DOCSLIB.ORG

(12) United States Patent (10) Patent No.: US 6,686,494 B1 Wynne Et Al

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
(12) United States Patent (10) Patent No.: US 6,686,494 B1 Wynne Et Al US006686494B1 (12) United States Patent (10) Patent No.: US 6,686,494 B1 Wynne et al. (45) Date of Patent: Feb. 3, 2004 (54) SYNTHESIS OF S-ALKYLANDS-ARYL Hitoshi Kuniyasu, Hiroshi Hiraike, Masaki Morita, Aoi THIOCARBAMATES, ONE-POTTWO-STEP Tanaka, Kunihiko Sugoh & Hideo Kurosawa, “Palladium GENERAL SYNTHESIS Catalyzed Azathiolation of Carbon Monoxide,” J. Org. Chem., 1999, 64, 7305-7308. (75) Inventors: James W. Wynne, Alexandria, VA Achim Bohme & Hans-Joachim Gais, “Palladium(O) cata (US); Arthur W. Snow, Alexandria, VA lyzed enantioselective rearrangement of O-allylic thiocar (US) bamates to S-allylic thiocarbamates: asymmetric Synthesis (73) Assignee: The United States of America as of allylic thiols.” Tetrahedron: Asymmetry, 1999, 10, represented by the Secretary of the 2511-2514. Navy, Washington, DC (US) Josemon Jacob, Kelly A. Reynolds, William D. Jones, Stephen A. Godleski & Ronald R. Valente, “Nickel-Medi (*) Notice: Subject to any disclaimer, the term of this ated Selective Carbonylation Routes to Thiocarbamates.” patent is extended or adjusted under 35 Organometallics, 2001, 20, 1028-1031. U.S.C. 154(b) by 0 days. Robert A. Batey, Chiaki Yoshina-Ishii, Scott D. Taylor & V. Santhakumar," A New Protocal for the Formation of Car (21) Appl. No.: 10/384,928 bamates and Thiocarbamates using Carbamoyl Imidazolium Salts.” Tetrahedron Lett., 1999, 40, 2669-2672. (22) Filed: Mar. 6, 2003 T. Indrasena Reddy, B. M. Bhawal & S. Rajappa, “A Facile (51) Int. Cl." ..................... C07C 315/00; CO7C 317/00; General Method for the Preparation of S-Methyl Thiolcar C07C 229/00; CO7C 333/00 bamates using Zeolite Catalysts.” Tetrahedron Lett., 1992, (52) U.S. Cl. ....................... 558/232; 562/555; 562/556; 33, 2857-2860. 562/27; 560/12; 560/132 M. Beiji, H. Sbihi, A. Baklouti & A. Cambon, “Synthesis of (58) Field of Search ................................. 562/553,555, F-alkyl N-sulfonyl carbomates and thiocarbamates,” J. 562/556, 27; 558/232; 560/12, 132 Fluorine Chem., 1999, 99, 17–24. E. N. Zil Berman & A. Ya. Lazaris, “The Reaction of (56) References Cited Organic Thiocyanates with Water in Presence of Hydrogen U.S. PATENT DOCUMENTS Chloride,” J. Gen. Chem. USSR, 1963, 33, 1012–1014. Advanced Organic Chemistry 5th Ed., Michael B. Smith and 3,582,314 A 6/1971 Konnai et al. Jerry March, Eds., Wiley Interscience: New York, 2001, OTHER PUBLICATIONS Chapter 16. Maeda, DE-Pat. 1,817,662, Kumiai Chemical Industry Co., Primary Examiner Shailendra Kumar LTD., Chem. Abstr. 74, 12864 (1970). ASSistant Examiner Karl Puttlitz Harold Kwart & E. Robert Evans, “The Vapor Phase Rear rangement of Thioncarbonates and Thioncarbamates,” J. (74) Attorney, Agent, or Firm John J. Karasek; Rebecca Org. Chem., 1966, 31, 410–413. L. Forman Melvin S. Newman & Harold A. Karnes, “The Conversion (57) ABSTRACT of Phenols to Thiophenols via Dialkylthiocarbamates,” J. Org. Chem., 1966, 31, 3980–3984. A method for preparing S-alkyl and S-aryl thiocarbamates Melvin S. Newman & Frederick W. Hetzel, “Preparation of comprising reacting a precursor thiol reagent