公开(公告)号：US5962680A

公开(公告)日：1999-10-05

申请号：US839576

申请日：1997-04-15

Applicant: Thomas Carl Eisenschmid ,  John Robert Briggs ,  Diane Lee Packett ,  Kurt Damar Olson ,  John Michael Maher

Inventor： Thomas Carl Eisenschmid ,  John Robert Briggs ,  Diane Lee Packett ,  Kurt Damar Olson ,  John Michael Maher

IPC: B01J31/24 ,  C07B61/00 ,  C07D201/02 ,  C07D201/08 ,  C07D223/10 ,  C08G69/02 ,  C08G69/14 ,  C08G69/36

CPC classification number: C07D201/02 ,  C07D201/08 ,  C08G69/02 ,  C08G69/14 ,  C08G69/36 ,  Y02P20/582

Abstract: This invention relates in part to processes for producing one or more substituted or unsubstituted epsilon caprolactams, e.g., epsilon caprolactam, which comprises: (a) subjecting one or more substituted or unsubstituted alkadienes to hydroxycarbonylation in the presence of a hydroxycarbonylation catalyst, e.g., a metal-organophosphorus ligand complex catalyst, and neutralization with a base to produce one or more substituted or unsubstituted pentenoic acid salts; (b) subjecting said one or more substituted or unsubstituted pentenoic acid salts to hydroformylation in the presence of a hydroformylation catalyst, e.g., a metal-organophosphorus ligand complex catalyst, to produce one or more substituted or unsubstituted formylvaleric acid salts and/or one or more substituted or unsubstituted epsilon caprolactam precursors; and (c) subjecting said one or more substituted or unsubstituted formylvaleric acid salts and/or said one or more substituted or unsubstituted epsilon caprolactam precursors to reductive amination in the presence of a reductive amination catalyst and cyclization optionally in the presence of a cyclization catalyst to produce said one or more substituted or unsubstituted epsilon caprolactams. This invention also relates in part to reaction mixtures containing one or more substituted or unsubstituted epsilon caprolactams as the principal product(s) of reaction.

Abstract translation: 本发明部分地涉及用于制备一种或多种取代或未取代的ε-己内酰胺（例如ε-己内酰胺）的方法，其包括：（a）在羟基羰基化催化剂存在下使一种或多种取代或未取代的烷撑二醇进行羟基羰基化， 金属有机磷配体络合物催化剂，并用碱中和以产生一种或多种取代或未取代的戊烯酸盐; （b）使所述一种或多种取代或未取代的戊烯酸盐在加氢甲酰化催化剂（例如金属 - 有机磷配体配合物催化剂）存在下进行加氢甲酰化，以产生一种或多种取代或未取代的甲酰基戊酸盐和/或一种或多种 更多取代或未取代的ε己内酰胺前体; 和（c）在还原胺化催化剂存在下使所述一种或多种取代或未取代的甲酰基戊酸盐和/或所述一种或多种取代或未取代的己内酰胺前体进行还原胺化，任选地在环化催化剂存在下进行环化， 产生所述一种或多种取代或未取代的ε己内酰胺。 本发明还部分涉及含有一种或多种取代或未取代的ε-己内酰胺作为反应主要产物的反应混合物。

公开(公告)号：US5892036A

公开(公告)日：1999-04-06

申请号：US926449

申请日：1997-09-10

Applicant: Irena Lukic

Inventor： Irena Lukic

IPC: A61K31/395 ,  A61K31/397 ,  A61P31/04 ,  A61P35/00 ,  C07D201/02 ,  C07D205/08

CPC classification number: A61K31/395 ,  C07D205/08 ,  Y02P20/55

Abstract: The invention relates to novel 2-bromo- and 2-nitroxy derivatives of 3-,bromo- and 3-dibromo-4-oxo-azetidines, to processes for the preparation thereof and to the use thereof.According to the invention 2-bromo- and 2-nitroxy derivatives of 3-bromo- and 3-dibromo-4-oxo-azetidines are prepared by reacting derivatives of protected penicillanic lanic acid 1,1-dioxides with DBN reactant (1,5-diazabicyclo/3.4.0/non-5-ene) and then the obtained DBN salt of sulfinic acid or isolated sulfinic acid is treated with thionyl chloride and, after eliminating thionyl chloride by evaporation, the obtained residue is passed through a silica gel column with methylene chloride or some other solvent as eluant or the obtained residue is dissolved in tetrahydrofuran or some other suitable solvent and treated with tetrabutyl ammonium bromide and after the treatment a derivative of 2-bromo, 3-bromo or 2-bromo-3,3-dibromo-4oxo-azetidine is isolated, which derivative may be subjected to a reaction with silver nitrate in 2-propanol and, after the treatment of the reaction mixture, derivatives of 2-nitroxy-, 3-bromo- or 2-nitroxy-3,3-dibromo-4-oxo-azetidine are isolated.The obtained substances are useful intermediates in the syntheses of beta lactam analogons or as components in formulations having antibacterial, inhibitory, anti-tumour or antagonistic action.

