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Efficient and novel method for preparing aminophosphonate through catalytic synthesis of hafnium tetrachloride

A hafnium tetrachloride-catalyzed synthesis of aminophosphonate and hafnium tetrachloride technology, which is applied in the field of aminophosphonate synthesis, can solve the problems of poor catalytic effect and no catalytic effect, and achieve fast reaction speed and mild reaction conditions , The effect of high product yield

Inactive Publication Date: 2016-06-08
JIANGXI SCI & TECH NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, these methods generally require the use of 5mol% to 20mol% catalysts, and are mainly suitable for aryl aldehydes and arylamine substrates with better reactivity, while the catalytic effect is lower for alkyl aldehydes and alkylamines with poor reactivity. Poor, some not even catalytic

Method used

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  • Efficient and novel method for preparing aminophosphonate through catalytic synthesis of hafnium tetrachloride
  • Efficient and novel method for preparing aminophosphonate through catalytic synthesis of hafnium tetrachloride
  • Efficient and novel method for preparing aminophosphonate through catalytic synthesis of hafnium tetrachloride

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Experimental program
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Effect test

Embodiment 1

[0017] Synthesis of phenyl-alpha-(anilino)methylphosphonic acid dimethyl ester (formula 1):

[0018] Benzaldehyde (1.00g, 9.43mmol), aniline (0.88g, 9.43mmol), dimethyl phosphite (1.09g, 9.90mmol) and catalyst hafnium tetrachloride (60mg, 0.19mmol) were dissolved in ethanol (6.7mL ), the concentrations of benzaldehyde and aniline were 1.0mol / L, and reacted at 60°C for 0.5 hours. The reaction solution was concentrated to obtain a crude product, and silica gel column chromatography (petroleum ether / ethyl acetate volume ratio = 1:2) gave 2.69 g of dimethyl phenyl-α-(anilino)methylphosphonate (Formula 1), the yield 98%.

Embodiment 2

[0020] Synthesis of phenyl-α-(4-methylanilino) methylphosphonic acid diethyl ester (formula 7):

[0021] Benzaldehyde (1.00g, 9.43mmol), 4-methylaniline (1.01g, 9.43mmol), triethyl phosphite (1.64g, 9.90mmol) and catalyst hafnium tetrachloride (60mg, 0.19mmol) were dissolved in Ethanol (5.8 mL), the concentrations of benzaldehyde and 4-methylaniline were all 1.0 mol / L, and reacted at 60° C. for 0.5 hour. The reaction solution was concentrated to obtain a crude product, and silica gel column chromatography (petroleum ether / ethyl acetate=1:2) yielded 3.19 g of phenyl-α-(4-methylanilino)methylphosphonic acid diethyl ester (Formula 7), Yield 97%.

Embodiment 3

[0023] Synthesis of cyclohexyl-α-(4-cyanoanilino) methylphosphonic acid dimethyl ester (formula 14):

[0024] Dissolve cyclohexanal (1.00g, 8.93mmol), 4-cyanoaniline (1.05g, 8.93mmol), dimethyl phosphite (1.03g, 9.38mmol) and catalyst hafnium tetrachloride (57mg, 0.18mmol) In ethanol (6.2 mL), the concentrations of cyclohexanal and 4-cyanoaniline are both 1.0 mol / L, and react at 60° C. for 1 hour. The reaction solution was concentrated to obtain a crude product, and silica gel column chromatography (petroleum ether / ethyl acetate=1:2) gave dimethyl cyclohexane-α-(4-cyanoanilino)methylphosphonate (Formula 14) 2.79 g, yield 97%.

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Abstract

The invention discloses an efficient and novel method for preparing aminophosphonate through catalytic synthesis of hafnium tetrachloride. With hafnium tetrachloride as a catalytic reagent, aryl / alkyl aldehyde, aryl / alkyl amine and phosphorous acid diester / triester as raw materials, and ethyl alcohol as a solvent, a one-pot reaction is performed for 0.5-2.0 h at 60 DEG C to generate corresponding aminophosphonate, wherein the dosage of the hafnium tetrachloride catalytic reagent is 2 mol% that of aldehyde, and the concentration of aldehyde in an ethanol solution and the concentration of amine in the ethanol solution are both 1.0 mol / L. Hafnium tetrachloride used in the method is high in catalytic activity, small in dosage, capable of achieving the optimum catalytic effect at the dosage of 2 mol%, universally applicable to various aryl aldehyde / amine substrates and alkyl aldehyde / amine substrates and high in product yield. According to the method, reaction conditions are mild, heating is performed just at 60 DEG C, the ethyl alcohol solvent does not need drying, a reaction system does not need gas protection, the reaction speed is high, aftertreatment and purification are easy, and it is only needed to concentrate the reaction system and directly perform conventional silica-gel column chromatography.

Description

technical field [0001] The invention relates to a synthesis method of amino phosphonate, in particular to a new efficient method for synthesizing amino phosphonate by hafnium tetrachloride. Background technique [0002] As structural analogs of natural amino acids, aminophosphonic acid and aminophosphonate compounds are powerful transition-state analog inhibitors (transition-state analog inhibitors) for many enzymes with physiological and pathological activities. Current studies have found that aminophosphonic acid and aminophosphonate can exert strong inhibitory effects on metalloproteases, aspartate hydrolases, phosphohydrolases, ligases, and glycosyltransferases. Therefore, this type of compound has good antibacterial, antiviral, antifungal and anticancer activities. In addition, such compounds also have regulating effects on nerve signal transduction, cardiovascular and cerebrovascular diseases, and growth of plants and insects. [0003] At present, the synthesis metho...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/40C07F9/655
CPCC07F9/4006C07F9/4018C07F9/4056C07F9/65515
Inventor 孙麒龚珊珊李小川曾德云
Owner JIANGXI SCI & TECH NORMAL UNIV
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