EP0897380A1 - PROCEDE DE PRODUCTION DE CETONES $g(g), $g(d)-INSATUREES PAR REACTION D'ALCOOLS ALLYLIQUES TERTIAIRES AVEC DES ETHERS D'ALCENYLALKYLE - Google Patents

PROCEDE DE PRODUCTION DE CETONES $g(g), $g(d)-INSATUREES PAR REACTION D'ALCOOLS ALLYLIQUES TERTIAIRES AVEC DES ETHERS D'ALCENYLALKYLE

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Publication number
EP0897380A1
EP0897380A1 EP97951226A EP97951226A EP0897380A1 EP 0897380 A1 EP0897380 A1 EP 0897380A1 EP 97951226 A EP97951226 A EP 97951226A EP 97951226 A EP97951226 A EP 97951226A EP 0897380 A1 EP0897380 A1 EP 0897380A1
Authority
EP
European Patent Office
Prior art keywords
radical
general formula
reaction
alkyl
optionally substituted
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Withdrawn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
EP97951226A
Other languages
German (de)
English (en)
Inventor
Stefan Käshammer
Detlef Ruff
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.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0897380A1 publication Critical patent/EP0897380A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
    • C07C403/16—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms not being part of —CHO 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
    • C07C45/51—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
    • C07C45/511—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 involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/513—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 involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
    • 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
    • C07C2601/14—The ring being saturated

