108-85-0Relevant articles and documents
Addition of Hydrohalogenic Acids to Alkenes in Aqueous-Organic, Two-Phase Systems in the Presence of Catalytic Amounts of Onium Salts
Landini, Dario,Rolla, Franco
, p. 3527 - 3529 (1980)
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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.
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.
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.
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Traynham,J.G. et al.
, p. 1302 - 1307 (1969)
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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.
Clive,Denyer
, p. 1112 (1971)
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Yoshida et al.
, p. 1809 (1978)
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A Novel Synthesis of Cyclohexanol Derivatives by the Catalytic Hydrogenation of Benzene with Acid Additives
Yasuhara, Yutaka,Nishino, Masaki
, p. 2779 - 2784 (1994)
The hydrogenation of benzene over a platinum group metal in the presence of various strong acids was carried out.Cyclohexanol derivatives (C6H11X, X=OH, OAc, Cl, Br) were found to be produced by the catalytic hydrogenation of benzene with acid additives.The following two sequences of adsorption strength were observed between platinum metals (adsorbent) and additive reagents (adsorbate): Ru >> Rh > Pd > Ir > Pt (I) and HI, HCOOH >> HBr > HCl >> AcOH, H2O. (II).When a weak adsorbate, such as acetic acid or water, was used as an additive reagent, ruthenium, the strongest adsorbent, exhibited the best selectivity.When hydrogen chloride, a strong adsorbate in the sequence (II), was used an additive reagent, palladium or rhodium, moderately strong adsorbent, exhibited excellent selectivity.By the reaction of 2 ml of benzene, 5 ml of 35percent HCl and 0.2 g of 5percent Pd/SiO2, under 10 atm-G (P atm-G=1.013(P+1)*105 Pa) hydrogen at 100 deg C for 20 h, 8,4percent of the yield of chlorocyclohexane was obtained at 64.2percent of the selectivity (13.1percent of the conversion of benzene).
A hexanuclear mixed-valence oxovanadium(IV,V) complex as a highly efficient alkane oxidation catalyst
Sutradhar, Manas,Kirillova, Marina V.,Guedes Da Silva, M. Fátima C.,Martins, Luísa M.D.R.S.,Pombeiro, Armando J. L.
, p. 11229 - 11231 (2012)
The new hexanuclear mixed-valence vanadium complex [V3O 3(OEt)(ashz)2(μ-OEt)]2 (1) with an N,O-donor ligand is reported. It acts as a highly efficient catalyst toward alkane oxidations by aqueous H2O2. Remarkably, high turnover numbers up to 25000 with product yields of up to 27% (based on alkane) stand for one of the most active systems for such reactions.
Mononuclear Nonheme High-Spin (S=2) versus Intermediate-Spin (S=1) Iron(IV)–Oxo Complexes in Oxidation Reactions
Bae, Seong Hee,Seo, Mi Sook,Lee, Yong-Min,Cho, Kyung-Bin,Kim, Won-Suk,Nam, Wonwoo
, p. 8027 - 8031 (2016)
Mononuclear nonheme high-spin (S=2) iron(IV)–oxo species have been identified as the key intermediates responsible for the C?H bond activation of organic substrates in nonheme iron enzymatic reactions. Herein we report that the C?H bond activation of hydrocarbons by a synthetic mononuclear nonheme high-spin (S=2) iron(IV)–oxo complex occurs through an oxygen non-rebound mechanism, as previously demonstrated in the C?H bond activation by nonheme intermediate (S=1) iron(IV)–oxo complexes. We also report that C?H bond activation is preferred over C=C epoxidation in the oxidation of cyclohexene by the nonheme high-spin (HS) and intermediate-spin (IS) iron(IV)–oxo complexes, whereas the C=C double bond epoxidation becomes a preferred pathway in the oxidation of deuterated cyclohexene by the nonheme HS and IS iron(IV)–oxo complexes. In the epoxidation of styrene derivatives, the HS and IS iron(IV) oxo complexes are found to have similar electrophilic characters.
