Correlation of substituent – inducted chemical shifts of aromatic protons: Substituted benzonitriles and methyl benzoates

1991 ◽  
Vol 56 (11) ◽  
pp. 2234-2250 ◽  
Author(s):  
Otto Exner ◽  
Miloš Buděšínský
Keyword(s):  
Principal Component Analysis ◽  
Short Range ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Specific Effect ◽  
Principal Component ◽  
Close Correlation ◽  
Coupling Constants ◽  
The Other ◽  
Range Effect

Proton NMR spectra in deuteriochloroform are reported for 53 meta- and para-substituted benzonitriles and 61 methyl benzoates. The substituent-induced chemical shifts (SCS) were correlated with dual substituent parameters (DSP), with 13C SCS of the adjoining carbon, and with the other 1H SCS using the principal component analysis (PCA). They are controlled by different factors in each position to the variable substituent. In the position 4 the long-range polar effects, as expressed by DSP, are decisive, the conjugative component being more important. Remarkable is also very close correlation of 13C and 1H SCS in this position which has no analogy in the other position. In the position 3 there is an additional specific effect of heavier halogens. In the position 2 the short-range effect can be quantified by special constants, only for a subgroup of simple donor substituents it is proportional to DSP. In all positions SCS are practically independent of the second substituent, so that the total chemical shifts can be calculated by an additive scheme. The coupling constants J(2,3), J(5,6), and J(2,6) depend on substitution in the same manner, probably are controlled mainly by substituent electronegativity.

Phosphorus-31 nuclear magnetic resonance spectra of methylplatinum(II) and methylpalladium(II) cations containing 4-substituted pyridine ligands

1979 ◽  
Vol 57 (9) ◽  
pp. 958-960 ◽  
Author(s):  
Howard C. Clark ◽  
Charles R. Milne
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Lone Pair ◽  
Coupling Constants ◽  
The Other ◽  
Pyridine Ligands ◽  
Trans Influence ◽  
Nuclear Magnetic Resonance Spectra

The 31P nmr spectra of the compounds cis-[M(CH3)(L)diphos]PF6, where M = Pd, Pt; L = 4-C5H4NX; X = CH3, H, NMe2, COOMe, COMe, CN; diphos = 1,2-bisdiphenylphosphino ethane, have been recorded. The 31P chemical shifts and 31P–195Pt coupling constants decrease regularly as the ρ values of the substituent on pyridine decrease. These trends are attributed to decreasing lone pair donation from phosphorus as the electron donating ability of the other ligands on the metal increases. The trans influence of the coordinated pyridine molecule, as measured by J(195Pt–31P), is greater than its cis influence on the phosphorus atoms.

1H NMR spectra of some chloro-alkenes

1981 ◽  
Vol 46 (11) ◽  
pp. 2924-2934
Author(s):  
Seán Cawley ◽  
Jan Schraml ◽  
Petr Svoboda ◽  
Robert Ponec ◽  
Václav Chvalovský
Keyword(s):  
Nmr Spectra ◽  
Chemical Shifts ◽  
Dipole Moments ◽  
Coupling Constants ◽  
The Other ◽  
Dominant Factor ◽  
Proton Proton ◽  
Electric Field Effects ◽  
H Nmr ◽  
Proton Coupling

1H NMR spectra and electric dipole moments of a series of propene derivatives, (CH3)3-nCln.CCH=CH2 (n = 0-3), were measured and the spectra analyzed. Discrepancies in literature data on compounds with n = 0 and 3 are probably due to systematic spectrometer errors. Vinylic proton chemical shifts are found to vary linearly with n in the direction expected on the electronegativity ground (the variations with n occurs in the order HA > HB ≥ HC). Calculations show that even with the extreme reported values of C-C and C-Cl bond magnetic anisotropies, the shift variations with n cannot be accounted for by magnetic anisotropy effects of a freely rotating (CH3)3-nClnC group. Similar calculations rule out electric field effects as the dominant factor. On the other hand, the electron charge distribution, as obtained from CNDO/2 calculations, including d-orbitals and employing Del Bene-Jaffé parametrization, is linearly related to the vinylic proton shifts. This finding supports the earlier interpretation of NMR spectra of vinylsilanes in terms of back-bonding. The vinyl proton-proton coupling constants decrease with increasing n, the changes being larger in the constants which couple proton A (cis) to the other two.

