US3835192A - Precursor of sesquiterpine derivatives of the eremophilane group - Google Patents

Precursor of sesquiterpine derivatives of the eremophilane group Download PDF

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US3835192A
US3835192A US00154960A US15496071A US3835192A US 3835192 A US3835192 A US 3835192A US 00154960 A US00154960 A US 00154960A US 15496071 A US15496071 A US 15496071A US 3835192 A US3835192 A US 3835192A
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formula
nootkatone
mixture
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H Boelens
Der Linde L Van
J Witteveen
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NAARDEN CHEM FAB
Nv Chem Fab Naarden nl
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    • 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
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/40—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with ozone; by ozonolysis
    • 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
    • C07C45/61—Preparation 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
    • C07C45/63—Preparation 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 introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • 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
    • C07C45/61—Preparation 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
    • C07C45/64—Preparation 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 introduction of functional groups containing oxygen only in singly bound form
    • 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
    • C07C45/61—Preparation 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
    • C07C45/65—Preparation 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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • 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
    • C07C45/61—Preparation 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
    • C07C45/65—Preparation 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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • C07C45/66—Preparation 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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
    • 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
    • C07C45/61—Preparation 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
    • C07C45/67—Preparation 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
    • 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
    • C07C45/61—Preparation 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
    • C07C45/67—Preparation 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
    • C07C45/68—Preparation 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 increase in the number of carbon atoms
    • C07C45/70—Preparation 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 increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
    • C07C45/71—Preparation 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 increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
    • 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
    • C07C45/61—Preparation 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
    • C07C45/67—Preparation 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
    • C07C45/68—Preparation 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 increase in the number of carbon atoms
    • C07C45/72—Preparation 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 increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • 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
    • Y10S585/947—Terpene manufacture or recovery

