EP1467963A1 - Arylierung von olefinen - Google Patents

Arylierung von olefinen

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Publication number
EP1467963A1
EP1467963A1 EP02792778A EP02792778A EP1467963A1 EP 1467963 A1 EP1467963 A1 EP 1467963A1 EP 02792778 A EP02792778 A EP 02792778A EP 02792778 A EP02792778 A EP 02792778A EP 1467963 A1 EP1467963 A1 EP 1467963A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
independently
aryl
general formula
palladium
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Withdrawn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
EP02792778A
Other languages
German (de)
English (en)
French (fr)
Inventor
Florian Rampf
Markus Eckert
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.)
Saltigo GmbH
Original Assignee
Bayer Chemicals 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 Bayer Chemicals AG filed Critical Bayer Chemicals AG
Publication of EP1467963A1 publication Critical patent/EP1467963A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide 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
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines

Definitions

  • the invention relates to a process for the arylation of olefins by reacting halogen aromatics or aryl sulfonates with olefins in the presence of a palladium catalyst and a sterically demanding nitrogen base, optionally in a dipolar aprotic solvent.
  • Aryl olefins are often prepared by palladium-catalyzed coupling of aromatics of iodine or bromine, more rarely aromatics of chlorine or aryl sulfonates, with olefins. Due to the high price and the large amounts of waste caused by the high molar masses, the use of iodine and
  • Aromatic bromine aromatics disadvantageous. However, the more readily available and therefore cheaper chloroaromatics show comparatively low reactivity.
  • n stands for one or two
  • X each independently represents chlorine, bromine, iodine or a sulfonate
  • Ar in the context of the invention is, for example and preferably, carbocyclic aromatic radicals having 6 to 24 carbon atoms or heteroaromatic
  • carbocyclic aromatic radicals or heteroaromatic radicals can be substituted with up to five identical or different substituents per cycle, selected from the group consisting of hydroxyl, fluorine, nitro, cyano, free or protected formyl, -C ⁇ -alkyl, C 5 -Ci 4- aryl, C 6 -C 15 arylalkyl, -PO - [(C ⁇ _-C 8 ) alkyl] 2 , -PO - [(C 5 -C 14 ) aryl] 2> -PO [(C 1 - C 8 ) -alkyl) (C 5 -C 14 ) -aryl)], Tri CrCs-alkytysiloxyl or residues of the general formula (II),
  • A is absent or represents a C 8 -C 8 alkylene radical
  • B is absent or represents oxygen, sulfur or NR 1 ,
  • R 1 is hydrogen, CrC 8 alkyl, C 6 -C 5 arylalkyl or C 5 -C 1 aryl and
  • D represents a carbonyl group
  • E represents R 2 , OR 2 , NHR 3 or N (R 3 ) 2 ,
  • R 2 is CC 8 alkyl, C 6 -C 15 arylalkyl, CC 8 haloalkyl or C 5 - C 14 aryl and
  • R 3 each independently represents Ci-Cs-alkyl, C 6 -C 15 arylalkyl or C 6 -C 14 aryl or N (R 3 ) 2 together represents a cyclic amino radical, or residues of the general formulas (Illa-e)
  • A, B, E and R 2 have the meaning given above and W represents OH, NH 2 , or OM, where M can mean an alkali metal ion, half an equivalent of an alkaline earth metal ion, an ammonium ion or an organic ammonium ion.
  • alkyl or alkylene or alkoxy each independently means a straight-chain, cyclic, branched or unbranched alkyl or alkylene or alkoxy radical, which may optionally be further substituted by Cr alkoxy radicals.
  • alkylene part of an arylalkyl radical The same applies to the alkylene part of an arylalkyl radical.
  • -Co-alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-Penty ⁇ , cyclohexyl and n-hexyl, C - C 8 - alkyl, for example for n-heptyl, n-octyl or iso-octyl, CrC 12 -
  • Alkyl furthermore for example for n-decyl and n-dodecyl and C1-C20 nocn furthermore for n-hexadecyl and n-octadecyl.
