3-Nitrobenzaldehyde → 3,5-Pyridinedicarboxylic acid, 1,4-dihydro-2,6-dimethyl-4-(3-nitrophenyl)-, 3-(2-cyanoethyl) 5-methyl ester
Reaktionsgleichung
[NH2:1]/[C:2](/[CH3:8])=[CH:3]\[C:4]([O:6][CH3:7])=[O:5].[N+:9]([C:12]1[CH:13]=[C:14]([CH:17]=[CH:18][CH:19]=1)[CH:15]=O)([O-:11])=[O:10].O=[C:21]([CH3:30])[CH2:22][C:23]([O:25][CH2:26][CH2:27][C:28]#[N:29])=[O:24]>>[CH3:8][C:2]1[NH:1][C:21]([CH3:30])=[C:22]([C:23]([O:25][CH2:26][CH2:27][C:28]#[N:29])=[O:24])[CH:15]([C:14]2[CH:17]=[CH:18][CH:19]=[C:12]([N+:9]([O-:11])=[O:10])[CH:13]=2)[C:3]=1[C:4]([O:6][CH3:7])=[O:5]Komponenten
Versuchsvorschrift
Compounds of formula 1 may also be prepared via Scheme IV. A dihydropyridine of formula 12 is prepared as in Scheme I, and the compound condensed with an intermediate of formula 9 to form a compound of formula 1. For example, methyl 3-aminocrotonate, 3-nitrobenzaldehyde, and 2-cyanoethyl 3-oxobutanoate are heated together to form 2,6-dimethyl-3-carbomethoxy-4-(3-nitrophenyl)-5-(2-cyano)ethoxycarbonyl-1,4-dihydropyridine. The cyanoethyl ester is hydrolyzed using NaOH followed by HCl, converted to an acid halide (e.g., using thionyl chloride), and condensed with a compound of the formula HO--A--X, for example, 3-bromopropanol, to form a compound of formula 12. For example, 2,6-dimethyl-3-carbomethoxy-4-(3-nitrophenyl)-5-(2-cyano)ethoxycarbonyl-1,4-dihydropyridine is treated sequentially with NaOH, HCl, and thionyl chloride, then condensed with 3-bromopropanol to form 2,6-dimethyl-3-carbomethoxy-4-(3-nitrophenyl)-5-(3-bromopropoxycarbonyl)-1,4-dihydropyridine (12). The resulting bromo derivative is then condensed with 4-(2-tetrahydropyran-2-yloxyethyl)phenol to form 2,6 -dimethyl-3-carbomethoxy-4-(3-nitrophenyl)-5-(3-[4-(2-tetrahydropyran-2-yloxyethyl)phenyl]propoxycarbonyl)-1,4-dihydropyridine (1).
Quellen und Nachweise
- ORD-Eintrag
- ord-9af2632e39c04f88b153f930bc1dc4fb
- Quelldatensatz
- uspto-grants-1988_08
- Patentnummer
- US04761420
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