Title:
ONE-STEP METHOD FOR PREPARING C-N COUPLING PRODUCT USING NITROAROMATIC HYDROCARBON AND ALKYL OR PHENYLBORONIC ACID
Document Type and Number:
WIPO Patent Application WO/2023/024532
Kind Code:
A1
Abstract:
Disclosed in the present invention is a one-step method for preparing a C-N coupling product using nitroaromatic hydrocarbon and alkyl or phenylboronic acid. The method comprises: adding nitroaromatic hydrocarbon, alkyl or phenylboronic acid, a reducing agent, and a catalyst into a polar solvent, then placing same into a reactor for reaction under room temperature and light conditions, using thin-layer chromatography (TLC) to track a reaction process during reaction, and finally obtaining a coupling product by means of column chromatography. Compared with the prior art, the present invention has the following advantages: (1) the method of the present invention relates to using the commercialized inexpensive nitroaromatic hydrocarbon as a nitrogen source, using an organic boric acid as a substrate, and performing one-step reaction in the presence of the reducing agent and the catalyst to synthesize a series of novel C-N coupling products, thereby providing a practical method for an organic amine compound that is difficult to be synthesized by means of a traditional method; and (2) the reaction is conducted at room temperature, and thus, the reaction condition is mild; and the method is simple to operate, is economical and efficient, has a high yield, and has an important application value.
Inventors:
CAI XINGWEI (CN)
SONG HENG (CN)
SHEN YANG (CN)
ZHAO YUYUAN (CN)
CHEN LEI (CN)
SONG HUA (CN)
XU CHEN (CN)
WANG YANRU (CN)
TONG YANJIA (CN)
ZHOU ZHEN (CN)
HUANG CUIPING (CN)
SONG HENG (CN)
SHEN YANG (CN)
ZHAO YUYUAN (CN)
CHEN LEI (CN)
SONG HUA (CN)
XU CHEN (CN)
WANG YANRU (CN)
TONG YANJIA (CN)
ZHOU ZHEN (CN)
HUANG CUIPING (CN)
Application Number:
PCT/CN2022/087551
Publication Date:
March 02, 2023
Filing Date:
April 19, 2022
Export Citation:
Assignee:
UNIV JIANGSU SCIENCE & TECH (CN)
ZHENJIANG RUIFU INTELLIGENT TECH CO LTD (CN)
ZHENJIANG RUIFU INTELLIGENT TECH CO LTD (CN)
International Classes:
C07C253/30; C07B43/04; C07C209/36; C07C211/52; C07C211/61; C07C213/02; C07C217/92; C07C221/00; C07C223/06; C07C225/22; C07C227/06; C07C229/60; C07C255/58; C07C319/20; C07C323/36; C07D209/08; C07D213/74; C07D213/803; C07D239/42; C07D307/88; C07D311/04
Foreign References:
| CN113801037A | 2021-12-17 | |||
| CN103342651A | 2013-10-09 |
Other References:
SONG HENG, SHEN YANG, ZHOU HU, DING DANLI, YANG FU, WANG YEMEI, XU CHEN, CAI XINGWEI: "Light-Promoted Low-Valent-Tungsten-Catalyzed Ambient Temperature Amination of Boronic Acids with Nitroaromatics", THE JOURNAL OF ORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY, vol. 87, no. 8, 15 April 2022 (2022-04-15), pages 5303 - 5314, XP093040929, ISSN: 0022-3263, DOI: 10.1021/acs.joc.2c00138
MANNA KARTIC, GANGULY TANUSREE, BAITALIK SUJOY, JANA RANJAN: "Visible-Light- and PPh 3 -Mediated Direct C–N Coupling of Nitroarenes and Boronic Acids at Ambient Temperature", ORGANIC LETTERS, AMERICAN CHEMICAL SOCIETY, US, vol. 23, no. 21, 5 November 2021 (2021-11-05), US , pages 8634 - 8639, XP093040930, ISSN: 1523-7060, DOI: 10.1021/acs.orglett.1c03343
