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Effect of Ortho Substituents on Carbonyl Carbon 13C NMR Chemical Shifts Effect of ortho substituents on carbonyl carbon 13C NMR chemical shifts in substituted phenyl benzoates Ilmar A Koppel, Mare Piirsalu, Vilve Nummert, Vahur Mäemets, Signe Vahur To cite this version: Ilmar A Koppel, Mare Piirsalu, Vilve Nummert, Vahur Mäemets, Signe Vahur. Effect of ortho sub- stituents on carbonyl carbon 13C NMR chemical shifts in substituted phenyl benzoates. Journal of Physical Organic Chemistry, Wiley, 2009, 22 (12), pp.1155. 10.1002/poc.1569. hal-00495777 HAL Id: hal-00495777 https://hal.archives-ouvertes.fr/hal-00495777 Submitted on 29 Jun 2010 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Journal of Physical Organic Chemistry Effect of ortho substituents on carbonyl carbon 13 C NMR chemical shifts in substituted phenyl benzoates For Peer Review Journal: Journal of Physical Organic Chemistry Manuscript ID: POC-08-0302.R1 Wiley - Manuscript type: Research Article Date Submitted by the 03-Apr-2009 Author: Complete List of Authors: Koppel, Ilmar Piirsalu, Mare; University of Tartu, Institute of Chemistry Nummert, Vilve; University of Tartu, Institute of Chemistry Mäemets, Vahur; University of Tartu, Institute of Chemistry Vahur, Signe; University of Tartu, Institute of Chemistry NMR spectra of benzoates, carbonyl carbon NMR chemical shifts, Keywords: phenyl benzoates, substituent effects, ortho effect http://mc.manuscriptcentral.com/poc Page 1 of 22 Journal of Physical Organic Chemistry 1 2 3 4 13 5 Effect of ortho substituents on carbonyl carbon C NMR 6 7 chemical shifts in substituted phenyl benzoates 8 1 2 3 4 5 9 Vilve Nummert , Mare Piirsalu , Vahur Mäemets , Signe Vahur and Ilmar A. Koppel 10 Institute of Chemistry, University of Tartu, Jacobi 2, 51014 Tartu, Estonia 11 e-mail : [email protected] , [email protected] , 3vahur. [email protected] , 12 [email protected] , [email protected] 13 14 13 15 C NMR spectra of 37 ortho -, meta - and para -substituted phenyl benzoates, containing 16 substituents in benzoyl and phenyl moiety, 4 ortho -substituted methyl and 5 ethyl 17 benzoates, as well as 9 R-substituted alkyl benzoates have been recorded. The influence 18 of the ortho substituents on the carbonyl carbon 13 C NMR chemical shift, δ , was 19 CO 20 found to be describedFor by a linear Peer multiple regressionReview equation containing the inductive, B 21 σI, resonance, σ°R, and steric, Es , or υ substituent constants. For all the ortho - 22 substituted esters containing substituents in acyl part as well as phenyl part the 23 substituent–induced reverse inductive effect ( ρI < 0), the normal resonance effect ( ρR > 24 B 25 0), and the negative steric effect (δortho < 0) with the Es were observed. In the case of 26 ortho substituents in phenyl part the resonance effect was negligible. Due to inductive 27 effect the ortho electron-withdrawing substituents showed upfield shift or shielding of 28 the carbonyl carbon, while the electron-donating substituents had an opposite effect. 29 Because of the sterical consequences ortho substituents revealed deshielding effect on 30 the 13 C NMR chemical shift of the carbonyl carbon. For all the meta- and para- 31 32 substituted esters the reverse substituent-induced inductive and resonance effects ( ρI < 33 0, ρR < 0) were found to be significant. In alkyl benzoates the alkyl substituents showed 34 the reverse inductive and steric effects. The log k values for the alkaline hydrolysis in 35 water, aqueous 0.5 M Bu NBr and 2.25 M Bu NBr and the IR frequencies, ν , for 36 4 4 CO ortho -, meta - and para -substituted phenyl benzoates and alkyl benzoates were 37 13 38 correlated nicely with the corresponding C NMR substituent chemical shifts, ∆δCO . 39 40 Keywords : NMR spectra of benzoates; carbonyl carbon NMR chemical shifts; phenyl 41 benzoates; substituent effects; ortho effect. 42 43 44 INTRODUCTION 45 46 Earlier the influence of substituent effects, especially ortho effect, on the rates of the 47 alkaline hydrolysis (see Refs [1-6] and references cited therein) and on the infrared 48 [7,8 ] 49 stretching frequencies of carbonyl group, νCO , for esters of benzoic acid containing 50 substituents in the benzoyl and phenyl (alkyl) moiety was studied. 51 It was interesting to study the influence of substituent effects, mainly ortho effect, 52 13 on the carbonyl carbon C NMR chemical shifts, δCO , in substituted phenyl benzoates 53 and to compare with those in the rates of the alkaline hydrolysis as well as in the 54 55 infrared stretching frequencies of carbonyl group, νCO , in the case of the corresponding 56 substituted phenyl benzoates. 