US3505412A - Preparation of terpinen-1-ol-(4) - Google Patents

Preparation of terpinen-1-ol-(4) Download PDF

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Publication number
US3505412A
US3505412A US520088A US52008866A US3505412A US 3505412 A US3505412 A US 3505412A US 520088 A US520088 A US 520088A US 52008866 A US52008866 A US 52008866A US 3505412 A US3505412 A US 3505412A
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Prior art keywords
terpinen
terpinolene
methyl
hydroperoxide
oxygen
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Expired - Lifetime
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US520088A
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English (en)
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Erich Klein
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C35/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic
    • C07C35/08—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a six-membered rings
    • C07C35/18—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a six-membered rings with unsaturation at least in the ring
    • 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

Definitions

  • the present invention relates to a process for the manufacture of a terpene derivative.
  • Terpinen-1-ol-(4) i.e. 1-methyl-4-isopropyl-cyclohexen- 1-ol-(4), is an important constituent of many essential oils.
  • the present invention provides a process for the manufacture of terpinen-1-ol-(4) by oxidizing terpinolene (i.e., 1-methyl-4-isopropylidene-cyclohexene-(1)) to l-methyl- 4-isopropenyl-cyclohexene-1-hydroperoxide-(4), and reducing the said hydroperoxide to form terpinen-1-ol-(4).
  • terpinolene i.e., 1-methyl-4-isopropylidene-cyclohexene-(1)
  • l-methyl- 4-isopropenyl-cyclohexene-1-hydroperoxide-(4) reducing the said hydroperoxide to form terpinen-1-ol-(4).
  • the first stage of the reaction may advantageously be carried out by photosensitized oxidation of terpinolene.
  • an oxidation with oxygen or an oxygen-containing gas (e.g. air) is known per se (for example from German specification No. 933,925) and would normally be expected to give rise to a mixture of hydroperoxides, since oxygen would be expected to attack both the tri-substituted endocyclic and the tetra-substituted exocyclic double bond (see G. O. Schenk et al., Liebigs Annalen 1953, 584, 192).
  • the first stage of the process of the present invention is based on the observation that, up to the consumption of 1 mole of oxygen per mole of terpinolene, the exocyclic double bond is exclusively attacked to form the desired 1-methyl-4-isopropenyl cyclohexene-l-hydroperoxide-(4) in good yield.
  • the oxygen takes up the tertiary position on carbon atom 4 of the para-menthane skeleton.
  • a small quantity of a x-paratrimethylbenzyl alcohol is formed, stemming from the simultaneously occurring unsensitized autoxidation of terpinolene.
  • the tri-substituted endocyclic double bond of terpinolene is not attacked if the reaction is discontinued as soon as 1 mole of oxygen per mole of terpinolene has been absorbed.
  • the hydroperoxide resulting from the photo-oxidation may then be reduced according to the present invention in a manner known per se to the hydroxy compound.
  • the photosensitized oxidation may be carried out, for example, in the presence of suitable dyestuffs as sensitizers, for example methylene blue, Rose Bengal, Sudan-G, chlorophyll, eosine, zinc tetraphenyl-porphine, dinaphthylene-thiophene, or thionine, with the use of artificial or natural light and of oxygen or an oxygen-containing gas, for example air.
  • suitable dyestuffs as sensitizers
  • suitable dyestuffs for example methylene blue, Rose Bengal, Sudan-G, chlorophyll, eosine, zinc tetraphenyl-porphine, dinaphthylene-thiophene, or thionine
  • suitable dyestuffs for example methylene blue, Rose Bengal, Sudan-G, chlorophyll, eosine, zinc tetraphenyl-porphine, dinaphthylene-thiophene, or thi
  • the 1-methyl-4-isopropenyl-cyclohexene 1 hydroperoxide-(4) resulting from the photosensitized oxidation is then reduced in known manner to the corresponding alcohol.
  • the reduction may be carried out, for example, with aqueous sodium sulphite solution or with triphenylphosphine or with an alkali metal-aluminum hydride, for example LiAlH
  • the resulting alcoholthat is 1-methyl-4-isopropenylcyclohexen-1-ol-(4)- is finally converted into terpinen-lol-(4) by selective partial hydrogenation with hydrogen in the presence of a catalyst; the yield is quantitative.
  • the relatively mildly acting catalysts such as Raney nickel or Raney cobalt.
  • other conventional metal catalysts such as palladium or platinum, are used, the desired selective hydrogenation is likewise achieved but these catalysts involve a greater risk of an excessive hydrogenation effect.
  • the hydrogenation can also be performed, in known manner in a solvent.
  • Particularly suitable solvents are lower alcohols containing 1 to 3 carbon atoms. Methanol is preferred.
  • the photosensitized oxidation is generally carried out at a low temperature, advantageously within the range from 10 to +30 C., but as a rule room temperature is used.
  • a process for the manufacture of terpinen-1-ol-(4) which comprises oxidizing terpinolene to 1-methyl-4-isopropenyl-cyclohexene-l-hydroperoxide by contacting terpinolene with at most 1 mole of oxygen per mole of terpinolene at -10 to 30 C.
  • sensitizer is methylene blue, Rose Bengal, Sudan-G, chlorophyll, eosine, zinc tetraphenyl-porphine, dinaphthylene thiophene, or thionine.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US520088A 1965-11-13 1966-01-12 Preparation of terpinen-1-ol-(4) Expired - Lifetime US3505412A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DED48643A DE1235306B (de) 1965-11-13 1965-11-13 Verfahren zur Herstellung von Terpinen-1-ol-(4)