The conversion of alcohols to halides using a filterable phosphine source
Pollastri, Michael P.,Sagal, John F.,Chang, George
, p. 2459 - 2460 (2001)
The conversion of primary and secondary alcohols to chlorides and bromides using 1,2-bis(diphenylphosphino)ethane (diphos) is described. Use of this reagent in lieu of the typical triphenylphosphine-carbontetrahalide complex provides a facile means of purifying the desired halide from the phosphine-oxide byproduct.
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Bellucci,G. et al.
, p. 1017 - 1018 (1969)
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Free-Radicals in the Oxidation and Halogenation of Alkanes by Dimethyldioxirane: an Oxygen Rebound Mechanism
Minisci, Francesco,Zhao, Lihua,Fontana, Francesca,Bravo, Anna
, p. 1697 - 1700 (1995)
The oxidation of alkanes by dimethyldioxirane (DMD) in the presence of CBrCl3 provides strong evidence that free-radicals are involved in the reaction; enthalpic and polar effects and an "oxygen rebound" mechanism are suggested to explain the exceptional oxidation selectivity.
Mild one-pot preparation of glycosyl bromides
Hunsen, Mo,Long, David A.,D'Ardenne, Christopher R.,Smith, Amanda L.
, p. 2670 - 2674 (2005)
Mild one-pot protocols for the preparation of glycosyl bromides and alkyl bromides via in situ generation of HBr is reported here.
Tufariello,Hovey
, p. 372 (1970)
ORGANOBORANES FOR SYNTHESIS. 10. THE BASE-INDUCED REACTION OF BROMINE WITH ORGANOBORNES. A CONVENIENT PROCEDURE FOR THE CONVERSION OF ALKENES INTO ALKYL BROMIDES VIA HYDROBORATION
Brown, Herbert C.,Lane, Clinton F.
, p. 2763 - 2772 (1988)
The reaction of trialkylboranes with bromine is greatly accelerated by base.Bromination in the presence of sodium hydroxide provides alkyl bromide along with a large amount of the corresponding alcohol.The use of sodium methoxide as a base eliminates this undesirable side reaction and provides an improved yield of alkyl bromide.Consequently, hydroboration, followed by bromination in the presence of sodium methoxide, provides a convenient new procedure for the conversion of alkenes into alkyl bromides.The organoboranes, obtained via hydroboration of terminal alkenes, react with the utilization of all three alkyl groups attached to boron, providing nearly quantitative yields of alkyl bromides. This procedure also accommodates common organic functional groups, as demonstrated by the preparation of methyl 11-bromoundecanoate and 11-bromoundecyl acetate from the corresponding functionally substituted alkenes.Under these conditions, secondary and bulky primary alkyl groups react more sluggishly.However, a procedure involving simultaneous addition of bromine and methanolic sodium methoxide provides improved results for such derivatives.Surprisingly, the base-induced bromination of tri-exo-nobornylborane results in an inversion of configuration at the reaction center to give predominantly endo-2-bromonorbornane.A mechanism is proposed to account for this remarkable inversion.
Metal-free and copper-promoted single-pot hydrocarboxylation of cycloalkanes to carboxylic acids in aqueous medium
Kirillova, Marina V.,Kirillov, Alexander M.,Pombeiro, Armando J. L.
, p. 2936 - 2948 (2009)
A simple and effective method for the transformation, under mild conditions and in aqueous medium, of various cycloalkanes (cyclopentane, cyclohexane, methylcyclohexane, cis- and trans-1,2dimethylcyclohexane, cycloheptane, cyclooctane and adamantane) into the corresponding cycloalkanecarboxylic acids bearing one more carbon atom, is achieved. This method is characterized by a singlepot, low-temperature hydrocarboxylation reaction of the cycloalkane with carbon monoxide, water and potassium peroxodisulfate in water/acetonitrile medium, proceeding either in the absence or in the presence of a metal promoter. The influence of various reaction parameters, such as type and amount of metal promoter, solvent composition, temperature, time, carbon monoxide pressure, oxidant and cycloalkane, is investigated, leading to an optimization of the cyclohexane and cyclopentane carboxylations. The highest efficiency is observed in the systems promoted by a tetracopper(II) triethanolaminate-de rived complex, which also shows different bond and stereoselectivity parameters (compared to the metalfree systems) in the carboxylations of methylcyclohexane and stereoisomeric 1,2-dimethylcyclohexanes. A free radical mechanism is proposed for the carboxylation of cyclohexane as a model substrate, involving the formation of an acyl radical, its oxidation and consequent hydroxylation by water. Relevant features of the present hydrocarboxylation method, besides the operation in aqueous medium, include the exceptional metal-free and acid-solvent-free reaction conditions, a rare hydroxylating role of water, substrate versatility, low temperatures (ca. 50°C) and a rather high efficiency (up to 72% carboxylic acid yields based on cycloalkane).
