RSC Advances Structure, synthesis and application of azines: A Historical Perspective Journal: RSC Advances Manuscript ID: RA-REV-05-2014-004870.R2 Article Type: Review Article Date Submitted by the Author: 04-Sep-2014 Complete List of Authors: Gandomi, Soheila; Laboratory of Organic Compound Research, Department of Organic Chemistry, College of Chemistry, University of Kashan, Safari, Javad; University of Kashan, Page 1 of 28 RSC Advances Journal Name RSC Publishing ARTICLE Structure, synthesis and application of azines: A Historical Perspective † Cite this: DOI: 10.1039/x0xx00000x Javad Safari,* Soheila Gandomi-Ravandi butadienesـdiaza-1,3ـThe present review provides a general survey of the chemistry of 2,3 Received 00th January 2012, (azines). We first briefly describe azines and then discuss the literature concerning the Accepted 00th January 2012 synthesis, properties, applications, and reactivity of these compounds. Finally, we illustrate their relevance and examine their organometallic chemistry. Such detailed survey of the broad DOI: 10.1039/x0xx00000x chemical aspects of azine derivatives seems appropriate, as it has not previously been www.rsc.org/ provided. Contents 2.2.2. Synthesis by treatment of erythro -1,2-diaryl-2-(2- tosylhydrazino)-ethan-1-ol derivatives (61) and formic acid 1. Introduction 2.2.3. Synthesis from acetamidrazone hydrochloride 2. Synthesis of azines (65) and/or S-methylthioacetamidate hydroiodide 2.1. Synthesis of symmetrical azines (71) 2.1.1. Synthesis from iodoalkylzinc iodide (19) 2.2.4. Synthesis by reaction of 2.1.2. Synthesis by reaction of 4-oxo-4,5,6,7- triisopropylsilylhydrazine (72) with aldehydes tetrahydrothianaphthene (22) with hydrazine and ketones 2.1.3. Synthesis by reaction of phenyldiazomethane 2.2.5. Synthesis by reaction of N-heterocyclic carbenes with 1-diazo-1-phenylethane with diazoalkanes 2.1.4. Synthesis by treatment of a ketone (28) and 2.2.6. Synthesis by reaction of nitro-substituted bishydrazone (27) (hetero)aromatic aldehydes with 2-methylthio-1,3- 2.1.5. Synthesis by reaction of a homoallenylaldehyde dithiolium salts (77) (30) and hydrazine monohydrate 2.2.7. Synthesis by Schiff condensation of hydrazone 2.1.6. Synthesis by thermolysis of aryl semicarbazones with 4-formyl-benzo-15-crown -5 ether (84) (32) 2.2.8. Synthesis by oxidative coupling of 3-alkyl-2- 2.1.7. Decomposition of diazo compounds catalyzed by hydrazono-4-thiazolines (85) and α-naphthol (86) platinum(0) complexes catalyzed by horseradish peroxidase (HRP) 2.1.8. Synthesis by treatment of 1-oxo-1,2,3,4- 2.2.9. Synthesis by metallation of naphthaldehyde with tetrahydrocarbazoles (38) with hydrazine hydrate butyllithium followed by reaction with ferrocene 2.1.9. Synthesis by reaction of hydrazinecarboxamide with carboxaldehyde aldehydes 2.2.10. Reaction of 2-acetylbenzofuranhydrazone (95) 2.1.10. Synthesis from glycidyl-terminated azine and with aromatic aldehydes aromatic dimercapto compounds 2.2.11. Synthesis by treatment of hydrazone in the 2.1.11. Synthesis through reaction of tetrazole with presence of sodium hydride and another carbonyl excess cyclooctyne compound 2.1.12. Synthesis by radical trifluoromethylation of vinyl 2.2.12. Synthesis from tetrahydropyran (102) azides 2.2.13. Synthesis from benzophenone hydrazone (107) 2.2. Synthesis of unsymmetrical azines and ketones or aldehydes 2.2.1. Synthesis by exchange of alkylidene group 2.2.14. Synthesis from 2-ketomethylquinolines (110) and between azines and imines † hydrazine Dedicated to the memory of Prof. R. Arshady & Prof. M. N. 2.2.15. Synthesis by reaction of aldehydes with ketone- Sarbolouki derived N-tosylhydrazones This journal is © The Royal Society of Chemistry 2013 J. Name ., 2013, 00 , 1-3 | 1 RSC Advances Page 2 of 28 ARTICLE Journal Name 3. Properties of azines 6.9. Synthesis of novel dinuclear azine-bis(alkylidene) 3.1. Delocalization complexes (246) 3.2. NLO properties 6.10. Preparation of Ag complexes of the azine- 3.3. LC properties based ligand, phenyl-2-pyridyl ketone azine (249) 3.4. Isomerization 6.11. Synthesis of novel aldazine-based 4. Applications of azines colorimetric chemosensors by complexation with Cu 2+ 4.1. Chemical applications and Fe 3+ 4.2. Biological applications 6.12. Synthesis of new tetradentate azine complexes of Re and 4.3. Physical applications Ru 5. Reactions of azines 7. Conclusions 5.1. Formation of a stilbene derivative with evolution of 8. Acknowledgment nitrogen on heating 9. Notes and references 5.2. Exchange of the =N–N= group with an azo group 5.3. Action of Grignard reagents on phenanthrenequinone benzophenone azine 1. Introduction 5.4. Oxidation of azines by lead tetraacetate The term azine has two meanings in chemistry: In 5.5. Reaction of acetone azine with p-toluenesulfonyl heterocyclic chemistry, azines are aromatic six-membered rings azide (143) containing one (pyridine) to six N atoms (hexazine). In alicyclic 5.6. Photochemical reactions of benzophenone azine chemistry, azines are compounds resulting from the reaction of 5.7. Rearrangement of the azine of salicylaldehyde two molecules of identical carbonyl compounds (symmetrical propargyl ether (154) azines 1) or, more commonly, from the reaction of two different 5.8. Reaction of ketenes and ketene precursors with azines carbonyl compounds (unsymmetrical azines 2) with hydrazine 5.9. Treatment of acyl isocyanates with azine phosphoranes (Figure 1). The compounds are called aldazines or ketazines (160) depending on whether the carbonyl compound is an aldehyde or 1 5.10. Reaction between acid chloride and azine a ketone, respectively. 