US3647847A - Isolongifolene esters - Google Patents

Isolongifolene esters Download PDF

Info

Publication number
US3647847A
US3647847A US860638A US3647847DA US3647847A US 3647847 A US3647847 A US 3647847A US 860638 A US860638 A US 860638A US 3647847D A US3647847D A US 3647847DA US 3647847 A US3647847 A US 3647847A
Authority
US
United States
Prior art keywords
esters
isolongifolene
mixture
perfumery
oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US860638A
Other languages
English (en)
Inventor
Anthony John Curtis
Brian George Jaggers
John Francis Janes
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bush Boake Allen Ltd
Original Assignee
Bush Boake Allen Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bush Boake Allen Ltd filed Critical Bush Boake Allen Ltd
Application granted granted Critical
Publication of US3647847A publication Critical patent/US3647847A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/929—Special chemical considerations
    • Y10S585/947—Terpene manufacture or recovery

Definitions

  • R-il-O wherein R is a C -C alkyl group are prepared by allylic substitution, e.g. oxidation, of isolongifolene, followed by replacement of the substituent by an RCO group.
  • Said esters have valuable perfumery properties particularly as replacements for vetiverol derivatives.
  • This invention relates to perfumery compositions of the type where a number of odoriferous materials, of synthetic or natural origin, are admixed or compounded to form a perfumery concentrate.
  • Such concentrates may find use as such or after dilution, but more usually they are added in small proportions to other materials, such as to space sprays or to soap, detergent, cosmetic or deodorant compositions, or to substrates such as fabrics, fibres or paper products, in order to provide them with agreeable olfactory properties.
  • Such concentrates (as well as the aforesaid perfumed materials) are products of commerce and the perfumery concentrates may comprise a simple or complex mixture of individual perfumery compounds.
  • the sesquiterpane longifolene (I) is obtainable as a by-product in the refining of Indian oil of turpentine. It is known that it may be isomerised to isolongifolene (II) by a number of means, and isolongifolene may be subjected to controlled oxidation to yield a mixture of ketones having valuable perfumery properties. It is also known (see Tetrahedron Letters 8,417.424 (1964)) that one of these ketones, having the structure III may be reduced to give an epimeric mixture of alcohols of the general structure IV.
  • this invention provides isolongifolenyl carboxylate esters of the structure Where R is an alkyl group having 1 to 5 carbon atoms.
  • the invention provides compounded perfumery compositions comprising an isolongifolenyl carboxylate ester of the invention.
  • Longifolene may be isomerised to isolongifolene by methods known in terpene chemistry, e.g. by treatment below C. with acetic acid or another weak acid in the presence of a little sulphuric acid. or other strong protonating agent; or by the action of boron trifluoride etherate.
  • the controlled oxidation of isolongifolene to a mixture of ketones is described for example in Tetrahedron 8, 42-48 (1960) and it may be accomplished by the action of an acidic solution of a hexavalent chromium compound; e.g. by chromium trioxide in a mixture of tertiary butanol, acetic acid and acetic anhydride; or by sodium dichromate in sulphuric acid and acetic acid.
  • a mixture of vanadium pentoxide and hydrogen peroxide in acetone might be used.
  • the reaction mixture is maintained below 50 C. to prevent undue over-oxidation.
  • the isomerisation and oxidation of longifolene is conveniently carried out without the isolation of the intermediate isolongifolene.
  • the second Class B of possible routes from isolongifolene to the novel isolongifolenyl esters of the invention embraces a number of reactions for achieving this transformation, either directly or through the formation of other intermediates.
  • isolongifolene may be subjected to allylic chlorination e.g. by reaction with chlorine in the presence of sodium carbonate the resulting chloroisolongifolene then being converted to the desired ester by replacement reaction, e.g. by reaction with the sodium salt of the appropriate carboxylic acid in the presence of a tertiary amine such as triethylamine.
  • isolongifolene may be treated with an organic peroin'de such as tertAbutyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide or ter.-butyl-perbenzoate, in the presence of cuprous chloride and the appropriate carboxylic acid; or, where the acetate is required it may be treated with lead tetra-acetate or mercuric acetate, again in the presence of the carboxylic acid, i.e. acetic acid. In all such reactions it will generally be necessary simply to stir the reactants together for as long as is found necessary to produce the maximum or optimum yield.
  • an organic peroin'de such as tertAbutyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide or ter.-butyl-perbenzoate, in the presence of cuprous chloride and the appropriate carboxylic acid; or, where the acetate is required it may be treated with lead te
  • the group R in the compounds of the invention is an alkyl group containing from one to five carbon atoms.
  • Appropriate carboxylic acids for use in the formation reactions mentioned therefore include acetic, propionic, butyric, pentanoic and hexoic acids.
  • the preferred ester is the acetate, that is where R is methyl.
  • esters for present uses have a distinctive woody odour note somewhat akin to the esters of vetiverol which are expensive materials derived from vertiverol a constituent of vetivert oil. Accordingly, the compounded perfumery concentrates of the invention will often be formulated to take maximum advantage of this note and be similar to the formulations wherein the vertiverol esters have found use or would have found use if it had not been for their high price.
  • esters be blended with one or more ionone compounds, such as the -,8 and a-ionOnes, the n-methylionones and/or isomethylionones; and/or with musk compounds, such as musk ketone or ethylene brassylate, each of which may have been prepared synthetically or isolated from natural sources or used in combination with other ingredients in less refined extracts of natural origin.
  • ionone compounds such as the -,8 and a-ionOnes, the n-methylionones and/or isomethylionones
  • musk compounds such as musk ketone or ethylene brassylate
  • the aforesaid esters will generally be used only in a small amount in perfumery compositions since even in such amounts the desirable woody note is manifested.
  • the compounded perfumery compositions of the invention will usually comprise from 0.1 to preferably 0.5 to 10%, by weight of the said esters based on the total weight of perfumery ingredients.
  • the invention envisages the use of blends of the esters with at least one ionone and/or musk compound for subsequent incorporation into compounded perfumery compositions of more complex formulations.
  • the perfumery compositions of the invention will often comprise a considerable number of perfumery components.
  • the blends of the esters of the invention with ionone and/or musk compounds may comprise, for example up to 60% by weight of the novel esters.
  • the novel esters have been found to blend particularly satisfactorily with vertiveryl acetate, vetiverol, vetivert oil, sandalwood oil, cedarwood oil, labdanum oil, oakmoss oil and patchouli oil. Blends of isolongifolenyl esters of the invention with any of these aforesaid compounds are included within the scope of the invention.
  • compositions of the invention find use in a wide variety of perfumed materials, for example, the compositions may find particular use in contourier-type perfumes, cologne or toilet waters, space sprays or they can be blended in soap, detergent or deodorant compositions including bath salts, shampoos, or in cosmetic preparations, such as face creams, talcum powders, body lotions, sun cream preparations and particularly, because of the nature of their perfumery note, in male toilet products such as shave lotions and creams.
  • the compositions can also be used to perfume substrates such as fibres, fabrics and paper products.
  • the chlorides were then placed in a 2 l. flask fitted with a stirrer and were heated with acetic acid (1.000 ml.) and sodium acetate (100 gms.) for 48 hours at 80 C.
  • the last compound, ionone cyclic ether, is a benzopyran of the formula wherein the unsatisfied carbon valencies are filled by hydrogen atoms, according to the conventional nomenclature. These compounds may be prepared by isomerisation of p-ionone.
  • R-il-O wherein R is an alkyl group containing from 1 to 5 carbon atoms.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)
US860638A 1968-09-27 1969-09-24 Isolongifolene esters Expired - Lifetime US3647847A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB4605668 1968-09-27

