Part I Asymmetric Reduction of Ketones with the Grignard Reagent from R-1

Total Page:16

File Type:pdf, Size:1020Kb

Part I Asymmetric Reduction of Ketones with the Grignard Reagent from R-1 University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Spring 1970 PART I ASYMMETRIC REDUCTION OF KETONES WITH THE GRIGNARD REAGENT FROM R-1-BROMO-2-PHENYLETHANE-1,1,2-DEUTERIUM(3) PART II ELECTROPHILICALLYASSISTED NUCLEOPHILIC OPENING OF OPTICALLY ACTIVE STYRENE-OXIDE JOSEPH EDWARD TOMASZEWSKI Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation TOMASZEWSKI, JOSEPH EDWARD, "PART I ASYMMETRIC REDUCTION OF KETONES WITH THE GRIGNARD REAGENT FROM R-1-BROMO-2-PHENYLETHANE-1,1,2-DEUTERIUM(3) PART II ELECTROPHILICALLYASSISTED NUCLEOPHILIC OPENING OF OPTICALLY ACTIVE STYRENE-OXIDE" (1970). Doctoral Dissertations. 925. https://scholars.unh.edu/dissertation/925 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. PART I. ASYMMETRIC REDUCTION OF KETONES WITH THE GRIGNARD REAGENT FROM R-1 -BROMO- 2 -PHENYLETHANE-1,1,2-d s PART II. ELECTROPHILICALLY ASSISTED NUCLEOPHILIC OPENING OF OPTICALLY ACTIVE STYRENE OXIDE by JOSEPH EDWARD TOMASZEWSKI B. S., University of Scranton, 1965 A THESIS Submitted to the University of New Hampshire In Partial Fulfillment of The Requirements for the Degree of Doctor of Philosophy Graduate School Department of Chemistry March, 1970 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. This thesis has been examined and approved. ?s D. Morrison, Research Director rbciate Professor of Chemistry Rob'er't E . Lyle Professor of Chemistry Associate Professor of Chemistry (], Charles V. Berney Assistant Professor of Chemistry Richard H. skutt Associate Professor of Electrical Engineering 'Tntnd % m o Date Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENTS I would like to thank Dr. James D. Morrison for his invaluable assistance as a research director and friend throughout the years of my studies at the University and especially for his comments during the preparation of this thesis. I would also like to thank Dr. Robert E. Lyle for his comments as the second reader of this thesis and for the use of his gas chromatographic equipment. Special thanks are due to Dr. Harry S. Mosher and Jim Dale of Stanford University for carrying out the NMR analysis of the Grignard reduction products; to my wife- Mary, who persevered through the typing of this thesis to make it a work of art; and also to Bill Walton who allowed the typing to be easier than it might have been. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS LIST OF TABLES ..................................... vii LIST OF FIGURES ................................... ix ABSTRACT ........................................... x*i PART I. ASYMMETRIC REDUCTION OF KETONES WITH THE GRIGNARD REAGENT FROM R-1-BROMO-2-PHENYLETHANE-1,1,2-d3 INTRODUCTION................................... 1 Statement of the P r o b l e m ...................... 9 RESULTS AND DISCUSSION ............................ 10 The Preparation of the Grignard Reagent .... 10 Reactions of the Grignard Reagent ............. 18 EXPERIMENTAL....................................... 39 A n a l y s e s ....................................... 39 Gas-Liquid Phase Chromatography............. 39 Infra-Red....................................... 39 Mass Spectra ................................... 39 Melting Points ................................ 40 NMR ............................................. 40 Optical Rotations .............................. 