公开(公告)号：US6075152A

公开(公告)日：2000-06-13

申请号：US286566

申请日：1999-04-05

申请人： Holger Geissler ,  Ralf Pfirmann

发明人： Holger Geissler ,  Ralf Pfirmann

IPC分类号： B01J31/24 ,  C07B61/00 ,  C07D311/76 ,  C07D311/74

CPC分类号： C07D311/76

摘要： The present invention relates to a process for preparing an isochroman-3-one of the formula (I) by reacting a 1,2-bishalomethylbenzene of the formula (II) ##STR1## in which X is chlorine, bromine or iodine with carbon monoxide and water at a CO pressure of from 0.1 to 50 MPa and a temperature of from 20 to 200.degree. C. in the presence or absence of an ionic halide, in the presence of a palladium catalyst and a dipolar aprotic solvent, where in the formulae (I) and (II) the radicals R.sup.1, R.sup.2, R.sup.3 and R.sup.4 independently of one another denote:a hydrogen or fluorine atom;a HO.sub.2 CCH.dbd.CH--, NC-- or F.sub.3 C group;an alkyl, alkoxy or acyloxy radical having in each case 1 to 18 carbon atoms; or a C.sub.6 -C.sub.18 -aryloxy, aryl or heteroaryl radical, where the heteroatoms present are 1 to 3 atoms from the group O, N and/or S;a R.sup.5.sub.2 P(.dbd.O)--, R.sup.6 C(.dbd.O)--, R.sup.6 OC(.dbd.O)--, R.sup.6 OC(.dbd.O)CH.dbd.CH--, R.sup.7 C(.dbd.O)--, R.sup.7 OC(.dbd.O)CH.dbd.CH-- or R.sup.7.sub.2 P(.dbd.O) radical; in which R.sup.5 is a C.sub.1 -C.sub.4 -alkyl radical, R.sup.6 is a C.sub.1 -C.sub.18 -alkyl radical and R.sup.7 is a C.sub.6 -C.sub.18 -aryl radical; or in which at least one of the radicals R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is substituted by a radical R.sup.8, where R.sup.8 has the same meaning as R.sup.1 ; or where at least two of the radicals R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are linked with one another and form at least one aliphatic or aromatic ring having 5 to 18 carbon atoms.

摘要翻译： 本发明涉及通过使式（II）的1,2-二沙甲基苯（其中X为氯，溴或碘）与一氧化碳和水反应制备式（I）的异苯并二氢吡喃-3-酮的方法， 在钯催化剂和偶极非质子传递溶剂存在下，在离子型卤化物存在或不存在下，在0.1至50MPa的CO压力和20至200℃的温度下，其中式（I） 和（II）基团R 1，R 2，R 3和R 4彼此独立地表示：氢或氟原子; HO2CCH = CH-，NC-或F3C组; 在每种情况下具有1至18个碳原子的烷基，烷氧基或酰氧基; 或C 6 -C 18芳氧基，芳基或杂芳基，其中存在的杂原子是基团O，N和/或S 1至3个原子; （= O） - ，R6C（= O） - ，R6OC（= O） - ，R6OC（= O）CH = CH-，R7C（= O） - ，R7OC（= O）CH = CH-或R72P （= O）基团; 其中R 5是C 1 -C 4 - 烷基，R 6是C 1 -C 18烷基，R 7是C 6 -C 18芳基; 或其中基团R 1，R 2，R 3和R 4中的至少一个被基团R 8取代，其中R 8具有与R 1相同的含义; 或者其中基团R 1，R 2，R 3和R 4中的至少两个彼此连接并形成至少一个具有5至18个碳原子的脂族或芳族环。

