Ambident neighbouring groups. Part V. Mechanism of cyclization of 2-halogenoethylsulphonamides to aziridines

Coy, J. H.; Hegarty, A. F.; Flynn, Edward J.; Scott, F. L.

doi:10.1039/p29740000053

Cited by 5 publications

(2 citation statements)

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“…Specifically, the p K a values for ethylenediamine and o -phenylenediamine are 9.92 and 4.63, respectively, , indicating the former is capable of presenting a rate of nucleophilic reaction with phosgene higher than that of the latter. Additionally, for ring-closure reactions via an intramolecular nucleophilic substitution mechanism, it has been demonstrated that five-membered nitrogen heterocycles are formed substantially faster than three-, four-, or six-membered rings under identical conditions, which is likely a result of the balance of the entropy terms and the enthalpy ones. , Thus, the relatively high reactivity of ethylenediamine in the nucleophilic substitution reactions and cyclization rate of ring-closure reactions jointly contributes to the faster response rate of 8-EDAB for phosgene detection compared to that found in previously reported results. , …”

Section: Resultsmentioning

confidence: 69%

A BODIPY-Based Fluorescent Probe for Detection of Subnanomolar Phosgene with Rapid Response and High Selectivity

Zhang

Peng

Jie

et al. 2017

ACS Appl. Mater. Interfaces

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A new type of phosgene probe with a limit of detection down to 0.12 nM, response time of less than 1.5 s, and high selectivity over other similarly reactive toxic chemicals was developed using ethylenediamine as the recognition moiety and 8-substituted BODIPY unit as the fluorescence signaling component. The probe undergoes sequential phosgene-mediated nucleophilic substitution reaction and intramolecular cyclization reaction with high rate, yielding a product with the intramolecular charge transfer (ICT) process from amine to the BODIPY core significantly inhibited. Owing to the emission feature of 8-substituted BODIPY that is highly sensitive to the substituent's electronic nature, such inhibition on the ICT process strikingly generates strong fluorescence contrast by a factor of more than 23 300, and therefore creates the superhigh sensitivity of the probe for phosgene. Owing to the high reactivity of ethylenediamine of the probe in nucleophilic substitution reactions, the probe displays a very fast response rate to phosgene.

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Section: Resultsmentioning

confidence: 69%

A BODIPY-Based Fluorescent Probe for Detection of Subnanomolar Phosgene with Rapid Response and High Selectivity

Zhang

Peng

Jie

et al. 2017

ACS Appl. Mater. Interfaces

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“…300°C (dec.; ref. [24] m.p. N-(4-Nitrophenylsulfonyl)glycine (7): Glycine (1.5 g, 39.96 mmol) was suspended in 5 mL water and completely dissolved by the addition of 1  aqueous sodium hydroxide solution (10 mL).…”

Section: Nnј-bis(4-nitrophenylsulfonyl)piperazine (4)mentioning

confidence: 97%

Mimics of a R₂²(8) Hydrogen‐Bond Dimer Motif: Synthesis and Influence on the Crystallisation of Sulfathiazole and Sulfapyridine

2010

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The bis[4‐(hydroxyamino)phenylsulfonyl]piperazine 5, diketopiperazine 10 and benzene 14 were synthesised as mimics of an R22(8) motif, which occurs in one crystal polymorph of sulfathiazole and in several polymorphs of sulfapyridine. When present in crystallisations of sulfathiazole and sulfapyridine, these mimics were found to have little or no effect under crystallisation conditions that favour the formation of polymorphs not containing R22(8) motifs. However, the mimics were found to completely or partially inhibit the formation of form I sulfathiazole, which contains the R22(8) dimer, in crystallisations of sulfathiazole from 1‐propanol. In crystallisations of sulfapyridine, the mimics were found to promote the formation of form III, which does not contain the R22(8) motif. These compounds therefore appear to act as “tailor‐made” additives, displaying polymorph‐selective crystal nucleation inhibition based on interaction with hydrogen‐bond network motifs.

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ChemInform Abstract: AMBIDENT NEIGHBOURING GROUPS PART 5, MECHANISM OF CYCLIZATION OF 2‐HALOGENOETHYLSULPHONAMIDES TO AZIRIDINES

Coy¹,

Hegarty²,

Flynn³

et al. 1974

Chemischer Informationsdienst

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Ambident neighbouring groups. Part V. Mechanism of cyclization of 2-halogenoethylsulphonamides to aziridines

Cited by 5 publications

References 1 publication

A BODIPY-Based Fluorescent Probe for Detection of Subnanomolar Phosgene with Rapid Response and High Selectivity

A BODIPY-Based Fluorescent Probe for Detection of Subnanomolar Phosgene with Rapid Response and High Selectivity

Mimics of a R₂²(8) Hydrogen‐Bond Dimer Motif: Synthesis and Influence on the Crystallisation of Sulfathiazole and Sulfapyridine

ChemInform Abstract: AMBIDENT NEIGHBOURING GROUPS PART 5, MECHANISM OF CYCLIZATION OF 2‐HALOGENOETHYLSULPHONAMIDES TO AZIRIDINES

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Ambident neighbouring groups. Part V. Mechanism of cyclization of 2-halogenoethylsulphonamides to aziridines

Cited by 5 publications

References 1 publication

A BODIPY-Based Fluorescent Probe for Detection of Subnanomolar Phosgene with Rapid Response and High Selectivity

A BODIPY-Based Fluorescent Probe for Detection of Subnanomolar Phosgene with Rapid Response and High Selectivity

Mimics of a R22(8) Hydrogen‐Bond Dimer Motif: Synthesis and Influence on the Crystallisation of Sulfathiazole and Sulfapyridine

ChemInform Abstract: AMBIDENT NEIGHBOURING GROUPS PART 5, MECHANISM OF CYCLIZATION OF 2‐HALOGENOETHYLSULPHONAMIDES TO AZIRIDINES

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Mimics of a R₂²(8) Hydrogen‐Bond Dimer Motif: Synthesis and Influence on the Crystallisation of Sulfathiazole and Sulfapyridine