13C substituent effects in monosubstituted benzenes

A brief analysis is presnted of the current understanding of substituent perturbations in monosubstituted benzenes as determined by substituent induced carbon chemical shifts. A critical tabulation of the four substituent chemical shifts is given for c. 700 monosubstituted benzenes.     

Methyl substituent effects in the 13C spectra of cyclohexanone O-methyl oximes and N,N-dimethylhydrazones

The ¹³C NMR spectra of a series of 4-t-butylcyclohexane-O-methyl oximes and N,N-dimethylhydrazones containing α-methyl substituents have been measured. The effects of α-methyl substitution (syn-axial, anti-axial and anti-equatorial) on the carbons α, β and γ to the substitution site are similar to those previously found in cyclohexanones. Use has been made of these substituent parameters to determine the conformational equilibria of the mobile 2-methylcyclohexanone derivatives.     

Chlorine substituent effects for indole and tryptophan in 13C NMR

The ¹³C and ¹H nmr spectra of chloroindoles and chlorotryptophans in methanol-d₄ were assigned based on 1-D and 2-D nmr techniques, including COSY, inverse-detected direct (HMQC) and long-range (HMBC) correlation. Chlorine substitutent effects in chemical shifts (SCS) for chlorotryptophans and chloroindoles were calculated and compared. The correlations were linear except for 4-chlorotryptophan, which suggests structural changes on the indole ring between 4-chlorotryptophan and 4 chloroindole. The conformational analysis based on the coupling constants of the side chain also showed a change in the fractional population of the rotamers between 4-chlorotryptophan and the other chlorotryptophans.     

13C nmr assignments of selected octahydroindolizines

Several octahydroindolizines including the four geometrical isomers of 3-butyl-5-methyloctahydroindolizine, which is an attractant of Pharaoh's and [Monomorium pharaonis(L.)], have been examined by ¹H and ¹³C nmr spectroscopy. The conformations of these compounds are discussed.     

Methyl substituent effects in radical cation Diels-Alder reactions

The effect of methyl substitution on the Diels-Alder radical cation reaction was studied using B3LYP with a 6-31G* basis set. Five separate pathways, one concerted and four stepwise, were examined for each possible position of a methyl substituent. None of the concerted transition structures could be located without symmetry constraints, and all but one of the structures obtained under these conditions were destabilized by a second-order Jahn-Teller distortion. A concerted pathway with simultaneous bond formation at C1 and C4 is therefore excluded. Stepwise pathways that had the methyl group either on a carbon involved in the initial bond formation or in a position where it could not stabilize the radical/cation were a few kcal/mol above alternate pathways. High transition state energies for the formation of vinylcyclobutane derivatives cause it to be a minor product in general. The pathway that proceeds through an anti-intermediate is the most favored, while the pathways forming the gauche-out intermediate that converts to the anti-intermediate is also strongly represented. Both of the major pathways lead directly to the formation of the methylcyclohexene product.     

13C?13C coupling constants and substituent effects on 13C chemical shifts in 13C labelled pyrene and pyrene derivatives

Long range inter-ring ¹³C? ¹³C couplings are found to be effective in the title compounds, and the magnitudes of coupling constants and of substituent effects on ¹³C chemical shifts, as well as the signs of the latter, alternate with respect to the number of connecting bonds.     

1H and 13C nmr studies of salicylalanilines

Several substituted salicylanilines (I) are studied by ¹H (chemical shifts) and ¹³C (chemical shifts and T₁ relaxation times) NMR in order to obtain information on molecular geometry changes and the transmission of the electronic effects due to substituents, as well as on the relative rates of the overall molecular tumbling and of the flipping of the phenyl rings. In particular, a good linear correlation of the OH proton shifts (affected by intramolecular hydrogen bonding) with Hammett's σ constants for p-substitution in the aniline moiety is found. Changes in rigidity of the rings expected as a result of the OH...N interaction and of p-substitution are reflected on the phenyl carbon relaxation times.     

Spatial substituent effects of various fluorinated groups on the 13C chemical shifts in cyclohexanes

The effect of introduction of fluorinated groups (CH(2)F, CHF(2), CF(3), C(2)F(5), OCF(3), SCF(3)) on the (13)C NMR chemical shifts in cyclohexanes is examined. The two main effects are caused by location at the alpha and gamma carbon positions. Comparison of the various data allowed the calculation of increments corresponding to the introduction of fluorinated groups at axial or equatorial positions on the cyclohexane ring. The introduction of fluorine atoms in methoxy and thiomethoxy groups has only a slight effect through the heteroatom on the (13)C chemical shifts.     

Remote polar substituent effects on 13C NMR spectra of olefinic and aromatic carbons

Chemical shifts of the olefinic carbons of ω-substituted 1-pentenes and 1-butenes and the aromatic carbons of phenylethanes and phenylpropanes have been measured. Correlations with various substitutent constants, electronegativities, NMR data from related chemical systems and calculated electrical fields were evaluated. Although the pattern of results is quite consistent with expectations for a field-induced shift of π-electron density, simple correlations of high statistical precision are not found. The general problem of correlating substitutent effects with reactivity and NMR shifts is discussed.     

