3-Nitrobenzaldehyde → 3-Methyl 5-(1-methylethyl) 1,4-dihydro-2,6-dimethyl-4-(3-nitrophenyl)-3,5-pyridinedicarboxylate

HRID 845582Notes

Reaction equation

HRID 845582 reaction equation
[C:1]([O:7][CH3:8])(=[O:6])[CH2:2][C:3]([CH3:5])=O.[NH2:9]/[C:10](/[CH3:18])=[CH:11]\[C:12]([O:14][CH:15]([CH3:17])[CH3:16])=[O:13].[N+:19]([C:22]1[CH:23]=[C:24]([CH:27]=[CH:28][CH:29]=1)[CH:25]=O)([O-:21])=[O:20]>CC(O)C.ClCCl>[CH3:5][C:3]1[NH:9][C:10]([CH3:18])=[C:11]([C:12]([O:14][CH:15]([CH3:17])[CH3:16])=[O:13])[CH:25]([C:24]2[CH:27]=[CH:28][CH:29]=[C:22]([N+:19]([O-:21])=[O:20])[CH:23]=2)[C:2]=1[C:1]([O:7][CH3:8])=[O:6]

Participants

6

Reactant 3

HCID 74493-NitrobenzaldehydeHCID 7757Methyl acetoacetateHCID 111372742-Butenoic acid, 3-amino-, 1-methylethyl ester

Product 1

HCID 42514483-Methyl 5-(1-methylethyl) 1,4-dihydro-2,6-dimethyl-4-(3-nitrophenyl)-3,5-pyridinedicarboxylateYield 62.1%

Reagents, catalysts & solvents 2

HCID 3776IsopropanolSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of methyl acetoacetate (6.73 g, 58 mmol), 1-methylethyl 3-aminocrotonate (52) (8.34 g, 58 mmol) and 3-nitro-benzaldehyde (8.75 g, 58 mmol) in 2-propanol (80 mL0 was refluxed for 9 h. The mixture was diluted with dichloromethane (300 mL0 and dried (MgSo4), and the solvent was removed with a rotary evaporator. The crude product was recrystallized from ethyl acetate/hexane to afford 13.5 g (36 mmol, 62%) of 81 as a yellow crystalline solid: mp 142°-144° C. (lit.81 mp 147° C.); IR (CH2Cl2) 3440, 2960, 1695, 1622, 1530, 1470, 1352, 1215, 1100 cm-1 ; 1H NMR (CDCl3) δ 1.10 (d, J=6.2 Hz, 3H), 1.25 (d, J=6.2 Hz, 3H), 2.33 (s, 6H), 3.64 (s, 3 H), 4.95 (septet, J=6.2 Hz, 1H), 5.07 (s, 1H) 6.30 (s, 1H), 7.34-8.12 (m, 4H); 13C NMR (CDCl3) δ 19.95, 20.04, 22.35, 22.68, 40.53, 51.67. 67.98, 103.48, 104.19, 121.89, 123.61, 129.23, 135.07, 145.38, 145.91, 148.81, 150.61, 167.29, 168.35.

Workup

  1. customdried (MgSo4)
  2. customthe solvent was removed with a rotary evaporator
  3. customThe crude product was recrystallized from ethyl acetate/hexane

Sources & evidence

ORD record
ord-7fc55d68f5cd4d7b91fa6c57175a2add
Source dataset
uspto-grants-1988_07
Patent number
US04758669

Reaction notes

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