DOCSLIB.ORG

Jan 0 5 1.995 Chemistry 1

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Jan 0 5 1.995 Chemistry 1 1 R ECEt abr~ FINAL TECHNICAL PROGRESS REPORT JAN 0 5 1.995 CHEMISTRY 1. SYNTHESIS AND 8ECEPTOR AFFINITIES OF NEW 3-QUINUCLIDINYL ALPHA- HETEROARYL-ALPHA-ARYL-ALPHA-HYDROXYACETATES (see Schemes in App. 1.1). Five analogues of 3-quinuclidinyl benzilate were prepared in which one phenyl ring was substituted by a heterocycle; a bromine was included on either the remaining phenyl or the heterocycle to provide information relating to the affinity of potential radiohalogenated derivatives. The required methyl 4- bromophenylglyoxalate ( 1 ) was synthesized from the reaction between 4-bromophenylmagnesium bromide with an excess of dimethyl oxalate at -700 C. The reaction between ethyl oxalyl chloride with 2-bromothiphene provides ethyl 2-(5-bromothienyl)glyoxatate (2). Compounds ( 1) and (2) react with an equivalent amount of Grignard reagent to provide methyl or ethyl alpha-aryl-alpha- heteroarylglycolates (3). Transesterification of the methyl or ethyl esters (3) with (R,S)-3- quinuclidinol (4) in the presence of sodium metal provides the final products As a result of screening the novel compounds, we found a heterocyclic derivative of QNB that may(5). surpass IQNB as a CNS receptor radioligand. This novel compound binds to mAChRs with an affinity that is greater than that of IQNB, i5 selective for the ml subtype, and is less lipophilic than IQNB, which should reduce the serum proteip binding relative to IQNB. Cohen, Gibson, Fan, De La Cruz, Gitler, Hariman, Reba J. Pharm. Sci., 8'1, 326-329, 1992; App. 1.l. 2. SYNTHESIS AND STRUCTURE-ACTIVITY RELATIONSHIP OF SOME 5- [ [ [ ( D IA LKY LA M I N 0)ALKYL]- 1 -PIPE RI D I NY L] ACETYL] - 1 0,l 1 -D IHY D RO-5 H-D IB EN20 [ b, e] [ 1,4] DIAZEPIN- 1 1-ONES AS rn2-SELECTIVE ANTlMUSCARlNlCS (see Schemes in App. 1.2). The required 1 1-oxo-1 0,l 1-dihydro-5H-dibenzo[b,e] [1,4]diazepine (9) was prepared from the reaction between 2-chlorobenzoic acid and o-phenylenediamine. The reaction between 2- and 4- vinylpyridines (5a,b) and dialkylamines (6a-e) provided 2- and 4-(dialkylamino)ethylpyridines (7). 4-Picolyllithium '(5~)reacted with 3-(dimethyl- or diethy1amino)propyl chloride to provide 4-[4-( dimethyl- or diethylamino) butyllpyridines (7). [(Dialkylamino)alkyl]pyridines -(7) were converted into the respective piperidines (8) by catalytic reduction(p1atinum oxide). Condensation of the tricycle (9) with chlocoacetyl chloride provided 5-(chloroacety1)-1 0,l 1-dihydro-SH- dibenzo[b,e][1,4] diazepin-1 l-one ( 1 0). Subsequent reaction with [(dialkylamino)alkyl]piperidines (8) yielded the final products (4)- Compounds (4a-g,iIj) and two reference compounds (Table 111 in App. 1.2) were tested for their apparent affinities for the ml and m2 subtypes. Table 111 compares the selectivity and potency of these compounds to other compounds. These data demonstrate that (4j) is the most potent compound in the series. This compound is selective for m2 receptors over ml receptors by approximately 8-fold. These results also demonstrate that (41) is approxhately 10 times more potent at m2 receptors than AQ-RA 741. However, (4j) does not significantly penetrate the BBB. Cohen, Baumgold, Jin, de la Cruz, Rzeszotarski, Reba, J. Med. Chem. 36, 162-1 65, 1993a; App.. 1.2. .