白皮杉醇PIC与OH自由基反应机理的理论研究

doi:10.7503/cjcu20150114

摘要/Abstract

摘要：

采用M05-2X/6-311++G(d,p)水平对白皮杉醇PIC清除OH自由基的气相反应机理进行了研究, 并采用极化连续介质模型考察了极性溶剂对该反应机理的影响. 结果表明, 在气相和水溶液中OH自由基的抽氢反应均最易发生在B环的C4'OH位的酚羟基上, 加成反应优先在乙烯双键和C4'原子上进行. 在298 K的气相条件下, 抽氢与加成反应主通道总速率常数 $k Total CVT / SCT$ 分别为5.46×10¹⁵和2.72×10¹⁴ L·mol^-1·s^-1, 抽氢反应为优势通道, 且抽氢与加成反应均具有负温度效应.

关键词: 白皮杉醇, OH自由基, 反应机理, 密度泛函理论

Abstract:

At M05-2X/6-311++G(d,p) level, the reaction mechanisms between piceatannol and OH free radical were studied in gas phase, the effect of solvent polarity on the reaction mechanisms were also considered using the polarizable continuum model. The results show that the active position is C4'OH(OH is connected with C4') with B ring both in the gas and aqueous phase for hydrogen atom transfer mechanism. For radical adduct formation mechanism, OH radical preferred to adduct on C_α, C_β and C4'. At the temperature of 298 K, the total rate constants of hydrogen atom transfer and radical adduct formation are 5.46×10¹⁵ and 2.72×10¹⁴ L·mol^-1·s^-1, the more favorable channel is hydrogen atom transfer. Furthermore, the results also manifest that there is a negative correlation between the rate constants and temperature.

Key words: Piceatannol, OH radical, Reaction mechanism, Density functional theory

中图分类号:

O643.1

TrendMD:

王帅, 王渭娜, 高志芳, 王文亮. 白皮杉醇PIC与OH自由基反应机理的理论研究. 高等学校化学学报, 2015, 36(8): 1588.

WANG Shuai, WANG Weina, GAO Zhifang, WANG Wenliang. Theoretical Study on the Mechanism of Reaction Between Piceatannol and Hydroxyl Radical^†. Chem. J. Chinese Universities, 2015, 36(8): 1588.

图/表 10

Fig.1 Structure of piceatannol Bond lengths are in nm.

Scheme 1 Possible reaction channels of piceatannol and OH radical

Fig.2 Optimized geometries of the stationary points for the C4'OH(A) and C3'OH(B) channels of HATBond lengths are in nm.

Fig.3 Optimized geometries of the stationary points for the Cα and Cβ channels of RAFBond lengths are in nm.

Fig.4 Potential energy profile for HAT mechanism(A) B ring; (B) A ring.

Fig.5 Potential energy profile for RAF mechanism(A) B ring and ethylenic bond; (B) A ring.

Table 1 Energies of HAT and RAF channels in the gas phase and liquid phase at M05-2x/6-311++G(d,p) level*

Reaction	Position	Gas-phase			Water-phase
Reaction	Position	Δ $E ele g ≠$ /(kJ·mol^-1) (RC→TS)	Δ $E app g ≠$ /(kJ·mol^-1) (R→TS)	ΔE^g/(kJ·mol^-1) (R→P)	Δ $E ele w ≠$ /(kJ·mol^-1) (RC→TS)	Δ $E app w ≠$ /(kJ·mol^-1) (R→TS)	ΔE^w/(kJ·mol^-1) (R→P)
HAT	C4'OH	9.00	-15.49	-171.00	-2.36	-12.18	-170.87
	C3'OH	18.96	-6.76	-156.75	18.88	7.99	-155.89
	C3OH	7.84	-5.68	-36.79	7.93	11.01	-101.40
	C5OH	8.20	-6.16	-36.33	8.48	11.12	-101.41
RAF	C_α	2.05	-17.96	-146.80	-0.50	-16.20	-141.32
	C_β	4.35	-15.66	-145.30	0.30	-15.40	-136.67
	C1	37.84	19.13	-51.70	34.03	18.63	-47.68
	C2	4.46	-15.70	-104.61	-0.70	-17.07	-101.09
	C3	16.66	-3.52	-83.18	23.15	6.78	-73.72
	C4	3.22	-18.84	-115.78	-0.71	-12.35	-78.86
	C5	17.54	-1.21	-85.48	24.62	9.13	-76.77
	C6	5.90	-12.85	-95.44	-0.29	-15.78	-92.68
	C1'	31.73	9.21	-64.13	6.07	4.69	-60.19
	C2'	11.26	-3.22	-87.78	4.40	-5.27	-83.80
	C3'	18.80	-3.60	-88.95	3.69	-4.56	-89.25
	C4'	1.59	-20.09	-128.80	-2.26	-10.51	-117.04
	C5'	10.85	-13.60	-84.85	10.38	-8.63	-70.83
	C6'	6.87	-13.60	-110.30	3.52	-9.21	-101.85

