Heterodiene syntheses—X : Reaction of arylidene-pyrazolones and -isoxazolones with dihydropyran: Nature of the transition state

Dihydropyran reacts easily with the α, β-unsaturated carbonyl system of heterocyclic rings (pyrazoles or isoxazoles) in accordance with a 1,4-cycloaddition.     

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.     

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%).     

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.     

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.     

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.     

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.     

Quinone Studies—II : Reduction potentials of some 3-substituted phenanthrene quinones

Polarographic reduction potentials of seven 3-substituted phenanthrenequinones have been determined in aqueous dioxan and aqueous ethanol under different pH conditions. The substituent effects on the reduction potentials could be correlated with the Hammett σ- constants (correlation coefficients > 0·995). The possibility of using reduction potentials as an accurate measure of resonance energy has been pointed out.     

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.     

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.     

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.     

MO-berechnungen an heterocyclen—VII : Tautomerieprobleme an substituierten 1,3,8-triazaindolizinen

The electronic spectra of some derivatives of 5-hydroxy-7-methyl-1,3,8-triazaindolizine have been calculated with the PPP-procedure. With the electronic spectra and heats of atomization the tautomeric structures of the compounds 6-ch]or-5-hydroxy-7-methyl-1,3,8-triazaindolizine, 6-brom-5-hydroxy-7-methyl-1,3,8-triazaindolizine, 6-carboxy-5-hydroxy-7-methyl-1,3,8-triazaindolizine, 2-carboxy-5-hydroxy-7-methyl-1,3,8-triazaindolizine, 2-mercapto-5-hydroxy-7-methyl-1,3,8-triazaind and 5-amino-7-methyl-1,3,8-triazaindolizine are discussed. The possible structures of the compounds 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 depending on the pH-value of the solution have been investigated.     

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).     

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.     

The chemistry of terpenes—IV : The configuration and conformation of the isomeric 3-aminopinanes

Tris(dipivaloylmethanato)europium has been successfully used in the analysis of the NMR spectra of the isomeric 3-aminopinanes. The previously assigned configurations of the 2-methyl and 3-amino groups have been confirmed and the preferred conformations have been shown to be those in which the 2-Me group is quasi-equatorial.     

The rearrangement of cyclopropyl chlorides to allyl chlorides : Stereospecificity in the recapture of the chloride ion

The cyclopropyl chlorides (1 and 2) rearrange on heating to give stereospecifically the allyl chlorides (3 and 4, respectively). In the presence of nucleophiles such as methoxide ion, the corresponding allyl ethers (5 and 6, respectively) are formed. Analysis of the stereochemistry of these products indicates that they are formed from the corresponding allyl chlorides (3 and 4), which are evidently the first-formed products of the reaction even in the presence of strong nucleophiles. The reaction of the allyl chlorides (3 and 4) with sodium phenylthioxide in aprotic non-polar solvents goes predominantly with retention of configuration, but in methanol is normal in giving predominantly inversion of configuration.