US3505412A - Preparation of terpinen-1-ol-(4) - Google Patents
Preparation of terpinen-1-ol-(4) Download PDFInfo
- 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
- Authority
- US
- United States
- Prior art keywords
- terpinen
- terpinolene
- methyl
- hydroperoxide
- oxygen
- 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
Links
Classifications
-
- 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 |
Family
ID=7051326
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US520088A Expired - Lifetime US3505412A (en) | 1965-11-13 | 1966-01-12 | Preparation of terpinen-1-ol-(4) |
Country Status (6)
Country | Link |
---|---|
US (1) | US3505412A (de) |
CH (1) | CH453344A (de) |
DE (1) | DE1235306B (de) |
FR (1) | FR1456297A (de) |
GB (1) | GB1100748A (de) |
NL (1) | NL6515048A (de) |
Cited By (5)
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)
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)
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 |
-
1965
- 1965-11-13 DE DED48643A patent/DE1235306B/de active Pending
- 1965-11-18 GB GB49115/65A patent/GB1100748A/en not_active Expired
- 1965-11-19 NL NL6515048A patent/NL6515048A/xx unknown
- 1965-11-23 CH CH1609665A patent/CH453344A/de unknown
- 1965-12-01 FR FR40508A patent/FR1456297A/fr not_active Expired
-
1966
- 1966-01-12 US US520088A patent/US3505412A/en not_active Expired - Lifetime
Patent Citations (4)
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)
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 |
---|---|
FR1456297A (fr) | 1966-10-21 |
DE1235306B (de) | 1967-03-02 |
GB1100748A (en) | 1968-01-24 |
NL6515048A (de) | 1967-05-16 |
CH453344A (de) | 1968-06-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Farmer et al. | 22. The course of autoxidation reactions in polyisoprenes and allied compounds. Part I. The structure and reactive tendencies of the peroxides of simple olefins | |
Trevoy et al. | Mechanism of lithium aluminum hydride reactions | |
Rao et al. | Terpenoids—XXI: The structure of costunolide, a new sesquiterpene lactone from costus root oil | |
US5030739A (en) | Process for the catalytic oxidation of isoprenoids having allylic groups | |
US3505412A (en) | Preparation of terpinen-1-ol-(4) | |
Mathur et al. | Terpenoids—LXX: Structure of dehydrocostus lactone | |
US3382276A (en) | Mixtures of oxygenated acyclic terpenes | |
Fielding et al. | 898. The chemistry of fungi. Part XXXIX. The structure of monascin | |
US3514489A (en) | Sec-butyl cyclohexane carboxaldenhydes | |
Herbst et al. | Terpenoids. XLIV. 1 Synthetic Confirmation of the Structure and Absolute Configuration of Petasin2 | |
Schulte‐Elte et al. | Macrocyclic Ring Closure of OH‐assisted Prins Reaction. A new and efficient synthesis of (R, S)‐muscone | |
Buechi et al. | Photochemical reactions. XIV. Additions to ethyl propiolate | |
US3452105A (en) | 3-hydroxy-7-isobutyl-1,6-octadiene | |
US3676504A (en) | Preparation of a terepene alcohol | |
US3532762A (en) | Hydrocarbon and a process for the manufacture thereof | |
US3723478A (en) | Monoepoxidized products of dodecatriene | |
Cambie et al. | 783. Chemistry of the higher fungi. Part XVI. Polyacetylenic metabolites from Aleurodiscus roseus | |
US3660489A (en) | Novel caranone derivatives perfume compositions containing same and process for their preparation | |
Matsumoto et al. | Oxygenations of vitamin E (. alpha.-tocopherol) and its model compound, 2, 2, 5, 7, 8-pentamethylchroman-6-ol, in the presence of potassium superoxide suspended in tetrahydrofuran, and unusual acyloin rearrangements | |
US2655548A (en) | Chx r r | |
Barton et al. | 454. Triterpenoids. Part XXIV. Further investigations on the constitution of zeorin | |
Matic et al. | 506. The chemistry of polymerised oils. Part III. Reduction of some organic peroxides with lithium aluminium hydride | |
Eliel et al. | A NEW SYNTHESIS OF HYDROXYETHERS AND THIOETHERS | |
Bowden et al. | 313. Researches on acetylenic compounds. Part XII. The preparation of conjugated diacetylenic glycols by the oxidative coupling of various types of ethynylcarbinols | |
US4260526A (en) | Perfume compositions containing 2,6,10,10-tetra-methyl-1-oxa-spiro[4,5]-decan-7-one |