US3887622A - Process for the preparation of sesquiterpene ketones - Google Patents
Process for the preparation of sesquiterpene ketones Download PDFInfo
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- US3887622A US3887622A US380054A US38005473A US3887622A US 3887622 A US3887622 A US 3887622A US 380054 A US380054 A US 380054A US 38005473 A US38005473 A US 38005473A US 3887622 A US3887622 A US 3887622A
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- sesquiterpene
- ketones
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- -1 sesquiterpene ketones Chemical class 0.000 title claims abstract description 42
- 229930004725 sesquiterpene Natural products 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- CQUAYTJDLQBXCQ-NHYWBVRUSA-N (-)-isolongifolene Chemical compound C([C@@H](C1)C2(C)C)C[C@]31C2=CCCC3(C)C CQUAYTJDLQBXCQ-NHYWBVRUSA-N 0.000 claims description 9
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical class CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 claims description 5
- IRAQOCYXUMOFCW-CXTNEJHOSA-N cedrene Chemical compound C1[C@]23[C@H](C)CC[C@H]3C(C)(C)[C@H]1C(C)=CC2 IRAQOCYXUMOFCW-CXTNEJHOSA-N 0.000 claims description 5
- IRAQOCYXUMOFCW-UHFFFAOYSA-N di-epi-alpha-cedrene Natural products C1C23C(C)CCC3C(C)(C)C1C(C)=CC2 IRAQOCYXUMOFCW-UHFFFAOYSA-N 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 abstract description 5
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- BQOFWKZOCNGFEC-UHFFFAOYSA-N carene Chemical compound C1C(C)=CCC2C(C)(C)C12 BQOFWKZOCNGFEC-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical group 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- VCOCESNMLNDPLX-BTXGZQJSSA-N (3s,6s)-2,2,8,8-tetramethyl-octahydro-1h-2,4a-methanonapthalene-10-one Chemical compound O=C1CCC(C)(C)[C@@]2(C3)C1C(C)(C)[C@H]3CC2 VCOCESNMLNDPLX-BTXGZQJSSA-N 0.000 description 2
- CHPQWDBBFXQHQC-UHFFFAOYSA-N 68891-95-2 Chemical compound C1C23C(C)CCC3C(C)(C)C1C(C)C(=O)C2 CHPQWDBBFXQHQC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- AHXGRMIPHCAXFP-UHFFFAOYSA-L chromyl dichloride Chemical compound Cl[Cr](Cl)(=O)=O AHXGRMIPHCAXFP-UHFFFAOYSA-L 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000004354 sesquiterpene derivatives Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- NPNUFJAVOOONJE-ZIAGYGMSSA-N β-(E)-Caryophyllene Chemical compound C1CC(C)=CCCC(=C)[C@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-ZIAGYGMSSA-N 0.000 description 2
- WTOYNNBCKUYIKC-JMSVASOKSA-N (+)-nootkatone Chemical compound C1C[C@@H](C(C)=C)C[C@@]2(C)[C@H](C)CC(=O)C=C21 WTOYNNBCKUYIKC-JMSVASOKSA-N 0.000 description 1
- CAULGCQHVOVVRN-UHFFFAOYSA-N (3Z,9E)-Germacra-3,7(11),9-trien-6-on Natural products CC(C)=C1CC=C(C)CCC=C(C)CC1=O CAULGCQHVOVVRN-UHFFFAOYSA-N 0.000 description 1
- CAULGCQHVOVVRN-SWZPTJTJSA-N (E,E)-germacrone Chemical compound CC(C)=C1C\C=C(C)\CC\C=C(C)\CC1=O CAULGCQHVOVVRN-SWZPTJTJSA-N 0.000 description 1
- ZVSZHMFUICOVPY-UHFFFAOYSA-N Germacrone Natural products CC(=C)C1CC=C(/C)CCC=C(/C)CC1=O ZVSZHMFUICOVPY-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical group 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- NPNUFJAVOOONJE-UHFFFAOYSA-N beta-cariophyllene Natural products C1CC(C)=CCCC(=C)C2CC(C)(C)C21 NPNUFJAVOOONJE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- NPNUFJAVOOONJE-UONOGXRCSA-N caryophyllene Natural products C1CC(C)=CCCC(=C)[C@@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-UONOGXRCSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- WTOYNNBCKUYIKC-UHFFFAOYSA-N dl-nootkatone Natural products C1CC(C(C)=C)CC2(C)C(C)CC(=O)C=C21 WTOYNNBCKUYIKC-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229930003658 monoterpene Natural products 0.000 description 1
- 150000002773 monoterpene derivatives Chemical class 0.000 description 1
- 235000002577 monoterpenes Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- KIEOKOFEPABQKJ-UHFFFAOYSA-N sodium dichromate Chemical compound [Na+].[Na+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KIEOKOFEPABQKJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings
-
- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/385—Saturated compounds containing a keto group being part of a ring
- C07C49/417—Saturated compounds containing a keto group being part of a ring polycyclic
- C07C49/423—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system
- C07C49/453—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having three rings
Definitions
- the invention relates to a process for the preparation of sesquiterpene ketones.
