Chloroform solvent shifts 118

Using the data shown in Table 3.4, a linear plot of 13C versus 1H solvent shifts is obtained [92], Moreover, 13C solvent shifts correlate linearly with the one-bond carbon-13-proton coupling constants [92]. This is attributed to changes in the average distance of bonding electrons in the C — H bond of chloroform due to intermolecular association [92], Since much smaller solvent shifts of the carbon tetrachloride 13C resonance are found [92], interactions between chlorine and the solvent can be disregarded. Thus,... 

It is important that the occurrence of aromatic solvent shifts be recognised as the magnitude of the shifts induced in polar molecules can be large, e.g. the resonance of chloroform moves upfield 1.5 ppm when... 

Q to 35 transitions with Intensities above 0.05 could be assigned In each spectrum. Table IV shows the concentration gradients of h shifts In I for (a] chloroform-d and (b] carbon disulphide, together with shifts at Infinite dilution. Vhen the solvent shifts from carbon disulphide to chloroform, which are In the sequence H [4) CLl) (1) tZ) C3), are treated In L15CA as If they emanated From a point dipole, there 1s a suggestion of a weak dipolar complex or cluster of chloroform... 

The UV spectrum of 5-phenyl-3 hydroxythiophene is very similar to that of its methyl ether in alcoholic solution, indicating that it exists largely in the enol form in this solvent. The same coincidence of the wavelength maxima was also obtained for 5-phenyl-2-hydroxy-thiophene and its methyl ether. In chloroform solution, the maxima were shifted toward longer wavelengths, suggesting that the tautomeric equilibrium in this solvent is displaced more toward the keto form. ... 

There have been very few examples of PTV derivatives substituted at the vinylene position. One example poly(2,5-thienylene-1,2-dimethoxy-ethenylene) 102 has been documented by Geise and co-workers and its synthesis is outlined in Scheme 1-32 [133]. Thiophene-2,5-dicarboxaldehyde 99 is polymerized using a benzoin condensation the polyacyloin precursor 100 was treated with base to obtain polydianion 101. Subsequent treatment with dimethyl sulfate affords 102, which is soluble in solvents such as chloroform, methanol, and DMF. The molar mass of the polymer obtained is rather low (M = 1010) and its band gap ( ,.=2.13 eV) is substantially blue-shifted relative to PTV itself. Despite the low effective conjugation, the material is reasonably conductive when doped with l2 (cr=0.4 S cm 1). 

Poly[2,5-dialkoxy-l,4-phenylene) vinylenejs with long solubilizing alkoxy chains dissolve in conventional organic solvents such as chloroform, toluene, or tetrahydrofuran [21, 28, 32-36]. Their emission and absorption spectra are red-shifted relative to PPV itself, and the polymers fluorescence and electroluminescence quantum yields are greater than parent PPV. This benefit may be a consequence of the long alkyl chains isolating the polymer chains from each other. 

The extinction coefficients of carotenoids have been listed completely bnt solvent effects can shift the absorption patterns. If a colorant molecnle is transferred into a more polar environment, then the absorption will be snbjected to a bathochro-mic (red) shift. If the colorant molecnle is transferred into a more apolar enviromnent, the absorption will be subjected to a hypsochromic (blue) shift. If a carotenoid molecule is transferred from a hexane or ethanol solution into a chloroform solution, the bathochromic shift will be 10 to 20 nm. 

If one of the species is anionic and we need to transport it to the organic phase, then a phase-transfer catalyst may be employed. Consider the example of benzyl penicillin where the reaction between phenyl acetic acid and the penicillin carboxylate ion, with penicillin amidase as a catalyst, is relevant, and which at pH 4.5 - 5.0 is shifted in the desired direction. Here a catalyst like tetrabutylammonium halide works, and with chloroform as a solvent 60% yield can be realized in contrast to a yield of only 5 - 10 % in water. 

A phenomenological study was performed to determine the effect of solvent on Sn NMR spectra of these organoraetallic polymers. Samples were dissolved in chloroform, benzene, n-hexane, acetone, tetrahydrofuran, methanol, and pyridine. The Sn NMR spectra in these solvents are given in Figure 1. The appearance and location of the H Sn resonance changes drastically over the range of selected solvents. The chemical shift moves upfield in the order chloroform, benzene, n-hexane, acetone, tetrahydrofuran, pyridine, and methanol. The amount of structural information and, conversely, the broadening of the resonance increases in the same order with methanol and pyridine reversed. 

