公开(公告)号：US08530645B2

公开(公告)日：2013-09-10

申请号：US13254217

申请日：2010-03-04

Applicant: Junichi Kugimoto ,  Tsunemi Sugimoto

Inventor： Junichi Kugimoto ,  Tsunemi Sugimoto

IPC: C07D201/04 ,  C07D225/02

CPC classification number: C07D225/02 ,  C07D201/04

Abstract: This invention relates to a process for producing an amide compound by Beckmann rearrangement of an oxime compound using a compound having at least two electron-withdrawing leaving groups as a rearrangement catalyst, the process comprising a pre-preparation step in which the rearrangement catalyst and at least a part of the oxime compound are mixed and reacted; and a rearrangement reaction step in which the oxime compound is rearranged at a temperature higher than that in the pre-preparation step.

Abstract translation: 本发明涉及通过使用具有至少两个吸电子离去基团的化合物作为重排催化剂的肟化合物的贝克曼重排制备酰胺化合物的方法，该方法包括预制备步骤，其中重排催化剂和 将至少一部分肟化合物混合并反应; 和重排反应步骤，其中肟化合物在比预制备步骤中高的温度下重新排列。

公开(公告)号：US08524895B2

公开(公告)日：2013-09-03

申请号：US12501699

申请日：2009-07-13

Applicant: Tung-Han Tsai ,  Pin-To Yao ,  Cheng-Fa Hsieh

Inventor： Tung-Han Tsai ,  Pin-To Yao ,  Cheng-Fa Hsieh

IPC: C07D201/04 ,  C07D223/10

CPC classification number: C07D201/04 ,  C07D223/10

Abstract: The present invention provides a method for preparing amides, in which an amino acid ionic liquid is used as both a reaction medium and a catalyst to catalyze Beckman rearrangement of a ketoxime, so as to produce an amide. In the method, the rearrangement is conducted by catalyzing a ketoxime with an amino acid ionic liquid having the asymmetric property at a moderate reaction temperature during a short reaction time, so as to produce an amide without adding other catalysts such as concentrate sulfuric acid. The method has advantages such as avoiding corrosion in equipments with pipelines, the high conversion rate of ketoximes and the high selectivity of amides.

Abstract translation: 本发明提供了一种制备酰胺的方法，其中使用氨基酸离子液体作为反应介质和催化贝克曼重排酮肟的催化剂，以产生酰胺。 在该方法中，通过在短的反应时间内在适度的反应温度下用具有不对称性质的氨基酸离子液体催化酮肟进行重排，从而在不加入其它催化剂如浓硫酸的情况下生成酰胺。 该方法具有避免管道设备腐蚀，酮肟转化率高，酰胺选择性高等优点。

公开(公告)号：US08367865B2

公开(公告)日：2013-02-05

申请号：US12627681

申请日：2009-11-30

Applicant: Tung-Han Tsai ,  Cheng-Fa Hsieh ,  Chi-Yuan Chen

Inventor： Tung-Han Tsai ,  Cheng-Fa Hsieh ,  Chi-Yuan Chen

IPC: C07C231/04 ,  B01J31/04

CPC classification number: C07C231/10 ,  B01J31/0201 ,  B01J31/0202 ,  B01J31/0209 ,  B01J31/0217 ,  B01J31/0218 ,  B01J31/0222 ,  B01J31/0238 ,  B01J31/0247 ,  B01J31/0251 ,  B01J31/0279 ,  B01J31/0285 ,  C07B43/06 ,  C07C229/24 ,  C07D201/04 ,  C07D223/10

Abstract: The present invention provides a catalyst composition for preparing an amide, including an amino acid ionic liquid having a cation of formula (I) and an anion selected from the group consisting of an inorganic acid group, an organic acid group and a combination thereof, wherein the numbers of the anion and the cation are such that the amino acid ionic liquid is electroneutral; and a Bronsted acid. The present invention also provides a method for preparing an amide in the presence of the catalyst composition, and the method has advantages such as decreasing viscosity of ionic liquid, and increasing conversion rate of ketoximes and selectivity of amides.

