tris(2-chloroethyl) phosphite

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: 8.2 g of E-5-bromo-2-formylamino-4-methyl-3-pentenoic acid ethyl ester and 19 ml of tris-(2-chloroethyl)-phosphite are stirred at a bath temperature of 70° for 20 hours. The resulting mixture is chromatographed on silica gel using ethyl acetate and ethyl acetate/isopropanol (7:1) as eluant, and the product is crystallised from ethyl acetate/diethyl ether. In this manner there is obtained E-2-formylamino-4-methyl-5-di(2-chloroethyl)phosphono-3-pentenoic acid ethyl ester, m.p. 47°-49°. The resulting mixture is chromatographed on silica gel the product is crystallised from ethyl acetate/diethyl ether

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

Procedure: 8.2 g of E-5-bromo-2-formylamino-4-methyl-3-pentenoic acid ethyl ester and 19 ml of tris-(2-chloroethyl)-phosphite are stirred at a bath temperature of 70° for 20 hours. The resulting mixture is chromatographed on silica gel using ethyl acetate and ethyl acetate/isopropanol (7:1) as eluant, and the product is crystallised from ethyl acetate/diethyl ether. In this manner there is obtained E-2-formylamino-4-methyl-5-di(2-chloroethyl)phosphono-3-pentenoic acid ethyl ester, m.p. 47°-49°. The resulting mixture is chromatographed on silica gel the product is crystallised from ethyl acetate/diethyl ether

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

Procedure: The same equipment and procedure as in Example 1 was employed. The reaction flask was charged with 100 ml ethylene dichloride and 85 g acetyl chloride (1.1 mole). The addition of 270 g (1.0 mole) tris (β-chloroethyl) phosphite was commenced dropwise and continued for one hour during which there was a slow exotherm to 35° C. After addition of the triphosphite the reaction continued with a self-maintained exotherm at about 40° C. for three hours and then a slow return to ambient temperature while stirring overnight. The pink acetyl bis(β-chloroethyl) phosphite was isolated by rotary evaporatory at 50° C. and 15 torr. The yield was 261 g; acid number 2; purity by infrared analysis was about 75%. to 35° C continued with a self-maintained exotherm at about 40° C. for three hours

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

Procedure: Tris-(2-chloroethyl) phosphite is prepared from phosphorus trichloride and ethylene oxide, and bis(2-chloroethyl) 2-chloroethanephosphonate, inter alia, is formed therefrom by Arbusov rearrangement. After phosgenation and splitting off of hydrogen chloride by means of heat, vinylphosphonic acid dichloride results, which, after purification by distillation, is hydrolyzed with water to give pure vinylphosphonic acid. is formed

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

Procedure: Tris-(2-chloroethyl) phosphite is prepared from phosphorus trichloride and ethylene oxide, and bis(2-chloroethyl) 2-chloroethanephosphonate, inter alia, is formed therefrom by Arbusov rearrangement. After phosgenation and splitting off of hydrogen chloride by means of heat, vinylphosphonic acid dichloride results, which, after purification by distillation, is hydrolyzed with water to give pure vinylphosphonic acid. is formed

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

Procedure: Ethylene oxide, 816 g. (18.5 m) is added subsurface to a stirred solution of 824 g. (6.0 m) of phosphorus trichloride and 8.2 g. of 2-chloroethanol in 2.75 hr with cooling at 15°-20° C. The resulting reaction mixture consists of about 90% tris(2-chloroethyl) phosphite, the remainder being a mixture of phosphonates, is warmed to 80°, and 389 g. (5.4 m.) of acrylic acid containing 100 ppm of hydroquinone monomethyl ether is added in 1.2 hr with cooling at 80°-85°. The reaction mixture is warmed to 130° in 0.5 hr and kept at 130°-140° for 3.25 hr. Stripping to 165°/1 mm leaves 1881 g. of yellow liquid which is a mixture of 2-chloroethyl phosphonates, acidity 9.7 meq/100 g. Washing of a 622 g. portion with 5% sodium carbonate solution, followed by stripping at reduced pressure, gives 590 g. acidity 3.7 meq./100 g. Distillation of a portion of the washed material gives bis(2-chloroethyl) 2-chloroethylphosphonate, b.p. 148°-151°/0.5 mm., and 2-chloroethyl 3-[bis(2-chloroethoxy)phosphinyl]propionate, b.p. 189°-191°/0.1 mm, leaving a mixture containing higher molecular weight 2-chloroethyl phosphonates as undistilled residue. (18.5 m) is added subsurface to a stirred solution of 824 g The resulting reaction mixture is warmed to 80° with cooling at 80°-85° The reaction mixture is warmed to 130° in 0.5 hr Stripping to 165° leaves 1881 g Washing of a 622 g gives 590 g Distillation of a portion of the washed material

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

Procedure: Ethylene oxide, 816 g. (18.5 m) is added subsurface to a stirred solution of 824 g. (6.0 m) of phosphorus trichloride and 8.2 g. of 2-chloroethanol in 2.75 hr with cooling at 15°-20° C. The resulting reaction mixture consists of about 90% tris(2-chloroethyl) phosphite, the remainder being a mixture of phosphonates, is warmed to 80°, and 389 g. (5.4 m.) of acrylic acid containing 100 ppm of hydroquinone monomethyl ether is added in 1.2 hr with cooling at 80°-85°. The reaction mixture is warmed to 130° in 0.5 hr and kept at 130°-140° for 3.25 hr. Stripping to 165°/1 mm leaves 1881 g. of yellow liquid which is a mixture of 2-chloroethyl phosphonates, acidity 9.7 meq/100 g. Washing of a 622 g. portion with 5% sodium carbonate solution, followed by stripping at reduced pressure, gives 590 g. acidity 3.7 meq./100 g. Distillation of a portion of the washed material gives bis(2-chloroethyl) 2-chloroethylphosphonate, b.p. 148°-151°/0.5 mm., and 2-chloroethyl 3-[bis(2-chloroethoxy)phosphinyl]propionate, b.p. 189°-191°/0.1 mm, leaving a mixture containing higher molecular weight 2-chloroethyl phosphonates as undistilled residue. (18.5 m) is added subsurface to a stirred solution of 824 g The resulting reaction mixture is warmed to 80° with cooling at 80°-85° The reaction mixture is warmed to 130° in 0.5 hr Stripping to 165° leaves 1881 g Washing of a 622 g gives 590 g Distillation of a portion of the washed material

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: Vinylphosphonic acid, CH2 =CH--PO(OH)2, can be prepared in a known manner by the following method: Phosphorus trichloride is reacted with ethylene oxide, the resulting tris(2-chloroethyl) phosphite is rearranged to give bis(2-chloroethyl) 2-chloroethylphosphonate, followed by reaction of the bis(2-chloroethyl) 2-chloroethylphosphonate with phosgene in the presence of suitable catalysts to give 2-chloroethylphosphonic dichloride (German Patent No. 2,132,962). The 2-chloroethylphosphonic dichloride can then be converted into vinylphosphonic acid by eliminating HCl in the presence of suitable catalysts (BaCl2) and subsequent hydrolysis of the vinylphosphonic dichloride formed (Chem. Abstr. 54, page 265 (1960)).