Definitions

  • the invention relates to improvements in a method for producing ⁇ , ⁇ -unsaturated ketones by a Carroll reaction.
  • a number of ⁇ , ⁇ -unsaturated ketones have proven themselves as valuable fragrances and as intermediates for the production of vitamins E, Ki or carotenoids.
  • DE 1 193 490 discloses a process for the preparation of ⁇ . ⁇ -unsaturated ketones by reacting a tertiary alcohol with enol ethers in the presence of an acidic catalyst at elevated temperature.
  • Phosphoric acid is mentioned here as a particularly suitable acid catalyst.
  • the reaction times required to achieve complete conversion of the tertiary alkyl alcohol are 13 to 18 hours at temperatures from 125 to 140 ° C., a pressure of approx. 10 bar and a phosphoric acid concentration of 0.1 to 0.2% .-.
  • the disadvantage of this process is the long reaction times, which cause large reaction volumes and thus high investment costs in a technical process.
  • the invention accordingly relates to a process for the preparation of ⁇ , ⁇ -unsaturated ketones of the general formula I.
  • R 1 and R 2 represent a saturated or unsaturated, branched or unbranched alkyl radical which is optionally substituted by oxygen-containing groups, an aryl radical or an alkylaryl radical,
  • R 1 and R 2 together for a possibly. stand for one or more lower alkyl group (s) substituted tetramethylene or pentamethylene,
  • R 4 represents a Ci to C alkyl radical
  • R 5 represents hydrogen or a C ⁇ to C 4 alkyl radical
  • R 3 represents a C 1 -C 4 -alkyl radical, preferably a methyl radical
  • R 4 and R 5 have the meaning given above
  • A can additionally stand for -H or -OH or
  • a and B together for a tetramethylene or pentamethylene radical optionally substituted with one or more alkyl groups having 1 or 2 carbon atoms or an optionally substituted 1,2-phenyl-diol radical or optionally substituted 1, 1 '-Binaphthyl-2, 2' -diol residue are,
  • the process according to the invention is particularly advantageous if the reaction of the tertiary allyl alcohol of the general formula II with the alkenylalkyl ether of the general formula III in the presence of phosphoraryl or phosphoraryloxy derivatives.
  • Phenylphosphonic acid, diphenylphosphinic acid, phenylphosphate and diphenylphosphate may be mentioned in particular.
  • a mixture of phenyl phosphate and diphenyl phosphate is generally used, as is obtained in a simple and inexpensive manner in the reaction of phenol with P0C1 3 and subsequent hydrolysis.
  • the catalysts claimed for the process according to the invention are readily accessible preparatively using standard methods (cf. Houben-Weyl, "Methods of Organic Chemistry", 4th edition, 1964, volume 12.2, pages 143 to 376 for phosphoric acid esters; volume 12, 1, pages 220 to 266 for the phosphinic acids and volume 12.1, pages 348 to 550 for the phosphonic acids).
  • They are generally used in a concentration of 0.0001 mol to 1 mol, preferably 0.001 mol to 0.05 mol, of catalyst per kg of reaction mixture. They can be used in the form of a solid, a melt or in the form of a solution. The addition is either continuous or in portions.
  • solvents for the catalysts are water, acetone, methanol, dimethyl sulfoxide or toluene.
  • tertiary allyl alcohol of the general formula II used as starting material as a solvent for the catalysts.
  • Suitable tertiary allyl alcohols of the general formula II are preferably allyl alcohols of the formula II in which
  • Ri represents a saturated or unsaturated, branched or unbranched alkyl radical, an aryl radical or an alkylaryl radical,
  • R2 represents a C 1 to C 4 alkyl radical, in particular a methyl radical
  • R 1 and R 2 together for a possibly. are substituted by one or more lower alkyl group (s) tetramethylene or pentamethylene.
  • 3-methyl-1-buten-3-ol hydrolinalool (3,7-dimethyl-1-octen-3-ol), 1-vinyl-cyclohexanol, nerolidol (3,7,11-rimethyl-dodeca- 1,6,10-trien-3-ol), linalool (3,7-dimethyl-octa-2,6-dien-3-ol), hydronerolidol (3,7,11-trimethyl-dodeca-1, 6-dien-3-ol) and tetrahydronerolidol (3,7 , 11-trimethyl-dodecan-3-ol).
  • Alkenyl alkyl ethers of the general formula III are preferably alkenyl alkyl ethers of the formula II, in which
  • R 3 represents a methyl radical or ethyl radical
  • R 4 represents hydrogen or a methyl radical
  • R 5 represents a methyl radical
  • alkenyl alkyl ethers examples include:
  • isopropenyl methyl ether is often used in the form of an azeotrope of isopropenyl methyl ether and methanol, as is produced in the production by thermal cleavage of dimethoxipropane, since there are no significant losses in yield and the time-consuming removal of methanol from the azeotrope can be eliminated.
  • the molar ratio of tertiary allyl alcohol of the general formula II to the alkenyl alkyl ether of the general formula III in the process according to the invention is generally 1: 2.0 to 1: 5.0, preferably 1: 2.1 to 1: 3.0.
  • the reaction is generally carried out at from 100 to 200.degree. C., preferably from 100 to 170.degree. C., in particular from 130 to 160.degree. C., in a pressure vessel under the pressure which arises at the reaction temperatures.
  • 100 to 200.degree. C. preferably from 100 to 170.degree. C., in particular from 130 to 160.degree. C.
  • the procedure is generally such that either a mixture of the tertiary allyl alcohol and the alkenyl alkyl ether is placed in the reaction vessel and, after the mixture has been heated to the reaction temperature, the catalyst in the form of a solid, a melt or, in particular, dissolved in a suitable solvent, either continuously or in portions, or that only the alkenyl alkyl ether, if appropriate with part of the allyl alcohol, is introduced and, after it has been heated, a mixture or a solution from the catalyst of general formula IV and the tertiary alcohol - or in the tertiary alcohol either continuously or in portions.
  • the reaction time is generally 6 to 10 hours, preferably 7 to 9 hours.
  • the reaction can be carried out batchwise or continuously.
  • the reaction is generally carried out continuously on an industrial scale.
  • a cascade of stirred tanks or tubes designed for reactions under pressure or a cascade of corresponding stirred tanks and tubes is then used as the reaction vessel.
  • reaction mixture it is generally distilled, if appropriate after neutralization or buffering. It is only important here that the mixture to be distilled is non-basic, at most weakly basic.
  • the ⁇ , ⁇ -unsaturated ketones of the general formula I which are cited as fragrances or as intermediates for vitamins and carotenoids, can be prepared in very good yields in comparatively short reaction times.
  • a pressure vessel made of corrosion-resistant material (HC4 steel) with a volume of 300 ml the amount of the tertiary allyl alcohol shown in Table 1 and the amount of an isopropenyl methyl ether mixture containing about 9% by weight of methanol, as shown in Table 1, were Methanol azeotrope (IMA) and the amount of the catalyst shown in Table 1 presented in Table 1, the pressure vessel closed, flushed with nitrogen and then heated within 30 minutes (min) to the reaction temperature shown in Table 1. After the reaction time shown in Table 1, the pressure vessel was emptied and, if necessary after neutralization or buffering, distilled. The yields of unsaturated ketone achieved determined by gas chromatographic analysis (GC) against an internal standard and are given in Table 1.
  • GC gas chromatographic analysis
  • the reaction discharge was mixed with 60 mg of sodium acetate and distilled.
  • the yield of geranylacetone was 89%.
  • Example 1 from DE 11 93 490 ** cf.
  • Example 10 of DE 11 93 490 *** cf.
  • Example 12 from DE 11 93 490

