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Preparation method of sulfonyl-containing completely substituted parazole

A fully substituted pyrazole technology, applied in the field of preparation of fully substituted pyrazoles, can solve problems such as limited application and complex starting material synthesis operations, and achieve the effects of reduced production costs, wide application range, and simple post-processing

Inactive Publication Date: 2014-08-13
南京凯莫森医药科技有限公司
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  • Summary
  • 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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  • Preparation method of sulfonyl-containing completely substituted parazole
  • Preparation method of sulfonyl-containing completely substituted parazole
  • Preparation method of sulfonyl-containing completely substituted parazole

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023]

[0024] TBAI (20 mol%, 148 mg), compound 1a (2 mmol, 200 mg), compound 2a (5 mmol, 930 mg), Co(OAc) 2 . 4H 2 O (20 mol%, 100 mg), TBHP (0.6 mL, 4.4 mmol), ethyl acetate (8.0 mL). 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 (40 mL × 3), and then adsorbed with silica gel to dry the solvent in vacuo, finally with petroleum ether and The mixed solvent of dichloromethane can be obtained by simple column chromatography 3a , the yield is 85%. 1 H NMR (400 MHz, CDCl 3 ) δ 7.91 – 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 C NMR (100 MHz, CDCl 3 )δ 151.1, 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 ): υ 1585, 1549, 1171, 660.

Embodiment 2

[0026]

[0027] TBAI (20 mol%, 148 mg), compound 1a (2 mmol, 200 mg), compound 2a (5 mmol, 930 mg), Co(OAc) 2 . 4H 2 O (20 mol%, 100 mg), TBHP (0.6 mL, 4.4 mmol), toluene (8.0 mL). 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 (40 mL × 3), and then adsorbed with silica gel to dry the solvent in vacuo, finally with petroleum ether and The mixed solvent of dichloromethane can be obtained by simple column chromatography 3a , the yield is 80%. 1 H NMR (400 MHz, CDCl 3 ) δ 7.91 – 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 C NMR (100 MHz, CDCl 3 )δ 151.1, 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 C19 h 21 N 2 o 4 S 2 : 405, Found: 405 (M+H + ); IR (neat, cm -1 ): υ 1585, 1549, 1171, 660.

Embodiment 3

[0029]

[0030] KI (20 mol%, 66 mg), compound 1a (2 mmol, 200 mg), compound 2a (5 mmol, 930 mg), Co(OAc) 2 . 4H 2 O (20 mol%, 100 mg), TBHP (0.6 mL, 4.4 mmol), ethyl acetate (8.0 mL). 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 (40 mL × 3), and then adsorbed with silica gel to dry the solvent in vacuo, finally with petroleum ether and The mixed solvent of dichloromethane can be obtained by simple column chromatography 3a , the yield is 75%. 1 H NMR (400 MHz, CDCl 3 ) δ 7.91 – 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 C NMR (100 MHz, CDCl 3 )δ 151.1, 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 ): υ 1585, 1549, 1171, 660.

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Abstract

The invention discloses a preparation method of sulfonyl-containing completely substituted parazole. The preparation method of the sulfonyl-containing completely substituted parazole comprises the step of carrying out a condensation reaction on 1,3-diketone and aromatic sulfonyl hydrazine as reaction substrates, iodide as a catalyst, peroxy-tertiary butanol as an oxidant, and cobalt acetate tetrahydrate or anhydrous cobalt chloride as an additive in ethyl acetate or benzene as a solvent, so that the sulfonyl-containing completely substituted parazole is obtained. The preparation method disclosed by the invention has the advantages that good and even excellent yield can be realized for multiple aryl sulfonyl hydrazides and 1,3-diketones, and the highest yield can be 97%; compatibility of functional groups of the substrates is high, and application range of the substrates is wide compared with the traditional method; meanwhile, a preparation process is controllable, so that the preparation method disclosed by the invention is applicable to industrial production of the sulfonyl-containing completely substituted parazole.

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 Applications(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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