DOCSLIB.ORG

United States Patent 0 ICC Patented Apr

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
United States Patent 0 ICC Patented Apr 1 3,806,467 United States Patent 0 ICC Patented Apr. 23, 1974 1 2 glycol which is then partially esteri?ed together with a 3,806,467 fatty acid. ORGANIC TIN COMPOUND CONTAINING Also newly proposed is a method (U.S. Pats. 3,360,584, CATALYST SYSTEM USEFUL FOR PRO and 3,351,635) wherein an ole?n and an organic hydro DUCING EPOXY COMPOUNDS peroxide are brought into contact with each other in the Yoshihiro Watanabe, Kobe, Toshio Nishizawa, Takatsuki, 5 and Jiro Kobayashi, Ibaraki, Japan, assignors to Sumi presence of a metallic compound comprising vanadium, tomo Chemical C0,, Ltd., Osaka, Japan molybdenum, tungsten, selenium or mixture. However, No Drawing. Original application Mar. 10, 1970, Ser. No. such method has drawbacks that the organic hydroperox 18,335. Divided and this application Sept. 30, 1971, ide itself is expensive, and that, in principle, a correspond Ser. No. 185,369 ing alcohol in an amount equivalent to the formed epox Int. Cl. C07d 1/08, 1/06 ide compound is by-produced and therefore the economi US. Cl. 252—--429 R 2 Claims cal merit of this method is likely to be in?uenced by the marketability of the by-product. ABSTRACT OF THE DISCLOSURE As described above, the conventional methods of epoxi 15 dizing ole?ns have been not fully satisfactory. Catalyst system useful for producing epoxy compound Recently hydrogen peroxide has come to be economi containing ( 1) at least one organic tin compound as a ?rst cally mass-produced due to the development of improved component having at least one hydroxyl group or a co oxidation of secondary alcohols or quinone compounds ordination group which is capable of being converted and has come to be very cheap particularly in the state to a hydroxyl group in the presence of water or hydrogen 20 before puri?cation or concentration. peroxide and (2) a second component selected from com Therefore, some attempts to utilize hydrogen peroxide pounds of molybdenum, tungsten, vanadium, selenium, directly as an epoxidizing agent have been made, e.g. boron and mixtures thereof. Bull. Chem. Soc. Jap. 42, 1604, 69 (I), J. Org. Chem. 22, 1682, ’57 (II). In the former method (I), the epoxy This is a division of application Ser. No. 18,335, ?led 25 compounds of C8, C12 cyclic ole?ns are produced mainly Mar. 10, 1970. by oxidation with hydrogen peroxide in the presence of This invention relates to a novel method of oxidizing a selenium dioxide catalyst. However a very large amount organic compounds and more particularly to a novel proc of the catalyst is required and this publication does not ess for producing epoxy compounds from ole?ns in the mention the epoxidability of aliphatic ole?ns. In the presence of a special catalyst. 30 method (II), grycohol of C5 cyclic ole?n is produced Epoxy compounds play an important role in the in mainly in the presence of such metallic compounds as of dustry as intermediate materials for industrial chemicals, H2WO4 as catalyst. synthetic resins, rubbers, etc. However, a small amount of epoxy compounds have There are already known many methods of epoxidizing been isolated as only intermediates. What can be generally ole?ns. For example, the most typical industrial method 35 said is that, with such simple catalyst systems, the is the gas phase oxidation of ethylene. However, such epoxidizing activity of hydrogen peroxide is so low that, method can proceed in considerably high yields for ethyl as mentioned also in the above literatures, the forma ene which has the simplest chemical structure among tion of a small amount of epoxy compound is recognized ole?ns but is low in the yield for other ole?ns, particularly only on very speci?c compounds, especially cyclic com propylene, so that it has been found to be difficult to 4.0 pounds, and the reaction proceeds to a diol in most cases. industrialize such method in respect to ole?ns other than From such viewpoint, the investigation to use hydrogen ethylene. peroxide directly for an epoxidation has not been estab The most widely used method of epoxidizing ole?ns is lished practically. Therefore, it has been necessary to convert hydrogen peroxide into a peracid as mentioned the so-called chlorohydrin method long known in the art. 45 However, this method has such drawbacks as the high cost hereinbefore or to employ an organic hydroperoxide. required for large electrolytic equipment, corrosion of An object of the present invention is to provide an the apparatus and the waste of expensive chlorine. There advantageous and industrially practical method wherein, fore, a more economical method has been strongly hoped by the adoption of newly discovered catalyst system, hydrogen peroxide may be used effectively and directly as for. 50 From such