DOCSLIB.ORG

Ep 0557122 B1

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text

Load more

Patentamt Europaisches |||| ||| 1 1|| ||| ||| || || |||| || || || |||| || (19) J European Patent Office Office europeen des brevets (1 1 ) EP 0 557 122 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) int. CI.6: C07C 307/04, C07D 207/26, of the grant of the patent: C07D 207/12, C07D 501/04, 15.01.1997 Bulletin 1997/03 C07D 477/00 (21) Application number: 93301235.3 (22) Date of filing : 1 9.02.1 993 (54) A production method for sulfamide Verfahren zur Herstellung von Sulfamic! Methode de production de sulphamide (84) Designated Contracting States: • Nishino, Yutaka AT BE CH DE DK ES FR GB GR IE IT LI LU MC NL Neyagawa-shi, Osaka (JP) PTSE (74) Representative: Nash, David Allan et al (30) Priority: 21.02.1992 JP 35366/92 Haseltine Lake & Co. 08.07.1992 JP 180930/92 28 Southampton Buildings 20.08.1992 JP 221767/92 Chancery Lane London WC2A1 AT (GB) (43) Date of publication of application: 25.08.1993 Bulletin 1993/34 (56) References cited: EP-A- 0 050 927 (73) Proprietor: SHIONOGI SEIYAKU KABUSHIKI KAISHA • CHEMICAL ABSTRACTS, vol. 85, no. 5, 1976, trading under the name of Columbus, Ohio, US; abstract no. 3331 3n, SHIONOGI & CO. LTD. GRYNKIEWICZ, GRZEGORZ 'Reaction of 1,2:3,4 Osaka 541 (JP) -di-O-isopropylidene-alpha-D-galactopyrano se with dialkyl azodicarboxylate in the presence of (72) Inventors: triphenylphosphine' • Sendo, Yuji • CHEMICAL ABSTRACTS, vol. 103, no. 17, 1985, Itami-shi, Hyogo-ken (JP) Columbus, Ohio, US; abstract no. 142095d, • Kii, Makoto OSIKAWA, TATSUO. 'Dialkyl phosphonate- Amagasaki-shi, Hyogo-ken (JP) promoted reaction of alcohols with diethyl • Nishitani, Yasuhiro azodicarboxylate and triphenylphosphine: Izumi-shi, Osaka (JP) preparation of diethyl 1 -substituted-1 ,2- • Irie, Tadashi hydrazinedicarboxylate.' Suita-shi, Osaka (JP) CO CM CM LO Note: Within nine months from the publication of the mention of the grant of the European patent, give LO any person may notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in o a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. Q_ 99(1) European Patent Convention). LU Printed by Rank Xerox (UK) Business Services 2.13.13/3.4 EP 0 557 122 B1 Description 1 . Field of the Invention: 5 The present invention relates to a production method of sulfamides which are useful for producing medicaments, medicines for plants and animals, polymers and stereoisomer alcohol compounds. 2. Description of the Related Art: 10 The production of sulfamides from alcohol generally includes 4 to 5 steps: Alcohol is converted into a halogen com- pound or sulfonyl ester, the halogen or the sulfonyl ester group is substituted with an azido group to obtain an azide compound, and the azido group is reduced to an amino group. Alternatively, alcohol is converted into a halogen com- pound or sulfonyl ester, the halogen or the sulfonyl ester group is substituted with a phthalimido group, and a phthaloyl group in the phthalimido group is removed with hydrazine to obtain an amino group. The amine produced in either of 15 the above described methods is reacted with a sulfamoylating agent, thereby obtaining a sulfamide. The resultant sul- famide is deprotected, if necessary. The above-mentioned production steps are disclosed in R. Kuhn, and W. Jahn, Chem. Ber., 98, 1699(1965); W. Jahn, Chem. Ber., 98, 1705(1965); M. G. Stout et al, J. Med. Chem., 12, 658(1969); D. A. Shuman at al, J. Am. Chem. Soc, 92, 3434(1970); Richard C. Larock, 'Comprehensive Organic Transformations: A Guide to Functional Group Prep- 20 arations' VCH Publishers, Inc., New York, 1989; G. W. Muller and G. E. DuBois, J. Org. Chem., 54, 4471(1989); B. Unterhalt and G. A. Hanewacker, Arch. Pharm., 321, 375(1988); and C.-H. Lee, Bull. Korean Chem. Soc, 14, 762(1993)). This method has the following problems: the above-mentioned steps are complicated; it is necessary to introduce or remove a protecting group which is adaptable to the reaction condition in each step when the compound to be 25 reacted has a functional group which may generate a side reaction in its molecule; and the azide compound and hydra- zine, which are highly explosive and toxic, are required. SUMMARY OF THE INVENTION 30 The method for producing a sulfamide of this invention comprises the steps of: conducting a condensation reaction between an alcohol and an oxycarbonysulfamide compound in the presence of a trivalent phosphorus compound and an azodicarboxylic acid derivative, wherein the sulfamide is represented by Formula I, the alcohol is represented by Formula II, and the oxycarbonylsulfamide compound is represented by Formula III: 35 R3NHS02NR1R2 (I) wherein R1 and R2 are independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, a heterocyclic group, and alkyl substituted with the heterocyclic group, respectively, said heterocyclic group 40 being selected from the group consisting of pyranosyl, furanosyl, piperidinyl, pyrrolidinyl, an azetidinone ring, a cephem ring, a penem ring, and a carbapenem ring; R3 is selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, a heterocyclic group, alkyl substituted with the heterocyclic group, and pyrrolidinyl-methyl, said heterocyclic group being selected from the group consisting of pyranosyl, furanosyl, piperidinyl, pyrrolidinyl, an azetidinone ring, a cephem ring, a penem ring, and a carbapenem ring; 45 R3OH (II) wherein R3 is defined as above; so R4OOC-NHS02NR1R2 (III) wherein R1 and R2 are defined as above; and R4 is a carboxy protecting group; and subjecting the resulting compound (IV) to a deprotection reaction: 55 R3N(COOR4)S02NR1R2 (IV) wherein R1, R2, R3 and R4 are defined as above. According to another aspect of the present invention, there is provided a method for producing a sulfamide com- prising the step of: 2 EP 0 557 122 B1 conducting a condensation reaction between an alcohol and an oxycarbonylsulfamide compound in the pres- ence of a trivalent phosphorus compound and an azodicarboxylic acid derivative, wherein the sulfamide is represented by Formula IV, the alcohol is represented by Formula II, and the oxycarbonylsulfamide compound is represented by For- mula III: 5 R3N(COOR4)S02NR1R2 (IV) wherein R1 and R2 are independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, a heterocyclic group, and alkyl substituted with the heterocyclic group, respectively, said heterocyclic group 10 being selected from the group consisting of pyranosyl, furanosyl, piperidinyl, pyrrolidinyl, an azetidinone ring, a cephem ring, a penem ring, and a carbapenem ring; R3 is selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, a heterocyclic group, alkyl substituted with the heterocyclic group, and pyrrolidinylmethyl, said heterocyclic group being selected from the group consisting of pyranosyl, furanosyl, piperidinyl, pyrrolidinyl, an azetidinone ring, a cephem ring, a penem ring, and a carbapenem ring; and R4 is a carboxy protecting group; 15 R3OH (II) wherein R3 is defined as above; 20 R4OOC-NHS02NR1R2 (III) wherein R1, R2 and R4 are defined as above. Thus, the invention described herein makes possible the advantages of (1) providing a production method for a sul- famide comprising two steps of a condensation reaction and a deprotection reaction both of which can be conducted 25 under a mild and neutral condition, which requires 4 to 5 steps in conventional methods; (2) providing a simple method for producing sulfamides useful as materials for synthesizing physiologically active materials such as antibacterial agents, antipyretics, analgesics, sweetners, sleeping agents and anticonvulsants; and (3) providing a method for pro- ducing such sulfamides in a high yield. These and other advantages of the present invention will become apparent to those skilled in the art upon reading 30 and understanding the following detailed description. DESCRIPTION OF THE PREFERRED EMBODIMENTS The following are abbreviations used herein: Ac : acetyl Boc : t-butoxycarbonyl Bz : benzene DCM : dichloromethane EtOAc : ethyl acetate Et : ethyl Me : methyl PMB : p-methoxybenzyl PNB : p-nitrobenzyl Ph : phenyl THF : tetrahydrofuran To : toluene t-Bu : t-butyl so In the production method for sulfamides (I) according to the present invention, an alcohol (II) and an oxycarbonyl- sulfamide compound (III) are reacted in the presence of a trivalent phosphorus compound and an azodicarboxylic acid derivative. The method of the present invention is exemplified by the following scheme: 3 EP 0 557 122 B1 RlR2NS02NR3 RlR2NS02NH + HOR3 r!r2nS02NR3 COOR4 H 5 COOR4 (1) (TV) (I) 10 wherein R1 and R2 are, for example, one independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, a heterocyclic group such as pyranosyl, furanosyl, piperidinyl, pyrrolidinyl, an azetidinone ring, a cephem ring, a penem ring and a carbapenem ring, and alkyl substituted with such a heterocyclic group, respectively; R3 is, for example, one selected from the group consisting of alkyl, alkenyl, alkynyl, aralkyl, a hete- 15 rocyclic group such as pyranosyl, furanosyl, piperidinyl, pyrrolidinyl, an azetidinone ring, a cephem ring, a penem ring and a carbapenem ring, and alkyl substituted with the heterocyclic group, and R3 is preferred to be pyrrolidinylmethyl; and R4 is a carboxy protecting group. The method will now be described concretely.
Recommended publications
  • Sulfamide Chemistry Applied to the Functionalization of Self-Assembled Monolayers on Gold Surfaces

