Volume 32, Issue 6

Single crystals of the compound Ho 2 Cu 2 O 5 were obtained by melting the oxide mixture (2 CuO : 1 Ho 2 O 3 ), using KF as a flux. The crystal structure was investigated by single crystal X-ray data (Space group C 2v 9 -P 2 1 nb, lattice constants: a = 1247.8, b = 1081.3, c = 349.5 pm).

The new compounds AMg 2 B 2 (A = Ca, Sr, Ba; B = As, Sb, Bi) have been prepared and structurally characterized by X-ray single crystal investigations. They are isotypic and crystallize trigonally in the ordered anti-La 2 O 3 (Ce 2 O 2 S)-type. The lattice constants (in Å ± 0.01) are [xxx] The compounds belong to the Zintl-phases, the coordination polyhedra of the element(V)-atoms are compared with those in the A 2 B and A 5 B 3 compounds.

Sb 2 O 3 and Sb 2 O 4 can be converted under high oxygen pressure at 700 °C into deep yellow crystals of Sb 2 O 5 .

The new intermetallic compound Ba 10 Al 3 Ge 7 crystallizes hexagonal in a new structure type (a = 974.9(5) pm, c =1647(1) pm, c/a = 1.69, P6 3 /mcm). The Al-atoms, together with the Ge-atoms, form propeller-like Al 3 Ge 7 -units.

The Raman spectra of (TBA)-trans[OsX 4 (CO) 2 ] salts (X = Br, I; TBA+ = Tetrabutylammonium) show up to nine overtones and many combination tones of the totally symmetric stretching modes ν(OsX), ν(OsC) and ν(CO). The intensities of the overtones depend on the electronic spectra. The anharmonicity of the vibrations is small. All fundamentals are assigned by IR and Raman data.

As[N(CH 3 ) 2 ]3 reacts with the following isocyanates: FSO 2 NCO, n-C 4 F 9 SO 2 NCO, SO 2 (NCO) 2 and (CH 3 ) 3 SiNCO. The products which result from reaction of FSO 2 NCO and n-C 4 F 9 SO 2 NCO are the acyclic tri- and bisubstituted arsines [xxx] In contrast, SO 2 (NCO) 2 and (CH 3 ) 3 SiNCO form eight- and four-membered ring compounds, where the skeleton consists of the atoms As 2 S 2 N 4 (3) and As 2 N 2 (4). The new compounds were characterized by NMR and mass spectra.

Li 2 Ga crystallizes orthorhombic, space group Cmcm—D 17 2h , a = 456.2(2), b = 954.2(5) and c = 436.4(2) (pm). The Ga substructure consists of zig-zag-chains. Li 3 Ga 2 is isotypic with Li 3 Al 2 : trigonal-rhomboedric, space group R3̅m—D 3 5 d, α = 436.7(1), c = 1389.6(5), the Ga atoms forming layers of puckered six-membered rings. Both phases crystallize in an ordered variant of the bcc packing. Relations to the phases with the same packing in the systems Li-Αl and Li—Sn are discussed.

The UV spectrum of dicobaltoctacarbonyl in a solution of n-heptane was reinvestigated under variing conditions of concentration, CO-pressure and temperature. From the influence of the temperature on the spectral change and from the comparison with the spectrum of the hydridocobalttetracarbonyl an attempt was made to correlate the absorption bands to the corresponding electron transfers. A qualitative term scheme is proposed. Furthermore, the photochemical formation of tetracobaltdodecarbonyl at room temperature and its delayed formation under gamma-rays is reported.

The preparation of the complexes of oxamic acid with Cu(II), Ni(II), Co(II) and Cr(III) is reported. From the study of IR, diffuse reflectance spectra and the magnetic moments it is concluded that in all complexes the metal is coordinated with the amidic nitrogen, after ionization of one amidic hydrogen, and with the carboxyl oxygen. Octahedral structures are proposed for the complexes K 2 [Ni(oxamic) 2 ] · 2 H 2 O and K 3 [Cr(oxamic) 3 ] and planar configurations for K 2 [Cu(oxamic) 2 ] and K 2 [Co(oxamic) 2 ].