The Electron Effect of Aromatic Group: Control Conformation of 2-Aromatic Cyclododecanone Derivatives

2020 ◽  
Vol 24 (10) ◽  
pp. 1139-1147
Author(s):  
Yang Mingyan ◽  
Wang Daoquan ◽  
Wang Mingan
Keyword(s):  
1H Nmr ◽  
13C Nmr ◽  
Nmr Spectra ◽  
Coupling Constants ◽  
The Other ◽  
Repulsive Interaction ◽  
X Ray Diffraction ◽  
X Ray ◽  
Electron Effect ◽  
Group Control

2-Phenylcyclododecanone and 2-cyclohexylcyclododecanone derivatives were synthesized and characterized by 1H NMR, 13C NMR, HR-ESI-MS and X-ray diffraction. Their preferred conformations were analyzed by the coupling constants in the 1H NMR spectra and X-ray diffraction, which showed the skeleton ring of these derivatives containing [3333]-2-one conformation, and the phenyl groups were located at the side-exo position of [3333]-2-one conformation due to the strong π-π repulsive interaction between the π- electron of benzene ring and π-electron of carbonyl group. The cyclohexyl groups were located at the corner-syn or the side-exo position of [3333]-2-one conformation depending on the hindrance of the other substituted groups. The π-π electron effect played a crucial role in efficiently controlling the preferred conformation of 2-aromatic cyclododecanone and the other 2-aromatic macrocyclic derivatives with the similar preferred square and rectangular conformations.

17O and 13C NMR spectra of some geminal diacetates

1988 ◽  
Vol 53 (3) ◽  
pp. 588-592 ◽  
Author(s):  
Antonín Lyčka ◽  
Josef Jirman ◽  
Jaroslav Holeček
Keyword(s):  
13C Nmr ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
The Other ◽  
13C Nmr Spectra ◽  
Other Hand ◽  
Carboxylic Esters ◽  
C Nmr ◽  
Oxygen Atoms

The 17O and 13C NMR spectra of eight geminal diacetates RCH(O(CO)CH3)2 derived from simple aldehydes have been measured. In contrast to the dicarboxylates R1R2E(O(CO)R3)2, where E = Si, Ge, or Sn, whose 17O NMR spectra only contain a single signal, and, on the other hand, in accordance with organic carboxylic esters, the 17O NMR spectra of the compound group studied always exhibit two well-resolved signals with the chemical shifts δ(17O) in the regions of 183-219 ppm and 369-381 ppm for the oxygen atoms in the groups C-O and C=O, respectively.

Carbon-13 and nitrogen-14 NMR spectra of 1-(substituted phenyl)pyridinium salts

1980 ◽  
Vol 45 (10) ◽  
pp. 2766-2771 ◽  
Author(s):  
Antonín Lyčka
Keyword(s):  
Heavy Water ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Coupling Constants ◽  
Pyridinium Salts ◽  
Nmr Signals ◽  
C Nmr

The 13C and 14N NMR spectra of 1M solutions of 1-(substituted phenyl)pyridinium salts (4-CH3, 4-OCH3, H, 4-Cl, 4-Br, 4-I, 3-NO2, 4-NO2, 2,4-(NO2)2 (the 13C NMR only)) have been measured in heavy water at 30 °C. The 13C and 14N chemical shifts, the 1J(CH) coupling constants, some 3J(CH) coupling constants, and values of half-widths Δ 1/2 of the 14N NMR signals are given. The 13C chemical shifts of C(4) correlate with the σ0 constants (δC(4) = (1.79 ± 0.097) σ0 + (147.67 ± 0.041)), whereas no correlation of the nitrogen chemical shifts with the σ constants has been found. The half-widths Δ 1/2 correlate with the σ0 constants (Δ 1/2 = (76.2 ± 4.9) σ0 + (106.4 ± 2.2)) except for 1-phenylpyridinium chloride.

