Water → (+)-Trimethyl 3-nitro-2-(2,4,6-trimethoxyphenyl)propane-1,1,3-tricarboxylate

HRID 553270Notes

Reaction equation

HRID 553270 reaction equation
[O-]S(C(F)(F)F)(=O)=O.[Mg+2].[O-]S(C(F)(F)F)(=O)=O.O.C1(C2O[C@@H]3CC4C=CC=CC=4[C@@H]3N=2)(C2O[C@@H]3CC4C=CC=CC=4[C@@H]3N=2)CC1.[CH3:46][O:47][C:48](=[O:66])/[C:49](/[N+:63]([O-:65])=[O:64])=[CH:50]\[C:51]1[C:56]([O:57][CH3:58])=[CH:55][C:54]([O:59][CH3:60])=[CH:53][C:52]=1[O:61][CH3:62].[C:67]([O:74][CH3:75])(=[O:73])[CH2:68][C:69]([O:71][CH3:72])=[O:70].CN1CCOCC1>CO.C(Cl)(Cl)Cl>[N+:63]([CH:49]([C:48]([O:47][CH3:46])=[O:66])[CH:50]([C:51]1[C:56]([O:57][CH3:58])=[CH:55][C:54]([O:59][CH3:60])=[CH:53][C:52]=1[O:61][CH3:62])[CH:68]([C:67]([O:74][CH3:75])=[O:73])[C:69]([O:71][CH3:72])=[O:70])([O-:65])=[O:64]

Participants

9

Reactant 6

HCID 962WaterHCID 7943Dimethyl malonateHCID 79724-MethylmorpholineHCID 2734125Magnesium trifluoromethanesulfonateHCID 9850233(3aS,3a'S,8aR,8a'R)-2,2'-(Cyclopropane-1,1-diyl)bis(8,8a-dihydro-3aH-indeno[1,2-d]oxazole)HCID 86641484(E)-Methyl-2-nitro-3-(2,4,6-trimethoxyphenyl)acrylate

Product 1

HCID 72254933(+)-Trimethyl 3-nitro-2-(2,4,6-trimethoxyphenyl)propane-1,1,3-tricarboxylate

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6212ChloroformSolvent2×

Conditions

Temperature
40 °C

Procedure

In a two-necked 500 mL round-bottomed flask maintained under nitrogen, chloroform (10 mL), magnesium triflate (0.161 g, 0.5 mmol) and water (0.036 mL, 2.0 mmol) were added. To this stirred solution, (3aS,3a′S,8aR,8a′R)-2,2′(cyclopropane-1,1-diyl)bis(8,8a-dihydro-3aH-indeno[1,2-d]oxazole) (bis(oxazoline)) (0.196 g, 0.55 mmol) was added and the reaction mixture stirred for 1 hour. At the end of 1 hour, chloroform (30 mL) and molecular sieves (2 g) were added and the mixture stirred for another 90 mins. (E)-Methyl-2-nitro-3-(2,4,6-trimethoxyphenyl)acrylate (3.1 g, 0.01 mol), dimethyl malonate (1.92 g, 0.014 mol) and N-methylmorpholine (0.06 g, 0.6 mmol) were added and the reaction mixture was stirred for 12 hours followed by heating at 40° C. for 4 hours. Petroleum ether (15 mL) was added to the reaction mixture, stirred for 10 mins. and the mixture filtered. The molecular sieves were washed with methyl-t-butyl ether and the combined organic layer was washed with 5% phosphoric acid (10 mL) and brine (15 mL). The organic layer was concentrated under reduced pressure to give an oil. The oil was dissolved in methanol (10 mL), cooled and filtered to give a white crystalline solid.

Workup

  1. temperatureIn a two-necked 500 mL round-bottomed flask maintained under nitrogen
  2. stirringthe mixture stirred for another 90 mins
  3. stirringthe reaction mixture was stirred for 12 hours
  4. stirringstirred for 10 mins
  5. filtrationand the mixture filtered
  6. washThe molecular sieves were washed with methyl-t-butyl ether
  7. washthe combined organic layer was washed with 5% phosphoric acid (10 mL) and brine (15 mL)
  8. concentrationThe organic layer was concentrated under reduced pressure
  9. customto give an oil
  10. temperaturecooled
  11. filtrationfiltered
  12. customto give a white crystalline solid

Sources & evidence

ORD record
ord-43f1da2a058c4afea6e3de94f3c9ad80
Source dataset
uspto-grants-2011_05
Patent number
US07951961B2

Reaction notes

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