Definitions

  • the invention relates to product and process for the preparation of sesquiterpene derivatives of the eremophilane group.
  • sesquiterpenes having an eremophilane skeleton are characterized by a bicyclo [4-4-0] decane structure, as shown in the formula of FIG. 1, with methyl substituents at the positions and 6, and a branched chain C substituent at the position 8.
  • the invention relates more particularly to those structures in which both methyl groups are disposed on the same side of the molecule (i.e., on the same side of a plane drawn through the carbons of the sixmembered rings), while the substituent at C is either disposed at the opposite side or connected with the C by means of a double bond.
  • Said group of compounds will be referred to hereinafter by the name of nootkatane group.
  • Valerianol occurs in the oil of Valeriana officinalis
  • a-Vetivone (formula of FIG. 3) is found in vetiver oil (from Vetiveria zizanoides)
  • nootkatone (formula of FIG. 4) is found in the oil of the Alaska yellow cedar (Chamaecyparis nootkatensis) and in a great number of citrus oils, specifically grapefruit oil (from Citrus paradisi).
  • Nardostachone (formula of FIG. 5) is a constituent of spikenard oil (from Nardostachis jatamansi).
  • Nootkatone (fonnula of FIG. 4) may be prepared by oxidation of valencene (formula of FIG. 6) with tertiary butyl chromate [cf. J. Food Sci., 30, 876 (1965)]. If (+)valencene is used as the starting material, it will yield optically active nootkatone which is dextrorotatory, as is the natural isomer, and has the absolute configuration which is shown in the formula of FIG. 4.
  • a disadvantage of the aforementioned method for the preparation of nootkatone is that valencene is not sufficiently commercially available in an economical way to warrant its use.
  • Nootkatone may also be prepared from nootkatene by a process consisting of various steps (see the Dutch Pat. Application No. 69,14545, laid open for public inspection), a substance which, in accordance with Acta Chim. Scand., 11, 1157 (1957), may be isolated from the wood of Chamaecyparis nootkatensis, giving a yield of about 0.25 percent.
  • the sesquiterpenes thus obtained are not optically active, but are mixtures of equal amounts of optical antipodes; for example, of (+)nootkatone (FIG. 4) and ()nootkatone (FIG. 7).
  • the compound having the formula of FIG. 8 is new. According to the invention it can be produced easily on a technical scale if methylpropenyl ketone (formula of FIG. 9), in accordance withthe reaction 1, is condensed with 2-methylsabina-ketone (formula of FIG. 10) under the influence of a strong base, such as sodium hydride or sodium amide.
  • a strong base such as sodium hydride or sodium amide.
  • sabinene is oxidized with a strong oxidizing agent, such as ozone, into sabina ketone having the formula of FIG. 12, and into this sabina ketone a methyl group is introduced in the activated a-position, for instance, by direct methylation with methyl iodide or dimethylsulphate, or by the introduction of a group which by means of reduction can be converted into a methyl group, such as a methylene group or a hydroxymethylene group (see reaction 2).
  • Sabina ketone may be prepared by means of a synthetic process as well [see J. Org. Chem, 33, 1656 (1968)].
  • optically active sesquiterpenes of the nootkatane series If the reaction 1 is carried out with optically active and dextrorotatory 2methyl-sabina ketone (which is derived from laevorotatory l-sabinene), there is obtained optically active and laevorotatory 5,6-dimethyl-8-isopropyltricyclo [4.4.0.0 l-decene-3-one having the absolute configuration, as shown in the formula of FIG. 13.
  • the compound having the formula of FIG. 8 is treated with acid, as described in the examples.
  • Compounds having a carbon skeleton, as in the formula of FIG. 1, representing the desired configuration are formed upon opening of the cyclopropane ring. This process is shown in the reaction scheme 3, if dextrorotatory 5,6-dimethyl-8-isopropyl-tricyclo [4.4.0.0' 1-decene-3- one (FIG. 8) is used as the starting material. If the laevorotatory isomer is used as the starting material, it is understood that in this instance the optical antipodes will be formed. Reaction of the compound having the formula of FIG.
  • FIG. 17 yields l1-halodihydro-nootkatone, having the formula of FIG. 18, identical with the product which can be obtained from nootkatone (having the formula of FIG. 7) by the addition of hydrohalic acid.
  • This product may also be formed directly from 7-halodihydro-nootkatone (having the formula of FIG. 16), e.g., by treatment with a moderately concentrated sulphuric acid in the presence of hydrohalic acid or a halide.
  • a conversion of the compound of FIG. 8 into the compound of FIG. 18 in high yield and directly may be effected by adding hydrohalic acid in ethanol, followed by addition of sulphuric acid and water.
  • ll-l-Iydroxydihydronootkatone (FIG. 19) is also formed upon treatment of the compound of FIG. 17 with water in acid medium.
  • Dehydrohalogenation of ll-halodihydronootkatone or dehydration of 11-hydroxydihydronootkatone yields mixtures of a-vetivone (FIG. 20) and nootkatone (FIG. 7) which can be separated from one another.
  • the relative quantities of the compounds of FIGS. 20 and 7 will vary depending on the method of dehydrohalogenation or dehydration employed in the process. Dehydrohalogenation with sodium acetate in glacial acetic acid will afford a nearly complete conversion into nootkatone. This is also true if the acetate of 11-hydroxydihydronootkatone is subjected to pyrolysis. On being treated with a catalytic amount of a strong acid, such as p-toluene-sulphonic acid, at an elevated temperature, ll-hydroxydihydronootkatone will mainly yield the a-vetivone.
  • a strong acid such as p-toluen
  • Suitable methods are, for example, dehydrohalogenation by heating with a base, such as potassium hydroxide or potassium methoxide in methanol or with an organic nitrogen base, such as dimethylaniline or picoline and dehydration by treating with phosphorus oxychloride or thonyl-chloride in pyridine.
  • a base such as potassium hydroxide or potassium methoxide in methanol
  • an organic nitrogen base such as dimethylaniline or picoline
  • reaction temperature C. A solution of 128 g of sabina ketone in 160 ml of glacial acetic acid and 200 g of N-piperidinemethanol was refluxed for 15 hours (reaction temperature C.). After cooling the reaction mixture was poured out onto a mixture of water, ice and hydrochloric acid. The oil layer was separated and the aqueous layer was extracted three times with 200 ml of pentane each time. Oil layer and extracts were combined, washed until neutral, dried and filtered off. After removal of the solvent and distillation, there was thus obtained 30 g of 2- methylene-sabina ketone. B.p. 67C. at 2 mm.
  • reaction product was present in the aqueous layer in the form of a salt of the Mannich base.
  • the acid aqueous layer was rendered alkaline with sodium carbonate and was extracted three times with 100 ml of carbon tetrachloride each time. After drying and evaporation of the solvent there was thus obtained 142 g of Mannich base.
  • the Mannich base was quatemized by boiling with 100 g of methyl iodide. The solid was sucked off and washed with toluene. There was thus obtained 150 g of quaternary ammonium salt.
  • This salt was boiled with 60 g of sodium carbonate in a mixture of 500 ml of methanol and 60 ml of water for 2.5 hours. The reaction mixture was poured out into water and extracted four times with 200 ml of pentane.
  • EXAMPLE VIII The aqueous mixture was extracted three times with 50 ml of chloroform each time. The combined extracts were washed with 50 ml of a 5 percent solution of sodium bicarbonate, 50 ml of water and 50 ml of a saturated solution of sodium chloride successively. After drying and filtering, the solvent was removed under reduced pressure. The residue (5.6 g) solidified on standing. Crystallization from hexane with 10 percent of benzene yielded 4.1 g of ll-chlorohydronootkatone (formula of FIG. 18), mp. 84.5-85.5C.
  • the main fraction (2.35 g) had a b.p. of 161163C. at 2 mm and consisted of 1 1-hydroxydihydronootkatone (formula of FIG. 19) with a content of more than 95 percent (gas chromatographic analysis). [a 155 (C H Ol-l).
  • the residue (4.3 g) consisted, as shown by analysis by means of nuclear magnetic resonance spectometry, of a mixture of about percent nootkatone, 10 percent a-vetivone and 5 percent of the acetate of ll-hydroxydihydronootkatone. This mixture was fractionated. There was thus obtained 3.4 g of nootkatone (formula of FIG. 7), b.p. 122l23C. at 1 mm. Content, shown by gas chromatographic analysis, 92 percent. 237 m (C H OH)-E,,,,, 16,400. M.p. 3335C.

