GB701911A - Improvements in or relating to new compounds having an ambergris scent and their preparation process - Google Patents

Improvements in or relating to new compounds having an ambergris scent and their preparation process

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Publication number
GB701911A
GB701911A GB26165/50A GB2616550A GB701911A GB 701911 A GB701911 A GB 701911A GB 26165/50 A GB26165/50 A GB 26165/50A GB 2616550 A GB2616550 A GB 2616550A GB 701911 A GB701911 A GB 701911A
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United Kingdom
Prior art keywords
mixture
acid
product
epoxide
ester
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Expired
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GB26165/50A
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Individual
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Individual
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Publication of GB701911A publication Critical patent/GB701911A/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00Compounds having —CHO groups
    • C07C47/20Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/225Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing rings other than six-membered aromatic rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/60Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in six-membered rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/673Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00Compounds having —CHO groups
    • C07C47/02Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • C07C47/19Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing hydroxy groups
    • C07C47/192Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing hydroxy groups containing rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Epoxy Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention comprises (1) compounds of the formula <FORM:0701911/IV (b)/1> where R11 is -CH2-CH2-, -CH2-CH2-CH2- or -CH2-CH=CH-; and (2) a mixture containing at least two of the isomers represented by the formulae <FORM:0701911/IV (b)/2> <FORM:0701911/IV (b)/3> <FORM:0701911/IV (b)/4> where R1 is -CH2OH or -CHO. A typical mixture of alcohols has a B.P. of 116-7 DEG C. at 0.01 mm. and yields a 3 : 5-dinitrobenzoate of M.P. 133-5 DEG C. A similar mixture of aldehydes has a B.P. of 100-5 DEG C. at 0.01 mm., d420 of 0.993-5 and nD20 of 1.512-4, and gives a semicarbazone of M.P. 223-5 DEG C. The compounds are made from a 2 : 5 : 5 : 9-tetramethyl-decalin having halogen hydroxy or acetoxy in the 2-position and one of the following in the 1-position: -CH2CH2OH, -CH2CHO, -CH2CH2CH2OH or -CH2 CH2CHO, by splitting off the 2-substituent together with a hydrogen atom from an adjacent carbon atom or from the hydroxy group in the 1-position (aldehyde reacting in its enolic form). The reaction may be effected by distillation under reduced pressure or by heating with a dehydration catalyst such as copper bronze or alumina (at 200-300 DEG C.). The starting materials which contain 16 carbon atoms are obtained from the ozonlysis of sclareol oxide (degradation product of sclareol from oil of sage), which yields inter alia 2-acetoxy-2 : 5 : 5 : 9-tetramethyl - decalyl-ethanel and the corresponding aldehyde and acid. The acid may be reduced to the alcohol directly or via the ester obtained by alcoholysis of the 2-acetoxy group (e.g. with methanolic sulphuric acid; lactone is intermediate). Reduction of acid, ester or aldehyde to alcohol may be effected before, after or simultaneously with elimination of the 2-substituent; thus the saturated ester yields the unsaturated ester on heating with iodine or methanolic sulphuric acid. The starting materials with 17 carbon atoms are obtained from ambrein (scentless constituent of ambergris) either by ozonolysis and reduction or by oxidation to ambreinolide and reduction; ambrienolide may also be obtained from sclareol oxide or manool or by cyclization of farnesylacetic acid. In the examples, (1) the neutral fraction from the ozonolysis of sclareol oxide is distilled under reduced pressure over copper bronze or sebacic acid and fractionated to give a mixture of aldehydes of the above formulae (R1=-CHO); alternatively the crude ozonolysis product is so treated and the acidic fraction subsequently removed; (2) the acidic fraction from the ozonolysis of sclareol oxide (or the product of permanganate oxidation of the neutral fraction) is heated in vacuo with copper bronze and the resulting unsaturated acid reduced with lithium aluminium hydride to give a mixture of alcohols of the above formula (R1 = -CH2OH); (3) the starting material of (2) is heated with methanolic sulphuric acid and the resulting 2-hydroxy-2 : 5 : 5 : 9-tetramethyldecalyl-1-acetic acid methyl ester dehydrated by heating with iodine; the resulting unsaturated ester is reduced with lithium aluminium hydride to the same product as (2); if sufficient sulphuric acid is used the iodine treatment is unnecessary; (4) the first step of (3) is carried out in two stages by treatment of the material with alcoholic potash to give a lactone and alcoholysis of the latter with methanolic sulphuric acid; (5) the lactone of (4) is reduced with lithium aluminium hydride or with sodium and alcohol to 2-hydroxy - 2 : 5 : 5 : 9 - tetramethyldecalyl - 1 - ethanol; vacuum distillation over alumina then yields the product of (2); (6) the lactone of (4) is treated with ethanolic hydrogen chloride to give 2-chloro-2 : 5 : 5 : 9-tetramethyldecalyl-1-acetic acid ethyl ester; vacuum distillation yields an unsaturated ester which is reduced to the product of (2) by the Bouveault method or by lithium aluminium hydride; (7) the glycol of (5) is heated with naphthalene-2-sulphonic acid and fractionally distilled under reduced pressure to give the epoxide of the above formula (R11 = -CH2-CH2-); (8) as in (7) using alumina for dehydration; an unsaturated alcohol is also obtained: (9) ambrein ozonide is catalytically reduced to 2-hydroxy-2 : 5 : 5 : 9-tetramethyldecalyl-1-propionaldehyde which is treated as in (8) to yield the epoxide of the above formula (R11 = -CH2-CH = CH-) which may be catalytically reduced to the epoxide (R11 = -CH2-CH2-CH2-); (10) sclareol oxide is ozonized and the ozonide reduced with lithium aluminium hydride; the product which is a mixture of the glycol of (5) and the epoxide of (7) may be treated as in (7) or (8); (11) 2-hydroxy-2 : 5 : 5 : 9-tetramethyldecalyl-1-propanol (from lithium aluminium hydride reduction of ambreinolide) is heated with methanolic sulphuric acid to give the epoxide (R11= -CH2-CH2-CH2-) and the mixture of alcohols (R1= -CH2-CH2-OH); the latter (3 : 5-dinitrobenzoate described) is oxidized by chromic acid to the aldehyde (R1= -CH2-CHO; semicarbazone described); (12) the glycol of (5) is treated with ethereal hydrogen chloride, giving (a) the epoxide (R11= -CH2-CH2-); (b) 2-chloro-2 : 5 : 5 : 9-tetramethyldecalyl-1-ethanol; (c) the product of (2); and (d) an unsaturated chloride; heating the mixture in vacuo converts (b) into (a) and (c), (a) being a stereoisomer of the product of (7) and (8); distilling the mixture followed by hydrolysis with caustic potash gives a mixture of (a) and (c) which can be separated by chromatography on alumina.ALSO:Perfumes are made from ambergris-scented compounds of the formula <FORM:0701911/VI/1> where R11 is -CH2-CH2-,-CH2-CH2-CH2- or -CH2-CH = CH- or a mixture of at least two of the isomers represented by the formulae <FORM:0701911/VI/2> where R1 is -CH2-OH- or CHO; mixtures of these may be used. A typical composition contains a mixture of alcohols (R1 = CH2OH), the epoxide (R11 = -CH2-CH2-), a -and b - amyrins anod g -dihydroionone.
GB26165/50A 1949-11-03 1950-10-26 Improvements in or relating to new compounds having an ambergris scent and their preparation process Expired GB701911A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH701911X 1949-11-03

