DOCSLIB.ORG

Routes to Novel Azo Compounds Paul M. Iannarelli, Mchem Thesis Presented for the Degree of Doctor of Philosophy, the University

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Routes to Novel Azo Compounds Paul M. Iannarelli, Mchem Thesis Presented for the Degree of Doctor of Philosophy, the University Routes to Novel Azo Compounds Paul M. Iannarelli, MChem Thesis presented for the degree of Doctor of Philosophy, The University of Edinburgh May 2008 Declaration I declare that this thesis is my own composition, that the work which is described has been carried out by myself, unless otherwise stated, and that it has not been submitted in any previous application for a higher degree. This thesis describes the results of research carried out in the Department of Chemistry, University of Edinburgh, under the supervision of Prof. Hamish McNab. Paul Michael Iannarelli University of Edinburgh February 2008 Signed:- Date:- II Acknowledgements I would like to thank Professor Hamish McNab for his invaluable support, encouragement and advice throughout my PhD. I would also like to thank Dr Clive Foster, Dr Lilian Monahan and Mr Alan Dickinson of Fujifilm Imaging Colorants for their help and advice. My thanks also go to the technical staff at the University of Edinburgh, especially John Millar for his training on the running of NMR spectra, and Robert Smith for LC- MS training. My thanks also go to my parents who have supported me throughout my university studies. Thanks also to all those in the McNab group, past and present, who have helped. III Lecture Courses Attended Organic Research Seminars, University of Edinburgh, School of Chemistry (3 years attendance). Organic Colloquia, University of Edinburgh, School of Chemistry (3 years attendance). Royal Society of Chemistry, Perkin Division, Annual Scottish Meeting (3 years attendance). Fujifilm Imaging Colorants Colour Course, Stephen Westland (5 lectures). Postgraduate NMR Course, Dr Dusan Uhrin (5 lectures). SCI Conference, University of Glasgow, April 2005. ISRIUM International Conference, University of Edinburgh, July 2005. WestChem Organon Meeting, University of Glasgow, September 2005. RSC Symposium, University of Edinburgh, October 2005, (4 lectures). Supramolecular Chemistry Symposium, University of Edinburgh, (4 lectures). EPSRC Mass Spectrometry Summer School, University of Swansea, September 2006. Process Chemistry Course, Pfizer, Sandwich, November 2006. IV Abstract Routes to novel heterocyclic azo compounds and components of use as potential inkjet dyes were investigated. A new route to fluorenones from biphenyl acid chlorides using FVP (Flash Vacuum Pyrolysis) has been discovered. Fluorenone and 4-methylfluoren-9-one were prepared by FVP of 2-phenylbenzoyl chloride and 2-methylbiphenyl-2-carbonyl chloride respectively. Xanthen-9-one and thioxanthen-9-one were also prepared by FVP from the corresponding acid chlorides. 9-Phenanthrol could also be prepared via the FVP of biphenylacetyl choride and the application of this method to a heterocylic thiophene system afforded naphtho[1,2-b]thiophen-4-ol. Naphtho[2,1-b]thiophen-4-ol and naphtho[1,2-b]furan- 4-ol could be obtained in low yields by the FVP of (2-thiophen-3-ylphenyl)acetic acid methyl ester and (2-furan-2-ylphenyl) acetic acid methyl ester over a tungsten trioxide catalyst. Coupling of these systems with the diazonium salt of Acid Yellow 9 afforded the corresponding azo compounds. New heterocyclic dyes were also prepared from the condensation of heterocyclic hydrazines with 4,9-disulfophenanthrenequinone. Pyridine, pyridazine, phthalazine, isoquinoline and 2-quinoline disulfophenanthrene quinone metallised 2:1 nickel complexed magenta dyes were prepared. Industrial tests by standard methods revealed the pyridazine dye has a particularly impressive balance of light and ozone fastness over similar magenta dyes. The reaction of an arylnitro compound with 2-aminopyridine