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Lane,Brown
, p. C51,C53 (1971)
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Reid,Ruhoff,Burnett
, p. 26 (1935)
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IONIC BROMINATION OF NORMAL ALKANES AND CYCLOALKANES BY BROMINE IN THE PRESENCE OF APROTIC ORGANIC SUPERACIDS
Orlinkov, A. V.,Akhrem, I. S.,Afanas'eva, L. V.,Vol'pin, M. E.
, p. 1965 (1988)
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The functionalization of saturated hydrocarbons. Part 39. Further evidence for the role of the iron-carbon bond in Gif chemistry
Barton, Derek H.R.,Costas Salgueiro, Miquel,MacKinnon, John
, p. 7417 - 7428 (1997)
The functionalization of saturated hydrocarbons utilizing the Gif oxidation system is considered to occur via an intermediate containing an Fe-C bond. Iodine and iodide ion have been found to capture efficiently the Fe-C bond to give the corresponding alkyl iodide in both the Fe(II)-Fe(IV) and Fe(III)-Fe(V) manifolds. This trapping of the Fe-C bond in both manifolds is shown to be non-radical in nature.
Thiourea-Mediated Halogenation of Alcohols
Mohite, Amar R.,Phatake, Ravindra S.,Dubey, Pooja,Agbaria, Mohamed,Shames, Alexander I.,Lemcoff, N. Gabriel,Reany, Ofer
supporting information, p. 12901 - 12911 (2020/11/26)
The halogenation of alcohols under mild conditions expedited by the presence of substoichiometric amounts of thiourea additives is presented. The amount of thiourea added dictates the pathway of the reaction, which may diverge from the desired halogenation reaction toward oxidation of the alcohol, in the absence of thiourea, or toward starting material recovery when excess thiourea is used. Both bromination and chlorination were highly efficient for primary, secondary, tertiary, and benzyl alcohols and tolerate a broad range of functional groups. Detailed electron paramagnetic resonance (EPR) studies, isotopic labeling, and other control experiments suggest a radical-based mechanism. The fact that the reaction is carried out at ambient conditions, uses ubiquitous and inexpensive reagents, boasts a wide scope, and can be made highly atom economic, makes this new methodology a very appealing option for this archetypical organic reaction.
N -Hydroxyphthalimide/benzoquinone-catalyzed chlorination of hydrocarbon C-H bond using N -chlorosuccinimide
Li, Zi-Hao,Fiser, Béla,Jiang, Biao-Lin,Li, Jian-Wei,Xu, Bao-Hua,Zhang, Suo-Jiang
supporting information, p. 3403 - 3408 (2019/04/01)
The direct chlorination of C-H bonds has received considerable attention in recent years. In this work, a metal-free protocol for hydrocarbon C-H bond chlorination with commercially available N-chlorosuccinimide (NCS) catalyzed by N-hydroxyphthalimide (NHPI) with 2,3-dicyano-5,6-dichlorobenzoquinone (DDQ) functioning as an external radical initiator is presented. Aliphatic and benzylic substituents and also heteroaromatic ones were found to be well tolerated. Both the experiments and theoretical analysis indicate that the reaction goes through a process wherein NHPI functions as a catalyst rather than as an initiator. On the other hand, the hydrogen abstraction of the C-H bond conducted by a PINO species rather than the highly reactive N-centered radicals rationalizes the high chemoselectivity of the monochlorination obtained by this protocol as the latter is reactive towards the C(sp3)-H bonds of the monochlorides. The present results could hold promise for further development of a nitroxy-radical system for the highly selective functionalization of the aliphatic and benzylic hydrocarbon C-H.
