, 1610, 1490, 1460, 1380, 770, 710 cm "1.

EXAMPLE 2

100 ml (5 mol.) Of anhydrous HF were placed in a polyethylene bottle. To this, a solution of 27.2 g (0.2 mol.) Of camphene in 60 g of (0.77 mol.) Benzene was added dropwise with stirring and cooling at a temperature of 3 ° C - 10 ° C. After an hour, the reaction mixture was poured into ice, treated with a saturated aqueous solution of potassium acetate and extracted with cyclohexane.

The extract was distilled off after washing with water and drying on Na2SO4, the cyclohexane and the benzene and the residue was distilled in vacuo. 38 g (0.18 mol.) Of C 1 -g-terpenylbenzene, boiling point 114 ° C - 116 ° C / 26 Pa. obtained. Gas chromatography showed that the C- ^ Q-terpenylbenzene consisted of 5 isomers in the ratio 29/7/34/27/3, measured in the order of 78 0 9 5 57 -9 -, <* retention time. I.R. spectrum: 3060, 3020, 2950, 2880, 1610, 1490, 1460, 1380, 770, 710 cm An amount of 32 g (0.15 mol.) of the terpenyl benzene was dissolved in 100 ml of dichloroethane, the solution was cooled and 5 with good stirring, 21 g (0.16 mol) of powdered AlCl 3 were added. At a temperature of 25 ° C, a solution of 13 g (0.17 mol.) Of acetyl chloride in 15 ml of dichloroethane was slowly added dropwise to the mixture and then the mixture was added at a temperature of about 35 ° C for 1 hour. Kept at C-40 ° C. The reaction product was poured into a mixture of ice and dilute hydrochloric acid. The resulting organic layer was separated, washed with water and dried over Na 2 SO 4. After filtration, the dichloroethane was distilled off and the residue was distilled in vacuo 1.5. 30 g of para-C ^-terpenylacetophenone (bp 156 ° C-159 ° C / 7 Pa) were obtained.

It was demonstrated by gas chromatography that this product, like the CjQ terpenylbenzene used as starting material, consisted of 5 isomers. I.R. spectrum: 20 2910,1670,1600,1440,1410,1350,1260,1180,1020,950,840 cm EXAMPLE 3

19 g (0.07 mol) of dissolved in 50 ml of propionic acid and 200 mg of manganese acetate were obtained from the para-C 1 -ter-penylacetophenone obtained according to Example 2. Under intensive stirring, oxygen was passed through (10 1 / h) at a temperature of about 130 ° C. After 2.5 hours, the propionic acid was distilled off and the residue dissolved in cyclohexane. The resulting solution was washed well with water and dilute aqueous bicarbonate solution.

The para-C 10 terpenyl benzoic acid was extracted from the cyclohexane solution with 8% aqueous KOH solution.

From the lye extract, 17.5 g of para-C 18 terpenyl benzoic acid were obtained by neutralization and extraction. A small portion was converted to the methyl-25 ester, boiling point 172 ° C-175 ° C / 26 Pa) for identification. The ester consisted of a mixture of 5 isomers. Infrared spectrum of the methyl ester of p-terpenyl benzoic acid: 2980, 1730, 1610, 1450, 1430, 1280, 1190, 1110, 860 cm -1.

780 9 5 57 -10- EXAMPLE 4

In a 200 ml round bottom flask with stirrer and placed in a cooling bath, 13.6 g of camphene were dissolved in a mixture of 50 ml of benzene and 50 ml of cyclohexane. 3.6 g of dry HCl gas was introduced at a temperature of 0 ° C with good stirring. After 1 hour, stirring at 0 ° C with good stirring

3.1 g of AlClg-CHjNOj complex (1: 1 weight ratio AlCl 2: nitromethane) were added dropwise. The mixture was then kept at room temperature for an hour and then poured into a mixture of ice with dilute hydrochloric acid. The organic layer.

10 was separated, washed with water and dried. The benzene and the cyclohexane were evaporated and the residue was distilled in vacuo. The resulting C 1 -T-terpenylbenzene had a boiling point of 115 ° C-118 ° C / 39 Pa. Yield 19.8 g. Gas chromatography showed that the product consisted of 5 isomers in the ratio of 39/3/28/21/4 measured in the order of the retention time. I.R. spectrum: 3060, 3020, 2950, 2880, 1610, 1490, 1460, 1380, 770, 710 cm "1.