The reaction of Re 2 (CO) 10 and Re 2 (CO) 9 C(OCH 3 )R [R = C 6 H 5 ; C 6 H 4 CH 3-p ] with lithium aryls and subsequent alkylation with trimethyloxonium tetrafluoroborate exceeds the stage of the carbene compound to form new μ-methylidene complexes.

The ESCA spectra of the complexes [(TPE) 2 Ir(S 2 )]Cl, [(TPE) 2 Ir(S 2 O)]PF 6 and [(TPE) 2 Ir(S 2 O 2 )]Cl, (TPE = Ph 2 P(CH 2 ) 2 PPh 2 , “diphos”), have been investigated. The binding energy data for the S 2p, Ir 4f and P 2p electrons were measured and are discussed.

The study on the mass spectroscopic behavior of the title compounds is based on AP-measurements, the investigation of deuterated derivatives, and the analysis of chain length effects. It is shown that, among other things, the stable [M-STol] + -ions produced by 9 homologs will not enter a cyclization reaction within 10 -5 sec. The reactive [M-STol] + -species of S,S′-di-p-tolyl dithioadipate possess an abnormal fragmentation behavior (consecutive lass of CO and H 2 O), the details of which are elucidated by employment of 2 H-labelled compounds and investigation of S,S′-di-p-tolyl 2,5-dimethyldithioadipate. Obviously, the sulfur of the thiol ester group seems to play a decisive role in this and other decomposition processes.

The structures as well as the genesis of the C 5 H 7 O 2 + ions from some different ethylenacetal derivatives have been established. It is shown that the title ions do not isomerize to a common intermediate or a mixture of equilibrating structures prior to or during collisional activation.

Starting with (1- 14 C)ethanol (2z) octachloro-(2- 14 C)propane (1 z) is synthesized according to Scheme 1. The skeleton of 1 z is rearranged by AlCl 3 . The equilibrium octachloropropane (1)/tetrachloromethane (11) + perchloroethylene (12) is proved by gaschromatography.

The abstraction of hydrogen atoms by benzoyl radicals in the photolyses of 2,2′-dihalogeno-benzil dimethylketals and of S-p-tolyl esters of substituted thio benzoic acids was investigated by the CIDNP technique. The present study supports previous conclusions that in the absence of scavengers the formyl H atoms of the benzaldehydes thus formed originate from cyclohexadienyl-like free radical precursors.

A sample consisting of 427 one- and multi-step organic name reactions has been classified in terms of a previously determined empirical set of 43 general reaction-matrix types (R), according to procedures outlined originally by UGI et al. 14 . The resulting distribution of R-matrices is similar to the overall pattern of other random and specialized sample analyses. The metathesis reaction accounts for 60% of all single-step synthetic transformations; subsets consisting of the primary three and ten R-matrices describe some 78% and 93% of the population, respectively. The results represent a valid experimental basis for the mathematical description of the constitution of organic chemistry.

The X-ray photoelectron spectral data of a series of heterocyclic immonium salts are correlated with the CNDO/2-atomic charges of the nitrogen atoms and the molecular potential. The atomic charges of the nitrogen atoms are surprisingly close to zero.

The polarographic reduction of tetraarylcyclopentadienones is studied in connection with quantummechanical calculations basing on the well known structure of the corresponding ketyls. A linear free energy relationship is found assuming a change in conformation between the redox components. Comparison of the ketone geometry with the conformation of tetraarylpyrryls gives a prove for this surprising result.

The origin and nature of the radicals arising during the photolysis of 2-nitrobenzaldehyde in the presence of olefin quenchers is discussed. The radicals, assigned an alkenylaryl nitroxide structure, arise via a dark Diels-Alder reaction involving product nitroso benzoic acid and the olefine.

