Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
  • C07C403/02—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains containing only carbon and hydrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
  • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
  • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
  • C07C49/613—Unsaturated compounds containing a keto groups being part of a ring polycyclic
  • C07C49/617—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system
  • C07C49/643—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system having three rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/56—Ring systems containing bridged rings
  • C07C2603/58—Ring systems containing bridged rings containing three rings
  • C07C2603/76—Ring systems containing bridged rings containing three rings containing at least one ring with more than six ring members
  • C07C2603/80—Ring systems containing bridged rings containing three rings containing at least one ring with more than six ring members containing eight-membered 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
  • Y10S585/94—Opening of hydrocarbon ring

Definitions

• This application relates to a process for obtaining Seychellene, which is a Z-methylene-3,6,8-trimethyl-tricyclo[5,3,1,0 ]undecane of the formula:
• Seychellene is a constituent of patchouli oil, which is used in perfume compositions and in flavoring compositions. Seychellene is of particular usefulness in perfumes. However, previously known syntheses have been somewhat un satisfactory for providing Seychellene of perfume grade.
• Seychellene is obtained by heating a mixture comprising a l,2,3,6-tetramethyl-tricyclo[5,43,0 1 undecan-Z-ol of the formula:
• a thickened tapered line V indicates a substituent which is in the fl-orientation (above the plane of the molecule), and a dotted line indicates a substituent which is in the ot-orientation (below the plane of the molecule). It is to be understood that the pictorial representations of the compounds given throughout the specification are set forth for convenience and are to be construed as inclusive of other forms, including enantiomers and racemates and are not to be construed as limited to the particular form shown.
• the process of this application can be carried out merely by heating a mixture containing the tetramethylundecan-2-ol of formula II, sodium acetate and glacial acetic acid.
• temperature and pressure are not critical, and temperatures of C. to 150 C. and atmospheric pressure can be suitably utilized.
• a temperature of 80 C. to 118 C. is utilized in this reaction.
• this reaction can be carried out in a conventional inert organic solvent, such as hexane, methylenchlorid, benzene etc.
• the ratio of reactants in the reaction mixture is not critical.
• the tetramethyl-undecan-Z-ol of formula II can be obtained from a 1,3,6-trimethyl-tricyclo[5,4,0,0 ]undeca- 5,l0-dien-2one of the formula:
• the tetramethyl-undecan-Z-ol of formula II is obtained by first hydrogenating the trimethyl-undeca-S,10-dien-2- one of formula III to form a mixture of cis and trans 1,3,6 trimethyl-tricyclo[5,4,0,0 ]undecan-2-oue isomers said isomers having the formulae:
• trans trimethyl-undecan-Z-one isomer of formula V is then converted to the tetramethyl-undecan-Z-ol of formula II by treatment thereof with methyl lithium.
• the hydrogenation of the trimethyl-undecan-S,10-dien- 2-one of formula III can be carried out in a conventional manner in an inert organic solvent in the presence of a hydrogenation catalyst.
• Seychellene in accordance with the process of this application from the trimethyl-undecan-S,10-dien- 2-one of formula III, it is not necessary to isolate the isomer intermediates of formulae II and V as pure materials.
• the tetramethyl-undecan-Z-ol of formula II can be suitably formed by treating a mixture of cis and trans trimethyl-undecan-2-one isomers of formulae IV and V with methyl lithium.
• the tetramethyl-undecan-2-ol of formula II can be suitably converted to Seychellene if it is in admixture with the tetramethyl-undecan- 2-01 of formula VI and the ketones of formulae IV and V, and such a mixture can be used in the process of this application without further working-up.
