Showing papers in "Russian Chemical Bulletin in 1979"
TL;DR: In this article, it was shown that mercuric chloride has a specific oxidative effect on the anions of dicarbadodecahydronidoundecaborates in THF or pyridine, which consists in the preferential replacement of hydride hydrogen by the ligand in the 8 position of the anion.
Abstract: It was found that mercuric chloride has a specific oxidative effect on the anions of dicarbadodecahydronidoundecaborates in THF or pyridine, which consists in the preferential replacement of hydride hydrogen by the ligand in the 8 position of the anion.
20 citations
TL;DR: Palladium chloride is a catalyst for the preparation of phenylisocyanates by the carbonylation of nitro compounds and is promoted by pyridine and its homologs and also by transition-metal oxides as mentioned in this paper.
Abstract: Palladium chloride which is a catalyst for the preparation of phenylisocyanates by the carbonylation of nitro compounds is promoted by pyridine and its homologs and also by transition-metal oxides, which provide for the conversion of nitro compounds into phenyl-, methylphenyl-, and chlorophenylisocyanates in 75–92% yield and 84–97% selectivity at 200°C and 50–100 atm CO.
19 citations
TL;DR: In this paper, the authors showed that ethanol, containing 10−30 mole% of C2H5I, is converted mainly to diethyl ether in the presence of zeolites NaX, NaY, HY, and HM at a temperature of 160−200° and atmospheric pressure.
Abstract: Ethanol, containing 10–30 mole% of C2H5I, is converted mainly to diethyl ether in the presence of zeolites NaX, NaY, HY, and HM, at a temperature of 160–200° and atmospheric pressure. Intense dehydration of the ethanol to ethylene occurs without the C2H5I.
15 citations
TL;DR: In this article, a general preparative method for the alkylation of BBU with various structures using alkyl iodides and liquid ammonia by the action of sodium amide in the presence of alkali halide salts was developed.
Abstract: A general preparative method has been developed for the alkylation of BBU with various structures using alkyl iodides and liquid ammonia by the action of sodium amide in the presence of alkali halide salts
14 citations
TL;DR: In this article, a general scheme for the formation and development of micro and supermicropore systems in the activation of carbonized organic materials is given, which is used as a basis for pore form characterization.
Abstract: 1.
Discussion is given of a general scheme for the formation and development of micro and supermicropore systems in the activation of carbonized organic materials. This scheme is used as a basis for pore form characterization.
2.
Discussion is also given of the various experimentally determined parameters for this model: the diameters of the carbon crystallites and the gyration radii of the pores as determined from x-ray scattering at both large and small angles, and the characteristic energy of adsorption of the standard vapor (benzene) as calculated from a single adsorption isotherm through the theory of bulk micropore filling.
3.
The earlier x-ray and adsorptional studies on charcoal adsorbents with differing micropore structures have been generalized. To a good degree of approximation, the gyration radii of the micro- and supermicropores are inversely proportional to the characteristic energy of adsorption. It has been shown that the relation between the characteristic micro-and supermicropore radii and the characteristic adsorption energy gives a basis for pore classification.
4.
The model adopted here has been used to calculate parameter values for micro- and supermicropores, the latter considered as plane fissures formed in the carbon crystals under partial or total burn off of the individual layers of carbon atoms or crystals.
13 citations
TL;DR: In this paper, a method is found for obtaining isotopically labeled compounds, based on the reaction of============πρατεραγεργεγεηραβε βαγαβαβγεβα βεγγε βεβγα βαββεγαγγααβη βε ββεββαα ββγβαγηβεαβρα βγγρα αβγγγβε αβ
Abstract: 1.
During reaction of 2,2,6,6-tetramethyl-1-oxopiperidinium salts
with alkalies (KOH, NaOH)3 the metal 2,2,6,6-tetramethylpiperidine 1,1-dioxides
are formed.
2.
The oxidative properties of aqueous solutions of the salts
salts with respect to alcohols, iodides, H2O2, and 2,2,6,6-tetramethyl-1-hydroxypiperidine is attributed to the equilibrium
and reaction of
with these compounds.
3.
A method is found for obtaining isotopically labeled
, based on the reaction of
with HX in H218O, and for obtaining 2,2,6,6-tetramethylpiperidin-1-oxyl-18O, based on reduction of
with hydrogen peroxide in H218O.
11 citations
TL;DR: It has been shown that the region of diamond thermodynamic stability depends on the dimensions of the carbon particles in small-particle systems as mentioned in this paper, and that at high supersaturation realized in vacuum condensation and chemical decomposition, there is an increase in the ratio of the probabilities for diamond and graphite nucleation.
