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The effects of substituents in oxazoles on their13C,14N, and1H NMR spectra
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The effects of substituents in oxazoles on their13C,14N, and1H NMR spectra
作者:
V.S.Bogdanov,
M.A.Aitzhanova,
I.A.Abronin,
L.B.Medvedskaya,
期刊:
Bulletin of the Academy of Sciences of the USSR, Division of chemical science
(Springer Available online 2004)
卷期:
Volume 29,
issue 2
页码: 224-234
ISSN:0568-5230
年代: 2004
DOI:10.1007/BF00961751
出版商: Springer_US-Boston
数据来源: Springer
摘要:
1.In oxazoles electron-donor substituants in position 2 shield the14N nucleus of the ring nitrogen atom and the13C nucleus of the C5carbon but have little effect on C4. Electron-donor substituents in position 5 shield, and electron-acceptor substituants deshielded the13C nuclei of the C4and C2carbons and have a weak effect onδ14N. The following linear correlations were found:$$\delta _{C^2 } - \delta _{C^4 } ,\delta _{C^5 } $$electronegativity of substituent R5,$$\delta _{C^4 } - \delta _{C^5 } ,\delta _{C^2 } - \delta _{2 - H} ,\delta _{C^4 } - \delta _{4 - H} $$andδ13C for 4,5-disubstituted oxazoles with o-disubstituted benzenes.2.Regression analysis has established the additivity of the chemical shifts of the13C carbons of the oxazole ring. Correlations of the theoretical values with the experimental values were obtained for C2with r=0.996, C4with r=0.995, and C5with r=0.999. The possibility has been demonstrated of calculatingδ13C from three parameters ΔC2, ΔC4, and ΔC5), which characterize the contributions of the substituents in shielding the C2, C4, and C5carbons.3.The effect of substituents at C5on the constants$$^1 J_{C^4 } $$, 4−H and$$^1 J_{C^2 } $$, 2−H,$$^1 J_{C^4 } $$,4−H was found to increase in the series 5-Me<5-NM
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