108-86-1Relevant articles and documents
Comments on a Conversion of Epoxides to Halohydrins with Elemental Halogen Catalyzed by Phenylhydrazine: Tandem Electrophilic Halogenation of Aromatic Compounds and Epoxide Ring Opening to Halohydrins
Soroka, Miroslaw,Goldeman, Waldemar,Malysa, Piotr,Stochaj, Monika
, p. 2341 - 2344 (2003)
The halogenation of aromatic compounds by bromine or chlorine in the presence of an epoxide gives the corresponding halogenated aromatics and 2-halohydrins, both with good yields.
A convenient new method for the bromination of deactivated aromatic compounds
Duan, Jianxin,Zhang, Lian Hao,Dolbier Jr., William R.
, p. 1245 - 1246 (1999)
Treatment of deactivated aromatic compounds with N-bromosuccinimide in trifluoroacetic acid solvent in the presence of sulfuric acid gave the corresponding monobromoaromatic compounds in good to excellent yields.
Photoelectrochemistry with Quinone Radical Anions-Photoassisted Reduction of Halobenzenes and Carbonyl Compounds
Robertson, Peter K. J.,Eggins, Brian R.
, p. 1829 - 1832 (1994)
Photoexcited electrochemically generated quinone radical anions reduced 1,2-dibromobenzene to bromobenzene, 1,4-dibromobenzene to bromobenzene and 4-chlorobenzonitrile to benzonitrile.In the presence of anthracene, 2-bromophenyl-, 4-bromophenyl- and 4-cyanophenyl-anthracenes were formed.With acetaldehyde, acetone, acetophenone, benzaldehyde and benzophenone, the major products were the corresponding pinacols, with small amounts of the two-electron secondary alcohols.In acetonitrile as solvent, cinnamonitriles, hydrocinnamonitriles and phenylglutaronitriles were formed in addition to the alcohols.Glyoxylic acid was reduced to tartaric, glycolic and malic acids.The reduction of CO2 was unsuccessful.
C?I-Selective Cross-Coupling Enabled by a Cationic Palladium Trimer
Diehl, Claudia J.,Scattolin, Thomas,Englert, Ulli,Schoenebeck, Franziska
, p. 211 - 215 (2019)
While there is a growing interest in harnessing synergistic effects of more than one metal in catalysis, relatively little is known beyond bimetallic systems. This report describes the straightforward access to an air-stable Pd trimer and presents unambiguous reactivity data of its privileged capability to differentiate C?I over C?Br bonds in C?C bond formations (arylation and alkylation) of polyhalogenated arenes, which typical Pd0 and PdI-PdI catalysts fail to deliver. Experimental and computational reactivity data, including the first location of a transition state for bond activation by the trimer, are presented, supporting direct trimer reactivity to be feasible.
Directly Observed Reductive Elimination of Aryl Halides from Monomeric Arylpalladium(II) Halide Complexes
Roy, Amy H.,Hartwig, John F.
, p. 13944 - 13945 (2003)
Monomeric, three-coordinate arylpalladium(II) halide complexes undergo reductive elimination of aryl halide to form free haloarene and Pd(0). Reductive elimination of aryl chlorides, bromides, and iodides were observed upon the addition of P(t-Bu)3/
Vibrational Spectroscopy and Photodissociation Properties of Ions As Determined by Two-Laser Photodissociation Techniques.
Honovich, Jeffrey P.,Dunbar, Robert C.
, p. 3755 - 3758 (1983)
Iodobenzene, bromobenzene, and m-iodotoluene cations trapped in an ion cyclotron resonance (ICR) mass spectrometer undergo an enhanced visible photodissociation process in the presence of infrared irradiation.The infrared wavelength dependence in the 9.7-10.7-μm region for this effect exhibits features wich relate to the infrared spectroscopy of these ions.The variation in extent of the infrared enhancement with visible wavelength is interpreted as reflecting two different mechanisms: at short wavelengths the enhancement is attributed to changes invisible-absorption cross section with increasing internal energy and gives a useful means of observing such effects, while at long wavelengths the enhancement is attributed to a perturbation of the two-photon dissociation kinetics.The photodissociation rates of several other ions were shown not to undergo an enhancement effect when irradiated with the infrared laser.
