公开(公告)号：US5618980A

公开(公告)日：1997-04-08

申请号：US640022

申请日：1996-04-30

申请人： Teruyuki Nagata ,  Chiyuki Kusuda ,  Masaru Wada ,  Kenichi Satou ,  Masae Uchida

发明人： Teruyuki Nagata ,  Chiyuki Kusuda ,  Masaru Wada ,  Kenichi Satou ,  Masae Uchida

IPC分类号： C07C209/00 ,  C07C209/28 ,  C07C209/52 ,  C07C209/68

CPC分类号： C07C209/00 ,  C07C209/28 ,  C07C209/52 ,  C07C209/68

摘要： Disclosed are (1) a method for preparing an aromatic secondary amino compound which comprises reacting an N-cyclohexylideneamino compound in the presence of a hydrogen moving catalyst and a hydrogen acceptor by the use of a sulfur-free polar solvent and/or a cocatalyst, and(2) a method for preparing an aromatic secondary amino compound which comprises reacting cyclohexanone or a nucleus-substituted cyclohexanone, an amine and a nitro compound corresponding to the amine in a sulfur-free polar solvent in the presence of a hydrogen moving catalyst, a cocatalyst being added or not added. In a further aspect, a method is provided for the preparation of aminodiphenylamine by reacting phenylenediamine and cyclohexanone in the presence of a hydrogen transfer catalyst in a sulfur-free polar solvent while using nitroaniline as a hydrogen acceptor.

摘要翻译： 公开的是（1）一种制备芳香族仲氨基化合物的方法，其包括在氢移动催化剂和氢受体存在下，通过使用无硫极性溶剂和/或助催化剂使N-亚环己基氨基化合物反应， 和（2）一种制备芳族仲氨基化合物的方法，其包括在氢移动催化剂存在下，在无硫极性溶剂中使环己酮或核取代的环己酮，对应于胺的胺和硝基化合物反应， 添加或不添加助催化剂。 在另一方面，提供了一种通过在氢转移催化剂存在下，在无硫极性溶剂中使苯二胺和环己酮反应制备氨基二苯胺的方法，同时使用硝基苯胺作为氢受体。

公开(公告)号：US5545752A

公开(公告)日：1996-08-13

申请号：US458294

申请日：1995-06-02

申请人： Teruyuki Nagata ,  Chiyuki Kusuda ,  Masaru Wada

发明人： Teruyuki Nagata ,  Chiyuki Kusuda ,  Masaru Wada

IPC分类号： C07C209/18 ,  C07C209/28

CPC分类号： C07C209/18 ,  C07C209/28

摘要： A processes for the preparation of diphenylamine or a nucleus-substituted derivative thereof, which comprise, upon feeding into a reaction system a phenol compound and reacting in the reaction system a cyclohexanone compound with an aniline compound in the presence of a hydrogen transfer catalyst and a catalytic amount of the cyclohexanone compound corresponding to the phenol compound while using the phenol compound as a hydrogen acceptor and forming the cyclohexanone compound in the reaction system, (1) conducting reaction while adding dropwise the aniline compound and (2) employing a hydroxide, carbonate or bicarbonate of an alkali metal and/or alkaline earth metal when the hydrogen transfer catalyst is one of noble metals of Group VIII of the periodic table, respectively.

摘要翻译： 一种二苯胺或其取代衍生物的制备方法，其包括在反应体系中加入酚化合物，并在氢转移催化剂存在下使反应体系中的环己酮化合物与苯胺化合物反应， 催化量的对应于酚化合物的环己酮化合物，同时使用酚化合物作为氢受体并在反应体系中形成环己酮化合物，（1）在滴加苯胺化合物的同时进行反应，和（2）使用氢氧化物，碳酸酯 或氢过渡催化剂分别为周期表第Ⅷ族贵金属之一时，碱金属和/或碱土金属的碳酸氢盐。

公开(公告)号：US5449829A

公开(公告)日：1995-09-12

申请号：US260903

申请日：1994-06-15

申请人： Chiyuki Kusuda ,  Masaru Wada ,  Teruyuki Nagata

发明人： Chiyuki Kusuda ,  Masaru Wada ,  Teruyuki Nagata

IPC分类号： C07C209/26 ,  C07C209/28 ,  C07C209/04

CPC分类号： C07C209/28 ,  C07C209/26

摘要： A diphenylamine with both the phenyl groups being substituted is prepared by reacting a phenol with ammonia in the presence of a hydrogen transfer catalyst and a cyclohexanone; or by converting a portion of the phenol to the cyclohexanone in the presence of a hydrogen transfer catalyst and under hydrogen pressure and then reacting the remaining portion of the phenol with ammonia in the presence of the cyclohexanone so converted and the hydrogen transfer catalyst. The diphenylamine can be obtained very efficiently.