    Sulfamide Chemistry Applied to the Functionalization of Self-Assembled Monolayers on Gold Surfaces

    Sulfamide chemistry applied to the functionalization of self-assembled monolayers on gold surfaces Loïc Pantaine1, Vincent Humblot2, Vincent Coeffard*3 and Anne Vallée*1 Full Research Paper Open Access Address: Beilstein J. Org. Chem. 2017, 13, 648–658. 1Institut Lavoisier de Versailles, UMR 8180, Université Paris-Saclay, doi:10.3762/bjoc.13.64 Université de Versailles Saint-Quentin, 45 avenue des Etats-Unis, 78035 Versailles Cedex, France, 2Sorbonne Universités, UPMC Univ. Received: 23 January 2017 Paris 06, Laboratoire de Réactivité de Surface, UMR CNRS 7197, 4 Accepted: 13 March 2017 place Jussieu, 75005 Paris, France and 3Université de Nantes, Published: 04 April 2017 CNRS, CEISAM, UMR 6230, Faculté des Sciences et des Techniques, rue de la Houssinière, BP 92208, 44322 Nantes Cedex Associate Editor: P. J. Skabara 3, France © 2017 Pantaine et al.; licensee Beilstein-Institut. Email: License and terms: see end of document. Vincent Coeffard* - [email protected]; Anne Vallée* - [email protected] * Corresponding author Keywords: gold surfaces; hydrolysis; IRRAS; reversibility; SAM; sulfamide; XPS Abstract Aniline-terminated self-assembled monolayers (SAMs) on gold surfaces have successfully reacted with ArSO2NHOSO2Ar (Ar = 4-MeC6H4 or 4-FC6H4) resulting in monolayers with sulfamide moieties and different end groups. Moreover, the sulfamide groups on the SAMs can be hydrolyzed showing the partial regeneration of the aniline surface. SAMs were characterized by water contact angle (WCA) measurements, Fourier-transform infrared reflection absorption spectroscopy (IRRAS) and X-ray photoelec- tron spectroscopy (XPS). Introduction Self-assembled monolayers (SAMs) have raised considerable of reactive end groups in the monolayers enabling the chemical interest in the past decades because of their potential applica- functionalization of solid surfaces [3,5-7].
  • Risto Laitinen/August 4, 2016 International Union of Pure and Applied Chemistry Division VIII Chemical Nomenclature and Structur

    Risto Laitinen/August 4, 2016 International Union of Pure and Applied Chemistry Division VIII Chemical Nomenclature and Structur