A study of substituent effect on 1H and 13C nmr spectra of N‐ and C‐substituted carbazoles

¹H and ¹³C nmr spectra of several N‐ and C‐substituted carbazoles (Series 1, 2, 3 and 4) were measured. Correlations between chemical shifts and substituent constants show that these parameters describe properly the substituent effect on the nmr phenomena. Atomic charge densities for carbazoles of Series 1, 2, 3 and 4 were calculated by using the semi empirical PM3 method. These values also show a linear correlation with the ¹³C chemical shifts. The synthesis of several carbazole derivatives 1a – 1g, 2a – 2g, 3a – 3j and 4a – 4g have been carried out according to literature procedures. The carbazoles 3i, 3j and 4c have been synthesized and fully characterized for the first time.     

Carbon-13 NMR substituent effects in para-substituted benzophenones

The carbon-13 NMR spectra for a series of benzophenones was obtained and analyzed, using the dual substituent parameter (DSP) equation. The DSP analysis indicates that transmission of the substituent effect to the substituted ring is primarily resonance controlled while the transmission to the second phenyl ring involves a π-bond polarization mechanism. The DSP analysis of the C'₄ chemical shifts (para carbon in ring B) was found to compare very favorably with the fluorine “tag” data for analogous systems. Data for some para-para' benzophenones is also given.     

Diamagnetic contribution and substituent effects on 13C n.m.r. spectra

Correction of measured chemical shifts by subtracting the diamagnetic contributions caused by certain substituents on various carbons of a molecule leads to data that allow a reasonable interpretation of substituent effects on chemical shifts in ¹³C n.m.r. spectroscopy. It is shown that both paramagnetic and diamagnetic terms increase on all carbons of a molecule when the atomic number of a substituent increases down the same group of the periodic table. An explanation of α-, β-, and γ- effects for methyl substitution using the same procedure is attempted.     

Long range substituent effects relfected in the 13C NMR spectra of allyl alcohols and their derivatives

Acylation of allyl alcohols induces strong carbon shifts, shielding γ and deshielding δ effects. These shifts are a consequence of through-bond polarization of the olefinic carbons. Allyl ethers show similar, but milder perturbations. The olefinic carbon shifts reveal a strong concentration dependence. This effect, in greatly reduced form, is also observed in non-oxygenated alkenes. Hydrogen bonding by alcohols enhances the chemical shift difference in olefinic carbon pairs by increased polarization.     

Interpretation of substituent effects on 13C and 15N NMR chemical shifts in 6-substituted purines

A range of purine derivatives modified at position 6 of the basic purine skeleton exhibit a variety of biological activities. Several derivatives are used or tested nowadays for pharmacological treatments. The present work aims to analyze the effects of substituents on the electron distribution in the purine core as reflected by NMR chemical shifts. We collected a comprehensive set of experimental NMR data for a variety of 6-substituted purines (-NH(2), -NHMe, -NMe(2), -OMe, -Me, -CCH, and -CN) and determined the molecular and crystal structures of three derivatives (-NHMe, -CCH, and -CN) by X-ray diffraction. The density-functional methods calibrated in our recent study (Phys. Chem. Chem. Phys., 2010, 12, 5126) have been employed to enable understanding of the substituent-induced changes in the NMR chemical shifts of the atoms in the purine skeleton. Analyses of the nuclear shielding using localized molecular orbitals (LMOs), specifically the natural LMOs (NLMOs) and Pipek-Mezey LMOs, were used to break down the values of the isotropic (13)C and (15)N NMR chemical shifts and the chemical shift tensors into the contributions of the individual LMOs. The experimental and calculated trends in the chemical shift of the N-3 atom correlate nicely with the Hammett constants (σ(para)) and the calculated natural charges on N-3, whereas the contributions of the LMOs to the N-1 and C-6 chemical shifts are found to be more complex.     

Investigation of substituent effects of chalcones by 13C n.m.r. spectroscopy

¹³C chemical shifts for 23 para- and meta-substituted chalcones of the types 1 and 2 have been determined. The aromatic shieldings are compared with previous results for other aromatic derivatives. Correlations of the ¹³C chemical shifts of vinyl carbons and carbonyl carbons as well as ring carbons with Hammett σ parameters, π electron densities and the reactivity parameters of Swain and Lupton provide a consistent picture of electronic effects transmitted through the carbon framework of the compounds studied.     

13C NMR substituent effects in tetracyclic diterpenoids

The ¹³C NMR chemical shifts of ent-beyer-15-ene, and one hydroxy and four acetoxy derivatives are reported. The substituent effects of the acetoxy groups upon the saturated and olefinic carbon atoms are discussed. Conformational aspects of the molecules are considered in the light of these effects.     

Methyl substituent effects on the 13C chemical shifts at the carbenium center of 2-aryl-2-propyl cations

Methyl substituent effects on ¹³C NMR shifts of arylcarbenium ions are examined as a probe of charge distribution and are compared to methyl effects on the solvolysis rates of 1-arylethyl derivatives.