Publications (1)

Publication Number Publication Date
GB701911A true GB701911A (en) 1954-01-06

Family

ID=4530104

Family Applications (1)

Application Number Title Priority Date Filing Date
GB26165/50A Expired GB701911A (en) 1949-11-03 1950-10-26 Improvements in or relating to new compounds having an ambergris scent and their preparation process

Country Status (1)

Country Link
GB (1) GB701911A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0212254A2 (en) * 1985-08-12 1987-03-04 Firmenich Sa Process for the preparation of oxygenated decaline compounds
EP0282798A2 (en) * 1987-03-17 1988-09-21 Firmenich Sa Aliphatic bicyclic alcools and their use as flavouring compounds
WO1996014310A1 (en) * 1994-11-05 1996-05-17 Henkel Kommanditgesellschaft Auf Aktien METHOD FOR PREPARING 8-α,12-OXIDO-13,14,15,16-TETRANORLABDANUM

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0212254A2 (en) * 1985-08-12 1987-03-04 Firmenich Sa Process for the preparation of oxygenated decaline compounds
EP0212254A3 (en) * 1985-08-12 1988-09-14 Firmenich Sa Process for the preparation of oxygenated decaline compounds
EP0282798A2 (en) * 1987-03-17 1988-09-21 Firmenich Sa Aliphatic bicyclic alcools and their use as flavouring compounds
EP0282798A3 (en) * 1987-03-17 1990-06-13 Firmenich Sa Aliphatic bicyclic alcools and their use as flavouring compounds
WO1996014310A1 (en) * 1994-11-05 1996-05-17 Henkel Kommanditgesellschaft Auf Aktien METHOD FOR PREPARING 8-α,12-OXIDO-13,14,15,16-TETRANORLABDANUM
US5811560A (en) * 1994-11-05 1998-09-22 Henkel Kommanditgesellschaft Auf Aktien Process for the production of 8α, 12-oxido-13, 14,15,16-tetranorlabdane

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