DOCSLIB.ORG

2U11/158249 Al

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
2U11/158249 Al (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 \ / ; 22 December 2011 (22.12.2011) 2U1n 1/158249ft Al (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C07D 209/48 (2006.01) C07C 231/12 (2006.01) kind of national protection available): AE, AG, AL, AM, C07D 307/93 (2006.01) C07C 237/24 (2006.01) AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, (21) International Application Number: DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, PCT/IN20 11/000387 HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, (22) International Filing Date: KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, June 201 1 (09.06.201 1) ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, PE, PG, PH, PL, PT, RO, RS, RU, SC, SD, (25) Filing Language: English SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, (26) Publication Language: English TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: (84) Designated States (unless otherwise indicated, for every 1809/MUM/2010 16 June 2010 (16.06.2010) IN kind of regional protection available): ARIPO (BW, GH, GM, KE, LR, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, (71) Applicant (for all designated States except US): GLEN- ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, MARK GENERICS LIMITED [IN/IN]; Glenmark TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, House, HDO- Corporate Bldg, Wing-A, B. D. Sawant EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, ΓΓ, LT, LU, Marg, Chakala, Andheri (East), Mumbai 400099 (IN). LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, (72) Inventors; and GW, ML, MR, NE, SN, TD, TG). (75) Inventors/ Applicants (for US only): JAMBUKAR, Nagambar Genuji [IN/IN]; Flat No. A/401, Lenaydri Declarations under Rule 4.17 : Park CHSL, Adharwdi Chowk, Kalyan (West), Thane — as to applicant's entitlement to apply for and be granted 421301, Maharashtra (IN). GHARPURE, Milind a patent (Rule 4.1 7(H)) [IN/IN]; Flat No. C-401, Patel heights, Sector-7, Ghan- soli, Navi Mumbai 400709, Maharashtra (IN). SINARE, — of inventorship (Rule 4.1 7(iv)) Sudani Nanabhau [IN/IN]; Shantidut Apartment, Published: AL5 11917, Sector-5, Airoli, Navi Mumbai 400708, M a harashtra (IN). THOMBRE, Pravin Chhaburao — with international search report (Art. 21(3)) [IN/IN]; D002, Chandresh Park CHS, Deslepada, Near — before the expiration of the time limit for amending the Ganesh Mandir, Dombivili (East), Thane 421201, Mah a claims and to be republished in the event of receipt of rashtra (IN). KHAN, Mubeen Ahmed [IN/IN]; H2-0: l , amendments (Rule 48.2(h)) Panchdeep Society, Sector-29, Vashi, 400 703 Navi Mumbai, Maharashtra, (IN). (54) Title: PROCESS FOR PREPARATION OF MILNACIPRAN INTERMEDIATE AND ITS USE IN PREPARATION OF PURE MILNACIPRAN v (57) Abstract: Disclosed is a process for the preparation of milnacipran intermediate, a compound of formula III, and its use in the preparation of pure milnacipran. PROCESS FOR PREPARATION OF MILNACIPRAN INTERMEDIATE AND ITS USE IN PREPARATION OF PURE MILNACIPRAN PRIORITY [0001] This application claims the benefit to Indian Provisional Application No. 809/MUM/2010, filed on June 16, 2010, and entitled "PROCESS FOR PREPARATION OF MILNACIPRAN INTERMEDIATE AND ITS USE IN PREPARATION OF PURE MILNACIPRAN", which is incorporated herein by reference. BACKGROUND OF THE INVENTION Technical Field [0002] The present invention relates to a process for the preparation of a compound cis-(±)-2-[(l,3-dioxo-l,3-dihydro-2H-isoindol-2-yl)methyl]-N,N-diethyl-l- phenylcyclopropane carboxamide and/or its pharmaceutically acceptable salts and its conversion to milnacipran. Description of the Related Art [0003] Milnacipran, also known as (±)-[lR(S), 2S(R)]-2-(aminomethyl)-N,N- diethyl-l-phenylcyclopropanecarboxamide, is represented by the structure of formula II: [0004] Milnacipran hydrochloride, formula I, a selective norepinephrine and serotonin reuptake inhibitor, is found useful in the treatment of depression and chronic pain conditions like fibromyalgia syndrome and lupus. Milnacipran hydrochloride inhibits norepinephrine uptake with greater potency than serotonin. Milnacipran hydrochloride is marketed in the United States under the brand name Savella® in the form of 12.5, 25. 