GB2032429A - Creation of Inventions and Patents with Artificial Intelligence

GB2032429A – Para-terpenylbenzoic Acid and Salts, Esters and Anhydrides Thereof
– Google Patents

GB2032429A – Para-terpenylbenzoic Acid and Salts, Esters and Anhydrides Thereof
– Google Patents
Para-terpenylbenzoic Acid and Salts, Esters and Anhydrides Thereof

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GB2032429A

GB2032429A
GB7932321A
GB7932321A
GB2032429A
GB 2032429 A
GB2032429 A
GB 2032429A
GB 7932321 A
GB7932321 A
GB 7932321A
GB 7932321 A
GB7932321 A
GB 7932321A
GB 2032429 A
GB2032429 A
GB 2032429A
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para
acid
terpenylbenzoic
temperature
reaction
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1978-09-20
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Shell Internationale Research Maatschappij BV

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Shell Internationale Research Maatschappij BV
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1978-09-20
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1979-09-18
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1980-05-08

1979-09-18
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1980-05-08
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1982-10-27
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1982-10-27
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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

C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring

C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms

C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring

C07C2/64—Addition to a carbon atom of a six-membered aromatic ring

C07C2/66—Catalytic processes

C07C2/68—Catalytic processes with halides

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms

C07C2/64—Addition to a carbon atom of a six-membered aromatic ring

C07C2/66—Catalytic processes

C07C2/70—Catalytic processes with acids

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring

C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms

C07C37/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by replacing a carboxyl or aldehyde group by a hydroxy group

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

C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds

C07C2527/06—Halogens; Compounds thereof

C07C2527/08—Halides

C07C2527/12—Fluorides

C07C2527/1206—Hydrogen fluoride

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds

C07C2527/06—Halogens; Compounds thereof

C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium

C07C2527/126—Aluminium chloride

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C2602/00—Systems containing two condensed rings

C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common

C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

Abstract

Para-C10-terpenylbenzoic acid and salts, esters, and anhydrides thereof, their preparation, and their use as starting material in the preparation of the aroma chemical 3- C10-terpenylcyclohexanol by converting e.g. para-C10- terpenylbenzoic acid into meta- terpenylbenzoic by oxidation and decarboxylation in the presence of a copper compound, and hydrogenating the meta-terpenylphenol formed. Para-C10-terpenylbenzoic acid is prepared by (1) converting a bicyclic terpene having the formula C10H16 or a hydrogen halide addition product thereof into C10-terpenylbenzene by reaction with benzene in the presence of a Friedel-Crafts catalyst, (2) acetylating the C10-terpenylbenzene to form para-C10-terpenylacetophenone, and (3) oxidizing the para-C10- terpenylacetophenone to form para- C10-terpenylbenzoic acid.

