Volume 30, Issue 9-10

A novel preparation is reported for AgCrO 2 from elemental silver and Cr 2 O 3 in the presence of thallium oxide. A refinement of the structure was undertaken by the use of diffractometric single-crystal data. The newly determined lattice parameters of the compounds (Delafossite-type), which crystallizes in the space group R 3 m, are : α = 2.985 Å, c = 18.51 Å; c/a = 6.20; number of formula units Z = 3 (d exp = 6.63; d rö = 6.69 gcm -3 ). For the oxygen particles in the point position 6c z (O) = 0.1119.

Gold(III) bromide crystallizes monoclinic in the space group P2 1 /c with four Au 2 Br 6 molecules in a cell of dimensions α = 6.831 Å, b = 20.41 Å, c = 8.105 Å; β = 119.74°. Within the well separated molecules each Au atom has four Br neighbours in a square planar arrangement. The Au-Br distances to the terminal Br atoms are in the range from 2.383 to 2.410 A, whereas the distances to the bridging atoms are slightly longer (2.457-2.471 A).

A study of the kinetic parameters involved in the formation of basic zinc carbonate by the action of carbon dioxide and water vapour on zinc oxide has been undertaken. A contracting sphere model is used to explain the reaction but its applicability is dependent upon the carbon dioxide pressure used. Water vapour pressures close to saturated water vapour pressure are necessary for the reaction to proceed and the role of the necessary near-liquid surface water layer in the absorption reaction is discussed.

The IR spectra (33-4000 cm -1 ) and the RAMAN spectra (0-2500 cm -1 ) of the complexes M(II)[Pt(CN) 6 ] (M = Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd) have been recorded. In the region 33-300 cm -1 , the IR spectra of the isotopic compounds with 64 Zn and 68 Zn 68 Zn and with 58 Ni and 62 Ni have been obtained. The observed frequencies are assigned to the normal modes of the lattices. A normal coordinate analysis has been carried out for the above coordination polymers. The force constants of the Pt(CN) 6 moiety are with one exception identical with those obtained for the isolated ion. The CN valency force constant is slightly shifted to higher values. The valency force constants of the coordinative bonds M(II)-N are in the range 0,1-1 mdyn/Å. This variability is considered to stem primarly from ligand field effects.

The intermetallic compounds Sr 2 Ge, BaCaSi, BaCaGe, BaCaSn, BaCaPb, CaLiBi and SrLiBi crystallize in the anti-PbCl 2 -structure. They belong to the Co 2 P-subgroup of this structure type.

The aminogallanes Ga[N(CH 3 ) 2 ]3 (1), ClGa[N(CH 3 ) 2 ] 2 (2) and Ga[N(Si(CH 3 ) 3 ) 2 ] 3 (3) are prepared by reacting GaCl 3 with LiN(CH 3 ) 2 and NaN[Si(CH 3 ) 3 ] 2 , respectively. Excess LiN(CH 3 ) 2 leads to LiGa[N(CH 3 ) 4 ] which reacts with GaCl 3 to yield 1. CS 2 inserts into all Ga—N bonds of 1 yielding monomeric Ga[S 2 CN(CH 3 ) 3 ) 2 ] 3 (4). 1 dimerizes via dimethylamino bridges. In contrast, 1 H. NMR spectra indicate group exchange for dimeric 2. Assoziation of 3 is prevented due to steric hindrance. The gallium atom in 4 exhibits hexacoordination, and there is evidence for the binding of the (CH 3 ) 2 NCS 2 groups through S atoms only.

ZnAs 2 and CdAs 2 decompose at high pressure and temperature. The determined decomposition boundaries are presented. From synthesis experiments in the systems Cd 3 As 2 —As and Zn 3 As 2 —As, the decomposition products were found to be mixtures of CdAs + As and ZnAs + As. The high pressure phases CdAs and ZnAs are orthorhombic, space group D 15 2h — Pbca, with α o = 5.993 A, b o = 7.819 A, c o = 8.010 Å and α o = 5.679 A, b o = 7.277 A, c o = 7.559 Å, respectively. Further phases are recovered from the high temperature region at high pressure.