    Approved Minutes, Busan 2015 Risto Laitinen/August 4, 2016 International Union of Pure and Applied Chemistry Division VIII Chemical Nomenclature and Structure Representation Approved Minutes of Division Committee Meeting in Busan, Korea, 8–9 August, 2015 1. Welcome, introductory remarks and housekeeping announcements Karl-Heinz Hellwich (KHH) welcomed everybody to the meeting, extending a special welcome to those who were attending the Division Committee meeting for the first time. He described house rules and arrangements during the meeting. KHH also regretfully reported that it has come to his attention that since the Bangor meeting in August 2014, Prof. Derek Horton (Member, Division VIII task groups on Carbohydrate and Flavonoids nomenclature; Associate Member, IUBMB-IUPAC Joint Commission on Biochemical Nomenclature) and Dr. Libuse Goebels, Member of the former Commission on Nomenclature of Organic Chemistry) have passed away. The meeting attendees paid a tribute to their memory by a moment of silence. 2. Attendance and apologies Present: Karl-Heinz Hellwich (president, KHH) , Risto Laitinen (acting secretary, RSL), Richard Hartshorn (past-president, RMH), Michael Beckett (MAB), Alan Hutton (ATH), Gerry P. Moss (GPM), Michelle Rogers (MMR), Jiří Vohlídal (JV), Andrey Yerin (AY) Observers: Leah McEwen (part time, chair of proposed project, LME), Elisabeth Mansfield (task group chair, EM), Johan Scheers (young observer, day 1; JS), Prof. Kazuyuki Tatsumi (past- president of the union, part of day 2) Apologies: Ture Damhus (secretary, TD), Vefa Ahsen, Kirill Degtyarenko, Gernot Eller, Mohammed Abul Hashem, Phil Hodge (PH), Todd Lowary, József Nagy, Ebbe Nordlander (EN), Amélia Pilar Rauter (APR), Hinnerk Rey (HR), John Todd, Lidija Varga-Defterdarović.
  • Sulfamides and Sulfamide Polymers Directly from Sulfur Dioxide

    Sulfamides and Sulfamide Polymers Directly from Sulfur Dioxide

    Supplementary Information Sulfamides and sulfamide polymers directly from sulfur dioxide Alexander V. Leontiev, H. V. Rasika Dias, and Dmitry M. Rudkevich* Department of Chemistry & Biochemistry, The University of Texas at Arlington, Arlington, TX 76019-0065, USA E-mail: [email protected] General X-ray analysis was performed on a Bruker Smart Apex CCD based X-ray diffractometer with the Oxford Cryosystem low temperature setup. FTIR spectra were measured on Bruker Vector 22 spectrometer in KBr. 1H 13 and C NMR spectra were recorded at 295K on JEOL 300 and 500 MHz spectrometers in CDCl3 or DMSO-d6. Chemical shifts were measured relative to residual non-deuterated solvents resonances. SO2 was purchased from AirGas, Inc. and dried prior the use by passing through P2O5. MS analyses were performed on an Agilent ESI- TOF spectrometer. CHN and Cl elemental analyses were done at QTI, Inc. Melting points were measured on a Mel-Temp II apparatus and are uncorrected. S1 O O S SO2 NH2 NH NH I2, Py(Et3N) RR MeCN R 3 1 R = H, Me, Cl, Br, OMe, NO2, CN, CF3 SO2 O H2 N NH2 N N S H H n I2, Py(Et3N) O Me CN 4 2 General procedure for preparation of sulfamides 1a-o: SO2 gas was bubbled through the ice-cold MeCN solution (5 mL) of Py or Et3N (3 mmol) for 10 min. I2 (1 mmol) was then added, and after it dissolved, arylamines 3a-o (1 mmol) were added. The reaction mixture was stirred for 2 h at rt and then poured into 10% aq NaOH (20 mL).
  • Synthesis and Nucleic-Acid-Binding Properties of Sulfamide and 3'-N-Sulfamate-Modified

    Synthesis and Nucleic-Acid-Binding Properties of Sulfamide and 3'-N-Sulfamate-Modified

