US3689562A - Synthesis of alkyl cyclopentyl ketones - Google Patents

Synthesis of alkyl cyclopentyl ketones Download PDF

Info

Publication number
US3689562A
US3689562A US807120A US3689562DA US3689562A US 3689562 A US3689562 A US 3689562A US 807120 A US807120 A US 807120A US 3689562D A US3689562D A US 3689562DA US 3689562 A US3689562 A US 3689562A
Authority
US
United States
Prior art keywords
pyrolysis
ketone
ketones
methyl
pyrolyzed
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
US807120A
Other languages
English (en)
Inventor
John C Leffingwell
Ronald E Shackelford
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.)
RJ Reynolds Tobacco Co
Original Assignee
RJ Reynolds Tobacco Co
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 RJ Reynolds Tobacco Co filed Critical RJ Reynolds Tobacco Co
Application granted granted Critical
Publication of US3689562A publication Critical patent/US3689562A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
    • 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
    • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
    • C11B9/003—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing less than six carbon atoms

Definitions

  • alkyl cyclopentyl ketones are obtained by vapor phase pyrolysis of certain trans-lhydroxy-Z-acetoxycyclohexanes.
  • trans-1- hydroxy-Z-acetoxycyclohexanes are subjected to vapor phase pyrolysis at temperatures of approximately 400 C. to 550 C., preferably 425 C. to 475 C., with the formation of alkyl cyclopentyl ketones which are then recovered.
  • the alkyl cyclopentyl ketones have desirable olfactory characteristics and can be used in compounding perfumeries.
  • the use in perfumeries of alkyl cyclopentyl ketones of the type produced in accordance with this invention is disclosed, for example, in US. Pat. No. 2,946,823 which issued July 26, 1960.
  • R methyl, isopropyl or isopropenyl
  • an allylic alcohol (11) is also formed by pyrolysis.
  • the alkyl cyclopentyl ketone (I) can be separated from the allylic alcohol by fractional distillation, chromatography and the like.
  • the pyrolysis apparatus employed consisted of a vertical tube, 18 inch long and 1 inch diameter filled with A inch glass helices, mounted in a combustion furnace.
  • the sample was directed through the apparatus by means of a pressure equalizing funnel mounted on the top of the pyrolysis tube.
  • the sample was carried through the pyrolysis tube by gravity and the pressure due to vaporization.
  • the effluent pyrolyzate was condensed by means of a cold water condenser and trapped in an ice cooled vessel.
  • the samples used in pyrolysis were 20 percent hydroxyacetates by weight in acetone (a solvent being employed for convenience but not required). A drop rate of 0.5-2.0 drops/second was generally employed.
  • reaction temperatures reported are external wall temperatures of the pyrolysis tube. After pyrolyses were complete, the samples were neutralized with a sodium bicarbonate solution and extracted with either hexane or ether. Multiple vapor phase chromatographic analyses were done on each sample using a 10 foot, 10 percent diethyleneglycolsuccinate column under several conditions. Product analyses were done by comparison of the retention times and spectra with known samples, when available.
