Band 34, Heft 1

The Compound TlFeS 2 was synthesized from TlS/Fe/S-mixtures. Crystals are mono-clinic (space group C2/m) with a = 1164.4(6) pm, b = 530.8(3) pm, c = 1050.9(5) pm, β = 144.58° and Z = 4. The structure comprises [FeS 2 -]∞-chains parallel b, built from edge-shared FeS 4 -tetrahedra. Relations between TlFeS 2 and orthorhombic CsFeS 2 are discussed. Tetragonal or monoclinic distorted tetragonal ternary phases occur with composition Fe x Tl 2 S 4 (2.6 < x < 3.6 ).

Bis(tetrachloromolybdenum)diazene, [MoNCl 4 ] 2 is prepared by the reaction of molybdenum pentachloride with iodine azide as well as by the reaction of molybdenum pentachloride with nitrogen trichloride. The IR spectrum, the mass spectrum and the magnetic moment (μ eff = 1.63 B.M.) are in agreement with a N-N-bonded dimeric structure and Mo ≡ N-triple bonds.

High temperature Guinier photographs of As 2 O 5 indicate a continuous phase transition to HT-As 2 O 5 , which is accomplished at 305 ± 3 °C. The crystal structure of HT-As 2 O 5 has been derived from the low temperature form; space group and lattice constants are P4 1 2 1 2-D 4 4 and a = 857.2 pm, c = 463.6pm (310 °C), respectively. According to symmetry considerations, the phase transition is expected to be of pure ferroelastic-paraelastic type (422F 222).

The compounds CaAgP and CaAgAs have been prepared and their structures have been determined. They are isotypic and crystallize in a modified Fe 2 P-structure (space group P6̄2m-D 3 3h ) with the lattice constants: CaAgP a = 704,5(1) pm, c = 417,4(1) pm, CaAgAs a = 720,4(1) pm, c = 427,0(1) pm.

The interaction of (CH 3 ) 3 M III or (CH 3 ) 2 M III Hal with (CH 3 ) 3 M V Hal 2 and (CH 3 ) 4 M V Hal, respectively, yields methylhalogeno metalates of the general composition [(CH 3 ) 4 M V ] + [(CH 3 ) 4-x M III Hal x ] - . (With M V = As, Sb; M III = Ga, In; Hal = Br, I and x = 1-3.) The vibrational spectra of these ionic compounds are reported and discussed.

From HAuCl 4 and tri-tert-butyl phosphine in methanol the gold(I) complex [(CH 3 ) 3 C] 3 P-Au-Cl (1) has been synthesized and converted into the bromide 2 and iodide 3, using KBr and KI, respectively, in acetone solvent. The corresponding P-Cl functional complexes [(CH 3 ) 3 C] 2 PCl-AuCl (4) and (CH 3 ) 3 CPCl 2 - AuCl (5) could be obtained from (carbonyl)gold chloride ClAu(CO) and the chlorophosphine in benzene, with evolution of CO. The di-tert-butyl-phosphine analog, [(CH 3 ) 3 C] 2 PH - AuCl (7) results from a lowtemperature reduction of HAuCl 4 with this phosphine. All these gold(I) complexes are soluble in many solvents as monomers. The corresponding silver compounds, prepared from [(CH 3 ) 3 C] 3 P and AgCl, Br, I in an inert solvent, appear to be oligomers, however, and showed dimer or tetramer association in halocarbon or benzene solvent. Infrared and 1 H, 13 C, 31 P NMR spectra have been used for further characterization of the compounds.

Reaction of NPClNH-n-Bu(NSOCl) 2 with benzene in the presence of AlCl 3 (molar ratio ring compound: AlCl 3 =1:2) yields NPClNH-n-Bu(NSOPh) 2 in three isomeric forms. Using an excess of AlCl 3 , two isomers with formula NPNH 2 Ph(NSOPh) 2 are formed. These NH 2 derivatives can also be isolated from the reaction mixture of NPClPyr(NSOPh) 2 (Pyr = pyrrolidino), benzene and an excess of AlCl 3 .

Tetramethyldiphosphinomethane (CH 3 ) 2 PCH 2 (CH 3 ) 2 (1a) reacts with HCl/ether to form the mono-and bisquaternary salts [(CH 3 ) 2 PCH 2 P(H)(CH 3 ) 2 ]Cl (2) and [(CH 3 ) 2 (H)PCH 2 P(H)(CH 3 ) 2 ]Cl 2 (3), respectively. The system 1a/HCl, incorporating 1 a/2/3, represents a useful tool for studying the appearance of XnAA′X′n-spin type systems. These compounds are also prototypes for a variety of other mono-or bis-phosphonium salts, which are formed in the reactions of the diphosphines (CH 3 ) 2 PCH 2 PR 2 (R = CH 3 , t-C 4 H 9 , C 6 H 5 ) (1a-c) with (CH 3 ) 2 CO + HCl, CH 3 I, t-C 4 H 9 Br, C 6 H 5 COCl, (CH 3 ) 2 PCl and Br(CH 2 ) n Br (n = 1, 2). Heterocycles are not obtained. The dioxide 14 and the disulfide 15 are also described. Some properties and spectroscopic data (IR, 1 H, 31 P and 13 C NMR) of 26 new compounds are reported and briefly discussed.