Description

SPECIFICATION
Para-C10-Terpenylbenzoic Acid and Salts,
Esters, and Anhydrides thereof, the
Preparation of these Compounds, and their
Application in the Preparation of 3-C,O- Terpenylcyclohexanol
The invention relates to para-C10terpenylbenzoic acid and to salts, esters, and anhydrides thereof, to the preparation of these compounds, and to their application in the preparation of the aroma chemical 3-C,O- terpenylcyclohexanol.
The article “Investigating the composition of
Santalydol” by I. S. Aulchenko and L. A. Kheifits in “American Perfumer and Cosmetics”, Vol. 85,
July 1970, pages 37-45, reports that 3terpenylcyclohexanols, such as cis- and trans-3isocamphylcyclohexanol and cis- and trans-3isobornylcylohexanol, possess an intense sandalwood smell, whereas 2- and 4terpenylcyclohexanols are practically odourless.
C10-terpenylcyclohexanols may in general be prepared by catalytic hydrogenation of C10- terpenylphenols which have been obtained by reaction of camphene with phenol in the presence of a Friedel-Crafts catalyst. However, the preparation of meta-C,O-terpenylphenol, from which 3-C,O-terpenylcyclohexanol, desirable for its odorant properties, is formed by hydrogenation is less simple because the Friedel-Crafts reaction product consists mainly of para-terepenylphenol.
According to U.S. patent specification No.
3,930,758, however, it is possible to obtain by isomerization an equilibrium mixture having a higher meta-terpenylphenol content by heating this reaction product to a temperature between 100 and 1 500C in the presence of aluminium chloride. Since it is extremely difficult to separate meta-terpenylphenol therefrom, this mixture, after distillation to remove unconverted phenol, is hydrogenated without further purification, yielding meta-terpenylphenol contaminated with ortho- and para-terpenylphenol.
In Netherlands patent application No.
7708060 the reaction between phenol and camphene is carried out in the presence of anhydrous hydrogen fluoride in order to obtain a higher yield of the desired meta-isomer. With this method, too, a considerable quantity (approximately 50% by weight of the total reaction product) of the undesired para and orthoisomers is formed in addition to the meta-isomer.
The known methods therefore have the disadvantage that in the preparation of 3terpenylcyclohexanol it is only possible to use meta-terpenylphenol which is highly contaminated by ortho and para-terpenylphenol.
It has now surprisingly been found that meta CaO-terpenylphenol which is not contaminated with the said isomers can be prepared in a simple manner and in a good yield by oxidation and deca rboxylation of para-C10-terpenylbenzoic acid or salts, esters or anhydrides thereof, in the presence of a copper compound. Hydrogenation of the resultant meta-C10-terpenylphenol yields 3
C10-terpenylcyclohexanol with good odour properties.
Para-C10-terpenylbenzoic acid and salts, esters and an hydrides thereof are novel compounds and the invention therefore relates to these compounds, to their preparation and to their application as starting material in the preparation of 3-C10-terpenylcyclohexanol. The terpenyl group may, for example, be an isocamphyl group or an isomer thereof, for example an isobornyl or an isofenchyl group. In the preparation methods described below, mixtures of para-C,O- terpenylbenzoic acids with various isomeric C10- terpenyl groups are usually formed.
Para-CrO-terpenylbenzoic acid may, for example, be prepared by (1) converting a bicyclic terpene having the formula C10H or a hydrogen halide addition product thereof into C,O-terpenyl benzene by reaction with benzene in the presence of a Friedel-Crafts catalyst, (2) by acetylating the C,O-terpenylbenzene to para-C,O- terpenylacetophenone, and (3) by oxidizing the para-C,O-terpenylacetophenone to para-C,O- terpenylbenzoic acid.
Preferred bicyclic terpenes or hydrogen halide addition products thereof are camphene and alpha- and beta-pinene and the HCI-addition products thereof (bornyl chloride, isobornyl chloride).
The preparation of C,O-terpenylbenzene (stage 1) is also referred to as “alkylation” below.
Examples of useful FriedelCrafts catalysts for this stage are HFS03, H2 SO4, HF, TiCI4, BF3, SbF5 and
AICI3. Very good results are obtained with HF or an AlC!3-nitroalkane complex.
