Decomposition of Benzenediazonium-2-Carboxylate

Stiles, Martin K.; Miller, R. C.

doi:10.1021/ja01499a094

Cited by 124 publications

(36 citation statements)

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“…Apparently, the pyridyl‐functionality interferes with the species involved in the formation of the aryne. Several reagents known to generate benzyne in situ were also tested without any success, such as 2‐iodophenoltosylate in combination with i PrMgCl or benzenediazonium‐ o ‐carboxylate . Similarly, the use of diethyl acetylenedicarboxylate or maleic anhydride as typical dienophiles did not lead to the desired 1‐phosphabarrelene, either …”

Section: Resultsmentioning

confidence: 99%

“…However,w er easoned that the photolysis of coordinated phosphabarrelene 8 might be more selective. Indeed,e xposing as olution of Rh I complex 11 in tetrahydrofuran to sunlight, the slow transformationo f11 into an ew species ( 14)w as noticeda fter several hours (Figure 8, spectra (a) and( b)). [8]: P(1)ÀC(1): 1.845(5); P(1)ÀC(5): 1.8330(5);P (1)ÀC(23): 1.864(5);P(1)ÀFe(1):2.1439 (15);N(1)ÀFe(1):2.057(4); C(23)ÀC(24): 1.327 (7);C(1)ÀC(2): 1.325 (7);C(2)ÀC(3): 1.538 (7);C (3)ÀC(4): 1.542(6);C(4)À C(5): 1.330 (7).…”

Section: Introductionmentioning

confidence: 99%

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Pyridyl‐Functionalized 1‐Phosphabarrelene: Synthesis, Coordination Chemistry and Photochemical di‐π‐Methane Rearrangement

Bruce

Papke

Ehlers

et al. 2019

Chemistry A European J

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Dedicatedtothe element phosphorus on the 350th anniversary of its discovery.Abstract: The [4+ +2] cycloaddition of 2-(2'-pyridyl)-4,6-diphenyl-l 3 -phosphinine with the highly reactive dienophile hexafluoro-2-butyne has been studied and the first pyridylfunctionalized 1-phosphabarrelenew as obtained and structurally characterized. Although monodentate CF 3 -1-phosphabarrelenes show only ap oorc oordination ability,t he chelating nature of the novel P, N-hybrid ligand gives accesst ov arious transition-metal complexes.U pon irradiation with UV light, the pyridyl-functionalized 1-phosphabarrelene undergoes ar ather selective di-p-methane rearrangementi nt he coordination sphere of the metal center, leading to the formation of ac omplex based on ah itherto unknown pyridylfunctionalized 5-phosphasemibullvalene derivative.D FT calculations provide first insights into the mechanism of this reaction.[a] Dr.M.B ruce, Dr.M .P apke,M.W eber,Prof.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Pyridyl‐Functionalized 1‐Phosphabarrelene: Synthesis, Coordination Chemistry and Photochemical di‐π‐Methane Rearrangement

Bruce

Papke

Ehlers

et al. 2019

Chemistry A European J

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“…To contrast the desilylation protocol with the cheapest alternative, we examined the original method for benzyne preparation in non-basic media. 53 When first introduced, the thermolysis of benzenediazonium-2-carboxylate 19 ( Table 2) provided significant advantages over the organometallic protocols prevalent in the 1960s. The study of diazotized anthranilic acids ‡ greatly increased the types of benzyne which could be prepared under neutral conditions.…”

Section: Benzyne-diels-alder Reactionmentioning

confidence: 99%

Valorization of 2,5-furandicarboxylic acid. Diels–Alder reactions with benzyne

Serum

Selvakumar

Zimmermann³

et al. 2018

Green Chem.

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“…The used dienophile, benzyne, is highly reactive and must be generated in situ [21–24]. This can be achieved by chemical decomposition initiated by fluoride [25], lithium [22,26], an oxidizing agent [27] or by physical decomposition by radiation [28] or heating [29–31] of a precursor system. Here, we used benzenediazonium-2-carboxylate as a benzyne precursor, which thermally decomposes by elimination of nitrogen and carbon dioxide.…”

Section: Introductionmentioning

confidence: 99%

Integrating reaction and analysis: investigation of higher-order reactions by cryogenic trapping

Stockinger¹,

Trapp

2013

Beilstein J. Org. Chem.

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SummaryA new approach for the investigation of a higher-order reaction by on-column reaction gas chromatography is presented. The reaction and the analytical separation are combined in a single experiment to investigate the Diels–Alder reaction of benzenediazonium-2-carboxylate as a benzyne precursor with various anthracene derivatives, i.e. anthracene, 9-bromoanthracene, 9-anthracenecarboxaldehyde and 9-anthracenemethanol. To overcome limitations of short reaction contact times at elevated temperatures a novel experimental setup was developed involving a cooling trap to achieve focusing and mixing of the reactants at a defined spot in a fused-silica capillary. This trap functions as a reactor within the separation column in the oven of a gas chromatograph. The reactants are sequentially injected to avoid undefined mixing in the injection port. An experimental protocol was developed with optimized injection intervals and cooling times to achieve sufficient conversions at short reaction times. Reaction products were rapidly identified by mass spectrometric detection. This new approach represents a practical procedure to investigate higher-order reactions at an analytical level and it simultaneously provides valuable information for the optimization of the reaction conditions.

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Decomposition of Benzenediazonium-2-Carboxylate

Cited by 124 publications

References 0 publications

Pyridyl‐Functionalized 1‐Phosphabarrelene: Synthesis, Coordination Chemistry and Photochemical di‐π‐Methane Rearrangement

Pyridyl‐Functionalized 1‐Phosphabarrelene: Synthesis, Coordination Chemistry and Photochemical di‐π‐Methane Rearrangement

Valorization of 2,5-furandicarboxylic acid. Diels–Alder reactions with benzyne

Integrating reaction and analysis: investigation of higher-order reactions by cryogenic trapping

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