57 The main purpose of the present work was to check how in the case of ortho 58 13 substituents the carbonyl carbon C NMR chemical shifts, δCO , of substituted phenyl 59 benzoates containing substituents in benzoyl and phenyl moiety (X-C H CO C H , 60 6 4 2 6 5 C6H5CO 2C6H4-X) are influenced by the inductive, resonance and the steric effects. To 1 http://mc.manuscriptcentral.com/poc Journal of Physical Organic Chemistry Page 2 of 22 1 2 3 4 compare the influence of meta and para substituents as well as alkyl substituents on the 5 13 6 C NMR chemical shift of the carbonyl carbon in substituted phenyl and alkyl 7 benzoates were analyzed as well. 8 To our knowledge, the influence of ortho substituents on the 13 C NMR chemical 9 shift of the carbonyl carbon in substituted phenyl benzoates using correlation equations, 10 has not been studied in the literature. More thoroughly the influence of the substituent 11 13 12 effects on the carbonyl carbon C NMR chemical shifts in substituted phenyl, methyl 13 and ethyl benzoates and phenyl acetates was investigated for meta and para 14 derivatives. [9-22 ] In the case of meta - and para -substituted esters mainly the substituent- 15 induced reverse inductive and resonance effects were observed ( ρI < 0, ρR < 16 [9,11,16,18,19,37 ] 17 0). The electron-withdrawing substituents showed shielding leading to a 18 smaller positive charge on the carbonyl carbon. The electron-donating substituents had 19 an opposite effect. In carbonyl compounds the influence of the substituent-induced 20 13 resonance effect onFor the carboxyl Peer carbon CReview NMR chemical shift ( ρR < 0, ρR > 0) was 21 found to be dependent on the polarization of the π-electron system in the carbonyl C=O 22 [9,11,19 ] 23 bond. 13 24 The influence of the ortho effect on the C NMR chemical shift of the side-chain 25 functional group was studied for substituted methyl benzoates, [17,20,21 ] ethyl 26 benzoates, [26 ] benzoic acids, [21,23-25 ] thiocyanatobenzenes, [27 ] arylacetamides, [28-30 ] 27 [31 ] [32-36 ] [27 ] 28 acetonitriles, acetophenones and benzaldehydes, . Guy obtained the excellent 13 29 correlations for the C NMR chemical shift in ortho -substituted thiocyanatobenzenes 30 with the inductive, resonance and the steric substituent parameters. The influence of 31 substituents in alkyl chain on the carbonyl carbon 13 C NMR chemical shift was studied 32 [37-39 ] 33 mainly the in case of esters containing substituents in the acyl part. 34 Earlier (see Refs [1-6]) we found the log k values for the alkaline hydrolysis of 35 phenyl esters of ortho -substituted benzoic acids, X-C6H4CO 2C6H5, and substituted 36 phenyl esters of benzoic acid, C 6H5CO 2C6H4-X, to be correlated with the Charton 37 equation using the Taft inductive ( σI) and resonance ( σ°R) constants and the steric scale 38 B 39 for ortho substituents, Es . In the alkaline hydrolysis of substituted benzoates in pure 40 water, the ortho inductive effect and the meta and para polar effect in acyl part were 41 1.5-fold and steric influence 2.7-fold higher than the corresponding influences in the 42 aryl part of phenyl benzoates. In the alkaline hydrolysis of phenyl esters of ortho - 43 substituted benzoic acids, X-C6H4CO 2C6H5, in water the resonance term was negligible 44 45 (( ρ°R)ortho ca 0.3). In the case of phenyl esters of ortho -substituted benzoic acids, X- 46 C6H4CO 2C6H5, the infrared stretching frequencies of the carbonyl group, νCO , for the cis 47 and trans conformers of ortho derivatives appeared to be correlated with dual parameter B + 48 equations: ( νCO )cis = ( νCO )o + 16.4 σI − 22.6 Es and ( νCO )trans = ( νCO )o + 12.6 σp − 49 11.9 E B.[7] Recently we found [8] a good correlations between the log k values of the 50 s 51 alkaline hydrolysis of ortho-substituted phenyl benzoates and the infrared stretching 52 frequencies of carbonyl group, νCO , when the additional resonance and steric scales 53 were included. 54 To study the influence of substituent effects on the carbonyl carbon 13 C NMR 55 56 chemical shifts the values of the chemical shifts, δCO , for ortho -, meta - and para - 57 substituted phenyl benzoates, (X-C6H4CO 2C6H5,), methyl and ethyl benzoates (X- 58 C6H4CO 2CH 3, X-C6H4CO 2C2H5), phenyl acetates (CH 3CO 2C6H4-X) and alkyl 59 benzoates (C 6H5CO 2R) were submitted to correlation analysis involving the scales for 60 the corresponding inductive, resonance, and steric factors. 2 http://mc.manuscriptcentral.com/poc Page 3 of 22 Journal of Physical Organic Chemistry 1 2 3 4 The second purpose of the present work was to compare the substituent effects on 5 13 6 the carbonyl carbon C NMR chemical shift, δCO , in substituted phenyl benzoates with 7 those in the rates of the alkaline hydrolysis and the infrared stretching frequencies of 8 carbonyl group, νCO .
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