appeared to be an attractive and high yielding route to 2-(phenylazo)pyridine. However, application of this reaction to substituted and naphthalene systems failed. This afforded by- products due to nucleophilic substitution of groups such as methoxy and the relatively uncommon nucleophilic substitution of hydrogen with none of the required azo products obtained. Therefore it appeared that the reaction of a nitro and amine was not a robust and versatile route to heterocyclic azo compounds. An alternate route to heterocyclic azo compounds involved the use of the Mills reaction by the condensation o-anisidine, p-chloroaniline, 2-aminophenol, 3- aminophenol, naphthylamine, 8-amnioquinoline and 2-acetylamino-5-amino- benzenesulfonic acid with 2-nitrosopyridine afforded the heterocyclic azo products in moderate to high yields. The Mills reaction does appear to be the favored route to heterocyclic azo compounds. V Several factors were identified which affect the process of bisazo coupling of chromotropic acid and products obtained. Reaction at the ipso position of monoPACAs (2-phenylazochromotropic acid) leading to increased yields of the ipso substitution monoPACA by-product as opposed to the expected bisazo coupling position was a major problem. Studies indicated reactivity at the ipso position was greatly reduced by the presence of electron withdrawing groups around the phenyl ring of the monoPACA. Further study indicated reaction at the bisazo coupling position increased with the strength of the diazonium salt used in bisazo coupling. Therefore the electronic nature of the monoPACA starting material and the diazonium salt used in bisazo coupling greatly affected the products obtained. Reaction pH studies also revealed attack at the bisazo coupling position increases with pH and at lower pH (5.0 – 8.0) attack at the ipso position dominated. Reactivity of the monoPACA starting material also increased with pH. The influence of steric effects upon bisazo coupling revealed, in the cases where ortho sulfonic acid groups were present in the monoPACA, a reduction in attack at the ipso position. Hence the reaction appeared to be directed towards the required bisazo coupling position. VI Contents 1.0: Introduction Preamble 1 1.1: Inkjet Printing 1 1.2: History and Concept 2 1.3: Continuous Technology 3 1.4: Drop on Demand Technology 4 1.5: Inks Used in Inkjet Printing 5 1.6: Composition of the Ink 6 1.7: The Origin of Colour 7 1.8: The Origin of Colour in Dyes 9 1.9: UV–Vis Spectra 9 1.10: Colour Measurement 10 1.11: Dye Requirements 12 1.12: Papers 13 1.13: Structure of Dyes 14 1.14: Azo/Hydrazone Tautomerism 14 1.15: Fastness Properties of Dyes 15 1.16: Metallisation 20 1.17: Electron Deficient Azo Dyes 21 1.18: 1st Generation Dyes 22 1.19: 2nd Generation Dyes 23 1.20: Current Trends 24 1.21: Conclusions 26 2.0: Routes to Heterocyclic Phenanthrol System Dyes 27 2.1: Introduction to Acid Chloride Pyrolysis 29 2.2: FVP Route to Phenanthrol Based Dyes 38 2.3: Study of the Mechanism of Acid Chloride Pyrolysis 43 2.3.1: Radical Formation 43 2.3.2: Other Examples of Acid Chloride Pyrolysis 45 2.3.3: Comparison of Temperature Profiles 48 2.3.4: Proposed Mechanisms 50 2.4: Revised Route to 9-Phenanthrol 54 VII 2.5: Substituted Example 56 2.6: Alternate Tungsten Trioxide FVP Routes to 9-Phenanthrol 58 2.7: Heterocyclic Examples 61 2.7.1: 2-Thiophene Systems 61 2.7.2: 3-Thiophene Systems 62 2.7.3: Furan Systems 65 2.7.4: Acid Chloride Route to Furan Systems 68 2.7.5: Conclusions 68 2.8: Preparation of Phenanthrol Azo Dyes 69 2.8.1: Azo Coupling to Phenanthrol Systems 70 2.8.2: Effect of Heteroatom upon Dye Properties 71 2.9: Introduction to Hydrazine Routes to Azo Compounds 74 2.9.1: Initial Literature 74 2.9.2: Heterocyclic Systems 75 2.9.3: Conclusions 80 2.10: Routes to New Heterocyclic Quinone Dyes 81 2.11: Synthesis of New Heterocyclic Azo Compounds 86 2.12: Metallisation of Azo Compounds 88 2.13: Dye Testing 