公开(公告)号：US06348603B1

公开(公告)日：2002-02-19

申请号：US09668915

申请日：2000-09-25

申请人： Holger Geissler ,  Ralf Pfirmann

发明人： Holger Geissler ,  Ralf Pfirmann

IPC分类号： C07D40700

CPC分类号： C07D311/76

摘要： The present invention relates to a process for the preparation of an isochroman-3-one of the formula (I) by reaction of a 1,2-bishalomethylbenzene of the formula (II) in which X is chlorine, bromine or iodine, with carbon monoxide and a compound of the formula (III) R5R6R7C—OH  (III) at a CO pressure of 0.1 to 50 MPa and a temperature of 20 to 200° C. in the presence or absence of an ionic halide, in the presence of a palladium catalyst and of a dipolar aprotic solvent, with addition of water or without addition of water, where in the formulae (I) and (II) the radicals R1, R2, R3 and R4 independently of one another are: a hydrogen or fluorine atom; an NC or F3C group; an alkyl, alkoxy or acyloxy radical, in each case having 1 to 18 carbon atoms; or a C6-C18-aryloxy, aryl or heteroaryl radical, where 1 to 3 atoms from the group consisting of O, N and/or S are present as heteroatoms; or in which at least two of the radicals R1, R2, R3 and R4 are linked to one another and form at least one aliphatic or aromatic ring having 5 to 18 carbon atoms, and in formula (III) the radicals R5, R6 and R7 are identical or different and are a C1-C18-alkyl, an HOC(═O)—, H3CC(═O)CH2— or (C6-C18-aryl)-CH2— radical or at least two of the radicals R5, R6 and R7 are linked to one another and form at least one aliphatic or aromatic ring having 5 to 18 carbon atoms.

摘要翻译： 本发明涉及一种制备式（I）的异苯并二氢吡喃-3-酮的方法，其中X为氯，溴或碘的式（Ⅱ）的1,2-二沙甲基苯与碳 一氧化碳和式（III）化合物在CO 2压力为0.1〜50MPa，温度为20〜200℃的条件下，在钯催化剂存在或不存在下，在钯催化剂和偶极 非质子溶剂，加入水或不加入水，其中在式（I）和（II）中，基团R 1，R 2，R 3和R 4彼此独立地为：氢或氟原子; NC或F3C组; 烷基，烷氧基或酰氧基，每种情况具有1至18个碳原子; 或C 6 -C 18芳氧基，芳基或杂芳基，其中以O，N和/或S为基的1至3个原子作为杂原子存在;或其中至少两个基团R 1，R 2，R 3和 R4彼此连接并形成至少一个具有5至18个碳原子的脂族或芳族环，并且在式（III）中，基团R 5，R 6和R 7相同或不同，为C 1 -C 18烷基，HOC （= O） - ，H 3 C（= O）CH 2 - 或（C 6 -C 18 - 芳基）-CH 2 - 基或基团R 5，R 6和R 7中的至少两个彼此连接并形成至少一个脂族或芳族 具有5至18个碳原子的环。

公开(公告)号：US06407029B1

公开(公告)日：2002-06-18

申请号：US09617470

申请日：2000-07-17

申请人： Berthold Schiemenz ,  Thomas Wessel ,  Ralf Pfirmann ,  Andreas Beck ,  Walter Hahn

发明人： Berthold Schiemenz ,  Thomas Wessel ,  Ralf Pfirmann ,  Andreas Beck ,  Walter Hahn

IPC分类号： B01J2714

CPC分类号： C07C45/63 ,  C07B39/00 ,  C07F9/572 ,  C07F9/59 ,  C07C47/55

摘要： The present invention relates to mixtures comprising from 70 to 99.5% by weight of a compound of the formula (R)4P+X− (1) and from 30 to 0.5% by weight of a compound of the formula (R)3P═O (2), where R is in each case a radical and X− is an inorganic or organic anion or the equivalent of a multiply charged inorganic or organic anion, also to a process for preparing the mixtures by reacting a phosphorus pentahalide with pyrrolidine or piperidine in the molar ratio 1:6 to 1:50 in the presence of an inert solvent initially at −20 to 80° C., subsequently continuing the reaction at 90 to 180° C., treating the resulting reaction product at 0 to 80° C. with aqueous alkali at a pH of 7 to 15, and separating aqueous and organic phase from one another, and to the use of the mixtures as catalyst and cocatalyst for phase-transfer reactions, nucleophilic substitution reactions or halogen-fluorine exchange reactions.

