Synthesis and photolysis of doxyl derivatives of 5β-androstan-3-ones

In an unsuccessful attempt to effect remote functionalization at C9, 4,4-dimethyloxazolidine-N-oxyl (doxyl) derivatives at C3 of 5β-androstan-3,17-dione and 5β-androstan-17β-ol-3-one were prepared and photolyzed. The former doxyl yielded its C13 stereoisomer; the latter was converted very slowly to intractable material.     

Regioselective hydroborations of methylvinylchlorosilanes

The regioselectivity of the hydroboration of the methylchlorovinylsilanes, Cl_nMe_3?nSiCHCH₂ (n= 0 ? 3), has been investigated using BH₃←THF, 9-BBN, disiamyl- and dicyclohexylborane. Methylation of the adducts with methylmagnesium bromide is complicated by formation of tetraalkylboronates. Alkaline hydrogen peroxide oxidation of the boronates gives reasonable yields of the corresponding α- and β-trimethylsilylethanols forn= 0 and 1. Forn= 2 and 3, conversion of the adducts to the corresponding α- and β- deuteroethylsilanes by treatment with excess sodium methoxide in methanol-0-d provides a more effective means of derivatization. Addition of the alkenes,n= 2 or 3, to excess BH₃←THF givesca. 90% of the α-boro-organo-chlorosilanes. For all of the alkenes, the dialkylboranes giveca. 80% of the β-boron adducts.     

Reactions of 6-diazopenicillanates with allylic sulphides,selenides, and bromides

6-Diazopenicillanates react with allylic sulphides, selenides and bromides, to give 6,6-disubstituted penicillanates $\text{via}$ [2,3]-sigmatropic rearrangements.     

Phase relations and exsolution phenomena in the system NiOTiO2

The phase relations in the system NiOTiO₂ were studied between 1000 and 1600°C using quenched powder specimens, DTA runs, and single crystal diffusion couples. Quenching experiments establish the stable phases TiO₂ (rutile), NiTiO₃ an ilmenite structure type, Ni_2(1+x)Ti_1?xO₄ (x ≥ 0.16), a cation-excess spinel, and Ni_1?2xTi_xO (rocksalt structure type). DTA runs reveal the existence of an additional nonstoichiometric ilmenite phase Ni_1?2xTi_1+xO₃ (x ≤ 0.03) above 1260°C. In quenched (1500, 1450°C) or slowly cooled single crystal diffusion couples, mutual oriented exsolutions occur in the rutile crystal and in the ilmenite diffusion zone. Orientation relations are: {101}_rutile{1120}_ilmenite; ∥010〉_rutile∥00.1〉_ilmenite. The cation-excess spinel decomposes below 1375°C into oriented intergrowth of NiTiO₃ (ilmenite) and NiO: {111}_NiO{0001}_NiTiO3; ∥110〉_NiO∥21.0〉_NiTiO3.     

A COMPARISON OF MAMMALIAN CELL SENSITIVITY TO EITHER 254 nm OR ARTIFICIAL "SOLAR" SIMULATED RADIATION

The sensitivity of six mammalian cell strains to either germicidal (254 nm) or artificial "solar" simulated radiation was tested. The solar simulator used had an output similar, in some respects, to natural sunlight. Cellular capacity for Herpes simplex virus production was used as the assay procedure. The tested cells were a strain of African green monkey kidney cells and five human skin fibroblast cell strains. The latter included a "normal" cell strain, and four photosensitive cell strains; three of which were strains of xeroderma pigmentosum cells, and one strain of Bloom's syndrome cells. When comparing the D¹⁰ values, the different cell strains varied by a factor of six in response to germicidal radiation, but only by a factor of two to artificial "solar" simulated radiation. The relative sensitivity of the cells to either type of radiation also varied from 1.7 to 10.9. Large variations in response occurred even among the xeroderma pigmentosum cell strains. These responses suggest that mammalian cell sensitivity to 254 nm radiation may not be a true indicator of a cell's responses to natural sunlight.     

Synthesis and X-Ray Analysis of a Nickel Triphenyl-Cyclopropenyl Complex. A mo-interpretation of the geometry and bonding in the (C3H3)ML3-type of complexes

The reaction of [(C₃Ph₃)Ni(PPh₃)₂]ClO₄ with P(CH₂CH₂PPh₂)₃(pp₃) and NaBPh₄ yields the [(C₃Ph₃)Ni(pp₃)]BPh₄-complex. After long exposure of the solution of this compound in acetone/butanol to the air a new derivative [(C₃Ph₃)-Ni(pp₂po)]BPh₄· 0.5 C₄H₉OH, where pp₂po is (Ph₂PCH₂CH₂)₂P(CH₂ CH₂POPh₂), is obtained. Complete X-ray analysis has been carried out for the latter complex: a=18.303 (5); b=29.445 (6), c=13.305 (5) Å, β=112.70 (9)°; space group monoclinic, P2₁/a, Z=4. Disorder problems were encountered in the refinement of the structure. The best R is 0.093. One of the arms of the parent pp₃-molecule, not coordinated to the metal, undergoes oxidation. The Ni-atom, coordinated by the three remaining P-atoms of the ligand, is also linked in a roughly η³-mode to the cyclopropenium ligand. The geometry of the molecule is examined in detail. Extended HMO-calculations were performed to interpret how the variation of P? Ni? P angles affects the bonding between the NiP₃- and C₃H₃-fragments. The conclusion is that the overall energy of the complex may be lowered in spite of a weakening of the Ni-cyclopropenium linkage. Extensions are made to other systems containing a linkage between a metal and a X₃-ring (X=P,As).     

Multi-residue method for the determination of chlorinated phenol metabolites in urine

Electron-capture-gas chromatographic (EC-GC) methods for the determination of chlorinated phenol metabolites of hexachlorobenzene (HCB) and pentachlorophenol (PCP) in urine are presented. After extraction the sample was reacted with diazomethane to produce the methyl ether of each metabolite prior to determination by EC-GC. An acid alumina column was used for cleanup and separation of methylated phenols into groups. Average recoveries of greater than 80% were obtained from urine fortified with known amounts of the phenol metabolites under investigation. A level of 1 ppb¹ was established as minimum detection limit for each phenol metabolite. Previously unreported urinary metabolites of HCB and PCP were found as a result of a rat feeding study. Levels of chlorinated phenol residues from (a) human general population and (b) a worker occupationally exposed to PCP are also included.     

Semiclassical study of collision-induced predissociation: Comparison of the Landau-Zener model with the method of analytic continuation

Semiclassical calculations are carried out by two methods for the problem of collision-induced predissociation of electronically excited I₂. The first method is that of surface-hopping with the Landau-Zener model. The second method is similar to surface-hopping, except that analytic continuation of the adiabatic potential energy surfaces replaces the Landau-Zener model. Results of the calculations by the two methods compare favorably with each other and with experiment. The possible advantages of the second method are discussed.Camille and Henry Dreyfus Teacher-Scholar, Alfred P. Sloan Research Fellow.     

Development and publication of work with selective ion-sensitive electrodes

Features concerning development, response, selectivity and applications of selective ion-sensitive electrodes are reviewed. Recommendations are made concerning investigations involving the development and applications of electrodes and attention given to the manner of presenting data for publication.