Effects of Solvent and Additives on the Rearrangement Pathway of the Seyferth Reaction
Lambert, Joseph B.,Boch, Richard J.,Larson, Eric G.
, p. 3054 - 3059 (1985)
The Seyferth reagent has dual reactivity with electron-deficient alkenes. trans-1,2-Dichloroethene reacts both with the free carbene to give cyclopropane stereospecifically and with a complex between carbene and a second molecule of Seyferth reagent (homogeneous catalysis) to give a rearranged propene.The addition of other materials to the reaction mixture can have a profound effect on the ratio of the two pathways.Good ? donors such as p-xylene decrease the pathway to rearranged propene via the complexed carbene.Such materials thus serve as inhibitors to the process of homogeneous catalysis by forming a competing complex that does not go on to propene but instead reverts to free carbene.The existence of the inhibitor-carbene complex is supported by concentration studies.The presence of insoluble materials such as zinc chloride, on the other hand , serves to decrease the pathway that leads through free carbene to the cyclopropane.Free carbene may react with the surface of the additive and be removed as a reactive species.This latter process would have no effect on carbene previously complexed with the homogeneous catalyst, the Seyferth reagent , which could still proceed to rearranged propene.
A study on Zr-Ir multiple bonding active for C-H bond cleavage
Oishi, Masataka,Oshima, Masato,Suzuki, Hiroharu
, p. 6634 - 6654 (2014)
Zr-Ir hydrido complexes with ansa-(cyclopentadienyl)(amide) as the supporting ligand in the zirconium fragment, e.g., (L1ZrR) (Cp*Ir)(μ-H)3 [L1 = Me2Si(η 5-C5Me4)(NtBu), R = Cl (5), Ph (7), Me (10), alkyl, and aryl] were designed, synthesized, and isolated as tractable early-late heterodinuclear complexes. Despite the presence of the three supporting hydride ligands, Zr-Ir distances in the crystal structures of 5, alkyl, and aryl complexes [2.74-2.76 A] were slightly longer than the sum of the element radii of Zr and Ir [2.719 A]. These hydrocarbyl complexes displayed the thermolytic C-H activation of a variety of aromatic compounds and several organometallic compounds. Also, the substrate scope and limitation in the Zr-Ir system were studied. The regiochemical outcomes during the C-H activation of pyridine derivatives and methoxyarenes suggested the in situ generation of a Lewis acidic active intermediate, i.e., (L1Zr) (Cp*IrH2) (III). The existence of III and relevant σ-complex intermediates {L1Zr(η2-R-H)} (Cp*IrH2) (IIR) (R = Me, Ph) in the ligand exchange was demonstrated by the direct isolation of a Et3PO-adduct of III (39b) from 7 and kinetic studies. The structure of the direct Zr-Ir bonds in IIPh, IIMe, III, and 39b were probed using computational studies. The unprecedented strong M-M′ interactions in the early-late heterobimetallic (ELHB) complexes have been proposed herein.
The Addition Reaction of Benzynes Generated Electrochemically from Dihalobenzenes with Tertiary Amines
Egashira, Naoyoshi,Takenga, Jun,Hori, Fumikai
, p. 2671 - 2673 (1987)
The electroreduction of dihalobenzenes was carried out in the presence of tertiary amines as benzyne acceptors in DMF-TBAP, giving the addition products in yields more than 10percent.For o-dibromobenzene, the yield of the addition product, N-phenylpiperidine, increased to 21percent in the presence of N-ethylpiperidine.
ON THE ABSOLUTE REACTIVITY OF ARYL CATIONS: SELECTIVITY TOWARD HALIDE IONS AS A FUNCTION OF VISCOSITY
Lorand, John P.
, p. 7337 - 7340 (1989)
The selectivities toward bromide and chloride ions observed in the dediazoniation of three arenediazonium salts are found to be independent of viscosity.It is inferred that the capture of aryl cations by these halide ions is diffusion controlled.
