WO2000017132A1 - Verfahren zur herstellung von olefinen - Google Patents
Verfahren zur herstellung von olefinen Download PDFInfo
- Publication number
- WO2000017132A1 WO2000017132A1 PCT/EP1999/006589 EP9906589W WO0017132A1 WO 2000017132 A1 WO2000017132 A1 WO 2000017132A1 EP 9906589 W EP9906589 W EP 9906589W WO 0017132 A1 WO0017132 A1 WO 0017132A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkyl
- stilbene
- additive
- bromobenzene
- selectivity
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
- C07B37/04—Substitution
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/266—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of hydrocarbons and halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
Definitions
- the present invention relates to a new method for the synthesis of olefins with aromatic substituents using a very simple catalyst system.
- Olefins with aromatic substituents play an important role in industrial chemistry.
- aryl-substituted olefins One possibility for the synthesis of aryl-substituted olefins is the so-called Heck reaction, in which iodine, bromine or chloroaromatics ArX (I, Br, Cl) with olefins in the presence of stoichiometric amounts of a base and catalytic amounts of a palladium compound such as Pd ( PPh 3 ) 4 (RF Heck, "Vinyl Substitutions with Organopalladium Intermediates” in Comprehensive Organic Syntheses, Vol. 4, Pergamon Press, Oxford, 1991, p. 833; RF Heck, Palladium Reagents in Organic Syntheses, Acade ic Press, London, 1985; RF Heck, Org. React.
- Heck reaction in which iodine, bromine or chloroaromatics ArX (I, Br, Cl) with olefins in the presence of stoichiometric amounts of a base
- bromoaromatics can be converted smoothly, even with only 0.01 mol% palladacycle.
- catalysts are expensive or require multiple synthesis steps using the expensive tris (o-tolyl) phosphine or other difficult to access phosphines.
- an active catalyst system consisting of PdCl 2 (PhCN) 2 , Ph ⁇ Cl " and N, N-dimethylglycine (DMG) has recently been described as an additive; in the absence of the phosphonium salt Ph4P + Cl " , no reaction takes place (MT Reetz , G. Lohmer, R. Schwickardi, Angew. Chem. 1998, HO, 492-495; Angew.
- the new catalyst system consists of cheap palladium (II) salts in the presence of nitrogen-containing additives such as N, N-dimethylglycine (DMG) and a base. This eliminates the need for phosphines.
- the reaction proceeds without an additive, even if the reaction times are significantly longer.
- the additive has a strongly accelerating effect only at concentrations of more than 0.5 mol percent palladium.
- Pd (OAc) 2 , PdCl 2 (PhCN) 2 , PdCl 2 , PdCl 2 (CH 3 CN) 2, CoEHsPdCl or Pd (NO 3 ) 2 or their dimeric or oligomeric form is preferably used.
- Aprotic dipolar solvents such as dimethylformamide (DMF), dimethylacetamide (DMA), dimethyl sulfoxide, propylene carbonate, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone (DMPU) or l-methyl serve as solvents -2- pyrrolidinone (NMP), but also protic solvents such as methanol, ethanol or diethylene glycol. DMF, NMP or methanol is preferably used.
- Metal salts such as sodium, potassium, cesium, calcium or magnesium salts of carboxylic acids or the corresponding carbonates or bicarbonates or amines such as triethylamine or trioctylamine, preferably sodium acetate, serve as the base.
- the ratio of base to aryl halide is between 1: 1 and 5: 1, preferably 1.5: 1 to 2: 1.
- Reaction temperatures between 60 ° C and 180 ° C can be selected, preferably the reactions are allowed to run between 100 ° C and 140 ° C.
- aryl component ArX As far as the aryl component ArX is concerned, quite different aryl and heteroaryl halides, preferably aryl bromides, but also -O-tosylates, -O-mesylates or -O-triflates can be used, for example benzene, naphthalene, pyridine or quinoline derivatives. Aryldiazonium salts can also be reacted.
