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The dienamine (a mixture of isomers) obtained from citral and diethylamine is converted to a mixture of citral anhydro cyclodimers by the action of weak proton-donor agents. The principal reaction product corresponds to [4 + 2]-cycloaddition of 1-diethylamino-7-methyl-3-methylene-1,6-octadiene (the minor component in the starting dienamine) to the enimmonium form of the protonated dienamine.

The double bond formed in the Horner-Emmons reaction has only E configuration independently of the structure of the saturated linear, α-branched, and β-branched aliphatic aldehydes upon their reaction with the diethyl ester of 3-ethoxycarbonyl-2-methyl-2-propenylphosphonic acid, while the ratio of the2E,4E and2Z,4E isomers in the reaction product varies only from 58∶42 to 62∶38. An increase in the aldehyde concentration leads to an increase in the fraction of the2Z,4E isomer in the ethyl ester of 2E/Z,4E-3,7-dimethyl-2,4-octadienoic acid formed.

Cyclohexenyl cations that are long-lived at −50°C are stabilized by the GeCl3 − anion and are detected and characterized spectrally in reactions of HGeCl3 with 1,3-dialkoxybenzenes. Further reactions of the cyclohexenyl cations are studied. The x-ray crystal and molecular structure of the final reaction product of HGeCl3 with 1,3-diethoxybenzene — 1,1,3,5-tetrakis(trichlorogermyl)-3-ethoxycyclohexane — is solved.

A magnetic isotope effect was found in the photochemical reduction of uranyl nitrate by p-methoxyphenol. The initial238U/235U ratio equal to 8.93±0.008 was altered during the reaction to 8.945±0.008-8.970±0.005 in the reaction product, namely, uranium tetrafluoride.

1. The reduction of 1,1,1,5-tetrachloropentane by various reducing systems gave 1,1,5-trichloropentane (as the main reaction product) and 1,1,5,5-tetrachloropentane. The formation of 1,1,5,5-tetrachloropentane testifies to the rearrangement of the CCl2CH2CH2CH2CH2Cl radical to the CHCl2CH2CH2CH2CHCl radical with 1,5-migration of the H atom. 2. The rearrangement product was not found when 1,1,1-trichloropentane was reduced under comparable conditions. 3. The reduction of 1,1,1,5-tetrachloropentane by various reducing systems disclosed that a decrease in the concentration of the H donor or in its efficiency leads to an increase in the relative yield of the rearranged product.

1. 2-Hydroxymethylbicyclo[2.2.1]2,5-heptadiene effects protolysis of only one of the Al-C bonds in organoaluminum compounds. The composition and structures of the protolysis products have been established based on1H- and13C-NMR data, UV spectroscopy, and cryoscopic and volumetric analysis, which have also provided evidence for the formation of intramolecular complexes. 2. Reaction of 2-hydroxymethylbicyclo[2.2.1]2,5-heptadiene with organoaluminum compounds does not change the electronic state of the double bond at C5. The reaction product is of interest as a monomer containing a protected polar functional group.

The nitration of fluoroethylenes with sulfuric-nitric mixtures and added sulfuric anhydride was studied. It was shown that acid fluorides of halogenonitroacetic acids are formed in the nitration of fluoroethylenes containing the fluorochloromethylene fragment, whereas nitroethylfluorosulfates are the main reaction product in the nitration of ethylenes having the difluoromethylene grouping. The structure of the compounds obtained was shown by the data of19F and1H NMR and IR spectroscopy.

1. The reaction of phenyl dithiobenzoate with N-nitroso-p-toluidine proceeds with complete capture of the tolyl radicals formed in the decomposition of NAT by the thione group. The major reaction product is 1,2-bisphenylthio-1,2-bistolylthio-1,2-diphenylethane, which indicates the intermediate formation of the radical-adduct PhĊ(SPh)STol (A). 2. A side-reaction leading to the formation of S-tolyl and S-phenyl thiolbenzoates and diaryl disulfides is explained by the oxidation of radical-adduct A and subsequent fragmentation due to loss of an ArS. radical. 3. The reaction of N-butylthioacetamide with N-nitrosoacetanilide involves oxidation of radical-adduct MeĊ(SPh)NHBu and subsequent fragmentation, which is the major pathway of the reaction leading to the formation of N-butylacetamide, diphenyl disulfide, and diphenyl sulfide.

