Hydroxyl group, analysis

In this work the products from the thermal dissolution of subbitu-minous Kaiparowitz coal at 427 C in tetralin are examined by spectroscopic ( C, H, NMR), molecular weight (GPC and vapor pressure osmometry (VPO)), and elemental and hydroxyl group analysis. Some of the data presented here are a refinement and extension of data presented in part in earlier work (5). The use of 1,1-dideuterotetralin (5) in con junction with NMR to monitor the time dependence of introduction of deuterium into aliphatic and aromatic structures is presented along with the structural distributions of deuterium transferred. 

Analysis Using the branch-point, in the largest side chain as a guide, we can put in a hydroxyl group (as in frame 72). 

Analysis There is a series of 1,2 relationships here ifs easiest to start with the free hydroxyl group ... 

Analysis We must put in a hydroxyl group instead of a double bond and the best place to do this is, as usual, at the branch point ... 

Although acetyl chloride is a convenient reagent for deterrnination of hydroxyl groups, spectroscopic methods have largely replaced this appHcation in organic chemical analysis. Acetyl chloride does form derivatives of phenols, uncompHcated by the presence of strong acid catalysts, however, and it finds some use in acetylating primary and secondary amines. 

Functional Group Analysis. The total hydroxyl content of lignin is determined by acetylation with an acetic anhydride—pyridine reagent followed by saponification of the acetate, and followed by titration of the resulting acetic acid with a standard 0.05 W sodium hydroxide solution. Either the Kuhn-Roth (35) or the modified Bethge-Liadstrom (36) procedure may be used to determine the total hydroxyl content. The aUphatic hydroxyl content is determined by the difference between the total and phenoHc hydroxyl contents. 

Hydroxyl number and molecular weight are normally determined by end-group analysis, by titration with acetic, phthaUc, or pyromellitic anhydride (264). Eor lower molecular weights (higher hydroxyl numbers), E- and C-nmr methods have been developed (265). Molecular weight deterrninations based on coUigative properties, eg, vapor-phase osmometry, or on molecular size, eg, size exclusion chromatography, are less useful because they do not measure the hydroxyl content. 

The other analytical methods necessary to control the typical specification given in Table 5 are, for the most part, common quality-control procedures. When a chemical analysis for purity is desired, acetylation or phthalation procedures are commonly employed. In these cases, the alcohol reacts with a measured volume of either acetic or phthalic anhydride in pyridine solution. The loss in titratable acidity in the anhydride solution is a direct measure of the hydroxyl groups reacting in the sample. These procedures are generally free from interference by other functional groups, but both are affected adversely by the presence of excessive water, as this depletes the anhydride reagent strength to a level below that necessary to ensure complete reaction with the alcohol. Both procedures can be adapted to a semimicro- or even microscale deterrnination. 

Alkalinity An expression of the total basic anions (hydroxyl groups) present in a solution. It also represents, particularly in water analysis, the bicarbonate, carbonate, and occasionally, the borate, silicate, and phosphate salts which will react with water to produce the hydroxyl groups. 

Cevanthrol, C jH gO, crystallises from benzene in plates, m.p. 197-8°, behaves as a phenol and gives an acetyl derivative, m.p. 138-9°. X-ray analysis (Bloxmt and Crowfoot indicates that it is a phenanthrene derivative, with a hydroxyl group, possibly at C . 

We now tum our attention to the C21-C28 fragment 158. Our retrosynthetic analysis of 158 (see Scheme 42) identifies an expedient synthetic pathway that features the union of two chiral pool derived building blocks (161+162) through an Evans asymmetric aldol reaction. Aldehyde 162, the projected electrophile for the aldol reaction, can be crafted in enantiomerically pure form from commercially available 1,3,4,6-di-O-benzylidene-D-mannitol (183) (see Scheme 45). As anticipated, the two free hydroxyls in the latter substance are methylated smoothly upon exposure to several equivalents each of sodium hydride and methyl iodide. Tetraol 184 can then be revealed after hydrogenolysis of both benzylidene acetals. With four free hydroxyl groups, compound 184 could conceivably present differentiation problems nevertheless, it is possible to selectively protect the two primary hydroxyl groups in 184 in... 

We reacted 2 first with bromine in chloroform at 10 C. iH NMR studies have revealed that the reaction mixture was very complex and consisted of six products. This mixture was submitted to silica gel column chromatography. Careful repeated chromatography followed by fractional crystallization allowed us to isolate ten products (Scheme 3). IR analysis indicated that a hydroxyl group was incorporated in compounds lfi-19. Therefore, we assume that these products have been formed by partial hydrolysis of compounds lfl-14. Structural determination of compounds lfl-19 revealed that the barrelene skeleton was rearranged completely. 

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