with trichlo Olefins by Pyrolysis of O-Alkyl Dimethylthiocarbabmates.” roacetyl chloride to produce an S-alkyl and S-aryl trichlo J. Org. Chem., 1969, 34, 3604-3606. roacetyl thioester intermediate, which is reacted with an R. E. Hackler & T. W. Balko, “The 3.3-Sigmatropic amine to yield the corresponding thiocarbamate product. Rearrangement of Allylic Dialkylthiocarbamates,” J. Org. Also disclosed is the method for preparing S-alkyl and Chem., 1973, 38, 2106-2109. S-aryl thiocarbamates comprising reacting an amine with William D. Jones, Kelly A. Reynolds, Caroline K. Sperry, trichloroacetyl chloride to produce a trichloroacetamide Rene J. Lachicotte, Stephen A. Godleski & Ronald R. intermediate, which is then reacted with the precursor thiol Valente, “Selective Carbonylation Routes to Thiocarbam to yield the corresponding thiocarbamate product. ates. An Alternative to Phosgene,” Organometallics, 2000, 19, 1661-1669. 20 Claims, No Drawings US 6,686,494 B1 1 2 SYNTHESIS OF S-ALKYLAND S-ARYL gaseous carbonyl sulfide (COS), which condenses with a THIOCARBAMATES, ONE-POTTWO-STEP Secondary amine, followed by Subsequent treatment with GENERAL SYNTHESIS base and an alkyl halide. This three-step process is limited to secondary amines. See Reddy, T, I., Bhawal, B. M.; Rajappa, S. Tetrahedron Lett. 1992, 33, 2857-2860, incor BACKGROUND OF THE INVENTION porated herein by reference. 1. Field of the Invention Condensation of a thiol with an isocyanate affords the The present invention relates to thiocarbamates and, more corresponding thiocarbamate; however, this route was only Specifically, to a Synthetic method for preparing S-alkyl and demonstrated when alkoxy and aroxySulfonyl isocyanates S-aryl thiocarbamates. were employed. See Beiji, M.; Sbihi, H.; Baklouti, A.; Cambon, A. J. Fluorine Chem. 1999, 99, 17-24, incorpo 2. Description of Related Art rated herein by reference. Moreover, the hydration of a The importance of S-alkyl and S-aryl thiocarbamate com variety of organic thiocyanates have been reported to afford pounds as herbicides, pesticides and other biological appli the desired compound in the presence of hydrogen chloride; cations has been recognized for many years. The basic 15 however, this method is limited to only N,N-unsubstituted S-alkyl and S-aryl thiocarbamate (S-alkylthiourethane) thiocarbamates. See Zilberman, E. N.; Lazaris, A.Y.J. Gen. Structure is as follows: Chem. USSR 1963, 33, 1012–1014, incorporated herein by reference. S-alkyl thiocarbamates have also been prepared O from Salts of dithiocarbamic acid, which are prepared by the addition of Secondary amines to carbon disulfide (CS). See R us Y R2 Ns N Advanced Organic Chemistry 5' Ed.; Smith, M.B.; March, J., Eds.; Wiley Interscience: New York, 2001; Chapter 16, Ye incorporated herein by reference. Despite being a novel approach, this method is limited to N,N-disubstituted thio Such compounds have been of interest due to their numerous 25 carbamates. Although there are numerous variations, there biological effects including anesthetic, fungicidal, lacks a simple comprehensive Synthetic approach for the bactericidal, pesticidal and antiviral activity. These com facile preparation of both N-substituted, N,N-disubstituted pounds are most noted for their use as commercial herbi and N,N-unsubstituted S-alkylthiocarbamates. cides and thus have received considerable attention in the literature. See Maeda, T, DE-Pat. 1817662, Kumiai Chemi SUMMARY OF THE INVENTION cal Industry Co., LTD.; Chem. Abstr. 