公开(公告)号：US06632964B2

公开(公告)日：2003-10-14

申请号：US09886215

申请日：2001-06-22

Applicant: Masaru Fujii ,  Tohru Setoyama

Inventor： Masaru Fujii ,  Tohru Setoyama

IPC: C07C51245

CPC classification number: C07D201/08 ,  B01J29/061 ,  B01J29/072 ,  B01J29/14 ,  C07C51/313 ,  Y02P20/588 ,  C07C59/147 ,  C07C55/14

Abstract: A process of producing an aliphatic aldehyde-acid (e.g., adipaldehyde-acid) and/or an aliphatic dicarboxylic acid (e.g., adipic acid) comprising oxidizing a cyclic ketone (e.g., cyclohexanone) with molecular oxygen in the presence of a fixed catalyst which comprises a composite of a carrier and at least one metal element belonging to the groups 4 to 11 of the Periodic Table supported on the carrier and has an acid amount of 0.06 mmol/g or more per unit weight of the carrier.

Abstract translation: 一种生产脂肪族醛酸（例如己二酸 - 酸）和/或脂族二羧酸（例如己二酸）的方法，包括在固定催化剂存在下用分子氧氧化环酮（例如环己酮） 包括载体和属于载体上的元素周期表第4至11族的至少一种金属元素的复合物，并且每单位载体的酸量为0.06mmol / g以上。

公开(公告)号：US06632951B2

公开(公告)日：2003-10-14

申请号：US10280622

申请日：2002-10-25

Applicant: Todd Werpy ,  John G. Frye, Jr. ,  Yong Wang ,  Alan H. Zacher

Inventor： Todd Werpy ,  John G. Frye, Jr. ,  Yong Wang ,  Alan H. Zacher

IPC: C07C207263

CPC classification number: C07D207/267 ,  C07D201/02 ,  C07D201/08

Abstract: The present invention provides methods for making N-methylpyrrolidine and analogous compounds via hydrogenation. Novel catalysts for this process, and novel conditions/yields are also described. Other process improvements may include extraction and hydrolysis steps. Some preferred reactions take place in the aqueous phase. Starting materials for making N-methylpyrrolidine may include succinic acid, N-methylsuccinimide, and their analogs.

Abstract translation: 本发明提供了通过氢化制备N-甲基吡咯烷和类似化合物的方法。 还描述了用于该方法的新型催化剂和新的条件/收率。 其他工艺改进可以包括提取和水解步骤。 一些优选的反应发生在水相中。 用于制备N-甲基吡咯烷的原料可包括琥珀酸，N-甲基琥珀酰亚胺及其类似物。

公开(公告)号：US20030114687A1

公开(公告)日：2003-06-19

申请号：US10280577

申请日：2002-10-25

Inventor： Todd Werpy ,  John G. Frye JR. ,  Yong Wang ,  Alan H. Zacher

IPC: C07D207/12

CPC classification number: C07D207/267 ,  C07D201/02 ,  C07D201/08

Abstract: The present invention provides methods for making N-methylpyrrolidine and analogous compounds via hydrogenation. Novel catalysts for this process, and novel conditions/yields are also described. Other process improvements may include extraction and hydrolysis steps. Some preferred reactions take place in the aqueous phase. Starting materials for making N-methylpyrrolidine may include succinic acid, N-methylsuccinimide, and their analogs.

公开(公告)号：US06579979B2

公开(公告)日：2003-06-17

申请号：US09860437

申请日：2001-05-21

Applicant: Philippe Leconte

Inventor： Philippe Leconte

IPC: C07D20116

CPC classification number: C07D201/08 ,  C07D201/16

Abstract: Lactam liquid media of reaction which comprise at least one lactam final product, notably &egr;-caprolactam, are treated and purified to convert impurities contained therein into harmless species or species easily removed downstream, by hydrogenating such liquid media of reaction in the presence of a hydrogenation catalyst and during which hydrogenation the liquid media of reaction have effective lactam-purifying amounts of ammonia dissolved therein.

