TRIFLUOROPERACETIC ACID 1 Trifluoroperacetic Acid1 Original Commentary

Total Page:16

File Type:pdf, Size:1020Kb

TRIFLUOROPERACETIC ACID 1 Trifluoroperacetic Acid1 Original Commentary TRIFLUOROPERACETIC ACID 1 Trifluoroperacetic Acid1 Original Commentary Kenneth C. Caster O Union Carbide Corporation, South Charleston, WV, USA F3C H OO A. Somasekar Rao & H. Rama Mohan Indian Institute of Chemical Technology, Hyderabad, India [359-48-8] C2HF3O3 (MW 130.03) General Considerations. InChI = 1S/C2HF3O3/c3-2(4,5)1(6)8-7/h7H Trifluoroperacetic acid oxidizes InChIKey = XYPISWUKQGWYGX-UHFFFAOYSA-N simple alkenes, alkenes carrying a variety of functional groups (such as ethers, alcohols, esters, ketones, and amides), aromatic compounds, alkanes,11 amines and N-heterocycles. Ketones un- dergo oxygen insertion reactions (Baeyer–Villiger oxidation). (electrophilic reagent capable of reacting with many functional groups; delivers oxygen to alkenes, arenes, and amines;1 useful Epoxidations of Alkenes. Due to the presence of the strongly 27,44 reagent for Baeyer–Villiger oxidation of ketones ) electron withdrawing CF3 group, TFPAA is the most powerful organic peroxy acid and as such is more reactive than performic21 Alternative Names: TFPAA; peroxytrifluoroacetic acid. or 3,5-dinitroperbenzoic acids.41 It reacts readily even with Solubility: sol CH Cl , dichloroethane, ether, sulfolane, 2 2 electron-poor alkenes to furnish the corresponding epoxides (see acetonitrile. m-Chloroperbenzoic Acid). Form Supplied in: not available commercially. Trifluoroacetic acid is a strong acid which opens epoxides Analysis of Reagent Purity: assay using iodometry.2 readily.12,44 Since TFPAA is a much weaker acid than trifluo- Preparative Methods: the preparation and handling of TFPAA roacetic acid (pK 3.7 vs. 0.3), the latter reagent can be selectively should be carried out behind a safety shield. A mixture of a neutralized with Na CO or Na HPO , leading to the isolation of Trifluoroacetic Anhydride (46.2 g; 0.22 mole) and CH Cl 2 3 2 4 2 2 epoxides in high yields. When the substrate is highly reactive, (50 mL) is cooled with stirring in an ice bath. 90% H O 2 2 Na CO is used as buffer; when the substrate reacts sluggishly, (caution: for hazards see Hydrogen Peroxide) (5.40 mL, 0.20 2 3 Na HPO is used as buffer.12 The TFPAA reagent is rapidly de- mol) is added in 1 mL portions over a period of 10 min. When 2 4 composed by Na CO . the mixture has become homogeneous, it is allowed to warm 2 3 Since monosubstituted alkenes are not electron rich, they react to rt and then again cooled to 0 ◦C.3 TFPAA prepared from sluggishly with the standard organic peroxy acids. By contrast, the 30% aqueous H O and Trifluoroacetic Acid has been used for 2 2 monosubstituted alkene 1-pentene (1) is epoxidized efficiently by some reactions.4–6 Hydrogen peroxide of high concentration TFPAA (eq 1).12 TFPAA prepared from 0.3 mol of 90% H O and (70%) is not widely available due to hazards involved in han- 2 2 0.36 mol of trifluoroacetic anhydride in CH Cl is added during dling, storage, and transportation. The commercially available 2 2 30 min to a stirred mixture of (1) (0.2 mol), Na CO (0.9 mol), Hydrogen Peroxide–Urea (UHP) system, which is safe to han- 2 3 and CH Cl (200 mL). Since the alkene is volatile the reaction dle, has been introduced recently as a substitute for anhydrous 2 2 flask is fitted with an efficient ice water-cooled condenser. The H O in the preparation of TFPAA.2,7,8 2 2 reaction mixture boils during the addition of the peracid. After all Purification: in the preparation of TFPAA, a slight