EXAMPLE 5

The experiment described in Example 4 was repeated with 4 g AlCl 2 CH 2 CHNO 2 CHg complex (20 AlCl 2 nitropropane weight ratio 1: 1) instead of 3.1 g AlClg. CHgNO2 complex as a catalyst. The reaction mixture was kept at room temperature for 2 hours. 18.5 g of C 1 -T-terpenylbenzene with a boiling point of 117 ° C-120 ° C / 26 Pa was obtained. It was shown by gas chromatography that the product consisted of 4 isomers in a ratio of 3/8/82/7.

The I.R. spectrum showed the same bands as the product of Example 4, but with slight intensity differences in the 1490, 1460, 1380 cm 1 bands. EXAMPLE 6 The experiment described in Example 4 was repeated with beta-pinene instead of camphene. From 17.6 g of beta-pinene, 17.5 g of CjQ terpenylbenzene was obtained.

The infrared spectrum and gas chromatography demonstrated that the product was identical to that of 78 0 9 5 57 .......... '^ f- ** - * · -11-

Example 4.

EXAMPLE 7

The test described in Example 4 was repeated with alpha-pinene instead of camphene. However, the introduction of the HCl gas took 8 hours. From 13.6 g of alpha-pinene 5, 16.3 g of C 1 -Q-terpenylbenzene were obtained. The product obtained was identical to that of Example 4.

EXAMPLE 8

A mixture of 13.6 g of alpha and beta pinene and camphene (weight ratio 1: 1: 1) was treated with 3.6 g of dry HCl gas at 0 ° C. After 8 hours, 3 g of AlCl-1 was stirred at 0 ° C with good stirring. CH2NO2 complex (weight ratio AlCl2-triotromethane 1: 1) was added. The mixture was then kept at room temperature for an additional 2 hours and then worked up in the manner described in Example 4. 16.8 g of C 10 -terpenylbenzene, bp 15 116 ° C-119 ° C / 26 Pa, was obtained. It was shown by gas chromatography that the product consisted of 5 isomers in the ratio 37/4/29/20/10 measured in the order of the retention time. i

The experiment was repeated using borayl chloride in place of the HCl addition product of alpha and betapine and camphene as starting material. The yield of C10 terpenylbenzene was 67 mol%.

EXAMPLE 9

A solution of 108.8 g of camphene in a mixture of 200 ml of cyclohexane and 200 ml of benzene was placed in a 1 liter round bottom flask. While stirring and cooling well, 30.4 g of dry hydrochloric acid gas were introduced at a temperature of 0 ° C. After standing at 0 ° C for 1 hour, 16 g of 4101 ^ .0 ^ ^ 2 complex (wt. Ratio AlCl2: nitromethane 1: 1) was slowly added over 15 minutes with good stirring.

The temperature was kept below 10 ° C by cooling. The reaction mixture was stirred at 25 ° C for an additional 2 hours. In a film evaporator, the cyclohexane and excess benzene were removed in vacuo at a bottom temperature of up to 40 ° C.

400 ml of dichloroethane were then added to the residue.

108 g of powdered AlClg were added portionwise to the resulting solution under cooling and stirring, then a solution of 80 g of CH 2 COCl in 100 ml of dichloroethane at a temperature of 10 ° C over a period of half an hour. The reaction mixture was stirred for an additional 2b hours at a temperature of 30 ° C and then poured into a mixture of ice and dilute hydrochloric acid. After hydrolysis, the dichloroethane layer was separated and the water layer was extracted with small portions of dichloroethane. The combined dichlorethane solutions were washed with a dilute aqueous HCl solution and then with a dilute aqueous bicarbonate solution. After drying over Na 2 SO 4, the dichloroethane was distilled off, the residue was dissolved in 1 l of propionic acid and 6 g of manganese acetate were added to the solution. Oxygen was then passed through (2 1 / min.) At a temperature of 130 ° C. After 5 hours, 96% of the para-C 1 -T-terpenylactophenone was oxidized.

The propionic acid was distilled off in vacuo.