公开(公告)号：US20020038022A1

公开(公告)日：2002-03-28

申请号：US09925730

申请日：2001-08-10

Inventor： Frank P.W. Agterberg ,  Nicolaas F. Haasen ,  Rudolf P.M Guit

IPC: C07D223/10

CPC classification number: C07D201/08

Abstract: Process for the preparation of null-caprolactam comprising treating 6-aminocaproic acid, 6-aminocaproate ester, 6-aminocaproamide, oligomers or polymers of these compounds or mixtures comprising at least two of these compounds in a cyclization reactor in the presence of superheated steam in which a gaseous product stream comprising null-caprolactam, lights and heavies is obtained, wherein the product stream, after condensation and at least partial removal of water and lights, is split into a null-caprolactam stream and a heavies stream containing heavies and null-caprolactam and the heavies stream is recycled to a cyclization reactor.

Abstract translation: 包括在过热蒸汽存在下在环化反应器中处理6-氨基己酸，6-氨基己酸酯，6-氨基己酰胺，这些化合物的低聚物或包含至少两种这些化合物的混合物的方法， 其中获得包含ε-己内酰胺，光和重质的气态产物流，其中在冷凝和至少部分除去水和光之后，产物流被分裂成ε-己内酰胺流和含有重质和ε-己内酰胺的重质流， 己内酰胺和重质物流再循环至环化反应器。

公开(公告)号：US20020030014A1

公开(公告)日：2002-03-14

申请号：US09860437

申请日：2001-05-21

Inventor： Philippe Leconte

IPC: C02F001/26

CPC classification number: C07D201/08 ,  C07D201/16

Abstract: Lactam liquid media of reaction which comprise at least one lactam final product, notably null-caprolactam, are treated and purified to convert impurities contained therein into harmless species or species easily removed downstream, by hydrogenating such liquid media of reaction in the presence of a hydrogenation catalyst and during which hydrogenation the liquid media of reaction have effective lactam-purifying amounts of ammonia dissolved therein.

Abstract translation: 包含至少一种内酰胺最终产物，特别是ε-己内酰胺的反应液体反应介质被处理和纯化，以将其中所含的杂质转化成无害物质或容易从下游去除的物质，通过在氢化存在下氢化这种反应液体介质 催化剂，在此期间氢化反应液体介质有有效的内酰胺纯化量溶于其中。

公开(公告)号：US6069246A

公开(公告)日：2000-05-30

申请号：US297016

申请日：1999-07-27

Applicant: Henri Chiarelli ,  Philippe Leconte

Inventor： Henri Chiarelli ,  Philippe Leconte

IPC: C07D201/08 ,  C07D201/16

CPC classification number: C07D201/08

Abstract: The present invention relates to the treatment of lactams obtained directly from their synthesis process, avoiding the formation of oligomers as far as possible. The invention consists, more precisely, of a process for treating a lactam using the reaction flow obtained from a cyclizing hydrolysis of an aminonitrile, characterized in that the reaction flow leaving the hydrolysis reactor is cooled, over a period of less than or equal to 1 hour, to a temperature below or equal to 150.degree. C. before it is fractionated.

Abstract translation: PCT No.PCT / FR97 / 01903 Sec。 371日期：1999年7月27日 102（e）1999年7月27日PCT 1997年10月23日PCT公布。 公开号WO98 / 17641 日期：1998年04月30日本发明涉及直接从其合成方法获得的内酰胺的处理，尽可能避免形成低聚物。 本发明更准确地说是使用由氨基腈的环化水解获得的反应流程来处理内酰胺的方法，其特征在于，离开水解反应器的反应流在小于或等于1的时间内被冷却 小时，然后分馏至低于或等于150℃的温度。

公开(公告)号：US5922589A

公开(公告)日：1999-07-13

申请号：US108729

申请日：1998-07-01

Applicant: Robert Di Cosimo ,  Robert Donald Fallon ,  John Edward Gavagan ,  Frank Edward Herkes