50 and 100 mg tablets for fibromyalgia syndrome; while in Europe, it is available under the brand name Ixel® in the form of 25, 50 and 100 mg tablets for depression. l 10005] U.S. Patent No. 4,478,836 ("the '836 patent") discloses milnacipran and its hydrochloride salt form. The '836 patent discloses a process for the preparation of milnacipran hydrochloride by the reaction of an acid chloride of cis- 1-phenyl- 1- ethoxycarbonyl-2-aminomethylcyclopropane with diethylamine and salifying with hydrochloric acid. The rocess is schematically represented b scheme I : [0006] Patent Publication WO2008/1 04957 (the '957 publication) discloses a multistep process for the preparation of milnacipran hydrochloride by the reaction of (Z)- l-phenyl-l-diethylaminocarbonyl-2-phthalimidomethylcyclopropane of formula III with hydrazine hydrate and the resultant milnacipran product isolated as a wet compound with a significant amount of phthalimide by-products, which are removed by acid-base treatment and whereupon the milnacipran is directly converted to its hydrochloride salt form. The process disclosed in the '957 publication is schematically represented by scheme II: (III) Milnacipran hydrochloride Scheme II [0007] U.S. Patent No. 5,034,541 ("the '541 patent") discloses a process for preparation ofmilnacipran intermediate, cis-(±)-2-[(l,3-dioxo-l,3-dihydro-2H-isoindol-2- yl)methyl]-N,N-diethyl-l-phenylcyclopropanecarboxamide of compound of formula III. The process comprises opening the cis-(±)-l-phenyl-3-oxabicyclo[3.1.0]hexan-2-one of formula VI using diethylamine with the aid of a Lewis acid, converting the cis-(±)-l- phenyl-l-diethylaminocarbonyl-2-hydroxymethylcyclopropane of formula V resulting into its 2-chloro derivative of formula IV by the action of a chlorination reagent, then the 2-chloro derivative is converted into the compound of formula III by reaction with a phthalimide salt at 110°C. [0008] The final step of the '541 patent process was carried out at high temperature; which may have led to formation of impurities in milnacipran. The process disclosed in the '541 patent is schematically represented by scheme III: S che III [0009] Impurities in milnacipran or any active pharmaceutical ingredient (API) are undesirable and, in extreme cases, might even be harmful to a patient being treated with a dosage form containing the API. [0010] It is also known in the art that impurities in an API may arise from degradation of the API itself, which is related to the stability of the pure API during storage, and the manufacturing process, including the chemical synthesis. Process impurities include unreacted starting materials, chemical derivatives of impurities contained in starting material, synthetic by-products, and degradation products. [0011] The purity of the API produced in the commercial manufacturing process is clearly a necessary condition for commercialization. Impurities introduced during commercial manufacturing processes must be limited to very small amounts, and are preferably substantially absent. For example, the International Conference on Harmonization of Technical Requirements for Registration for Human Use ("ICH") Q7A guidance for API manufacturers requires that process impurities be maintained below set limits by specifying the quality of raw materials, controlling process parameters, like temperature, pressure, time, and stoichiometric ratios, and including purification steps