Title:
METHOD FOR SYNTHESIZING CARBOXYLIC ACID OR KETONE COMPOUNDS FROM ALCOHOL OR ALDEHYDE USING OXYGEN OR OXYGEN IN AIR AS OXIDANT
Document Type and Number:
WIPO Patent Application WO/2021/031756
Kind Code:
A1
Abstract:
Disclosed is a new method for synthesizing carboxylic acid or ketone compounds from an alcohol or corresponding aldehyde using oxygen or oxygen in the air as an oxidant. Under the catalysis of a nitrate/4-hydroxy-2,2,6,6-tetramethylpiperidine oxide and under the action of additives, an alcohol or corresponding aldehyde is oxidized to a corresponding carboxylic acid or ketone compound. When an additional inorganic chloride is added, the reaction is accelerated. The invention has advantages such as a low catalyst price, easy operation, a high yield, rich substrate diversity, mild reaction conditions, and being environmentally friendly. The invention is not only suitable for laboratory synthesis but also suitable for industrial synthesis of carboxylic acid or ketone compounds.
Inventors:
MA SHENGMING (CN)
LIU JINXIAN (CN)
LIU JINXIAN (CN)
Application Number:
PCT/CN2020/102499
Publication Date:
February 25, 2021
Filing Date:
July 16, 2020
Export Citation:
Assignee:
UNIV ZHEJIANG (CN)
International Classes:
C07B41/06; C07B41/08; C07C45/38; C07C45/39; C07C49/203; C07C49/213; C07C53/126; C07C53/19; C07C57/46; C07C57/68
Foreign References:
| CN101544548A | 2009-09-30 | |||
| CN106800492A | 2017-06-06 | |||
| CN107176899A | 2017-09-19 | |||
| CN102336619A | 2012-02-01 |
Other References:
JIANG XINGGUO, LIU JINXIAN, MA SHENGMING: "Iron-Catalyzed Aerobic Oxidation of Alcohols: Lower Cost and Improved Selectivity", ORGANIC PROCESS RESEARCH & DEVELOPMENT, AMERICAN CHEMICAL SOCIETY, US, vol. 23, no. 5, 17 May 2019 (2019-05-17), US, pages 825 - 835, XP055781449, ISSN: 1083-6160, DOI: 10.1021/acs.oprd.8b00374
ZHAI DI, MA SHENGMING: "Copper catalysis for highly selective aerobic oxidation of alcohols to aldehydes/ketones", ORGANIC CHEMISTRY FRONTIERS, vol. 6, no. 17, 20 August 2019 (2019-08-20), pages 3101 - 3106, XP055781453, DOI: 10.1039/C9QO00740G
WANG, X. ; LIANG, X.: "Aerobic Oxidation of Alcohols to Carbonyl Compounds Catalyzed by Fe(NO"3)"3/4-OH-TEMPO under Mild Conditions", CHINESE JOURNAL OF CATALYSIS / DALIAN INSTITUTE OF CHEMICAL PHYSICS, ELSEVIER, AMSTERDAM, NL, vol. 29, no. 9, 1 September 2008 (2008-09-01), AMSTERDAM, NL, pages 935 - 939, XP025572780, ISSN: 1872-2067, DOI: 10.1016/S1872-2067(08)60075-3
JIANG XINGGUO, ZHAI YIZHAN, CHEN JUNYU, HAN YULIN, YANG ZHENG, MA SHENGMING: "Iron-Catalyzed Aerobic Oxidation of Aldehydes: Single Component Catalyst and Mechanistic Studies", CHINESE JOURNAL OF CHEMISTRY, ZHONGGUO KEXUEYUAN, CN, vol. 36, no. 1, 1 January 2018 (2018-01-01), CN, pages 15 - 19, XP055781777, ISSN: 1001-604X, DOI: 10.1002/cjoc.201700576
