(13)C-(1)H and (13)C-(13)C NMR J-couplings in (13)C-labeled N-acetyl-neuraminic acid: correlations with molecular structure

N-acetyl-neuraminic acid (Neu5Ac, 2) was prepared enzymatically containing single sites of (13)C-enrichment at C1, C2, and C3. Aqueous solutions of the three (13)C isotopomers were studied by (1)H and (13)C NMR spectroscopy at p(2)H 2 and pH 8 to obtain J(CH) and J(CC) values involving the labeled carbons. Experimental studies were complemented by DFT calculations of the same set of J-couplings in protonated and ionized structural mimics of 2 to determine how well theoretical predictions match the experimental findings in saccharides bearing ionizable functionality. Results show that: (a) (2)J(C2,H3ax/eq) values in 2 depend on anomeric configuration, thus complementing (3)J(C1,H3ax/eq) behavior, (b) J(CH) and J(CC) values involving C2 depend on anomeric configuration, the C1-C2 bond torsion, and solution pH, and (c) long-range (4)J(C2,H7) is sensitive to glycerol side-chain conformation. Intraring J(HH) and most (2)J(CH), (3)J(CH), (2)J(CC), and (3)J(CC) involving C1-C3 of 2 appear largely unaffected by the ionization state of the carboxyl group. In vacuo and solvated DFT calculations of geminal and vicinal J(CH) and J(CC) values are similar and reproduce the experimental data well, but better agreement with experiment was observed for (1)J(C1,C2) in the solvated calculations. The present work provides new information for future treatments of trans-glycoside couplings involving Neu5Ac residues by (a) providing new standard values of intraring J(CC) for coupling pathways that mimic those for trans-glycoside J(CC), (b) identifying potential effects of solution pH on trans-glycoside couplings inferred through the behavior of related intraring couplings, and (c) providing specific guidelines for more reliable DFT predictions of J(CH) and J(CC) values in ionizable saccharides.     

Application of 1D BIRD or X-filtered DEPT long-range C-C relay for detection of proton and carbon via four bonds and measuring long-range 13C-13C coupling constants

We propose the 13C-detecting 1D DEPT long-range C-C relay to detect super long-range H-C connectivity via four bonds (1H-13C-X-X-13C, X represents 12C or heteronuclear). It is derived from the DEPT C-C relay which detects the H-C correlations via two bonds (1H-13C-13C) by setting the delays for J(CC) in the C-C relay sequence to the (LR)J(CC). This sequence gives correlation signals split by small (LR)J(CC), which seriously suffers from residual center signal. The unwanted signal is due to long-range C-H couplings ((LR)J(CH)). The expected relayed magnetization transfer 1J(CH) --> (LR)J(CC) occurs in the 1H-13C-X-(X)-13C isotopomer, whereas the unwanted signal of (LR)J(CH) comes from 1H-12C-(X)-13C isotopomers, whose population is 100 times larger than that of the 1H-13C-X-(X)-13C isotopomer. The large dispersive line of this unwanted center signal would be a fatal problem in the case of detecting small (LR)J(CC) couplings. This central signal could be removed by an insertion of BIRD pulse or X-filter. DEPT spectrum editing solved a signal overlapping problem and enabled accurate determination of particular (LR)J(CC) values. We demonstrate here the examples of structure determination using connectivity between 1H and 13C via four bonds, and the application of long-range C-C coupling constants to discrimination of stereochemical assignments.     

Comparison of methyl rotation axis order parameters derived from model-free analyses of (2)H and (13)C longitudinal and transverse relaxation rates measured in the same protein sample.

