Synthesis of Thiophosphates by Coupling of Phosphates with Bunte Salts under Mild Conditions

Cong Min; Rongxing Zhang; Qian Liu; Sen Lin; Zhaohua Yan

doi:10.1055/s-0037-1609556

Synlett, Table of Contents

Synlett 2018; 29(15): 2027-2030
DOI: 10.1055/s-0037-1609556

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Synthesis of Thiophosphates by Coupling of Phosphates with Bunte Salts under Mild Conditions

Cong Min

College of Chemistry, Nanchang University, Nanchang, Jiangxi 330031, P. R. of China Email: senlin@ncu.edu.cn Email: yanzh@ncu.edu.cn

,

Rongxing Zhang

College of Chemistry, Nanchang University, Nanchang, Jiangxi 330031, P. R. of China Email: senlin@ncu.edu.cn Email: yanzh@ncu.edu.cn

,

Qian Liu

College of Chemistry, Nanchang University, Nanchang, Jiangxi 330031, P. R. of China Email: senlin@ncu.edu.cn Email: yanzh@ncu.edu.cn

,

Sen Lin*

College of Chemistry, Nanchang University, Nanchang, Jiangxi 330031, P. R. of China Email: senlin@ncu.edu.cn Email: yanzh@ncu.edu.cn

,

Zhaohua Yan*

College of Chemistry, Nanchang University, Nanchang, Jiangxi 330031, P. R. of China Email: senlin@ncu.edu.cn Email: yanzh@ncu.edu.cn

› Author Affiliations

Abstract

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Abstract

A simple, green, and efficient method has been developed for the preparation of thiophosphates with sodium S-benzyl thiosulfates. The method uses an NaBr-catalyzed coupling reaction of Bunte salts with phosphonates in the presence of an acid and hydrogen peroxide (30%), and the desired products were obtained in good yields.

Key words

hydrogen peroxide - thiophosphates - Bunte salts - synthesis - acids

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References

References and Notes

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16 Phosphorothioates 3; General Procedure Dialkyl phosphonate 1 (0.2 mmol) was added to a stirred mixture of sodium S-benzyl thiosulfate 2 (0.3 mmol), NaBr (0.04 mmol, 20 mol%), and HOAc (2.0 equiv) in CH₃CN (1 mL). H₂O₂ (2.0 equiv) was added and the reaction mixture was stirred for 0.5 h at 80 °C. After the reaction was completed, it was cooled down to r.t. The resulting solution was diluted and extracted with EtOAc (3 ×10 mL). The organic layer was washed with saturated salt water and dried with anhydrous sodium sulfate. The pure product 3 was obtained by column chromatography. Compound 3bc was obtained in 77% yield (46.6 mg) according to the general procedure as a colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.27–7.19 (m, 2 H), 7.10 (d, J = 7.8 Hz, 2 H), 4.79–4.55 (m, 2 H), 4.01 (d, J = 12.3 Hz, 2 H), 2.31 (s, 3 H), 1.32 (d, J = 6.2 Hz, 6 H), 1.28 (d, J = 6.2 Hz, 6 H) ppm. ¹³C NMR (101 MHz, CDCl₃): δ = 137.27, 134.24, 129.28, 128.79, 72.59 (d, J = 6.3 Hz), 34.96 (d, J = 3.8 Hz), 23.81 (d, J = 4.1 Hz), 23.51 (d, J = 5.6 Hz), 21.08 ppm. ³¹P NMR (243 MHz, CDCl₃): δ = 24.38 ppm. HRMS (ESI+): m/z calcd for C₁₄H₂₃O₃PS [M + H]⁺: 303.1178; found: 303.1193.

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