Phosphoryl trichloride, 88-9

The mixtures of sodium with phosphorus, phosphoryl trichloride or with phosphorus pentachloride combust spontaneously and/or detonate. There is an instantaneous ignition when powdered aluminium is mixed with trichloride or phosphorus pentachloride. 

Oxygen in contact with phosphorus trichloride between 100 and 700°C forms phosphoryl trichloride. The reaction proved to be dangerous (the nature of the accidents was not mentioned). 

The reaction of acetic anhydride with glycerol in the presence of phosphoryl trichloride as a catalyst was carried out the following way ... 

When there is no diluent, organic acid chlorides and metal halides react very violently with DMSO. This goes for acetyl chloride, benzenesulphonyl (C6H5SO2CI), cyanuryl chloride, phosphorus and phosphoryl trichlorides, tetrachlorosilane, sulphur, thionyl, and sulphuryl chlorides. With oxalyl chloride, the reaction is explosive at ambient temperature, but can be controlled at -60°C in a solution with dichloromethane. The dangerous reactions are thought to be... 

The kinetics of deuterium isotope exchange between diphenyl phosphine and t-butylthiol have been studied by H n.m.r. spectroscopy.274 A negative temperature coefficient was observed for the reaction of a perf1uoroalky1 phosphite with a fluorinated aldehyde.275 The kinetics for the reaction of alcohols with phosphoryl trichloride bore strong similarities to those of carboxylic acid derivatives.276 An interesting report desribed the solvolysis of ary 1 hydroxymethyl-phosphonates. It was shown that a phosphoryl group does not prevent carbocation formation on an immediately adjacent carbon atom.277... 

M-Benzyl-O-methyl-L-serinoate (173) was condensed with phosphoryl trichloride giving cyclic chloridate 174 that reacted with the Tegafur derivative 175 with the formation of almost equal amounts of 2-alkoxy-l,3,2 oxazaphospholidine-2-oxides 176a and 176b (Scheme 49) [80],... 

POClj phosphoryl trichloride 6. NOCI nitrosyl chloride... 

Phosphoryl triamide is formed when ammonia reacts with phosphoryl trichloride in chloroform under good cooling 1... 

While the mixture is stirred well, a steady stream of ammonia maintained, and the temperature held at —15°, the phosphoryl trichloride solution is allowed to drip into the ammonia-saturated chloroform over a period of 2 hours. The stream of ammonia is maintained for another hour. Then the cooling mixture is removed and the reaction mixture may remain overnight. The precipitate formed is sucked off rapidly by means of a Buchner funnel, washed with dry chloroform, and dried under vacuum. The yield is approximately 110 g. 

Zyk et al. <2000RJ0794> reported the synthesis of fused-ring thietanes by the reaction of the bis-morpholine sulfide-phosphoryl trihalide complex 85 with norbornadiene. The formation of 4-thiatricyclo[3.2.1.03,6]octane 86 was demonstrated and yields varied slightly depending on the phosphoryl trihalide used. When phosphoryl trichloride was used, the yield was 69% in the case of phosphoryl tribromide, it was 72%. The complex 84 was obtained by the reaction of the bis-morpholine sulfide with phosphoryl trihalide in dichloromethane at —40°C (Scheme 15). The same authors <1996RCB2393> performed a similar reaction of norbornadiene with bis-morpholine disulfide-phos-phoryl tribromide complex 87, which led to the formation of the same thietane 86 in 63% yield (Scheme 15). These reactions have also been described by Robin and Rousseau in a review <2002EJ03099>. 

Primary amides are dehydrated to nitriles using a dehydrating agent like thionyl chloride (SOCl3), phosphorus pentoxide (P2Os), phosphoryl trichloride (POCl3), or acetic anhydride o... 

The use of polyols such as pentaerythritol, mannitol, or sorbitol as classical char formers in intumescent formulations for thermoplastics is associated with migration and water solubility problems. Moreover, these additives are often not compatible with the polymeric matrix and the mechanical properties of the formulations are then very poor. Those problems can be solved (at least partially) by the synthesis of additives that concentrate the three intumescent FR elements in one material, as suggested by the pioneering work of Halpern.29 b-MAP (4) (melamine salt of 3,9-dihydroxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]-undecane-3,9-dioxide) and Melabis (5) (melamine salt of bis(l-oxo-2,6,7-trioxa-l-phosphabicyclo[2.2.2]octan-4-ylmethanol)phosphate) were synthesized from pentaerythritol (2), melamine (3), and phosphoryl trichloride (1) (Figure 6.4). They were found to be more effective to fire retard PP than standard halogen-antimony FR. 

More recently, Bourbigot et al. reported the preparation a neutralized intumescent flame retardant (NIFR) by reacting pentaerythritol, phosphoryl trichloride, and melamine.71 The addition of a small amount of the anhydrous zinc borate (2wt.% at the expense of NIFR) in PP leads to a... 

Phosphorous oxide ignites spontaneously in chlorine, burning with a greenish flame and forming a clear liquid which on distillation yielded phosphoryl trichloride and a residue of metaphosphoryl chloride —... 

PCI3O] phosphoryl trichloride, or phosphorus trichloride oxide phosphoryl trichloride trichloridooxidophosphorus... 

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