excess of tri- the reagent has been added, the reaction mixture is heated under fluoroacetic anhydride is used to ensure that no water is present reflux for 30 min, cooled, and the insoluble salts are removed in the reagent. The reaction between H O and trifluoroacetic 2 2 by centrifugation. The salt is thoroughly washed with CH Cl . anhydride is very fast; the reagent is ready for use after the 2 2 Fractional distillation of the combined CH Cl extracts furnishes reactants have been mixed and the solution has become homo- 2 2 the epoxide 2 in 81% yield. geneous. No special purification steps are employed. Suitable buffers (Na2CO3,Na2HPO4) are used to neutralize the highly O 1.5 equiv TFPAA, CH2Cl2 reactive and strongly acidic trifluoroacetic acid which is present (1) 4.5 equiv Na2CO3, reflux, 30 min along with TFPAA in the reagent. (1)81% (2) Handling, Storage, and Precautions: the reagent can be stored at − ◦ 9 20 C for several weeks and exhibits no loss in active oxygen The alkene (3), which is resistant to epoxidation by m-CPBA 40 content after 24 h in refluxing CH2Cl2. However, since it can or Peracetic Acid, has been epoxidized with TFPAA to furnish in be prepared in a short time, the usual practice is to prepare the 83% yield a mixture of esters (4) and (5) (eq 2).13 Esters (4) and reagent when needed. Note that solutions of TFPAA in CH2Cl2 (5) undergo facile deacylation when chromatographed on silica 41 can lose activity by evaporation of the volatile peracid. Since gel to furnish alcohols (6) and (7). peroxy acids are potentially explosive, care is required while carrying out the reactions and also during workup of the reac- O O O tion mixture. Solvent removal from excess H O –CF CO H OR OR OR 2 2 3 2 O O O experiments can result in explosions; the peroxide must be de- 5 equiv TFPAA stroyed by addition of MnO (until a potassium iodide test is O + O (2) 2 Na HPO , rt, 4 h 10a Br 2 4 Br Br negative) before solvent removal. For a further discussion of 83% 10b safety, see Luxon. This reagent should only be handled in a (3) (4) R = COCF3 (5) R = COCF3 fume hood. R = H (6) R = H (7) R = H 2 TRIFLUOROPERACETIC ACID Epoxidation of allyldiphenylphosphine oxide (8) with TFPAA this selectivity is due to the formation of the hydrogen bond of furnishes in quantitative yield the corresponding epoxide, 2- the type shown in (14). The stereoselectivity in the epoxidation (diphenylphosphinoylmethyl)oxirane; m-CPBA epoxidation of of (15) is solvent dependent. When (15) is epoxidized in THF (8) furnishes the epoxide in only 56% yield.14 Epoxide (9)is (which disrupts hydrogen bonding) the ratio of syn:anti epoxides obtained in 80% yield through regio- and stereoselective epoxi- obtained is 1:12. The epoxidation of the allyl alcohol (16) with dation of the corresponding alkene with TFPAA in CH2Cl2 in the TFPAA is highly syn selective (syn:anti epoxidation = 100:1); the 15 presence of Na2HPO4 buffer. syn selectivity in the epoxidation of (16) with m-CPBA is much less (syn:anti epoxidation = 5.2:1). MeO O OAc O N H K2HPO4, TFPAA, CH2Cl2 H O O 40 °C, 30 min Ph O O H OMe 75% P H R MeO O Ph O OAc (8) (12) (9) R = O O (5) O (Z) MeO O O H The tertiary amine of (10) is expected to react more readily than the disubstituted double bond on treatment with an organic R peracid. Selective epoxidation of the double bond in (10)was R achieved by initially treating it with CF CO H. This led to salt O O 3 2 O O H O R3 formation due to protonation of the amine. Epoxidation of the O O HO salt with TFPAA and subsequent workup furnished the epoxide H (11) (eq 3).16 R1 R2 R1 R2 (13) (14) H H O