Abstract translation: 本发明提供一种制备酰胺的催化剂组合物，其包括具有式（I）的阳离子的氨基酸离子液体和选自无机酸基，有机酸基及其组合的阴离子，其中 阴离子和阳离子的数量使得氨基酸离子液体是电中性的; 和布朗斯台德酸。 本发明还提供了在催化剂组合物存在下制备酰胺的方法，该方法具有降低离子液体的粘度，提高酮肟的转化率和酰胺选择性的优点。

公开(公告)号：US20120184733A1

公开(公告)日：2012-07-19

申请号：US13332834

申请日：2011-12-21

Applicant: Tung-Han Tsai ,  Cheng-Fa Hsieh ,  Hung-Hung Hseuh ,  Chien-Chuan Shih

Inventor： Tung-Han Tsai ,  Cheng-Fa Hsieh ,  Hung-Hung Hseuh ,  Chien-Chuan Shih

IPC: C07D201/04 ,  B01J31/02

CPC classification number: C07D201/04 ,  B01J31/0237 ,  B01J31/0244 ,  B01J2231/52 ,  C07C231/10 ,  Y02P20/584 ,  C07C233/07 ,  C07C233/05

Abstract: The present invention provides a method for preparing an amide. The method includes the steps of performing in a reactor including a catalyst composition having a nitrogen-containing heterocyclic compound and sulfuric acid Beckman rearrangement of a ketoxime to form a product stream having the amide, wherein a molar ratio of the nitrogen-containing heterocyclic compound to the sulfuric acid is from 1:1 to 1:8; and separating an organic phase having the amide and an aqueous phase having the catalyst composition from the product stream. The present invention facilitates the regeneration of the catalyst composition with low water content, so as to increase the conversion rate of a ketoxime and the selectivity of an amide.

Abstract translation: 本发明提供一种制备酰胺的方法。 该方法包括以下步骤：在包括具有含氮杂环化合物的催化剂组合物和酮肟的硫酸贝克曼重排反应器的反应器中进行，以形成具有酰胺的产物流，其中含氮杂环化合物与 硫酸为1:1至1:8; 并从产物流中分离出具有酰胺的有机相和具有催化剂组成的水相。 本发明有助于低水含量的催化剂组合物的再生，从而提高酮肟的转化率和酰胺的选择性。

公开(公告)号：US20110034687A1

公开(公告)日：2011-02-10

申请号：US12988758

申请日：2009-04-22

Applicant: Yasuhisa Fukuda ,  Junichi Kuglmoto ,  Nobuhiro Il

Inventor： Yasuhisa Fukuda ,  Junichi Kuglmoto ,  Nobuhiro Il

IPC: C07D225/02

CPC classification number: C07D201/04 ,  C07D225/02 ,  Y02P20/52

Abstract: The present invention relates to a process for producing an amide or lactam, particularly laurolactam, wherein catalytic amounts of an acidic chloride and a Lewis acid are used in Beckmann rearrangement of an oxime compound. In accordance with the process, side reactions during Beckmann rearrangement can be so controlled that selectivity can be improved and strong coloring in the reaction can be prevented, giving a high-quality amide or lactam.

Abstract translation: 本发明涉及一种制备酰胺或内酰胺，特别是月桂内酰胺的方法，其中在肟化合物的贝克曼重排中使用催化量的酸性氯化物和路易斯酸。 根据该方法，可以控制Beckmann重排期间的副反应，从而可以改善选择性，并且可以防止反应中的强烈着色，得到高质量的酰胺或内酰胺。

公开(公告)号：US07351820B2

公开(公告)日：2008-04-01

申请号：US10557771

申请日：2004-05-17

Applicant: Petrus Jozef Hubertus Thomissen ,  Joannes Albertus Wilhelmus Lemmens ,  Theodorus Maria Smeets

Inventor： Petrus Jozef Hubertus Thomissen ,  Joannes Albertus Wilhelmus Lemmens ,  Theodorus Maria Smeets

IPC: C07D201/04

CPC classification number: B01F5/0428 ,  B01F5/0415 ,  B01J19/26 ,  B01J2219/00164 ,  C07D201/04

Abstract: The invention relates to a process for preparing caprolactam by Beckmann rearrangement of cyclohexanone oxime by feeding cyclohexanone oxime to a reaction mixture comprising (i) sulfuric acid (ii) SO3 and (iii) caprolactam , wherein the SO3 content of the reaction mixture is between 9 and 20 wt. % and the molar ratio M of the reaction mixture defined as (nso3+nH2SO4)/ncap is between 1 and 1.4, wherein nso3=quantity of SO3 in reaction mixture, in mol nso3=quantity of H2SO4 in reaction mixture, in mol ncap=quantity of caprolactam in reaction mixture, in mol.