The 119m Sn and 57 Fe Mößbauer spectra of the complexes [M(CO) 6 -n(SnX 3 ) 2 ] n- (n = 1,2,3,6) and [Fe(CO) 4 SnX 3 ]- are reported. With increasing substitution of CO by [SnX 3 ]-the isomer shift increases, reflecting also the π-acceptor strength of [SnX 3 ]-. The π-back-bonding ability especially of [SnCl 3 ]⁻ is similar to PCl 3 . A direct relationship between the isomer shift and the electronegativity of the halogen atoms of [SnX 3 ]- and an inverse correlation between δ and Δ is observed.

The title compound has been synthesized by three different methods and its structure determined from three dimensional X-ray data by Patterson and Fourier methods. The crystals are triclinic with unit cell dimensions a = 1022.60 ± 0.07 pm, b = 638.69 ± 0.27 pm, c = 1478.00 ± 0.19 pm, α = 78.48 ±0.02°, β = 131.049 ± 0.008°, γ = 87.16 ± 0.03 °, space group C i 1 —PT and Z = 2. Least squares refinement by use of 2160 independent reflections measured on a diffractometer has reached R = 5.4%. There are discrete (CH 3 ) 3 C—C 7 H 7 Mo(CO) 3 molecules, the central molybdenum atom is octahedrally coordinated.

MICHAELIS-ARBUSOV reaction of diastereoisomeric 2-methoxy-4-methyl-1,3,2-dioxaphosphorinans with benzyl halides is non-stereospecific. Cis- and trans-2-benzyl-2-oxo-4-methyl-1,3,2-dioxaphosphorinans were separated and analysed by means of IR, 31 P and 13 C NMR spectroscopy. 2-Benzyl-2-seleno-4-methyl-1,3,2-dioxaphosphorinans were synthesized and stereospecifically converted to 2-oxo-analogues. Stereochemistries are assigned to the geometrical isomers of all new compounds described in this paper. Application of direct spin-spin coupling constant values for structural elucidation is emphasized.

Pentamethylendiazirine (N͡=N) has been found in metal carbonyl compounds as a monodentate two electron ligand (π-CH 3 C 5 Η 4 Mn(CO) 2 N͡=N, (OC) 5 W N͡=N) or as a bidentate four electron ligand ((OC 4 M (N͡=N) 2 M(CO) 4 (M = Mo, W), (OC) 4 Fe N͡=N Fe(CO)4). The reaction of Fe 2 (CO 9 with diazirine affords the isocyanate and/or methylenamino-bridged complexes (OC) 3 Fe(NCO) (N=C< )Fe(CO) 3 and (OC) 3 Fe (N=C< ) 2 Fe(CO) 3 .

New adducts of nitrogen triiodide with several tertiary N-bases have been prepared. Their analyses, general properties, IR-spectra and structures are reported briefly. Experiments to crystallize a compound with a ratio N : I : chinuclidin = 1 : 4 : 1 resulted in the preparation of cristallized chinuclidiniumpentaiodide (chin H)I 3 • I 2 , the X-ray structure analysis of which is reported.

The interaction of dialkyl tert-butylperoxy phosphates, (RO) 2 P(O)OOCMe 3 (1) with primary and secondary cycloalkylamines, R′R″NH, R′ = cyclo-C 6 H 11 , R″= H; R′= R″= cyclo-C 6 H 11 (2) in the presence and absence of water, produces the corresponding dialkyl cycloalkyl ammonium phosphates, (RO) 2 P(O)O-N + H 2 R″R′ (3), and tert-butanol. In carbon tetrachloride the reaction produces in addition to 3 the corresponding cyclohexylammonium chloride. Possible mechanisms of the reaction are discussed.