The alkylanon temperature is in general between -20 and 800 C, preferably between -20 and 300C. The reaction may very suitably be carried out by introducing the quantity of HCI calculated for the formation of camphene hydrochloride into a mixture of camphene and benzene and subsequently gradually adding a complex of AICI3 with nitromethane or 2nitropropane as catalyst. If desired, the alkylation may be carried out in a solvent such as, for example, cyclohexane, dioxane or tetrahydrofuran and/or in an excess of benzene.
The acetylation of the resultant C10- terpenylbenzene (stage 2) may be effected in the usual manner, for example with acetyl chloride or acetic acid anhydride in the presence of a catalyst, for example AICI3. The reaction temperature is generally between -20 and +800C, preferably between 20 and 600C. The acetylation can suitably be carried out in a solvent, for example dichloroethane or monochlorobenzene. By working up the reaction mixture in the usual manner, para-C,O- terpenylacetophenone is obtainedin a good yield and uncontaminated with the ortho-isomer. If AICI3 is used as catalyst in the alkylation, the acetylation may, if desired, be carried out in the same reactor as the alkylation. It is then not necessary completely to work up the reaction
mixture obtained during the alkylation.It is
sufficient to remove the excess benzene and/or the solvent by distillation and to add to the
resultant residue fresh AlCI3, solvent and acetyl
chloride.
The oxidation of para-C10- terpenylacetophenone (stage 3) is preferably carried out by introducing oxygen or an oxygencontaining gas at elevated temperature into a solution of para-C,O-terpenylacetophenone in an
alkanoic acid, for example propionic acid, to which a catalytic quantity of manganese acetate has been added. The oxidation is preferably carried out at a temperature between 100 and 2500C.
Para-C,O-terpenylbenzoic acid may also be prepared by reacting CaO-terpenylbenzene with oxalyl chloride (CoCI2) in the presence of AICI3, preferably at a temperature between -20 and 500C. This reaction is preferably carried out in a solvent, for example cyclohexane, dichloroethane or chlorobenzene.
Another suitable process for the preparation of para-C,O-terpenylbenzoic acid consists in reacting terepenylbenzene and an alkali cyanate in anhydrous HF, preferably at a temperature between -30 and OOC. The resultant product, which consists of approximately 90% paraterpenylbenzamide and 10% orthoterpenylbenzamide, is converted into a mixture of the corresponding benzoic acids by hydrolysis with an acid or a base. This mixture is a suitable starting material for the conversion described below of para-C,O-terpenylbenzoic acid into meta C10-terpenylphenol, because in this process metaterpenylphenol is also formed from the orthoterpenylbenzoic acid present.
Para-C,O-terpenylbenzoic acid may be converted in any usual manner into salts, esters or anhydrides thereof.
The process for the preparation of 3-C,O- terpenylcyclohexanol according to the invention comprises the oxidation and the carboxylation of para-C,O-terpenylbenzoic acid or salts or esters or anhydrides thereof in the presence of a copper compound and the hydrogenation of the resultant meta-C,O-terpenylphenol.
The oxidation and decarboxylation of benzoic acid or substituted benzoic acids in the presence of a copper compound is generally known from, for example, the Netherlands patent specification No. 90,684. According to this patent specification it is possible to use as starting material instead of benzoic acid or a substituted benzoic acid a salt, ester or anhydride of such an acid. However, it was not obvious that, starting from para-C,O- terpenylbenzoic acid, which compound is substituted in the para-position with an oxidizable group, it would be possible to prepare meta-C,O- terpenylphenol in a practicable manner in a good yield. It appears from an article by W. G. Toland in
J. Am. Chem.Soc., Vol.83, pages 2507-2512 (1961) that, for example, the reaction with pmethylbenzoic acid proceeds with a considerablylower yield than the reaction with benzoic acid.
The oxidation and decarboxylation can be carried out by heating the para-terpenylbenzoic acid or a salt, ester or anhydride thereof in the
molten state or in an inert reaction medium in the presence of a copper compound at a temperature between 200 and 4000 C, preferably between 220 and 300″C. The quantity of copper compound is in general between 0.001 and 1 mol., preferably between 0.01 and 0.20 mol. per mol. of starting material. The copper compound used may, for example, be a salt or an oxide of copper. Both cuprous and cupric compounds are suitable, the cupric compounds are preferred, however. Examples of suitable cupric compounds are cupric acetate, cupric benzoate, cupric para CaO-terpenyl benzoate, cupric salicylate, cupric carbonate, cupric chloride and cupric sulphate.
