307. The mobility of groups in 4-chloro-2-nitrodiphenylsulphones

Loudon, J. D.; Shulman, Nathan

doi:10.1039/jr9380001618

Cited by 6 publications

(5 citation statements)

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“…The diaryl ethers obtained were purified by column chromatography on silica gel by using n-hexane as eluent. Sulfides 5 to 8 were synthesized from appropriate sodium thiophenoxide and chloronitrobenzene as reported previously [27] and purified by recrystallisation from ethanol. Amines 10 to 12 were synthesized from appropriate chloronitrobenzene and toluidine, as previously reported [5,28].…”

Section: Synthesismentioning

confidence: 99%

Protonated nitro group as a gas-phase electrophile: Experimental and theoretical study of the cyclization of o-nitrodiphenyl ethers, amines, and sulfides

Moolayil

George

Srinivas

et al. 2007

J. Am. Soc. Mass Spectrom.

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A novel gas-phase electrophilic cyclization, initiated by the protonation of a nitro group, occurs for 2-nitrophenyl phenyl ether and for the analogous sulfide and amine, leading to heterocyclic intermediates in each case. Subsequently, the cyclic intermediates dissociate via two pathways: (1) unusual step-wise eliminations of two OH radicals to afford heterocyclic cations, [phenoxazine − H] + , [phenothiazine − H] + and [phenazine + H] + , and (2) expulsion of H 2 O, to yield a heterocyclic ketone, followed by loss of CO. The proposed structures of the gas-phase product ions and reaction mechanisms are supported by chemical substitution, deuterium labeling, accurate mass measurements at high mass resolving power, product-ion mass spectra obtained by tandem mass spectrometry, mass spectra of reference compounds, and molecular orbital calculations. Using a mass spectrometer as a reaction vessel, we demonstrate that, upon protonation, a nitro group becomes an electrophile and participates in cyclization reactions in the gas-phase.

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Section: Synthesismentioning

confidence: 99%

Protonated nitro group as a gas-phase electrophile: Experimental and theoretical study of the cyclization of o-nitrodiphenyl ethers, amines, and sulfides

Moolayil

George

Srinivas

et al. 2007

J. Am. Soc. Mass Spectrom.

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“…Thus ammonia, aqueous sulfide ion, methoxide, and thiophenoxide introduce amino, mercapto, methoxy, and thiophenoxy groups. Likewise, a sulfo group in the 2or 4-position of pyridine is readily replaced by amines (405); with the 4-sulfo group there may be a combination of hydrolysis and self-condensation in aqueous solution ( 162 A large number of replacements of arylsulfonyl groups by reagents such as the thiophenoxide ion, the methoxide ion, ammonia, piperidine, and sulfinate ions have been reported by Loudon and coworkers (371,387,388,389,392,393,394). Sulfonamide (S02NH2) groups undergo analogous replacements but somewhat less readily (393).…”

Section: N02mentioning

confidence: 99%

“…Likewise, a sulfo group in the 2or 4-position of pyridine is readily replaced by amines (405); with the 4-sulfo group there may be a combination of hydrolysis and self-condensation in aqueous solution ( 162 A large number of replacements of arylsulfonyl groups by reagents such as the thiophenoxide ion, the methoxide ion, ammonia, piperidine, and sulfinate ions have been reported by Loudon and coworkers (371,387,388,389,392,393,394). Sulfonamide (S02NH2) groups undergo analogous replacements but somewhat less readily (393). In the Smiles rearrangement (Section VIII) suitably activated o-hydroxyor o-aminodiphenyl sulfones rearrange to o-phenoxy-or o-anilinobenzenesulfinates.…”

Section: N02mentioning

confidence: 99%

“…Similar reasoning explains the displacement of nitro groups rather than bromine atoms in reactions of alkoxides with 1,3,5tribromo-2,4,6-trinitrobenzene (306,307). Loudon and coworkers (387,388,389,392,393,394) studied the reactions of a number of isomeric or nearly isomeric chloronitrophenyl aryl sulfones with four principal reagents: sodium p-thiocresoxide, sodium methoxide, ammonia, and piperidine. (The departure from a strictly isomeric relationship arose from the aryl group being phenyl in some cases and p-tolyl in others.)…”

Section: B the Relative Mobilities Of The Halogens And The Nitro Groupmentioning

confidence: 99%

See 1 more Smart Citation

Aromatic Nucleophilic Substitution Reactions.

Bunnett¹,

Zahler²

1951

Chem. Rev.

1,033

500

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“…Thiol esters can be converted by halogens or halogenating agents to sulfonyl halides or, under anhydrous conditions, to sulfenyl halides, similar to the reaction of sulfides described above (page 37). With chlorine in carbon tetrachloride, the sulfenyl chloride is formed quantitatively (154), while chlorination in concentrated sulfuric acid, followed by addition of aqueous acetic acid, gives the sulfonyl chloride (262). The action of chlorine on ethyl thiolacetate in water 02X 02X…”

Section: \C2h6ohmentioning

confidence: 99%