  • C 1 -C 4 -alkylene in all contexts is preferably methylene, 1,1-ethylene, 1,2-ethylene, 1,1-propylene, 1,2-propylene, 1,3-propylene, 1,1-
  • Ci-C-j-alkoxy in all contexts preferably represents methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy and tert-butoxy, Ci-Cg-
  • Alkoxy also for cyclohexyloxy.
  • aryl as a substituent encompasses carbocyclic radicals and heteroaromatic radicals in which none, one, two or three backbone atoms per cycle, but in the rest at least one backbone atom are heteroatoms selected from the group consisting of nitrogen, sulfur or oxygen.
  • C 5 -C 10 aryl is, for example and preferably phenyl, pyridyl, o-, m- or p-tolyl, C5-Ci4-aryl furthermore anthracenyl.
  • C ⁇ - s-arylalkyl stands for example and preferably for benzyl.
  • Haloalkyl or fluoroalkyl in the context of the invention each independently means a straight-chain, cyclic, branched or unbranched alkyl radical which can be substituted by one, more or completely selected from halogen fluorine, chlorine, or bromine or fluorine independently of one another ,
  • -C 8 -haloalkyl for example and preferably is -C 8 -haloalkyl, in all contexts preferably for trifluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl and nonafluorobutyl, Ci-Cg-fluoroalkyl for trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl and nonafluorobutyl.
  • Protected formyl means a formyl radical which is protected by conversion into an aminal, acetal or a mixed aminal acetal, where the aminals,
  • Acetals and mixed amino acetals can be acyclic or cyclic.
  • protected formyl is a l, l- (2,5-dioxy) cyclopentylene radical.
  • Ar stands for a substituted or unsubstituted aromatic radical and is selected from the group phenyl, naphthyl, biphenyl, binaphthyl, phenanthrenyl, anthracenyl, fluorenyl, pyridinyl, oxazolyl, thiophene-yl, benzo
  • X represents chlorine, bromine, iodine, -CC 8 perfluoroalkylsulfonyloxy such as trifluoromethanesulfonyloxy or nonafluorobutanesulfonyloxy or benzenesulfonyloxy or tolylsulfonyloxy.
  • n one and Ar represents a phenyl radical which can be further substituted by none, one, two or three radicals which are each independently selected from the group
  • X represents chlorine or bromine.
  • 4-Chlorobenzotrifluoride is very particularly preferably used.
  • Palladium complexes for example, are preferably used as the palladium catalyst.
  • Palladium complexes can be generated, for example, from palladium compounds and suitable ligands in the reaction solution, or can be used in the form of already isolated palladium complexes.
  • Palladium complexes are suitable as isolated palladium complexes for the process according to the invention which, as ligands, contain phosphorus compounds such as e.g. Phosphines, phosphites, phosphonites or mixtures thereof, preferably contain phosphines.
  • phosphorus compounds such as e.g. Phosphines, phosphites, phosphonites or mixtures thereof, preferably contain phosphines.
  • Palladium complexes which may contain phosphorus compounds as ligands are, for example and preferably, those of the general formula (IV),
  • An is an anion, preferably chloride, bromide, iodide, acetate, propionate, allyl or cyclopentadienyl.
  • L can each represent a monophosphorus compound or half an equivalent of a diphosphorus compound.
  • Monophosphorus compounds are, for example and preferably, those of the general formula (Va)
  • R 5 for Ci-C ⁇ -alkyl, dC 8 -alkoxy, chlorine, fluoro-, N (CrC 6 -alkyl) 2 , CO 2 - (Ci-C ⁇ -alkyl), -C0N (C 1 -C 6 -alkyl) 2 , cyano or CO (dC 6 alkyl.
  • Particularly preferred monophosphorus compounds are those of the general formula (Va) in which E is absent and R 4 independently of one another represents dC 8 -alkyl or unsubstituted, one, two or three times substituted by R 5 phenyl- or naphthyl- or ferrocenyl, where
  • R 5 represents Ci-Cg-alkyl, -CC 8 alkoxy, chlorine or fluorine.
