Quaternary carbons values

The GASPE spectrum of podophyllotoxin is shown. The signals at 8 56.0,108.6, and 152.0 each represent two carbons in identical magnetic environments, while the signal at 8 147.6 also represents two carbons that accidentally appear at the same chemical shift. Assign chemical shift values to various protonated and quaternary carbons in the structure. 

The GASPE spectrum of vasicinone is shown. The peak at 8 126.5 is a cluster of three peaks at 8 126.3 and 126.7 representing methine carbons. Similarly, the signal at 8 160 on the positive phase of the spectrum represents two close singlets at 8 160.4 and 160.5. Predict the chemical shift values of various protonated and quaternary carbons in the structure. 

The study of Fuji et al. shows that the addition of lithium enolate 75 to ni-troamine 74 is readily reversible quenching conditions are thus essential for getting a good yield of product 76. An equilibrium mixture of the adducts exists in the reaction mixture, and the elimination of either the prolinol or lactone moiety can take place depending on the workup condition (Scheme 2-34). A feature of this asymmetric synthesis is the direct one pot formation of the enantiomer with a high ee value. One application of this reaction is the asymmetric synthesis of a key intermediate for indole type Aspidosperma and Hun-teria alkaloids.68 Fuji69 has reviewed the asymmetric creation of quaternary carbon atoms. 

Figure 9 exhibits the 13C NMR spectra of 50 and 52. The monomer has acetylenic carbon peaks at 70 and 82 ppm, but 52 does not show these peaks. Instead, the olefinic carbon peaks of the 52 backbone appear at 123 and 141 ppm, although the value for the quaternary carbon is very weak. The peak of the methylene carbon adjacent to the polymer backbone is shifted from 20 to 43 ppm on polymerization. 

However, symmetry considerations cannot be the sole determinants in such cases. If we return to the substituted adamantane and replace all its methylene groups by identical (CHj), bridges of sufficient lengths to allow a permutation at one quaternary carbon without disturbing the others, a single descriptor can no longer be used. Thus one must further question the validity of the idea of die unoccupied center if its existence depends on the value of n. 

C-21 methyl protons. The C-3 and C-16 melhine protons appeared at 8 3.82 and 4.99, respectively. The downfield chemical shift values of C-3 and C-6 methine protons were indicative of the presence of geminal oxygen functionahties. The C-6 resonated at 8 5.36 while the sp hybridized C-28 methylene protons resonated as two singlets, integrating for one proton each, at 8 5.56 and 6.06. A combination of H and C-NMR spectral data indicated to us that compound 11 has a steroidal skeleton. A detailed interpretation of broad C-NMR and DEPT spectra revealed the presence of three metlyl, ten methylene, eight methine and five quaternary carbon atoms in 11. The stereochemistry at various chiral centers was estabhshed with the aid of NOESY spectrum. 

In the case of alkanes with tertiary or quaternary carbon atoms the characteristic decomposition mode is usually the fragment alkane elimination (Sec. 2.6) and its yield can be used to estimate G(S i) values. Based on the fragment alkane elimination yield Pitchuozhkin et al. [162] calculated a singlet G value of 3.3 1 for 2,2,4-trimethylpentane. 

A simple method for estimating enthalpies of vaporization is the CHLP protocol . The quantities and req in equation 1 refer respectively to the number of quaternary carbon atoms and non-quaternary carbon atoms in the compound, and is a value that is characteristic of the functional group bonded to the hydrocarbon parent. 

The study of the stereoregularity of the polymers prepared, provides also Information about the stereoregulating mechanism. The probability of formation of the different types of sequences, was determined on the basis of the resonance of the quaternary carbon of pVP (12). The NMR spectrum performed at 15 MHz allows one to determine the concentration of triads. The values summarized In Table 4 do not agree with those expected for bernoullllan statistics. Hence, more than the last unit of the living chain Is Involved In the process. In order to obtain more precise Information about the process, It is necessary to measure the probability of formation of pentads. Such measurements are possible with spectra performed at 63 MHz (Figure 18). In spite... 

Empirically determined chemical shift additivity parameters have been determined- for diene-type polymers. The shift contribution of a quaternary carbon which is fllto the carbon in question was not determined by those authors. However, using their additivity parameters and the shift positions of the ( carbons in Figure 8, a value of +15.4 ppm can be estimated for the contribution of a neighboring (0() quaternary carbon. Using this value, the shift positions of the carbons in structures VII and VIII are calculated as shown. If the first 1,2 unit were on the chain in a 2,1 manner, the methylene carbon resonance would be at a considerably higher field, but it would be difficult to estimate its position with any certainty because the quaternary effect... 

The J-MODulated (JMOD) C experiment, also known as Attached Proton Test (APT) was the first and simplest way to determine "C multiplicities. In contrast to DEPT no polarization transfer is included in the pulse sequence (Fig. 3.16) and as a consequence the signals of quaternary carbons are visible in the spectrum, but the sequence is far less sensitive than DEPT or INEPT. The value of D2 is used to differentiate between the different carbon multiplicities. The signal intensities of quaternary carbons are not influenced by the value of D2 for D2 equal to 1 CH and CH, groups have maximum negative intensity and CHj has maximum positive intensity. For D2 equal to 1 /C2 J, ) only the signals of quaternary carbons are visible. 

Although there is some disagreement in the calculated and observed values for C and C2, the values calculated for C3 and C4 are quite close to those observed. Off-resonance coupling experiments (Fig. 14) confirm the assignments. The peak assigned to Ct and C2 appears as a triplet, indicative of methylene carbon. The peak at 32.07 remains a singlet indicating a quaternary carbon, C3, and the peak at 27.56 appears as a quartet expected from a methyl carbon. 

The assignments of the purine resonances [460, 749, 751, 758, 759, 761] of proton broadband-decoupled 13C NMR spectra of nucleosides and nucleotides are made using the following aids [749, 761] Correlation with the signals of the parent bases and analogous nucleosides or nucleotides comparison of the 13C NMR spectrum with that of a specifically analogue correlations of the chemical shift values with the 7r-electron densities [749, 761] and, in addition, proton off-resonance decoupling, which affords the identification of quaternary carbon atoms. 

Multinuclear NMR data for homologous senes of fluoromethylated malo-nates [72] and trimethylsilanes [97] are compiled in Table 11. In both senes, fluoromethyl attachment is to a quaternary site These compounds are readily synthesized using fluorohalomethanes to incorporate the final fluoromethyl moiety All the malonates, except diethyl methyltnfluoromethylmalonate (4) [93], are isopropyl-substituted diethyl esters [72]. The silane data, with the exception of trimethyltrifluoromethylsilane (5) [95], are from reference 97 Chemical shift data are very comparable, with the malonates having higher proton and fluorine chemical shifts but slightly lower carbon values. The magnitudes of cf and 2J jp coupling are similar for both sets of compounds. 

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