    View Article Online / Journal Homepage / Table of Contents for this issue PERKIN Synthesis and nucleic-acid-binding properties of sulfamide- and 3Ј-N-sulfamate-modified DNA† Kevin J. Fettes,a,b Nigel Howard,b David T. Hickman,a,b Steven Adah,c Mark R. Player,c Paul F. Torrence d and Jason Micklefield*a a Department of Chemistry, University of Manchester Institute of Science and Technology, 1 Faraday Building, PO Box 88, Manchester, UK M60 1QD b Department of Chemistry, Birkbeck College, University of London, 29 Gordon Square, London, UK WC1H 0PP c Laboratory of Medicinal Chemistry, NIDDK, NIH Bethesda, MD, 20892-0805, USA d Department of Chemistry, Northern Arizona University, Flagstaff, AZ, 86011-5698, USA Received (in Cambridge, UK) 19th November 2001, Accepted 13th December 2001 First published as an Advance Article on the web 29th January 2002 A novel synthetic route for the preparation of sulfamide- and 3Ј-N-sulfamate-modified dinucleosides has been developed. The synthesis utilises 4-nitrophenyl chlorosulfate to prepare 4-nitrophenyl 3Ј- or 5Ј-sulfamates (e.g., 18 and 27), which couple smoothly with the alcohol or amine functionalities of other nucleosides. The conformational properties of the sulfamide- and 3Ј-N-sulfamate-modified dinucleosides d(TnsnT) and d(TnsoT) were compared with the native dinucleotide d(TpT) using NMR and CD spectroscopy. Whilst both modifications result in a shift in the conformational equilibrium of the 5Ј-terminal ribose rings from C2Ј-endo to a preferred C3Ј-endo conformation, only the 3Ј-N-sulfamate-modified dimer exhibits an increased propensity to adopt a base-stacked helical conformation.
  • Dulaneyspr15.Pdf (409.1Kb)

    Dulaneyspr15.Pdf (409.1Kb)

    Adventures in Organophosphorus Chemistry James W. Dulaney, III (Faculty Mentor: David E. Lewis) Department of Chemistry, University of Wisconsin-Eau Claire, Eau Claire, WI 54702-4004 Background Challenges with the Mitsunobu reaction What is required in a replacement to make the reaction Azodicarboxylates, an important component of the re- “green”? Organophosphorus compounds have been an increasingly important part of organic synthesis since the discovery action, are very hazardous: of the Arbuzov rearrangement in 1905. In the century that followed this discovery, the applications of phosphorus- O Green? based reagents in synthesis has grown to incorporate the Wittig and Horner-Wadsworth-Emmons reactions for OEt • They are highly explosive (especially diethyl azodi- N alkene formation, as well as the Mitsunobu inversion reaction, which is used to convert alcohols to a wide range carboxylate). N Green reactions are run under more environmentally sustainable conditions with a view to of products with inversion of configuration. O minimizing environmental impact: • They are highly toxic (especially diethyl azodicar- OEt boxylate). diethyl azodicarboxylate • They are highly regulated. (DEAD) • Wherever possible, renewable sources are used • Wherever possible, hazardous materials are eliminated completely or replaced by The Wittig reaction Ph Ph Ph BuLi Ph less hazardous materials P R P R Regulations have been put into place by the DOT that O Ph Ph O-i-Pr • Wherever possibler, catalytic reactions are used Reaction between an ylide and an aldehyde or ketone to give an alkene. make azodicarboxylic esters even more difficult to ob- N • Hazardous waste is minimized wherever possible (e.g. organic solvents can be re- Reaction gives mainly the Z isomer with aldehydes O tain and use.
  • Working with Hazardous Chemicals

