Solid state reactivity of organic compounds with inorganic compounds II.

Cobalt acetate reacts with aniline, 2-, 3- and 4-chloroanilinehydrobromides in the solid state to give the products CoBr₂. 2 amine in which the acetate is replaced by bromide and the amine gets attached to the metal in a concerted step. The products have been identified by elemental, spectral and thermoanalytical methods. The kinetics of these reactions have been studied by the mass loss method. The values of energy of activation are 142.0, 41.0, 77.0 and 71.4 kJ mol^?1. The greater reactivity of 2-chloro is due to ortho effect. An intermediate adduct (RNH₃)₂(Co(CH₃COO)₂Br₂) has also been characterized.     

Substitution reactions with the participation of organoaluminum compounds. 7. Reaction of organoaluminum compounds with monochlorodimethyl ether

Conclusions The reaction of monochlorodimethyl ether with different organoaluminum compounds is only a convenient method for the isolation of alkyl methyl ethers in the case of trialkylalanes.For previous communication 6, see [12].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 425–428, February, 1988.     

Phenoxyaluminium compounds : VII. Reactions of organoaluminium compounds with hindered phenols

Reactions of Me₃Al, i-Bu₃Al, Me₂AlCl and Me₂AlCCMe with 2,6-di-t-butyl-4-methylphenol have been studied at different molar ratios of the reactants.It is found that in the reaction with the phenol, trimethylaluminium forms monomeric methylaluminium diphenoxide; triisobutylaluminium gives both monomeric mono- and di-phenoxyaluminium (depending on molar ratios of the reactants) and dimethylchloroaluminium forms dimeric methylphenoxyaluminium chloride.It is found that methylpropynylaluminium phenoxide is unstable and disproportionates in hydrocarbon solutions.The mechanisms of some of these reactions are suggested.     

Sulphur substituted organotin compounds. Part 6. Reactions of mercaptomethyltin compounds with arenesulphenyl chlorides

Reactions between Ph₃SnCH₂SAr and 2-NO₂C₆H₄SC? lead to the formation of 2-(ArSCH₂-6-NO₂C₆H₃SSC₆H₄NO₂-2 via the [2,3]sigmatropic rearrangement of the S-arylthio-sulphonium ylides $\text{C}$H₂$\text{S}\text{+}$(Ar)SC₆H₄NO₂2.     

Pyridazines. LXX. Reactions of azidoazolopyridazines with unsaturated compounds

Cycloaddition reactions of azidoazolopyridazines with unsaturated esters, cyclic enol ethers, styrene, 2-vinyl-pyridine, bicyclo[2.2.1]heptene, dicyclopentadiene and dehydrobenzene were investigated. The reaction proceed via the intermediate Δ² -1,2,3-triazolines which were in most cases termolabile and decomposed further to give the final products which were enamines, imines of fused aziridines.     

Boron-nitrogen compounds. 94. Reactions of Dimethylaminoboranes with Pyrazole

Depending on the reaction conditions, the interaction of tris(dimethylamino)borane with pyrazole (Hpz) yields (CH₃)₂HNBpz₃ (III) or the pyrazaboles B₂pz₄[N(CH₃)₂]₂ (IV, cis and trans isomer), B₂pz₅N(CH₃)₂ (Va), or B₂pz₆. There is evidence that the reactions proceed via the extremely short-lived [(CH₃)₂N]₂ Bpz and, in particular, monomeric (CH₃)₂NBpz₂; the latter species can be identified in the mass spectrometer. In the system bis(dimethylamino)phenylborane/pyrazole the species (CH₃)₂HNB(C₆H₅)pz₂ and the pyrazabole B₂pz₃(C₆H₅)₂N(CH₃)₂ (VII, cis and trans isomer) were obtained. Also, some data on the pyrazabole B₂pz₂(C₆H₅)₂[N(CH₃)₂]₂ were collected although the compound could not be isolated in the pure state. The existence of the monomer (CH₃)₂NB(C₆H₅)pz could be established.     