96 2.13.1: Formulation of the Generic Inks 97 2.13.2: Applications Testing 97 2.13.3: Formulation of Specific Inks 104 2.13.4: Dye Testing Conclusions 108 2.14: Conclusions 109 3.0: Novel Routes to Heterocyclic Azo Compounds 3.1: Requirements of Synthetic Dyes 110 3.2: The Mills Reaction 112 3.2.1: Heterocyclic Examples 114 3.2.2: Preparation of Azo Systems from Heterocyclic Nitroso Compounds 117 3.2.3: Heterocyclic Azo Systems from Nitroaryls Compounds 120 3.2.4: Conclusions 125 3.3: Synthesis of Azo Systems from Nitroaryl Compounds 126 3.3.1: Preparation of 2-(Phenylazo)pyridine 126 VIII 3.3.2: Preparation of Substituted Azopyridines 129 3.3.3: Reaction of Substituted Nitro compounds to Give Azo Products 130 3.3.4: Reaction at the Ortho Position to give By-products 138 3.4: Metallisation Targets 147 3.5: Conclusions: Azo Compounds from Nitroaryl Compounds 148 3.6: The Mills Reaction 150 3.6.1: Synthesis of Heterocyclic Azo Compounds under Acid Conditions 150 3.6.2: Protected Hydroxyl Systems 156 3.6.3: Application of Mills Reaction to Water Soluble Compounds 159 3.6.4: Synthesis of Heterocyclic Azo Compounds under Basic Conditions 160 3.7: Metallisation of Appropriate Dyes 163 3.8: Conclusions 167 4.0: Azo Coupling Reactions of Chromotropic Acid 169 4.1: Azo / Hydrazone Tautomerism 171 4.2: Literature Examples 172 4.3: Ipso Substitution 176 4.4: Preparation of Electron Rich and Poor 2-Monoazo Derivatives 179 4.5: Tautomeric Forms of 2-Monoazo Derivatives 181 4.6: Preparation of Bisazos 182 4.6.1: Initial Bisazo Coupling Experiments 184 4.6.2: Reactvity of p-MethoxyPACA and p-NitroPACA 190 4.6.3: Effect of MonoPACA p-Substituents on Ipso Substitution 197 4.6.4: Stability of Diazonium Salts 202 4.6.5: Initial Conclusions 203 4.7: Reactivity of Isolated MonoPACAs 204 4.8: Dilute Buffered Conditions 206 4.8.1: Reactivity of p-MethoxyPACA 206 4.8.2: Reactivity of Variety of MonoPACAs 209 4.9: Effect of pH upon Bisazo Coupling 212 4.10: Effect of NMP upon Bisazo
Load more

Recommended publications
  • Synthesis and in Vitro Antimicrobial and Anthelminthic Evaluation of Naphtholic and Phenolic Azo Dyes
    Hindawi Journal of Tropical Medicine Volume 2020, Article ID 4850492, 8 pages https://doi.org/10.1155/2020/4850492 Research Article Synthesis and In Vitro Antimicrobial and Anthelminthic Evaluation of Naphtholic and Phenolic Azo Dyes Joseph Kwasi Adu ,1 Cedric Dzidzor Kodjo Amengor ,2 Nurudeen Mohammed Ibrahim ,1 Cynthia Amaning-Danquah,3 Charles Owusu Ansah,1 Dorcas Dzifa Gbadago,1 and Joseph Sarpong-Agyapong1 1Department of Pharmaceutical Chemistry, Faculty of Pharmacy and Pharmaceutical Sciences, College of Health Sciences, Kwame Nkrumah University of Science and Technology (KNUST), Kumasi, Ghana 2Department of Pharmaceutical Chemistry, School of Pharmacy, University of Health and Allied Sciences, Ho, Ghana 3Department of Pharmacology, Faculty of Pharmacy and Pharmaceutical Sciences, College of Health Sciences, Kwame Nkrumah University of Science and Technology (KNUST), Kumasi, Ghana Correspondence should be addressed to Joseph Kwasi Adu; [email protected] Received 29 February 2020; Accepted 11 May 2020; Published 1 June 2020 Academic Editor: Sukla Biswas Copyright © 2020 Joseph Kwasi Adu et al. *is is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. *e antimicrobial activity of 2-naphtholic and phenolic azo compounds was determined against seven microbial species, Staphylococcus aureus (ATCC 25923), Streptococcus pyrogenes (clinical), and Enterococcus faecalis (ATCC 29212), Salmonella typhi (clinical), Pseudomonas aeruginosa (ATCC 27853), Escherichia coli (ATCC 251922), and Candida albicans (ATCC 10231), using the high-throughput spot culture growth inhibition assay (HT-SPOTi). *e minimum inhibitory concentrations (MIC) were determined for the active azo dyes. All the azo compounds (A1–B4) were screened for anthelmintic activity against adult Ghanaian earthworms, Hyperiodrilus spp.