Abstract: It has been shown that the region of diamond thermodynamic stability depends on the dimensions of the carbon particles in small-particle systems. At the high supersaturation realized in vacuum condensation and chemical decomposition, there is an increase in the ratio of the probabilities for diamond and graphite nucleation.
8 citations
TL;DR: In this article, a modified method was proposed for running the Wilgerodt-Kindler reaction for substituted benzaldehydes for o-, m-, and p-phthaldehydes.
Abstract: 1.
A modified method was proposed for running the Wilgerodt-Kindler reaction for substituted benzaldehydes.
2.
We were the first to run the Wilgerodt-Kindler reaction for the o-, m-, and p-phthalaldehydes.
8 citations
TL;DR: In this paper, the authors studied the telomerization of 2-chloropropene with CCl4, initiated by coordination initiators based on Fe(CO)5, and here they isolated telomers of structure CCl3(CH2CClCH3)n Cl with n=1, 2.
Abstract: 1.
We studied the telomerization of 2-chloropropene with CCl4, initiated by coordination initiators based on Fe(CO)5, and here we isolated telomers of structure CCl3(CH2CClCH3)n Cl with n=1, 2. The main reaction product under the selected conditions is the telomer with n=1 (T1).
2.
Telomer T1 enters slightly into a secondary reaction to give (CH3CCl2CH2)2CCl2.
8 citations
TL;DR: In this paper, a new method has been proposed for the synthesis of α-amino- and α-alkylaminophosphonic acids, and N-formyl, N-trifluoroacetyl, and n-carbobenzoxy derivatives were synthesized.
Abstract: 1.
A new method has been proposed for the synthesis of α-amino- and α-alkylaminophosphonic acids.
2.
N-formyl, N-trifluoroacetyl, and N-carbobenzoxy derivatives of α-aminophosphonic acids were synthesized.
3.
Methods were developed for obtaining monoesters of α-aminophosphonic acids.
4.
Formation of pyridoxamine from pyridoxal and α-aminoisobutylphosphonic acid was not found under conditions for nonenzymatic transamination.
7 citations
TL;DR: In this article, the ionization of ClF3, ClF2, and ClF molecules with the formation of positive and negative ions has been studied and the lower limit of the electron affinity of the ClF molecule has been determined.
Abstract: 1
Study has been made of the ionization of ClF3, ClF2, and ClF molecules with the formation of positive and negative ions
2
The energy of atomization of ClF2, the heat of formation of ClF2, and the F2Cl-F and FCl-F bond energies have been calculated
3
The lower limit of the electron affinity of the ClF molecule has been determined
TL;DR: In aqueous solutions of 2,2,6,6-tetramethyl-1-oxopiperidinium salts and salts of 1-hydroxypiperidine 1-oxide, the oxopiperinium cation was found to be amphoteric; it is a weak protic acid and a strong base for the conjugated
Abstract: 1
In aqueous solutions of 2,2,6,6-tetramethyl-1-oxopiperidinium salts and salts of 1-hydroxypiperidine 1-oxide, the oxopiperidinium cation
is in equilibrium with 1-hydroxypiperidine 1-oxide
, and the piperidine 1,1-dioxide anion,
At [OH−] > 2 mole/liter, this equilibrium is shifted by more than 95% to the
side, and at pH < 12 shifted to more than 98% to the
side
2
2,2,6,6-Tetramethyl-1-hydroxypiperidine 1-oxide is amphoteric; it is a weak protic acid and a strong base for the conjugated
acid
3
It is possible that the oxoimmonium cations,
, are intermediates for the synthesis of carbonyl compounds from nitronic acids and nitroalkanes (Nef reaction)
TL;DR: The primary reaction product is 4-(trifluorovinyl)-3,3,4,4 trifluoro-1-oxa-2-thiacyclobutane 2,2-dioxide (a 3-sultone), the corresponding polyperfluoropyrosulfate, and SO2.
Abstract: 1.
Hexafluorobutadiene and sulfur trioxide do not form the Diels-Alder adducts. The primary reaction product is 4-(trifluorovinyl)-3,3,4-trifluoro-1-oxa-2-thiacyclobutane 2,2-dioxide (a 3-sultone).
2.
When stored or heated the β-sultone undergoes retrocycloaddition and isomerization to a 6-sultone and a linear 1,4-copolymer of hexafluorobutadiene and SO3 (1:1).
3.
The oxidation-reduction reaction of the β-sultone with SO3 forms 4-(trifluorovinyl)-4,5,5-trifluoro-1,3-dioxa-2-thiacyclopentane 2,2-dioxide (a β-sulfate), the corresponding polyperfluoropyrosulfate, and SO2.
4.
The β-sulfate is thermally isomerized to δ -sulfate (4,4,5,6,7,7-hexafluoro-1,3-dioxa-2-thia-5-cycloheptene 2,2-dioxide).