    Working with Hazardous Chemicals

    A Publication of Reliable Methods for the Preparation of Organic Compounds Working with Hazardous Chemicals The procedures in Organic Syntheses are intended for use only by persons with proper training in experimental organic chemistry. All hazardous materials should be handled using the standard procedures for work with chemicals described in references such as "Prudent Practices in the Laboratory" (The National Academies Press, Washington, D.C., 2011; the full text can be accessed free of charge at http://www.nap.edu/catalog.php?record_id=12654). All chemical waste should be disposed of in accordance with local regulations. For general guidelines for the management of chemical waste, see Chapter 8 of Prudent Practices. In some articles in Organic Syntheses, chemical-specific hazards are highlighted in red “Caution Notes” within a procedure. It is important to recognize that the absence of a caution note does not imply that no significant hazards are associated with the chemicals involved in that procedure. Prior to performing a reaction, a thorough risk assessment should be carried out that includes a review of the potential hazards associated with each chemical and experimental operation on the scale that is planned for the procedure. Guidelines for carrying out a risk assessment and for analyzing the hazards associated with chemicals can be found in Chapter 4 of Prudent Practices. The procedures described in Organic Syntheses are provided as published and are conducted at one's own risk. Organic Syntheses, Inc., its Editors, and its Board of Directors do not warrant or guarantee the safety of individuals using these procedures and hereby disclaim any liability for any injuries or damages claimed to have resulted from or related in any way to the procedures herein.
  • (TETS) Hapten Library: Synthesis, Electrophysiological Studies and Immune Response in Rabbits

    (TETS) Hapten Library: Synthesis, Electrophysiological Studies and Immune Response in Rabbits

    HHS Public Access Author manuscript Author ManuscriptAuthor Manuscript Author Chemistry Manuscript Author . Author manuscript; Manuscript Author available in PMC 2018 June 22. Published in final edited form as: Chemistry. 2017 June 22; 23(35): 8466–8472. doi:10.1002/chem.201700783. Development of tetramethylenedisulfotetramine (TETS) hapten library: synthesis, electrophysiological studies and immune response in rabbits Bogdan Barnych Dr.a, Natalia Vasylieva Dr.a, Tom Josepha, Susan Hulsizerb, Hai M. Nguyen Dr.c, Tomas Cajka Dr.d, Isaac Pessah Prof.b, Heike Wulff Prof.c, Shirley J. Geea, and Bruce D. Hammock Prof.a aDepartment of Entomology and Nematology, and UCD Comprehensive Cancer Center, University of California Davis, Davis, California 95616, United States bDepartment of Molecular Biosciences, School of Veterinary Medicine, University of California Davis, Davis, California 95616, United States cDepartment of Pharmacology, School of Medicine, University of California Davis, Davis, California 95616, United States dUC Davis Genome Center-Metabolomics, University of California Davis, Davis, California 95616, United States Abstract There is a need for fast detection methods for the banned rodenticide tetramethylenedisulfotetramine (TETS), a highly potent blocker of the γ-aminobutyric acid (GABAA) receptors. General synthetic approach toward two groups of analogues was developed. Screening of the resulting library of compounds by FLIPR or whole-cell voltage-clamp revealed that despite the structural differences some of the TETS analogues retained GABAA receptor inhibition, however their potency was an order of magnitude lower. Antibodies raised in rabbits against some of the TETS analogues conjugated to protein recognized free TETS and will be used for the development of an immunoassay for TETS.
  • Organic Synthesis Using Carbon Dioxide As Phosgene-Free Carbonyl Reagent*

    Organic Synthesis Using Carbon Dioxide As Phosgene-Free Carbonyl Reagent*

    Pure Appl. Chem., Vol. 84, No. 3, pp. 581–602, 2012. http://dx.doi.org/10.1351/PAC-CON-11-05-04 © 2011 IUPAC, Publication date (Web): 1 September 2011 Organic synthesis using carbon dioxide as phosgene-free carbonyl reagent* An-Hua Liu, Yu-Nong Li, and Liang-Nian He‡ State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China Abstract:CO2 is very attractive as a typical renewable feedstock for manufacturing com- modity chemicals, fuel, and materials since it is an abundant, nontoxic, nonflammable, and easily available C1 resource. The development of greener chemical methodologies for replac- ing the utility of hazardous and environmentally undesirable phosgene largely relies on ingenious activation and incorporation of CO2 into valuable compounds, which is of para- mount importance from a standpoint of green chemistry and sustainable development. Great efforts have been devoted to constructing C–C, C–O, and C–N bond on the basis of CO2 acti- vation through molecular catalysis owing to its kinetic and thermodynamic stability. The aim of this article is to demonstrate the versatile use of CO2 in organic synthesis as the alterna- tive carbonyl source of phosgene, with the main focus on utilization of CO2 as phosgene replacement for the synthesis of value-added compounds such as cyclic carbonates, oxa - zolidinones, ureas, isocyanates, and polymers, affording greener pathways for future chemi- cal processes. Keywords: atom economy; aziridines; carbon dioxide; carbonylation; catalysis; green chemistry; ionic liquids; organic carbonate; phosgene-free process; urea. INTRODUCTION CO2 as an abundant, nontoxic, easily available, and typical renewable C1 source as well as an impor- tant “greenhouse” gas has been drawing more and more attention in line with the need for development of green chemistry and a sustainable society.
  • Diethyl Azodicarboxylate, Conventionally Abbreviated As DEAD and Sometimes As DEADCAT, Is an Organic Compound with the Structural Formula

