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Volumn 73, Issue 13, 2008, Pages 5029-5038

The case for the intermediacy of monomeric metaphosphate analogues during oxidation of H-phosphonothioate, H-phosphonodithioate, and H-phosphonoselenoate monoesters: Mechanistic and synthetic studies

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL COMPOUNDS; CHEMICAL OXYGEN DEMAND; CHEMICAL REACTIONS; COMPLEXATION; HEALTH; HYDROGEN; INDUSTRIAL CHEMICALS; IODINE; IODINE COMPOUNDS; MATHEMATICAL TRANSFORMATIONS; NONMETALS; SELENIUM; SELENIUM COMPOUNDS; SULFUR;

EID: 46849086201     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo8006072     Document Type: Article
Times cited : (11)

References (111)
  • 60
    • 46849097018 scopus 로고    scopus 로고
    • Isolation not attempted. 31P NMR (THF) and MS data: 10a, δP 59.7 ppm, m, HRMS m/z 154.9930, M-H, C3H8O3PS- calcd 154.9937, 10b, δP 58.2 ppm, qu, 3J, 8.2 Hz, HRMS m/z 169.0100, M-H, C4H 10O3PS- calcd 169.0094, 10c, δP 55.9 ppm, q, 3J, 8.6 Hz, HRMS m/z 183.0270, M-H, C5H12O3PS, calcd 183.0250, 10d, δP 49.8 ppm, t, 3J, 8.0 Hz, HRMS m/z 197.0401, M-H, C6H14O3PS- calcd 197.0407
    • - calcd 197.0407).
  • 62
    • 46849102427 scopus 로고    scopus 로고
    • The most reliable method to check whether more reactive alcohols also choose to react via metaphosphate or not are kinetic studies. Since an alcohol molecule is not involved in the formation of metathiophosphate 8, neither in path A nor in path B (Scheme 2, the rates of these reactions were expected to be independent of the alcohol concentration. On the other hand, if the bimolecular displacement occurs (Scheme 2, path C) the overall reaction rate should display first-order dependence on the alcohol concentration. See, e.g, ref 31
    • The most reliable method to check whether more reactive alcohols also choose to react via metaphosphate or not are kinetic studies. Since an alcohol molecule is not involved in the formation of metathiophosphate 8, neither in path A nor in path B (Scheme 2), the rates of these reactions were expected to be independent of the alcohol concentration. On the other hand, if the bimolecular displacement occurs (Scheme 2, path C) the overall reaction rate should display first-order dependence on the alcohol concentration. See, e.g., ref 31.
  • 69
    • 46849114793 scopus 로고    scopus 로고
    • P 51.0, 50.9 (neat t-BuOH), 50.7, 50.5 (THF), 51.3, 51.2 ppm (MeCN).
    • P 51.0, 50.9 (neat t-BuOH), 50.7, 50.5 (THF), 51.3, 51.2 ppm (MeCN).
  • 96
    • 46849085248 scopus 로고    scopus 로고
    • Isolation not attempted. 31P NMR (THF) and MS data: 11b, δP 57.3, 57.0 ppm, HRMS m/z 667.1913, M-H, C33H36N2O 9PS- calcd 667.1885, 18, δP 113.5 ppm, HRMS m/z 683.1623, M-H, C33H 36N2O8PS2- calcd 683.1656, 19, δP 52.4, 52.2 ppm, HRMS m/z 715.1278[M-H, C33H36N2O 9PSe- calcd 715.1329
    • - calcd 715.1329).
  • 100
    • 46849121866 scopus 로고    scopus 로고
    • P-D = 224 Hz.
    • P-D = 224 Hz.
  • 110
    • 46849117602 scopus 로고    scopus 로고
    • Excess of nucleosidic component 20 could be efficiently recovered during chromatography (see the Supporting information).
    • Excess of nucleosidic component 20 could be efficiently recovered during chromatography (see the Supporting information).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.