Abstract translation: 本发明涉及通过将环己酮肟进料到包含（i）硫酸（ⅱ）SO 3>和（ⅲ）己内酰胺的反应混合物中的贝克曼重排环己酮肟而制备己内酰胺的方法，其中SO 反应混合物的含量为9至20重量％。 ％且反应混合物的摩尔比M定义为（n 3 SO 3 H + H 2 SO 4）/ n 在1和1.4之间，其中 在反应混合物中，SO 3 SO 3的量为H 2 SO 3的量，其中n 3 = 在反应混合物中，以摩尔数计，反应混合物中的己内酰胺的量为1摩尔％。

公开(公告)号：US07339056B2

公开(公告)日：2008-03-04

申请号：US10557753

申请日：2004-05-17

Applicant: Joannes Albertus Wilhelmus J. A. W. Lemmens ,  Frank F. Mostert ,  Theodorus Maria T. M. Smeets

Inventor： Joannes Albertus Wilhelmus J. A. W. Lemmens ,  Frank F. Mostert ,  Theodorus Maria T. M. Smeets

IPC: C07D201/04

CPC classification number: B01F5/0428 ,  B01F5/0415 ,  B01J19/26 ,  B01J2219/00164 ,  C07D201/04

Abstract: The invention relates to a continuous process for preparing caprolactam by Beckmann rearrangement of cyclohexanone oxime, said process comprising a) feeding (i) oleum and (ii) cyclohexanone oxime into a first reaction mixture comprising caprolactam, sulfuric acid and SO3, b) feeding (iii) a portion of the first reaction mixture and (iv) cyclohexanone oxime into a second reaction mixture comprising caprolactam, sulfuric acid and SO3, c) withdrawing a portion of the second reaction mixture, wherein the process further comprises obtaining the cyclohexanone oxime that is fed to the reaction mixtures by: 1) preparing an organic medium comprising cyclohexanone oxime dissolved in an organic solvent 2) separating, by distillation, cyclohexanone oxime from said organic medium.

Abstract translation: 本发明涉及通过Beckmann重排环己酮肟制备己内酰胺的连续方法，所述方法包括a）将（i）发烟硫酸和（ii）环己酮肟进料到包含己内酰胺，硫酸和SO 3的第一反应混合物中， b）将（iii）一部分第一反应混合物和（iv）环己酮肟进料到包含己内酰胺，硫酸和SO 3 N的第二反应混合物中，c）将一部分 第二反应混合物，其中所述方法还包括通过以下步骤获得进料到反应混合物中的环己酮肟：1）制备溶解在有机溶剂中的包含环己酮肟的有机介质2）通过蒸馏从所述有机介质中分离出环己酮肟 。

公开(公告)号：US20070055061A1

公开(公告)日：2007-03-08

申请号：US10557753

申请日：2004-05-17

Applicant: Joannes Albertus Wilhelmus Lemmens ,  Frank Mostert ,  Theordorus Maria Smeets

Inventor： Joannes Albertus Wilhelmus Lemmens ,  Frank Mostert ,  Theordorus Maria Smeets

IPC: C07D201/04

CPC classification number: B01F5/0428 ,  B01F5/0415 ,  B01J19/26 ,  B01J2219/00164 ,  C07D201/04

Abstract: The invention relates to a continuous process for preparing caprolactam by Beckmann rearrangement of cyclohexanone oxime, said process comprising a) feeding (i) oleum and (ii) cyclohexanone oxime into a first reaction mixture comprising caprolactam, sulfuric acid and SO3, b) feeding (iii) a portion of the first reaction mixture and (iv) cyclohexanone oxime into a second reaction mixture comprising caprolactam, sulfuric acid and SO3, c) withdrawing a portion of the second reaction mixture, wherein the process further comprises obtaining the cyclohexanone oxime that is fed to the reaction mixtures by: 1) preparing an organic medium comprising cyclohexanone oxime dissolved in an organic solvent 2) separating, by distillation, cyclohexanone oxime from said organic medium.

