Microwave-assisted methylation of dihydroxybenzene derivatives with dimethyl carbonate

被引：20

作者：

Lui, Matthew Y. ^{[1
]}

Lokare, Kapil S. ^{[2
]}

Hemming, Ellen ^{[1
]}

Stanley, Jessica N. G. ^{[3
]}

Perosa, Alvise ^{[4
]}

Selva, Maurizio ^{[4
]}

Masters, Anthony F. ^{[1
]}

Maschmeyer, Thomas ^{[1
,5
]}

机构：

[1] Univ Sydney, Sch Chem F11, Lab Adv Catalysis Sustainabil, Sydney, NSW 2006, Australia

[2] Humboldt Univ, Inst Chem, Brook Taylor Str 2, D-12489 Berlin, Germany

[3] Univ New S Wales, Sch Chem Engn, Sydney, NSW 2052, Australia

[4] Univ Ca Foscari, Ctr Sustainable Chem Technol, Dept Mol Sci & Nanosyst, Venice, Italy

[5] Univ Sydney, Australian Inst Nanoscale Sci & Technol, Sydney, NSW 2006, Australia

来源：

RSC ADVANCES | 2016年 / 6卷 / 63期

关键词：

VAPOR-PHASE REACTIONS; SELECTIVE O-METHYLATION; CATALYTIC FAST PYROLYSIS; MG-AL HYDROTALCITES; ALKYL ARYL ETHERS; ORGANIC-SYNTHESIS; CARBOXYLIC-ACIDS; GREEN CHEMISTRY; BASE CATALYSTS; WOOD BIOMASS;

D O I：

10.1039/c6ra09841j

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Using a focused microwave reactor, methylation with dimethyl carbonate (DMC) of 1,2- and 1,4-dihydroxybenzene derivatives, found in the product spectrum of lignin depolymerisation, leads to the respective aromatic bis-methyl ethers with excellent isolated yields. Stoichiometric as well as catalytic amounts of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) are effective for the bis-methylation of these dihydroxybenzenes at relatively mild temperatures (160-190 degrees C). Conversion of resorcinol (1,3-dihydroxybenzene) under similar conditions leads to a mixture of 1,3-dimethoxybenzene and methyl 2,4-dimethoxybenzoate. The unusual reactivity of resorcinol's phenyl ring towards DMC can be explained by the synergic effect of its two strongly activating ortho/para directing groups.

引用

页码：58443 / 58451

页数：9

共 91 条

[1] Catalytic upgrading of woody biomass derived pyrolysis vapours over iron modified zeolites in a dual-fluidized bed reactor [J].

Aho, A. ;

Kumar, N. ;

Lashkul, A. V. ;

Eranen, K. ;

Ziolek, M. ;

Decyk, P. ;

Salmi, T. ;

Holmbom, B. ;

Hupa, M. ;

Murzin, D. Yu. .

FUEL, 2010, 89 (08) :1992-2000

[2] PROPERTIES OF ATOMS IN MOLECULES - ELECTROPHILIC AROMATIC-SUBSTITUTION [J].

BADER, RFW ;

CHANG, C .

JOURNAL OF PHYSICAL CHEMISTRY, 1989, 93 (08) :2946-2956

[3] O-methylation of dihydroxybenzenes with methanol in the vapour phase over alkali-loaded SiO2 catalysts:: A kinetic analysis [J].

Bal, R ;

Mayadevi, S ;

Sivasanker, S .

ORGANIC PROCESS RESEARCH & DEVELOPMENT, 2003, 7 (01) :17-21

[4] PENTAALKYLGUANIDINES AS ETHERIFICATION AND ESTERIFICATION CATALYSTS [J].

BARCELO, G ;

GRENOUILLAT, D ;

SENET, JP ;

SENNYEY, G .

TETRAHEDRON, 1990, 46 (06) :1839-1848

[5] ANALYSIS OF CHEMICAL INTERMEDIATES FROM LOW-TEMPERATURE STEAM GASIFICATION OF BIOMASS [J].

BARROWS, RD ;

ELLIOTT, DC .

FUEL, 1984, 63 (01) :4-8

[6]

Bauer K., 1975, US Pat, Patent No. [US3895076(A), 3895076]

[7] Conversion of lignin to aromatic-based chemicals (L-chems) and biofuels (L-fuels) [J].

Beauchet, R. ;

Monteil-Rivera, F. ;

Lavoie, J. M. .

BIORESOURCE TECHNOLOGY, 2012, 121 :328-334

[8] 2,1,3-Benzoxadiazole and 2,1,3-benzothiadiazole-based fluorescent compounds: Synthesis, characterization and photophysical/electrochemical properties [J].

Behramand, Behramand ;

Molin, Fernando ;

Gallardo, Hugo .

DYES AND PIGMENTS, 2012, 95 (03) :600-605

[9] Microwave-assisted methylation of phenols with DMF-DMA [J].

Belov, Pavel ;

Campanella, Veronica L. ;

Smith, Alison W. ;

Priefer, Ronny .

TETRAHEDRON LETTERS, 2011, 52 (21) :2776-2779

[10] Determination of the overlapping pKa values of resorcinol using UV-visible spectroscopy and DFT methods [J].

Blanco, SE ;

Almandoz, MC ;

Ferretti, FH .

SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, 2005, 61 (1-2) :93-102

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