摘要翻译： 具有两个苯基取代的二苯胺通过在氢转移催化剂和环己酮的存在下使苯酚与氨反应来制备; 或者通过在氢转移催化剂的存在下和在氢气压力下将一部分酚转化为环己酮，然后在所转化的环己酮和氢转移催化剂的存在下使酚的剩余部分与氨反应。 可以非常有效地获得二苯胺。

公开(公告)号：US5283365A

公开(公告)日：1994-02-01

申请号：US896696

申请日：1992-06-10

申请人： Teruyuki Nagata ,  Katsuji Watanabe ,  Yoshitsugu Kono ,  Akihiro Tamaki ,  Takashi Kobayashi

发明人： Teruyuki Nagata ,  Katsuji Watanabe ,  Yoshitsugu Kono ,  Akihiro Tamaki ,  Takashi Kobayashi

IPC分类号： C07C209/36

CPC分类号： C07C209/36

摘要： A process for the continuous preparation of aniline by hydrogenating nitrobenzene is disclosed which comprises the steps of suspending, in an aniline solvent, a catalyst of palladium or palladium-platinum which is deposited on a lipophilic carbon having an oil absorbency of at least 100, adding a zinc compound and an alkali metal carbonate or a zinc compound and an alkali metal bicarbonate as promotors to the reaction system, and carrying out reaction at a temperature of from 150 to 250.degree. C. substantially in the absence of water while aniline and water formed in said reaction are continuously distilled off as vapor from the reaction product, and the concentration of nitrobenzene in the reaction solution is maintained at 0.01% by weight or less.

摘要翻译： 公开了通过氢化硝基苯连续制备苯胺的方法，其包括以下步骤：在苯胺溶剂中悬浮沉积在吸油性至少为100的亲脂性碳上的钯或钯 - 铂催化剂，加入 锌化合物和碱金属碳酸盐或锌化合物和碱金属碳酸氢盐作为反应体系的促进剂，并且在150-250℃的温度下进行反应，基本上在不存在水的同时形成苯胺和水 在所述反应中作为蒸气从反应产物中连续蒸馏出来，反应溶液中硝基苯的浓度保持在0.01重量％以下。

公开(公告)号：US5194559A

公开(公告)日：1993-03-16

申请号：US854583

申请日：1992-03-20

申请人： Koju Okazaki ,  Masahiko Kusumoto ,  Hiroyuki Yamashita ,  Teruyuki Nagata

发明人： Koju Okazaki ,  Masahiko Kusumoto ,  Hiroyuki Yamashita ,  Teruyuki Nagata

IPC分类号： C08G18/38 ,  C08G18/70 ,  C08G18/77 ,  C08G18/80 ,  G02B1/04

CPC分类号： C08G18/8064 ,  C08G18/3876 ,  C08G18/70 ,  C08G18/775 ,  G02B1/04

摘要： Optical urethane resins according to the present invention are each obtained by reacting an active hydrogen compound with an isocyanate compound containing as a stabilizer a phenolic compound. Owing to their low yellowness, high light transmittance and optical-strain-free quality, these resins are useful as optical materials for plastic lenses or the like which are required to be colorless, transparent and uniform.

公开(公告)号：US4978792A

公开(公告)日：1990-12-18

申请号：US323087

申请日：1989-03-14

申请人： Teruyuki Nagata ,  Akihiro Tamaki ,  Katsuzi Watanabe ,  Akihiro Yamaguchi

发明人： Teruyuki Nagata ,  Akihiro Tamaki ,  Katsuzi Watanabe ,  Akihiro Yamaguchi

IPC分类号： C07C209/36

CPC分类号： C08G59/504 ,  C07C209/36

摘要： A commercially advantageous process for producing m- or p-aminobenzylamine is provided, which is characterized by subjecting m- or p-nitrobenzaldehyde and ammonia to catalytic reduction in the presence of a reducing catalyst in an organic solvent; in the reduction, when nitrobenzaldehyde and ammonia are in advance made a mixed solution in an organic solvent, and this solution is added in divided manner, the yield being further improved.

