Phosphorus amidate

Hindered rotation around the P-N bond has been observed at low temperature in tetrasubstituted phosphorus amides [28]. For PhjPNJSiMCjJj, two different Me3Si groups are observed below -65 °C, the calculated activation energy for P-N rotation being 10.2 Real moT [29]. Chiral phosphinous amides with stereogenic phosphorus atoms have been prepared [30,31 ]. 

Compounds 160 are still under investigation for their biological activity, as they are expected to exhibit such activity, because of their structure similarity to phosphorus amides bearing 2-chloroethyl substituent at nitrogen. It is well known that... 

A range of mechanisms is possible for the acidolysis of phosphorus amides, depending on the nucleophilicity of the departing amine. A recent study of phosphinic amides (160) in acidic media demonstrated that, when R2 is aryl, the presence of an o-Me group reduced the hydrolysis rate significantly, and also that the mechanism appears to be of an associative type.128 The phosphinic halides (161 X = Cl or F R = Me) are more reactive, probably for steric reasons, than the corresponding halides (161 R = Bu1) in 5 n2(P) solvolyses with aqueous acetone and with alkali. In the case of the t-butyl compounds, the fluoride is more reactive to OH- than is the chloride.129... 

ALKYLHALOPHOSPHINES, ALKYLPHOSPHINES tert-BUTYL PEROXOPHOSPHATE ESTERS iV-CHLORINATED PHOSPHORUS AMIDES HALOPHOSPHINES, METAL PHOSPHINATES METAL PHOSPHORUS TRISULFIDES NON-METAL OXIDES, NON-METAL SULFIDES PHOSPHINES, PHOSPHORUS ESTERS... 

Histidine-specific protein kinases form a phosphorus amide with the 1 or 3 position of His. The members of this enzyme family also phosphorylate Lys and Arg residues. 

Chemical plant safety, 68 Chemical stability/reactivity assessment, 68 Chemical vapour deposition (cvd), 69 Chlorinated paraffins, 69 N-chlorinated phosphorus amides, 69 Chlorinated poly(dimethylsiloxanes), 69 Chlorinated rubber, 69 Chlorine-containing systems, 70 Chlorite salts, 70 Chlorofluorocarbons, 71 N-Chloronitroamines, 71 Chlorophyll, 71... 

According to the method used by Zybill et al. [9], structural type C compounds can be synthesized by the reaction of (H2C=CH)SiCl3 (1) with K2[Cr(CO)5] (2) in THF at -30 °C in the presence of HMPA (Do) (HMPA = hexamethyl phosphorus-amide). The l-chromium-2-sila-l,3-diene complex 3 can be isolated in 60 % yield after recrystallization from THF/npentane solution. 

The reaction of tervalent phosphorus amides containing a NH with activated olefins predictably gives phosphine imines, e.g. (24), through addition and proton transfer. 

The number of compounds mentioned as insect chemosterilants in the literature is more than a thousand. However, only alkylating agents of aziridine and alkanesulfonate type and the nonalkylating phosphorus amides are on the verge of practical application (Bofkovec, 1974). At the same time, the use of chemosterilants offers great possibilities for plant protection. Thus, further research aimed at the elimination of undesirable side-effects by the development of compounds with more selective action seems to be necessary. 

Nitrogen substitution of iminophosphoranes <2002CHE95, 2002PS1701, 1999PS11> and phosphorus amides <2003SL801> has also been used for the synthesis of 1,2-azaphosphinanes (Scheme 19). 

With sodamide, mono- and diamido salts are obtained directly (Chapter 7.3). Ethyl alcohol reacts with the pentoxide to give a mixture of ethyl phosphoric acids (5.291). With phosphorus amides, reaction (4.52) occurs. 

Polymeric phosphorus amide inide is produced directly by reacting phosphorus trichloride with ammonia in ethereal solution at -20°C. 

Olefinic phosphorus amides can form homopolymers with free radical initiation (12.190), while some N derivatives easily form cross-linked polymers (12.191). 

Polyorganophosphazenes are generally more stable to hydrolysis and often more heat resistant than the halides. The waxy [(CF3)2PN] is stable to boiling concentrated adds and does not decompose below 380°C. This polymer is made by chlorination of bis(perfluoro-alkyl)phosphorus amide followed by dehydrohalogenation of the product (12.232). Alternatively, it can be obtained from lithium azide according to Equation 12.233. 

HMPA hexamethyl phosphorus amide TMS tetramethyl silane... 

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