such as washing with water or solvent, crystallization, distillation, and extraction, in the manufacturing process. [0012] Thus there is a need in the art for improved processes for preparing pure milnacipran and its intermediates, which are more industrially applicable. SUMMARY OF THE INVENTION [0013] The present invention is drawn towards the preparation of compounds, that may be used as intermediates in the preparation of milnacipran or its pharmaceutically acceptable salts. The subsequent milnacipran or its pharmaceutical salts contain levels of impurity that render their favorable use as API. [0014] In one aspect , the present invention provides a one-pot process for the preparation of cis-(±)-2-[(l,3-dioxo-l,3-dihydro-2H-isoindol-2-yl)methyl]-N,N-diethyl- 1-phenylcyclo-propanecarboxamide, a compound of formula III: comprising: a) reacting cis-(±)-l-phenyl-3-oxabicyclo[3.1.0]hexan-2-one, a compound of formula VI with diethylamine in the presence of a Lewis acid and an organic solvent to form cis-i 1-phenyl- 1-diethylaminocarbonyl-2-hydroxymethylcyclopropane, a compound formula V, b) reacting cis-(±)-l -phenyl- l-diethylaminocarbonyl-2-hydroxymethylcyclopropane, the compound of formula V with a chlorinating agent to form cis-(±)-l -phenyl- 1- diethylaminocarbonyl-2-chloromethylcyclopropane, a compound of formula IV and IV c) reacting cis-(±)-l -phenyl- l-diethylaminocarbonyl-2-chloromethylcyclopropane, the compound of formula IV with a phthalimide salt at a temperature range between about 20°C to about 60°C to form the compound of formula III. [0015] In another embodiment, the present invention provides a process for the preparation of cis-(±)-2-[(l,3-dioxo-l,3-dihydro-2H-isoindol-2-yl)methyl]-N,N-diethyl- 1-phenylcyclo-propanecarboxamide, a compound of formula III, the process comprising, reacting cis-(±)-l -phenyl- 1-diethylaminocarbonyl-2- chloromethylcyclopropane, a compound of formula IV IV with a phthalimide salt, in the presence of an organic solvent at a temperature range between about 20°C to about 60°C.
Load more

Recommended publications
  • Direct Synthesis of Some Significant Metal Alkoxides
    SD0000032 DIRECT SYNTHESIS OF SOME SIGNIFICANT METAL ALKOXI'DE BVYU EMI1JG A THESIS SUBMITTED FOR THE DEGREE OF Mi.Sc. IN CHEMISTRY SUPERVISOR: Dr. O.Y.OMER DEPARTMENT OF CHEMISTRY FACULTY OF EDUCATION UNIVERSITY OF KHARTOUM NOVEMBER, 1998 31/28 DISCLAIMER Portions of this document may be illegible in electronic image products. Images are produced from the best available original document. Please be aware that all of the Missing Pages in this document were originally blank pages Dedication To my three children: Regina, Maria and Samuel CONTENTS Page Dedication i Contents ii List of Tables v List of Figures vii Acknowledgement viii Abstract (Arabic) ix Abstract (English) x CHAPTER 1.0 CHAPTER ONE - INTRODUCTION 1 2.0 CHAPTER TWO - LITERATURE REVIEW 5 2.1 Introduction to Literature Review 5 2.2 Definition of metal alkoxides 5 2.3 Metal elements and (heir chemistry 8 2.3.1 Sodium metal 8 2.3.2 Magnesium metal 12 2.3.3 Aluminium metal 16 2.3.3.1 Hydrolysis of aluminium compounds 20 2.3.4 Tin metal 21 2.4 Preparative methods and uses ofalkoxides ofNa, Mg, Al & Sn. 25 2.4.1 Sodium alkoxide 25 2.4.2 Mamiesium alkoxide 26 2.4.3 Aluminium alkoxide 27 2.4.4. Tin alkoxide 30 2.5 General properties of metal alkoxides 31 2.5.1 1 lydrolysis in metal alkoxide 34 3.0 CHAPTER THREE - MATERIALS AND EXPERIMENTAL PROCEDURE 36 3.1 General procedures 36 3.1.1 Start ing material s 3 6 3.1. I.I Apparatus 36 3.1.1.2 Dry ethanol and isopropanol 36 3.1.1.3 Na, Mg, Al & Sn metals 36 3.1.2 Infrared spectra (Ir) 37 3.2 Reactions procedures 37 3.2.1 Reaction between sodium metal and absolute ethanol 37 3.2.2 Reaction of magnesium metal with absolute ethanol 37 3.2.3 Reaction of magnesium mclal with absolute ethanol using mercury (11) chloride catalyst.