摘要翻译： 本发明涉及包含70-99.5重量％的式（R）4P + X-（1）的化合物和30至0.5重量％的式（R）化合物3P = O的混合物 （2），其中R在每种情况下是基团，X是无机或有机阴离子或相当于多电荷无机或有机阴离子，也是通过使五卤化磷与吡咯烷或哌啶反应制备混合物的方法 摩尔比1:6至1:50，最初在-20至80℃的惰性溶剂存在下，随后在90至180℃下继续反应，在0至80℃下处理所得反应产物 与碱水溶液在pH为7至15，并分离水相和有机相，并将混合物用作催化剂和助催化剂用于相转移反应，亲核取代反应或卤素 - 氟交换反应。

公开(公告)号：US5945556A

公开(公告)日：1999-08-31

申请号：US29414

申请日：1998-04-14

申请人： Theodor Papenfuhs ,  Ralf Pfirmann ,  Stefan Krause ,  Doris Neumann-Grimm

发明人： Theodor Papenfuhs ,  Ralf Pfirmann ,  Stefan Krause ,  Doris Neumann-Grimm

IPC分类号： C07C227/18 ,  C07C229/58 ,  C07C229/40

CPC分类号： C07C227/18

摘要： A process for preparing N-carboxymethylene-4-chloroanthranilic acid, and its dialkyl esters. The invention relates to a process for preparing N-carboxymethylene-4-chloroanthranilic acid and its dialkyl esters, which comprises reacting 2,4-dichlorobenzoic acid in the presence of a base, of a solvent and of a catalyst with glycine to give N-carboxymethylene-4-chloroanthranilic acid and, where appropriate, reacting the latter in the presence of a base and of a solvent with a dialkyl sulfate, dialkyl carbonate or alkyl halide to give the dialkyl ester.

摘要翻译： PCT No.PCT / EP69 / 03630 Sec。 371日期：1998年4月14日 102（e）1998年4月14日PCT PCT 1996年8月19日PCT公布。 出版物WO97 / 08129 日期1997年3月6日制备N-羧基亚甲基-4-氯邻氨基苯甲酸及其二烷基酯的方法。 本发明涉及一种制备N-羧基亚甲基-4-氯邻氨基苯甲酸及其二烷基酯的方法，其包括在碱，溶剂和催化剂与甘氨酸的存在下使2,4-二氯苯甲酸反应，得到N- 羧基亚甲基-4-氯邻氨基苯甲酸，并且在适当的情况下，使其在碱和溶剂的存在下与硫酸二烷基酯，碳酸二烷基酯或烷基卤反应，得到二烷基酯。

公开(公告)号：US5874608A

公开(公告)日：1999-02-23

申请号：US858357

申请日：1997-05-19

申请人： Ralf Pfirmann ,  Theodor Papenfuhs

发明人： Ralf Pfirmann ,  Theodor Papenfuhs

IPC分类号： C07B61/00 ,  C07C67/11 ,  C07C69/76 ,  C07C227/18 ,  C07C229/54 ,  C07C319/20 ,  C07C323/62

CPC分类号： C07C67/11

摘要： The present invention relates to a process for the preparation of compounds of the formula (1)R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 ArCOOR (1)in which R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are identical or different and are hydrogen, a halogen, an alkyl or alkoxy group having 1 to 6 carbon atoms or OR, NHR, NR.sub.2, SR or COOR, in which R is an alkyl radical having 1 to 4 carbon atoms, Ar is an aryl radical having 6 to 12 carbon atoms and the radical R shown in formula (1) has the above meaning, by reacting a compound of the formula (2)R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 ArCOOH (2)in which R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are identical or different and are hydrogen, a halogen, an alkyl or alkoxy group having 1 to 6 carbon atoms, OH, NH.sub.2, NHR, SH or COOH and Ar has the same meaning as in formula (1), with a sulfate of the formula (RO).sub.2 SO.sub.2, in which R has the above meaning, in the presence of a water-insoluble tertiary amine and water at a temperature of 10.degree. to 120.degree. C. in the presence or absence of a water-insoluble solvent and with the addition of a base, at a pH of 5 to 12.

摘要翻译： 本发明涉及制备式（1）化合物的方法，R1R2R3R4R5ArCOOR（1）其中R1，R2，R3，R4和R5相同或不同，为氢，卤素，烷基或烷氧基，其具有 1至6个碳原子或OR，NHR，NR 2，SR或COOR，其中R是具有1至4个碳原子的烷基，Ar是具有6至12个碳原子的芳基，并且式（1）中所示的基团R ）具有上述含义，通过使式（2）R 1 R 2 R 3 R 4 R 5 ArCOOH（2）的化合物与其中R 1，R 2，R 3，R 4和R 5相同或不同且为氢，卤素，烷基或烷氧基， 6个碳原子，OH，NH 2，NHR，SH或COOH和Ar的定义与式（1）中的含义相同，式（RO）2 SO 2的硫酸盐，其中R具有上述含义， 水不溶性叔胺和水，在存在或不存在水不溶性溶剂的情况下，在10〜120℃的温度下加入碱，在pH为 5至12。