  • Monophosphorus compounds are very particularly preferred are those of the general formula (Va) in which E is absent
  • radicals R 4 independently of one another are dC 8 -alkyl and none or one radical R 4 is unsubstituted, mono-, di- or trisubstituted by R 5 phenyl- or naphthyl-, where
  • R s represents dC 8 alkyl, Ci-Cs alkoxy, chlorine or fluorine.
  • Tri- (tert-butyl) phosphine, phenyldi (tert-butyl) phosphine and ferrocenyl-di- (tert-butyl) phosphine are even more preferred as monophosphorus compounds.
  • Diphosphorus compounds can, for example and preferably, be those of the general formula (Vb)
  • each independently and independently of R 6 and Z is absent or represents oxygen and the radicals R 6 independently of one another represent dC 8 alkyl or unsubstituted, mono-, di- or trisubstituted by R 7 phenyl, naphthyl or heteroaryl with 5 to 12 carbon atoms, where
  • R 7 is in each case independently selected from the group dC 8 alkyl, dC 8 alkoxy, fluorine or cyano and
  • Preferred isolated palladium complexes are palladium (II) bistriphenylphosphine dichloride, palladium (0) tetrakistriphenylphosphine, palladium (0) bistri-o-tolylphosphine, palladium (0) tricyclohexylphosphanediallyl ether complex, palladium (0) bistricyclohexylphosphine.
  • Palladium complexes which are produced from palladium compounds and ligands in the reaction solution are preferred as palladium catalysts for the process according to the invention.
  • Pd 2 dibenzylidene acetone 3 or allyl palladium chloride or bromide or those of the general formula (Via), for example and preferably, can be used as palladium compounds,
  • Pd (Y 1 ) 2 (Via) in the Y 1 represents an anion, preferably chloride, bromide, acetate, propionate, nitrate, methanesulfonate, trifluoromethanesulfonate, acetylacetonate, allyl or cyclo- • pentadienyl,
  • Y is an anion, preferably chloride, bromide, acetate, methanesulfonate or trifluoromethanesulfonate, afonafluorobutanesulfonate, tetrafluoroborate or hexafluorophosphate and
  • L in each case represents a nitrite, preferably acetonitrile, benzonitrile or benzyl nitrile, or an olefin, preferably cyclohexene or cyclooctene, or
  • L 2 together represents a diolefin, preferably ⁇ orbornadiene or 1,5-cyclooctadiene,
  • Y 3 represents a halide, preferably chloride or bromide
  • M represents lithium, sodium, potassium, ammonium or organic ammonium.
  • Preferred palladium compounds are palladium (II) acetate, palladium (II) chloride,
  • Phosphorus compounds of the general formulas (Na) and (Nb) are preferably used as ligands for the production of palladium complexes in the reaction solution, monophosphorus compounds of the general formula (Na) being even more preferred.
  • monophosphorus compounds of the general formula (Na) being even more preferred.
  • the molar ratio of phosphorus to palladium in the reaction mixture can be, for example, 1: 1 to 100: 1, 2: 1 to 15: 1 is preferred, 2: 1 to 10: 1 is particularly preferred.
  • the molar ner ratio of X to be exchanged in compounds of the general formula (I) to palladium can be, for example, 10 to 20,000, a ratio of 100 to 5,000 is preferred, very particularly preferably 500 to 2,000.
  • the process according to the invention is carried out in the presence of at least one, preferably one, sterically demanding nitrogen base.
  • Sterically demanding nitrogen bases are, for example, amines of the general formula
  • R 8 , R 9 and R 10 each independently represent C 1 -C 20 -aryl, C5 to C 14 aryl or Cg-cis-arylalkyl or two or three of the radicals R 8 , R 9 and R 10 with the nitrogen atom with a mono-, bi- or tricyclic heterocycle
  • Residues which can be bonded to the nitrogen atom via a tertiary or quaternary sp carbon atom are, for example and preferably, isopropyl, isobutyl, tert-butyl, 1-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2 dimethylpropyl,