- the invention provides a process for the oxydation of sesquiterpene hydrocarbons, containing a single ethylenic bond, with the aid of hydrogen peroxyde in such a way that sesquiterpene ketones free from isomeric ketones are obtained.
- the product is obtained by the oxydation of isolongifolene with sodium bichromate in acid medium and consists of a mixture of at least three ketones. Oxydation with hydrogen peroxyde and V in acetone again leads to a mixture of ketones together with unreacted isolongifolene. No yields have been mentioned.
- the British Pat. Specification No. 1,216,048 covers the preparation and use as a fragrance material of novel thuyopsanones obtained from thuyopsene.
- thuyopsene is preferentially performed with peracetic acid or chromylchloride but other reagents such as MnO KMnO, and oxygen in combination with actinic radiation may be used as well.
- the yield of thuyopsanone isomers obtained is 70% of the theoretical value in the case of peracids, whereas yields of 35.4% and 30% are obtained when chromylchloride or oxygen are used.
- sesquiterpene hydrocarbons C H containing one olefinic bond in endocyclic position on treatment with hydrogen peroxyde and a lower alkyl formate, under reaction conditions which deviate from those claimed in US. Pat. No. 2.555.927, do not yield vicinal diols but give rise to the formation of sesquiterpene ketones.
- sesquiterpene hydrocarbons -H which contain one olefinic linkage and follow the process of the invention are cedrenc. isolongifolene, thuyopsene and the like (formula 1. 2. and 3 rcsp.).
- sesquiterpene hydrocarbons containing more than one olefinic linkage such as beta-caryophyllene. when reacted according to the invention. produce a mixture of unidentified compounds besides much polymeric material.
- sesquiterpene hydrocarbons containing one olefinic linkage in exocyclic position do not produce a carbonyl compound.
- the invention is therefore limited to sesquiterpene hydrocarbons containing one olefinic linkage in endocyclic position.
- the preferred reaction conditions leading to diols according to US. Pat. No. 2,555,927 comprise the use per mol olefin of 1.1 -1.2 moles of hydrogen peroxyde of 5 15% by weight concentration combined with 50 mol based on hydrogen peroxyde, of low boiling alkyl formate, preferably methylformate, at a temperature in the range between 25 and 100C in a period between 12 and 48 hours.
- sesquiterpene hydrocarbon 1 mol is reacted with 1.3 1.5 moles of hydrogen peroxyde of a concentration of 20 -50% by weight, a lower alkylformate chosen from the group of methyl-, ethyl-, propyl-, and butylformates, preferably ethylformate, in an amount of -200 mol on hydrocarbon at a temperature in the range between 40 and 100C. in period between 6 and 12 hours.