Ethyl 5-nitroindan-1,3-dione-2-carboxylate (3; 5-NO 2 ) was prepared via esterification of 3-nitrophthalic acid and subsequent treatment of the resulting diester with ethyl acetate in sodium ethoxide solution. Attempted synthesis of 3; 4-NO 2 via a similar route was obscured by unability to effect diesterification of 1: 3-NO 2 by ethanol and hydrochloric acid. The diester 2: 3-NO 2 could be prepared by the action of ethanol on the anhydride 5. This ester could be then converted into 3: 4-NO 2 by treatment with ethyl acetate and sodium ethoxide. Compounds 3 (4- and 5-NO 2 ) could be converted into the corresponding indeno[2,3-d]-pyrimidine derivatives (9 a, b) by their reaction with thiourea. The behaviour of 9 a, b toward the action of hydrazinehydrate, monochloroacetic acid and hydrogen peroxide is reported.

4-Benzoyl-5-phenyl-2,3-dihydrofuran-2,3-dione (1) reacts with aldehydes or ketones via the acylketene-intermediate (2) yielding the 1,3-dioxin-4-ones (3). The aldehyde derivatives (3 a-e) can be converted into the anilino-chalcone (5) or the anilino acrylic acid (6) by treating with aniline at 20 °C. 6 and diazomethane combine to the acrylic acid methyl ester (7), which by heating (200 °C) is cyclisized to the quinolin-4-ole (8). On the other hand, the keto derivatives 3f-h and aniline give the dibenzoyl acetic acid anilide (9).

Tetramanganesedecahexacarbonyl has been prepared. The configuration of this polynuclear carbonyl has been derived by IR-and mass-spectrometric measurements.

(1 - Diphenylphosphoryl -1 H - trifluoromethyl)-diphenylphosphinate crystallizes monoclinic in the centrosymmetric space group P2 1 /c with 4 molecules in the unit cell. The crystal structure was refined to a R value of 0.027.

The crystal structure of β-NaSn (low temperature modification) has been determined. It crystallizes tetragonally, a= 1046 ± 2, c = 1739 ± 3 pm, isotypic with NaPb. The short distance between Sn-atoms of different Sn 4 -groups is discussed.

With the aid of Mössbauer spectroscopy the influence of F- ions on the behavior of Fe 3+ doped VO 2 was studied for very low concentration of iron (x = 0.0026) between 4.2 and 600 K.

trans -Bromotetracarbonyl (aryl)carbyne chromium and tungsten react with KOH, NaOC 2 H 5 and LiC 6 H 5 to give carboxylic acids, carboxylic esters and ketones.

PhOP(S)Cl 2 reacts with methylhydrazine to give three dihydrazido derivatives. The NMR and IR Data are given. By the further reaction with PhOP(S)Cl 2 2,5-dimethyl-1,4-diphenoxy-1,4-dithioxo-2,3,5,6-tetraza-1,4-diphosphacyclohexane is obtained.

Thiocyanogen reacts with [(η-C 5 H 5 )Fe(CO)(PPh 3 )I] and [(η-C 5 H 5 )Fe(CO)2(PPh 3 )]I to form the 1/1 adducts [(η-C 5 H 5 )Fe(CO)(PPh 3 )I • (SCN) 2 ] and [(η-C 5 H 5 )Fe(CO) 2 (PPh 3 )][I • (SCN) 2 ], respectively. The stretching frequencies and the 31 P NMR data of the adducts are reported and discussed.

Chloro- and bromosulfenic acid 2,2,6,6-tetramethylpiperidides were obtained by S–S bond cleavage of the corresponding disulfide with chlorine or bromine. Fluorination of the chlorosulfenic acid amide with cesium fluoride yielded the fluoro derivative.

The synthesis and spectroscopic properties of low molecular and polymeric complexes of etioporphyrin-germanium IV are described.

In the γ-radiolysis of polycrystalline N-acetyl-D-glucosamine 19 products have been identified and their G-values determined. Major products are 2-acetamido-2-deoxyhexodialdose (G = 1.2) and 2-acetamido-2,5-dideoxyhexodialdose (G = 1.1). It is suggested that the high radiation sensitivity of mucopolysaccharides with respect to biological effects is probably not due to extraordinary high G-values.

The structure of the non irritant diterpene ester 4a-sapinine, isolated from Sapium indicum Willd. (Euphorbiaceae) is deduced to be 13-O-acetyl-4-deoxy-12-O-(N-methylanthraniloyl)-4a-phorbol. It is the first diterpene ester alkaloid of the tigliane type.