Synthetic method of allyl halosulfide

A technique for the synthesis of allyl halides, which is applied in the field of organic synthesis, can solve the problems of narrow substrate range, low yield, and preparation of reagents in advance, and achieve simple and reasonable process conditions, high chemical selectivity, and good conversion rate Effect

Active Publication Date: 2019-07-02
上海贝通色彩科技有限公司 +1
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

There are some problems in the above method, (1) the addition of halogenated sulfides to alkynes is relatively straightforward, but the reagents need to be prepared in advance, and the properties are unstable and easy to decompose; (2) the yield of individual reactions is not high, and the chemoselectivity needs to be improved , the substrate range is narrow; (3) need to add excess auxiliary reagent or additional metal catalyst

Method used

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  • Synthetic method of allyl halosulfide
  • Synthetic method of allyl halosulfide

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] In a 25mL Teflon tube, add 20.4mg (0.2mmol) phenylacetylene, 6.6mg (0.04mmol) azoisobutyronitrile, 27.3mg (0.22mmol) 4-methylthiophenol and 49.5mg (0.22mmol) N -Iodosuccinimide, then add 1mL of acetonitrile, heat to 80°C and stir for 12h. After the reaction, the solvent was distilled off from the reaction liquid under reduced pressure to obtain a crude product, and finally the mixture of ethyl acetate and petroleum ether with a volume ratio of 1:20 was used as an eluent, and trans-1-( Phenyl)-1-(iodovinyl)-4-chlorophenylsulfide 45.4 mg, yield 61%.

[0026] 1 H NMR (500MHz, CDCl 3 )δ7.45(dt, J=7.3,2.6Hz,2H),7.40(d,J=8.4Hz,1H),7.34(dd,J=8.5,6.8Hz,2H),7.32-7.28(m,2H ), 7.23(d, J=7.2Hz, 2H), 7.04-7.01(m, 1H);

[0027] GCMS(EI)Calcd.for C 14 h 10 ClIS 371.92, found 371.95.

Embodiment 2

[0029] In a 25mL Teflon tube, add 23.2mg (0.2mmol) 4-methylphenylacetylene, 6.6mg (0.04mmol) azoisobutyronitrile, 24.2mg (0.22mmol) thiophenol and 29.3mg (0.22mmol) N - Chlorosuccinimide, then add 1 mL of acetonitrile, heat to 80 ° C and stir for 16 h. After the reaction, the solvent was distilled off from the reaction liquid under reduced pressure to obtain a crude product, and finally the mixture of ethyl acetate and petroleum ether with a volume ratio of 1:20 was used as an eluent, and trans-1-( 4-methylphenyl)-1-(chlorovinyl)-phenylene sulfide 30.2 mg, yield 58%.

[0030] 1 H NMR (500MHz, CDCl 3 )δ7.38-7.33(m,2H),7.20(dd,J=5.1,2.0Hz,3H),7.11-7.06(m,2H),6.92(d,J=7.9Hz,2H),6.52(s ,1H),2.21(s,3H);

[0031] GCMS(EI)Calcd.for C 15 h 13 ClS 260.04, found 260.09.

Embodiment 3

[0033] Add 36.0mg (0.2mmol) 4-bromophenylacetylene, 6.6mg (0.04mmol) azoisobutyronitrile, 27.3mg (0.22mmol) 4-chlorothiophenol and 39.2mg (0.22mmol) to a 25mL Teflon tube ) N-bromosuccinimide, then add 1 mL of acetonitrile, heat to 80 ° C and stir for 24 h. After the reaction, the solvent was distilled off from the reaction liquid under reduced pressure to obtain a crude product, and finally the mixture of ethyl acetate and petroleum ether with a volume ratio of 1:20 was used as an eluent, and trans-1-( 4-bromophenyl)-1-(bromovinyl)-4-bromophenylene sulfide 30.2 mg, yield 60%.

[0034] 1 H NMR (500MHz, CDCl 3 )δ7.43-7.33 (m, 4H), 7.30 (d, J = 8.2Hz, 3H), 7.19 (s, 1H), 6.77 (s, 1H);

[0035] GCMS(EI)Calcd.for C 14 h 9 BrClS 401.85, found 401.89.

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Abstract

The invention discloses an allyl halogenated sulfide synthesis method, wherein a phenylacetylene derivative is used as raw material and completely reacts at a temperature of 60-80 DEG C in the presence of a free radical initiator azoisobutyronitrile by using acetonitrile as a solvent and using mercaptan and N-halogenated succinimide as addition reagents, and after the reaction is completely performed, the reaction liquid is subjected to separation purification to obtain the allyl halogenated sulfide. According to the present invention, the synthesis method has advantages of reasonable processconditions, simple operation, stable conversion rate, stable yield and broad substrate range, uses the simple and stable halogenated reagent so as to convenient treat, does not require metal catalysts, and is the efficient method for constructing the allyl C-S bond and C-X bond.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and relates to a method for synthesizing allyl halosulfides, in particular to a method for synthesizing allyl halosulfides from phenylacetylene derivatives as raw materials. [0002] technical background [0003] Allyl sulfide is an important organic intermediate and has a wide range of applications in the field of dyes. The introduction of halogen at the allyl position can be used as a switch for molecular reactions, and other new carbon-carbon bonds and carbon-heterobonds are introduced by breaking carbon-halogen bonds, which greatly enriches the diversity of compounds. Based on the above properties, many biologically active natural products contain allylsulfide structures, which have potential applications in medicine. Therefore, it is very important to develop methods for the synthesis of allyl halosulfides. [0004] At present, the methods for synthesizing allyl halosulfides mainl...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C319/18C07C323/09C07C323/07C07C323/62C07B45/06
CPCC07B45/06C07C319/18C07C323/09C07C323/07C07C323/62
Inventor 李剑锋马晶晶赫五卷丁天琪易文斌
Owner 上海贝通色彩科技有限公司
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