Publications (1)

Publication Number Publication Date
US3647847A true US3647847A (en) 1972-03-07

Family

ID=10439678

Family Applications (1)

Application Number Title Priority Date Filing Date
US860638A Expired - Lifetime US3647847A (en) 1968-09-27 1969-09-24 Isolongifolene esters

Country Status (7)

Country Link
US (1) US3647847A (enrdf_load_stackoverflow)
JP (1) JPS4812977B1 (enrdf_load_stackoverflow)
CH (1) CH525275A (enrdf_load_stackoverflow)
DE (1) DE1948536A1 (enrdf_load_stackoverflow)
FR (1) FR2019039A1 (enrdf_load_stackoverflow)
GB (1) GB1256535A (enrdf_load_stackoverflow)
NL (1) NL6914630A (enrdf_load_stackoverflow)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3887622A (en) * 1972-07-20 1975-06-03 Naarden International Nv Process for the preparation of sesquiterpene ketones
US3907873A (en) * 1970-05-14 1975-09-23 Int Flavors & Fragrances Inc Novel fragrance materials and process
US4100110A (en) * 1974-08-09 1978-07-11 Bush Boake Allen Limited Isolongifolene Prins reaction compounds in perfumery
US4246129A (en) * 1979-04-18 1981-01-20 The Procter & Gamble Company Surfactant cake compositions containing solubility reducing agents
US4929599A (en) * 1988-04-27 1990-05-29 Firmenich Sa Perfuming ingredient
US5693606A (en) * 1994-02-23 1997-12-02 Dragoco Gerberding & Co. Ag Isolongifolanol derivatives, their production and their use
US20030166974A1 (en) * 2000-08-03 2003-09-04 Examiner Rosalynd Keys In Group Isolongifolenyl ethers, their preparation and their use
US7378557B1 (en) * 2007-07-13 2008-05-27 The United States Of America As Represented By The Secretary Of Agriculture Methods for preparing isolongifolenone and its use in repelling arthropods
US20090018192A1 (en) * 2007-07-13 2009-01-15 Aijun Zhang Methods for Repelling Arthropods Using Isolongifolenone Analogs

