DOCSLIB.ORG

Acta 45.1).Indd 1 3/28/2012 11:41:17 AM 1 VOL

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Acta 45.1).Indd 1 3/28/2012 11:41:17 AM 1 VOL VOL. 45, NO. 1 • 2012 “Designer”-Surfactant-Enabled Cross-Couplings in M ICHI ICA A DR C L TA A Water at Room Temperature 2 8 th 0 6 1 9 2 The Growing Impact of Niobium in Organic 1 4 A N 5 Y R Synthesis and Catalysis N I V E R S A For convenient General Reaction Equation trifluoromethylation N N Cu I CF3 of aryl iodides. CF 3 DMF, 25-50 oC, 18 h Representative Reaction Scope CF3 CF3 CF3 H Me Hartwig Trifluoromethylations MeO 96% O 89% O 93% Aldrich Chemistry would like to introduce Trifluoromethylator™, a highly efficient trifluoromethylation reagent from the CF3 CF3 CF3 laboratory of Professor John Hartwig and Catylix, Inc. Trifluoromethylator™ (Phen)Cu-CF3 (Prod. No. L510009) is a EtO2C BnO AcHN convenient, thermally stable, single-component reagent for 94% 89% 85% the trifluoromethylation of aryl iodides. It provides: O CF CF CF • Tolerance of electrophilic functional groups, including 3 3 H 3 aldehydes, nitroarenes, ketones and esters O2N Ph OAc • High yields under mild conditions for electron-rich and quant. 83% 68% OMe electron-deficient iodoarenes, as well as sterically hindered iodoarenes O BOM Br CF3 CF3 Increased flexibility for carrying out ester hydrolysis in N • O your synthesis O N 89% 78% BOM CF3 Cl N N F3C CF3 Cu N CF3 Cl N CO2Et L510009 89% 99% Boc 69% Solutions of Trifluoromethylator™ in toluene CF3 CF3 are safe to use at process scale. n-C6H11 99% OMOM OMOM To request custom and bulk quantities Reference: Morimoto, H.; Tsubogo, T.; Litvinas, N. D.; Hartwig, J. F. CF3 of Trifluoromethylator™, visit Angew. Chem. Int. Ed. 2011, 50, 3793. 97% Aldrich.com/catylix Trifl uoromethylator is a trademark of Catylix, Inc. 78095 78095_ALD Trifluoromethylator Ad (Acta 45.1).indd 1 3/28/2012 11:41:17 AM 1 VOL. 45, NO. 1 • 2012 Aldrich Chemical Co., Inc. “PLEASE BOTHER US.” 6000 N. Teutonia Ave. Milwaukee, WI 53209, USA Dear Fellow Chemists, To Place Orders We have had many suggestions for the DalPhos ligands shown below. These were recently developed by Professor Mark Stradiotto and his group Telephone 800-325-3010 (USA) at Dalhousie University. Both are air-stable, chelating N,P ligands that enable FAX 800-325-5052 (USA) the Pd-catalyzed cross-coupling of ammonia. Mor-DalPhos is also effective in or 414-438-2199 coupling hydrazine and acetone, and in the gold–catalyzed hydroamination. Mail P.O. Box 2060 The catalysts are used with low loadings and exhibit excellent functional Milwaukee, WI 53201, USA group tolerance and chemoselectivty. Customer & Technical Services (a) Lundgren, R. J.; Peters, B. D.; Alsabeh, P. G.; Stradiotto, M. Angew. Chem., Int. Ed. 2010, 49, 4071. (b) Lundgren, R. J.; Stradiotto, M. Angew. Chem., Int. Ed. 2010, 49, 8686. Customer Inquiries 800-325-3010 Technical Service 800-231-8327 N CH SAFC® 800-244-1173 N 3 P O Custom Synthesis 800-244-1173 P CH3 Flavors & Fragrances 800-227-4563 International 414-438-3850 24-Hour Emergency 414-438-3850 751618 751413 Website sigma-aldrich.com 751618 Di(1-adamantyl)-2-morpholinophenylphosphine (Mor-DalPhos) 250 mg Email [email protected] 1 g 751413 Di(1-adamantyl)-2-dimethylaminophenylphosphine (Me-DalPhos) 250 mg General Correspondence 1 g Editor: Sharbil J. Firsan, Ph.D. P.O. Box 2988, Milwaukee, WI 53201, USA We welcome fresh product ideas from you. Do you need a compound that isn’t listed in our [email protected] catalog? Ask Aldrich! For over 60 years, your research needs and suggestions have shaped the Aldrich product offering. To submit your suggestion visit Aldrich.com/pleasebotherus. Subscriptions Request your FREE subscription to the Aldrichimica Acta, through: John Radke Web: Aldrich.com/acta Director of Marketing, Chemistry Email: [email protected] TABLE OF CONTENTS “Designer”-Surfactant-Enabled Cross-Couplings in Water at Room Temperature ................3 Phone: 800-325-3010 (USA) Bruce H. Lipshutz* and Subir Ghorai, University of California, Santa Barbara, and Sigma-Aldrich Co., Mail: Attn: Mailroom Sheboygan Falls, Wisconsin Aldrich Chemical Co., Inc. The Growing Impact of Niobium in Organic Synthesis and Catalysis .................................... 