Generation Of Benzyne Research Articles

Gas Phase Chemistry of Ketenes, Carbenes, Acetylenes and Arynes: Synthetic Consequences

The development of methyleneketene and methylenecarbene chemistry is outlined, and its relationship to recent gas phase synthetic reactions involving acetylene - methylenecarbene and aryne - exocyclic carbene rearrangements is described. Such synthetic reactions offer new approaches to polycyclic aromatic compounds, particularly those containing five-membered rings. 1. Introduction 2. Generation of Ketenes by FVP 3. Syntheses Based on Intramolecular Reactions of Substituted Methyleneketenes 4. Generation and Rearrangement of Acyloxycarbenes 5. Syntheses Based on the Acetylene to Methylenecarbene Rearrangement 6. Generation of Benzyne by FVP and the Benzyne to Cyclopentadienylidenecarbene Rearrangement 7. Syntheses Based on Intramolecular Trapping of Cyclopentadienylidenecarbenes 8. Conclusion

Benzyne generation from aryl triflates

The use of aryl triflates to form arynes as reactive intermediates is described. This allows the first general use of phenols as aryne precursors. Phenyl triflate reacts with LDA at −78 o C to form benzyne, which then reacts with diisopropylamine generating N,N-diisopropylaniline. Yields of diisopropylarylamines from aryne intermediates are superior to those previously reported. Regioisomeric ratios are similar to those obtained with use ofother benzyne precursors

Generation of benzyne in the thermal decomposition of 2-carboxyphenyl p-toluenesulfonate

The scope and the mechanism of title reaction have been studied. 1,2-Dehydrobenzene, which can be trapped with dienic of nucleophilic reagents, is formed in a nonconcerted process with the intermediacy of a species C 6 H 4 CO 2 (probably benzoxet-2-one). A complex mixture of disalicylide, trisalicylide, and some other polysalicylides is formed, in the absence of trapping agents, by polymerisation of this intermediate

ChemInform Abstract: A New Source for Generation of Benzyne and Pyridyne: Reactions of o‐Halophenyl (or 3‐Bromo‐4‐pyridyl) Phenyl Sulfoxides with Grignard Reagents.

AbstractThe 2‐halophenyl sulfoxides (I) react with the Grignard compounds (II) to yield the sulfoxides (IV) and the halophenylmagnesium bromides (III).

A new source for generation of benzyne and pyridyne: Reactions of O-halophenyl (or 3-bromo-4-pyridyl) phenyl sulfoxides with grignard reagants

o-Chloro- and o-bromophenyl phenyl sulfoxides and (3-bromo-4-pyridyl) phenyl sulfoxide were treated with Grignard reagents to generate benzyne (or 3,4-pyridyne) in THF. The o-iodophenyl derivative, on the other hand, gave mainly o-(arylsulfinyl)phenyl Grignard reagent.

Photochemical reactions. Part 20. Photolysis of o-nitrobenzaldehyde N-acylhydrazones leading to benzyne and 5-nitrophthalazines

Irradiation of o-nitrobenzaldehyde N-acetyl-N-alkylhydrazones resulted in the generation of benzyne via decomposition of o-(N-acetyl-N-alkyltriazeno)benzoic acids derived from o-nitrosobenzoyl-N-acetyl-N-alkylhydrazides which are initially formed in an analogous fashion to the o-nitrobenzylideneaniline rearrangement. Photolysis of o-nitrobenzaldehyde N-acylhydrazones, however, resulted in photocyclisation leading to 1-substituted 5-nitrophthalazines, with benzyne generation only as a minor process.

ChemInform Abstract: Photochemistry of o‐Nitrobenzaldehyde N‐Acylhydrazones. Formation of 1‐Alkyl‐5‐nitrophthalazines and Benzotriazinone, and Generation of Benzyne via an Intermediacy of Indazolone.

AbstractAus dem o‐Nitrobenzaldehydhydrazon (I) erhält man bei der Photolyse neben dem Amid (III) Dehydrobenzol (II).

Photochemistry of o-Nitrobenzaldehyde N-Acylhydrazones Formation of 1-Alkyl-5-nitrophthalazines and Benzotriazinone, and Generation of Benzyne via an Intermediacy of Indazolone

Photochemistry of o-Nitrobenzaldehyde N-Acylhydrazones Formation of 1-Alkyl-5-nitrophthalazines and Benzotriazinone, and Generation of Benzyne via an Intermediacy of Indazolone

Attempted generation of triplet benzyne

Attempted generation of triplet benzyne

Generation of benzyne from 1-(2-carboxyphenyl)triazenes

3-Substituted 1-(2-carboxyphenyl)triazenes, on being heated in solution with 2,3,4,5-tetraphenylcyclo-pentadienone, afford 1,2,3,4-tetraphenylnaphthalene, a benzyne adduct, in good yields, providing a new route for generating benzyne.

The generation of benzyne - A warning

The synthesis of benzyne by the diazotization of anthranilic acid may result in an explosion; an improved procedure to avoid this problem is presented.

ISOBENZOFURANE, A TRANSIENT INTERMEDIATE

A study of Diels–Alder reactions of tetraphenylcyclopentadienone (II) coupled with development of two improved procedures for the generation of benzyne, one of which affords a practical route to the reactive dienophile 1,4-dihydronaphthalene-1,4-endo-oxide (Ia), led to an investigation of the reaction of Ia and II. At 80° these reactants combine readily to give the adduct IIIa, which is cleaved on pyrolysis to isobenzofurane VIIIa and 1,2,3,4-tetraphenylbenzene (IX). The transient existence of isobenzofurane (VIIIa) was established by trapping it with the 1,4-endo-oxide Ia and isolation of the adducts X and XI. In confirmation of the interpretation, X and XI were obtained by independent synthesis from the adduct Va from Ia and α-pyrone and thermal decomposition of Va in the presence of Ia as trapping agent. Parallel experiments with 1,4-dimethyl-1,4-dihydronaphthalene-1,4-endo-oxide, as well as mixed additions, supported the interpretations advanced. Evidence is presented to show that isobenzofurane (VIIIa) invariably adds exo to the bicyclic dienophile.

Aprotic Generation of Benzyne from Diphenyliodonium-2-Carboxylate

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAprotic Generation of Benzyne from Diphenyliodonium-2-CarboxylateEugene. Le GoffCite this: J. Am. Chem. Soc. 1962, 84, 19, 3786Publication Date (Print):October 1, 1962Publication History Published online1 May 2002Published inissue 1 October 1962https://doi.org/10.1021/ja00878a050RIGHTS & PERMISSIONSArticle Views1849Altmetric-Citations41LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (146 KB) Get e-Alerts Get e-Alerts