108-85-0Relevant articles and documents
New Alkane Functionalization Reactions Based on Gif-Type Chemistry in the Presence of Alkali Metal Salts.
Barton, Derek H. R.,Beviere, Stephane D.,Chavasiri, Warinthorn,Doller, Dario,Hu, Bin
, p. 1871 - 1874 (1993)
Cycloalkanes are transformed into monosubstituted cycloalkyl derivatives (chloride, azide, cyanide, thiocyanate, dicycloalkyl disulfide, or nitroalkane) in mostly good efficiencies by treatment with tert-butyl hydroperoxide in pyridine/acetic acid containing Fe(NO3)3*9H2O, in the presence of alkali metal salts (LiCl, NaN3, CN, NaSCN, Na2S, or NaNO2, respectively).In comparison, ionic trapping with Cu(OAc)2 gave efficient trapping with chloride ion, very inefficient capture of thiocyanate, and a significant difference in reactivity towards azide ion.
Amavadine as a catalyst for the peroxidative halogenation, hydroxylation and oxygenation of alkanes and benzene
Reis,Silva,Frausto da Silva,Pombeiro
, p. 1845 - 1846 (2000)
Synthetic amavadine models, [V(HIDPA)2]2- and [V(HIDA)2]2- [where HIDPA and HIDA stand for the basic forms of 2,2'-(hydroxyimino)dipropionic and 2,2'-(hydroxyimino)diacetic acid, respectively], exhibit haloperoxidase- or peroxidase-type activities, and act as catalysts for the selective peroxidative monohalogenation, hydroxylation or oxo-functionalization of alkanes or aromatic compounds such as benzene and mesitylene at room temperature.
Comparison of gif-type reactivity towards alkanes with standard radical reaction selectivity. Gif oxidation of n-butane and propane
Barton, Derek H. R.,Csuhai, Eva,Doller, Dario,Ozbalik, Nubar,Senglet, Nathalie
, p. 3097 - 3100 (1990)
A precise comparison has been made between radical bromination of a series of saturated hydrocarbons using BrCCl3 and the bromination of the same series with the same reagent under Gif-type (GoAggIII) conditions. The relative reactivities in the two series are completely different and confirm a difference in mechanism. Experiments with n-butane and with propane have shown that these gases react with the usual Gif selectivity to furnish 2-butanone and acetone respectively.
Free radical addition of cyclopentane and cyclohexane to halogeno derivatives of 1,2-difluoroethene
Cooper, Julian A.,Copin, Elodie,Sandford, Graham
, p. 83 - 90 (2002)
Free radical addition reactions between cyclopentane and cyclohexane and a range of difluoroalkenes, CF2=CXY (X, Y = H, F, Cl, Br) gave a series of adducts bearing difluoromethylene substituents, R-CF2-CXYH (R = c-C5H9 or c-C6H11), in reasonable yield even though telomerisation and halogen transfer (when X, Y = Cl, Br) can compete. Dehydrofluorination of the adducts gave several new polyhalogenated alkenes.
Facile Conversion of Alkenes into Alkyl Bromides via Reaction of Organoboranes with Bromine or Bromine Chloride
Kabalka, George W.,Sastry, Kunda A. R.,Hsu, Henry C.,Hylarides, Mark D.
, p. 3113 - 3115 (1981)
Organoboranes react with either bromine or bromine chloride in aqueous media to yield the corresponding alkyl bromides under surprisingly mild conditions.The reaction is ideal for the synthesis of functionally substituted organic bromides.Sodium bromide may be utilized as the bromine source via its in situ conversion to bromine chloride by using mild oxidizing agents.
Studies on the bromination of saturated hydrocarbons under GoAggIII conditions
Barton, Derek H. R.,Csuhai, Eva,Doller, Dario
, p. 3413 - 3416 (1992)
The bromination reaction of saturated hydrocarbons under GoAggIII conditons (FeCl3.6H2O picolinic acid, H2O2 in pyridine/acetic acid) and under radical chain conditions (dibenzoyl peroxide in pyridine/acetic acid or initiation by UV light) are compared. Differences in the selectivity and kinetic behavior for a series of polyhaloalkanes are in agreement with a non-radical mechanism for GoAggIII bromination. Comparison of the kinetic order of reactivity for a series of polyhaloalkanes under chain radical conditions and under GoAggIII conditions is in agreement with a non-radical reaction pathway for the Gif-type bromination reaction.
