Substituent effects on carbon-13 chemical shifts in 2,6-disubstituted adamantanes

Carbon-13 NMR spectral data for a series of symmetrical 2,6-disubstituted adamantanes (O?, CH₂?, CH₃, OH, OCOCH₃) are presented. The substituent effects on ¹³C chemical shifts are additive, except for carbons 2 and 6 in 2,6-adamantanedione. The non-additivity of the substituent effect in the diketone can be interpreted in terms of a through-space interaction of the carbonyl π-electrons; the additivity in the other derivatives indicates that there is no appreciable interaction between the substituents.     

13C NMR-spectroscopy of substituted xanthones—III: Computer supported structure elucidation of polyhydroxy xanthones

A procedure for developing ¹³C NMR chemical shift additivity rules for all 136 polyhydroxy xanthones, which is based on the method of multiple linear regression analysis with dummy parameters, is reported. A computer search program is presented, which rapidly identifies unkown polyhydroxy xanthones with the help of these additivity rules. The working mode is described and its selectivity demonstrated by means of examples from literature.     

Computer supported structure elucidation of polymethoxy- and polyacetoxyxanthones. V—13C NMR spectroscopy of substituted xanthones

A procedure for developing ¹³C NMR chemical shift additivity rules for all 136 polymethoxyxanthones and all 136 polyacetoxyxanthones, based on multiple linear regression analysis, is reported. The influence of steric interactions between the substituents on the chemical shifts of the carbon atoms in the xanthone ring system is discussed and included in the calculations of the additivity rules for the polymethoxyxanthones. The derived chemical shift increments are implemented into the computer program SEOX 1. The extended program, SEOX 2, allows an automated structure elucidation of polyhydroxy-, polymethoxy- and polyacet-oxyxanthones. The increments are tested using the leave-one-out method in conjunction with SEOX 2, and have been found to be very suitable for this purpose.     

Comprehensive parameter set for the prediction of the 13C-NMR chemical shifts of sp3-hybridized carbon atoms in organic compounds

A parameter set is described for prediction of the carbon-13 chemical shifts of sp³-hybridized carbon atoms based on a simple linear additivity relationship. It was tested against 88 692 known chemical shift values. Many of the previously reported parameters were amended and new parameters added. With this parameter set, the chemical shifts in 99.7% of the 88 692 cases can be estimated with an overall standard deviation of 5.6 ppm for the predicted values relative the the experimental ones. The additivity parameters reported here can be used per se or in connection with a recent computer program for the estimation of carbon-13 chemical shifts, which automatically selects and applies additivity rules appropriate for the individual carbon atoms of the chemical constitution entered.     

13C and 19F chemical shifts of bridgehead halogenated adamantanes

The ¹³C chemical shifts of the sixteen bridgehead substituted mono-, di-, tri- and tetrahaloadamantanes (halo = F, Cl, Br, I) and four mixed 1,3-dihaloadamantanes are reported. The effect of bridgehead halogens on the shift values of carbons in β and δ positions is well correlated by the simple additivity relationship based on substituent shifts of 1-monohaloadamantanes. A substituted α-carbon is shifted upfield with an increase in the number of halogens at other bridgehead positions and this shift is relatively greater in the order F < Cl < Br < I. This observed upfield shift of α-carbons is opposite to the downfield shift expected from additivity. An unsubstituted bridgehead γ-carbon is moved to lower fields by one, two and three bromines (or iodines) at other bridge-heads while, in contrast, a third fluorine weakly shields the remaining unsubstituted γ-carbon. Some special noncumulative effects of halogens operating across the 1,3-bridgehead positions of adamantane are indicated by the data. The ¹⁹F chemical shifts of 1-fluoro-, 1,3-difluoro-, 1,3,5-trifluoro- and 1,3,5,7-tetrafluoroadamantanes are contrary to expectations based on inductive effects in that they move progressively upfield. Other 1-fluoroadamantanes with chloro, bromo, or methyl groups present also show substituent-induced chemical shifts which shield the fluorine.     

