Arenechromium Tricarbonyl Complexes: Conformational
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Porphyrin Carbene Complexes: (5,10,15,20-Tetra-P-Tolylporphyrinato )
Chemistry Publications Chemistry 8-1994 Properties and Molecular Structures of Osmium(ll) Porphyrin Carbene Complexes: (5,10,15,20-Tetra-p-tolylporphyrinato )osmium Di-p-tolylmethylidene and (5,10,15,20-Tetra-p- tolylporphyrinato)osmium (Trimethylsilyl)methylidene Jean-Pierre Djukic Iowa State University Daniel A. Smith Iowa State University Victor G. Young Jr. Iowa State University Follow this and additional works at: http://lib.dr.iastate.edu/chem_pubs L. Keith Woo IowaP Satrate of U ntheiversitCyhe, kmiwoo@istryas Ctaommonte.edu s The ompc lete bibliographic information for this item can be found at http://lib.dr.iastate.edu/ chem_pubs/727. For information on how to cite this item, please visit http://lib.dr.iastate.edu/ howtocite.html. This Article is brought to you for free and open access by the Chemistry at Iowa State University Digital Repository. It has been accepted for inclusion in Chemistry Publications by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Properties and Molecular Structures of Osmium(ll) Porphyrin Carbene Complexes: (5,10,15,20-Tetra-p-tolylporphyrinato )osmium Di-p- tolylmethylidene and (5,10,15,20-Tetra-p-tolylporphyrinato)osmium (Trimethylsilyl)methylidene Abstract The first molecular structures of two (porphyrinato)osmium(II) alkylidene complexes are described. The carbene fragments of (5,10,15,20-tetra-p-tolylporphyrinato)osmium (trimethylsilyl) methylidene (1) and (5,10,15,20-tetra-p-tolylporphyrinato)osmium di-p-tolylmethylidene (2) adopt different conformations in the solid state. With respect to the porphyrin ring nitrogen atoms, a staggered conformation is found for the complex 1 carbene moiety (dos-e = 1. -
Retention Indices for Frequently Reported Compounds of Plant Essential Oils
Retention Indices for Frequently Reported Compounds of Plant Essential Oils V. I. Babushok,a) P. J. Linstrom, and I. G. Zenkevichb) National Institute of Standards and Technology, Gaithersburg, Maryland 20899, USA (Received 1 August 2011; accepted 27 September 2011; published online 29 November 2011) Gas chromatographic retention indices were evaluated for 505 frequently reported plant essential oil components using a large retention index database. Retention data are presented for three types of commonly used stationary phases: dimethyl silicone (nonpolar), dimethyl sili- cone with 5% phenyl groups (slightly polar), and polyethylene glycol (polar) stationary phases. The evaluations are based on the treatment of multiple measurements with the number of data records ranging from about 5 to 800 per compound. Data analysis was limited to temperature programmed conditions. The data reported include the average and median values of retention index with standard deviations and confidence intervals. VC 2011 by the U.S. Secretary of Commerce on behalf of the United States. All rights reserved. [doi:10.1063/1.3653552] Key words: essential oils; gas chromatography; Kova´ts indices; linear indices; retention indices; identification; flavor; olfaction. CONTENTS 1. Introduction The practical applications of plant essential oils are very 1. Introduction................................ 1 diverse. They are used for the production of food, drugs, per- fumes, aromatherapy, and many other applications.1–4 The 2. Retention Indices ........................... 2 need for identification of essential oil components ranges 3. Retention Data Presentation and Discussion . 2 from product quality control to basic research. The identifi- 4. Summary.................................. 45 cation of unknown compounds remains a complex problem, in spite of great progress made in analytical techniques over 5. -
Xerox University Microfilms, Ann Arbor, M Ichigan 48106