TL;DR: In this paper, the position of the ΝN\(\mathop - \limits^ \bullet \)O band in the spectra of cyclic nitroxyl radicals depends on the size of the ring.
Abstract: 1.
The use of the Raman spectroscopy method makes it possible to unequivocally determine the position of the band of the stretching vibrations of the
group in the spectra of cyclic nitroxyl radicals.
2.
In the vibrational spectra of five-membered cyclic nitroxyl radicals the band of the stretching vibrations of the
group is found in the 1433–1443 cm−1 region. The position of the ΝN\(\mathop - \limits^ \bullet \)O band in the spectra of cyclic nitroxyl radicals depends on the size of the ring.
TL;DR: The existence of a tautomeric equilibrium between the aldehyde and lactol forms of gossypol has been demonstrated through NMR spectroscopy in this paper.
Abstract: 1.
The existence of a tautomeric equilibrium between the aldehyde and lactol forms gossypol has, for the first time, been demonstrated through NMR spectroscopy. In DMSO, gossypol exists primarily in the lactol form, and primarily in the aldehyde form in acids, bases, and inert solvents.
2.
The method of preparation of the ethers of this compound determines the form of the product obtained.
TL;DR: In this paper, the authors investigated electron shock ionization of the NF3 molecule with formation of positive and negative ions and measured the appearance potential and initial kinetic energies of the ions.
Abstract: 1.
The authors have investigated electron shock ionization of the NF3 molecule with formation of positive and negative ions. They have measured the appearance potential and the initial kinetic energies of the ions.
2.
They have calcualted the splitting energies of the bonds D0(FN-F) and D0(N-F) and the lower limit of the electron affinity of the NF2 radical.
TL;DR: The preferred form in nonpolar solution is an equilibrium mixture of three conformers of the salicyloylhydrazones of several different aldehydes, these differing in the degree of rotation around the amide N-C bond and in the type of H-bonding as discussed by the authors.
Abstract: 1.
The aroylhydrazones with intramolecular hydrogen bonding exist in acylhydrazone form with a high degree of electron delocalization.
2.
The preferred form in nonpolar solution is an equilibrium mixture of three conformers of the salicyloylhydrazones of several different aldehydes, these differing in the degree of rotation around the amide N-C bond and in the type of H-bonding (-OH...O=C or N-H...-OH).
TL;DR: The application of high pressures results in an increase in the dielectric constant of organic compounds, which may be attributed to distortions of the distribution of the electron density in the molecules as discussed by the authors.
Abstract: 1.
The application of high pressures results in an increase in the dielectric constant of organic compounds, which may be attributed to distortions of the distribution of the electron density in the molecules and an increase in the effective dipole moments. Increasing the temperature causes an increase in the dielectric constant of the organic compounds investigated, and compression under heating conditions is accompanied by irreversible effects.
2.
High pressures reduce the conductivity of some organic compounds due to an increase in the number of defects in the crystals. However, in the case of compounds with strong hydrogen bonds (maleic acid), high pressures can increase the conductivity. The conductivity of the compounds investigated increased during plastic deformation, and this is apparently due to the excitation of the molecules upon absorption of the elastic energy liberated.
TL;DR: In this paper, the corresponding o-phosphorus-substituted anisoles with hydrobromic acid were dealkylated by dealkyclic acid.
Abstract: 1.
o-Diethyl- and o-diphenylphosphinylphenol and o-(2-diethylphosphinylethyl)phenol are prepared by dealkylating the corresponding o-phosphorus-substituted anisoles with hydrobromic acid.
2.
o-Diethyl- and o-diphenylphosphinylmethylphenol are prepared by Arbuzov rearrangement of the corresponding salicyl phosphinite esters.
3.
o-(2-Diphenylphosphinylethyl)phenol is prepared by cleavage of coumaran with sodium diphenylphosphide followed by oxidation of the resulting phosphinophenol.
TL;DR: The method of inhibitors has been used to show that chemiluminescence in the oxidational destruction of 1,10-phenanthroline results from interaction of the latter compound with O(O_2^{\underset{\raise0.3em\hbox{$\smash{\scriptscriptscriptstyle\cdot}$}}{\_} } \) radical ions.
Abstract: 1.
The suggestion has been made and confirmed that chemiluminescence arises through breakdown of a dioxetane derivative of 1,10-phenanthroline.
2.
The method of inhibitors has been used to show that chemiluminescence in the oxidational destruction of 1,10-phenanthroline results from interaction of the latter compound with\(O_2^{\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle\cdot}$}}{\_} } \) radical ions.
TL;DR: In this article, a four-stage reaction has been developed for the synthesis of 4-alkyl(cycloalkyl, phenyl)thiacyclohexanes, starting from α-olefins.