  • Aryl residues which are substituted once or twice in the ortho positions are, for example, o-tolyl, 2,6-dimethylphenyl, 2-ethyl-6-methylphenyl, 2,6-diisopropylphenyl, o-anisyl and 2,6 -Dimethoxyphenyl.
  • Monocyclic heterocycles for the purposes of the invention are, for example, N-methyl-2,2,6,6-tetramethylpiperidine and N-methyl-2,5-dimethylpyrolidine.
  • 2,6-disubstituted pyridines such as 2,6-lutidine, 2,6-
  • ethyldiisopropylamine very particularly preferred for the ner driving according to the invention as sterically demanding nitrogen bases are ethyldiisopropylamine, triisopropylamine, diisopropylaniline, triisobutylamine, ethyldiisobutylamine, dicyclohexylmethylamine, Dicyclohexyethylamine, cyclohexyldiethylamine, cyclohexyldimethylamine and 2,6-bis-diisopropylpyridine are used,
  • dicyclohexylmethylamine, dicyclohexyethylamine, cyclohexyldiethylamine, cyclohexyldimethylamine are even more preferred.
  • the molar amount of the base used can be, for example, 0.5 to 100 times based on the X to be exchanged in the general formula (I), preferably 1.0 to 10 times, more preferably 1.0 to 1.5 times times and very particularly preferably 1.0 to 1.2 times.
  • the sterically demanding nitrogen base can be used in combination with another base.
  • 1 to 95% of the amount of sterically demanding nitrogen base can be replaced by a non-sterically demanding nitrogen base.
  • Non-sterically demanding nitrogen bases in the sense of the invention are, for example, alkali and alkaline earth metal carboxylates such as, for example, acetates, propionates,
  • alkali and alkaline earth metal carbonates hydrogen carbonates, phosphates, hydrogen phosphates, hydroxides.
  • Alkali metals are preferably lithium, sodium, potassium and cesium
  • alkaline earth metals are preferably calcium, magnesium and barium.
  • olefins which carry at least one hydrogen atom on the double bond are those of the general formula (VIII)
  • R 11 is hydrogen or methyl
  • R 12 is hydrogen or methyl
  • R 13 can stand for hydrogen, cyano, SO 3 M, dC 8 -alkyl, carbocyclic aromatic radicals with 6 to 18 structural carbon atoms or heteroaromatic radicals with 5 to 18 structural carbon atoms in which none, one, two or three structural carbon atoms per cycle, in total Molecule at least one carbon atom, may be substituted by heteroatoms selected from the group nitrogen, sulfur or oxygen
  • G is OM, OH, NH 2 , OR 14 , NHR 14 or N (R 14 ) 2 and R 14 is dC 12 - alkyl, C 6 -C 15 arylalkyl or C 5 -C ⁇ aryl or
  • the carbocyclic aromatic radicals and heteroaromatic radicals can be substituted in the same way as described under the aromatic compounds of the general formula (I).
  • Preferred examples of olefins of the general formula (VIII) are ethene, propene, butene, l, l, l-trifluoro-2-propene, optionally substituted vinyl-Cg-Cio-aro ⁇ ate 11 such as styrene or the isomeric vinylnaphthalenes, 2- , 3- or 4-fluorostyrene, 2-, 3- or 4-chlorostyrene, 2-, 3- or 4-bromostyrene, 2-, 3- or 4-iodostyrene, 2-, 3- or 4-cyanostyrene, 2-, 3- or 4- (C 1 -C 12 ) alkoxystyrene such as 2-, 3- or 4-methoxystyrene, 2-, 3- or 4-nitrostyrene, 2-, 3- or 4-styrene carboxylic acid,
  • Particularly preferred olefins with at least one hydrogen substituent are ethylene, propene, acrylonitrile, acrylic acid, methyl acrylate, acrylic acid (2-ethylhexyl) ester, acrylic acid amide, l, l, l-trifluor-2-propene and styrene, where
  • the amount of olefin used can be, for example, 0.2 to 200 times (when used as a solvent) based on the molar amount of the aromatic
  • aromatic compounds of the general formula (I) or olefins of the general formula (VIII) used are aromatic compounds of the general formula (I) or olefins of the general formula (VIII) used, the free acid group such as sulfonic acid or carry carboxylic acid groups, the amount of base used, sterically demanding nitrogen base or the non-sterically demanding nitrogen base must be increased accordingly.
  • the process according to the invention is aprotic in the presence of dipolar
