1,721,026 research outputs found
Gaseous Sf3 +: An Efficient Electrophilic Monofluorinating Agent For Five-membered Heteroaromatic Compounds
No full textReactions of gaseous SF3 + ions with furan, thiophene, pyrrole, and several of their alkyl derivatives were performed via MS2 experiments and found to occur readily both by electron abstraction and F+ transfer. Then, by performing MS3 experiments, the F+ transfer products - the protonated monofluorinated molecules - were mass-selected and deprotonated by a second reaction with a stronger base. F+ transfer from gaseous SF3 + followed by deprotonation promotes therefore C-H by C-F replacement in five-membered heteroaromatic compounds and the efficient gas-phase synthesis of their neutral monofluorinated derivatives.651339203925Liebman, J.F., Greenberg, A., Dolbier, W.R., (1988) Fluorine Containing Molecules: Structure, Reactivity, Synthesis and Applications, , VCH: New YorkWalker, S.B., (1989) Fluorine Compounds as Agrochemicals, , Fluorochem Limited: GlossopBanks, R.E., (1979) Organofluorine Chemicals and Their Industrial Applications, , Ellis Horwood: ChichesterKirk, K.L., (1991), 9 B. , Biochemistry of the Elements SeriesFrieden, E., Ed.Plenum Press: New YorkRozen, S., (1996) Acc. Chem. Res., 29, p. 243Wilkinson, J.A., (1992) Chem Rev., 92, p. 505Cartwright, M.M., Woolf, A.A., (1984) J. Fluorine Chem., 25, p. 263Cartwright, M.M., Woolf, A.A., (1981) J. Fluorine Chem., 19, p. 10Chrite, K.O., (1984) J. Fluorine Chem., 25, p. 269Chrite, K.O., (1983) J. Fluorine Chem., 22, p. 519Rozen, S., Gal, C., (1984) Tetrahedron Lett., 25, p. 449Rozen, S., Gal, C., (1988) J. Org. Chem., 53, p. 2803Hewitt, C.D., Silvester, M.J., (1988) Aldrichimica Acta, 21, p. 3Moissan, (1986) J. Fluorine Chem., p. 33Olah, G.A., Welch, J.T., Vankar, Y.D., Nojima, M., Kerekes, I., Olah, J.A., (1979) J. Org. Chem., 44, p. 3872Mascaretti, O., (1993) Aldrichimica Acta, 26, p. 47Burger, K., Helmreich, B., (1994) Heterocycles, 39, p. 819Qiu, Z., Burton, D.J., (1994) Tetrahedron Lett., 35, p. 4319Sham, H.L., Betebenner, D.A., (1991) J. Chem. Soc., Chem. Commun., p. 1135Shi, G., Sclosser, M., (1993) Tetrahedron, 49, p. 1445Kassmi, A.E., Fache, F., Lemaire, M., (1994) Synth. Commun., 24, p. 95Cerichelli, G., Crestoni, M.E., Fornarini, S., (1990) Gazz. Chim. Ital., 120, p. 749Moraes, L.A.B., Pimpim, R.S., Eberlin, M.N., (1996) J. Org. Chem., 61, p. 8726Moraes, L.A.B., Gozzo, F.C., Eberlin, M.N., Vainiotalo, P., (1997) J. Org. Chem., 62, p. 5096Brodbelt, J.S., (1997) Mass Spectrom. Rev., 16, p. 91Gozzo, F.C., Moraes, L.A.B., Sparrapan, R., Eberlin, M.N., (1998) J. Org. Chem., 63, p. 4889Chou, P.K., Thoen, K.K., Kenttämaa, H.I., (1998) J. Org. Chem., 63, p. 4470Williamson, B.L., Creaser, C.S., (1998) Eur. Mass Spectrom., 4, p. 103Gerbaux, P., Haverbeke, Y.V., Flammang, R., (1998) Int. J. Mass Spectrom., 184, p. 39Mendes, M.A., Moraes, L.A.B., Sparrapan, R., Eberlin, M.N., Kostiainen, R., Kotiaho, T., (1998) J. Am. Chem. Soc., 120, p. 7869Takashima, K., Riveros, J.M., (1998) Mass Spectrom. Rev., 17, p. 409Wang, F., Tao, W.A., Gozzo, F.C., Eberlin, M.N., Cooks, R.G., (1999) J. Org. Chem., 64, p. 3213Cacace, F., De Petris, G., Pepi, F., Rosi, M., Sgamellotti, A., (1999) Angew. Chem., Int. Ed., 38, p. 2408Sharifi, M., Einhorn, J., (1999) Int.J. Mass Spectrom., 190-191, p. 253Frank, A.J., Turecek, F., (1999) J. Phys. Chem. A, 103, p. 5348Brönstrup, M., Schröder, D., Schwarz, H., Organometallics (1999), 18, p. 1939Sparrapan, R., Mendes, M.A., Carvalho, M., Eberlin, M.N., (2000) Chem. Eur. J., 6, p. 321Moraes, L.A.B., Eberlin, M.N., (2000) Chem. Eur. J., 6, p. 897Dillard, J.G., Troester, J.H., (1975) J. Phys. Chem., 79, p. 2455Javahery, G., Becker, H., Korobov, M.V., Farber, M., Cooper, D., Bohme, D.K., (1994) Int. J. Mass Spectrom. Ion Proc., 133, p. 73Cipollini, R., Crestoni, M.E., Fornarini, S., (1997) J. Am. Chem. Soc., 119, p. 9499Grandinetti, F., Pepi, F., Ricci, A., (1996) Chem. Eur. J., 2, p. 495Aschi, M., Grandinetti, F., Vinciguerra, V., (1998) Chem. Eur. J., 4, p. 2366Sparrapan, R., Mendes, M.A., Ferreira, I.P.P., Eberlin, M.N., Santos, C., Nogueira, J.C., (1998) J. Phys. Chem. A, 102, p. 5189Sparrapan, R., Mendes, M.A., Eberlin, M.N., (1999) Int. J. Mass Spectrom. Ion Proc., 182-183, p. 369Wong, P.S.K., Ma, S., Yang, S.S., Cooks, R.G., Gozzo, F.C., Eberlin, M.N., (1997) J. Am. Soc. Mass Spectrom., 8, p. 68noteChriste, K.O., Dixon, D.A., (1992) J. Am. Chem Soc., 114, p. 2978Schwartz, J.C., Wade, A.P., Enke, C.G., Cooks, R.G., (1990) Anal. Chem., 62, p. 1809Eberlin, M.M., (1997) Mass Spectrom. Rev., 16, p. 113Juliano, V.F., Gozzo, F.C., Eberlin, M.N., Kascheres, C., Lago, C.L., (1996) Anal. Chem., 68, p. 1328Tiernan, T.O., Futrell, J.H., (1968) J. Phys. Chem., 72, p. 3080Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Zakrzewski, V.G., Pople, J.A., (1998), Gaussian 98, Revision A.6, Gaussian, Inc., Pittsburgh, PAMøller, C., Plesset, M.S., (1934) Phys. Rev., 46, p. 618Gill, P.M.W., Johnson, B.G., Pople, J.A., (1992) Chem. Phys. Lett., 197, p. 499Lee, C., Yang, W., Parr, R.G., (1988) Phys. Rev. B, 37, p. 785Becke, A.D., (1988) Phys. Rev. A, 38, p. 3098Schaftenaar, G., (1992) QCPE Bull., 12, p. 3. , http:// www.caos.kun.nl/~schaft/molden/molden.htmlBosshard, P., Eugster, C.H., (1966), 7, p. 377. , Advances in Heterocyclic ChemistryKatritzky,A.R., Boulton,A.J., Eds.Academic Press: New YorkGronowitz, S., (1963), 2, p. 1. , Advances in Heterocyclic ChemistryKatritzky,A.R., Ed.Academic Press: New YorkAlan Jones, R., (1970), 11, p. 384. , Advances in Heterocyclic ChemistryKatritzky,A.R., Boulton,A.J., Eds.Academic Press: New YorkHealth, T.G., Allison, J., Watson, J.T., (1991) J. Am. Chem. Soc., 2, p. 27
The Simplest Azabutadienes In Their N-protonated Forms. Generation, Stability, And Cycloaddition Reactivity In The Gas Phase