I I I 77-2394 EDWARDS, Robert Charles, 1949- SYNTHESES AND CHARACTERIZATION OF CHROMIUM COMPLEXES WITH TETRAAZA MACROCYCLIC LIGANDS. The Ohio State University, Ph.D., 1976 Chemistry, inorganic Xerox University Microfilms, Ann Arbor, Michigan 48106 SYNTHESES AND CHARACTERIZATION OF CHROMIUM COMPLEXES WITH TETRAAZA MACROCYCLIC LIGANDS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Robert Charles Edwards, B.S. The Ohio State University 1976 Reading Committee: Approved by Professor Daryle H. Busch Professor Devon W. Meek Professor Eugene P. Schram Advised Department of Chemistry To Debra and Marie & # 5J: aj: % # # # ACKNOWLEDGEMENTS I would like to acknowledge the help given to me by fellow graduate students, post-doctoral fellows in Dr. Busch's group, and the staff in the Department of Chemistry. I want to especially thank Professor Daryle H„ Busch for his guidance and understanding,, iii CURRICULUM VITAE March 2, 1949. ................ ... ..................................................... Born, Marion, Ohio 1971 .................................................. ................................................ B .S., Heidelberg College Tiffin, Ohio 1971-1974. ....................................................................................... Teaching Associate, Dept, of Chemistry, The Ohio State University, Columbus, Ohio 1974-197 5 ................................................................................. Allied-Chemical -
Cyanosilylation of Aldehydes Catalyzed by Ag(I)- and Cu(II)-Arylhydrazone Coordination Polymers in Conventional and in Ionic Liquid Media
catalysts Article Cyanosilylation of Aldehydes Catalyzed by Ag(I)- and Cu(II)-Arylhydrazone Coordination Polymers in Conventional and in Ionic Liquid Media Gonçalo A. O. Tiago 1, Kamran T. Mahmudov 1,2,*, M. Fátima C. Guedes da Silva 1,* , Ana P. C. Ribeiro 1,* , Luís C. Branco 3, Fedor I. Zubkov 4 and Armando J. L. Pombeiro 1 1 Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049–001 Lisboa, Portugal; [email protected] (G.A.O.T.); [email protected] (A.J.L.P.) 2 Department of Chemistry, Baku State University, Z. Xalilov Str. 23, Az 1148 Baku, Azerbaijan 3 LAQV-REQUINTE, Departamento de Química, Faculdade de Ciências e Tecnologias da Universidade Nova de Lisboa, Quinta da Torre, 2829-516 Caparica, Portugal; [email protected] 4 Organic Chemistry Department, Faculty of Science, Peoples’ Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St., Moscow 117198, Russian; [email protected] * Correspondence: [email protected] or [email protected] (K.T.M.); [email protected] (M.F.C.G.d.S.); [email protected] (A.P.C.R.) Received: 22 February 2019; Accepted: 15 March 2019; Published: 20 March 2019 0 Abstract: The novel Ag(I) and Cu(II) coordination polymers [Ag(m3-1κO;2:3κO ;4κN-HL)]n·n/2H2O(1) − and [Cu(en)2(m-1κO;2κN-L)]n·nH2O(2) [HL = 2-(2-(1-cyano-2-oxopropylidene)hydrazinyl)benzene sulfonate] were synthesized and characterized by IR and ESI-MS spectroscopies, elemental and single crystal X-ray diffraction analyses. -
Trimethylsilyl Trifluoromethanesulfonate-Mediated Additions to Acetals, Nitrones, and Aminals Chelsea Safran
University of Richmond UR Scholarship Repository Honors Theses Student Research 4-1-2013 Trimethylsilyl trifluoromethanesulfonate-mediated additions to acetals, nitrones, and aminals Chelsea Safran Follow this and additional works at: http://scholarship.richmond.edu/honors-theses Recommended Citation Safran, Chelsea, "Trimethylsilyl trifluoromethanesulfonate-mediated additions to acetals, nitrones, and aminals" (2013). Honors Theses. Paper 71. This Thesis is brought to you for free and open access by the Student Research at UR Scholarship Repository. It has been accepted for inclusion in Honors Theses by an authorized administrator of UR Scholarship Repository. For more information, please contact [email protected]. Trimethylsilyl trifluoromethanesulfonate-mediated additions to acetals, nitrones, and aminals By Chelsea Safran Honors Thesis In Program In Biochemistry and Molecular Biology University of Richmond Richmond, VA Spring 2012 Advisor: Dr. C. Wade Downey This thesis has been accepted as part of the honors requirements in the Program in Biochemistry and Molecular Biology ______________________________ _________________ (advisor signature) (date) ______________________________ _________________ (reader signature) (date) Table of Contents i. Acknowledgements ii ii. Abstract iii iii. Chapter I: Introduction 1-4 iv. Chapter II: Amides 4-15 v. Chapter III: I. Bisthione Synthesis 16-18 II. Reactions with other N,O-acetals 18-22 vi. Chapter IV: I. Additions to Nitrones 22-25 II. Future Work 25 vii. Chapter V: Experimental I. N,O-acetal Formation 25-28 II. Addition to Nitrones 28-29 viii. Chapter VI: References 30 i Acknowledgments I would like to acknowledge my research Dr. Wade Downey for all of his time and dedication to my research for the past two years. -
