MO-berechnungen an heterocyclen—VI : Elektronenspektren und elektronenstruktur von azaindolizinen,methyl- und hydroxysubstituierten polyazaindolizinen

The electronic spectra and electronic structure of some azaindolizines, methyl- and hydroxy-substituted polyazaindolizines were calculated by means of the PPP-procedure. With the electronic spectra and heats of atomization the tautomerism of 5-hydroxy-1,3,8-triazaindolizine, 5-hydroxy-7-methyl-1,3,8-triazaindolizine, 5-hydroxy-7-methyl-1,2,8-triazaindolizine, and 5-hydroxy-7-methyl-1 ,2,3,8-tetrazaindolizine was investigated.     

Trimethylsilyl-substituted diazoalkanes : I. Trimethylsilyldiazomethane

Trimethylsilyldiazomethane was prepared by the action of aqueous KOH on nitroso-N-(trimethylsilylmethyl)urea. The spectroscopic properties of this stable, greenish-yellow liquid which can be isolated by gas chromatography are discussed. Its reaction with acetic acid gives the expected CH₃CO₂CH₂SiMe₃ in addition to SiC cleavage products, CH₃CO₂CH₃ and CH₃CO₂SiMe₃. Products of the 1,3-dipolar addition of Me₃SiCHN₂ to activated olefins were not very stable, and only the adduct with acrylonitrile was isolated as a pure material Trimethylsilyldiazomethane undergoes Me₃SiCH transfer to olefins, giving trimethylsilyl-substituted cyclopropanes, in the presence of CuCI in benzene, but other products are formed as well. Thus such a reaction with cyciohexenegave anti-7-trimethylsilylnorcarane (65%), syn-7-trimethylsilylnorcarane (7%), cis- and trans-l,2-bis(trimethylsilyl)ethylene (9% and 13%, respectively), and an unidentified Me₃SiCH trimer (2.3%).     

Etudes photochimiques—XIV : Photoreactions des methylisothiazoles

Photorearrangement of methylisothiazoles proceeds via a zwitterion and the amount of rearranged products increases with solvent polarity. When irradiated in the presence of primary amines, 3-methylisothiazole which is the less isomerised, and 5 methylisothiazole give charge transfer complexes. The amine cation radical is hydrolysed to an aldehyde. 4-Methyl isothiazole does not lead to a charge transfer complex.     

Nitroxydes—XLVII: Nitroxydes isoquinuclidiniques

5 and 7 substituted 1,3,3-trimethyl isoquinuclidines are prepared by the action of ammonia on piperitenone and 4-methyl piperitenone. Reduction of 1,3,3-trimethyl 5-isoquinuclidone, and the different alcohols obtained are described. The nitroxydes obtained by oxidation of these amines exhibit long range couplings.     

Rotational isomerism—XIII : Rotational isomerism in furfuraldehyde

The equilibrium between the cis and trans isomers of furfuraldehyde has been studied by measuring the stereospecific coupling constants between the aldehyde and ring protons in various solvents. These values when combined with the observed values of the couplings in the individual conformers at low temperatures give the energy difference between the cis and trans forms in these solvents. These values together with other previous measurements demonstrate the large solvent effect on this equilibrium. E(cis)-E(trans) is +1·5 kcals/mole in the vapour, much smaller in non-polar solvents (+0·3 kcals/mole in CF₂Cl₂), ca 0 in CHCl₃ and becomes negative in polar media (−1·0 kcals/mole in the pure liquid). This solvent dependence is given a quantitative explanation in terms of a known theory of solvation.     

Vinylamine—XII : Untersuchungen zur substituentenabhängigkeit der imin-enamin-tautomerie an β-aryl-vinylaminen

The equilibria of imine-enamine tautomeric compounds 3–6 have been determined by NMR spectroscopy. With exception of the 4-nitro group, the influence of the substituents R² is represented by the Hammett σ-values. The same is true for the cis-trans-isomerism of 3E–5E. It is shown that the trans-enamine is stabilized by electron-withdrawing substituents R². Slopes and intercepts of the regression lines depend largely on the substituents on nitrogen or α-carbon. The enamine isomer is favored by an aryl substituent in the α-position.     

Metal carbonyl-trifluorophosphine systems : X. Mono-and triruthenium carbonyls

Triruthenium dodecacarbonyl reacts with high pressure PF₃ or with PF₃/CO mixtures to yield two series of compounds. At high PF₃ pressures, the mononuclear species Ru(PF₃)_x(CO)_5−x (x = 5, 4 and 3) are the main products with only traces of Ru(PF₃)₂(CO)₃ and Ru(PF₃)(CO)₄ being found. With high carbon monoxide pressure and less PF₃, the species Ru₃(PF₃)_y(CO)_12−y (y = 0–6) are the main products. It is seen that Ru₃(CO)₁₂ can have up to six CO groups replaced sequentially before the cluster is broken followed by the formation of the mononuclear species. The evidence shows that the Ru(PF₃)_x(CO)_5−x species are stereochemically non-rigid.     

