公开(公告)号：US20100217015A1

公开(公告)日：2010-08-26

申请号：US12663536

申请日：2008-05-27

申请人： Antje Hieronymi ,  Lars Rodefeld

发明人： Antje Hieronymi ,  Lars Rodefeld

IPC分类号： C07D333/10

CPC分类号： C07D333/08

摘要： A process is described for the preparation of substituted heteroaromatics of the general formula (I) where X is oxygen, sulphur or NR5 where R5 is hydrogen, C1-C20-alkyl or C5-C6-aryl and R4 is C1-C20-alkyl, C5-C6-aryl or heteroaryl, R1, R2, R3 is hydrogen, halogen, C1-C20-alkyl, C5-C6-aryl or heteroaryl, by reaction A) of a halogenated heteroaromatic of the general formula (II) where X has the meaning given for formula (I) and R6 is bromine, iodine or chlorine and R1, R2 and R3 have the meaning given for formula (I), with a Grignard reagent of the general formula (III) R4MgHal  (III) where R4 has the meaning given for formula (I) and Hal is bromine, iodine or chlorine or B) reaction of the halogenated heteroaromatics of the formula (II) with magnesium firstly to give a Grignard compound of the general formula (IIIa) where Hal is bromine, iodine or chlorine and X and R1, R2 and R3 have the meaning given for formula (I), and further reaction with a halogenated compound of the general formula (IV) R4Hal  (IV) where R4 has the meaning given for formula (I) and Hal is bromine, iodine or chlorine, where the reactions A) or B) are in each case carried out in the presence of an Ni or Pd catalyst, characterized in that the process is carried out in the presence of cycloalkyl alkyl ether as solvent and optionally a further solvent. Likewise described is the use of cycloalkyl alkyl ethers, in particular cyclopentyl methyl ether, in the Kumada reaction for the preparation of substituted heteroaromatics, in particular substituted thiophenes.

摘要翻译： 描述了制备通式（I）的取代杂芳族化合物的方法，其中X是氧，硫或NR 5，其中R 5是氢，C 1 -C 20 - 烷基或C 5 -C 6 - 芳基，R 4是C 1 -C 20烷基， C 2 -C 6 - 芳基或杂芳基，R 1，R 2，R 3是氢，卤素，C 1 -C 20烷基，C 5 -C 6 - 芳基或杂芳基，通过反应A）通式（II）的卤代杂芳基，其中X具有 对于式（I）和R6给出的含义是溴，碘或氯，并且R 1，R 2和R 3具有式（I）给出的含义，通式（III）的格利雅试剂R4MgHal（III）其中R4具有 式（I）给出的含义和Hal是溴，碘或氯或B）式（II）的卤化杂芳族化合物与镁的反应首先得到通式（IIIa）的格利雅化合物，其中Hal是溴， 碘或氯，X和R 1，R 2和R 3具有式（I）给出的含义，并进一步与本发明的卤代化合物反应 式（IV）R4Hal（IV）其中R4具有式（I）给出的含义，Hal是溴，碘或氯，其中反应A）或B）在每种情况下在Ni或 Pd催化剂，其特征在于该方法在环烷基烷基醚作为溶剂和任选的另外的溶剂的存在下进行。 同样地描述了在Kumada反应中使用环烷基烷基醚，特别是环戊基甲基醚来制备取代的杂芳族化合物，特别是取代的噻吩。

公开(公告)号：US08258314B2

公开(公告)日：2012-09-04

申请号：US12663536

申请日：2008-05-27

申请人： Antje Hieronymi ,  Lars Rodefeld

发明人： Antje Hieronymi ,  Lars Rodefeld

IPC分类号： C07D405/00

CPC分类号： C07D333/08

摘要： A process is described for the preparation of substituted heteroaromatics of the general formula (I) where X is oxygen, sulphur or NR5 where R5 is hydrogen, C1-C20-alkyl or C5-C6-aryl and R4 is C1-C20-alkyl, C5-C6-aryl or heteroaryl, R1, R2, R3 is hydrogen, halogen, C1-C20-alkyl, C5-C6-aryl or heteroaryl, by reaction A) of a halogenated heteroaromatic of the general formula (II) where X has the meaning given for formula (I) and R6 is bromine, iodine or chlorine and R1, R2 and R3 have the meaning given for formula (I), with a Grignard reagent of the general formula (III) R4MgHal  (III) where R4 has the meaning given for formula (I) and Hal is bromine, iodine or chlorine or B) reaction of the halogenated heteroaromatics of the formula (II) with magnesium firstly to give a Grignard compound of the general formula (IIIa) where Hal is bromine, iodine or chlorine and X and R1, R2 and R3 have the meaning given for formula (I), and further reaction with a halogenated compound of the general formula (IV) R4Hal  (IV) where R4 has the meaning given for formula (I) and Hal is bromine, iodine or chlorine, where the reactions A) or B) are in each case carried out in the presence of an Ni or Pd catalyst, characterized in that the process is carried out in the presence of cycloalkyl alkyl ether as solvent and optionally a further solvent. Likewise described is the use of cycloalkyl alkyl ethers, in particular cyclopentyl methyl ether, in the Kumada reaction for the preparation of substituted heteroaromatics, in particular substituted thiophenes.