- 3. SY~THESIS OF SOME DIBENZODIAZEPINONES AS - POTENT m2-SELECTIVE ANTlMUSCARlNlC COMPOUNDS (see Schemes in App. 1.3). 4-[4-(Chloro)butyl]cyclohexylacetic acid (4) was obtained by catalytic reduction of 4-[4-(chloro) butyl]phenylacetic acid (3). Reaction of acid derivatives (4, 5) with thionyl chloride, followed by condensation with tricycle (S), and then reaction with secondary amines provided the final products (1, 2). To increase the lipophilicity in this series, we replaced the piperidine ring in the cationic head by cyclohexyl ring (Table I in App. 1.3). Compounds (1 a-h), and (2a,b) and three reference compounds were tested for their apparent affinities for ml and m2 subtypes. The ICgo's for the muscarinic ligands were determined by competitive ligand binding assay against [3H]QNB. These data demonstrate that (2b) is the most potent compound in the series. The data (Table 111 in App. 1.3.) reveal that neither preinjection nor coinjection of the m2-selective compound (2b) at a dose of 500 nmol or 2000 nmol affects the re ional (R,R)-[1251]lQNB accumulation in the rat brain. There was no displacement of (R,R)- [1%%JIQNBfrom specific brain regions by the unlabeled compound (2b). Cohen, Jin, Gitler, de la Cruz, Rzeszotarski, Zeeberg, Baumgold, Reba; J. Heterocyclic Chem. in press; App. 1.3. DISTRIBUTION OF THIS DOCUMENT IS UNLIMITED 9b ~~~~~~~ 4. 1 We have Synthesized 1,s- benzodiazepinesTHE SYNTHESIS (Scheme OF1.h SUBSTITUTEDApp. 1.4). where ,S-BENZODIAZEPINES.crotonic acid (1)'or methacrilic acid (2) react with 1,2-~henylenediamine (Sa) or 4-chloro-l,2-phenylenediamine (3 b) leading to tetrahydro-2H- 1,5-benzodiazepihe-2-ones (4),, Condensation of (4) with bromoacetyl chloride followed by 2- diethy laminoethyl-piperidine ;( 6), 4-dimethylaminobutyl-piperidine (7), or diethylaminobutyl- piperidine (8) afforded substituted 1,s-benzodiazepines (9). The reduction in size of the tricycle resulted in a loss of affinity. Cohen, Jin, Reba, J.Heterocyclic Chem. 30, 835-837, 1993; App. 1.4. 5. NOVEL POTENT AND M2-SELECTIVE ANTIMUSCARINIC COMPOUNDS WHICH PENETRATE THE BLOOD BRAIN BARRIER. These compounds (1 a-n) were prepared according to the Scheme in App. 1.5. The 4-(methoxyalkyl)phenylacetonitriles were converted to 4- (bromoalkyl) phenylacetic acids (Sa-d) by hydrolysis, cleavage, and halogenation. Subsequent reaction of (Sa-d) with thionyl chloride, followed by condesation with 1 1-oxo-1 0,ll -dihydro-SH- dibenzo[b,e] [ 1,4]diazepin (6) yielded the 5-[[4-(haloalkyl)-l -phenyl]acetyl]-1 0,ll -dihydro- SH-dibenzo[b,e][l,4]diazepin-l1 -ones (7a-d). The reaction of (7a-d) with secondary aliphatic amines provided (1 a-n). Further synthetic details are described in the enclosed manuscript. Compounds (la-n) and three reference compounds (Table V in App. 1.5) were tested for their apparent affinities for the ml and m2 subtypes. The results demonstrate that (1 h) (DIBD) is the most potent compound in the series. DIBD is selective for m2 receptors over ml receptors by approximately 7-fold. These results also demonstrate that DlBD is approximately 10 times more potent at m2 .: receptors than is AQ-RA 741. Cohen, Jin, Gitler, de la Cruz, Boulay, Zeeberg, Reba, submitted to Eur. J. Med. Chem.; App. 1.5. 