40 G e n e r a l ......................................... 40 Phenyl -t-Butyl Ketone (36J 42 Phenyl Trifluoromethyl Ketone (38) 42 S-(+)-Methyl Mandelate (18) ................... 43 S-(+)-Methyl-O-Mesyl Mandelate (23) ........... 44 R-(+)-2-Phenylethanol-l,1,2-ds (22) ........... 44 R-l-Bromo-2-Phenylethane-l,l,2~dj (24) .... 45 iv Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Solvolysis to Remove l-Bromo~l-Phenylethane . 46 Grignard Reagent from R-l-Bromo-2-Pheny1- ethane-1,1,2-ds (25) 46 S-(+)“l-Phenylethane-l,2,2-d3 (3j4) ........... 47 Reactions of the Grignard Reagent ............. 47 Phenyl -t-Butyl K e t o n e ..................... 47 Phenyl Trifluoromethyl Ketone . * ......... 48 BIBLIOGRAPHY ....................................... 50 APPENDIXES......................................... 54 I. Determination of Deuterium Content by Mass Spectroscopy ........................ 54 II. Chemical Shifts of the Diastereomeric MTPA Esters of Phenyl'--£-butylcarbinol (37) and Phenyltrifluoromethylcarbinol(39) . 57 PART II. ELECTROPHILICALLY ASSISTED NUCLEOPHILIC OPENING OF OPTICALLY ACTIVE STYRENE OXIDE INTRODUCTION....................................... 61 Synthesis of Optically Active Styrene Oxide . 61 The Reaction of Epoxides with Mixed Hydride R e a g e n t s ..................... 65 Reaction of Epoxides with Borane ............. 78 The Reaction of Epoxides with Grignard Reagents and R a M g ....................................... 84 Statement of the P r o b l e m ..................... 92 RESULTS AND DISCUSSION ............................ 94 The Preparation of Optically Active Styrene O x i d e ........................................... 94 The Reaction of R-(+)-Styrene Oxide with Alane R e a g e n t s ....................................... 97 The Reaction of R-(+)-Styrene Oxide with the B2D6/BF3*OEt2 Reagent .......................... 105 The Reaction of R-(+)-Styrene Oxide with DiethyImagnesium/Magnesiurn Bromide Dioxanate....................................... 110 EXPERIMENTAL.................................... 114 v Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. G e n e r a l ......................................... 114 R-(-)-Methyl Mandelate (64) ................... 115 R-(-)-l-Phenyl-l,2-Ethanediol ( 2 ) ............. 115 R- (-) -2-Brosyloxy-l-Phenylethanol (65^) .... 115 R-(+)-Styrene Oxide (4) ....................... 116 Reactions of R-(+)-Styrene O x i d e ............. 117 Reaction with AlDs/EtaO Reagent ........... 117 Reaction with AlDa/THF Reagent ............. 118 Reaction with B2D 6/BF3*0Et2 Reagent .... 119 Reaction with Die thylmagnes ium/Magnes i urn Bromide*Dioxanate .......................... 120 S-(-)-Styrene Oxide (S-_4)..................... 122 BIBLIOGRAPHY....................................... 123 vi Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OF TABLES PART I. ASYMMETRIC REDUCTION OP KETONES WITH THE GRIGNARD REAGENT FROM R-l-BROMO-2-PHENYLETHANE-l,1,2-d3 Table Page 1. Asymmetric Reduction of Alkvl Phenyl Ketones by Grignard Reagents ...................... 4 2. Deuterium Analysis of R-(+)-2-Phenylethanol- 1,1,2-dj (22) and R~l--Bromo-2- Phenylethane-l/l,2-d3 (24) by Mass Spectroscopy .............................. 17 3. Rotations of R-(+)-2-Phenylethanol-l,1,2-dj (22) and S-(+)-1-Phenylethane-l,2,2-dj ( 3 4 ) ....................................... 21 4. Reduction Products from the Reaction of the Grignard Reagent 25 with Phenyl £-Butyl and Phenyl Trifluoromethyl Ketones .... 