- R 1 , R 2 and R 3 independently of one another represent hydrogen, alkyl- (C ⁇ -Cs), phenyl, 1- or 2-naphthyl, vinyl, O-alkyl- (C ⁇ -C 8 ), O-phenyl, CN, CO 2 H, CO 2 alkyl- (C ⁇ - C 8 ), CO 2 - phenyl, CONH 2 , CONH-alkyl- (C ⁇ - C 5 ), CON (alkyl) 2 - (C ⁇ - C 5 ), fluorine, chlorine, PO (phenyl) 2 , PO (alkyl) - (- C 5 ), CO-phenyl, CO-alkyl- (C ⁇ - C 5 ), NH-alkyl- (Ci - C 4 ), SO 3 H, PO3H, SO 3 -alkyl- (C ⁇ - C 4 ) or SO 2 -alkyl- (C
- Example 10 The procedure is as described in Example 1, but no dimethylglycine is used: 40% conversion based on bromobenzene; the yield of Heck products is 26% (selectivity: 93.5% trans-stilbene, 0.7% cis-stilbene and 5.8% 1,1-diphenylethene).
- Example 10 The procedure is as described in Example 1, but no dimethylglycine is used: 40% conversion based on bromobenzene; the yield of Heck products is 26% (selectivity: 93.5% trans-stilbene, 0.7% cis-stilbene and 5.8% 1,1-diphenylethene).
- Example 10 Example 10:
- Example 16 The procedure is as described in Example 1, but the catalysis is carried out in air: 92% conversion based on bromobenzene; the yield of Heck products is 89% (selectivity: 96.3% trans-stilbene, 3.1% cw-stilbene and 0.6% 1, 1-diphenylethene).
- Example 16 The procedure is as described in Example 1, but the catalysis is carried out in air: 92% conversion based on bromobenzene; the yield of Heck products is 89% (selectivity: 96.3% trans-stilbene, 3.1% cw-stilbene and 0.6% 1, 1-diphenylethene).
- Example 16 Example 16:
- Example 20 The procedure is as described in Example 1, but 0.1 ml of a PaUadium stock solution (3.8 mg [0.01 mmol] PdCl 2 (C 6 H 5 CN) 2 / 20.4 mg [0.2 mmol] dimethylglycine in 100 ml methanol / dichloromethane instead of PdCl 2 ( C 6 H 5 CN) 2 and dimethylglycine in air and the mixture is stirred for 96 hours at 130 ° C. 96% conversion based on bromobenzene; the yield of Heck products is 91% (selectivity: 92.9% tr ⁇ ns-stilbene, 0.7% cw stilbene and 6.4% 1,1-diphenylethene).
- Example 20 Example 20:
- Example 26 The procedure is as described in Example 22, but the mixture is stirred at 150 ° C. for 30 hours: 70% conversion based on bromobenzene; the yield of Heck products is 65% (selectivity: 92.0% tr ⁇ n-stilbene, 1.0% cis-stilbene and 7.0% 1, 1-diphenylethene).
- Example 26 The procedure is as described in Example 22, but the mixture is stirred at 150 ° C. for 30 hours: 70% conversion based on bromobenzene; the yield of Heck products is 65% (selectivity: 92.0% tr ⁇ n-stilbene, 1.0% cis-stilbene and 7.0% 1, 1-diphenylethene).
- Example 26 Example 26:
- Example 31 The procedure is as described in Example 1, but 22.5 mg (0.3 mmol) of glycine are weighed in instead of dimethylglycine: 90% conversion based on bromobenzene; the yield of Heck products is 83% (selectivity: 92.9% trans-stilbene, 0.7% -stilbene and 6.4% 1,1-diphenylethene).
