EP1112245A1 - Procede pour preparer des cetones gamma,delta-insaturees par reaction de carroll - Google Patents

Procede pour preparer des cetones gamma,delta-insaturees par reaction de carroll

Info

Publication number
EP1112245A1
EP1112245A1 EP99946093A EP99946093A EP1112245A1 EP 1112245 A1 EP1112245 A1 EP 1112245A1 EP 99946093 A EP99946093 A EP 99946093A EP 99946093 A EP99946093 A EP 99946093A EP 1112245 A1 EP1112245 A1 EP 1112245A1
Authority
EP
European Patent Office
Prior art keywords
general formula
reaction
methyl
carroll
aluminum
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Withdrawn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
EP99946093A
Other languages
German (de)
English (en)
Inventor
Hagen Jaedicke
Michael John
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
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 BASF SE filed Critical BASF SE
Publication of EP1112245A1 publication Critical patent/EP1112245A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C07C45/673—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 change of size of the carbon skeleton
    • C07C45/676—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 change of size of the carbon skeleton by elimination of carboxyl groups

Definitions

  • a Carroll reaction is the chain extension of an allyl or propargyl alcohol with acetoacetate or diketene to form ⁇ , ⁇ -unsaturated ketones. For example, it can proceed according to the following reaction scheme:
  • the new acetoacetic ester of the unsaturated alcohol which is primarily formed from the allyl or propargyl alcohol and the acetoacetic acid ester or diketene, is rearranged in a Claisen rearrangement to give ⁇ -keto acid, which then spontaneously decarboxylates.
  • the terpenes required as essential precursors for vitamin A and vitamin E are 2-methyl-2-hepten-6-one, 6, 10-dimethyl-5, 9-undecadien-2-one (geranylacetone) and 6, 10 , 14-Trimethyl-5, 9, 13-pentadecatrien-2-one (farnesylacetone), produced on an industrial scale by the Carroll reaction.
  • aluminum alcoholates in particular the aluminum isopropylate of the formula AI (0-CH (CH 3 ) 2 ) 3 , were used as catalysts for Carroll reactions in amounts of 0.8 to 2.5 mol% on the alcohol used as the starting material.
  • aluminum complexes with acetylacetone or acetoacetic esters such as aluminum tri (acetylacetonate), aluminum tri (methyl acetoacetate) or aluminum tri (ethyl acetoacetate), were used as catalysts for Carroll reactions.
  • the invention relates to a process for the preparation of ⁇ , ⁇ -unsaturated ketones of the general formula I
  • an acetoacetic acid alkyl ester at temperatures of 150 to 45 220 ° C in an optionally modified Carroll reaction in the presence of an aluminum catalyst and distilling off the alkanol which is formed, which is characterized in that an acetoacetic acid ester of the general formula III as the acetoacetic acid alkyl ester
  • R 2 represents an alkyl group having 1 to 4 carbon atoms.
  • n stands for an integer from 1 to 5 and x and y either stand for H, or x stands for methoxy and y stands for H or x and y together for an additional bond between the C and X bearing y Atoms are, such as 3, 7-dimethyl-1,6-octadien-3-ol (linalool),
  • R 4 is branched or unbranched alkyl or alkoxy groups with 1 to 4 C atoms, preferably methyl or ethyl groups
  • R 5 and R 5 is branched or unbranched alkyl or alkoxy groups with 1 to 5 C atoms, preferably one Are methyl or a 2-butyl group
  • R 7 is a branched or unbranched alkyl group having 1 to 4 carbon atoms and m and n can be an integer from 0 to 3, where n + m 3 3, and Aluminum triaryloxylates into consideration.
  • Liquid aluminum compounds, in particular aluminum compounds, in which R 5 is a methyl radical, R 6 is a butyl radical and the sum of n + m ⁇ 3 and the ratio n / m> 0.3 are particularly preferred.