Recombinant HIV-1 protease was obtained from bacteria grown on a 98% D(2)O medium containing 3-(13)C pyruvic acid as the sole source of (13)C and (1)H. The purified protein is highly deuterated at non-methyl carbons, but contains significant populations of (13)CHD(2) and (13)CH(2)D methyl isotopomers. This pattern of isotope labeling permitted measurements of (1)H and (13)C relaxation rates of (13)CHD(2) isotopomers and (2)H (D) relaxation rates of (13)CH(2)D isotopomers using a single sample. The order parameters S(axis)(2), which characterize the motions of the methyl rotation axes, were derived from model-free analyses of R(1) and R(2) data sets measured for (13)C and (2)H spins. Our primary goal was to compare the S(axis)(2) values derived from the two independent types of data sets to test our understanding of the relaxation mechanisms involved. However, S(axis)(2) values derived from the analyses depend strongly on the geometry of the methyl group, the sizes of the quadrupolar and dipolar couplings, and the effects of bond vibrations and librations on these couplings. Therefore uncertainties in these basic physical parameters complicate comparison of the order parameters. This problem was circumvented by using an experimental relationship, between the methyl quadrupolar, (13)C-(13)C and (13)C-(1)H dipolar couplings, derived from independent measurements of residual static couplings of weakly aligned proteins by Ottiger and Bax (J. Am. Chem. Soc. 1999, 121, 4690-4695) and Mittermaier and Kay (J. Am. Chem. Soc. 1999, 121, 10608-10613). This approach placed a tight experimental restraint on the values of the (2)H quadrupolar and (13)C-(1)H dipolar interactions and greatly facilitated the accurate comparison of the relative values of the order parameters. When applied to our data this approach yielded satisfactory agreement between the S(axis)(2) values derived from the (13)C and (2)H data sets.     

Raman,infrared and force field studies of K2(12)C2O4 x H2O and K2(13)C2O4 x H2O in the solid state and in aqueous solution,and of (NH4)2(12)C2O4 x H2O and (NH4)2(13)C2O4 x H2O in the solid state

The Raman and infrared spectra of solid K2(12)C2O4 x H2O are reported together with, for the first time, the corresponding Raman and infrared spectra of solid K2(13)C2O4 x H2O. Raman spectra of aqueous solutions of both isotopomers are also reported. In the solid state the oxalate anion is planar with D2h symmetry in this salt, whereas in aqueous solution the Raman spectra of the anion are best interpreted on the basis of D2d symmetry. The Raman spectra of solid (NH4)2(12)C2O4 x H2O and (NH4)2(13)C2O4 x H2O, in which the oxalate anion is twisted from planarity by 28 degrees about the CC bond, have also been recorded. Several reassignments have been made. The harmonic force field for the oxalate anion in the D2h, D2 and D2d geometries has been determined in part, and approximate values of key valence force constants determined. All the observed band wavenumbers and 12C/13C isotopic shifts are well reproduced by the force fields. The potential energy distribution of the totally symmetric normal modes of planar oxalate indicates that each mode consists of extensively mixed symmetry corrdinates and that the labels previously used for the bands seen here at 475 and 879 cm(-1) would better be described as v(CC) and deltaS(CO2), respectively, putting them in the same wavenumber order as v(NN) and deltaS(NO2) for the isoelectronic and isostructural molecule N2O4. The stretching force constants of N2O4 and planar C2O4(2-) are established to be in the order f(NN) < f(CC) and f(NO) > f(CO), consistent with the known relative bond lengths.     

13C?13C coupling constants in diacetylene (1,3-butadiyne) and its bis(triethylsilyl) derivative

Completely ¹³C-labelled diacetylene and its bis(triethylsilyl) derivative have been synthesized and all the possible spin–spin couplings between the acetylenic carbon nuclei have been determined from their Fourier transform ¹³C NMR spectra. J(CC) values in diacetylene have been also computed by means of the finite perturbation INDO method. Carbon–proton coupling constants in diacetylene have been determined from the spectrum at natural abundance. It has been established that J(CC) values across the triple bond in diacetylene and bis(triethylsilyl)diacetylene are greater than in acetylene and triethylsilylacetylene, respectively. The increase is interpreted in terms of σ- and π-electronic changes which occur with the coupling of two isolated triple bonds into a dimer-like system. All CC coupling constants are greater in diacetylene than in bis(triethylsilyl)diacetylene, which indicates that strong (p→d)π interaction takes place in the latter compound.     

