Synthetic method for alkyl group phosphorous acid diester compounds or alkyl group phosphinic acid ester compounds

A technology of alkylphosphonite diester and alkylphosphinate, which is applied in the field of chemical synthesis, can solve the problems of poor stability, many reaction by-products, difficult purification, etc., and meet the requirements of low reaction conditions and environmental protection pollution Effects of small, broad application prospects

Inactive Publication Date: 2017-03-29
WENZHOU UNIVERSITY
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  • Abstract
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Problems solved by technology

[0003] Taking the synthesis of alkyl phosphonite as an example, the traditional method is generally synthesized by Albuzov reaction of halogenated hydrocarbon and phosphite at high temperature. Halogenated hydrocarbons are used as alkylating reagents, and the reaction will produce small molecule halogenated hydrocarbons with high activity and low boiling point as by-products, causing pollution
At present, there is also a method for preparing alkyl

Method used

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  • Synthetic method for alkyl group phosphorous acid diester compounds or alkyl group phosphinic acid ester compounds
  • Synthetic method for alkyl group phosphorous acid diester compounds or alkyl group phosphinic acid ester compounds
  • Synthetic method for alkyl group phosphorous acid diester compounds or alkyl group phosphinic acid ester compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Preparation of Diethyl Benzyl Phosphinate from Triethyl Phosphite and Benzyl Alcohol

[0024]

[0025] Benzyl alcohol (54.0mg, 0.50mmol), triethyl phosphite (166.0mg, 1.0mmol, 2.0equiv.) and tetrabutylammonium iodide (3.7mg, 0.01mmol, 2mol% ), vacuumed under nitrogen protection, and then heated to 120°C for 24h under solvent-free conditions. After the completion of the reaction monitored by TLC, the product was separated and purified by column chromatography, and the separation yield was 90%. 1 H NMR (500MHz, CDCl 3 )δ7.44–6.87(m,5H),3.99–3.84(m,4H),3.08(d,J=21.5Hz,2H),1.17(t,J=7.0Hz,6H). 13 C NMR (125MHz, CDCl 3 )δ131.62(d, J=9.0Hz), 129.77(d, J=6.5Hz), 128.50(d, J=3.0Hz), 126.84(d, J=3.6Hz), 62.09(d, J=6.8 Hz), 33.79(d, J=138.2Hz), 16.34(d, J=6.0Hz). 31 P NMR (202MHz, CDCl 3 )δ26.48(s).

Embodiment 2

[0027] Preparation of Diethyl 4-Fluorobenzylphosphonite from Triethyl Phosphite and 4-Fluorobenzyl Alcohol

[0028]

[0029] 4-Fluorobenzyl alcohol (63.0mg, 0.50mmol), triethyl phosphite (166.0mg, 1.0mmol, 2.0equiv.) and tetrabutylammonium iodide (3.7mg, 0.01mmol) were sequentially added to a 20mL tubular reactor ,2mol%), vacuumed under nitrogen protection, and then heated to 120°C for 24h under solvent-free conditions. After the reaction was complete as monitored by TLC, the product was separated and purified by column chromatography, and the separation yield was 81%. 1 H NMR (500MHz, CDCl 3 )δ7.29–7.24(m,2H),7.00(t,J=8.5Hz,2H),4.07–3.90(m,4H),3.12(d,J=21.5Hz,2H),1.25(t,J =7.0Hz,6H). 13 C NMR (126MHz, CDCl 3 )δ161.93(dd, J=245.3,3.9Hz),131.24(dd,J=7.9,6.7Hz),127.31(dd,J=9.2,3.3Hz),115.41(dd,J=21.5,3.0Hz) ,62.18(d,J=6.8Hz),32.90(d,J=139.2Hz),16.35(d,J=6.0Hz). 31 P NMR (202MHz, CDCl 3 )δ26.15 (d, J=5.7Hz).

Embodiment 3

[0031] Preparation of Diethyl 4-Bromobenzylphosphonite from Triethyl Phosphite and 4-Bromobenzyl Alcohol

[0032]

[0033] 4-Bromobenzyl alcohol (93.0mg, 0.50mmol), triethyl phosphite (166.0mg, 1.0mmol, 2.0equiv.) and tetrabutylammonium iodide (3.7mg, 0.01mmol) were sequentially added to a 20mL tubular reactor ,2mol%), vacuumed under nitrogen protection, and then heated to 120°C for 24h under solvent-free conditions. After the completion of the reaction monitored by TLC, the product was separated and purified by column chromatography, and the separation yield was 90%. 1 H NMR (500MHz, CDCl 3 )δ7.44(d,J=8.0Hz,2H),7.17(dd,J=8.0,2.0Hz,2H),4.10–3.94(m,4H),3.09(d,J=21.5Hz,2H), 1.25(t,J=7.0Hz,6H). 13 C NMR (126MHz, CDCl 3 )δ131.64(d, J=3.0Hz), 131.43(d, J=6.6Hz), 130.78(d, J=9.1Hz), 120.93(d, J=4.6Hz), 62.22(d, J=6.8 Hz), 33.28(d, J=138.7Hz), 16.37(d, J=5.9Hz). 31 P NMR (202MHz, CDCl 3 )δ25.51(s).

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Abstract

The invention discloses a synthetic method for alkyl group phosphorous acid diester compounds or alkyl group phosphinic acid ester compounds. According to the synthetic method, alcohols which are cheap, easy to get, wide in source, stable and low in toxicity serve as alkylating reagents, iodine salt which is cheap and easy to get serves as catalysts, no solvent is needed, and the alkyl group phosphorous acid diester compounds can be selectively directly obtained after a reaction. The reaction method is simple, the condition is mild, no organic solvent is needed and operation is simple. According to the method, the requirements for reaction conditions are low, various types of alcohols such as a benzyl group type, an allyl type and a fat type can be utilized as the alkylate reagents to implement the synthesis of different types of substituted alkyl group phosphorous acid diester, and the method can be further expanded to the synthesis of the alkyl group phosphinic acid ester compounds through the reaction between the substituted phosphonous acid diester and the alcohols.

Description

technical field [0001] The invention belongs to the field of chemical synthesis, and in particular relates to a method for synthesizing an alkyl phosphinate diester compound or an alkyl phosphinate compound under the catalysis of an iodine salt. Background technique [0002] Alkyl phosphinate and alkyl phosphinate structures and their derivatives are abundant in natural products and pharmacologically active compounds. They can also be used as intermediate products and can be further converted into alkylphosphinic acid and alkylphosphinic acid compounds, as well as alkenes and other biologically active molecules with good anticancer and antioxidative abilities. Therefore, the synthesis of alkyl phosphinates and alkyl phosphinate compounds has attracted the attention of more and more organic chemists. [0003] Taking the synthesis of alkyl phosphonites as an example, the traditional method is generally synthesized by the Arbuzov reaction of halogenated hydrocarbons and phosph...

Claims

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Application Information

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IPC IPC(8): C07F9/32C07F9/40C07F9/572C07F9/6553
CPCC07F9/4056C07F9/3241C07F9/4015C07F9/5728C07F9/655345
Inventor 徐清马献涛苏陈良韩立彪
Owner WENZHOU UNIVERSITY
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