Novel reactions of arylmalonate carbanions. The reaction with phenyl isocyanate resulting in carbamates by 1,3-C→N migration of the ethoxycarbonyl group

Linchenko, O. A.; Krasnova, I. Yu.; Petrovskii, P. V.; Garbuzova, I. A.; Khrustalev, Victor N.; Gololobov, Yu. G.

doi:10.1007/s11172-007-0259-x

Cited by 4 publications

(3 citation statements)

References 4 publications

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“…We have previously shown [16] that carbanions formed from phenyland para-nitrophenyldiethylmalonates 10 had reacted with PhNCO with formation of carbamates 13a and 13b with satisfactory yields (Scheme 5). The reaction does not stop at the formation of intermediates 11a and 11b.…”

Section: Resultsmentioning

confidence: 99%

Formation of carbamates by reaction between ester carbanions and isocyanates: General regularities and scope

Gololobov

Borisov

Slepchenkov

et al. 2010

Heteroatom Chemistry

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Section: Resultsmentioning

confidence: 99%

Formation of carbamates by reaction between ester carbanions and isocyanates: General regularities and scope

Gololobov

Borisov

Slepchenkov

et al. 2010

Heteroatom Chemistry

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“…During consideration of mechanism for the formation of carbamates by the reaction of isocyanates with carban ions 1 based on phosphorus containing zwitterions, 1,2 phenylcyanacetic esters, 3 and pyridinium ylides 4 , it was suggested that N anion 2 is formed as an intermediate (Scheme 1). The formation of the intermediate 2 was confirmed by the data of quantum chemical calculations for the reaction of pyridinium ylide, malonic ester deriva tive, with phenyl isocyanate.…”

mentioning

confidence: 99%

“…NMR spectra were recorded on a Bruker AMХ 400 spectrometer in the solvent CDCl3 . IR spectra were recorded on a Nicolet Magna IR 750 Fourier spectrometer(KBr).N p Tolylsulfonyl[bis(ethoxycarbonyl)phenyl]acetamide (7a).…”

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confidence: 99%

On the nature of intermediates in the reactions of carbanions of diethyl arylmalonates with isocyanates

et al. 2009

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A reaction of ethyl phenyl and 4 nitrophenylmalonate carbanions with para tolylsulfonyl isocyanate leads to stable addition products, the corresponding substituted para tolyl sulfonylacylamides.Key words: ethyl phenyl and 4 nitrophenylmalonate carbanions, para tolylsulfonyl iso cyanate, para tolylsulfonylacylamides.During consideration of mechanism for the formation of carbamates by the reaction of isocyanates with carban ions 1 based on phosphorus containing zwitterions, 1,2 phenylcyanacetic esters, 3 and pyridinium ylides 4 , it was suggested that N anion 2 is formed as an intermediate (Scheme 1). The formation of the intermediate 2 was confirmed by the data of quantum chemical calculations for the reaction of pyridinium ylide, malonic ester deriva tive, with phenyl isocyanate. 4 At the same time, experi ments using 1 H NMR spectroscopy and kinetic data 2 did not show formation of intermediate 2 as kinetically stable species on the reaction coordinate.To answer the question whether the intermediate N anion 2 is formed in the transformations under study, Scheme 1 R = Ph; Py (+) ; ; R´3P (+) CH 2 , R´ = Pr n , Pr i , Bu n , Et 2 N; X = O, S; Alk = Me, Et, allyl, CH≡CCH 2 ; R″ = Me, cyclo C 6 H 11 , Ar.we considered a model reaction of carbanions 5a,b with tosyl isocyanate (Scheme 2). We presumed that if the reactions with aryl isocyanates proceed according to Scheme 1 through the formation of N anions 2, then the analogous reaction with tosyl isocyanate according to Scheme 2 will lead in the first step to the stable intermedi ate 6, the nucleophilicity of which should be extremely low due to the strong electron withdrawing power of the tosyl group. Scheme 2 R = R´ = H (a); R = NO 2 , R´ = H (b). Ts = SO 2 C 6 H 4 Me pIn fact, the reaction of tosyl isocyanate with carban ions obtained in the solution of THF from CH acid 5a,b and NaH proceeds at room temperature and, after acidifi

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ChemInform Abstract: Novel Reactions of Arylmalonate Carbanions. The Reaction with Phenyl Isocyanate Resulting in Carbamates by 1,3‐C→N Migration of the Ethoxycarbonyl Group.

et al. 2008

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Novel reactions of arylmalonate carbanions. The reaction with phenyl isocyanate resulting in carbamates by 1,3-C→N migration of the ethoxycarbonyl group

Cited by 4 publications

References 4 publications

Formation of carbamates by reaction between ester carbanions and isocyanates: General regularities and scope

Formation of carbamates by reaction between ester carbanions and isocyanates: General regularities and scope

On the nature of intermediates in the reactions of carbanions of diethyl arylmalonates with isocyanates

ChemInform Abstract: Novel Reactions of Arylmalonate Carbanions. The Reaction with Phenyl Isocyanate Resulting in Carbamates by 1,3‐C→N Migration of the Ethoxycarbonyl Group.

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