22 5. NMR Analysis of the MTPA Esters of Phenyl- -t-butylcarbinol (37) and Phenyltrifluoro- methylcarbinol (39) 27 6 . Calculated Free Energy Differences Between the Competing Modes of Reduction for Phenyl £~Butyl (36) and Phenyl Trif luoro­ methyl Ketones ( 3 8 ) ..................... 32 PART II. ELECTROPHILICALLY ASSISTED NUCLEOPHILIC OPENING OF OPTICALLY ACTIVE STYRENE OXIDE 1. Reduction of Styrene Oxide with "Mixed Hydride" Reagents ........................ 67 2. Reduction of Epoxides with "Mixed Hydride" R e a g e n t s .................................. 67 3. Reduction of 3-Methylcyclohexene Oxide with Hydride Reagents .......................... 69 4. Reduction of Epoxides with Alane/THF Reagent and LiAlHi*................................ 74 vii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Table Page 5. Reaction of Epoxides with B3H6/BF3»0Et2 R e a g e n t .................................. 84 6. Results of the Reduction of R-(+)-Styrene Oxide with the AlDs/EtjO Reagent ..... 98 7. Results of the Reduction of R-(+)-Styrene Oxide with the AID3/THF Reagent . 99 8. Results of the Reaction of R-(+)-Styrene Oxide with the B2D6/BF3«0Et2 Reagent . 106 9. Results of the Reaction of R-(+)-Styrene Oxide with Et2Mg/MgBr2 *Dioxanate . Ill viii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OP FIGURES PART I. ASYMMETRIC REDUCTION OF KETONES WITH THE GRIGNARD REAGENT FROM R-1-BROMO-2-PHENYLETHANE-l,1,2-d3 Figure Page 1. Reduction and Addition Reactions of Carbonyl Compounds with Grignard Reagents ................................ 1 2. Whitmore Mechanism for Grignard Reductions .............................. 2 3. Competing Transition States in the Asymmetric Reduction Reaction ........... 4 4. Preparation of the Grignard Reagent 25 . 13 5. Green Scheme for the Preparation of S- (-) - 2-Phenylethanol-2-d ...................... 14 6. DePuy Scheme for the Preparation of Optically Active 2-Phenylethanol-2-d
Recommended publications
  • WO 2008/096257 Al
    (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (43) International Publication Date PCT (10) International Publication Number 14 August 2008 (14.08.2008) WO 2008/096257 Al (51) International Patent Classification: 500038 (IN). BURIDIPADU, Sunil Kumar [IN/IN]; C07D 239/42 (2006.01) Aurobindo Pharma Limited, Plot No.2, Maitrivihar, Ameerpet, Andhra Pradesh, Hyderabad 500038 (IN). (21) International Application Number: MEENAKSHISUNDERAM, Sivakumaran [IN/IN]; PCT/IB2008/000290 Aurobindo Pharma Limited, Plot No.2, Maitrivihar, Ameerpet, Andhra Pradesh, Hyderabad 500038 (IN). (22) International Filing Date: 4 February 2008 (04.02.2008) (81) Designated States (unless otherwise indicated, for every (25) Filing Language: English kind of national protection available): AE, AG, AL, AM, AO, AT,AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, CA, (26) Publication Language: English CH, CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, (30) Priority Data: IL, IN, IS, JP, KE, KG, KM, KN, KP, KR, KZ, LA, LC, 277/CHE/2007 8 February 2007 (08.02.2007) IN LK, LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, 1121/CHE/2007 29 May 2007 (29.05.2007) IN MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, PG, PH, PL, PT, RO, RS, RU, SC, SD, SE, SG, SK, SL, SM, SV, (71) Applicant (for all designated States except US): AU- SY, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ROBINDO PHARMA LIMITED [IN/IN]; Plot No.2, ZA, ZM, ZW Maitrivihar, Ameerpet, Andhra Pradesh, Hyderabad 500038 (IN).
