Sodium phosphoramidate

Sodium phosphoramidate, Na2P03NH2, 6 100, 101 Sodium phosphorothioate, Na3-P03S, 6 102 12-hydrate, 5 103 Sodium pyrophosphates, 3 98 Na2H2P2C>7, 3 99 Na4P2C>7, 3 100 Sodium pyrosullite, 2 162, 164 and its 7-hydrate, 2 165 Sodium rare earth sulfates, 2 42, 46... 

The resonance in the trimer is justified by the fact that all the NP distances are the same (1-67 A) which are less than that expected for a PN single bonds (1,78°A) as in sodium phosphoramidate. 

In phosphates containing amino groups, zwitterion formation in the solid state is quite common. It occurs for example in sodium phosphoramidate NaHPOj NHj, where the crystal lattice contains a network of O-H-0 and N-H-O bonds formed from units of Na+[03P NH3] (Figure 13.5) [19]. This compound is isoelectronic with sulphamic add H3N+-SOJ (7.60b). 

Condensation of sodium phenoxide witli 2,2,2-trifluoroethyl iodide gives a product of direct substitution in a low yield, several other ethers are formed by eliminatton-addition reactions [7] Use of mesylate as a leaving group and hex amethyl phosphoramide (HMPA) as a solvent increases the yield of the substitution [S] Even chlorine can be replaced when the condensation is performed with potassium fluoride and acetic acid at a high temperature [9] (equations 6-8)... 

See Chlorine Nitrogen compounds, or Dimethyl phosphoramidate Phosphorus pentachloride Urea Sodium chloride Nitrogen compounds See other irradiation decomposition incidents... 

N1 -acylsulfanilamides, 23 508 A21-heterocyclic derivatives, 23 508 Ar -heterocyclic-Ar -acylsulfanilamides, 23 508 A21-heterocyclic sulfanilamides, 23 507—508 2V-(2-aminoethyl)-l,3-propylenediamine physical properties, 5 486t 2V-(2-aminoethyl)-piperazine (AEP), 5 485 N2 oxidation, Birkeland-Eyde process of, 27 291-292, 316. See also Dinitrogen entries Nitrogen entries N3 -P5 phosphoramidates, 27 630-631 Na+, detection in blood, 24 54. See also Sodium entries Nabarro-Herring creep, 5 626 Nacol 18, chain length and linearity, 2 10t Nacreous pigments, 7 836-837 19 412 Nacrite, 6 659... 

REDUCTION OF ALKYL HALIDES AND TOSYLATES WITH SODIUM CYANOBOROHYDRIDE IN HEXAMETHYL-PHOSPHORAMIDE (HMPA) A. 1-IODODECANE TO n—DECANE B. 1-DODECYL TOSYLATE TO n-DODECANE, 53, 107 REDUCTION OF KETONES BY USE OF TOSYLHYDRAZONE DERIVATIVES ANDROSTAN-17 0—OL, 52, 122 REDUCTIVE AMINATION WITH SO-... 

Diethyl 7V-(t-butoxycarbonyl)phosphoramidate 18 is obtained from diethyl phospho-ramidate by successive treatment with oxalyl chloride and t-butyl alcohol. It forms a stable non-hydroscopic sodium salt, which reacts with a variety of alkyl halides in benzene in the presence of tetrabutylammonium bromide under phase-transfer conditions to give the corresponding TV-alkyl derivatives. The latter are cleaved by hydrogen chloride in benzene to yield amine hydrochlorides (equation 16)48. 

An Arbuzov reaction of triethyl phosphite with A-chloroamines RNHC1 (R = i-Pr, cyclohexyl or PhCH2), prepared from the corresponding amines and aqueous sodium hypochlorite, leads to the phosphoramides 357 with the elimination of ethyl chloride395. 

Dehydroprogesterone (1) was purchased from Sigma Chemical Company and used without further purification. Cuprous bromide-dimethyl sulfide complex was prepared according to House s procedure.2 Hexamethyl-phosphoramide, chlorotrimethylsilane, and triethylamine were purchased from Tokyo Kasei Kogyo Co., Ltd., Japan and distilled from calcium hydride (CaH2>. Tetrahydrofuran (THF) was distilled from sodium-benzophenone ketyl immediately prior to use. Methylene chloride was distilled from phosphorus pentoxide (P2O5). 

Treatment of the A -Q3-haloalkyl)phosphoramidate anti-1 (X = Br) with sodium ethoxide gave tra .v-l-(diethoxyphosphinyl)-2-methyl-3-phenylaziridine (97%) reduction with lithium aluminum hydride in diethyl ether gave trafw-2-methyl-3-phenylaziridine in 90% yield93. 

The sodium salt of diethyl N-(r-butoxycarbonyl)phosphoramidate (98) reacted with alkyl halides in boiling benzene in the presence of tetrabutylammonium bromide to give the corresponding N-alkyl derivatives (99) in 71-95% yields for primary alkyl halides and 38-58% yields for secondary a-halo esters (in MeCN). The phosphoryl and r-butoxycarbonyl groups were removed by treatment overnight with benzene saturated with dry HCl (Scheme 41). ... 

One of the two hydrogen atoms of phosphoramidates can be temporarily blocked with a trimethylsilyl group. The sodium salt of diethyl V-(trimethylsilyl)phosphoramidate (102) reacted with alkyl bromides in benzene in the presence of 10 mol % of tetra-n-butylammonium bromide to afford, after desilylation, the corresponding V-alkyl derivatives (103) in 79-95% yields for primary alkyl halides. Secondary alkyl halides gave poor results (Scheme 43). The addition of the quaternary ammonium salt is essential to promote the alkylation reaction. Hexamethyldisilazane and its cyclic analogs can also be utilized in the preparation of amines under moderate conditions (Scheme 43). ... 

Use in synthesis. Wadsworth and Emmons condensed diethyl phosphonate with carbon tetrachloride and cyclohexylamine according to A. R. Todd (1945) to produce diethyl cyclohexylaminephosphoramidate (3). The initially formed trichloro-methylphosphonate (2) reacts with a second mole of amine with elimination of chloroform to give (3). Treatment of this phosphoramidate with sodium hydride in... 

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