viewpoint, some improved methods have an epoxidizing agent for the epoxidation of ole?ns. been proposed. Thus, for example, there has been pro It has now been found that, when a catalyst system hav posed a method wherein a strong active substance such ing the below described speci?c composition is used dis as a peracid, particularly peracetic acid is used as an. solved or suspended in the reaction solvent and ole?n, epoxidizing agent for ole?ns. However, this method has hydrogen peroxide can be advantageously used as an various drawbacks that peracetic acid itself is produced 55 epoxy oxygen source. from hydrogen peroxide and acetic acid or acetaldehyde According to the present invention, there is used a cat and oxygen; and therefore its production cost is high, alyst system comprising a combination of (1) at least one that peracetic acid is explosive and there is required a tin compound as a ?rst component and (2) a second com special care for its handling. ponent selected from the group consisting of compounds Further, there is also known an “in situ” method (I.E.C. of vanadium, molybdenum, tungsten, selenium, and 47, 147) wherein hydrogen peroxide is utilized as an boron, and mixtures of any two or more of these com epoxidizing agent in the presence of an acid catalyst pounds. together with a fatty acid. However, there is a great dis As for the tin compound which is the ?rst component, advantage that, due to the use of the strong acid catalyst, both organic tin and inorganic tin compounds may be the formed epoxide is hydrolyzed partially to become 65 used. 3,806,467 3 4 As for the organic tin compounds, there can be exem ?rst component to the second component is not inde pli?ed tin compounds having at least one hydroxyl group pendent of reaction products, the ratio may be varied or having a coordination group which can be converted widely. But, the ratio of atom of the ?rst component is to a hydroxyl group in the presence of water or hydrogen preferable more than that of the second component. The peroxide. More particular examples are those having any element of the second component per one tin atom is of the following formulae: 1—0.00l, preferably 0.1-0.01. Generally, a concentration (by weight ratio) of the mixture of the ?rst component and the second component in the reaction system is about 1/l0,000 to 1/ 10, preferably about 1/ 100 to 1/1,000. 10 However, generally, in case a boron compound is used for the second component, the higher the concentration of boron, the better the result. It is desirable therefore to use such boron compound as a saturated solution, if possible. 15 As regards the working mechanism of the catalyst sys tem of the present invention, there have been recognized wherein each of R1, R2, R3, R4, R5 and R6 represents an some phenomena which can explain that the ?rst compo alkyl group, aralkyl group, phenyl group, phenoxy group, nent, the second component and hydrogen peroxide form alkoxy group, hydrogen atom, carbonyl group, nitrile an active complex compound effective or favorable to the group, hydroxyl group, acyl group, halogen group, epoxidizing reaction. --—S—R or —O-R and R represents an alkyl or phenyl The solvent to be used in carrying out the method of group. It is also possible to employ a synthesized solu the present invention may be selected from a consider tion or extract containing such tin compound. ably wide range of ordinary organic compounds, provided Examples of the inorganic tin compounds, are tin chlo that they do not quickly react with the ole?n, hydrogen ride, tin sul?de, sodium stannate, tin oxide and organic acid salts of tin. 25 peroxide and/or catalyst. However, it has been found Generally, an organic tin compound has an activity that, in some solvents, the compatibility with ole?n and much higher than that of an inorganic compound. hydrogen peroxide is low so that the reaction system sepa The second component of the catalyst system of this in rates into a plurality of phases and, in case the reaction vention is selected from organic and inorganic compounds is continued for a long time or in case the reaction tem 30 perature is elevated, the tin compound is deposited on the containing molybdenum, tungsten, vanadium, selenium or wall and bottom of the reaction vessel. boron. Examples of the soluble second component are From the industrial viewpoint, when the solubility and naphthenates, stearates, octoates, carbonyls, acetylace stability of the raw material ole?n and catalyst system tonates polyacid, and the like, of the above-mentioned metals. Examples of the insoluble second component are and the stability of hydrogen peroxide are considered, 35 the proper selection of the solvent is important to the oxides, ammonium salts, phosphates, nitrates, sulfates, method of the present invention.
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]