公开(公告)号：US6066490A

公开(公告)日：2000-05-23

申请号：US987938

申请日：1997-12-10

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 ,  C12N1/12

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：US5973143A

公开(公告)日：1999-10-26

申请号：US141406

申请日：1998-08-21

Applicant: Rudolf P. M. Guit ,  Samuel L. Lane ,  Wim Buijs

Inventor： Rudolf P. M. Guit ,  Samuel L. Lane ,  Wim Buijs

IPC: C07D201/08

CPC classification number: C07D201/08

Abstract: Process to prepare .epsilon.-caprolactam starting from a liquid aqueous mixture containing an alcohol and 6-aminocaproic acid by cyclization of 6-aminocaproic acid in the aqueous mixture at an elevated temperature. The alcohol is separated from the starting aqueous mixture before performing the cyclization to such extent that the concentration of alcohol in the aqueous mixture during the cyclization is less than 1 wt. %. The advantages include reduced amounts of undesirable by-product.

Abstract translation: 通过在高温下在含水混合物中环化6-氨基己酸，从含有醇和6-氨基己酸的液体含水混合物中制备ε-己内酰胺的方法。 在进行环化之前，将醇与起始含水混合物分离，使得环化过程中含水混合物中醇的浓度小于1wt。 ％。 优点包括减少不希望的副产物的量。

公开(公告)号：US5925754A

公开(公告)日：1999-07-20

申请号：US956745

申请日：1997-10-23

Applicant: John Michael Maher ,  David Robert Bryant ,  Johnathan Eugene Holladay ,  Thomas Carl Eisenschmid ,  John Robert Briggs ,  Kurt Damar Olson

Inventor： John Michael Maher ,  David Robert Bryant ,  Johnathan Eugene Holladay ,  Thomas Carl Eisenschmid ,  John Robert Briggs ,  Kurt Damar Olson

IPC: E02B5/08 ,  C02F1/00 ,  C07C29/16 ,  C07C45/49 ,  C07C45/50 ,  C07C45/68 ,  C07C47/19 ,  C07D201/02 ,  C07D201/08 ,  C07D213/16 ,  C07D213/30 ,  C07D213/55 ,  C07F9/6574 ,  C08G69/02 ,  C08G69/14 ,  C08G69/36 ,  C07D223/10

CPC classification number: C07D201/02 ,  C07C45/49 ,  C07C45/50 ,  C07C45/68 ,  C07C47/19 ,  C07D201/08 ,  C07F9/65744 ,  C08G69/02 ,  C08G69/14 ,  C08G69/36 ,  Y02P20/582

Abstract: This invention relates to a composition comprising (a) epsilon caprolactam and (b) one or more of 5-�4,5-di(3-carboxypropyl)-2-pyridyl!pentanoic acid or salt or amide, 4-�4,5-di(2-carboxypropyl)-2-pyridyl!-2-methylbutanoic acid or salt or amide, 2-�2-(2-carboxybutyl)-5-(1-carboxypropyl)-4-pyridyl!butanoic acid or salt or amide, 5-�3,5-di(3-carboxypropyl)-2-pyridyl!pentanoic acid or salt or amide, 4-�3,5-di(2-carboxypropyl)-2-pyridyl!-2-methylbutanoic acid or salt or amide, 2-�-2-(2-carboxybutyl)-5-(1-carboxypropyl)-3-pyridyl!butanoic acid or salt or amide, 5-amino-4-methylpentanamide, 4-amino-3-ethylbutanamide, 5-�4,5-di(4-hydroxybutyl)-2-pyridyl!pentanol, 4-�4,5-di(2-methoxypropyl)-2-pyridyl!-2-methylbutanol, 2-�2-(2-methoxybutyl)-5-(1-methoxypropyl)-4-pyridyl!butanol, 5-�3,5-di(4-hydroxybutyl)-2-pyridyl!pentanol, 4-�3,5-di(2-methoxypropyl)-2-pyridyl!-2-methylbutanol, 2-�2-(2-methoxybutyl)-5-(1-methoxypropyl)-3-pyridyl!butanol, 5-amino-4-methyl-1-pentanol, 5-imino-2-methyl-1-pentanamine, 5-amino-2-methyl-1-pentanol, 5-imino-4-methyl-1-pentanamine and 2-butyl-4,5-dipropylpyridine, wherein the weight ratio of component (a) to component (b) is at least about 99 to 1. The epsilon caprolactam compositions are useful in the preparation of nylon 6.