    [Show full text]
  • The Development of Simplified Microreactors for Use in Multi-Step Reaction Sequences
    THE DEVELOPMENT OF SIMPLIFIED MICROREACTORS FOR USE IN MULTI-STEP REACTION SEQUENCES A Dissertation Presented to the Faculty of the Graduate School of Cornell University In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy by Andrew R. Bogdan August 2009 © 2009 Andrew R. Bogdan THE DEVELOPMENT OF SIMPLIFIED MICROREACTORS FOR USE IN MULTI-STEP REACTION SEQUENCES Andrew R. Bogdan, Ph. D. Cornell University 2009 This dissertation describes the development of simplified microreactors to be used in multi-step reaction sequences. Microreactors are a developing technology with numerous benefits and whose modular design permits multi-step reaction sequences to be performed in a continuous flow process. The first chapter discusses the physical properties of microreactors and describes how performing reactions in these miniaturized reactors leads to safer, more efficient and more selective chemical transformations. A brief discussion of multi-step reaction sequences already performed in flow will also be presented. These multi-step reaction sequences, however, rarely rely on catalysis to facilitate chemical transformations. This area therefore has room for great improvement. The next two chapters discuss the development and application of solid-supported catalysts to be used in flow. In the first of these two chapters, two catalysts are immobilized on a solid-support and used in a simplified flow reactor. These reactions proved to be more efficient than similar batch reaction and the catalysts were highly recyclable. The next chapter presents a supported TEMPO catalyst used to oxidize alcohols to carbonyl species. These three catalysts set the foundation for multi-step flow reaction to be potentially performed in the group.
    [Show full text]
  • United States Patent Office Paterated Feb
    3,306,895 United States Patent Office Paterated Feb. 28, 1967 1. 2 3,306,895 The compounds of this invention are obtained by treat HETEROCYCLIC DERVATIVES OF TRPHENYL ment of triphenylethylene derivatives of the type: , ETHYLENES, TRIPHENYLETHANES AND TRI PHENYLETHANOLS Edward McCreery Roberts, George Philip Claxton, and 5 Frances Gertrude Fallon, Cincinnati, Ohio, assignors to Richardson-Merrell Inc., New York, N.Y., a corpo ration of Delaware No Drawing. Filed June 27, 1962, Ser. No. 205,551 10 Claims. (C. 260-240) k This invention relates to a series of novel and useful O where R and R' are as previously defined, with an ap compounds and processes for preparing the same. More propriate organometallic derivative such as cy-picolyl particularly, this invention relates to a series of triphenyl lithium (as in Examples 2 and 5), 3-pyridyl lithium (as ethanes, triphenylethylenes, and triphenylethanols, in in Example 6), or 2-pyridyl lithium (as in Examples 1 which one of the phenyl groups is substituted with a pyri and 4). Such treatment is conveniently carried out by dyl or reduced pyridyl ring which is separated from the mixing the reactants in an inert solvent such as ether, aromatic portion of the molecule by an oxygenated alkyl benzene, toluene, or combinations of such inert solvents fragment of one, two or three carbon atoms. The inven at appropriate temperatures chosen in the range of tion also includes nontoxic, water-soluble addition salts, -60° C. to 80° C. The resulting imine is hydrolyzed to quaternary ammonium derivatives and N-oxide deriva the corresponding ketone without being isolated by being tives of the new compounds.
    [Show full text]
  • Benzopinacolate Promoted Radical Carbon-Carbon Bond Forming