© Copyright 2013 Jennifer L. Steele
© Copyright 2013 Jennifer L. Steele DIVALENT TRANSITION METAL CENTERS: THE SYNTHESIS OF NEW CHEMICAL VAPOR DEPOSITION PRECURSORS AND STUDIES OF ETHYLENE POLYMERIZATION AND OLIGOMERIZATION CATALYSTS BY JENNIFER L. STEELE DISSERTATION Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry in the Graduate College of the University of Illinois at Urbana-Champaign, 2013 Urbana, Illinois Doctoral Committee: Professor Gregory S. Girolami, Chair Assistant Professor Alison R. Fout Professor John A. Katzenellenbogen Professor Thomas B. Rauchfuss Abstract Volatile transition metal complexes that contain boron hydride ligands are desirable for their potential as precursors for metal diboride films for microelectronics applications. Recently our group has discovered a new class of potential precursors in the metal complexes of the chelating borohydride, N,N-dimethylaminodiboranate (DMADB). To date, attempts to synthesize homoleptic complexes of the late transition metals have afforded intractable mixtures, likely the result of overreduction of the metal center. This work has focused on the synthesis and characterization of heteroleptic complexes of the late transition metals that contain both DMADB and 1,2,3,4,5,-pentamethylcyclopentadienyl ligands. The reaction of metal complexes of the form [Cp*MX]n, where Cp* is 1,2,3,4,5,- pentamethylcyclopentadienyl, M = Cr, Fe, Co, or Ru, and X = Cl or I with sodium dimethylaminodiboranate (NaDMADB) in diethyl ether affords the divalent complexes [Cp*M(DMADB)]. Additionally, the analogous vanadium compound [Cp*V(DMADB)] can be synthesized from the reduction of [Cp*VCl2]3 with NaDMADB in diethyl ether. All of these compounds are volatile under static vacuum at room temperature, but are also thermally sensitive; the iron and ruthenium derivatives decompose at room temperature over a day. -
RIFM Fragrance Ingredient Safety Assessment, 2-Isopropyl-4- Methylanisole, CAS Registry Number 31574-44-4
Food and Chemical Toxicology 110 (2017) S545eS551 Contents lists available at ScienceDirect Food and Chemical Toxicology journal homepage: www.elsevier.com/locate/foodchemtox Short review RIFM fragrance ingredient safety assessment, 2-isopropyl-4- methylanisole, CAS Registry Number 31574-44-4 * A.M. Api a, , D. Belsito b, D. Botelho a, D. Browne a, M. Bruze c, G.A. Burton Jr. d, J. Buschmann e, M.L. Dagli f, M. Date a, W. Dekant g, C. Deodhar a, M. Francis a, A.D. Fryer h, K. Joshi a,S.LaCavaa, A. Lapczynski a, D.C. Liebler i,D.O’Brien a, R. Parakhia a,A.Patela, T.M. Penning j, G. Ritacco a, J. Romine a, D. Salvito a, T.W. Schultz k, I.G. Sipes l, Y. Thakkar a, E.H. Theophilus a, A.K. Tiethof a, Y. Tokura m, S. Tsang a, J. Wahler a a Research Institute for Fragrance Materials, Inc., 50 Tice Boulevard, Woodcliff Lake, NJ 07677, USA b Columbia University Medical Center, Department of Dermatology, 161 Fort Washington Ave., New York, NY 10032, USA c Malmo University Hospital, Department of Occupational & Environmental Dermatology, Sodra Forstadsgatan 101, Entrance 47, Malmo SE-20502, Sweden d School of Natural Resources & Environment, University of Michigan, Dana Building G110, 440 Church St., Ann Arbor, MI 58109, USA e Fraunhofer Institute for Toxicology and Experimental Medicine, Nikolai-Fuchs-Strasse 1, 30625 Hannover, Germany f University of Sao Paulo, School of Veterinary Medicine and Animal Science, Department of Pathology, Av. Prof. dr. Orlando Marques de Paiva, 87, Sao Paulo CEP 05508-900, Brazil g University of Wuerzburg, Department of Toxicology, Versbacher Str. -
Divergent Enantioselective Synthesis of Hapalindole-Type Alkaloids Using Catalytic Cite This: Chem
Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue Divergent enantioselective synthesis of hapalindole-type alkaloids using catalytic Cite this: Chem. Sci.,2016,7,4725 asymmetric hydrogenation of a ketone to construct the chiral core structure† Yang Liu,‡a Li-Jie Cheng,‡a Hai-Tao Yue,a Wen Che,a Jian-Hua Xie*a and Qi-Lin Zhouab A divergent enantioselective approach to hapalindole-type alkaloids is described. The route features a ruthenium-catalyzed asymmetric hydrogenation of a ketone via DKR to construct the chiral trans-1- indolyl-2-isopropenylcyclohexane skeleton and a switchable sequence of methylation and acetylation/ aldol reaction to access a chiral quaternary stereocenter. (+)-Hapalindole Q (1, 13 steps, 5.9% overall Received 15th February 2016 yield), (À)-12-epi-hapalindole Q isonitrile (2, 15 steps, 5.5% overall yield), (À)-hapalindole D (3, 14 steps, Accepted 12th April 2016 2.3% overall yield), and (+)-12-epi-fischerindole U isothiocyanate (4, 14 steps, 3.0% overall yield) were Creative Commons Attribution-NonCommercial 3.0 Unported Licence. DOI: 10.1039/c6sc00686h synthesized in 13–15 steps from a commercially available material to demonstrate the application of this www.rsc.org/chemicalscience approach. Introduction (+)-p-menth-1-en-9-ol.3,5f However, only one catalytic enantiose- lective synthesis of a hapalindole-type alkaloid has been re- 7 Owing to the unique and diverse molecular architectures of ported: Kinsman and Kerr used an organocatalyzed hapalindole-type alkaloids and their broad range of biological asymmetric Diels–Alder reaction as a key step in the synthesis of activities, they have recently attracted great interest as synthetic (+)-hapalindole Q (1). -
Reactions of Aromatic Compounds Just Like an Alkene, Benzene Has Clouds of Electrons Above and Below Its Sigma Bond Framework
Reactions of Aromatic Compounds Just like an alkene, benzene has clouds of electrons above and below its sigma bond framework. Although the electrons are in a stable aromatic system, they are still available for reaction with strong electrophiles. This generates a carbocation which is resonance stabilized (but not aromatic). This cation is called a sigma complex because the electrophile is joined to the benzene ring through a new sigma bond. The sigma complex (also called an arenium ion) is not aromatic since it contains an sp3 carbon (which disrupts the required loop of p orbitals). Ch17 Reactions of Aromatic Compounds (landscape).docx Page1 The loss of aromaticity required to form the sigma complex explains the highly endothermic nature of the first step. (That is why we require strong electrophiles for reaction). The sigma complex wishes to regain its aromaticity, and it may do so by either a reversal of the first step (i.e. regenerate the starting material) or by loss of the proton on the sp3 carbon (leading to a substitution product). When a reaction proceeds this way, it is electrophilic aromatic substitution. There are a wide variety of electrophiles that can be introduced into a benzene ring in this way, and so electrophilic aromatic substitution is a very important method for the synthesis of substituted aromatic compounds. Ch17 Reactions of Aromatic Compounds (landscape).docx Page2 Bromination of Benzene Bromination follows the same general mechanism for the electrophilic aromatic substitution (EAS). Bromine itself is not electrophilic enough to react with benzene. But the addition of a strong Lewis acid (electron pair acceptor), such as FeBr3, catalyses the reaction, and leads to the substitution product. -
RIFM Fragrance Ingredient Safety Assessment, Anisyl Alcohol, CAS Registry T Number 105-13-5 A.M