  • Preferred dipolar aprotic solvents are amidic solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone or N-methylcaprolactam.
  • Sulfoxides and sulfones such as dimethyl sulfoxide or tetramethylene sulfone (sulfonlan) or mixtures of such solvents.
  • Nitriles such as Acetonitrile, benzonitrile and benzyl nitrile, ketones, e.g. Dimethyl ketone, diethyl ketone, methyl tert-butyl ketone.
  • Dimethylformamide, dimethylacetamide and N-methylpyrrolidone are particularly preferred.
  • Dimethylacetamide is very particularly preferred.
  • the amount of the solvent optionally used can be, for example, 50 ml to 5000 ml, preferably 100 to 500 ml per mole of the aromatic compound of the general formula (I).
  • the reaction temperature can be, for example, 20 ° C. to 200 ° C., preferably 80 to 150 ° C. and particularly preferably 80 ° C. to 120 ° C.
  • the reaction can be carried out, for example, at 0.2 to 100 bar, normal pressure is preferred.
  • the reaction time can be, for example, 0.2 h to 72 h, 1 to 36 h are preferred.
  • the reaction is preferably carried out under a protective gas atmosphere with largely exclusion of oxygen and moisture.
  • Protective gases are, for example, nitrogen and noble gases such as argon or mixtures of such gases.
  • the aromatic compound of the general formula (I) together with the olefin, the base, the palladium compound and the ligand are placed in a reaction vessel under protective gas in a reaction vessel and the batch is heated to the reaction temperature with stirring.
  • the mixture is poured onto water. Solid products then fall out and can be suctioned off and e.g. be washed with water. Liquid products can be extracted with an organic solvent that is immiscible or difficult to mix with water and worked up, for example, by distillation.
  • Solid products can, e.g. can be further purified by recrystallization or falling over.
  • the aromatic compound of the general formula (I) together with the olefin, the base and the ligand can also be introduced into a reaction vessel and the palladium compound can be metered in.
  • the aromatic compound of the general formula (I) can also be introduced together with the base, the ligand and the palladium compound in a reaction vessel and the olefin can be metered in. Furthermore, the olefin can also be placed together with the base, the ligand and the palladium compound in a reaction vessel and the aromatic compound of the general formula (I) can be metered in.
  • the base, the ligand and the aromatic compound of the general formula (I) can also be placed in a reaction vessel and the palladium compound can be metered in.
  • the ligand can also be added together with the palladium compound.
  • the base can be recovered, for example, by alkalizing and extracting the washing liquid with an organic solvent.
  • Aryl olefins of the general formula (X) are obtained in a manner according to the invention
  • Ar and n have the meaning given under the general formula (I) and RÜ, R ⁇ , R13 under the general formula (VIII).
  • R * 2 has the meaning given under the general formula (X)
  • R 3 represents cyano or radicals of the general formula (XI) with the meaning given there.
  • the advantage of the process according to the invention lies in the ease with which it can be carried out and the high yields of aromatic olefins. Furthermore, high catalyst turnover numbers (TON) of well over 100 moles of halogen aromatic / mole of palladium catalyst are achieved.
  • both tubes are placed in the same oil bath at 130 ° C (the mixture with dioxane in the pressure tube) and stirred for 3 hours. Before the reaction and after the end of the reaction, a sample is taken and the conversion is calculated from this by HPLC. In dimethylacetamide (Example 15) 52% conversion (TON 469; TOF 156h “1 ) was achieved after 3 hours, in dioxane (Example 16) no conversion.

