Photochemical reactions of 9-trimethylstannylanthracene in various solvents

9-Trimethylstannylanthracene (1) was synthesized and its photolysis by 365-nm light was studied. In aprotic solvents, the dimerization of 1 involves positions 9 and 10 and yields a head-to-tail dimer. The main route of the photolysis of 1 in alcohols is the cleavage of the C-Sn bond with the formation of anthracene. The quantum yields of the photoreaction and the lifetimes and quantum yields of 1 fluorescence were determined.     

Photochemical reactions of some mono- and diketo derivatives of adamantane in various solvents

Adamantanes are photoactive in the presence of CCl₄ and CDCl₃. The mechanism of their photolysis, involving the formation of singlet or triplet excited donor-acceptor complexes has been suggested.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1833–1835, September, 1995.This work was partially financially supported by the Russian Foundation for Basic Research (Project No. 93-03-18102).     

Photochemical reactions of organomercury compounds in organic solvents

The quantum yields of photolysis of organomercury compounds in different organic solvents have been measured. It was shown that the quantum yields of photolysis of nitro derivatives of mercury compounds and the symmetric (methylnaphtyl)mercury compound are equal to unity. The photolysis of halo derivatives of benzylmercury proceeds with lower quantum yields as compared with photolysis of analogous dibenzylmercury derivatives. The quantum yields of photolysis of organomercury compounds are almost independent of the solvent.     

Photodecomposition of di(B-carboranyl)mercury in solution

Conclusions ESR spectroscopy was used to record the radical adducts of the boron-centered and mercury-centered radicals formed upon the photodecomposition of di(B-carboranyl) mercury compounds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2644–2646, November, 1985.     

Photochemical reactions of 1-methyl-4,6-diaryl-2(1H)-pyrimidinones in the presence of thiols

Photochemical reactions of 1-methyl-4,6-diaryl-2(1H)pyrimidinones 1a-b in the presence of thiols 2 are described. Irradiation of 1-methyl-4,6-diaryl-2(1H)-pyrimidinones 1a-b in benzene in the presence of thiols 2 gave the unexpected 2:1-adducts, 3-methyl-4,6-diaryl-5-aralkylthio-6-(1′-methyl-4′,6′-diaryldihydro-pyrimidin-2-on)yl-1,3-diazabicyclo[2.2.0]hexan-2-ones 3-6, of 1 and 2, whereas irradiation of 1a-b alone in benzene resulted in recovery of the unchanged 1a-b.     

Crosslinking reactions of 1,3,5-tris(2-methylaziridinyl-1-methyl)benzene (TRIMAM) with carboxyl terminated polybutadiene

Curing reactions of a new crosslinking agent, 1,3,5-tris(2-methylaziridinyl-1-methyl)benzene (TRIMAM) with carboxylterminated polybutadiene have been studied by dynamic differential thermal analysis and by IR spectroscopy. The crosslinking reactions are found to be faster for this new compound compared with the conventional tris-1-(2-methyl) axiridinyl phosphine oxide (MAPO).     

Synthesis and reactions of bis(benzylchromiumtricarbonyl)mercury

Conclusion Bis(benzylchromiumtricarbonyl)mercury was synthesized by the reaction of dibenzylmercury with (NH₃)₃Cr(CO)₃inboilingdioxane. Its reaction was studied with iodine, LiAlH₄, HgCl₂, and CuCl₂.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1131–1134, May, 1982.     

High-speed microwave-promoted hetero-Diels-Alder reactions of 2(1H)-pyrazinones in ionic liquid doped solvents

Inter- and intramolecular hetero-Diels-Alder reactions in a series of functionalized 2(1H)-pyrazinones were investigated under controlled microwave irradiation. The cycloaddition reactions were efficiently performed in sealed tubes, utilizing either a combination of 1,2-dichloroethane and a thermally stable ionic liquid, or 1,2-dichlorobenzene as reaction medium. In all cases, a significant rate-enhancement using microwave flash heating as compared to thermal heating was observed.     

Spectroscopic behaviour of fluorescein and its di(mercury acetate) adduct in glasses

Fluorescence spectra of fluorescein and fluorescein mercury acetate (FMA) in glassy media reveal the presence of two differently charged species depending on the environment. The efficiency of singlet-singlet and singlet-triplet transitions are estimated for the two species.     

Selective synthesis of di(propen-1-yl)sulfone and di(propen-1-yl)sulfoxide

Convenient selective methods of synthesis of the title compounds, based on oxidation of di(propen-1-yl)sulfide with 30% H₂O₂, have been developed.Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 664033 Irkutsk. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 675–679, March, 1992.     