19 Sigma-Aldrich Corporation Valdemar Lacerda, Jr.,* Deborah Araujo dos Santos, Luiz Carlos da Silva-Filho, Sandro José Greco, and P.O. Box 2988 Reginaldo Bezerra dos Santos, Universidade Federal do Espírito Santo and Universidade Estadual Milwaukee, WI 53201-2988 Paulista (Brasil) ABOUT OUR COVER Venice: The Dogana and San Giorgio Maggiore (oil on canvas, 91.5 × 122.0 cm) was completed in 1834 by Joseph Mallord William Turner (London, 1775–1851). A prolific British artist and an influential member of the Romantic Movement of the late eighteenth and first half of the nineteenth century, he elevated landscape painting to a level not achieved before The entire Aldrichimica Acta archive is also available free of and introduced several innovations to the genre. His talent charge at Aldrich.com/acta. manifested itself very early in life, and he was much admired Aldrichimica Acta (ISSN 0002-5100) is a publication of Aldrich. as an artist in life and death, with institutions, works, and artistic Detail from Venice: The Dogana and San Giorgio Maggiore. Aldrich is a member of the Sigma-Aldrich Group. prizes dedicated to preserving his legacy. Photograph © Board of Trustees, National Gallery of Art, Washington. This painting depicts a bustling maritime scene in the Grand Canal of Venice, which Turner had visited several ©2012 Sigma-Aldrich Co. LLC. All rights reserved. SIGMA, times. (Another Venetian cityscape, painted seven years earlier by another British Romantic Movement artist, R. SAFC, SIGMA-ALDRICH, ALDRICH, and SUPELCO are trademarks P. Bonington, has graced the cover of Aldrichimica Acta, Vol. 43, No. 1.) Turner intended this work as a celebration of Sigma-Aldrich Co. LLC, registered in the US and other of commerce, as symbolized by the statue of Fortune atop the Dogana (Customs building) in the foreground. countries. Add Aldrich is a trademark of Sigma-Aldrich Co. LLC. Aldrich brand products are sold through Sigma-Aldrich, Inc. While Turner was not concerned with a faithful depiction of the scene, as evidenced by the apparent widening Purchaser must determine the suitability of the product(s) of the canal and placement of San Giorgio’s church, his skill as a draftsman and his mastery of perspective for their particular use. Additional terms and conditions may drawing are evident in his precise, linear rendering of the buildings and sharp angles. His color combinations, apply. Please see product information on the Sigma-Aldrich freely handled layers of paint, and the sparkling water and light sky exemplify his lifelong preoccupation with website at www.sigmaaldrich.com and/or on the reverse side the effects and significance of light in an awe-inspiring natural world. of the invoice or packing slip. This painting is part of the Widener Collection at the National Gallery of Art, Washington, DC. TPGS-750-M Cat. No. 733857 O CH3 O O H3CO O H3C n O O CH3 Want to n = ~16 H3C H C CH3 3 run transition- 3 transition metal catalyst partner A TPGS-750-M metal-catalyzed + product C water, rt reactions in water at partner B Heck Sonogashira room temperature? O O MeO 97% 99% Suzuki-Miyaura Negishi-like CO Et OMe 2 4 87% (E/Z = 99/1) Congratulations to Professor Bruce Lipshutz, University of 88% California, Santa Barbara, winner of the 2011 Presidential Green Chemistry Challenge Award: Academic, for the development C-H activation Fujiwara-Moritani of TPGS-750-M, an amphiphile that enables transition-metal- OMe CO n-Bu catalyzed reactions to be run in water, at room temperature. 