The reaction of di(hydroxymethyl)phenylphosphine and the isobutyl ester of diphenylboric acid gives a cyclic phosphorus-containing ester of diphenylboric acid with tetracoordinated P and B atoms and a hydroxymethyl group at the P atom instead of the expected re-esterification product diphenylborylhydroxymethyl(hydroxymethyl)phenylphosphine. The reactions of the product obtained with sulfur, amines, and MeONa gives derivatives of diphenylborylhydroxymethyl (hydroxymethyl)phenylphosphine.

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.

1. Podands with C2 symmetry have been synthesized from 1,4;3,6-dianhydro-D-mannitol. 2. Bis-(1,4;3,6-dianhydro-D-mannitol)-24-crown-6-ether with D2 symmetry has been synthesized. 3. A convenient method of adding ethylene glycol segments of a polyether chain to a dianhydromannitol matrix has been developed; it proceeds via O-alkylation with 2-tetrahydro-pyranyloxy-1-bromoethane in superbasic medium and conversion of the reaction product.

1. During the reduction of 1,1,1,7-tetrachloroheptane with isopropanol in the presence of Fe(CO)5, together with the main reaction product 1,1,7-trichloroheptane (II), 1,1,5,7-tetrachloroheptane (III), 1,1,4,7-tetrachloroheptane (IV) and 7,7-dichloro-1-heptene (V) are formed in a total yield of 7% of theoretical. 2. The formation of (III), (IV), and (V) is explained by an unusual rearrangement of the CCl2(CH2)6Cl radicals into less stable radicals with 1,5-, 1,4-, and 1.6-migration of hydrogen atoms, respectively, with preferential formation of the rearrangement product and 1,5-migration of the hydrogen atom. 3. Certain regularities in the13C NMR spectra of polychlorohydrocarbons with a normal structure, containing the CHCl2, CH2Cl, and CHCl groups with different disposition of the CHCl group in the chain are discussed.

The main products of the pyrolysis of 8,8-dimethyl-8-sila-2,3,4,5-tetrathiabicycIo-[4.3.0]nonane at 400‡ are 1,1-dimethylsilacyclopent-3-ene and 1,1-dimethyl-1-sila-2-thiacyclo-hexa-3, 5-diene, and at 600‡ carbon disulfide and thiophene; silacyclopentene is the sole reaction product, characteristic for the mass-spectrometric decomposition of the initial tetrasulfide.

1. In the reaction ofβ-chlorovinylketones with Fe2(CO)9, (RCOCH=CHCl)Fe(CO)4 (I) (principal reaction product) and (RCOCH=CHCl)Fe(CO)3 (II). 2. A structure analogous to the structure of complexes (diene-1,3)Fe(CO)3 and including coordination of the Fe atom at C=C and C=O bonds was proposed for the complexes (II) on the basis of the IR and NMR spectra. 3. The photochemical conversion of (I) to (II) was accomplished. 4. The photochemical interaction ofβ chlorovinylketones with Fe(CO)5, leading to virtually simultaneous formation of the complexes (I) and (II), was studied.

1. We were the first to study the reaction of tetrafluorohydrazine with perfluorobutadiene and perfluorocyclobutene. In both cases the reaction product is the previously unknown 1,4-bis- difluoroamino)perfluoro-2-butene. 2. Perfluorocyclobutene, when heated with substances that easily yield free radicals (for example, N2O4 and N2F4), reacts with opening of the ring. A mechanism was proposed for the indicated reaction, which apparently has a quite general character. 3. The oxidation of 1,4-bis-(difluoroamino)-1,1′,4,4′-tetrafluoro-2-butene with potassium permanganate is carbonate solution gave 1,4-bis-(difluoroamino)-1,1′,4,4′-tetrafluoro-2,3-butanediol.

1. Silicates of composition Pr2O3·SiO2, 2Pr2O3·3SiO2, and Pr2O3·2SiO2 are formed by the interaction of praeseodymium oxide with silica. 2. The silicates can be obtained by interaction of silica with Pr2O11 in an atmosphere of hydrogen or of air. 3. At 1200–1300° in an atmosphere of hydrogen or air, orthosilicate is formed as the predominant reaction product phase, regardless of the ratio of praeseodymium oxide to silica in the initial mixture within the range 1∶1,2∶3, and 1∶2. The orthosilicate is unstable at the higher temperatures 1400–1650° and decomposes into the silicates Pr2O3·SiO2 and Pr2O3·2SiO2. 4. The pyrosilicate Pr2O3·2SiO2 is formed at 1400–1650° in a secondary stage of the reaction, by interaction of more basic praeseodymium silicates with silica. The oxyorthosilicate Pr2O3·SiO2, slightly contaminated with orthosilicate, can be produced at 1600–1650°.