The extraction of nickel(II) from aqueous hydrochloric acid solution by I-phenyl -3-methyl-4-benzoylpyrazol-5-one (PMBP·OH) dissolved in carbon tetrachloride has been studied. The extraction of nickel(II) from the aqueous solution in the range of 1.0-5.0 M hydrogen ion concentration has been found to be much higher compared to that of cobalt(II). The extraction of nickel with PMBPOH is simple, fast and selective. The composition of the extracted species in solution as well as in solid form have been studied. The IR bands for the reagent and the metal complexes are reported.

The structure of 2,8-dimethyldibenzo[c,g][1,2,5,6]tetrathiaocin (1b) has been determined by X-ray methods and discussed in connection with the preferred conformations of diaryl disulfides. The compound has the anti-form I. The SS-distance is 205.8 pm, the mean CSS-angle 104.1°, and the CSS/SSC-dihedral angle 111.1°.

Kinetics of oxidation of potassium thiocyanate by the oxidant chloramine-T (CAT) in presence of NaOH has been studied at 30 °C. At low substrate concentrations, the approximate rate law is, - d[CAT]/dt = k[CAT][KNCS]/[NaOH] 2 . At higher substrate concentrations, the rate law simplifies to, -d[CAT]/dt = k[CAT]/[NaOH]. Ionic strength and addition of p-toluene sulphonamide have negligible influence on the rate. The rate of reaction decreases in D 2 O medium and the value of the inverse solvent isotope effect, k H2O /k D2O is 0.46. The reaction has been studied at different temperatures and the activation parameters have been calculated.

Chloroaminocyclotriphosphazatrienes, N 3 P 3 Cl 6-n R n [R = NHMe (n = 2), NHEt (n= 1, 2), NHPr n (n = 4), NHPr i ( n = 1, 4), NHBu t (n = 2, 4), NHCH 2 Ph ( n = 1), NEt 2 (n= 1, 2, 3), N(CH 2 Ph) 2 (n = 1)] react with benzene in the presence of anhydrous aluminium chloride to give phenylated products: phosphazenes and/or hydrocarbons. The structures of the phenylphosphazenes are assigned from their NMR spectra. Reactions of N 3 P 3 Cl 5 R (R = NMe 2 , NC 5 H 10 ) have been reinvestigated. The influence of the amino groups on rates and products is discussed.

Carboxamides react under basic conditions with quaternary 3-cyanoquinolinium salts to give stable insertion products with 1,2-or 1,4-dihydroquinoline structure. Six examples are given.

A formal concept for the treatment of the bond and electron shifts in pericyclic reactions is developed. A new data structure for the representation of molecules allows the design of efficient algorithms. This resulted in a computer program for the exhaustive generation of pericyclic reactions.

The thermal copper ion catalyzed peroxyester reaction of t-butyl N,N-dimethylperoxyamidate (1, R = N(CH 3 ) 2 ) with cyclohexene results in the formation of the corresponding N,N-dimethylamidate 6 in 20% yield, and 3,3′-dicyclohexenyl (5) in 40% yield. Under analogous conditions, the reaction of 1, R = N(CH 3 ) 2 , with tetrahydrofuran gives the corresponding amidate 7 in 6% yield. Only a 2% yield of 6 and no 7 were isolated in the photochemical variant of the peroxyester reaction. Compound 6 is also obtained in a 12% yield from the reaction of 2-cyclohexen-1-ol (9) with N,N-dimethyl carbamoyl chloride (4) in the presence of pyridine.

For alkyl groups it is shown that new inductive substituent constants, σ I (R), can be calculated accurately from previously obtained polar substituent constants, σ * (R), from the simple relation σ I (R) = σ I (Me) [I-2σ * (R)]. In similar fashion, the two reaction constants are related by ρ I /ρ * = σ * (H)/σ I (Me) = 10.6. Many new σ I values are presented for groups for which no previous estimate has been available. The attentuation of σ I (R) with alkyl size for n-alkyl groups is shown to be a function of the number of C atoms, n c : σ I (R) = -0.137 n c /(2n c + 1). The effect of branching of R is also discussed.

The elimination of HCN from 9-dicyanomethyl-fluorene (2), 1,1-diphenyl-1,2,2-tricyanoethane (3), and 2-phenyl-1,1,2-tricyanopropane (4) in anhydrous methanol has been studied and shown to occur via an (E l) anion mechanism. Elimination of HCN from 2 in acidic, buffered and MeO-/MeOH solutions have also been studied. Addition of water or benzene to the reaction medium shifts the mechanism to (E 1 CB)ʀ. Elimination of HCN from N,N-dimethyl-4-(1,1,2-tricyanoethyl) aniline (5) in anhydrous methanol occurs via an (E 1 cB)ʀ mechanism and the kinetics indicate that addition of HCN to the product alkene occurs. Activation parameters, isotope effects and solvent effects have been examined in an effort to obtain information about the nature of the transition states of these reactions.