No full textThe simplest azabutadienes, i.e. 1-aza-1,3-butadiene and 2-aza-1,3-butadiene, are generated in their N-protonated forms 1 and 2 via gas-phase dissociative electron ionization of allylamine and piperidine, respectively. Formation of 1 and 2 is suggested by simple dissociation mechanisms, and supported by high-accuracy G2 ab initio calculations, which show the ions to be stable, non-interconverting species. Whereas 1 and 2 are unreactive toward ethylene and cyclohexene, 2 reacts with alkenes activated by electron-donating (OC2H5), electron-withdrawing (CN, COCH3), and vinyl and phenyl substituents most likely by polar [4+ + 2] cycloaddition, as suggested by MS3 experiments and ab initio calculations. The cycloadduct of 2 with ethyl vinyl ether is unstable and dissociates promptly by ethanol loss; hence, net C2H2 addition occurs. This novel vinylation reaction is proposed as a potential structurally diagnostic test for both 2-azabutadienes and vinyl ethers. Isomer 1 is in general much less reactive, and abundant adducts are only formed in reactions with alkenes activated by electron-withdrawing substituents. In reactions of 1 and 2 with esters (methyl acetate and dimethyl carbonate), hydrogen-bridged ion-neutral complexes are formed as the most abundant and stable products, as suggested by the ab initio calculations. Acetone, fluoroacetone and acetonitrile form abundant adducts with both 1 and 2; however, the experimental and theoretical results on these adducts provide no clear structural information. Reactions of 1 with DMSO occur almost exclusively by proton transfer, whereas 2 forms an abundant complex with DMSO. Limited reactivity is observed for 1 and 2 with acetyl chloride and thionyl chloride; the minor products observed were those of either dissociative proton transfer or charge exchange. The distinctive reactivities of 1 and 2 with styrene, ethyl vinyl ether, and dimethyl sulfoxide contrast to their identical low energy CID behavior, and allow their straightforward differentiation in the gas phase.631548894897Schoffstall, A.M., Padwa, A., (1990) Advances in Cycloaddition, 2, p. 1. , Curran, D. P., Ed.JAI Press: Greenwich, CTSchmidt, R.R., (1973) Angew. Chem., Int. Ed. Engl., 12, p. 212Boger, D.L., Weinreb, S.N., (1987) Hetero Diels-Alder Methodology in Organic Synthesis, , Wasserman, H. H., Ed.Academic Press: New YorkGassman, P.G., Singleton, D.A., Wilwerding, J.J., Chavan, S.P., (1987) J. Am. Chem. Soc., 109, p. 2182Kim, T., Pye, R.J., Bauld, N.L., (1990) J. Am. Chem. Soc., 112, p. 6285Bellville, D.J., Wirth, D.D., Bauld, N.L., (1981) J. Am. Chem. Soc., 103, p. 718Mattay, J., (1987) Angew. Chem., Int. Ed. Engl., 26, p. 825Bauld, N.L., (1992) Adv. Electron-Transfer Chem., 2, p. 1Schmittel, M., Burghart, A., (1997) Angew. Chem., Int. Ed. Engl., 36, p. 2550Castle, L.W., Gross, M.L., (1989) Org. Mass Spectrom., 24, p. 637Groenewold, G.S., Chess, E.K., Gross, M.L., (1984) J. Am. Chem. Soc., 106, p. 539Bowers, M.T., Elleman, D.D., O'Malley, R.M., Jennings, K.R., (1970) J. Phys. Chem., 74, p. 2583Van Tilborg, M.W.E.M., Van Doorn, R., Nibbering, N.M.M., (1980) Org. Mass Spectrom., 15, p. 152Shay, B.J., Eberlin, M.N., Cooks, R.G., Wesdemiotis, C., (1992) J. Am. Soc. Mass Spectrom., 3, p. 518Dass, C., (1990) Mass Spectrom. Rev., 9, p. 1Busch, K.L., Glish, G.L., McLuckey, S.A., (1988) Mass Spectrometry/Mass Spectrometry: Techniques and Applications of Tandem Mass Spectrometry, , VHC: New YorkSchwartz, J.C., Wade, A.P., Enke, C.G., Cooks, R.G., (1990) Anal. Chem., 62, p. 1809Eberlin, M.N., (1997) Mass Spectrom. Rev., 16, p. 113Eberlin, M.N., Sorrilha, A.E.P.M., Gozzo, F.C., Sparrapan, R., (1997) J. Am. Chem. Soc., 119, p. 3550Eberlin, M.N., Cooks, R.G., (1993) J. Am. Chem. Soc., 115, p. 9226Eberlin, M.N., Morgon, N.H., Yang, S.S., Shay, B.J., Cooks, R.G., (1994) J. Am. Soc. Mass Spectrom., 6, p. 1Basheer, M.M., Sparrapan, R., Eberlin, M.N., Riveros, J.M., submitted for publicationLu, L., Yang, S.S., Wang, Z., Cooks, R.G., Eberlin, M.N., (1995) J. Mass Spectrom., 30, p. 581Barluenga, J., Aznar, F., Fustero, S., Tomás, M., (1990) Pure Appl. Chem., 62, p. 1957Knoelker, H.-J., Baum, G., Gonser, P., (1995) Tetrahedron Lett., 36, p. 8194Beifuss, U., Ledderhose, S., (1995) J. Chem. Soc., Chem. Commun., p. 2137Budzikiewicz, H., Djerassi, C., Williams, D.H., (1964) Interpretation of Mass Spectra of Organic Compounds, , Holden-Day Inc.: San FranciscoPorter, Q.N., (1985) Mass Spectrometry of Heterocyclic Compounds, , Taylor, E. C., Weissberger, A., Eds.Wiley: New YorkEberlin, M.N., Kotiaho, T., Shay, B.J., Yang, S.S., Cooks, R.G., (1994) J. Am. Chem. Soc., 116, p. 2457Gozzo, F.C., Eberlin, M.N., (1995) J. Am. Soc. Mass Spectrom., 6, p. 554Sorrilha, A.E.P.M., Gozzo, F.C., Pimpim, R.S., Eberlin, M.N., (1996) J. Am. Soc. Mass Spectrom., 7, p. 1126Moraes, L.A.B., Pimpim, R.S., Eberlin, M.N., (1996) J. Org. Chem., 61, p. 8726Moraes, L.A.B., Gozzo, F.C., Eberlin, M.N., Vainiotalo, P., (1997) J. Org. Chem., 62, p. 5096Carvalho, M., Sparrapan, R., Mendes, M.A., Gozzo, F.C., Kaschers, C., Eberlin, M.N., (1998) Chem. Eur. J., 4, p. 1159Juliano, V.F., Gozzo, F.C., Eberlin, M.N., Kascheres, C., Lago, C.L., (1996) Anal. Chem., 68, p. 1328Frisch, M.J., Trucks, G.W., Schlegel, H.B., Gill, P.M.W., Johnson, B.G., Robb, M.A., Cheeseman, J.R., Pople, J.A., (1995) Gaussian 94, Revision B.3, , Gaussian, Inc., Pittsburgh, PACurtis, L.A., Raghavachari, K., Pople, J.A., (1993) J. Chem. Phys., 98, p. 1293Hehre, W.J., Ditchfield, R., Pople, J.A., (1972) J. Chem. Phys., 56, p. 2257Hariharan, P.C., Pople, J.A., (1973) Theor. Chem. Acta, 28, p. 213Gordon, M.S., (1980) Chem. Phys. Lett., 76, p. 163Frisch, M.J., Pople, J.A., Binkley, J.S., (1984) J. Chem. Phys., 80, p. 3265Møller, C., Plesset, M.S., (1934) Phys. Rev., 46, p. 618Duffield, A.M., Budzikiewicz, H., Williams, D.H., Djerassi, C., (1965) J. Am. Chem. Soc., 87, p. 810Bouchoux, G., Flament, J.P., Hopilliard, Y., Tortajada, J., Flammang, R., Maquestiau, A., (1989) J. Am. Chem. Soc., 111, p. 5560Wincel, H., Fokkens, R.H., Niberring, N.M.M., (1989) Int. J. Mass Spectrom. Ion Proc., 91, p. 339Bouchoux, G., Nguyen, M.T., Longevialle, P., (1992) J. Am. Chem. Soc., 114, p. 10000Kenttämaa, H.I., Cooks, R.G., (1989) J. Am. Chem. Soc., 111, p. 4122Abboud, J.-L.M., Mó, O., De Paz, J.L.G., Yáñez, M., Essefar, M., Bouad, W., El-Mouhtadi, M., Noatario, R., (1993) J. Am. Chem. Soc., 115, p. 12468Turecek, F., Hanus, V., (1984) Mass Spectrom. Rev., 3, p. 85Hussain, M., Robertson, J.S., Watson, T.R., (1970) Org. Mass Spectrom., 4, p. 109Migron, Y., Bergmann, E.D., (1977) Org. Mass Spectrom., 12, p. 500Eberlin, M.N., Cooks, R.G., (1993) Org. Mass Spectrom., 28, p. 679Kenttämaa, H.I., Cooks, R.G., (1989) J. Am. Chem. Soc., 111, p. 4122noteUggerud, E., (1992) Mass Spectrom. Rev., 11, p. 389noteLias, S.G., Bartmess, J.E., Liebman, J.F., Holmes, J.L., Levin, R.D., Mallard, W.G., (1988) J. Phys. Chem. Ref. Data, 17 (1 SUPPL.)Boys, S.F., Bernardi, F., (1970) Mol. Phys., 19, p. 553Longevialle, P., (1992) Mass Spectrom. Rev., 11, p. 15
Novel [3 + 2] 1,3-cycloaddition Of The Ionized Carbonyl Ylide +ch2och2· With Carbonyl Compounds In The Gas Phase