    [Show full text]
  • Experiment 19: Combinatorial Synthesis of Azo Dyes
    1 Experiment 19: Combinatorial Synthesis of Azo Dyes When a new pharmaceutical is needed to treat a medical condition, modern chemists sometimes utilize a research technique known as combinatorial chemistry to find molecules that have the necessary biological activity. In combinatorial chemistry, a large number of structurally related compounds, called a library, is generated using a single common reaction. The diversity of the compounds in the library can arise from varying the substituents of the molecule, the functional groups or both. For instance, a library of esters can be generated by reacting a variety of different alcohols and carboxylic acids together. Once a library has been generated, the compounds must be screened for the desired activity. An example of a class of drugs that was explored using combinatorial methods are the benzodiazepines, which are used to treat anxiety disorders. Two approaches to combinatorial syntheses are employed. In a parallel synthesis, each compound is prepared individually, and the tests are performed separately on each compound. In a split synthesis, the library of compounds is both prepared and tested in mixtures of the compounds. In the latter case, the results of the tests are complex and usually require deconvolution, although a savings is realized in terms of time and materials. In either case, combinatorial chemistry allows the researcher to draw conclusions about the relationship between structure and function in molecules. The technique has been so successfully exploited that it is now utilized in other areas of chemistry besides pharmaceutical research, including catalysis and materials research. In this experiment, your lab section will generate a library of dye compounds using a parallel synthesis.
    [Show full text]
  • United States Patent Office 2,083,691 Method of Producing a Kama, Perg)
    Patented June 15, 1937 2,083,691 UNITED STATES PATENT OFFICE 2,083,691 METHOD OF PRODUCING A KAMA, PERG). Ot - George Lewis Cunningham, Niagara Falls, N. Y. assignor to The Mathieson Alkali Works, no, New York, N. Y., a corporation of Virginia No Drawing. Application 29, 1988 serial No. 105,103 6 Claims. (C123-184) This invention relates to the production of than about 2:1 and the proportion of benzene anhydrous sodium peroxide, Na2O. The inven being sufficient to maintain the hydrazo and azo tion provides a process for manufacturing an compounds in solution. The alcohols and alco hydrous sodium peroxide producing a product of. holates of the alcohols having not more than 4 5 high purity with good economy, with respect both carbon atoms are useful in the process of the to material costs and operating costs. - invention. The oxidation reaction may be typi The generally practiced processes for the pro fled as follows: duction of sodium peroxide all involve the use of metallic sodium and the use of rather high 10 temperatures, and consequently involve high 0. The process is made cyclic by regenerating the costs in both of these respects. The process of hydrazo benzene by reducing the azo benzene re temperaturesthis invention, unnecessary however, makes and, theinstead use ofof high re sulting from the oxidation with a sodium amal quiring metallic sodium, is applicable to the sodi gam, this reaction also producing the sodium . 5 um amalgam produced in conventional mercury alcoholate consumed in the oxidation. This re 5 cathode electrolytic cells. duction reaction may be typified as follows: Manchot & Herzog have hitherto described the production of sodium peroxide by reaction be tween oxygen and a methyl alcohol solution of 20 hydrazo benzene and sodium methylate (Anna For the complete cylic process, the reaction ma 20 len, 1901, 316, 331).
