Reaktionen des phenyllithiums mit nitrobenzol und nitrosobenzol

Buck, Peter Henry; Köbrich, Gert

doi:10.1016/s0040-4039(00)91002-5

Cited by 27 publications

(18 citation statements)

References 8 publications

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“…The CϪO bond lengths in 1 and 2 are similar to those observed in other sterically encumbered phenols. [14,16,17] As in most structures with bulky terphenyl ligands [8] the flanking aryl rings subtend almost vertical angles (83.1Ϫ85.7°) with the central ring and this is maintained in solution, as evidenced by the observation of two sets of methyl doublets for the iPr groups.…”

Section: Structuresmentioning

confidence: 91%

“…70% yield for both of the very bulky aryl substituents Ar ϭ Ar* and ArЈ. The above route was discovered in 1966Ϫ67 [14] during the investigation of the reactions of various substituted benzenes with organolithium compounds. The reaction of o-nitrobromobenzene with phenyllithium readily afforded the expected o-nitrophenyllithium.…”

Section: Synthesismentioning

confidence: 95%

“…It seems likely that the steric effects of the flanking aryl rings and the low solubility of the aryl halide precursors in aqueous phases prevent efficient reactions in these cases. There are other routes to terphenols in the literature [12,13] but since we already had terphenyllithium reagents to hand, we were drawn to the, apparently little used, anhydrous route, [14] which involves the reaction between nitrobenzene and an aryllithium derivative and afforded as products the nitrosobenzene and the lithium aryloxide salt as depicted below.…”

Section: Synthesismentioning

confidence: 99%

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Synthesis and Characterization of the Very Bulky Phenols ArOH and Ar′OH (Ar = C₆H₃‐2,6‐Trip₂, Trip = C₆H₂‐2,4,6‐iPr₃; Ar′ = C₆H₃‐2,6‐Dipp₂, Dipp = C₆H₃‐2,6‐iPr₂) and Their Lithium and Sodium Derivatives (LiOAr′)₂ and (NaOAr*)₂

et al. 2003

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The very bulky phenols Ar*OH (1) and Ar′OH (2), where Ar* = C6H3‐2,6‐Trip2 (Trip = C6H2‐2,4,6‐iPr3) and Ar′ = C6H3‐2,6‐Dipp2 (Dipp = C6H3‐2,6‐iPr2), as well as their lithium and sodium derivatives (LiOAr*)2 (3), (LiOAr′)2 (4) and (NaOAr*)2 (5) have been synthesized and characterized. The terphenols 1 and 2 were obtained by the reaction of the aryllithium reagents with nitrobenzene and were isolated in ca. 70% yield. The lithium or sodium salts 3−5 were isolated by the reaction of 1 or 2 with nBuLi or sodium metal. All compounds were characterized spectroscopically, and by X‐ray crystallography in the case of 1, 2, 4 and 5. The large terphenyl substituents prevent hydrogen‐bonded association of the phenols 1 and 2. Instead, the O−H hydrogens interact with the π‐electron cloud on one of the flanking Trip or Dipp rings. The dimeric structures of 4 and 5 are relatively rare examples of structurally characterized alkali metal phenoxides that are unsolvated by internal electron pair donors or classical Lewis bases such as ethers or amines. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Section: Structuresmentioning

confidence: 91%

Section: Synthesismentioning

confidence: 95%

Section: Synthesismentioning

confidence: 99%

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Synthesis and Characterization of the Very Bulky Phenols ArOH and Ar′OH (Ar = C₆H₃‐2,6‐Trip₂, Trip = C₆H₂‐2,4,6‐iPr₃; Ar′ = C₆H₃‐2,6‐Dipp₂, Dipp = C₆H₃‐2,6‐iPr₂) and Their Lithium and Sodium Derivatives (LiOAr′)₂ and (NaOAr*)₂

et al. 2003

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“…However, hitherto, this hypothesis is not supported by conclusive evidences. 7 Reaction product distribution depends upon many factors, but, independently from the nature of the metallic counterion and from the solvent and temperature conditions employed, the reaction generally follows path (ii) and / or path (i) 1,4 when the negative charge lies on an sp3 carbon as in alkyl carbanions. Viceversa when the negative charge occupies an sp2 orbital as in aryp.…”

Section: Introductionmentioning

confidence: 99%

“…Viceversa when the negative charge occupies an sp2 orbital as in aryp. 5,7 and vinyl 8 carbanions the reaction generally follows path (iii).…”

Section: Introductionmentioning

confidence: 99%

Polar Versus Electron Transfer Pathway in the Reaction of Alkyl Lithium and Alkyl Grignard Reagents with Mononttroarenes: Factors Affecting Product Distribution

Bartoli

Bosco

Dalpozzo

et al. 1989

Paramagnetic Organometallic Species in Activation/Selectivity, Catalysis

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The reaction of nitroarenes with alkyl lithium and alkyl Grignard reagents can mainly give 1,4 and 1,6-addition products, nitroarene radical anion and alkyl radical decay products. Employing magnesium instead of lithium derivatives and low temperatures, the yields in conjugate addition products increase to the detriment of the amount of nitroarene radical anion; while steric hindrances favour the redox process. These findings can be interpreted on the basis of a single electron transfer (SET) pathway in which conjugate addition derivatives and nitroarene radical anion can be considered as typical in-cage and out-of-cage products respectively. However, there are no conclusive evidences to exclude that the so-called cage products can arise from a polar pathway. Nevertheless, this question can be settled if the existence of a continuos mechanistic spectrum from 'full polar' to 'full SET' pathways is accepted on the basis of the Pross's electron shift theory.