    Diethyl Azodicarboxylate, Conventionally Abbreviated As DEAD and Sometimes As DEADCAT, Is an Organic Compound with the Structural Formula

    DBU • 1,5-Diazabicyclo[5.4.0]undec-7-ene, or more commonly DBU, is a chemical compound and belongs to the class of amidine compounds. • It is used in organic synthesis as a catalyst, a complexing ligand, and a non-nucleophilic base. • . It is also used as a curing agent for epoxy. • It is used in fullerene purification with trimethylbenzene (it reacts with C 70 and higher fullerenes, but not to C 60 fullerenes) • It is also used as a catalyst in polyurethane production. • It has a strong catalyst effect for the reactions of alicyclic and aliphatic isocyanates. • It also exhibited its dual character (base and nucleophile) in the synthesis of aryl- and styryl-terminal acetylenes. DEAD • Diethyl azodicarboxylate, conventionally abbreviated as DEAD and sometimes as DEADCAT, is an organic compound with the structural formula CH3CH2O2CN=NCO2CH2CH3. Its molecular structure consists of a central azo functional group, RN=NR, flanked by two ethyl ester groups. • It is an oxidising agent • This orange-red liquid is a valuable reagent but also quite dangerous and explodes upon heating. • Therefore, commercial shipment of pure diethyl azodicarboxylate is prohibited in the United States and is carried out either in solution or on polystyrene particles. • DEAD is an aza-dienophile and an efficient dehydrogenating agent, converting alcohols to aldehydes, thiols to disulfides and hydrazo groups to azo groups; it is also a good electron acceptor. • DEAD dissolves in most common organic solvents, such as toluene, chloroform, ethanol, tetrahydrofuran and dichloromethane but has low solubility in water or carbon tetrachloride; the solubility in water is higher for the related azo compound dimethyl azodicarboxylate.
  • Hetero)Aryl Sulfamides

    Hetero)Aryl Sulfamides

    Photochemically-mediated nickel-catalyzed synthesis of N-(hetero)aryl sulfamides R. Thomas Simons, Georgia E. Scott, Anastasia L. Gant Kanegusuku and Jennifer L. Roizen* Duke University, Department of Chemistry, Box 90346, Durham, NC, 27708-0354, USA Corresponding Author - E-mail: [email protected] Table of Contents/Abstract Graphic: (pin)B S O O O O O O S S S H2N N N N N N H H O Ir Ni O O ArBr F3C tBu O O O O O O O O S Me S Me (hetero)aryl bromide S Me S Me H2N N H2N N N N N N Boc H H Boc Me Me readily accessible sulfamides under mild conditions broad access to N-(hetero)aryl sulfamides ABSTRACT: A general method for the N-arylation of sulfamides with aryl bromides is described. The protocol leverages a dual-catalytic system of nickel and a photoexcitable iridium complex and proceeds at room temperature under visible light irradiation. Using these tactics, aryl boronic esters and aryl chlorides can be carried through the reaction untouched. Thereby, this method complements known Buchwald-Hartwig coupling methods for N-arylation of sulfamides. INTRODUCTION N-Aryl sulfamides are critical components of active pharmaceutical1 and agrochemical2 agents (Figure 1).3,4 In drug discovery, sulfamides can be valuable analogues of sulfamate, sulfonamide, urea, carbamate, and amide functional groups.1a In reactions, N,N’-disubstituted sulfamides are useful as chiral auxiliaries,5 as organocatalysts,6 as reagents to promote dehydration,7 as precursors to sterically encumbered carbon–carbon bonds8 and as directing groups for C–H functionalization processes.9 Despite the potential of this valuable functional group, sulfamides may be underutilized due to limitations in practical methods for their preparation.10, 11, 12 Figure 1.
  • Information Extraction from Chemical Patents

