EP1102736A2 - Preparation de cetones macrocycliques par addition des cetones a des alcenes - Google Patents

Preparation de cetones macrocycliques par addition des cetones a des alcenes

Info

Publication number
EP1102736A2
EP1102736A2 EP99928094A EP99928094A EP1102736A2 EP 1102736 A2 EP1102736 A2 EP 1102736A2 EP 99928094 A EP99928094 A EP 99928094A EP 99928094 A EP99928094 A EP 99928094A EP 1102736 A2 EP1102736 A2 EP 1102736A2
Authority
EP
European Patent Office
Prior art keywords
reaction
ketone
alkyl
macrocyclic
methyl
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.)
Withdrawn
Application number
EP99928094A
Other languages
German (de)
English (en)
Inventor
David Munro
Kenneth John Palmer
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.)
Givaudan Nederland Services BV
Original Assignee
Quest International BV
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 Quest International BV filed Critical Quest International BV
Priority to EP99928094A priority Critical patent/EP1102736A2/fr
Publication of EP1102736A2 publication Critical patent/EP1102736A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C11B9/0038—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing more than six carbon 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
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • 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
    • C07C45/62—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 hydrogenation of carbon-to-carbon double or triple bonds
    • 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
    • C07C45/67—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
    • C07C45/69—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 addition to carbon-to-carbon double or triple bonds
    • 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
    • C07C45/74—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 combined with dehydration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds

Definitions

  • This invention concerns the preparation of macrocyclic ketones by a reaction sequence wherein one step in the sequence is the addition of a ketone to an alkene.
  • the invention provides a process for the preparation of macrocyclic ketones by a reaction sequence wherein one step in the sequence is the radical addition of ketone to alkene and wherein said alkene is selected from alkenes having the formula :
  • Ri and R 2 are preferably lower alkyl groups.
  • the term "lower alkyl” is used in this specification to mean an alkyl group having from 1 to 4 carbon atoms.
  • the ketone has the general formula:
  • Suitable ketones include, for example, acetone, 2-butanone, 3-pentanone etc.
  • Initiation of the addition reaction is preferably carried out by in situ generation of manganese (III) from manganese (II) by redox reaction, e.g. mediated by potassium permanganate, as this gives good chemoselectivity (see T. Linker et al. Tetrahedron, 51, 9917, (1995)).
  • Manganese (III) may alternatively be generated in situ from manganese (II) by anodic oxidation (e.g. as described in I. Nishiguchi et al, Tetrahedron, 47, 831 (1991) and R. Warsinsky, E. Steckhan, J. Chem. Soc. Perkin 1, 2027, (1994)).
  • a further possibility is direct use of manganese (III) acetate, although this is less favoured because of difficulties of preventing over-oxidation of the intermediate radical educts.
  • Alkene starting materials can be obtained commercially or can be synthesised. e.g. by Wittig reaction.
  • the final products of the process of the invention are macrocyclic ketones, such as muscone. with useful fragrance properties.
  • the reaction products of the addition of ketone to alkene must be capable of forming a macrocyclic ketone, and, therefore, there need to be sufficient carbon atoms between the two keto-functionalities or the keto- and ester functionalities (depending upon the starting alkene) of these intermediate products.
  • the ultimate product has too high a molecular weight (e.g. being produced from a long chain ester and a larger ketone) it will be outside the range of olfaction. Smaller ketones, particularly acetone and 2-butanone, are therefore generally favoured as reactants.
  • Muscone is the common name of (-)-3-methylcyclopentadecanone which has the following structure:
  • Muscone is the principal odorous constituent of the musk deer gland, and is a useful fragrance material. Since elucidation of its structure in 1926 (see Ruzicka. L., Helv. Chim. Acta, 9, 230 (1926)), many syntheses both of the optically-active material and racemic muscone have been reported. These syntheses, while elegant, generally involve many stages and may require expensive and/or inaccessible starting materials. Hitherto there has thus been no short and efficient method of producing muscone which utilises inexpensive and readily accessible starting materials.
  • 1,9-decadiene may be prepared in known manner, e.g. by ethenylation of cyclooctene (Szmant, H.H., 'Organic Building Blocks of the Chemical Industry', Wiley Interscience, New York, p310 (1989)).
  • the resulting 2,15 hexadecanedione may be converted to muscone, e.g. in various known ways including by intramolecular aldol reaction (Stoll, M., Rouve, A. Helv. Chim. Acta, 30, 2019, (1947), Tsuji. J., et al., Tet. Lett., 2257 (1979), Tsuji, J., et al, Bull. Chem. Soc. Jpn., 1417, 53 (1980) and Sakurai, H., et al, J. Organomet. Chem., 264, 229, (1984)), followed by hydrogenation (see Figure 2).
  • a further approach is high temperature cyclisation over a suitable catalyst, as described in EP 400509 of BASF.
  • methyl undecylenate acetone methyl 13-oxotetradecanoate The resulting methyl 13-oxotetradecanoate can then be converted, e.g. using known techniques, to muscone. For example, in a subsequent 4 step conversion.
  • Muscone can be seoarated from the resulting mixture, e.g. by silica gel chromatography However, the mixture has good olfactive properties and can be used as a fragrance or perfume ingredient
  • the macrocyclic ketones which are the products of the process of the invention may be produced separately or m the form of mixtures. Both separate ketones and mixtures may have fragrance properties that render the mate ⁇ als suitable for perfumery use in known manner
  • the m ⁇ ention also covers macrocyclic ketones which are the direct product of the method of the ention, in particular mixtures of muscone, with 4-methylcyclopentadecanone, produced directly by the method of the invention.
  • macrocyclic ketones which are the direct product of the method of the ention, in particular mixtures of muscone, with 4-methylcyclopentadecanone, produced directly by the method of the invention.
  • Such mixtures normally contain other components that are an incidental product of the reaction and mixtures which are the direct product of the process of the invention without further purification are a further aspect of the invention.
  • substantially pure macrocyclic ketones can be isolated by further purification of the reaction product by conventional means such as chromatography or fractional distillation.
  • the macrocyclic ketones may be used as ingredients of perfumes (or fragrance compositions) and perfumed products m known manner, e.g. as desc ⁇ bed in WO
  • a perfume or perfumed product according to this aspect of the invention comprises a mixture containing macrocyclic ketone, particularly muscone, produced by the method of the invention, in an olfactively effective amount.
