4-(diethoxyphosphorylmethyl)aniline

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: By the same procedure as described in example 1, diethyl 4-(amino)benzylphosphonate (1.94 g; 8 mmoles), triethylamine (0.87 g; 8.6 mmoles), and methacryloyl chloride (0.9 g; 8.6 mmoles) in toluene (9 ml) afford diethyl 4-(methacrylamido)benzylphosphonate as a slight yellow solid (2.3 g; yield 92%).

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of diethyl 4-(amino)benzylphosphonate (2.02 g; 8.3 mmoles) and triethylamine (1.02 g; 9 mmoles) in toluene (7 ml) cooled to 0-5° C., is added dropwise a solution of acryloyl chloride (0.91 g of 95% purity; 10 mmoles) in toluene (2 ml) for 30 min. Thereafter, more toluene (5 ml) is poured into the flask and the mixture is stirred at room temperature for two more hours. The reaction is terminated by addition of water (10 ml). The organic phase is extracted with diethyl ether, dried over MgSO4 and stripped of solvent under vacuum to afford a pale-yellow solid (2.22 g; yield 90%). The reaction is terminated by addition of water (10 ml) The organic phase is extracted with diethyl ether dried over MgSO4 to afford a pale-yellow solid (2.22 g; yield 90%)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: {4-[N′-(3,5-Diaminopyrazol-4-ylidene)hydrazino]benzyl}phosphonic acid diethyl ester was prepared using [4-(N′-dicyanomethylenehydrazino)benzyl]phosphonic acid diethyl ester (0.16 g, 0.5 mmol) which was derived from diethyl 4-aminobenzylphosphonate (0.243 g, 1.0 mmol) and malononitrile (1.5 mmol) in a manner similar to that described in Example 2, and hydrazine hydrate. The title compound was purified by flash chromatography and isolated as a golden solid (0.116 g, 66%); 1H NMR (ppm, 200 MHz, DMSO-d6) δ 1.20 (t, 6H), 3.23 (d, 2H), 3.95 (q, 4H), 6.0 (brs, 4H), 7.28 (d, 2H), 7.60 (d, 2H), 10.70. The title compound was purified by flash chromatography