Nucleophilic attacks on carbon-nitrogen double bonds. 3. Diversity of mechanisms for the substitution of diarylimidoyl chlorides by amines in acetonitrile

Ta‐Shma, Rachel; Rappoport, Zvi

doi:10.1021/ja00442a024

Cited by 13 publications

(7 citation statements)

References 7 publications

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“…Reaction of the benzimidoyl chlorides with ammonia, anilines, and alkylamines in chlorinated solvents at room temperature, in the presence of triethylamine, gave amidine hydrochlorides 5 , and workup with aqueous hydroxide brought about cyclization and furnished the desired imidazolines 6a − i (method A). The picolinimidoyl chlorides were much less reactive but gave the pyridyl imidazolines 6j , k on treatment with amines in refluxing acetonitrile and workup with aqueous hydroxide (method B). Formamides were converted into chloroethyl amides 3 using a small excess of thionyl chloride, and the imidoyl chlorides were formed using phosphorus pentachloride in refluxing chloroform.…”

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confidence: 99%

A Novel General Route for the Preparation of Enantiopure Imidazolines

et al. 2002

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A novel procedure for the preparation of enantiopure 1,4-disubstituted 2-imidazolines is reported. Enantiopure beta-amino alcohols are converted into N-hydroxyethylamides, which are reacted with excess thionyl chloride, or with thionyl chloride followed by phosphorus pentachloride to yield N-chloroethylimidoyl chlorides. These intermediates are treated with amines and anilines to produce N-chloroethylamidines, which are converted into imidazolines upon workup with aqueous hydroxide. The method is simple and efficient and has been used to prepare a wide variety of enantiopure imidazolines, in a modular fashion, from readily available amino alcohols.

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A Novel General Route for the Preparation of Enantiopure Imidazolines

et al. 2002

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“…-determining elimination has been reported to be accompanied by a large decrease of AS* in nucleophilic vinylic substitution reactions 18. …”

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Broensted plots in the reactions of 2,4-dinitrophenyl acetate and methyl phenyl carbonate with substituted pyridines

Castro¹,

Freudenberg²

1980

J. Org. Chem.

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“…There are several studies (7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17) on nucleophilic substitutions at the C-N double bond. A nucleophilic additionelimination mechanism or a pathway involving a nitrilium ion intermediate has been suggested.…”

Section: Methodsmentioning

confidence: 99%

2-Azabuta-1,3-diene-4-carbonitriles: stereoselective synthesis and nucleophilic substitution at the carbon–nitrogen double bond

Lorente¹,

Casillas²,

Gomez-Sal³

et al. 1996

Can. J. Chem.

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Abstract:The synthesis of (E)-l-methoxy-2-azabuta-1,3-diene-4-carbonitriles was performed by methylation of Nalkenylamides 9 and 11. The Z isomers were obtained by treatment of (E)-I-methylthio-2-azabuta-I ,3-diene-4,4-dicarbonitriles with sodium methoxide in methanol. We also describe the reactions of (E)-1-methylthio-2-azabuta-1,3-diene-4,4-dicarbonitriles with pyrrolidine, which afforded 1-(1-pyrrolidinyl) derivatives 20,21, and 23. X-ray crystallographic analyses of 21 and 23 established the E stereochemistry of the C-N double bond. K~) Jwordr: 2-azabuta-l,3-diene-4-carbonitriles: stereoselective synthesis, nucleophilic substitution and X-ray diffraction; Nalkenylamides: methylation.Resume : On a effectui la synthkse des (E)-l-mithoxy-2-azabuta-1,3-di~ne-4-carbonitriles en effectuant la mithylation des Nalkinylamides 9 et 11. On a obtenu les isomkres Zen traitant les (0-1-mithylthio-2-azabuta-1,3-dikne-4,4-dicarbonitriles avec du mithylate de sodium dans le mithanol. On dicrit aussi les riactions des (E)-l-mithylthio-2-azabuta-I,3-dikne-4,4-dicarbonitriles avec la pyrrolidine qui conduisent aux dirivis 1-(I-pyrrolidinyle) 20,21 et 23. On a ditermini la stiriochimie E de la double liaison C-N par une analyse cristallographique par diffusion des rayons X.

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Nucleophilic attacks on carbon-nitrogen double bonds. 3. Diversity of mechanisms for the substitution of diarylimidoyl chlorides by amines in acetonitrile

Cited by 13 publications

References 7 publications

A Novel General Route for the Preparation of Enantiopure Imidazolines

A Novel General Route for the Preparation of Enantiopure Imidazolines

Broensted plots in the reactions of 2,4-dinitrophenyl acetate and methyl phenyl carbonate with substituted pyridines

2-Azabuta-1,3-diene-4-carbonitriles: stereoselective synthesis and nucleophilic substitution at the carbon–nitrogen double bond

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