合成路线:The title compound has been obtained by several related ways:The reaction of 2-chloro-3-nitropyridine (I) with methylboronic acid by means of Pd(PPh3)4 and K2CO3 in hot dioxane gives 2-methyl-3-nitropyridine (III),which is condensed with dimethylformamide dimethylacetal (IV) to yield 2-[2-(dimethylamino)vinyl]-3-nitropyridine (V).The oxidation of (V) by means of NaIO4 affords 3-nitropyridine-2-carbaldehyde (VI),which is condensed with semicarbazide (VII) to provide the corresponding semicarbazone (VIII).Finally,the nitro group of (VIII) is reduced with SnCl2 or Na2S to furnish the target 3-aminopyridine-2-carbaldehyde semicarbazone.2-Methyl-3-nitropyridine (III) can also be obtained by condensation of 2-chloro-3-nitropyridine (I) with diethyl malonate (II) by means of Na,followed by decarboxylative hydrolysis with H2SO4 at 125 C.The direct oxidation of 2-methyl-3-nitropyridine (III) with SeO2 in dioxane gives carbaldehyde (VI),which is treated with ethyleneglycol (IX) and Ts-OH to yield the cyclic acetal (X).The reduction of (X) with H2 over Pd/C in ethanol affords 3-aminopyridine-2-carbaldehyde ethylene ketal (XI),which is treated with semicarbazide (VI) and HCl to afford the target 3-aminopyridine-2-carbaldehyde semicarbazone.The condensation of 2-chloro-3-nitropyridine (I) with tributyl vinyl tin (XII) Pd(PPh3)4 and PPH3 in refluxing toluene gives 3-nitro-2-vinylpyridine (XIII),which is oxidized with O3 and Me2S in methanol to yield 3-nitropyridine-2-carbaldehyde (VI).This compound is condensed with semicarbazide (VII) and reduced to the target compound as already described.
参考文献标题:Process for the synthesis of ribonucleotide reductase inhibitors 3-AP and 3-AMP
文献作者:Doyle,T.W.; Li,J.; Chen,S.-H.; Li,X.; Niu,C.-S.(Vion Pharmaceuticals,Inc.)
参考来源:US 5869676; WO 9851670
合成路线:The title compound has been obtained by several related ways:The reaction of 2-chloro-3-nitropyridine (I) with methylboronic acid by means of Pd(PPh3)4 and K2CO3 in hot dioxane gives 2-methyl-3-nitropyridine (III),which is condensed with dimethylformamide dimethylacetal (IV) to yield 2-[2-(dimethylamino)vinyl]-3-nitropyridine (V).The oxidation of (V) by means of NaIO4 affords 3-nitropyridine-2-carbaldehyde (VI),which is condensed with semicarbazide (VII) to provide the corresponding semicarbazone (VIII).Finally,the nitro group of (VIII) is reduced with SnCl2 or Na2S to furnish the target 3-aminopyridine-2-carbaldehyde semicarbazone.2-Methyl-3-nitropyridine (III) can also be obtained by condensation of 2-chloro-3-nitropyridine (I) with diethyl malonate (II) by means of Na,followed by decarboxylative hydrolysis with H2SO4 at 125 C.The direct oxidation of 2-methyl-3-nitropyridine (III) with SeO2 in dioxane gives carbaldehyde (VI),which is treated with ethyleneglycol (IX) and Ts-OH to yield the cyclic acetal (X).The reduction of (X) with H2 over Pd/C in ethanol affords 3-aminopyridine-2-carbaldehyde ethylene ketal (XI),which is treated with semicarbazide (VI) and HCl to afford the target 3-aminopyridine-2-carbaldehyde semicarbazone.The condensation of 2-chloro-3-nitropyridine (I) with tributyl vinyl tin (XII) Pd(PPh3)4 and PPH3 in refluxing toluene gives 3-nitro-2-vinylpyridine (XIII),which is oxidized with O3 and Me2S in methanol to yield 3-nitropyridine-2-carbaldehyde (VI).This compound is condensed with semicarbazide (VII) and reduced to the target compound as already described.
参考文献标题:Synthesis and antitumor activity of amino derivatives of pyridine-2-carboxaldehyde thiosemicarbazone
文献作者:Liu,M-C.; Lin,T.S.; Sartorelli,A.C.