2 H H N Applicable to many transition-metal-catalyzed reactions N N • O O • Scalable OMe OMe • Highly water-soluble 68% 83% • No frothing at workup ring-closing metathesis cross-metathesis Easily separated from reaction product(s) and recycled • N O Ts OTBS • Amenable to high-throughput screening 88% 74% aminations H N For greener chemistry N in your lab, Add Aldrich. 98% Aldrich.com/tpgs750m Lipshutz, B. H. et al. J. Org. Chem. 2011, 76, 4379. 78375 78375_ALD Lipshutz TPGS-750-M Ad (Acta 45.1).indd 1 3/23/2012 11:16:59 AM 3 VOL. 45, NO. 1 • 2012 “Designer”-Surfactant-Enabled Cross-Couplings in Water at Room Temperature Bruce H. Lipshutz*,a and Subir Ghoraib a Department of Chemistry & Biochemistry University of California Santa Barbara, CA 93106, USA Email: [email protected] b Catalysis R&D Sigma-Aldrich Co. 5485 County Road V Prof. Bruce H. Lipshutz Dr. Subir Ghorai Sheboygan Falls, WI 53085, USA Keywords. green chemistry; micellar catalysis; designer surfactants; within their lipophilic cores (Figure 1). While a disaster of this cross-couplings; PTS; TPGS-750-M. magnitude needs the tincture of time to assess its full impact on the environment, from a purely chemical perspective, tremendous hope Abstract. New methodologies are discussed that allow for several has been placed on these surfactants in anticipation that they will commonly used transition-metal-catalyzed coupling reactions to prevent further damage to wildlife and shores. be conducted within aqueous micellar nanoparticles at ambient This micellar chemistry undertaken on a grand scale by the temperatures. petroleum industry highlights the potential for simple amphiphilic molecules to “solubilize” organic materials in a purely aqueous Outline medium. Many other industries use surfactants routinely; examples 1. Introduction include paint, cosmetics, cleaning, leather, carpet, asphalt, and pulp 2. Background & paper companies.3 Relatively small amounts have been used for 3. Chemistry in PTS–H2O, an Update: a 1st-Generation Amphiphile decades in highly controlled environments, e.g., as “excipients” in for Transition-Metal-Catalyzed Cross-Couplings the pharmaceutical arena, to help increase dissolution of otherwise 3.1.
Load more

Recommended publications
  • Cyclohexane Oxidation Continues to Be a Challenge Ulf Schuchardt A,∗, Dilson Cardoso B, Ricardo Sercheli C, Ricardo Pereira A, Rosenira S
    Applied Catalysis A: General 211 (2001) 1–17 Review Cyclohexane oxidation continues to be a challenge Ulf Schuchardt a,∗, Dilson Cardoso b, Ricardo Sercheli c, Ricardo Pereira a, Rosenira S. da Cruz d, Mário C. Guerreiro e, Dalmo Mandelli f , Estevam V. Spinacé g, Emerson L. Pires a a Instituto de Qu´ımica, Universidade Estadual de Campinas, P.O. Box 6154, 13083-970 Campinas, SP, Brazil b Depto de Eng. Qu´ımica, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil c College of Chemistry, University of California, Berkeley, CA 94720, USA d Depto Ciências Exatas e Tecnológicas, Universidade Estadual de Santa Cruz, 45650-000 Ilhéus, BA, Brazil e Universidade Federal de Lavras, Lavras, MG, Brazil f Instituto de Ciências Biológicas e Qu´ımicas, PUC-Campinas, 13020-904 Campinas, SP, Brazil g Sup. Caracterização Qu´ımica, IPEN, 05508-900 São Paulo, SP, Brazil Received 3 October 2000; received in revised form 21 December 2000; accepted 28 December 2000 Abstract Many efforts have been made to develop new catalysts to oxidize cyclohexane under mild conditions. Herein, we review the most interesting systems for this process with different oxidants such as hydrogen peroxide, tert-butyl hydroperoxide and molecular oxygen. Using H2O2, Na-GeX has been shown to be a most stable and active catalyst. Mesoporous TS-1 and Ti-MCM-41 are also stable, but the use of other metals such as Cr, V, Fe and Mo leads to leaching of the metal. Homogeneous systems based on binuclear manganese(IV) complexes have also been shown to be interesting. When t-BuOOH is used, the active systems are those phthalocyanines based on Ru, Co and Cu and polyoxometalates of dinuclear ruthenium and palladium.