6Li, 6Li-cosy - a new tool for structure determinations of lithium organic compounds in solution

A homonuclear ⁶Li, ⁶Li shift correlation experiment has been successfully performed for 3,4-dilithio-2,5-dimethyl-2,4-hexadiene, thereby providing information about the structure of this compound.     

Chemistry of the SO Bond. 8—A stereochemical investigation of some methyl-substituted trimethylene sulphites (1,3,2-Dioxathian 2-Oxides) via 13C nuclear magnetic resonance

¹³C NMR chemical shifts for trimethylene sulphite and 35 derivatives are presented. From the magnitudes of the β shifts it has been possible to establish chemical shift additivity relationships for a series of compounds. The results are discussed in terms of probable conformations in solution.     

Proximity and the heteroatom effects on the carbon-13 chemical shifts of methyl-substituted phenols,anilines and thiophenols

Upfield substituent-induced ¹³C chemical shifts for aryl carbons of polymethyl substituted benzenes, phenols, anilines and thiophenols were investigated as a function of the proximity between substituents X and CH₃ (X = CH₃, NH₂, OH and SH). The results indicate that the induced shifts of the substituted aryl carbons are, in general, independent of the polar substituent but depend on the number of adjacent substituted aryl carbons. A ?2.0 ppm upfield shift was found for a substituted aryl carbon adjacent to one substituted aryl carbon and a ?3.8 ppm upfield shift for a substituted aryl carbon bound by two substituted aryl carbons. It is suggested that the near additivity of the upfield shifts is the result of changes in the bond order between the aromatic ring carbons in the region of the substituted aryl carbons due to distortion of the ring. The ¹³C chemical shifts of the methyl substituents for methyl substituted phenols, anilines and thiophenols were determined, and it was found that the values could be predicted from the additivity parameters reported for the analogous methylbenzenes plus an additional pair-interaction term associated with the through-space electronic influence of the heteroatom.     

The combined effects of two chlorine substituents and the non-additivities of chemical shifts in aliphatic dichloro esters

Carbon-13 NMR spectra were measured for 25 methyl esters of aliphatic dichlorocarboxylic acids for substituted propanoic to hexanoic acids. Observed ¹³C shifts are compared with calculated shift values obtained from the shifts of the corresponding monochloro esters by applying a simple sum method. The greatest failures from additivity are observed for αβ and αα substituted carbons. The combined effects of two chlorine substituents were determined, and compared with those obtained from chlorine substituent effects in monochloro esters by assuming additivity. The trends displayed by the combined effects, and also by the non-additivity effects, are discussed.     

Influence of methyl substituents on the chemical shift of the ring protons in mono-, di- and trimethylcyclohexanes a 300 MHz study of the 1H NMR spectrum of cis-1,3-dimethylcyclohexane

From a 300 MHz spectral study of mono-to trisubstituted cyclohexanes, allowing a re-examination of some of their ¹H NMR spectral parameters, it is shown that it is possible to predict with reasonable accuracy the shifts (in CCl₄) of the ring protons. A substantial feature in this is the validity of the (questioned) additivity of multiple effects. It is also shown that with respect to shift alterations, equatorial ring protons behave anomalously, which cannot be explained by any existing theoretical model.     

Trends in shift rules in carbon-13 nuclear magnetic resonance spectroscopy and computer-aided shift prediction

A major problem in the use of ¹³C-NMR spectroscopy for structure identification is to estimate the ¹³C shifts of compounds known or suspected to be present in the spectrum. The substituent chemical shifts of different functional groups were studied and new, detailed empirical rules are reported. Trends in these shift parameters are noted. It appears that for functional groups containing more than one nucleus, the observed shift parameters (x=α, β, γ, δ shifts) can be approximated by the shift parameters of the component nuclei (x_comp) in the functional group, i.e., x_obs ≈ x_comp. The detailed shift behavior and shift additivity rules were computerized. The resulting program (CSPEC) has many user friendly features, e.g., ease of input, modification of structure, storage and retrieval of known shifts, and rapid computation.     