摘要翻译： 描述了制备通式（I）的取代杂芳族化合物的方法，其中X是氧，硫或NR 5，其中R 5是氢，C 1 -C 20 - 烷基或C 5 -C 6 - 芳基，R 4是C 1 -C 20烷基， C 2 -C 6 - 芳基或杂芳基，R 1，R 2，R 3是氢，卤素，C 1 -C 20烷基，C 5 -C 6 - 芳基或杂芳基，通过反应A）通式（II）的卤代杂芳基，其中X具有 对于式（I）和R6给出的含义是溴，碘或氯，并且R 1，R 2和R 3具有式（I）给出的含义，通式（III）的格利雅试剂R4MgHal（III）其中R4具有 式（I）给出的含义和Hal是溴，碘或氯或B）式（II）的卤化杂芳族化合物与镁的反应首先得到通式（IIIa）的格利雅化合物，其中Hal是溴， 碘或氯，X和R 1，R 2和R 3具有式（I）给出的含义，并进一步与本发明的卤代化合物反应 式（IV）R4Hal（IV）其中R4具有式（I）给出的含义，Hal是溴，碘或氯，其中反应A）或B）在每种情况下在Ni或 Pd催化剂，其特征在于该方法在环烷基烷基醚作为溶剂和任选的另外的溶剂的存在下进行。 同样地描述了在Kumada反应中使用环烷基烷基醚，特别是环戊基甲基醚来制备取代的杂芳族化合物，特别是取代的噻吩。

公开(公告)号：US20090270629A1

公开(公告)日：2009-10-29

申请号：US12418847

申请日：2009-04-06

申请人： Andreas Job ,  Denys Baskakov ,  Ralf Krahwinkel ,  Antje Hieronymi

发明人： Andreas Job ,  Denys Baskakov ,  Ralf Krahwinkel ,  Antje Hieronymi

IPC分类号： C07D211/60

CPC分类号： C07D211/46

摘要： What is described is a process for preparing compounds of the general formula (I) in which R1, R2 and R3 independently of one another represent hydrogen, an alkyl group or an aryl group, wherein compounds of the general formula (II) in which R1 and R2 have the meaning given for formula (I), are reacted with an alkylating agent of the general formula (III) R3X   (III) in which X represents a halogen atom and R3 has the meaning given for formula (I), if appropriate in a solvent.

摘要翻译： 描述的是制备通式（I）的化合物的方法，其中R 1，R 2和R 3彼此独立地表示氢，烷基或芳基，其中通式（II）的化合物其中R1 和R2具有式（I）给出的含义，与通式（III）的烷基化剂R 3 X（III）反应，其中X表示卤素原子，并且R 3具有式（I）给出的含义，如果合适 在溶剂中。

公开(公告)号：US08309732B2

公开(公告)日：2012-11-13

申请号：US12418847

申请日：2009-04-06

申请人： Andreas Job ,  Denys Baskakov ,  Ralf Krahwinkel ,  Antje Hieronymi

发明人： Andreas Job ,  Denys Baskakov ,  Ralf Krahwinkel ,  Antje Hieronymi

IPC分类号： C07D211/46

CPC分类号： C07D211/46

摘要： What is described is a process for preparing compounds of the general formula (I) in which R1, R2 and R3 independently of one another represent hydrogen, an alkyl group or an aryl group, wherein compounds of the general formula (II) in which R1 and R2 have the meaning given for formula (I), are reacted with an alkylating agent of the general formula (III) R3X  (III), in which X represents a halogen atom and R3 has the meaning given for formula (I), if appropriate in a solvent.

摘要翻译： 描述的是制备通式（I）的化合物的方法，其中R 1，R 2和R 3彼此独立地表示氢，烷基或芳基，其中通式（II）的化合物其中R1 和R2具有式（I）给出的含义，与通式（III）R3X（III）的烷基化剂反应，其中X表示卤素原子，并且R3具有式（I）给出的含义，如果 适用于溶剂。

公开(公告)号：US20090259053A1

公开(公告)日：2009-10-15

申请号：US12419570

申请日：2009-04-07

申请人： Antje Hieronymi ,  Andreas Martin ,  Witold Broda

发明人： Antje Hieronymi ,  Andreas Martin ,  Witold Broda

IPC分类号： C07D333/28

CPC分类号： C07D333/28 ,  Y02E10/549 ,  Y02P70/521

摘要： What is described is a process for brominating alkylthiophene, in which an alkylthiophene of the general formula (I) where R is a branched or unbranched alkyl radical having 1 to 12 carbon atoms is contacted with stoichiometric amounts of HBr and H2O2, optionally in the presence of a solvent.

摘要翻译： 所描述的是溴化烷基噻吩的方法，其中通式（I）的烷基噻吩（其中R是具有1至12个碳原子的支链或非支链烷基）与化学计量的HBr和H 2 O 2接触，任选地存在 的溶剂。

公开(公告)号：US08115018B2

公开(公告)日：2012-02-14

申请号：US12419570

申请日：2009-04-07

申请人： Antje Hieronymi ,  Andreas Martin ,  Witold Broda

发明人： Antje Hieronymi ,  Andreas Martin ,  Witold Broda

IPC分类号： C07D333/28

CPC分类号： C07D333/28 ,  Y02E10/549 ,  Y02P70/521

摘要： What is described is a process for brominating alkylthiophene, in which an alkylthiophene of the general formula (I) where R is a branched or unbranched alkyl radical having 1 to 12 carbon atoms is contacted with stoichiometric amounts of HBr and H2O2, optionally in the presence of a solvent.

摘要翻译： 所描述的是溴化烷基噻吩的方法，其中通式（I）的烷基噻吩（其中R是具有1至12个碳原子的支链或非支链烷基）与化学计量的HBr和H 2 O 2接触，任选地存在 的溶剂。