Food and Chemical Toxicology 134 (2019) 110702 Contents lists available at ScienceDirect Food and Chemical Toxicology journal homepage: www.elsevier.com/locate/foodchemtox Short Review RIFM fragrance ingredient safety assessment, anisyl alcohol, CAS registry T number 105-13-5 A.M. Apia, D. Belsitob, S. Bisertaa, D. Botelhoa, M. Bruzec, G.A. Burton Jr.d, J. Buschmanne, M.A. Cancellieria, M.L. Daglif, M. Datea, W. Dekantg, C. Deodhara, A.D. Fryerh, S. Gadhiaa, L. Jonesa, K. Joshia, A. Lapczynskia, M. Lavellea, D.C. Liebleri, M. Naa, D. O'Briena, A. Patela, T.M. Penningj, G. Ritaccoa, F. Rodriguez-Roperoa, J. Rominea, N. Sadekara, D. Salvitoa, ∗ T.W. Schultzk, F. Siddiqia, I.G. Sipesl, G. Sullivana, , Y. Thakkara, Y. Tokuram, S. Tsanga a Research Institute for Fragrance Materials, Inc., 50 Tice Boulevard, Woodcliff Lake, NJ, 07677, USA b Member Expert Panel, Columbia University Medical Center, Department of Dermatology, 161 Fort Washington Ave., New York, NY, 10032, USA c Member Expert Panel, Malmo University Hospital, Department of Occupational & Environmental Dermatology, Sodra Forstadsgatan 101, Entrance 47, Malmo SE, 20502, Sweden d Member Expert Panel, School of Natural Resources & Environment, University of Michigan, Dana Building G110, 440 Church St., Ann Arbor, MI, 58109, USA e Member Expert Panel, Fraunhofer Institute for Toxicology and Experimental Medicine, Nikolai-Fuchs-Strasse 1, 30625, Hannover, Germany f Member Expert Panel, University of Sao Paulo, School of Veterinary Medicine and Animal Science, Department of Pathology, Av. Prof. dr. Orlando Marques de Paiva, 87, Sao Paulo, CEP 05508-900, Brazil g Member Expert Panel, University of Wuerzburg, Department of Toxicology, Versbacher Str. -
Cr(CO)6 System, While for the Mo(CO)6 and W(CO)E
The photochemistry of M(CO)6 and (rj6-pyridine)Cr(CO )3 (M = Cr, Mo, or W) and related systems. This thesis is presented to Dublin City University for the degree, Doctor of Philosophy, by Ciara Breheny BSc Supervisor Dr Conor Long School of Chemical Sciences, Dublin City University 1996 Declaration This thesis has not been submitted as an exercise for a degree at this or at any other university. Except as otherwise stated, this work has been carried out by the author alone. Signed Ciara Breheny. Dedication This thesis is dedicated to my family, Mum, Dad, Conor, and Saibh HI Acknowledgements I would like to say a most sincere thank you to all the following people, Dr Conor Long, for his constant support, help, and advice over the past few years All members past and present of the CLRG, namely Irene, Mick, Maureen, Celia, Mary, Siobhan, and Deirdre Everyone in AG07 who made the past few years enjoyable and unforgettable All members of the chemistry department, especially the technicians, who were always at hand to help when a problem arose (as it invariably did) A word of thanks to my friends outside DCU without whom the past few years would not have been the same, namely, Mane, Ger, Siobhan, Orla, Greg, Ciaran, Shivaun, Ciara, Teresa, Monica, Susan, Bronagh, Anna, Dawn, and Fiona Also a special thanks to Paul for his support over the past year Finally, to my family for their never-ending patience with the seemingly endless student life I have undertaken Without their love and support these past few years would have been a lot more difficult -
Transcription 11.12.07
Lab 17A • 12/07/11 [lab quiz] Nomenclature of alkenes The first molecule that I want to look at is this one, where we have the two methyl groups on one side, two hydrogens on the other side. Would it be appropriate to use cis or trans, or E or Z, or both, or neither? One carbon of the double bond versus the other, those are the two different sides of the double, then the top versus the bottom are the two faces of the double bond. If we notice, on both the top face and the bottom face, we have a methyl group that is pointed the same way as a hydrogen. There is a steric factor as far as what alkene would prefer to form thermodynamically, so there is an importance that there’s some interaction there. That methyl group with one hydrogen is exactly the same interaction as you’d have the methyl group and the other hydrogen pointed the opposite way – meaning that if you were to switch the two hydrogens, you’d end up with exactly the same molecule again. The only reason that we use the term cis or trans or E or Z is to describe that it is one configuration versus another, but since there’s only one configuration possible, there’s therefore no term that should be used. It would, in fact, be wrong to call this cis, trans, E, or Z. When an alkene has two of the same substituent on the same side, there is only one unique configuration of that alkene, and so it cannot be called cis, trans, E, or Z.