Optionally, the copper compound can be produced in situ by adding elemental copper to the reaction mixture. It is likely that during the oxidation and decarboxylation process a portion of the copper is invariably present as cupric salt of the terpenylbenzoic acid to be converted.
Suitabie solvents in which the reaction can be carried out are, for example, benzene, toluene, xylene and biphenyl. Since esters of para-C,O- terpenylbenzoic acid and the resultant meta-C,O- terpenylphenol occur as side-products, the oxidation and decarboxylation are preferably carried out in the presence of steam. Optionally, it is also possible to use water as solvent and to allow the reaction to proceed in a pressurized vessel. The esters formed are hydrolysed by the presence of water or steam.
Preferably, the reaction is carried out in the presence of oxygen, for example by passing oxygen or an oxygen-containing gas, for example air, through the reaction mixture. As a consequence the resultant cuprous compounds are again converted into cupric compounds.
Oxygen or the oxygen-containing gas and steam can be passed through the reaction mixture simultaneously or alternately. Preferably an oxygen-containing gas is first passed through the reaction mixture, for example for a period of 1-6 hours, and subsequently a mixture of this gas and steam, for example for 0.5-3 hours.
The reaction can be carried out batchwise or continuously. To promote the catalytic activity it is possible to add as promoter salts or oxides of lithium, sodium, potassium, barium, magnesium, manganese, rare earth metals or cobalt, preferably in a quantity between 0.04 and 0.17 gram equivalent per gram equivalent of acid.
The reaction mixture may, for example, be worked up by diluting it with a solvent which is not completely miscible with water, for example toluene, by heating the resultant solution, after filtration, with a diluted inorganic acid, for example sulphuric acid or hydrochloric acid, in order to hydrolyse any esters present and to extract the copper compounds from the solution.
After the solution has been washed free of acid, unconverted para-C,O-terpenylbenzoic acid can be extracted with an aqueous solution of NaOH or
KOH in a concentration between 4 and 1 5% by weight. The meta-C10-terpenylphenol can be recovered from the solution by extraction with
Claisen’s alkali (35 g of KOH, 25 ml of H20 and 100 ml of methanol).
The hydrogenation of meta-C10-terpenylphenol can be carried out in a manner known per se in the presence of a catalyst, for example rhodium or platinum, optionally supported on a carrier.
Example I
A quantity of 200 ml of anhydrous HF (10 mol.) was introduced into a Hastelloy B 400 ml autoclave provided with a stirrer. With stirring and cooling, solution of 45 g of camphene (0.33 mol.) in 78 g of benzene (1 mol.) was added at OOC over a period of 20 minutes. The mixtures was stirred for a further hour, during which period the temperature rose to 1 00C, after which the mixture was cooled to approximately -300C. A quantity of 27 g (0.33 mol.) of pulverulent dry potassium cyanate was then added at this temperature with care portionwise with thorough stirring. The autoclave was closed and heated to 300C. After 4 hours the excess HF was distilled off and the HF still present neutralized with a concentrated solution of K2CO3 in water.The resultant emulsion was extracted with cyclohexane several times and the extract was washed with water and dried over Na2SO4. The residue consisted of a mixture of 10% of ortho
C,0-terpenylbenzamide and 90% of para-C,0- terpenylbenzamide.
IR spectrum: 3450, 2980, 1660, 1620, 1610, 1480, 1450,800 and 750 cm~’.
The residue was boiled with a 15% solution of
H2SO4 in water for one hour in order to obtain the corresponding terpenylbenzoic acids. The hydrolyzed product was taken up in cyclohexane and, after washing with water, treated with a 10% solution of potassium hydroxide in water to extract the terpenylbenzoic acids. By neutralization and extraction, 33g (0.13 mol.) of ortho- and para-terpenylbenzoic acid were obtained from the alkaline extract. For analysis purposes a small portion was converted into the methyl esters by reaction with methanol in the presence of H2SO4, followed by distilling off the esters, boiling point 1 69a1 750C/26 Pa. IR spectrum:3010,2910, 1660,1440,1410, 1350, 1260, 1 180, 1020, 860, 730 cm-‘.
