3- Nitro-bromobenzene,

Bromobenzene, iodobenzene and benzyl chloride behave somewhat similarly. The />-nitro-derivatives of the first two compounds frequently crystallise out even before pouring into water p-nitrobenzyl chloride usually remains as an oil for several minutes before solidifying. 

Reaction of potassium phenoxide with p-nitro-bromobenzene in the presence of 18-crown-6 [3] anddibenzo-18-crown-6 111] at 100°C ... 

Glutathione conjugation Glutathione (GSH) GSH-S-transferase (cytosol, microsomes) Epoxides, arene oxides, nitro groups, hydroxylamines Acetaminophen, ethacrynic acid, bromobenzene... 

N 7.53% Three isomers exist and are described in the literature l-Nitroso-2-bromobenzene, col ndls, mp 97.5 98° l-Nitroso-3-bromobenzene, crysts, mp 78° and l-Nitroso-4-bromobenzene, col ndls(from ale), mp 95°- Other props methods of prepn are given in Beil Ref Beil 5, 232, (124) [l7l] Mononitrobromobenzene, 02N.C6H4.Br mw 202.02, N 6.94%. Three isomers are described in the literature l-Nitro-2-bromobenzene, It yel slender ndls, mp 38-45° l-Nitro-3-bromobenzene, exists in unstable form, mp 17.5° in stable form as rhomb prisms, mp 54-6° and l-Nitro-4 bromobenzene, triclinic prisms, mp 125 7°, explodes on heating to 755° The prepn other props are given in the Ref Ref Beil 5, 247-8, (131 2) [l88]... 

Note Higher nitro derivs of bromobenzene were not found in Beil or in CA thru 1956... 

Cognate preparation. 3,3,5-Trimetkyl-l-methylenecyclohexane. Prepare an ethereal solution of phenyllithium by the procedure described in Expt 8.32, using 2.7 g (0.39 mol) of lithium shavings, 26 g (17.5 ml, 0.16 mol) of dry redistilled bromobenzene and 85 ml of anhydrous ether. After the conversion to phenyllithium is complete dilute the solution with a 15 ml portion of anhydrous ether and decant the solution from any unreacted lithium [Expt 8.32 Note (2)] into a clean three-necked 250-ml flask equipped with a nitro-... 

This is supposed to stop the reaction by making the C-Br bond stronger. This is nonsense. The reaction doesn t happen on simple aryl halides because there is no available mechanism. It is easy to show that the false textbook reason is wrong. The conjugation in this nitro compound is much better than in bromobenzene, so it should be even less reactive. 

Epoxidation and hydroxylation A-Dealkylation O-Dealkylation -Dealkylation -Oxidation A-Oxidation P-Oxidation Desulfuration Dehalogenation Nitro reduction Azo reduction Cytochrome P450 (CYP) Aflatoxin, aldrin, benzo[a]pyrene, bromobenzene, naphthalene Ethylmorphine, atrazine, dimethylnitrocarbamate, dimethylaniline p-Nitroanisole, chlorfenvinphos, codeine Methylmercaptan Thiobenzamide, phorate, endosulfan, methiocarb, chlorpromazine 2-Acetylaminofluorene Diethylphenylphosphine Parathion, fonofos, carbon disulfide CCLt, CllCb Nitrobenzene O-Aminoazotoluene Flavin-Containing Monooxygenase (FMO)... 

Homocoupling of halobenzenes. lodo- and bromobenzene couple to biphenyls in the presence of this activated Ni(0). Yields are definitely higher with the former substrate. ort/io-Substituents, particularly nitro groups, inhibit coupling. The main by-products result from reduction. This coupling reaction is generally superior to the Ullmann reaction. 

Heating of diarylcarbodiimides with o-nitro substituents in bromobenzene affords benzo-triazoles. For example, an 85 % yield of 2-(o-nitrophenyl)benzotriazole 647 is obtained from 2,2 -dinitrodiphenylcarbodiimide 646. ... 

Studies using experimental diabetic animal models have indicated that xenobiotic-induced hepatotoxicity is modulated in diabetes. Hepatotoxicity of several structurally and mechanistically diverse chemicals, such as chloroform, thioacetamide, menadione, nitro-soamines, bromobenzene, and CCI4, is significantly increased in type 1 diabetic rats. It was reported that thioacetamide-induced hepatotoxicity was potentiated in alloxan- or streptozotocin-diabetic rats. Recent studies have confirmed the potentiation of thioacetamide hepatotoxicity in streptozotocin-diabetic rats. Several studies have shown that hepatotoxicity of CCI4 is potentiated in alloxan- or streptozotocin-induced type 1 diabetic rats. 

The nitro-carbodi-imides (55.1) are cyclized into the triazole by heating in bromobenzene. 

There is good evidence that some nucleophilic substitution reactions do involve a single electron transfer, but the best established use a slightly different mechanism. These are the SrnI reactions, with the subscript RN standing for radical nucleophilic. Examples are the reaction of the nitronate anion 4.14 with p-nitrobenzyl chloride 4.15, 251 and the reaction of the pinacolone enolate 4.16 with bromobenzene.252 The former might have been a straightforward SN2 reaction, but actually takes the S l pathway because the nitro groups make the electron transfer exceptionally easy. The latter cannot take place by a conventional Sn2 reaction, because aryl (and vinyl) halides are not susceptible to direct displacement, and the S l pathway overcomes this difficulty. 

Nitrobromobenzenes, Br.C6H4.NO2.—Three compounds of this formula exist. When bromobenzene is nitrated, the bromine atom sends the nitro group to the para and ortho positions, the chief product of the reaction being p-nitrobromobenzene (m.p. 126°). On the other hand, when nitrobenzene is bromi-nated, the negative nitro group sends the halogen atom to the meta position, and an excellent yield of m-nitrobromobenzene (m.p. 56°) is formed. 

The compounds formed by nitrating the isomeric nitro-bromobenzenes furnish an illustration of the principle in regard to the orienting effect of substituents on entering groups. The structures of the products formed are shown by the following formulas —... 

Much research has been carried out on the Ugand-free palladium-catalysed Suzuki reaction. Already in 1989, Beletskaya reported a Ugand-free Suzuki reaction in water, between iodobenzoates and phenylboronic acid using Pd(OAc)2 as catalyst [81]. Later, Novak took up the quest to develop a highly active catalyst for the Suzuki reaction and since he noted that this reaction suffers from phosphine inhibition he decided to test three Ugand-free palladium catalyst precursors Pd(OAc)2, [(Ti -CsHsjPd PdCl]2, and Pd2(dba)3.QH6 [82]. All three catalysts performed well in the Suzuki reaction between 4-nitro-iodobenzene and phenylboronic acid. In the reaction with 4-nitro-bromobenzene the first and last catalyst were clearly superior with yields of 96-98% (Scheme 10.7). Novak suggests that... 

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