20 residue taken up in cyclohexane and the solution washed with a dilute aqueous bicarbonate solution. The para-C 10 terpenyl benzoic acid was isolated from the solution by extracting it 6x with 100 ml portions of a 15% aqueous KOH solution. The extract obtained was washed with cyclohexane and acidified with dilute SO 2. The separated product was taken up in cyclohexane, the solution washed with water and dried. After evaporation of the cyclohexane, 171 g of a pale yellow highly viscous to glassy material was obtained. For analysis, a small amount was converted into the methyl ester by esterification with methanol and sulfuric acid. The para-C 1 -T-terpenyl benzoic acid methyl ester had a boiling point of 172 ° C-175 ° C / 26 Pa. and an infrared spectrum; 2980, 2880, 1730, 1620, 1460, 1440, 1290, 1195, 35 1120, 1030, 860 cm -1. It was shown by gas chromatography that the product consisted of 5 isomers in a ratio of 36/3/26/24/11 in the order of 780 95 57 ... '. . -1.3-. the retention time.

EXAMPLE 10

A solution of 27.2 g of camphene in 100 ml of benzene was placed in a 250 ml round bottom flask.

Dry HCl gas was introduced at 0 ° C and after 1 hour 4 g 5 AlClg.CH ^ CHNt ^ CH-j (weight ratio AlClynitropropane 1: 1) was added. After stirring at 30 ° C for 3 hours, the benzene was distilled off in vacuo. Then 80 ml of monochlorobenzene and 26 g of AlCl 2 were added to the reaction mixture with stirring and cooling. With a good stirring and cooling, a cooled solution of 24 g oxalyl chloride in 20 ml monochlorobenzene was slowly added to the resulting mixture at a temperature of -15 ° C to -10 ° C. After this, the mixture was kept at -5 ° C for 3 hours and then slowly poured into a mixture of 15 ice and concentrated HCl (2: 1) with good stirring. The temperature was kept below 0 ° C during the hydrolysis until the evolution of carbon monoxide gas had ceased. After the mixture reached room temperature, the organic layer was separated and the water layer extracted with ether.

The combined organic phases were washed with dilute hydrochloric acid, dilute aqueous bicarbonate solution and water. After drying over Na2SO4 and filtering, chlorobenzene and ether were evaporated in vacuo. The residue was taken up in cyclohexane and the solution extracted with an 11Z-solution of 10% in water. The lye extract was neutralized and extracted with ether. After washing and drying the extract, the ether was evaporated. 33 g of a yellow glassy product which did not crystallize were obtained. A small portion of this was converted into methyl para-C18 terpenyl benzoate (bp 176 ° C-178 ° C / 26 Pa). It was shown by gas chromatography that the mixture consisted of 4 isomers in the ratio 6/5/81/8 in the order of the retention time.

Infrared spectrum: 2990, 2880, 1740, 1620, 1470, 1440, 35 1280, 1190, 1120, 1030, 860 cm-1.

78 0 9 5 57 -14- EXAMPLE 11

In a 100 ml long neck flask, 25 g of para-C 2 -T-terpenyl benzoic acid (prepared according to the method described in Example 9) was mixed with 3 g of CuCoOCCH 2) 1 · 2H 2 O and this mixture was stirred in a metal bath 5 a temperature of 270 ° C-290 ° C is heated. Air was passed through this mixture with stirring for 4 hours and then air to which superheated steam had been added. For another 3 hours, 16 l / h air and 8 g / h steam were passed through at a temperature of 270 ° C-290 ° C. After cooling, the contents of the flask were diluted with toluene, the toluene solution filtered and boiled for 1 hour with a 20% aqueous solution of 10 SO 2. The toluene solution was rinsed well with 20Zig HjSO4 until the solution was copper free. After washing several times with water, the unreacted para-C 1 -g-terpenyl benzoic acid was extracted with an 8Z aqueous KOH solution. After washing with water, the solution was anhydrified as much as possible by azeotropic distillation and then twice the volume of cyclohexane was added. Then the phenol was extracted with Claisen's alkali (35 g KOH, 25 ml HjO and 100 ml methanol). The extract was diluted with water, neutralized and extracted with cyclohexane.

The cyclhexane solution was washed, dried and the cyclohexane evaporated. 11.5 g of meta-C18 g-ter-penylphenol, bp 163 ° C-165 ° C / 39 Pa, were obtained. It was shown by gas chromatography that the product consisted of 5 isomers in a ratio of 42/4/25/23/6 in the order of the retention time. I.R. spectrum: 3380, 3020, 2960, 2860, 1600, 1480, 1450, 1370, 1250, 1165, 30 880, 790, 700 cm -1.