A new series of hexahydro-bis-benzodipyrazolones (2a-e) were obtained by the inter-action of 1 with hydrazines. These pyrazolones underwent coupling reaction with different diazonium salts to give 7a-g. Compound 1 when treated with acid hydrazides gave 3 a, b, and when subjected to Japp-Klingemann reaction in alkaline medium gave 6a-e. The hexahydro-bis-benzodiazepine (8), and dithiopyrimidoquinazolinetetrone (10) were obtained by the interaction of 1 with o-phenylenediamine and thiourea respectively.

Reaction of thiophosgene or phosgene on 2′-aminonaphthanilides (2, 5) gave the corresponding 2-substituted-6-oxonaphth[2′,3′: 5,6]-1,3-oxazino[3,2-b]benzimidazoles (3) and 6-oxonaphth[1′,2′:5,6]-1,3-oxazino[3,2-b]benzimidazoles (6) respectively. The mechanism of such reactions has been studied by carrying reaction between 2′-hydroxy - anthranilide (7 a) and thiophosgene in acidic and basic media.

Reaction of the N,N-dimethyl enehydrazines 1 a-c with acetylene carboxylates gives the 1-dimethylamino-7,8-dihydro-2,5(1H,6H)-quinolinediones 5a and 6a-c together with some by-products of the enehydrazine (2a, 3a, 4a) and 4,5,6,7-tetrahydro-1H-indol-4-one type (7a-c). Compounds 6b and 6c have been degraded to the fully aromatic 1-dimethylamino- 2(1H)-quinolinones 12 b and 12 c.

Phenyl-bis(perfluoropinacolyl)phosphorane could be obtained by reacting difluoro-phenyl -perfluoropinacolylphosphorane with dilithium-perfluoropinacolate or by oxidative addition of hexafluoroacetone to phenyl-perfluoropinacolyl-phosphine. The 19 F NMR shows nonrigidity of the molecule.

Complexes of the type CpTi(OR) 3-n [N(Ph)COOR] n where R = Et, Pr i and Bu t , n = 1, 2 or 3, have been synthesized by the reactions of cyclopentadienyl titanium trialkoxides with phenylisocyanate. All these complexes have been characterized by the elemental analysis and infrared spectra.

Rheniumoxychloride forms with antimony pentaehloride a donor-acceptor complex, ReO 3 Cl·SbCl 5 . According to the Raman spectrum the complex contains a Re-O-Sb bridge.

Photokinetic experiments show that the dechlorination reaction of dichlorobenzenes, chloroanilins, and chlorophenols is dependent on nature of solvent, but undependent on oxygen. Quantum yields determined in n-hexane indicate that there is a strong deviation within the ortho, meta, and para products.

The structure and magnetic properties of the new ferromagnetic compounds TlFe 1+x S 2 (0,25 ≤ x ≤ 0,85) were investigated. A new monoclinic phase Tl 3 Fe 2 S 4 (a = 1303, b = 1114, c = 738,3 pm, β= 124,5°, Z = 4, space group C 5 2h ) was characterized by single crystal X-ray techniques.

The general synthetic routes to aromatic triorganylelement(IV b) diorganylphosphines are summarized and briefly discussed. By metathetical reaction of lithium or sodium diphenylphosphide and triphenylelement(IVb) chloride, triphenyltin diphenylphosphine (1) and the new compound triphenylsilyl diphenylphosphine (2) are obtained in good yields.

It is shown that substituent effects on one-bond and long-range carbon-proton coupling constants in monosubstituted allenes parallel quantitatively ab initio STO-3G carbon 2s-hydrogen 1 s overlap populations, irrespectively of whether the substituents are bonded to the allenic skeleton via first-row (C, O) or second-row (Si, S, Cl) atoms.

It is shown that Cu 2+ -bentonite produces high yields of mono-t-butyl-benzene in Friedel-Crafts-alkylation. The ratio of mono-and di-product is investigated in dependence of the content of water in the bentonite: dry Cu 2+ -bentonite produces high yields of mono-product, moistered Cu 2+ -bentonite leads to di-alkylated products.

In the reaction of lithiated N-(fluorodimethylsilyl)-2,4,6-trimethylaniline with bis(trimethylsilyl)-sulfurdiimide LiF is eliminated and a benzo(c)-1 λ 4 ,2-thiazol is formed. Trifluoroacetic acid reacts with this thiazol to give the trifluoroacetate.

η 4 (1,2-Di-tert-butyl-3,4,5,6-tetramethylbenzo-cyclobutadiene)tricarbonyliron (2) is prepared by reaction of the respective free benzocyclo-butadiene (1) and nonacarbonyl-diiron at room temperature. X-ray data of the free and complexed ligand are compared.

In the presence of oxygen and light magnesium free derivatives of bacteriochlorophyll c form linear tetrapyrroles by oxidative ring cleavage. The structure of these photobilines has been determined by spectroscopic methods.

The structure of photobilin c is determined by oxidative degradation of 18 O-labeled material which is prepared by photooxidation of a derivative of bacteriochlorophyll c in the presence of molecular 18 O 2 .