29Si chemical shifts and additivity in pertrimethylsilylated O-methyl,O-benzyl,O-benzoyl and O-acetyl methyl β-D-xylopyranosides

²⁹Si chemical shifts in pertrimethylsilylated O-methyl, O-benzoyl, O-benzoyl and O-acetyl methyl β-D -xylopyranoside derivatives are reported. The chemical shifts in monotrimethylsilyl derivatives with the same O-substituents are in the order: δ(Si-2) > δ(Si-4) > δ(Si-3). When the chemical shifts in bis (trimethylsilyl) and tris(trimethylsilyl) derivatives are assigned according to this rule, all the chemical shifts agree well with a direct additivity rule. The only significant deviation from additivity occurs for methyl 2,4-di-O-benzoyl-3-O-trimethylsilyl-β-D -xylopyranoside, which has a different average conformation from the other compounds studied.     

Carbon-13 NMR spectra of heterocycles. Sultones and sultams.

The ¹³C NMR spectra of 1,3-propanesultam, 2,4-butanesultam, 1,4-butanesultam, 1,3-propanesultone and 1,4-butanesultone, as well as some of their unsaturated analogs 2,4-dimethylbuta-1,3-diene-1,4-sultone and 2,4-dimethylbuta-1,3-diene-1,4-sultam, have been recorded. The observed chemical shift data for the sultams and sultones can be explained mainly on the basis of inductive effects. The δ values of the dienesultone and the dienesultam are mainly affected by M-effects. ¹H NMR as well as mass spectra have.     

A new approach to NMR chemical shift additivity parameters using simultaneous linear equation method

A new approach to NMR chemical shift additivity parameters using simultaneous linear equation method has been introduced. Three general nitrogen-15 NMR chemical shift additivity parameters with physical significance for aliphatic amines in methanol and cyclohexane and their hydrochlorides in methanol have been derived. A characteristic feature of these additivity parameters is the individual equation can be applied to both open-chain and rigid systems. The factors that influence the (15)N chemical shift of these substances have been determined. A new method for evaluating conformational equilibria at nitrogen in these compounds using the derived additivity parameters has been developed. Conformational analyses of these substances have been worked out. In general, the results indicate that there are four factors affecting the (15)N chemical shift of aliphatic amines; paramagnetic term (p-character), lone pair-proton interactions, proton-proton interactions, symmetry of alkyl substituents and molecular association.     

60, 90 and 250 MHz 1H NMR spectra of sultams and sultones

The high-field ¹H NMR spectra of 1,3-propanesultams (2), 2,4-butanesultams (3) and 2,4-dimethyl-1,3-butadienesultams (6) are reported. Comparison of 2,3 and 6 with 1,3-propanesultone (1) and 2,4-dimethyl-1,3-butadienesultone (5) reveals that the paramagnetic shift induced by the NH group is smaller than that induced by oxygen. NMR spectra at lower temperature show coupling effects with the NH proton. A half-chair conformation was deduced for 2,4-butanesultam from coupling constants and from a conformational analysis based on the R values, but a chair-chair interconversion could not be detected in the temperature range between 210 and 330 K. An unambiguous assignment was carried out for the methyl signals in the spectrum of 5 by homodecoupling experiments.     

Pairwise effects of chlorine substituents on the 13C NMR chemical shifts of dichlorobicyclo[2.2.1]heptanes (norbornanes)

The ¹³C NMR spectra of nine dichlorinated bicyclo[2.2.1]heptanes (norbornanes) have been measured and assigned. The pairwise effects of chlorine substituents which cause deviations from the additivity of single-substituent effects were investigated and are discussed. The largest effect found is the high-field shift of carbons bearing vicinal cis substituents. In the case of geminal substitution deviations from additivity were found to be to low field and large in the γ, smaller in the β and negligible in the α chemical shifts. The observed deviations for 1,3-disubstituted cases vary from ?3.2 to +1.1 ppm at different carbons, allowing no simple explanation. Replacement of α-hydrogen in a diaxial 1,3-arrangement by CH₃, OH or CI causes the single substituent effect, namely the γ_a effect, to change considerably.     