• Example 1 A 1 molar solution of 2,6-dimethylphenol in benzene was treated with sodium hydride, and, after the termination of the hydrogen evolution, the mixture was treated with a 10% molar excess of 3-methyl-penta-2,4-dienyl-1- bromide. After stirring overnight at -5 C., the mixture was taken up in diethyl ether and extracted by shaking with water, with 10% aqueous potassium hydroxide solution and again with water. The dried organic phase contained 6-(3-methyl-penta-2,4-dienyl)-2,6-dimethyl-cyclohexa-2,4-dien-1-one; 80-90% yield.
• Example 2 5 g. of 6-(3-methyl-penta-2,4-dienyl)-2,6-dimethyl-cyclohexa-2,4-dien-1-one was dissolved in 25 ml. of benzene and treated with 5 g. of 2,6-dimethylphenol. The mixture was heated for 6 hours under reflux. After cooling to room temperature (22 C.), the mixture was extracted by shaking portionwise with a solution of 35 g. of potassium hydroxide, 25 ml. of water and 100 ml. of methanol. The organic phase was concentrated and the residue dis tilled at 7090 C./0.03 mm. Hg.
• the distillate contained 1,3,6-trimethy1-tricyclo[5,4,0,0 ]undeca-5,10-dien- 2-one and 1,3,6-trimethyl-tricyclo[5,3,1,0 ]undeca-5,9- dien-Z-one in the approximate molar ratio of 3:1.
• Example 3 27 g. of 1,3,6-trimethyl-tricyclo[5,4,0,0 ]undeca-5,10- dien-2-one was hydrogenated in 200 ml. of methanol with 3 g. of 10% Pd/ C catalyst. After 4.5 hours, the reduction ended with the absorption of 2 mol of hydrogen. The mixture was worked up by chromatography on silica gel. 27 g. of a mixture of isomers of 1,3,6-trimethyl-tricyclo- [5,4,0,0 ]undecan-2-one was obtained, having a boiling point of 80-85 C./0.03 mm. Hg. Gas chromatography showed the mixture to be 65.5% by wt. of 6-cis isomer and 34.5% by Wt. of 6-trans isomer.
• Example 4 The 27 g. mixture of ketone diastereomers, prepared in Example 3, was dissolved in 200 ml. of diethyl ether, and treated dropwise at 5 C. with 50 ml. of a ca 2-N solution of methyl lithium in diethyl ether. Then, the mixture was stirred for 2 hours at 5 C. The excess methyl lithium was subsequently decomposed with a small amount of ethanol, the mixture was poured onto water, and the aqueous phase was extracted with diethyl ether. After drying and evaporating the ethereal extract, the residual, colorless oil was distilled in a bulb tube at 90" C./0.03 mm. Hg. There was obtained 27 g.
• Example 5 The 27 g. mixture, obtained by the procedure of Example 4, was heated at C. for 20 hours with 45 g. of sodium acetate in 300 ml. of glacial acetic acid. Then, the mixture was poured onto 2 liters of water and extracted with pentane. The organic phase was washed neutral, dried and evaporated. The residual oil was chromatographed on 750 g. of silica gel with pentane/diethyl ether (9:1 parts by volume). There was obtained 8.6 g. of hydrocarbon fraction, consisting of 57.5% by wt. of (:)-seychellene and 39.5% by wt. and 3% by wt. of two unidentified compounds, and 16 g.
• ketone fraction consisting of 98.5% by wt. of 1,3,6-trimethyltricyclo[5,4,0,0 ]undecan-Z-one (6-cis isomer) and 1.5% by wt. of 1,3,6-trimethyl-tricyclo[5,4,O,0 ]undecan-Z-one (6-trans isomer).
• hydrocarbon fraction was separated on 170 g. of silica gel impregnated with 10% by wt. silver nitrate. The mixture was applied with pentane. Elution was carried out initially with pentane. Then 4.9 g. of i)-seychellene was eluted with pentane/diethyl ether (1:1 parts by volume); boiling point C./l2 mm. Hg.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=4369967

Family Applications (1)

Country Status (6)

• 1972
  • 1972-07-25 CH CH1109372A patent/CH564498A5/xx not_active IP Right Cessation
• 1973
  • 1973-06-14 NL NL7308283A patent/NL7308283A/xx unknown
  • 1973-07-05 DE DE19732334274 patent/DE2334274A1/de active Pending
  • 1973-07-16 US US00379865A patent/US3839476A/en not_active Expired - Lifetime
  • 1973-07-24 GB GB3513573A patent/GB1386747A/en not_active Expired
  • 1973-07-25 FR FR7327155A patent/FR2193804B1/fr not_active Expired

Also Published As

Similar Documents