Cellulose Trityl EtherThe trityl (triphenylmethyl) ether of cellulose has been mentioned several times in the literature, Its original preparation, by Helferich and Koesterlb in 1924, gave a product which by carbon and hydrogen analysis and by weight of trityl chloride recovered on hydrolysis contained about one trityl group for each glucose unit. They stated that the substituted groups would appear to be on the 6 position but that this had not been proved and served only as a working explanation.Sakurada and Kitabatake* 2 followed Helferich's procedure and stated without further proof that the product was 6-monotritylcellulose. In 1937Schorygin and co-workers3 prepared trityl cellulose and attempted to xanthate, methylate and acetylate it without much success. They then tritylated a dimethyl cellulose and a cellulose diacetate and in the latter case stated arbitrarily that only the primary groups were tritylated.

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The adduct from dimethyl acetylenedicarboxylate and 4,4'-dimethylhydrazobenzene yielded no indole derivative under the conditions of the Diels-Reese reaction but did give, by heating in a-picoline, 2-hydroxy-3-(p-toluino)-4-carbometh~x~-~-methylquinoline.The adduct from dimethyl acetylenedlcarboxylate and 4,4'-dichlorohydrazobenzene gave both dimethyl 5-chloroindole-2,3-dicarboxylate and Z-hydroxy-3-(P~h~orani~ino)-4-carbomethoxy-6-chloroquinoline under suitable conditions. The latter was degraded t o 2,3-dihydroxy-6-chloroquinoline. The adduct from dimethyl acetylenedicarboxylate and 4-acetoxyhydrazobenzene did not yield any indole derivative but did produce, by heating in a-picoline, 2-hydroxy-3-anilino-4-carbomethoxy-6-acetoxyqu~nol~ne. The latter was degraded t o the hitherto unknown 2,3,6-trihydroxyquinoline which was also prepared by an independent synthesis.The latter was degraded t o 2,3-dihydroxy-6-methylquinoline.Diels and Reese3 found that dimethyl acetylenedicarboxylate and hydrazobenzene react in warm methanol to form a 1: 1 adduct which could be transformed under suitable conditions to three types of heterocyclic compounds. In glacial acetic acid, the adduct yielded 1,2-diphenyl-3-carbomethoxy-5-pyrazolone (111), in xylene it gave dimethyl indole-2,3-dicarboxylate (IV, R = R1 = H) while in pyridine it afforded 2-hydroxy-3-anilino-4-carbomethoxyquinoline (V, R = R' = H). V (R = R' = H) was degraded4 to 2,3-dihydroquinoline (VII, R = R1 = H) by decarboxylation of the derived acid (VI, R = R1 = H) followed by hydrolysis of the anilino group.We have completely substantiated this remarkable series of reactions reported by Diels and Reese and have now extended the above reactions to three substituted hydrazobenzenes. The formation of the corresponding pyrazolones, however, has not been studied since they are readily prepared by simpler procedures. The hydrazobenzenes used were the 4,4'-dimethyl-, the 4,4'-dichloro-and the 4-acetoxy-. All formed adducts readily with dimethyl acetylenedicarboxylate in good yield.The adduct from 4,4'-dimethylhydrazobenzene when heated in a-picoline gave the expected 2-hydroxy -3 -( p -to1uino)-4 -carbomethoxy-6-methylquinoline (V, R = R1 = CH,) which on saponification gave the free acid (VI, R = R1 = CH3). VI (R = R' = CH3) on hydrolysis and decarboxylation produced 2,3-dihydroxy-6-methylquinoline (VII, R = CH3). This same adduct when heated in xylene did not give the corresponding indole, however, but only the quinoline derivative listed above V (R = R 1 = CH3).The adduct from 4,4'-dichlorohydrazobenzene gave the expected products. In a-picoline, it yielded 2-hydroxy-3-(p-chloroanilino) -4-carbomethoxy-6-chloroquinoline (V, R = R' = Cl) which was saponified to the free acid (VI, R = R' = Cl), which, in turn, was hydrolyzed and decarboxylated with hydriodic acid (neither hydrochloric nor hydrobromic acids were effective) to the corresponding 2,3-dihydroxy-6-chloroquinoline (VII, R = Cl). The adduct readily gave dimethyl 5-chloroindole-2,3-dicarboxylate (IV, R = C1) when heat...

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