The Photochemical Decomposition of Aryldiazonium Salts I—Stability and Quantum Yields

Barraclough, R.; Jones, Frank; Patterson, David; Tetlow, A.

doi:10.1111/j.1478-4408.1972.tb03035.x

Cited by 6 publications

(1 citation statement)

References 6 publications

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“…It is known that such salts liberate N 2 under photochemical or transition-metal-catalyzed processes. 107,108 Under our hyperpolarized regime, addition of CuI saw its rapid conversion into N 2 and consequently a strong signal was seen at δ N 308.…”

Section: ■ Results and Discussionmentioning

confidence: 78%

Real-Time High-Sensitivity Reaction Monitoring of Important Nitrogen-Cycle Synthons by ¹⁵N Hyperpolarized Nuclear Magnetic Resonance

et al. 2022

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Here, we show how signal amplification by reversible exchange hyperpolarization of a range of 15N-containing synthons can be used to enable studies of their reactivity by 15N nuclear magnetic resonance (NO2 – (28% polarization), ND3 (3%), PhCH2NH2 (5%), NaN3 (3%), and NO3 – (0.1%)). A range of iridium-based spin-polarization transfer catalysts are used, which for NO2 – work optimally as an amino-derived carbene-containing complex with a DMAP-d 2 coligand. We harness long 15N spin-order lifetimes to probe in situ reactivity out to 3 × T 1. In the case of NO2 – (T 1 17.7 s at 9.4 T), we monitor PhNH2 diazotization in acidic solution. The resulting diazonium salt (15N-T 1 38 s) forms within 30 s, and its subsequent reaction with NaN3 leads to the detection of hyperpolarized PhN3 (T 1 192 s) in a second step via the formation of an identified cyclic pentazole intermediate. The role of PhN3 and NaN3 in copper-free click chemistry is exemplified for hyperpolarized triazole (T 1 < 10 s) formation when they react with a strained alkyne. We also demonstrate simple routes to hyperpolarized N2 in addition to showing how utilization of 15N-polarized PhCH2NH2 enables the probing of amidation, sulfonamidation, and imine formation. Hyperpolarized ND3 is used to probe imine and ND4 + (T 1 33.6 s) formation. Furthermore, for NO2 –, we also demonstrate how the 15N-magnetic resonance imaging monitoring of biphasic catalysis confirms the successful preparation of an aqueous bolus of hyperpolarized 15NO2 – in seconds with 8% polarization. Hence, we create a versatile tool to probe organic transformations that has significant relevance for the synthesis of future hyperpolarized pharmaceuticals.

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Section: ■ Results and Discussionmentioning

confidence: 78%

Real-Time High-Sensitivity Reaction Monitoring of Important Nitrogen-Cycle Synthons by ¹⁵N Hyperpolarized Nuclear Magnetic Resonance

et al. 2022

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Zur Interpretation des UV/Vis‐Spektralverhaltens substituierter Benzendiazoniumionen

1981

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Interpretation of the UV/vis Spectral Behaviour of Substituted Benzenediazonium Ions In order to synthesize new, potent, wide‐range photosensitive diazonium compounds, an explanation of the various influences on the position of the longest wavelength absorption band (λmax) of the diazonium ions should be given. For this purpose, SCF‐LCI calculations according to the Pariser, Parr, Pople method were made. The absorption behaviour of the diazonium ions can be explained on the basis of simple perturbation‐theoretical MO considerations. According to the regularities mentioned, it is possible to consider 4‐aminosubstituted benzenediazonium ions as meropolymethines. With the perturbation theory it is also possible to define the limit of λmax attainable with benzenediazonium compounds.

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Zum photoinduzierten Zerfall von Phenylazonaphtholen in Polymermatrizen

Haeßner

Epperlein

Marx

1980

Zeitschrift fuer Chemie

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The Photochemical Decomposition of Aryldiazonium Salts I—Stability and Quantum Yields

Cited by 6 publications

References 6 publications

Real-Time High-Sensitivity Reaction Monitoring of Important Nitrogen-Cycle Synthons by ¹⁵N Hyperpolarized Nuclear Magnetic Resonance

Real-Time High-Sensitivity Reaction Monitoring of Important Nitrogen-Cycle Synthons by ¹⁵N Hyperpolarized Nuclear Magnetic Resonance

Zur Interpretation des UV/Vis‐Spektralverhaltens substituierter Benzendiazoniumionen

Zum photoinduzierten Zerfall von Phenylazonaphtholen in Polymermatrizen

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The Photochemical Decomposition of Aryldiazonium Salts I—Stability and Quantum Yields

Cited by 6 publications

References 6 publications

Real-Time High-Sensitivity Reaction Monitoring of Important Nitrogen-Cycle Synthons by 15N Hyperpolarized Nuclear Magnetic Resonance

Real-Time High-Sensitivity Reaction Monitoring of Important Nitrogen-Cycle Synthons by 15N Hyperpolarized Nuclear Magnetic Resonance

Zur Interpretation des UV/Vis‐Spektralverhaltens substituierter Benzendiazoniumionen

Zum photoinduzierten Zerfall von Phenylazonaphtholen in Polymermatrizen

Contact Info

Product

Resources

About

Real-Time High-Sensitivity Reaction Monitoring of Important Nitrogen-Cycle Synthons by ¹⁵N Hyperpolarized Nuclear Magnetic Resonance

Real-Time High-Sensitivity Reaction Monitoring of Important Nitrogen-Cycle Synthons by ¹⁵N Hyperpolarized Nuclear Magnetic Resonance