Dimethyl 4-(4,5-Dimethoxy-2-(methoxymethoxy)phenyl)-5-(3,4-dimethoxyphenyl)-1,2-diazine-3,6-dicarboxylate → Dimethyl 3-(4,5-Dimethoxy-2-(methoxymethoxy)phenyl)-4-(3,4-dimethoxyphenyl)pyrrole-2,5-dicarboxylate

HRID 1297196Notes

Reaction equation

HRID 1297196 reaction equation
[CH3:1][O:2][C:3]1[C:8]([O:9][CH3:10])=[CH:7][C:6]([C:11]2[C:16]([C:17]3[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[C:19]([O:25][CH3:26])[CH:18]=3)=[C:15]([C:27]([O:29][CH3:30])=[O:28])N=[N:13][C:12]=2[C:31]([O:33][CH3:34])=[O:32])=[C:5]([O:35][CH2:36][O:37][CH3:38])[CH:4]=1.CCOC(C)=O.C(Cl)Cl>CC(O)=O.CO.C(Cl)(Cl)Cl.[Zn]>[CH3:1][O:2][C:3]1[C:8]([O:9][CH3:10])=[CH:7][C:6]([C:11]2[C:16]([C:17]3[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[C:19]([O:25][CH3:26])[CH:18]=3)=[C:15]([C:27]([O:29][CH3:30])=[O:28])[NH:13][C:12]=2[C:31]([O:33][CH3:34])=[O:32])=[C:5]([O:35][CH2:36][O:37][CH3:38])[CH:4]=1

Participants

6

Reactant 2

HCID 10602237Dimethyl 4-(4,5-Dimethoxy-2-(methoxymethoxy)phenyl)-5-(3,4-dimethoxyphenyl)-1,2-diazine-3,6-dicarboxylateHCID 21226138Dichloromethane ethylacetate

Product 1

HCID 10164718Dimethyl 3-(4,5-Dimethoxy-2-(methoxymethoxy)phenyl)-4-(3,4-dimethoxyphenyl)pyrrole-2,5-dicarboxylateYield 62%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalyst2×HCID 176Acetic AcidSolventHCID 21584188Chloroform methanolSolvent

Procedure

A solution of 7 (1.01 g, 1.91 mmol, 1.0 equiv) in HOAc (25 mL) under Ar at 25° C. was treated with activated Zn dust (1.25 g, 19.1 mmol, 10 equiv), stirred for 4 h, and then treated with additional Zn dust (1.25 g, 10 equiv). After 14.5 h, the slurry was diluted with 10% MeOH/CHCl3 (25 mL) and stirred 3 h at 25° C. The mixture was filtered through Celite, rinsed with 10% MeOH/CHCl3, and the filtrate was washed with saturated aqueous NaHCO3, dried (Na2SO4), and concentrated in vacuo. Chromatography (SiO2, 4.5×15 cm, 25% EtOAc/CH2Cl2) afforded 8 (0.61 g, 62% yield) as an orange oil. An analytically pure sample could be prepared by recrystallization from EtOAc-hexanes: mp 162-163° C.; MALDIHRMS (DHB) m/z 515.1800 (M+, C26H29NO10 requires 515.1791).

Workup

  1. waitAfter 14.5 h
  2. stirringstirred 3 h at 25° C
  3. filtrationThe mixture was filtered through Celite
  4. washrinsed with 10% MeOH/CHCl3
  5. washthe filtrate was washed with saturated aqueous NaHCO3
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-b5860c613c034c21bc994483929051a9
Source dataset
uspto-grants-2007_07
Patent number
US07250409B2

Reaction notes

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