Vicarious Nucleophilic Hydroxylation of aromatic nitro compounds with organic hydroperoxides

Brose, Thomas; Holzscheiter, F.; Mattersteig, Gunter; Pritzkow, W.; Voerckel, V.

doi:10.1002/prac.19923340609

Cited by 16 publications

(8 citation statements)

References 17 publications

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“…The changes of the VNS/S N Ar ratio in the reactions of halonitroarenes with sulfenamides indicated that in the case of hydrogen substitution ( ii , Scheme ), contrary to the halogen substitution (path iii ), the rate of conversion of the σ H adduct depended on the strength and concentration of the base. This conclusion strongly supports the hypothesis that the mechanism of the reaction includes base-promoted β-elimination, and this is consistent with the previous studies on the mechanisms of the VNS alkylation and hydroxylation …”

Section: Resultssupporting

confidence: 93%

“…The vicarious nucleophilic substitution (VNS) reaction offers a great potential for nucleophilic substitution of hydrogen with carbon and oxygen groups. , This process consists of the addition of nucleophiles containing leaving groups X at the anionic center to nitroarenes followed by base induced β-elimination of HX from the initially formed σ H adducts (Scheme ). Nitrophenols can be obtained in this way when nitroarenes are treated with tert -butyl or cumyl hydroperoxides in the presence of a base.…”

Section: Introductionmentioning

confidence: 99%

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Nitroarylamines via the Vicarious Nucleophilic Substitution of Hydrogen: Amination, Alkylamination, and Arylamination of Nitroarenes with Sulfenamides

Mąkosza

Bialecki

1998

J. Org. Chem.

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Section: Resultssupporting

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Nitroarylamines via the Vicarious Nucleophilic Substitution of Hydrogen: Amination, Alkylamination, and Arylamination of Nitroarenes with Sulfenamides

Mąkosza

Bialecki

1998

J. Org. Chem.

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“…Similar, but generally more stable aryl peroxides, ArOOR, have been prepared and undergo either decomposition to the phenol or, frequently, rearrangement. [4,20-22]…”

Section: Discussion Of Some Unresolved Problemsmentioning

confidence: 99%

The Elbs and Boyland-Sims peroxydisulfate oxidations

Behrman¹

2006

Beilstein J. Org. Chem.

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This paper reviews the recent literature on the title reactions and updates a 1988 review.Page 1 of (page number not for citation purposes) 10The Elbs and Boyland-Sims oxidations are shown in Scheme 1:Scheme 1: The Elbs and Boyland-Sims Oxidations.Both of these reactions, last reviewed in 1988 [1], are nucleophilic displacements on a peroxide oxygen of the peroxydisulfate ion. In the Elbs oxidation, the nucleophile is a phenolate anion (or a tautomer) and in the Boyland-Sims oxidation, it is a neutral aromatic amine. There is no radical involvement in either case (except in side reactions, see below). The products are aromatic sulfates whose orientation relative to the phenolic group is preferentially para in the Elbs oxidation and ortho in the Boyland-Sims case. These sulfates are useful in synthesis themselves or may be hydrolyzed in acid to the dihydric phenols (or aminophenols).The yields of products are typically low to moderate, but the simplicity of the reactions frequently recommends their use. Reactions are usually carried out by dissolving the phenol or amine in an alkaline aqueous medium, sometimes with the addition of a co-solvent such as pyridine, and then adding a peroxy- Page 2 of (page number not for citation purposes) 10 disulfate salt. The ammonium and sodium salts are much more soluble than the potassium salt. This low solubility may be used to advantage to ensure slow addition of the peroxydisulfate as it is established that higher yields are achieved when the phenol(amine)-peroxydisulfate ratio is large. Isolation of the product usually takes advantage of the high water solubility of the intermediate sulfate ester; acidification of the reaction mixture is followed by extraction of the unreacted starting material (in the case of phenols) by an appropriate organic solvent. The sulfate ester remains in the aqueous phase. Hydrolysis of the sulfate ester in aqueous acid produces the (usually) organic-soluble dihydric phenol. Reactions are usually run at room temperature or below to reduce the incursion of free radical reactions. The rates are rather slow with typical secondorder rate constants (at room temperature) in the range 0.1-20 L mol -1 min -1 .[1] Mechanisms of the reactionsThe mechanisms of both reactions have been clarified. In both cases this was done by synthesis of postulated intermediates. In the Boyland-Sims oxidation, the amine-O-sulfonate was the obvious choice that was supported by a number of kinetic studies. In the Elbs oxidation, since the product is preferentially the p-sulfate, the question was whether the initial attack was at the phenolate oxygen(3) followed by rearrangement to the p-sulfate(4) or whether the initial attack was by the tautomeric p-carbanion(5) (Scheme 3).Here it was possible to synthesize the first possibility by displacement of the fluoride ion from three dinitrofluorobenzenes by reaction with Caro's acid anion .[4] The key example was for 2,5-dinitrofluorobenzene(6) which offers both an ortho and a para position for the rearrangement. Fluoride 6...

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“…With acid chlorides in basic media, TBHP acts as a nucleophile, and with acid chlorides give appropriate t-butyl peroxy esters [61][62][63][64], while epoxides are transformed into hydroxydialkyl peroxides [65]. TBHP, and other organic hydroperoxides, in the presence of strong bases, react with aromatic nitro compound via vicarious nucleophilic substitution of hydrogen to form substituted oand pnitrophenols [66][67][68].…”

Section: Hydroperoxides In Alkaline Mediamentioning

confidence: 99%

Non-Metal and Enzymatic Catalysts for Hydroperoxide Oxidation of Organic Compounds

Młochowski¹

2011

TOCATJ

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Oxidation of different groups of organic compounds, with hydroperoxides catalyzed by non-heavy metal containing low-molecular-weight compounds and enzymes is reviewed. This article is concentrated mainly on the hydrogen peroxide and tert-butyl hydroperoxide, however other less common hydroperoxides are also mentioned. Since hydroperoxides themselves are inactive toward most of the organic substrates, in situ activation of the oxidant is necessary. For this purpose various activators have been applied in stoichiometric or catalytic amounts. The carboxylic acids, nitriles, amides and urea are representative for the first category. The organocatalysts such as-halo carbonyl compounds, ketones, imines, iminium salts, nitroxyl radicals and polyaminoacids, selenium compounds and enzymes are presented. They are involved in oxygen, and electron transfer processes whose mechanisms are briefly discussed, and their applications in laboratory and industrial synthesis are indicated.

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Vicarious Nucleophilic Hydroxylation of aromatic nitro compounds with organic hydroperoxides

Cited by 16 publications

References 17 publications

Nitroarylamines via the Vicarious Nucleophilic Substitution of Hydrogen: Amination, Alkylamination, and Arylamination of Nitroarenes with Sulfenamides

Nitroarylamines via the Vicarious Nucleophilic Substitution of Hydrogen: Amination, Alkylamination, and Arylamination of Nitroarenes with Sulfenamides

The Elbs and Boyland-Sims peroxydisulfate oxidations

Non-Metal and Enzymatic Catalysts for Hydroperoxide Oxidation of Organic Compounds

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