Addition Mechanisms of Phenol toward Formaldehyde under Acidic Condition： a Theoretical Investigation

• 作者: DU Guan-Ben LI Tao-Hong SHI Yu-Qing XIE Xiao-Guang XIONG Shan-Shan XU Wen-Feng
• 来源期刊: 结构化学
• 学科: 化学
• 关键词: 反应机制 苯酚甲醛 酸性条件 质子转移 酸性溶液 加合物 水分子 溶剂效应
• 年，卷（期）: 2012,（6）
• 页码范围: 821-828
• 页数: 8页
• 分类号: O625.4|TS255.44
• 语种: 英文

摘要

The reaction mechanisms of phenol with formaldehyde in the first and second addition at the ortho- and para-position in acid solution were theoretically investigated at the PW91/DNP level with solvent effects included. The reaction of phenol with protonated methanediol firstly forms an adduct intermediate, via a SN2 mechanism with a water molecule as the leaving group. From the adduct intermediate, there are two reaction channels involving a proton transfer to form the addition products. One is that a proton directly transfers via a four-membered ring transition state with a notable energy barrier （Four-member mechanism）. Another mechanism involving a water molecule as catalyst to mediate the proton transfer （WCP mechanism）, is a barrierless process, indicating that the formation of the adduct intermediate, the first reaction step, is rate-limiting. The reaction products are free hydroxymethyl phenols and/or hydroxybenzy carbocation （HOC6H4CH2＋） which plays an important role in the following formation of methylene and methylene ether linkages. The second addition reactions between formaldehyde and hydroxymethyl phenol at all possible reaction sites of the phenol ring in acid solution were also investigated and discussed.

作者信息

序号	姓名	单位	发文数	被引次数	H指数	G指数
1	XU Wen-Feng		1	0	0.0	0.0
2	XIONG Shan-Shan		1	0	0.0	0.0
3	SHI Yu-Qing		1	0	0.0	0.0
4	LI Tao-Hong		1	0	0.0	0.0
5	DU Guan-Ben		1	0	0.0	0.0
6	XIE Xiao-Guang		1	0	0.0	0.0