Method for solvent-free solid phase catalytic synthesis of hydroxyl phosphonic acid ester

A solvent-free technology for synthesizing hydroxyphosphonates, applied in the field of solvent-free solid-phase catalytic synthesis of hydroxyphosphines and synthesizing hydroxyphosphonates, can solve the problems of easy deliquescence, complicated operation process, difficult synthesis, etc., and avoid the generation of waste water , the effect of simplifying the synthesis process and reducing the cost

Inactive Publication Date: 2013-12-25
XINXIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the reaction conditions are harsh, the catalyst is highly toxic or the preparation process and operation process are complicated
[0004] Based on various documents and related patents, the synthesis of hydroxyphosphonate still has a small yield, and the following shortcomings are common: the strong base catalyst rearranges hydroxyphosphonate into phosphate, the catalyst is highly toxic, deliquescent, difficult to synthesize, and the synthesis process is difficult.

Method used

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  • Method for solvent-free solid phase catalytic synthesis of hydroxyl phosphonic acid ester

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] In a 100mL three-necked flask, add furfural (0.96g, 10mmoL), dimethyl phosphite (1.2g, 11mmoL) and potassium carbonate (1.38g, 10mmoL), stir, heat to 30°C to melt furfural, and react for about 60 Minutes, all the reactants solidified. Then 40 mL of ethyl acetate was added, stirred for 20 minutes to dissolve the product, and filtered. The filtrate was concentrated and recrystallized to obtain the product (1.94 g), with a yield of 94%. Recover solvent. Dry the filter cake for later use. 1 HNMR (CDCl 3 , TMS, 400Hz) δ 3.74–3.85 (m, 6H, 2×(O–CH 3 )), 6.38 (d, 1H, J = 13.6Hz), 6.42–6.76(m, 3H, C 4 h 3 O–); HRMS Calcd. for C 7 h 11 o 5 P: 206.0344, found: 207.1061.

Embodiment 2

[0024] In a 100mL three-necked flask, add 2-thiophenecarbaldehyde (1.12g, 10mmoL), diethyl phosphite (1.52g, 11mmoL) and potassium acetate (0.49g, 5mmoL), stir, and heat to 50°C to make 2-thiophene The formaldehyde melted and reacted for about 10 hours, and all the reactants solidified. Then 20 mL of dichloromethane was added, stirred for 20 minutes to dissolve the product, and filtered. The filtrate was concentrated and recrystallized to obtain the product (2.30 g), with a yield of 92%. Recover solvent. Dry the filter cake for later use. 1 HNMR (CDCl 3 , TMS, 400Hz) δ 1.42 (m, 6H, 2×(C–CH 3 )), 3.70–3.81(m, 6H, 2×(O–CH 3 )), 6.51 (d, 1H, J = 13.3Hz), 6.69–7.23 (m, 3H, C 4 h 3 S–); HRMS Calcd. for C 9 h 15 o 4 PS: 250.0429, found: 251.1161.

Embodiment 3

[0026] In a 100mL three-necked flask, add 2-acetylfuran (1.10g, 10mmoL), dibutyl phosphite (1.14g, 11mmoL) and potassium carbonate (0.69g, 5mmoL), stir, and heat to 70°C to make 2-acetylfuran The furan melted and reacted for about 24 hours, and all reactants solidified. Then 40 mL of ethyl acetate was added, stirred for 20 minutes to dissolve the product, and filtered. The filtrate was concentrated and recrystallized to obtain the product (2.86g) with a yield of 94%. Recover solvent. Dry the filter cake for later use. 1 HNMR (CDCl 3 , TMS, 400Hz) δ 1.31 (m, 12H, 4×(C–CH 3 )), 1.5 (m, 2H, 2×(O–CH) ) 1.67 (d, 3H, J = 15.6Hz, CH 3 ), 3.70–3.81 (m, 6H, 2×(O–CH 3 )), 6.47 (d, 1H, J = 13.6Hz), 6.62-7.27 (m, 3H, C 4 h 3 O–); HRMS Calcd. for C 12 h 21 o 5 P: 276.1127, found: 277.2081.

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Abstract

The invention discloses a method for solvent-free solid phase catalytic synthesis of hydroxyl phosphonic acid ester, and belongs to the field of organic chemistry. According to the structure of the hydroxyl phosphonic acid ester, R1 is hydrogen or C1-5 alkyl group or phenyl group, R2 is hydrogen or C1-alkyl group or phenyl group, R1 and R2 form a 3-5-membered heterocyclic ring, and R3 is methyl or ethyl or propyl group or isopropyl or butyl or isobutyl. The synthetic method comprises the steps that ketone or aldehyde compounds, phosphite ester and solid catalysts are heated to enable compounds with raw materials including carbonyl to be melted, and stirring and reactions are carried out; the compounds are cooled to be indoor temperature, solvents are added, and the hydroxyl phosphonic acid ester is obtained through filtering and recrystallization. The method has the advantages that the technological process is simple, the catalysts and the solvents can be recycled and reused, production cost is low and the quality of the hydroxyl phosphonic acid ester is high, and is suitable for the industrialized synthesis of the hydroxyl phosphonic acid ester.

Description

technical field [0001] The invention relates to a method for synthesizing hydroxyphosphonate, in particular to a solvent-free solid-phase catalytic synthesis of hydroxyphosphine [0002] An ester method belongs to the field of organic chemistry. Background technique [0003] Hydroxyphosphonate compounds have important biological activities and are widely used in enzyme inhibitors, anti-virus, anti-parasite, anti-AIDS and other drugs. Hydroxyphosphonate compounds are also important raw materials for the synthesis of hydroxyphosphonate derivatives . The traditional method for synthesizing quaternary carbohydroxyphosphonate compounds is to obtain them under the catalysis of various bases. However, strong bases make it difficult for base-sensitive ketones to obtain target compounds, and the products are easily rearranged to form by-products. Recently, triethylamine, tetraisopropyl titanate, potassium hydrogen phosphate, metal amino complexes, and 2,6-pyridinedicarboxyl...

Claims

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Application Information

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IPC IPC(8): C07F9/6574C07F9/6553C07F9/655
CPCY02P20/584
Inventor 王储备周建伟王颖刘颖褚亮亮苏新梅
Owner XINXIANG UNIV
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