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Volumn 26, Issue 12, 2013, Pages 989-996

Substituent effects on the dehydration of arene hydrates in aqueous solution

Author keywords

arene hydrates; dehydration; substituent effects

Indexed keywords

CARBOCATIONS; DATA POINTS; GENERAL ACID CATALYSIS; HAMMETT PLOTS; PSEUDO-FIRST-ORDER RATE CONSTANT; SECOND-ORDER RATE CONSTANTS; SUBSTITUENT EFFECT; UV SPECTROPHOTOMETRY;

EID: 84888430142     PISSN: 08943230     EISSN: 10991395     Source Type: Journal    
DOI: 10.1002/poc.3174     Document Type: Article
Times cited : (7)

References (38)
  • 9
    • 84984551774 scopus 로고
    • d) L. Young, Biochem. J., 1947, 41, 417-422.
    • (1947) Biochem. J. , vol.41 , pp. 417-422
    • Young, L.1
  • 33
    • 84888438601 scopus 로고    scopus 로고
    • The mono-epoxides used in the final ring-opening step were a mixture of diastereomers
    • The mono-epoxides used in the final ring-opening step were a mixture of diastereomers.
  • 34
    • 84888433598 scopus 로고    scopus 로고
    • A ratio of kHClO4/kDClO4 ∼ 1 was observed for the dehydration reaction of arene hydrate 8e. A rate constant of kDClO4 = 2.0 (± 0.2) × 10-4 s-1 was determined by 1H NMR spectroscopy for the reaction of 8a in 2.5 mM DClO4 in D2O solution. A rate constant of kHClO4 = 2.25 (± 0.08) × 10-4 s-1 can be calculated for reaction of 8a in 2.5 mM HClO 4 in H2O solution from the second order rate constant for acid-catalyzed dehydration kH = 0.0899 M-1s-1, thus giving a kHClO4/ kDClO4 of ~1.
    • A ratio of kHClO4/kDClO4 ∼ 1 was observed for the dehydration reaction of arene hydrate 8e. A rate constant of kDClO4 = 2.0 (± 0.2) × 10-4 s-1 was determined by 1H NMR spectroscopy for the reaction of 8a in 2.5 mM DClO4 in D2O solution. A rate constant of kHClO4 = 2.25 (± 0.08) × 10-4 s-1 can be calculated for reaction of 8a in 2.5 mM HClO 4 in H2O solution from the second order rate constant for acid-catalyzed dehydration kH = 0.0899 M-1s-1, thus giving a kHClO4/ kDClO4 of ~1.
  • 35
    • 84888432210 scopus 로고    scopus 로고
    • Preliminary calculations using Gaussian 2003 B3Lyp6-31g* level of theory have shown that the presence of the hydroxyl group in the carbocation formed from diols 4 results in puckering of the two saturated carbons relative to the diene, whereas the hydrate carbocation centre is co-planar with the diene.
    • Preliminary calculations using Gaussian 2003 B3Lyp6-31g* level of theory have shown that the presence of the hydroxyl group in the carbocation formed from diols 4 results in puckering of the two saturated carbons relative to the diene, whereas the hydrate carbocation centre is co-planar with the diene.
  • 36
    • 84888428601 scopus 로고    scopus 로고
    • Our preliminary calculations using Gaussian 2003 B3Lyp6-31g* level of theory have shown that the most stable conformation for all of the hydrates places the hydroxyl group in an axial position, thus permitting an 'aromatic' hyperconjugative interaction between the developing vacant carbocation p-orbital and one of the β-CH2 hydrogens in the ring.
    • Our preliminary calculations using Gaussian 2003 B3Lyp6-31g* level of theory have shown that the most stable conformation for all of the hydrates places the hydroxyl group in an axial position, thus permitting an 'aromatic' hyperconjugative interaction between the developing vacant carbocation p-orbital and one of the β-CH2 hydrogens in the ring.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.