Negative cotton effect

The 260 nm band of chiral thiiranes is optically active and a Cotton effect is observed R) (+)-methylthiirane shows a negative Cotton effect at ca. 250 nm followed by a positive effect below 200 nm. An MO analysis indicates that charge transfer contributions are most important in determining the optical activity of the transition (81JCS(F2)503). The... 

Circular Dichroism. - The absolute configuration of the ot-hydr oxyphosphonat e (49) was established through its negative Cotton effect at 215 nm.144... 

Figure 2 Comparison of positive and negative Cotton effects.

In contrast, the CD spectra of 50, 51, and 52 exhibit negative Cotton effects, as shown in Figure 4.36 for 50. This implies a helical conformation, but of the opposite preferential screw sense to 48 and 49, even though the enantiopure chiral moiety in all cases is the (5 )-2-methylbutyl group. Similarly, the Cotton effect is of greatest magnitude (negative) at low temperature and almost very much reduced at 80°C. 

From the positive Cotton effect observed in the amylose case and the negative Cotton effect in the SPG case, it is clear that the oligosilane adopts opposite screw sense helical conformations in the two cases.337 It now appears possible to associate an d/-screw sense helix with a positive sign Cotton effect (and vice versa), although other experimental confirmations of this are desirable. 

The UV and CD spectra of 117 and 121 (V) are shown in Figure 48. Considering 117, at —40°C a negative Cotton effect, coincident with the UV absorption, is evident, and at —5 °C a positive Cotton effect, coincident with the UV absorption (both of which are slightly red-shifted with respect to the —40°C profiles), is observed. It is thus apparent that 117 underwent a helix-helix transition at some temperature between —5 and —40°C. In contrast, the Cotton effects of 121(V) were positive at all temperatures, indicating that no helix-helix transition occurred. Similarly to 121, 88 did not undergo a helix-helix transition. These results are due to the different stiffness of the molecules, which is quantified by the viscosity index, a. 

Methyl alkyl sulfoxides that do not contain other strongly perturbing groups have negative Cotton effects centered at the strong absorption band near 200 nm and have the (i > configuration. 

Figure 4 shows CD spectra of (a) the DNA-lipid complex in organic solution containing a small amount of water (CHCl3/Et0H/Fl20 =4 1 0.07, 790 mM of H2O), and (b) native DNA in an aqueous buffer solution (20 mM NaCl, 10 mM Tris, pH 7.8). The DNA-lipid complex shows a positive Cotton effect at 270 nm and a negative Cotton effect at 245 nm similar to native DNA in aqueous solution, which indicates the B-form structure for the DNA strands [11]. Thus, the DNA-lipid complex forms a double helical B-form... 

The structure of 58 was elucidated as 1-hydroxy-2-oxoeremophil-1(10),7(1 l),8(9)-trien-12(8)-olide. This proposal was corroborated by an X-ray analysis. Finally, the absolute configuration of compound 58 was proposed as depicted on the basis of the CD spectrum which displayed a strong negative Cotton effect on 378 nm. Furthermore, as (-) ligu-larenoHde, whose absolute stereochemistry was determined by chemical correlation, compound 58 possesses a negative optical rotation. 

On the other hand, Iransoid geometry of the / , -unsaturated ketone [Figure 6 (b)] may either lead to a positive or to a negative Cotton effect the sign and magnitude of the Cotton effect depends on the cosine of the angle between the C = 0 and C = C bonds46. 

Exciton coupling between the two styryl chromophores in each of the conformers (A)-(C) leads to a negative Cotton effect at around 270 nm, as shown by theoretical analysis using the 71-electron SCF Cl dipole velocity MO method. Therefore, the tram-2,.1-disubstituted spirocyclo-propane-1,9 -fluorene derivative 6, from which the distyryl derivative was obtained, must have accordingly the 2S3S absolute configuration122. 

A difference CD method can be used to determine the absolute configuration of the allylic position in polyols. The difference CD spectrum between the allylic tetrabenzoate 12 and saturated tetrabenzoate 13 displays a negative Cotton effect, Ae —4.9 (224 nm), thus establishing R configuration of the allylic carbon atom (Figure 18)154. 

The chirality of [2.2]paracyclophane derivatives has been deduced as being (—)(R) on the basis of the exciton theory of coupled oscillators 67) and confirmed by experimental results (see 2.9.1 and 2.9.3). In these compounds a negative Cotton effect at 270 nm (corresponding to the p-band) seems to be specific for the (R)-chirality 54). 

The absolute stereochemistry of broussonetine L (8) was determined by the combination of the benzoate chirality method and the Mosher s method [35-37]. A carbamate (8a) was prepared from broussonetine F (4) by reaction with phenyl chloroformate in tetrahydrofuran-H20 (7 3), and a diacetate (8b) was prepared from 8a with acetic anhydride in pyridine. Finally, a dibenzoate (8c) was obtained by benzoylation of 8b. The CD curve of 8c showed a negative Cotton effect (Ae237 -30.9) and a positive effect (Ae223 +15.9) to confirm a counter-clockwise chirality between two benzoyl groups, Fig. (3) [20]. 

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