1H, 13C and 15N NMR Spectra of Coupling Products of Benzenediazonium Salts with Aliphatic Nitro Compounds and Study of Their E/Z Isomerism

1996 ◽  
Vol 61 (4) ◽  
pp. 589-596 ◽  
Author(s):  
Antonín Lyčka
Keyword(s):  
Dimethyl Sulfoxide ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Nitro Compounds ◽  
Coupling Constants ◽  
15N Nmr ◽  
Geometrical Isomers ◽  
Sodium Salts ◽  
Aliphatic Nitro Compounds ◽  
Tautomeric Forms

The 1H, 13C and 15N NMR spectra have been measured of coupling products of benzenediazonium salts with nitromethane, nitroethane, 1-nitropropane, 2-nitroethanol and of their sodium salts, and the chemical shifts have been unambiguously assigned. The coupling products have been found to exist only in their hydrazone tautomeric forms. Stereospecific behaviour of the coupling constants 2J(15N,1H) and 2J(15N,13C) in the 15N isotopomers and NOESY have been used to differentiate between the E and Z geometrical isomers. The above-mentioned compounds exist as Z isomers in deuteriochloroform and predominantly (>95%) as E isomers in dimethyl sulfoxide, while the sodium salts are present only as E isomers in dimethyl sulfoxide.

The High Resolution NMR Spectra of Pesticides. II. The DDT-Type Compounds

1969 ◽  
Vol 52 (5) ◽  
pp. 1074-1092 ◽  
Author(s):  
L H Keith ◽  
A L Alford ◽  
A W Garrison
Keyword(s):  
Nuclear Magnetic Resonance ◽  
High Resolution ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Coupling Constants ◽  
Aromatic Rings ◽  
Nuclear Magnetic Resonance Spectra ◽  
High Resolution Nmr ◽  
Related Compounds ◽  
Deshielding Effect

Abstract The high resolution nuclear magnetic resonance spectra of the DDT class of pesticides and related compounds are discussed, including a study of the resonances of the aromatic protons as they are affected by various substiluents. The CCl3 moiety on the α-carbon strongly deshields the ortho protons on the aromatic rings, and this deshielding effect is greatly enhanced by substitution of a chlorine ortho rather than para on the aromatic ring. These deshielding effects are explained by a consideration of the electronegativity of the substituents and the stereochemistry of the molecule. The chemical shifts and coupling constants are tabulated.

scholarly journals Discrimination of brazilian red varietal wines according to their sensory descriptors

2011 ◽  
Vol 35 (6) ◽  
pp. 1172-1176 ◽  
Author(s):  
Alberto Miele ◽  
Luiz Antenor Rizzon
Keyword(s):  
Principal Component Analysis ◽  
Total Variation ◽  
Principal Component ◽  
Pinot Noir ◽  
The Other ◽  
Sensory Characteristics ◽  
Cabernet Sauvignon ◽  
Sensory Panel ◽  
Red Grape ◽  
Grape Varieties

The purpose of this paper was to establish the sensory characteristics of wines made from old and newly introduced red grape varieties. To attain this objective, 16 Brazilian red varietal wines were evaluated by a sensory panel of enologists who assessed wines according to their aroma and flavor descriptors. A 90 mm unstructured scale was used to quantify the intensity of 26 descriptors, which were analyzed by means of the Principal Component Analysis (PCA). The PCA showed that three important components represented 74.11% of the total variation. PC 1 discriminated Tempranillo, Marselan and Ruby Cabernet wines, with Tempranillo being characterized by its equilibrium, quality, harmony, persistence and body, as well as by, fruity, spicy and oaky characters. The other two varietals were defined by vegetal, oaky and salty characteristics; PC 2 discriminated Pinot Noir, Sangiovese, Cabernet Sauvignon and Arinarnoa, where Pinot Noir was characterized by its floral flavor; PC 3 discriminated only Malbec, which had weak, floral and fruity characteristics. The other varietal wines did not show important discriminating effects.

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