Canosa-Mas Carlos E, Flugge Mark L, King Martin D, Wayne Richard P
Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, UK.
Phys Chem Chem Phys. 2005 Feb 21;7(4):643-50. doi: 10.1039/b416574h.
The relative-rate technique has been used to obtain rate coefficients for the reaction between the NO3 radical and alpha,beta-unsaturated esters and ketones: methyl E-2-butenoate (k1), methyl 3-methyl-2-butenoate (k2), methyl E-2-methyl-2-butenoate (k3), 3-methyl-3-buten-2-one (k4), E-3-penten-2-one (ks), 4-methyl-3-penten-2-one (k6), and E-3-methyl-3-penten-2-one (k7). The rate constants obtained by the relative-rate method at T = 298 +/- 2 K and P = 760 +/- 5 Torr (N2 as bath gas) are: k1 = (1.85 +/- 0.56) x 10(-15) cm3 molecule(-1) s(-1), k2 = (1.41 +/- 0.23) x 10(-14) cm3 molecule(-1) s(-1), k3 = (4.91 +/- 1.15) x 10(-14) cm3 molecule(-1) s(-1), k4 = (8.27 +/- 6.44) x 10(-15) cm3 molecule(-1) s(-1), k5 = (1.03 +/- 0.31) x 10(-14) cm3 molecule(-1) s(-1), k6 = (1.44 +/- 0.26) x 10(-13) cm3 molecule(-1) s(-1) and k7 = (1.55 +/- 0.20) x 10(-13) cm3 molecule(-1) s(-1). The rate constants are used to show the effect of increased substitution at the carbon-carbon double bond. Group-reactivity factors for the ketone and ester groups are also determined. Atmospheric lifetimes of the compounds against night-time attack by NO3 are estimated.
相对速率技术已被用于获取硝酸根自由基与α,β-不饱和酯和酮之间反应的速率系数：E-2-丁烯酸甲酯（k1）、3-甲基-2-丁烯酸甲酯（k2）、E-2-甲基-2-丁烯酸甲酯（k3）、3-甲基-3-丁烯-2-酮（k4）、E-3-戊烯-2-酮（k5）、4-甲基-3-戊烯-2-酮（k6）和E-3-甲基-3-戊烯-2-酮（k7）。在T = 298 ± 2 K和P = 760 ± 5 Torr（以氮气作为缓冲气体）条件下，通过相对速率法获得的速率常数为：k1 = (1.85 ± 0.56) × 10⁻¹⁵ cm³·分子⁻¹·秒⁻¹，k2 = (1.41 ± 0.23) × 10⁻¹⁴ cm³·分子⁻¹·秒⁻¹，k3 = (4.91 ± 1.15) × 10⁻¹⁴ cm³·分子⁻¹·秒⁻¹，k4 = (8.27 ± 6.44) × 10⁻¹⁵ cm³·分子⁻¹·秒⁻¹，k5 = (1.03 ± 0.31) × 10⁻¹⁴ cm³·分子⁻¹·秒⁻¹，k6 = (1.44 ± 0.26) × 10⁻¹³ cm³·分子⁻¹·秒⁻¹，k7 = (1.55 ± 0.20) × 10⁻¹³ cm³·分子⁻¹·秒⁻¹。这些速率常数用于展示碳-碳双键上取代基增加的影响。同时还确定了酮基和酯基的基团反应活性因子。估算了这些化合物在夜间受到硝酸根攻击时的大气寿命。
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