In donating solvents the subtle effects determining the chemical shift in chloroform, benzene, and hexane are apparently masked. In hexane, which is considered a poor solvent, self-association is possible and would explain the appearance of the Sn spectrum. Chloroform and benzene are excellent solvents for organometallic polymers, and the structure and downfield position support a well-solvated, unassociated environment. 

The divalent Co(salen) complex (69a) is one of the most versatile and well-studied Co coordination compounds. It has a long and well-documented history and we shall not restate this here. Recent applications of (69a) as both a synthetic oxygen carrier and as a catalyst for organic transformations are described in Sections 6.1.3.1.2 and 6.1.4.1 respectively. Isotropic shifts in the HNMR spectrum of low-spin Co(salphn) (69b) were investigated in deuterated chloroform, DMF, DMSO, and pyridine.319 Solvent-dependent isotropic shifts indicate that the single unpaired electron, delocalized over the tetradentate 7r-electron system in CHCI3, is an intrinsic property of the planar four-coordinate complex. The high-spin/low-spin equilibrium of the... 

Of course, you don t have to use either of the above standards at all. In the case of samples run in deutero chloroform/methanol and dimethyl sulfoxide, it is perfectly acceptable, and arguably preferable, to reference your spectra to the residual solvent signal (e.g., CD2HOH) which is unavoidable and always present in your spectrum (see Table 2.2). These signals are perfectly solid in terms of their shifts (in pure solvent systems) though the same cannot be said for the residual HOD signal in D2O and for this reason, we would advise adhering to TSP for all samples run in D20. 

Similar measurements and analysis have been carried out for the red solution. In this case the concentration of polymer in the chloroform-hexane solvent is limited to less than 4 x 10 r.u./cm. Therefore, the errors for y t and Y"t are larger than in the case of the yellow solution. In addition, the absorption band of the red solution is shifted to the red with respect to that of the yellow solution. Therefore, 2(i)j can only be extended up to 32 000 cm l. 

In the more polar solvent, chloroform, linear Arrhenius correlations were observed for the rearrangements of both 10a and 10b from —55 to 60°C. Arrhenius parameters were a = 3.6 kcal/mol and log A = 10.4 s-1 for 10a, and Ea = 4.05 kcal/mol and log A = 10.3 s 1 for 10b.66 These results accord with the idea that polar solvents stabilize the polar 1,2-H shift, hydride-like transition state (51), accelerating this reaction at the expense of potential competitors.4,22... 

Convincing evidence was found that the majority of acyclic aldo-nitrones exist in the Z-form, by investigating the ASIS-effect (aromatic solvent induced shift effect) (399). However, in some cases, specified by structural factors and solvent, the presence of both isomers has been revealed. Thus, in C -acyl-nitrones the existence of Z -and -isomers was detected. Their ratio appears to be heavily dependant on the solvent polar solvents stabilize Z-isomers and nonpolar, E-isomers (399). A similar situation was observed in a- methoxy-A-tert-butylnitrones. In acetone, the more polar Z-isomer was observed, whereas in chloroform, the less polar E-isomer prevailed. The isomer assignments were made on the basis of the Nuclear Overhauser Effect (NOE) (398). /Z-Isomerization of acylnitrones can occur upon treatment with Lewis acids, such as, MgBr2 (397). Another reason for isomerization is free rotation with respect to the C-N bond in adduct (218) resulting from the reversible addition of MeOH to the C=N bond (Scheme 2.74). The increase of the electron acceptor character of the substituent contributes to the process (135). 

Streck and coworkers showed that in a range of solvents, the 13C carbonyl shifts in dialkyl ketones were affected similarly by branching at the a-position.127 In chloroform, the carbonyls of di-tert-butylketone and diisopropylketone were 11-12 ppm downfield of that of acetone, which they attributed to a mixture of inductive and steric effects. With tertiary systems, particularly in dipolar solvents, hindrance to solvent stabilisation of the polar, basic form of the carbonyl offsets the inductive stabilisation of the branched alkyl. 13C NMR data presented here support this. 

---