M. Krishnaiah

SYNTHESIS OF 8-SUBSTITUTED-16H-DINAPHTHO [2,1-d:1′,2′-g] 1, 3, 2-DIOXAPHOSPHOCIN 8-OXIDES

Abstract A new family of phosphorus heterocycles, namely 8-substituted-16H-dinaphtho[2, 1-d: 1′,2′-g]1, 3, 2- dioxaphosphocin 8-oxides, has been obtained via a synthesis from reaction of bis(2-hydroxy-1-naphthyl)methane with a series of aryl phosphorodichloridates in dry benzene in the presence of triethylamine. NMR analysis of a solution of the title compounds revealed essentially no coupling between the bridged methylene protons and the P atom which suggested the dioxaphosphocin ring may exist in a boat conformation in solution. An X-ray diffraction analysis of a crystal of 8-(2′,3′-dimethylphenoxy)- 16H-dinaphtho[2,1-d:1′,2′-g]1,3,2-dioxaphosphocin 8-oxide does indicate that in the solid state the dioxaphosphocin ring is in a distorted and extended boat-like conformation with the P[dbnd]O and bridged CH2 groups directed away from each other. Electron impact mass spectral analysis confirmed the structures of the esters and showed M+, (M — R)+, and (M – OR)+ ions containing the dioxaphosphocin ring system.

SYNTHESIS, SPECTRAL, X-RAY DIFFRACTION ANALYSIS AND ANTIMICROBIAL ACTIVITY OF 6-ARYLOXY/TRICHLOROMETHYL/CHLOROETHOXY-12-OXO-DIBENZO[d,g] [1,3,2] DIOXAPHOSPHOCIN 6-OXIDES

Abstract Syntheses of several 6-aryloxy-12-oxo-dibenzo[d,g][1,3,2] dioxaphosphocin 6-oxides (3a-i), trichloromethyl-12-oxo-dibenzo[d,g][1,3,2]dioxaphosphocin 6-oxide (3j) and 7-chloroethoxy-12-oxo-dibenzo[d,g](1,3,2]dioxaphosphocin 6-oxide (3k) were accomplished by the reaction of equimolar quantities of 2,2′-dihydroxy benzophenone (1) with various aryl/alkyl phosphorodichloridates (2a-i,2k) and trichloromethyl phosphonicdichloride (2j) in the presence of triethylamine at 45–50[ddot]C. An X-ray diffraction analysis of 6-(4′-methyl phenoxy)-12-oxo-dibenzo[d,g][1,3,2]dioxaphosphocin 6-oxide(3d) revealed that the dioxaphosphocin ring is in distorted-boat conformation with the “oxo” group in a pseudo equatorial arrangement and phosphoryl oxygen (P=O) in equatorial orientation in the solid state. The proposed structures of the title compounds are supported by IR, 1H, 13C and 31P NMR and Mass spectral data. Compounds 3f, 3g, 3h, 3i, 3j and 3k are found to possess significant antibacterial and antifungal activity.

Diethyl [(5-chloro-2-hydroxy-anilino)(4-chloro-phen-yl)meth-yl]phospho-nate.

In the title compound, C17H20Cl2NO4P, the P atom is bonded in a distorted tetrahedral environment. The dihedral angle between the two benzene rings is 80.5 (1)°. In the crystal structure, intermolecular O—H⋯O and N—H⋯O hydrogen bonds link pairs of molecules into centrosymmetric dimers. These dimers, are in turn, linked by weak intermolecular C—H⋯O hydrogen bonds into one-dimensional chains along [010]. Additional stabilization is provided by very weak C—H⋯Cl interactions.

1-(2,4-Dinitrophenyl)-3,5-dimethylpyrazole

The asymmetric unit of the title compound consists of two independent molecules of C 11 H 10 N 4 O 4 . The pyrazole and dinitrophenyl rings are individually planar and are twisted about the N-C sp2 bond joining them by 64°. The two nitro groups attached to the phenyl ring show different degrees of rotation away from the plane of the phenyl ring, with those groups at the para positions rotated by 8.2 (3) and 14.8 (2)°, and those at the ortho positions rotated by 33.5 (1) and 33.2 (1)°. The crystal structure is stabilized by van der Waals interactions.

4-(4-Chloro-phen-yl)-5-phenyl-isoxazole.

The title compound, C15H10ClNO, is a functionalized isoxazole with a chlorophenyl and a phenyl substitutent. The mean plane of the isoxazole ring is inclined to those of the two benzene ring mean planes by 38.32 (16) and 43.91 (18)°.

6-Bromo-2-(4-nitro­phen­oxy)-3-(1-phenyl­ethyl)-3,4-dihydro-1,3,2-benzoxaza­phosphinine 2-oxide

In the title compound, C21H18BrN2O5P, the six-membered oxazaphosphinine ring is in a twist-boat conformation. One of the phosphoryl O atoms is in an equatorial configuation while the other is axial with respect to the oxazaphosphinine ring. The mean planes of the benzene ring to which the nitro group is attached and the phenyl ring form a dihedral angle of 83.5 (1)°. In the crystal structure, weak intermolecular C—H⋯O hydrogen bonds link the molecules into chains along [100].

2,4-Pentanedione Bis(2,4-dinitrophenylhydrazone)

The title molecule, C 17 H 16 N 8 O 8 has approximate non-crystallographic twofold symmetry. The bond lengths in the chain of atoms connecting the two dinitrophenyl groups are consistent with some delocalization of the double bonds in the chain. The molecule adopts an E,E conformation, which favours intramolecular NH...O hydrogen bonding. The dihedral angle between the planes of the phenyl rings is 69.6 (1)°.

2,4,8,10,13-Penta­methyl-6-phenyl-13,14-dihydro-12H-6λ5-dibenzo[d,i][1,3,7,2]dioxaza­phosphecin-6-thione

In the title compound, C25H28NO2PS, the cyclodecene ring exhibits a crown conformation. The two dimethylbenzene rings which are fused symmetrically on either side of the ten-membered ring, make dihedral angles of 20.2 (1) and 18.0 (1)°. The phenyl ring substituted at P is perpendicular to the heterocyclic ring, making a dihedral angle of 88.4 (1)°. The crystal structure is stabilized by very weak intramolecular C—H⋯O hydrogen bonding.

2-Bromo-1,2-diphenylethenyl 4-methyl­phenyl sulfoxide

In the title compound, C21H17BrO2S, the two phenyl rings attached to the ethene group are oriented at dihedral angles of 76.19 (10) and 57.99 (8)° with respect to the Br—C=C—S plane [r.m.s. deviation 0.003 Å]. The sulfonyl-bound phenyl ring forms a dihedral angle of 83.26 (8)° with the above plane. The crystal structure is stabilized by weak C—H⋯π interactions.

3-(6-Methyl-2-pyrid-yl)-2-phen-oxy-3,4-dihydro-1,3,2-benzoxaza-phosphirine 2-oxide.

In the title compound, C19H17N2O3P, the six-membered 1,3,2-oxazaphosphorine ring adopts a twist-boat conformation with the phosphoryl O atom in an equatorial position. The P=O(oxide) bond length is 1.457 (1) Å and the average value of the P—O distances is 1.588 Å. The crystal structure is stabilized by C—H⋯O and C—H⋯π interactions.