74, 12864 (1970); and U.S. Pat. No. 3,582,314 to Konnai et al., which are incor It is the object of this invention to teach a new synthesis porated herein by reference. They have been used for control method for the preparation of S-alkylthiocarbamate and of annual grasses and broadleaf weeds and in large-scale on S-arylthiocarbamate compounds. This is a one-pot two-step crops. Such as rice, celery and lettuce. 35 general Synthesis of thiocarbamate compounds having two Earliest reports make use of phosgene as a starting routes to the same product compound depending on the material; however, this reagent is extremely toxic and haz order of reagent addition. In the preferred route, a precursor ardous to handle, especially in large quantities. Many reports thiol reagent is first reacted with trichloroacetyl chloride to illustrate the intramolecular rearrangement of various produce an isolatable S-alkyl or S-aryl trichloroacetyl derivatives to afford S-alkylthiocarbamates; however, these 40 thioester intermediate, which is then reacted with an amine rearrangements are extremely limited in Starting Substrates. to yield the corresponding thiocarbamate product. In the See Kwart, H.; Evans, E. R. J. Org. Chem. 1966, 31, alternate route, the amine is first reacted with trichloroacetyl 410-413; Newman, M. S.; Karmes, H. A. J. Org. Chem. chloride to produce an isolatable trichloroacetamide 1966, 31,3980–3984; Newman, M. S.; Hetzel, F. W. J. Org. intermediate, which is then reacted with the precursor thiol Chem. 1969, 34, 3604-3606; Hackler, R. E.; Balko, T. W. J. 45 to yield the corresponding thiocarbamate product. This new Org. Chem. 1973, 38, 2106–2109, all of which are incor method has the following features and advantages: (1) porated herein by reference. Similarly, transition metal cata Structural generality (i.e. aliphatic or aromatic thiol used in lysts containing elements Such as palladium, nickel, and combination with ammonia, a primary or a Secondary amine rhodium have also been employed to promote rearrangement whose Substituents may also be aromatic or aliphatic); (2) and product formation. See Jones, W. D.; Reynolds, K. A.; 50 facile purification; (3) high isolated yields; (4) one-pot Sperry, C. K.; Lachicotte, R. J.; Godleski, S.A.; Valente, R. two-step simplified procedures; and (5) avoidance of toxic R. Organometallics 2000, 19, 1661-1669; Kuniyasu, H.; and environmentally objectionable reagents (e.g. phosgene, Hiraike, H., Morita, M.; Tanaka, A., Sugoh, K., Kurosawa, carbon monoxide, carbonyl Sulfide, carbon disulphide). H. J. Org. Chem. 1999, 64, 7305-7308; Böhme, A.; Gais, H.-J. Tetrahedron: Asymmetry 1999, 10, 2511-2514; and 55 DETAILED DESCRIPTION OF THE Jacob, J.; Reynolds, K. A.; Jones, W. D., Godleski, S. A.; PREFERRED EMBODIMENTS Valente, R. R. Organometallics 2001, 20, 1028–1031, all of which are incorporated herein by reference. There are a A method of preparing S-alkyl and S-aryl thiocarbamates variety of other known methods;
Load more

Recommended publications
  • Environmental Properties of Chemicals Volume 2