Abstract translation: 本发明涉及包含（a）ε-己内酰胺和（b）一种或多种5- [4,5-二（3-羧丙基）-2-吡啶基]戊酸或其盐或酰胺的组合物，4- [ 2-（2-羧基丙基）-2-吡啶基] -2-甲基丁酸或盐或酰胺，2- [2-（2-羧基丁基）-5-（1-羧基丙基）-4-吡啶基]丁酸或盐 或酰胺，5- [3,5-二（3-羧丙基）-2-吡啶基]戊酸或盐或酰胺，4- [3,5-二（2-羧丙基）-2-吡啶基] -2-甲基丁酸 酸或盐或酰胺，2- [ - 2-（2-羧丁基）-5-（1-羧基丙基）-3-吡啶基]丁酸或盐或酰胺，5-氨基-4-甲基戊酰胺，4-氨基-3 乙基丁酰胺，5- [4,5-二（4-羟丁基）-2-吡啶基]戊醇，4- [4,5-二（2-甲氧基丙基）-2-吡啶基] -2-甲基丁醇，2- [2 - （2-甲氧基丁基）-5-（1-甲氧基丙基）-4-吡啶基]丁醇，5- [3,5-二（4-羟基丁基）-2-吡啶基]戊醇，4- [3,5-二 2-甲氧基丙基）-2-吡啶基] -2-甲基丁醇，2- [2-（2-甲氧基丁基）-5-（1-甲氧基丙基）-3-吡啶基]丁醇，5-氨基-4-甲基-1-戊醇 ，5-亚氨基-2-甲基-1-戊酰胺 5-氨基-2-甲基-1-戊醇，5-亚氨基-4-甲基-1-戊胺和2-丁基-4,5-二丙基吡啶，其中组分（a）与组分（b）的重量比为 至少约99至1。ε-己内酰胺组合物可用于制备尼龙6。

公开(公告)号：US5780623A

公开(公告)日：1998-07-14

申请号：US605883

申请日：1996-02-23

Applicant: Rudolf P.M. Guit ,  Samuel L. Lane ,  Wim Buijs

Inventor： Rudolf P.M. Guit ,  Samuel L. Lane ,  Wim Buijs

IPC: C07D201/08

CPC classification number: C07D201/08

Abstract: Process to prepare .epsilon.-caprolactam starting from a liquid aqueous mixture containing an alcohol and 6-aminocaproic acid by cyclization of 6-aminocaproic acid in the aqueous mixture at an elevated temperature. The alcohol is separated from the starting aqueous mixture before performing the cyclization to such extent that the concentration of alcohol in the aqueous mixture during the cyclization is less than 1 wt. %. The advantages include reduced amounts of undesirable by-product.

公开(公告)号：US5717089A

公开(公告)日：1998-02-10

申请号：US616748

申请日：1996-03-15

Applicant: Henricus F. W. Wolters ,  Samuel L. Lane ,  Wim Buijs ,  Frank E. Herkes ,  Nicolaas F. Haasen

Inventor： Henricus F. W. Wolters ,  Samuel L. Lane ,  Wim Buijs ,  Frank E. Herkes ,  Nicolaas F. Haasen

IPC: C07D201/08

CPC classification number: C07D201/08

Abstract: Process for the preparation of .epsilon.-caprolactam starting from an aldehyde compound comprising at least one member from among 5-formylvaleric acid, ester or amide in which the aldehyde compound is allowed to react in the presence of ammonia and hydrogen and a subsequent cyclization of the reaction products thus formed (.epsilon.-caprolactam-precursors) to .epsilon.-caprolactam is performed in the presence of water, involved the combination of steps (a) contacting the 5-formylvaleric acid, ester or amide with ammonia and water under non-hydrogenation conditions, (b) contacting the resulting mixture of step (a) with hydrogen in the presence of ammonia under hydrogenation conditions, wherein the water content is greater than 10 wt. %, (c) heating the resulting mixture of step (b) at a temperature between 200.degree. and 350.degree. C. in order to convert the reaction products of step (b) to .epsilon.-caprolactam.

