ISSN:
0894-3230
Keywords:
Organic Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The ambident reactivity of phenoxide ion towards 1,3,5-trinitrobenzene (TNB) was re-examined by means of a novel reaction system(CD3CN-glyme-d10) which allows the investigation of species formed at low temperatures (-40°C), contrasting with previous studies in dimethyl sulfoxide (DMSO) at ambient temperature. The new method coupled with 400 MHz NMR spectroscopy has allowed the definitive observation of both O- and C-bonded phenoxide σ-complex adducts for the first time, confirming the formation of the former through kinetic control and of the latter through thermodynamic control. The corresponding O-bonded σ-adduct in the TNB-mesitoxide system (whereC-bonded σ-adduct formation is not possible but where there is competing nitro group displacement) has also been characterized by 1H and 13C NBR. Another O-bonded aryloxide adduct characterized is that from the reaction of TNB with3,5-di-tert-butylphenoxide; in this system there is also competing NO2 displacement. Stereoelectronic factors in the O-bonded σ-adducts and aryl ethers are discussed.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/poc.610060202
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