公开(公告)号：US6013816A

公开(公告)日：2000-01-11

申请号：US676032

申请日：1996-07-05

Applicant: Onko J. Gelling ,  Imre Toth

Inventor： Onko J. Gelling ,  Imre Toth

IPC: C07D201/08 ,  B01J31/22 ,  C07B61/00 ,  C07C51/235 ,  C07C51/373 ,  C07C55/14 ,  C07C59/147 ,  C07C67/347 ,  C07C69/716 ,  C07C227/08 ,  C07C229/08 ,  C07C255/17 ,  C07C227/00

CPC classification number: C07C255/17 ,  C07C51/373 ,  C07C67/347

Abstract: Process for the preparation of a linear .omega.-formyl-carboxylic acid or a corresponding linear formylnitrile compound starting from an internally unsaturated C.sub.4 -C.sub.12 carboxylic acid or a corresponding ester or nitrile by means of hydroformylation in the presence of carbon monoxide, hydrogen and a catalyst system, wherein the hydroformylation is carried out in an aqueous medium and in that the catalyst system comprises platinum and a water-soluble organic bidentate ligand.

Abstract translation: 在一氧化碳，氢气和催化剂存在下通过加氢甲酰化从内部不饱和C4-C12羧酸或相应的酯或腈开始制备线性ω-甲酰基羧酸或相应的线性甲酰腈化合物的方法 系统，其中加氢甲酰化在水性介质中进行，并且催化剂体系包含铂和水溶性有机二齿配位体。

公开(公告)号：US5952493A

公开(公告)日：1999-09-14

申请号：US202094

申请日：1998-12-09

Applicant: Eberhard Fuchs

Inventor： Eberhard Fuchs

IPC: C07D201/08 ,  C07D201/16 ,  C07D223/10

CPC classification number: C07D201/16

Abstract: Crude caprolactam is purified by reaction with a complex hydride of boron or of aluminum.

Abstract translation: PCT No.PCT / EP98 / 03098 371 1998年12月9日第 102（e）日期1998年12月9日PCT提交1997年6月13日PCT公布。 公开号WO97 / 47596 日期1997年12月18日粗制己内酰胺通过与硼或铝的复合氢化物反应而纯化。

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。

公开(公告)号：US5496941A

公开(公告)日：1996-03-05

申请号：US375410

申请日：1995-01-18

Applicant: Josef Ritz ,  Rolf Fischer ,  Werner Schnurr ,  Gu/ nther Achhammer ,  Hermann Luyken ,  Eberhard Fuchs

Inventor： Josef Ritz ,  Rolf Fischer ,  Werner Schnurr ,  Gu/ nther Achhammer ,  Hermann Luyken ,  Eberhard Fuchs

IPC: C07D201/08 ,  C07D201/16

CPC classification number: C07D201/16 ,  Y02P20/52

Abstract: Crude capronitrile is purified by hydrogenation, subsequent treatment in an acidic medium and subsequent distillation in an alkaline medium, by a process in which(a) 6-aminocapronitrile is converted into crude caprolactam by reaction with water,(b) high boilers and low boilers are separated off from the crude caprolactam from step (a),(c) the crude caprolactam from step (b) is treated with hydrogen at from 50.degree. to 150.degree. C. and from 1.5 to 250 bar in the presence of a hydrogenation catalyst and, if desired, of a solvent to give a mixture A,(d1) mixture A in a solvent is passed, at from 30.degree. to 80.degree. C. and from 1 to 5 bar, over an ion exchanger containing terminal acid groups to give a mixture B1, or(d2) mixture A is distilled in the presence of sulfuric acid, any solvent present being removed before the addition of the sulfuric acid, to give a mixture B2, and(e) mixture B1 or mixture B2 is distilled in the presence of a base to give pure caprolactam.

Abstract translation: 通过氢化纯化粗碳腈，随后在酸性介质中处理，随后在碱性介质中进行蒸馏，其中（a）通过与水反应将（a）6-氨基己腈转化为粗己内酰胺，（b）高锅炉和低锅炉 与步骤（a）中的粗己内酰胺分离，（c）步骤（b）中的粗己内酰胺在氢化催化剂存在下在50-150℃和1.5-250巴下用氢处理 并且如果需要，得到溶剂以得到混合物A，（d1）溶剂中的混合物A在30℃至80℃和1至5巴条件下通过含有末端酸基团的离子交换剂 得到混合物B1，或（d2）在硫酸存在下蒸馏混合物A，在加入硫酸之前，除去存在的任何溶剂，得到混合物B2，并且（e）蒸馏出混合物B1或混合物B2 在碱的存在下得到纯己内酰胺。

公开(公告)号：US5478950A

公开(公告)日：1995-12-26

申请号：US284545

申请日：1994-08-08

Applicant: Manfred Bergfeld ,  Gunter Wiesgickl

Inventor： Manfred Bergfeld ,  Gunter Wiesgickl

IPC: B01J23/86 ,  B01J29/035 ,  B01J29/08 ,  B01J29/83 ,  B01J29/85 ,  C07B61/00 ,  C07D201/08 ,  C07D207/267 ,  C07D315/00

CPC classification number: C07D315/00 ,  C07D201/08

Abstract: The invention relates to a process for producing pyrrolidone and N-alkyl pyrrolidones from saturated or unsaturated 1,4-dicarboxylic acids or their anhydrides, hydrogen, and a primary amine, characterized in that the dicarboxylic acid or its anhydride is allowed to react in an appropriate reactor with hydrogen or ammonia via a first catalyst bed and the unisolated intermediate product is subsequently reacted with the primary amine or ammonia directly via a second, downstream catalyst bed.

Abstract translation: PCT No.PCT / EP93 / 00239 Sec。 371日期1994年8月8日 102（e）日期1994年8月8日PCT提交1993年2月3日PCT公布。 出版物WO93 / 16042 日本公开日1993年8月19日。本发明涉及由饱和或不饱和1,4-二羧酸或其酸酐，氢和伯胺生产吡咯烷酮和N-烷基吡咯烷酮的方法，其特征在于二羧酸或其 使酸酐在合适的反应器中通过第一催化剂床与氢气或氨反应，然后将非分离的中间产物与伯胺或氨直接经由第二下游催化剂​​床反应。

公开(公告)号：US5434273A

公开(公告)日：1995-07-18

申请号：US191649

申请日：1994-02-04

Applicant: Hans-Juergen Weyer ,  Rolf Fischer

Inventor： Hans-Juergen Weyer ,  Rolf Fischer

IPC: C07D207/26 ,  C07D207/267 ,  C07D201/08 ,  C07D201/16

CPC classification number: C07D207/267

Abstract: The preparation of N-substituted 2-pyrrolidones (I) by the reaction of maleic acid, fumaric acid, or succinic acid or functional derivatives of these acids (compounds II) with a primary amine (III) or by the reaction of amides or imides derived from II and III under hydrogenating conditions in a synthesis stage followed by isolation, by distillation, of I and other volatile components from the resulting reaction mixture, in which the residues present following distillation are subjected to further hydrogenation treatment and the compound (I) thus formed is isolated by distillation.

Abstract translation: 通过马来酸，富马酸或琥珀酸或这些酸（化合物II）的官能衍生物与伯胺（III）的反应或通过酰胺或酰亚胺的反应制备N-取代的2-吡咯烷酮（I） 在合成阶段在氢化条件下衍生自II和III，然后通过蒸馏从所得反应混合物中分离I和其它挥发性组分，其中在蒸馏之后存在的残余物进行进一步氢化处理，化合物（I） 由此形成的蒸馏分离。