Ethylammonium Nitrate (EAN)/Tf2O and EAN/TFAA: Ionic Liquid Based Systems for Aromatic Nitration

被引：83

作者：

Aridoss, Gopalakrishnan ^{[1
]}

Laali, Kenneth K. ^{[1
]}

机构：

[1] Univ N Florida, Dept Chem, Jacksonville, FL 32224 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2011年 / 76卷 / 19期

关键词：

SOLVENT-FREE CONDITIONS; NITRIC-ACID; ORGANIC-COMPOUNDS; SILICA-GEL; ANHYDRIDE; CATALYST; REAGENT; MEDIA; SALTS; MILD;

D O I：

10.1021/jo201374a

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Acting as in situ sources of triflyl nitrate (TfONO2) and trifluoroacetyl nitrate (CF3COONO2), the EAN/Tf2O and EAN/TFAA systems, generated via metathesis in the readily available ethylammonium nitrate (EAN) ionic liquid as solvent, are powerful electrophilic nitrating reagents for a wide variety of aromatic and heteroaromatic compounds. Comparative nitration experiments indicate that EAN/Tf2O is superior to EAN/TFAA for nitration of strongly deactivated systems. Both systems exhibit low substrate selectivity (K-T/K-B = 5-10) in between values reported for covalent nitrates and preformed nitronium salts.

引用

页码：8088 / 8094

页数：7

共 53 条

[1] ELECTROPHILIC TETRAALKYLAMMONIUM NITRATE NITRATION .1. CONVENIENT NEW ANHYDROUS NITRONIUM TRIFLATE SYNTHESIS AND IN-SITU HETEROCYCLIC N-NITRATION [J].

ADAMS, CM ;

SHARTS, CM ;

SHACKELFORD, SA .

TETRAHEDRON LETTERS, 1993, 34 (42) :6669-6672

[2]

Aridoss G., 2011, EUR J ORG C IN PRESS

[3] Building Heterocyclic Systems with RC(OR)2+ Carbocations in Recyclable Bronsted Acidic Ionic Liquids: Facile Synthesis of 1-Substituted 1H-1,2,3,4-Tetrazoles, Benzazoles and Other Ring Systems with CH(OEt)3 and EtC(OEt)3 in [EtNH3][NO3] and [PMIM(SO3H)][OTf] [J].

Aridoss, Gopalakrishnan ;

Laali, Kenneth K. .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2011, 2011 (15) :2827-2835

[4] Electrophilic chemistry of propargylic alcohols in imidazolium ionic liquids: Propargylation of arenes and synthesis of propargylic ethers catalyzed by metallic triflates [Bi(OTf)3, Sc(OTf)3, Yb(OTf)3], TfOH, or B(C6F5)3 [J].

Aridoss, Gopalakrishnan ;

Sarca, Viorel D. ;

Ponder, James F., Jr. ;

Crowe, Jessica ;

Laali, Kenneth K. .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2011, 9 (07) :2518-2529

[5] A fast and mild method for the nitration of aromatic rings [J].

Bak, RR ;

Smallridge, AJ .

TETRAHEDRON LETTERS, 2001, 42 (38) :6767-6769

[6] Novel functionalized melamine-based nitroheterocycles: synthesis and activity against trypanosomatid parasites [J].

Baliani, Alessandro ;

Peal, Valerie ;

Gros, Ludovic ;

Brun, Reto ;

Kaiser, Marcel ;

Barrett, Michael P. ;

Gilbert, Ian H. .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2009, 7 (06) :1154-1166

[7]

Behnische R., 1992, METHODEN ORG CHEM ED, VE16d, P262

[8] Microwave promoted rapid nitration of phenolic compounds with calcium nitrate [J].

Bose, AK ;

Ganguly, SN ;

Manhas, MS ;

Rao, S ;

Speck, J ;

Pekelny, U ;

Pombo-Villars, E .

TETRAHEDRON LETTERS, 2006, 47 (12) :1885-1888

[9] IPSO-ATTACK AT THE 4-POSITION IN THE NITRATION OF 4-NITROPHENOL [J].

CLEMENS, AH ;

RIDD, JH ;

SANDALL, JPB .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1983, (07) :343-344

[10] FORMATION OF 4-HALO-4-NITROCYCLOHEXA-2,5-DIENONES ON NITRATION OF P-HALOPHENOLS AND P-HALOPHENYL ACETATES [J].

CLEWLEY, RG ;

CROSS, GG ;

FISCHER, A ;

HENDERSON, GN .

TETRAHEDRON, 1989, 45 (05) :1299-1310

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