  • the nuclear magnetic resonance spectrum exhibited a doublet methyl at 9.01 'r (J E 7 cps, 3H); the isopropyl methyls appeared as a doublet at 8.95 'r (J 7 cps, 6H); the isopropyl proton adjacent to the carbonyl appeared as a 5 peaked multiplet at 7.40 1' (ll-I) and the ring proton adjacent to the ketone carbonyl appeared as unresolved multiplet at 7.0 1- (lI-I).
  • the mass spectrum gave a parent molecular ion at m/e 154.
  • the 3-isopropy1- cyclopentyl methyl ketone was identified by its charac- ,Dimethyl 3 acetyl bicyclo I3 l '0] hexane teristic spectra and semicarbazone.
  • the infrared spectrum of this ketone exhibited a saturated carbonyl absorption at 5.83 p..
  • the nuclear magnetic resonance spectrum had resonance signals at 9.12 'r (doublet, .1 6 cps, 611), an acetyl methyl at 7.95 r (singlet, 3H) and the ring proton adjacent to the carbonyl appeared at 7.13 1- (multiplet, 11-1).
  • the mass spectrum exhibited a molecular ion at m/e 154; other fragment peaks appeared at m/e 139, 136, 111, 96, 84, 71, 69, 55, 43, 41 and a metastable peak at 120.1 corresponding to the m/e 154 136 transformation.
  • the semicarbazone melted at 156-158 [reported literature m.p. 156l5 7].
  • EXAMPLE 111 Pyrolysis of l-l-lydroxyneoisocarvomenthylacetate 1-1-1ydroxyneoisocarvomenthylacetate (c1 28. 1, n 1.4651) was prepared by acetylation of l-hydroxyneoisocarvomenthol (5 g., m.p. 8586, [01],; 2.4l) with acetic anhydride.
  • the infrared spectrum exhibited absorptions at 2.97, 3.34, 3.40, 3.45, 6.84, 7.25, 7.33 (doublet), 7.53, 8.15-8.37, 8.58, 8.92 (strong), 9.47, 10.22, 10.58, 10.90, 11.65, 12.30, 12.45, 13.50 and 13.90 microns.
  • the nuclear magnetic resonance spectrum exhibited doublet isopropyl methyls centered at 9.1 1' (J E 6 cps, 6H), a singlet methyl at 8.74 1' (3H), saturated methylene protons at 8.1-8.8 'r and an unresolved singlet for the olefinic protons at 4.38 1' (21-1).
  • the ketone exhibited infrared absorptions at 3.31 (cyclopropyl C1-1), 3.40, 3.48, 5.83 (methyl ketone carbonyl), 6.85, 7.00, 7.25, 7.35, 8.23, 8.40, 8.87, 11.87 and 12.6 microns.
  • the nuclear magnetic resonance spectrum exhibited resonance signals at 9.05 1' (singlet, 61-1) corresponding to the cyclopropyl gem methyl groups, cyclopropyl protons at 8.83 r (multiplet, 21-1) and an acetyl methyl at 7.9 1- (singlet, 31-1); the ring proton adjacent to the carbonyl appeared at 7.28 as a multiplet (1H).
  • the mass spectrum exhibited a molecular ion at m/e 152 with other fragments at m/e 137,119,109, 95, 93 and 91.
  • the second product peak eluting on preparative vapor phase chromatography solidified and, when sublimed onto a microscope slide cover, melted at 6566.
  • This material was identified as the sylvestrene derivative trans-4,8-m-menthadien- 1 ol from knowledge of the configuration of the starting hydroxyacetate coupled with the observed spectral data.
  • the infrared spectrum exhibited a strong Ol-l absorption at 3.05 L and other absorptions at 3.32, 3.43, 3.50, 6.06 (strong, olefinic), 6.85, 7.26, 7.48, 7.56, 7.75, 7.85,
  • optically active products are obtained from optically active starting materials and racemic products from racemic starting materials.
  • R methyl, isopropyl or isopropenyl
  • R R diemthylmethylene; treating the pyrolysis products with a base to effect neutralization of acidic components and recovering an alkyl cyclopentyl ketone from said products.

