Intramolecular nature of the rearrangement of benzimidates

Wheeler, Owen H.; Roman, Fernanda; Rosado, Oscar

doi:10.1021/jo01256a041

Cited by 17 publications

(10 citation statements)

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“…21e24 This methodology has even been applied in polymer chemistry, enabling the easy preparation of thermally stable polyamides from polyimidates. 25 The intramolecularity of the aryl migration was postulated by Chapman, and further confirmed by Rowland 26 and Wheeler 27 through cross-over and isotopic labeling studies, respectively. Aryl migration is thought to occur via a four-membered cyclic transition state, and consists in a nucleophilic ipso-replacement of O by N, at the arylic carbon.…”

Section: Introductionmentioning

confidence: 84%

First observation of Chapman rearrangement of a pseudosaccharyl ether in the solid state: the thermal isomerization of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide revisited

et al. 2008

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3-(Methoxy)-1,2-benzisothiazole 1,1-dioxide, a pseudosaccharyl ether, was long ago known to undergo a thermal Chapman-like [1,3 0 ]-isomerization to the corresponding N-methyl pseudosaccharin at temperatures above its melting point (ca. 184 C) [Hettler H., Tetrahedron Lett. 1968, 15, 1793]. In the present study, it is shown that this rearrangement can also take place in the solid state, at temperatures as low as 150 C. This was the first observation of a Chapman-like [1,3 0 ]-isomerization in pseudosaccharyl ethers in the solid state. The study has been carried out by a multidisciplinary approach using temperature dependent infrared spectroscopy, differential scanning calorimetry (DSC), and polarized light thermomicroscopy, complemented by theoretical methods.

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Section: Introductionmentioning

confidence: 84%

First observation of Chapman rearrangement of a pseudosaccharyl ether in the solid state: the thermal isomerization of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide revisited

et al. 2008

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“…Both of finite difference and Janak's approximations are used for calculations of chemical potential [Eqs. (3) and (5)] and hardness [Eqs. (4) and (6)] values.…”

Section: Computational Detailsmentioning

confidence: 99%

“…The rearrangement is carried out by heating an arylimino ester to 200 ℃ . Both intramolecular [2][3][4] and intermolecular [5][6][7] mechanisms are assumed for this rearrangement; but the former, which involves a four-membered cycle transition state (Scheme 1), was confirmed through cross-over and isotopic labeling studies. 1,8 It is also shown that the rearrangement obeys first order kinetics and its mechanism involves intramolecular nucleophilic-aromatic substitution.…”

Section: Introductionmentioning

confidence: 95%

A Theoretical Study on Chapman Rearrangement

Noorizadeh

Ozhand

2010

Chin. J. Chem.

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Some Chapman rearrangements are investigated using HF and B3LYP methods combined with two different basis sets (6-31G** and 6-31＋＋G**) and both finite difference model and Janak's approximation. It is shown that although minimum polarizability (MPP) and maximum hardness (MHP) principles are always valid in these reactions, minimum electrophilicity principle (MEP) is followed just when DFT method (B3LYP) is used. The Morrel's rules are also successfully applied in predicting the validity of MEP in these rearrangements. Therefore, it seems that in the study of this kind of reaction, the results of DFT are more reliable than those of HF.

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“…Known that the Chapman Thermal isomerization of aromatic iminoether in N, N-diarilamidy aromatic carboxylic acids [85][86][87]:…”

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confidence: 99%

A New Approach to Modification of Rearrangements in Metallorganic Chemistry of Phosphorus, Arsenic, Antimony and Bismuth

Zhakenovich¹,

Stepanovna²,

Vladimirovna³

et al. 2015

JCCE

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Abstract:We discovered a new approach modification Bamberger, Barton, Beckmann, Wallach, Gabriel, Hofmann, Hofmann A.W. Martius, Dimroth, Semmler-Wolff-Schroeter, Sus, Claisen, Newman-Kwart, Orton, Pistschimuka, Robev, Smiles, Sawdey, Sommelet, Stevens, Tiemann, Fischer-Hepp, Chapman, Chattaway, Schonberg, Stieglitz Rearrangements with of phosphorous, arsine, stibine and bismuthine in organometallic chemistry. The authors have proposed a new mechanism for possible reactions.

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Intramolecular nature of the rearrangement of benzimidates

Cited by 17 publications

References 0 publications

First observation of Chapman rearrangement of a pseudosaccharyl ether in the solid state: the thermal isomerization of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide revisited

First observation of Chapman rearrangement of a pseudosaccharyl ether in the solid state: the thermal isomerization of 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide revisited

A Theoretical Study on Chapman Rearrangement

A New Approach to Modification of Rearrangements in Metallorganic Chemistry of Phosphorus, Arsenic, Antimony and Bismuth

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