6. FACILE AND GENERAL SYNTHESIS OF 2-, 30, OR 4-[(DIALKYLAMINO) ALKYLIPYRIDINES AND PIPERIDINES. Reaction of N,N-dialkyiaminoalkyl chloride with picolyllithiurns ( 1 ) provided the pyridine derivative from which the piperidine (3) was synthesized by catalytic hydrogenation. Cohen, Jin, Reba, Liebigs(2) Ann. Chem. pp. 809-81 0, 1993. H 1 2 3 7. SYNTHESIS OF 20. AND 4-IODO-5-[[4-[4-(DIISOBUTYLAMlNO)BUTYL]-l- PHENYLIACETYLFl0,l l-DIHYDRO~5H-DiBENZO[b,e] [ 1,4]DIAZEPIN-ll-ONES ( 1 0a, b ) ;/( S C H E M E) : 2 - I 0 D 0- 5 - [ [ 4-.[ 4 - ( D I I S 0B U T Y LA M I N 0) 6 U T Y L ]- 1- P H E N Y L ]- ACETYL]-1 0,l 1-DIHYDRO-5H-DIBENZO[b,e][ 1,,4]DIAZEPIN-l1-ONE (24DIBD, 1 Oa). It was synthesized according to Scheme. o-Phenylenediamine was condensed with 2-chloro-5- nitrobenzoic acid as described by Giani (1985), to give 2-nitro-1 1-oxo-1 0,ll -dihydro-5H- dibenzo[b,e][ 1,4]diazepine (1a). 2-Nitro-1 1-oxo-1 0,ll -dihydro-5H-dibenzo[b,e]- [1,4]diazepine (1 a) was converted into the 2-mino-1 1-oxo-1 0,l 1-dihydro-SH- dibenzo[ b,e] [ 1,4]diazepine (2a) by catalytic-reduction (palladium on activated carbon). Reaction of (2a) with benzylchloroformate (3) by a modification of Holley (1 954) provided 2- benzyloxycarbonyl(Z)amino-1 1-oxo1 0,ll -dihydro-SH-dibenzo[b,e][ 1,4]diazepine (4a). The 2- benzyloxyca r bony1(Z) a mi no-5-[ [4- [4-( bromo) butyl]- 1-p heny I]acetyl] - 1 0,ll -di hydro- 5 H-di- benzo[b,e] [1,4]diazepin-l1 -one (sa) was prepared by treating (4a) with 4-[4-( bromo)butyl]- phenylacetyl chloride (5). The desired 2-benzyioxycarbonyl(Z)amino-5-[ [4-[4- (diisobutylamino) butyl]-1 -phenyl]acetyl]-1 0,ll -dihydro-SH-dibenzo[b,e][ 1,4]diazepin-l1 -one (8a) was synthesized from reaction of the (6a) with diisobutylamine (7) in acetonitrile by the method described by Cohen (App. 1S). Compound (8a) was hydrogenated at room temperature in the presence of palladium on active carbon according to Fletcher (1 979) to give the respective amine (ga). The 2-iodo-5-[[4-[4-(diisobutylamino)butyl]-l -phenyl]acetyl] 10,l 1-dihydro-SH- dibenzo[b,e][ 1,4] diazepine-11-one (1Oa) was synthesized from reaction of the diazonium intermediate with potassium iodide by the method described by Cohen (1 989). The residue was purified by flash column chromatography elution with chloroform/methanol 10: 1); mp = 137%. in vitro competition binding studies against [f HlQN6 provided the following IC50 values. Thus, iodination in the 2-position significantly reduces the binding affinity of DIBD, whereas iodination in the 4- position retain the aff inity, but reduces the subtype specificity. 1 2 4 6 8 9 10 - - compound ml m2 ml/m2 DIBD 25 3.2 7.81 2-IDIBD 200 90 2.22 - 4-1~i~b 10 S 2.0 8. SY NTHES I S 0 F 5-[ [ 4-14-1 D I ( 2-M ETHY LALLY L) AMI N 01 BUTYL] - 1 -PHENYL] ACETYL]:JP, 1 1,4]DIAZEPIN-l 1 -ONE [unsaturated precursor for preparingl-DIHYDRO-SH-DiBENZO[b~e][ tritiated DlBD (UDIBD)] The best m2-selective antimuscarinic agent studied in the above (section S) series of compound is 5-[[4-[4-(diisobutylarnino)butyl]-l- phenyllacetyll-10,ll -dihydro-SH-dibenzo[b,e] [ 1,4]diazepin-11 -one (DIBD), which penetrates the blood brain barrier and displays in vivo selectivity for the m2-subtype.
