Volume 31, Issue 10

In the reaction of magnesium with trimethylchlorosilane and t-butyldichlorophosphane the hitherto unknown tri-t-butyl-cyclotriphosphane, (t-BuP) 3 (1), is produced besides the partially silylated phosphanes t-BuP(SiMe 3 ) 2 and (t-BuPSiMe 3 ) 2 as well as the cyclotetraphosphane (t-BuP) 4 . Shortly after the beginning of the reaction the amount of 1 is about 50 mole-% and decreases during the reaction time. Thermally and in solution the P 3 ring compound (1) is surprisingly stable and can be isolated in a pure state by fractional distillation. (t-BuP) 3 clearly differs from the oligomeric (t-BuP) 4 by the lower melting point, the molar mass and by the 31 P NMR and IR spectra. The t-butyl groups in 1 are situated above and below the P 3 ring plane.

A high yield synthesis of tri-t-butyl-cyclotriphosphane from magnesium and tertbutyldichlorophosphane is described.

The electrical conductivity of polycrystalline pellets of ZnSO 4 · 7 H 2 O, MgSO 4 · 7 H 2 O, CuSO 4 · 5 H 2 O, KAl(SO 4 ) 2 · 12 H 2 O, NH 4 Al(SO 4 ) 2 · 12 H 2 O and KCr(SO 4 ) 2 · 12 H 2 O was measured. By coulometry the role of protons as charge carriers was determined. A correlation is given between the strength of hydrogen bonds and the activation energies for the proton conductivity.

By reaction of carbon tetrachloride with lithium tris(trimethylsilyl)hydrazide and then with lithium butyl a compound with formula (Me 3 Si) 2 N 2 C is formed. From the way of preparation, spectroscopic investigations, and chemical reactions the substance is characterized as bis(trimethylsilyl)aminoisocyanide (3). 3 hydrolyzes, and does not react with oxygen. The compound combines with chlorine and bromine forming aminoisocyanide dihalides, and with carbon disulfide forming an adduct. At higher temperatures 3 isomerizes to bis(trimethylsilyl)carbodiimide (1).

New compounds of stoichiometry [Pt(II)L 2 ](TCNQ) 2 , [Pt(II)L 2 ](TCNQ) 3 and [Pt(II)L 2 ](TCNQ) 4 (with L = one bidentate or two monodentate neutral nitrogen donor ligands like ethylenediamine (en), 1,10-phenanthroline (phen) or ammonia) have been prepared and characterized. The complexes of stoichiometry [Pt(II)L 2 ](TCNQ) 2 with only negatively charged TCNQ- units have relatively low conductivities (in the range of 10 -7 —10 -8 Ω -1 cm -1 ) while the compounds [Pt(II)L 2 ](TCNQ) 3 containing one neutral TCNQ molecule per formula unit (“complex TCNQ-salts”) conduct much better (in the range of 10 -2 —10 -3 [Ω -1 · cm -1 ] for pellets). Most of them show appreciable deviations from a Curie law behaviour. A sharp transition from an antiferromagnetic low temperature to a paramagnetic high temperature modification can be observed for [Pt(II)dipy 2 ](TCNQ) 2 (dipy = 2,2′-dipyridyl) at 87°C.

The 100 MHz 1 H NMR spectrum of vinyl-p-anisyl-dithiophosphinic acid trimethylsilylester is analyzed by iterative methods. Data for ABCX and [AB] 2 X spinsystems are reported.

Reaction between (η-C 5 H 5 ) 2 TiCl and Zn(B 10 H 12 ) in tetrahydrofurane leads to a green, paramagnetic [(η-C 5 H 5 ) 2 Ti · OC 4 H 8 · OC 3 H 6 ] 2 [Zn(B 10 H 12 ) 2 ] · OC 4 H 8 whose structure was solved by statistical and Fourier methods.