MA SHENGMING, LIU JINXIAN, LI SUHUA, CHEN BO, CHENG JIAJIA, KUANG JINQIANG, LIU YU, WAN BAOQIANG, WANG YULI, YE JUNTAO, YU QIONG, : "Development of a General and Practical Iron Nitrate/TEMPO-Catalyzed Aerobic Oxidation of Alcohols to Aldehydes/Ketones: Catalysis with Table Salt", ADVANCED SYNTHESIS AND CATALYSIS, vol. 353, no. 6, 18 April 2011 (2011-04-18), pages 1005 - 1017, XP055781776, ISSN: 1615-4150, DOI: 10.1002/adsc.201100033
JINXIAN LIU, XI XIE, SHENGMING MA: "Aerobic Oxidation of Propargylic Alcohols to α, β-Unsaturated Alkynals or Alkynones Catalyzed by Fe(NO3)39H2O, TEMPO and Sodium Chloride in Toluene", SYNTHESIS, vol. 44, no. 10, 25 April 2012 (2012-04-25), pages 1569 - 1576, XP009526117, ISSN: 0039-7881, DOI: 10.1055/s-0031-1290811
JINXIAN LIU, SHENGMING MA: "Iron-Catalyzed Aerobic Oxidation of Allylic Alcohols: The Issue of CâC Bond Isomerization", ORGANIC LETTERS, AMERICAN CHEMICAL SOCIETY, US, vol. 15, no. 20, 1 January 2013 (2013-01-01), US, pages 5150 - 5153, XP002753707, ISSN: 1523-7060, DOI: 10.1021/ol402434x
LIU JINXIAN; MA SHENGMING: "Room temperature Fe(NO3)3�9H2O/TEMPO/NaCl-catalyzed aerobic oxidation of homopropargylic alcohols", TETRAHEDRON, ELSEVIER SIENCE PUBLISHERS, AMSTERDAM, NL, vol. 69, no. 47, 1 January 1900 (1900-01-01), AMSTERDAM, NL, pages 10161 - 10167, XP028756308, ISSN: 0040-4020, DOI: 10.1016/j.tet.2013.08.082
JIANG XINGGUO, ZHANG JIASHENG, MA SHENGMING: "Iron Catalysis for Room-Temperature Aerobic Oxidation of Alcohols to Carboxylic Acids", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, US, vol. 138, no. 27, 13 July 2016 (2016-07-13), US, pages 8344 - 8347, XP055781772, ISSN: 0002-7863, DOI: 10.1021/jacs.6b03948
JIANG XINGGUO, MA SHENGMING: "Studies on Iron-Catalyzed Aerobic Oxidation of Benzylic Alcohols to Carboxylic Acids", SYNTHESIS, GEORG THIEME VERLAG, STUTTGART, DE., vol. 50, no. 08, 1 April 2018 (2018-04-01), STUTTGART, DE., pages 1629 - 1639, XP055781769, ISSN: 0039-7881, DOI: 10.1055/s-0036-1591761
WAN YU ϼ, SHAN YU-HUA, SHI JUN, TIAN YUAN, ZHENG YI-TIAN, FENG YANG-YANG, LI MING-SHI, LU MO-HONG: "Base-free Catalytic Oxidation of 2-Ethylhexanol to 2-Ethylhexnoic Acid with Oxygen", FINE CHEMICALS, vol. 33, no. 6, 1 June 2016 (2016-06-01), pages 654 - 659, XP055781768, DOI: 10.13550/j.jxhg.2016.06.009
ZHAI DI, MA SHENGMING: "Copper catalysis for highly selective aerobic oxidation of alcohols to aldehydes/ketones", ORGANIC CHEMISTRY FRONTIERS, vol. 6, no. 17, 20 August 2019 (2019-08-20), pages 3101 - 3106, XP055781453, DOI: 10.1039/C9QO00740G
WANG, X. ; LIANG, X.: "Aerobic Oxidation of Alcohols to Carbonyl Compounds Catalyzed by Fe(NO"3)"3/4-OH-TEMPO under Mild Conditions", CHINESE JOURNAL OF CATALYSIS / DALIAN INSTITUTE OF CHEMICAL PHYSICS, ELSEVIER, AMSTERDAM, NL, vol. 29, no. 9, 1 September 2008 (2008-09-01), AMSTERDAM, NL, pages 935 - 939, XP025572780, ISSN: 1872-2067, DOI: 10.1016/S1872-2067(08)60075-3