Thermodynamics of Cobalt(III) Schiff base complexes in various solvents

The electronic and steric effects of some Schiff bases and the solvent on the thermodynamic parameters of the pentacoordinate Co(III) Schiff base complexes were studied. The formation constants and the thermodynamic parameters were measured spectrophotometrically for 1:1 adduct formation of the complexes as acceptors with tributylphosphine (PBu₃) as donor, in some solvents (acetonitrile, tetrahydrofuran, butanol, ethanol and N,N-dimethylformamide) in constant ionic strength (I = 0.01 M, sodium perchlorate) and at various temperatures. The trend of the reactivity of the pentacoordinate cobalt(III) Schiff base complexes toward tributylphosphine according to the solvent is as follows: acetonitrile > tetrahydrofuran > butanol > ethanol > N,N-dimethylformamide. The trend of the reactivity of pentacoordinate cobalt(III) Schiff base complexes toward the donor in a given solvent according to the equatorial Schiff base is as follows: BBE > BAE > Salen.     

Photochemical Reactions of Alkyl Phenylglyoxylates(1)

Three new photoproducts, ethyl O-benzoyl mandelate (5a), ethyl O-acetylmandelate (6a), and biphenyl triketone (7a) are isolated and identified in the reactions of ethyl phenylglyoxylate (1a) in benzene. Quantum yields and initial rate constants of product formation are shown to be concentration dependent. For the formation of carbonyl product 3 at lower starting material concentrations (<0.01 M), quantum yields greater than 1 are observed. Variations in the quantum yields as a function of reaction time are due to the accumulation of alpha-hydroxyphenyl ketene (D). The relative reactivities of triplet excited states of phenylglyoxylates 1 and phenyl ketones are compared. A mechanism involving both intramolecular gamma-H abstraction and intermolecular H abstraction, which leads to radical chain reaction, is proposed. Rate constants for intramolecular gamma-H abstraction (k(N)) and intermolecular H abstraction (k(I)) of methyl phenylglyoxylate (1d) are measured.     

Investigation of reactions in carboxyl-terminated polybutadiene and tris-[1-(2-methyl)aziridinyl] phosphine oxide

The functionalities of a series of carboxyl-terminated polybutadiene samples (CTPB) were calculated from an infrared spectroscopic study of the samples reacting to the gel point with tris-[1-(2-methyl)aziridinyl] phosphine oxide (MAPO), Epon X801, and glycerol. Identical functionalities were calculated when Epon X801 and glycerol were used as curing agents. Higher functionalities for CTPB with MAPO were due to additional reactions that MAPO underwent with hydroxyl groups and water, present in carboxyl-terminated polybutadiene, and with itself (homopolymerization). Rate constants were calculated for the homopolymerization of MAPO in Nujol, in nonfunctional polybutadiene, and in CTPB. The homopolymerization resulted in an increase and then a gradual decrease in MAPO functionality, which was in agreement with that predicted from theoretical considerations.     

Combustion of poly(1-methyl hexamethylene) and poly(1-methyl tetramethylene) and identification of the main decomposition products

The Bayer-ICI-Shell apparatus has been used to carry out combustion experiments on poly(1-methyl hexamethylene) (PH) and poly(1-methyl tetramethylene) (PT) using different air flow rates at various combustion temperatures. The products were adsorbed on charcoal followed by benzyl-alcohol desorption. They were separated and identified using gas chromatography.The non-oxidized products were identified as short chain, saturated and unsaturated hydrocarbons while the main oxidized products are short chain ketones and alcohols. The intensities of the chromatographic peaks of the separated products depend upon the temperatures and air flow rates in the combustion apparatus.     

Synthesis and Crystal Structure of Mercury Bridged Biferrocene Trinuclear Complex Hg(FcL)_2,Bis(S-methyl-N-(1-ferrocenyl-1-methyl)methylenedithiocarbazate)mercury(Ⅱ)

1INTRODUCTIONRecently,transitionmetalorganometallicandcoordinationcomplexeshaveemergedaspotentialbuidingblocksfornonlinearoptical(NLO)materialstl--st.Comparedtoorganicmolecules,metalcomplexesofferalargervarietyofstructures,comparableor,insomecases,higherenvironmentalstabilityandamuchgreaterdiversityoftunableelectronicpropertiesbyvirtueofthecoordinatedmetalcenter{63.ThethioSchiffbaseligandderivedfromdithiocarbazidesandthiosemicarbazidescancoordinatereadilywithtransitionmetalstogivestablec…