The ground-state rotational spectrum and molecular geometry of ethynylstannane

The ground-state rotational spectra of 24 isotopomers of ethynylstannane have been observed by pulsed-jet, Fourier-transform microwave spectroscopy. The spectroscopic constants, B(0,)D(J) and D(JK) are reported for symmetric-top isotopomers H(3)(n)Sn(12)C(12)CH, where n = 116, 117, 118, 119, 120, 122 and 124, D(3)(n)Sn(12)C(12)CH, where n = 116, 118, 120, 122 and 124, H(3)(n)Sn(13)C(12) CH and H(3)(n)Sn(12)C(13)CH , where n = 116,118 and 120, and H(3)(n)Sn(12)C(12)CD, where n = 116, 118 and 120. In addition, the values of A(0), B(0), C(0), Delta(J) and Delta(JK) were obtained for the three asymmetric-top isotopomers DH(2)(n)Sn(12)C(12)CH, where n = 116, 118 and 120. Hyperfine structure was resolved and assigned in the transitions of the isotopomers H(3)(n)SnCCD, where n = 116, 118 and 120, and in the isotopomers H(3)(117)SnCCH and H(3)(119)SnCCH. In the former group, the hyperfine structure arises from D nuclear quadrupole coupling while in the latter group its origin lies in the spin-rotation coupling of the I = 1/2 Sn nuclear spin to the rotational motion. For these isotopomers, D nuclear quadrupole and spin-rotation coupling constants are determined where appropriate. The rotational constants obtained for the 24 isotopomers of H(3)SnCCH were used to obtain the following types of molecular geometry for ethynylstannane: r(0), r(s), and r(m).     

内氢键对芳环~(13)C化学位移的影响

本文讨论水杨醛、邻——基苯乙酮及2——基雌甾化合物的分子内氢键对芳环~13C化学位移的影响。采用量子化学CNDO/2方法,计算取代芳烃各原子的净电荷,从碳原子的净电荷与化学位移的对应关系进一步论证了此种影响.首次得到形成内氢键的甲甲基、乙乙基及及基对所在碳的取代基增量的校正值,经校正后化学位移的计算值与实测值很好符合。     

H(C)P and H(P)C triple-resonance experiments at natural abundance employing long-range couplings

Modified two-dimensional (2D) triple-resonance H(C)P and H(P)C experiments based on INEPT/HMQC and double-INEPT schemes are applied to the study of organophosphorus compounds at natural abundances. The implementation of effective (1)H--(13)C gradient selection, additional purging pulsed field gradients, spinlock pulses, and improved phase cycling is demonstrated to allow weak correlation signals based on long-range couplings to be readily observed. Through the combination of two heteronuclear long-range coupling constants, (n)J(CH) and (n)J(PC) in H(C)P experiments or (n)J(PH) and (n)J(PC) in H(P)C experiments, protons can be correlated to a second heteronucleus through 4-7 chemical bonds. These experiments thus overcome the inherit limitations of classical (1)H-X HMBC experiments, which require a nonzero value of the heteronuclear coupling constant (n)J(XH). Ultra-broadband inversion composite pulses are successfully employed in the H(P)C INEPT/HMQC and H(P)C double-INEPT pulse sequences to increase the utility of the experiments and the quality of obtained spectra. This work extends and completes a set of 2D phase-sensitive triple-resonance experiments applicable at natural abundances, and also offers insight into the methodology of triple-resonance experiments and the application of pulsed field gradients. A one-dimensional triple-resonance experiment employing carbon detection is suggested for accurate determination of small (n)J(PC).     

13C-labeled N-acetyl-neuraminic acid in aqueous solution: detection and quantification of acyclic keto, keto hydrate, and enol forms by 13C NMR spectroscopy

Aqueous solutions of N-acetyl-neuraminic acid (Neu5Ac, 1) labeled with (13)C at C1, C2, and/or C3 were analyzed by (13)C NMR spectroscopy to detect and quantify the acyclic forms (keto, keto hydrate, enol) present at varying pHs. In addition to pyranoses, solutions contained the keto form, based on the detection of C2 signals at approximately 198 ppm (approximately 0.7% at pH 2). Spectra of [2-(13)C] and [3-(13)C] isotopomers contained signals arising from labeled carbons at approximately 143 and approximately 120 ppm, respectively, which were attributed to enol forms. Solution studies of [1,2,3-(13)C3] 1 substantiated the presence of enol (approximately 0.5% at pH 2). Enol was not detected at pH > 6.0. A C2 signal observed at approximately 94 ppm was identified as C2 of the keto hydrate (approximately 1.9% at pH 2), based partly on its abundance as a function of solution pH. Density functional theory (DFT) calculations were used to study the effect of enol and hydrate structure on J(CH) and J(CC) values involving C2 and C3 of these forms. Solvated DFT calculations showed that (2)J(C2,H3) in cis and trans enols have similar magnitudes but opposite signs, making this J-coupling potentially useful to distinguish enol configurations. Solvent deuterium exchange studies of 1 showed rapid incorporation of (2)H from (2)H2O at H3 axial in the pyranoses at p(2)H 8.0, followed by slower exchange at H3 equatorial. The acyclic keto form, which presumably participates in this reaction, must assume a pseudo-cyclic conformation in solution in order to account for the exchange selectivity. Weak (13)C signals arising from labeled species were also observed consistently and reproducibly in aqueous solutions of (13)C-labeled 1, possibly arising from products of lactonization or intermolecular esterification.     