Abstract translation: 从含有至少一种甲酰戊酸，酯或酰胺的成分的醛化合物制备ε-己内酰胺的方法，其中使醛化合物在氨和氢的存在下反应，随后环化 如此形成的（ε-己内酰胺前体）与ε-己内酰胺的反应产物在水的存在下进行，涉及步骤（a）在非氢化条件下使5-甲酰基戊酸，酯或酰胺与氨和水接触 ，（b）在氢气条件下，在氨的存在下使所得步骤（a）的混合物与氢气接触，其中水含量大于10wt。 ％，（c）在200-350℃的温度下加热步骤（b）的所得混合物，以将步骤（b）的反应产物转化成ε-己内酰胺。

公开(公告)号：US5495016A

公开(公告)日：1996-02-27

申请号：US358411

申请日：1994-12-19

Applicant: Gunther Achhammer ,  Eberhard Fuchs

Inventor： Gunther Achhammer ,  Eberhard Fuchs

IPC: C07D201/08 ,  C07D223/10

CPC classification number: C07D201/08 ,  Y02P20/584

Abstract: Caprolactam is prepared by reacting a solution of 6-aminocapronitrile with water in the liquid phase at elevated temperatures by a process in which(a) an aqueous solution of 6-aminocapronitrile in the liquid phase is heated without the addition of a catalyst in a reactor A to give a mixture I consisting essentially of water, caprolactam and a high-boiling fraction (high boiler), then(b) the water is removed from the resulting mixture I to give a mixture II consisting essentially of caprolactam and the high boilers, then(c) the caprolactam and the high boilers from mixture II are separated from one another by distillation, and then either(d1) the high boilers from stage (c) are fed into the reactor A of stage (a) or(d2) the high boilers are heated similarly to stage (a) in a further reactor B and then worked up similarly to stages (b) and (c) to give further caprolactam, or(d3) the high boilers are heated under reduced pressure in the presence of a base in a reactor C and the reacted mixture is worked up by distillation to give caprolactam.

Abstract translation: 己内酰胺通过以下方法制备：在高温下使6-氨基己腈与水在液相中反应，其中（a）将液相中的6-氨基己腈水溶液加热而不在反应器中加入催化剂 A得到基本上由水，己内酰胺和高沸点馏分（高锅炉）组成的混合物I，然后（b）从所得混合物I中除去水，得到基本上由己内酰胺和高锅炉组成的混合物II， 然后（c）通过蒸馏将己内酰胺和来自混合物II的高沸点物彼此分离，然后（d1）将来自阶段（c）的高沸点物（d）进料到步骤（a）或（d2）的反应器A中， 类似于在另一个反应器B中的阶段（a）类似地加热高锅炉，然后类似于阶段（b）和（c）进行加工以得到进一步的己内酰胺，或（d3）在存在下在减压下加热高锅炉 的反应器C和反应器中的碱 通过蒸馏处理混合物以得到己内酰胺。

公开(公告)号：US5493021A

公开(公告)日：1996-02-20

申请号：US360623

申请日：1994-12-21

Applicant: David Barratt ,  Laurent Gilbert

Inventor： David Barratt ,  Laurent Gilbert

IPC: C07D223/12 ,  B01J27/18 ,  B01J27/195 ,  C07D201/02 ,  C07D201/08

CPC classification number: C07D201/08 ,  Y02P20/52

Abstract: Lactams, in particular epsilon-caprolactam (a basic starting material for the production of nylon 6), are selectively prepared by cyclizing/reacting the corresponding aminonitriles with water, in the presence of a catalytically effective amount of a deactivation-resistant solid metal phosphate having the general formula (II):MH.sub.h (PO.sub.4).sub.n .multidot.(Imp).sub.pin which M is a divalent, trivalent, tetravalent or pentavalent element selected from among those of Groups 2a, 3b, 4b, 5b, 6b, 7b, 8, 2b, 3a, 4a and 5a of the Periodic Table, or mixture thereof, or M=0; Imp is a basic impregnating compound which comprises an alkali or alkaline earth metal, or mixture thereof, together with an electrical neutrality-ensuing counteranion therefor; n is 1, 2 or 3; h is 0, 1 or 2; and p is a number ranging from 0 to 1/3, corresponding to the molar ratio between the moiety Imp and the moiety MH.sub.h (PO.sub.4).sub.n.