    [Show full text]
  • Safety Data Sheet
    SAFETY DATA SHEET Revision Date 15-Jan-2021 Revision Number 2 SECTION 1: IDENTIFICATION OF THE SUBSTANCE/MIXTURE AND OF THE COMPANY/UNDERTAKING 1.1. Product identifier Product Description: Aluminum ethoxide Cat No. : 41336 Synonyms Aluminium ethoxide CAS-No 555-75-9 Molecular Formula C6 H15 Al O3 Reach Registration Number - 1.2. Relevant identified uses of the substance or mixture and uses advised against Recommended Use Laboratory chemicals. Uses advised against No Information available 1.3. Details of the supplier of the safety data sheet Company Alfa Aesar . Avocado Research Chemicals, Ltd. Shore Road Port of Heysham Industrial Park Heysham, Lancashire LA3 2XY United Kingdom Office Tel: +44 (0) 1524 850506 Office Fax: +44 (0) 1524 850608 E-mail address [email protected] www.alfa.com Product Safety Department 1.4. Emergency telephone number Call Carechem 24 at +44 (0) 1865 407333 (English only); +44 (0) 1235 239670 (Multi-language) SECTION 2: HAZARDS IDENTIFICATION 2.1. Classification of the substance or mixture CLP Classification - Regulation (EC) No 1272/2008 Physical hazards Flammable solids Category 2 (H228) Substances/mixtures which, in contact with water, emit flammable gases Category 2 (H261) Health hazards ______________________________________________________________________________________________ ALFAA41336 Page 1 / 11 SAFETY DATA SHEET Aluminum ethoxide Revision Date 15-Jan-2021 ______________________________________________________________________________________________ Skin Corrosion/Irritation Category 1 B (H314) Environmental hazards Based on available data, the classification criteria are not met Full text of Hazard Statements: see section 16 2.2. Label elements Signal Word Danger Hazard Statements H261 - In contact with water releases flammable gases H228 - Flammable solid H314 - Causes severe skin burns and eye damage EUH014 - Reacts violently with water Precautionary Statements P301 + P330 + P331 - IF SWALLOWED: rinse mouth.
    [Show full text]
  • 中文名稱英文名稱CAS.NO. 二乙縮醛acetal 105-57-7 乙醛
    中文名稱 英文名稱 CAS.NO.
    [Show full text]
  • WO 2014/009767 Al 16 January 2014 (16.01.2014) P O PCT
    (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 WO 2014/009767 Al 16 January 2014 (16.01.2014) P O PCT (51) International Patent Classification: Pramod Kumar [IN/IN]; Micro Labs Limited, API Divi C07D 307/33 (2006.01) C07C 235/40 (2006.01) sion, Plot No. 43-45, K.I .A.D.B., Jigani-Bommasandra C07C 231/10 (2006.01) C07C 237/24 (2006.01) Link Road, Anekal Taluk, Bangalore-560 105, Karnataka C07C 233/58 (2006.01) (IN). (21) International Application Number: (74) Agents: NAIR, Manoj Vasudevan et al; M/s Lex Orbis PCT/IB20 12/00 1765 (Intellectual Property Practice), 709/710, Tolstoy House, 15-17 Tolstoy Marg, New Delhi - 110 001 (IN). (22) International Filing Date 12 September 2012 (12.09.2012) (81) Designated States (unless otherwise indicated, for every kind of national protection available): AE, AG, AL, AM, English (25) Filing Language: AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, (26) Publication Language: English BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (30) Priority Data: HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, 2752/CHE/2012 7 July 2012 (07.07.2012) IN KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, (71) Applicant (for all designated States except US): MICRO ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, LABS LIMITED [IN/IN]; No.27, Race Course Road, NO, NZ, OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, Bangalore 560 001 (IN).