Microwave investigation of the CO-CH4 van der Waals complex

Rotational spectra of eight isotopomers of the weakly bound van der Waals complex CO-CH4 were recorded in the frequency range from 4 to 19 GHz using a pulsed molecular beam Fourier transform microwave spectrometer. For the isotopomers containing methane monomers of Td symmetry, namely, 12C16O-12CH4, 12C16O-13CH4, 12C16O-12CD4, 13C16O-12CH4, and 13C18O-12CH4, three rotational progressions were observed that correlate to the jm=0, 1, and 2 rotational levels of free methane. For those containing partially deuterated methane monomers with C3V symmetry, namely, 12C16O-12CH3D and 12C16O-12CHD3, only two progressions were recorded, correlating to the jk=0(0) and 1(1) rotational levels of free CH3D and CHD3, respectively. The van der Waals bond distance R, intermolecular stretching frequency nus, and the corresponding stretching force constant ks were derived from the obtained spectroscopic results. The results obtained for the jm=0 ground state are compared to the previous infrared and millimeter wave data. A 17O nuclear quadrupole coupling constant was determined from the resolved hyperfine structure of 13C17O-12CH4 and was used to obtain angular information about the carbon monoxide subunit. A Coriolis interaction was deduced from the irregular spectral pattern involving levels with jm=1. Qualitative information about the extent of the perturbation was obtained from a comparison of spectroscopic constants of different isotopomers.     

CP/MAS (13)C NMR study of cellulose and cellulose derivatives. 2. Complete assignment of the (13)C resonance for the ring carbons of cellulose triacetate polymorphs

Complex ring (13)C resonance lines of the cross-polarization/magic angle spinning (CP/MAS) (13)C NMR spectra of cellulose triacetate (CTA) I and CTA II were completely assigned, for the first time, by (13)C-enriched CTA allomorphs. The (13)C-enriched CTA I was prepared by heterogeneous acetylation of bacterial cellulose which was biosynthesized by Acetobacter xylinum (A. xylinum) ATCC10245 from culture medium containing D-(2-(13)C)-, D-(3-(13)C)-, or D-(5-(13)C)glucose as a carbon source, while CTA II samples were obtained by solution acetylation of the (13)C-enriched bacterial celluloses. From comparison of the spectra of normal CTA prepared from ramie with those of the enriched CTA samples, it was revealed that all carbons composed of CTA I appeared as a singlet, while those of CTA II except for C1 were shown as equal-intensity doublets in the CP/MAS (13)C NMR spectrum. This finding suggests that CTA I is made up of one kind of glucopyranose residue while there are two magnetically inequivalent sites in the unit cell of CTA II in the same population.     

The rotational spectrum and theoretical study of a dinuclear complex, MnRe(CO)(10)

The first rotational spectrum of a dinuclear complex, MnRe(CO)(10), has been obtained using a high-resolution pulsed beam microwave spectrometer. Sixty-four hyperfine components of the J=11-->J(')=12 and J=12-->J(')=13 rotational transitions were measured for two rhenium isotopomers. The B values obtained from the experiment are B=200.36871(18) MHz for the (187)Re isotopomer and B=200.5561(10) MHz for the (185)Re isotopomer. The measured rotational constants are in reasonably good agreement with the B values calculated from the x-ray diffraction structural data, and from theoretical calculations. The gas-phase Mn-Re bond distance is approximately 2.99 A, and the calculated value is only slightly longer. The experimental quadrupole coupling constant for the manganese atom is eQq(aa) ((55)Mn)=-16.52(5) MHz, and the corresponding quadrupole coupling constants for the two rhenium isotopomers are eQq(aa) ((187)Re)=370.4(4) MHz and eQq(aa) ((185)Re)=390.9(6) MHz. The quadrupole coupling constants were also determined from a variety of theoretical calculations, with very large Gaussian orbital bases. The best estimates, at a nonrelativistic level, are eQq(aa) ((55)Mn)=0.68 MHz and eQq(aa) ((187)Re)=327.6 MHz with a 874 GTO basis set, but the results are very basis set dependent, especially the sign of the Mn quadrupole coupling. Very slight bending of angles MnC(eq)O(eq) and ReC(eq)O(eq) angles is found in the calculations.     