Load more

Recommended publications
  • Inventory Size (Ml Or G) 103220 Dimethyl Sulfate 77-78-1 500 Ml
    Inventory Bottle Size Number Name CAS# (mL or g) Room # Location 103220 Dimethyl sulfate 77-78-1 500 ml 3222 A-1 Benzonitrile 100-47-0 100ml 3222 A-1 Tin(IV)chloride 1.0 M in DCM 7676-78-8 100ml 3222 A-1 103713 Acetic Anhydride 108-24-7 500ml 3222 A2 103714 Sulfuric acid, fuming 9014-95-7 500g 3222 A2 103723 Phosphorus tribromide 7789-60-8 100g 3222 A2 103724 Trifluoroacetic acid 76-05-1 100g 3222 A2 101342 Succinyl chloride 543-20-4 3222 A2 100069 Chloroacetyl chloride 79-04-9 100ml 3222 A2 10002 Chloroacetyl chloride 79-04-9 100ml 3222 A2 101134 Acetyl chloride 75-36-5 500g 3222 A2 103721 Ethyl chlorooxoacetate 4755-77-5 100g 3222 A2 100423 Titanium(IV) chloride solution 7550-45-0 100ml 3222 A2 103877 Acetic Anhydride 108-24-7 1L 3222 A3 103874 Polyphosphoric acid 8017-16-1 1kg 3222 A3 103695 Chlorosulfonic acid 7790-94-5 100g 3222 A3 103694 Chlorosulfonic acid 7790-94-5 100g 3222 A3 103880 Methanesulfonic acid 75-75-2 500ml 3222 A3 103883 Oxalyl chloride 79-37-8 100ml 3222 A3 103889 Thiodiglycolic acid 123-93-3 500g 3222 A3 103888 Tetrafluoroboric acid 50% 16872-11-0 1L 3222 A3 103886 Tetrafluoroboric acid 50% 16872-11-0 1L 3222 A3 102969 sulfuric acid 7664-93-9 500 mL 2428 A7 102970 hydrochloric acid (37%) 7647-01-0 500 mL 2428 A7 102971 hydrochloric acid (37%) 7647-01-0 500 mL 2428 A7 102973 formic acid (88%) 64-18-6 500 mL 2428 A7 102974 hydrofloric acid (49%) 7664-39-3 500 mL 2428 A7 103320 Ammonium Hydroxide conc.
    [Show full text]
  • Ethylene Glycol
    Ethylene glycol Ethylene glycol (IUPAC name: ethane-1,2-diol) is an organic Ethylene glycol compound with the formula (CH2OH)2. It is mainly used for two purposes, as a raw material in the manufacture of polyester fibers and for antifreeze formulations. It is an odorless, colorless, sweet-tasting, viscous liquid. Contents Production Industrial routes Biological routes Historical routes Uses Coolant and heat-transfer agent Antifreeze Precursor to polymers Other uses Dehydrating agent Hydrate inhibition Applications Chemical reactions Toxicity Environmental effects Names Notes Preferred IUPAC name References Ethane-1,2-diol External links Other names Ethylene glycol 1,2-Ethanediol Production Ethylene alcohol Hypodicarbonous acid Monoethylene glycol Industrial routes 1,2-Dihydroxyethane Ethylene glycol is produced from ethylene (ethene), via the Identifiers intermediate ethylene oxide. Ethylene oxide reacts with water to CAS Number 107-21-1 (http produce ethylene glycol according to the chemical equation: s://commonche mistry.cas.org/d C2H4O + H2O → HO−CH2CH2−OH etail?cas_rn=10 7-21-1) 3D model (JSmol) Interactive This reaction can be catalyzed by either acids or bases, or can occur image (https://ch at neutral pH under elevated temperatures. The highest yields of emapps.stolaf.e ethylene glycol occur at acidic or neutral pH with a large excess of du/jmol/jmol.ph water. Under these conditions, ethylene glycol yields of 90% can be p?model=OCC achieved. The major byproducts are the oligomers diethylene glycol, O) triethylene glycol, and tetraethylene glycol. The separation of these oligomers and water is energy-intensive. About 6.7 million tonnes 3DMet B00278 (http://w are produced annually.[4] ww.3dmet.dna.af frc.go.jp/cgi/sho A higher selectivity is achieved by use of Shell's OMEGA process.
    [Show full text]
  • Preferential Synthesis of Ethanol from Syngas Via Dimethyl Oxalate Hydrogenation Over an Integrated Catalyst Chemcomm Chemical Communications Rsc.Li/Chemcomm
    Showcasing research from Professor Yujun Zhao’s laboratory As featured in: at Tianjin University, Tianjin, China. Volume 55 Number 39 14 May 2019 Pages 5527–5672 Preferential synthesis of ethanol from syngas via dimethyl oxalate hydrogenation over an integrated catalyst ChemComm Chemical Communications rsc.li/chemcomm The cooperation of Fe5 C2 and CuZnO–SiO2 remarkably inhibited the formation of byproducts, resulting in a significantly high ethanol yield of about 98%. It opens a new route for the preferential synthesis of ethanol from syngas via hydrogenation of dimethyl oxalate. ISSN 1359-7345 COMMUNICATION Ying He et al . Enantioselective iridium catalyzed α-alkylation of azlactones by a tandem asymmetric allylic alkylation/aza-Cope rearrangement See Yujun Zhao et al ., Chem . Commun ., 2019, 55 , 5555. rsc.li/chemcomm Registered charity number: 207890 ChemComm COMMUNICATION Preferential synthesis of ethanol from syngas via dimethyl oxalate hydrogenation over an Cite this: Chem. Commun., 2019, 55, 5555 integrated catalyst† Received 27th March 2019, Accepted 11th April 2019 Xin Shang, Huijiang Huang, Qiao Han, Yan Xu, Yujun Zhao, * Shengping Wang and Xinbin Ma DOI: 10.1039/c9cc02372k rsc.li/chemcomm An integrated catalyst that contains Fe5C2 and CuZnO–SiO2 with a (B553 K) is necessary for the synthesis of ethanol via DMO hydro- dual-bed configuration was designed for the preferential synthesis of genation, the formation of C3–4OH via the Guerbet reaction would ethanol via dimethyl oxalate hydrogenation. The cooperation of the two be highly facilitated by the surface basic sites on the Cu-based catalyst components remarkably inhibited the formation of various catalysts.17 Li’s group18 achieved a high ethanol yield of 95% by byproducts, resulting in a significantly high ethanol yield of about 98%.