    [Show full text]
  • POLYMERISATION of SOME CYCLIC ETHERS and ALLYL COMPOUNDS at Higf PRESSURES
    POLYMERISATION OF SOME CYCLIC ETHERS AND ALLYL COMPOUNDS AT HIGf PRESSURES. THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY IN THE FACULTY OF SCIENCE UNIVERSITY OF LONDON BY MUSTAFIZUR RAHMAN. DEPARTMENT OF CHEMICAL ENGINEERING AND CHEMICAL TECHNOLOGY, IMPERIAL COLLEGE OF SCIENCE AND TECHNOLOGY, LONDON, S.W.7. SEPTEMBER, 1967. ABSTRACT. The polymerizations of seven cyclic ethers and two allyl compounds have been studied at high pressures (up to 12,000 atm.). BF3.(C2H5)20 was usually used as catalyst to polymerize the ethers, except for 1,4-epoxycyclohexane with wilich the co-catalyst epichlorohydrin was employed. Benzoyl peroxide and azo-isobutyronitrile were used to polymerize the allyl compounds. The polymerizations of 1,4-epoxycyclohexane and tetrahydrofuran (THF) have been studied most extensively. From the lag rate vs. pressure graphs, "overall volumes of activation" Air*pol were calculated and compared with those for vinyl compounds. Conductances of solutions of BP3.(C2H5)20 in tetrahydropyran were measured and the results discussed in relation to the kinetic measurements. The variation of the polymerization ceiling temperature of THF with pressure was determined between 1 and 2500 atm. The polymerizations of cyclohexene oxide, styrene cxide, cyclooctene oxide, tetrahydropyran, triallyl phosphate, triallyl phosphite and the co-polymerization of triallyl phosphate and styrene, have been studied briefly. The results, wherever possible, have been explained in terms of existing ideas. 3. Polymers from viscous liquid to insoluble solids were obtained during this investigation and the molecular weights were determined, where possible. 4 ACKNOWLEDGEBENTS. The author wishes to express his gratitude to Dr. K.E.Weale for his kind supervision, valuane guidance and constant encouragement during the course of this study.
    [Show full text]
  • Chem 314 Preorganic Evaluation
    Organic Reaction Guide Beauchamp 1 Chem 316 / Beauchamp Reactions Review Sheet Name SN2 Reactions - special features: biomolecular kinetics Rate = kSN2[RX][Nu ], single step concerted reaction, E2 is a competing reaction o o o o relative order of reactivity: CH3X > 1 RX > 2 RX >> 3 RX (based on steric hinderance, no SN2 at 3 RX) allylic & benzylic RX are very reactive, adjacent pi bonds help stabilize transition state and lower TS energy (Ea) o complete substitution at Cα (3 RX) or Cβ (neopentyl pattern) almost completely inhibits SN2 reactions vinyl & phenyl are very unreactive, bonds are stronger and poor backside approach leaving group ability: OTs = I > Br > Cl in neutral or basic conditions (just like E2, SN1 adn E1), and neutral molecule leaving groups are good from protonated, cationic intermediates in acid conditions, + + + + -OH2 , -ORH , -OR2 , -NR3 , etc. we will consider all anions, ammonia, amines, thiols and sulfides to be strong nucleophiles (favors SN2 and E2 reactions) in our course some electron pair donors are mainly nucleophiles (sulfur, azide, cyanide, carboxylates) and - + + - + - some are mainly bases (t-BuO K , Na H2N , Na H ) polar, aprotic solvents work best for SN2 reactions because nucleophiles are relatively unencombered for electron doantion (dimethyl sulofoxide = DMSO, dimethylformamide = DMF, acetonitrile = AN, acetone, etc.) in our course some electron pair donors are mainly nucleophiles (sulfur, azide, cyanide, carboxylates) and we will consider neutral solvent molecules such as water, alcohols and acids to be weak nucleophiles (favors SN1 and E1) stereoselectivity: 100% inversion of configuration from backside atack regioselectivity: reacts at carbon with leaving group, completely unambiguous chemoselectivity: N/A The following list is designed to emphasize SN2 reactions.
