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。

公开(公告)号：US5814508A

公开(公告)日：1998-09-29

申请号：US910260

申请日：1997-08-13

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.-nitrile-carboxylic 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，首先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的组合（在水溶液中将ω-腈 - 羧酸的铵盐转化为ω-腈 - 羧酸的铵盐， EC 4.2.1.84）和酰胺酶（EC 3.5.1.4）活动。 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：US5652362A

公开(公告)日：1997-07-29

申请号：US643819

申请日：1996-05-06

Applicant: Pine-Sci Kuo ,  Shiao-Jung Chu ,  Chu-Ching Dai ,  Ching-Tang Lin ,  Hsi-Yen Hsu

Inventor： Pine-Sci Kuo ,  Shiao-Jung Chu ,  Chu-Ching Dai ,  Ching-Tang Lin ,  Hsi-Yen Hsu

IPC: C07D201/08

CPC classification number: C07D201/08

Abstract: A method of making caprolactam from aminohexanoic acid or aminohexanoate ester comprising the steps of: (a) obtaining a reactor containing at least one catalyst, the catalyst being a metal oxide having acid-base-paired active sites; (b) charging a reaction feed into the reactor, the reaction feed containing a reactant, which is either amniohexanoic acid or C.sub.1 to C.sub.12 alkyl aminohexanoate ester, and a solvent; (c) reacting the reaction feed at a reaction temperature between 140.degree. and 300.degree. C. and a reaction pressure between 10 and 100 atm, to form a product stream; and (d) separating caprolactam from the product stream. The metal oxide catalyst is prepared from a process comprising the steps of: (a) dissolving at least a metal salt, which is not a metal oxide, in a solvent to form a metal salt solution, wherein: (i) the metal salt contains a metal element selected from the group consisting of silicon, titanium, tin, barium, calcium, magnesium, aluminum, and zinc; (ii) the solvent is selected from the group consisting of water, alcohol, ether, and mixtures thereof, and (iii) the metal salt is a salt which is soluble in the solvent; (b) adjusting the pH of the metal salt solution to be between 8 and 11, to thereby cause a precipitation of metal hydroxide; and (c) calcining the metal hydroxide at 300.degree. to 1,000.degree. C. to form a metal oxide.

Abstract translation: 一种由氨基己酸或氨基己酸酯制备己内酰胺的方法，包括以下步骤：（a）获得含有至少一种催化剂的反应器，该催化剂是具有酸碱配位活性位点的金属氧化物; （b）将反应进料装入反应器中，反应进料含有反应物，其为氨基己酸或C 1至C 12烷基氨基己酸酯，和溶剂; （c）使反应进料在140℃至300℃的反应温度和10至100atm的反应压力下反应，形成产物流; 和（d）从产物流中分离己内酰胺。 金属氧化物催化剂由包括以下步骤的方法制备：（a）将至少一种不是金属氧化物的金属盐溶解在溶剂中以形成金属盐溶液，其中：（i）金属盐包含 选自硅，钛，锡，钡，钙，镁，铝和锌的金属元素; （ii）溶剂选自水，醇，醚及其混合物，和（iii）金属盐是可溶于溶剂的盐; （b）将金属盐溶液的pH调节至8〜11，使金属氢氧化物析出; 和（c）在300-1,000℃下煅烧金属氢氧化物以形成金属氧化物。