    [Show full text]
  • Octadecenoic Acid
    SAFETY DATA SHEET In accordance with 453/2010 and 1272/2008 (All references to EU regulations and directives are abbreviated into only the numeric term) Issued 2015-06-04 SECTION 1: IDENTIFICATION OF THE SUBSTANCE/MIXTURE AND OF THE COMPANY/UNDERTAKING 1.1. Product identifier Dimethyl Oxalate Trade name 1.2. Relevant identified uses of the substance or mixture and uses advised against Identified uses Laboratory chemicals 1.3. Details of the supplier of the safety data sheet Company Larodan AB Karolinska Institutet Science Park Retzius väg 8 SE-171 65 SOLNA Sweden Telephone +46 20 15 22 00 E-mail [email protected] Website www.larodan.com 1.4. Emergency telephone number In case of emergency contact toxicological information, emergency tel 112 (within Europe) or 1-800-222-1222 (for USA). For other countries, use the built-in emergency number in your cell phone For non-emergency poison information, see http://www.who.int/gho/phe/chemical_safety/poisons_centres/en/ SECTION 2: HAZARDS IDENTIFICATION 2.1. Classification of the substance or mixture Classification in accordance with 1272/2008 Upon assessment, this substance is not classified as hazardous according to 1272/2008. 2.2. Label elements Label information in accordance with 1272/2008 Hazard pictograms Not applicable Signal words Not applicable Hazard statements Not applicable 2.3. Other hazards Not relevant. SECTION 3: COMPOSITION/INFORMATION ON INGREDIENTS This product is composed of a pure or almost pure substance. 3.1. Substances Synonyms Ethanedioic acid, 1,​2-​dimethyl ester Chemical formula C4H6O4 Molecular weight 118.09 Constituent Purity DIMETHYL OXALATE >98% CAS No 553-90-2 Occurrence of any impurity, stabilising additive, or individual ingredients other than the main ingredient is indicated by the chemical name and the purity level.
    [Show full text]
  • Palladium Supported Catalysts in CO + RONO Reactions by X.-Z
    Palladium Supported Catalysts in CO + RONO Reactions By X.-Z. Jiang Department of Chemistry, University of Zhejiang, Hangzhou, P. R. China In the past decade much effort has been This article is a summary of our recent studies directed towards the synthesis of dialkyl oxalates on palladium supported catalysts in CO + and dialkyl carbonates directly from carbon MeONO (or EtONO) reactions at atmospheric monoxide and alcohols over palladium supported pressure in the vapour phase (6 - 8). It was found catalysts, under mild reaction conditions (I -4). that the carbonylation reactions of RONO, Although the mechanism of the reactions has not where R represents a methyl or ethyl group, been fully elucidated, the key reactions can be were very sensitive to the support, and that the illustrated by the following equations: main product was particularly dependent on the ,0-R nature of the support, as illustrated in Figure I. CO + 2RONO O=C + 2NO (i) -. Monocarbonylation ‘0- R 0 = C-OR The monocarbonylation of methanol or ethanol 2CO + 2RONO- I + 2NO (ii) can be achieved by introducing the correspon- 0 = C-0-R ding nitrites (methyl nitrite, MeONO, with b.p. (where R represents an alcohol residue). -12OC, or ethyl nitrite, EtONO, with b.p. The conditions required for these chemical 17OC) which were prepared according to reactions to take place are quite mild; for exam- established procedures (9). The nitrite was then ple, dimethyl or diethyl carbonate and oxalate able to react directly with carbon monoxide to can be efficiently prepared in the vapour phase form dimethyl carbonate or diethyl carbonate by bringing carbon monoxide into contact with over fured catalyst beds of palladium supported methyl nitrite or ethyl nitrite, respectively, on on active carbon catalysts, in the gas phase and a palladium fixed bed catalyst, at atmospheric at atmospheric pressure.