    1 t ENVIRONMENTAL 1 PROTECTION Esa Nikunen . Riitta Leinonen Birgit Kemiläinen • Arto Kultamaa Environmental properties of chemicals Volume 2 1 O O O O O O O O OO O OOOOOO Ol OIOOO FINNISH ENVIRONMENT INSTITUTE • EDITA Esa Nikunen e Riitta Leinonen Birgit Kemiläinen • Arto Kultamaa Environmental properties of chemicals Volume 2 HELSINKI 1000 OlO 00000001 00000000000000000 Th/s is a second revfsed version of Environmental Properties of Chemica/s, published by VAPK-Pub/ishing and Ministry of Environment, Environmental Protection Department as Research Report 91, 1990. The pubiication is also available as a CD ROM version: EnviChem 2.0, a PC database runniny under Windows operating systems. ISBN 951-7-2967-2 (publisher) ISBN 952-7 1-0670-0 (co-publisher) ISSN 1238-8602 Layout: Pikseri Julkaisupalvelut Cover illustration: Jussi Hirvi Edita Ltd. Helsinki 2000 Environmental properties of chemicals Volume 2 _____ _____________________________________________________ Contents . VOLUME ONE 1 Contents of the report 2 Environmental properties of chemicals 3 Abbreviations and explanations 7 3.1 Ways of exposure 7 3.2 Exposed species 7 3.3 Fffects________________________________ 7 3.4 Length of exposure 7 3.5 Odour thresholds 8 3.6 Toxicity endpoints 9 3.7 Other abbreviations 9 4 Listofexposedspecies 10 4.1 Mammais 10 4.2 Plants 13 4.3 Birds 14 4.4 Insects 17 4.5 Fishes 1$ 4.6 Mollusca 22 4.7 Crustaceans 23 4.8 Algae 24 4.9 Others 25 5 References 27 Index 1 List of chemicals in alphabetical order - 169 Index II List of chemicals in CAS-number order
    [Show full text]
  • ||||IIIHIIIHIIII USOO5151540A United States Patent (19) 11) Patent Number: 5,151,540 Aslam Et Al
    ||||IIIHIIIHIIII USOO5151540A United States Patent (19) 11) Patent Number: 5,151,540 Aslam et al. 45) Date of Patent: Sep. 29, 1992 (54) THIO CARBAMATES AND THEIR Attorney, Agent, or Firm-Marvin Turken; Donald R. DERVATIVES Cassady 75) Inventors: Mohammad Aslam; Kenneth G. (57) ABSTRACT Davenport, both of Corpus Christi, A method is provided for preparing N-acylaminothio Tex. phenols, e.g., N-acetyl-para-aminothiophenol, or 73 Assignee: Hoechst Celanese Corporation, aminothiophenols, e.g., para-aminothiophenol, or N.S.- diacylaminothiophenols, e.g., N.S.-diacetyl-para-amino Somerville, N.J. thiophenol, by reacting any of certain sulfur-containing 21 Appl. No.: 935,461 ketones, viz., an S-(acylary) N,N-di(organo)thiocarba mate, e.g., S-(4'-acetophenyl)-N,N-dimethylthiocarba 22 Filed: Nov. 26, 1986 mate, an acylthiophenol acylate ester, e.g., 4-acetothio 51) Int. Cl. ................... C07C333/00; CO7C 211/00 phenol acetate, or a free acylthiophenol, e.g., 4-aceto 52 U.S. Cl. .................................... 558/232; 558/242; thiophenol with hydroxylamine or a hydroxylamine 558/234; 558/241; 564/428 salt, to form the oxime of the ketone, subjecting the 58 Field of Search ............... 558/242, 232, 234, 241; oxime to a Beckmann rearrangement in the presence of y 564/428 a catalyst to form an S-(N-acyl-aminoaryl) N,N-di(or gano)thiocarbamate, e.g., S-(N-acetyl-para-aminophe 56 References Cited nyl) N,N-dimethylthiocarbamate, an N,S-diacylamino U.S. PATENT DOCUMENTS thiophenol, e.g., N.S.-diacetyl-paraaminothiophenol, or 3,476,791 1 1/1969 Newman et al.