摘要翻译： 提供了一种商业上有利的生产对 - 或对氨基苄胺的方法，其特征在于在还原催化剂存在下在有机溶剂中使对 - 硝基苯甲醛和氨进行催化还原; 在还原时，预先将硝基苯甲醛和氨在有机溶剂中制成混合溶液，分开加入该溶液，进一步提高收率。

公开(公告)号：US4952731A

公开(公告)日：1990-08-28

申请号：US232011

申请日：1988-08-15

申请人： Teruyuki Nagata ,  Akihiro Tamaki ,  Nobuyuki Kajimoto ,  Masaru Wada

发明人： Teruyuki Nagata ,  Akihiro Tamaki ,  Nobuyuki Kajimoto ,  Masaru Wada

IPC分类号： C07C209/18 ,  C07C85/06

CPC分类号： C07C209/18

摘要： Diphenylamines or N,N'-diphenyl-phenylenediamines can be obtained by heat-reacting an aniline or a phenylenediamine with preferably an excess of a phenol in an amount of 4 to 20 moles per mole of the aniline or phenylenediamine in th presence of a hydrogen transfer catalyst and a cyclohexanone corresponding to said phenol.The excess phenol used in the reaction undergoes reduction in the reaction system to form a cyclohexanone, which in turn reacts with the aniline or phenylenediamine to form a Schiff base and is thus consumed. The Schiff base forms the intended product by means of a dehydrogenation reaction, and the hydrogen evolved at this time reduces the phenol to form a cyclohexanone.The phenol present in excess thus becomes in the system a solvent, a starting material for the cyclohexanone, and an acceptor of the hydrogen that forms as a by-product at the time of formation of the intended product. Hence, it becomes possible to obtain the intended product at a high selectivity from the anilines and phenylenediamines.The process of this invention is an advantageous process for the industrial production of especially the nuclearly substituted diphenylamines.

公开(公告)号：US4918186A

公开(公告)日：1990-04-17

申请号：US320228

申请日：1989-03-07

申请人： Nobuyuki Kajimoto ,  Teruyuki Nagata ,  Masaru Wada

发明人： Nobuyuki Kajimoto ,  Teruyuki Nagata ,  Masaru Wada

IPC分类号： C07D233/32 ,  C07D239/10 ,  C07D243/04 ,  C07D263/22

CPC分类号： C07D239/10 ,  C07D233/32 ,  C07D243/04 ,  C07D263/22

摘要： A process for producing a cyclic urea is provided. The process comprises reacting a diamine expressed by the formula (II)R-HN-R'-NH-R (II)wherein R represents hydrogen atom or a lower alkyl group and R' represent dimethylene group, a lower alkyl group-substituted dimethylene group, trimethylene group, a lower alkyl group-substituted trimethylene group, tetramethylene group, a lower alkyl group-substituted tetramethylene group, but a case where R represents hydrogen atom and R' represent dimethylene group, a case where R represents hydrogen atom and R' represents a lower alkyl group-substituted dimethylene group and a case where R represent methyl group and R' represents dimethylene group are excluded, with phosgene in the presence of a dehydrochlorinating agent. In the process, the diamine is first converted to its hydrochloride, followed by reacting the hydrochloride with phosgene in water solvent while maintaining a pH of the reaction liquid in the range of 5.0 to 8.0 by said dehydrochlorinating agent to obtain a cyclic urea expressed by the formula (I) ##STR1## wherein R and R' are each as defined above.

摘要翻译： 提供了一种制备环状尿素的方法。 该方法包括使由式（II）R-HN-R'-NH-R（II）表示的二胺反应，其中R表示氢原子或低级烷基，R'表示二亚甲基，低级烷基取代的二亚甲基 基团，三亚甲基，低级烷基取代的三亚甲基，四亚甲基，低级烷基取代的四亚甲基，但是R表示氢原子，R'表示二亚甲基的情况，R表示氢原子，R '表示低级烷基取代的二亚甲基，并且在脱氯化氢剂的存在下，光气被排除在外，R表示甲基，R'表示二亚甲基的情况。 在此过程中，首先将二胺转化为盐酸盐，然后将盐酸盐与光气在水溶剂中反应，同时用上述脱氯化氢将反应液的pH值保持在5.0〜8.0的范围内，得到由 式（I）其中R和R'各自如上所定义。