  • radicals R 1 , R 2 and R 3 are H, methyl or ethyl, preferably H or methyl and R 4 is H, methyl, ethyl, isopropyl, phenyl or methoxymethyl, preferably H or methyl , as a solvent.
  • Particularly suitable 5-ring lactones of the general formula VII are v-butyrolactone and 3-methyl- ⁇ -butyrolactone, in particular ⁇ -butyrolactone. 15
  • ⁇ -butyrolactones of the general formula VII used according to the invention can also be prepared on an industrial scale by dehydrogenation of the corresponding butanediols.
  • the alkanol formed in the reaction surprisingly attacks the cyclic carbonates or lactones under the reaction conditions so little that, for example, when using propylene carbonate, the solvent can be reused for up to 10 reaction cycles without any purification
  • the 5-ring carbonates and 5-ring lactones are generally used in amounts of 50 to 1000% by weight, preferably 100 to 500% by weight, based on the ⁇ , ⁇ -unsaturated ketone formed.
  • the Carroll reaction can advantageously also be carried out without the addition of substantial amounts of a solvent. This has advantages when working up the reaction mixture.
  • the process according to the invention can be carried out batchwise and continuously.
  • the procedure is advantageously such that the starting compounds and the catalyst are combined with a
  • reaction vessel with attached condensation device for the alcohol released and for the discharge of Pumped carbon dioxide and pumps the reaction product with the help of an overflow.
  • the wished ⁇ , ⁇ -unsaturated ketones of the general formula I can be obtained in a simple manner with surprisingly high yields.
  • the tertiary alcohols released from the acetoacetic acid ester can be recovered almost completely.
  • a mixture of a mixture of 50 ml (45 g) 1, 2-propylene carbonate and 2.8 g of a separately (according to GB 886 353) aluminum tri-methylacetoacetate catalyst was made at 170 ° C within 2 hours 25.7 g of a 92% 2-methyl-3-butene-2-ol and 39.8 g of acetoacetic acid tert. -butyl ester added dropwise.
  • the mixture was stirred for a further 10 minutes (min) until the evolution of gas had ended and then cooled.
  • reaction discharge was distilled under a pressure reduced to 0.1 mbar.
  • a total of 139.7 g of 6, 10-dimethyl-5, 9-undecadien-2-one (geranylacetone) was obtained in two fractions, which corresponds to a yield of 96% of theory.
  • Example 2a 5.6 g of the aluminum catalyst described there were introduced as in Example 2a) and a mixture of 115.4 g of linalool and 94 g of methyl acetoacetate was pumped in at an internal temperature of 180 ° C. This spontaneously formed C0 2 and methanol, which was condensed. As in Example 2a), the reaction mixture was stirred for a further 20 min until the CO 2 evolution had ceased and then cooled. It was distilled under reduced pressure and 133 g of geranyl acetone were obtained. The yield was 91.5% of theory. As a side pro Products had formed 1.6 g of 6, 10-dimethyl-5, 9-undecadien-2-ol, which were not detectable in Example 2a).
  • E E-geranyllinalool. This solution was pumped evenly into the horizontal reactor vessel described in Example 3a). The pumping rate was matched to the available reaction volume so that there was an average residence time of 10 ⁇ 0.5 min. At 190-200 ° C 35 internal temperature, the mixture reacted continuously to geranylgeranylacetone. After the feed had ended, the contents of the reactor were heated for a further 10 minutes and then added to the cooled reaction discharge. It was distilled at 0.3 mbar and 84.2 g of geranylgeranylacetone with a purity of 40 97.1% were obtained in the main fraction. This corresponds to a yield of 85% of theory.
  • Example 6a A comparison of Example 6a with Comparative Example 6b clearly shows that the reaction with the acetoacetic acid tert. - Butyl ester runs much faster (3 to 10 times faster) than that with the methyl acetoacetate previously used for Carroll reactions.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