    [Show full text]
  • Synthesis of New Azo Compounds Based on N-(4- Hydroxypheneyl)Maleimide and N-(4-Methylpheneyl)Maleimide
    Molecules 2010, 15, 7498-7508; doi:10.3390/molecules15107498 OPEN ACCESS molecules ISSN 1420-3049 www.mdpi.com/journal/molecules Article Synthesis of New Azo Compounds Based on N-(4- Hydroxypheneyl)maleimide and N-(4-Methylpheneyl)maleimide Issam Ahmed Mohammed * and Asniza Mustapha School of Industrial Technology, Universiti Sains Malaysia, 11800 Penang, Malaysia Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +604-6533888; Fax: +604-6573678. Received: 1 October 2010; in revised form: 14 October 2010 / Accepted: 18 October 2010 / Published: 25 October 2010 Abstract: Maleic anhydride was reacted with p-aminophenol and p-toluidine in the presence of di-phosphorus pentoxide (P2O5) as a catalyst to produce two compounds: N-(4-hydroxy- phenyl)maleimide (I) and N-(4-methylphenyl)maleimide (II). The new azo compounds I(a-c) and II(a-c) were prepared by the reaction of I and II with three different aromatic amines, namely aniline, p-aminophenol and p-toluidine. The structures of these compounds were confirmed by CHN, FT-IR, 1H-NMR, 13C-NMR, mass spectrum and UV/Vis spectroscopy. Keywords: synthesis; azo compounds; aromatic amines; N-(4-hydroxylpheneyl)maleimide 1. Introduction Small molecules and macromolecules containing imide groups exhibit great electrical properties, good solubility in polar media, resistance to hydrolysis and high thermal stability [1-8]. Due to their excellent properties many efforts have been made to produce different compounds containing imide groups consisting of two carbonyl groups bound to nitrogen. The most common unsubstituted cyclic imides were prepared by heating dicarboxylic acids or their anhydrides with reactants including ammonia, urea, formamide lithium nitride or primary amines [9-12], but the reaction needs to be carried out at high temperatures for efficient ring closure.
    [Show full text]
  • Reduction of Nitro to Azo Compounds
    Singh, V. P. , Gates, P., & Engman, L. (2017). Nitro-, Azo- and Amino Derivatives of Ebselen: Synthesis, Structure and Cytoprotective Effects. Journal of Organic Chemistry, 82(1), 313. https://doi.org/10.1021/acs.joc.6b02418 Peer reviewed version Link to published version (if available): 10.1021/acs.joc.6b02418 Link to publication record in Explore Bristol Research PDF-document This is the accepted author manuscript (AAM). The final published version (version of record) is available online via American Chemical Society at http://doi.org/10.1021/acs.joc.6b02418. Please refer to any applicable terms of use of the publisher. University of Bristol - Explore Bristol Research General rights This document is made available in accordance with publisher policies. Please cite only the published version using the reference above. Full terms of use are available: http://www.bristol.ac.uk/red/research-policy/pure/user-guides/ebr-terms/ Nitro-, Azo- and Amino Derivatives of Ebselen: Synthesis, Structure and Cytoprotective Effects Vijay P. Singh,*,† Jia-fei Poon,† Jiajie Yan,† Xi Lu,‡ Marjam Karlsson Ott,‡ Ray J. Butcher,§ Paul J. Gates¶ and Lars Engman*,† †Department of Chemistry – BMC, Uppsala University, Box 576, SE-751 23 Uppsala, Sweden ‡Division of Applied Materials Science, Department of Engineering Sciences, Uppsala University, Sweden §Department of Chemistry, Howard University, Washington D.C. 20059, United States ¶University of Bristol, School of Chemistry, Bristol, BS8 1TS, United Kingdom Abstract: Novel azo-bis-ebselen compounds 7 were prepared by reduction of 7-nitro-2-aryl-1,2- benzisoselenazol-3(2H)-ones 3 and 6 with sodium benzenetellurolate, NaTeC6H5, and by reaction of 2-bromo-3-nitrobenzamides with Na2Se2.