公开(公告)号：US5663410A

公开(公告)日：1997-09-02

申请号：US554185

申请日：1995-11-06

申请人： Matthias Beller ,  Ralf Pfirmann

发明人： Matthias Beller ,  Ralf Pfirmann

IPC分类号： C07B53/00 ,  C07C253/30 ,  C07C253/34 ,  C07C255/37 ,  C07C255/07

CPC分类号： C07C253/34 ,  C07C255/37

摘要： The present invention relates to the compounds cis-4-(2,2,3,3-tetrafluoropropoxy)cinnamonitrile and trans-4-(2,2,3,3-tetrafluoropropoxy)cinnamonitrile and to a process for their preparation. The process relates to the preparation of cis-4-(2,2,3,3-tetrafluoropropoxy)cinnamonitrile and trans-4-(2,2,3,3-tetrafluoropropoxy)cinnamonitrile or optionally one of these two compounds, by fractionally distilling a mixture containing cis- and trans-4-(2,2,3,3-tetrafluoropropoxy)cinnamonitrile under reduced pressure, separating off a main fraction containing at least 80% by weight of cis-4-(2,2,3,3-tetrafluoropropoxy)cinnamonitrile and a main fraction containing at least 80% by weight of trans-4-(2,2,3,3-tetrafluoropropoxy)cinnamonitrile, further purifying these main fractions by means of fractional crystallization or melt crystallization or adjusting one of these main fractions by isomerization to the cis/trans isomer ratio corresponding to the particular thermodynamic equilibrium and returning it to the process and returning the remaining fractions to the process directly or after isomerization.

摘要翻译： 本发明涉及顺式-4-（2,2,3,3-四氟丙氧基）肉桂腈和反式-4-（2,2,3,3-四氟丙氧基）肉桂腈的化合物及其制备方法。 该方法涉及顺式-4-（2,2,3,3-四氟丙氧基）肉桂腈和反式-4-（2,2,3,3-四氟丙氧基）肉桂腈或任选的这两种化合物之一的制备 在减压下蒸馏含有顺式和反式-4-（2,2,3,3-四氟丙氧基）肉桂腈的混合物，分离出含有至少80重量％的顺式-4-（2,2,3,3-四氟丙氧基） ，3-四氟丙氧基）肉桂腈和含有至少80重量％反式-4-（2,2,3,3-四氟丙氧基）肉桂腈的主要馏分，通过分级结晶或熔融结晶或调节进一步纯化这些主要馏分 这些主要部分之一通过异构化到对应于特定热力学平衡的顺式/反式异构体比例并将其返回到该方法中，并将剩余部分直接或异构化后返回至该方法。

公开(公告)号：US5468863A

公开(公告)日：1995-11-21

申请号：US19096

申请日：1993-02-18

申请人： Ralf Pfirmann ,  Theodor Papenfuhs

发明人： Ralf Pfirmann ,  Theodor Papenfuhs

IPC分类号： B01J31/24 ,  C07B61/00 ,  C07D213/61 ,  C07D211/38

CPC分类号： C07D213/61

摘要： The invention relates to a novel process for the preparation of substituted 2,3-difluoropyridines by reaction of substituted 2,3-halopyridines with fluoride salts in the presence of phase transfer catalysts, preferably in polar aprotic solvents, without removing the resulting substituted 2,3-difluoropyridines continuously from the reaction mixture. The substituted 2,3-difluoropyridines which can be prepared according to the invention are, inter alia, starting materials for the preparation of plant protection agents or pharmaceuticals.

摘要翻译： 本发明涉及通过在相转移催化剂存在下，优选在极性非质子传递溶剂中使取代的2,3-卤代吡啶与氟化物盐反应来制备取代的2,3-二氟吡啶的新方法， 从反应混合物中连续加入3-二氟吡啶。 可根据本发明制备的取代的2,3-二氟吡啶类尤其是用于制备植物保护剂或药物的原料。