1. A scheme is proposed for the reactions of the isobutyl peroxide radical during gaseous-phase oxidation of n-butane, which is in satisfactory agreement with the experimental data. The proposal is made to explain the formation of acetone from n-butane that the radical isomerizes with the free valence going to the β-carbon atom. 2. Kinetic curves for the buildup of reaction products and consumption of butane in experiments with and without added acetaldehyde have given the decomposition rates of the isobutyl peroxide radical in the three directions, and the rate at which this radical reacts with butane. About 60% of the radical reacts, skipping the hydroperoxide formation stage. 3. Acetic and formic acids are not products of the further oxidation of aldehydes, and it is proposed that the acids are formed from the hydroperoxide. Peracetic acid has been observed as an intermediate reaction product, and is apparently one of the substances responsible for the chain branching in butane oxidation.

1. The catalytic reaction 1-butene — 2-butene was studied both in presence and in absence of hydrogen, the conditions being those for the hydrocondensation of carbon monoxide with olefins, carbon monoxide, however, being absent. 2. It was shown that, in absence of hydrogen, the isomerization of 1-butene into 2-butene and vice versa did not occur to an appreciable extent. 3. In presence of 10% of hydrogen, 1-butene was 1-omerized into 2-butene, the relative amounts of 1- and 2-butenes in the products being 1: 1,1 (at a space velocity of 66 hour−1). 4. In experiments on the isomerization of butenes in presence of 10% and 26.6% of hydrogens at space velocities of 60 and 100 hour−1 no appreciable amount of 1-butene could be detected in the reaction product. 5. In experiment with 1-butene, hydrogenation of the olefin proceeded much more rapidly (about twice as fast) than in experiments with 2-butene under similary conditions.

1. An investigation was made of the contact-catalysis reactions of decane at 460° in presence of platinized alumina in a flow system, hydrogen being present at a pressure of 30 or 50 atm. 2. It was shown that, under the conditions described, this hydrocarbon undergoes some far reaching transformations: the reaction product was found to contain aromatic hydrocarbons, cyclopentane and cyclonexane hydrocarbons, and C7-C10 mono- and di-substituted alkanes. C19 monosubstituted alkanes formed 70% of the total amount of C10 isomers present.

1. Treatment of 1,1-dichloropentene-1 with nitric acid gave butyric andα-chlorovaleric acids, 1,1,1,2-tetrachloropentane, 1,1,1-trichloro-2-nitropentane and 1,1-dichloro-1,2-dinitropentane. The reaction with 1,1,5-trichloropentene-1 takes a similar course. 2. Nitryl chloride adds on to 1,1-dichloropentene-1 with formation of 1,1,1-trichloro-2-nitropentane (main reaction product), 1,1,1,2- tetra chloropentane and 1,1-dichloro-1,2-dinitropentane. The reaction with 1,1,5-trichloropentene-1 goes in similar fashion. 3. 1,1,1-Trichloro-2-nitropentane was converted to ethylα-nitrovalerate, reduction of which gaveα-amino-valeric acid.

1. It was shown that, under the conditions of catalytic hydrogenation at 280–290° and 100–120 atm. 3,3,4-trimethyl-2-pentanol yields a mixture of 2,3,3- and 2,3,4-trimethylpentanes, the latter predominating. The formation of this mixture of isomers is due to the isomerization of the initial reaction product. 3,3,4-trimethyl-1-pentene. 2. It was shows that in the pyrolysis of the acetic ester of 3,3,4-trimethyl-2-pentanol at 430–450° isomerization again occurs, not only 3,3,4-trimethyl-1-pentene being formed, but also much 2,3,4-trimethyl-1-pentene [4]. This method for the preparation of hydrocarbons cannot therefore be recommended at a general method for the preparation of the higher branched olefins. 3. For comparison with the octane isomers obtained by the hydrogenation of 3,3,4-trimethyl-2-pentanol and by the pyrolysis of its acetic ester, 2,3,3-trimethylpentane was synthesized by the Grignard method.