    [Show full text]
  • New CO2 Chemistry for Fine Chemical Synthesis
    New CO2 Chemistry for Fine Chemical Synthesis By Ath’enkosi Msutu Town Cape Thesis presentedof for the degree of Master of Science In the Department of Chemistry University University of Cape Town January 2011 Supervisor: Professor Roger Hunter The copyright of this thesis vests in the author. No quotation from it or information derived from it is to be published without full acknowledgementTown of the source. The thesis is to be used for private study or non- commercial research purposes only. Cape Published by the University ofof Cape Town (UCT) in terms of the non-exclusive license granted to UCT by the author. University Plagiarism Declaration 1. I know that plagiarism is wrong. Plagiarism is to use another’s work and pretend that it is one’s own. 2. I have used the Royal Society of Chemistry convention for citation and referencing. Each contribution to, and quotation in, this thesis from the work(s) of other people has been attributed, and has been cited and referenced. 3. This thesis is my own work. 4. I have not allowed, and will not allow, anyone to copy my work with the intention of passing it off as his or her own work. 5. I acknowledge that copying someone else’s work, or part of it, is wrong, and declare that this is my own work. Abstract There is a great need in the chemical industry for developing CO2 as a C1 building block as an important step towards “green chemistry”. CO2 is also attractive as a chemical feedstock because it is readily available, inexpensive, nontoxic and it can replace toxic building blocks such as phosgene and CO.
    [Show full text]
  • This Item Is the Archived Peer-Reviewed Author-Version Of
    This item is the archived peer-reviewed author-version of: Iodide-catalyzed synthesis of secondary thiocarbamates from isocyanides and thiosulfonates Reference: Mampuys Pieter, Zhu Yan-Ping, Sergeyev Sergey, Ruijter Eelco, Orru Romano V.A., Van Doorslaer Sabine, Maes Bert.- Iodide-catalyzed synthesis of secondary thiocarbamates from isocyanides and thiosulfonates Organic letters / American Chemical Society - ISSN 1523-7060 - 18:12(2016), p. 2808-2811 Full text (Publisher's DOI): http://dx.doi.org/doi:10.1021/ACS.ORGLETT.6B01023 To cite this reference: http://hdl.handle.net/10067/1339400151162165141 Institutional repository IRUA Iodide-Catalyzed Synthesis of Secondary Thiocarbamates from Isocyanides and Thiosulfonates. Pieter Mampuys,[a] Yanping Zhu,[a] Sergey Sergeyev,[a] Eelco Ruijter,*[b] Romano V. A. Orru,[b] Sabine Van Doorslaer,[c] and Bert U. W. Maes*[a] [a] Organic Synthesis, Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp (Belgium) [b] Department of Chemistry and Pharmaceutical Sciences and Amsterdam Institute for Molecules, Medicines and Systems (AIMMS), VU University Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam (The Netherlands) [c] Biophysics and Biomedical Physics (BIMEF), Department of Physics, University of Antwerp, Universiteitsplein 1, 2610 Antwerp (Belgium) Abstract: A new method for the synthesis of secondary thiocarbamates from readily available isocyanides and thiosulfonates with broad functional group tolerance is reported. The reaction proceeds under mild reaction conditions in isopropanol and is catalyzed by inexpensive sodium iodide. Thiocarbamates constitute an important class of biologically active compounds with various applications, including their use as herbicides (Thiobencarb, Orbencarb, and Molinate), pesticides, antifertility agents and antivirals.1 Secondary thiocarbamates are hitherto far less explored than the tertiary ones.
    [Show full text]
  • Enzymatic Reactions Involving the Heteroatoms from Organic Substrates
    Anais da Academia Brasileira de Ciências (2018) 90(1 Suppl. 1): 943-992 (Annals of the Brazilian Academy of Sciences) Printed version ISSN 0001-3765 / Online version ISSN 1678-2690 http://dx.doi.org/10.1590/0001-3765201820170741 www.scielo.br/aabc | www.fb.com/aabcjournal Enzymatic reactions involving the heteroatoms from organic substrates CATERINA G.C. MARQUES NETTO1,2, DAYVSON J. PALMEIRA1, PATRÍCIA B. BRONDANI3 and LEANDRO H. ANDRADE1 1Departamento de Química Fundamental, Universidade de São Paulo, Avenida Prof. Lineu Prestes, 748, 05508-000 São Paulo, SP, Brazil 2Departamento de Química, Universidade Federal de São Carlos, Rodovia Washington Luis, s/n, Km 235, 13565-905 São Carlos, SP, Brazil 3Departamento de Ciências Exatas e Educação, Universidade Federal de Santa Catarina, Rua João Pessoa, 2750, 89036-256 Blumenau, SC, Brazil Manuscript received on September 20, 2017; accepted for publication on January 1, 2018 ABSTRACT Several enzymatic reactions of heteroatom-containing compounds have been explored as unnatural substrates. Considerable advances related to the search for efficient enzymatic systems able to support a broader substrate scope with high catalytic performance are described in the literature. These reports include mainly native and mutated enzymes and whole cells biocatalysis. Herein, we describe the historical background along with the progress of biocatalyzed reactions involving the heteroatom(S, Se, B, P and Si) from hetero-organic substrates. Key words: heteroatom, biocatalysis, enzymes, biotransformation. INTRODUCTION see: Gao et al. 2015, Applegate and Berkowitz 2015, Guan et al. 2015, Wallace and Balskus 2014, Enzymes act as Nature’s machinery to obtain Anobom et al. 2014, Fesko and Gruber-Khadjawi new molecules through energetically favorable 2013, Matsuda 2013) or organometallic protocols reactions.