    [Show full text]
  • Reducing the Cost of Production of Bimetallic Aluminium Catalysts for the Synthesis of Cyclic Carbonates Michael North* and Carl Young[A]
    DOI: 10.1002/cssc.201100239 Reducing the Cost of Production of Bimetallic Aluminium Catalysts for the Synthesis of Cyclic Carbonates Michael North* and Carl Young[a] Bimetallic aluminium complexes of general formula [(salen)- most expensive chemicals by less expensive alternatives. The Al]2O or [(acen)Al]2O catalyse the formation of cyclic carbo- largest cost saving was associated with the formation of alumi- nates from carbon dioxide and terminal epoxides under excep- nium triethoxide in situ, which reduced the cost of the chemi- tionally mild reaction conditions. To improve the potential for cals need for production of the catalysts by 49–87 %. Further industrial scale application of these catalysts, the cost of their savings were made by avoiding the use of tetrabutylammoni- production has been evaluated and reduced significantly by um bromide and acetonitrile, resulting in overall cost savings optimization of the synthesis, including replacement of the of 68–93 %. Introduction The increasing prominence of climate change related issues[1] the use of dimethyl carbonate as an oxygenating agent for and the limited nature of fossil fuel reserves[2] for use as transport fuel.[16] energy and chemical feedstocks has driven the development Current commercial processes for the production of cyclic of green chemical processes involving alternative solvents, re- carbonates employ catalysts that require the use of tempera- newable materials and minimal waste.[3] One area that is re- tures above 1808C, pressures above 50 atm (1 atm = ceiving increasing attention is the use of carbon dioxide as an 101325 Pa) and highly purified carbon dioxide.[17] The carbon inexpensive, readily available and renewable starting material dioxide emitted as a result of generating the energy required for the synthesis of commercially important chemicals.[4] Urea to achieve these reaction conditions negates any benefit from is currently manufactured from carbon dioxide on a the use of carbon dioxide in the synthesis of cyclic carbonates.
    [Show full text]
  • Hydrocalumite-Based Catalysts for Glycerol Revalorization
    HYDROCALUMITE-BASED CATALYSTS FOR GLYCEROL REVALORIZATION. Judith Cecilia Granados Reyes Dipòsit Legal: T 1362-2015 ADVERTIMENT. L'accés als continguts d'aquesta tesi doctoral i la seva utilització ha de respectar els drets de la persona autora. Pot ser utilitzada per a consulta o estudi personal, així com en activitats o materials d'investigació i docència en els termes establerts a l'art. 32 del Text Refós de la Llei de Propietat Intel·lectual (RDL 1/1996). Per altres utilitzacions es requereix l'autorització prèvia i expressa de la persona autora. En qualsevol cas, en la utilització dels seus continguts caldrà indicar de forma clara el nom i cognoms de la persona autora i el títol de la tesi doctoral. No s'autoritza la seva reproducció o altres formes d'explotació efectuades amb finalitats de lucre ni la seva comunicació pública des d'un lloc aliè al servei TDX. Tampoc s'autoritza la presentació del seu contingut en una finestra o marc aliè a TDX (framing). Aquesta reserva de drets afecta tant als continguts de la tesi com als seus resums i índexs. ADVERTENCIA. El acceso a los contenidos de esta tesis doctoral y su utilización debe respetar los derechos de la persona autora. Puede ser utilizada para consulta o estudio personal, así como en actividades o materiales de investigación y docencia en los términos establecidos en el art. 32 del Texto Refundido de la Ley de Propiedad Intelectual (RDL 1/1996). Para otros usos se requiere la autorización previa y expresa de la persona autora. En cualquier caso, en la utilización de sus contenidos se deberá indicar de forma clara el nombre y apellidos de la persona autora y el título de la tesis doctoral.