    Bis(trimethylstannyl)benzopinacolate Promoted Radical Carbon-Carbon Bond Forming Reactions and Related Studies Dissertation Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Franklin Lee Seely Graduate Program in Chemistry The Ohio State University 2010 Dissertation Committee: Robert S. Coleman, Co-Advisor David J. Hart, Co-Advisor T. V. RajanBabu Abstract This research has dealt primarily with the development of novel methods for radical carbon-carbon bond formation. A major focus of this research has been the hydrogen atom free generation of trialkyltin radicals. The bulk of this thesis will deal with the use of bis(trimethylstannyl)benzopinacolate 1 in mediating radical reactions. We have demonstrated that these conditions allow a wide variety of inter and intramolecular free radical addition reactions. We have given evidence that these reactions proceed via a novel non-chain free radical mechanism. ii Dedication This thesis is dedicated to Tracy Lynne Court. You have given me the courage to try again. iii Acknowledgments I would like to sincerely thank Dr. David J. Hart for all his help, the countless hours of work he put in, and for making this possible. I would like to thank Dr. Robert S. Coleman for agreeing to act as my advisor, and all the support and guidance he has given. I would like to than Dr. T. V. RajanBabu for reading my thesis and all his thoughtful suggestions. iv Vita Education 1981-1985 ………………………………………………………..B.S., The University
    [Show full text]
  • (12) United States Patent (10) Patent No.: US 6,800,658 B2 Brugnara Et Al
    USOO6800658B2 (12) United States Patent (10) Patent No.: US 6,800,658 B2 Brugnara et al. (45) Date of Patent: Oct. 5, 2004 (54) SUBSTITUTED DIPHENYL INDANONE, 5,273,992 A 12/1993 Brugnara et al. ........... 514/398 NDANE AND INDOLE COMPOUNDS AND 5,358,959 A 10/1994 Halperin et al. ...... ... 514/396 ANALOGUES THEREOF USEFUL FOR THE 5,430,062 A 7/1995 Cushman et al. ..... ... 514/646 5,512.563 A * 4/1996 Albright et al. ............ 514/217 TREATMENT OF PREVENTION OF 2002/0128256 A1 * 9/2002 Brugnara et al. ...... 514/212.02 DISEASES CHARACTERIZED BY ABNORMAL CELL PROLIFERATION FOREIGN PATENT DOCUMENTS (75) Inventors: Carlo Brugnara, Newton Highlands, DE 37O6427 9/1988 DE 1OOO4654 8/2001 MA (US); Jose Halperin, Brookline, EP O323 740 A2 7/1989 MA (US); Rudolf Fluckiger, Brookline, EP 483632 5/1992 MA (US); Emile M. Bellott, Jr., EP O 583 665 A2 2/1994 Beverly, MA (US); Richard John EP O 636 608 A1 2/1995 Lombardy, Littleton, MA (US); John JP OS 58894 3/1993 J. Clifford, Arlington, MA (US); JP OSOSO771 3/1993 Ying-Duo Gao, Meshanie Station, NJ WO WO 89/08096 9/1989 (US); Reem M. Haidar, Woburn, MA WO WO95/26720 10/1995 (US); Eugene W. Kelleher, Somerville, WO WO 96/08240 3/1996 MA (US); Adel M. Moussa, WO WO 96/08242 3/1996 Burlington, MA (US); Yesh P. WO WO 96/36631 11/1996 Sachdeva, Concord, MA (US); WO WO 99/26624 6/1999 Minghua Sun, Cambridge, MA (US); WO WO O2/32465 4/2002 Heather N.
    [Show full text]
  • Iron-Catalysed Enantioconvergent Suzuki-Miyaura Cross-Coupling to Afford Enantioenriched 1,1-Diarylalkanes
    Electronic Supplementary Material (ESI) for Chemical Communications. This journal is © The Royal Society of Chemistry 2020 Iron-Catalysed Enantioconvergent Suzuki-Miyaura Cross-Coupling to Afford Enantioenriched 1,1-Diarylalkanes Chet C. Tyrol, Nang S. Yone, Connor F. Gallin, Jeffery A. Byers* Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, United States General Considerations .................................................................................................. 1 Synthetic Procedures ...................................................................................................... 3 Figure S1. Synthesis of cyano-bis(oxazoline) ligands and iron complexes ..................... 3 Synthesis of Diarylalkanes ............................................................................................. 18 Preparation of arylboronic pinacol esters ..................................................................... 30 Preparation of benzylic halides ...................................................................................... 31 Figure S2. Resubjection of enantiomerically-enriched product ......................................... 36 Table S1. Solvent and additive screen .............................................................................. 37 Table S2. Bis(oxazoline) ligand screen ............................................................................. 38 Table S3. Effect of catalyst loading ..................................................................................