公开(公告)号：US5304655A

公开(公告)日：1994-04-19

申请号：US126794

申请日：1993-09-24

申请人： Theodor Papenfuhs ,  Ralf Pfirmann

发明人： Theodor Papenfuhs ,  Ralf Pfirmann

IPC分类号： C07D209/48

CPC分类号： C07D209/48

摘要： Compounds of the formula ##STR1## in which X is the radical ##STR2## where R.sub.1 and R.sub.2 are in each case a hydrogen atom, an alkyl-(C.sub.1 -C.sub.10) group, aryl group, alkyl(C.sub.1 -C.sub.6)-CO group or aryl-CO group, where the aryl or aryl-CO group in the case of R.sub.1 and R.sub.2 can be substituted on the aromatic ring by fluorine and/or chlorine atoms and/or alkyl(C.sub.1 -C.sub.4) groups, or R.sub.1 and R.sub.2 together are a phthaloyl radical which can be substituted on the aromatic ring by 4 chlorine atoms or 4 fluorine atoms, or where X is the radical ##STR3## which can be substituted on the aromatic ring by fluorine and/or chlorine atoms and/or alkyl(C.sub.1 -C.sub.4) groups, and processes for their preparation.

摘要翻译： 式（1）的化合物，其中X是基团，其中R 1和R 2各自为氢原子，烷基 - （C 1 -C 10）基团，芳基，烷基（C 1 -C 6） -CO基或芳基-CO基，其中在R1和R2的情况下的芳基或芳基-CO基可以在芳环上被氟和/或氯原子和/或烷基（C1-C4）基团取代，或 R1和R2一起是可以在芳环上被4个氯原子或4个氟原子取代的邻苯二甲酰基，或其中X是可以在芳环上被氟和/或氯原子取代的基团， /或烷基（C 1 -C 4）基团，及其制备方法。

公开(公告)号：US5227535A

公开(公告)日：1993-07-13

申请号：US957674

申请日：1992-10-07

申请人： Ralf Pfirmann ,  Theodor Papenfuhs ,  Klaus Forstinger

发明人： Ralf Pfirmann ,  Theodor Papenfuhs ,  Klaus Forstinger

IPC分类号： C07C201/12 ,  C07C205/26

CPC分类号： C07C201/12

摘要： The present invention relates to a process for the preparation of isomerically pure 2-nitro-5-fluoro- or -5-chlorophenol, by reacting 2,4-difluoronitrobenzene or 2,4-dichloronitrobenzene with aqueous alkali metal or alkaline earth metal hydroxide solution or suspension in the absence of organic solvents or other solubility promoting substances at temperatures from about 20.degree. C. to about 190.degree. C., adjusting the pH of the reaction mixture to about 1 to about 6 by the addition of acid, steam distilling the resultant product and isolating it from the distillate after cooling.

摘要翻译： 本发明涉及通过2,4-二氟硝基苯或2,4-二氯硝基苯与碱金属或碱土金属氢氧化物水溶液的反应来制备异构纯的2-硝基-5-氟 - 或-5-氯苯酚的方法 或在约20℃至约190℃的温度下不存在有机溶剂或其它促溶解物质的悬浮液，通过加入酸将反应混合物的pH调节至约1至约6，蒸馏蒸馏 冷却后将其与馏出物分离。

公开(公告)号：US5849959A

公开(公告)日：1998-12-15

申请号：US763758

申请日：1996-12-11

申请人： Ralf Pfirmann ,  Rainer Wingen

发明人： Ralf Pfirmann ,  Rainer Wingen

IPC分类号： B01J23/72 ,  C07B61/00 ,  C07C37/00 ,  C07C37/62 ,  C07C39/24 ,  C07C39/26 ,  C07C39/27 ,  C07C41/18 ,  C07C43/225 ,  C07C41/00

CPC分类号： C07C39/27 ,  C07C43/225

摘要： The present invention relates to compounds of the formula (1) ##STR1## where R is H, a straight-chain or branched alkyl radical with 1 to 6 carbons, a fluorinated straight-chain or branched alkyl radical with 1 to 6 carbons, a benzyl radical, or a benzyl radical substituted by an alkyl group or alkoxy group with 1 to 4 carbons each, or by halogen, X is H, Cl, Br or I, and X is different from R, and a process for their preparation.

摘要翻译： 本发明涉及式（1）的化合物：其中R是H，具有1至6个碳的直链或支链烷基，具有1至6个碳原子的氟化直链或支链烷基 碳原子，苄基或被各自具有1至4个碳的烷基或烷氧基取代的苄基或卤素，X是H，Cl，Br或I，并且X不同于R 他们的准备。