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3907873A (en) * 1970-05-14 1975-09-23 Int Flavors & Fragrances Inc Novel fragrance materials and process
US3887622A (en) * 1972-07-20 1975-06-03 Naarden International Nv Process for the preparation of sesquiterpene ketones
US4100110A (en) * 1974-08-09 1978-07-11 Bush Boake Allen Limited Isolongifolene Prins reaction compounds in perfumery
US4246129A (en) * 1979-04-18 1981-01-20 The Procter & Gamble Company Surfactant cake compositions containing solubility reducing agents
US4929599A (en) * 1988-04-27 1990-05-29 Firmenich Sa Perfuming ingredient
US5693606A (en) * 1994-02-23 1997-12-02 Dragoco Gerberding & Co. Ag Isolongifolanol derivatives, their production and their use
US20030166974A1 (en) * 2000-08-03 2003-09-04 Examiner Rosalynd Keys In Group Isolongifolenyl ethers, their preparation and their use
US6734159B2 (en) * 2000-08-03 2004-05-11 Symrise Gmbh & Co. Kg Isolongifolenyl ethers, their preparation and their use
US7378557B1 (en) * 2007-07-13 2008-05-27 The United States Of America As Represented By The Secretary Of Agriculture Methods for preparing isolongifolenone and its use in repelling arthropods
US20090018192A1 (en) * 2007-07-13 2009-01-15 Aijun Zhang Methods for Repelling Arthropods Using Isolongifolenone Analogs
US7579016B2 (en) * 2007-07-13 2009-08-25 The United States Of America As Represented By The Secretary Of Agriculture Methods for repelling arthropods using isolongifolenone analogs
EP2641890A1 (en) 2007-07-13 2013-09-25 The United States of America, as represented by the Secretary of Agriculture Composition for repelling arthropods using isolongifolenone

Also Published As

Publication number Publication date
FR2019039A1 (enrdf_load_stackoverflow) 1970-06-26
DE1948536A1 (de) 1970-10-01
NL6914630A (enrdf_load_stackoverflow) 1970-04-01
CH525275A (de) 1972-07-15
JPS4812977B1 (enrdf_load_stackoverflow) 1973-04-24
GB1256535A (enrdf_load_stackoverflow) 1971-12-08

Similar Documents

Publication Publication Date Title
US3647847A (en) Isolongifolene esters
JP5479466B2 (ja) 匂い物質として適するイソロンギホラニル誘導体
USRE36493E (en) Fragrant macrocyclic lactones
US3029255A (en) Compounds having an ambergris scent and their preparation process
US4671798A (en) 1,2,3,4,4a,5,8,8a-octahydro-2,2,6,8-tetramethyl-1-naphthalenol, its use as perfuming ingredient and process for making same
JPS6159285B2 (enrdf_load_stackoverflow)
CA1136552A (en) Acetyl trimethyl bicyclo non-ene as perfume
US3579550A (en) Oxygenated derivatives of acyclic olefins
US3407225A (en) 4, 7-methanoindene derivatives
US3598745A (en) Substituted 4,7-methanoindenes perfume compositions
US3455957A (en) Dihydropyran perfume
US2809996A (en) Compounds having an ambergris scent and their preparation
DE1214819B (de) Riechstoff
JPS58134071A (ja) 新規芳香物質
US3309276A (en) Perfume composition containing 2-(2-methyl-1-propenyl)-2, 4, 6-trimethydihydro-4, 5-pyran
US3709929A (en) 4-methyl-2-pentanol crotonate
US4904640A (en) 2-alkylidene-3,3,5(3,5,5)-trimethyl cyclopentanones
US3417132A (en) 4,7-methanoindene derivatives
US2759022A (en) Musk odorant
US3557188A (en) 4,7-methanoindene derivatives
US3915901A (en) 2,6,10-Trimethyl-10-hydroxy-dodeca-2,6,11-trien-al as a perfuming agent
US3702343A (en) 2-methyl-2-(tertiary alkyl cyclohexyl) pentan-4-ones and processes
EP0078925B1 (en) (+)- or (-)-7-hydroxymethyl-2,6,6-trimethyltricyclo-(6,2,1,0 1,5) undecane, a process for producing them and a perfume composition
US4457862A (en) Odorant substances
US3383284A (en) Cosmetic compositions containing cyclic c18 and c20 alcohols