l'invention concerne un procédé de préparation de cétones η,δ-insaturées de la formule générale (I), par réaction d'un alcool d'allyle ou d'un alcool de propargyle de la formule générale (II) dans laquelle R1 désigne H ou un reste hydrocarbure ramifié saturé ou insaturé, éventuellement substitué par des groupes méthoxy et ayant entre 1 et 33 atomes de C, la ligne pointillée pouvant désigner une autre liaison entre les atomes de C la portant, avec un ester d'alkyle d'acide acétylacétique à des températures comprises entre 150 et 220 °C, dans une réaction de Carroll éventuellement modifiée, en présence d'un catalyseur aluminium et par séparation par distillation de l'alcanol formé à cette occasion. Ce procédé se caractérise en ce que l'ester d'alkyle d'acide acétylacétique utilisé est un ester d'acide acétylacétique de la formule générale (III) dans laquelle R2 désigne un groupe alkyle ayant entre 1 et 4 atomes de C.
EP99946093A 1998-09-07 1999-09-02 Procede pour preparer des cetones gamma,delta-insaturees par reaction de carroll Withdrawn EP1112245A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19840746 1998-09-07
DE19840746A DE19840746A1 (de) 1998-09-07 1998-09-07 Verfahren zur Herstellung gamma,delta-ungesättigter Ketone durch Carroll-Reaktion
PCT/EP1999/006447 WO2000014046A1 (fr) 1998-09-07 1999-09-02 PROCEDE POUR PREPARER DES CETONES η,δ-INSATUREES PAR REACTION DE CARROLL

Publications (1)

Publication Number Publication Date
EP1112245A1 true EP1112245A1 (fr) 2001-07-04

Family

ID=7880056

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99946093A Withdrawn EP1112245A1 (fr) 1998-09-07 1999-09-02 Procede pour preparer des cetones gamma,delta-insaturees par reaction de carroll

Country Status (10)

Country Link
EP (1) EP1112245A1 (fr)
JP (1) JP2002524435A (fr)
KR (1) KR20010074970A (fr)
CN (1) CN1348434A (fr)
AU (1) AU5858399A (fr)
CA (1) CA2343521A1 (fr)
DE (1) DE19840746A1 (fr)
ID (1) ID27392A (fr)
IL (1) IL141689A0 (fr)
WO (1) WO2000014046A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002121166A (ja) * 2000-10-16 2002-04-23 Kuraray Co Ltd 不飽和ケトンの製造方法
JP2002121165A (ja) * 2000-10-16 2002-04-23 Kuraray Co Ltd 不飽和ケトンの製造方法
WO2008047690A1 (fr) * 2006-10-11 2008-04-24 Eisai R & D Management Co., Ltd. Procédé de préparation de la géranylgéranylacétone
CN102050714B (zh) * 2010-12-08 2014-02-05 重庆恒韵医药有限公司 一种合成替普瑞酮的方法
CN103058839B (zh) * 2013-01-25 2014-12-17 四川源基制药有限公司 替普瑞酮合成及纯化工艺
CN104513117B (zh) * 2013-10-08 2016-08-10 中国科学院大连化学物理研究所 一种手性β-乙炔基酮化合物的催化不对称合成方法
CN104326890B (zh) * 2014-11-21 2016-08-24 山东新和成药业有限公司 一种Carroll反应连续化工艺方法
CN106946671A (zh) 2015-12-11 2017-07-14 帝斯曼知识产权资产管理有限公司 制造6,10,14‑三甲基十五烷‑2‑酮的方法
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
CN116212943A (zh) * 2022-12-05 2023-06-06 江苏宏邦化工科技有限公司 一种新型碱性催化剂的制备方法及其在制备甲基庚烯酮中的应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH493453A (de) * 1968-07-23 1970-07-15 Basf Ag Verfahren zur Herstellung von 6,10-Dimethyl-undecatrien-(3,5,10)-on-(2)
DE2928944A1 (de) * 1979-07-18 1981-02-12 Basf Ag Verbessertes verfahren zur herstellung von hoeheren ungesaettigten ketonen
DE19647117A1 (de) * 1996-11-14 1998-05-28 Basf Ag Verfahren zur Herstellung gamma,delta-ungesättigten Ketonen durch Caroll-Reaktion in cyclischen Carbonaten oder gamma-Lactonen als Lösungsmittel
US6051741A (en) * 1997-10-17 2000-04-18 Basf Aktiengesellschaft Preparation of γ,δ-unsaturated ketones by the Carroll reaction, novel catalysts therefor and the preparation thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0014046A1 *

