The reaction of N(CH2CH2NHMe)3 with P(NMe2)3 or P(NMe2)2Cl yields the phosphatrane precursor N(CH2CH2NMe)2P,4. With oxydizing agents or electrophiles 4 is converted to the untransannulated four‐coordinated derivatives N(CH2CH2NMe)3PX, (X: O, S, Se, N3Ph, NPh, I CS2, 1/2 PtCl2). The structures of the compounds described are discussed by 1H, 13C, and 31P n.m.r. data.

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Five phosphorus-containing reagents of the general formula C1P0CR1R2CR3R40 where Rx-R4 ¡= (1), Me (2), or Et (5); Rx-R3 = H and R4 = Me (3); and R1, R4 = H and R2, R3 = Me (4) have been used to derivatize model organic compounds including phenols, aliphatic alcohols, aromatic acids, aliphatic acids, amines, and thiols. The proton-decoupled 31P chemical shifts of these derivatives reveal that, in general, the resonances fall into separated regions for the derivatized classes of these organic compounds. The existence of geometrical isomers of 3 and 4 leads to peak doubling, which militates against these reagents as suitable candidates for the analysis of mixtures of labile H functionalities in coal materials. Reagents 1, 2, and 5, however, serve as suitable reagents for the identification of different functional groups in liquid coal-derived samples. The best results were obtained with reagent 2. Derivatization of pyridine extracts of Illinois No. 6 coal revealed the presence of phenols, carboxylic acids, and aliphatic alcohols. Similar derivatizations of a low-temperature pyrolysis condensate from Illinois No. 6 coal showed no detectable concentrations of carboxylic acids, a relatively small amount of aliphatic alcohols, but considerable quantities of a variety of phenols, several of which could be identified with reagent 2. Other low-temperature condensates derived from Illinois No. 6, Kentucky No. 6, and Pittsburgh No. 8 coals showed a very similar composition of phenolic compounds, regardless of coal type and conditions of pyrolysis.

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