H H R H N N TFPAA, Na2HPO4 TFPAA, H2O2, CH2Cl2 (3) CH Cl , –40 °C t-Bu 2 2 23 °C, 3 h; 0 °C, 8 h 89% 76% (15) R = OTBDMS (16) R = OH OMe OMe R (10) (11) R (6) Alkenes have been epoxidized efficiently employing TFPAA O + O prepared by the UHP method (eq 4).2 t-Bu t-Bu syn:anti 2.5 equiv TFPAA, 10 equiv UHP C6H13 C6H13 (4) The diol (17) is epoxidized stereoselectively to furnish (18) 8.8 equiv Na HPO , CH Cl , reflux, 0.5 h 2 4 2 2 20 88% O (eq 7). OH OH α,β-Unsaturated esters and α,β-unsaturated ketones are resis- TFPAA, Na2HPO4 tant to epoxidation by organic peracids since the double bonds are OH OH (7) not electron rich; however, these compounds can be epoxidized by CH2Cl2 O 90% TFPAA. 1-Acetylcyclohexene17 and methyl methacrylate12 fur- NHTs NHTs nish the corresponding epoxides in 50% and 84% yields, respec- (17) (18) tively, when treated with TFPAA/Na2HPO4 in CH2Cl2 (reflux for about 0.5 h). The α,β-unsaturated ester (12) has been epoxidized stereoselectively by TFPAA (eq 5).18 With m-CPBA, this epoxi- Oxidation of Alkenes to Diols and Ketones. Alkenes react dation requires a higher reaction temperature which results in the readily with a CF3CO3H/CF3CO2H mixture to furnish hydroxy formation of a complex mixture. trifluoroacetates, e.g. (19) → (20) (eq 8).21 In this reaction, high With organic peracids, allyl alcohols form hydrogen bonds in- molecular weight byproducts are formed due to the condensa- volving the hydrogen of the alcohol, as in (13).19 Ganem has tion of hydroxy trifluoroacetates with the epoxides formed from suggested that, with TFPAA, allylic ethers form hydrogen bonds alkenes. The formation of the byproduct can be avoided by adding involving the hydrogen of the peracid (14). triethylammonium trifluoroacetate. After the formation of the gly- Epoxidation of (15) having an allylic ether substituent axially col ester is complete, the solvent is evaporated under reduced pres- oriented is syn selective (syn:anti epoxidation = 12.4:1) (eq 6);.19 sure and the crude ester is subjected to methanolysis to furnish the TRIFLUOROPERACETIC ACID 3 vicinal diol (21).
Recommended publications
  • Chemistry 301-301A - Hour Examination #3, December 11, 2003
    Chemistry 301-301A - Hour Examination #3, December 11, 2003 “.....as we know, there are known unknowns; there are things we know we know. We also know there are known unknowns; that is to say we know there are some things we do not know. But there are also unknown unknowns - the ones we don't know we don't know.” Donald Rumsfeld (winner of a British award given to the worst mangler of the English language in 2003) “I know, a proof is a proof. What kind of a proof is a proof? A proof is a proof and when you have a good proof it's because it's proven." Jean Chrétien (hon. mention for the same award) 1[18 points] (a) Acid-catalyzed addition of water to 3-methyl-1-butene (1) results in formation of large amounts of a rearranged alcohol (2), in addition to the expected alcohol (3). Explain, with excellent arrow formalisms. H2O + H O+ 3 OH OH 1 3 2 (b) On the other hand hydroboration of 1, followed by oxidation, does not lead to any rearranged product. Only alcohol 4 is formed. Explain. Detailed mechanisms are not needed here, but a drawing of the transition state for the hydroboration step is. 1. BH3 OH 2. HOOH/HO – 1 4 (c) But there are some strange things that happen in hydroboration. For example when 2-methyl-2-butene (5) is hydroborated at high temperature, then treated with HOOH/HO–, alcohol 4 is still one of the products. Explain mechanistcally. Hint: at high temperature hydroboration is reversible.