Publications (1)

Publication Number Publication Date
US3505412A true US3505412A (en) 1970-04-07

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US520088A Expired - Lifetime US3505412A (en) 1965-11-13 1966-01-12 Preparation of terpinen-1-ol-(4)

Country Status (6)

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US (1) US3505412A (enrdf_load_stackoverflow)
CH (1) CH453344A (enrdf_load_stackoverflow)
DE (1) DE1235306B (enrdf_load_stackoverflow)
FR (1) FR1456297A (enrdf_load_stackoverflow)
GB (1) GB1100748A (enrdf_load_stackoverflow)
NL (1) NL6515048A (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4000050A (en) * 1975-02-19 1976-12-28 International Flavors & Fragrances Inc. Photochemical preparation of polycycloalkyl oxyalkanes and oxyalkenes
US5620569A (en) * 1993-12-23 1997-04-15 Haarmann & Reimer Gmbh Process for the photooxidation of terpene olefins
US5894020A (en) * 1997-04-18 1999-04-13 Concha; Jose Soap composition containing antifungal agent
US20050148568A1 (en) * 2001-03-30 2005-07-07 Hofmann Robert F. Targeted oxidative therapeutic formulation
CN111393345A (zh) * 2020-04-09 2020-07-10 福州大学 一种柠檬烯氢过氧化物的制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3609197A (en) * 1968-03-08 1971-09-28 Reynolds Tobacco Co R Preparation of a terpene alcohol
US3676504A (en) * 1970-09-10 1972-07-11 Reynolds Tobacco Co R Preparation of a terepene alcohol
US4570022A (en) * 1984-01-16 1986-02-11 Union Camp Corporation Preparation of terpinen-4-ols

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2387304A (en) * 1941-10-02 1945-10-23 Hercules Powder Co Ltd Stabilization of terpene products
DE933925C (de) * 1943-12-24 1955-10-06 Guenther O Dr Phil Schenck Verfahren zur Herstellung von Pinocarveylhydroperoxyd
US2950237A (en) * 1957-11-13 1960-08-23 Monsanto Chemicals Photoxidation processes utilizing novel catalysts
FR1319202A (fr) * 1961-04-07 1963-02-22 Studiengesellschaft Kohle Mbh Procédé de préparation de produits d'oxydation à partir de composés non saturés

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2387304A (en) * 1941-10-02 1945-10-23 Hercules Powder Co Ltd Stabilization of terpene products
DE933925C (de) * 1943-12-24 1955-10-06 Guenther O Dr Phil Schenck Verfahren zur Herstellung von Pinocarveylhydroperoxyd
US2950237A (en) * 1957-11-13 1960-08-23 Monsanto Chemicals Photoxidation processes utilizing novel catalysts
FR1319202A (fr) * 1961-04-07 1963-02-22 Studiengesellschaft Kohle Mbh Procédé de préparation de produits d'oxydation à partir de composés non saturés

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4000050A (en) * 1975-02-19 1976-12-28 International Flavors & Fragrances Inc. Photochemical preparation of polycycloalkyl oxyalkanes and oxyalkenes
US5620569A (en) * 1993-12-23 1997-04-15 Haarmann & Reimer Gmbh Process for the photooxidation of terpene olefins
US5894020A (en) * 1997-04-18 1999-04-13 Concha; Jose Soap composition containing antifungal agent
US20050148568A1 (en) * 2001-03-30 2005-07-07 Hofmann Robert F. Targeted oxidative therapeutic formulation
CN111393345A (zh) * 2020-04-09 2020-07-10 福州大学 一种柠檬烯氢过氧化物的制备方法

Also Published As

Publication number Publication date
NL6515048A (enrdf_load_stackoverflow) 1967-05-16
DE1235306B (de) 1967-03-02
FR1456297A (fr) 1966-10-21
GB1100748A (en) 1968-01-24
CH453344A (de) 1968-06-14

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