Abstract translation: 本发明涉及3-，溴 - 和3-二溴-4-氧代 - 氮杂环丁烷的新型2-溴 - 和2-硝基氧基衍生物，其制备方法及其用途。 根据本发明，3-溴 - 和3-二溴-4-氧代 - 氮杂环丁烷的2-溴 - 和2-硝基氧基衍生物是通过将受保护的青霉烷基酸兰酸1,1-二氧化物的衍生物与DBN反应物（1,5 - 二氮杂双环/ 3.4.0 /非-5-烯），然后将得到的亚磺酸DBI盐或分离的亚磺酸用亚硫酰氯处理，在通过蒸发除去亚硫酰氯后，将所得残余物通过硅胶柱 用二氯甲烷或一些其它溶剂作为洗脱剂，或将所得残余物溶于四氢呋喃或一些其它合适的溶剂中，并用四丁基溴化铵处理，处理后，将2-溴，3-溴或2-溴-3,3 分离出二溴-4-氧代 - 氮杂环丁烷，该衍生物可以与硝酸银在2-丙醇中进行反应，并且在处理反应混合物后，将2-硝基氧基，3-溴 - 或2-硝基氧基 - 分离出3,3-二溴-4-氧代 - 氮杂环丁烷。 获得的物质是合成β-内酰胺类似物或作为具有抗细菌，抑制，抗肿瘤或拮抗作用的制剂中的组分的有用中间体。

公开(公告)号：US5670638A

公开(公告)日：1997-09-23

申请号：US272206

申请日：1994-07-08

Applicant: Irena Lukic

Inventor： Irena Lukic

IPC: A61K31/395 ,  A61K31/397 ,  A61P31/04 ,  A61P35/00 ,  C07D201/02 ,  C07D205/08

CPC classification number: A61K31/395 ,  C07D205/08 ,  Y02P20/55

Abstract: The azetidines of the present invention have the formula I ##STR1## wherein R.sup.1 is hydrogen or bromine, R.sup.2 is hydrogen or bromine, wherein at least one of R.sup.1 or R.sup.2 is bromine, R.sup.3 is hydrogen; Me.sub.2 --C.dbd.C--COOR.sup.4 wherein R.sup.4 is hydrogen, methyl, benzyl or some other carboxy-protective group, and X is bromine or nitroxy group (--ONO.sub.2). According to the invention 2-bromo- and 2-nitroxy derivatives of 3-bromo- and 3-dibromo-4-oxo-azetidines are prepared by reacting derivatives of protected penicillanic acid 1,1-dioxides with DBN reactant (1,5-diazabicyclo/3.4.0/non-5-ene) and then the obtained DBN salt of sulfinic acid or isolated sulfinic acid is treated with thionyl chloride and, after eliminating thionyl chloride by evaporation, the obtained residue is passed through a silica gel column with methylene chloride or some other solvent as eluant or the obtained residue is dissolved in tetrahydrofuran or some other suitable solvent and treated with tetrabutyl ammonium bromide and after the treatment a derivative of 2-bromo, 3-bromo or 2-bromo-3,3-dibromo-4-oxo-azetidine is isolated, which derivative may be subjected to a reaction with silver nitrate in 2-propanol and, after the treatment of the reaction mixture, derivatives of 2-nitroxy-, 3-bromo- or 2-nitroxy-3,3-dibromo-4-oxo-azetidine are isolated. The obtained substances are useful intermediates in the syntheses of beta lactam analogons or as components in formulations having antibacterial, inhibitory, antitumour or antagonistic action.

