EP1115679A1 - Procede de production d'olefines - Google Patents

Procede de production d'olefines

Info

Publication number
EP1115679A1
EP1115679A1 EP99969404A EP99969404A EP1115679A1 EP 1115679 A1 EP1115679 A1 EP 1115679A1 EP 99969404 A EP99969404 A EP 99969404A EP 99969404 A EP99969404 A EP 99969404A EP 1115679 A1 EP1115679 A1 EP 1115679A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
stilbene
additive
bromobenzene
selectivity
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Withdrawn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
EP99969404A
Other languages
German (de)
English (en)
Inventor
Manfred T. Reetz
Gunther Lohmer
Renate Lohmer
Elke Westermann
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.)
Studiengesellschaft Kohle gGmbH
Original Assignee
Studiengesellschaft Kohle gGmbH
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 Studiengesellschaft Kohle gGmbH filed Critical Studiengesellschaft Kohle gGmbH
Publication of EP1115679A1 publication Critical patent/EP1115679A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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

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

Selon l'invention, on peut synthétiser des oléfines comportant des substituants aromatiques sans ajouter des sels de phosphonium ou des phosphanes, à l'aide d'un composé de Pd-II, comme catalyseur, en présence d'additifs azotés tels que la N, N-diméthylglycine et d'une base.
EP99969404A 1998-09-21 1999-09-07 Procede de production d'olefines Withdrawn EP1115679A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19843012 1998-09-21
DE19843012A DE19843012A1 (de) 1998-09-21 1998-09-21 Verfahren zur Herstellung von Olefinen
PCT/EP1999/006589 WO2000017132A1 (fr) 1998-09-21 1999-09-07 Procede de production d'olefines

Publications (1)

Publication Number Publication Date
EP1115679A1 true EP1115679A1 (fr) 2001-07-18

Family

ID=7881552

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99969404A Withdrawn EP1115679A1 (fr) 1998-09-21 1999-09-07 Procede de production d'olefines

Country Status (6)

Country Link
US (1) US6392111B1 (fr)
EP (1) EP1115679A1 (fr)
JP (1) JP2002526460A (fr)
CA (1) CA2345017A1 (fr)
DE (1) DE19843012A1 (fr)
WO (1) WO2000017132A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005000596A1 (fr) 2003-06-25 2005-01-06 Sanko Co., Ltd. Procede de production d'un materiau contenant un sensibilisateur disperse pour un article de thermogravure et article de thermogravure

Families Citing this family (5)

* Cited by examiner, † Cited by third party
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
JP4806351B2 (ja) * 2003-09-05 2011-11-02 ディーエスエム アイピー アセッツ ビー．ブイ． スチルベン誘導体を製造する方法
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
EP1637581B1 (fr) * 2004-09-16 2008-07-09 Firmenich S.A. Utilisation de dérivés des nitriles comme agents parfumants
JP7019912B2 (ja) * 2017-12-25 2022-02-16 ピーティーティー グローバル ケミカル パブリック カンパニー リミテッド 二酸化炭素およびオレフィンからの不飽和カルボン酸塩およびその誘導体の生成プロセスのための触媒組成物

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4013305A1 (de) * 1990-04-26 1991-10-31 Hoechst Ag Verfahren zur herstellung von (alpha)-fluorstyrol
DE4447068A1 (de) * 1994-12-29 1996-07-04 Hoechst Ag Verfahren zur Herstellung aromatischer Olefine
DE19712388A1 (de) * 1997-03-25 1998-10-01 Studiengesellschaft Kohle Mbh Verfahren zur Synthese von aromatisch substituierten Olefinen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0017132A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005000596A1 (fr) 2003-06-25 2005-01-06 Sanko Co., Ltd. Procede de production d'un materiau contenant un sensibilisateur disperse pour un article de thermogravure et article de thermogravure

Also Published As

Publication number Publication date
DE19843012A1 (de) 2000-03-23
CA2345017A1 (fr) 2000-03-30
WO2000017132A1 (fr) 2000-03-30
JP2002526460A (ja) 2002-08-20
US6392111B1 (en) 2002-05-21

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