The new ternary compounds NaAlSe 2 , NaAlTe 2 , NaGaTe 2 and KAlTe 2 crystallize in the Tl I Tl III Se 2 -structure type. The analogous Tl-compounds build up the same structure but show a variable composition within the limits (Na x Tl 1-x )TlSe 2 (0 < x < 0.47) and (K x Tl 1-x )TlSe 2 (0 < x < 0.56). The compounds KAlSe 2 , KGaSe 2 , KInSe 2 and KGaTe 2 crystallize in a new structure type.

Na 2 Ga 2 Se 3 crystallizes trigonal/rhomboedric with a = 3.96 ± 0.02 Å and c = 25.01 ± 0.006 Å, c/a = 6.31. Na-atoms and Ga 2 -dumbbells occupy distorted octahedral sites in a close-packed ... ABCABC ... arrangement of Se-atoms. The final R-value is 0.143.

The three new compounds crystallize orthorhombic, space group Cmcm with Na 2 CuAs: a = 8.86(2) Å, b = 7.22(2) Å, c = 5.34(2) Å; K 2 CuAs: a = 10.02(2) Å, b = 7.56(2) Å, c = 5.89(2) Å; K 2 CuSb: a = 10.50(2) Å, b = 7.93(2) Å, c = 6.23(2) Å. There are Cu–E(V)–Cu–E(V)-zigzag-chains in the structure, in which the Cu-atoms are linearly bonded to the E(V)-atoms.

The preparation of the mixed complexes mer-[OsBr n I 3-n (Py) 2 (Mepyz)], n = 1, 2, by substituting or oxidizing exchange of the halide ligands and the chromatographic isolation of the pure compounds is described. Some steps of the successive substitution reactions take a stereospecific course due to the different trans-effects of I - and Br - .

Decacarbonyldimanganese reacts with the tritertiary phosphine 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos) to give the ionic complex [Mn(CO) 3 triphos][Mn(CO) 5 ]. Treatment of [Mn(CO) 3 triphos][Mn(CO) 5 ] with Na[B(C 6 H 5 ) 4 ], HClO 4 and NH 4 PF 6 yields the manganese(I) salts [Mn(CO) 3 triphos]Y (Y = B(C 6 H 5 ) 4 , ClO 4 , PF 6 ). The IR (2100-300 cm -1 ) and FIR spectra (350-200 cm -1 ) of all compounds are reported. Based on Raman polarization data the assignment of the v(CO) (A 1 + E), δ(MnCO) (A 1 + 2 E), v(MnC) (A 1 + E) and v(MnP) (A 1 ) modes was possible for the coordination polyhedra cis-Mn(CO) 3 P 3 (point group C 3v ). The v(MnP) (E) mode was unobserved due to its very low frequency.

The crystal structure of (PyH) 2 (Mo 2 O 4 Cl 4 ) · 3 H 2 O, earlier formulated as tetrameric di-μ-oxo-bis(di-µ-oxo-oxotetrachloroaquodimolybdate(V)), [(PyH) 4 ][Mo 4 O 8 Cl 8 (H 2 O) 2 ], has been determined. The structure consists of the dimeric anions [Mo 2 O 4 Cl 4 ] 2 - with strong Mo=O ••• Mo interactions along the short c axes (c = 4.11 Å). The polymeric [N(CH 3 ) 4 ] 2 [Mo 2 O 3 (C 2 O 4 )(NCS) 4 ] and the dimeric [(PyH) 4 ][Mo 2 O 3 (C 2 O 4 ) 2 (NCS) 4 ] have been synthetized and characterized by infrared spectra and magnetic properties.

Cyclic carbamoyl complexes (2) and (3) result from the reaction of metal carbonyl hydrides with 3,3-pentamethylen diaziridine (1). 1 is cleaved at the metal by reaction with substituted metal carbonyls of Mo and W formally into ‘nitrene’ and cyclohexanone imine, which are isolated as isocyanate and ketimine complexes, respectively. 1 forms adducts with cobalt and nickel(II) chlorides.