Flechteninhaltsstoffe—XCIII : Struktur der (−)-Placodiolsäure

The structure of(−)-placodiolic acid, a new dibenzofurane derivative of the lichen Lecanorarubina (Vill.) Ach. has been established as (−)-isousnic acid isomethoxide (I).     

Tellurium in organic chemistry—I : A novel synthesis of biaryls

Treatment of bis(aryl)tellurium dichlorides or diaryl tellurides with degassed Raney nickel readily affords the corresponding biaryls. The bis(aryl)tellurium dichlorides were prepared from TeCl₄ and the appropriate aromatics, with or without a Lewis acid as a catalyst, depending on the reactivity of the aromatic. The diaryl tellurides were prepared by reduction of the dichlorides with hydrazine. Attempts to prepare unsymmetrical dichlorides frequently resulted in exchange reactions (RTeCl₃ + R′H → R′TeCl₃ + RH).     

Isochinolinio-amidate : Synthese und einige reaktionen von N-acyl- und N-sulphonyl-derivaten

Three methods have been developed for the synthesis of N-acyl- and N-sulfonyl-aminoisoquinolinium chlorides (6) and the corresponding dipolar bases (7): (1) ring closures of N-acyl- and N-sulfonyl-N-{2-[β-(2,4-dinitranilino)vinyl]benzylidene}hydrazines(5β), (2) acylation of N-aminoisoquinolinium chloride (6a) and (3) transacylations of N-(2-isoquinolinio)-ethoxycarbonylamidate (7i). IR and NMR spectra as well as some reactions of compounds 7 are discussed.     

Luminescence studies in polymers—II : Temperature effect on polyvinylcarbazole fluorescence

Polyvinylcarbazole (PVCa) films and solutions emit normal and excimer fluorescence between 77 and 425 K. The absolute (I_M and I_D) and relative (I_M/I_D) intensities emitted strongly depend on temperature. The usual U-shaped curve is obtained for log I_M/I_D as a function of 1/T in the case of polymer films. In solution, two minima corresponding to two different excimers are observed. The formation and dissociation of PVCa excimers in films and solutions have been interpreted according to the usual kinetic scheme. The binding energies for the excimer in films and for the high temperature excimer in solutions are respectively 4 and 2·8 kcal mole⁻¹.     

Tetrazolo-azido isomerization in heteroaromatics—IV : Reactions of tetrazolopolyazines with triphenylphosphine

Formation of iminophosphoranes from tetrazolopolyazines and triphenylphosphine has been studied kinetically in various solvents, and the mechanism explained as nucleophilic attack of the phosphine moiety on the trazolo ring. In the equilibrium system of tetrazolopolyazine (9) and azidopyrazine (9a) in chloroform, it is concluded that tetrazolo and azido moieties react competitively with triphenylphosphine. The mechanism of the reaction of tetrazolopolyazines with triphenylphosphine in chloroform is discussed on a phosphinium radical cation intermediate proposed.     

Electroorganic chemistry—XI : The stereochemistry of electroreduction of cyclic ketones

Cyclic ketones were electrolytically reduced in isopropanol and in H₂SO₄H₂OMeOH. It was found that, in isopropanol the stereoisomer ratios of the products were approximately equal to the thermodynamic relative stabilities, whereas in H₂SO₄H₂OMeOH the thermodynamically unstable epimeric alcohols formed were more than that anticipated from the relative stabilities. The mechanism of this electroreduction involving the stereoselective adsorption and electron transfer is discussed.     

Massenspektroskopische fragmentierungsreaktionen—III : Das scheinbar anomale verhalten von 3-hydroxytetrahydropyransystemen

Tetrahydropyran derivatives may lose C-2 together with a substituent from C-3 accompanied by ring contraction. This explains why, e.g., compounds derived from 3-hydroxytetrahydropyran sometimes fragment in a manner expected for an isomeric tetrahydrofuran system. The prerequisities for this rearrangement and its mechanism are discussed.     

Low-frequency vibrations of molecular solids: XV. Globular molecule 1,2-dichloroethane

The far infrared and Raman spectra of polycrystalline 1,2-dichloroethane and 1,2-dichloroethane-d₄ for the low temperature modification have been measured from 450 to 33 cm⁻¹ at various temperatures from −100 to −182°C. Raman spectra of the high temperature crystalline modification for both samples were also investigated. The Raman data are in conflict with those previously reported. Assignments are made for the lattice vibrations in terms of the crystallographic unit cell C_2h⁵ (P_21/c) with two molecules per unit cell. The spectra of the high temperature modification are consistent with those expected for orientationally disordered crystals.     

Organogermanium compounds : II. Reduction of organic halides with hydrogermanes

The scope of the reduction of organic halides with trialkylgermanes under homolytic condition has been studied. Germanium hydrides can reduce polyhaloalkane without catalysts under mild conditions, the homolytic mechanism being, however, established for the uncatalyzed reduction. The observed orders of reactivity and selectivity in the reduction are consistent with a radical chain mechanism involving free germyl radicals. Some synthetic applications are described.