Radical-nucleophilic substitution (SRN1) reactions. Part 7. Reactions of aliphatic α-substituted nitro compounds.

Al-Khalil, Suleiman; Bowman, W. Russell; Gaitonde, Katherine; Marley, Madeleine A.; Richardson, Geoffrey

doi:10.1039/b103350f

Cited by 11 publications

(8 citation statements)

References 28 publications

(40 reference statements)

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“…4,7,8 For instance, the reaction between phenylthiolate anions and α-halogenonitroalkanes gives substitution to α-(phenylsulfanyl)nitroalkanes in dipolar aprotic solvent by an S RN 1 mechanism but switches to yielding disulfides in protic solvents by nucleophilic attack on the halide. 4,8 In a further example of apparent S RN 1 substitution, reactions between 2,6-diiodophenols and their phenolates anions to yield dityrosines, proceed by a non-SET nucleophilic substitution. 7 The diagnostic tests for the S RN 1 chain reaction are well worked out and should always be used to assign the S RN 1 mechanism.…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3] We have shown that benzothiazoles can be synthesized by intramolecular S RN 1 substitution but we were only able to initiate the single electron transfer chain (SET) reaction using the process on entrainment with enolate anions of acetone and diethyl phosphite. 2 Substitution of side chain anions onto o-halogenoarenes is a good synthetic procedure and we sought to extend our S RN 1 studies 2,4 to the synthesis of 1H-quinazolin-4-ones.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of 1H-quinazoline-4-ones using intramolecular aromatic nucleophilic substitution

Bowman¹,

Heaney²,

Smith³

2003

Arkivoc

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The anions of 1-(2-bromobenzoyl)-3-phenylthiourea 1, 1-(2-chlorobenzoyl)-3-phenylthiourea 2 and 1-(2-bromobenzoyl)-3-phenylurea 8 undergo intramolecular nucleophilic substitution (putative S N Ar mechanism), and not intramolecular S RN 1 substitution, to yield 1-phenyl-2-thioxo-2,3-dihydro-1H-quinazolin-4-one 6 and 1-phenyl-1H-quinazoline-2,4-dione 9 respectively. Under the same reaction conditions with the addition of copper(I) iodide, phenylthioureas 1 and 2 gave a rearrangement to the respective 2-halogeno-N-phenylbenzamides.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis of 1H-quinazoline-4-ones using intramolecular aromatic nucleophilic substitution

Bowman¹,

Heaney²,

Smith³

2003

Arkivoc

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“…[13] Oxidation under DDQ constructed the quinoline skeleton and 6 (6CNÀ 7N 3 Q) was successfully obtained after the transformation of nitro to azido group via an S RN 1 reaction. [14,15] Compound 11 (3CNÀ 7N 3 Q) was synthesized via a slightly different pathway. To obtain the precursor 3-bromo substituted quinoline, a reaction sequence was adjusted in which the bromination was carried out after quinoline formation.…”

Section: Synthesismentioning

confidence: 99%

Cyano Derivatives of 7‐Aminoquinoline That Are Highly Emissive in Water: Potential for Sensing Applications

Chang

Chao

Yang

et al. 2021

Chemistry A European J

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6‐Cyano‐7‐aminoquinoline (6CN−7AQ) and 3‐cyano‐7‐aminoquinoline (3CN−7AQ) were synthesized and found to exhibit intense emission with quantum yield as high as 63 % and 85 %, respectively, in water. Conversely, their derivatives 6‐cyano‐7‐azidoquinoline (6CN−7N3Q) and 3‐cyano‐7‐azidoquinoline (3CN−7N3Q) show virtually no emission, which makes them suitable to be used as recognition agents in azide reactions based on fluorescence recovery. Moreover, conjugation of 6CN−7AQ with a hydrophobic biomembrane‐penetration peptide PFVYLI renders a nearly non‐emissive 6CN−7AQ‐PFVYLI composite, which can be digested by proteinase K, recovering the highly emissive 6CN−7AQ with ∼200‐fold enhancement. The result provides an effective early confirmation for RT‐qPCR in viral detection.

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“…A similar behavior has been previously observed with 2-bromo-2-nitropropane. 13 Thiocyanate anion failed to react with this activated bromide by an S RN 1mechanism, even under entrainment conditions with Me 2 CNO 2 -. This anion adds easily to the 2-nitro-2-propyl radical (under oxidative conditions with Fe III), but the radical anion dissociates rapidly, as showed by ESR spectroscopic studies, suggesting that dissociation is faster than ET to the substrate, inhibiting the propagation cycle of the S RN 1 reaction.…”

Section: Introductionmentioning

confidence: 99%

“…This anion adds easily to the 2-nitro-2-propyl radical (under oxidative conditions with Fe III), but the radical anion dissociates rapidly, as showed by ESR spectroscopic studies, suggesting that dissociation is faster than ET to the substrate, inhibiting the propagation cycle of the S RN 1 reaction. 13 The thiourea anion (3) affords, after a photoinduced reaction with bromide 5 and quenching with MeI, 1-(methylthio)naphthalene (37%), bis(1-naphthyl) sulfide (32%) and naphthalene (13%). When the reaction was performed with a ratio nucleophile/substrate of 10, the substitution products increased, and after only fifteen minutes the conversion was 91%.…”

Section: Introductionmentioning

confidence: 99%

Reactivity of sulfur centered nucleophiles in photoinduced reactions with 1-bromonaphthalene

Argüello¹,

Schmidt²,

Peñéñory³

2003

Arkivoc

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The reactivity of S 2-(1), -SCN (2) and -SCNH(NH 2 ) (3) in photoinduced substitution reactions with 1-bromonaphthalene (5) in DMSO was studied. The photostimulated reaction of ion 1 with 5 renders after quenching with MeI 1-(methylthio)naphthalene (16%), bis (1-naphthyl) sulfide (17.5%) and naphthalene (42%). The lack of reaction in the dark and the inhibition of the photoinduced one by the presence of di-tert-butylnitroxide (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain mechanism for these substitution reactions. On the other hand, ion 2 was unreactive towards 5, both as an electron donor under photostimulation and as a nucleophile. Finally the thiourea anion (3) affords after a photoinduced reaction with 5 and quenching with MeI, 1-methylthionaphthalene (50%), bis (1-naphthyl) sulfide (22%) and naphthalene (9%). This reaction does not occur in the dark and is inhibited in the presence of DTBN. By using hydrogen abstraction from DMSO as competitive reaction, the absolute rate constants for the addition of ions 1, 3 and benzene thiolate ions (4) to 1-naphthyl radicals have been determined to be 0.5 x 10 9 M -1 s -1 , 1.0 x 10 9 M -1 s -1 and 5.1 x 10 9 M -1 s -1 respectively.

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Radical-nucleophilic substitution (SRN1) reactions. Part 7. Reactions of aliphatic α-substituted nitro compounds.

Cited by 11 publications

References 28 publications

Synthesis of 1H-quinazoline-4-ones using intramolecular aromatic nucleophilic substitution

Synthesis of 1H-quinazoline-4-ones using intramolecular aromatic nucleophilic substitution

Cyano Derivatives of 7‐Aminoquinoline That Are Highly Emissive in Water: Potential for Sensing Applications

Reactivity of sulfur centered nucleophiles in photoinduced reactions with 1-bromonaphthalene

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