    [Show full text]
  • Azo Polymerization Initiators Comprehensive Catalog
    Azo Polymerization Initiators Comprehensive Catalog FUJIFILM Wako Pure Chemical Corporation 4-1 Nihonbashi Honcho 2-Chome, Japan Chuo-Ku, Tokyo 103-0023, Japan TEL+81-3-3244-0305 FUJIFILM Wako Chemicals U.S.A. Corporation 1600 Bellwood Road Richmond, USA VA 23237, U.S.A. TEL+1-804-271-7677 FUJIFILM Wako Chemicals Europe GmbH Fuggerstrasse 12 D-41468 Neuss GERMANY Germany TEL+49-2131-311-0 Wako Chemicals (Shanghai) Co., Ltd. C1-C2, 26F, Junyao International Plaza, China 789 Zhaojiabang Road, Shanghai 200032, China TEL+86-21-6407-0511 Specialty Chemicals Web Site http://www.wako-chem.co.jp/kaseihin_en/ 180401 K2 SI 01 Introduction/What is Radical Polymerization? What is Azo Polymerization Initiator? Radical Formation Mechanism 01 INDEX 01 Introduction/What is Radical Polymerization? P1 07 Detailed Explanations 1. Azo Nitrile P11-14 What are Azo Polymerization Initiator? What are Azo Polymerization Initiator? Radical Formation Mechanism P2 2. Azo Ester P15-16 An azo polymerization initiator is a compound having an azo group (R-N=N-R’), which decomposes with heat 3. Azo Amide P17-18 Characteristics of Azo Polymerization Initiators and Comparison with Peroxides P3 02 4. Azo Imidazoline P19-20 and/or light, and forms carbon radical. The formed carbon radical is excellent in reactivity, and progresses polym- Examples of radical reactions using Azo Polymerization Initiators P4 5. Azo Amidine P21-22 erization and halogenation reactions of different types of vinyl monomers. 03 Selection Guide P5-6 6. Macro Azo Initiator P23-26 04 Decomposition
    [Show full text]
  • Aromatic Amines from Azo Dye Reduction: Status Review with Emphasis on Direct UV Spectrophotometric Detection in Textile Industry Wastewaters
    Dyes and Pigments 61 (2004) 121–139 www.elsevier.com/locate/dyepig Aromatic amines from azo dye reduction: status review with emphasis on direct UV spectrophotometric detection in textile industry wastewaters H.M. Pinheiroa, E. Touraudb,*, O. Thomasb aCentro de Engenharia Biolo´gica e Quı´mica, Instituto Superior Te´cnico, Avenida Rovisco Pais, 1049-001 Lisboa, Portugal bLaboratoire de Ge´nie de l’Environnement Industriel, Ecole des Mines d’Ale`s, 6 Avenue de Clavie`res, 30319 Ale`s Cedex, France Received 28 July 2003; received in revised form 10 October 2003; accepted 17 October 2003 Abstract The present status of origins, known hazards, release restrictions and environmental fate of aromatic amines is reviewed. The specific case of aromatic amines arising from the reduction of the azo bond of azo colorants is addressed, with emphasis on the recalcitrance of azo dyes, their demonstrated vulnerability to azo bond reduction through dif- ferent mechanisms and the lack of data on the biodegradability of the resulting amines. The evolution and present array of analysis methods for aromatic amines in water samples is reviewed, highlighting the increased sophistication and sensitivity attained, and referring a few efforts towards fast analysis methodologies. The case for the application of direct ultraviolet spectral analysis with advanced deconvolution techniques for the monitoring of aromatic amines in textile effluent treatment is presented. # 2003 Elsevier Ltd. All rights reserved. Keywords: Aromatic amines; Azo dyes; Hazards; Textile wastewater; Analysis; UV spectra 1. Origin and types of aromatic amines in the some examples of environmentally or health-rela- environment ted important amines together with their major origins and potential impact.