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé amélioré de production de cétones η, δ-insaturées, recherchées comme parfum ou produits intermédiaires pour vitamines ou carotinoïdes, consistant à faire réagir des alcools d'allyle tertiaires et des éthers alcénylalkyle en présence de catalyseurs acides, à une température élevée. Ledit procédé est caractérisé en ce que ladite réaction est réalisée en présence d'un dérivé de phosphore de formule générale (IV), dans laquelle: A et B représentent un reste alkyle ou alcoxy à chaîne ramifiée ou non ramifiée, possédant 1 à 10 atomes de C, un reste aryle, cycloalkyle, aryloxy, éventuellement substitué, ou bien un reste cycloalkyloxy; A peut en outre représenter -H ou -OH, ou bien A est B représentent ensemble un reste tétraméthylène ou pentaméthylène éventuellement substitué ou bien un reste phényle-1,2-diol ou un reste 1,1'-binaphthyl-2,2'-diol substitué.
EP97951226A 1996-11-29 1997-11-18 PROCEDE DE PRODUCTION DE CETONES $g(g), $g(d)-INSATUREES PAR REACTION D'ALCOOLS ALLYLIQUES TERTIAIRES AVEC DES ETHERS D'ALCENYLALKYLE Withdrawn EP0897380A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19649564 1996-11-29
DE19649564A DE19649564A1 (de) 1996-11-29 1996-11-29 Verfahren zur Herstellung von gamma,delta-ungesättigter Ketone durch Umsetzung tertiärer Allylalkohole mit Alkenylalkylethern
PCT/EP1997/006425 WO1998023570A1 (fr) 1996-11-29 1997-11-18 PROCEDE DE PRODUCTION DE CETONES η, δ-INSATUREES PAR REACTION D'ALCOOLS ALLYLIQUES TERTIAIRES AVEC DES ETHERS D'ALCENYLALKYLE

Publications (1)

Publication Number Publication Date
EP0897380A1 true EP0897380A1 (fr) 1999-02-24

Family

ID=7813169

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97951226A Withdrawn EP0897380A1 (fr) 1996-11-29 1997-11-18 PROCEDE DE PRODUCTION DE CETONES $g(g), $g(d)-INSATUREES PAR REACTION D'ALCOOLS ALLYLIQUES TERTIAIRES AVEC DES ETHERS D'ALCENYLALKYLE

Country Status (6)