    [Show full text]
  • Cyclohexene Oxide/Carbon Dioxide Copolymerization by Chromium(III) Amino-Bis(Phenolato) Complexes and MALDI- TOF MS Analysis of the Polycarbonates
    Electronic Supplementary Material (ESI) for Polymer Chemistry. This journal is © The Royal Society of Chemistry 2015 Electronic Supplementary Information for Cyclohexene Oxide/Carbon Dioxide Copolymerization by Chromium(III) Amino-bis(phenolato) Complexes and MALDI- TOF MS Analysis of the Polycarbonates Katalin Devaine-Pressing,† Louise N. Dawe,†,‡ and Christopher M. Kozak*,† † Department of Chemistry, Memorial University of Newfoundland, St. John’s, Newfoundland, A1B 3X7, Canada. ‡ C-CART X-ray Diffraction Laboratory, Department of Chemistry, Memorial University of Newfoundland, St. John’s, Newfoundland, A1B 3X7, Canada. Current address: Department of Chemistry and Biochemistry, Wilfrid Laurier University, 75 University Ave. W. Waterloo, Ontario, N2L 3C5, Canada Experimental S3 Table S1. Crystallographic and structure refinement data for 1·THF, 1·DMAP and 2·THF S10 Figure S1. MALDI-TOF mass spectrum of 1·THF S11 Figure S2. MALDI-TOF mass spectrum of 1·THF higher mass region. S11 Figure S3. MALDI-TOF mass spectrum of 2·THF S12 Figure S4. MALDI-TOF mass spectrum of 1·DMAP S13 Figure S5. UV-Vis absorption spectrum of 1·THF S14 Figure S6. UV-Vis absorption spectrum of 2·THF S14 Figure S7. UV-Vis absorption spectrum of 1·DMAP S15 Figure S8. IR spectrum of 1·THF S16 Figure S9. IR spectrum of 2·THF S16 Figure S10. IR spectrum of 1·DMAP S17 Figure S11. The first 20 min of the reaction profile of the growth of the polycarbonate ν(C=O) BuBuPy catalyzed by 1·THF, 1·DMAP and CrCl[O2NN’] S17 Figure S12. The second stage of the propagation of the reaction catalyzed by BuBuPy CrCl[O2NN’] .
    [Show full text]
  • The Low Temperature Solvent-Free Aerobic Oxidation of Cyclohexene to Cyclohexane Diol Over Highly Active Au/Graphite and Au/Graphene Catalysts
    catalysts Article The Low Temperature Solvent-Free Aerobic Oxidation of Cyclohexene to Cyclohexane Diol over Highly Active Au/Graphite and Au/Graphene Catalysts Owen Rogers 1, Samuel Pattisson 1, Joseph Macginley 1 ID , Rebecca V. Engel 1, Keith Whiston 2, Stuart H. Taylor 1,* ID and Graham J. Hutchings 1,* ID 1 Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK; [email protected] (O.R.); [email protected] (S.P.); [email protected] (J.M.); [email protected] (R.V.E.) 2 INVISTA Performance Technologies, the Wilton Centre, Wilton, Redcar TS10 4RF, UK; [email protected] * Correspondence: [email protected] (S.H.T.); [email protected] (G.J.H.); Tel.: +44-2920-874-062 (S.H.T.); +44-2920-874-059 (G.J.H.) Received: 2 July 2018; Accepted: 28 July 2018; Published: 31 July 2018 Abstract: The selectivity and activity of gold-catalysts supported on graphite and graphene have been compared in the oxidation of cyclohexene. These catalysts were prepared via impregnation and sol immobilisation methods, and tested using solventless and radical initiator-free reaction conditions. The selectivity of these catalysts has been directed towards cyclohexene epoxide using WO3 as a co-catalyst and further to cyclohexane diol by the addition of water, achieving a maximum selectivity of 17% to the diol. The sol immobilisation catalysts were more reproducible and far more active, however, selectivity towards the diol was lower than for the impregnation catalyst. The results suggest that formation of cyclohexane diol through solventless oxidation of cyclohexene is limited by a number of factors, such as the formation of an allylic hydroperoxyl species as well as the amount of in situ generated water.
    [Show full text]
  • Oxidation of Cyclohexene with H2O2 Catalyzed by Vanadium Based Polyoxometalates Doped Modified Clays As Green Catalysts S
    Vol. 132 (2017) ACTA PHYSICA POLONICA A No. 3 Special issue of the 3rd International Conference on Computational and Experimental Science and Engineering (ICCESEN 2016) Oxidation of Cyclohexene with H2O2 Catalyzed by Vanadium Based Polyoxometalates Doped Modified Clays as Green Catalysts S. Boudjemaa;b;∗, H. Rabaha and A. Choukchou-Brahama aLaboratory of Catalysis and Synthesis in Organic Chemistry, Faculty of Sciences, University of Tlemcen, Algeria bKasdi Merbah University, Faculty of Hydrocarbons, Renewable Energy, Earth Sciences and Universe, Ouargla, Algeria The catalytic performance of supported heteropolyacids in various liquid–solid and gas–solid heterogeneous re- actions may be affected by the choice of support and/or the method of heteropolyacid deposition. Vanadium substi- tuted polyphosphomolybdate with the Keggin structure H4[PVMo11O40]·13H2O (PVMo) was dispersed throughout acid activated bentonite (clay from Hammam Boughrara, Maghnia, Algeria). A series of catalysts were prepared via modified impregnation. Modified preparation method employed ultrasonication as a means of the dispersion homogenization, followed by freeze-drying. The catalysts were characterized by the Brunauer–Emmett–Teller, the Fourier transform infrared, and 31P solid-state magic angle spinning-NMR spectroscopy. The catalytic performance of PVMo/Hmont was evaluated in the oxidation of cyclohexene. Intact Keggin anions were preserved on Hmont after deposition aided by ultrasonication. The obtained results showed that a better catalytic activity can be ob- tained with PVMo/bentonite (98% of conversion and 89% of cyclohexene oxide), by drop addition of H2O2, for 3 h. DOI: 10.12693/APhysPolA.132.469 PACS/topics: heteropolyacids, bentonite, acid catalyst, cyclohexene oxidation, hydrogen peroxide 1. Introduction lished on the immobilization of heteropolyacids on vari- ous supports including silica, alumina, titania, and zeo- Cyclohexene oxidation has been the subject of exten- lites [6–10].
