Synthetic method of phosphorothioate compound

A technology of phosphorothioate and synthesis method, which is applied in chemical instruments and methods, compounds of Group 5/15 elements of the periodic table, organic chemistry, etc., and can solve the problems of long reaction time, waste of raw materials, and inconsistency with atomic economy. and other problems, to achieve the effect of mild reaction conditions and easy operation.

Active Publication Date: 2015-08-19
中国人民解放军63975部队
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  • Description
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Problems solved by technology

However, the disadvantage of this method is that the reaction time is long, and it usually needs to be reacted at a high temperature of 140 ° C for 24 hours, and the amount of phosphite is 7 times that of arylsulfonyl chloride, resulting in waste of raw materials, which does not conform to atom economy. the rules

Method used

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  • Synthetic method of phosphorothioate compound
  • Synthetic method of phosphorothioate compound
  • Synthetic method of phosphorothioate compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Synthesis of 2,4-dimethylphenyl di-n-propyl phosphorothioate (3a) from 2,4-dimethylthiophenol (2a) and di-n-propyl phosphite (1a):

[0035]

[0036] Add 1,3-dichloro-5,5-dimethylhydantoin (0.0493g, 0.25mmol) and dichloromethane (1.5mL) into a 10mL reaction flask equipped with magnetons, stir evenly at room temperature, and pour Add di-n-propyl phosphite (1a, 0.083g, 0.5mmol) and 2,4-dimethylthiophenol (2a, 0.069g, 0.5mmol), cover the lid, and stir vigorously at room temperature for 10 minutes; The completion of the reaction was monitored; the reaction solution was filtered, spin-dried and separated by column chromatography to obtain 0.139 g of a colorless transparent liquid (3a), with a yield of 92%.

[0037] R f =0.33(V 正己烷 / V 乙酸乙酯 =4 / 1); 1 H NMR (300MHz, CDCl 3 )δ7.47(dd, J=7.9, 2.3Hz, 1H), 7.07(s, 1H), 6.98(d, J=7.9Hz, 1H), 4.12-3.94(m, 4H), 2.48(s, 3H ), 2.30(d, J=2.1Hz, 3H), 1.66(dt, J=13.7, 6.9Hz, 4H), 0.92(t, J=7.4Hz, 6H); 13 C NMR (75MHz, CDCl 3 )δ142...

Embodiment 2

[0039] Synthesis of 2,4-dimethylphenyl di-n-propyl phosphorothioate (3a) from 2,4-dimethylthiophenol (2a) and di-n-propyl phosphite (1a):

[0040]

[0041] Operation method is the same as embodiment 1. The difference is that trichloroisocyanuric acid (0.04 g, 0.175 mmol) was used instead of 1,3-dichloro-5,5-dimethylhydantoin as the chlorination reagent. Obtained 0.133 g of a colorless transparent liquid (3a), with a yield of 88%.

[0042] R f =0.33(V 正己烷 / V 乙酸乙酯 =4 / 1); 1 H NMR (300MHz, CDCl 3)δ7.47(dd, J=7.9, 2.3Hz, 1H), 7.07(s, 1H), 6.98(d, J=7.9Hz, 1H), 4.12-3.94(m, 4H), 2.48(s, 3H ), 2.30(d, J=2.1Hz, 3H), 1.66(dt, J=13.7, 6.9Hz, 4H), 0.92(t, J=7.4Hz, 6H); 13 C NMR (75MHz, CDCl 3 )δ142.20 (d, J=5.4Hz), 139.72 (d, J=3.3Hz), 136.36 (d, J=4.2Hz), 131.84 (d, J=2.8Hz), 127.70 (d, J=2.8 Hz), 122.24(d, J=7.4Hz), 69.61(d, J=7.1Hz), 23.74(d, J=7.2Hz), 21.35(d, J=17.7Hz), 10.14(s); 31 P NMR (121MHz, CDCl 3 )δ23.54(s); MS(70eV, EI)C 14 h 23 o 3 PS[M]: 302.09.

Embodiment 3

[0044] Synthesis of 2-methylphenyl di-n-propyl phosphorothioate (3b) from 2-methylthiophenol (2b) and di-n-propyl phosphite (1a):

[0045]

[0046] Operation method is the same as embodiment 1. The difference is that 2-methylthiophenol (2b) is used instead of 2,4-dimethylthiophenol (2a). 0.127 g of a colorless transparent liquid (3b) was obtained with a yield of 88%.

[0047] R f =0.34(V 正己烷 / V 乙酸乙酯 =4 / 1); 1 H NMR (300MHz, CDCl 3 )δ7.66-7.60 (m, 1H), 7.28 (d, J = 2.3Hz, 2H), 7.22-7.14 (m, 1H), 4.14-3.96 (m, 4H), 2.54 (d, J = 1.3Hz , 3H), 1.68(dd, J=14.0, 7.3Hz, 4H), 0.92(t, J=7.4Hz, 6H); 13 C NMR (75MHz, CDCl 3 )δ142.32 (d, J=5.7Hz), 136.28 (d, J=4.2Hz), 130.96 (d, J=2.6Hz), 129.50 (d, J=3.0Hz), 126.85 (d, J=2.7 Hz), 125.99(d, J=7.4Hz), 69.69(d, J=7.1Hz), 23.72(d, J=7.2Hz), 21.56(s), 10.12(s); 31 P NMR (121MHz, CDCl 3 )δ23.09(s); MS(70eV, EI)C 13 h 21 o 3 PS[M]: 288.02.

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Abstract

The present invention relates to a synthetic method of phosphorothioate compound. The preparation method adopts phosphite and thiophenol or mercaptan to synthesize the phosphorothioate under the promotion of a chlorate agent 1,3-dichloro-5,5-dimethylhydantoin / trichloroisocyanuric acid. The method is mild in condition, quick in reaction, free of alkalization and a catalyst in the reaction process, and has wide adaptability to substrates of different functional groups. The phosphite framework which is efficiently constructed by the preparation method provided by the invention is an important framework for many medicines, pesticides, biological active molecules and natural products. The synthetic method provided by the invention provides a widely applied preparation method for synthesizing the compounds.

Description

technical field [0001] The invention relates to a synthesis method of phosphorothioate compounds. Background technique [0002] Phosphorothioate compounds are a very important class of compounds, which are widely used in organic synthesis, medicine, bioactive molecules, pesticides, materials science and other fields. Especially in the fields of medicine and pesticides, phosphorothioate compounds play an important role, and some of the representative phosphorothioate compounds that have been applied have the following structural formula: [0003] [0004] For the synthesis methods of various phosphorothioate compounds, there are some reports in the literature at present. [0005] R.Harveyh et al. disclose a method for synthesizing phosphorothioate, which is to obtain the target object by adding strong alkali sodium hydride and then reacting with thioether. However, due to the strong alkalinity of sodium hydride, the poor compatibility of functional groups makes many subs...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/18C07F9/17C07F9/177C07F9/165
Inventor 肖军华毕晓静李君臣王红梅
Owner 中国人民解放军63975部队
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