    [Show full text]
  • Wo 2008/056828 A2
    (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date PCT 15 May 2008 (15.05.2008) WO 2008/056828 A2 (51) International Patent Classification: (74) Agents: TAKAMATSU, Takeshi et al; Koh-Ei Patent C07D 231/38 (2006.01) Firm, Kawabe Bldg., 7-9, Shimbashi 3-chome, Minato-ku, Tokyo 1050004 (JP). (21) International Application Number: PCT/JP2007/072240 (81) Designated States (unless otherwise indicated, for every kind of national protection available): AE, AG, AL, AM, (22) International Filing Date: AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, CA, CH, 9 November 2007 (09.1 1.2007) CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, IL, (25) Filing Language: English IN, IS, KE, KG, KM, KN, KP, KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, PG, PH, PL, PT, RO, (26) Publication Language: English RS, RU, SC, SD, SE, SG, SK, SL, SM, SV, SY, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW (30) Priority Data: 2006-304998 10 November 2006 (10.11.2006) JP (84) Designated States (unless otherwise indicated, for every 2006-304999 10 November 2006 (10.11.2006) JP kind of regional protection available): ARIPO (BW, GH, 2007-211816 15 August 2007 (15.08.2007) JP GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), (71) Applicant (for all designated States except US): FUJI- European (AT,BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FILM Corporation [JP/JP]; 26-30, Nishiazabu 2-chome, FR, GB, GR, HU, IE, IS, IT, LT,LU, LV,MC, MT, NL, PL, Minato-ku, Tokyo, 1060031 (JP).
    [Show full text]
  • Synthesis, Antibacterial and Antifungal Activities of Some New Azo Anils Containing Pyrazole Moiety
    Indian Journal of Chemistry Vol. 53B, February 2014, pp 227-237 Synthesis, antibacterial and antifungal activities of some new azo anils containing pyrazole moiety S Sharma*a, Jasvir Kaurb, Sandeep Kaurb & Poonam Sharmaa aDepartment of Plant Breeding & Genetics, Punjab Agricultural University, Ludhiana 141 004, India bDepartment of Chemistry, Punjab Agricultural University, Ludhiana 141 004, India E-mail: [email protected] Received 11 February 2013; accepted (revised) 31 October 2013 A series of azo compounds namely 3-(Phenylazo) benzaldehyde 1a-f, 3-(4-Nitrophenylazo) benzaldehyde 3a-f and 3- (1,5-Dimethyl–3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl-azo) benzaldehyde 6 were synthesized and then azo anils viz. 3-(Phenylazo)-1,5 dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H pyrazol-4-yl imino methyl benzene 2a-f, 4a-f and 7-9 have been synthesized from azo compounds by reacting with corresponding amines. All the compounds synthesized by conventional method are also prepared by using microwave irradiation method and are characterized by spectroscopic techniques (UV, FTIR and 1H NMR). The synthesized compounds have been screened for antimicrobial activity against bacteria viz. Mesorhizobium sp., Bacillus sp. and Pseudomonas sp., fungus (Ascochyta blight) and yeast (Sacchromycis cerevisiae). The azo anils show minor to moderate activity against bacteria and no activity against fungus and yeast. The activity shown by some compounds is due to substitution of chloro, methoxy or nitro group on phenyl ring or due to some heterocyclic moiety. Keywords: Azo anils, azo compounds, microwave irradiation, Mesorhizobium sp., Bacillus sp., Pseudomonas sp. Azo anil formation is of major importance in and pharmaceutical chemistry with several biological biological processes as many of these involve the applications.
    [Show full text]
  • Samantha Leier
    Chemoselective bioconjugation reactions of tyrosine residues for application in PET radiochemistry by Samantha Leier A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science in Cancer Sciences Department of Oncology University of Alberta © Samantha Leier, 2018 ABSTRACT Achieving chemoselectivity while maintaining bioorthogonality are among some of the major challenges in bioconjugation chemistry. Bioconjugation chemistry has important applications in PET radiochemistry. While modern bioconjugation techniques rely predominantly on lysine and cysteine residues as targets for bioconjugation, other bioconjugation techniques that selectively target other amino acids would contribute greatly to the development of new PET radiotracers. Although only modestly prevalent and often buried within the protein structure, tyrosine represents an attractive target for bioconjugation. Tyrosine residues can be selectively targeted by both luminol derivatives and aryl diazonium salts. Luminol derivatives react via an ene-like reaction where as diazonium compounds react via electrophilic aromatic substitution to produce a stable conjugate. Recently, luminol derivatives have been reported for the introduction of fluorescent probes into proteins and diazonium salts have been reported for the introduction of radiometals into tyrosinamide-containing polymers. To the best of our knowledge, neither technique has been applied to PET radiotracer synthesis. Therefore, the aim of this project is the chemoselective introduction of radionuclides onto tyrosine residues under mild conditions. Specifically, we describe the preparation of 18F-labeled luminol derivatives as well as 64Cu- and 68Ga-labeled diazonium salts as novel building blocks for subsequent coupling with tyrosine residues under mild conditions. Luminol derivative N-(4-[18F]fluorobenzyl)-2-methyl-1,4-dioxo- 1,2,3,4-tetrahydro-phthalazine-6-carboxamide (29) was synthesized in 48% radiochemical yield.
