From phosphorus trichloride and

Equations 2, 3, and 4 summarize the method proposed by the Germans for preparing parathion (compound E-605). Schrader 13) has reported that thiophosphoryl chloride was synthesized from phosphorus trichloride and sulfur by heating at 130° in a lead-lined autoclave. Woodstock and Adler 14) carried out a similar reaction at 150° to 160° C. 

Moller, T. et al., Inorg. Synth, 1954, 4, 72 During the preparation from phosphorus trichloride and sulfur, the quantity and quality of the aluminium chloride catalyst is critical to prevent the exothermic reaction going out of control. 

Both yellow and red phosphorus ignite on contact with fluorine and chlorine red ignites in liquid bromine or in a heptane solution of chlorine at 0°C. Yellow phosphorus explodes in liquid bromine or chlorine, and ignites in contact with bromine vapour or solid iodine [1]. Interaction of bromine and white phosphorus in carbon disulfide gives a slimy by-product which explodes violently on heating [2], Interaction of phosphorus and iodine in carbon disulfide is rather rapid [3], A less hazardous preparation of diphosphorus tetraiodide from phosphorus trichloride and potassium iodide in ether is recommended [4],... 

Acetals have been used in the presence of Lewis acids, particularly zinc chloride and ferric chloride, for the addition of phosphorus-halogen species to prepare 1-alkoxyphosphonic dichlorides and dialkyl 1-alkoxyphosphonates (from phosphorus trichloride and dialkyl phosphinous chlorides, respectively).143-145 It should be noted that good yields of these types of products have also been reported in the absence of catalysts.146 147 Other types of substrates have also been used in these types of processes. These include acylals,148 amidals,149 orthoformates,150 and orthoacetates.151... 

The tetraphosphorus(III)hexaazaadamantane derivative, P4(NMe)6, is obtained from phosphorus trichloride and methylamine, and a tricyclic compound of composition P4(NPT)6 is formed from ClP(NPri )2PNPri SiMcs by elimination of Me3SiCl. It isomerizes on heating into the adamantane structure. Another tricyclic compound, P4(NBfr)6 with nonadamantane structure is formed by reacting [ClPNBfr]2 with [(LiNBu )PNBfr]2- ... 

Since phosphenyl chloride is readily obtained from phosphorus trichloride and benzene, this method has been applied to the corresponding arsenic compound. Arsenic trichloride (1000 c.c.) and 500 c.c. of benzene are heated together for forty hours and the resulting product fractionated. The fraction between 240° and 260° C. yields fairly ppre product. The method, however, is not a particularly good one, and diphenylchloroarsine is formed at the same time. ... 

Chloromethylphosphoric dichloride, CICHaPOClj. Mol. wt. 167.38, b.p. 79-81 /10 mm. Preparation from phosphorus trichloride and paraformaldehyde at 250°. Supplier Stauffer Chemical Co. 

Reactions with Alkyl Halides.— The in situ generation and reaction of chlorodi-phenylphosphine (2) with a-chloro-ethers gives good yields of a-alkoxyalkylphosphine oxides (20). The phosphine (2) is made from phosphorus trichloride and benzene, and the sequence looks like a very convenient one-pot procedure - the dangers of certain chloro-ethers aside ... 

Finally I worked out the following hypothesis on paper. We know from phosphorus chemistry that the formation of phosphorus pentachloride from phosphorus trichloride and chlorine is a reversible reaction (equation 14). 

The Darzens synthesis of glycidic esters by condensation of carbonyl compounds with a-haloesters is an important and useful method" that has been extended in phosphorus chemistry. Unquestionably, the most general and perhaps most widely employed method for the synthesis of dialkyl 1,2-epoxyalkylphosphonates involves the reaction of dialkyl chloromethylphosphonates with carbonyl compounds. These synthetically useful phosphonates are readily obtained by standard alcoholysis of chloromethylphosphonic dichloride under anhydrous conditions. The latter is obtained in up to 67% yield from phosphorus trichloride and paraformaldehyde at 250°C. Several variations on the preparation of dialkyl 1,2-epoxyalkylphosphonates from dialkyl chloromethylphosphonates and different carbonyl partners have been reported. The conditions for generating the a-metallated dialkyl chloromethylphosphonates were found to be critical because of their notorious instability. 

Preparation.—From Halogenophosphine and Organometallic Reagents. An improved synthesis of trimethylphosphine from phosphorus trichloride and methyl-lithium at —78 °C has been described. Another improved high yield synthesis of the same phosphine uses the reaction of triphenyl phosphate with methylmagnesium iodide. Other trialkylphosphines have also been prepared by this latter method. 

A more convenient preparation is the reaction of phosphorus pentoxide with phosphorus pentachloride (formed in situ from phosphorus trichloride and chlorine) ... 

An improved preparation of (61) and of the new (62) has been published.Some new dialkyl trichloromethylphosphonites (63) have been prepared by a simplified method.The new, chelating bis-phosphite (64) has been prepared as shown.Some (methylthiomethyl)phosphonous acid derivatives (65)-(67) have been synthesized from phosphorus trichloride and the (methylthio-methyl)stannane (68). A series of unsymmetrically substituted (thiophosphonomethyl)phosphonous acid derivatives (69) and (70) has been prepared as shown for use as ligands. 

Kosolapoff (182), who prepared tri- cr -butyl phosphite from phosphorus trichloride and er -butyl alcohol, claimed that This phosphite could not be made to undergo the Michaelis-Arbuzov reaction with alkyl halides at temperatures under 80-90°, while above that temperature it began to decompose with evolution of isobutylene. Further support for the concept that the tertiary ester group is unreactive was provided by the... 

Ethyl phosphinoacetate, C2H502C.CH2.P0(0C2H5)2, occurs when sodium diethylphospliite (obtained from phosphorus trichloride and ethyl alcohol, follow ed by treatment with sodium in the presence of ether) reacts with ethyl chloroacetate. It may also be obtained in 95 per cent, ield w hen sodium ethoxide, diethylphosphite and ethyl chloroacetate react in absolute alcohol solution in other solvents, such as ether or light petroleum, the yields are considerably smaller. The ester boils at 140° to 141° C. at 9 to 10 mm., and reacts with ammonium hydroxide to form an amide, NH2.CO.CH2.PO(OC2H5)2, white glistening needles, M.pt. 78° to 80° C. (corr.). ... 

Dialkyl H-phosphonates are produced in the USA, Japan, Germany and other countries on an industrial scale primarily from phosphorus trichloride and alcohols. (The general procedure for the preparation of dialkyl H- phosphonates is given in the Appendix). 

A more elaborate method for obtaining VPA starts from phosphorus trichloride and ethylene oxide and follows five steps (Scheme 4.5). ... 

Preparation generally from phosphorus trichloride and cyclo-hexylmagnesium bromide. Alternatively by hydrogenation of PPh3 with a niobium catalyst. ... 

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