Acidity, xii

Mackenzie and Wood obtained low yields by this method, which is the basis of both the Muller and Wislicenus processes, and recommended instead the hydrolysis of acetophenonecyanohydrin (X) into atrolaetie acid (XI), conversion of the latter by distillation under reduced pressure into atropic acid (XII), which was then treated in ethereal solution with hydrochloric acid and the halogen in the resulting, 8-chlorohydratropie acid replaced by hydroxyl, by boiling the acid with aqueous sodium carbonate solution, giving tropic acid (XIII), thus ... 

In support of the above formulae for phosphonous acid (XII) ad phosphinic acid (XI) Professor Ingold2 kindly supplied the following note ... 

Jones and Peat23 separated methylated agar into an acidic and a neutral fraction by precipitation methods. From the hydrolyzate of the acidic fraction they isolated 2,4,6-trimethyl-D-galacto e, 2,3,4,6-tetra-methyl-D-galactose, and 3,6-anhydro-2,5-dimethyl-L-galactonic acid (XII, as the crystalline amide of m. p. 173°). The structure assignment of XII was made on the following basis. The rotation of its amide, [a]D —75.7°... 

The dried root was also found to contain purpuroxanthin (II) formed by separation of CO2. from munjistin (VII). Pseudopurpurin (XXIII) is probably decarboxylated with formation of purpurin (XXI) when the madder root is dried. The dried madder root also contains the following hydroxyanthraquinone dyes in small amounts nordamna-canthal (VI), quinizarin (IX), 1,4-dihydroxy-2-hydroxymethylanthra-quinone (XI), quinizarin-2-carboxylic acid (XII), anthragallol (XVIII), and anthragallol-3-methyl ether (XX) (32, 34, 39). 

A-Dihydroxy-2-hydroxy-methylanthraquinone (XI) Quinizarin-2-carboxylic acid (XII)... 

DiphenyI-2,5-anhydro-2,3,4-trihydroxyvaIeric acid (XII) CnHlfiOfi 111-117 201.7 17 EtOH 34... 

Further oxidation of the aldonic acids results in the formation of either 2-keto or 5-keto aldonic acids (XII and XIII). After this step, degradation of the carbon chain apparently occurs. This degradation also occurs normally vdth ketoses (IV), a trihydroxybutyric acid (XVIII) being the main degradation product. 

The oxidation of uronic acids (VIII) leads to the formation of saccharic acids (XIV) mild conditions are necessary to avoid damaging the sensitive uronic acid grouping. In a similar manner, osones (VII) may be converted to 2-keto aldonic acids (XII). 

The synthetic potentiality of the Kolbe dimerization has been well documented for a variety of symmetrical target molecules. For example, the dimerization of acids (XII and XIII) is the key step of the pentacyclosqualene [55] and o -onocerin [56] syntheses. A large-scale production of sebasic acid has been realized by the Kolbe dimerization of methyl adipate half-ester [57]. 

It is interesting that when the functional groups are not directly attached to the aromatic ring, orientation cannot be predicted from a consideration of the point of highest electron density. Cinnamic acid (XII),7 w-nitrostyrene (XIII),8 and 2-phenylethenesulfonyl chloride (XIV),9 all orient predominantly ortho-para, although we should expect these positions to be electronically deficient. 

Egloff, G. Davis, R.F. Polymerization of monoolefins with solid phosphoric acid, XII International Congress of Pure and Applied Chemistry, New York, 1951 10-13. 

Masui and Staple [126] and Gustafsson [127] isolated labeled varanic acid (3a,7 ,12a,24-tetrahydroxy-5 -cholestan-26-oic acid) (XII) after incubation of [ H]3 ,7 ,12a-trihydroxy-5j8-cholestan-26-oic acid with rat liver preparations. This acid is converted to cholic acid in rat and human in vivo [126,128] as well as in rat... 

Chimaerol, S S-bufol, 5j8-cyprinol, and scymnol are the 24-, 25-, and 27-hy-droxylated, and 24,27-dihydroxylated derivatives of 27-deoxy-5j8-cyprinol (IX), respectively. It is possible that these naturally occurring bile alcohols could be intermediates in alternative pathways for the formation of choUc acid (XIV) from 27-deoxy-5)8-cyprinol (IX). To test this possibility, these cholestanepolyols were labeled with tritium and given to guinea pigs or rats with a biliary fistula [133-136]. Of the tested bile alcohols, 5)3-chimaerol and 5 -cyprinol were converted efficiently to cholic acid [135,136]. However, these results do not provide conclusive evidence for alternative pathways of cholic acid formation since the conversion of these bile alcohols to cholic acid may merely reflect a lack of specificity of the enzyme systems involved in the conversion of 27-deoxy-5/8-cyprinol (IX) to cholic acid (XIV) via trihydroxy-5)3-cholestanoic acid (XII). 

It has been claimed that 2,3,5-trihydroxybenzoic acid X) and its triacyl derivatives possess antihyaluronidase and anti-arthritic activities , but later work by the same authors suggests that they are inactive as analgesic or anti-arthritic drugs . 2,3,4-Trihydroxybenzoic acid XI) is inactive at 200 mg/kg subcutaneously and 3,4,5-trihydroxybenzoic acid XII) is active at a subcutaneous dose of 118 mg/kg in a mouse vascular permeability test . 

FIGURE XVII.F-3 Theoretical conversion of glutamic acid XII to aminobutanoic acids XIII, XIV and aminopyridines XV-XVII. ... 

---