    [Show full text]
  • Cyclohexene Oxide 286-20-4 NTP NOMINATION HISTORY and REVIEW
    Cyclohexene oxide 286-20-4 NTP NOMINATION HISTORY AND REVIEW A. Nomination History 1. Source: National cancer Institute 2. Recommendations: -Mechanistic carcinogencity studies -Synergism studies or two-stage studies - Test with benzene or other chemicals deemed appropriate by NTP 3. Rationale/Remarks: -High annual production volume -Potential for human exposure based on its use as a research and industrial chemical -Environmental contaminant -Representative cycloalkene monoepoxide; suspicion of carcinogenicity as a member of the epoxides· chemical class 4. Priority: High 5. Date of Nomination: 4/93 B. Interagency Committee for Chemical Evaluation and Coordination Review \ 1. Date of Review: 2. Recommendations: 3. Priority: 4. NTP Chemical Selection Principles: 5. Rationale/Remarks: "' 286-20-4 Cyclohexene oxide SUMMARY OF DATA FOR CHEMICAL SELECTION CHEMICAL IDENTIFICATION CAS Registry Name: 286-20-4 Chemical Abstracts Name: 7-oxabicyclo[ 4.1.0]heptane(9CI,8CI) Synonyms and Trade Names: Cyclohexene oxide; cyclohexene epoxide; 1,2­ epoxycyclohexane; cyclohexane oxide tetramethyleneoxirane; CO; CHO Structure. Molecular Formula and Molecular Weight Mol. wt.: 98.15 Chemical and Physical Properties Description: Colorless liquid with strong (pungent, offensive) odor (Sax & Lewis, 1987;Uniroyal, 1990) Boiling Point 129-131°C; 266°F (Sax & Lewis, 1987; Uniroyal, 1990; Weast, 1989) Melting Point <-10°C (Weast, 1989) Solubilitv: Very soluble in benzene; soluble in alcohol, ether, acetone, chloroform; low water solubility (-0.5 g/L) (Sax & Lewis, 1987; BASF, 1990; Weast, 1989) DensitY: 0.967 g/cc@ 25°/4°C (Sax & Lewis, 1987; Uniroyal, 1990) Prepared for NCI by Technical Resources, Inc. under Contract No. N01-CP-56019 (9/91; rev. 2/93) 6'( II 286-20-4 Cyclohexene oxide Vapor Pressure: 12 mbar (BASF, 1990) Flash Point 27oC; 81 oF (Sax & Lewis, 1989; Uniroyal, 1990.) Stabiiitv: Stable at ambient temperatures and pressures.