No full textFor the first time [3 + 2] 1,3-cycloaddition of an ionized carbonyl ylide has been observed in gas phase ion-molecule reactions of +CH2OCH2· (1) with several carbonyl compounds. The reaction, which competes with electrophilic addition that leads to net CH2·+ transfer, occurs across the C=O double bond of acetaldehyde and several acyclic ketones yielding ionized 4,4-dialkyl-1,3-dioxolanes as unstable cycloadducts. Rapid n of the nascent cycloadducts by loss of a 4-alkyl substituent as a radical leads to the observed products, that is cyclic 4-alkyl-1,3-dioxolanylium ions. Cycloaddition of 1 with cyclic ketones yields bicyclic spiro adducts, which also undergo rapid dissociation. Cyclobutanone yields ionized 1,3-dioxaspiro[4,3]octane, which dissociates exclusively by neutral ethene loss to ionized 4-methylene-1,3-dioxolane. Ionized 1,3-dioxaspiro[4,4]nonane is formed in reactions with cyclopentanone, and its rapid dissociation by loss of C3H6 and C2H5· yields the ionized 4-methylene-1,3-dioxolanylium and the 4-ethenyl-1,3-dioxolanylium product ions, respectively. A systematic study of this novel reaction and characterization of the product ions carried out via pentaquadrupole (QqQqQ) multiple stage (MS2 and MS3) mass spectrometric experiments provide experimental evidence for the cycloaddition mechanism. The dissociation chemistry observed for the cycloaddition products correlate well with their proposed structures and was compared to that of both isomeric and reference ions. Ab initio MP2/6-31G(d,p)//HF/6-31G(d,p) + ZPE potential energy surface diagrams for the reactions of 1 with acetone, fluoroacetone, and 1,1,1-trifluoroacetone support the operation of the two competitive reaction pathways, that is CH2·+ transfer and [3 + 2] 1,3-cycloaddition/dissociation, and show that the cycloaddition process is favored by electron-withdrawing substituents.1191535503557Schoffstall, A.M., Padwa, A., (1990) Advances in Cycloaddition, 2, p. 1. , Curran, D. P., Ed.JAI Press: GreenwichSchmidt, R.R., (1973) Angew. Chem., Int. Ed. Engl., 12, p. 212Boger, D.L., Weinreb, S.N., (1987) Hetero Diets-Alder Methodology in Organic Synthesis, , Wasserman, H. H., Ed.Academic Press: New YorkGassman, P.G., Singleton, D.A., Wilwerding, J.J., Chavan, S.P., (1987) J. Am. Chem. Soc., 109, p. 2182Kim, T., Pye, R.J., Bauld, N.L., (1990) J. Am. Chem. Soc., 112, p. 6285Bauld, N.L., Bellville, D.J., Harirchian, B., Lorenz, K.T., Pabon Jr., R.A., Reynolds, D.W., Wirth, D.D., Marsh, B.K., (1987) Acc. Chem. Res., 20, p. 371Bellville, D.J., Wirth, D.D., Bauld, N.L., (1981) J. Am. Chem. Soc., 103, p. 718Mattay, J., (1987) Angew. Chem., Int. Ed. Engl., 26, p. 825Dass, C., (1990) Mass Spectrom. Rev., 9, p. 1Van Tilborg, M.W.E.M., Van Doom, R., Nibbering, N.M.M., (1980) Org. Mass Spectrom., 15, p. 152Keough, T., (1982) Anal. Chem., 54, p. 2540Nourse, B.D., Cox, K.A., Cooks, R.G., (1992) Org. Mass Spectrom., 27, p. 453Eberlin, M.N., Majumdar, T.K., Cooks, R.G., (1992) J. Am. Chem. Soc., 114, p. 2884Eberlin, M.N., Cooks, R.G., (1993) J. Am. Chem. Soc., 115, p. 9226Eberlin, M.N., Morgon, N.H., Yang, S.S., Shay, B.J., Cooks, R.G., (1995) J. Am. Soc. Mass Spectrom., 6, p. 1Basher, M.M., Pimpim, R.S., Eberlin, M.N., Riveros, J.M., to appearGozzo, F.C., Sorrilha, A.E.P.M., Eberlin, M.N., (1996) J. Chem. Soc., Perkin Trans. 2, p. 587Castle, L.W., Gross, M.L., (1989) Org. Mass Spectrom., 24, p. 637Groenewold, G.S., Chess, E.K., Gross, M.L., (1984) J. Am. Chem. Soc., 106, p. 539Bowers, M.T., Elleman, D.D., O'Malley, R.M., Jennings, K.R., (1970) J. Phys. Chem., 74, p. 2583Shay, B.J., Eberlin, M.N., Cooks, R.G., Wesdemiotis, C., (1992) J. Am. Soc. Mass Spectrom., 3, p. 518Bianchi, G., DeMicheli, C., Gandolfi, R., (1977) The Chemistry of Double Bonded Functional GroupsPart 1, Supplement A, 369. , Patai, S., Ed.John Wiley and Sons: New YorkPotts, K.T., (1984) 1,3-Dipolar Cycloaddition Chemistry, , Padwa, A., Ed.John Wiley and Sons: New YorkYamaguchi, Y., Schaefer III, H.F., Alberts, I.L., (1993) J. Am. Chem. Soc., 115, p. 5790Gillon, A., Ovadia, D., Kapon, M., Bien, S., (1982) Tetrahedron, 38, p. 1477Hoffmann, R.W., Luthardt, H.J., (1968) Chem. Ber., 101, p. 3861Do-Minh, T., Trozzolo, A.M., Griffin, G.W., (1970) J. Am. Chem. Soc., 92, p. 1402Yates, B.F., Bouma, W.J., Radom, L., (1984) J. Am. Chem. Soc., 106, p. 5805Yates, B.F., Bouma, W.J., Radom, L., (1986) Tetrahedron, 42, p. 6225Hammenim, S., (1988) Mass Spectrom. Rev., 7, p. 123Bouchoux, G., (1988) Mass Spectrom. Rev., 7, p. 1Stirk, K.M., Kiminkinen, L.K.M., Kenttämaa, H.I., (1992) Chem. Rev., 92, p. 1649Bouma, W.J., MacLeod, J.K., Radom, L., (1980) J. Am. Chem. Soc., 102, p. 2246Bouma, W.J., Nobes, R.H., Radom, L., (1983) J. Am. Chem. Soc., 705, p. 1743Radom, L., Bouma, W.J., Nobes, R.H., Yates, B.F., (1984) Pure Appl. Chem., 56, p. 1831Yates, B.F., Bouma, W.J., Radom, L., (1984) J. Am. Chem. Soc., 106, p. 5805Yates, B.F., Bouma, W.J., Radom, L., (1986) Tetrahedron, 42, p. 6225Sorrilha, A.E.P.M., Gozzo, F.C., Pimpim, R.S., Eberlin, M.N., (1996) J. Am. Soc. Mass Spectrom., 7, p. 1126noteBouma, W.J., MacLeod, J.K., Radom, L., (1980) Adv. Mass. Spectrom., 8 A, p. 178Fraser-Monteiro, M.L., Fraser-Monteiro, L., Baer, T., Hass, J.R., (1982) J. Phys. Chem., 86, p. 739Baumann, B.C., MacLeod, J.K., (1981) J. Am. Chem. Soc., 103, p. 6223Van Velzen, P.N.T., Van Der Hart, W., (1981) J. Chem. Phys. Lett., 83, p. 55Nobes, R.H., Bouma, W.J., MacLeod, J.K., Radom, L., (1987) Chem. Phys. Lett., 135, p. 78Eberlin, M.N., (1993) Proceedings of the 41st ASMS Conference on Mass Spectrometry and Allied Processes, p. 975. , San Francisco, CASchwartz, J.C., Shey, K.L., Cooks, R.G., (1990) Int. J. Mass Spectrom. Ion Processes, 101, p. 1Kotiaho, T., Shay, B.J., Cooks, R.G., Eberlin, M.N., (1993) J. Am. Chem. Soc., 115, p. 1004Eberlin, M.N., Kotiaho, T., Shay, B., Yang, S.S., Cooks, R.G., (1994) J. Am. Chem. Soc., 116, p. 2457Gozzo, F.C., Eberlin, M.N., (1995) J. Mass Spectrom., 50, p. 1553Juliano, V.F., Gozzo, F.C., Eberlin, M.N., Kascheres, C., Lago, C.L., (1996) Anal. Chem., 68, p. 1328Schwartz, J.C., Wade, A.P., Enke, C.G., Cooks, R.G., (1990) Anal. Chem., 62, p. 1809Frisch, M.J., Trucks, G.W., Schlegel, H.B., Gill, P.M.W., Johnson, B.G., Robb, M.A., Cheeseman, J.R., Pople, J.A., (1995) Gaussian 94, Revision B.3, , Gaussian, Inc.: Pittsburgh, PAHehre, W.J., Ditchfield, R., Pople, J.A., (1972) J. Chem. Phys., 56, p. 2257Hariharan, P.C., Pople, J.A., (1973) Theor. Chem. Acta, 28, p. 213Gordon, M.S., (1980) Chem. Phys. Lett., 76, p. 163Frisch, M.J., Pople, J.A., Binkley, J.S., (1984) J. Chem. Phys., 80, p. 3265Møller, C., Plesset, M.S., (1934) Phys. Rev., 46, p. 618Audier, H., Fétizon, M., Gramain, J.