The preparation of dialkyl tert-butylperoxy phosphates (2, R = alkyl) has been achieved by the reaction of the corresponding dialkyl phosphorochloridates (1, R = alkyl) with tert-butyl hydroperoxide either in the presence of pyridine or in the presence of aqueous potassium hydroxide solution. Neither of these routes is suitable for the preparation of dialkyl tert-butylperoxy phosphates in quantity since they yield peroxyphosphates which are contaminated either with the corresponding tetraalkyl pyrophosphates or dialkyl phosphates; the contaminants cannot easily be removed by conventional means from the peroxyphosphates. The method of choice for the preparation in high yield of large quantities of pure dialkyl tert-butylperoxy phosphates involves the interaction of the corresponding dialkyl phosphorochloridate with sodium tert-butyl peroxide which has been prepared in situ from the reaction of tert-butyl hydroperoxide with sodium hydride.

Under the influence of UV light (high pressure HPK 125, Philips) and in presence of acetone ethylene and formamide react under elevated pressure (12.5-100 kp/cm 2 ) to give odd-numbered n-alkane carbonic acid amides of chain lenghth C 3 -C 19 . Product yields improve with rising pressure. By increasing the concentration of aceton (0.1-8 mol-%), the reaction pressure the reaction time and at low temperatures the average mol.-weight is shifted to higher values. The chain distribution corresponds to a geometrical progression. Per 1 kwh electrical power input of the uv-equipment 0.5 kg of product is formed with chain length: 78% C 3 -C 7 , 12% C 9 , 10% C 11 -C 19 .

cis-Tetracarbonyl-trimethylphosphine-olefin-tungsten(0) complexes (olefin = maleic and fumaric acid dimethyl ester, ethylene) were synthesized to study the hindered rotation of the olefin ligands. The favourable orientations of the coordinated C-C double bonds with respect to the coordination octahedron were determined.

Studies of the interaction between 1:1 Th(IV)-DTPA chelate (where DTPA = diethylenetriaminepentaacetic acid) with certain bidentate ligands, such as salicylic acid (SA), 5-sulphosalicylic acid (SSA) and 8-hydroxy quinoline-5-sulphonic acid (HQSA) have been carried out potentiometrically. The nature of the titration curves indicates that the bidentate ligand is added stepwise to the initially formed metal diethylenetriaminepentaacetate. The formation constants (log K MAB ) of the resulting 1:1:1 mixed ligand derivatives have been determined at 30 ± 1 °C and μ = 0.1 (KNO 3 ). The order of stability in terms of the secondary ligand has been found to be SA > SSA > HQSA.

The reaction of benzylidene anilines with compounds having an activated CH,- or CH,-group in the presence of aliphatic or cyclic anhydrides (acetic anhydride, propionic anhydride or succinic anhydride) gives olefines in good yield.

Alkylidene aniles react with H 2 S and benzoicanhydride in diphenyl methane to the corresponding aliphatic thioketones in excellent yields. Similarly β-thioxo compounds are synthesized.

3-Hydroxy-3-phenylpropionic Acid Anilide, Catalytic Hydrogenation The catalytic hydrogenation (20 °C, 760 mm) of dimethylsulfoniumphenacyl-phenylcarbamoylmethylide (1 a) and the nitro derivative (1 b) yields the new β-keto-S-ylides (3 a) and (3 c). At higher temperature and pressure the same reaction gives under loss of dimethylsulfide the propionic acid anilides (2a) and (2b).

Triphenylphosphin dicarbethoxy- or dicarbophenoxy-methylene react with p-nitro-phenylisocyanate at 110 °C under the elemination of triphenylphosphinoxide yielding the quinolones (2a-b). With toluylene-2,4-diisocyanate the tetrahydropyrroloquinoline carboxylic esters (3 a-b) are formed.