Abstract translation: 特别是ε-己内酰胺（用于生产尼龙6的基本起始材料）的内酰胺可以通过在催化有效量的具有失活性的固体金属磷酸盐的存在下使相应的氨基腈与水环化/反应来选择性地制备， 通式（II）：MHh（PO4）nx（Imp）p，其中M是选自组2a，3b，4b，5b，6b，7b，8,2b中的二价，三价，四价或五价元素 ，3a，4a和5a，或其混合物，或M = 0; Imp是包含碱金属或碱土金属或它们的混合物的基本浸渍化合物，以及随之而来的电中性的抗衡阴离子; n为1,2或3; h为0,1或2; p是0至1/3的数，对应于部分Imp与部分MHh（PO4）n之间的摩尔比。

公开(公告)号：US5136051A

公开(公告)日：1992-08-04

申请号：US772814

申请日：1991-10-08

Applicant: Ludwig Schuster ,  Ulrich Koehler

Inventor： Ludwig Schuster ,  Ulrich Koehler

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

CPC classification number: C07D207/267 ,  C07D201/08

Abstract: A process for the preparation of a 2-pyrrolidinone of the general formula I ##STR1## in which R.sup.1 and R.sup.2 are independently hydrogen, C.sub.1 -C.sub.20 -alkyl, or C.sub.3 -C.sub.8 -cycloalkyl optionally substituted by C.sub.1 -C.sub.4 -alkyl, or phenyl optionally substituted by C.sub.1 -C.sub.4 -alkyl,by reacting a 3-cyanopropionate of the general formula II ##STR2## in which R.sup.1 and R.sup.2 have the meanings stated above and R.sup.3 denotes C.sub.1 -C.sub.8 -alkyl,with hydrogen at elevated temperature and pressure, wherein the reaction is carried out in the presence of ammonia and in contact with a catalyst containing cobalt, manganese, and phosphorus.

Abstract translation: 制备通式I（I）的2-吡咯烷酮的方法，其中R 1和R 2独立地是氢，C 1 -C 20 - 烷基或任选被C 1 -C 4 - 烷基取代的C 3 -C 8 - 环烷基 或任选被C 1 -C 4 - 烷基取代的苯基，通过使通式II的3-氰基丙酸酯（II）（其中R 1和R 2具有上述含义，R 3表示C 1 -C 8 - 烷基）与氢 在升高的温度和压力下，其中反应在氨的存在下进行并与含有钴，锰和磷的催化剂接触。

公开(公告)号：US4963672A

公开(公告)日：1990-10-16

申请号：US448899

申请日：1989-12-12

Applicant: Franz Merger ,  Rolf Fischer ,  Wolfgang Harder ,  Claus-Ulrich Priester ,  Uwe Vagt

Inventor： Franz Merger ,  Rolf Fischer ,  Wolfgang Harder ,  Claus-Ulrich Priester ,  Uwe Vagt

IPC: B01J23/46 ,  C07B61/00 ,  C07D201/08 ,  C07D201/16

CPC classification number: C07D201/08 ,  Y02P20/52

Abstract: Caprolactam is prepared in a process comprising the following steps:(a) reacting the 5-formylvaleric ester with liquid ammonia as reaction medium and hydrogen in the presence of a ruthenium catalyst in liquid phase at from 80.degree. to 140.degree. C. under a hydrogen partial pressure of from 40 to 100 bar,(b) replacing the reaction medium ammonia by an aromatic hydrocarbon having a boiling point of from 80.degree. to 240.degree. C. which is liquid under the reaction conditions,(c) heating the resulting mixture in liquid phase under superatmospheric pressure at 230.degree.-350.degree. C. to form caprolactam, and(d) isolating caprolactam from the resulting reaction mixture.

Abstract translation: 己内酰胺以包括以下步骤的方法制备：（a）使5-甲酰基戊酸酯与液氨作为反应介质和氢在钌催化剂存在下在液相中在80-140℃下在氢气 分压为40〜100巴，（b）在反应条件下用沸点为80〜240℃的芳烃替代反应介质氨，（c）将所得混合物加热 液相在超大气压下在230-350℃下反应形成己内酰胺，和（d）从所得反应混合物中分离己内酰胺。

公开(公告)号：US4800227A

公开(公告)日：1989-01-24

申请号：US642011

申请日：1984-08-20

Applicant: Michael S. Matson

Inventor： Michael S. Matson

IPC: C07D201/08

CPC classification number: C07D201/08

Abstract: A one-step method for the reductive amination of a heterocyclic to produce a nitrogen-containing heterocyclic. The feedstock is contacted with a mixed metal catalyst in which the metal comprises palladium and one of ruthenium, rhodium or rhenium.

Abstract translation: 用于还原胺化杂环以制备含氮杂环的一步法。 原料与其中金属包含钯和钌，铑或铼之一的混合金属催化剂接触。