-C., Schalbar, J., Waegel, B., (1964) Bull. Soc. Chim. Fr., p. 1880Van De Sande, C.C., McLafferty, F.W., (1975) J. Am. Chem. Soc., 97, p. 4613Holmes, J.L., Terlouw, J.K., (1975) Can J. Chem., 53, p. 2076Terlouw, J.K., Wezenberg, J., Burgers, P.C., Holmes, J.L., (1983) J. Chem. Soc., Chem. Commun., p. 1121noteBudzikiewicz, H., Djerassi, C., Williams, D.H., (1967) Mass Spectrometry of Organic Compounds, , Holden-Day: San Francisco, CAEberlin, M.N., Cooks, R.G., (1993) Org. Mass Spectrom., 28, p. 679Moraes, L.A.B., Pimpim, R.S., Eberlin, M.N., (1996) J. Org. Chem., 61, p. 8726Vaniotalo, P., Moraes, L.A.B., Gozzo, F.C., Eberlin, M.N., (1996) Proc. 44th ASMS Conference Mass Spectrometry Allied Topics, p. 453Moraes, L.A.B., Gozzo, F.C., Eberlin, M.N., Vainiotalo, P., J. Org. Chem., , Submitted for publicationThe term "structure" will be used throughout in a restricted sense, to denote connectivity rather than detailed structureYu, S.J., Gross, M.L., Fountain, K.R., (1993) J. Am. Soc. Mass Spectrom., 4, p. 117Gozzo, F.C., Eberlin, M.N., (1995) J. Am. Soc. Mass Spectrom., 6, p. 554Bouma, W.J., MacLeod, J.K., Radom, L., (1979) J. Am. Chem. Soc., 101, p. 5540Stirk, K.M., Orlowski, J.C., Leeck, D.T., Kenttämaa, H.I., (1992) J. Am. Chem. Soc., 114, p. 8604Smith, R.L., Franklin, R.L., Stirk, K.M., Kenttämaa, H.I., (1993) J. Am. Chem. Soc., 115, p. 10348notenoteBlair, A.S., Harrison, A.G., (1973) Can. J. Chem., 51, p. 703notenoteFukui, K., (1971) Acc. Chem. Res., 4, p. 57Fleming, I., (1976) Frontier Orbitals and Organic Chemical Reactions, , Wiley: Londonnot
The Kinetic Method As A Structural Diagnostic Tool: Ionized α-diketones As Loosely One-electron Bonded Diacylium Ion Dimers
No full textThe kinetic method is used to corroborate the description of ground state ionized α-diketones as loosely electron-bonded acylium ion dimers: R 1-C=O+ - e- - +O=C-R2. The abundance ratio of both the acylium ion fragments R1CO + and R2CO+ (summed to those of their respective secondary fragments) formed upon low energy (5 eV) collision-induced dissociation of several ionized α-diketones is found to correlate linearly with the ionization energies (IEs) of the corresponding R 1CO• and R2CO• free radicals as predicted by density functional theory calculations at the B3LYP/6-311++G(d,p) level. However, when these abundances are taken from 70 eV electron ionization mass spectra, lower and sometimes inverted ratios (2,3-pentanedione and 2,3-hexanedione) are observed. Inverted ratios are also observed via charge-exchange mass spectrometry/mass spectrometry (MS/MS) experiments for ionized 2,3-pentanodione formed with relatively high internal energies. Ionized α-diketones are found to display an effective temperature of 1705 K, which indicates an intermediate loosely-bonded nature. B3LYP/6-311++G(d,p) optimized geometries and charge and spin densities also corroborate the description of ground state ionized α-diketones as loosely electron-bonded diacylium ion dimers.94295304Cooks, R.G., Kruger, T.L., Intrinsic basicity determination using metastable ions (1977) J. Am. Chem. Soc., 99, p. 1279Cooks, R.G., Patrick, J.S., Kotiaho, T., McLuckey, S.A., Thermochemical determinations by the kinetic method (1994) Mass Spectrom. Rev., 13, p. 287Cooks, R.G., Wong, P.S.H., Kinetic method of making thermochemical determinations: Advances and applications (1998) Acc. Chem. Res., 31, p. 379Yang, S.S., Chen, G.D., Ma, S.G., Cooks, R.G., Gozzo, F.C., Eberlin, M.N., Relative carbonyl isocyanate cation [OCNCO](+) affinities of pyridines determined by the kinetic method using multiple-stage (MS(3)) mass-spectrometry (1995) J. Mass Spectrom., 30, p. 807Wong, P.S.H., Ma, S.G., Yang, S.S., Cooks, R.G., Gozzo, F.C., Eberlin, M.N., Sulfur trifluoride cation (SF3 +) affinities of pyridines determined by the kinetic method: Stereoelectronic effects in the gas phase (1997) J. Am. Soc. Mass Spectrom., 8, p. 68Wong, P.S.H., Ma, S.G., Wang, F., Cooks, R.G., Stereoelectronic effects and gas phase Co+, Ni+, CpFe+, CpCo+ and CpNi+ affinities of pyridines studied by the kinetic method (1997) J. Organomet. Chem., 539, p. 131Schroeter, K., Wesendrup, R., Schwarz, H., Substituent effects on the bond-dissociation energies of cationic arene-transition-metal complexes (1998) Eur. J. Org. Chem., p. 565Stöckigt, D., Hrusák, J., Schwarz, H., Isotope effects in radiative cooling - The Al(C6H 6)(+) systems (1995) Int. J. Mass Spectrom. Ion Proc., 150, p. 1Wright, L.G., McLuckey, S.A., Cooks, R.G., Wood, K.V., Relative gas-phase acidities from triple quadrupole mass spectrometers (1982) Int. J. Mass Spectrom. Ion Proc., 42, p. 115McLuckey, S.A., Cameron, D., Cooks, R.G., Proton affinities from dissociations of proton-bound dimers (1981) J. Am. Chem Soc., 103, p. 1313Boand, G., Houriet, R., Gaumann, T., Gas-phase acidity of aliphatic-alcohols (1983) J. Am. Chem. Soc., 105, p. 2203Ma, S.G., Wang, F., Cooks, R.G., Gas-phase acidity of urea (1998) J. Mass Spectrom., 33, p. 943Burinsky, D.J., Fukuda, E.K., Campana, J.E., Electron-affinities from dissociations of mixed negative-ion dimers (1984) J. Am. Chem. Soc., 106, p. 2770Chen, G., Cooks, R.G., Corpuz, E., Scott, L.T., Estimation of the electron affinities of C-60, corannulene, and coronene by using the kinetic method (1996) J. Am. Soc. Mass Spectrom., 7, p. 619Denault, J.W., Chen, G.D., Cooks, R.G., Electron affinity of 1,3,5,7-cyclooctatetraene determined by the kinetic method (1998) J. Am. Soc. Mass Spectrom., 9, p. 1141Chen, G.D., Ma, S.G., Cooks, R.G., Bronstein, H.E., Best, M.D., Scott, L.T., Electron affinities and C-60 anion clusters of certain bowl-shaped polycyclic aromatic hydrocarbons (1997) J. Mass Spectrom., 32, p. 1305Chen, G.D., Cooks, R.G., Estimation of ionization energies of polycyclic aromatic hydrocarbons using the kinetic method (1997) J. Mass Spectrom., 32, p. 333Eberlin, M.N., Kotiaho, T., Shay, B.J., Yang, S.S., Cooks, R.G., Gas-phase Cl+ affinities of pyridines determined by the kinetic method using multiple-stage [MS(3)] mass-spectrometry (1994) J. Am. Chem. Soc., 116, p. 2457Ma, S.G., Wong, P., Cooks, R.G., Gozzo, F.C., Eberlin, M.N., Stereoelectronic effects in phosphorus dichloride cation pyridine complexes (1997) Int. J. Mass Spectrom. Ion Process, 163, p. 89Yang, S.S., Wong, P., Ma, S.G., Cooks, R.G., SiCl3 + and SiCl+ affinities for pyridines