Abstract translation: 本发明的氮杂环丁烷具有式I其中R 1是氢或溴，R 2是氢或溴，其中R 1或R 2中的至少一个是溴，R 3是氢; Me2-C = C-COOR4，其中R4是氢，甲基，苄基或一些其它羧基保护基，X是溴或硝基氧基（-ONO 2）。 根据本发明，3-溴 - 和3-二溴-4-氧代 - 氮杂环丁烷的2-溴 - 和2-硝基氧基衍生物是通过将受保护的青霉烷酸1,1-二氧化物的衍生物与DBN反应物（1,5- 二氮杂双环/ 3.4.0 /非-5-烯），然后将得到的亚磺酸的DBN盐或分离的亚磺酸用亚硫酰氯处理，通过蒸发除去亚硫酰氯后，将所得残余物通过硅胶柱， 二氯甲烷或一些其它溶剂作为洗脱剂，或将所得残余物溶于四氢呋喃或其它合适的溶剂中并用四丁基溴化铵处理，处理后，将2-溴，3-溴或2-溴-3,3- 分离出二溴-4-氧代 - 氮杂环丁烷，该衍生物可以与硝酸银在2-丙醇中进行反应，在处理反应混合物后，将2-硝基氧基，3-溴 - 或2-硝基氧基 分离出-3,3-二溴-4-氧代 - 氮杂环丁烷。 获得的物质是合成β-内酰胺类似物或作为具有抗菌，抑制，抗肿瘤或拮抗作用的制剂中的组分的有用中间体。

公开(公告)号：US4012418A

公开(公告)日：1977-03-15

申请号：US616011

申请日：1975-09-23

Applicant: Sijbrandus E. Schaafsma ,  Leonardus H. Geurts

Inventor： Sijbrandus E. Schaafsma ,  Leonardus H. Geurts

IPC: C07D207/263 ,  C07D201/02 ,  C07D207/22 ,  C07D207/26

CPC classification number: C07D201/02 ,  C07D207/22

Abstract: Pyrrolidone-2, or N-substituted derivatives thereof, is prepared by heating an aqueous solution of the corresponding 2-amino-.DELTA. .sup.1 -pyrroline at a temperature of 90.degree.-290.degree. C. The process does not require the use of a Raney nickel catalyst and produces the pyrrolidone-2 product in substantial yields.

Abstract translation: 吡咯烷酮-2或N-取代的衍生物通过在90℃-290℃的温度下加热相应的2-氨基-TA-1-吡咯啉的水溶液来制备。该方法不需要使用阮内 镍催化剂并产生大量产率的吡咯烷酮-2产物。

公开(公告)号：US3933873A

公开(公告)日：1976-01-20

申请号：US477712

申请日：1974-06-10

Applicant: Richard F. Love ,  Kablaoui Mahmoud S. ,  Roger G. Duranleau

Inventor： Richard F. Love ,  Kablaoui Mahmoud S. ,  Roger G. Duranleau

IPC: C07C205/51 ,  C07D201/02 ,  C07D201/10 ,  C07C99/00

CPC classification number: C07D201/02 ,  C07C201/12 ,  C07C201/14 ,  C07C227/04 ,  C07C227/20 ,  C07D201/10 ,  C07C2101/20

Abstract: A method for preparing omega-aminoalkanoic acids by the steps of (1) nitro-oxidizing a cycloalkene to a cyclic alpha-nitroketone, (2) cleaving and esterifying a cyclic alpha-nitroketone with an alcohol to form an alkyl omega-nitroester, (3) catalytically hydrogenating the nitroester to an aminoester and (4) hydrolyzing the aminoester to an aminoalkanoic acid.

Abstract translation: 通过以下步骤制备ω-氨基链烷酸的方法：（1）将环烯烃硝基氧化成环状α-硝基酮，（2）用醇裂解和酯化环状α-硝基酮以形成烷基ω-硝基酯（ 3）将硝酯催化氢化成氨基酯，和（4）将氨基酯水解成氨基链烷酸。

公开(公告)号：US3914218A

公开(公告)日：1975-10-21

申请号：US43184574

申请日：1974-01-09

Applicant: PFIZER

Inventor： CELMER WALTER D ,  SCIAVOLINO FRANK C ,  CULLEN WALTER P ,  ROUTIEN JOHN B

IPC: C12P17/18 ,  A61K31/34 ,  A61K31/395 ,  A61K36/06 ,  A61P31/04 ,  C07D498/08 ,  C07G11/00 ,  C12P1/06 ,  C12R1/29 ,  C07D201/02

CPC classification number: A61K36/06 ,  C07D498/08 ,  C07G11/00 ,  Y10S435/863

Abstract: A new species of Micromonospora, designated Micromonospora lacustris sp. nov. Routien, when subjected to submerged aerobic fermentation under controlled conditions, produces a mixture of at least 13 antibiotics. Two of these antibiotics are rifamycin S and rifamycin SV. Two other members of the antibiotic mixture are the 3-thiomethyl derivatives of rifamycin S and rifamycin SV.

