Ortho substituent effects on transfer of aryl groups from oxygen to carbon in adducts from diaryloxycarbenes and DMAD

2002 ◽  
Vol 80 (3) ◽  
pp. 228-234 ◽  
Author(s):  
Xiaosong Lu ◽  
John Warkentin
Keyword(s):  
Cyano Group ◽  
Substituent Effects ◽  
Aromatic Substitution ◽  
Aryl Group ◽  
Electron Pairs ◽  
Work Support ◽  
Ipso Substitution ◽  
Positive Site ◽  
Methoxy Substituent ◽  
Ortho Substituent

Diaryloxycarbenes, generated by thermolysis of 2,2-diaryloxy-5,5-dimethyl-Δ3-1,3,4-oxadiazolines in benzene, reacted with dimethyl acetylenedicarboxylate (DMAD) to afford triesters. The triesters arose by aryl-group transfer from oxygen to carbon (ipso substitution). A cyano group in the para position had been shown earlier to favour the ipso substitution whereas a para-methoxy group disfavoured it. Surprisingly, the ortho-methoxy substituent also favoured ipso substitution. As a tentative rationale, we had proposed that a vinylogous diaryloxycarbene intermediate, with dipolar properties, is formed when a diaryloxycarbene attacks at the sp-carbon of DMAD and that an ortho substituent, with one or more unshared electron pairs, can stabilize the intermediate by donating electron density to the positive site. In the present work, support for that interpretation and for the importance of a steric effect, was provided by examining the competition between (i) p-tolyl and phenyl; (ii) o-tolyl and phenyl; (iii) o-iodophenyl and phenyl; (iv) o-iodophenyl and p-chlorophenyl; and (v) o-bromophenyl and p-chlorophenyl as potential migrating groups.Key words: aromatic substitution, carbene, ipso, diaryloxycarbene, oxadiazoline.

Kinetic study of hydrolysis of benzoates. part xxvii. ortho substituent effect in alkaline hydrolysis of phenyl esters of substituted benzoic acids in aqueous Bu4NBr

2009 ◽  
Vol 74 (1) ◽  
pp. 29-42 ◽  
Author(s):  
Vilve Nummert ◽  
Mare Piirsalu ◽  
Signe Vahur ◽  
Oksana Travnikova ◽  
Ilmar A. Koppel
Keyword(s):  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Pure Water ◽  
Substituent Effects ◽  
Benzoic Acids ◽  
Resonance Effects ◽  
The Media ◽  
Substituted Benzoic Acids ◽  
Hydrolysis Of ◽  
Ortho Substituent

The second-order rate constants k (in dm3 mol–1 s–1) for alkaline hydrolysis of phenyl esters of meta-, para- and ortho-substituted benzoic acids, X-C6H4CO2C6H5, have been measured spectrophotometrically in aqueous 0.5 and 2.25 M Bu4NBr at 25 °C. The substituent effects for para and meta derivatives were described using the Hammett relationship. For the ortho derivatives the Charton equation was used. For ortho-substituted esters two steric scales were involved: the EsB and the Charton steric (υ) constants. When going from pure water to aqueous 0.5 and 2.25 M Bu4NBr, the meta and para polar effects, the ortho inductive and resonance effects in alkaline hydrolysis of phenyl esters of substituted benzoic acids, became stronger nearly to the same extent as found for alkaline hydrolysis of C6H5CO2C6H4-X. The steric term of ortho-substituted esters was almost independent of the media considered. The rate constants of alkaline hydrolysis of ortho-, meta- and para-substituted phenyl benzoates (X-C6H4CO2C6H5, C6H5CO2C6H4-X) and alkyl benzoates, C6H5CO2R, in water, 0.5 and 2.25 M Bu4NBr were correlated with the corresponding IR stretching frequencies of carbonyl group, (ΔνCO)X.

Ortho-Substituent Effects on Diphenylurea Packing Motifs

2017 ◽  
Vol 17 (10) ◽  
pp. 5065-5072 ◽  
Author(s):  
Marina A. Solomos ◽  
Taylor A. Watts ◽  
Jennifer A. Swift
Keyword(s):  
Substituent Effects ◽  
Ortho Substituent

13C NMR spectroscopy of heterocycles: 3,5-diaryl-4-bromoisoxazoles

2015 ◽  
Vol 21 (5) ◽  
pp. 279-283 ◽  
Author(s):  
Jiayo Yu ◽  
Beatrice Edjah ◽  
Hector Argueta-Gonzalez ◽  
Stephanie Ross ◽  
Patrick Gaulden ◽  
...  
Keyword(s):  
Chemical Shift ◽  
Substituent Effects ◽  
13C Nmr Spectroscopy ◽  
Ring System ◽  
Aryl Group ◽  
Torsion Angles ◽  
Chemical Shift Data ◽  
Molecular Modeling Studies ◽  
Torsional Angles ◽  
Moderate Yield

AbstractA series of 3,5-diarylisoxazoles (1–9) underwent reaction with N-bromosuccinimide in acetic acid to yield the corresponding 3.5-diaryl-4-bromoisoxazoles (1Br–9Br) in low to moderate yield. The X-ray structure of 3-(4-chlorophenyl)-5-phenyl-4-bromoisoxazole showed torsion angles of ~40° and ~36° between the 3- and 5-aryl groups and the central ring system, respectively. Molecular modeling studies predicted the 3,5-phenylisoxazole ring system to be essentially coplanar and the 3,5-diphenyl groups of the 4-bromoisoxazole derivative to be twisted with torsional angles of 50° and 37°, respectively. Carbon-13 nuclear magnetic resonance (13C NMR) data of the 3,5-diaryl-4-bromoisoxazoles were obtained in dimethyl sulfoxide-d6 (DMSO-d6) at 50°C. Plots of the C4 chemical shift data for isoxazoles (1–9) vs. those for 4-bromoisoxazoles (1Br–9Br) showed a good linear correlation (r2 = 0.974) with a slope of 0.96. Substitution on the 3-aryl group had essentially no effect on the chemical shift for C4 of the 4-bromoisoxazole, whereas that on the 5-aryl group showed an excellent correlation with σ+ values. Despite the predicted torsion angle differences, distal transmission of substituent effects in the 4-bromo ring system was essentially analogous to that in the planar 3,5-diarylisoxazoles.

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