Band 33, Heft 9

Aminolysis of cis-NPCl 2 (NSOCl) 2 by piperidine in acetonitrile at room temperature proceeds via a non-geminal substitution pattern. During the first substitution step the reactivity of a SOCl-centre appears to be greater than that of a PCl 2 -centre. The second and third substitution step successively take place at the PCl 2 - and remaining SOCl-centre. The different isomeric forms of the mono-, bis-, tris-, and tetrakis(piperidino) derivatives are characterized by means of 31 P NMR data. Application of 13 C NMR leads in two cases to a structure assignment.

The aminolysis of the ring systems cis-NPCl 2 (NSOF) 2 and (NPCl 2 ) 2 NSOF by cyclic amines in acetonitrile at room temperature shows the S-F bond to be stable towards a nucleophilic attack. The amino derivatives are characterized by their spectral data. Structure assignments are based on 31 P NMR spectroscopy.

The preparation of some tetraalkylammonium-lithium-phthalocyanines is described. In contrast to the known dilithium-phthalocyanine these quarternary “onium”-salts are, dependent on the size of the alkyl groups, soluble in non-polar, aprotic solvents. The electronic spectra are investigated as a film on a quartz disk at 10 K. Under these conditions a large number of narrow bands is observed instead of the normally diffuse ones. Solid state resonance Raman spectra were studied at 85 K by a method involving spinning KBr disks. It is shown that nearly all the lines are as a rule very sensitive to excitation conditions. The vibrational spectra are compared with the structural features of the compounds.

It has been found that anhydrous sodium dithiocarboxylates are readily obtained by the reaction of dithiocarboxylic acid with sodium metal or sodium hydride.

The crystal and molecular structure of [(C 6 H 5 ) 4 P] 2 [Co(WS 4 ) 2 ] was determined from single crystal X-ray diffraction data (space group P2 1 /c with a = 18.542(4), b = 15.443(2), c= 18.713(2) Å, β= 108.73(1)°, Z = 4). In the complex anion Co is coordinated by two bidentate chelating WS 4 2- anions, with a nearly tetrahedral surrounding of Co. The bond lengths in the planar metal sulfur ring CoS 2 W are Co-S = 2.26 Å and W-S = 2.22 Å, while the terminal W-S bonds are 2.14 Å.

The compounds CaCuP(As), SrCuP(As), SrAgP(As) and EuCuAs were prepared and investigated by X-ray methods. They are isotypic and crystallize in a modified Ni 2 In structure (space group P 6 3 /mmc-D 6h 1 ) with the lattice constants: CaCuP a = 405.5(1) pm, c = 780.3(3) pm, CaCuAs a = 418.4(1) pm, c = 786.8(2) pm, SrCuP a = 414.6(1) pm, c = 837.6(3) pm, SrCuAs a = 427.3(2) pm, c = 845.2(3) pm, EuCuAs a = 425.4(2) pm, c = 827.4(3) pm, SrAgP a = 440.9(1) pm, c = 823.0(3) pm, SrAgAs a = 452.9(1) pm, c = 829.1(2) pm.

The preparation of complexes of oxamic acid with Al(III), Ga(III), In(III), Tl(III), Y(III), Fe(III), Mn(II) and V(III) is reported. From the study of the infrared and diffuse reflectance spectra and the magnetic moments (for the complexes of Fe(III), Mn(II) and V(III)) it is concluded that in all complexes the metal ion is coordinated with the carboxyl oxygen and the amidic nitrogen, after the ionization of one of the amidic hydrogens. Octahedral structures are proposed for all the complexes of the trivalent metal ions and the complex K 2 {Mn(oxamic) 2 } · 2 H 2 O.

By reaction of t-butyliodide with tris(trimethylstannyl)stibine di-t-butyl (trimethy 1 - stannyl)stibine as well as tetrakis(trimethylstannyl)distibane are formed.

The 15 N NMR spectra of HN 3 and CIN 3 solutions were recorded under triply labelled conditions. The chemical shifts and coupling constants are discussed with respect to the structure and in relation to other isoelectronic compounds.