Isonicotine hydrazide (INH) and picoline hydrazide (PH) complexes of lanthanides are described. Solid compounds of the compositions Ln(NO 3 ) 3, 3 INH where Ln-La, Nd, Gd, Er, Y; Ln(ClO 4 ) 3 , 5 INH where Ln-La, Pr, Nd and Ln(ClO 4 ) 3 , 3 INH. H 2 O when Ln-Gd, Dr and Y and Ln Cl 3 · 3 PH when Ln-La and Nd have been synthesized. The complexes have been characterized by visible (Pr, Nd) and IR spectra, conductance measurements and thermal studies. Some of the nitrate and perchlorate ions have been inferred to lie within the coordination sphere raising the coordination number beyond six.

The reaction of 3,3-dichloro-2,4-dioxo-tetrahydroquinolines with pyridine yields the corresponding pyridinium ylides. However, the reaction of 3-diazo-2,4-dioxo-tetrahydroquinolines with pyridine in the presence of copper gives Cu complexes of 4,4′-dihydroxy-3,3′-azo-2-quinolones.

The 5-aminopyrazole derivatives (1 a-c) react with acrylonitrile to yield the corresponding 1-β-cyanoethyl-5-aminopyrazole derivatives (2 a-c) which could be readily cyclised into the corresponding pyrazolo[1,5-a]pyrimidines (3 a-c). Under similar conditions 1 a-c has failed to react with methylacrylonitrile or methyl methactylate. However, when the reaction of 1 a-d with these reagents was conducted in ethanolic sodium ethoxide, the pyrazolo[1,5-a]pyrimidine derivatives (3d-f) were formed. Structures of resulting products was established by their synthesis via interaction of β-cyanoethylhydrazine (4) and β-cyanopropylhydrazine (10) with the appropriate β-bifunctionalnitrile. Compounds 1 a, b also reacted with methyl phenylpropiolate to yield the pyrazolo[1,5-a]pyrimidine derivatives (18).

In the case of a number of N-(pyridyl)-pyrrole derivatives a linear relation was found between the PMR chemical shifts of the olefinic and aromatic protons and the adjacent carbon net charges. The charge distribution was obtained as a sum of σ- and π-parts, calculated by the Del Re and PPP methods, respectively. Steric effects were treated on the basis of chemical shift anomalies.

During a reinvestigation of the 13 C NMR spectra of 1-fluoronaphthalene (1) and of 2-fluoronaphthalene (2) at 20 and 25.16 MHz, uncertainties that existed in the literature about signal assignments for 1 could be cleared. In the spectral analyses for 2 given so far, five out of ten signals were incorrectly assigned. The corrected assignment is supported by extensive 13 C{ 1 H} double resonance experiments, by recording of proton-coupled 13 C and 13 C{ 19 F} spectra and by off-resonance 13 C{ 1 H} noise-decoupling. The results show a strong + M-effect of the fluorine substituents on 13 C chemical shifts similar to the effects of OH and OCH 3 groups. 1 H NMR spectra of 1 and 2 could be partially assigned by decoupling of the 19 F resonances and by iterative analysis.

The 13 C NMR spectra of twelve amino-, dimethylamino-, diamino-, and bis(dimethylamino)naphthalenes are completely assigned by selective 13 C{ 1 H} double resonance and by interpretation of proton-coupled spectra. Strong substituent effects (Δδ) upon chemical shifts are observed and can largely be accounted for by mesomerism. The pronounced high-field shifts of C-6 in the 2-amino- and 2-dimethylaminonaphthalenes coincide with the enhanced reactivity of this position towards electrophilic reagents. In 1-dimethylaminonaphthalene and even more so in 1-dimethylamino-2-methylnaphthalene, conjugation is inhibited for steric reasons and Δδ’s are greatly diminished, thus giving an estimate for the contribution of resonance to substituent-induced shifts in the unhindered compounds. In two 1,8-disubstituted naphthalenes there are large deviations from additivity of substituent effects.