Table 1 Energies of HAT and RAF channels in the gas phase and liquid phase at M05-2x/6-311++G(d,p) level*

Reaction	Position	Gas-phase			Water-phase
Reaction	Position	Δ $E ele g ≠$ /(kJ·mol^-1) (RC→TS)	Δ $E app g ≠$ /(kJ·mol^-1) (R→TS)	ΔE^g/(kJ·mol^-1) (R→P)	Δ $E ele w ≠$ /(kJ·mol^-1) (RC→TS)	Δ $E app w ≠$ /(kJ·mol^-1) (R→TS)	ΔE^w/(kJ·mol^-1) (R→P)
HAT	C4'OH	9.00	-15.49	-171.00	-2.36	-12.18	-170.87
	C3'OH	18.96	-6.76	-156.75	18.88	7.99	-155.89
	C3OH	7.84	-5.68	-36.79	7.93	11.01	-101.40
	C5OH	8.20	-6.16	-36.33	8.48	11.12	-101.41
RAF	C_α	2.05	-17.96	-146.80	-0.50	-16.20	-141.32
	C_β	4.35	-15.66	-145.30	0.30	-15.40	-136.67
	C1	37.84	19.13	-51.70	34.03	18.63	-47.68
	C2	4.46	-15.70	-104.61	-0.70	-17.07	-101.09
	C3	16.66	-3.52	-83.18	23.15	6.78	-73.72
	C4	3.22	-18.84	-115.78	-0.71	-12.35	-78.86
	C5	17.54	-1.21	-85.48	24.62	9.13	-76.77
	C6	5.90	-12.85	-95.44	-0.29	-15.78	-92.68
	C1'	31.73	9.21	-64.13	6.07	4.69	-60.19
	C2'	11.26	-3.22	-87.78	4.40	-5.27	-83.80
	C3'	18.80	-3.60	-88.95	3.69	-4.56	-89.25
	C4'	1.59	-20.09	-128.80	-2.26	-10.51	-117.04
	C5'	10.85	-13.60	-84.85	10.38	-8.63	-70.83
	C6'	6.87	-13.60	-110.30	3.52	-9.21	-101.85

Table 2 Energies of SET channel at M05-2x/6-311++G(d,p) level*

Δ $G SET g 0$ / (kJ·mol^-1)	Δ $E g SET$ / (kJ·mol^-1)	λ^g/ (kJ·mol^-1)	Δ $G SET g ≠$ / (kJ·mol^-1)	Δ $G SET w 0$ / (kJ·mol^-1)	Δ $E w SET$ / (kJ·mol^-1)	λ^w/ (kJ·mol^-1)	Δ $G SET w ≠$ (kJ·mol^-1)
547.57	568.13	20.56	3925.39	68.50	86.73	18.23	21.68

Table 2 Energies of SET channel at M05-2x/6-311++G(d,p) level*

Δ $G SET g 0$ / (kJ·mol^-1)	Δ $E g SET$ / (kJ·mol^-1)	λ^g/ (kJ·mol^-1)	Δ $G SET g ≠$ / (kJ·mol^-1)	Δ $G SET w 0$ / (kJ·mol^-1)	Δ $E w SET$ / (kJ·mol^-1)	λ^w/ (kJ·mol^-1)	Δ $G SET w ≠$ (kJ·mol^-1)
547.57	568.13	20.56	3925.39	68.50	86.73	18.23	21.68