JIANG XINGGUO, ZHAI YIZHAN, CHEN JUNYU, HAN YULIN, YANG ZHENG, MA SHENGMING: "Iron-Catalyzed Aerobic Oxidation of Aldehydes: Single Component Catalyst and Mechanistic Studies", CHINESE JOURNAL OF CHEMISTRY, ZHONGGUO KEXUEYUAN, CN, vol. 36, no. 1, 1 January 2018 (2018-01-01), CN, pages 15 - 19, XP055781777, ISSN: 1001-604X, DOI: 10.1002/cjoc.201700576
MA SHENGMING, LIU JINXIAN, LI SUHUA, CHEN BO, CHENG JIAJIA, KUANG JINQIANG, LIU YU, WAN BAOQIANG, WANG YULI, YE JUNTAO, YU QIONG, : "Development of a General and Practical Iron Nitrate/TEMPO-Catalyzed Aerobic Oxidation of Alcohols to Aldehydes/Ketones: Catalysis with Table Salt", ADVANCED SYNTHESIS AND CATALYSIS, vol. 353, no. 6, 18 April 2011 (2011-04-18), pages 1005 - 1017, XP055781776, ISSN: 1615-4150, DOI: 10.1002/adsc.201100033
JINXIAN LIU, XI XIE, SHENGMING MA: "Aerobic Oxidation of Propargylic Alcohols to α, β-Unsaturated Alkynals or Alkynones Catalyzed by Fe(NO3)39H2O, TEMPO and Sodium Chloride in Toluene", SYNTHESIS, vol. 44, no. 10, 25 April 2012 (2012-04-25), pages 1569 - 1576, XP009526117, ISSN: 0039-7881, DOI: 10.1055/s-0031-1290811
JINXIAN LIU, SHENGMING MA: "Iron-Catalyzed Aerobic Oxidation of Allylic Alcohols: The Issue of CâC Bond Isomerization", ORGANIC LETTERS, AMERICAN CHEMICAL SOCIETY, US, vol. 15, no. 20, 1 January 2013 (2013-01-01), US, pages 5150 - 5153, XP002753707, ISSN: 1523-7060, DOI: 10.1021/ol402434x
LIU JINXIAN; MA SHENGMING: "Room temperature Fe(NO3)3�9H2O/TEMPO/NaCl-catalyzed aerobic oxidation of homopropargylic alcohols", TETRAHEDRON, ELSEVIER SIENCE PUBLISHERS, AMSTERDAM, NL, vol. 69, no. 47, 1 January 1900 (1900-01-01), AMSTERDAM, NL, pages 10161 - 10167, XP028756308, ISSN: 0040-4020, DOI: 10.1016/j.tet.2013.08.082
JIANG XINGGUO, ZHANG JIASHENG, MA SHENGMING: "Iron Catalysis for Room-Temperature Aerobic Oxidation of Alcohols to Carboxylic Acids", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, US, vol. 138, no. 27, 13 July 2016 (2016-07-13), US, pages 8344 - 8347, XP055781772, ISSN: 0002-7863, DOI: 10.1021/jacs.6b03948
JIANG XINGGUO, MA SHENGMING: "Studies on Iron-Catalyzed Aerobic Oxidation of Benzylic Alcohols to Carboxylic Acids", SYNTHESIS, GEORG THIEME VERLAG, STUTTGART, DE., vol. 50, no. 08, 1 April 2018 (2018-04-01), STUTTGART, DE., pages 1629 - 1639, XP055781769, ISSN: 0039-7881, DOI: 10.1055/s-0036-1591761
WAN YU ϼ, SHAN YU-HUA, SHI JUN, TIAN YUAN, ZHENG YI-TIAN, FENG YANG-YANG, LI MING-SHI, LU MO-HONG: "Base-free Catalytic Oxidation of 2-Ethylhexanol to 2-Ethylhexnoic Acid with Oxygen", FINE CHEMICALS, vol. 33, no. 6, 1 June 2016 (2016-06-01), pages 654 - 659, XP055781768, DOI: 10.13550/j.jxhg.2016.06.009
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MSJLAW OFFICE (CN)
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