A kind of preparation method of fully substituted pyrazole containing sulfone group

A technology of fully substituted pyrazoles, which is applied in the field of preparation of fully substituted pyrazoles, can solve problems such as limited applications and complex starting material synthesis operations, and achieve the effects of reduced production costs, wide application range, and safe reactions

Inactive Publication Date: 2016-02-10
南京凯莫森医药科技有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] Although the above methods can prepare fully substituted pyrazoles, they all require complex starting materials or multi-step synthetic operations, which greatly limits their application in industry.

Method used

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  • A kind of preparation method of fully substituted pyrazole containing sulfone group
  • A kind of preparation method of fully substituted pyrazole containing sulfone group
  • A kind of preparation method of fully substituted pyrazole containing sulfone group

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023]

[0024] Load TBAI (20mol%, 148mg) successively in the reaction bottle, compound 1a (2mmol, 200mg), compound 2a (5mmol, 930mg), Co(OAc) 2 . 4H 2 O (20mol%, 100mg), TBHP (0.6mL, 4.4mmol), ethyl acetate (8.0mL). Then the system was heated in the air at 70°C for about 2 hours, quenched with saturated sodium sulfite solution, extracted with ethyl acetate (40mL×3), then adsorbed with silica gel and spin-dried the solvent in vacuo, and finally washed with petroleum ether and bismuth The mixed solvent of methyl chloride is subjected to simple column chromatography to obtain the product 3a , the yield is 85%. 1 HNMR (400MHz, CDCl 3 )δ7.91–7.83(m,2H),7.76–7.70(m,2H),7.40–7.26(m,4H),2.85(s,3H),2.48–2.32(m,9H); 13 CNMR (100MHz, CDCl 3 )δ151.1, 146.6, 146.5, 144.4, 139.1, 133.8, 130.2, 129.8, 128.0, 126.6, 121.7, 21.6, 21.4, 13.6, 11.6; MS (ESI-quadrupole): Anal. Calcd. For C 19 h 21 N 2 o 4 S 2 :405,Found:405(M+H + );IR(neat,cm -1 ):υ1585, 1549, 1171, 660.

Embodiment 2

[0026]

[0027] Load TBAI (20mol%, 148mg) successively in the reaction bottle, compound 1a (2mmol, 200mg), compound 2a (5mmol, 930mg), Co(OAc) 2 . 4H 2 O (20mol%, 100mg), TBHP (0.6mL, 4.4mmol), toluene (8.0mL). Then the system was heated in the air at 70°C for about 2 hours, quenched with saturated sodium sulfite solution, extracted with ethyl acetate (40mL×3), then adsorbed with silica gel and spin-dried the solvent in vacuo, and finally washed with petroleum ether and bismuth The mixed solvent of methyl chloride is subjected to simple column chromatography to obtain the product 3a , the yield is 80%. 1 HNMR (400MHz, CDCl 3 )δ7.91–7.83(m,2H),7.76–7.70(m,2H),7.40–7.26(m,4H),2.85(s,3H),2.48–2.32(m,9H); 13 CNMR (100MHz, CDCl 3 )δ151.1, 146.6, 146.5, 144.4, 139.1, 133.8, 130.2, 129.8, 128.0, 126.6, 121.7, 21.6, 21.4, 13.6, 11.6; MS (ESI-quadrupole): Anal. Calcd. For C 19 h 21 N 2 o 4 S 2 :405,Found:405(M+H + );IR(neat,cm -1 ):υ1585, 1549, 1171, 660.

Embodiment 3

[0029]

[0030]Load KI (20mol%, 66mg) successively in the reaction bottle, compound 1a (2mmol, 200mg), compound 2a (5mmol, 930mg), Co(OAc) 2 . 4H 2 O (20mol%, 100mg), TBHP (0.6mL, 4.4mmol), ethyl acetate (8.0mL). Then the system was heated in the air at 70°C for about 2 hours, quenched with saturated sodium sulfite solution, extracted with ethyl acetate (40mL×3), then adsorbed with silica gel and spin-dried the solvent in vacuo, and finally washed with petroleum ether and bismuth The mixed solvent of methyl chloride is subjected to simple column chromatography to obtain the product 3a , the yield is 75%. 1 HNMR (400MHz, CDCl 3 )δ7.91–7.83(m,2H),7.76–7.70(m,2H),7.40–7.26(m,4H),2.85(s,3H),2.48–2.32(m,9H); 13 CNMR (100MHz, CDCl 3 )δ151.1, 146.6, 146.5, 144.4, 139.1, 133.8, 130.2, 129.8, 128.0, 126.6, 121.7, 21.6, 21.4, 13.6, 11.6; MS (ESI-quadrupole): Anal. Calcd. For C 19 h 21 N 2 o 4 S 2 :405,Found:405(M+H + );IR(neat,cm -1 ):υ1585, 1549, 1171, 660.

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Abstract

The invention discloses a preparation method of fully substituted pyrazoles containing sulfone groups, comprising the following steps: taking 1,3-diketone and aromatic sulfonyl hydrazide as reaction substrates, using iodide as catalyst, and tert-butanol peroxide as an oxidizing agent, cobalt acetate tetrahydrate or anhydrous cobalt chloride as an additive, ethyl acetate or benzene as a solvent, and a fully substituted pyrazole containing a sulfone group is prepared through condensation reaction. The preparation method disclosed in the invention can achieve good or even excellent yields for various arylsulfonylhydrazides and 1,3-diketones, etc., and the yield can reach up to 97%; the functional group compatibility of the substrate is high, compared with the traditional The method has a wide range of substrates; and the preparation process is controllable, which is suitable for industrial production of fully substituted pyrazoles containing sulfone groups.

Description

technical field [0001] The invention relates to a method for preparing pyrazole compounds, in particular to a method for preparing fully substituted pyrazoles containing sulfone groups. Background technique [0002] Pyrazole is a five-membered heterocyclic aromatic compound containing two adjacent nitrogen atoms. The first synthetic pyrazole compound was in 1883. L. Knott synthesized 1-phenyl-3- from ethyl acetoacetate and phenylhydrazine Methyl pyrazolone, named after "pyrazole". Because of high efficiency, low toxicity and multi-directional transformation of substituents on the pyrazole ring, fully substituted pyrazoles have become a very important class of organic compounds, which are widely used in biology, medicine, pesticides, materials, etc. [0003] The traditional methods for synthesizing fully substituted pyrazoles mainly include the following three methods: 1. Condensation cyclization of monosubstituted hydrazine and substituted 1,3-bis-electrophiles, and this me...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D231/18
CPCC07D231/18C07D401/14C07D409/14
Inventor 万小兵张杰邵莺王宏祥罗强陈继军徐冬梅
Owner 南京凯莫森医药科技有限公司
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