determined by using the kinetic method with multiple stage mass spectrometry: Agostic effects in the gas phase (1996) J. Am. Soc. Mass Spectrom., 7, p. 198Wang, F., Ma, S., Wong, P., Cooks, R.G., Gozzo, F.C., Eberlin, M.N., Gas phase agostic bonding in pyridine SiFn + (n = 1, 3) cluster ions investigated by the kinetic method (1998) Int. J. Mass Spectrom. Ion Proc., 180, p. 195Jarrold, M.F., Bower, J.E., Collision-induced dissociation of metal cluster ions - Bare aluminum clusters, Al+ (n = 3-26) (1987) J. Chem. Phys., 86, p. 3876Grese, R.P., Cerny, R.L., Gross, M.L., Senge, M., Determination of structure and properties of modified chlorophylls by using fast atom bombardment combined with tandem mass-spectrometry (1990) J. Am. Soc. Mass Spectrom., 1, p. 172Hanley, L.H., Whitten, J.L., Anderson, S.L., Collision-induced dissociation and Ab initio studies of boron cluster ions - Determination of structures and stabilities (1992) J. Phys. Chem., 92, p. 5803Cheng, X.H., Wu, Z.C., Fenselau, C., Collision energy-dependence of proton-bound dimer dissociation - Entropy effects, proton affinities, and intramolecular hydrogen-bonding in protonated peptides (1993) J. Am. Chem. Soc., 115, p. 4844Cerda, B.A., Wesdemiotis, C., Li+, Na+, and K+ binding to the DNA and RNA nucleobases. Bond energies and attachment sites from the dissociation of metal ion-bound heterodimers (1996) J. Am. Chem. Soc., 118, p. 11884Cerda, B.A., Hoyau, S., Ohanesian, G., Wesdemiotis, C., Na+ binding to cyclic and linear dipeptides. Bond energies, entropies of Na+ complexation, and attachment sites from the dissociation of Na+-bound heterodimers and ab initio calculations (1998) J. Am. Chem. Soc., 120, p. 2437Gozzo, F.C., Eberlin, M.N., Primary and secondary kinetic isotope effects in proton (H +/D+) and chloronium ion (35Cl(+)/ 37Cl(+)) affinities (2001) J. Mass Spectrom., 36, p. 1140Tao, W.A., Zhang, D.X., Wang, F., Thomas, P.D., Cooks, R.G., Kinetic resolution of D,L-amino acids based on gas-phase dissociation of copper(II) complexes (1999) Anal. Chem., 71, p. 4427Shen, W.Y., Wong, P.S.H., Cooks, R.G., Stereoisomeric distinction by the kinetic method: 2,3-Butanediol (1997) Rapid. Commun. Mass Spectrom., 11, p. 71Guo, J.H., Wu, J.Y., Siuzdak, G., Finn, M.G., Measurement of enantiomeric excess by kinetic resolution and mass spectrometry (1999) Angew. Chem. Int. Ed., 38, p. 1755Vékey, K., Czira, G., Distinction of amino acid enantiomers based on the basicity of their dimers (1997) Anal. Chem., 69, p. 1700Tao, W.A., Gozzo, F.C., Cooks, R.G., Mass spectrometric quantitation of chiral drugs by the kinetic method (2001) Anal. Chem., 73, p. 1692Tao, W.A., Cooks, R.G., Chiral analysis by MS (2003) Anal. Chem., 75, pp. 25AAugusti, D.V., Carazza, F., Augusti, R., Tao, W.A., Cooks, R.G., Quantitative chiral analysis of sugars by electrospray ionization tandem mass spectrometry using modified amino acids as chiral reference compounds (2002) Anal. Chem., 74, p. 3458Drahos, L., Vékey, K., How closely related are the effective and the real temperature (1999) J. Mass Spectrom., 34, p. 79Denault, J.W., Wang, F., Cooks, R.G., Gozzo, F.C., Eberlin, M.N., Structural characterization of clusters formed from alkyl nitriles and the methyl cation (2000) J. Phys. Chem. A, 104, p. 11290Burinsky, D.J., Fukuda, E.K., Campana, J.E., Electron-affinities from dissociations of mixed negative-ion dimers (1984) J. Am. Chem. Soc., 106, p. 2770Wong, P.S.H., Ma, S.G., Cooks, R.G., Ionization energy determination by the kinetic method (1996) Anal. Chem., 68, p. 4254Chen, G.D., Wong, P., Cooks, R.G., Estimation of free radical ionization energies by the kinetic method and the relationship between the kinetic method and the Hammett equation (1997) Anal. Chem., 69, p. 3641Eberlin, M.N., Triple-stage pentaquadrupole (QqQqQ) mass spectrometry and ion/molecule reactions (1997) Mass Spectrom. Rev., 16, p. 113Juliano, V.F., Gozzo, F.C., Eberlin, M.N., Kascheres, C., Dolago, C.L., Fast multidimensional (3D and 4D) MS(2) and MS(3) scans in a high-transmission pentaquadrupole mass spectrometer (1996) Anal. Chem., 68, p. 1328Tiernan, T.O., Futrell, J.H., Ionic reactions in unsaturated compounds. 2. Ethylene (1968) J. Phys. Chem., 72, p. 3080Becke, A.D., Density-functional thermochemistry. 3. The role of exact exchange (1993) J. Chem. Phys., 98, p. 5648Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Zakrzewski, V.G., Pople, J.A., (1998) Gaussian 98, Revision A.6., , Gaussian, Inc., Pittsburgh, PA, USADrahos, L., Vekey, K., MassKinetics: A theoretical model of mass spectra incorporating physical processes, reaction kinetics and mathematical descriptions (2001) J. Mass Spectrom., 36, p. 237Lias, S.G., Bartmess, J.E., Liebman, J.F., Holmes, J.L., Levin, R.D., Mallard, W.G., Gas-phase ion and neutral thermochemistry (1988) J. Phys. Chem. Reference Data, 17, p. 1Stevenson, D.P., (1951) Discussions of the Faraday Society, 10, p. 35Depuy, C.H., Bierbaum, V.M., Damrauer, R., Relative gas-phase acidities of the alkanes (1984) J. Am. Chem. Soc., 106, p. 4051Damrauer, R., Depuy, C.H., Barlow, S.E., Gronert, S., The gas-phase chemistry of the silaacetylide anion, HCSi- (1988) J. Am. Chem. Soc., 110, p. 2005Murad, E., Inghram, M.G., Thermodynamic properties of acetyl radical + bond dissociation energies in aliphatic carbonyl compounds (1964) J. Chem. Phys., 41, p. 404Griffin, L.L., Traeger, J.C., Hudson, C.E., McAdoo, D.J., Why are smaller fragments preferentially lost from radical cations at low energies and larger ones at high energies? An experimental and theoretical study (2002) Int. J. Mass Spectrom., 217, p. 23Robinson, P.J., Holbrook, K.A., (1972) Unimolecular Reactions, , Wiley-Interscience, New YorkBaer, T., Mayer, P.M., Statistical Rice-Ramsperger-Kassel-Marcus quasiequilibrium theory calculations in mass spectrometry (1997) J. Am. Soc. Mass Spectrom., 8, p. 103Derrick, P.J., Lloyd, P.M., Christie, J.R., (1995) Adv. Mass Spectrom., 13, p. 23McLuckey, S.A., Collision energy effects in tandem mass-spectrometry as revealed by a proton-bound dimer ion (1984) Org. Mass Spectrom., 19, p. 545Lund, K.H., Bojesen, G., Measurements of the kinetic energy released in decompositions of proton-bound dimers of primary amines (1996) Int. J. Mass Spectrom. Ion Processes, 156, p. 203Lias, S.G., Bartmess, J.E., Liebman, J.F., Holmes, J.L., Levin, R.D., Mallard, W.G., (2001) Ion Energetics Data, , Ed by P.J. Linstrom and W.G. Mallard. National Institute of Standards and Technology, Gaithersburg, MDMcLuckey, S.A., Cameron, D., Cooks, R.G., Proton affinities from dissociations of proton-bound dimers (1981) J. Am. Chem. Soc., 103, p. 1313McLuckey, S.A., Cooks, R.G., Fulford, J.E., Gas-phase thermochemical information from triple quadrupole mass spectrometers - Relative proton affinities of amines (1983) Int. J. Mass Spectrom. Ion Phys., 52, p. 165Trikoupis, M.A., Terlouw, J.K., Burgers, P.C., Peres, M., Lifshitz, C., How do dimethyl oxalate ions CH3O-C(=O)-C(=O)-OCH 3 •+ break in half? Loss of CH3 • + CO2 versus CH3O-C=O (1999) J. Am. Soc. Mass Spectrom., 10, p. 869. , and references cited thereinDewar, M.J.S., Zoebisch, E.G., Healy, E.F., Stewart, J.J.P., The development and use of quantum-mechanical molecular-models. 