Landscapes

  • 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)
  • Manufacture Of Tobacco Products (AREA)
US807120A 1969-03-13 1969-03-13 Synthesis of alkyl cyclopentyl ketones Expired - Lifetime US3689562A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US80712069A 1969-03-13 1969-03-13

Publications (1)

Publication Number Publication Date
US3689562A true US3689562A (en) 1972-09-05

Family

ID=25195625

Family Applications (1)

Application Number Title Priority Date Filing Date
US807120A Expired - Lifetime US3689562A (en) 1969-03-13 1969-03-13 Synthesis of alkyl cyclopentyl ketones

Country Status (5)

Country Link
US (1) US3689562A (enExample)
CH (1) CH537351A (enExample)
FR (1) FR2037991A5 (enExample)
GB (1) GB1240423A (enExample)
NL (1) NL7003145A (enExample)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4250061A (en) * 1979-06-18 1981-02-10 Givaudan Corporation 2-Acetyl-1,3,3,4,4-pentamethylcyclopentene as a fragrance material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2803647A (en) * 1953-07-15 1957-08-20 Glidden Co Preparation of carveol and dihydrocarveol and their esters
US2945068A (en) * 1957-12-31 1960-07-12 Glidden Co Pyrolysis of limonene oxide
US2972632A (en) * 1953-04-14 1961-02-21 Glidden Co Conversion of verbenol to monocyclic and acyclic compounds
US3510510A (en) * 1966-06-30 1970-05-05 Procter & Gamble Novel reactions of 4-acyloxy-3-caranols and novel bicyclic compounds resulting from said reactions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2972632A (en) * 1953-04-14 1961-02-21 Glidden Co Conversion of verbenol to monocyclic and acyclic compounds
US2803647A (en) * 1953-07-15 1957-08-20 Glidden Co Preparation of carveol and dihydrocarveol and their esters
US2945068A (en) * 1957-12-31 1960-07-12 Glidden Co Pyrolysis of limonene oxide
US3510510A (en) * 1966-06-30 1970-05-05 Procter & Gamble Novel reactions of 4-acyloxy-3-caranols and novel bicyclic compounds resulting from said reactions

Also Published As

Publication number Publication date
GB1240423A (en) 1971-07-21
FR2037991A5 (enExample) 1970-12-31
DE2012093A1 (enExample) 1971-02-25
NL7003145A (enExample) 1970-09-15
CH537351A (de) 1973-05-31

Similar Documents

Publication Publication Date Title
Hirsch et al. Base-catalyzed alkylation of cyclopentadiene rings with alcohols and amines
Neureiter Pyrolysis of 1, 1-Dichloro-2-vinylcyclopropane Synthesis of2-Chlorocyclopentadiene
Skattebøl Chemistry of gem-Dihalocyclopropanes. V. 1 Formation of Tricyclo [4.1. 0.04, 6] heptane and Derivatives
Zarghami et al. Monoterpene aldehydes and isophorone-related compounds of saffron
Nickon et al. Homoenolization and Related Phenomena. VI. 1 Stereospecificity in Alkaline and Acid Media2, 3
Shinoda et al. Constituents of yuzu (Citrus junos) oil
DePuy et al. The synthesis of 2, 7-disubstituted norbornanes
Schaefer et al. Bicyclo [3.3. 1] nonanes. IV. Dehydration of the bicyclo [3.3. 1] nonane-2, 6-diols
Eisenbraun et al. Synthesis of polyalkyl-1-tetralones and the corresponding naphthalenes
US3689562A (en) Synthesis of alkyl cyclopentyl ketones
Bailey et al. Pyrolysis of Esters. XXIII. 2, 3-Divinyl-1, 3-butadiene1-3
Debrauwere et al. Constituents of peppers. Part VI. The oxygenated fraction of pepper essential oil
Wilcox Jr et al. The preparation of 5, 5-dimethylcyclopentadiene
Gassman et al. Reactions of trans-fused cyclopropanes. Synthesis and solvolysis of 4-hydroxy-trans-bicyclo [5.1. 0] octane p-bromobenzenesulfonate
Lu et al. Palladium-catalyzed reaction of nucleophiles with diacetates of allylic 1, 1-diols
Sorensen The Preparation of a Trivinyl Carbonium Ion
US2577538A (en) Process for the production of vitamin-a ethers and esters
US3754036A (en) Acyl-cyclododecenes,acyl-cyclododecanes and a process for producing them
Ouellette et al. The Cleavage of Cyclopropanes by Lead Tetraacetate
Brodsky et al. Enol ethers and monoketals of biacetyl
TRAYNELIS et al. Pyrolysis of γ-Hydroxyalkyl Quaternary Ammonium Hydroxides and Alkoxides. Cyclohexane Derivatives1, 2
McDonald et al. Molecular rearrangements. X. Boron trifluoride etherate catalyzed rearrangements of trans-2, 3-diphenyl-2, 3-epoxypropionitrile and its p-and p'-methyl derivatives
CA1282079C (en) Process for producing 4,4,7-trimethyl-3,4,7,8-tetrahydro -2(6h)-naphthalen-one in purified form or in a mixture with 3,5,5-trimethyl-4-butenyliden-cyclohex-2-en-1-one, products obtained thereby and their use as aroma chemicals and flavoring agents
Franzus et al. Synthesis of exo, exo-5, 6-dideuterio-syn-7-acetoxy-norbornene and exo, exo-k, 6-dideuterio-2-norbornene
Spangler et al. Alumina-catalyzed dehydration of methylhexadienols. A reinvestigation