水催化2个酯分子相互转化反应的理论研究

doi:10.7503/cjcu20140459

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (9): 1919.doi: 10.7503/cjcu20140459

水催化2个酯分子相互转化反应的理论研究

蒋举兴^1,², 王家俊^1,², 段焰青^1,², 刘亚^1,², 王文元^1,², 吴少华³

1. 云南中烟工业有限责任公司技术中心, 昆明 650202
2. 红云红河烟草(集团)有限责任公司技术中心, 昆明 650202
3. 云南大学云南省微生物研究所, 教育部微生物重点实验室, 昆明 650091

收稿日期:2014-05-14 出版日期:2014-09-10 发布日期:2019-08-01
作者简介:联系人简介: 吴少华, 女, 博士, 教授, 主要从事微生物代谢研究. E-mail: shwu123@126.com
基金资助:
国家自然科学基金(批准号: 21062027)、云南中烟基金(批准号: 2011JC08)和国家烟草专卖局基金(批准号: 110201201009 BR-03)资助

Theoretical Studies on Water Catalysis of Two Esters Interconversion Reaction^†

JIANG Juxing^1,², WANG Jiajun^1,², DUAN Yanqing^1,², LIU Ya^1,², WANG Wenyuan^1,², WU Shaohua^3,^*

1. Research and Development Center, China Tobacco Yunnan Industrial Co. Ltd.
2. Technology Center, Hongyun-Honghe Tobacco(Group) Co. Ltd., Kunming 650202, China
3. Key Laboratory for Microbial Resources of the Ministry of Education, Yunnan Institute of Microbiology,Yunnan University, Kunming 650091, China

Received:2014-05-14 Online:2014-09-10 Published:2019-08-01
Contact: WU Shaohua
Supported by:
Supported by the National Natural Science Foundation of China(No.21062027), the China Tobacco Yunnan Industrial Foundation(No.2011JC08) and State Tobacco Monopoly Administration of China(No.110201201009 BR-03)

摘要/Abstract

摘要：

从印楝植物内生真菌Phomopsis sp.培养液中分离得到的4-acetoxymultiplolide(1)和1-acetoxymultiplo-lide(2)在室温及水存在下能够相互转化. 提出二者相互转化最可能的4个途径(机理A~D). 在B3LYP/6-311+G(d,p)水平进行气相条件的优化, 结果表明, 无水催化的机理A中TS1和TS2的活化能均显著大于120 kJ/mol, 2个分子水催化的机理D中TS1和TS2的活化能则显著降低. 计算结果显示水的溶剂化效应能进一步降低机理D中TS1和TS2的活化能. 在MP2/6-311++G(2d,2p)//B3LYP/6-311+G(d,p)水平计算了单点能, 得到在水相时机理D中TS1和TS2的活化能分别为106.24和107.37 kJ/mol. 因此, 机理D是化合物1 和2在室温下及水存在时相互转化最可能的途径, 该途径是一种特殊的水催化分子内酯的醇解反应, 也是一种经典的亲核加成反应, 通过一种新的叔醇中间体实现.

关键词: 分子内酯交换反应, 水催化, 活化能, 密度泛函理论计算, 二级微扰理论计算

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

中图分类号:

O641.12

TrendMD:

蒋举兴, 王家俊, 段焰青, 刘亚, 王文元, 吴少华. 水催化2个酯分子相互转化反应的理论研究. 高等学校化学学报, 2014, 35(9): 1919.

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

图/表 11

参考文献 21

[1]	Wu S. H., Chen Y. W., Shao S. C., Wang L. D., Li Z. Y., Yang L. Y., Li S. L., Huang R., J. Nat. Prod., 2008, 71, 731—734
[2]	Umehara M., Takada Y., Nakao Y., Kimura J., Tetrahedron Lett., 2009, 50, 840—843
[3]	Frisch M.J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Mennucci B., Petersson G. A., Nakatsuji H., Caricato M., Li X., Hratchian H. P., Izmaylov A. F., Bloino J., Zheng G., Sonnenberg J. L., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Vreven T., Montgomery J. A. Jr., Peralta J. E., Ogliaro F., Bearpark M., Heyd J. J., Brothers E., Kudin K. N., Staroverov V. N., Kobayashi R., Normand J., Raghavachari K., Rendell A., Burant J. C., Iyengar S. S., Tomasi J., Cossi M., Rega N., Millam J. M., Klene M., Knox J. E., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Martin R. L., Morokuma K., Zakrzewski V. G., Voth G. A., Salvador P., Dannenberg J. J., Dapprich S., Daniels A. D., Farkas Ö., Foresman J. B., Ortiz J. V., Cioslowski J., Fox D. J., Gaussian 09, Revision A.02, Gaussian Inc., Wallingford CT, 2009
[4]	Siddiqui I. N., Zahoor A., Hussain H., Ahmed I., Ahmad V. U., Padula D., Draeger S., Schulz B., Meier K., Steinert M., J. Nat. Prod., 2011, 74, 365—373
[5]	Andres G. O., Pierini A. B., de Rossi R. H., J. Org. Chem., 2006, 71 , 7650—7656
[6]	Yang Y., J. Physical Chem. A, 2012, 116, 10150—10159
[7]	Ni Z. M., Shi W., Xia M. Y., Xue J. L., Chem. J. Chinese Universities,2013, 34(10), 2353—2362
	(倪哲明, 施炜, 夏明玉, 薛继龙. 高等学校化学学报, 2013, 34(10), 2353—2362)
[8]	Chen J., Wang M., Chem. Res. Chinese Universities,2013, 29(3), 584—588
[9]	Jin X. H., Hu B. C., Jia H. Q., Liu Z. L., Lü C. X., Chem. J. Chinese Universities,2013, 34(12), 2821—2826
	(金兴辉, 胡炳成, 贾欢庆, 刘祖亮, 吕春绪. 高等学校化学学报, 2013, 34(12), 2821—2826)
[10]	Ramirez A., Mudryk B., Rossano L., Tummala S., J. Org. Chem., 2012, 77, 775—779
[11]	Burt M. B., Fridgen T. D., J. Phys. Chem. A,2012, 117, 1283—1290
[12]	Han I. S., Kim C. K., Sohn C. K., Ma E. K., Lee H. W., Kim C. K., J. Phys.Chem. A,2011, 115, 1364—1370
[13]	Bender M. L., J. Am. Chem. Soc., 1951, 73, 1626—1629
[14]	Cox R. A., Int. J. Mol. Sci., 2011, 12, 8316—8332
[15]	Yates K., McClelland R. A., J. Am. Chem. Soc., 1967, 89, 2686—2692
[16]	Yang W., Drueckhammer D. G., Org. Lett., 2000, 2, 4133—4136
[17]	Hao J. J., Wang C. S., Acta Chimica Sinica,2009, 67(12), 1285—1290
	(郝娇娇, 王长生. 化学学报, 2009, 67(12), 1285—1290)
[18]	Jiang J. X., Li L. C., Wang M. F., Xia J. J., Wang W. Y., Xie X. G., Bull. Korean Chem. Soc., 2012, 33, 1722—1728
[19]	Roohi H., Gholipour Y., J. Quantum Chem., 2008, 108, 462—471
[20]	Kaczor A., Reva I., Fausto R., J. Phys.Chem. A,2013, 117, 888—897
[21]	Jaeqx S., Du W., Meijer E. J., Oomens J., Rijs A. M., J. Phys.Chem. A,2012, 117, 1216—1227