After extraction of the acids 38 g (0.1 8 mol.) of C10-terpenylbenzene were isolated from the cyclohexane solution. Gas chromatographic analysis showed that it was a mixture of five isomers. The terpenyl benzene had a boiling point of 11 40C-1 1 60C/39 Pa. IR spectrum: 3060, 3020,2950,2880,1610, 1490,1460,1380, 770, 710cm1.
Example II
100 ml (5 mol.) of anhydrous HF were introduced into a polyethylene bottle. A solution of 27.2 g (0.2 mol.) of camphene in 60 g (0.77 mol.) of benzene was added dropwise at a temperature between 50C and 1 00C with stirring and cooling. After one hour the reaction mixture was poured out into ice, treated with a saturated solution of potassium acetate in water, and extracted with cyclohexane.
After washing with water and drying over
Na2SO4, the cyclohexane and the benzene were distilled off from the extract and the residue was distilled in vacuo. 38 g (0.18 mol.) of C10- terpenylbenzene, boiling point 1 140C- 11 60C/26 Pa, were obtained. Gas chromatographic analysis showed that the C10- terpenylbenzene consisted of 5 isomers in the ratio 29/7/34/27/3, measured in sequence of the retention time. IR spectrum: 3060, 3020, 2950, 2880,1610, 149Q1460, 1380,770,710cm1.
A quantity of 32 g (0.1 5 mol.) of the terpenylbenzene was dissolved in 100 ml of dichloroethane, the solution was cooled and 21 g (0.16 mol.) of pulverulent AICI3 were added with thorough stirring. At a temperature of 25″C a solution of 13 g (0.17 mol.) of acetyl chloride in 1 5 ml of dichloroethane was then slowly added dropwise to the mixture, which was subsequently maintained for one hour at a temperature of approximately 350C-400C. The reaction product was poured out into a mixture of ice and dilute hydrochloric acid. The resultant organic layer was separated off, washed with water and dried over Na2SO4. After filtration the dichloroethane was distilled off and the residue distilled in vacuo.
A quantity of 30 g of para-Cr0- terpenylacetophenone (boiling point 1 560 C- 1 590C/7 Pa) was obtained. Gas chromatographic analysis showed that this product, like the Cw terpenylbenzene used as starting material, consisted of 5 isomers. IR spectrum: 2910, 1670, 1600,1440,1410,1350, 1260,1180,1020, 950,840 cm~’.
Example Ill
Of the para-C,0-terpenylacetophenone obtained in Example II, a quantity of 1 9 g (0.07 mol.) was dissolved in 50 ml of propionic acid and 200 mg of manganese acetate were added. While stirring vigorously, oxygen was passed through at a temperature of approximately 1 300C (10 I/h).
After 2.5 hours the propionic acid was distilled off and the residue was dissolved in cyclohexane. The resultant solution was thoroughly washed with water and dilute aqueous bicarbonate solution.
The para-CgO-terpenylbenzoic acid was extracted from the cyclohexane solution with aqueous 8%
KOH solution. A quantity of 17.5 g of para-CrO- terpenylbenzoic acid was obtained from the .alkaline extract by neutralization and extraction.
For identification purposes, a small portion was converted into the methyl ester (boiling point 1720C–1750C/26 Pa). The ester consisted of a mixture of 5 isomers. The IR-spectrum of the methyl ester of p-terpenylbenzoic acid: 2980, 1730,1610,1450,1430, 1280,1190,1110, 860 cm~’.
Example IV
Into a 200 ml round-bottomed flask with a stirrer, which was placed in a cooling bath, 13.6 g of camphene dissolved in a mixture of 50 ml of benzene and 50 ml of cyclohexane were introduced. A quantity of 3.6 g of dry HCI gas was introduced with thorough stirring at a temperature of OOC. After one hour 3.1 g of
AICI3. CH3NO2 complex (weight ratio between AICI3 and nitrnmethane 1:1) were added dropwise at OOC with thorough stirring. The mixture was subsequently kept at room temperature for half an hour and then poured out into a mixture of ice and dilute hydrochloric acid. The organic layer was separated off, washed with water and dried. The benzene and the cyclohexane were distilled off and the residue was distilled in vacuo.The resultant C,O-terpenylbenzene had a boiling point of 11 50C-1 1 80C/39 Pa. The yield was 19.8 g.
Gas chromatographic analysis showed that the product consisted of 5 isomers in the ratio 39/3/28/21/4 measured in sequence of the retention time. IR spectrum: 3060, 3020, 2950, 2880, 1610, 1490, 1460, 1380, 770, 710 cm-‘.