Abstract translation: 一种新的小单孢菌属，命名为小单孢菌属（Micromonospora lacustris sp。）。 nov。 Routien在受控条件下进行浸没需氧发酵时，产生至少13种抗生素的混合物。 其中两种抗生素为利福霉素S和利福霉素SV。 抗生素混合物的另外两个成员是利福霉素S和利福霉素SV的3-硫代甲基衍生物。

公开(公告)号：US3845086A

公开(公告)日：1974-10-29

申请号：US24223072

申请日：1972-04-07

Applicant: DU PONT

Inventor： MARSH F

IPC: C07C275/50 ,  C07D201/02 ,  C07D211/76 ,  C07D223/14 ,  C07C127/22

CPC classification number: C07D201/02 ,  C07C275/50 ,  C07D211/76 ,  C07D223/14

Abstract: R1-CO-N(-R2)-CO-NH2

WHEREIN R1 AND R2, ALKIKE OR DIFFERENT, ARE ALKYL OF UP TO 18 CARBON ATOMS.

1. A COMPOUND HAVING THE FORMULA

公开(公告)号：US3835124A

公开(公告)日：1974-09-10

申请号：US32556373

申请日：1973-01-22

Applicant: SNIA VISCOSA

Inventor： GIUFFRE L ,  SIOLI G ,  MATTONE R

IPC: C07D201/02 ,  C07C67/00 ,  C07C201/00 ,  C07C207/00 ,  C07C239/00 ,  C07C251/46 ,  C07D201/04 ,  C07D201/10 ,  C07D205/08 ,  C07D207/263 ,  C07D223/02 ,  C07D41/06

CPC classification number: C07D201/10

Abstract: A method for the preparation of omega lactams is disclosed, more particularly epsilon caprolactam or a precursor thereof (such as cyclohexanone oxime), using as the starting material a cyclomethylene ketene, with the simultaneous formation of side products such as cyclohexanecarboxylic acid, wherein an adduct is preliminarly formed between cyclomethylene ketene and sulphur dioxide. The adduct is then reacted with a nitrosating agent so as to obtain, under the appropriate reaction conditions, the expected lactam, more specifically epsilon caprolactam.

Abstract translation: 公开了制备ω内酰胺的方法，更特别的是ε己内酰胺或其前体（例如环己酮肟），其以起始材料为环亚甲基乙烯酮，同时形成副产物如环己烷羧酸，其中加合物 在环亚甲基乙烯酮和二氧化硫之间初步形成。 然后将加合物与亚硝化剂反应，以在适当的反应条件下获得预期的内酰胺，更具体地是ε己内酰胺。

公开(公告)号：US3757007A

公开(公告)日：1973-09-04

申请号：US3757007D

申请日：1971-08-10

Applicant: KANEGAFUCHI SPINNING CO LTD

Inventor： DEGUCHI S ,  FUJITA I ,  YONEYA T

IPC: C07C67/00 ,  C07C239/00 ,  C07C251/46 ,  C07D201/02 ,  C07D201/04 ,  C07D41/06

CPC classification number: C07D201/02 ,  C07D201/04

Abstract: A PROCESS FOR PRODUCING E-CAPROLACTAM AND O-ACETYLCYCLOHEXANONE OXIME COMPRISING REACTING 0.01 TO 100 MOLS OF CYCLOHEXANONE OXIME WITH ONE MOL OF N-ACETYLCAPROLACTAM AT A TEMPERATURE OF 30 TO 120*C. FOR 10 MINUTES TO 100 HOURS IN THE PRESENCE OF AN AORGANIC SOLVENT IN AN AMOUNT OF 0 TO 20 TIMES THE TOTAL WEIGHT OF N-ACETYLCAPROLACTAM AND CYCLOHEXANONE OXIME.

公开(公告)号：US3708472A

公开(公告)日：1973-01-02

申请号：US3708472D

申请日：1970-10-14

Applicant: TECHNI CHEM CO

Inventor： PIVAWER P

IPC: C07D201/02 ,  C07D41/06

CPC classification number: C07D201/02

Abstract: 2-NITROCYCLOHEXANONE IS CLEAVED IN THE PRESENCE OF 6AMINOCAPROIC ACID AS A CATALYST. 6-NITROCAPROIC ACID IS PRODUCED WHICH CAN BE REDUCED WITH HYDROGEN TO 6AMINOCAPROIC ACID AND THE LATTER CYCLIZED TO CAPROLACTAM BY HEATING IN FAIRLY DILUTE AQUEOUS SOLUTION, LESS THAN 25%. THE CAPROLACTAM FORMATION IS AN EQUILIBRIUM REACTION AND SOME AMINOCAPROIC ACID REMAINS WHICH CAN BE SEPARATED AND USED AS A CATALYST IN THE CLEAVAGE OF THE 2-NITROCYCLOHEXANONE.