Synthese von Tricyclo[4.4.1.13, 8]dodecan-4, 9-dion und Tricyclo[4.4.1.13, 8]dodeca-4, 9-dien

Treatment of 2, 6-bis-aminomethyladamantane-2, 6-diol (II) with nitrous acid gives tricyclo[4.4.1.1^{3, 8}]dodecane-4, 9-dione (III), which is converted into the tricyclo[4.4.1.1^{3, 8}]dodeca-4, 9-diene (V) by reduction to the corresponding diols (IV, R = H) and pyrolysis of their O-4-methylphenyl thiocarbonate O-esters. II is accessible from 2, 6-adamantanedione by reaction with diethyl aluminium cyanide and subsequent reduction with lithiumaluminium hydride. The physical properties of the new compounds including ¹³C NMR. spectra of III, V and tricyclo-[4.4.1.1^{3, 8}]dodecane are given.     

13-NMR Analysis of Branched Polyethyleneimine

A commercial, branched polyethyleneimine was analyzed by ¹³C-NMR. The chemical shift assignments for the eight principal peaks were compared to the calculated chemical shifts using an additivity relationship developed for low molecular weight acyclic aliphatic amines. The change in carbon chemical shift induced by H/D exchange at nearby nitrogens was examined for this polymer and low molecular weight model compounds. The direction and magnitude of the shift are determined by the number and proximity of exchangeable NH' and are described by a simple formula. The spin lattice relaxation times for the various methylenes indicate the usual decreasing mobility for units at chain ends, internal units, and units close to branch points in that order. The integrated spectrum, under equilibrium conditions, is not consistent with the reorted amine distribution, 1°:2°:3° = 1:2:1. Our results indicate 38k l°, 36% 2°, and 26% 3°.     

The structure of 1,2-dithioles studied by 13C n.m.r. spectroscopy

The charge separation between the dithiole ring and oxygen in 3-(1′,2′-dithiole-3′-ylidene)-6-methyl-2,3-dihydropyran-2,4-diones and 3-(1′,2′-dithiole-3′-ylidene)-2,3-dihydrobenzo[b] pyran-2,4-diones has been determined by ¹³C and ¹⁹F n.m.r. spectroscopy. By both methods it is found that these compounds are relatively polar. A correlation is established between the ¹³C chemical shift of some carbon atoms and the S2p binding energies measured by e.s.c.a. in the 1,2-dithiole derivatives. This correlation shows that these ¹³C shifts depend on the positive charge taken by the 1,2-dithiole ring and can then constitute a convenient evaluation of this charge.     

Synthetic approaches to 5,7- and 5,8-dimethoxyquinoline. Sonochemical dehalogenation of substituted 2,4-dichloroquinolines. Use of the 2D COLOC spectrum for the NMR assignment of 5,8-dimethoxyquinoline

Summary Sonochemical dehalogenation of 2,4-dichloroquinoline is very facile. However, with 5,7-dimethoxy-2,4-dichloroquinoline the reaction proceeds stepwise to provide the title dimethoxyquinolines which cannot be prepared via theSkraup reaction. The¹³C NMR chemical shift assignments for 5,8-dimethoxyquinoline are presented. These were made by utilising the coupling connectivities from the bridgehead carbons in the 2D COLOC spectrum.

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Synthese von 5,7- und 5,8-Dimethoxychinolin. Sonochemische Dehalogenierung von substituierten 2,4-Dichlorochinolinen. NMR-Spektroskopische Zuordnung von 5,8-Dimethoxychinolin mittels eines COLOC-Experiments

Zusammenfassung 2,4-Dichlorchinoline können sonochemisch leicht dehalogeniert werden. Mit 5,7-Dimethoxy-2,4-dichlorchinolin verläuft die Reaktion in mehreren Schritten zu den Titelverbindungen, die mittelsSkraup-Reaktion nicht hergestellt werden können. Das¹³C-NMR-Spektrum von 5,8-Dimethoxychinolin wurde, ausgehend von den Brückenkopfkohlenstoffatomen, mit Hilfe eines COLOC-Experiments zugeordnet.