With complexes of iridium as catalysts, induction periods are typical for homogeneous hydrogenation of olefins in bulk. The induction period decreases, as a rule with increasing activity, at higher temperatures and may be suppressed with dibenzoylperoxide, azobisisobutyrodinitrile, tetrachloro-1,4-benzoquinone or by preactivation. Triethylamin and SnCl 2 · 2H 2 O are unsuitable additives. The operation “preactivation” leads additionally to great substrate/catalyst-turnover numbers.

Complex compounds of platinum metals Ru(III), Rh(III), Os(IV), Ir(IlI) and Pt(IV) with the bidentate Schiff base ligand derived by the condensation of phenyl glyoxal with p-diethylamino aniline have been prepared and characterized. All the complexes are stable at room temperature. The complexes of Ru(III) and Os(IV) are Paramagnetic and the other complexes of Rh(III), Ir(III) and Pt(IV) are diamagnetic. The spectral studies and the calculation of ligand field parameters clearly indicate the octahedral structure of these complexes.

Arylidene-2-aminobenzthiazoles (1) were prepared by the condensation of 2-aminobenzthiazole with aromatic aldehydes. Cyclocondensation of mercaptoacetic acid and/or chloroacetyl chloride on 1 giving the corresponding 4-thiazolidinones (2) and/or azetidinones (3) respectively, in good yields. The biological activity of the prepared compounds were screened against some strains of bacteria.

The 1,2-5,6-Di-O-isopropylidene glucofuranose (7) reacts with triphenylphosphine/azodicarboxylate and methyliodide with formation of the relatively stable alkoxyphosphonium salt (8a). With water and alcohols 8 forms triphenylphosphine oxide and diacetone glucose 7. The reaction of 8 with sodium benzoate gives the glucofuranose-3-benzoat (10), the formal product of substitution under retention of configuration.

The reaction of 2-substituted malonaldehydes (7) with aromatic 1,2-diamines (5 or 6) in ethanol/acetic acid (10:1) leads to 6,13-disubstituted 1,4,8,11 -tetraaza[14]annulene derivatives (8 or 9) even in the absence of coordinating metal cations ("non-template" synthesis), and not to 3-substituted 1,5-benzodiazepines such as 4. Cobalt(II), nickel(II), and copper(II) complexes of the macrocyclic chelate ligands 8 and 9 have been observed by subsequent metallization with the corresponding acetates in N,N-dimethylformamide. The structures of 8-11 have been assigned mainly by their mass spectra.

N,N′-Dimethyl-5-anilinomethylene-barbituric acids and its thio analogues react with alkyl cyanoacetates or malodinitrile in DMF in the presence of KOH to give 1,2,3,4- Tetrahydro-7 H-pyrano[2,3-d]pyrimidines, whereas N-unsubstituted anilinomethylenebarbituric acids under the same conditiones afford 1,2,3,4-tetrahydro-pyrimidine-5-propenoic acid derivatives.

Treatment of cis-dihydroxykawainol = rel (5R, 6R)-(±)-5-hydroxy-4-methoxy-6- phenylethyl-5,6-dihydro-2H-pyran-2-on (cis-3) with potassium hydroxide in methanol (2.5%, 1 h, room temp.) leads to a 1:1 mixture of the corresponding erythro-butenolide 7 and threo-butenolide 8 by a ring contraction process that may have analogies with the biosynthesis of the piperolides 15. Trans-3 gives the same yields (about 70%) of the same mixture (7 and S), which can be separated by silica-gel columns. Starting from mixtures of cis-5-hydroxykawain (cis-4) and trans-5-hydroxykawain (trans-4), there were prepared and described the two epimeric dehydro-butenolides 9 and 10 and their O-methylderivatives 11 and 12. The threo- and erythro-series show consistant differences between J 5,6 and the 1 H NMR spectra. The constitution and configuration of (± )-erythro-5- (1-methoxy-3-phenylallyl)-4-methoxy-2(5H)-furanone (11) were established by X-ray analysis.

