Safe and Fast Flow Synthesis of Functionalized Oxazoles with Molecular Oxygen in a Microstructured Reactor

被引：45

作者：

Bay, Sarah ^{[1
]}

Baumeister, Tobias ^{[2
]}

Hashmi, A. Stephen K. ^{[1
,3
]}

Roeder, Thorsten ^{[2
]}

机构：

[1] Heidelberg Univ, Inst Organ Chem, Neuenheimer Feld 270, D-69120 Heidelberg, Germany

[2] Mannheim Univ Appl Sci, Inst Chem Proc Engn, Paul Wittsack Str 10, D-68163 Mannheim, Germany

[3] King Abdulaziz Univ, Dept Chem, Fac Sci, Jeddah 21589, Saudi Arabia

来源：

ORGANIC PROCESS RESEARCH & DEVELOPMENT | 2016年 / 20卷 / 07期

关键词：

BASE-CATALYZED CYCLIZATION; GOLD CATALYSIS; N-PROPARGYLAMIDES; ATOM ECONOMY; EFFICIENT CYCLOISOMERIZATION; 2,5-DISUBSTITUTED OXAZOLES; KITPHOS MONOPHOSPHINES; SUBSTITUTED OXAZOLES; DERIVATIVES; OXIDATION;

D O I：

10.1021/acs.oprd.6b00118

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

The synthesis of hydroperoxymethyl oxazoles by oxidation of alkylideneoxazoles with molecular oxygen was implemented in a microstructured reactor for increased safety and larger-scale applications. Elaborate studies on the influence of pressure and temperature were performed, and the apparent activation energy for the oxidation reaction was determined. Elevated temperatures up to 100 degrees C and pressures up to 18 bar(a) led to a conversion rate of approximately 90% within 4 h of the reaction time, thus displaying the high potential and beneficial effect of using a microreactor setup with liquid recycle loop for this oxidation. The in situ reduction of the generated hydroperoxide functionality shows the capability of this setup for follow-up transformations.

引用

页码：1297 / 1304

页数：8

共 56 条

[1] Gold(III) iminophosphorane complexes as catalysts in C-C and C-O bond formations [J].

Aguilar, David ;

Contel, Maria ;

Navarro, Rafael ;

Soler, Tatiana ;

Urriolabeitia, Esteban P. .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2009, 694 (04) :486-493

[2] Gold/Acid-Co-catalyzed Direct Microwave-Assisted Synthesis of Fused Azaheterocycles from Propargylic Hydroperoxides [J].

Alcaide, Benito ;

Almendros, Pedro ;

Teresa Quiros, M. .

CHEMISTRY-A EUROPEAN JOURNAL, 2014, 20 (12) :3384-3393

[3] Cul-catalyzed cycloisomerization of propargyl amides [J].

Alhalib, Ali ;

Moran, Wesley J. .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2014, 12 (05) :795-800

[4]

[Anonymous], 2011, CHEM, P4595

[5] Preparation of 2,5-disubstituted oxazoles from N-propargylamides [J].

Arcadi, A ;

Cacchi, S ;

Cascia, L ;

Fabrizi, G ;

Marinelli, F .

ORGANIC LETTERS, 2001, 3 (16) :2501-2504

[6] Two-Phase Flow Oxidation of Valeraldehyde with O2 in a Microstructured Reactor [J].

Baumeister, Tobias ;

Kitzler, Hannes ;

Obermaier, Klemens ;

Zikeli, Stefan ;

Roeder, Thorsten .

ORGANIC PROCESS RESEARCH & DEVELOPMENT, 2015, 19 (11) :1576-1579

[7] Intramolecular Pd(II)-catalyzed cyclization of propargylamides: Straightforward synthesis of 5-oxazolecarbaldehydes [J].

Beccalli, Egle M. ;

Borsini, Elena ;

Broggini, Gianluigi ;

Palmisano, Giovanni ;

Sottocornola, Silvia .

JOURNAL OF ORGANIC CHEMISTRY, 2008, 73 (12) :4746-4749

[8] THE MECHANISMS OF THE REARRANGEMENTS OF ALLYLIC HYDROPEROXIDES [J].

BECKWITH, ALJ ;

DAVIES, AG ;

DAVISON, IGE ;

MACCOLL, A ;

MRUZEK, MH .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (07) :475-476

[9] The chemistry of pseudomonic acid .18. Heterocyclic replacement of the alpha,beta-unsaturated ester: Synthesis, molecular modeling, and antibacterial activity [J].

Brown, P ;

Best, DJ ;

Broom, NJP ;

Cassels, R ;

OHanlon, PJ ;

Mitchell, TJ ;

Osborne, NF ;

Wilson, JM .

JOURNAL OF MEDICINAL CHEMISTRY, 1997, 40 (16) :2563-2570

[10] TANTAZOLES - UNUSUAL CYTOTOXIC ALKALOIDS FROM THE BLUE-GREEN-ALGA SCYTONEMA-MIRABILE [J].

CARMELI, S ;

MOORE, RE ;

PATTERSON, GML ;

CORBETT, TH ;

VALERIOTE, FA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (22) :8195-8197

← 1 2 3 4 5 6 →