Example V
The experiment described in Example IV was repeated with 4 g of AICI3. CH3CHNO2CH3 complex (weight ratio between AICI3 and nitropropane 1:1) instead of 3.1 g of
AICI3. CH3NO2 complex as catalyst. The reaction mixture was kept at room temperature for 2 hours. A quantity of 18.5 g of C10- terpenylbenzene was obtained having a boiling point of 1 170C-1200C/26 Pa. Gas chromatographic analysis showed that the product consisted of 4 isomers in a ratio 3/8/82/7.
The IR spectrum showed the same bands as the product of Example IV, but with slight differences of intensity in the 1490, 1460, 1380 cam~’ bands.
Example VI
The test described in Example IV was repeated with beta-pinene instead of camphene. A quantity of 1 7.5 g of C,0-terpenylbenzene was obtained from 13.6 g of beta-pinene. IR spectrum and gas chromatographic analysis showed that the product was identical with that of Example IV.
Example VII
The experiment described in Example IV was repeated with alpha-pinene instead of camphene.
However, the introduction of the HCI-gas lasted 8 hours. 1 6.3 g of C10-terpenylbenzene were obtained from 13.6 g of alpha-pinene. The resultant product was identical with that of
Example IV.
Example VIII
A mixture of 13.6 g of alpha- and beta-pinene and camphene (weight ratio 1:1:1) was treated at OOC with 3.6 g of dry HCI-gas. After 8 hours, 3 g of AICI3. CH3NO2 complex (weight ratio between AICI3 and nitromethane 1:1) were added with thorough stirring at OOC. The mixture was subsequently maintained at room temperature for 2 hours and then worked up in the manner described in Example IV. A quantity of 16.8 g of CaO-terpenylbenzene was obtained, boiling point 11 60C-1 1 90C/26 Pa. Gas chromatographic analysis showed that the product consisted of 5 isomers in the ratio 37/4/29/20/10 measured in sequence of the retention time.
The experiment was repeated with bornyl chloride instead of HCI addition product of alphaand beta-pinene and camphene as starting material. The yield of C,0-terpenylbenzene was 67 mol.%.
Example IX
Into a 1 I round-bottomed flask a solution of
108.8 g of camphene in a mixture of 200 ml of cyclohexane and 200 ml of benzene was introduced. With thorough stirring and cooling 30.4 g of dry hydrochloric acid gas were introduced at a temperature of OOC. After the mixture had been left to stand for one hour at OOC, 1 6 g of AICI3. CH3NO2 complex (weight ratio between AICI3 and nitromethane 1:1) were slowly added over a period of 15 minutes with thorough stirring. The temperature was kept below 1 00C by cooling. The reaction mixture was stirred for a further two hours at 250C. The cyclohexane and the excess benzene were removed in vacuo in a film evaporator at a bottom temperature of up to 400C.A quantity of 400 ml of dichloroethane was subsequently added to the residue.
With cooling and stirring, 108 g of pulverulent
AICI3 were added portionwise to the resultant solution and subsequently a solution of 80 g of
CH3COCI in 100 ml of dichloroethane at a temperature of 1 00C in a period of half an hour.
The reaction mixture was stirred for a further 2+ hours at a temperature of 300C and then poured out into a mixture of ice and diluted hydrochloric acid. After completion of the hydrolysis the dichloroethane layer was separated off and the water layer was extracted with small portions of dichloroethane. The combined dichloroethane solutions were washed with a dilute aqueous HCI solution and subsequently with a dilute aqueous
bicarbonate solution. After drying over Na2SO4 the dichloroethane was distilled off, the residue
was dissolved in 11 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 1 300C. After 5 hours 96% of the para-CrO-terpenylacetophenone had oxidized. The
propionic acid was distilled off in vacuo, the
residue taken up in cyclohexane and the solution washed with a dilute aqueous bicarbonate
solution. The para-C,0-terpenylbenzoic acid was
isolated from the solution by extracting it 6 times
with portions of 100 ml of an aqueous 15% KOH
solution. The resultant extract was washed with
cyclohexane and acidified with dilute H2SO4. The
separated product was taken up in cyclohexane,
the solution washed with water and dried. After flashing off the cyclohexane, 171 g of a lightyellow, highly viscous to glassy material were obtained.For the purpose of analysis, a small quantity was converted into the methyl ester by esterification with methanol and sulphuric acid,