The 1,4-Dimenthyl-9-antliracenyl group is useful as a ring current probe for a 9-phenyl substituent. The splitting between the 1- and 4-methyl group signals due to the diamagnetic ring current anisotropy of the 9-phenylring is 0.84 ppm (0.85 ppm in 9-mesityl- 1,4-dimethylanthracene and 0.86 ppm in 9-phenyl-l,4,6,7-tetramethylanthracene), much larger than in phenylmesitylene (0.32 ppm). In 9-phenyl-1,4-dimethyltriptycene the splitting is reduced to 0.55 ppm due to the change in geometry. By use of an assumed geometric model for all four compounds the magnitude of the splitting could be predicted with a maximum deviation of 0.09 ppm using the tables of Haigh and Mallion. As effective magnetic location for the methyl group the midpoint of the basis of the CH 3 cone was chosen. In 9-phenyl-1,4,5,8-tetramethyltriptycene the 9-phenyl ring is not orientated perpendicular but parallel to the 1,8-methyl groups and as the analysis of the ABCX-spin-spin system of the unsubstituted phenyl ring shows tilted by about 24 ° away from the 1,8- methylgroups.

Imidazolides of phosphorus 7, 9, and 13 are, in most cases, superior to the chloridates 4, 5 (Ṙ = 2,2,6,6-tetramethyl-1-oxyl-4-piperidyl), 6, 8, and 12 for the transformation of aliphatic and aromatic aldoximes to nitriles in yields generally exceeding 80%. The transformation is thought to occur via a phosphorylated intermediate, which was isolated in the case of the reaction bfn-butyraldoxime with the nitroxyl radical-labeled chloridate 4.

Selenium derivatives of pentavalent organophosphorus compounds 9, 10, 11 (Ṙ = 2,2,6,6- tetramethyl-1-oxyl-4-piperidyl), 12 and 13 were prepared in 79-99% yields via the reaction of the corresponding trivalent phosphorus compounds 14, 15, 16, 17, 18 with black selenium in benzene at room temperature in 20 hours.

The crystal structure of aluminium-dihydrogenphosphate- monohydrogenphosphate-monohydrate contains macromolecular units 2 ∞ [Al(H 2 PO 4 )(HPO 4 )(H 2 O)] consisting of Al(O) 5 (H 2 O) octahedra which share vertices with P(O) 2 (OH) 2 and P(O) 3 (OH) tetrahedra. Neighbouring layers are linked by hydrogen bonds.

Dibenzo(d,f )-1,3,2-dioxaphosphorepines, 2,2′ -Biphenylylenephosphoric Acids, Bis (2,2′ -biphenylylenedithiophosphato) - nickel (II), Gas Chromatography

Starting with SbCl 3 and 1,2-benzenedithiol, one can easily obtain heterocyclic 2-chloro- 1,3,2-benzodithiastibole [1], which, without isolation, can be treated with a solution of sodium methanethiolate to yield 2-methylthio-1,3,2- benzodithiastibole. Yellow crystals were obtained by recrystallization from acetonitrile. The compound was found to be monomeric in benzene solution. The crystal structure was solved by means of X-ray diffraction methods and could be refined to an R-value of 0.03 with 870 independent reflections observed. The monoclinic unit cell contains 4 formula units, the space group is P2 1 /c. The structure can be compared with that of 2-methoxi-1,3,2-benzodioxastibole, a preliminary report of which has been given [2]. The compounds are, however, not isomorphous. Interactions between neighbouring molecules in the thiastibole seem to be significantly weaker than in the corresponding oxygen compound.

Some new aspects of the synthesis and reactivity of nitrosyl complexes are given. The complexes [Cr(NO)(NCS 5 ] 3- , [Mo(NO)(NCS) 4 ] 2- [3a], [Os(NO)(NCS) 5 ] 2- and [Mo(NO)(CN) 5 ] 3- have been isolated as tetraphenylphosphonium salts.

Contrary to a recent report, 4-arylazo-3- methylisoxazol-5-thiones exist predominately as the 3 -methyl - 4-arylhydrazono-isoxazol- 5-thione tautomer.

The photoelectron spectra of the dithiapropel-lanes 1 to 5 have been recorded. The first bands have been assigned by comparison with the PE spectra of cyclic thioethers. The resonance inte-gral between the 3p orbitals of the sulfur centers in 1 to 5 is found to be -0.15 to -0.25 eV.

Reaction of α-arylcinnamonitriles with excess of alkylmagnesium halide yielded predominantly the erythro isomer of α,β-dialkyl-α,β-diarylpropionitriles. PMR spectra of the diastereoisomers have been described.

ReNCl 3 is prepared by the reactions of ReCl 5 with NCl 3 and Cl 3 VNCl, respectively.