EP0996609A1 - Procede de production de 6,10 et 6,9-dymethyl-5,10-undecadienyl-2-ones - Google Patents

Procede de production de 6,10 et 6,9-dymethyl-5,10-undecadienyl-2-ones

Info

Publication number
EP0996609A1
EP0996609A1 EP98936355A EP98936355A EP0996609A1 EP 0996609 A1 EP0996609 A1 EP 0996609A1 EP 98936355 A EP98936355 A EP 98936355A EP 98936355 A EP98936355 A EP 98936355A EP 0996609 A1 EP0996609 A1 EP 0996609A1
Authority
EP
European Patent Office
Prior art keywords
transition metal
pph3
propanol
compound
alkyl
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Withdrawn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
EP98936355A
Other languages
German (de)
English (en)
Inventor
Wilhelm Keim
Armin Kraus
Rainer Hahn
Klaus Huthmacher
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.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
Degussa Huels AG
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 Degussa GmbH, Degussa Huels AG filed Critical Degussa GmbH
Publication of EP0996609A1 publication Critical patent/EP0996609A1/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Withdrawn legal-status Critical Current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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/203—Unsaturated compounds containing keto groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • 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

  • the invention relates to a process for the preparation of 6,10- and 6, 9-dimethyl-5, 10-undecadienyl-2-ones by telomerization of isoprene with alkyl acetoacetates using transition metal compounds as catalysts and subsequent saponification and decarboxylation of the ⁇ -keto esters obtained .
  • telomeric products When using the asymmetrical diene, isoprene, there are 12 possible telomeric products, taking into account the linking pattern of the isoprene units, the direction of attack of the nucleophile in the 1- or 3-position and the E, Z isomerism of the internal double bond.
  • the object of the invention is to provide a method in which one obtains this connection as a product and also relatives that have proven to be valuable intermediate connections.
  • the invention relates to a process for the preparation of 6,10-and 6, 9-dimethyl-5, 10-undecadienyl-2-ones by telomerization of isoprene with alkyl acetoacetates in the presence of a catalyst system composed of a transition metal compound and a phosphorus component, characterized in that the process, if appropriate, in the presence of a protic addition of the general formula
  • R, R, R alkyl with C x to C 9 -C atoms, branched or unbranched, cycloalkyl with C 6 to C 8 C atoms, aryl, in particular phenyl, Arylalkyl, X inorganic or organic anion, in particular halide or sulfate y 1 or 2
  • Organic solvents are optionally used and are not limited to certain compounds, with the exception of the general principle that they are inert in the sense of a chemical reaction. This does not mean a protonating effect such as that of alcohols of the general formula (I) in the present reaction.
  • the solvents are also used in the form of mixtures, the compounds of the formula (I) simultaneously acting as protic additives and as solvents.
  • Aromatic solvents such as benzene, toluene or phenol, as well as phenols, ketones and aliphatic alcohols substituted by alkyl groups are suitable.
  • the selectivities can be controlled by suitable combinations of temperature, solvent and cocatalyst.
  • Example 2 The procedure was as in Example 1. The addition of 20 ml of i-propanol used there was exchanged for in each case 20 ml of another compound according to Table 1. In contrast, the turn over number (molp roduk . T mol pd ), TON and the selectivity to 6,10-dimethyl-5, 10-undecadien-2-one, 1-KS, based on the telomer fraction, are plotted.
  • Example 2 The procedure was as in Example 1. Instead of 20 ml of i-propanol, 20 ml of a compound according to the table were used. Triphenylphosphine was exchanged for another phosphorus compound according to the table. In contrast, the turn over number (mol product mol pd ), TON, and the selectivity to 6, 10-dimethyl-5, 10- undecadien-2-one, 1- S, based on the telomer fraction, are plotted.
  • npd np: n Acetess jg ester : n
  • Example I cocatalyst T / ° C reaction fraction of the telomer fraction / ton medium%

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 production de 6,10 et 6,9-diméthyl-5,10-undécadiényl-2-ones par télomérisation d'isoprène avec des alkylacéto-acétates, en présence d'un composé de métal de transition et d'un composant phosphoré en tant que système catalyseur, éventuellement en présence d'un additif protique. Les β-cétoester ainsi obtenus sont ensuite saponifiés et décarboxylés pour former les composés susmentionnés.
EP98936355A 1997-07-17 1998-06-17 Procede de production de 6,10 et 6,9-dymethyl-5,10-undecadienyl-2-ones Withdrawn EP0996609A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19730546 1997-07-17
DE19730546A DE19730546A1 (de) 1997-07-17 1997-07-17 Verfahren zur Herstellung von 6,10- und 6,9-Dimethyl-5,10-undecadienyl-2-onen
PCT/EP1998/003647 WO1999003811A1 (fr) 1997-07-17 1998-06-17 Procede de production de 6,10 et 6,9-dymethyl-5,10-undecadienyl-2-ones

Publications (1)

Publication Number Publication Date
EP0996609A1 true EP0996609A1 (fr) 2000-05-03

Family

ID=7835929

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98936355A Withdrawn EP0996609A1 (fr) 1997-07-17 1998-06-17 Procede de production de 6,10 et 6,9-dymethyl-5,10-undecadienyl-2-ones

Country Status (6)

Country Link
US (1) US6310259B1 (fr)
EP (1) EP0996609A1 (fr)
JP (1) JP2001510177A (fr)
CN (1) CN1264357A (fr)
DE (1) DE19730546A1 (fr)
WO (1) WO1999003811A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8558030B2 (en) * 2008-08-12 2013-10-15 Dow Global Technologies Llc Process for telomerization of butadiene
EP2655305B1 (fr) 2010-12-21 2019-09-04 Dow Global Technologies LLC Procédé de télomérisation du butadiène au moyen d'un catalyseur monosubstitué en ortho avec une alcoxy
US20170275235A1 (en) * 2016-03-23 2017-09-28 International Flavors & Fragrances Inc. Method for selective palladium-catalyzed telomerization of substituted dienes

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1289043B (de) * 1967-02-01 1969-02-13 Basf Ag Verfahren zur Herstellung von 6, 10, 14-Trimethylpentadecatrien-(5, 9, 14)-on-(2)
US3998872A (en) * 1970-10-05 1976-12-21 Universal Oil Products Company Preparation of unsaturated carbonyl compounds
JPS5411291B2 (fr) * 1972-10-05 1979-05-14
DE3163383D1 (en) * 1980-07-10 1984-06-07 Rhone Poulenc Sante Process for the selective addition of a compound having an activated carbon atom to a substituted conjugated diene
FR2657871B1 (fr) * 1990-02-08 1993-02-05 Rhone Poulenc Sante Procede de preparation de cetones terpeniques.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9903811A1 *

Also Published As

Publication number Publication date
DE19730546A1 (de) 1999-01-21
CN1264357A (zh) 2000-08-23
WO1999003811A1 (fr) 1999-01-28
JP2001510177A (ja) 2001-07-31
US6310259B1 (en) 2001-10-30

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