    [Show full text]
  • ME Manning Et Al., Chem. Abstract 94.102538, 1981
    USOO6992O79B2 (12) United States Patent (10) Patent No.: US 6,992,079 B2 Brugnara et al. (45) Date of Patent: *Jan. 31, 2006 (54) SUBSTITUTED 4,006,023 A 2/1977 McLaughlin et al. ....... 96/90 R 11-PHENYL-DBENZAZEPINE COMPOUNDS 4,806,685 A 2/1989 Abraham et al. ........... 563/324 USEFUL FOR THE TREATMENT OR 5,273,992 A 12/1993 Brugnara et al. ..... ... 514/398 5,358,959 A 10/1994 Halperin et al. ...... ... 514/396 ERR2E, RMAL cell 5,430,062. A 7/1995 Cushman et al. ........... 514/646 5,512.563 A * 4/1996 Albright et al. ............ 514/217 PROLIFERATION 6,063,921 A 5/2000 Moussa et al. (75) Inventors: Carlo Brugnara, Newton Highlands, 6,291,4496,201,120 B1 9/20013/2001 Ms t alal. MA (US); Jose Halperin, Brookline, 6,534,497 B1 * 3/2003 Brugnara et al. ........... 514/217 MA (US); Rudolf Fluckiger, Brookline, 2001/0007030 A1 7/2001 Moussa et al. MA (US); Emile M. Bellott, Jr., Beverly, MA (US); Richard John FOREIGN PATENT DOCUMENTS Lombardy, Littleton, MA (US); John EP O 323 740 A2 7/1989 J. Clifford, Arlington, MA (US); EP O 583 665 A2 2/1994 Ying-Duo Gao, Edison, NJ (US); Reem EP O 636 608 A1 2/1995 M. Haidar, Woburn, MA (US); Eugene JP OS 58894 3/1993 W. Kelleher, Medford, MA (US); Adel WO WO95/26720 10/1995 M. Moussa, Burlington, MA (US); WO WO 96/08240 3/1996 Yesh P. Sachdeva, Concord, MA (US); W W 't f1. Minghua Sun, Libertyville, IL (US); Heather N.
    [Show full text]
  • Chemfiles 9.3 Cover.Indd 1 6/18/2009 7:49:52 AM Vol
    Vol. 9, No. 3 Chiral Building Blocks Features include: A–Z Product Listings Heterocyclic Building Blocks Organic Building Blocks (S)-(–)-Glycidol: chiral epoxide building block used in synthesis of many pharmaceuticals and natural products 70978 ChemFiles 9.3 cover.indd 1 6/18/2009 7:49:52 AM Vol. 9 No. 3 Introduction Asymmetric synthesis remains a challenge to synthetic chemists as Aldrich Chemical Co., Inc. the demand for enantiomerically pure compounds continues to Sigma-Aldrich Corporation increase. Whether the building blocks are used in the development 6000 N. Teutonia Ave. of new and exciting chiral auxiliaries, ligands, or for obtaining Milwaukee, WI 53209, USA advanced and enantiomerically enriched druglike molecules, research scientists continually need access to a vast array of novel chiral building blocks and architectures to achieve success. To Place Orders In this edition of ChemFiles, we have endeavored to provide a comprehensive listing of over 1000 chiral building blocks. Within Telephone 800-325-3010 (USA) each section of this issue, products are listed by increasing FAX 800-325-5052 (USA) carbon content. Introduction Mark Redlich Sigma-Aldrich is lists over 5000 chiral products for the successful Product Manager Customer & Technical Services construction of complex asymmetric architectures—for a complete listing of products related to chiral chemistry and asymmetric synthesis, please visit us at Customer Inquiries 800-325-3010 sigma-aldrich.com/chiral. If you are unable to find a product for Technical Service 800-231-8327 your research, “Please Bother Us” at [email protected] or contact your local SAFC® 800-244-1173 Sigma-Aldrich office.