Inventor： Robert Di Cosimo ,  Robert Donald Fallon ,  John Edward Gavagan ,  Frank Edward Herkes

IPC: C07C255/19 ,  C07C255/23 ,  C07D201/08 ,  C07D207/26 ,  C07D211/76 ,  C07D223/10 ,  C12N9/78 ,  C12N9/88 ,  C12P13/00 ,  C12P17/10 ,  C12N1/20 ,  C12P17/12

CPC classification number: C07D211/76 ,  C07C255/19 ,  C07C255/23 ,  C07D201/08 ,  C07D207/26 ,  C07D223/10 ,  C12N9/78 ,  C12N9/88 ,  C12P13/002 ,  C12P13/02 ,  C12P17/10 ,  C12R1/01 ,  Y02P20/52

Abstract: A process for the preparation of five-membered or six-membered ring lactams from aliphatic .alpha., .omega.-dinitriles has been developed. In the process an aliphatic .alpha.,.omega.-dinitrile is first converted to an ammonium salt of an .omega.-nitrilecarboxylic acid in aqueous solution using a catalyst having an aliphatic nitrilase (EC 3.5.5.7) activity, or a combination of nitrile hydratase (EC 4.2.1.84) and amidase (EC 3.5.1.4) activities. The ammonium salt of the .omega.-nitrilecarboxylic acid is then converted directly to the corresponding lactam by hydrogenation in aqueous solution, without isolation of the intermediate .omega.-nitrilecarboxylic acid or .omega.-aminocarboxylic acid. When the aliphatic .alpha.,.omega.-dinitrile is also unsymmetrically substituted at the .alpha.-carbon atom, the nitrilase produces the .omega.-nitrilecarboxylic acid ammonium salt resulting from hydrolysis of the .omega.-nitrile group with greater than 98% regioselectivity, thereby producing only one of the two possible lactam products during the subsequent hydrogenation. A heat-treatment process to select for desirable regioselective nitrilase or nitrile hydratase activities while destroying undesirable activities is also provided.

Abstract translation: 已经开发了从脂肪族α，ω-二腈制备五元或六元环内酰胺的方法。 在该方法中，使用具有脂族腈水解酶（EC 3.5.5.7）活性的催化剂或腈水合酶（EC 4.2）的组合，首先将脂族α，ω-二腈转化为ω-二硝基甲酸的铵盐 .1.84）和酰胺酶（EC 3.5.1.4）活性。 然后通过在水溶液中氢化将ω-二硝基羧酸的铵盐直接转化成相应的内酰胺，而不分离中间体ω-二硝基甲酸或ω-氨基羧酸。 当脂肪族α，ω-二腈在α-碳原子处也不对称取代时，腈水解酶产生由ω-腈基水解产生的ω-亚硝基羧酸铵盐，其具有大于98％的区域选择性，从而仅产生 在随后氢化期间两种可能的内酰胺产物。 还提供了在破坏不期望的活性的同时选择期望的区域选择性腈水解酶或腈水合酶活性的热处理方法。

公开(公告)号：US5877314A

公开(公告)日：1999-03-02

申请号：US800324

申请日：1997-02-14

Applicant: Frank E. Herkes ,  Robert Pestman ,  Jeroen A.F. Boogers

Inventor： Frank E. Herkes ,  Robert Pestman ,  Jeroen A.F. Boogers

IPC: B01J23/46 ,  C07B61/00 ,  C07C227/08 ,  C07C229/08 ,  C07C231/14 ,  C07C237/06 ,  C07D201/08 ,  C07D201/02 ,  C07D201/16

CPC classification number: C07C231/14 ,  C07C227/08 ,  C07D201/08 ,  Y02P20/52

Abstract: This continuous process for preparing an aqueous mixture of .di-elect cons.-caprolactam and 6-aminocaproic acid and/or 6-aminocaproamide by involves, as the reductive amination step, continuously contacting 5-formylvaleric acid or an alkyl 5-formylvalerate in water as solvent with hydrogen and an excess of ammonia in the presence of a ruthenium on carrier, as a catalyst, wherein the carrier is at least one of titanium oxide or zirconium oxide. The aqueous mixture can be used to prepare .di-elect cons.-caprolactam.