    [Show full text]
  • Aluminum Ethoxide
    AKA060 - ALUMINUM ETHOXIDE ALUMINUM ETHOXIDE Safety Data Sheet AKA060 Date of issue: 08/05/2016 Version: 1.0 SECTION 1: Identification of the substance/mixture and of the company/undertaking 1.1. Product identifier Product form : Substance Physical state : Solid Substance name : ALUMINUM ETHOXIDE Product code : AKA060 Formula : C6H15AlO3 Synonyms : ALUMINUM ETHYLATE ALUMINUM TRIETHOXIDE ALUMINIUM TRIETHANOLATE TRI(ETHANOLATE), ALUMINUM ETHANOL, ALUMINIUM SALT Chemical family : METAL ALCOHOLATE 1.2. Relevant identified uses of the substance or mixture and uses advised against Use of the substance/mixture : Chemical intermediate For research and industrial use only 1.3. Details of the supplier of the safety data sheet GELEST, INC. 11 East Steel Road Morrisville, PA 19067 USA T 215-547-1015 - F 215-547-2484 - (M-F): 8:00 AM - 5:30 PM EST [email protected] - www.gelest.com 1.4. Emergency telephone number Emergency number : CHEMTREC: 1-800-424-9300 (USA); +1 703-527-3887 (International) SECTION 2: Hazards identification 2.1. Classification of the substance or mixture GHS-US classification Skin Irrit. 2 H315 Eye Irrit. 2A H319 Full text of H statements : see section 16 2.2. Label elements GHS-US labeling Hazard pictograms (GHS-US) : GHS07 Signal word (GHS-US) : Warning Hazard statements (GHS-US) : H315 - Causes skin irritation H319 - Causes serious eye irritation Precautionary statements (GHS-US) : P280 - Wear protective gloves/protective clothing/eye protection/face protection P264 - Wash hands thoroughly after handling P302+P352 - If on skin: Wash with plenty of soap and water P332+P313 - If skin irritation occurs: Get medical advice/attention P305+P351+P338 - IF IN EYES: Rinse cautiously with water for several minutes.
    [Show full text]
  • Synthesis of Biguanidines and Triazines, and Biguanidino-Aluminium Complexes As Intermediates
    (19) TZZ ¥__T (11) EP 2 231 679 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07F 5/06 (2006.01) C07D 413/04 (2006.01) 16.11.2011 Bulletin 2011/46 C07D 251/54 (2006.01) C07D 401/04 (2006.01) C07D 403/04 (2006.01) C07D 405/12 (2006.01) (2006.01) (21) Application number: 08862791.4 C07D 403/12 (22) Date of filing: 25.11.2008 (86) International application number: PCT/EP2008/009962 (87) International publication number: WO 2009/077059 (25.06.2009 Gazette 2009/26) (54) SYNTHESIS OF BIGUANIDINES AND TRIAZINES, AND BIGUANIDINO-ALUMINIUM COMPLEXES AS INTERMEDIATES SYNTHESE VON BIGUANIDEN UND TRIAZINEN SOWIE BIGUANIN-ALUMINIUM-KOMPLEXE ALS ZWISCHENPRODUKTE SYNTHÈSE DE BIGUANIDINES ET DE TRIAZINES ET COMPLEXES DE BIGUANIDINO- ALUMINIUM COMME INTERMÉDIAIRES (84) Designated Contracting States: (72) Inventor: FORD, Mark, James AT BE BG CH CY CZ DE DK EE ES FI FR GB GR 61389 Schmitten-Oberreifenberg (DE) HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR (56) References cited: • DATABASECA[Online]CHEMICALABSTRACTS (30) Priority: 14.12.2007 EP 07024256 SERVICE, COLUMBUS, OHIO, US; NANDI, S. D. ET AL: "Complexes of aluminum(III) and (43) Date of publication of application: beryllium(II) with biguanide" XP002476492 29.09.2010 Bulletin 2010/39 retrieved from STN Database accession no. 81: 144912 & ZEITSCHRIFT FUER (73) Proprietor: Bayer CropScience AG NATURFORSCHUNG, TEIL B: ANORGANISCHE 42789 Monheim (DE) CHEMIE, ORGANISCHE CHEMIE, BIOCHEMIE, BIOPHYSIK, BIOLOGIE , 29(5-6), 347-8 CODEN: ZENBAX; ISSN: 0044-3174, 1974, Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations.
