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    • 2. 发明公开
    • VERFAHREN ZUR HERSTELLUNG VON ALKYLSUBSTITUIERTEN AROMATEN UND HETEROAROMATEN DURCH KREUZKUPPLUNG VON ALKYLBORONSÄUREN MIT ARYL- ODER HETEROARYLHALOGENIDEN ODER -SULFONATEN UNTER PD-KATALYSE IN GEGENWART EINES LIGANDEN
    • 生产由与芳基烷基硼酸或杂芳基或磺酸盐交叉耦合烷基取代的芳族化合物和杂芳族化合物UNDER PD CATALYSIS在配体的存在下
    • EP1861343A2
    • 2007-12-05
    • EP06723260.3
    • 2006-03-07
    • Archimica GmbH
    • SCHERER, StefanMEUDT, AndreasNERDINGER, SvenLEHNEMANN, BerndJAGUSCH, ThomasSNIECKUS, Victor
    • C07B37/04C07C17/26C07C67/30C07C25/13C07C69/76C07F5/02
    • C07C1/321C07B37/04C07C17/263C07C67/343C07C2531/24C07D213/30C07C15/02C07C22/08C07C69/76
    • The invention relates to a method for producing alkyl-substituted aromatic and heteroaromatic compounds (III) by cross-coupling alkyl boronic acids (II) with aryl- or heteroaryl-halogenides or with aryl- or heteroaryl-sulfonates (I) in the presence of a catalyst and of a Brønsted base in a solvent or solvent mixture, in which: Hal represents chlorine, bromine, iodine, trifluoromethanesulfonate, nonafluorotrimethyl methane sulfonate, methane sulfonate, 4-toluolsulfonate, benzene sulfonate, 2- naphthalene sulfonate, 3-nitrobenzene sulfonate, 4-nitrobenzene sulfonate, 4-chlorobenzene sulfonate or 2,4,6-triisopropylbenzene sulfonate; X1-5, independent of one another, represent carbon, XiRi represents nitrogen, or each two adjacent XiRi's bound via a formal double bond represent, together, O (furane), S (thiophene), NH or NRi (pyrrole); radicals R1-5 represent substituents from the group consisting of {hydrogen, methyl, primary, secondary or tertiary, cyclic or acyclic alkyl radicals having 2 to 20 C atoms, in which optionally one or more hydrogen atoms are substituted by fluoride or chlorine or bromine, e.g. CF3, substituted cyclic or acyclic alkyl groups, hydroxy, alkoxy, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, phenyl, substituted phenyl, heteroaryl, substituted heteroaryl, thio, alkylthio, arylthio, diarylphosphino, dialkylphosphino, alkylarylphosphino, optionally substituted aminocarbonyl, CO2-, alkyl- or aryloxycarbonyl, hydroxyalkyl, alkoxyalkyl, fluorine or chlorine, nitro, cyano, aryl- or alkylsulfone, aryl- or alkylsulfonyl} or each two adjacent radicals R1-5 represent, together, an aromatic, heteroaromatic or aliphatic fused ring; alkyl represents any linear, branched or cyclic alkyl radical having 1 to 40 C atoms, in which optionally one or more hydrogen atoms are substituted by foreign atoms or functions of the group {fluorine, optionally chlorine or bromine, hydroxy, alkoxy, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, phenyl, substituted phenyl, heteroaryl, substituted heteroaryl, thio, alkylthio, arylthio, diarylphosphino, dialkylphosphino, alkylarylphosphino, optionally substituted aminocarbonyl, CO2-, alkyl- or aryloxycarbonyl, hydroxyalkyl, alkoxyalkyl, flourine or chlorine, nitro, cyano, aryl- or alkylsulfone}, R' and R'', independent of one another, represent the same or different radicals from the group consisting of {hydrogen, methyl, linear, branched or cyclic alkyl, optionally substituted, and phenyl, optionally substituted} or, together, form a ring and represent a bridging structure element from the group consisting of {optionally substituted alkylene, branched alkylene, cyclic alkylene or optionally substituted azaalkylene}.