76. Am1 - A new general-purpose quantum-mechanical molecular-model (1985) J. Am. Chem. Soc., 107 (13), p. 3902Kishore, K., Anklam, E., Aced, A., Asmus, K.D., Formation of intramolecular three-electron-bonded 2 sigma/1 sigma* radical cations upon reduction of dialkylsulfinyl sulfides by H-atoms (2000) J. Phys. Chem. A, 104, p. 9646De Visser, S.P., Bickelhaupt, F.M., De Koning, L.J., Nibbering, N.M.M., Sulfur-sulfur three-electron bond dissociation enthalpies of dialkyl sulfide dimer radical cations (1998) Int. J. Mass Spectrom., 180, p. 43Harcourt, R.D., Valence bond and molecular orbital descriptions of the three-electron bond (1997) J. Phys. Chem. A, 101, p. 596
Organoindate Room Temperature Ionic Liquids: Synthesis, Physicochemical Properties And Application
No full textThe combination of equimolar amounts of solid 1-n-butyl-3-methylimidazolum chloride (BMI·Cl) with solid indium trichloride affords the new room temperature and air stable ionic liquid BMI·InCl4 (mp -6°C). The major physicochemical properties (density, viscosity, electrical conductivity and electrochemical window) of BMI·InCl4 are complementary to those of classical tetrafluoroborate or hexafluorophosphate analogues. However, this liquid possesses similar Lewis acidity properties to those of organoaluminate melts and can be used as recyclable media, as demonstrated here for the tetrahydropyranylation of alcohols.811551158Dupont, J., De Souza, R.F., Suarez, P.A.Z., (2002) Chem. Rev., 102, p. 3667Fannin Jr.;, A.A., Floreani, D.A., King, L.A., Landers, J.S., Piersma, B.J., Stech, D.J., Vaughn, R.L., Williams, J.L., (1984) J. Phys. Chem., 88, p. 2614Hussey, C.L., (1983) Advances in Molten Salts Chemistry, 5, p. 185. , Mamantov, G.Mamantov, C., Eds.Elsevier: New YorkWilkes, J.S., Levisky, J.A., Wilson, R.A., Hussey, C.L., (1982) Inorg. Chem., 21, p. 1263Smith, G.P., Dworkin, A.S., Pagni, R.M., Zingg, S.P., (1989) J. Am. Chem. Soc., 111, p. 525Smith, G.P., Dworkin, A.S., Pagni, R.M., Zingg, S.P., (1989) J. Am. Chem. Soc., 111, p. 5075Riechel, T.L., Wilkes, J.S., (1993) J. Electrochem. Soc., 140, p. 3104Stenzel, O., Brull, R., Wahner, U.M., Sanderson, R.D., Raubenheimer, H.G., (2003) J. Mol. Catal. A: Chem., 192, p. 217Qiao, K., Deng, Y.Q., (2001) J. Mol. Catal. A: Chem., 171, p. 81Deng, Y.Q., Shi, F., Beng, J.J., Qiao, K., (2001) J. Mol. Catal. A: Chem., 165, p. 33Kumar, A., Pawar, S.S., (2003) J. Mol. Catal. A: Chem., , in pressDeCastro, C., Sauvage, E., Valkenberg, M.H., Holderich, W.F., (2000) J. Catal., 196, p. 86Dupont, J., Suarez, P.A.Z., Consorti, C.S., De Souza, R.F., (2002) Org. Synth., 79, p. 236Tian, P., Yang, J.Z., Xu, W.G., Zhang, P., Song, X.M., Liang, Z.D., (2002) Chin. Chem. Lett., 13, p. 1061(2002) Chem. Abstr., pp. 16997jYang, J.Z., Tian, P., He, L.L., Xu, W.G., (2003) Fluid Phase Equil., 204, p. 295Suarez, P.A.Z., Einloft, S., Dullius, J.E.L., De Souza, R.F., Dupont, J., (1998) J. Chim. Phys. Phys.-Chim. Biol., 95, p. 1626Blanchard, L.A., Brennecke, J.F., (2001) Ind. Eng. Chem. Res., 40, p. 287Tait, S., Osteryoung, R.A., (1984) Inorg. Chem., 23, p. 4352Dieter, M.K., Dymek Jr., C.J., Heimer, N.E., Rovang, J.W., Wilkes, J.S., (1988) J. Am. Chem. Soc., 110, p. 2722Elawi, A., Hitchcock, P.B., Seddon, K.R., Srinivasan, N., Tan, Y.M., Welton, T., Zora, J.A., (1995) J. Chem. Soc., Dalton Trans., p. 3467Suarez, P.A.Z., Dullius, J.E.L., Einloft, S., DeSouza, R.F., Dupont, J., (1996) Polyhedron, 15, p. 1217Cooks, R.G., Zhang, D.X., Koch, K.J., Gozzo, F.C., Eberlin, M.N., (2001) Anal. Chem., 73, p. 3646Koch, K.J., Gozzo, F.C., Nanita, S.C., Takats, Z., Eberlin, M.N., Cooks, R.G., (2002) Angew. Chem. Int. Ed., 41, p. 1721Meurer, E.C., Sabino, A.A., Eberlin, M.N., (2003) Anal. Chem., 75, p. 4701Gozzo, F.C., Consorti, C.S., Dupont, J., Eberlin, M.N., (2003) Chem.-Eur. J., , submittednoteCarpenter, M.K., Verbrugge, M.W., (1994) J. Mater. Res., 9, p. 2584Suarez, P.A.Z., Selbach, V.M., Dullius, J.E.L., Einloft, S., Piatnicki, C.M.S., Azambuja, D.S., De Souza, R.F., Dupont, J., (1997) Electrochim. Acta, 42, p. 2533Wilkes, J.S., Zaworotko, M.J., (1992) J. Chem. Soc., Chem. Commun., p. 965Yadav, J.S., Reddy, B.V.S., Gnaneshwar, D., (2003) New J. Chem., 27, p. 202Gordon, C.M., Ritchie, C., (2002) Green Chem., 4, p. 124Yadav, J.S., Reddy, B.V.S., Bhaishya, G., (2003) Green Chem., 5, p. 264Chen, S.L., Ji, S.J., Loh, T.P., (2003) Tetrahedron Lett., 44, p. 240
The Generation, Stability, Dissociation And Ion/molecule Chemistry Of Sulfinyl Cations In The Gas Phase
No full textSulfinyl cations [R-S+=O (R = CH3, Ph, Cl, CH 3O and C2H5O)] have been demonstrated by MO calculations in conjunction with pentaquadrupole multidimensional (2D and 3D) MS2 and MS3 mass spectrometric experiments to be stable and easily accessible gas phase species, and their dissociation and ion/molecule chemistry have been studied. Potential energy surface diagrams indicate that the sulfoxides (CH3)2S=O, Ph2S=O, Cl 2S=O, (CH3O)2S=O and (C2H 5O)2S=O do not undergo rearrangement upon dissociative ionization, yielding the corresponding sulfinyl cations as primary fragments. Ph(CH3)S=O+., on the other hand, is predicted to isomerize to CH3-S-O-Ph+. via a four-membered ring transition state, yielding upon further CH3 . loss the isomeric ion S=O+-Ph. The sulfinyl cations were found by ab initio calculations to be much more stable than their S=O+-R isomers, hence isomerization via [1,2-R] shifts is not expected. Direct cleavage of the R-SO+ bonds and/or processes that are preceded by isomerization dominate the low-energy collision dissociation chemistry of the sulfinyl cations, thus providing limited structural information. On the other hand, a general and structurally diagnostic ion/molecule reaction with 2-methyl-1,3-dioxolane occurs for all the sulfinyl cations