Abstract translation: 这种用于制备+ 53-己内酰胺和6-氨基己酸和/或6-氨基己酰胺的水混合物的连续方法涉及作为还原胺化步骤，将5-甲酰基戊酸或5-甲酰基戊酸烷基酯在水中作为溶剂连续接触， 氢和过量的氨在载体上的钌存在下作为催化剂，其中载体是氧化钛或氧化锆中的至少一种。 含水混合物可用于制备+ 53-己内酰胺。

公开(公告)号：US5858736A

公开(公告)日：1999-01-12

申请号：US650073

申请日：1996-05-17

Applicant: Robert Di Cosimo ,  Robert Donald Fallon ,  John Edward Gavagan ,  Frank Edward Herkes

Inventor： Robert Di Cosimo ,  Robert Donald Fallon ,  John Edward Gavagan ,  Frank Edward Herkes

IPC: C07C255/19 ,  C07C255/23 ,  C07D201/08 ,  C07D207/26 ,  C07D211/76 ,  C07D223/10 ,  C12N9/78 ,  C12N9/88 ,  C12P13/00 ,  C12P17/10 ,  C12P17/12

CPC classification number: C07D211/76 ,  C07C255/19 ,  C07C255/23 ,  C07D201/08 ,  C07D207/26 ,  C07D223/10 ,  C12N9/78 ,  C12N9/88 ,  C12P13/002 ,  C12P13/02 ,  C12P17/10 ,  C12R1/01 ,  Y02P20/52

Abstract: A process for the preparation of five-membered or six-membered ring lactams from aliphatic .alpha.,.omega.-dinitriles has been developed. In the process an aliphatic .alpha.,.omega.-dinitrile is first converted to an ammonium salt of an .omega.-nitrilecarboxylic acid in aqueous solution using a catalyst having an aliphatic nitrilase (EC 3.5.5.7) activity, or a combination of nitrile hydratase (EC 4.2.1.84) and amidase (EC 3.5.1.4) activities. The aimnonium salt of the .omega.-nitrilecarboxylic acid is then converted directly to the corresponding lactam by hydrogenation in aqueous solution, without isolation of the intermediate .omega.-nitrilecarboxylic acid or .omega.-monocarboxylic acid. When the aliphatic .alpha.,.omega.-dinitrile is also unsymmetrically substituted at the .alpha.-carbon atom, the nitrilase produces the .omega.-nitrilecarboxylic acid ammonium salt resulting from hydrolysis of the .omega.-nitrile group with greater than 98% regioselectivity, thereby producing only one of the two possible lactam products during the subsequent hydrogenation. A heat-treatment process to select for desirable regioselective nitrilase or nitrile hydratase activities while destroying undesirable activities is also provided.

Abstract translation: 已经开发了从脂肪族α，ω-二腈制备五元或六元环内酰胺的方法。 在该方法中，使用具有脂族腈水解酶（EC 3.5.5.7）活性的催化剂或腈水合酶（EC 4.2）的组合，首先将脂族α，ω-二腈转化为ω-二硝基甲酸的铵盐 .1.84）和酰胺酶（EC 3.5.1.4）活性。 然后通过在水溶液中氢化将ω-二硝基甲酸的目的盐直接转化成相应的内酰胺，而不分离中间体ω-二硝基甲酸或ω-单羧酸。 当脂肪族α，ω-二腈在α-碳原子处也不对称取代时，腈水解酶产生由ω-腈基水解产生的ω-亚硝基羧酸铵盐，其具有大于98％的区域选择性，从而仅产生 在随后氢化期间两种可能的内酰胺产物。 还提供了在破坏不期望的活性的同时选择期望的区域选择性腈水解酶或腈水合酶活性的热处理方法。