Controlled Autocatalytic Nitration of Phenol in a Microreactor

Ducry, Laurent; Roberge, Dominique M.

doi:10.1002/ange.200502387

Cited by 37 publications

(15 citation statements)

References 11 publications

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“…Calorimetric data were gathered for the nitration of phenol in mini batches indicating thermal runaway behavior, since even at a small scale (1 L) an increase of 55 K was seen [124]. In contrast, the hot-spot in the microreactor was only ca.…”

Section: Nitration Of Phenolmentioning

confidence: 99%

Novel Process Windows – Gate to Maximizing Process Intensification via Flow Chemistry

2009

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Driven by the economics of scale, the size of reaction vessels as the major processing apparatus of the chemical industry has became bigger and bigger [1,2]. Consequently, the efforts for ensuring mixing and heat transfer have also increased, as these are scale dependent. This has brought vessel operation to (partly severe) technical limits, especially when controlling harsh conditions, e.g., due to large heat releases. Accordingly, processing at a very large scale has resulted in taming of the chemistry involved in order to slow it down to a technically controllable level. Therefore, reaction paths that already turned out too aggressive at the laboratory scale are automatically excluded for later scale-up, which constitutes a common everyday confinement in exploiting chemical transformations. Organic chemists are barely conscious that even the small-scale laboratory protocols in their textbooks contain many slow, disciplined chemical reactions. Operations such as adding a reactant drop by drop in a large diluted solvent volume have become second nature, but are not intrinsic to the good engineering of chemical reactions. These are intrinsic to the chemical apparatus used in the past. In contrast, today's process intensification [3][4][5][6][7][8][9][10][11][12] and the new flow-chemistry reactors on the micro-and milli-scale allow such limitations to be overcome, and thus, enable a complete, ab-initio type rethinking of the processes themselves. In this way, space-time yields and the productivity of the reactor can be increased by orders of magnitude and other dramatic performance step changes can be achieved. A hand-in-hand design of the reactors and process re-thinking is required to enable chemistry rather than subduing chemistry around the reactor [40]. This often leads to making use of process conditions far from conventional practice, under harsh environments, a procedure named here as Novel Process Windows. Starting Point: Novel Process WindowsIntensify Rather than OptimizeThe aim of the following introductory remarks, and the paper as whole, is to make sensible -while everyone in the field would agree that microstructured reactors and micro-process technology [3-12] form a major direction within process intensification -that the exploitation of such innovation can still profit considerably by joining both concepts. It is frequently thought that the use of a microstructured reactor automatically and implicitly results in process intensification; simply because this is a major direction within process intensification and since the latter is also concerned with apparatus developments. This is only partly true and actually ignores significant chances for process breakthrough. In many investigations, the use of a microstructured reactor is still more concerned with process optimization, which is involves a slight to moderate improvement of processes using classical paths, in particular with the same or similar chemical and processing protocol. Often, the most radical and innovative step is the

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Section: Nitration Of Phenolmentioning

confidence: 99%

Novel Process Windows – Gate to Maximizing Process Intensification via Flow Chemistry

2009

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“…25,26, 27 In contrast, little attention has been given 70 to the nitration of phenolic compounds occurring via radical mechanisms, 28,29 because of the lower selectivity and of the difficulty to prepare large quantities of the reactant radical species. Because of the environmental interest of the photonitration processes, the present study is focused on the 75 understanding of the nitration mechanism of phenolic compounds in irradiated systems, using both quantum calculations and experimental evidence.…”

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confidence: 99%

Theoretical and experimental evidence of the photonitration pathway of phenol and 4-chlorophenol: A mechanistic study of environmental significance

Bedini

Maurino

Minero

et al. 2012

Photochem Photobiol Sci

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“…Ducry and Roberge [ 29 ] used a glass microreactor with <0.5 mm channel width and 2.0 mL internal volume for the continuous flow nitration of phenol ( Scheme 8 ). The nitration was investigated with a wide range of phenol concentrations as well as different equivalents of HNO 3 .…”

Section: Reviewmentioning

confidence: 99%

Continuous flow nitration in miniaturized devices

Kulkarni¹

2014

Beilstein J. Org. Chem.

131

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SummaryThis review highlights the state of the art in the field of continuous flow nitration with miniaturized devices. Although nitration has been one of the oldest and most important unit reactions, the advent of miniaturized devices has paved the way for new opportunities to reconsider the conventional approach for exothermic and selectivity sensitive nitration reactions. Four different approaches to flow nitration with microreactors are presented herein and discussed in view of their advantages, limitations and applicability of the information towards scale-up. Selected recent patents that disclose scale-up methodologies for continuous flow nitration are also briefly reviewed.

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Controlled Autocatalytic Nitration of Phenol in a Microreactor

Cited by 37 publications

References 11 publications

Novel Process Windows – Gate to Maximizing Process Intensification via Flow Chemistry

Novel Process Windows – Gate to Maximizing Process Intensification via Flow Chemistry

Theoretical and experimental evidence of the photonitration pathway of phenol and 4-chlorophenol: A mechanistic study of environmental significance

Continuous flow nitration in miniaturized devices

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