  • a “perfume” or “fragrance composition”, as used herein, means a composition comprising various fragrance materials, and optionally a solvent, formulated to have certain useful fragrance characteristics. In most cases fragrance compositions are formulated to have a fragrance generally considered at least inoffensive and, preferably, pleasing to intended users of the composition. Fragrance compositions are used for imparting a desired odour to the skin and/or any product for which an agreeable odour is indispensable or desirable.
  • Examples of such products are personal and household products including fabric washing powders, washing liquids, fabric softeners and other fabric care products; detergents and household cleaning, scouring and disinfection products; air fresheners, room sprays and pomanders; fine fragrances; soaps, bath and shower gels, shampoos, hair conditioners and other personal cleansing products; cosmetics such as creams, ointments, toilet waters, preshave, aftershave, skin and other lotions, talcum powders, body deodorants and antiperspirants etc. Fragrance compositions are also used in products that would normally have an unattractive or offensive odour to mask this odour and produce an odour that is less unattractive or offensive. Products in this category include fuel odorants.
  • the (generally pleasing) fragrance characteristics may be the main function of the product in to which the fragrance composition has been incorporated, as in the case of fine fragrances, or may be ancillary to the main function of the product, as, e.g., in the case of detergents, cleaning products and skin care products.
  • an amount of 0.01% by weight or more of a macrocyclic ketone produced according to the invention will generally have a clearly perceptible olfactive effect.
  • the amount is in the range 0.1 to 80% by weight, more preferably at least 1%.
  • the amount of the ketone produced according to the invention present in products will generally be at least 10 ppm by weight, preferably at least 100 ppm, more preferably at least 1000 ppm. However, levels of up to about 20% by weight may be used in particular cases, depending on the product to be perfumed.
  • Figure 1 shows the reaction scheme for radical addition of acetone to methyl undecylenate to produce methyl 13-oxotetradecanoate, and subsequent reaction of this to produce a mixture of muscone and 4-methylcyclopentadecanone;
  • Figure 2 shows the reaction scheme for radical addition of acetone to 1,9-decadiene to produce.2,15-hexadecanedione, and subsequent reaction of this to produce muscone.
  • Trimethyl phosphonoacetate (82 g; 0.45 mol) was added dropwise with stirring to a suspension of oil-free sodium hydride (12 g; 0.5 mol) in tetrahydrofuran (THF) (300 ml). After 1 hour, methyl 13-oxotetradecanoate, [102.4 g; 0.4 mol], dissolved in THF (150 ml) was added dropwise, and the reaction mixture refluxed, with stirring, under nitrogen for 3 hours. After cooling, the reaction mixture was poured into water and extracted into diethyl ether. The combined ether extracts were washed, and dried over MgSO
  • the mixture has good olfactive properties and is useful as a fragrance material as it stands.
  • Muscone can be separated from the mixture if desired, e.g. by silica gel chromatography.
  • Example 1 In a variant of Example 1, butan-2-one (2-butanone) was used in place of acetone and was added with high regioselectivity to methyl undecylenate. The product was homologated and cyclised to give a mixture of 3,4-dimethylcyclopentadecanone and 4,5- dimethylcyclopentadecanone in analogous manner to Example 1. The resulting mixture smelled musky.
  • Methyl undecylenate (80 g; 0.43 mol) was added, followed by portionwise addition of potassium permanganate (25.0 g) over 2 hours.
  • the reaction mixture was cooled to room temperature, water (2000 ml) was added, and the reaction mixture was extracted into diethyl ether. The organic extracts were washed thoroughly with water, then aqueous sodium bicarbonate. Removal of solvent gave a pale yellow oil, which was subjected to vacuum distillation through a Vigreux column. After a fore-run consisting of unreacted methyl undecylenate, the title material was obtained as a colourless oil (32.0 g) bp 146° C @ 0.6 mm Hg. M+270. H and C NMR confirmed the structure, and indicated the absence of the isomeric methyl 13- oxopentadecanoate.
  • Trimethyl phosphonoacetate (25.0 g; 0.133 mol) was added dropwise with stirring to a suspension of oil-free sodium hydride (3.6 g; 0.15 mol) in dry THF (150 ml). After complete addition, methyl 12-methyl- 13-oxotetradecanoate (32.0 g; 0.12 mol) was added dropwise. and the reaction mixture was refluxed with stirring for a total of 8 hours.
  • This unsaturated diester (25.0 g) was dissolved in methanol (250 ml), and 5% Pd/C added. The reaction mixture was hydrogenated @ 6 bar hydrogen pressure until uptake ceased. The catalyst was removed by filtration through Celite and the solvent removed in vacuo to give a colourless oil. Chromatography (conditions as above) gave a colourless oil (23.2 g), identified as dimethyl 3,4-dimethylpentadecanedioate. Glc [SE54: 100°C- 250° C @ 4° C/min] indicated 98% purity.
  • Dimethyl 3,4-dimethylpentadecanedioate (14.0 g: 0.042 mol) was dissolved in xylene (80ml), and added dropwise over 1 hour to a suspension of sodium (0.1 mm particle size) in xylene (80 ml). The addition was carried out under nitrogen, and the reaction mixture was refluxed for a further 30 minutes under nitrogen before cooling, and treating dropwise with ethyl alcohol (100 ml.), in a stream of nitrogen. The xylene solution was then washed free of alkali with water.
  • the 2.15-hexadecanedione may be converted to muscone in known manner, e.g. by an internal Aldol reaction followed by hydrogenation, e.g. using 5% palladium on carbon catalyst.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)