- EXAMPLE 1 A 6-liter glass reactor, equiped with a stirrer a dropping-funnel and a reflux condenser, is charged with 1,350 g. isolongifolene (6.6 moles) and 975 g. ethyl formate (13.2 moles). The contents are heated to about 57C and 975 g. hydrogen peroxyde (concentration 30% by wt., 8.6 moles) is added at such rate that no excessive foaming occurs. This takes between 1 and 2 hours after which refluxing is continued for another 6 hours. During the reaction the temperature in the bottom gradually increases to about 73C. The reaction mass is then cooled to about 25C. and theaqueous bottomlayer drained off and discarded.
- FIG. 2 is obtained.
- FIGS. 1 to 3 of the accompanying drawings show the infra-red spectra of the products of Examples 1 to 111, respectively.
- a process for the preparation of sesquiterpene ketones comprising reacting at a temperature of 40 to C. for a period of 6 to 12 hours 1 mol of sesquiterpene hydrocarbon having one olefinic linkage in an endocyclic position selected from the group consisting cedrene. isolongifolene and thuyopsene with 1.3 1.5 mols of hydrogen peroxide. having a concentration of from 20 50'/( by weight in the presence of from 200 mol 7c of a lower alkyl formate.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Abstract
A process for the preparation of sesquiterpene ketones, which includes reacting, at 40* to 100*C. for from 6-12 hours, a sesquiterpene hydrocarbon having one olefinic linkage in the endocyclic position with hydrogen peroxide in the presence of a lower alkyl formate such as ethyl formate.
Description
United States Patent [191 Boelens et a].
PROCESS FOR THE PREPARATION OF SESQUITERPENE KETONES Inventors: Harmannus Boelens, Huizen; Petrus C. Traas, Naarden, both of Netherlands Naarden International NV, Naarden-Bussum, Netherlands Filed: July 17, 1973 Appl. No.: 380,054
Assignee:
Foreign Application Priority Data July 20, 1972 United Kingdom 33960/72 US. Cl 260/586 P; 260/586 G; 260/586 F Int. Cl. C07c 45/04 Field of Search 260/587, 586 B, 586 P References Cited UNITED STATES PATENTS 6/1951 l-limel et al. 260/618 R June 3, 1975 3,647,847 3/1972 Curtis et al. ..260/587 3,718,698 2/1973 Hall ..260/587 Primary ExaminerBernard Helfin Assistant Examiner-Norman Morgenstern Attorney, Agent, or Firm-Stevens, Davis, Miller & Mosher 3 Claims, 4 Drawing Figures PATENTEU 3 AmcobmEv mc2m m m i 9 NF 2 9 m m w w m e m cm QN co ow 02. Dow com 009 00Ev coon 000m aauemwsuell PATENTEDJUH 3 I975 SHEET A oumtccm EE vtmm ucmEa m E2 086 52558. E
i 9 NF S 9 com com 009 wcocwcvmu *0 E5326 E aauemwsum Cedrene Thuyopsene lsolongifolene Delta -3carene PROCESS FOR THE PREPARATION OF SESQUITERPENE KETONES The invention relates to a process for the preparation of sesquiterpene ketones.
More particularly the invention provides a process for the oxydation of sesquiterpene hydrocarbons, containing a single ethylenic bond, with the aid of hydrogen peroxyde in such a way that sesquiterpene ketones free from isomeric ketones are obtained.
Although oxygen-containing sesquiterpene derivatives have found an increasing interest in the fragrance and flavour industry the number of sesquiterpene ketones actually used is still very small. S. Arctander, Perfume and Flavor Chemicals, Montclair, NJ. 1969) describes only cedranone (monograph no. 596), germacrone (no. 1463), nootkatone (no. 2382) and vetivone (no. 3089).
The increased interest is also reflected in some recent patent applications. The British Pat. Specification No. 1,197,579 discloses the use of an oxydation product of isolongifolene as an ingredient in perfume compositions.
The product is obtained by the oxydation of isolongifolene with sodium bichromate in acid medium and consists of a mixture of at least three ketones. Oxydation with hydrogen peroxyde and V in acetone again leads to a mixture of ketones together with unreacted isolongifolene. No yields have been mentioned.
The British Pat. Specification No. 1,216,048 covers the preparation and use as a fragrance material of novel thuyopsanones obtained from thuyopsene.
