WO1999003811A1 - Verfahren zur herstellung von 6,10- und 6,9-dimethyl-5,10-undecadienyl-2-onen - Google Patents
Verfahren zur herstellung von 6,10- und 6,9-dimethyl-5,10-undecadienyl-2-onen Download PDFInfo
- Publication number
- WO1999003811A1 WO1999003811A1 PCT/EP1998/003647 EP9803647W WO9903811A1 WO 1999003811 A1 WO1999003811 A1 WO 1999003811A1 EP 9803647 W EP9803647 W EP 9803647W WO 9903811 A1 WO9903811 A1 WO 9903811A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- transition metal
- pph3
- propanol
- compound
- alkyl
- Prior art date
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
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000503044A JP2001510177A (ja) | 1997-07-17 | 1998-06-17 | 6,10−および6,9−ジメチル−5,10−ウンデカジエニル−2−オンの製造法 |
EP98936355A EP0996609A1 (de) | 1997-07-17 | 1998-06-17 | Verfahren zur herstellung von 6,10- und 6,9-dimethyl-5,10-undecadienyl-2-onen |
US09/446,734 US6310259B1 (en) | 1997-07-17 | 1998-06-17 | Method for producing 6,10 and 6,9-dimethyl-5,10-undecadienyl-2-ones |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19730546A DE19730546A1 (de) | 1997-07-17 | 1997-07-17 | Verfahren zur Herstellung von 6,10- und 6,9-Dimethyl-5,10-undecadienyl-2-onen |
DE19730546.6 | 1997-07-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999003811A1 true WO1999003811A1 (de) | 1999-01-28 |
Family
ID=7835929
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1998/003647 WO1999003811A1 (de) | 1997-07-17 | 1998-06-17 | Verfahren zur herstellung von 6,10- und 6,9-dimethyl-5,10-undecadienyl-2-onen |
Country Status (6)
Country | Link |
---|---|
US (1) | US6310259B1 (de) |
EP (1) | EP0996609A1 (de) |
JP (1) | JP2001510177A (de) |
CN (1) | CN1264357A (de) |
DE (1) | DE19730546A1 (de) |
WO (1) | WO1999003811A1 (de) |
Families Citing this family (3)
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 (de) | 2010-12-21 | 2019-09-04 | Dow Global Technologies LLC | Verfahren zur telomerisierung von butadien mithilfe eines mono-orthoalkoxy-substituierten katalysators |
US20170275235A1 (en) * | 2016-03-23 | 2017-09-28 | International Flavors & Fragrances Inc. | Method for selective palladium-catalyzed telomerization of substituted dienes |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1203871A (en) * | 1967-02-01 | 1970-09-03 | Basf Ag | 6,10,14-trimethylpentadecatrien-(5,9,14)-one-(2),6,10-dimethylundecadien-(3,10)-one-(2) and method for the preparation thereof |
DE2350194A1 (de) * | 1972-10-05 | 1974-04-11 | Takasago Perfumery Co Ltd | Verfahren zur herstellung von 2-acetyl5-methyl-4-hexencarbonsaeureestern |
US3998872A (en) * | 1970-10-05 | 1976-12-21 | Universal Oil Products Company | Preparation of unsaturated carbonyl compounds |
EP0044771A1 (de) * | 1980-07-10 | 1982-01-27 | Rhone-Poulenc Sante | Verfahren zur selektiven Addition einer Verbindung mit einem aktivierten Kohlenstoffatom an ein substituiertes konjugiertes Dien |
EP0441708A1 (de) * | 1990-02-08 | 1991-08-14 | Rhone-Poulenc Nutrition Animale | Verfahren zur Herstellung von Terpenketonen |
-
1997
- 1997-07-17 DE DE19730546A patent/DE19730546A1/de not_active Withdrawn
-
1998
- 1998-06-17 US US09/446,734 patent/US6310259B1/en not_active Expired - Fee Related
- 1998-06-17 CN CN98807200.9A patent/CN1264357A/zh active Pending
- 1998-06-17 EP EP98936355A patent/EP0996609A1/de not_active Withdrawn
- 1998-06-17 WO PCT/EP1998/003647 patent/WO1999003811A1/de not_active Application Discontinuation
- 1998-06-17 JP JP2000503044A patent/JP2001510177A/ja active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1203871A (en) * | 1967-02-01 | 1970-09-03 | Basf Ag | 6,10,14-trimethylpentadecatrien-(5,9,14)-one-(2),6,10-dimethylundecadien-(3,10)-one-(2) and method for the preparation thereof |
US3998872A (en) * | 1970-10-05 | 1976-12-21 | Universal Oil Products Company | Preparation of unsaturated carbonyl compounds |
DE2350194A1 (de) * | 1972-10-05 | 1974-04-11 | Takasago Perfumery Co Ltd | Verfahren zur herstellung von 2-acetyl5-methyl-4-hexencarbonsaeureestern |