The Mössbauer investigations of V 1-x Fe x O 2 with x = 0.024 indicate that Fe enters two cation positions of M 2 and M 3 . At the phase transition the two quadrupole splittings show a discontinuous behavior whereas the isomer shift changes continuously with a crossingover at the M 2 , M 3 transition (T t′ = 275 K). Generally a first order phase transition is accompanied by a change of the cell volume V and a change of the isomer shift. The observed continuous behavior of the isomer shift points to a first order transition with δV ≠ 0.

The mass spectra of some aryl hydrazines under electron impact are reported. In every case studied fragmentation occurs via fission of the weak hydrazyl N—N bond and hydrogen migration. Metastable ion data is presented in support of a proposed mechanism and some comparisons made between electron and radiation induced processes.

The preparation of the key intermediate for spin labeling, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (2), was reinvestigated using sodium tungstate or phosphotungstic acid with or without either Trilon or Triton B. A two-fold and a 3.5-fold molar excess of a 30% aqueous hydrogen peroxide solution was used. The oxidation of 4-hydroxy-2,2,6,6-tetramethylpiperidine (1) with a two-fold molar excess of a 30% aqueous hydrogen peroxide solution in the presence of sodium tungstate alone, under vigorous stirring for two hours, is the superior method (A) for the preparation of 2 in virtually quantitative yield.

The phosphorodichloridates (1) of cholesterol, β-sitosterol, testosterone, diacetone-D-glucose, and tocopherol were prepared from phosphorus oxychloride in the presence of triethylamine. Tocopheryl phosphorodichloridate was too unstable to be isolated. Reaction of 1 with ethyleneimine in the presence of triethylamine gave the corresponding Ν,Ν,Ν′,N′-bis(ethylene)-phosphorodiamidates (2).

The phloroglucine derivatives (2 a–h) react with (+)-trans-p-menthadien-(2,8)-ol-(1) to give the oxygen analogous of (—)-Δ 8 -tetrahydrocannabinole such as 3 a–h. Some of these derivatives were converted by HCl-addition/elimination into the isomeric Δ 9 -compounds. The proposed structures of the derivatives are supported by spectroscopic data ( 1 H NMR, IR and MS).

6-Mercapto anhydro salts of imidazo(1,2-b)- (2) and s-triazolo(4,3-b)pyridazines (7) were prepared and investigated. They were transformed into the corresponding 6-methylthio derivatives (3 or 8). Compounds of the type 3 are thermally demethylated into 4, but in the case of the 2-unsubstituted compound (3, R = H) also ring opening occurred to give compound 5 as minor product.

9,10-Diazophenanthrone undergoes WOLFF rearrangement in alcoholic solvents and yields esters of 9-fluorene carboxylic acid. By flash light photolysis four intermediates could be detected. Kinetic measurements showed that the ketene formed by photolysis reacts with the solvent to give a cyclopentadienylic carbanion, which is protonated. A carbene or an oxirene intermediate could not be found.

4,6-Diaryl-2-carboxymethylthio-3,4,5,6-tetrahydro-s-triazines are cyclised to 5,6,7-trihydro-5,7-diarylthiazolo[3,2-b]-s-triazine-3(2H)-ones (3). 2-Arylmethylene-5,6,7-trihydro-5,7-diarylthiazolo[3,2-b]-s-triazin-3(2H)-ones (4) were prepared by several methods. Compounds 3 coupled with diazotised anilines to give 2,3,5,6,7-pentahydro-5,7-diarylthiazolo[3,2-b]-s-triazine-2,3-dione 2-arylhydrazones (5). The action of amines on 3 a opens the thiazolone ring with the formation of substituted (4,6-diphenyl-tetrahydrotriazin-2-ylthio)-acetamides (6).

