公开(公告)号：US20030100792A1

公开(公告)日：2003-05-29

申请号：US10210807

申请日：2002-08-01

Applicant: Clariant GmbH

Inventor： Manfred Koch ,  Detlef Wehle ,  Stefan Scherer ,  Klaus Forstinger ,  Andreas Meudt ,  Volker Hessel ,  Bernd Werner ,  Holger Lowe

IPC: C07F005/02

CPC classification number: C07F5/02 ,  C07F5/025 ,  C07F5/027

Abstract: Process for preparing arylboron and alkylboron compounds of the formulae (II) and (III) by reacting arylmagnesium and alkylmagnesium halides of the formula (I) with boron compounds in microreactors in accordance with equation I or equation II, 1 where Xnullidentical or different radicals MetnullMgY where Ynullfluorine, chlorine, bromine or iodine, nnull1, 2 or 3, and Rnullstraight-chain or branched C1-C6-alkyl, a substituted C1-C6-alkyl or substituted or unsubstituted 6-membered heteroaryl containing one or two nitrogen atoms, or 5-membered heteroaryl containing one or two heteroatoms or a substituted or unsubstituted bicyclic or tricyclic aromatic, in coolable/heatable microreactors whose outlet channels are, if necessary, connected to capillaries or flexible tubes which are a number of meters in length, with the reaction solutions being intensively mixed during a sufficient residence time.

Abstract translation: 通过使式（I）中的芳基镁和烷基镁卤化物与微量反应器中的硼化合物按照式I或式II反应制备式（II）和（III）的芳基硼和烷基硼化合物的方法，其中X =相同或不同的基团 Met = MgY其中Y =氟，氯，溴或碘，n = 1,2或3，R =直链或支链C 1 -C 6 - 烷基，取代的C 1 -C 6烷基或取代或未取代的6元 含有一个或两个氮原子的杂芳基，或含有一个或两个杂原子的5元杂芳基或取代或未取代的双环或三环芳香族的可冷却/可加热微反应器，如果需要，其出口通道与毛细管或柔性管相连， 长度为米，反应溶液在足够的停留时间内强烈混合。

公开(公告)号：US20010020104A1

公开(公告)日：2001-09-06

申请号：US09790757

申请日：2001-02-22

Applicant: Clariant GmbH

Inventor： Steffen Haber ,  Stefan Scherer ,  Heinz Georg Kautz ,  Andreas Meudt ,  Frank Vollmuller

IPC: C07C002/02 ,  C07C006/12

CPC classification number: C07B37/04 ,  C07C41/18 ,  C07C45/68 ,  C07C49/84 ,  C07C209/36 ,  C07C211/45 ,  C07C227/04 ,  C07C229/52 ,  C07C201/12 ,  C07C205/57 ,  C07C205/44 ,  C07C43/205

Abstract: The novel two-stage process described here makes it possible to obtain substituted benzyl compounds and toluene derivatives in a simple manner and in high yields by means of Suzuki-type coupling reactions of an aromatic with an organoboron compound, followed by a reduction. The process is particularly useful for preparing ortho-substituted benzyl compounds and toluene derivatives. The process can be applied to both intermolecular and intramolecular coupling reactions. Catalysts used for the coupling reaction are palladium compounds and/or nickel compounds. An advantageous aspect is that only very small amounts of catalyst are required.

Abstract translation: 这里描述的新颖的两阶段方法可以通过芳香族与有机硼化合物的铃木型偶联反应，然后进行还原，以简单的方式和高收率得到取代的苄基化合物和甲苯衍生物。 该方法对于制备邻位取代的苄基化合物和甲苯衍生物特别有用。 该方法可以应用于分子间和分子内的偶联反应。 用于偶联反应的催化剂是钯化合物和/或镍化合物。 有利的方面是仅需要非常少量的催化剂。