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US00154960A 1970-06-19 1971-06-21 Precursor of sesquiterpine derivatives of the eremophilane group Expired - Lifetime US3835192A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3925477A (en) * 1971-11-12 1975-12-09 Hoffmann La Roche Tricyclo{8 5,3,1,0{hu 3,8{b {9 undecan-2-ones and the corresponding mono- and di-unsaturated derivatives
US3962340A (en) * 1974-01-11 1976-06-08 Takasago Perfumery Co., Ltd. 1,2,6-Trimethyltricyclo[5,3,2,02,7 ]dodeca-5-one
US3963782A (en) * 1974-04-01 1976-06-15 Takasago Perfumery Co., Ltd. 5-Acetyl-1,2,6-trimethyltricyclo[5,3,2,02,7 ]dodeca-5-ene
US4322559A (en) * 1979-09-03 1982-03-30 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) 4(5)-Acetyl-9,9-dimethyltricyclo-[4,4,0,18,10 ]-undec-1-ene, its preparation and use in perfumery compositions and as an odorant
US20040005343A1 (en) * 2002-07-03 2004-01-08 Zhu Betty C. R. Dihydronootkatone and tetrahydronootkatone as repellents to arthropods
US20040157935A1 (en) * 2001-08-17 2004-08-12 Gregg Henderson Extracts of vetiver oil as a repellent and toxicant to ticks and cockroaches
US6890960B1 (en) 1999-10-19 2005-05-10 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Vetiver oil extracts as termite repellent and toxicant
WO2010019489A3 (en) * 2008-08-13 2010-05-20 Salk Institute For Biological Studies Method for making terpene derivatives
CN102070482A (zh) * 2010-12-31 2011-05-25 中山大学 天然产物s6-2衍生物及其制备方法和作为抗肿瘤药物的用途

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2671808A (en) * 1951-06-23 1954-03-09 Merck & Co Inc Processes for preparing polycyclic alpha, beta-unsaturated ketones
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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2671808A (en) * 1951-06-23 1954-03-09 Merck & Co Inc Processes for preparing polycyclic alpha, beta-unsaturated ketones
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

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3925477A (en) * 1971-11-12 1975-12-09 Hoffmann La Roche Tricyclo{8 5,3,1,0{hu 3,8{b {9 undecan-2-ones and the corresponding mono- and di-unsaturated derivatives
US3962340A (en) * 1974-01-11 1976-06-08 Takasago Perfumery Co., Ltd. 1,2,6-Trimethyltricyclo[5,3,2,02,7 ]dodeca-5-one
US3963782A (en) * 1974-04-01 1976-06-15 Takasago Perfumery Co., Ltd. 5-Acetyl-1,2,6-trimethyltricyclo[5,3,2,02,7 ]dodeca-5-ene
US4322559A (en) * 1979-09-03 1982-03-30 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) 4(5)-Acetyl-9,9-dimethyltricyclo-[4,4,0,18,10 ]-undec-1-ene, its preparation and use in perfumery compositions and as an odorant
US4363754A (en) * 1979-09-03 1982-12-14 Henkel Kommanditgesellschaft Auf Aktien 4(5)-Acetyl-9,9-dimethyltricyclo-[4,4,0,18,10 ]-undec-1-ene, its preparation and use in perfumery compositions and as an odorant
US6890960B1 (en) 1999-10-19 2005-05-10 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Vetiver oil extracts as termite repellent and toxicant
US20040157935A1 (en) * 2001-08-17 2004-08-12 Gregg Henderson Extracts of vetiver oil as a repellent and toxicant to ticks and cockroaches
US6906108B2 (en) 2001-08-17 2005-06-14 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Extracts of vetiver oil as repellent and toxicant to ants, ticks, and cockroaches
US20040005343A1 (en) * 2002-07-03 2004-01-08 Zhu Betty C. R. Dihydronootkatone and tetrahydronootkatone as repellents to arthropods
US6897244B2 (en) 2002-07-03 2005-05-24 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Dihydronootkatone and tetrahydronootkatone as repellents to arthropods
US20050171213A1 (en) * 2002-07-03 2005-08-04 Zhu Betty C.R. Dihydronootkatone and tetrahydronootkatone as repellents to arthropods
WO2010019489A3 (en) * 2008-08-13 2010-05-20 Salk Institute For Biological Studies Method for making terpene derivatives
US20110152563A1 (en) * 2008-08-13 2011-06-23 Noel Joseph P Method for making terpene derivatives
US8865930B2 (en) 2008-08-13 2014-10-21 Salk Institute For Biological Studies Method for making terpene derivatives
CN102070482A (zh) * 2010-12-31 2011-05-25 中山大学 天然产物s6-2衍生物及其制备方法和作为抗肿瘤药物的用途

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CH566954A5 (en, 2012) 1975-09-30
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