In the 13 C NMR spectrum of ] -aminopyrene (1) in [D6] acetone all carbon atoms are anisochronous. Most of the sixteen signals can be safely assigned by selective 13 C{ 1 H}double resonance experiments and by the interpretation of proton-coupled 13 C as well as with the aid of off-resonance noise-decoupled 13 C{ 1 H} spectra. Substituent effects on chemical shifts in rings A, B, and D are compared with those of the 1- and 2-aminonaphthalenes (2, 3). Even in ring C, most distant from the substituent, relatively strong high-field shifts are observed which are ascribed to mesomerism.

Three new ternary silicon-phases with the formulas LiCuSi, Li 8 Ag 3 Si 5 and Li 8 Au 3 Si 5 have been prepared and their crystal datas have been determined by single-crystal resp. powder methods.

Ternary phases of potassium with gallium resp. indium and germanium resp. tin have been prepared and investigated by X-ray diffraction. The results of the powder patterns show that the phases crystallize in a modified K 8 Ge 46 -type structure.

The ternary systems Na-Au-Ge and Na-Au-Sn have been investigated and two new phases with the formula Na 2 AuGe and NaAuSn were observed. They crystallize in the orthorhombic system. The crystal data have been determined.

Spin trapping with 2,4,6-trimethoxy-N-t-butylnitrone improves the identification of short-lived free radicals at concentrations too low for their direct detection by ESR.

Preparation, properties and mass spectrum of [PNCl 2 ] 2 [CNCl] are described.

Thionyl chloride reacts with both S 7 NH and C 6 H 5 HgNS 7 forming colorless crystals of (S 7 N) 2 SO whose infrared, Raman and mass spectrum are reported. The geometry at the N atoms is believed to be planar.

Schiff base, 2-acetylpropylideneamino-o-methylthiobenzene prepared by the condensation of o-methylthioaniline and acetylacetone, reacts with copper and nickel chlorides to split into o-methylthioaniline complexes of these halides.

The photo-induced carbonylation of (C 5 H 5 ) 2 (CH 3 ) 2 Ti and (C 9 H 7 ) 2 (CH 3 ) 2 Ti in pentane solution results in a cleavage of the methyl-metal bonds, and the formation of the corresponding carbonyl titanium complexes.

The crystal structure of the title complex 1 shows that its metal-metal bond length is not determined by the radii of the metal or phosphorus atoms but by steric hindrance between vicinal carbonyl groups.

With the catalyst-system NiCl 2 · 6 H 2 O and NaBH 4 dissolved in dimethylformamide 1.3- and 1.5-cyclooctadiene are selectively hydrogenated to cyclooctene under mild conditions.

A racemic bromide pentathiocyanate trihydrate salt of the tris[di-µ-hydroxo-bis-(ethylenediamine)cobalt(III)]cobalt(III) cation has been isolated. An X-ray structure analysis shows the cations to have Δ(ΛΛΛ)/Λ(ΔΔΔ) configuration. The conformation of the chelaterings is such that the point group of the cations is C 3 .

A rapid synthesis of the title compounds employing formaldehyde and sodium borohydride in acidic aqueous solution in combination with the unmethylated amines is described. High yields and the characteristics of the methylated amines allow the application of the method to gas chromatographic and mass spectrometric analyses.

Literature claims about cycloadditions of benzoylisocyanate and acetylenes to form 1 b and lc could not be reproduced. Chlorosulfonylisocyanate plus 1-alkoxy-1-alkynes yield compounds 5 instead of azetinones (1).

The title compounds yield 10 in aprotic media whereas 8 and 9 are formed in methanol. Diphenylcyclopropenon and an oxaziridine give tolane and β-amino-α-phenylcinnamic acid.

Chloroform/concentrated aqueous NaOH/catalyst transform testosterone acetate (1) into a mixture of the α- and β-stereoisomers of dichlorocyclopropyl derivatives (2) and tetrachlorospiropentane derivates (3). 2 are the precursors of 3. Formation of analog chloro as well as bromo derivatives of cholestenone was demonstrated.