    [Show full text]
  • Recent Developments in Homobimetallic Reagents and Catalysts for Organic Synthesis
    Review Organic Chemistry June 2011 Vol.56 No.17: 1753–1769 doi: 10.1007/s11434-011-4470-7 SPECIAL TOPICS: Recent developments in homobimetallic reagents and catalysts for organic synthesis WU Wei, GU DeLiang, WANG ShiMeng, NING YingNan & MAO GuoLiang* Provincial Key Laboratory of Oil and Gas Chemical Technology, College of Chemistry and Chemical Engineering, Northeast Petroleum University, Daqing 163318, China Received September 13, 2010; accepted November 4, 2010; published online May 10, 2011 Organometallics are a family of useful organic chemicals because they play important roles in organic synthesis as reagents and as catalysts. They can be classified according to the number of metals they contain. Bimetallic compounds are important or- ganometallics and they are either homobimetallic or heterobimetallic depending on whether the two metals are the same or dif- ferent. In this paper, we focus on homobimetallic compounds. Homobimetallic compounds are generally used as dianions to react with electrophiles in organic synthesis. Recently, homobimetallics have also been used as catalysts in organic reactions such as in asymmetric reactions. homobimetallics, reagent, catalyst, synthesis, application Citation: Wu W, Gu D L, Wang S M, et al. Recent developments in homobimetallic reagents and catalysts for organic synthesis. Chinese Sci Bull, 2011, 56: 1753−1769, doi: 10.1007/s11434-011-4470-7 1 Homobimetallic reagents for organic um exchange, transmetalation reactions, carbon-heteroatom synthesis bond cleavage and the lithiation of multiple carbon-carbon bonds, etc. [3]. Homobimetallic reagents can be classified according to the relative positions of the two carbon atoms that bear the 1.1 1,1-Bimetallic compounds metal atoms.
    [Show full text]
  • Hydrogenation of Dimethyl Oxalate to Ethylene Glycol Over Silica Supported Copper Catalysts
    University of South Carolina Scholar Commons Theses and Dissertations Fall 2020 Hydrogenation of Dimethyl Oxalate to Ethylene Glycol Over Silica Supported Copper Catalysts Xinbin Yu Follow this and additional works at: https://scholarcommons.sc.edu/etd Part of the Chemical Engineering Commons Recommended Citation Yu, X.(2020). Hydrogenation of Dimethyl Oxalate to Ethylene Glycol Over Silica Supported Copper Catalysts. (Doctoral dissertation). Retrieved from https://scholarcommons.sc.edu/etd/6129 This Open Access Dissertation is brought to you by Scholar Commons. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of Scholar Commons. For more information, please contact [email protected]. HYDROGENATION OF DIMETHYL OXALATE TO ETHYLENE GLYCOL OVER SILICA SUPPORTED COPPER CATALYSTS by Xinbin Yu Bachelor of Science Ningxia University, 2012 Master of Science Tianjin University, 2015 Submitted in Partial Fulfillment of the Requirements For the Degree of Doctor of Philosophy in Chemical Engineering College of Engineering and Computing University of South Carolina 2020 Accepted by: Christopher T. Williams, Major Professor John R. Monnier, Committee Member Andreas Heyden, Committee Member Aaron K. Vannucci, Committee Member Cheryl L. Addy, Vice Provost and Dean of the Graduate School © Copyright by Xinbin Yu, 2020 All Rights Reserved. ii DEDICATION I would like to dedicate this work to my family. iii ACKNOWLEDGEMENTS I would like to thank my family for encouraging and supporting me to pursue PhD degree abroad. I also would like to thank my advisor for giving me valuable suggestions in the research and thank national science foundation and industrial companies for sponsoring the research. I would like to thank my committee members for giving me a lot of valuable help and inspiring feedbacks and attending my defense.