Also Published As

Publication number Publication date
ID27392A (id) 2001-04-05
IL141689A0 (en) 2002-03-10
AU5858399A (en) 2000-03-27
WO2000014046A1 (fr) 2000-03-16
JP2002524435A (ja) 2002-08-06
DE19840746A1 (de) 2000-03-09
KR20010074970A (ko) 2001-08-09
CN1348434A (zh) 2002-05-08
CA2343521A1 (fr) 2000-03-16

Similar Documents

Publication Publication Date Title
EP3265451B1 (fr) Procédé de fabrication d'esters de tétrahydropyrane
EP1112245A1 (fr) Procede pour preparer des cetones gamma,delta-insaturees par reaction de carroll
DE2256347B2 (de) Verfahren zur Herstellung von a , ß -ungesättigten Ketonen
EP0983988B1 (fr) Procédé continu pour la préparation de cétones insaturées
EP0022955B1 (fr) Procédé pour la préparation de cétones supérieures non saturées
EP0570774B1 (fr) Procédé de préparation de vinylglycols par isomérisation
DE2418715C2 (de) Allensäureester
EP0842917B1 (fr) Procédé pour la préparation de cétones gamma, delta insaturées par la réaction de Carroll dans des carbonates cycliques ou des gamma-lactones comme solvant
EP1008582B1 (fr) Procédé de préparation de cétones insaturées
EP1000922B1 (fr) Procédé pour la préparation de cétones supérieures non saturées
EP0010656B1 (fr) Procédé pour la préparation de 4-acyloxy-2-méthylcrotonaldéhydes
DE2103686B2 (de) Verfahren zur Herstellung von a -Hydroxy- γ -lactonen
DE2523695C3 (de) Verfahren zur Herstellung von bicyclischen γ-Lactonen
DE1173454B (de) Verfahren zur Herstellung von N-Vinyl-carbaminsaeureestern
EP0502376B1 (fr) Procédé pour la fabrication d'aldéhydes et de cétones alpha,bêta-insaturées
DE1668802C3 (de) Verfahren zur Herstellung von Carbonsäurediestern von 1,6-Dihydroxyhexadienen-1,5
EP0735032B1 (fr) Procédé de préparation de 5-hydroxy-4-méthyl-2(5H)-furanon
DE1965377C3 (de) Verfahren zur Herstellung primärer oder sekundärer äthylenischer Alkohole
DE1793445B1 (de) Verfahren zur Herstellung von Pseudo jononen
EP0173026B1 (fr) Procédé de préparation d'éthers alkyliques et d'éthers énoliques des acétoines
EP0005472B1 (fr) Procédé pour la préparation d'esters d'acides carboxyliques gamma-substitués par halogène
DE3316223C2 (de) Verfahren zur Herstellung von Acetoin aus α-Hydroxyisobutyraldehyd
DE2652863C3 (fr)
DE2952044A1 (de) Verfahren zur herstellung von 5-oxoalkansaeuren
EP0039484A1 (fr) Procédé pour la fabrication de monoéthers d'hydroquinone, ainsi que les quinol-cétals formés comme intermédiaires au cours de ce procédé

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20010306

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17Q First examination report despatched

Effective date: 20010727

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 20020222