    [Show full text]
  • Adsorption Behavior of the Primary, Secondary and Tertiary Alkyl, Allyl and Aryl Alcohols Over Nanoscale (1 0 0) Surface of Γ-Alumina
    Adsorption Behavior of the Primary, Secondary and Tertiary Alkyl, Allyl and Aryl Alcohols Over Nanoscale (1 0 0) Surface of γ-Alumina Mehdi Zamani1,2*, Hossein A. Dabbagh2* 1) Department of Chemistry, Malek-ashtar University of Technology, Shahin-shahr P.O. Box 83145/115, Islamic Republic of Iran 2) Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Islamic Republic of Iran Abstract In this study, the adsorption behavior of the primary, secondary and tertiary alcohols over nanoscale (1 0 0) surface of defect spinel γ-alumina was investigated with the aid of density functional theory (DFT) at BLYP/DNP level of calculation. The influence of different substituents including alkyl, cycloalkyl, allyl and aryl were analyzed for free and adsorbed alcohols to shed light the adsorption selectivity of these compounds over γ-alumina surface. These results indicate that more branches at position of alcohol favor the adsorption, while a decrease in adsorption energy is achieved for the alcohols containing the substituents at the β position. The tertiary alcohols are adsorbed over the surface stronger than secondary and primary alcohols. Alcohols with larger alkyl chains have greater adsorption energies. Also the aryl alcohols are adsorbed over the surface better than the alkyl and allyl moieties. Keywords: Nanoscale surface of γ-Alumina; Alcohol; Molecular adsorption; DFT © 2014 Published by Journal of Nanoanalysis. 1. Introduction Alumina is well known catalyst by both acidic and basic properties. In recent years, many experimental and theoretical works have studied the structure, reactivity and selectivity of γ-alumina especially at nanoscale (1-23). Theoretical investigations of the adsorption on γ-alumina have focused mostly on Lewis acidity of the surface (1-4), and the reactivity with water (5-11), hydrogen sulfide (5,10,12), carbon monoxide (5,10,13), ammonia (6), pyridine (4,6), hydrogen chloride (7), alkenes (14,15), alkanes (16), alcohols (17-23) and ethers (23).
    [Show full text]
  • (12) United States Patent (10) Patent No.: US 8,349,977 B2 Koenig Et Al
    US008349977B2 (12) United States Patent (10) Patent No.: US 8,349,977 B2 Koenig et al. (45) Date of Patent: Jan. 8, 2013 (54) PROCESS FOR PREPARING W. W338 A .289 SETITY ISOBUTENE HOMO- OR WO WO 2010, 139684 A1 12/2010 OTHER PUBLICATIONS (75) Inventors: Hannah Maria Koenig, Mannheim (DE); Klaus Muellbach, Gruenstadt Edward C. Leonard. “High Polymers'. Wiley-Interscience, A Divi (DE); Matthias Kiefer, Ludwigshafen sion of John Wiley & Sons, Inc., vol. XXIV. (part 2), 1971, 1 front (DE); Sergei V. Kostjuk, Minsk (BY); page, pp. 713-733. 66/ - - - - - Irina Vasilenko, Minsk (BY): James D. Burrington, et al., Cationic polymerization using s s heteropolyacid salt catalysts'. Topics in Catalysis, vol. 23, Nos. 1-4. Alexander Frolov, Svisloch (BY) Aug. 2003, pp. 175-181. Sergei V. Kostjuk, et al., “Novel Initiating system based on AlCl (73) Assignee: BASFSE, Ludwigshafen (DE) etherate for quasiliving cationic polymerization of styrene'. Polymer Bulletin, vol. 52, 2004, pp. 227-234. (*) Notice: Subject to any disclaimer, the term of this Sergei V. Kostjuk, et al., “Cationic Polymerization of Styrene in patent is extended or adjusted under 35 Solution and Aqueous Suspension Using B(C6F5) as a Water-Toler U.S.C. 154(b) by 0 days. ant Lewis Acid', Macromolecules, vol.39, No. 9, Apr. 8, 2006, pp. 3110-3113. (21) Appl. No.: 13/029,413 U.S. Appl. No. 13/126,857, filed Apr. 29, 2011, Hildebrandt, et al. U.S. Appl. No. 13/305,132, filed Nov. 28, 2011, Koenig, et al. (22) Filed: Feb. 17, 2011 U.S. Appl. No. 13/305,283, filed Nov.
