SU857112A1 - Method of preparing n-substituted amino-o-quinones - Google Patents

Description

3 Kilylation of the silver salt of 2-hydroxy-, 4-naphthoquinone. As a result, a mixture of ortho-and para-isomers is formed separated by biosulfite derivatives. In addition, in the course of the reaction of SCH1I interactions of the primary amine with 4-ETOXI-1,2-naphthoquinoi, aminoquinone amines are formed together with the target product, which reduces the yield of the target product and requires additional purification. The purpose of the invention is to simplify the process and expand the range of target products. The goal is achieved by reacting the appropriate dialkipamino-ortho-quinones with 2.5-3.5 equivalents at room temperature in the presence of 1-5 equivalents of alkaline earth metal chloride for 0.5-24 hours. Preferably, the process is carried out in the presence of triethylamine. With this, quinones of the general formula T are isolated with a yield of 50-85 ,. A distinctive feature of the process is that the process is carried out in the presence of a catalyst (chl REED-alkaline earth metals) with the addition of triztilamine. The method of producing alkyl (aryl) amino-ortho-quinones allows starting from the available dialkylamino-ortho-quinones obtained in one step by oxidative amination of the corresponding phenols. Both naphtho and heterocyclic dialkylamnio-rt-quinones are readily available. In the interaction of dialkylamino-ortho-quinone with a primary amine in the presence of an alkaline earth metal salt, alkyl (aryl) amino-ortho-chinone is the only product and there is no aminoquinone imine formed. The proposed method allows the synthesis of both the previously described and the new N-substituted amino-ortho-quinones from the available dialkylamino-ortho-quinones obtained by the oxidative amination reaction9 from the corresponding phenols. Example I. A mixture of 0.24 g of 4-MORFOLIN-1,2-ifaftohiiioia, 0.13 g of CaCt ml of butylamine in 6 ml of methanol is stirred for 45 minutes, the precipitate is heated 1 a, washed with methanol, ether and dried. Example 2. Compound 1a is obtained similarly to the preceding one with measure 24 I, but 4-da | ethylamio iafto-1,2-quinone. Example 3. A mixture of 0.24 g of 4-piperidinone-naphtho-1,2-quinone, 0.13 g of CaCl, 0.42 ml of diethylamino-thylamine in 6 ml of methanol is stirred for 30 minutes, dissolved in chloroform, washed with a solution of water, C-UM solution x ° elaton-3, again with water is dried. The solvent is distilled off, the residue is crystallized and compound 16 is obtained. Example 4. Compound 1 is prepared in the same manner as in Example 3, but dimethylaminopropylamine is used as the amine. Example 5. A mixture of 0.24 g of 4-P1SHeridinone-naphtho-1,2-quinone, 0.13 g of CaCl, 0.36 ml of aniline and. 0.8 ml of triethylamine is stirred in 6 ml of methanol for 45 minutes, 20 ml of 5% HC1 are added, the precipitate is filtered off and washed with water and dried. Example 6. Compound 1 d receive analogously to example 5, but. p-aniridine is taken as amine. Example 7. A mixture of 0.24 g of 4-morpholinone-naphtho-5.2 quinone, 0.42 g of m-auger non-isoic acid, 0.65 g of C., 0.8 ml of triztilamine in 6 ml of methanol is stirred for 24 hours, 30 are added 5% HC 1, the precipitate is filtered off, washed with water, dried to obtain compound I a. PRI me R 8. Compounds of 1 g are prepared analogously to example 7, but p-atshobenzoic acid is taken as amyne. Example 9. A mixture of 0.24 f 8-morpholinoquinrlin-5,6-quinone, 0.13 g of Cacid, 0.36 g of p-aiizdin and 0.8 ml of trneethyl mine, alternated in b ml of methanol 30 1 sh, add 20 ml of 5% HCi, the precipitate is filtered off 1 3, washed with water and dried. Example 10, A mixture of 0.33 g of 2,8-dipiperidnequinoxalia-5,6-quinone, Q, i3 g CaCij ,, 0.3 ml of butylamine is stirred in 6 ml of methanol for 30 minutes, dissolved in x orofol, washed with 5% -NS, water and suvat NDZOD. The solvent {the solvent is distilled off; the residue is crystallized from alcohol to give compound 1 and; Example 11. The compound .. to receive analogously to example 10, but as the source take 2,8-dimor | foliioquinoxaline-5, 6-hion. Example 12. Compound 1 L is prepared analogously to Example 10 with the difference that 3,5-dipiperidinoisoquinoline-7, 8-quinone is taken as the initial one. Example 13. Compound i m is prepared analogously to example 10 with the difference that I-phenyl-D-piperidinobenzimide 3orf-6, 7-quinone is taken as the initial one. 857P 5 10 2 Example 1D. Compound i a is prepared analogously to example 1, but MgClj, is used as a catalyst. Example 5. Compound Ia is obtained analogously to Example 1 with the difference that BAC 12 is used as a catalyst. The outputs and coefficients of the compounds obtained are listed in the table.

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Claims (3)

four . Claims 1. A method for producing H-substituted amino orthoquinones of the formula T, where R and R, taken together, means a moiety condensed from a quinone aromatic or nitrogen-containing heteroaromatic cycle that may contain a morpholine residue, piperidine or a phenyl group; R CJ-CA alkyl, phenyl, substituted t), p-carboxy, lower p-alkoxy group, phenyl or di-C-C-alkylamino-C .j Cj-a-alkyl, by reacting quinone derivatives with the corresponding primary amines in an alcohol medium , distinguished by the fact that, in order to simplify the process and expand the assimilation of target products, the dialkylamino-orthoquin of formula II is used as the quinone derivative, where R and R are defined above; -NR is a residue of a secondary amine of piperidine, morpholine, diethylamine /, and the process is carried out in the presence of 2.53, 5 equivalents of primary amine and 1-5 equivalents of alkaline earth metal chloride. 2. A method according to claim 1, characterized in that the process is carried out in the presence of triethylamine. Sources of information taken into account in the examination 1. Japanese Patent 7D-41352, cl. 2 (3), Sat 143 (418), 1974. 2.J. Am. Chem. Soc, 73, 544, 1956. 3.F.J.Bullock efal, Antiprotozoal Q, uinones, J.Meed, Chem, 13.97, 1970 (prototype).