yielding abundant net oxirane (C2H 4O) addition products. The reaction probably occurs via a transketalization-like mechanism that leads to cyclic 2-thia-1,3-dioxolanylium ions. This reactivity parallels that of several acylium (R-C+=O) and thioacylium ions (R-C+=S), and is not shared by the isomeric ions SO+-Ph and CH2=S+-OH. While the corresponding acylium ions react extensively with isoprene by [4 + 2+] cycloaddition, only the phenylsulfinyl cation Ph-S+=O yields an abundant cycloadduct.4587596Carey, F.A., Sundberg, R.J., (1983) Advanced Organic Chemistry, , Plenum Press, New YorkOlah, G.A., Schilling, P., Westrman, P.W., Lin, H.C., (1974) J. Am. Chem. Soc., 96, p. 3581Rolston, J.H., Yates, K., (1969) J. Am. Chem. Soc., 91, p. 1469Mukaiyama, T., (1982) Org. React., 28, p. 203Mannich, C., Schumann, P., (1936) Chem. Ber., 69, p. 2299Blicke, F.F., (1942) Org. React., 1, p. 303(1964) Friedel-Crafts and Related Reactions, 3. , G. A. Olah (ed.), Wiley, New YorkOlah, G.A., Germain, A., White, A.M., (1976) Carbonium Ions, 5, p. 2049. , G. A. Olah and P. V. R. Schleyer (eds.), Wiley, New York, ch. 35(1979) Gas Phase Ion Chemistry, , M. T. Bowers (ed.), Academic Press, New YorkChapman, J.R., (1993) Practical Organic Mass Spectrometry, , Wiley, New YorkNobes, R.H., Bouma, W.J., Radom, L., (1983) J. Am. Chem. Soc., 105, p. 309Weber, R., Levsen, K., (1980) Org. Mass Spectrom., 15, p. 138Turecek, F., McLafferty, F.W., (1983) Org. Mass Spectrom., 18, p. 608Baar, B.V., Burgers, P.C., Terlouw, J.K., Schwarz, H., (1986) J. Chem. Soc., Chem. Commun., p. 1607Pihlaja, K., Kuosmanen, P., Vainiotalo, P., (1988) Org. Mass Spectrom., 23, p. 770Chatfield, D.A., Bursey, M.M., (1976) J. Am. Chem. Soc., 98, p. 6492Staley, R.H., Wieting, R.D., Beauchamp, J.L., (1977) J. Am. Chem. Soc., 99, p. 5964Kumakura, M., Sigiura, T., (1978) J. Phys. Chem., 82, p. 639Sparapani, C., Speranza, M., (1980) J. Am. Chem. Soc., 102, p. 3120Kim, J.K., Caserio, M.C., (1982) J. Am. Chem. Soc., 104, p. 4624Attinà, M., Cacace, F., (1983) J. Am. Chem. Soc., 105, p. 1122Caserio, M.C., Kim, J.K., (1983) J. Am. Chem. Soc., 105, p. 6896Paradisi, C., Kenttämaa, H., Le, Q.T., Caserio, M.C., (1988) Org. Mass Spectrom., 23, p. 521Rahman, N.A., Fisher, C.L., Caserio, M.C., (1988) Org. Mass Spectrom., 23, p. 517Eberlin, M.N., Majumdar, T.K., Cooks, R.G., (1992) J. Am. Chem. Soc., 114, p. 2884Eberlin, M.N., Cooks, R.G., (1993) J. Am. Chem. Soc., 115, p. 9226Eberlin, M.N., Cooks, R.G., (1993) Org. Mass Spectrom., 28, p. 679Olah, G.A., Surya Prakash, G.K., Nakajima, T., (1980) Angew. Chem., Int. Ed. Engl., 19, p. 812Lindner, E., Karmann, H.-G., (1968) Angew. Chem., Int. Ed. Engl., 7, p. 548McLafferty, F.W., (1983) Tandem Mass Spectrometry, , Wiley, New YorkBush, K.L., Glish, G.L., McLuckey, S.A., (1989) Mass Spectrometry/Mass Spectrometry: Techniques and Applications of Tandem Mass Spectrometry, , VCH, New YorkSchwartz, J.C., Wade, A.P., Enke, C.G., Cooks, R.G., (1990) Anal. Chem., 62, p. 1809Schwartz, J.C., Schey, K.L., Cooks, R.G., (1989) Int. J. Mass Spectrom. Ion Processes, 3, p. 305Juliano, V.F., Gozzo, F.C., Eberlin, M.N., Kascheres, C., Do Lago, C.L., Anal. Chem., , in the pressMorrison, J.D., Stanney, D.A., Tedder, J., (1986) Proc. 34th ASMS Conference on Mass Spectrometry and Allied Topics, p. 222. , Cincinnati, OHBeaugrand, C., Devant, G., Jaouen, Mestdagh, D.H., Morin, N., Rolando, C., (1989) Adv. Mass Spectrom., 11 A, p. 256Shay, B.J., Eberlin, M.N., Cooks, R.G., Wesdemiotis, C.J., (1992) J. Am. Soc. Mass Spectrom., 3, p. 518Kotiaho, T., Shay, B.J., Cooks, R.G., Eberlin, M.N., (1993) J. Am. Chem. Soc., 115, p. 1004Eberlin, M.N., Kotiaho, T., Shay, B., Yang, S.S., Cooks, R.G., (1994) J. Am. Chem. Soc., 116, p. 2457Sablier, M., Capron, L., Mestdgh, H., Rolando, C., (1994) Tetrahedron Lett., 35, p. 2895Gozzo, F.C., Eberlin, M.N., (1995) J. Am. Soc. Mass Spectrom., 6, p. 554Lu, L., Yang, S.S., Wang, Z., Cooks, R.G., Eberlin, M.N., (1995) J. Mass Spectrom., 30, p. 581Yang, S.S., Chen, G., Ma, S., Cooks, R.G., Gozzo, F.C., Eberlin, M.N., (1995) J. Mass Spectrom., 30, p. 807Meyerson, S., Drews, H., Fields, E.K., (1964) Anal. Chem., 36, p. 1294Appel, R., Fehlhaber, H.W., Häussgen, D., Schöllhorn, R., (1966) Chem. Ber., 99, p. 3108Potzinger, P., Stracke, H.U., Küpper, W., Gollnick, K.Z., (1975) Z. Naturforch., 30 A, p. 340Peers, A.M., Muller, J.C., (1975) Int. J. Mass Spectrom. Ion Phys., 16, p. 321Khmel'nitskii, R.A., Efremov, Yu.A., (1977) Russ. Chem. Rev., 46, p. 46Nixon, W.B., Woodward, W.S., Bursey, M.M., Henion, J.D., (1978) Int. J. Mass Spectrom. Ion Phys., 26, p. 115Liu, L.K., Luo, F.-T., (1983) Org. Mass Spectrom., 18, p. 22Pihlaja, K., (1988) The Chemistry of Sulphones and Sulphoxides, p. 125. , S. Patai, Z. Rappoport, C. Stirling, (eds.), ch. 6, Wiley, New YorkGu, M., Turecek, F., (1992) J. Am. Chem. Soc., 114, p. 7146(1979) Mass Spectrometry, 5, p. 277. , R. A. W. Johnstone (ed.), The Chemical Society, LondonCarlsen, L., Egsgaard, H., (1988) J. Am. Chem. Soc., 110, p. 6701Turecek, F., Drinkwater, D.E., McLafferty, F.W., (1989) J. Am. Chem. Soc., 111, p. 7696McGibbon, G.A., Burgers, P.C., Terlouw, J.K., (1994) Chem. Phys. Let., 218, p. 499Gozzo, F.C., Eberlin, M.N., (1995) J. Mass Spectrom., 30, p. 1553Dewar, M.J.S., Zoebisch, E.G., Healy, E.F., Stewart, J.J.P., (1985) J. Am. Chem. Soc., 107, p. 3902SPARTAN, Ver. 3.1, , Wavefunction, Inc. 18401 Von Karma, suite 370, Irvine, CA 92715, USAFrisch, M.J., Trucks, G.W., Head-Gordon, M., Gill, P.M.W., Wong, M.W., Foresman, J.B., Johnson, B.G., Pople, J.A., (1992) GAUSSIAN92, Revision C, , GAUSSIAN, Inc., Pittsburgh PAHehre, W.J., Ditchfield, R., Pople, J.A., (1972) J. Chem. Phys., 56, p. 2257Hariharan, P.C., Pople, J.A., (1973) Theor. Chem. Acta, 72, p. 650Gordon, M.S., (1980) Chem. Phys. Lett., 76, p. 163Frisch, M.J., Pople, J.A., Binkley, J.S., (1984) J. Chem. Phys., 80, p. 3265Møller, C., Plesset, M.S., (1934) Phys. Rev., 46, p. 618(1993) XMOL, Ver. 1.3.1, , Minessota Supercomputer Center, Inc., Minneapolis, MNMcLafferty, F.W., Turecek, F., (1993) Interpretation of Mass Spectra, , HD Science, New YorkBowie, J.H., Willians, D.H., Lawesson, S.-O., Madsen, J.Ø., Nolde, C., Schroll, G., (1966) Tetrahedron, 22, p. 3515Gozzo, F.C., Eberlin, M.N., (1993) Proceedings of the 41st ASMS Conference on Mass Spectrometry and Allied Topics, p. 974Bogert, M.T., Roblin, R.L., (1933) J. Am. Chem. Soc., 55, p. 3741Budzikiewicz, H., Djerassi, C., Williams, D.H., (1967) Mass Spectrometry of Organic Compounds, , Holden-Day, San FranciscoEberlin, M.N., Morgon, N.H., Yang, S.S., Shay, B.J., Cooks, R.G., (1995) J. Am. Soc. Mass Spectrom., 6, p. 1Basher, M.M., Pimpim, R.S., Eberlin, M.N., submitted for publicationTurecek, F., Hanus, V., (1984) Mass Spectrom. Rev., 3, p. 8
