Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Protonierung von CH 3 N 3 und CF 3 N 3 in Supersäuren: Isolierung und strukturelle Charakterisierung von langlebigen Methyl‐ und Trifluormethylamino‐Diazonium‐Ionen

Journal Article · · Angewandte Chemie
 [1];  [2]; ORCiD logo [1];  [1];  [1];  [1];  [3];  [3];  [4]; ORCiD logo [1]
  1. Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California University Park Los Angeles California 90089-1661 USA
  2. Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences Flemingovo nam. 2 160 00 Prague 6 Czech Republic, Department of Organic Chemistry Faculty of Science Charles University Hlavova 2030/8 128 43 Prague Czech Republic
  3. Department Chemistry The University of Alabama Tuscaloosa AL 35487 USA
  4. Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences Flemingovo nam. 2 160 00 Prague 6 Czech Republic
+ Show Author Affiliations

Abstract Die Methylaminodiazonium‐Kationen [CH 3 N(H)N 2 ] + und [CF 3 N(H)N 2 ] + wurden als ihre bei niedriger Temperatur stabilen [AsF 6 ]‐Salze durch Protonierung von Azidomethan und Azidotrifluormethan in supersauren Systemen hergestellt. Sie wurden durch NMR‐ und Raman‐Spektroskopie charakterisiert. Ein eindeutiger Nachweis der Protonierungsstelle wurde durch die Kristallstrukturen beider Salze erhalten, welche die Bildung der Alkylaminodiazonium‐Ionen bestätigte. Die Lewis‐Addukte CH 3 N 3 ⋅AsF 5 und CF 3 N 3 ⋅AsF 5 wurden ebenfalls hergestellt und durch Tieftemperatur‐NMR‐ und Raman‐Spektroskopie sowie im Falle von CH 3 N 3 ⋅AsF 5 durch Röntgenstrukturbestimmung charakterisiert. Elektronische Strukturberechnungen wurden durchgeführt, um zusätzliche Einblicke zu erhalten. Versuche zur elektrophilen Aminierung von Aromaten wie Benzol und Toluol mit Methyl‐ und Trifluormethylamino‐Diazonium‐Ionen waren erfolglos.

Sponsoring Organization:
USDOE
OSTI ID:
1631876
Journal Information:
Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 132 Journal Issue: 30; ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

References (43)