Signature of mobile hydrogen bonding of lysine side chains from long-range 15N-13C scalar J-couplings and computation

Amino acid side chains involved in hydrogen bonds and electrostatic interactions are crucial for protein function. However, detailed investigations of such side chains in solution are rare. Here, through the combination of long-range (15)N-(13)C scalar J-coupling measurements and an atomic-detail molecular dynamics (MD) simulation, direct insight into the structural dynamic behavior of lysine side chains in human ubiquitin has been gained. On the basis of (1)H/(13)C/(15)N heteronuclear correlation experiments selective for lysine NH(3)(+) groups, we analyzed two different types of long-range (15)N-(13)C J-coupling constants: one between intraresidue (15)Nζ and (13)Cγ nuclei ((3)J(NζCγ)) and the other between (15)Nζ and carbonyl (13)C' nuclei across a hydrogen bond ((h3)J(NζC')). The experimental (3)J(NζCγ) data confirm the highly mobile nature of the χ(4) torsion angles of lysine side chains seen in the MD simulation. The NH(3)(+) groups of Lys29 and Lys33 exhibit measurable (h3)J(NζC') couplings arising from hydrogen bonds with backbone carbonyl groups of Glu16 and Thr14, respectively. When interpreted together with the (3)J(NζCγ)-coupling constants and NMR-relaxation-derived S(2) order parameters of the NH(3)(+) groups, they strongly suggest that hydrogen bonds involving NH(3)(+) groups are of a transient and highly dynamic nature, in remarkably good agreement with the MD simulation results.     

(13)C natural abundance in the British diet: implications for (13)C breath tests

Surprisingly little information is available on the natural abundance of the minor isotope of carbon, (13)C, in common foodstuffs in the British diet. This study therefore aimed to examine the (13)C natural abundance of foodstuffs from a small cross-section of the British diet. The isotopic abundance, delta per mil, was calculated by measurement of the isotope ratio (13)C:(12)C by isotope ratio mass spectrometry. Results from this study were also compared with results from a North American study to highlight the difference in isotopic abundance between Northern European foodstuffs and North American foodstuffs. Such data should prove useful to those planning tracer studies using the stable isotope (13)C where enrichment is measured against a large and variable natural abundance in the body. Minimisation of this basal variation, for example in breath CO(2), can be achieved by controlling dietary intake of foods naturally abundant in (13)C.     

The indirect through-space F-F coupling in peri-difluoronaphthalene: is it anisotropic?

The (1)H, (19)F and (13)C spectra have been obtained of a sample of peri-difluoronaphthalene dissolved in the nematic liquid crystalline solvent ZLI 1695. The (13)C satellite spectra from the six, single-(13)C isotopomers at natural abundance in both the (1)H and (19)F spectra were identified and analysed to yield a set of residual total, anisotropic spin-spin couplings, T(ij). This was achieved by first obtaining residual (13)C-(19)F and (13)C-(1)H couplings from a proton-encoded, (13)C detected, local field 2D spectrum. The 45 values of T(HH), T(HF) and T(CH) were used to obtain the structure of the molecule, and then to estimate whether there is a significant contribution from the component along the magnetic field, J, of the anisotropic, electron-mediated, spin-spin coupling tensors for (13)C-(19)F and (19)F-(19)F pairs. It is found that there is strong evidence for a significant contribution of J to T(FF) but not for the (13)C-(19)F pairs.     

