孙存济, 嵇汝运. 带有羧基侧链的苯(月弟)酸的合成J. 药学学报, 1960, 8(4): 166-170.
引用本文: 孙存济, 嵇汝运. 带有羧基侧链的苯(月弟)酸的合成J. 药学学报, 1960, 8(4): 166-170.
SUN TSUN-TSI KYI ZU-YOONG, . THE PREPARATION OF PHENYLSTIBONIC ACIDS CARRYING CARBOXY-SUBSTITUTED SIDE CHAINSJ. Acta Pharmaceutica Sinica, 1960, 8(4): 166-170.
Citation: SUN TSUN-TSI KYI ZU-YOONG, . THE PREPARATION OF PHENYLSTIBONIC ACIDS CARRYING CARBOXY-SUBSTITUTED SIDE CHAINSJ. Acta Pharmaceutica Sinica, 1960, 8(4): 166-170.

带有羧基侧链的苯(月弟)酸的合成

THE PREPARATION OF PHENYLSTIBONIC ACIDS CARRYING CARBOXY-SUBSTITUTED SIDE CHAINS

  • 摘要: 对羧甲基、对羧乙基、对羧甲氧基及4-羧基-3-羟基苯胺与亚硝酸重氮化,再与三氯化锑生成复盐,然后脱氮分解,形成相应苯(月弟)酸.这些(月弟)酸与呲啶及浓盐酸作用,便成吡啶复盐.复盐如溶于稀盐酸中,再加入浓盐酸盐析,水解便成精制(月弟)酸.吡啶复盐倘在盐酸及乙醇混合剂中重结晶,再在中性液中水解,便生成对乙氧羰甲基、对乙氧羰乙基、对乙氧羰甲氧基苯(月弟)酸.对甲氧羰基苯(月弟)酸与水合肼作用,酯键肼解而生成对肼羰基苯(月弟)酸.

     

    Abstract: It was found in our previous work that p-carboxymethylmercaptobenzencstibonic acid(lb) was highly effective against schistosomiasis japonicum.In the present work p-carboxymethoxy- benzenestibonic acid(Ⅰc),a structure-related compound,was prepared for pharmacological examina- tion.Since p-carboxybenzenestibonic acid(Ⅰa)is also a valuable schistosomicide,its homologues, p-carboxymethyl(Ⅰd)and p-carboxyethyl(Ⅰe)as well as the hydrazide(Ⅰj)were therefore pre- pared.Moreover,the synthesis was extended to the stibonic acid derived from salicylic acid(Ⅲa). The stibonic acids were synthesized by means of the Scheller reaction,p-Carboxymethyl,p- carboxyethyl-,p-carboxymethoxy-and 4-carboxy-3-hydroxy-aniline were diazotized,and then treated with antimony trichloride.The double salts so formed were decomposed under the catalytic ac- tion of cuprous chloride and then hydrolyzed,giving the corresponding stibonic acids.The stibonic acids were purified through the formation of crystalline pyridinium double salts (Ⅱ,Ⅳ). The double salts were recrystallized by dissolving in dilute aqueous hydrochloric acid and then salting out on addition of concentrated hydrochloric acid.When the double salts were recrystal- lized in hot ethanolic hydrochloric acid,the carboxyls were esterified,and consequently the carbethoxy-substituted stibonic acids(Ⅰg,Ⅰh,Ⅰi,Ⅲb)were obtained.The hydrazide(Ⅰj)was prepared on treatment of p-carbomethoxybenzenestibonic acid with hydrazine hydrate.

     

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