    • 4. 发明授权
    • VERFAHREN ZUR HERSTELLUNG VON ALKYLSUBSTITUIERTEN AROMATEN UND HETEROAROMATEN DURCH KREUZKUPPLUNG VON ALKYLBORONSÄUREN MIT ARYL- ODER HETEROARYLHALOGENIDEN ODER -SULFONATEN UNTER PD-KATALYSE IN GEGENWART EINES LIGANDEN
    • 生产由与芳基烷基硼酸或杂芳基或磺酸盐交叉耦合烷基取代的芳族化合物和杂芳族化合物UNDER PD CATALYSIS在配体的存在下
    • EP1861343B1
    • 2009-03-04
    • EP06723260.3
    • 2006-03-07
    • Archimica GmbH
    • SCHERER, StefanMEUDT, AndreasNERDINGER, SvenLEHNEMANN, BerndJAGUSCH, ThomasSNIECKUS, Victor
    • C07B37/04C07C17/26C07C67/30C07C25/13C07C69/76C07F5/02
    • C07C1/321C07B37/04C07C17/263C07C67/343C07C2531/24C07D213/30C07C15/02C07C22/08C07C69/76
    • The invention relates to a method for producing alkyl-substituted aromatic and heteroaromatic compounds (III) by cross-coupling alkyl boronic acids (II) with aryl- or heteroaryl-halogenides or with aryl- or heteroaryl-sulfonates (I) in the presence of a catalyst and of a Brønsted base in a solvent or solvent mixture, in which: Hal represents chlorine, bromine, iodine, trifluoromethanesulfonate, nonafluorotrimethyl methane sulfonate, methane sulfonate, 4-toluolsulfonate, benzene sulfonate, 2- naphthalene sulfonate, 3-nitrobenzene sulfonate, 4-nitrobenzene sulfonate, 4-chlorobenzene sulfonate or 2,4,6-triisopropylbenzene sulfonate; X1-5, independent of one another, represent carbon, XiRi represents nitrogen, or each two adjacent XiRi's bound via a formal double bond represent, together, O (furane), S (thiophene), NH or NRi (pyrrole); radicals R1-5 represent substituents from the group consisting of {hydrogen, methyl, primary, secondary or tertiary, cyclic or acyclic alkyl radicals having 2 to 20 C atoms, in which optionally one or more hydrogen atoms are substituted by fluoride or chlorine or bromine, e.g. CF3, substituted cyclic or acyclic alkyl groups, hydroxy, alkoxy, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, phenyl, substituted phenyl, heteroaryl, substituted heteroaryl, thio, alkylthio, arylthio, diarylphosphino, dialkylphosphino, alkylarylphosphino, optionally substituted aminocarbonyl, CO2-, alkyl- or aryloxycarbonyl, hydroxyalkyl, alkoxyalkyl, fluorine or chlorine, nitro, cyano, aryl- or alkylsulfone, aryl- or alkylsulfonyl} or each two adjacent radicals R1-5 represent, together, an aromatic, heteroaromatic or aliphatic fused ring; alkyl represents any linear, branched or cyclic alkyl radical having 1 to 40 C atoms, in which optionally one or more hydrogen atoms are substituted by foreign atoms or functions of the group {fluorine, optionally chlorine or bromine, hydroxy, alkoxy, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, phenyl, substituted phenyl, heteroaryl, substituted heteroaryl, thio, alkylthio, arylthio, diarylphosphino, dialkylphosphino, alkylarylphosphino, optionally substituted aminocarbonyl, CO2-, alkyl- or aryloxycarbonyl, hydroxyalkyl, alkoxyalkyl, flourine or chlorine, nitro, cyano, aryl- or alkylsulfone}, R' and R'', independent of one another, represent the same or different radicals from the group consisting of {hydrogen, methyl, linear, branched or cyclic alkyl, optionally substituted, and phenyl, optionally substituted} or, together, form a ring and represent a bridging structure element from the group consisting of {optionally substituted alkylene, branched alkylene, cyclic alkylene or optionally substituted azaalkylene}.
    • 5. 发明公开
    • VERFAHREN ZUR HERSTELLUNG VON ALKENEN DURCH ELIMINIERUNG VON WASSER AUS ALKOHOLEN MIT ALKYLPHOSPHONSÄUREANHYDRIDEN
    • 用于生产烯烃BY除水由醇膦
    • EP1763497A1
    • 2007-03-21
    • EP05747587.3
    • 2005-06-04
    • Archimica GmbH
    • MEUDT, AndreasSCHERER, StefanBÖHM, Claudius
    • C07C1/24C07C15/46C07C11/02C07C13/11
    • C07D207/22C07C1/24C07C2601/08C07C15/46C07C13/11
    • The invention relates to a method for producing a) alkenes of formula (II) by the reaction of a) primary alcohols (R1R2CHCH2 - OH) or b) secondary alcohols (R1R2CHCHR3 - OH) or c) tertiary alcohols (R1R2CH - CR3R4OH) with cyclic alkylphosphonic acid anhydrides at a temperature ranging between -100 and +120 °C, whereby R and/or R1 and/or R2 and/or R3 and/or R4 represent H, a linear or branched C1-C12 alkyl group, or a C3-C10 cycloalkyl group, alkenyl group or an aryl group or heteroaryl group. Preferably, a 2,4,6-substituted 1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide of formula (I) is used as the cyclic phosphonic acid anhydride, where R' represents, (independently of one another), allyl, aryl or open-chained or branched C1 to C12 alkyl groups. Optionally the reaction can be carried out in the presence of a tertiary amine base NR53.
    • 本发明涉及一种用于制备式R 1 - [R 2 C-CR 3 - [R 4 通过的烯烃 a)一级alcolhols的反应(R 1 - [R 2 CHCH 2 OH)或b)的仲醇(R 1 < / SUP> - [R 2 CHCHR 3 -OH)或c)叔醇(R 1 - [R 2 CH- CR 3 - [R 4 与在范围内的温度的环状烷基膦酸酐OH)-100 C.,之间和+ 120°,由此R 1和/或R 1 < / SUP>和/或R 2 和/或R 3 和/或R 4 表示H,直链或支链的C 1 -C 12 烷基,或C 3 -C 10 的环烷基,链烯基或芳基或杂芳基 组。 优选地,2,4,6- substituiertem式(I)的-1,3,5,2,4,6- trioxatriphosphinane -2,4,6-三氧化物被用作环状膦酸酐,其中R“darstellt, (彼此独立地),烯丙基,芳基或开链的或支链的C 1 -C 12 烷基。 任选地,该反应可以在叔胺碱NR 5 3 的存在下进行。