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. The electron-domain geometries of the I atoms vis-a-vis secondary I...O bonds were explored. The presence of delocalized bonding in groupings of O and I atoms was suggested. A linear relationship between the C-I-O angles and the I-O bond orders was observed.

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. The Wittig-HTIB approach is a useful alternative to analogous sequences in which Tl(NO3)3.3H2O or the Prevost combination (AgNO3/I2) are employed in the oxidation step.

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. Tris(2-aminoethyl)amine (TREN) reacts with 2 in MeOH/THF on reflux to produce the isoindolequinone derivative of TREN. Water with 2 on reflux in MeOH forms an isobenzofuranquinone. This indicates that the formation of similar heterocycles from small molecules (e.g., Group VA and VIA hydrides) and 2 is likely. Readily synthesizable starting materials, ease of chromatographic isolation of the product, reaction generality, use of no catalyst, and cost-effective environmentally benign solvents such as MeOH/EtOH make this novel reaction simple and convenient.

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.

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 (175.7+/-1.6) degrees. The apexes are occupied by bridging oxide ligands where the I-O-I angles deviate only slightly from an ideal 120 degrees hexagonal angle (116.8+/-1.2) degrees, consistent with sp2 hybridization of the bridging oxygen atoms that participate in three-center four-electron bonds with iodine. These 12-atom hexagons are slightly "chair" distorted at the oxygen atoms. The planes of the rings are separated by layers containing the phenyl rings. The perchlorate ions reside in void spaces created by the three-up, three-down arrangement of the phenyl rings around each 12-membered I-O ring and are positioned directly above and below the I-O rings.