参考来源:J Med Chem 1992,35(20),3672
合成路线:The title compound has been obtained by several related ways:The reaction of 2-chloro-3-nitropyridine (I) with methylboronic acid by means of Pd(PPh3)4 and K2CO3 in hot dioxane gives 2-methyl-3-nitropyridine (III),which is condensed with dimethylformamide dimethylacetal (IV) to yield 2-[2-(dimethylamino)vinyl]-3-nitropyridine (V).The oxidation of (V) by means of NaIO4 affords 3-nitropyridine-2-carbaldehyde (VI),which is condensed with semicarbazide (VII) to provide the corresponding semicarbazone (VIII).Finally,the nitro group of (VIII) is reduced with SnCl2 or Na2S to furnish the target 3-aminopyridine-2-carbaldehyde semicarbazone.2-Methyl-3-nitropyridine (III) can also be obtained by condensation of 2-chloro-3-nitropyridine (I) with diethyl malonate (II) by means of Na,followed by decarboxylative hydrolysis with H2SO4 at 125 C.The direct oxidation of 2-methyl-3-nitropyridine (III) with SeO2 in dioxane gives carbaldehyde (VI),which is treated with ethyleneglycol (IX) and Ts-OH to yield the cyclic acetal (X).The reduction of (X) with H2 over Pd/C in ethanol affords 3-aminopyridine-2-carbaldehyde ethylene ketal (XI),which is treated with semicarbazide (VI) and HCl to afford the target 3-aminopyridine-2-carbaldehyde semicarbazone.The condensation of 2-chloro-3-nitropyridine (I) with tributyl vinyl tin (XII) Pd(PPh3)4 and PPH3 in refluxing toluene gives 3-nitro-2-vinylpyridine (XIII),which is oxidized with O3 and Me2S in methanol to yield 3-nitropyridine-2-carbaldehyde (VI).This compound is condensed with semicarbazide (VII) and reduced to the target compound as already described.
参考文献标题:Syntheses and antitumor activities of potent inhibitors of ribonucleotide reductase: 3-Amino-4-methylpyridine-2-carboxaldehyde-thiosemicarbazone (3-AMP),3-amino-pyridine-2-carboxaldehyde-thiosemicarbazone (3-AP) and its water-soluble prodrugs
文献作者:Li,J.; Zheng,L.M.; King,I.; Doyle,T.W.; Chen,S.H.
参考来源:Curr Med Chem 2001,8(2),121
合成路线:The title compound has been obtained by several related ways:The reaction of 2-chloro-3-nitropyridine (I) with methylboronic acid by means of Pd(PPh3)4 and K2CO3 in hot dioxane gives 2-methyl-3-nitropyridine (III),which is condensed with dimethylformamide dimethylacetal (IV) to yield 2-[2-(dimethylamino)vinyl]-3-nitropyridine (V).The oxidation of (V) by means of NaIO4 affords 3-nitropyridine-2-carbaldehyde (VI),which is condensed with semicarbazide (VII) to provide the corresponding semicarbazone (VIII).Finally,the nitro group of (VIII) is reduced with SnCl2 or Na2S to furnish the target 3-aminopyridine-2-carbaldehyde semicarbazone.2-Methyl-3-nitropyridine (III) can also be obtained by condensation of 2-chloro-3-nitropyridine (I) with diethyl malonate (II) by means of Na,followed by decarboxylative hydrolysis with H2SO4 at 125 C.The direct oxidation of 2-methyl-3-nitropyridine (III) with SeO2 in dioxane gives carbaldehyde (VI),which is treated with ethyleneglycol (IX) and Ts-OH to yield the cyclic acetal (X).The reduction of (X) with H2 over Pd/C in ethanol affords 3-aminopyridine-2-carbaldehyde ethylene ketal (XI),which is treated with semicarbazide (VI) and HCl to afford the target 3-aminopyridine-2-carbaldehyde semicarbazone.The condensation of 2-chloro-3-nitropyridine (I) with tributyl vinyl tin (XII) Pd(PPh3)4 and PPH3 in refluxing toluene gives 3-nitro-2-vinylpyridine (XIII),which is oxidized with O3 and Me2S in methanol to yield 3-nitropyridine-2-carbaldehyde (VI).This compound is condensed with semicarbazide (VII) and reduced to the target compound as already described.
参考文献标题:Synthesis of 3-aminopyridine-2-carboxaldehyde thiosemicarbazone (3-AP)
文献作者:Niu,C.; et al.
参考来源:Tetrahedron 1998,54(23),6311
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