Country Link
US (1) US6034279A (fr)
EP (1) EP0897380A1 (fr)
JP (1) JP2001504834A (fr)
CN (1) CN1228757A (fr)
DE (1) DE19649564A1 (fr)
WO (1) WO1998023570A1 (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19739716A1 (de) 1997-09-10 1999-03-11 Basf Ag Verfahren zur Herstellung von ungesättigten Ketonen
US7028899B2 (en) * 1999-06-07 2006-04-18 Metrologic Instruments, Inc. Method of speckle-noise pattern reduction and apparatus therefore based on reducing the temporal-coherence of the planar laser illumination beam before it illuminates the target object by applying temporal phase modulation techniques during the transmission of the plib towards the target
KR100651334B1 (ko) * 2000-10-05 2006-11-28 에스케이 주식회사 비타민 ｅ 제조용 불포화 케톤의 제조방법
JP2002121165A (ja) * 2000-10-16 2002-04-23 Kuraray Co Ltd 不飽和ケトンの製造方法
JP2002121166A (ja) * 2000-10-16 2002-04-23 Kuraray Co Ltd 不飽和ケトンの製造方法
DE10121058A1 (de) 2001-04-28 2002-10-31 Degussa Neues Verfahren zur Herstellung von ungesättigten Ketonen
KR101128256B1 (ko) * 2004-02-04 2012-03-26 디에스엠 아이피 어셋츠 비.브이. 메틸헵텐온의 제조방법
WO2009019132A1 (fr) * 2007-08-08 2009-02-12 Dsm Ip Assets B.V. Procédé de préparation de (e, e)-farnésyl acétone
WO2010046199A2 (fr) * 2008-10-21 2010-04-29 Dsm Ip Assets B.V. Fabrication de cétones gamma-delta-insaturées
MY195029A (en) 2012-12-18 2023-01-04 Dsm Ip Assets Bv (6R,10R)-6,10,14-Trimetylpentadecan-2-One Prepared From 6,10-Dimetylundeca-3,5,9-Trien-2-One
EP3323802A1 (fr) * 2016-11-18 2018-05-23 DSM IP Assets B.V. Nouvelle utilisation de dérivés d'acide arylphosphorique comme catalyseur
EP3541774B1 (fr) * 2016-11-18 2022-11-30 DSM IP Assets B.V. Nouvelle utilisation d'acide phénylphosphinique
WO2018091622A1 (fr) * 2016-11-18 2018-05-24 Dsm Ip Assets B.V. Nouveau procédé de fabrication de cétones gamma, delta-insaturées
WO2018108606A1 (fr) 2016-12-12 2018-06-21 Dsm Ip Assets B.V. Procédé de fabrication de 6,10-diméthylundécan-2-one, d'isophytol, d'alpha-tocophérol (acétate) et d'autres intermédiaires de celui-ci
EP4039671A1 (fr) 2021-02-08 2022-08-10 DSM IP Assets B.V. Fabrication de cétones insaturées en utilisant un produit d'addition d'une amine tertiaire avec du so3
CN116829528A (zh) 2021-02-08 2023-09-29 帝斯曼知识产权资产管理有限公司 在γ,δ-不饱和酮的形成中作为催化剂的有机叔铵盐或季铵盐

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL295084A (fr) * 1962-07-11 1900-01-01
US3453317A (en) * 1962-07-11 1969-07-01 Hoffmann La Roche Unsaturated carbonyl compounds and processes
US4892977A (en) * 1988-06-13 1990-01-09 Texaco Chemical Company Preparation of nonionic surfactants by oxyalkylation with a magnesium catalyst
US5077442A (en) * 1990-04-26 1991-12-31 Mitsubishi Kasei Corporation Method for producing 1,4-butanediol

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9823570A1 *

Also Published As

Publication number Publication date
CN1228757A (zh) 1999-09-15
DE19649564A1 (de) 1998-06-04
US6034279A (en) 2000-03-07
WO1998023570A1 (fr) 1998-06-04
JP2001504834A (ja) 2001-04-10

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