(Phenyl-iodos-yl)benzene tosyl-ate dihydrate.

The structure of the title salt (systematic name: oxodiphenyl-λ-iodanylium 4-methyl-benzene-sulfonate dihydrate), CHIO·CHOS·2HO, at 150 K, has monoclinic (2/) symmetry. The mol-ecular structure features an angular (phenyl-iodos-yl)benzene cation, the geometry of which was hitherto undescribed in the literature: in the cation, both I-C bonds are approximately normal to the I=O bond, forming a C-I-C angle of 95.36 (4)°.

Anhydrides of real and hypothetical [hydroxy(R-O)iodo]benzenes.

The anhydrides of [hydroxy(methanesulfonato-O)]iodobenzene (HMIB) and [hydroxy(toluenesulfonato-O)]iodobenzene (HTIB) were prepared by drying acetonitrile solutions of the compounds. The anhydrides of the hypothetical compounds [hydroxy(chloroacetato)-O]iodobenzene and [hydroxy(iodoacetato)-O]iodobenzene were obtained from aqueous solutions. Crystallographic structures were obtained for the anhydrides, except that of HTIB.

Application of [hydroxy(tosyloxy)iodo]benzene in the Wittig-ring expansion sequence for the synthesis of beta-benzocyclo-alkenones from alpha-benzocycloalkenones.

The conversion of alpha-benzocycloalkenones to homologous beta-benzocyclo-alkenones containing six, seven and eight-membered rings is reported. This was accomplished via a Wittig olefination-oxidative rearrangement sequence using[hydroxy(tosyloxy)iodo]-benzene (HTIB) is the oxidant, that enables the synthesis of regioisomeric pairs of methyl-substituted beta-benzocycloalkenones. The incorporation of carbon-13 at C-1 of the beta-tetralone nucleus was also demonstrated.

Preparation and structure of a solid-state hypervalent-iodine polymer containing iodine and oxygen atoms in fused 12-atom hexagonal rings.

The treatment of dilute aqueous solutions of [hydroxy(tosyloxy)iodo]benzene with aqueous Mg(ClO4)2 produced thin elongated-hexagonal plates exhibiting a supramolecular structure in which tetra-mu-oxopentaiodanyl dication repeat units are joined to each other by significantly ionic bonds and each unit is associated with two perchlorate ions. The linearly extended cationic structure is formed from the 12-atom hexagonal rings of alternating iodine and oxygen atoms, a novel structure. Each 12-membered ring forms a nearly planar hexagonal shape with sides defined by almost linear O-I-O segments (175.

Bis-ketol nucleoside triesters as prodrugs of the antiviral nucleoside triphosphate analogues of 3'-deoxythymidine and 3'-deoxy-2',3'-didehydrothymidine.

Derivatives of 3'-deoxythymidine (ddT) and 3'-deoxy-2',3'-didehydrothymidine (d4T) were prepared in which the 5'-hydroxyl group of the nucleoside was esterified to a bis-ketol phosphate. The resulting phosphate triesters are postulated to be prodrugs of the corresponding 5'-mononucleotides, which are formed intracellularly by the hydrolysis of the two ketol ester groups. The triesters were tested for anti-HIV activity with the result that those derived from ddT showed enhanced antiviral activity when compared to the parent nucleoside.

A Novel High-Yield Synthesis of Substituted Isoindolequinones.

The high-yield, general, one-pot synthesis of substituted isoindolequinones, a group of important radiosensitizers which sensitize hypoxic cells to the lethal effect of radiation in cancer radiotherapy, is described. Primary amines react with 2,3-bis[2-(trimethylsilyl)ethynyl]-5,6-dimethylhydroquinone (2) in methanol at room temperature under an inert atmosphere to give substituted isoindolequinones 2-alkyl-1,3,5,6-tetramethylisoindole-4,7-quinone (4) in almost quantitative yields. Moderate yields of 4 are also obtained using 2,3-diethynyl-5,6-dimethylhydroquinone (3) and amines as reactant and solvent under the similar conditions.