Diphenyl chlorophosphate

Diphenyl phosphorochloridate Diphenyl chlorophosphate Phosphorochloridic acid, diphenyl ester (8,9) (2524-64-3)... 

Note Several condensing agents for the direct poly condensation reaction such as diphenyl chlorophosphate-LiBr and tosyl chloride-DMF have also been developed by Higashi et al.311,312 (see Section 2.3.3.2). 

Reaction of the side chain hydroxyacetone in flumethasone (27-4) with periodic acid leads to cleavage of that function to give carboxylic acid (29-1) with the loss of the carbon atom at C-21. Further reaction of the very hindered acid group requires prior activation. Thus, acylation with diphenyl chlorophosphate leads to the mixed anhydride (29-2) this is not isolated, but treated immediately with methyl mercaptan. The product, tibecasone (29-3), is a quite effective topical anti-inflammatory agent [24]. Cleavage of the ester side chain would lead back to the inactive starting acid (29-1). 

Benzoylresorcinol based phosphate esters are obtained by reacting a benzoylresorcinol compound with a chlorophosphate, e.g., benzoylresorcinol with diphenyl chlorophosphate or phosphorus oxychloride. These esters can function both as flame retardants and UV stabilizers for PC/ABS and a series of other polymers (78). 

Diphenyl phosphorochl oridate (diphenyl chlorophosphate), from Aldrich Chemical Company, Inc., was used after purification by distillation at 165-168°C (5 mm). 

DHAP has also been prepared by phosphorylation of dihydroxyacetone with glycerol kinase in the presence of ATP, with in situ regeneration of ATP, giving yields in excess of 80%. The use of chemical methods260 c for the preparation of DHAP generates a pure product, which results in a cleaner aldol reaction. In an improved and commonly used chemical preparation, the protected dimer of dihydroxyacetone was phosphorylated with diphenyl chlorophosphate, followed by hydrogenolysis and hydrolysis, to give clean DHAP in 61% yield (Scheme 5.8).28... 

Materials. Diphenyl chlorophosphate, acetic anhydride, trimethylsilylisothiocyanate, anhydrous dimethylformamide (DMF), anhydrous acetonitrile, and anhydrous pyridine were from Aldrich. Water was purified on a Millipore Milli-Q system. Sodium trimethylsilanolate was obtained from Fluka. Diphenyl phosphoroisothiocyanatidate was synthesized as described (14). All of the peptides used in this study were either obtained from Bachem or Sigma. N-Acetyl proline was from Sigma. 

Two methods have been presented for the phosphonation of poly(bro-moaryloxyphosphazenes), viz. via sodium dialkyl phosphite as reagent or via a treatment with Bu Li in combination with dialkyl chlorophosphate. The reactions are visualized by the product formation of (206) and (208) from (205) and (207), respectively. Polyphosphazenes with diphenyl phosphonate groups (209) have been synthesized by the reaction of the bromophenoxy substituted polymer (207) with Bu Li followed by a rapid addition of diphenyl chlorophosphate in thf. Only 50% of the available bromophenoxy groups are converted to diphenyl phosphonate esters groups. ... 

Reaction with chlorophosphates. The nucleophilicity of DBU may dominate in such reactions. Instead of acting as a base DBU can participate directly, e.g., in forming 1 with diphenyl chlorophosphate. 

Very few cyclopropyloxy phosphorus compounds have been prepared directly from the corresponding cyclopropanol derivatives. Methyl 1-hydroxycyclopropanecarboxylate (1) was treated with sodium hydride followed by diethyl chlorophosphate to give the corresponding cyclopropyl diethyl phosphate 2. 2-Trimethylsilylethoxymethyl 1-hydroxycyclopropane-carboxylate (3) reacted in a similar manner with diphenyl chlorophosphate in the presence of 4-(dimethylamino)pyridine and triethylamine to give phosphate 4 in 70% isolated yield. ... 

End-labelling of the active centres with diphenyl chlorophosphate, combined with31P NMR spectroscopy, was shown to be an effective method for the determination of structure and concentration of the active species in the polymerization of several oxirane compounds.96 98 The chemical shifts of31P signals from the diphenylphosphoryl end-groups are sensitive to the structure of polymer chain end to which it is attached. Thus the 31P NMR spectrum provides information whether the propagating anion is secondary or primary. A similar... 

Replacement of side chain carbon C21 by thioester sulfur retains corticoid activity and at the same time provides a function that is destroyed by serum enzymes. The synthesis starts with the potent antiallergic agent flumethasone (32-1). Reaction of that steroid with periodic acid cleaves the terminal bond in the hydroxyacetone side chain to give the hydroxyl acid 32-2 (Scheme 7.32). Steric hindrance around the acid invoke the need for extra activation of that function. Reaction of 32-2 with diphenyl chlorophosphate thus provides the mixed anhydride 32-3. This intermediate is not isolated but reacted in situ with AA -thioformamido chloride. The transient new mixed anhydride, 32.4, then undergoes an internal O to S rearrangement to give the acyl thioacid 32-5. Saponification with sodium hydroxide affords the corresponding thioacid. Alkylation of that intermediate with fluoromethyl bromide then yields the fluoromethyl thioester fluticasone (32-6). 

One of the intermediate products from the reaction of phosphorus oxychloride with phenol, diphenyl chlorophosphate, (PhO)2POCI, interacts with N-hydroxysuccinimide in dichloromethane at 15 C to afford the mixed ester shown (ref.39). 

CTABr/n-butanol/hexadecane in alkaline solution diphenyl chlorophosphate gave... 

Hazardous Decomp. Prods. Heated to decomp., emits acrid smoke and irritating fumes Uses Plasticizer solvent chem. intermediate for synthesis of polycarbonate resins Manuf./Distrib. Aldrich http //www.sigma-aldrich.com] Fluka http //www.sigma-aldrich.com] Sigma Diphenyl chlorophosphate CAS 2524-64-3... 

Diphenyl phosphonate. See Diphenyl phosphite Diphenyl phosphorochloridate Diphenyl phosphoryl chloride. See Diphenyl chlorophosphate Diphenyl phthalate... 

DPA. See Propanil Diphenylamine 2,2-DPA. See Dalapon-sodium DPCF. See Di phenylcresyl phosphate DPCP DPCP. See Diphenyl chlorophosphate DPDP. See Diphenyl isodecyl phosphite DPG lo. See Dipropylene glycol DPG. See Diphenylguanidine Dipropylene glycol... 

Phosphorochlorendic acid diphenyl ester. See Diphenyl chlorophosphate Phosphorodichloridic acid, phenyl ester. See Phenyl dichlorophosphate Phosphorodithioic acid s-((t-butylthio) methyl)-0,0-diethyl ester. See Terbufos Phosphorodithioic acid, S-((6-chloro-2-oxo-3(2H)-benzoxazolyl) methyl) 0,0-diethyl ester. See Phosalone... 

Diphenyl chlorophosphate N,N -Diphenyl-p-phenylenediamine Diphenyl sulfide Ethylacetoacetate p-Ethylbenzaldehyde... 

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