The mass spectra of 1-substituted 3,5-dimethyl-1H-pyrazole-4-carbaldehyde bis(2-hydroxyethyl) dithioacetals and thioacetals were studied for the first time. The main fragmentation
pathways of their molecular ions generated under electron impact and chemical ionization were similar. Primary decomposition
of the molecular ions of bis(2-hydroxyethyl) dithioacetals involves elimination of 2-sulfanylethanol molecule with formation
of the corresponding 1,3-oxathiolane radical cation. Fragmentation of the molecular ions [M]+ · and [M + H]+ derived from 2-(3,5-dimethyl-1H-pyrazol-4-yl)-1,4,6-oxadithiocanes includes cleavage of the eight-membered heteroring and elimination of C4H9OS ·. Substituents in the heteroring of pyrazolecarbaldehydes inhibit decomposition processes related to the aldehyde group. 相似文献
Russian Journal of Organic Chemistry - Fragmentation of N, N-dialkyl-7-[alkyl and 2-(vinyloxy)ethyl]-2,7-dihydrothiopyrano[2,3-b]pyrrol-6-amines under electron impact (70 eV) and chemical... 相似文献
Triads of isomeric N-alkyl-N-methyl-3-phenylthiophen-2-amines, N-methyl-3-alkyl-4-methylidene-3-phenylthietan-2-imines, and N-methyl-4-alkylsulfanyl-2-phenylcyclobut-2-en-1-imines (Alk = Me, Et, Bu) were synthesized from 1,3-dilithio-3-phenylpropyne, methyl isothiocyanate, and alkyl halides, and their fragmentation under electron impact was studied. Primary decomposition of the molecular ions of 2-aminothiophenes is determined by the localization of a radical cation center on the nitrogen atom, and it follows a path typical of alkyl(aryl)amines with elimination of hydrogen atom or methyl or propyl radical from the α-carbon atom in the N-alkyl substituent. Fragmentation of the iminothietanes involves cleavage of the four-membered ring in half to give neutral MeNCS molecule and 1-alkyl-1-phenylallene radical cation. Alkylsulfanyl(imino)-cyclobutenes undergo cleavage at the sulfur-containing side chain according to general relations holding in the fragmentation of alkyl sulfides. 相似文献
Acetylene—allene rearrangement in propargyl systems XCH2CHCH (X = H, Me, NMe2, OMe, F, and SMe) was studied using the ab initio approach. The relative stabilities of the starting and final propyne structures and the corresponding allenes as well as the structure of intermediate carbanions were considered. n--Conjugation was shown to dominate in allene stabilization while the inductive effect of heteroatomic substituents makes at least comparable contribution to stabilization (or destabilization) of the propynyl structure. In particular, relative instability of 1-methoxypropyne can be rationalized by high electronegativity of O atom, which leads to dramatic decrease in the total electron density in the region of the neighboring CC triple bond. The influence of substituents on the mobility of the migrating proton was considered for the gas phase and with solvation effects included. Calculations involving electron correlation at the MP2 level of theory were shown to be insufficient for correct reproduction of the energy differences between the corresponding propynes and allene structures. The results of MP4 calculations with inclusion of ZPE correction are in good agreement with the available experimental data. 相似文献
Conclusions A detailed analysis of the pathways for the mass spectrometric decomposition of -acyloxyalkyltrihalosilanes indicates the absence of an intramolecular coordination interaction of the silicon and carbonyl oxygen in the gas phase.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2596–2598, November, 1986. 相似文献
A new class of organosilicon compounds containing a pentacoordinate silicon atom, (aroyloxymethyl)trifluorosilanes (AFS), has been prepared. The presence of an intramolecular coordinate F3Si ← OC bond is supported by X-ray diffraction, IR spectroscopy and dipole moment data. Si ← O coordination in AFS has been shown to remain intact in the gaseous and liquid states below 420 K as well as in solution in most organic solvents. The dielectric constant of the medium significantly affects the nature of the coordinate Si ← O bond and that of the SiF, CO, COC bonds. In pyridine the intramolecular coordinate Si ← O interaction is disturbed or greatly weakened.At 420–500 K a reversible reaction takes place: ArCF3 α ArCOOCH2SiF3 The changes in enthalpy and entropy are equal in this case: ?△H 8.1 ± 0.7 kcal/mol; ?°S 15.3 ± 0.8 e.u. T 450 K An assignment of bands in the IR spectra of AFS resulting from vibrations of atoms in the SiF3, >CO and COC groups is given. The electron impact-induced primary disintegration of the molecular ion 4-XC6H4COOCH2Si mainly involves abstraction of a fluorine atom. 相似文献
Alkylthiochloroacetylenes dimerize at room temperature in the system sodium sulfite-polar nonhydroxyl solvent (DMSO, DMF, HMPA) to form in 40-63% yields (Z)-1,4-bis(alkylthio)-1,2-dichloro-1- buten-3-ynes which are promising polyfunctional monomers and building blocks for fine organic synthesis. The structure of the resulting dimers was established by means of IR and 1H and 13C NMR spectroscopy, X-ray fluorescent analysis, and dielcometry and confirmed by mass spectrometry and elemental analysis. 相似文献
The behavior of new heterocyclic systems, viz., 3,6-dihalo-4,4-dimethyl-1,4-selena- silafulvenes 1a, b and 2,4-dihalo-2-dihalomethyl-3,3-dimethyl-1-selena-3-silacyclopent-4-enes 2a, b (Hal =Cl, Br), was studied under conditions of electron ionization and thermal decomposition. Their fragmentation is accompanied by skeletal rearrangements, and the positive charge is localized mainly on ions containing silicon. Selenasilafulvenes 1a, b form stable molecular ions. Selenasilacyclopent-4-ene 2a decomposes partially and compound 2b decomposes completely in the gas phase with the elimination of a hydrogen halide and a halogen molecules.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 639–642, March, 2005.The term “contribution” implies the ratio of the sum of peak intensities of all isotope varieties of the ion under consideration to the total ion current. 相似文献
In the gas phase at 350–410C allyl 2-thienyl sulfide is converted to thiophene-2-thiol, di(2-thienyl) sulfide, and 2-methylthieno[2,3-b]thiophene. In the presence of acetylene thieno[2,3-b]thiophene is formed in addition to these products. Allyl 2-thienyl selenide is converted quantitatively to 2,3-dihydro-2-methylselenopheno[2,3-b]thiophene during fractional distillation in vacuo. Thiophene, di(2-thienyl) selenide, di(2-thienyl) diselenide, thiophene-2-selenol, and 2-methylselenopheno[2,3-b]thiophene are formed in addition to these compounds in the thermolysis of allyl thienyl selenide in the gas phase. In the presence of acetylene the thermal decomposition of allyl thienyl selenide is accompanied by the formation of selenophene.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1312–1316, October, 1991. 相似文献