Abstract: 1.
A four-stage reaction has been developed for the synthesis of 4-alkyl(cycloalkyl, phenyl)thiacyclohexanes, starting from α-olefins.
2.
The new compounds 4-hexyl-, 4-phenyl- and 4-cyclohexylthiacyclohexane and the corresponding sulfones have been prepared.
TL;DR: In this paper, a simple method of synthesis of 1-boraadamantane and its complex compounds has been found which is based on the hydroboronation of 3methoxy-7methoxymethyl-3-borabicyclo.
Abstract: 1.
A simple method of synthesis of 1-boraadamantane and its complex compounds has been found which is based on the hydroboronation of 3-methoxy-7-methoxymethyl-3-borabicyclo[3.3. 1]non-6-ene by use of THF·BH3, Et3N·BH3, or B2H6 in Et2O.
2.
The isomerization of organoboron compounds under mild conditions has been observed for the first time.
TL;DR: In this article, a series of ferrocene cationic organogold complexes are obtained and auration of derivatives occurs primarily in position 2 both with donor and with acceptor substituents.
Abstract: 1.
Ferrocene and its derivatives are aurated by the tris(triphenylphosphinegold) oxonium salt.
2.
A series of ferrocene cationic organogold complexes are obtained.
3.
Auration of ferrocene derivatives occurs primarily in position 2 both with donor and with acceptor substituents.
TL;DR: The quantitative empirical characteristics of the efficiency of forming singlet oxygen in dye solutions were measured in this article, where the authors measured the quantitative empirical properties of the synthesis process of azo and anthraquinone dyes.
Abstract: 1.
The irradiation of solutions of azo and anthraquinone dyes leads to the efficient generation of singlet oxygen, which is generated mainly by the reaction of light with the photochemical transformation product of the dyes.
2.
The quantitative empirical characteristics of the efficiency of forming singlet oxygen in dye solutions were measured.
TL;DR: In this paper, the reaction of tetraalkyldiphosphine disulfides with organic disulfide and triaryl phosphites gives dialkyldithiophosphinite and -monothioph phosphinite esters respectively.
Abstract: 1.
Alkylation of tetraalkyldiphosphine disulfides with alkyl halides and alkylene dihalides gives the corresponding trialkylphosphine sulfides and tetraalkylalkylenediphosphine disulfides, and also dialkylthiophosphinyl halides.
2.
Reaction of tetraalkyldiphosphine disulfides with organic disulfides and triaryl phosphites gives dialkyldithiophosphinite and -monothiophosphinite esters respectively.
3.
Tetraalkyldiphosphine disulfides are cleaved by PCl3, PBr3, and POCl3 to form dialkylthiophosphinyl halides.
4.
Phosphonic acid dichlorides are reduced by tetraalkyldiphosphine disulfides to form dichlorophosphines, and at the same time react with the oxidation products of the tetraalkyldiphosphine disulfides to form dialkylthiophosphinyl chlorides.
TL;DR: In this article, the authors used a palladium alloy with 9.8% of ruthenium for the hydrogenation of cyclopentadiene (CPD) to cyclopsentene at membrane catalysts.
Abstract: 1.
Methane can be used as a heat-transfer agent for the monomerization of dicyclopentadiene and as carrier gas for the hydrogenation of cyclopentadiene (CPD) to cyclopentene at membrane catalysts consisting of a palladium alloy with 9.8% of ruthenium.
2.
Increases in the selectivity and in the yield of cyclopentene were found during hydrogenation of CPD with hydrogen passing through the membrane catalyst compared with the delivery of a mixture of CPD vapor and hydrogen at the same catalyst.
TL;DR: In the presence of nucleophilic and electrophilic catalysts, the oxides of internal perfluoroolefins are isomerized to ketones.
Abstract: 1.
A new, convenient method has been developed for the epoxidation of terminal and internal perfluoroolefins by alkali and alkaline-earth hypohalites in alkaline solution in the presence of aprotic solvents.
2.
In the presence of nucleophilic and electrophilic catalysts the oxides of internal perfluoroolefins are isomerized to ketones.
TL;DR: In this article, a new reactive reagent for the hydrometallation of olefins and acetylenes has been synthesized for the first time, and the possibility of its use as a reactive reagents for the hydride chloride has been demonstrated.
Abstract: 1.
Bis (cyclopentadienyl) hafnium hydride chloride has been synthesized for the first time, and the possibility of its use as a new reactive reagent for the hydrometallation of olefins and acetylenes has been demonstrated.
2.
The complex (η5-C5H5)HfClH can be used for the conversion of olefins and acetylenes into halides, alcohols, aldehydes, and ketones. The stereo- and regiospecificity of the hydrohafnation reaction have been investigated.