Green Synthesis of Haloformates from Olefins Using Formic Acid as Reactant, Protonic Acid, and Solvent

Ligeng Wang; Hualong Zhang; Qin Yu; Chun Feng; Jun Hu

doi:10.1055/s-0037-1610028

Synlett, Table of Contents

Synlett 2018; 29(12): 1611-1616
DOI: 10.1055/s-0037-1610028

letter

Green Synthesis of Haloformates from Olefins Using Formic Acid as Reactant, Protonic Acid, and Solvent

Ligeng Wang *

College of Chemical Engineering, Zhejiang University of Technology, Zhejiang 310014, P. R. of China Email: wanglg@zjut.edu.cn Email: hjzjut@zjut.edu.cn

,

Hualong Zhang

College of Chemical Engineering, Zhejiang University of Technology, Zhejiang 310014, P. R. of China Email: wanglg@zjut.edu.cn Email: hjzjut@zjut.edu.cn

,

Qin Yu

College of Chemical Engineering, Zhejiang University of Technology, Zhejiang 310014, P. R. of China Email: wanglg@zjut.edu.cn Email: hjzjut@zjut.edu.cn

,

Chun Feng

College of Chemical Engineering, Zhejiang University of Technology, Zhejiang 310014, P. R. of China Email: wanglg@zjut.edu.cn Email: hjzjut@zjut.edu.cn

,

Jun Hu*

College of Chemical Engineering, Zhejiang University of Technology, Zhejiang 310014, P. R. of China Email: wanglg@zjut.edu.cn Email: hjzjut@zjut.edu.cn

› Author Affiliations

Abstract

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Abstract

Bromoformates and iodoformates are successfully synthesized in high yields with regioselectivity and stereoselectivity by using ZnAl-BrO₃ ^– layered double hydroxides (LDHs) and KX (X = Br, I) in the presence of formic acid (HCOOH). The protocol exploits the versatile function of formic acid as solvent, nucleophilic reagent, and acidic medium simultaneously, simplifying the reaction and separation of the products.

Key words

olefins - formic acid - bromoformates - iodoformates - regioselectivity - stereoselectivity

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References

References and Notes

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22 Representative Procedure for the Synthesis of Bromoformate 2f Substrate (1f, 324.4 mg, 2 mmol), KBr (190.4 mg, 1.6 mmol), formic acid (10 mL) were added to a 50 mL three-necked flask, and KBr was absolutely dissolved in the mixture with proper stirring at room temperature. After ZnAl-BrO₃ ^–-LDHs (0.8 g) was added to the mixture, the reaction system was stirred at 40 °C with use of a reflux condenser in a water bath until the substrate completely disappeared (monitored by TLC). The molecular bromine was treated with sodium bisulfite solution right away. The solid phase ZnAl-BrO₃ ^–-LDHs was removed by centrifugation. Furthermore, the dichloromethane (3 × 5 mL) used for washing the ZnAl-BrO₃ ^–-LDHs was merged into the liquid mixture after centrifugation. Then, the products were extracted into the organic phase with dichloromethane (3 × 10 mL) and H₂O (30 mL). The organic phase was dried with sodium sulfate and concentrated in vacuum. The crude product was purified by column chromatography on silica gel. 2-Bromo-1-(4-acetoxylphenyl)ethyl formate (2f) Yield: 493.8 mg, 86%. Colorless oil. ¹H NMR (500 MHz, CDCl₃): δ = 8.15 (s, 1 H), 7.42–7.39 (m, 2 H), 7.14–7.12 (m, 2 H), 6.11 (dd, J = 8.3, 4.5 Hz, 1 H), 3.68 (dd, J = 11.0, 8.4 Hz, 1 H), 3.61 (dd, J = 11.0, 4.5 Hz, 1 H), 2.31 (s, 3 H) ppm. ¹³C NMR (126 MHz, CDCl₃): δ = 169.16, 159.52, 151.09, 134.49, 127.84, 122.00, 74.04, 33.51, 21.07 ppm. HRMS (ESI): m/z calcd for C₁₁H₁₁BrO₄ [M + H]⁺: 286.9919; found: 286.9917.

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