CHEMICAL ENGINEERING METHODS AND TECHNOLOGY N D EW EVELOPMENTS IN ALDEHYDES RESEARCH No part of this digital document may be reproduced, stored in a retrieval system or transmitted in any form or by any means. The publisher has taken reasonable care in the preparation of this digital document, but makes no expressed or implied warranty of any kind and assumes no responsibility for any errors or omissions. No liability is assumed for incidental or consequential damages in connection with or arising out of information contained herein. This digital document is sold with the clear understanding that the publisher is not engaged in rendering legal, medical or any other professional services. C E HEMICAL NGINEERING M T ETHODS AND ECHNOLOGY Additional books in this series can be found on Nova’s website under the Series tab. Additional E-books in this series can be found on Nova’s website under the e-book tab. CHEMICAL ENGINEERING METHODS AND TECHNOLOGY N D EW EVELOPMENTS IN ALDEHYDES RESEARCH LUCA TORRIONI AND EMILIA PESCASSEROLI EDITORS New York Copyright © 2013 by Nova Science Publishers, Inc. All rights reserved. No part of this book may be reproduced, stored in a retrieval system or transmitted in any form or by any means: electronic, electrostatic, magnetic, tape, mechanical photocopying, recording or otherwise without the written permission of the Publisher. For permission to use material from this book please contact us: Telephone 631-231-7269; Fax 631-231-8175 Web Site: http://www.novapublishers.com NOTICE TO THE READER The Publisher has taken reasonable care in the preparation of this book, but makes no expressed or implied warranty of any kind and assumes no responsibility for any errors or omissions. No liability is assumed for incidental or consequential damages in connection with or arising out of information contained in this book. The Publisher shall not be liable for any special, consequential, or exemplary damages resulting, in whole or in part, from the readers’ use of, or reliance upon, this material. Any parts of this book based on government reports are so indicated and copyright is claimed for those parts to the extent applicable to compilations of such works. Independent verification should be sought for any data, advice or recommendations contained in this book. In addition, no responsibility is assumed by the publisher for any injury and/or damage to persons or property arising from any methods, products, instructions, ideas or otherwise contained in this publication. This publication is designed to provide accurate and authoritative information with regard to the subject matter covered herein. It is sold with the clear understanding that the Publisher is not engaged in rendering legal or any other professional services. If legal or any other expert assistance is required, the services of a competent person should be sought. FROM A DECLARATION OF PARTICIPANTS JOINTLY ADOPTED BY A COMMITTEE OF THE AMERICAN BAR ASSOCIATION AND A COMMITTEE OF PUBLISHERS. Additional color graphics may be available in the e-book version of this book. Library of Congress Cataloging-in-Publication Data ISBN: (cid:28)(cid:26)(cid:27)(cid:16)(cid:20)(cid:16)(cid:25)(cid:21)(cid:23)(cid:20)(cid:26)(cid:16)(cid:19)(cid:28)(cid:20)(cid:16)(cid:20) (eBook) Published by Nova Science Publishers, Inc. † New York CONTENTS Preface vii  Chapter 1 Synthesis and Properties of Intermediates in Reactions of Aldehydes with P (III) Chlorides 1  M. B. Gazizov, R. A. Khairullin, R. F. Karimova and K. S. Gazizova  Chapter 2 Synthesis of Heterocyclic Compounds by Interaction of Aldehydes with Monoterpenoids 49  Oksana S. Mikhalchenko, Konstantin P. Volcho  and Nariman F. Salakhutdinov  Chapter 3 Update on Aliphatic Aldehydes in Lipid Foods 81  M. C. Pérez-Camino, R. B.Gómez-Coca and W. Moreda  Chapter 4 Inhibition of Microbial Biocatalysts by Biomass-Derived Aldehydes and Methods for Engineering Tolerance 101  Laura R. Jarboe and Zhanyou Chi  Chapter 5 Co-Oxidation Processes Promoted by N-Hydroxyphthalimide/Aldehyde System 121  Lucio Melone and Carlo Punta Chapter 6 Synthesis and Structure of Gossypol Condensation Bis-Product with 2-Amino-4,6-Dioxypyrimidine in Acidic Environment 139  K. Z. Tilyabaev, F. G. Kamaev, A. M. Yuldashev and B. T. Ibragimov  Index 145 PREFACE In this book, the authors present topical research in the study of aldehydes. Topics discussed in this compilation include the synthesis and properties of intermediates in reactions of aldehydes with P(III) chlorides; synthesis of heterocyclic compounds by interaction of aldehydes with monoterpenoids; update on aliphatic aldehydes in lipid foods; inhibition of microbial biocatalysts by biomass-derived aldehydes and methods for engineering tolerance; co-oxidation processes promoted by N-hydroxyphthalimide/ aldehyde systems; and the structure of gossypol condensation bis-product with 2-amino-4,6-dioxypyrimidine in acidic environment. Chapter 1 – For over a century the reaction of phosphorus trichloride 1a with aldehydes 2, which was discovered by Fossek, has been known and studied. An aqueous work-up or heating of the reaction mixture provides organic compounds with a P(IV) - C bond. All attempts had failed to determine the structure of intermediate products formed at the initial stages of this intricate reaction. Page, Kabachnik and Atherton postulated phosphite structure [(RCHClO) PCl , n = 1, 2, 3] 3 as primary intermediates, but it was thought that no n 3-n spectrometric or chemical evidence for the intermediacy of 1 could be found due to their easy addition of second aldehyde molecule and transformation into