Theoretical Studies on Water Catalysis of Two Esters Interconversion Reaction†

doi:10.7503/cjcu20140459

Abstract

Abstract:

Compounds 1 and 2 could interconverse to each other at room temperature when water was encountered. Four possible interconversion mechanisms, A, B, C and D, were put up. At B3LYP/6-311+G(d,p) level in gas phase, the optimized activation energies of TS1 and TS2 in mechanism A were all distinctively more than 120 kJ/mol. But as for mechanism D, the optimized activation energies of TS1 and TS2 were dramatically decreased. Further results showed that the solvation effects of water also reduced the activation energy. Meanwhile, the single point energy were calculated at MP2/6-311++G(2d,2p)//B3LYP/6-311+G(d,p) level. Finally the activation energies of TS1 and TS2 in mechanism D were 106.24 and 107.37 kJ/mol, respectively. Therefore, mechanism D was the most possible pathway for the interconversion between compounds 1 and 2 at room temperature. This preferred mechanism pathway was a special water-catalyzed intramolecular oxoester alcoholysis, which also was a conventional nucleophilic addition, producing a novel tetrahedral alcoholic intermediate.

Key words: Intramolecular ester exchange reaction, Water catalysis, Activation energy, Density functional theory calculation, Second-order Mϕ, ller-Plesset perturbation theory calculation

CLC Number:

O641.12

TrendMD:

JIANG Juxing, WANG Jiajun, DUAN Yanqing, LIU Ya, WANG Wenyuan, WU Shaohua. Theoretical Studies on Water Catalysis of Two Esters Interconversion Reaction^†[J]. Chem. J. Chinese Universities, 2014, 35(9): 1919.

Figures/Tables 11

References 21

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Species	Phase	ΔE/(kJ·mol^-1)	ΔG_{298 K}/(kJ·mol^-1)	ΔH_{298 K}(kJ·mol^-1)	P(%)	10³⁰ μ/C·m	10³⁰ μ_tot/C·m
1^*	Gas	0	0	0		11.34	11.34
1-a	Gas	0	0.003	0	90.1	11.34	10.61
1-b	Gas	8.48	7.04	8.23	5.3	7.27
2-a	Gas	8.28	7.38	8.24	4.6	9.64	9.64
1-a	Diethyl ether	0	0	0	85.4	11.34	10.44
1-b	Diethyl ether	5.50	5.22	5.18	10.4	7.27
2-a	Diethyl ether	5.43	7.49	5.52	4.2	14.91	14.91
1-a	Water	0	0	0	61.6	13.77	11.04
1-b	Water	4.26	1.94	3.81	28.1	9.07
2-a	Water	3.28	4.46	3.40	10.3	13.27	13.27

Species	Phase	ΔE/(kJ·mol^-1)	ΔG_{298 K}/(kJ·mol^-1)	ΔH_{298 K}(kJ·mol^-1)	P(%)	10³⁰ μ/C·m	10³⁰ μ_tot/C·m
1^*	Gas	0	0	0		11.34	11.34
1-a	Gas	0	0.003	0	90.1	11.34	10.61
1-b	Gas	8.48	7.04	8.23	5.3	7.27
2-a	Gas	8.28	7.38	8.24	4.6	9.64	9.64
1-a	Diethyl ether	0	0	0	85.4	11.34	10.44
1-b	Diethyl ether	5.50	5.22	5.18	10.4	7.27
2-a	Diethyl ether	5.43	7.49	5.52	4.2	14.91	14.91
1-a	Water	0	0	0	61.6	13.77	11.04
1-b	Water	4.26	1.94	3.81	28.1	9.07
2-a	Water	3.28	4.46	3.40	10.3	13.27	13.27

Species	Compd.	ΔH_{298 K}/ (kJ·mol^-1)	ΔG_{298 K}/ (kJ·mol^-1)	Species	Compd.	ΔH_{298 K}/ (kJ·mol^-1)	ΔG_{298 K}/ (kJ·mol^-1)	10³⁰μ/ (C·m)
Mechanism A^a	1	0	0	Mechanism D^d	1	0	0	3.67
	TS1	191.03	202.31		TS1	115.18	132.40	6.60
	Int.	49.38	61.36		Int.	33.83	43.14	14.34
	TS2	177.27	188.82		TS2	113.99	129.20	9.17
	2	8.24	7.38		2	3.20	-3.01	3.17
Mechanism B^b	1	0	0	Mechanism D	1	0	0
	TS1	132.14	152.34	in water phase^e	TS1	108.48	128.15
	Int.	30.00	45.09		Int.	32.67	43.39
	TS2	127.58	153.69		TS2	110.95	131.24
	2	5.00	7.39		2	-7.15	-18.19
Mechanism C^c	1	0	0	SPE with mechanism	1	0	0
	TS1	137.85	154.24	D in water phase^f	TS1	106.24	110.94
	Int.	33.83	43.14		Int.	19.11	21.68
	TS2	125.46	145.30		TS2	107.37	112.22
	2	3.20	-3.01		2	1.05	-1.58

Species	Compd.	ΔH_{298 K}/ (kJ·mol^-1)	ΔG_{298 K}/ (kJ·mol^-1)	Species	Compd.	ΔH_{298 K}/ (kJ·mol^-1)	ΔG_{298 K}/ (kJ·mol^-1)	10³⁰μ/ (C·m)
Mechanism A^a	1	0	0	Mechanism D^d	1	0	0	3.67
	TS1	191.03	202.31		TS1	115.18	132.40	6.60
	Int.	49.38	61.36		Int.	33.83	43.14	14.34
	TS2	177.27	188.82		TS2	113.99	129.20	9.17
	2	8.24	7.38		2	3.20	-3.01	3.17
Mechanism B^b	1	0	0	Mechanism D	1	0	0
	TS1	132.14	152.34	in water phase^e	TS1	108.48	128.15
	Int.	30.00	45.09		Int.	32.67	43.39
	TS2	127.58	153.69		TS2	110.95	131.24
	2	5.00	7.39		2	-7.15	-18.19
Mechanism C^c	1	0	0	SPE with mechanism	1	0	0
	TS1	137.85	154.24	D in water phase^f	TS1	106.24	110.94
	Int.	33.83	43.14		Int.	19.11	21.68
	TS2	125.46	145.30		TS2	107.37	112.22
	2	3.20	-3.01		2	1.05	-1.58

Mechanism	Species	O1—Hx/nm	C5—O6/nm	∠C2C3O4/(°)	∠C3C2O1/(°)
A	Compound 1	0.09636	0.12056	103.1	111.4
	TS1	0.13791	0.13076	101.1	107.9
	Difference	0.04155	0.01020	-2.0	-3.5
B	Compound 1	0.09712	0.12113	108.3	113.0
	TS1	0.12379	0.12888	100.9	105.5
	Difference	0.02667	0.00775	-7.4	-7.5
C	Compound 1	0.09733	0.12036	108.1	109.7
	TS1	0.13549	0.12883	101.9	104.2
	Difference	0.03816	0.00847	-6.2	-5.5
D	Compound 1	0.09733	0.12036	108.1	109.7
	TS1	0.12818	0.12662	102.9	103.6
	Difference	0.03085	0.00626	-5.2	-6.1