13C-detected IPAP-INADEQUATE for simultaneous measurement of one-bond and long-range scalar or residual dipolar coupling constants

The sensitivity of cryoprobes, which are rapidly becoming available, means that the measurement of coupling constants involving 13C, 13C pairs at the natural abundance of 13C can now, in principle, be done by using tens rather then hundreds of milligrams of compounds. However, a robust method that would yield reliable values of small long-range carbon--carbon coupling constants is still missing. In this Communication, we describe a novel 13C-detected incredible natural-abundance double-quantum transfer experiment (INADEQUATE) experiment for simultaneous correlation of one-bond and long-range 13C- 13C pairs and the measurement of both types of coupling constants in 13C natural abundance samples. This method yields accurate values of one-bond and long-range coupling constants by manipulation of pure phase in-phase (IP) and antiphase (AP) doublets, and is referred to as 13C-detected IPAP-INADEQUATE. It is illustrated by the measurement of interglycosidic (3)J(CCOC) coupling constants in a disaccharide molecule providing important information about the conformation of the glycosidic linkage. Owing to the simplicity of INADEQUATE spectra the carbon-carbon coupling constants are particularly suitable for studies of partially oriented molecules through the measurement of carbon-carbon residual dipolar couplings (RDCs). An example of this approach is presented. We expect the method to find a variety of applications in the conformational analysis of small molecules, determination of diastereoisomers and enantiomers, and studies of molecules in aligned media.     

Experimental and theoretical analysis of vicinal and long-range proton-proton coupling constants for anthracene derivatives

We studied vicinal and long-range coupling constants for 9-anthracene derivatives, e.g., Br, CN, CHO, NO2, CH2Cl, CH2OH, and OCH3. We performed the accurate measurements using modified J doubling in the frequency domain, even for the smallest couplings immersed within the line width. Density functional theory allowed us to reproduce and exhaustively analyze the physical contributions to the values of these spectroscopic parameters. The theory of atoms in molecules defines a delocalization index that correlates linearly with vicinal and long-range coupling constants when they are grouped in terms of the number of bonds between the coupled nuclei. An exception to this behavior is obtained for 4J(H4,H10) values, which have a negative Fermi contact and the largest delocalization index for each molecule. This observation can be explained by a characteristic "gable roof" arrangement formed by the five nuclei involved in the coupling.     

High-accuracy residual 1HN-13C and 1HN-1HN dipolar couplings in perdeuterated proteins

Truncation by the presence of many short-range residual dipolar couplings (RDCs) hinders the observation of long-range RDCs in weakly aligned biomacromolecules. Perdeuteration of proteins followed by reprotonation of labile hydrogen positions greatly alleviates this problem. Here we show that for small perdeuterated proteins, a large number (up to 10 in protein G) of long-range RDCs to 13C and 1HN can be observed from individual amide protons. The 1HN <--> 13C RDCs comprise correlations to 13Calpha, 13Cbeta, and 13C' nuclei of the same and the preceding amino acid, as well as 13C' nuclei of hydrogen-bonded amino acids. The accuracy of the coupling constants is very high and defines individual internuclear distances to within few picometers. Deviations between measured RDC values and values predicted from the 1.1 A crystal structure of protein G are mainly found in two surface-exposed loop regions. The deviations show a strong correlation to the B-factor of the crystal structure.     

Ab initio study of (13)C(alpha) chemical shift anisotropy tensors in peptides

This study reports magnitudes and the orientation of the (13)C(alpha) chemical shift anisotropy (CSA) tensors of peptides obtained using quantum chemical calculations. The dependency of the CSA tensor parameters on the energy optimization of hydrogen atom positions and hydrogen bonding effects and the use of zwitterionic peptides in the calculations are examined. Our results indicate that the energy optimization of the hydrogen atom positions in crystal structures is necessary to obtain accurate CSA tensors. The inclusion of intermolecular effects such as hydrogen bonding in the calculations provided better agreement between the calculated and experimental values; however, the use of zwitterionic peptides in calculations, with or without the inclusion of hydrogen bonding, did not improve the results. In addition, our calculated values are in good agreement with tensor values obtained from solid-state NMR experiments on glycine-containing tripeptides. In the case of peptides containing an aromatic residue, calculations on an isolated peptide yielded more accurate isotropic shift values than the calculations on extended structures of the peptide. The calculations also suggested that the presence of an aromatic ring in the extended crystal peptide structure influences the magnitude of the delta(22) which the present level of ab initio calculations are unable to reproduce.     

Natural abundance 13C NMR investigation of substituted bromobenzene using noise decoupling of proton resonances

The natural abundance ¹³C NMR spectra of bromobenzene and ten derivatives have been obtained using the technique of noise modulated decoupling of the proton resonances. Assignments have been made for all ¹³C resonance signals using an additivity rule. The chemical shifts of the aromatic carbon nuclei in the para-substituted compounds are discussed in terms of the Taft parameters (σ_R, σ_I) and the electronegativity of the substituent.