    [Show full text]
  • Synthesis of Cyclic Carbonates from Epoxides and Carbon Dioxide Using Bimetallic Aluminium(Salen) Complexes
    Reviews and Accounts ARKIVOC 2012 (i) 610-628 Synthesis of cyclic carbonates from epoxides and carbon dioxide using bimetallic aluminium(salen) complexes Michael North School of Chemistry, Bedson Building, University of Newcastle, Newcastle upon Tyne NE1 7RU, UK E-mail: [email protected] DOI: http://dx.doi.org/10.3998/ark.5550190.0013.115 Abstract Over the last six years, highly active catalysts for the synthesis of cyclic carbonates from epoxides and carbon dioxide have been developed. Initial studies showed that bimetallic aluminium(salen) complexes [Al(salen)]2O formed active catalysts and kinetic studies allowed the catalytic cycle to be determined. The catalysts could be immobilized on silica, allowing them to be used in a gas phase flow reactor as well as in batch reactors. The compatibility of the catalysts with waste carbon dioxide present in power station flue gas has been investigated and studies to enhance the commercial applicability of the catalysts by reducing the cost of their production carried out. Keywords: Carbon dioxide, epoxide, cyclic carbonate, catalyst, aluminium, salen Table of Contents 1. Introduction 2. Catalyst Discovery 3. Reaction Mechanism 4. One-Component and Immobilized Catalysts 5. Use of Waste Carbon Dioxide 6. Catalyst Cost Reduction 7. Conclusions 8. Acknowledgements 9. References Page 610 ©ARKAT-USA, Inc. Reviews and Accounts ARKIVOC 2012 (i) 610-628 1. Introduction The world currently generates most of its energy by the combustion of fossil fuels (coal, oil and natural gas) and despite efforts to develop alternative, renewable energy sources, fossil fuels are likely to remain the predominant energy source for the next 20–40 years.
    [Show full text]
  • Metal Salen Catalysts for Reactions of Epoxides and Heterocumulenes
    Christopher Beattie Metal salen catalysts for reactions of epoxides and heterocumulenes A thesis submitted for the degree of Doctor of Philosophy 2014 Abstract This thesis details the research carried out into the reaction of epoxides with various heterocumulenes, forming five-membered heterocyclic products. The catalyst systems used are numerous forms of metal salen compounds. It begins with the introduction, which summarises the body of literature outlining the reactions of epoxides with heterocumulenes. Previously developed catalytic systems are discussed along with any mechanistic studies that have taken place. A conclusion regarding the most active systems for each reaction is given, which will provide an understanding of the requirements needed to be a successful catalyst. The results and discussion section is divided into four main chapters. It begins with a study into forming novel one-component catalysts for the synthesis of cyclic carbonates from epoxides and carbon dioxide. Four new catalysts are conceived and tested on this reaction, but with very limited success due to the level of steric hindrance present in the backbone of the salen ligands. The catalysts that are successfully synthesised are then examined for other reactions for which they may be suited, namely the synthesis of thiocarbonates from epoxides and carbon disulphide and asymmetric cyanohydrin synthesis. Both reactions gave mixed results. The activity exhibited for thiocarbonate synthesis ranged from 0-100 % conversion, while the asymmetric induction of the cyanohydrin products was disappointing (18-79 % ee). Both proving to be less active than previously devised salen-based systems. The next chapter describes a mechanistic exploration of previously developed monometallic and bimetallic catalyst systems for the reaction of epoxides with isocyanates.