    [Show full text]
  • Tyrosine Conjugation Methods for Protein Labelling Dimitri Alvarez Dorta, David Deniaud, Mathieu Mével, Sébastien Gouin
    Tyrosine conjugation methods for protein labelling Dimitri Alvarez Dorta, David Deniaud, Mathieu Mével, Sébastien Gouin To cite this version: Dimitri Alvarez Dorta, David Deniaud, Mathieu Mével, Sébastien Gouin. Tyrosine conjugation meth- ods for protein labelling. Chemistry - A European Journal, Wiley-VCH Verlag, 2020, Online ahead of print. 10.1002/chem.202001992. inserm-02877776 HAL Id: inserm-02877776 https://www.hal.inserm.fr/inserm-02877776 Submitted on 16 Nov 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Tyrosine-click chemistry for protein labelling Dimitri Alvarez Dorta,[a] David Deniaud,[a] Mathieu Mével,[b] Sébastien G. Gouin*[a] Dedicated to the memory of Carlos F. Barbas III [a] Title(s), Initial(s), Surname(s) of Author(s) including Corresponding Author(s) Department Institution Address 1 E-mail: [b] Title(s), Initial(s), Surname(s) of Author(s) Department Institution Address 2 Supporting information for this article is given via a link at the end of the document.((Please delete this text if not appropriate)) Abstract: Over the last two decades, the development of chemical most reactive Lys residues.11–14 Indeed, Lys reactivity is strongly biology and the need for more defined protein conjugates have affected by the neighbouring AAs with regard to their accessibility fostered active research on new bioconjugation techniques.
    [Show full text]
  • Characterising Particulate Organic Nitrogen at a Savannah-Grassland Region in South Africa
    atmosphere Article Characterising Particulate Organic Nitrogen at A Savannah-Grassland Region in South Africa Wanda Booyens 1, Pieter G. Van Zyl 1,* , Johan P. Beukes 1, Jose Ruiz-Jimenez 2, Matias Kopperi 2, Marja-Liisa Riekkola 2 , Ville Vakkari 1,3, Miroslav Josipovic 1, Markku Kulmala 4 and Lauri Laakso 1,3 1 Unit for Environmental Science and Management, North-West University, Private Bag X6001, Potchefstroom 2520, South Africa 2 Department of Chemistry, University of Helsinki, PO Box 55, 00014 Helsinki, Finland 3 Finnish Meteorological Institute, PO Box 503, 00101 Helsinki, Finland 4 Department of Physical Sciences, University of Helsinki, P.O. Box 64, 00014 Helsinki, Finland * Correspondence: [email protected]; Tel.: +27-18-299-2353 Received: 29 July 2019; Accepted: 20 August 2019; Published: 26 August 2019 Abstract: Although atmospheric organic N compounds are considered to be important, especially in new particle formation and their contribution to brown carbon, these species are not that well understood. This can be partially attributed to their chemical complexity. Therefore, the aim of this study was to assess the characteristics of organic N compounds utilising comprehensive two-dimensional gas chromatography coupled with a time-of-flight mass spectrometer (GCxGC-TOFMS) in aerosol samples that were collected at a savanna-grassland background region and to determine the possible sources. 135 atmospheric organic N compounds were tentatively characterised and semi-quantified, which included amines, nitriles, amides, urea, pyridine derivatives, amino acids, nitro-and nitroso compounds, imines, cyanates and isocyanates, and azo compounds. Amines contributed to 51% of the semi-quantified concentrations, while nitriles, pyridine derivatives, and amides comprised 20%, 11%, and 8%, respectively, of the semi-quantified concentrations.
    [Show full text]