Mechanistic elucidation of C-H oxidation by electron rich non-heme iron(IV)-oxo at room temperature
Rana, Sujoy,Dey, Aniruddha,Maiti, Debabrata
, p. 14469 - 14472 (2015)
Non-heme iron(iv)-oxo species form iron(iii) intermediates during hydrogen atom abstraction (HAA) from the C-H bond. While synthesizing a room temperature stable, electron rich, non-heme iron(iv)-oxo compound, we obtained iron(iii)-hydroxide, iron(iii)-alkoxide and hydroxylated-substrate-bound iron(ii) as the detectable intermediates. The present study revealed that a radical rebound pathway was operative for benzylic C-H oxidation of ethylbenzene and cumene. A dissociative pathway for cyclohexane oxidation was established based on UV-vis and radical trap experiments. Interestingly, experimental evidence including O-18 labeling and mechanistic study suggested an electron transfer mechanism to be operative during C-H oxidation of alcohols (e.g. benzyl alcohol and cyclobutanol). The present report, therefore, unveils non-heme iron(iv)-oxo promoted substrate-dependent C-H oxidation pathways which are of synthetic as well as biological significance.
Mechanism of Hydroxylation of Alkanes by Dimethyldioxirane. A Radical-Clock Study
Vanni, Raffaella,Garden, Simon J.,Banks, Jeffrey T.,Ingold, Keith U.
, p. 7999 - 8002 (1995)
The oxidation of 2-cyclopropylpropane by dimethyldioxirane (DMD) to 2-cyclopropylpropan-2-ol is not a free-radical chain reaction.It is suggested the free-radical chain observed by Minisci et al. when alkane/DMD reactions were carried out in the presence of CCl3Br involves H-atom abstraction from the alkane by Cl3COO. (in air) and by Me2C(O.)OCCl3 as well as by the Cl3C. radical.
Halogen Exchange Reaction of Aliphatic Fluorine Compounds with Organic Halides as Halogen Source
Mizukami, Yuki,Song, Zhiyi,Takahashi, Tamotsu
, p. 5942 - 5945 (2015)
The halogen exchange reaction of aliphatic fluorine compounds with organic halides as the halogen source was achieved. Treatment of alkyl fluorides (primary, secondary, or tertiary fluorides) with a catalytic amount of titanocene dihalides, trialkyl aluminum, and polyhalomethanes (chloro or bromo methanes) as the halogen source gave the corresponding alkyl halides in excellent yields under mild conditions. In the case of a fluorine/iodine exchange, no titanocene catalyst is needed. Only C-F bonds are selectively activated under these conditions, whereas alkyl chlorides, bromides, and iodides are tolerant to these reactions.
The Reaction of Bromine with Cyclohexene in Carbon Tetrachloride. Part 2. Reactions in the Presence of Added Hydrogen Bromide, and of Imides, and in the Absence of Additives
Hart, Lionel S.,Whiting, Mark C.
, p. 1087 - 1092 (1983)
The addition of bromine to cyclohexene in carbon tetrachloride containing added hydrogen bromide takes place rapidly, and is of first order in each of these species.When bromine is added to cyclohexene in solutions containing succinimide or phthalimide, the addition reaction follows an expression of order 1.5 in bromine and 0.5 in the imide.When no other component is present, the addition of bromine to cyclohexene is extremely sensitive to unintentional additives, but is usually of order 1.5 in bromine and of small positive order in water.We suggest reasonable reaction mechanisms for these processes, involving species stoicheiometrically equivalent to HBr3 and HBr5, and discuss their applicability to the second, fast phase of the scavenged reactions described in Part 1.