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

水催化2个酯分子相互转化反应的理论研究

Theoretical Studies on Water Catalysis of Two Esters Interconversion Reaction^†

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 21

相关文章 15

编辑推荐

Metrics

本文评价

[1]	赵东霞, 张海霞, 冯文娟, 杨忠志. 分子形貌所指示的羟基卡宾及其衍生物的质子转移反应[J]. 高等学校化学学报, 2021, 42(7): 2187.
[2]	蔡利海, 郭宝华, 张诚, 徐军, 黄忠耀. 以时温等效方法研究尼龙1010应力松弛行为及使用寿命预测[J]. 高等学校化学学报, 2019, 40(4): 832.
[3]	李成, 王承健, 晋万军, 韩健利, 杨梅芳, 郜茜, 黄琳娟, 王仲孚. 银杏种子糖蛋白的SDS-PAGE分离及N-糖链的质谱分析[J]. 高等学校化学学报, 2019, 40(1): 69.
[4]	匡敬忠, 原伟泉, 徐力勇, 李琳, 黄震. La(NO₃)₃和Pr(NO₃)₃对高岭石脱羟基动力学的影响[J]. 高等学校化学学报, 2015, 36(7): 1395.
[5]	刘清宇, 何圣贵. 原子团簇上一氧化碳的氧化[J]. 高等学校化学学报, 2014, 35(4): 665.
[6]	李彤, 金葆康. 离子液体中对苯醌的电化学行为[J]. 高等学校化学学报, 2014, 35(4): 847.
[7]	汤海燕, 赵茂爽, 冯莉, 曹泽星. 褐煤模型化合物中含氧官能团脱出反应的理论研究[J]. 高等学校化学学报, 2014, 35(11): 2370.
[8]	吕浩挺, 刘婷婷, 张明涛, 刘洁, 孙怀林. η⁶-[三(三甲基硅基)苯基硅烷]三羰基铬类化合物的合成及其分子内硅硅键与金属铬之间相互作用的理论研究[J]. 高等学校化学学报, 2014, 35(11): 2341.
[9]	许琼, 王睿, 张田雷, 张浩林, 王志银, 王竹青. 单个水分子对HO₂+H₂S反应主通道影响的理论研究[J]. 高等学校化学学报, 2014, 35(10): 2191.
[10]	李恒东, 苏小龙, 陈平华, 谢莉莉, 袁耀锋. 5-二茂铁基吡唑啉衍生物的合成及性质[J]. 高等学校化学学报, 2013, 34(7): 1653.
[11]	郭来辉方省众王贵宾吴忠文. 热塑性聚酰亚胺与聚醚醚酮共混物的等温结晶动力学[J]. 高等学校化学学报, 2011, 32(12): 2908.
[12]	孙颖任爱民李作盛闵春刚任雪峰封继康. 海萤荧光素类似物发光反应机理的理论研究[J]. 高等学校化学学报, 2011, 32(11): 2586.
[13]	姚同伟, 杜立波, 杨屹, 徐元超, 贾宏瑛, 刘扬. 阿魏酸丙三酯的分子内协同抗氧化作用研究[J]. 高等学校化学学报, 2009, 30(7): 1431.
[14]	张大力, 柯家骏, 卢立柱. 气固色谱中分子热运动能的作用[J]. 高等学校化学学报, 2009, 30(4): 777.
[15]	许秀芳, 尚贞锋, 李瑞芳, 赵学庄. C₅₀(D_5h)与1,3-丁二烯及2,3-二取代的1,3-丁二烯的Diels-Alder环加成反应机理的理论研究[J]. 高等学校化学学报, 2009, 30(11(1)): 16.

水催化2个酯分子相互转化反应的理论研究

Theoretical Studies on Water Catalysis of Two Esters Interconversion Reaction†

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 21

相关文章 15

编辑推荐

Metrics

本文评价

Theoretical Studies on Water Catalysis of Two Esters Interconversion Reaction^†