    [Show full text]
  • ||||||||||||III USOO5292.917A United States Patent (19) (1) Patent Number: 5,292,917 Nishihira Et Al
    ||||||||||||III USOO5292.917A United States Patent (19) (1) Patent Number: 5,292,917 Nishihira et al. 45 Date of Patent: Mar. 8, 1994 54 PROCESS FOR PURIFYING DIMETHYL 58) Field of Search ......................................... 558/277 CARBONATE 56 References Cited 75 Inventors: Keigo Nishihira; Shinichi Yoshida; Shuji Tanaka, all of Ube, Japan U.S. PATENT DOCUMENTS 4,467,109 8/1984 Tahara et al. ....................... 560/193 73) Assignee: Ube Industries, Ltd., Yamaguchi, Japan 4,663,477 5/1987 Crandall et al. .................... 560/204 Primary Examiner-Mary C. Lee 21 Appl. No.: 56,891 Assistant Examiner-Michael Ambrose 22 Filed: May 5, 1993 Attorney, Agent, or Firn-Finnegan, Henderson, Farabow, Garrett & Dunner Related U.S. Application Data 57 ABSTRACT 63 Continuation of Ser. No. 837,881, Feb. 9, 1992. Disclosed a process for purifying dimethyl carbonate (30) Foreign Application Priority Data which comprises distillating a mixture of dimethyl car bonate and methanol in the presence of dimethyl oxa Feb. 26, 1991 (JP Japan .................................. 2-053148 late to separate and remove methanol. 51) int. Cli.............................................. CO7C 69/96 52 U.S.C. .................................................... 558/277 4 Claims, 1 Drawing Sheet U.S. Patent Mar. 8, 1994 5,292,917 F. G. ... O O.9 | | | | | | U-2 O. 8 | | | | I-4-31 O.7 | || 424 y O.6 41 || 4 || O.5 4 || 4 || | O. 4 /YA/P | 14 | ||| | ||| | | O.3 // 1 | | | | | | O.2 //1 || | | | | | O. 4 || | | | | || O O O. O.2 O.3 O.4 O5 O.6 O.7 O.8 O.9 1.O X o Without addition of dimethyl oxalate O Addition of dimethyl oxalate F.
    [Show full text]
  • Coal to Desired Fuels and Chemicals
    Coal to Desired Fuels and Chemicals Maohong Fan SER Professor in the Department of Chem. & Petroleum Eng. UNIVERSITY OF WYOMING 2-4-2013 [email protected] Phone: (307) 766 5633 1 I’m dirty I’m sticky I’m smelly Oil Coal Without me, life isn’t easy! I’m picky I’m rusty I’m sneaky Trona Iron ore Rare earth Maohong Fan’s Research Group UW’s Clean Coal Technology Development Map CO + small amout of CH CO 2 4 H2 IGCC Electric Dried coal impregnated Separation Power with catalysts Light tar separation Catalytic pyrolysis (note: One of the (into naphthalene, 1‐ objectives is to minimize Synthetic mode in the same naphthaleneacetic Urea Feed gases: CO2 + ammonia reactor CH4 production in acid, anthracene, limited O2 DME pyrolyis and gasification phenol, diesel modes) Olefins High‐value Synthesis of Char/coke carbon based methanol H2O Chemicals 1st choice of feed gases: materials Synthesis conversion Gasoline CO2 + H :CO≈2 + near zero CH F‐Tsynthesis Catalytic gasification (converting the CO & H 2 4 limited O2 2 nd nd mode in the same obtained with 2 choice Jet/Diesel 2 choice of feed gases: CO2 reactor CO2 of feed gases) higher + CH4 (natural gas) alcohols limited O2 + H2O CO+CO2 CO + zero H + zero CH Cleaning & Catalytic CO coupling 2 4 Oxalic acid separating CO +CO2 (converting the CO obtained with 1st obtained with 1st choice choice of feed gases of feed gases) Ethylene Polyester glycol CO2 Ethanol Three Sample Projects to Be Presented Catalytic Coal Pyrolysis and Gasification ◦ Na-Fe based Syngas to liquids ◦ Ethylene glycol Environmental management
    [Show full text]
  • Safety Data Sheet
    SAFETY DATA SHEET Creation Date 17-May-2010 Revision Date 15-Jan-2021 Revision Number 4 SECTION 1: IDENTIFICATION OF THE SUBSTANCE/MIXTURE AND OF THE COMPANY/UNDERTAKING 1.1. Product identifier Product Description: Dimethyl oxalate Cat No. : A15359 Synonyms Methyl oxalate CAS-No 553-90-2 EC-No. 209-053-6 Molecular Formula C4 H6 O4 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 Thermo Fisher (Kandel) GmbH . Erlenbachweg 2 76870 Kandel Germany Tel: +49 (0) 721 84007 280 Fax: +49 (0) 721 84007 300 E-mail address [email protected] www.alfa.com Product safety Tel + +049 (0) 7275 988687-0 1.4. Emergency telephone number Carechem 24: +44 (0) 1235 239 670 (Multi-language emergency number) Poison Information Center Mainz www.giftinfo.uni-mainz.de Telephone: +49(0)6131/19240 Exclusively for customers in Austria: Poison Information Center (VIZ) Emergency call 0-24 clock: +43 1 406 43 43 Office hours: Monday to Friday, 8am to 4pm, tel: +43 1 406 68 98 SECTION 2: HAZARDS IDENTIFICATION 2.1. Classification of the substance or mixture CLP Classification - Regulation (EC) No 1272/2008 Physical hazards ______________________________________________________________________________________________ ALFAAA15359 Page 1 / 10 SAFETY DATA SHEET Dimethyl oxalate Revision Date 15-Jan-2021 ______________________________________________________________________________________________ Based on available data, the classification criteria are not met Health hazards Skin Corrosion/Irritation Category 2 (H315) Serious Eye Damage/Eye Irritation Category 2 (H319) Environmental hazards Based on available data, the classification criteria are not met Full text of Hazard Statements: see section 16 2.2.