the secondary intermediate X POCHROCHRCl 4. Phosphorus (III) chlorides 1 were found to contain HCl as a 2 contaminant, even after multiple distillations. HCl can be removed from 1 by treating with tertiary amine 5 or alkyl vinyl ether (AVE). The synthesis of 3 and a secondary possible intermediate 4 using low temperatures and purified 1is reported. Purified 1 does not react with 2. Under the same conditions commercial 1 reacts with 2 extremely exothermically showing the HCl catalysis. In turn AVE or a small amount of a tertiary amine gives rise to a violent reaction of 2 with purified 1 showing base catalysis. It was found that the addition of one or two molecules of 2 to one P - Cl bond depends on the concentration of 5. When 1-5 % of 5 is used, the adducts3 drived from the addition of one molecule of 2 are formed. The intermediate 3 reverts to 1 and 2 on heating, thus the reactions are reversible. We suppose that 5 not only makes the carbonyl oxygen more reactive but also protects its electrophilic centre from the addition of a second aldehyde molecule. Ten primary intermediates 3 were synthesized and their structures were confirmed by 1H, 13C and 31P NMR. It has been shown that electron acceptor substituents at P(III) and electron donor groups in aldehyde fragment stabilise the intermediates 3. The primary intermediates 3 containing chlorine atom at P(III) directly react with trialkyl orthoformates, acetals forming the P(IV) compounds, all being stable at room temperature. At the same time, intermediates without chlorine atom at P(III) decompose into 2 and 1 and the latter reacts with the nucleophiles. The adducts 3 were viii Luca Torrioni and Emilia Pescasseroli oxidised into P(IV) derivatives by using dimethyl sulphoxide and tert-butyl hypochlorite as oxidizers. We postulated that there might be a minimal concentration of 5 when its ability to protect the electrophilic centre of the carbonyl group is weakened, even though the catalysis is still present. Indeed, when the ratio 1, 2 and 5 is 1: 1 (or 2): 0.008 then the secondary intermediates Cl POCHROCHRCl (R=Me, i-Pr, n-Pr) 4a and (CCl CH O) POCHPr-iOCHPr- 2 3 2 2 iCl 4b are formed. At -20 oC 4 are stable. At temperatures higher that -10 oC due to low nucleophilicity of P(III) 4a easily decomposes into 1-chloro (1-chloroalkoxy)alkanes 6, which are separable by distillation. The intermediates 4a (R=Me, i-Pr, n-Pr) react with chlorine to produce 6 and POCl . Secondary intermediate 4b possesses enough nucleophilicity and 3 undergo intermolecular Michaelis-Arbuzov isomerization: (CCl CH O) POCHPr-iOCHPr- 3 2 2 iCl → (CCl CH O) P(O)CHPr-iOCHPr-iCl. 3 2 2 Chapter 2 – The review covers the reactions of aldehydes with monoterpenoids leading to chiral oxygen-containing heterocyclic compounds of various structural types. Almost all these reactions are catalyzed by acids, the Lewis acids and montmorillonite clays being typically used as the catalysts. Some of the resulting compounds exhibited significant biological activity. The most complex multistage transformations are observed when performing the reactions of aldehydes with oxygen-containing para-menthane, pinane and carane monoterpenoids in the presence of clays. Due to the ability of monoterpenoids of different structural types to rearrange into carbocations with the para-menthane framework upon protonation, a number of identical heterocyclic compounds can be obtained using various starting terpenoids. Chapter 3 – This review provides information on the procedures and methodologies for the isolation, subsequent description and quantitative determination of aliphatic aldehydes, including the short- (C3-al to C10-al) and medium- (C12-al to C18-al) chain aldehydes and the long-chain ones (C22-al to C32-al). Aldehydes occur in numerous matrices, having both biological and commercial importance. Their physiological roles, the relevance of their presence and the incidence of their chain length are shown. Their relationship with other minor compounds such as alcohols and hydrocarbons is also reported. Special emphasis is put on the studies on the content and composition of the fractions containing the aldehydes in seed lipids and lipids from fruits and leaves. Also their presence in edible materials is commented. The different methodologies developed showed hexanal (C6-al) and nonanal (C9-al) as the most active compounds among the short-chain aldehydes, and hexacosanal (C26-al), octacosanal (C28-al) and dotriacontanal (C32-al) among the long-chain ones. In edible oils such as extra virgin olive oils, long-chain aliphatic aldehydes with even carbon- atom numbers from C22 to C30 are also present and can be isolated from the waxy fraction in quantities around a hundred mg kg-1 oil, being the C26 aldehyde the most abundant one in all of the studied samples. Chapter 4 – In our effort to fermentatively produce biorenewable fuels and chemicals that are economically competitive with petroleum, it is desirable to use sugars derived from lignocellulosic biomass. However, the recalcitrance of this biomass requires some sort of depolymerization treatment to release the fermentable substrates. This depolymerization can be performed by enzymes, ionic liquids, hydrolysis or pyrolysis. Each depolymerization method has its own benefits and challenges. The challenge that is described here is the fact that hydrolysis and pyrolysis both result in the production of compounds that are inhibitory to the biocatalyst, limiting utilization of these carbon- and energy-rich streams. Specifically, we consider biocatalyst inhibition by aldehydes such as furfural, 5-hydroxymethylfurfural (5-