    [Show full text]
  • Chemical Inventory
    Name CAS Number SOP Status Supplier Size Qt. Location Received Purchaser Hazards (1,3-bis)2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethyl aminosulfonyl)phenyl]methylene Ru(II) dichloride918870-76-5 100mg 1 Storage # 3 (2-bromoethyl) benzene 98% 103-63-9 100G 2 Storage # 3 (3-aminopropyl)triethoxysilane 919-30-2 Sigma 100 mL 1 Storage #3 Apr-13 Stephanie Flammable, toxic, corrosive (3-aminopropyl)trimethoxysilane 13822-56-5 Sigma 100 mL 1 small fridge May-13 Stephanie Corrosive, irritant (3-iodopropyl)trimethoxysilane 14867-28-8 1 Storage # 2 (3-mercaptopropyl) trimethoxysilane 95% 4420-74-0 25g 1 Shelf # 3 (3-mercaptopropyl)-trimethoxysilane 95% 4420-74-0 25G 2 Storage # 2 (iodomethyl)trimethylsilane 4206-67-1 5mL 1 Storage # 2 (Propan-2-yloxy) benzene 2741-16-4 Enamine 1g 1 Storage # 3 Nov-14 Zach (Trimethylsilyl)methyllithium, 1.0M solution in pentane 1822-00-0 SOP on file-Lithium reagents Aldrich 50ml 1 Large fridge Highly flammable 0.5% Rhodium on 1/8 Alumina pellets 7440-16-6 25g 2 Shelf # 1 1% Pt-Al-1DR 7440-06-4 74292-90-5 0.05kg 1 Shelf # 1 1-(2-hydroxyethyl)-2-pyrolidinone 98% 3445-11-2 5ml 2 Storage # 3 1-(Trimethylsiloxy)cyclohexene 6651-36-1 Alfa 1g 1 Small fridge Mar-14 Bethany 1,1,1,3,3,3-Hexafluoro-2-propanol, 99+% 920-66-1 25g 1 Storage # 4 1,1,1,3,3,3-Hexafluoro-2-propanol-d9, 99 atom%D 38701-74-5 1g 2 Storage #7 1,1,1,3,3,3-hexamethyl-disilane 99.9% 1450-14-2 100mL 2 Storage # 2 1,1,2,2-Tetra chloroethane-D2 (D, 99.6%) 33685-54-0 SOP on file- Acutely toxic chem.
    [Show full text]
  • In Presenting the Dissertation As a Partial Fulfillment of The
    In presenting the dissertation as a partial fulfillment of the requirements for an advanced degree from the Georgia Institute of Technology, I agree that the Library of the Institute shall make it available for inspection and circulation in accordance with its regulations governing materials of this type. I agree that permission to copy from, or to publish from, this dissertation may be granted by the professor under whose direction it was written, or, in his absence, by the Dean of the Graduate Division when such copying or publication is solely for scholarly purposes and does not involve potential financial gain. It is under­ stood that any copying from, or publication of, this dis­ sertation which involves potential financial gain will not be allowed without written permission. 7/2^/68 THE REACTION OF ATOMIC OXYGEN WITH ORGANIC COMPOUNDS A THESIS Presented to The Faculty of the Graduate Division by Arthur Joseph Mosher In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the School of Chemistry Georgia Institute of Technology March 1970 THE REACTION OF ATOMIC OXYGEN WITH ORGANIC COMPOUNDS Approved: Uhaiaraan •9 Date Approved by Chairman ACKNOWLEDGMENTS I would like to thank Dr. Erling Grovenstein, Jr. for acting as my research advisor; without his penetrating analysis this thesis would not have been possible. I would also thank Drs. Thomas F. Moran and Charles J_. Liotta for serving on the reading committee. Discussions with the latter were quite beneficial to this thesis. Special recognition is due to John McKelvey, whose exciting mind and cheerful disposition are a source of inspiration to all.
    [Show full text]
  • Catalogue of China Dangerous Chemical, Ver. 2002
    Catalogue of China Dangerous Chemical, Ver. 2002 China DG No. Category Sub-Category Chinese Name Chinese Alias English Name English Alias CAS No. UN No. No Barium azide,dry or 迭氮(化)钡［干的或含水 1 Explosive 1.1 11018 wetted with less than 18810-58-7 224 <50%］ 50％ water,by mass Lead azide, wetted with not less than 20％ 迭氮(化)铅［含水或水加 2 Explosive 1.1 11019 water, or mixture of 13424-46-9 129 乙醇≥20%］ alcohol andwater,by mass 3 Explosive 1.1 11020 重氮甲烷 Diazomethane 334-88-3 Diazodinitrophenol,wette d with not less than 40％ 二硝基重氮酚［含水或水 4 Explosive 1.1 11021 重氮二硝基苯酚 water,or mixture of Dinitrodiazophenol 87-31-0 74 加乙醇≥40%］ alcohol and water,by mass Lead trinitroresorcinate,wetted 三硝基间苯二酚铅［含水 with not less than 20％ 