The para-C,O-terpenylbenzoic acid methyl ester had a boiling point of 172″C–1750C/26 Pa and an IR spectrum: 2980,2880, 1710, 1620, 1460, 1440, 1290, 1 195, 1120, 1030,860cm1.Gas chromatographic analysis showed that the product consisted of 5 isomers in a ratio of 36/3/26/24/11 in sequence of the retention time.
Example X
Into a 250 ml round-bottomed flask a solution of 27.2 g of camphene in 100 ml of benzene was introduced. Dry HCI gas was introduced at OOC and after one hour 4 g of AICI3 . CH3CHNO2-CH3 (weight ratio AlCI3:nitropropane 1:1) were added.
After 3 hours’ stirring at 300C the benzene was distilled off in vacuo. Then 80 ml of monochlorobenzene and 26 g of AICI3 were added to the reaction mixture with stirring and cooling. With thorough stirring and cooling a cooled solution of 24 g of oxalyl chloride in 20 ml of monochlorobenzene was slowly added to the resultant mixture at a temperature between -1 50C and -1 00C. Subsequently, the mixture was kept at -50C for 3 hours, after which it was poured out slowly with thorough stirring into a mixture of ice and concentrated HCI (2:1). During the hydrolysis the temperature was kept below OOC until the formation of carbon monoxide gas had stopped.After the mixture had risen to 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 distilled off in vacuo. The residue was taken up in cyclohexane and the solution was extracted with an 11% solution of KOH in water. The alkaline extract was neutralized and extracted with ether. After washing and drying of the extract the ether was distilled off. A quantity of 33 g of a yellow glassy product was obtained which did not crystallize. A small portion of this product was converted into methyl para-C,0- terpenylbenzoate (boiling point 1 760C- 1 780C/26 Pa).Gas chromatographic analysis showed that the mixture consisted of 4 isomers in the ratio 6/5/81/8 in sequence of the retention time. IR spectrum: 2990, 2880, 1740, 1620, 1470,1440,1280,1190, 1120,1030,860 cm~’.
Example XI
Into a 100 mklong-necked flask 25 g of para C,O-terpenylbenzoic acid (prepared according to the process described in Example IX) were mixed with 3 g of Cu(OOCCH3)2.1 H2O and this mixture was heated with stirring in a metal bath to a temperature of 2700C-2900C. Air was passed through this mixture with stirring for 4 hours and
subsequently air to which superheated steam had
been added. In this way a further 1 6 I/h of air and
8 g/h of steam were passed through for 3 hours at
a temperature of 270-2900C. After cooling the
contents of the flask were diluted with toluene,
the toluene solution was filtered and boiled for 1
hour with a 20% solution of H2SO4 in water.The
solution in toluene was thoroughly washed with
20% H2SO4 until the solution was free of copper.
After washing with water several times, the
unconverted para-C,O-terpenylbenzoic acid was
extracted with an aqueous 8% KOH solution. After
washing with water the solution was rendered as
anhydrous as possible by means of azeotropic
distillation and then twice the volume of
cyclohexane was added. The phenol was then
extracted with Claisen’s alkali (35 g of KOH, 25
ml of H2O and 100 ml of methanol). The extract
was diluted with water, neutralized and extracted
with cyclohexane. The cyclohexane solution was
washed and dried and the cyclohexane removed
by distillation. A quantity of 11.5 g of meta-C,O- terpenylphenol was obtained, boiling point 1630C–1650C/39 Pa. Gas chromatographic
analysis showed that the product comprised 5
isomers in a ratio of 42/4/25/23/6 in sequence of
retention time.IR spectrum : 3380, 3020, 2960, 2860,1600,1480,1450, 1370,1250,1165, 880, 790, 700 cm-‘.
Example XII
A quantity of 10 g of meta-C10-terpenylphenol obtained in accordance with Example Xl was dissolved in 30 ml of cyclohexane and the solution was introduced into a 100 ml autoclave together with 1 g of catalyst. The catalyst contained 5% by weight of Rh and 0.7% by weight of Na on Al2O3.
The autoclave was closed and heated with thorough stirring to 1 500C at a hydrogen pressure of 80 bar. After 5 hours no more H2 was taken up. After cooling the hydrogen was released, the autoclave flushed with cyclohexane and the collected solution was filtered. After flashing off the cyclohexane a colourless thick oil was obtained which had a strong sandalwood odour, boiling point 1 490C-1 520C/26 Pa. IR spectrum: 3520,2980,2820, 1470, 1440, 1175, 1280, 1060-1 cm. The yield of 3 terpenylcyclohexa nol was quantitatively calculated on meta-terpenylphenol.