YANG FU, DONG XUEXUE, SHEN YANG, LIU MENGTING, ZHOU HU, WANG XUYU, LI LULU, YUAN AIHUA, SONG HENG: "Reductive C−N Coupling of Nitroarenes: Heterogenization of MoO 3 Catalyst by Confinement in Silica", CHEMSUSCHEM, WILEY-VCH, DE, vol. 14, no. 16, 23 August 2021 (2021-08-23), DE , pages 3413 - 3421, XP093040931, ISSN: 1864-5631, DOI: 10.1002/cssc.202101203
DATABASE REGISTRY ANONYMOUS : "[1,1'-Biphenyl]-3-amine, N-(4-chlorophenyl)- (CA INDEX NAME)", XP093040942, retrieved from STN
DATABASE REGISTRY ANONYMOUS : "2-Pyrimidinamine, N-(4-chlorophenyl)-5-fluoro- (CA INDEX NAME) ", XP093040943, retrieved from STN
DATABASE REGISTRY ANONYMOUS : "2-Pyridinamine, N-phenyl-5-(trifluoromethyl)- (CA INDEX NAME)", XP093040944, retrieved from STN
DATABASE REGISTRY ANONYMOUS : "1H-Indol-5-amine, N-(4-chlorophenyl)- (CA INDEX NAME)", XP093040945, retrieved from STN
DATABASE REGISTRY ANONYMOUS : "3-Pyridinamine, 6-methoxy-N-phenyl- (CA INDEX NAME) ", XP093040947, retrieved from STN
DATABASE REGISTRY ANONYMOUS : "2-Pyridinecarbonitrile, 5-(phenylamino)- (CA INDEX NAME) ", XP093040948, retrieved from STN
DATABASE REGISTRY ANONYMOUS : "Benzenamine, 4-chloro-N-cyclopentyl- (CA INDEX NAME) ", XP093040949, retrieved from STN
DATABASE REGISTRY ANONYMOUS : "Methanone, [4-[(4-chlorophenyl)amino]phenyl]phenyl- (CA INDEX NAME)", XP093040950, retrieved from STN
DATABASE REGISTRY ANONYMOUS : "1H-Indol-5-amine, 1-methyl-N-phenyl- (CA INDEX NAME)", XP093040951, retrieved from STN
DATABASE REGISTRY ANONYMOUS : "Benzenamine, 4-chloro-N-(4-ethylphenyl)- (CA INDEX NAME) ", XP093040952, retrieved from STN
SAMUEL SUÁREZ‐PANTIGA; RAQUEL HERNÁNDEZ‐RUIZ; CINTIA VIRUMBRALES; MARÍA R. PEDROSA; ROBERTO SANZ: "Reductive Molybdenum‐Catalyzed Direct Amination of Boronic Acids with Nitro Compounds", ANGEWANDTE CHEMIE INTERNATIONAL EDITION, VERLAG CHEMIE, HOBOKEN, USA, vol. 58, no. 7, 18 January 2019 (2019-01-18), Hoboken, USA, pages 2129 - 2133, XP072098273, ISSN: 1433-7851, DOI: 10.1002/anie.201812806
LI GEN, NYKAZA TREVOR V., COOPER JULIAN C., RAMIREZ ANTONIO, LUZUNG MICHAEL R., RADOSEVICH ALEXANDER T.: "An Improved P III /P V ═O-Catalyzed Reductive C–N Coupling of Nitroaromatics and Boronic Acids by Mechanistic Differentiation of Rate- and Product-Determining Steps", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, vol. 142, no. 14, 8 April 2020 (2020-04-08), pages 6786 - 6799, XP093040932, ISSN: 0002-7863, DOI: 10.1021/jacs.0c01666
LI GANG, YANG LIU, LIU JIAN‐JUN, ZHANG WEI, CAO RUI, WANG CHAO, ZHANG ZUNTING, XIAO JIANLIANG, XUE DONG: "Light‐Promoted C–N Coupling of Aryl Halides with Nitroarenes", ANGEWANDTE CHEMIE INTERNATIONAL EDITION, VERLAG CHEMIE, HOBOKEN, USA, vol. 60, no. 10, 1 March 2021 (2021-03-01), Hoboken, USA, pages 5230 - 5234, XP093040933, ISSN: 1433-7851, DOI: 10.1002/anie.202012877
MANNA KARTIC, GANGULY TANUSREE, BAITALIK SUJOY, JANA RANJAN: "Visible-Light- and PPh 3 -Mediated Direct C–N Coupling of Nitroarenes and Boronic Acids at Ambient Temperature", ORGANIC LETTERS, AMERICAN CHEMICAL SOCIETY, US, vol. 23, no. 21, 5 November 2021 (2021-11-05), US , pages 8634 - 8639, XP093040930, ISSN: 1523-7060, DOI: 10.1021/acs.orglett.1c03343