EP0044771A1 (de) * | 1980-07-10 | 1982-01-27 | Rhone-Poulenc Sante | Verfahren zur selektiven Addition einer Verbindung mit einem aktivierten Kohlenstoffatom an ein substituiertes konjugiertes Dien |
EP0441708A1 (de) * | 1990-02-08 | 1991-08-14 | Rhone-Poulenc Nutrition Animale | Verfahren zur Herstellung von Terpenketonen |
Non-Patent Citations (1)
Title |
---|
HATA G ET AL: "Palladium-catalyzed reactions of 1,3-dienes with active methylene compounds. II.", J. ORG. CHEM. (JOCEAH);71; VOL.36 (15); PP.2116-23, Toray Ind., Inc.;Basic Res. Lab.; Kamakura; Japan, XP002079776 * |
Also Published As
Publication number | Publication date |
---|---|
DE19730546A1 (de) | 1999-01-21 |
EP0996609A1 (de) | 2000-05-03 |
CN1264357A (zh) | 2000-08-23 |
JP2001510177A (ja) | 2001-07-31 |
US6310259B1 (en) | 2001-10-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE1945703A1 (de) | Verfahren zur Herstellung von Arylchlorcarbonylketenen | |
EP0015436B1 (de) | Verfahren zur stereospezifischen Herstellung von Verbindungen der Vitamin K1- und K2-Reihe sowie neue Ausgangsprodukte in diesem Verfahren | |
WO1999003811A1 (de) | Verfahren zur herstellung von 6,10- und 6,9-dimethyl-5,10-undecadienyl-2-onen | |
DE602005005354T2 (de) | Verfahren zur herstellung von 1,4-dialkyl-2,3-diol-1,4-butandion | |
DE3309159A1 (de) | Neue optisch aktive chromanderivate, verfahren zu deren herstellung sowie neue zwischenprodukte | |
EP0022955A1 (de) | Verbessertes Verfahren zur Herstellung von höheren ungesättigten Ketonen | |
DE2643205A1 (de) | Verfahren zur herstellung von alpha-formylpropionsaeurealkylestern | |
DE69731967T2 (de) | Verfahren zur selektiven herstellung von 2-hydroxybenzoesäure und von 4-hydroxybenzaldehyd und derivaten | |
DE3228770A1 (de) | Verfahren zur selektiven herstellung von aldehyden | |
DE2154370C3 (de) | Verfahren zur Herstellung von Äthern des 2,6-Dimethyl-2,7-octadien-1-ols und einige dieser Äther | |
EP0064605A1 (de) | Verfahren zur Herstellung von Resorcinderivaten sowie Verwendung bestimmter Resorcinderivate als Riechstoffe | |
EP0112502B1 (de) | Omega,omega-Diacyloxy-2,6-dimethyl-octatriensäureester und -aldehyde, Verfahren zu ihrer Herstellung und Verwendung zur Synthese von Terpenverbindungen | |
DE1955933C3 (de) | Verfahren zur Herstellung von 1-Alkoxyoctadienen-(2,7) | |
EP0882709B1 (de) | Verfahren zur Herstellung von Zeaxanthin, Zwischenprodukte für dieses Verfahren und Verfahren zu deren Herstellung | |
EP0054699B1 (de) | Verfahren zur katalytischen Hydrogenolyse von p-substituierten Benzaldehyd-dimethylacetalen zu den entsprechenden Benzylmethyl-ether-Derivaten | |
DE2318786C3 (de) | Verfahren zur Herstellung von γ-Aryloxyacetessigestern | |
EP0173226B1 (de) | Verfahren zur Herstellung von beta-Formylpropionsäure-tert.-butylester | |
DE3006745C2 (de) | Verfahren zur Herstellung von normal langkettigen Alkancarbonsäuren mit 26 bis 36 Kohlenstoffatomen | |
DE2807610C3 (de) | Palladiumphosphinkomplexe, Verfahren zu deren Herstellung und deren Anwendung | |
DE3441369A1 (de) | Verfahren zur herstellung von hydroxymethylen-alkoxyessigsaeureestern | |
EP0841332A1 (de) | Verfahren zur Herstellung von Alpha-Methylen-Beta-Methyl-Gamma-Butyrolacton und als Zwischenprodukt wertvolle 4-Hydroxy-Butyraldehyde sowie 2-Hydroxy-3-Methylen-4-Methyltetrahydrofuran | |
EP0360091A2 (de) | Verfahren zur Herstellung von alkylsubstituierten Zimtaldehyden | |
DE2930222A1 (de) | Verfahren zur herstellung von aromatischen hydroxy- und alkoxyaldehyden | |
DE3046059C2 (de) | 4-Halogen-5,5-dialkoxypentansäureester, Verfahren zu ihrer Herstellung und ihre Verwendung zur Herstellung von 2,2-Dialkyl-3-formylcyclopropancarbonsäureestern | |
DE3305000A1 (de) | Verfahren zur herstellung von cyclopentanon |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 98807200.9 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): CN JP US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1998936355 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09446734 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 1998936355 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1998936355 Country of ref document: EP |