    [Show full text]
  • Iron(III) Chloride
    Iron(III) chloride Iron(III) chloride is the inorganic compound with the Iron(III) chloride formula (FeCl3). Also called ferric chloride, it is a common compound of iron in the +3 oxidation state. The anhydrous compound is a crystalline solid with a melting point of 307.6 °C. The color depends on the viewing angle: by reflected light the crystals appear dark green, but by transmitted light they appear purple-red. Contents Structure and properties Anhydrous Iron(III) chloride (hydrate) Hydrates Aqueous solution Preparation Reactions Redox reactions With carboxylate anions With alkali metal alkoxides With organometallic compounds Uses Industrial Laboratory use Other uses Safety Iron(III) chloride (anhydrous) Natural occurrence See also Notes References Further reading Names IUPAC names Iron(III) chloride Structure and properties Iron trichloride Other names Anhydrous Ferric chloride Molysite Anhydrous iron(III) chloride has the BiI structure, with 3 Flores martis octahedral Fe(III) centres interconnected by two-coordinate chloride ligands.[3] Identifiers CAS Number 7705-08-0 (http://www.c Iron(III) chloride has a relatively low melting point and boils ommonchemistry.org/Ch at around 315 °C. The vapour consists of the dimer Fe Cl (cf. 2 6 emicalDetail.aspx?ref=7 aluminium chloride) which increasingly dissociates into the 705-08-0) monomeric FeCl3 (with D3h point group molecular 10025-77-1 (http://www. symmetry) at higher temperature, in competition with its commonchemistry.org/C reversible decomposition to give iron(II) chloride and hemicalDetail.aspx?ref= [8] chlorine gas. 10025-77-1) (hexahydrate) Hydrates 54862-84-9 (http://www. commonchemistry.org/C In addition to the anhydrous material, ferric chloride forms hemicalDetail.aspx?ref= four hydrates.
    [Show full text]
  • Synthesis of Cyclic Carbonates from Epoxides and Carbon Dioxide Using Bimetallic Aluminium(Salen) Complexes
    Reviews and Accounts ARKIVOC 2012 (i) 610-628 Synthesis of cyclic carbonates from epoxides and carbon dioxide using bimetallic aluminium(salen) complexes Michael North School of Chemistry, Bedson Building, University of Newcastle, Newcastle upon Tyne NE1 7RU, UK E-mail: [email protected] Abstract Over the last six years, highly active catalysts for the synthesis of cyclic carbonates from epoxides and carbon dioxide have been developed. Initial studies showed that bimetallic aluminium(salen) complexes [Al(salen)] 2O formed active catalysts and kinetic studies allowed the catalytic cycle to be determined. The catalysts could be immobilized on silica, allowing them to be used in a gas phase flow reactor as well as in batch reactors. The compatibility of the catalysts with waste carbon dioxide present in power station flue gas has been investigated and studies to enhance the commercial applicability of the catalysts by reducing the cost of their production carried out. Keywords: Carbon dioxide, epoxide, cyclic carbonate, catalyst, aluminium, salen Table of Contents 1. Introduction 2. Catalyst Discovery 3. Reaction Mechanism 4. One-Component and Immobilized Catalysts 5. Use of Waste Carbon Dioxide 6. Catalyst Cost Reduction 7. Conclusions 8. Acknowledgements 9. References 1. Introduction The world currently generates most of its energy by the combustion of fossil fuels (coal, oil and natural gas) and despite efforts to develop alternative, renewable energy sources, fossil fuels are Page 610 ©ARKAT-USA, Inc. Reviews and Accounts ARKIVOC 2012 (i) 610-628 likely to remain the predominant energy source for the next 20–40 years. Combustion of fossil fuels inevitably produces carbon dioxide which is released to the atmosphere.
    [Show full text]