YANG FU, DONG XUEXUE, SHEN YANG, LIU MENGTING, ZHOU HU, WANG XUYU, LI LULU, YUAN AIHUA, SONG HENG: "Reductive C−N Coupling of Nitroarenes: Heterogenization of MoO 3 Catalyst by Confinement in Silica", CHEMSUSCHEM, WILEY-VCH, DE, vol. 14, no. 16, 23 August 2021 (2021-08-23), DE , pages 3413 - 3421, XP093040931, ISSN: 1864-5631, DOI: 10.1002/cssc.202101203
DATABASE REGISTRY ANONYMOUS : "[1,1'-Biphenyl]-3-amine, N-(4-chlorophenyl)- (CA INDEX NAME)", XP093040942, retrieved from STN
DATABASE REGISTRY ANONYMOUS : "2-Pyrimidinamine, N-(4-chlorophenyl)-5-fluoro- (CA INDEX NAME) ", XP093040943, retrieved from STN
DATABASE REGISTRY ANONYMOUS : "2-Pyridinamine, N-phenyl-5-(trifluoromethyl)- (CA INDEX NAME)", XP093040944, retrieved from STN
DATABASE REGISTRY ANONYMOUS : "1H-Indol-5-amine, N-(4-chlorophenyl)- (CA INDEX NAME)", XP093040945, retrieved from STN
DATABASE REGISTRY ANONYMOUS : "3-Pyridinamine, 6-methoxy-N-phenyl- (CA INDEX NAME) ", XP093040947, retrieved from STN
DATABASE REGISTRY ANONYMOUS : "2-Pyridinecarbonitrile, 5-(phenylamino)- (CA INDEX NAME) ", XP093040948, retrieved from STN
DATABASE REGISTRY ANONYMOUS : "Benzenamine, 4-chloro-N-cyclopentyl- (CA INDEX NAME) ", XP093040949, retrieved from STN
DATABASE REGISTRY ANONYMOUS : "Methanone, [4-[(4-chlorophenyl)amino]phenyl]phenyl- (CA INDEX NAME)", XP093040950, retrieved from STN
DATABASE REGISTRY ANONYMOUS : "1H-Indol-5-amine, 1-methyl-N-phenyl- (CA INDEX NAME)", XP093040951, retrieved from STN
DATABASE REGISTRY ANONYMOUS : "Benzenamine, 4-chloro-N-(4-ethylphenyl)- (CA INDEX NAME) ", XP093040952, retrieved from STN
SAMUEL SUÁREZ‐PANTIGA; RAQUEL HERNÁNDEZ‐RUIZ; CINTIA VIRUMBRALES; MARÍA R. PEDROSA; ROBERTO SANZ: "Reductive Molybdenum‐Catalyzed Direct Amination of Boronic Acids with Nitro Compounds", ANGEWANDTE CHEMIE INTERNATIONAL EDITION, VERLAG CHEMIE, HOBOKEN, USA, vol. 58, no. 7, 18 January 2019 (2019-01-18), Hoboken, USA, pages 2129 - 2133, XP072098273, ISSN: 1433-7851, DOI: 10.1002/anie.201812806
LI GEN, NYKAZA TREVOR V., COOPER JULIAN C., RAMIREZ ANTONIO, LUZUNG MICHAEL R., RADOSEVICH ALEXANDER T.: "An Improved P III /P V ═O-Catalyzed Reductive C–N Coupling of Nitroaromatics and Boronic Acids by Mechanistic Differentiation of Rate- and Product-Determining Steps", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, vol. 142, no. 14, 8 April 2020 (2020-04-08), pages 6786 - 6799, XP093040932, ISSN: 0002-7863, DOI: 10.1021/jacs.0c01666
LI GANG, YANG LIU, LIU JIAN‐JUN, ZHANG WEI, CAO RUI, WANG CHAO, ZHANG ZUNTING, XIAO JIANLIANG, XUE DONG: "Light‐Promoted C–N Coupling of Aryl Halides with Nitroarenes", ANGEWANDTE CHEMIE INTERNATIONAL EDITION, VERLAG CHEMIE, HOBOKEN, USA, vol. 60, no. 10, 1 March 2021 (2021-03-01), Hoboken, USA, pages 5230 - 5234, XP093040933, ISSN: 1433-7851, DOI: 10.1002/anie.202012877
Attorney, Agent or Firm:
NANJING JINGWEI PATENT & TRADEMARK AGENCY CO., LTD (CN)
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