    [Show full text]
  • Synthetic Turf Scientific Advisory Panel Meeting Materials
    California Environmental Protection Agency Office of Environmental Health Hazard Assessment Synthetic Turf Study Synthetic Turf Scientific Advisory Panel Meeting May 31, 2019 MEETING MATERIALS THIS PAGE LEFT BLANK INTENTIONALLY Office of Environmental Health Hazard Assessment California Environmental Protection Agency Agenda Synthetic Turf Scientific Advisory Panel Meeting May 31, 2019, 9:30 a.m. – 4:00 p.m. 1001 I Street, CalEPA Headquarters Building, Sacramento Byron Sher Auditorium The agenda for this meeting is given below. The order of items on the agenda is provided for general reference only. The order in which items are taken up by the Panel is subject to change. 1. Welcome and Opening Remarks 2. Synthetic Turf and Playground Studies Overview 4. Synthetic Turf Field Exposure Model Exposure Equations Exposure Parameters 3. Non-Targeted Chemical Analysis Volatile Organics on Synthetic Turf Fields Non-Polar Organics Constituents in Crumb Rubber Polar Organic Constituents in Crumb Rubber 5. Public Comments: For members of the public attending in-person: Comments will be limited to three minutes per commenter. For members of the public attending via the internet: Comments may be sent via email to [email protected]. Email comments will be read aloud, up to three minutes each, by staff of OEHHA during the public comment period, as time allows. 6. Further Panel Discussion and Closing Remarks 7. Wrap Up and Adjournment Agenda Synthetic Turf Advisory Panel Meeting May 31, 2019 THIS PAGE LEFT BLANK INTENTIONALLY Office of Environmental Health Hazard Assessment California Environmental Protection Agency DRAFT for Discussion at May 2019 SAP Meeting. Table of Contents Synthetic Turf and Playground Studies Overview May 2019 Update .....
    [Show full text]
  • The Mechanism of the Baeyer–Villiger Rearrangement: Quantum Chemistry and TST Study Supported by Experimental Kinetic Data†
    PAPER www.rsc.org/obc | Organic & Biomolecular Chemistry The mechanism of the Baeyer–Villiger rearrangement: quantum chemistry and TST study supported by experimental kinetic data† J. Raul Alvarez-Idaboy,*a Lino Reyesa and Nelaine Mora-Diezb Received 15th August 2007, Accepted 19th September 2007 First published as an Advance Article on the web 2nd October 2007 DOI: 10.1039/b712608e The mechanism of the Baeyer–Villiger rearrangement is modelled for the reaction of propanone with trifluoroperacetic acid, catalyzed by trifluoroacetic acid in dichloromethane, using three DFT methods (B3LYP, BH&HLYP and MPWB1K) and MP2. These results are refined and used to calculate the overall reaction rate coefficient using conventional Transition State Theory. The excellent agreement between the calculated (1.00 × 10−3 L mol−1 s−1) and the experimental (1.8 × 10−3 L mol−1 s−1)rate coefficients at the MPWB1K level strongly supports the mechanism recently proposed by our group. This DFT method is then used to study the mechanism of a larger system: cyclohexanone + trifluoroperacetic acid, for which a very good agreement between the calculated and the experimental rate coefficients is also found (1.37 and 0.32 L mol−1 s−1, respectively). The modelled mechanism is not ionic but neutral, and consists of two concerted steps. The first one is strongly catalyzed while the second one, the migration step, seems not to be catalyzed for the systems under study. The results of this work could be of interest for understanding other reactions in non-polar solvents for which ionic mechanisms have been assumed.
    [Show full text]
  • Homogeneous Models of Thiophene Hds Reactions
    HOMOGENEOUS MODELS OF THIOPHENE HDS REACTIONS. SELECTIVITY IN THIOPHENE C-S CLEAVAGE AND THIOPHENE REACTIONS WITH DINUCLEAR METAL COMPLEXES. William D. Jones,* David A. Vicic, R. Martin Chin, James H. Roache, and Andy W. Myers. Department of Chemistry, University of Rochester, Rochester, NY 14627 Received August 1, 1996 - Abstract: The reactive 16 e metal fragment [(C5Me5)Rh(PMe3)] inserts into a wide variety of thiophene C-S bonds. The structures of the thiophene, benzothiophene, and dibenzothiophene insertion complexes have been determined. While the thiophene complex adopts a planar 6- membered ring structure the other metallacycles are bent, and all molecules possess localized diene structures. The mechanism of C-S cleavage was found to proceed by way of initial sulfur coordination. 2-Methylbenzothiophene gives a kinetic product resulting from cleavage of the sulfur-vinyl bond, but then rearranges to cleave the sulfur-aryl bond. A number of substituted dibenzothiophenes were examined, showing little electronic effect of substituents, but showing a large steric effect of substituents at the 4 and 6 positions. 4,6-Dimethyldibenzothiophene does not undergo cleavage, but instead forms an S-bound complex. Reactions of a cobalt analog, (C5Me5)Co(C2H4)2 with thiophenes also lead to C-S cleaved products, and the use of a dinuclear iridium system produces a butadiene complex in which both C-S bonds have been cleaved. Introduction of these sulfur containing compounds prior to The hydrodesulfurization of petroleum is one treatment. Figure 2 shows how this original mixture of several steps in the hydrotreating of oil in which of compounds is changed upon HDS treatment at sulfur is removed from thiols and thiophenes as temperatures of 350 - 390 °C.