2,3,4-Trioxo-l-phenyl-1,2,3,4-tetrahydro-quinoline (Ph—CHi) and 1,2,3-Trioxo-2,3,6,7-tetrahydro-1 H,5 H-benzo [ij] quinolizine (TMCHi) react with primary arylamines via “semiaminales” of type 1 to give quinolino-benzoxazinones of type 2 in high yields. Quinolino-benzoxazepines of type 3 are obtained with 2,6-dimethylaniline. However the N-unsubstituted 2,3,4-trioxo-1,2,3,4-tetrahydroquinoline (CHi) reacts under similar conditions only with 2-chloro- or 2,6-dimethyl-aniline to yield the corresponding ringclosed products 2 b and 3 a.

1,2,3-Trioxo-2,3-dihydro-phenalene (PT) and 1,2,3-trioxo-2,3,6,7-tetrahydro- 1 H, 5 H-benzo[ij]quinolizine (TMCHi) react with anthranilic acid (AS) primarily to give the spirolactones 1 a-1 b, which are thermically rearranged to the corresponding benzoxazine carboxylic acids 2 a-2 b. 1-phenyl-2,3,4-trioxo-1,2,3,4-tetrahydro-quinoline (PHCHi) reacts with AS yielding the spirolactone 1 c, which decomposes upon heating.

Synthetic routes to a new class of biologically active TRH derivatives of the general structure L—Pyr—L—His—L—Pro—NH—(CH 2 E) n —NH 2 are described.

Various synthetic approaches to the anti-cancer alkaloids vinblastine and vincristine are described. Methods for the generation of nine-membered nitrogen containing rings present in the indole moiety of vinblastine are discussed. Modes of joining the two moieties present in VLB in a natural configuration are presented.

The structure of the title compound was determined by X-ray crystallography. The compound is a cyclic dimer with short N···O and N···S contacts.

Silicon 29-chemical shifts can be described in some cases in terms of pairwise interaction parameters, although the influence of higher order effects is always perceptible. These are especially significant where fluorine or oxygen are the ligands around the silicon. Parameter of pairwise interaction for a number of ligands are given.

The complexes Na[(RS(O) 2 ) 2 PdClL] (L = CH 3 CN (2), (CH 3 ) 2 CO (3), THF (4)), stable in solid state, are obtained by substitution of H 2 O by weak donor ligands from Na[(RS(O) 2 ) 2 PdCl(OH 2 )] (1). Their special reactivity in solution is shown by the ready substitution of all ligands, RSO 2⁻ included. The IR spectra are discussed.

[(CH 3 ) 4 As][(CH 3 ) 2 InBr 2 ] has been prepared by reaction of (CH 3 ) 3 AsBr 2 with ln(CH 3 ) 3 . The compound crystallizes in the orthorhombic space-group P2 1 2 1 2 1 and four formula units in the cell. The structure was refined by least square analysis to a R-value of 0.072. As in [(CH 3 ) 4 As][CH 3 InCl 3 ] or [(CH 3 ) 4 Sb][CH 3 InCl 3 ] isolated cationic and anionic tetrahedra are found in the new compound.

The preparation, infrared and electronic spectra of the salts [(C 6 H 5 ) 4 A]CrO 3 J (A = As, P) are reported and discussed.

The rapid conversion of phosphorus thiocyanates into isothiocyanates is caused by nucleophilic reagents. Thiocyanate structures can be stabilized by adding BF 3 . The mechanisms of conversion and stabilization are discussed.

Single crystals of Ba 2 Si have been prepared. From a complete X-ray structure determination follows the anti-PbCl 2 structure type.

By photooxidation of acetoneazine the unstable tetramethyl-1,2-dioxa-4,5-diazine and the trimeric acetoneperoxide are obtained. The dioxadiazine cleaves into acetone and nitrogen with a half live of ~ 20 min at 40°C (in CH 2 Cl 2 ) and induces luminescence in added fluorescent dyes.

The photoreactions of 1-hydroxy- 1 H-benzotriazole and its salts are spectrophotometrically analyzed dependent on oxygen concentration in acetonitrile. Quantum yields have been determined.