According to this patent application the oxydation of thuyopsene is preferentially performed with peracetic acid or chromylchloride but other reagents such as MnO KMnO, and oxygen in combination with actinic radiation may be used as well. The yield of thuyopsanone isomers obtained is 70% of the theoretical value in the case of peracids, whereas yields of 35.4% and 30% are obtained when chromylchloride or oxygen are used.
It has now been found that high yields of sesquiterpene ketones are obtained when suitable sesquiterpene hydrocarbons are reacted with hydrogen peroxyde in the presence of a lower alkylformate. No allylic oxydation occurs.
it is known from US. Pat. No. 2,555,927 that unsaturated organic compounds on treatment with hydrogen peroxyde and an alkyl formate boiling below 100C as a catalyst yield vicinal diols. The reaction applies to the hydroxylation of olefinic linkages in monoolefins, diolefins, unsaturated fatty acids, unsaturated alcohols, olefins substituted with a cyclic structure and to cyclic olefins which may be substituted by a saturated group.
In contrast to this it was found the sesquiterpene hydrocarbons C H containing one olefinic bond in endocyclic position, on treatment with hydrogen peroxyde and a lower alkyl formate, under reaction conditions which deviate from those claimed in US. Pat. No. 2.555.927, do not yield vicinal diols but give rise to the formation of sesquiterpene ketones.
Examples of sesquiterpene hydrocarbons -H which contain one olefinic linkage and follow the process of the invention are cedrenc. isolongifolene, thuyopsene and the like (formula 1. 2. and 3 rcsp.).
sesquiterpene hydrocarbons containing more than one olefinic linkage such as beta-caryophyllene. when reacted according to the invention. produce a mixture of unidentified compounds besides much polymeric material.
It was also found that sesquiterpene hydrocarbons containing one olefinic linkage in exocyclic position do not produce a carbonyl compound.
Comparison of related structures in the process of the invention, e.g. thuyopsene with delta-3-carene (formula 4) shows that with monoterpenes side reactions. such as opening of the cyclopropane ring and polymerisation. occur whereas the sesquiterpenes give a high yield of ketones.
The invention is therefore limited to sesquiterpene hydrocarbons containing one olefinic linkage in endocyclic position.
The preferred reaction conditions leading to diols according to US. Pat. No. 2,555,927 comprise the use per mol olefin of 1.1 -1.2 moles of hydrogen peroxyde of 5 15% by weight concentration combined with 50 mol based on hydrogen peroxyde, of low boiling alkyl formate, preferably methylformate, at a temperature in the range between 25 and 100C in a period between 12 and 48 hours.
For the introduction of a keto group into sesquiterpene hydrocarbons according to this invention the following conditions apply:
1 mol of sesquiterpene hydrocarbon is reacted with 1.3 1.5 moles of hydrogen peroxyde of a concentration of 20 -50% by weight, a lower alkylformate chosen from the group of methyl-, ethyl-, propyl-, and butylformates, preferably ethylformate, in an amount of -200 mol on hydrocarbon at a temperature in the range between 40 and 100C. in period between 6 and 12 hours.
The process of the invention may be illustrated by the following examples.
EXAMPLE 1 A 6-liter glass reactor, equiped with a stirrer a dropping-funnel and a reflux condenser, is charged with 1,350 g. isolongifolene (6.6 moles) and 975 g. ethyl formate (13.2 moles). The contents are heated to about 57C and 975 g. hydrogen peroxyde (concentration 30% by wt., 8.6 moles) is added at such rate that no excessive foaming occurs. This takes between 1 and 2 hours after which refluxing is continued for another 6 hours. During the reaction the temperature in the bottom gradually increases to about 73C. The reaction mass is then cooled to about 25C. and theaqueous bottomlayer drained off and discarded. The toplayer is washed in succession with 900 m1. saturated sodium bicarbonate solution and 900 ml. water and then dried over anhydrous magnesiumsulphate. On fractionation under vacuum 1014 g. isolongifolanone bp l131l7C/2 mm. n /D= 1,5011 lR-spectrum FIG. 2 is obtained.
