Organic-soluble lanthanide nuclear magnetic resonance shift reagents for sulfonium and isothiouronium salts

Abstract

London, A 1981, 300, 15-41. Wilson, M. A.; Rottendorf. H.; Collin, P. J.; Vassallo, A. M.; Barron, P. F. fuel 1982, 6 1 , 321-328. Schafer, H. N. S. Fuel 1972, 5 1 , 4-9. Thurman, E. M.; Malcolm, R. L. In Aquatic and Terrestrial Humic Materials; Ann Arbor Science: Ann Arbor, MI, 1983; pp 1-24. Oades. J. M.; Vassallo, A. M.; Waters, A. G.; Wilson, M. A. Aust. J . Soil Res ., in press. Wilson, M. A.; Collin, P. J.; Pugmire, R. J.; Grant, D. M . Fuel 1982, 6 1 , 959-967. Ollivier, P.; Gerstein, B. C. Carbon 1984, 22, 409-412. Pugmire, R. J.; Zilm. K. W.; Grant, D. M.; Larter, S. R.; Allen, J.; Senftle, J. R.; Davis, A.; Spackman, W. ACS Symp. Ser. 1981, No. Pugmire, R. J.; Zilm, K. W.; Woolfenden, W. R.; Grant, D. M.; Dyrkacz, G. R.; Bloomquist, C. A. A,; Horwitz, E. P. Org. Geochem. 1982, 4 , 79-84. Pugmire, R. J.; Woolfenden, W. R.; Mayne, C. L.; Karas, J.; Grant, D. M. ACS Symp. Ser. 1984, No. 252, 79-97. Wilson, M. A.; Pugmlre, R. J.; Karas, J.; Alemany, L. B.; Woolfenden, W. R.; Grant, D. M.; Given, P. H. Anal. Chem. 1984, 56, 933-943. Zilm, K. W.; Pugmire, R. J.; Larter, S. R.; Alien, J.; Grant, D. M. fuel 1981, 60, 717-722. Karas, J.; Pugmire, R. J.; Woolfenden. W. R.; Grant, D. M.; Blair, S. 6,6,7,7,8,8,8-heptafiuoro-2,2-dlmethyl-3,5-octanedlone) are eff ectlve organlc-soluble nuclear magnetlc resonance shlft reagents for sulfonlum and lsothlouronlum salts. The shlft reagent Is formed in solution from Ln(fod), and Ag(fod) or K(fod). The selectlon of Ag(fod) or K(fod) In forming the shift reagent is dependent on the anion of the organic salt. Ag(fod) Is more effectlve wlth halide salts, whereas K(fod) is preferred with tetrafluoroborate salts. Resolution of diastereotopic hydrogen atoms was observed In the shifted spectra of certain substrates. Enantlomerlc resoiutlon was obtained In the spectrum of sec-butyllsothlouronium chlorkle wlth a chlrai shift reagent. The reagents can be employed In solvents such as chloroform and benzene. Int. Lanthanide complexes of the formula [Ln(fod),]-(fod, EXPERIMENTAL SECTIONReagents. The compounds 1-iodobutane, iodomethane, 1bromopentane, 1-bromononane, I-chlorobutane, benzyl chloride,

Application ofS-alkylsulfonium salts of aromatic sulfides as new thermal latent cationic initiators

“…5‐Methyldibenzothiophenium tetrafluoroborate [ 3a ; mp = 149.5–151.0 °C (149–151 °C in the literature11)], 2,8‐dibromo‐5‐methyldibenzothiophenium tetrafluoroborate ( 3f ),11 methyldiphenylsulfonium tetrafluoroborate [ 4a ; mp = 59.5–62.0 °C (58–60 °C in the literature14)], and methyltetrahydrothiophenium tetrafluoroborate [ 5 ; mp = 230–237 °C (239–245 °C in the literature15)] were prepared by the reported methods. 10‐Methylphenoxathiinium tetrafluoroborate [ 6a ; mp = 206.5–208.0 °C (201–203 °C in the literature16)] and 5‐methylthianthrenium tetrafluoroborate [ 6b ; mp = 194.0–197.0 °C (188–190 °C in the literature16)] were prepared by the same procedure as 3a 11 in 80% and 78% yields, respectively.…”

Organic analytical reagents in nuclear magnetic resonance spectroscopy

“…None of these mononuclear LSRS, however, induce changes in the chemical shifts of are significantly larger than those with Eu(fod)3 [33,34].…”

Methylation of tetrakis(fod) europate NMR shift reagent byS-methyldibenzothiophenium ion

“…All possible methylated products are shown in Scheme 1. There are three possible C-methylated products which are in potential equilibrium, including one keto form (1) and two enol forms (2 and 3). There are two possible O-methylated products due to the unsymmetrical nature of the fod anion (4 and 5).…”