Specific Enhancement of Catalytic Activity by a Dicopper Core: Selective Hydroxylation of Benzene to Phenol with Hydrogen Peroxide

被引：77

作者：

Tsuji, Tomokazu ^{[1
]}

Zaoputra, Antonius Andre ^{[1
]}

Hitomi, Yutaka ^{[1
]}

Mieda, Kaoru ^{[2
]}

Ogura, Takashi ^{[2
]}

Shiota, Yoshihito ^{[3
]}

Yoshizawa, Kazunari ^{[3
]}

Sato, Hiroyasu ^{[4
]}

Kodera, Masahito ^{[1
]}

机构：

[1] Doshisha Univ, Dept Mol Chem & Biochem, Kyoto 6100321, Japan

[2] Univ Hyogo, Dept Life Sci, Kouto 2-1, Kamigori, Hyogo 6781297, Japan

[3] Kyushu Univ, Inst Mat Chem & Engn, Fukuoka 8190395, Japan

[4] Rigaku Corp, Applicat Lab, Akishima, Tokyo 1968666, Japan

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2017年 / 56卷 / 27期

关键词：

arenes; copper; oxidation; reaction mechanisms; structure elucidation; MESOPOROUS SILICA-ALUMINA; ROOM-TEMPERATURE; MU-ETA(2)-ETA(2)-PEROXODICOPPER(II) COMPLEX; CRYSTAL-STRUCTURE; OXIDATION; REACTIVITY; BINDING; MEMBRANE; REAGENT; METHANE;

D O I：

10.1002/anie.201702291

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A dicopper(II) complex, stabilized by the bis(tpa)ligand 1,2-bis[2-[bis(2-pyridylmethyl)aminomethyl]-6-pyridyl]ethane (6-hpa), [Cu-2(mu-OH)(6-hpa)](3+), was synthesized and structurally characterized. This complex catalyzed selective hydroxylation of benzene to phenol using H2O2, thus attaining large turnover numbers (TONs) and high H2O2 efficiency. The TON after 40 hours for the phenol production exceeded 12000 in MeCN at 50 degrees C under N-2, the highest value reported for benzene hydroxylation with H2O2 catalyzed by homogeneous complexes. At 22% benzene conversion, phenol (95.2%) and p-benzoquinone (4.8%) were produced. The mechanism of H2O2 activation and benzene hydroxylation is proposed.

引用

页码：7779 / 7782

页数：4

共 50 条

[41] Catalytic hydroxylation of benzene and cyclohexane using in situ generated hydrogen peroxide: new mechanistic insights and comparison with hydrogen peroxide added directly
Remias, JE
Pavlosky, TA
Sen, A
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2003, 203 (1-2) : 179 - 192
[42] Selective oxidation of phenol with hydrogen peroxide using two types of catalytic microreactor
Yube, Kunio
Furuta, Masashi
Mae, Kazuhiro
CATALYSIS TODAY, 2007, 125 (1-2) : 56 - 63
[43] Iron Oxychloride as an Efficient Catalyst for Selective Hydroxylation of Benzene to Phenol
ElMetwally, Ahmed E.
Eshaq, Ghada
Yehia, Fatma Z.
Al-Sabagh, Ahmed M.
Kegnaes, Soren
ACS CATALYSIS, 2018, 8 (11): : 10668 - 10675
[44] Hydroxylation of phenol with hydrogen peroxide over tungstovanadophosphates with Dawson structure
Yu, JF
Yang, PP
Yang, Y
Wu, TH
Parquette, JR
CATALYSIS COMMUNICATIONS, 2006, 7 (03) : 153 - 156
[45] Hydroxylation of phenol with hydrogen peroxide over titanium silicalite catalysts
Wróblewska, A
Milchert, E
PRZEMYSL CHEMICZNY, 2002, 81 (08): : 515 - 518
[46] Copper nanoparticles as active catalysts in hydroxylation of phenol by hydrogen peroxide
Karakhanov, Edward A.
Maximov, Anton L.
Kardasheva, Yulia S.
Skorkin, Vitaliy A.
Kardashev, Sergey V.
Predeina, Viktoriya V.
Talanova, Marta Yu.
Lurie-Luke, Elena
Seeley, Jeffrey A.
Cron, Scott L.
APPLIED CATALYSIS A-GENERAL, 2010, 385 (1-2) : 62 - 72
[47] Catalytic performance in phenol hydroxylation by hydrogen peroxide over a catalyst of V-Zr-O complex
Yu, RB
Xiao, FS
Wang, D
Sun, JM
Liu, Y
Pang, GS
Feng, SH
Qiu, SL
Xu, RR
Fang, CG
CATALYSIS TODAY, 1999, 51 (01) : 39 - 46
[48] The study of complex oxide catalysts in phenol hydroxylation with hydrogen peroxide
Wu, TH
Yu, JF
Liu, QS
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1999, 217 : U371 - U371
[49] Kinetics and mechanism of catalytic hydroxylation of phenol by hydrogen peroxide .4. Modeling of the stage of dihydroxybenzene oxidation
Litvintsev, IY
Timofeev, SV
Sapunov, VN
KINETICS AND CATALYSIS, 1996, 37 (02) : 193 - 201
[50] THE EFFECTIVE HYDROXYLATION OF BENZENE BY HYDROGEN-PEROXIDE IN A HETEROPHASE SYSTEM
KARAKHANOV, EA
NARIN, SY
DEDOV, AG
CATALYSIS LETTERS, 1989, 3 (01) : 31 - 36

← 1 2 3 4 5 →