The Proton-bound Dimer Of Acetone [2]
No full text[No abstract available]401127128Derrick, P.J., (1982) Mass Spectrom. Rev., 2, p. 285Nourse, B.D., Cooks, R.G., (1991) Int. J. Mass Spectrom. Ion Processes, 106, p. 249Dang, T.T., Motell, E.L., Travers, M.J., Clifford, E.P., Ellison, G.B., DePuy, C.H., Bierbaum, V.M., (1993) Int. J. Mass Spectrom. Ion Processes, 123, p. 171O'Hair, R.A.J., Gronert, S., Williams, T.D., (1994) Org. Mass Spectrom., 29, p. 151Norman, K., McMahon, T.B., (1999) Int. J. Mass Spectrom., 182-183, p. 381Schröder, D., Semialjac, M., Schwarz, H., (2004) Int. J. Mass Spectrom., 223, p. 103Gozzo, F.C., Eberlin, M.N., (2001) J. Mass Spectrom., 36, p. 1140Eberlin, M.N., (1997) Mass Spectrom. Rev., 16, p. 113Juliano, V.F., Gozzo, F.C., Eberlin, M.N., Rascheres, C., Do Lago, C.L., (1996) Anal. Chem., 68, p. 1328Santos, L.S., Pavam, C.H., Almeida, W.P., Coelho, F., Eberlin, M.N., (2004) Angew. Chem. Int. Ed., 43, p. 4330Sabino, A.A., Machado, A.H.L., Correia, C.R.D., Eberlin, M.N., (2004) Angew. Chem. Int. Ed., 43, p. 2514Eberlin, M.N., Kotiaho, T., Shay, B.J., Yang, S.S., Cooks, R.G., (1994) J. Am. Chem. Soc., 116, p. 2457Yang, S.S., Wong, P., Ma, S.G., Cooks, R.G., (1996) J. Am. Soc. Mass Spectrom., 7, p. 198Meurer, E.C., Gozzo, F.C., Augusti, R., Eberlin, M.N., (2003) Eur. J. Mass Spectrom., 9, p. 295Denault, J.W., Wang, F., Cooks, R.G., Gozzo, F.C., Eberlin, M.N., (2000) J. Phys. Chem. A, 104, pp. 11 290Chen, G., Cooks, R.G., Corpuz, E., Scott, L.T., (1996) J. Am. Soc. Mass Spectrom., 7, p. 61
Going Beyond Counting First Authors in Author Co-citation Analysis
Full text linkThe present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
A New Platinum Complex With Tryptophan: Synthesis, Structural Characterization, Dft Studies And Biological Assays In Vitro Over Human Tumorigenic Cells
No full textA new platinum(II) complex with the amino acid L-tryptophan (trp), named Pt-trp, was synthesized and characterized. Elemental, thermogravimetric and ESI-QTOF mass spectrometric analyses led to the composition [Pt(C 11H11N2O2)2] ×6H2O. Infrared spectroscopic data indicate the coordination of trp to Pt(II) through the oxygen of the carboxylate group and also through the nitrogen atom of the amino group. The 13C CP/MAS NMR spectroscopic data confirm coordination through the oxygen atom of the carboxylate group, while the 15N CP/MAS NMR data confirm coordination of the nitrogen of the NH2 group to the metal. Density functional theory (DFT) studies were applied to evaluate the cis and trans coordination modes of trp to platinum(II). The trans isomer was shown to be energetically more stable than the cis one. The Pt-trp complex was evaluated as a cytotoxic agent against SK-Mel 103 (human melanoma) and Panc-1 (human pancreatic carcinoma) cell lines. The complex was shown to be cytotoxic over the considered cells. © 2013 Elsevier B.V. All rights reserved.122209215Barefoot, R.R., (2001) J. Chromatogr. B, 751, pp. 205-211Lebwohl, D., Canetta, R., (1998) Eur. J. Cancer, 34, pp. 1522-1534Rafique, S., Idrees, M., Nasim, A., Akbar, H., Athar, A., (2010) Biotechnol. Mol. Biol. Rev., 5, pp. 38-45Kelland, L., (2007) Nat. Rev. Cancer, 7, pp. 573-584Ivanov, A.I., Christodoulou, J., Parkinson, J.A., Barnham, K.J., Tucker, A., Woodrow, J., Sadler, P.J., (1998) J. Biol. Chem., 273, pp. 14721-14730Khalailar, I., Allardyce, C.S., Verna, C.S., Dyson, P.J., (2005) ChemBioChem, 6, pp. 1788-1795Cutillas, N., Yellol, G.S., Haro, C., Vicente, C., Rodriguez, V., Ruiz, J., (2013) Coord. Chem. Rev., 257, pp. 2784-2797Chiririwa, H., Moss, J.R., Hendricks, D., Smith, G.S., Meijboom, R., (2013) Polyhedron, 49, pp. 29-35Castello, W.S., Spera M B, M., Gomes, A.F., Gozzo, F.C., Lustri, W.R., Formiga, A.L.B., Corbi, P.P., (2011) J. Coord. Chem., 64, pp. 272-280Spera, M.B.M., Quintão, F.A., Ferraresi, D.K.D., Lustri, W.R., Magalhães, A., Formiga, A.L.B., Corbi, P.P., (2011) Spectrochim. Acta A, 78, pp. 313-318Corbi, P.P., Massabni, A.C., Moreira, A.G., Medrano, F.J., Jasiulionis, M.G., Costa-Neto, C.M., (2005) Can. J. Chem.-Revue Canadienne de Chimie, 83, pp. 104-109Corbi, P.P., Massabni, A.C., (2006) Spectrochim. Acta A, 64, pp. 418-419Cavicchioli, M., Massabni, A.C., Heinrich, T.A., Costa-Neto, C.M., Abrão, E.P., Fonseca, B.A.L., Castellano, E.E., Leite, C.Q.F., (2010) J. Inorg. Biochem., 104, pp. 533-540Dunbar, R.C., Steill, J.D., Polfer, N.C., Oomens, J., (2008) J. Phys. Chem. A, 112, pp. 10823-10830Wagner, C.C., Baran, E.J., (2004) Acta Farm. Bonaerense, 23, pp. 339-342Kazachenko, A.S., Legler, A.V., Peryanova, O.V., Vstavskaya, Y.A., (2000) Pharm. Chem. J., 34, pp. 257-258Carvalho, M.A., Souza, B.C., Paiva, R.E.F., Bergamini, F.R.G., Gomes, A.F., Gozzo, F.C., Lustri, W.R., Corbi, P.P., (2012) J. Coord. Chem., 65, pp. 1700-1711Carvalho, M.A., De Paiva, R.E.F., Bergamini, F.R.G., Gomes, A.F., Gozzo, F.C., Lustri, W.R., Formiga, A.L.B., Corbi, P.P., (2013) J. Mol. Struct., 1031, pp. 125-131Schmidt, M.W., Baldridge, K.K., Boatz, J.A., Elbert, S.T., Gordon, M.S., Jensen, J.H., Matsunaga, S.K.N., Montgomery, Jr.J.A., (1993) J. Comput. Chem., 14, pp. 1347-1363Hay, P.J., Wadt, W.R., (1985) J. Chem. Phys., 82, pp. 299-310Ditchfie, R., Hehre, W.J., Pople, J.A., (1971) J. Chem. Phys., 54, pp. 724-728Hehre, W.J., Ditchfie, R., Pople, J.A., (1972) J. Chem. Phys., 56, pp. 2257-2261Francl, M.M., Pietro, W.J., Hehre, W.J., Binkley, J.S., Gordon, M.S., Defrees, D.J., Pople, J.A., (1982) J. Chem. Phys., 77, pp. 3654-3665Harihara, P.C., Pople, J.A., (1973) Theor. Chim. Acta, 28, pp. 213-222Becke, A.D., (1993) J. Chem. Phys., 98, pp. 5648-5652Lee, C.T., Yang, W.T., Parr, R.G., (1988) Phys. Rev. B, 37, pp. 785-789Miertus, S., Scrocco, E., Tomasi, J., (1981) Chem. Phys., 55, pp. 117-129Bonacin, J.A., Formiga, A.L.B., Melo, V.H.S., Toma, H.E., (2007) Vib. Spectrosc., 44, pp. 133-141Scott, A.P., Radom, L., (1996) J. Phys. Chem., 100, pp. 16502-16513Mosmann, T., (1983) J. Immunol. Methods, 65, pp. 55-63(1994) Powder Diffraction Database - CD ROM, , File 46-1043 (JCPDS-ICDD)Hu, J., Fu, R., Ye, C., (1992) Chem. Phys. Lett., 195, pp. 159-162Çakir, S., Biçer, E., (2010) J. Chil. Chem. Soc., 55, pp. 236-239Gao, H., (2011) Spectrochim. Acta A, 79, pp. 687-69
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