    [Show full text]
  • Spectra Library Index SDBS Library
    S p e c t r a L i b r a r y I n d e x SDBS Library KBr ライブラリー名:スタンダードライブラリーKBr 商品番号:40001-40 株式会社 エス・ティ・ジャパン 〒103-0014 東京都中央区日本橋蛎殻町 1-14-10 Tel: 03-3666-2561 Fax:03-3666-2658 http://www.stjapan.co.jp 1 【販売代理店】(株)テクノサイエンス Tel:043-206-0155Fax:043-206-0188 http://www.techno-lab-co.jp/ (((3,4-DIHYDROXY-9,10-DIOXO-9,10-DIHYDRO-2-ANTHRYL)METHYL)IMINO)DIACETIC ACID (((N-BENZYLOXYCARBONYL-L-PHENYLALANYL)-O-ACETYL-L-THREONYL)-L-PROLYL-L-PHENYLALANYL)-N(OMEGA)-NITRO-L-ARGININE 4-NITROBENZYL ESTER ((1,2-DIETHYLETHYLENE)BIS(P-PHENYLENE))DIACETATE ((1-BENZOTRIAZOLYL)OXY)TRIS(DIMETHYLAMINO)PHOSPHONIUM HEXAFLUOROPHOSPHATE ((2-(3-BENZYLSULFONYL-4-METHYLCYCLOHEXYL)PROPYL)SULFONYLMETHYL)BENZENE ((2,4,6-TRIOXOHEXAHYDRO-5-PYRIMIDINYL)IMINO)DIACETIC ACID ((2-BENZOTHIAZOLYL)AMINOMETHYLENE)MALONONITRILE ((2-CARBOXYETHYL)IMINO)DIACETIC ACID ((2-CYANOETHYLAMINO)(3-INDOLYL)METHYLENE)MALONONITRILE ((2-HYDROXYETHYL)IMINO)DIACETIC ACID ((2-HYDROXYETHYLAMINO)(3-INDOLYL)METHYLENE)MALONONITRILE ((2-NITROBENZYL)IMINO)DIACETIC ACID ((2-OXOPROPYL)IMINO)DIACETIC ACID ((2-PYRIDYLAMINO)METHYLENE)MALONONITRILE ((2-QUINOLINYL)AMINOMETHYLENE)MALONONITRILE ((2-SULFOETHYL)IMINO)DIACETIC ACID ((2-THIAZOLYLAMINO)METHYLENE)MALONONITRILE ((3-(1-BROMO-1-METHYLETHYL)-7-OXO-1,3,5-CYCLOHEPTATRIEN-1-YL)OXY)DIFLUOROBORANE ((3-INDOLYL)(1-PYRROLIDINYL)METHYLENE)MALONONITRILE ((3-INDOLYL)(METHYLTHIO)METHYLENE)MALONONITRILE ((3-INDOLYL)MORPHOLINOMETHYLENE)MALONONITRILE ((3-INDOLYL)PIPERIDINOMETHYLENE)MALONONITRILE ((3-METHYL-2-PYRIDYLAMINO)METHYLENE)MALONONITRILE ((4-METHYL-2-PYRIDYLAMINO)METHYLENE)MALONONITRILE
    [Show full text]
  • Photochemical Synthesis of Β-Lactones and Β- Lactams William Raymond Adams Iowa State University
    Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1967 Photochemical synthesis of β-lactones and β- lactams William Raymond Adams Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Adams, William Raymond, "Photochemical synthesis of β-lactones and β-lactams " (1967). Retrospective Theses and Dissertations. 3988. https://lib.dr.iastate.edu/rtd/3988 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. This dissertation has been microiihned exactly as received 68—2796 ADAMS, William Raymond, 1936- PHOTOCHEMICAL SYNTHESIS OF /3 -LACTONES AND J3 -LACTAMS. Iowa State University, Ph.D., 1967 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan 0? /3-LAC20KZ3 AND /?-LACTAMS by '.Villiam RayTiOnd Adar;.3 A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of •The Requirements for the Degree of aOCTOR 0? PHII030PHY \ %ajor Subject: Organic Che:nis":ry Approved: Signature was redacted for privacy. In Chi or \/oj.'K Signature was redacted for privacy. Signature was redacted for privacy. Iowa Sta":e Univers Of Science and Technology Ames, lov/a 1967
    [Show full text]