Amidophosphates

STMP reacts with other nucleophiles such as aqueous ammonia to yield amidophosphates, which contains a P—N bond. STMP is used for the modification of the physical properties of starch and proteins by reaction with the amino and hydroxyl groups. 

Phosphorus derivatives of different structures have been prepared including pyrazol-1-ylphosphines PPzs, PhPPz2 and Ph2PPz (Pz for pyrazolate anion (72CRV497,80MI40402)). By transamination with tris(dimethylamino)phosphine, pyrazoles and indazole are converted into (291) and (292), respectively (67CR(C)(265)1507). 3,5-Dimethylpyrazole reacts with amidodichlorophosphates to yield triamides (293) whereas 1-substituted pyrazolones yield amidophosphates (294) (71LA(750)39). 

Pyrrolization takes place in both polar aprotic solvents (sulfoxides and more reluctantly, amidophosphates) and mixtures thereof with nonpolar and low polarity solvents (dioxane, benzene) taken in a volume ratio to cyclohexanone oxime of (1-25) (1-10). The use of mixed DMSO-... 

Phosphoryl triamide forms colorless crystals, probably monoclinic. It is readily soluble in methanol, very soluble in water, but unstable in this solution as it is transformed into orthophosphate via amidophosphates it is insoluble in ethanol. When heated with sodium hydroxide diamido-phosphate is formed. 

Sodium amide, 1 74, 2 80, 128, 134 Sodium amidophosphate (Na2P03NH2), 6 100 anhydrous, for preparation of tetrasodium imidodiphos-phate, 6 101 Sodium azide, 2 139 purification of, 1 79 Sodium azidodithiocarbonate, solution of, 1 82 Sodium butoxide, 1 88 Sodium carbonate, Na2C03, light, for preparation of chlorine (I) oxide, 5 159... 

During examination [48, 49, 115, 116] of the reactions of indole with triamidophosphates, diamidomethylphosphonates, amidophosphate esters, and diamidophosphate esters in the opinion of the authors phosphorylation takes place at position 3 of indole in the first two cases only [49]. 

Diethyl monochlorophosphate is a colorless liquid of irritating, unpleasant odor, with boiling point 89° (at 15 mm.), n 5, 1.4150. It fumes in moist air and reacts vigorously with water. It reacts with ammonia to give ethyl-amidophosphate and with amines to give substituted ethylamidophosphates.5... 

POsF(NH4)2 Ammonium mono-fluorophosphate, 2 155 P03FNa2 Sodium monofluorophos-phate, 3 106, 108 POaHa Phosphorous acid, 4 55 P03NH2(C2Hj)2 Diethyl mono-amidophosphate, 4 77 (POaNa) Sodium polymetaphosphate, 3 104... 

Monamidophosphoric Acid, NH2PO(OH)2, has been obtained by several reactions, among which are the hydrolysis of diphenyl amidophosphate by means of alkali, thus... 

The interaction of cellulose phosphites with carbon tetrachloride and alcohol or amine leads to the formation of intermediate phosphates (VI) and amidophosphates (VII) of cellulose in just the same way as with low-molecular-weight phosphites. 

A single-step synthesis of aziridines has been described by nucleophilic attack of an amidophosphate ester anion on the least-substituted carbon atom of oxiranes (Eq. 181). ... 

Similar to carboxamides, sulfonamides [229,230] and amidophosphates [230] may also be a-methoxylated at the anode. p-Tolysulfonamides of primary amines undergo a rearrangement during anodic oxidation in methanol in the presence of KBr and KOH, leading to a-amino aldehydes [231]. Bromide ion is involved as inorganic redox catalyst. 

Sulfonamides and amidophosphates have been used as starting materials as well... 

E. Suarez and co-workers prepared chiral 7-oxa-2-azabicyclo[3.2.1]octane and 8-oxa-6-azabicyclo[3.2.1]octane ring systems derived from carbohydrates via an intramolecular hydrogen abstraction reaction promoted by A/-centered radicals. The A/-centered radicals were obtained under mild conditions (Suarez modification) from phenyl and benzyl amidophosphates and alkyl and benzyl carbamate derivatives of aminoalditols by treatment with PIDA/I2 or PhlO/l2. The initial A/-radical undergoes a 1,5-hydrogen abstraction to form an alkyl radical, which is oxidized to the corresponding stabilized carbocation (oxocarbenium ion) under the reaction conditions. The overall transformation may be considered as an intramolecular N-glycosidation reaction. 

Reactions of phosphites at centres other than carbon have also been reported. Treatment of the azide (123) with triethyl phosphite in toluene initially yields the Staudinger product (124), which undergoes an unexpected ethyl migration to form the amidophosphate (125). This reaction can be... 

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