- Example 31
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- 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 (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99969404A EP1115679A1 (de) | 1998-09-21 | 1999-09-07 | Verfahren zur herstellung von olefinen |
JP2000574047A JP2002526460A (ja) | 1998-09-21 | 1999-09-07 | オレフィンの製造法 |
US09/787,786 US6392111B1 (en) | 1998-09-21 | 1999-09-07 | Method for producing olefins |
CA002345017A CA2345017A1 (en) | 1998-09-21 | 1999-09-07 | Method for producing olefins |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19843012A DE19843012A1 (de) | 1998-09-21 | 1998-09-21 | Verfahren zur Herstellung von Olefinen |
DE19843012.4 | 1998-09-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000017132A1 true WO2000017132A1 (de) | 2000-03-30 |
Family
ID=7881552
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1999/006589 WO2000017132A1 (de) | 1998-09-21 | 1999-09-07 | Verfahren zur herstellung von olefinen |
Country Status (6)
Country | Link |
---|---|
US (1) | US6392111B1 (de) |
EP (1) | EP1115679A1 (de) |
JP (1) | JP2002526460A (de) |
CA (1) | CA2345017A1 (de) |
DE (1) | DE19843012A1 (de) |
WO (1) | WO2000017132A1 (de) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10037390A1 (de) * | 2000-08-01 | 2002-02-14 | Covion Organic Semiconductors | Verfahren zur Herstellung von olefinsubstituierten Aromaten oder Heteroaromaten |
JP3945705B2 (ja) | 2003-06-25 | 2007-07-18 | 三光株式会社 | 増感剤分散体の製造方法及び感熱記録体 |
EP1663926A2 (de) * | 2003-09-05 | 2006-06-07 | DSM IP Assets B.V. | Verfahren zur herstellung von stilbenderivativen |
JP2005232036A (ja) * | 2004-02-17 | 2005-09-02 | Kyoto Univ | 多置換オレフィン及びその選択的製造方法 |
ATE400632T1 (de) * | 2004-09-16 | 2008-07-15 | Firmenich & Cie | Verwendung von nitrilderivaten als parfümkomponente |
WO2019132784A1 (en) * | 2017-12-25 | 2019-07-04 | Ptt Global Chemical Public Company Limited | A catalyst composition for a producing process of an unsaturated carboxylic acid salt and its derivatives from carbon dioxide and olefin |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1991016286A1 (de) * | 1990-04-26 | 1991-10-31 | Hoechst Aktiengesellschaft | VERFAHREN ZUR HERSTELLUNG VON α-FLUORSTYROL |
EP0719758A1 (de) * | 1994-12-29 | 1996-07-03 | Hoechst Aktiengesellschaft | Verfahren zur Herstellung aromatischer Olefine |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19712388A1 (de) * | 1997-03-25 | 1998-10-01 | Studiengesellschaft Kohle Mbh | Verfahren zur Synthese von aromatisch substituierten Olefinen |
-
1998
- 1998-09-21 DE DE19843012A patent/DE19843012A1/de not_active Withdrawn
-
1999
- 1999-09-07 WO PCT/EP1999/006589 patent/WO2000017132A1/de not_active Application Discontinuation
- 1999-09-07 US US09/787,786 patent/US6392111B1/en not_active Expired - Fee Related
- 1999-09-07 CA CA002345017A patent/CA2345017A1/en not_active Abandoned
- 1999-09-07 EP EP99969404A patent/EP1115679A1/de not_active Withdrawn
- 1999-09-07 JP JP2000574047A patent/JP2002526460A/ja active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1991016286A1 (de) * | 1990-04-26 | 1991-10-31 | Hoechst Aktiengesellschaft | VERFAHREN ZUR HERSTELLUNG VON α-FLUORSTYROL |
EP0719758A1 (de) * | 1994-12-29 | 1996-07-03 | Hoechst Aktiengesellschaft | Verfahren zur Herstellung aromatischer Olefine |
Non-Patent Citations (2)
Title |
---|
M. T. REETZ: "A highly active phosphine-free catalyst system for Heck reactions of aryl bromides", TETRAHEDRON LETTERS, vol. 39, no. 46, 12 November 1998 (1998-11-12), OXFORD GB, pages 8449 - 8452, XP004139440 * |
S. CACCHI: "A novel approach to alpha-keto acid derivatives via palladium-catalyzed arylation and vinylation of methyl alpha-methoxyacrylate", TETRAHEDRON LETTERS, vol. 28, no. 26, 1987, OXFORD GB, pages 3039 - 3042, XP002125136 * |
Also Published As
Publication number | Publication date |
---|---|
DE19843012A1 (de) | 2000-03-23 |
US6392111B1 (en) | 2002-05-21 |
EP1115679A1 (de) | 2001-07-18 |
CA2345017A1 (en) | 2000-03-30 |
JP2002526460A (ja) | 2002-08-20 |
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