US3887622A - Process for the preparation of sesquiterpene ketones - Google Patents

Process for the preparation of sesquiterpene ketones Download PDF

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Publication number
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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United States
Prior art keywords
sesquiterpene
ketones
preparation
mol
hours
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Expired - Lifetime
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US380054A
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English (en)
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Harmannus Boelens
Petrus C Traas
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Naarden International NV
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Naarden International NV
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    • 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)
US380054A 1972-07-20 1973-07-17 Process for the preparation of sesquiterpene ketones Expired - Lifetime US3887622A (en)

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)

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US3887622A true US3887622A (en) 1975-06-03

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US380054A Expired - Lifetime US3887622A (en) 1972-07-20 1973-07-17 Process for the preparation of sesquiterpene ketones

Country Status (8)

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US (1) US3887622A (enrdf_load_stackoverflow)
JP (1) JPS5735170B2 (enrdf_load_stackoverflow)
CH (1) CH582121A5 (enrdf_load_stackoverflow)
DE (1) DE2336798A1 (enrdf_load_stackoverflow)
FR (1) FR2193808B1 (enrdf_load_stackoverflow)
GB (1) GB1434035A (enrdf_load_stackoverflow)
IN (1) IN138032B (enrdf_load_stackoverflow)
NL (1) NL154493B (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
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 (fr) * 1995-12-18 1997-06-26 Firmenich S.A. Procede pour la preparation de la nootkatone
EP2644688A2 (en) 2012-03-27 2013-10-02 International Flavors & Fragrances Inc. Novel pyrimidine derivatives and their use in perfume compositions
CN111499502A (zh) * 2020-05-15 2020-08-07 南京林业大学 一种罗汉柏木烷酮的合成方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1519443A (en) * 1974-08-09 1978-07-26 Bush Boake Allen Ltd Isolongifolene derivatives

Citations (3)

* Cited by examiner, † Cited by third party
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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 (fr) * 1995-12-18 1997-06-26 Firmenich S.A. Procede pour la preparation de la 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 (zh) * 2020-05-15 2020-08-07 南京林业大学 一种罗汉柏木烷酮的合成方法

Also Published As

Publication number Publication date
IN138032B (enrdf_load_stackoverflow) 1975-11-22
FR2193808A1 (enrdf_load_stackoverflow) 1974-02-22
JPS5735170B2 (enrdf_load_stackoverflow) 1982-07-27
DE2336798A1 (de) 1974-01-31
JPS4980057A (enrdf_load_stackoverflow) 1974-08-02
FR2193808B1 (enrdf_load_stackoverflow) 1977-08-12
NL154493B (nl) 1977-09-15
GB1434035A (en) 1976-04-28
CH582121A5 (enrdf_load_stackoverflow) 1976-11-30
NL7309628A (enrdf_load_stackoverflow) 1974-01-22

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