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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)
EP02792778A 2001-12-03 2002-11-20 Arylierung von olefinen Withdrawn EP1467963A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10159269A DE10159269A1 (de) 2001-12-03 2001-12-03 Arylierung von Olefinen
DE10159269 2001-12-03
PCT/EP2002/012994 WO2003048107A1 (de) 2001-12-03 2002-11-20 Arylierung von olefinen

Publications (1)

Publication Number Publication Date
EP1467963A1 true EP1467963A1 (de) 2004-10-20

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US (1) US6858756B2 (enExample)
EP (1) EP1467963A1 (enExample)
JP (1) JP4426301B2 (enExample)
AU (1) AU2002358519A1 (enExample)
DE (1) DE10159269A1 (enExample)
IL (1) IL162238A0 (enExample)
WO (1) WO2003048107A1 (enExample)

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CN1890253A (zh) * 2003-12-12 2007-01-03 索尔维亚斯股份公司 制备邻位金属化和邻位取代芳族化合物的方法
WO2005123662A1 (en) * 2004-06-18 2005-12-29 Janssen Pharmaceutica N.V. Modified heck reaction
US8193182B2 (en) 2008-01-04 2012-06-05 Intellikine, Inc. Substituted isoquinolin-1(2H)-ones, and methods of use thereof
DK2240451T3 (da) 2008-01-04 2017-11-20 Intellikine Llc Isoquinolinonderivater substitueret med en purin, der er anvendelig som pi3k-inhibitorer
PE20180318A1 (es) 2011-01-10 2018-02-09 Infinity Pharmaceuticals Inc Procedimiento para preparar isoquinolinonas y formas solidas de isoquinolinonas
TW201238603A (en) 2011-03-10 2012-10-01 Lonza Ag Method for preparation of 3-(2,3-dimethylphenyl)-2-butenal
US8828998B2 (en) 2012-06-25 2014-09-09 Infinity Pharmaceuticals, Inc. Treatment of lupus, fibrotic conditions, and inflammatory myopathies and other disorders using PI3 kinase inhibitors
LT2914296T (lt) 2012-11-01 2018-09-25 Infinity Pharmaceuticals, Inc. Vėžio gydymas, panaudojant p13 kinazės izoformos moduliatorius
US20150320755A1 (en) 2014-04-16 2015-11-12 Infinity Pharmaceuticals, Inc. Combination therapies
UA125216C2 (uk) 2016-06-24 2022-02-02 Інфініті Фармасьютікалз, Інк. Комбінована терапія
CN114085300B (zh) * 2021-12-24 2023-09-15 南亚新材料科技股份有限公司 改性聚丁二烯树脂及其制备方法、应用

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Publication number Priority date Publication date Assignee Title
US3922299A (en) * 1974-03-05 1975-11-25 Univ Delaware Vinylic substitution reactions
CH654286A5 (de) * 1981-11-04 1986-02-14 Ciba Geigy Ag Verfahren zur pd-katalysierten arylierung von olefinen mit arylhalogeniden.
DE19825454A1 (de) * 1998-06-06 1999-12-16 Aventis Res & Tech Gmbh & Co Verfahren zur Herstellung von aromatischen Olefinen unter Katalyse von Palladiumkatalysatoren mit Phosphitliganden

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03048107A1 *

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AU2002358519A1 (en) 2003-06-17
JP2005511682A (ja) 2005-04-28
IL162238A0 (en) 2005-11-20
WO2003048107A1 (de) 2003-06-12
DE10159269A1 (de) 2003-06-18
US6858756B2 (en) 2005-02-22
US20030114707A1 (en) 2003-06-19
JP4426301B2 (ja) 2010-03-03

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