    [Show full text]
  • Highly Efficient Camphor-Derived Oxaziridines for the Asymmetric
    Highly Efficient Camphor-Derived Oxaziridines for the Asymmetric Oxidation of Sulfides to Chiral Sulfoxides Vassilios Meladinis, Uwe Verfürth, and Rudolf Herrmann* Organisch-Chemisches Institut der Technischen Universität München, Lichtenbergstraße 4, D-8046 Garching, Bundesrepublik Deutschland Dedicated to Prof. Dr. Ivar Ugi on the occasion o f his 60th birthday Z. Naturforsch. 45b, 1689- 1694 (1990); received May 18, 1990 Asymmetric Oxidation, N-Sulfonyl-oxaziridines, Chiral Sulfoxides, Camphorsulfonic Acid Chiral N-sulfonyl-oxaziridines derived from 8 -camphorsulfonic acid and fenchone have been evaluated as asymmetric oxidizing agents for the conversion of sulfides to chiral sulf­ oxides. There is no correlation between the redox potentials nor the lvO NMR chemical shifts of the oxaziridines and their relative oxidation rates, nor with the enantiomeric excesses achieved, indicating that steric effects are responsible for their behaviour. The results are con­ sistent with an attack of one sulfur lone pair at the oxaziridine oxygen in such a way that both sulfur lone pairs lie in the plane of the oxaziridine ring. The most efficient oxaziridines, the camphorlactone-sulfonyloxaziridine [(4aS,9aR)-10,10-dimethyl-6,7-dihydro-4H-4a,7-meth- ano-oxazirino[3,2-j]oxepino[3,4-c]isothiazol-9(5 H)-one 3,3-dioxide] and the 3-endo-bromo- camphorsulfonyloxaziridine [(4aS,8 S ,8 aR)-8-bromo-9,9-dimethyl-5,6,7,8-tetrahydro-4 H- 4a,7-methano-oxazirino-2,l-benzisothiazole 3,3-dioxide] allow the preparation of chiral sul­ foxides with up to 85% enantiomeric excess. Introduction crowded oxaziridines activated by an electron- Chiral sulfoxides play a prominent role among withdrawing sulfonyl group at nitrogen give the the chiral auxiliaries used for the synthesis of enan- best results.
    [Show full text]
  • Synthesis of New Camphor-Based Auxiliaries
    UNIVERSITY OF HAWAllllB~ PART 1: SYNTHESIS OF NEW CAMPHOR-BASED AUXILIARIES PART 2: ISOMERIZATION / CYCLIZATION OF ACETYLENIC KETONES TO CYCLOPENTENONES A THESIS SUBMITTED TO THE GRADUATE DIVISION OF THE UNIVERSITY OF HAWAI'I IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE IN CHEMISTRY MAY 2003 By Jeremy S. Forest Thesis Committee: Marcus A. Tius, Chairperson Thomas K. Hemscheidt Craig M. Jensen ACKNOWLEDGEMENTS I would first like to give my sincere thanks to my advisor, Dr. Marcus A. Tius. His endless guidance and support inside the laboratory are lessons that I will carry along forever in my journey through life. I would also like to thank the members of my dissertation committee for their time and effort. I would like to extend a special thanks to Dr. Thomas Hemscheidt for his tireless efforts in the review of this thesis. Many thanks go to Wesley Yoshida and Mike Burger for their help in obtaining NMR and mass spectra. I would also like to thank the members of the Tius group, especially Brad Tokeshi, Cisco Bee, Frank Cordaro, and Eric LeClerc, for their endless help and companionship during my time here. Once again, I would like to thank Dr. Marcus A. Tius for his generous financial support in the form of a research assistantship. I cannot take full credit for this work without recognizing my parents, Bill and Felicia. Their unconditional love and support has kept me going in everything that I do. Finally, I have to thank the fellas: Dave, Scott, Nick, Mitch, and brother Josh. They always believed in me and encouraged me to work through the good and the bad.