Abstract translation: 本发明涉及通过Beckmann重排环己酮肟制备己内酰胺的连续方法，所述方法包括a）将（i）发烟硫酸和（ii）环己酮肟进料到包含己内酰胺，硫酸和SO 3的第一反应混合物中， b）将（iii）一部分第一反应混合物和（iv）环己酮肟进料到包含己内酰胺，硫酸和SO 3 N的第二反应混合物中，c）将一部分 第二反应混合物，其中所述方法还包括通过以下步骤获得进料到反应混合物中的环己酮肟：1）制备溶解在有机溶剂中的包含环己酮肟的有机介质2）通过蒸馏从所述有机介质中分离出环己酮肟 。

公开(公告)号：US07022844B2

公开(公告)日：2006-04-04

申请号：US10251335

申请日：2002-09-21

Applicant: Alan Levy ,  Gregory Cleotelis, II ,  James Sawyer ,  Nolan Henrich, III ,  Mohammed Loya ,  Matthew Warren ,  Gregory Moore

Inventor： Alan Levy ,  Gregory Cleotelis, II ,  James Sawyer ,  Nolan Henrich, III ,  Mohammed Loya ,  Matthew Warren ,  Gregory Moore

IPC: C07D201/04 ,  C07D201/16

CPC classification number: C07D201/04

Abstract: Methods are disclosed of producing and purifying at least one amide. In accordance with one of the methods disclosed herein, the at least one amide is produced by providing an organic liquid comprising at least one oxime, providing at least one catalyst, adding the at least one catalyst to the organic liquid to form a rearrangement mass, wherein the rearrangement mass comprises at least one amide, at least one impurity, and the at least one catalyst, and heating the rearrangement mass to a temperature of at least about 115° C. for a period of time in order to sulfonate, break down and/or reduce the concentration of some of the at least one impurity in the rearrangement mass.

公开(公告)号：US20060004194A1

公开(公告)日：2006-01-05

申请号：US11165538

申请日：2005-06-24

Applicant: Masahiro Hoshino ,  Masaru Kitamura ,  Keisuke Sugita

Inventor： Masahiro Hoshino ,  Masaru Kitamura ,  Keisuke Sugita

IPC: B01J29/40 ,  C07D201/04

CPC classification number: C07D201/04 ,  B01J29/035 ,  B01J37/06 ,  B01J2229/38 ,  B01J2229/40 ,  C01B37/02

Abstract: The present invention provides a method for manufacturing a zeolite comprising following steps of: (1): calcining crystals obtained by hydrothermal synthesis reaction of a silicon compound; (2): contact treating a calcined product obtained by the step (1) with an aqueous solution including an amine and/or a quaternary ammonium compound; (3): calcining a treated product obtained by the step (2); and (4): contact treating the calcined product obtained by the step (3) with an aqueous solution including ammonia and/or an ammonium salt. According to the present invention, a method is also provided wherein ε-caprolactam is manufactured by Beckmann rearrangement reaction of cyclohexanone oxime in a gaseous phase in the presence of the zeolite manufactured by the above-described method.

Abstract translation: 本发明提供一种制造沸石的方法，包括以下步骤：（1）：煅烧通过硅化合物的水热合成反应获得的晶体; （2）：用包含胺和/或季铵化合物的水溶液接触步骤（1）得到的煅烧产物; （3）：煅烧通过工序（2）得到的处理物; 和（4）：用包含氨和/或铵盐的水溶液接触处理由步骤（3）获得的煅烧产物。 根据本发明，还提供了一种方法，其中ε-己内酰胺通过在通过上述方法制造的沸石存在下，在气相中通过环己酮肟的贝克曼重排反应制造。