公开(公告)号：US20030055283A1

公开(公告)日：2003-03-20

申请号：US10162485

申请日：2002-06-04

Applicant: Clariant GmbH

Inventor： Frank Vollmuller ,  Andreas Meudt ,  Stefan Scherer

IPC: C07F005/02

CPC classification number: C07F5/025

Abstract: A process for purifying formylphenylboronic acids of the formula (I) 1 where the formyl function is located in the ortho, meta or para position relative to the boronic acid function, by dissolving the crude formylphenylboronic acids in an alkaline solvent having a pH in the range from 8 to 11 separating off the insoluble organic impurities and subsequently acidifying the alkaline boronic acid solution and separating off and working up the precipitated boronic acid. The crude formylphenylboronic acid is preferably dissolved in aqueous alkali metal or alkaline earth metal oxide, hydroxide, carbonate or phosphate solutions at temperatures in the range from 5 to 50null C. The formylphenylboronic acids obtained have a purity of null99% and are suitable as precursors for liquid-crystalline compounds, as liquid crystals or as constituents of liquid-crystalline mixtures or as pharmaceutical intermediates.

Abstract translation: 通过将粗甲酰基苯基硼酸溶解在碱性溶剂中，其中pH为在下列范围内，其中甲酰基官能位于相对于硼酸官能团的邻位，间位或对位的式（I）的甲酰基苯基硼酸的方法 分离出不溶性有机杂质，然后酸化碱性硼酸溶液，分离和处理沉淀的硼酸。 粗甲酰基苯基硼酸优选在5至50℃的温度范围内溶解在碱金属或碱土金属氧化物，氢氧化物，碳酸盐或磷酸盐水溶液中。所得甲酰基苯基硼酸的纯度> 99％，适用于 液晶化合物的前体，液晶或液晶混合物的成分或药物中间体

公开(公告)号：US20030018192A1

公开(公告)日：2003-01-23

申请号：US10171444

申请日：2002-06-13

Applicant: Clariant GmbH

Inventor： Andreas Meudt ,  Michael Erbes ,  Klaus Forstinger

IPC: C07D471/02 ,  C07D491/02 ,  C07D498/02 ,  C07F007/02

CPC classification number: C07D307/12 ,  C07B37/04 ,  C07C1/26 ,  C07C41/16 ,  C07C41/26 ,  C07C41/30 ,  C07C45/59 ,  C07C45/68 ,  C07C319/20 ,  C07D213/50 ,  C07C15/44 ,  C07C323/22 ,  C07C43/23 ,  C07C43/205

Abstract: A process for preparing compounds of the formula (II), 1 where the substituents R1 to R5 are each independently H, CH3, straight-chain or branched C1-C8-alkyl, CH(OC1-C5-alkyl)2, CH(C1-C5-alkyl)(OC1-C5-alkyl), CH2(OC1-C5-alkyl), CH(CH3)(OC1-C5-alkyl), C1-C8-alkoxy, N(C1-C5-alkyl)2, phenyl, substituted phenyl, aryl, heteroaryl, S(C1-C5-alkyl) or a radical Caryl, alkyl, and the symbols X1 to 5 are each carbon or a maximum of two neighboring X1-5 are nitrogen or X1R1 and X2R2 together are O, NH, N(C1-C5-alkyl), N(CnullOnullC1-C5-alkyl), N(SiR3)2 or S, or where neighboring radicals R1 to R5 form the following structural unit, 2 where X6 to X9 and R6 to R9 have the same meaning as X1 to X5 and R1 to R5 which comprises reacting chloro- or fluoroaromatics of the formula (I) with carbon electrophiles and lithium metal.

Abstract translation: 一种制备式（II）化合物的方法，其中取代基R 1至R 5各自独立地为H，CH 3，直链或支链C 1 -C 8 - 烷基，CH（OC 1 -C 5烷基）2，CH（C1- （OC 1 -C 5 - 烷基），CH（CH 3）（OC 1 -C 5 - 烷基），C 1 -C 8 - 烷氧基，N（C 1 -C 5 - 烷基） ，取代的苯基，芳基，杂芳基，S（C 1 -C 5 - 烷基）或基团羧基，烷基，符号X 1至5各自为碳或最多两个相邻的X1-5为氮或X1R1和X2R2一起为O ，NH，N（C 1 -C 5 - 烷基），N（C = O-C 1 -C 5 - 烷基），N（SiR 3）2或S，或其中相邻基团R 1至R 5形成以下结构单元，其中X 6至X 9 并且R 6至R 9具有与X 1至X 5和R 1至R 5相同的含义，其包括使式（I）的氯代或氟代芳族化合物与碳亲电体和锂金属反应。