5.11. Reactions of titanocene with azines 5.12. Reductive coupling of aromatic azines to 1,2-diamines H H using ZnMsOH or ZnTiCl 4 5.13. Crisscross cycloaddition of acetylene 1 R N R N derivatives with aldazines and ketazines N R N R2 5.14. Polymerizability of alkyl aldehyde azines 5.15. Reaction of aryl azine with 2- H H mercaptoethanol 5.16. Reaction of cyclohexanone azine with cyanoacetic acid 1 2 acetic anhydride Figure 1. 5.17. Intramolecular crisscross cycloaddition of diaza analogs ofـhomoallenyl azines Azines that are N-N-linked diimines are 2,3 butadiene. They are a class of compounds with interestingـCycloaddition reactions of thermally stable 1,3 .5.18 N-heterocyclic silylene (187) with acetone azine chemical properties and undergo a wide variety of chemical 5.19. Synthesis from hydrazone and synthesis of processes. 2 The two imine bonds that form the azine moiety the corresponding boron complex may be considered as polar acceptor groups oriented in 5.20. Intramolecular cycloaddition of opposite directions, as they include an N–N bond. 3 On the basis unsymmetrical homoallenyl azines of their relationship to butadiene, electronic delocalization may 5.21.Selective conversion of azines to their corresponding be expected. Two resonance structures illustrating carbonyl compounds delocalization are represented by 3 and 4 (Scheme 1). However, 5.22. Dimerization of azines crystallographic data, nuclear magnetic resonance (NMR) 6. Complexes of azine spectroscopic studies, and theoretical calculations provide little 6.1. Synthesis of two new tetrafunctional azine ligands and evidence for delocalization within the azine backbone. Thus, it study of their complexing ability was concluded that an azine bridge between two conjugated 6.2. Synthesis of complexes of cobalt(II) halides with systems, termed as a “conjugation stopper”, prevents hydrazine derivatives delocalization, as shown by the resonance structure 5 (Scheme 4 6.3. Study of the optical activity of complexes of azine by 2). replacement of the bridging acetate with ( R)-2- chloropropionate 6.4. Synthesis of bimetallic azine-bridged complexes 6.5. Synthesis of boron chelates of salicylaldehyde and 2α- D D .. .. hydroxyacetophenone azomethines N N 6.6. Preparation of nickel(II) complexes of azine N.. N.. diphosphine ligands A A 6.7. Treatment of azine ligands derived from hydrazine 3 4 and benzaldehyde derivatives bearing halogen with D = OMe, NH2, OPh A=F, Cl, Br,I, CN, NO 2 Fe 2(CO) 9 6.8. Synthesis of various types of hexacarbonyl diiron Scheme 1. complexes with five different coordination modes 2 | J. Name ., 2012, 00 , 1-3 This journal is © The Royal Society of Chemistry 2012 Page 3 of 28 RSC Advances Journal Name ARTICLE Ar D D Ar N H .. .. .. 2 O + NH2NH2 + 2 H2O N H N N H N.. N.. Ar 12 13 14 A A 3 5 Scheme 3. D = OMe, NH2, OPh A =F,Cl, Br,I,CN,NO2 Formaldehyde azine, the simplest azine, was prepared in 1959 Scheme 2. by Neureiter. 5 The rate of reaction of hydrazine with various carbonyl compounds decrease in the following order: aldehyde During the past several years, one of the active areas of > dialkyl ketone > alkaryl ketone > diaryl ketone. Reaction of organic chemistry is the study of systems containing two aldehydes and dialkyl ketones with hydrazine in water or conjugated double bonds. Within this general classification of alcoholic medium produce the hydrazone or azine. 9 Aldazines compounds, three types of molecules that have attracted the form more quickly than do ketazines. In fact, the reaction of most attention are 1,3-dienes 6, enones 7, and 1,2-diones 8 hydrazones of aldehyde with a second molecule of aldehyde is (Figure 2). 5 faster than reaction with hydrazine itself; thus, aldazine is the normal product. On the other hand, ketazines require the presence of excess ketone together with acetic or formic acid as C O O catalyst (Scheme 4). 10 C C C C C C C C O R R" RR'C N NH 2 + R'R"CO CN NC 6 7 8 15 16 R' 17 R' Figure 2. Scheme 4. In addition to the molecules mentioned above, azines 9, Azines are useful for the isolation, purification, and enimines 10a and 1 0b , and 1,2-diimines 11a and 11b constitute characterization of carbonyl compounds.