A panel of six trained perfumers was unanimously of the opinion that the odour of the isolongifolanone thus obtained is preferred to that of the isomeric mixture of ketones known as isolongifolene oxidate from British Patent Specification No. 1,197,579.
EXAMPLE 11 In a similar 1 liter reactor 204 g. (1 mol) cedrene, 165 g 30% hydrogen peroxyde (1.45 moles) and g. ethyl formate are reacted as described in Example I. The temperature in the bottom increases from 58C to 82C in 6 hours. 154 g. cedranone bp 124 126C/O.2
3 mm; n /D 1.5026; IR-spectrum FIG. 2 is obtained.
EXAMPLE Ill Thuyopsene is reacted as in Example 11. Temperature increases from 57 to 78C in hours. 195 g. thuyopsanone is obtained. bp ll6-l22C/1.8 mm; Di /D 1,5022; lR-spectrum FIG. 3.
EXAMPLE IV The preparation according to example 111 is repeated, but ethyl formate is replaced by butyl formate (1,5 moles) 182 g thuyopanone is obtained.
The formulae 1 to 4 referred to herein are shown in FIG. 4 of the accompanying drawings. FIGS. 1 to 3 of the accompanying drawings show the infra-red spectra of the products of Examples 1 to 111, respectively.
What we claim is:
1. A process for the preparation of sesquiterpene ketones comprising reacting at a temperature of 40 to C. for a period of 6 to 12 hours 1 mol of sesquiterpene hydrocarbon having one olefinic linkage in an endocyclic position selected from the group consisting cedrene. isolongifolene and thuyopsene with 1.3 1.5 mols of hydrogen peroxide. having a concentration of from 20 50'/( by weight in the presence of from 200 mol 7c of a lower alkyl formate.
2. Process according to claim 1 wherein said lower alkyl formate is chosen from the group of methyl-. cthyl-, propyl-, and butylformates.
3. Process according to claim 2 wherein said lower
Claims (3)
1. A PROCESS FOR THE PREPARATION OF SESQUITERPENE KETONES COMPRISING REACTING AT A TEMPERATURE OF 40* TO 100*C. FOR A PERIOD OF 6 TO 12 HOURS 1 MOL OF SESQUITERPENE HYDROCARBON HAVING ONE OLEFINIC LINKAGE IN AN ENDOCYCLIC POSITION SELECTED FROM THE GROUP CONSISTING CEDRENE, ISOLONGIFOLENE AND THUYOPSENE WITH 1.3 - 1.5 MOLS OF HYDROGEN PEROXIDE, HAVING A CONCENTRATION OF FROM 20 - 50% BY WEIGHT IN THE PRESENCE OF FROM 120 - 200 MOL % OF A LOWER ALKYL FORMATE.
1. A process for the preparation of sesquiterpene ketones comprising reacting at a temperature of 40* to 100*C. for a period of 6 to 12 hours 1 mol of sesquiterpene hydrocarbon having one olefinic linkage in an endocyclic position selected from the group consisting cedrene, isolongifolene and thuyopsene with 1.3 - 1.5 mols of hydrogen peroxide, having a concentration of from 20 - 50% by weight in the presence of from 120 - 200 mol % of a lower alkyl formate.
