塔夫特方程
取代基 | Es | σ* |
---|---|---|
–H | 1.24 | 0.49 |
–CH3 | 0 | 0 |
–CH2CH3 | –0.07 | –0.1 |
–CH(CH3)2 | –0.47 | –0.19 |
–C(CH3)3 | –1.54 | –0.3 |
–CH2Ph | –0.38 | 0.22 |
–Ph | –2.55 | 0.6 |
塔夫特方程(英語:Taft equation)是物理有機化學中的一種線性自由能關係方程,用於研究反應機理和有機化合物的定量結構-活性關係。1952年由羅伯特·W·塔夫特提出,作為對哈米特方程的一種改進。[2][3][4] 哈米特方程考慮了場效應、誘導效應和共振的影響[5] ,塔夫特方程則進一步考慮了位阻效應的影響。
塔夫特方程的形式為:
式中是帶有某取代基的有機物的取代反應與參考反應(取代基為甲基時)的反應速率常數比;是該反應對極性效應的敏感因子;是極性取代常數,可以描述取代基的場效應和誘導效應;是該反應對位阻效應的敏感因子,而是位阻取代基常數。
參考文獻
編輯- ^ Eric Anslyn, E.; Dougherty, D. A. Modern Physical Organic Chemistry; University Science Books, 2006, p 455.
- ^ Taft, Robert W. Linear Free Energy Relationships from Rates of Esterification and Hydrolysis of Aliphatic and Ortho-substituted Benzoate Esters. Journal of the American Chemical Society. June 1952, 74 (11): 2729–2732 [2024-07-16]. ISSN 0002-7863. doi:10.1021/ja01131a010. (原始內容存檔於2024-07-16) (英語).
- ^ Taft, Robert W. Polar and Steric Substituent Constants for Aliphatic and o-Benzoate Groups from Rates of Esterification and Hydrolysis of Esters1. Journal of the American Chemical Society. 1952-06-01, 74 (12): 3120–3128. ISSN 0002-7863. doi:10.1021/ja01132a049.
- ^ Taft, Robert W. Linear Steric Energy Relationships. Journal of the American Chemical Society. 1953-09-01, 75 (18): 4538–4539. ISSN 0002-7863. doi:10.1021/ja01114a044.
- ^ Hammett, Louis P. The Effect of Structure upon the Reactions of Organic Compounds. Benzene Derivatives. Journal of the American Chemical Society. 1937-01-01, 59 (1): 96–103. ISSN 0002-7863. doi:10.1021/ja01280a022.