公开(公告)号：US20020161230A1

公开(公告)日：2002-10-31

申请号：US10085368

申请日：2002-02-28

Applicant: Clariant GmbH

Inventor： Andreas Meudt ,  Michael Erbes ,  Klaus Forstinger

IPC: C07F005/02

CPC classification number: C07F5/025

Abstract: A process for preparing boronic acids of the formula (I) and borinic acids of the formula (II), 1 by reaction of chloroaromatics of the formula (III) with lithium metal and boron compounds BWnullWnullWnullnull, where Wnull, Wnull and Wnullnull are each, independently of one another, C1-C6-alkoxy, fluorine, chlorine, bromine, iodine, N(C1-C6-alkyl)2 or S(C1-C5-alkyl), in a solvent at temperatures in the range from null100 to 80null C. 2

Abstract translation: 通过式（III）的氯芳族化合物与锂金属和硼化合物BW'W'W“'的反应制备式（I）的硼酸和式（II）的硼酸，其中W' ，W'和W“各自独立地为C 1 -C 6 - 烷氧基，氟，氯，溴，碘，N（C 1 -C 6 - 烷基）2或S（C 1 -C 5 - 烷基） 溶剂，温度范围为-100至80℃。

公开(公告)号：US20020115880A1

公开(公告)日：2002-08-22

申请号：US10073568

申请日：2002-02-11

Applicant: Clariant GmbH

Inventor： Andreas Meudt ,  Stefan Scherer ,  Frank Vollmuller ,  Heinz Georg Kautz

IPC: C07C255/50 ,  C07C243/22 ,  C07C231/10 ,  C07C025/00

CPC classification number: C07C253/00 ,  C07B37/04 ,  C07C17/093 ,  C07C209/62 ,  C07C209/68 ,  C07C231/14 ,  C07C25/18 ,  C07C211/45 ,  C07C233/07 ,  C07C255/50

Abstract: A process for preparing 4-substituted 2-alkylbiphenyls and 2-alkoxybiphenyls of the formula (I), 1 by reaction of phenylboronic acids of the formula (II) with 4-bromo- or 4-iodo-alkyl- or -alkoxy-anilines or -anilides of the formula (III) to form compounds of the formula (IV), 2 if appropriate subsequent deacylation to form (V) and subsequent diazotization to form compounds of the formula (VI) and reaction with a nucleophile X, a Cu salt by the Sandmeyer reaction or a reducing agent to give 4-substituted 2-alkylbiphenyls and 2-alkoxybiphenyls of the formula (I). 3

Abstract translation: 通过式（II）的苯基硼酸与4-溴 - 或4-碘 - 烷基 - 或 - 烷氧基 - 苯胺反应制备式（I）的4-取代的2-烷基联苯和2-烷氧基联苯的方法，或 （III）的酰胺化物，以形成式（IV）的化合物，如果适当，随后脱酰作用形成（V）并随后进行重氮化以形成式（VI）化合物，并与亲核试剂X，Cu盐通过 Sandmeyer反应或还原剂，得到式（I）的4-取代的2-烷基联苯和2-烷氧基联苯。

公开(公告)号：US20040073032A1

公开(公告)日：2004-04-15

申请号：US10677412

申请日：2003-10-02

Applicant: Clariant GmbH

Inventor： Andreas Meudt ,  Michael Erbes ,  Klaus Forstinger

IPC: C07F007/02 ,  C07C017/266 ,  C07D213/72

CPC classification number: C07D307/12 ,  C07B37/04 ,  C07C1/26 ,  C07C41/16 ,  C07C41/26 ,  C07C41/30 ,  C07C45/59 ,  C07C45/68 ,  C07C319/20 ,  C07D213/50 ,  C07C15/44 ,  C07C323/22 ,  C07C43/23 ,  C07C43/205