Über die Reaktion von Methylazid und Stickstoffwasserstoffsäure mit Antimon(V)-chlorid und tert.-Butylchlorid bzw. Chlorwasserstoff journal September 1966
Intramolecular Schmidt reactions of azides with carbocations: synthesis of bridged-bicyclic and fused-bicyclic tertiary amines journal November 1993
Electrophilic amination of aromatics with sodium azide in BF3–H2O journal January 2016
The aminodiazonium cation, H2N3+ journal March 1993
Superacid Chemistry book January 2009
Intramolecular cyclization of arylnitrenium ions. Formation of carbon-carbon bonds and of lactones journal November 1982
Synthetic methods and reactions. 188. Triflic acid catalyzed phenylamination of aromatics with phenyl azide journal November 1993
Protonation of nitriles: isolation and characterization of alkyl- and arylnitrilium ions journal January 2016
Heterosubstituted diazonium ions FNN+, HONN+, and H2NNN+. Automerization, dediazoniation, and deprotonation journal October 1991
Studien über Arylazide journal January 1925
Solid-State Structure of Protonated Ketones and Aldehydes journal November 2017
The Cambridge Structural Database
  • Groom, Colin R.; Bruno, Ian J.; Lightfoot, Matthew P.
  • Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 72, Issue 2, p. 171-179 https://doi.org/10.1107/S2052520616003954
journal April 2016
Trimethylsilyl azide/triflic acid, a highly efficient electrophilic aromatic amination reagent journal March 1989
Theoretical analysis of the barrier to nitrogen inversion in N-fluoroformimine and formaldoxime journal January 1982
Convenient Access to α-Fluorinated Alkylammonium Salts journal October 2015
Reaktionen mit organischen Aziden. II. Über die Reaktion von Alkylaziden mit Carbeniumionen journal June 1963
Reactive Intermediate Chemistry Edited by R. A. Moss (Rutgers University), M. S. Platz (Ohio State University), and M. Jones, Jr. (Princeton University). Wiley-Interscience, Hoboken, NJ. 2004. viii + 1072 pp. 16 × 24 cm. $95.95. ISBN 0-471-23324-2. journal July 2004
Über die Gefahren beim Umgang mit Methylazid journal September 1950
DFT studies on the acid-catalyzed Curtius reaction: the Schmidt reaction journal May 2017
A Study of Superacid Solutions. i. the use of the Chloranil Electrode in Glacial Acetic acid and the Strength of Certain weak Bases journal December 1927
Lewis adduct formation of hydrogen cyanide and nitriles with arsenic and antimony pentafluoride journal January 2019
Methyl nitrate, hydrazoic acid, and their conjugate acids. A configuration interaction study of the gas-phase proton transfer equilibrium and of acid-catalyzed fragmentation reactions journal August 1992
The Syntheses and Structures of Ph4EN3 (E = P, As, Sb), an Example for the Transition from Ionic to Covalent Azides within the Same Main Group journal October 2005
Über die Reaktion des Methylazids mit Antimon(V)-chlorid und Chlorwasserstoff. Stabilisierung des Methylenimins durch Salzbildung journal March 1964
Onium ions. 26. Aminodiazonium ions: preparation, proton, carbon-13, and nitrogen-15 NMR structural studies, and electrophilic amination of aromatics journal August 1983
Protonierung von Nitraminen: Bildung des O- oder N-protonierten Kations journal July 2017
Intramolecular Schmidt Reactions of Alkyl Azides with Ketones: Scope and Stereochemical Studies journal October 1995
Die Reaktion von Triphenylsilylazid mit Triäthyloxonium-tetrafluoroborat [1] journal May 1964
Solid-State Structure of Protonated Ketones and Aldehydes journal November 2017
Mechanism of the Acid-Promoted Intramolecular Schmidt Reaction: Theoretical Assessment of the Importance of Lone Pair–Cation, Cation−π, and Steric Effects in Controlling Regioselectivity journal December 2011
The Reaction of Aryl Azides with Hydrogen Halides 1,2 journal June 1951
Reactions of Alkyl Azides and Ketones as Mediated by Lewis Acids:  Schmidt and Mannich Reactions Using Azide Precursors journal August 2000
N- and C-Attacks of phenylnitrenium ions generated from phenyl azides in the presence of trifluoroacetic acid and/or trifluoromethanesulphonic acid journal January 1986
Ab Initio Approach to Understanding the Stereoselectivity of Reactions between Hydroxyalkyl Azides and Ketones journal May 2004
Remote intramolecular functionalization of arylnitrenium ions. ipso-substitution and spiro-lactone formation journal January 1986
Einfacher Zugang zu α-Fluoralkylammoniumsalzen journal October 2015
An Explosion with Methyl Azide journal April 1963
Importance of the anisotropy of atoms in molecules for the representation of electron density distributions with Lewis structures. A case study of aliphatic diazonium ions journal March 1993
19F,14N and15N NMR spectroscopic studies on triazadienyl fluoride, N3F journal February 1992
Properties of azidotrifluoromethane journal August 1981
Protonation of Nitramines: Where Does the Proton Go? journal July 2017
Intramolecular Cyclizations via Arylnitrenium Ions. Formation of a Six-Membered Ring Rather than a Macrocycle journal August 1999
Cyclisation of arylnitrenium ions to the aporphine ring system: remarkable formation of a sixteen-membered ring by an intramolecular electrophilic aromatic substitution journal January 1989

Similar Records

Related Subjects