The two new azaphosphatranes HP(RNCH,CH,),N'Cl~ (R = Et, 2c and R = i-Pr, 2d) were prepared from the corresponding (RNHCH,CH,),N and CIP(NEt,),. They were transformed into the title proazaphosphatranes 3c and 3d, respectively, with tert-BuOK. Alternatively, 3d was prepared by the transamination reaction of PCl(NMe,), with (isoPrNCH,CH,),N followed by deprotonation with tert-BuOK. Azaphosphatrane cation salts of 3d, [Z-P (iso-PrNCH,CH,),N]were obtained from the reaction of 3d with ZC1. Competitive deprotonations of azaphosphatrane cation pairs with a stoichiometric deficit of tert-BuOK in DMSO showed the order of basicity: 3e > 3d > P (MeNCH,CH,),N (3b). Compound 3d is also a more efficient catalyst for the trimerization of phenyl isocyanate to phenylisocyanurate than is 3b. A strong correlation (r = 0.996) of the transannular distance with the distance of the P from the plane of its amido nitrogens in nine compounds of the type [ZP (RNCH,CH,),N] + is observed. The molecular structure of 3d shows a P-N,, distance of 3.29 A, which is 1.8% shorter than the sum of the corresponding van der Waals radii. Crystal data for 3d: u = 9.380 (2) A, b = 11.979 (2) A, c = 16.063(3) A, = 95.62(1)", V = 1796.2(6) A3, Z = 4, space group P2,/nd R(e) = 3.62%. The molecular structure of 2d exhibits a transannular R-N,, bond of 1.95 A in a nearly undistorted trigonfl bipyramidalphosphorus. Crystal data for 2d: u = 9.143(4) A, b = 9.319(4) A, c = 11.616(3) A, GL = 87.07(3) ", = 88.64(3)", 7 = 80.62(3)", V = 972.8(6) A,, Z = 2, space group Pi, R = 3.42%.

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.

The efficient synthesis of a new series of acyclonucleotide analogues with a 1,2,3-triazole linker is described starting from diethyl azidomethyl-, 2-azidoethyl-, 3-azidopropyl-, 4-azidobutyl-, 2-azido-1-hydroxyethyl-, 3-azido-2-hydroxypropyl- and 3-azido-1-hydroxypropylphosphonates and selected alkynes under microwave irradiation. Several O,O-diethylphosphonate acyclonucleotides were transformed into the respective phosphonic acids. All compounds were evaluated in vitro for activity against a broad variety of DNA and RNA viruses and cytostatic activity against murine leukaemia L1210, human T-lymphocyte CEM and human cervix carcinoma HeLa cells. Acyclonucleotide 22e exhibited activity against both herpes simplex viruses (HSV-1, HSV-2) in HEL cell cultures (EC₅₀ = 17 μM) and feline herpes virus (EC₅₀ = 24 μM) in CRFK cell cultures, while compounds 20k, 21k, 22k and 23k preferentially inhibited proliferation of human T-lymphocyte CEM cells at IC₅₀ in the 2.8-12 μM range.

A general procedure for the preparation of 1,2,3-triazole analogs of nucleosides from diethyl 2-azidoethoxymethyl- and 2-azidoethoxyethylphosphonates was elaborated. The application of microwave irradiation shortened the reaction time to 10 min in comparison to ca. 48 h when 1,3-dipolar cycloadditions were performed under standard conditions. All compounds were evaluated in vitro for inhibitory activity against a broad variety of DNA and RNA viruses. None of the compounds were antivirally active at subtoxic concentrations. Compound 17k exhibited moderate inhibitory effects on the proliferation of human T-lymphocyte cells (IC50=64 µM for CEM).

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