    Information Extraction from Chemical Patents

    Information Extraction from Chemical Patents David Matthew Jessop Fitzwilliam College This dissertation is submitted for the degree of Doctor of Philosophy Preface This dissertation is the result of my own work and includes nothing which is the outcome of work done in collaboration except where specifically indicated in the text This dissertation does not exceed the word limit (60000) set by the Degree Committee i Abstract Information Extraction from Chemical Patents David Matthew Jessop The automated extraction of semantic chemical data from the existing literature is demonstrated. For reasons of copyright, the work is focused on the patent literature, though the methods are expected to apply equally to other areas of the chemical literature. Hearst Patterns are applied to the patent literature in order to discover hyponymic relations describing chemical species. The acquired relations are manually validated to determine the precision of the determined hypernyms (85.0%) and of the asserted hyponymic relations (94.3%). It is demonstrated that the system acquires relations that are not present in the ChEBI ontology, suggesting that it could function as a valuable aid to the ChEBI curators. The relations discovered by this process are formalised using the Web Ontology Language (OWL) to enable re-use. PatentEye – an automated system for the extraction of reactions from chemical patents and their conversion to Chemical Markup Language (CML) – is presented. Chemical patents published by the European Patent Office over a ten-week period are used to demonstrate the capability of PatentEye – 4444 reactions are extracted with a precision of 78% and recall of 64% with regards to determining the identity and amount of reactants employed and an accuracy of 92% with regards to product identification.
  • (CDR) by CASRN Or Accession Number

    (CDR) by CASRN Or Accession Number

    List of Chemicals Reported for the 2012 Chemical Data Reporting (CDR) by CASRN or Accession Number For the 2012 CDR, 7,674 unique chemicals were reported by manufacturers (including importers). Chemicals are listed by CAS Registry Number (for non-confidential chemicals) or by TSCA Accession Number (for chemicals listed on the confidential portion of the TSCA Inventory). CASRN or CASRN or ACCESSION ACCESSION NUMBER CA INDEX NAME or GENERIC NAME NUMBER CA INDEX NAME or GENERIC NAME 100016 Benzenamine, 4-nitro- 10042769 Nitric acid, strontium salt (2:1) 10006287 Silicic acid (H2SiO3), potassium salt (1:2) 10043013 Sulfuric acid, aluminum salt (3:2) 1000824 Urea, N-(hydroxymethyl)- 10043115 Boron nitride (BN) 100107 Benzaldehyde, 4-(dimethylamino)- 10043353 Boric acid (H3BO3) 1001354728 4-Octanol, 3-amino- 10043524 Calcium chloride (CaCl2) 100174 Benzene, 1-methoxy-4-nitro- 100436 Pyridine, 4-ethenyl- 10017568 Ethanol, 2,2',2''-nitrilotris-, phosphate (1:?) 10043842 Phosphinic acid, manganese(2+) salt (2:1) 2,7-Anthracenedisulfonic acid, 9,10-dihydro- 100447 Benzene, (chloromethyl)- 10017591 9,10-dioxo-, sodium salt (1:?) 10045951 Nitric acid, neodymium(3+) salt (3:1) 100185 Benzene, 1,4-bis(1-methylethyl)- 100469 Benzenemethanamine 100209 1,4-Benzenedicarbonyl dichloride 100470 Benzonitrile 100210 1,4-Benzenedicarboxylic acid 100481 4-Pyridinecarbonitrile 10022318 Nitric acid, barium salt (2:1) 10048983 Phosphoric acid, barium salt (1:1) 9-Octadecenoic acid (9Z)-, 2-methylpropyl 10049044 Chlorine oxide (ClO2) 10024472 ester Phosphoric acid,