Abstract: A process for preparing compounds of the formula (II), 1 where the substituents R1 to R5 are each independently H, CH3, straight-chain or branched C1-C8-alkyl, CH(OC1-C5-alkyl)2, CH(C1-C5-alkyl)(OC1-C5-alkyl), CH2(OC1-C5-alkyl), CH(CH3)(OC1-C5-alkyl), C1-C8-alkoxy, N(C1-C5-alkyl)2, phenyl, substituted phenyl, aryl, heteroaryl, S(C1-C5-alkyl) or a radical Caryl, alkyl, and the symbols X1 to 5 are each carbon or a maximum of two neighboring X1-5 are nitrogen or X1R1 and X2R2 together are O, NH, N(C1-C5-alkyl), N(CnullOnullC1-C5-alkyl), N(SiR3)2 or S, or where neighboring radicals R1 to R5 form the following structural unit, 2 where X6 to X9 and R6 to R9 have the same meaning as X1 to X5 and R1 to R5 which comprises reacting chloro- or fluoroaromatics of the formula (I) with carbon electrophiles and lithium metal.

Abstract translation: 一种制备式（II）化合物的方法，其中取代基R 1至R 5各自独立地为H，CH 3，直链或支链C 1 -C 8 - 烷基，CH（OC 1 -C 5 - 烷基） 2，CH（C1-C5-烷基）（OC1-C5-烷基），CH2（OC1-C5-烷基），CH（CH3）（OC1-C5-烷基），C1-C8-烷氧基，N（C1-C5 - 烷基）2，苯基，取代的苯基，芳基，杂芳基，S（C 1 -C 5 - 烷基）或基团羧基，烷基，符号X 1至5>各自为碳或最多两个相邻X < -5>是氮或X 1 R 1和X 2 R 2一起是O，NH，N（C 1 -C 5 - 烷基），N（C = O-C 1 -C 5 - 烷基） ，N（SiR 3）2或S，或其中相邻基团R 1至R 5形成以下结构单元，其中X 6至X 9和R 6至R 9具有 与X 1至X 5和R 1至R 5的含义相同，其包括使式（I）的氯代或氟代芳族化合物与碳亲电体和锂金属反应。

公开(公告)号：US20030220516A1

公开(公告)日：2003-11-27

申请号：US10425389

申请日：2003-04-29

Applicant: Clariant GmbH

Inventor： Steffen Haber ,  Andreas Meudt ,  Stefan Scherer ,  Frank Vollmueller

IPC: C07F005/02 ,  C07F005/04 ,  C07F007/02

CPC classification number: C07F5/025 ,  C07F3/02 ,  Y02P20/55

Abstract: Compounds of the formula (I) 1 in which Q1 and Q2 are each OH or form a trimeric boric anhydride, Z is CHO, CH2Y, X or a protected aldehyde group, and X is CN, COOH, COCl, CONH2 or C(OR)3, and Y is OH or NH2, and Z is in the o-, m- or p-position to the boronic acid radical, are prepared by a) reacting a compound of the formula (II) 2 nullwith Mg in the presence of an anthracene compound and, if desired, a transition-metal halide and, if desired, an Mg halide or in the presence of a transition-metal halide and, if desired, an Mg halide, to give the corresponding arylmagnesium chloride, b) reacting the latter with a borate of the formula B(ORnull)3 and hydrolyzing the product, with removal of the aldehyde protecting group, c) and, if desired, oxidizing or reducing the free aldehyde group.

Abstract translation: 其中Q 1和Q 2各自为OH或形成三聚硼酸酐的式（I）化合物，Z为CHO，CH2Y，X或受保护的醛基，X为CN，COOH，COCl， CONH2或C（OR）3，Y是OH或NH2，Z与硼酸基的邻位，间位或对位是通过以下方法制备的：a）使式（II）的化合物与 Mg的存在下，如果需要，可以使用过渡金属卤化物，如果需要，可以使用卤化镁或过渡金属卤化物，如果需要的话，还可以使用卤化镁，得到相应的芳基镁 氯化物，b）使后者与式B（OR'）3的硼酸酯反应并水解产物，除去醛保护基，c），如果需要，氧化或还原游离醛基。