    [Show full text]
  • Asymmetric Synthesis of Tertiary Thiols by Lithiation of Thiocarbamates
    Asymmetric Synthesis of Tertiary Thiols by Lithiation of Thiocarbamates A thesis submitted to the University of Manchester for the degree of Doctor of Philosophy In the Faculty of Engineering and Physical Sciences 2010 Paul MacLellan School of Chemistry 2 Contents Abstract 6 Declaration and copyright statement 7 Acknowledgements 8 Abbreviations and conventions 9 Preface 13 Chapter 1: Asymmetric synthesis of tertiary thiols and thioethers 14 1.0.1 Asymmetric synthesis 15 1.0.2 Organosulfur compounds 15 1.0.3 Tertiary thiols 16 1.1 Carbon-sulfur bond formation 17 1.1.1 SN2 displacement of a leaving group 17 1.1.1.1 Sulfonate leaving groups 17 1.1.1.2 Epoxide ring opening 20 1.1.1.3 Mitsunobu reactions 22 1.1.2 Conjugate addition 28 1.2 Carbon-carbon bond formation 34 1.2.1 Electrophilic addition to α-thioenolates 34 1.2.2 Electrophilic addition to α-thioorganolithiums 36 1.2.2.1 Configurational stability in α-thioorganolithiums 37 1.2.2.2 Lithiation of thiocarbamates 41 Chapter 2: Previous work and aims of the project 45 2.1 Discovery of aryl migration in lithiated ureas 45 2.2 Application to carbamates 50 2.3 Aims of the project 52 Chapter 3: Preparation of thiocarbamate precursors 54 3.1 Approach to thiocarbamates 54 3.2 Preparation of thiol 184 55 3.3 Preparation of a series of thioacetates 57 3.4 Addition to isocyanates 59 3 3.5 Addition to carbamoyl chlorides 62 3.6 Addition to carbamoylimidazolium salts 65 3.7 Preparation of chiral benzylic thiocarbamates 67 3.8 Preparation of heteroaromatic benzylic thiocarbamates 69 3.9 Preparation
    [Show full text]
  • Development and Application of Carbonyl Sulfide-Based Donors For
    Article Cite This: Acc. Chem. Res. 2019, 52, 2723−2731 pubs.acs.org/accounts Development and Application of Carbonyl Sulfide-Based Donors for H2S Delivery Carolyn M. Levinn,† Matthew M. Cerda,† and Michael D. Pluth* Department of Chemistry and Biochemistry, Materials Science Institute, Institute of Molecular Biology, University of Oregon, Eugene, Oregon 97403, United States fi CONSPECTUS: In addition to nitric oxide and carbon monoxide, hydrogen sul de (H2S) has been recently recognized as an important biological signaling molecule with implications in a wide variety of processes, including vasodilation, cytoprotection, and neuromodulation. In parallel to the growing number of reports highlighting the biological impact of H2S, interest in ff developing H2S donors as both research tools and potential therapeutics has led to the growth of di erent H2S-releasing strategies. Many H2S investigations in model systems use direct inhalation of H2S gas or aqueous solutions of NaSH or Na2S; however, such systems do not mimic endogenous H2S production. This stark contrast drives the need to develop better sources ff of caged H2S. To address these limitations, di erent small organosulfur donor compounds have been prepared that release H2S in the presence of specific activators or triggers. Such compounds, however, often lack suitable control compounds, which limits ff the use of these compounds in probing the e ects of H2S directly. To address these needs, our group has pioneered the fi development of carbonyl sul de (COS) releasing compounds as a new class of H2S donor motifs. Inspired by a commonly used carbamate prodrug scaffold, our approach utilizes self-immolative thiocarbamates to access controlled release of COS, which is rapidly converted to H2S by the ubiquitous enzyme carbonic anhydrase (CA).