Chemistry of sym-tetracyanoethane. 2. Condensation with carbonyl compounds

The reaction of tetracyanoethane with carbonyl compounds proceeds via the scheme of aldol addition with subsequent cyclization of the resulting adducts to give 5-amino-2,3-dihydrofuran derivatives, the structures of which were confirmed by the ¹³C NMR and mass spectra.See [1] for Communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1605–1610, December, 1982.     

Organoboron compounds. Communication 136. Boron-germanium compounds

Summary Triethyl- and triphenyl-germanes add to dimethyl 2-propene-1-boronate with formation of dimethyl 3-(triethylgermyl)- and 3-(triphenylgermyl)-1-propaneboronates respectively.The NMR spectrum was measured by V. F. Bystrov, whom the authors thank. The authors also thank V. F. Mironov for the provision of a sample of 3-(triethylgermyl)-1-propanol.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 68–72, January, 1965     

Phenoxyaluminium compounds: VI. Complex and reaction mechanism of methylaluminium compounds with anisole

The reactions of anisole with organoaluminium compounds Me_nAlX_3−n have been investigated.The formation of a complex is the first reaction step, followed by cleavage and elimination of the gases MeX and small amounts of hydrocarbons. The yield of the gases and the cleavage rate decreases in the order: AlCl₃ >/ MeAlCl₂ > Me₂AlCl > Me₃Al and Me₂AlI > Me₂AlCl > Me₂AlBr. For most of the investigated reactions a marked decrease in gas evolution was observed after a short period of time. This is explained by the formation of an almost inactive mixed dimer (I) which at the

reaction temperature is more stable than the Me₂(Cl)Al : O(Me)Ph complex. It is suggested that dimer I is formed after the intramolecular reaction of the 2 : 1 complex II after elimination of MeX.

     

Metal complex compounds with mixed acido ligands. 6. Zirconium and hafnium compounds with three different acido ligands

Conclusions The authors have synthesized and investigated zirconium and hafnium complex compounds containing simultaneously three ligands: fluoro with oxalato and carbonato groups, or fluoro with sulfato and selenato groups.For communication 5 see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 270–274, February, 1978.     

有机磷化合物的研究IX.某些具有活泼亚甲基化合物的碳磷酰化反应

The formation of P -- C bond is one of the important problems in synthetic organophosphorous chemistry. This paper describes the study of the formation of P -- C linkage via phosphorylation of carbon atom containing active hydrogen. p-Substituted phenylacetonitrile possessing an active methylene group undergoes stepwise C -- phosphorylation smoothly with diethyl phosphoryl chloride in the presence of naphthalene-sodium. Phosphonyl chloride reacts analogously. Being a deprotonizing agent naphthalene-sodium is distinguished by its availability, effectiveness and mild reaction conditions. The presence of an electron-withdrawing group in the benzene ring reduces the yield of phosphorylation seriously. The chemical shift of ^3^1P NMR of the resulted α-cyano-benzylphosphonates (1) correlates linearly with the Hammett \s\ constants of the substituents. As indicated by ^1H NMR studies the protons in the ester ethyl groups are magnetically nonequivalent. Compound 1 can be alkylated with alkyl halide or condensed with aromatic aldehyde by Hornor-Wittig type reaction due to the presence of active hydrogen atom. The structure-reactivity studies of diethyl phosphoryl chloride on reacting with various β- and β-diketones and β-keto esters (5) as regiospecific reaction were reported. The influences of metal ions in the enolates on the reactivity of the latter were examined and discussed. Only vinyl phosphates with predominantly Z configuration have been isolated exclusively. The C atom with an active hydrogen in the β-diketones investigated is inert to phosphorylation. These experimental results are well supported by reaction selectivity in terms of Eqo/Ecoc based on EHMO calculation.     

Photometric determination of quaternary ammonium compounds with hexanitrodiphenylamine. I.

Dissociation contants, partition coefficients and absorption spectra have been determined for hexanitrodiphenylamine and pentanitrodiphenylamine. The two compounds have quite different dissociation constants and can be easily separated. Both substances give compounds with quater- nary ammonium ions which can be extracted with chloroform or methylene chloride from an aqueous solution. to obtain a pure hexanitrodiphenylamine compound the reagent must be free from pentadinitrodiphenylamine and the extraction made at high pH.