    [Show full text]
  • Synthesis, Reactions and Biological Activity of Quinoxaline Derivatives
    American Journal of Organic Chemistry 2015, 5(1): 14-56 DOI: 10.5923/j.ajoc.20150501.03 Synthesis, Reactions and Biological Activity of Quinoxaline Derivatives Ameen Ali Abu-Hashem1,2,* 1Photochemistry Department (Heterocyclic Unit), National Research Centre, Giza, Egypt 2Chemistry Department, Faculty of Science, Jazan University, Saudi Arabia Abstract The review deals with synthesis and reactions of quinoxaline derivatives as well as their diverse pharmacological and biological properties. Quinoxalines and fused ring systems show diverse pharmacological activities. Syntheses of quinoxaline derivatives via many different methods of synthetic strategies have been presented. Keywords Quinoxalines, o-phenylenediamine, Oxidation, Nitration, Diazotization, Alkylation, Addition, Condensation, Cyclization, Substitutions reactions 1. Introduction 2.1. Antimicrobial Activity Quinoxaline-1, 4-di-N-oxide derivatives, Quinoxaline derivatives have different pharamacological pyrazoloquinoxalines and 2-[4-arylidene hydrazinocarbonyl) activities such as bacteriocides and insecticides [1], aniline]-3-methyl quinoxalines (274, 275, 276, 277, 278) antibacterial [2-5], antifungal [2, 6], antitubercular [2, 7-9, respectively have been identified as antibacterial, Antifungal 10], analgesic [4, 11] and anti-inflammatory [11, 12]. The agents and antimicrobial activity [2, 52, 53, 54, 55] as shown importance of quinoxaline derivatives comes from its in (Figure 2). nitrogen contents (heterocyclic compounds). A structure of ring fused with quinoxalines, display 2.2. Anti-Amoebic, Anti-Proliferative Activity diverse pharmacological activities (antibacterial, anticancer 2-(5-substituted-3-phenyl-2-pyrazolinyl)-1, 3-thiazolino and antiviral) [13, 14], antimalarial [15, 16] and anti- [5, 4-b] quinoxaline 279 was tested in vitro as anti-amoebic depressant activities [17]. Quinoxaline-diones derivatives activity against strain of (E. histolytica) [56].
    [Show full text]
  • A Sustainable Process Design to Produce Diethyl Oxalate Considering
    Computers and Chemical Engineering 115 (2018) 198–212 Contents lists available at ScienceDirect Computers and Chemical Engineering journal homepage: www.elsevier.com/locate/compchemeng A sustainable process design to produce diethyl oxalate considering NO x elimination ∗ Jiaxing Zhu 1, Lin Hao 1, Yaozhou Sun, Bo Zhang, Wenshuai Bai, Hongyuan Wei School of Chemical Engineering and Technology, Tianjin University, Tianjin, China a r t i c l e i n f o a b s t r a c t Article history: Diethyl oxalate (DEO) is widely used in fine chemical industry. In comparison with traditional esterifica- Received 15 December 2017 tion process, carbon monoxide coupling process is a novel routine for DEO production. This environmen- Revised 20 March 2018 tally friendly process provides better selectivity and yield. Its unique feature is that a closed regeneration- Accepted 2 April 2018 coupling circulation is formed. Toxic byproduct-nitric oxide (NO) from coupling reaction is recycled to Available online 10 April 2018 re-produce ethyl nitrite through regeneration reaction. This avoids significant amount of NO x emission. Keywords: However, due to a few NO x emission, a contaminant handling system is applied for environmental pro- Design tection. A systematical environmental analysis is also carried out to assess this process. Regeneration- Diethyl oxalate coupling circulation brings interaction behaviors and some trade-offs including reactor size and recycle NOx emission flowrate, regeneration and coupling reaction, loss of reactants and NO emission. Thus, a rigorous steady Contaminant handling system simulation is established to investigate these trade-offs. Then DEO process is optimized to obtain the Systematical environmental analysis optimal design.
    [Show full text]