    [Show full text]
  • A Plausible Prebiotic Synthesis of Thiol-Rich Peptides: the Reaction of Aminothiols with Aminonitriles
    A plausible prebiotic synthesis of thiol-rich peptides : the reaction of aminothiols with aminonitriles Ibrahim Shalayel To cite this version: Ibrahim Shalayel. A plausible prebiotic synthesis of thiol-rich peptides : the reaction of aminoth- iols with aminonitriles. Organic chemistry. Université Grenoble Alpes, 2018. English. NNT : 2018GREAV055. tel-02131562 HAL Id: tel-02131562 https://tel.archives-ouvertes.fr/tel-02131562 Submitted on 16 May 2019 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. THÈSE Pour obtenir le grade de DOCTEUR DE LA COMMUNAUTÉ UNIVERSITÉ GRENOBLE ALPES Spécialité : Chimie organique Arrêté ministériel : 25 mai 2016 Présentée par Ibrahim SHALAYEL Thèse dirigée par Yannick VALLEE, UGA préparée au sein du Laboratoire Département de Chimie Moléculaire dans l'École Doctorale Chimie et Sciences du Vivant Synthèse prébiotique plausible de peptides riches en thiol : la réaction des aminothiols avec les aminonitriles A plausible prebiotic synthesis of thiol-rich peptides: the reaction of aminothiols with aminonitriles Thèse soutenue
    [Show full text]
  • (12) Patent Application Publication (10) Pub. No.: US 2010/0233083 A1 Dias Et Al
    US 2010O233O83A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0233083 A1 Dias et al. (43) Pub. Date: Sep. 16, 2010 (54) MICROPARTICLES COMPRISINGA merisable compound (having at least a functionality equal to CROSSLINKED POLYMER n); each Y independently is optionally present, and if present—each Y independently represents a moiety selected (75) Inventors: Aylvin Jorge Angelo Anthasius from the group of O, S and NRo:—each Ro is independently Dias, Maastricht (NL); Audrey chosen from the group of hydrogen and Substituted and Petit, Maastricht (NL) unsubstituted, aliphatic, cycloaliphatic and aromatic hydro carbon groups which groups optionally contain one or more Correspondence Address: moieties selected from the group of ester moieties, ether NIXON & VANDERHYE, PC moieties, thioester moieties, thioether moieties, carbamate 901 NORTH GLEBE ROAD, 11TH FLOOR moieties, thiocarbamate moieties, amide moieties and other ARLINGTON, VA 22203 (US) moieties comprising one or more heteroatoms, in particular one or more heteroatoms selected from S. O, P and N, each Ro (73) Assignee: DSM IPASSETS B.V., Heerlen in particular independently being chosen from the group of (NL) hydrogen and Substituted and unsubstituted alkyl groups, which alkyl groups optionally contain one or more heteroat (21) Appl. No.: 12/293,640 oms, in particular one or more heteroatoms selected from P. S. O and N: each Z is independently chosen from O and (22) PCT Filed: Mar. 21, 2007 S;—each R is independently chosen from the group of Sub stituted and unsubstituted, aliphatic, cycloaliphatic and aro (86). PCT No.: PCT/EP2007/002514 matic hydrocarbon groups which groups optionally contain S371 (c)(1), one or more moieties selected from the group of ester moi (2), (4) Date: Nov.