    [Show full text]
  • Some Aspects the Baeyer-Villicer Reaction
    SOME ASPECTS THE BAEYER-VILLICER REACTION - by - JOHN EDVARD BOLLIG-ER. B.So, CSyd.) A. Thesis submitted for the degree of MASTER OF SCIENCE - at the - UNIVERSITY OP NEW SOUTH WALES April, 1963- CONTENTS Page No. Summary . .. 1 The Baeyer-Villiger Reaction .. 2 Discussion: .. .. 26 Baeyer-Villiger Oxidation of 2-Bromocholestan-3-one 32 Baeyer-Villiger Oxidation of 2-Bromofriedelin 50 Baeyer-Villiger Oxidation of 2-Chlorocholestan-3-one 53 Baeyer-Villiger Oxidation of 2-Iodocholestan-3-one 54 Baeyer-Villiger Oxidation of Gerin 56 Experimental .. .. 61 Acknowledgments .. .. 87 Bibliography .. .. 88 1 SUMMARY V/ith a view to synthesising suitable inter­ mediates for intramolecular Darzen's glycidic ester syntheses, certain steroid and triterpenoid a- substituted ketones have been subjected to Baeyer- Yilliger oxidation. In some cases the oxidation yielded unexpected products and possible mechanisms for their formation are discussed. In other cases the expected products were obtained but readily under­ went an unusual rearrangement. The structures of the rearranged products have been chemically elucidated and the mechanism of the rearrangement is discussed. This thesis is prefaced by a discussion of the Baeyer-Villiger reaction. THE BAEYER-VTLLIGER REACTION The reaction of ketones with peracids to give esters was first observed by Baeyer and Villiger in 1899 . The scope of this reaction, now known as the Baeyer-Yilliger reaction, has since been widely extended and it has found many useful applications in organic chemistry. Among its representative uses, illustrated by many examples in p the literature , are the formation of esters from simple aliphatic or aromatic ketones, formate esters from aldehydes, anhydrides from o—diketones, lactones from alicyclic ketones and enol lactones from a,0-unsaturated alicyclic ketones.
    [Show full text]
  • Progress Toward the Total Synthesis of Terpenoid Natural Products: the Neomangicols and the Yohimbine Alkaloids
    Progress Toward the Total Synthesis of Terpenoid Natural Products: the Neomangicols and the Yohimbine Alkaloids By Jessica Louise Wood A dissertation in submitted in partial satisfaction of the requirements for the degree of Doctor of Philosophy in Chemistry in the Graduate Division of the University of California, Berkeley Committee in charge: Professor Richmond Sarpong, Chair Professor F. Dean Toste Professor Leonard Bjeldanes Fall 2011 Abstract Progress Toward the Total Synthesis of Terpenoid Natural Products: the Neomangicols and the Yohimbine Alkaloids by Jessica Louise Wood Doctor of Philosophy in Chemistry University of California, Berkeley Professor Richmond Sarpong, Chair Progress has been made toward the total synthesis of a diverse array of natural products. Chapter 1 begins by introducing the isolation, bioactivity, and biosynthesis of the neomangicol and mangicol sesterterpenoids. Subsequent to that introduction, a summary of previous synthetic approaches to these natural products is presented. In the third section, our synthetic approaches are detailed, beginning with a first generation synthesis of the ABD tricycle, followed by a description of our revised route to the neomangicol tetracyclic core and our work toward the rearrangement of that core to the mangicol spirocyclic core. This chapter concludes with a summary of our accomplishments in this natural product area and outlines several strategies to achieve the desired rearrangement. The last section also includes our initial studies into the formation of the mangicol core. Preliminary work toward the synthesis of the ABD tricycle was performed by Dr. Brian Pujanauski. Chapter 2 details our work in the area of the yohimbine alkaloids. It begins with an introduction to these pentacyclic indole-containing natural products, discussing their isolation, proposed biosynthesis and giving a brief overview of the rich bioactivity that has been ascertained for these molecules.