公开(公告)号：US20030069420A1

公开(公告)日：2003-04-10

申请号：US10210435

申请日：2002-08-01

Applicant: Clariant GmbH

Inventor： Manfred Koch ,  Detlef Wehle ,  Stefan Scherer ,  Klaus Forstinger ,  Andreas Meudt

IPC: C07F001/00

CPC classification number: C07F5/02 ,  C07F5/025 ,  C07F5/027

Abstract: Process for preparing arylboron and alkylboron compounds of the formulae (II) and (III) by reacting lithioaromatics and lithiated aliphatics of the formula (I) with boron compounds in microreactors in accordance with equation I or equation II, 1 where Xnullidentical or different radicals, nnull1, 2 or 3, and Rnullstraight-chain or branched C1-C6-alkyl, substituted C1-C6-alkyl, phenyl substituted by a radical or substituted or unsubstituted 6-membered heteroaryl containing one or two nitrogen atoms, or 5-membered heteroaryl containing one or two heteroatoms, or a substituted or unsubstituted bicyclic or tricyclic aromatic, in one or more coolable/heatable microreactors connected in series whose outlet channels are, if necessary, connected to capillaries or flexible tubes which are a number of meters in length, with the reaction solutions being intensively mixed during a sufficient residence time. The reaction is preferably carried out at temperatures in the range from null60null C. to null30null C.

Abstract translation: 通过使式（I）的锂离子化学和锂化脂族化合物与微量反应器中的硼化合物按照式I或式II反应制备式（II）和（III）的芳基硼和烷基硼化合物的方法，其中X =相同或不同的基团 n = 1,2或3，R =直链或支链C 1 -C 6 - 烷基，取代的C 1 -C 6 - 烷基，被含有一个或两个氮原子的自由基或取代或未取代的6元杂芳基取代的苯基， 或含有一个或两个杂原子的五元杂芳基，或取代或未取代的双环或三环芳族，在一个或多个串联连接的可冷却/可加热的微反应器中，如果需要，其出口通道连接到作为数字的毛细管或柔性管 长度为米，反应溶液在足够的停留时间内强烈混合。 反应优选在-60℃至+ 30℃的温度下进行。

公开(公告)号：US20020010332A1

公开(公告)日：2002-01-24

申请号：US09897566

申请日：2001-07-02

Applicant: Clariant GmbH

Inventor： Frank Vollmuller ,  Andreas Meudt ,  Stefan Scherer

IPC: C07F005/04 ,  C07F007/02

CPC classification number: C07F5/025

Abstract: A process for purifying formylphenylboronic acids of the formula (I) 1 where the formyl function is located in the ortho, meta or para position relative to the boronic acid function, by dissolving the crude formylphenylboronic acids in an alkaline solvent having a pH in the range from 8 to 11 separating off the insoluble organic impurities and subsequently acidifying the alkaline boronic acid solution and separating off and working up the precipitated boronic acid. The crude formylphenylboronic acid is preferably dissolved in aqueous alkali metal or alkaline earth metal oxide, hydroxide, carbonate or phosphate solutions at temperatures in the range from 5 to 50null C. The formylphenylboronic acids obtained have a purity of null99% and are suitable as precursors for liquid-crystalline compounds, as liquid crystals or as constituents of liquid-crystalline mixtures or as pharmaceutical intermediates.

Abstract translation: 通过将粗甲酰基苯基硼酸溶解在碱性溶剂中，其中pH为在下列范围内，其中甲酰基官能位于相对于硼酸官能团的邻位，间位或对位的式（I）的甲酰基苯基硼酸的方法 分离出不溶性有机杂质，然后酸化碱性硼酸溶液，分离和处理沉淀的硼酸。 粗甲酰基苯基硼酸优选在5至50℃的温度范围内溶解在碱金属或碱土金属氧化物，氢氧化物，碳酸盐或磷酸盐水溶液中。所得甲酰基苯基硼酸的纯度> 99％，适用于 液晶化合物的前体，液晶或液晶混合物的成分或药物中间体