    [Show full text]
  • Synthesis of Porphyrin Glycoconjugates Bearing Thiourea
    Dyes and Pigments 107 (2014) 69e80 Contents lists available at ScienceDirect Dyes and Pigments journal homepage: www.elsevier.com/locate/dyepig Synthesis of porphyrin glycoconjugates bearing thiourea, thiocarbamate and carbamate connecting groups: Influence of the linker on chemical and photophysical properties Juliana C.C. Dallagnol a, Diogo R.B. Ducatti b, Sandra M.W. Barreira a, Miguel D. Noseda b, Maria Eugênia R. Duarte b, Alan Guilherme Gonçalves a,* a Departamento de Farmácia, Universidade Federal do Paraná, Av. Lothario Meissner, 3400, Jardim Botânico, Curitiba, Paraná, Brazil b Departamento de Bioquímica, Universidade Federal da Paraná, Av. Cel. Francisco H. dos Santos, 100, Jardim das Américas, Curitiba, Paraná, Brazil article info abstract Article history: In the present work, we have synthesized new porphyrin conjugates bearing thiourea, thiocarbamate Received 17 January 2014 and carbamate linkers using conventional and ultrasound-assisted methods. These molecules were Received in revised form synthesized by addition reactions using isothiocyanate derivates and amino- or hydroxyl-functionalized 19 March 2014 meso-tetra(aryl)porphyrins to give porphyrin analogs linked to glycosyl or benzyl moieties. Glyco- Accepted 21 March 2014 porphyrin derivates could be obtained with better yields than their respective benzyl analogs. Thiourea Available online 29 March 2014 and carbamate glycoporphyrins were also successfully synthesized through an ultrasound protocol with a remarkable decreasing of the reaction time. By NMR experiments we were able to evaluated the linker Keywords: Porphyrins conformations which showed a preferred Z,Z conformation for the thiourea and carbamate derivatives. In e Glycoporphyrins addition, porphyrins were evaluated in terms of their UV Vis spectra, singlet oxygen production, pho- Photostability tostability and aggregation properties.
    [Show full text]
  • Benzylic Thio and Seleno Newman–Kwart Rearrangements
    Article Cite This: J. Org. Chem. 2018, 83, 10786−10797 pubs.acs.org/joc Benzylic Thio and Seleno Newman−Kwart Rearrangements Kristina Eriksen, Anne Ulfkjær, Theis I. Sølling, and Michael Pittelkow* Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen, Denmark *S Supporting Information → → ABSTRACT: The thermally induced OBn SBn and OBn SeBn migration reactions facilitate the rearrangement of O-benzyl thio- and selenocarbamates [BnOC( X)NMe2] (X = S or Se) into their corresponding S-benzyl thio- and Se-benzyl selenocarbamates [BnXC( O)NMe2] (X = S or Se). A series of substituted O- benzyl thio- and selenocarbamates were synthesized and rearranged in good yields of 33−88%. The reaction rates are higher for substrates with electron-donating groups in the 2 or 4 position of the aromatic ring, but the rearrangement also proceeds with electron-withdrawing substituents. The rearrangement follows first- order reaction kinetics and proceeds via a tight ion pair intermediate consisting of the benzylic carbocation and the thio- or selenocarbamate moiety. Computational studies support these findings. ■ INTRODUCTION Scheme 1. Original Newman−Kwart Rearrangements (top) and the Two New Benzylic Newman−Kwart Thiols and selenols play important parts in a range of 1−6 Rearrangements Presented Here (bottom) chemistry, biochemistry, and materials applications. Their uses as ligands in inorganic chemistry and as components in − supramolecular assemblies are two central examples.7 9 The subtle interplay between the thiol/disulfide and the selenol/ diselenide through oxidation/reduction reactions is a defining − trait of the chemical properties of these functional groups.10 13 Prominently, both the thiol and selenol are parts of chiral amino acids as cysteine and selenocysteine, respectively.
    [Show full text]