Methine carbon hydroxylation

Carbon-13 NMR spectra. A carbon-13 NMR spectrum of HTE polymer (Rn S 500) is shown in Figure 3. The carbon-13 NMR spectra of HTE polymers show the carbon chemical shifts at 79.3 and 72.7 ppm for the backbone and the terminal methine carbons respectively, at 43.9 and 46.2 ppm for the backbone and the terminal chloromethyl carbons, respectively, and in the range of 69.7-72.0 ppm as a multiplet for the methylene carbon. It is a characteristic feature of hydroxyl-terminated polyethers that the terminal carbon exhibits a up-field shift due to the substituent effect of the hydroxyl group, whereas the (0 carbon(s) to the terminal hydroxyl group exhibits a down-field shift (Table III). The terminal methine carbon also suggests that the hydroxyl groups are predominantly secondary. 

Carbohydrate Methine proton Hydroxyl proton Carbon Oxygen... 

Chemically, the triarylmethane dyes are monomethine dyes with three terminal aryl systems of wind] one or more arc substituted with primary, secondary, or tertiary amino groups or hydroxyl groups in the para position to the methine carbon atom. Additional substituents such as carboxyl, sulfonic acid, halogen, alkyl, and alkoxy groups may be present on the aromatic rings. The number, nature, and position of these substituents determine both the hue or color of the dye and the application class to which the dye belongs. 

Triptohypol F (18) showed the presence of one double bond, two methine carbons attached to an oxygen function and one methoxy group, according to the 13C NMR spectrum. From these data and its H NMR and MS spectra, it was assumed to be an oleanane-type triterpene. The location of the double bond and the hydroxyl and methoxy groups were determined by a HMBC experiment. The stereochemistry of the hydroxyl and methoxy groups were determined by a NOESY spectrum. According to these data the structure of (18) was established as showed above. 

The NMR spectra of ethers (72)-(75) contain signals characteristic of the parent compounds. COSY experiments established that in (73)-(75) the methine protons of the ether function resonated at 8 3.23 for H(10) and 3.43 for H(9 ) the signal of proton H(IO ), on the hydroxyl-bearing carbon, appeared at 83.49 and the signal of proton H(9), attached to the ester-bearing carbon, was at 8 5.02. In structure (72), the protons were assigned on the basis of spectral comparisons with the diacetate derivative protons H(9) and H(IO ) on hydroxyl bearing carbons resonated at 8 3.57, whereas those attached to the carbons of the ether function, H(10) and H(9 ) were found at 8 3.32. The C-NMR spectra of (73)-(75)... 

Stereoselective hydroxylation at methine carbons in other than chiral substrates has rarely been reported, but the hydroxylation of tiie racemic lactone 7 (Fig. 8) at C-5 by Fusarium culmorum may be a reaction of this type. Transformation of ( )-7 proceeds with a low degree of selectivity for the (+) 1(5),5(R) substrate, but the extent to which is this due to the formation of the major product 8 (Fig. 8), rather than hydroxylation at C-5, is not clear,... 

The H NMR spectram (CDClj, 500 MHz) of 12 showed two singlets (8 0.83 and 8 0.95), each integrating for three protons due to the C-18 and C-19 methyl protons. Three 3H doublets at 8 0.78 (J= 6.5 Hz), 8 0.79 (J= 6.5 Hz) and 8 0.85 (J = 7.0 Hz) were due to the secondary C-26, C-27 and C-21 methyl protons, respechvely. The C-3 methine proton resonated as a one-proton double doublet at 8 3.63 (JJ= 10.5 Hz and J2= 3.5 Hz) and its downfield chemical shift value was indicative of the presence of a geminal hydroxyl funchonality. A one-proton mulhplet at 8 5.21 was ascribed to the C-6 olefinic proton. The C-28 exocyclic methylene protons appeared as two broad singlets at 8 5.40 and 5.58. The C-NMR spectram (CDCl, 125 MHz) showed the resonance of all 28 carbon atoms. The combination of H and C-NMR data suggested that compound 12 has a sterol like structure as most of the H and C-NMR chemical shift values of 12 were similar to those of sterols reported in the literature [19, 20]. The H and C-NMR chemical shift values were assigned with the aid of COSY-45 , HSQC and HMBC spectral data. Compound 12 was found to have modest inhibitory activity against C. xerosis and S. aureus with minimal inhibitory concentration values of 82.35 and 146 pg/ml, respectively. 

Typically, substitution reactions occur by attack of a nucleophilic reagent on a benzyl carbon present in the form of a carbonium ion or a methine group in a quinonemethide structure. Several representative substitution reactions are illustrated in Fig. 1.5. At moderate temperatures ( 100°C) and under mildly alkaline conditions, benzylic hydroxyl groups in phenolic units are converted to thiols by reaction with bisulfide (Q, Fig. 1.5). At higher temperatures and alkalinities, e.g., under kraft pulping conditions, the mercaptide group undergoes a series of transformations in which the sulfur is ultimately eliminated. 

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