    [Show full text]
  • A Publication of Reliable Methods for the Preparation of Organic Compounds
    A Publication of Reliable Methods for the Preparation of Organic Compounds Working with Hazardous Chemicals The procedures in Organic Syntheses are intended for use only by persons with proper training in experimental organic chemistry. All hazardous materials should be handled using the standard procedures for work with chemicals described in references such as "Prudent Practices in the Laboratory" (The National Academies Press, Washington, D.C., 2011; the full text can be accessed free of charge at http://www.nap.edu/catalog.php?record_id=12654). All chemical waste should be disposed of in accordance with local regulations. For general guidelines for the management of chemical waste, see Chapter 8 of Prudent Practices. In some articles in Organic Syntheses, chemical-specific hazards are highlighted in red “Caution Notes” within a procedure. It is important to recognize that the absence of a caution note does not imply that no significant hazards are associated with the chemicals involved in that procedure. Prior to performing a reaction, a thorough risk assessment should be carried out that includes a review of the potential hazards associated with each chemical and experimental operation on the scale that is planned for the procedure. Guidelines for carrying out a risk assessment and for analyzing the hazards associated with chemicals can be found in Chapter 4 of Prudent Practices. The procedures described in Organic Syntheses are provided as published and are conducted at one's own risk. Organic Syntheses, Inc., its Editors, and its Board of Directors do not warrant or guarantee the safety of individuals using these procedures and hereby disclaim any liability for any injuries or damages claimed to have resulted from or related in any way to the procedures herein.
    [Show full text]
  • Synthesis of an Unsymmetrically Pentafunctionalized Corannulene Derivative (Part I) Synthesis of Platinum and Ethynyl-Platinum Corannulenes (Part II)
    Zurich Open Repository and Archive University of Zurich Main Library Strickhofstrasse 39 CH-8057 Zurich www.zora.uzh.ch Year: 2012 Synthesis of an Unsymmetrically Pentafunctionalized Corannulene Derivative (Part I) Synthesis of Platinum and Ethynyl-Platinum Corannulenes (Part II) Maag, Roman M Posted at the Zurich Open Repository and Archive, University of Zurich ZORA URL: https://doi.org/10.5167/uzh-164179 Dissertation Published Version Originally published at: Maag, Roman M. Synthesis of an Unsymmetrically Pentafunctionalized Corannulene Derivative (Part I) Synthesis of Platinum and Ethynyl-Platinum Corannulenes (Part II). 2012, University of Zurich, Faculty of Science. Part I: Synthesis of an Unsymmetrically Pentafunctionalized Corannulene Derivative and Part II: Synthesis of Platinum and Ethynyl-Platinum Corannulenes Dissertation zur Erlangung der naturwissenschaftlichen Doktorwurde¨ Dr. sc. nat. vorgelegt der Mathematisch-naturwissenschaftlichen Fakult¨at der Universit¨at Zurich¨ von Roman M. Maag von Winkel ZH Promotionskommitee: Prof. Dr. Jay S. Siegel (Vorsitz) Prof. Dr. Kim K. Baldridge Prof. Dr. Cristina Nevado Prof. Dr. Roger Alberto Zurich,¨ 2012 Abstract of the Dissertation Part I: Synthesis of an Unsymmetrically Pentafunctionalized Corannulene Derivative and Part II: Synthesis of Platinum and Ethynyl-Platinum Corannulenes by Roman M. Maag University of Zurich, 2012 Prof. Dr. Jay S. Siegel, Chair Corannulene (C20H10) is a polyaromatic hydrocarbon that can be considered as the smallest fragment of Buckminsterfullerene exhibiting a curved surface. Among the in- teresting properties of corannulene are rapid bowl inversion and esthetically appealing fivefold symmetry (C5v), which is rare in chemistry. Whereas the first synthesis in 1968 only afforded milligram quantities, several improvements in the synthetic strategy finally culminated in the development of an efficient process which today furnishes corannulene in kilogram quantities.
