A novel synthesis of vinyl esters from vinylversatate-10

Vinylversatate-10 (VV10)¹ has successfully been used to synthesise a large number of lower vinyl esters by transvinylation in presence of mercuric acetate and sulfuric acid. The synthesis of vinylhalo esters proceeds with more difficulty. It has been observed that neither Hg(OAc)₂ nor H₂SO₄ alone is capable of initiating the transvinylation. Furthermore, it has been found that a molar ratio 2:1 of VV10 to carboxylic acid is sufficient to drive the reaction to the right by continuous distillation of the vinyl ester formed, and as a result a high yield of vinyl ester is obtained. A mechanism for this reaction and for the formation of side products has been proposed.     

Simultaneous measurement of gamma-rays and neutron fluences</p> using a HPGE detector</o:p></p> </p>

Summary A simultaneous determination of gamma and neutron fluences in a mixed neutron + gamma field can be achieved by gamma-ray spectrometry, optimizing the moderator-converter-detector assembly and measuring both the direct gamma-lines and the neutron induced prompt gammas. For the prompt gamma-lines a combination of high efficiency and low background is the goal, and it can be best achieved if the gamma-energy is in the range above about 1 MeV up to 2.5 MeV. The optimal moderator-converter thickness can be determined experimentally. Most converter elements produce gamma-rays in the low energy range. If chlorine is used as a converter, the 1164.7 keV peak and the 1950-1960 keV peaks seems to be a good choice. A very practical material containing chlorine is PVC. It is an efficient moderator, it is solid, common, and can be handled easily.</p> </p>     

Fluoroaliphatic esters of fluorosulfonic acid. 6. Interaction of fluorine-containing α,β-bis-fluorosulfatocarbonyl compounds with nucleophilic reagents

Fluorine-containing ,-fluorosulfatocarbonyl compounds interact with halides of alkali metals with the formation of -halogeno--dicarbonyl derivatives.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 177813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 715–719, March, 1992.     

Oxamic acid derivaties in heterocyclic synthesis: Preparation of 1,2,4-triazolo[1,5-a]pyrazine derivatives

N-Aryl-N-(α-phenylphenacyl)oxamoyl chlorides react with N³-arylsubstituted amidrazones to give functionalized 1,2,4-triazoles which undergo ring-closure by the action of thionyl chloride to give 1,2,4-triazolo[1,5-a]-pyrazinium chlorides in excellent yields.     

Nucleophilic isomerization of perfluoropentenes

Conclusions The isomerization of perfluoro-1-pentene by CsF in polar aprotic solvents leads to a mixture of trans- and cis-perfluoro-2-pentene in an isomer ratio of 61.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2646–2647, November, 1981.     

Fused Mesoionic Heterocycles: Synthesis of 1,2,4-triazolo(4,3-b)-1,2,4-triazole derivatives

A number of mesoionic compounds derivatives of the bicyclic system 1,2,4-triazolo(4,3-b)-1,2,4-triazole have been prepared from 4-amino-1-methyl-3,5-bis(methylthio)-1,2,4-triazolium iodide and aryl isothiocyanates.     

NMR chemical shifts in the low–pH form of a-chymotrypsin. A QM/MM and ONIOM–NMR study

 The relationship between hydrogen bonding and NMR chemical shifts in the catalytic triad of low-pH α-chymotrypsin is investigated by combined use of the effective fragment potential [(2001) J Phys Chem A 105:293] and ONIOM–NMR [(2000) Chem Phys Lett 317:589] methods. Our study shows that while the His57 N^δ1−H bond is stretched by a relatively modest amount (to about 1.060 ?) this lengthening, combined with the polarization due to the molecular environment, is sufficient to explain the experimentally observed chemical shifts of 18.2 ppm. Furthermore, the unusual down-field shift of H^ɛ1 (9.2 ppm) observed experimentally is reproduced and shown to be induced by interactions with the C=O group of Ser214 as previously postulated. The free-energy cost of moving H^δ1 from His57 to Asp102 is predicted to be 5.5 kcal/mol. Received: 26 September 2001 / Accepted: 6 September 2002 / Published online: 21 January 2003 Contribution to the Proceedings of the Symposium on Combined QM/MM Methods at the 222nd National Meeting of the American Chemical Society, 2001 Correspondence to: J. H. Jensen e-mail: jan-jensen@uiowa.edu Acknowledgements. This work was supported by a Research Innovation Award from the Research Corporation and a type G starter grant from the Petroleum Research Fund. The calculations were performed on IBM RS/6000 workstations obtained through a CRIF grant from the NSF (CHE-9974502) and on supercomputers at the National Center for Supercomputer Applications at Urbana-Champaign. The authors are indebted to Visvaldas Kairys for help with the CHARMM program, and to Daniel Quinn for many helpful discussions.     

Electrophilic isomerization of fluoroaliphatic oxygen-containing compounds

An unusual electrophilic cyclization of fluorine-containing carbonyl compounds and -oxides was discovered. Upon the action of SbF₅, perfluorinated ketones, diketones, and -oxides isomerize to oxolanes. This reaction proceeds with the obligatory participation of the terminal CF₃ group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2611–2618, November, 1991.