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Electrophilic Amination of Carbanions, Enolates, and Their Surrogates

Ciganek

2009

Organic Reactions

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This chapter deals with the formation of carbon‐nitrogen bonds by reaction of carbon nucleophiles with electrophilic aminating reagents. The former encompass aliphatic and aromatic carbanions, enolates and their surrogates such as enamines, enol esters, and enol ethers, as well as carbanions stabilized by cyano or sulfone groups or by phosphorus. A section entitled Reagents and Mechanisms lists the many aminating reagents available and discusses the mechanisms by which the more important ones react. Among the electrophiles discussed are halo amines, various hydroxylamine derivatives, oxaziridines, imines, oximes, diazonium salts, diazo compounds, azo compounds, and azides. The section on Scope and Limitations is organized by carbon nucleophiles and attempts to suggest the best reagents for each class. A number of electrophilic aminating reagents that have been omitted from the scope of this chapter are briefly discussed, with references to reviews, in the section on Comparison with Other Methods. Tables listing references to the preparation of the various aminating reagents are found in the section on Experimental Conditions. References to the conversion of non‐amine products into amines are also provided there. The literature is covered to the middle of 2007.

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Reaktionen des phenyllithiums mit nitrobenzol und nitrosobenzol

Cited by 27 publications

References 8 publications

Synthesis and Characterization of the Very Bulky Phenols ArOH and Ar′OH (Ar = C₆H₃‐2,6‐Trip₂, Trip = C₆H₂‐2,4,6‐iPr₃; Ar′ = C₆H₃‐2,6‐Dipp₂, Dipp = C₆H₃‐2,6‐iPr₂) and Their Lithium and Sodium Derivatives (LiOAr′)₂ and (NaOAr*)₂

Synthesis and Characterization of the Very Bulky Phenols ArOH and Ar′OH (Ar = C₆H₃‐2,6‐Trip₂, Trip = C₆H₂‐2,4,6‐iPr₃; Ar′ = C₆H₃‐2,6‐Dipp₂, Dipp = C₆H₃‐2,6‐iPr₂) and Their Lithium and Sodium Derivatives (LiOAr′)₂ and (NaOAr*)₂

Polar Versus Electron Transfer Pathway in the Reaction of Alkyl Lithium and Alkyl Grignard Reagents with Mononttroarenes: Factors Affecting Product Distribution

Electrophilic Amination of Carbanions, Enolates, and Their Surrogates

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Reaktionen des phenyllithiums mit nitrobenzol und nitrosobenzol

Cited by 27 publications

References 8 publications

Synthesis and Characterization of the Very Bulky Phenols Ar*OH and Ar′OH (Ar* = C6H3‐2,6‐Trip2, Trip = C6H2‐2,4,6‐iPr3; Ar′ = C6H3‐2,6‐Dipp2, Dipp = C6H3‐2,6‐iPr2) and Their Lithium and Sodium Derivatives (LiOAr′)2 and (NaOAr*)2

Synthesis and Characterization of the Very Bulky Phenols Ar*OH and Ar′OH (Ar* = C6H3‐2,6‐Trip2, Trip = C6H2‐2,4,6‐iPr3; Ar′ = C6H3‐2,6‐Dipp2, Dipp = C6H3‐2,6‐iPr2) and Their Lithium and Sodium Derivatives (LiOAr′)2 and (NaOAr*)2

Polar Versus Electron Transfer Pathway in the Reaction of Alkyl Lithium and Alkyl Grignard Reagents with Mononttroarenes: Factors Affecting Product Distribution

Electrophilic Amination of Carbanions, Enolates, and Their Surrogates

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Synthesis and Characterization of the Very Bulky Phenols ArOH and Ar′OH (Ar = C₆H₃‐2,6‐Trip₂, Trip = C₆H₂‐2,4,6‐iPr₃; Ar′ = C₆H₃‐2,6‐Dipp₂, Dipp = C₆H₃‐2,6‐iPr₂) and Their Lithium and Sodium Derivatives (LiOAr′)₂ and (NaOAr*)₂

Synthesis and Characterization of the Very Bulky Phenols ArOH and Ar′OH (Ar = C₆H₃‐2,6‐Trip₂, Trip = C₆H₂‐2,4,6‐iPr₃; Ar′ = C₆H₃‐2,6‐Dipp₂, Dipp = C₆H₃‐2,6‐iPr₂) and Their Lithium and Sodium Derivatives (LiOAr′)₂ and (NaOAr*)₂