    [Show full text]
  • Dioxiranes: Synthesis and Reactions of Methyldioxiranes
    J. Org. Chem. 1985,50, 2847-2853 2847 30 min at -15 "C, about 60% of the SO2 was removed. The liquid that at 5.54 to collapse to a 4.5 Hz d. Anal. Calcd for was stirred into diethyl ether, the ether was decanted, and acetone C14H17N3011S2:C, 35.97; H, 3.67; N, 8.99. Found: C, 36.24; H, was added to yield upon filtration 29 g (85%) of 15. 3.54; N, 8.96. Preparation of 15 in CH2C12. To 70 g of CH2C12and 20 g 1-(2-Thienyl)tetrahydrothiopheniumPicrate (17). To 75 (0.23 mol) of THT at -30 "C was added 14 g (0.40 mol) of chlorine g of SO2 and 16 g (0.18 mol) of THT at -30 "C was added 21.7 followed by addition of 18.1 g (0.17 mol) of styrene. After 30 min, g (0.16 mol) of S02C12followed by 13.96 g (0.16 mol) of thiophene. the solution was stirred into ether, the ether was decanted, and After 30 min at -5 "C 30 mL of H20 was added and the SO2 was acetone was added to give 4.2 g (9.2%) of 15: 60-MHz 'H NMR removed. After extraction twice with both chloroform and hex- (D20)6 7.5 (5 H, b, phenyl), 5.48 [l H, t, J = 7 Hz, C(2) HI, 3.96 anol, the material was converted to the picrate by the usual [2 H, AB of ABX, J(AB) = 13 Hz, C(1) H2], 3.4 (4 H, m, width manner to give 9.3 g (14.6%) of 17: 100-MHz 'H NMR 20 Hz, THT+ a H), 2.14 (4 H, m, width 14 Hz, THT' /3 H); (Me2SO-d6)6 8.61 (2 H, s, picrate), 8.22 [lH, dd, J = 5.1 Hz, J' 60-MHz 'H NMR (CF,COOH) 6 7.5 (5 H, b, phenyl), 5.45 (1 H, = 1.4 Hz, C(5) HI, 8.00, [l H, dd, J = 3.8 Hz, J'= 1.4 Hz, C(3) t, J = 7 Hz), 3.85 (2 H, t, J = 7 Hz), 3.55 (4 H, m, width 25 Hz), HI, 7.34 [l H, dd, J = 5.1 Hz, J'= 3.8 Hz, C(4) HI, 3.88 (4 H, 2.36 (4 H, m, width 15 Hz).
    [Show full text]
  • Dibenzothiophene (DBT), and Carbazole (CA) from Benzofuran (BF), Benzothiophene (BT), and Indole (IN) with Cyclopentadienyl Radical
    International Journal of Molecular Sciences Article The Gas-Phase Formation Mechanism of Dibenzofuran (DBF), Dibenzothiophene (DBT), and Carbazole (CA) from Benzofuran (BF), Benzothiophene (BT), and Indole (IN) with Cyclopentadienyl Radical 1, 1, 1,2 1 1,2, 3 Xuan Li y, Yixiang Gao y, Chenpeng Zuo , Siyuan Zheng , Fei Xu *, Yanhui Sun and Qingzhu Zhang 1 1 Environment Research Institute, Shandong University, Qingdao 266237, China; [email protected] (X.L.); [email protected] (Y.G.); [email protected] (C.Z.); [email protected] (S.Z.); [email protected] (Q.Z.) 2 Shenzhen Research Institute, Shandong University, Shenzhen 518057, China 3 College of Environment and Safety Engineering, Qingdao University of Science & Technology, Qingdao 266042, China; [email protected] * Correspondence: [email protected]; Tel.: +86-532-58631992 These authors contributed equally to this article. y Received: 11 August 2019; Accepted: 28 October 2019; Published: 31 October 2019 Abstract: Benzofuran (BF), benzothiophene (BT), indole (IN), dibenzofuran (DBF), dibenzothiophene (DBT), and carbazole (CA) are typical heterocyclic aromatic compounds (NSO-HETs), which can coexist with polycyclic aromatic hydrocarbons (PAHs) in combustion and pyrolysis conditions. In this work, quantum chemical calculations were carried out to investigate the formation of DBF, DBT, and CA from the reactions of BF, BT, and IN with a cyclopentadienyl radical (CPDyl) by using the hybrid density functional theory (DFT) at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants of crucial elementary steps were deduced over 600 1200 K, using canonical − variational transition state theory with a small-curvature tunneling contribution (CVT/SCT).
    [Show full text]