1. Dienic δ-amino ketoesters, δ-amino ketones, and δ-amino esters have a trans-configuration of the protons at theγ, δ-double bond and exist predominantly in the S-trans-conformation. The dienic δ-amino ketones and δ-amino esters exist as the thermodynamically stable trans-isomers at theα, β-double bond, while the dienic δ-amino ketoesters represent equilibrium mixtures of the geometric isomers at the same double bond. 2. A rapid, on the NME time scale, rotation around theα,β-double bond under the equilibrium conditions was detected in the dienic δ-amino ketoesters. A hindering of the rotation around the C-N bond was noted in these compounds. 3. The kinetic reaction product of the addition of diethylamine to vinylacetylenic ketones and ketoesters is the cis-isomer at theα, β,-double bond, while the trans-isomer is formed as the result of subsequent isomerization. A scheme for the mechanism of these reactions was proposed.

The reaction of trimethyliodosilane with tetraalkoxysilanes, taken in a 1–3 ∶1 mole ratio, leads to a mixture of trimethylsiloxy derivatives [(CH3)3SiO]nSi(OR)4-n with n = 1–4. Tetrakis(trimethylsiloxy)silane (n = 4) is the main reaction product at a 4∶1 mole ratio of the reactants. It is formed together with hexakis(trimethylsiloxy)disiloxane, which was obtained in 82–98% yield when trimethyliodosilane is reacted with a hexaalkoxydisiloxane.

1. The NCP rate when 2,6-di-tert-butyl-1,4-benzoquinone diazide is reacted with propylamine was studied. 2. The behavior of the NMR emission signal of the main reaction product is satisfactorily described by the sum of two different kinetic equations. 3. The effective rate constant of the process was obtained by two independent methods.

1. The thermocatalytic decomposition of 4-propenyl-1,3-dioxane, which supposedly proceeds via the intermediate formation of 2,4-hexadien-1-ol and 2-methyl-5,6-dihydro-(2H)-pyran, leads to 1,3,5-hexatriene and methylcyclopentadienes. 2. The nature of the catalyst exerts the determining-effect on the direction of the conversion of 4-propenyl-1,3-dioxane; in particular, when calcium phosphates are used the main reaction product is 1,3,5-hexatriene.

1. Ethylidenethioacetoacetic ester was obtained by the reaction of ethylideneacetoacetic ester with phosphorus pentasulfide. 2. The reaction of ethylidenethioacetoacetic ester with trimethyl phosphite was studied. The end reaction product is 2-oxa-2-methoxy-3,5-dimethyl-4-carbethoxy-l,2-oxaphospholene.

1. A study was made of the products and rate of methanolysis of 4-methyl-1,3-dioxane in the presence of H2SO4. 2. The methanolysis of 4-methyl-1,3-dioxane proceeds with the successive cleavage of the C2 -O1 and C2-O3 bonds of the ring; 3-methyl-4,6-dioxa-1-heptanol is formed as an intermediate reaction product.

2,6-Didesoxy-α-L-arabinohexopyranosyl phosphate was synthesized by the fusion of 1,3,4-tri-Oacetyl-2,6-didesoxy-L-arabinohexopyranose with crystalline orthophosphoric acid. A nonreductng disaccharide was identified as being the main reaction product of the given acetate with HBr.

1. The triphenylphosphine complex of palladium(0), which contains either the 1,3-pentadiene or the 2-methyl-1,3-butadiene molecule as a ligand, catalyzes the oligomerization of dienes. 2. The main reaction product is the linear dimer, which contains conjugated C=C bonds.

1. When potassium chloropalladoate is reacted with anilium chloranilate, in aqueous DMF, the chloranilic acid anion does not react. 2. As the reaction product we isolated a crystalline complex of composition PdCl2(NH2C6H5)2·2HCON-(CH3)2, whose structure was studied by the x-ray structure analysis method.

1. A study was made of the reaction of technical potassium superoxide with nitrogen oxide (both pure and diluted with argon). 2. The process proceeds at considerable speeds at the start, with a subsequent rapid slowing up and then a complete cessation of the reaction. 3. The reaction goes with the formation of potassium nitrite as the main reaction product and potassium nitrate as the secondary reaction product.

The chlorine atom in the 4 positionis replaced by a phosphono group in the reaction of 3,4,5-trichloro-2(5H)-furanone with trimethyl phosphite. The structure of dimethyl 3,5-dichloro-2(5H)-furanon-4-ylphosphonate was determined by x-ray diffraction analysis.