Claims (23)

Claims

1. Para-C,0-terpenylbenzoic acid and salts, esters, and anhydrides thereof.

2. A process for the preparation of para-C,O- terpenylbenzoic acid which comprises (1) converting a bicyclic terpene having the formula C,OH,6 or a hydrogen halide addition product thereof into C,O-terpenylbenzene by reaction with benzene in the presence of a Friedal-Crafts catalysts (2) acetylating the CtO-terpenylbenzene to form para-C,O-terpenylacetophenone, and (3) oxidizing the para-C,0-terpenylacetophenone to form para-C,O-terpenylbenzoic acid.

3. A process as claimed in claim 2 in which the bicyclic terpene is camphene or alpha- or betapinene.

4. A process as claimed in claim 2 or 3, in which the Friedel-Crafts catalyst used is HF or anAICL3 nitroalkane complex.

5. A process as claimed in claim 4, in which the reaction ofthe bicyclic terpene or the hydrogen halide addition product thereof with benzene is carried out at a temperature between -20 and +800C, in particular between -20 and +300C.

6. A process as claimed in any one of claims 1 to 5, in which the acetylation with acetyl chloride or acetic acid anhydride is carried out at a temperature between 20 and 600 C.

7. A process as claimed in any one of claims 2 to 6, in which the oxidation of para-C,0- terpenylacetophenone is carried out by passing oxygen or an oxygen-containing gas at a temperature between 100 and 2500C through a solution of para-C,0-terpenylacetophenone in an alkanoic acid to which manganese acetate has been added.

8. A process as claimed in any one of claims 2 to 7, substantially as hereinbefore described with particular reference to any one of Examples II to
IX.

9. A process for the preparation of para-C,O- terpenylbenzoic acid, in which Cld terpenylbenzene is reacted with oxalyl chloride in the presence of AICI3.

10. A process as claimed in claim 9, in which the reaction is carried out at a temperature between -20 and 50C.

11. A process as claimed in claim 9 or 10,
substantially as hereinbefore described with
particular reference to Example X.

12. A process for the preparation of para-C,O- terpenylbenzoic acid, in which C10 terpenylbenzene is reacted in anhydrous HF with
an alkali cyanate, and the resultant para-C,0
terpenylbenzamide is hydrolyzed.

13. A process as claimed in claim 12, in which the reaction with alkali cyanate is carried out at a temperature between -30 and OOC.

14. A process as claimed in claim 12 or 13, substantilly as hereinbefore described with particular reference to Example

1 5. A process for the preparation of 3-C,0- terpenylcyclohexanol, in which para-C,0- terpenylbenzoic acid or salts, esters or anhydrides thereof are oxidized and decarboxylated in the presence of a copper compound, and the resultant meta-C,0-terpenylphenol is hydrogenated.

1 6. A process as claimed in claim 15, in which para-C,0-terpenylbenzoic 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 to a temperature between 200 and 4000C.

17. A process as claimed in claim 1 5 or 16, in which the quantity of copper compound is between 0.001 and 1 mol., in particular between 0.01 and 0.20 mol. per mol. of starting material.

18. A process as claimed in any one of claims 1 5 to 17, in which the copper compound is a cupric compound.

19. A process as claimed in any one of claims 15 to 18, in which the oxidation and decarboxylation are carried out in the presence of water or steam.

20. A process as claimed in any one of claims 1 5 to 19, in which oxygen or an oxygencontaining gas is passed through the reaction mixture.

21. A process as claimed in anyoneofclaims 15 to 20, in which an oxygen-containing gas is first passed through the reaction mixture for a period of 1 to 6 hours and subsequently a mixture of this gas and steam for 0.5 to 3 hours.

22. A process as claimed in any one of claims 1 5 to 21, substantially as hereinbefore described with particular reference to Examples Xl and XII.

23.3-C,O-terpenylcyclohexanol when prepared by a process as claimed in any one of claims 1 5 to 22.

GB7932321A
1978-09-20
1979-09-18
Paraterpenylbenzoic acid and salts esters and anhydrides thereof

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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.

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Paraterpenylbenzoic acid and salts esters and anhydrides thereof

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METHOD FOR PRODUCING AROMATIC CARBONIC ACIDS

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Preparation of a phenol derivative

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