Diethyl chlorophosphate

This treatment produced a fabric with durable flame resistance and good strength retention, but an undesirable afterglow this was eliminated by phosphorylation with diethyl chlorophosphate [814-49-3]. 

Diethyl chlorophosphate, supplied by Aldrich Chemical Company, Inc., was used by the submitters without purification and was handled in a glove bag under an atmosphere of dry nitrogen in a well-ventilated hood. The reagent was distilled and stored under nitrogen by the checkers. Aliquots were withdrawn with a syringe as needed. 

Diethyl chlorophosphate Phosphorochloridic acid, diethyl ester (3,9) (814-49-3)... 

Diethyl aniline, 54 Diethylcarbaniazine citrate, 54 Diethyl carbamyl chloride, 54 Diethyl chlorophosphate, 54 Diethylene triamine, 54 Diethyl ether, 54 Di(2-ethylhexyl) phthalate, 54 Diethyl ketone, 54 Diethyl-p-phenylenediamine, 54 Diethyl phthalate, 54 Diethylstilbestrol, 55 Diethyl sulfate, 55 Diethyl zinc, 55 Difluoromethane chloride, 55 Digitoxin, 55 Diglycidyl ether, 55 Digoxin, 55 Diisobutyl ketone, 55 Diisopropylamine, 55 Diisopropyl ether, 55 DIKAMIN , 2,4-D, 55 DIKONIRT , 2,4-D, 55 Dimefox, 55 Dimethoate, 55 3,3 -Dimethoxybenzidine, 55 n,n-Dimethylacetamide, 56 Dimethylamine, 56 4-Dimethylaminoazobenzene, 56 Dimethylaminoethanol, 56 n,n-Dimethyl aniline, 56 7,12-Dimethylbenz[a]anthracene, 56 3,3 -Dimethylbenzidine, 56... 

The synthesis of S-phosphonothiazolin-2-one 133 started with 2-bromothiazole 129. Nucleophilic displacement of the 2-bromide proceeded cleanly with hot anhydrous sodium methoxide to give 2-methoxythiazole 130. Low-temperature metalation of 130 with n-butyl lithium occurred selectively at the 5-position (76), and subsequent electrophilic trapping with diethyl chlorophosphate produced the 5-phosphonate 131. Deprotection of 131 was accomplished either stepwise with mild acid to pn uce the thiazolin-2-one intermediate 132, or directly with trimethylsilyl bromide to give the free phosphonic acid 133, which was isolated as its cyclohexylammonium salt. 

Diethyl chlorophosphate can also be prepared from ethyl alcohol and phosphoryl chloride in the presence of base, but the method shown is reported to give better yields. The intermediate diethyl chlorophosphate has been condensed with nitrophenol in a manner similar to that used for parathion (Equation 39). 

Schrader prepared the ester (38) in 60% yield by reaction of sodium p-nitrophenate with diethyl chlorophosphate, using xylene as solvent for the reaction. He made it, but in lower yields, from p-nitrophenol and diethyl chlorophosphate, using, respectively, pyridine and sodium cyanide as acceptors for hydrogen chloride. Schrader also prepared it in 96% yield by nitrating diethyl phenyl phosphate at 0° C. or below. Under the conditions he used, Schrader claims that the nitro group is directed to the para position. No yield is given for the diethyl phenyl phosphate, which he presumably made from sodium phenate and diethyl chlorophosphate. Diethyl chlorophosphate may be prepared in high yield (30) from diethyl phosphite and chlorine. 

A charge-transfer complex of diethyl chlorophosphate with DMF as the one-carbon source effects the cyclization of thiohydrazides into thiadiazoles 142 (Equation 50) <2004S17>. 

Diethyl chlorophosphate (97%) was obtained from Aldrich Chemical Company, Inc., and distilled before use (bp 58-60°C at 2 mm). This material is a highly toxic acetylcholinesterase inhibitor and must be handled with caution. 

Diethyl chlorophosphate Phosphorochloridic acid, diethyl ester (8,9) (814-49-3) Isoamyl nitrite Nitrous acid, isopentyl ester (8) Nitrous acid, 3-methylbutyl ester (9) (110-46-3)... 

Ti(H2P04,)3 has been prepared by treating titanium disilicide, TiSi2, with H 3 PO4. The reaction of diethyl chlorophosphate, (EtO)2 P(0)C1, with anhyd rous TiCl3 at elevated temperatures leads to de-ethylation of the phosphate and the precipitation of Ti(ethoxychlorophosphate)3. ... 

An oven-dried, 500-mL, two-necked, round-bottomed flask equipped with a magnetic stirring bar, rubber septum inlet, and an outlet connected to a mercury bu oler is flushed with nitrogen and charged with 100 mL of tetrahydrcruran (THF) (Note 1). To this are added sequentially at 0°C, diIsopropyl amine (Note 2) (10.6 g, 14.7 mL, 105 mmol) and butyllithium in hexane (Note 3) (2.22 M, 47.3 mL, 105 nmol). The reaction mixture is stirred for 30 min and cooled to -78°C. 6-Ionone (Note 4) (19.2 g, 20.3 mL, 100 mmol) is slowly added. After stirring the mixture for 1 hr at -78°C, diethyl chlorophosphate (Note 5) (18.1 g, 15.2 mL, 105 mmol) is added, and the reaction mixture is allowed to warm to room temperature over 2-3 hr (Reaction mixture A) (Note 6). 

The submitters used diethyl chlorophosphate available from Aldrich Chemical Company. 

The reactions with l-Iithio-2-butyI- and l-Iithio-2-phenyI-l,2-dihydro-pyridines have. been described with several other reagents including isocyanates, esters, and diethyl chlorophosphate.147 A less familiar adduct from 10-methyl-10//-pyrido[3,2-ft][l,4]benzothiazine and butyllithium has also been tested for reaction with water, deuterium oxide, and diethyl chlorophosphate.148... 

Diethyl chlorophosphate, see Diethyl phosphorochloridate, 1675 Diethyl diazomalonate, 2824 Diethyl-3-diethylaminopropylaluminium, 3408 Diethyl l,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate, 3609 3,6-Diethyl-3,6-dimethyl-1,2,4,5-tetraoxane, 3047... 

Thiophenol Phosphoric acid Acetyl chloride Hydrogen chloride Chlorophosphate Hydrogen chloride Dicyclohexylcarbodiimide Copper iodide Diethyl chlorophosphate... 

In the case of diethyl chlorophosphate 1-ethylindole, the formation of which agrees with data on the alkylating ability of the derivatives of the phosphorus acids, was isolated [114]. In the transition to the dichlorides of P(IV) acids, where the electrophilicity of the phosphorus atom is increased in comparison with the monochlorides, the reaction takes place under milder conditions (at about 0°C) and is accompanied by an insignificant exothermic effect. In the reaction products (121) the phosphorus atom is bonded to the nitrogen atom of indole ... 

However, two other areas are of interest (Fig. 9) namely, a) derivatisation of phenols or amines to phosphorus-containing compounds and b) on-column methylation. In the former, phosphorylation of 7 alcohols and 12 phenols with diethyl chlorophosphate in the presence of triethylamine at 60-70 C in benzene has been reported (35). Aliphatic alcohols, such as methanol, butanol or isoamyl alcohol react instantaneously while phenol and cresols require ca 1-1 1/2 hrs. and xylenols 3-4 hrs. for best results. 

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