1. It was shown that cyclopentadiene can be condensed with acetylene with formation of 2,5-norbornadiene in a flow system without use of a phlegmatizer at temperatures of 325–435°, pressures of 1–6 atm, and space velocity for the feed of cyclopentadiene of 0.05-0.30 h−1. 2. At 4 atm and 370° with a molar ratio of cyclopentadiene to acetylene of 1∶1.3 the 2,5-norbornadiene content of the reaction products is about 40%, which corresponds to a yield of 70.1% based on the cyclopentadiene that reacts. 3. At higher temperatures the main reaction product becomes cycloheptatriene, the content of which in the reaction products at, for example, 4 atm and 415° attains 42%.

1. A Chromatographie method was proposed for isolating 1-N-(α-benzyl-N'-carbobenzoxy-β-L-as-partyl-2-acetamido-4,6-O-benzylidene-1,2-didesoxy-β-D-glucosamine (IV) from the reaction mixture in the pure state. 2. The complete removal of dicyclohexylurea from product (IV) is achieved by adsorption chroma-tography on silica gel in chloroform. 3. Together with the main reaction product, theα-benzyl ester of N-carbobenzoxyasparagine (VI) is also formed as a by-product. 4. A method was found for separating the main and side reaction products by chromatographing on Sephadex LH-20.

1. Phenol is formed as a secondary reaction product in the ozonolysis of benzene. 2. The rate constant for the reaction of ozone with benzene and the effective rate constant for the accumulation of phenol during the ozonolysis of benzene in the absence of a solvent were measured.

1. Dibromo(diphenylamino)borane was synthesized by the reaction of BBr3 with diphenylamine. 2. The reaction of excess pyridine with dibromo(diphenylamino)borane gives the adduct (C6H5 2NBBr2. 2C5H5N, which has the structure of a boronium salt in which the cation has a +1 charge.

The dehydrogenation of 1,4-benzoquinone dioxitne by phenoxyl radicals was studied and it was shown that the quinol ethers are formed as the sole reaction product when stable phenoxyls are used. A universal method was developed for the synthesis of the indicated ethers.

Nitronium tetrafluoborate and nitrogen pentoxide nitrate the tetraalkyl derivatives of methylenediamine to the corresponding secondary nitramines. In the case of nitronium tetrafluoborate a second reaction product is the dialkylmethyleneimmonium tetrafluoborate.

1. The oxidation of ethylene chlorohydrin by oxides of nitrogen has been studied. 2. The main reaction product is chloroacetic acid, with a maximum yield of 74.88 % of theoretical. 3. The oxidation of the OH group in ethylene chlorohydrin is activated by the negative effect of the chlorine atom to the same degree as the oxidation of glucosides and polysaccharides is activated by the glucopyranosidic ring.

The structure of the reaction product of phenolphthalein and epichlorohydrin in alkaline medium was established, and it was shown that it contains the lactone ring of the phthalide grouping.

The reaction of the 3-acetate of the 20-ketal of 16α,17α-oxido-Δ5-pregnenol-3β-one-20 with methylmagnesium iodide and subsequent hydrolysis of the reaction product yielded 16β-methyl-Δ5-pregnenediol-3β −17α-one −20. 18-Nor-17β-methyl-17-iso-Δ5.11-pregnadienediol-3β,16β-one-20 was formed as a by-product.

The fluorination of nitroform or its salts with elemental fluorine in aqueous solution has been accomplished. The main reaction product is fluoronitroform.

1. It was shown that the bipolar ion of 2,2-dinitroaminoethane can be fluorinated with elemental fluorine to give 2-fluoro-2,2-dinitroaminoethane. 2. The end reaction product of 2-fluoro-2,2-dinitroaminoethane with formaldehyde in the presence of HCl is tris-1,3,5-(2′-fluoro-2′,2′-dinitroethyl)-1,3,5-triazacyclohexane.

1. We have studied the reaction of trichloroethylidene acetone and amido esters of phosphorous acid and amido esters of phosphorous acid and established that it leads to formation of the corresponding dichlorodivinyl phosphates. 2. Diethyl phosphorous acid adds on to trichloroethylidene acetone in the presence of an equimolar amount of triethylamine, and the latter then removes hydrogen chloride from the reaction product.