Abstract

La présente invention concerne un procédé permettant de préparer des cétones macrocycliques à l'aide d'une séquence de réaction comprenant une étape d'addition radicalaire d'une cétone à un alcène de la forme (1), où R3 représente H ou un alkyle inférieur; R4 représente H ou un alkyle inférieur; m représente un nombre de 4 à 8; ou de la forme (2), où R1 représente un alkyle; R2 représente H ou un alkyle; n représente un nombre de 4 à 8. Le procédé de l'invention peut être utilisé pour produire des mélanges de cétones macrocycliques, en particulier des cétones renfermant de la muscone qui sont utilisées dans la production de produits parfumés.
EP99928094A 1998-07-06 1999-06-25 Preparation de cetones macrocycliques par addition des cetones a des alcenes Withdrawn EP1102736A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP99928094A EP1102736A2 (fr) 1998-07-06 1999-06-25 Preparation de cetones macrocycliques par addition des cetones a des alcenes

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP98305368A EP0976714A1 (fr) 1998-07-06 1998-07-06 Addition de cétones à des alcénes
EP98305368 1998-07-06
EP99928094A EP1102736A2 (fr) 1998-07-06 1999-06-25 Preparation de cetones macrocycliques par addition des cetones a des alcenes
PCT/GB1999/001999 WO2000001648A2 (fr) 1998-07-06 1999-06-25 Preparation de cetones macrocycliques par addition des cetones a des alcenes

Publications (1)

Publication Number Publication Date
EP1102736A2 true EP1102736A2 (fr) 2001-05-30

Family

ID=8234917

Family Applications (2)

Application Number Title Priority Date Filing Date
EP98305368A Withdrawn EP0976714A1 (fr) 1998-07-06 1998-07-06 Addition de cétones à des alcénes
EP99928094A Withdrawn EP1102736A2 (fr) 1998-07-06 1999-06-25 Preparation de cetones macrocycliques par addition des cetones a des alcenes

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP98305368A Withdrawn EP0976714A1 (fr) 1998-07-06 1998-07-06 Addition de cétones à des alcénes

Country Status (3)

Country Link
EP (2) EP0976714A1 (fr)
JP (1) JP2002519396A (fr)
WO (1) WO2000001648A2 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10023886A1 (de) 2000-05-17 2001-11-22 Basf Ag Acetessigsäure-Derivate, Verfahren zu ihrer Herstellung und ihre Verwendung
EP1608626A1 (fr) 2003-03-28 2005-12-28 Cornell Research Foundation, Inc. Compositions de substances analogues a la migrastatine et leurs utilisations
JP5149001B2 (ja) 2004-05-25 2013-02-20 スローン−ケッタリング・インスティテュート・フォー・キャンサー・リサーチ 癌の処置におけるマイグラスタチンアナログ
US8188141B2 (en) 2004-09-23 2012-05-29 Sloan-Kettering Institute For Cancer Research Isomigrastatin analogs in the treatment of cancer
US8940940B2 (en) * 2012-06-13 2015-01-27 Basf Se Process for preparing macrocyclic ketones
CN118221504A (zh) * 2024-03-22 2024-06-21 宏济堂制药(商河)有限公司 一种14-甲基-2-羟基-环十五酮杂质及其对照品的制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1757830A (en) * 1926-07-31 1930-05-06 Commercial Solvents Corp Production of ketones
DE3918015A1 (de) * 1989-06-02 1990-12-06 Basf Ag Verfahren zur herstellung von muscon, zwischenprodukte fuer dieses verfahren sowie deren herstellung
EP0925269A1 (fr) * 1996-09-02 1999-06-30 Quest International B.V. 2-cyclohexyl-propan-1-ol substitue et son utilisation dans des compositions pour parfums

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0001648A3 *

Also Published As

Publication number Publication date
WO2000001648A2 (fr) 2000-01-13
JP2002519396A (ja) 2002-07-02
EP0976714A1 (fr) 2000-02-02
WO2000001648A3 (fr) 2000-04-13

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