2. Process according to claim 1 wherein said lower alkyl formate is chosen from the group of methyl-, ethyl-, propyl-, and butylformates.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB3396072A GB1434035A (en) | 1972-07-20 | 1972-07-20 | Process for the preparation of sesquiterpene ketones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3887622A true US3887622A (en) | 1975-06-03 |
Family
ID=10359605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US380054A Expired - Lifetime US3887622A (en) | 1972-07-20 | 1973-07-17 | Process for the preparation of sesquiterpene ketones |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3887622A (en) |
| JP (1) | JPS5735170B2 (en) |
| CH (1) | CH582121A5 (en) |
| DE (1) | DE2336798A1 (en) |
| FR (1) | FR2193808B1 (en) |
| GB (1) | GB1434035A (en) |
| IN (1) | IN138032B (en) |
| NL (1) | NL154493B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5260459A (en) * | 1991-11-19 | 1993-11-09 | Brunke Ernst Joachim | Cyclic isolongifolanone-ketals - their manufacture and their application |
| WO1997022575A1 (en) * | 1995-12-18 | 1997-06-26 | Firmenich S.A. | Method for preparing nootkatone |
| EP2644688A2 (en) | 2012-03-27 | 2013-10-02 | International Flavors & Fragrances Inc. | Novel pyrimidine derivatives and their use in perfume compositions |
| CN111499502A (en) * | 2020-05-15 | 2020-08-07 | 南京林业大学 | Synthetic method of thujopsis japonica ketonic acid |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1519443A (en) * | 1974-08-09 | 1978-07-26 | Bush Boake Allen Ltd | Isolongifolene derivatives |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2555927A (en) * | 1949-05-25 | 1951-06-05 | Phillips Petroleum Co | Hydroxylation of unsaturated compounds |
| US3647847A (en) * | 1968-09-27 | 1972-03-07 | Bush Boake Allen Ltd | Isolongifolene esters |
| US3718698A (en) * | 1969-11-24 | 1973-02-27 | Int Flavors & Fragrances Inc | Isolongifolene processes and product |
-
1972
- 1972-07-20 GB GB3396072A patent/GB1434035A/en not_active Expired
-
1973
- 1973-07-10 NL NL737309628A patent/NL154493B/en not_active IP Right Cessation
- 1973-07-17 DE DE19732336798 patent/DE2336798A1/en not_active Ceased
- 1973-07-17 US US380054A patent/US3887622A/en not_active Expired - Lifetime
- 1973-07-18 IN IN1683/CAL/73A patent/IN138032B/en unknown
- 1973-07-19 FR FR7326513A patent/FR2193808B1/fr not_active Expired
- 1973-07-20 CH CH1069573A patent/CH582121A5/xx not_active IP Right Cessation
- 1973-07-20 JP JP8079573A patent/JPS5735170B2/ja not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2555927A (en) * | 1949-05-25 | 1951-06-05 | Phillips Petroleum Co | Hydroxylation of unsaturated compounds |
| US3647847A (en) * | 1968-09-27 | 1972-03-07 | Bush Boake Allen Ltd | Isolongifolene esters |
| US3718698A (en) * | 1969-11-24 | 1973-02-27 | Int Flavors & Fragrances Inc | Isolongifolene processes and product |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5260459A (en) * | 1991-11-19 | 1993-11-09 | Brunke Ernst Joachim | Cyclic isolongifolanone-ketals - their manufacture and their application |
| WO1997022575A1 (en) * | 1995-12-18 | 1997-06-26 | Firmenich S.A. | Method for preparing nootkatone |
| US5847226A (en) * | 1995-12-18 | 1998-12-08 | Firmenich Sa | Process for the preparation of nootkatone |
| EP2644688A2 (en) | 2012-03-27 | 2013-10-02 | International Flavors & Fragrances Inc. | Novel pyrimidine derivatives and their use in perfume compositions |
| EP2851415A1 (en) | 2012-03-27 | 2015-03-25 | International Flavors & Fragrances Inc. | Novel quinazoline derivatives and their use in perfume compositions |
| CN111499502A (en) * | 2020-05-15 | 2020-08-07 | 南京林业大学 | Synthetic method of thujopsis japonica ketonic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2193808B1 (en) | 1977-08-12 |
| FR2193808A1 (en) | 1974-02-22 |
| IN138032B (en) | 1975-11-22 |
| JPS5735170B2 (en) | 1982-07-27 |
| NL7309628A (en) | 1974-01-22 |
| DE2336798A1 (en) | 1974-01-31 |
| JPS4980057A (en) | 1974-08-02 |
| NL154493B (en) | 1977-09-15 |
| GB1434035A (en) | 1976-04-28 |
| CH582121A5 (en) | 1976-11-30 |
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