EXAMPLE 12 10 g of Meta-C18 terpenylphenol obtained according to Example 11 was dissolved in 30 ml of cyclohexane and the solution was placed in a 100 ml autoclave together with 1 g of catalyst.

The catalyst contained 5 wt.% Rh + 0.7 wt.% Na on A 2 O 4.

The autoclave was closed and heated with good stirring at 150 ° C at an ice pressure of 80 bar. No Hj was taken after 5 hours. After cooling, the hydrogen was released, the autoclave rinsed with cyclohexane and the collected solution filtered. After evaporation of the cyclo-5 hexane, a colorless thick oil was obtained which had a strong odor of sandalwood, boiling point 1490C-152 ° C / 26 Pa. I.R. spectrum: 3520, 2980, 2820, 1470, 1440, 1175, 1280, 1060 cm "*. The yield of 3-terpenylcyclohexanol was quantitatively based on meta-terpenylphenol.

7809557

Claims (18)

1. Para-C 18 terpenyl benzoic acid and its salts, esters and anhydrides. 2. Process for the preparation of para-C 1 -g-terpenyl-benzoic acid, characterized in that (1) a bicyclic terpene of the formula C 1 -H 2 or a hydrogen halide addition product thereof is reacted with benzene in the presence of a Friedel-Crafts catalyst, converts to C 1 -g-terpenylbenzene, (2) acetyls the C 1 -g-terpenylbenzene to para-C 2 -g-terpenylacetophenone and (3) oxidizes the para-C 2 -g-terpenyl-10-acetophenone to para -C1-2 terpenyl benzoic acid. The method according to claim 2, characterized in that the bicyclic terpene is camphene or alpha or beta pinqen. 4. Process according to claim 2 or 3, characterized in that HF or an AlCl 2 -nitroalkane complex is used as Friedel-Crafts catalyst. 5. Process according to claim 4, characterized in that the reaction of the bicyclic terpene or its hydrogen halide addition product with benzene is carried out at a temperature between -20 and 80 ° C, in particular between -20 and 30 ° C. . Process according to claims 1 to 5, characterized in that acetylation with acetyl chloride or acetic anhydride is carried out at a temperature between 20 and 60 ° C. 25 7. Process according to claims 2-6, characterized in that the oxidation of para-C18-terpenylacetophenone is carried out by passing oxygen or an oxygen-containing gas through a solution of para at a temperature between 100 and 250 ° C. -C 7 g-terpenylacetophenone in an alkane-carboxylic acid to which manganese acetate has been added. 8. Process for preparing para-C10-terpenylbenzoic acid, characterized in that C10-terpenylbenzene is reacted with oxalyl chloride in the presence of AlCl2. 9. Process according to claim 8, characterized in that the reaction is carried out at a temperature between 7809557 -17 -20 and 5 ° C. 10. Process for the preparation of para-C 10 terpenylbenzoic acid, characterized in that C 8 terpenyl benzene is reacted in anhydrous HF with an alkali cyanate and the para-C 10 terphenyl benzene obtained is hydrolyzed. Process according to claim 10, characterized in that the reaction with alkali cyanate is carried out at a temperature between -30 and 0 ° C. 12. Process for the preparation of 3-CjQ-terpenylcyclo-10-hexanol, characterized in that para-CjQ-terpenylbenzoic acid or its salts, esters or anhydrides are oxidized and decarboxylated in the presence of a copper compound and the resulting metal CjQ-terpenylphenol hydrogenates. Process according to claim 12, characterized in that para-C 8 -terpenyl benzoic acid or a salt, ester or anhydride thereof is heated in the molten state or in an inert reaction medium in the presence of a copper compound at a temperature between 200 and 400 ° C. Method according to claim 12 or 13, characterized in that the amount of copper compound is between 0.001 and 1 mole, in particular between 0.01 and 0.20 mole, per mole of starting material. 15. Process according to claims 12-14, characterized in that a copper compound is used as copper compound. A method according to claims 12-15, characterized in that the oxidation and decarboxylation is carried out in the presence of water or steam. Process according to claims 12-16, characterized in that oxygen or an oxygen-containing gas is passed through the reaction mixture. 18. Process according to claims 12-17, characterized in that an oxygen-containing gas is first passed through the reaction mixture for 1-6 hours and then a mixture of this gas and steam for 0.5-3 hours. 780 95 57