Table 3 Rate constants(k) for more favorable channels for HAT and RAF

T/K	HAT			RAF
T/K	$k C 4' OH CVT / SCT$ / (L·mol^-1·s^-1)	$k C 3' OH CVT / SCT$ / (L·mol^-1·s^-1)	$k Total CVT / SCT$ / (L·mol^-1·s^-1)	$k C α CVT / SCT$ / (L·mol^-1·s^-1)	$k C β CVT / SCT$ / (L·mol^-1·s^-1)	$k C 4' CVT / SCT$ / (L·mol^-1·s^-1)	$k Total CVT / SCT$ / (L·mol^-1·s^-1)
298	5.45×10¹⁵	7.51×10¹²	5.46×10¹⁵	1.42×10¹³	5.05×10¹²	2.53×10¹⁴	2.72×10¹⁴
300	5.13×10¹⁵	7.16×10¹²	5.14×10¹⁵	1.35×10¹³	4.83×10¹²	2.40×10¹⁴	2.58×10¹⁴
400	5.70×10¹⁴	1.20×10¹²	5.71×10¹⁴	2.11×10¹²	8.92×10¹¹	2.87×10¹³	3.17×10¹³
500	1.61×10¹⁴	4.09×10¹¹	1.61×10¹⁴	6.72×10¹¹	3.15×10¹¹	8.06×10¹²	9.05×10¹²
600	7.63×10¹³	1.83×10¹¹	7.65×10¹³	2.80×10¹¹	1.41×10¹¹	3.46×10¹²	3.88×10¹²
700	3.08×10¹³	1.65×10¹¹	3.10×10¹³	2.59×10¹¹	1.37×10¹¹	1.90×10¹²	2.30×10¹²
800	2.42×10¹³	9.63×10¹⁰	2.43×10¹³	1.46×10¹¹	8.04×10¹⁰	1.20×10¹²	1.43×10¹²
900	1.85×10¹³	7.02×10¹⁰	1.86×10¹³	1.04×10¹¹	5.86×10¹⁰	8.43×10¹¹	1.01×10¹²

Table 3 Rate constants(k) for more favorable channels for HAT and RAF

T/K	HAT			RAF
T/K	$k C 4' OH CVT / SCT$ / (L·mol^-1·s^-1)	$k C 3' OH CVT / SCT$ / (L·mol^-1·s^-1)	$k Total CVT / SCT$ / (L·mol^-1·s^-1)	$k C α CVT / SCT$ / (L·mol^-1·s^-1)	$k C β CVT / SCT$ / (L·mol^-1·s^-1)	$k C 4' CVT / SCT$ / (L·mol^-1·s^-1)	$k Total CVT / SCT$ / (L·mol^-1·s^-1)
298	5.45×10¹⁵	7.51×10¹²	5.46×10¹⁵	1.42×10¹³	5.05×10¹²	2.53×10¹⁴	2.72×10¹⁴
300	5.13×10¹⁵	7.16×10¹²	5.14×10¹⁵	1.35×10¹³	4.83×10¹²	2.40×10¹⁴	2.58×10¹⁴
400	5.70×10¹⁴	1.20×10¹²	5.71×10¹⁴	2.11×10¹²	8.92×10¹¹	2.87×10¹³	3.17×10¹³
500	1.61×10¹⁴	4.09×10¹¹	1.61×10¹⁴	6.72×10¹¹	3.15×10¹¹	8.06×10¹²	9.05×10¹²
600	7.63×10¹³	1.83×10¹¹	7.65×10¹³	2.80×10¹¹	1.41×10¹¹	3.46×10¹²	3.88×10¹²
700	3.08×10¹³	1.65×10¹¹	3.10×10¹³	2.59×10¹¹	1.37×10¹¹	1.90×10¹²	2.30×10¹²
800	2.42×10¹³	9.63×10¹⁰	2.43×10¹³	1.46×10¹¹	8.04×10¹⁰	1.20×10¹²	1.43×10¹²
900	1.85×10¹³	7.02×10¹⁰	1.86×10¹³	1.04×10¹¹	5.86×10¹⁰	8.43×10¹¹	1.01×10¹²

Fig.6 Spin density of the stationary points for the C4'OH (A) and the C3'OH (B) channels of HAT

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