公开(公告)号：US4871875A

公开(公告)日：1989-10-03

申请号：US246014

申请日：1988-09-14

申请人： Teruyuki Nagata ,  Akihiro Tamaki ,  Nobuyuki Kajimoto ,  Masaru Wada

发明人： Teruyuki Nagata ,  Akihiro Tamaki ,  Nobuyuki Kajimoto ,  Masaru Wada

IPC分类号： C07C209/18

CPC分类号： C07C209/18

摘要： Diphenylamines or N,N'-diphenyl-phenylenediamines can be obtained by heat-reacting an aniline or a phenylenediamine with preferably an excess of a phenol in an amount of 4 to 20 moles per mole of the aniline or phenylenediamine in the presence of a hydrogen transfer catalyst and a cyclohexanone corresponding to said phenol.The excess phenol used in the reaction undergoes reduction in the reaction system to form a cyclohexanone, which in turn reacts with the aniline or phenylenediamine to form a Schiff base and is thus consumed. The Schiff base forms the intended product by means of a dehydrogenation reaction, and the hydrogen evolved at this time reduces the phenol to form a cyclohexanone.The phenol present in excess thus becomes in the system a solvent, a starting material for the cyclohexanone, and an acceptor of the hydrogen that forms as a by-product at the time of formation of the intended product. Hence, it becomes possible to obtain the intended product at a high selectivity from the anilines and phenylenediamines.The process of this invention is an advantageous process for the industrial production of especially the nuclearly substituted diphenylamines.

摘要翻译： 二苯胺或N，N'-二苯基 - 苯二胺可以通过使苯胺或苯二胺与优选过量的苯酚反应来获得，苯酚的量为4至20摩尔/摩尔苯胺或苯二胺在氢气存在下 转移催化剂和对应于所述苯酚的环己酮。 在反应中使用的过量苯酚经历还原反应体系以形成环己酮，该环己酮又与苯胺或苯二胺反应形成希夫碱，因此被消耗。 希夫碱通过脱氢反应形成预期的产物，此时放出的氢还原酚形成环己酮。 因此，过量存在的苯酚在体系中形成溶剂，环己酮的起始原料和在形成所需产物时形成副产物的氢的受体。 因此，可以从苯胺和苯二胺以高选择性获得目标产物。 本发明的方法是工业生产特别是核取代的二苯胺的有利方法。

公开(公告)号：US4804783A

公开(公告)日：1989-02-14

申请号：US80440

申请日：1987-07-31

申请人： Teruyuki Nagata ,  Akihiro Tamaki ,  Nobuyuki Kajimoto ,  Masaru Wada

发明人： Teruyuki Nagata ,  Akihiro Tamaki ,  Nobuyuki Kajimoto ,  Masaru Wada

IPC分类号： C07C209/18 ,  C07C85/06

CPC分类号： C07C209/18

摘要： Diphenylamines or N,N'-diphenyl-phenylenediamines can be obtained by heat-reacting an aniline or a phenylenediamine with preferably an excess of a phenol in an amount of 4 to 20 moles per mole of the aniline or phenylenediamine in the presence of a hydrogen transfer catalyst and a cyclohexanone corresponding to said phenol.The excess phenol used in the reaction undergoes reduction in the reaction system to form a cyclohexanone, which in turn reacts with the aniline or phenylenediamine to form a Schiff base and is thus consumed. The Schiff base forms the intended product by means of a dehydrogenation reaction, and the hydrogen evolved at this time reduces the phenol to form a cyclohexanone.The phenol present in excess thus becomes in the system a solvent, a starting material for the cyclohexanone, and an acceptor of the hydrogen that forms as a by-product at the time of formation of the intended product. Hence, it becomes possible to obtain the intended product at a high selectivity from the anilines and phenylenediamines.The process of this invention is an advantageous process for the industrial production of especially the nuclearly substituted diphenylamines.

摘要翻译： 二苯胺或N，N'-二苯基 - 苯二胺可以通过使苯胺或苯二胺与优选过量的苯酚反应来获得，苯酚的量为4至20摩尔/摩尔苯胺或苯二胺在氢气存在下 转移催化剂和对应于所述苯酚的环己酮。 在反应中使用的过量苯酚经历还原反应体系以形成环己酮，该环己酮又与苯胺或苯二胺反应形成希夫碱，因此被消耗。 希夫碱通过脱氢反应形成预期的产物，此时放出的氢还原酚形成环己酮。 因此，过量存在的苯酚在体系中形成溶剂，环己酮的起始原料和在形成所需产物时形成副产物的氢的受体。 因此，可以从苯胺和苯二胺以高选择性获得目标产物。 本发明的方法是工业生产特别是核取代的二苯胺的有利方法。