5 Explosive 1.1 11022 收敛酸铅 Lead styphnate 63918-97-8 130 或水加乙醇≥20%］ water,or mixture of alcohol and water,by mass Guanyl nitrosaminoguanylidene 脒基亚硝氨基脒基叉肼 6 Explosive 1.1 11023 hydrazine, wetted with 113 ［含水≥30%］ not less than30％ water,by mass Guanyl nitrosaminoguanyltetraz 脒基亚硝氨基脒基四氮烯 ene, wetted with not less 7 Explosive 1.1 11024 ［含水或水加乙醇≥ 四氮烯; 特屈拉辛 Tetrazene 109-27-3 114 than 30％ water,or 30%］ mixture of alcohol and water,by mass www.randis.cn 1/215 Catalogue of China Dangerous Chemical, Ver. 2002 China DG No. Category Sub-Category Chinese Name Chinese Alias English Name English Alias CAS No. UN No. No Mercury fulminate,wetted with not less than 20％ 雷(酸)汞［含水或水加乙 8 Explosive 1.1 11025 water,or mixture of 628-86-4 135 醇≥20%］ alcohol and water,by mass Perchloric 9 Explosive 1.1 11026 高氯酸［浓度＞72%］ 7601-90-3 acid(containing＞72%) Nitroguanidine,dry
    [Show full text]
  • Aerobic Catalytic Oxidation of Cyclohexene Over Tizrco Catalysts
    catalysts Article Aerobic Catalytic Oxidation of Cyclohexene over TiZrCo Catalysts Tong Liu 1,2,3, Haiyang Cheng 1,2,*, Weiwei Lin 1,2, Chao Zhang 1,2, Yancun Yu 1,2 and Fengyu Zhao 1,2,* 1 State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China; [email protected] (T.L.); [email protected] (W.L.); [email protected] (C.Z.); [email protected] (Y.Y.) 2 Laboratory of Green Chemistry and Process, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China 3 University of Chinese Academy of Sciences, Beijing 100049, China * Correspondence: [email protected] (H.C.); [email protected] (F.Z.); Tel.: +86-431-8526-2454 (H.C.); Tel./Fax: +86-431-8526-2410 (F.Z.) Academic Editor: Michalis Konsolakis Received: 8 December 2015; Accepted: 12 January 2016; Published: 29 January 2016 Abstract: The aerobic oxidation of hydrocarbon is of great significance from the viewpoints of both fundamental and industry studies as it can transfer the petrochemical feedstock into valuable chemicals. In this work, we investigated the aerobic oxidation of cyclohexene over TiZrCo catalysts, in which 2-cyclohexen-1-one was produced with a high selectivity of 57.6% at a conversion of 92.2%, which are comparable to the best results reported for the aerobic oxidation of cyclohexene over heterogeneous catalysts. The influences of kinds of solvent, substrate concentration and reaction temperature were evaluated. Moreover, the catalytic performance of the TiZrCo catalyst and the main catalytic active species were also discussed.
    [Show full text]
  • Structure-Reactivity Relations for Thiol-Disulfide Interchange Janette Houk and George M
    J. Am. Chem. SOC.1987, 109, 6825-6836 6825 ‘H NMR (22 OC, benzene-d6): 6 3.26 (s, OSCMe), 3.03 (s, 2JwH= A systematic search of a limited hemisphere of reciprocal space lo- 8.54 Hz, CH2CMe3next to S), 2.85 (s, ’JWH= 9.98 Hz, CH2CMe3next cated a set of diffraction maxima with systematic absences corresponding to Oh 2.32 (s. O,CMe), 2.26 (s,.- 0,CMe trans to OSCMe) 1.49, 1.46 (s, to the unique monoclinic space group P2,/a. Subsequent solution and CH2CMe3): refinement confirmed this choice. IR: 324 (m), 333 (m), 375 (w), 450 (w), 620 (w), 627 (w), 668 (ms), The structure was solved by a combination of direct methods 680 (m). 907 (mw), 932 (w). 1018 (w), 1040 (w), 1088 (vs), 1175 (ms), (MULTAN~S)and Fourier techniques and refined by full-matrix least 1202(mw), 1236 (ms), 1349 (m), 1361 (ms), 1374 (ms), 1438 (vs), 1460 squares. Many of the hydrogen atom positions were visible in a difference (s), 1492 (m) cm-I. Fourier phased on the non-hydrogen parameters. The positions of all W2(np)2(02CNMe2)4.In a Schlenk flask W2(np)2(NMe2)4(0.30 g, hydrogens were calculated and placed in fixed idealized positions (d(C- 0.44 mmol) was dissolved in CH2C12and then frozen in liquid N,. A H) = 0.95 A) for the final cycles. The hydrogen atoms were assigned large excess (>4 equiv) of C02was condensed into the flask. The so- a thermal parameter of 1 + Bise of the carbon atom to which they were lution was then slowly warmed to room temperature while the flask was bound.
    [Show full text]