Toluene → Ethyl 2-(4-methoxybenzoyl)-4-nitromethyl-3-(1,3-benzodioxole-5-yl)butyrate

HRID 496753

Reaction equation

HRID 496753 reaction equation
[CH2:1]([O:3][C:4](=[O:16])[CH2:5][C:6](=[O:15])[C:7]1[CH:12]=[CH:11][C:10]([O:13][CH3:14])=[CH:9][CH:8]=1)[CH3:2].[N+:17]([CH:20]=[CH:21][C:22]1[CH:30]=[CH:29][C:25]2OCOC=2C=1)([O-:19])=[O:18].[C:31]([O:34][CH2:35][CH3:36])(=[O:33])C.[C:37]1(C)C=CC=CC=1>C(Cl)Cl.N12CCCN=C1CCCCC2>[CH3:14][O:13][C:10]1[CH:9]=[CH:8][C:7]([C:6]([CH:5]([CH:22]([C:30]2[CH:29]=[CH:25][C:36]3[O:33][CH2:31][O:34][C:35]=3[CH:37]=2)[CH2:21][CH2:20][N+:17]([O-:19])=[O:18])[C:4]([O:3][CH2:1][CH3:2])=[O:16])=[O:15])=[CH:12][CH:11]=1

Participants

7

Reactant 4

HCID 1140Toluene2×HCID 8857Ethyl AcetateHCID 76150Benzenepropanoic acid, 4-methoxy-beta-oxo-, ethyl esterHCID 949455-(2-Nitroethenyl)-1,3-benzodioxole

Product 1

HCID 22322609Ethyl 2-(4-methoxybenzoyl)-4-nitromethyl-3-(1,3-benzodioxole-5-yl)butyrate

Reagents, catalysts & solvents 2

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneCatalyst2×HCID 6344DichloromethaneSolvent

Conditions

Temperature
80 °C

Procedure

To ethyl(4-methoxybenzoyl)acetate (23.0 g, 0.104 mol), prepared by the method of Krapcho et al., Org. Syn. 47, 20 (1967), and 5-(2-nitrovinyl)-1,3-benzodioxole (17.0 g, 0.088 mol) dissolved in 180 mL of toluene and heated to 80° C. was added 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU, 0.65 g) with stirring. The mixture was heated until all the nitro starting material dissolved. The solution was stirred without heating for 30 minutes (min) and then an additional 0.65 g of DBU was added. After stirring an additional 45 minutes, thin layer chromatography (5% ethyl acetate in methylene chloride) indicated the absence of nitro starting material. Toluene (200 mL) was added, and the organic phase was washed with dilute hydrochloric acid and NaCl solution. The organic phase was dried over sodium sulfate and then concentrated under reduced pressure. The residue obtained was chromatographed on silica gel eluting with 3:1 hexane-ethyl acetate to give 21.22 g of the desired product as a mixture of isomers and 9.98 g. of recovered ethyl(4-methoxybenzoyl)acetate.

Workup

  1. dissolutiondissolved
  2. stirringThe solution was stirred
  3. temperaturewithout heating for 30 minutes (min)
  4. stirringAfter stirring an additional 45 minutes
  5. washthe organic phase was washed with dilute hydrochloric acid and NaCl solution
  6. dry with materialThe organic phase was dried over sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe residue obtained
  9. customwas chromatographed on silica gel eluting with 3:1 hexane-ethyl acetate

Sources & evidence

ORD record
ord-a558280064cc45938c923dd66c1c888e
Source dataset
uspto-grants-2005_09
Patent number
US06946481B1

Linked notes

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