Hydrochloric Acid → Dimethyl 2-[(4-nitrophenyl)methyl]propanedioate

HRID 327799Notes

Reaction equation

HRID 327799 reaction equation
[CH3:1][O:2][C:3](=[O:19])[C:4]([C:15]([O:17][CH3:18])=[O:16])=[CH:5][C:6]1[CH:11]=[CH:10][C:9]([N+:12]([O-:14])=[O:13])=[CH:8][CH:7]=1.CC(C)(C([O-])=O)C([O-])=O.[N+](C1C=CC(C=O)=CC=1)([O-])=O.C([BH3-])#N.[Na+].Cl>CO.O>[CH3:1][O:2][C:3](=[O:19])[CH:4]([C:15]([O:17][CH3:18])=[O:16])[CH2:5][C:6]1[CH:7]=[CH:8][C:9]([N+:12]([O-:14])=[O:13])=[CH:10][CH:11]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 5414-NitrobenzaldehydeHCID 609671Dimethyl (4-nitrobenzylidene)malonate2×HCID 5003444Sodium cyanoborohydrideHCID 6946994Dimethylmalonat

Product 1

HCID 4156732Dimethyl 2-[(4-nitrophenyl)methyl]propanedioateYield 93%

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 962WaterSolvent

Conditions

Temperature
25 °C

Procedure

2-Carbomethoxy-3-(4-nitrophenyl)propenoic acid methyl ester was made from the Knovenagle condensation of dimethylmalonate and p-nitrobenzaldehyde according to the method of J. Chem. Soc., 2125 (1927): Melting point observed (mpobs)=133-134° C. Melting point reported in the literature (mplit)=136-137° C. 2-Carbomethoxy-3-(4-nitrophenyl)propenoic acid methyl ester (23.0 grams (g), 86.7 millimoles (mmole)) was dissolved in 175 milliliters (mL) of methanol (MEOH) under nitrogen and sodium cyanoborohydride (6.0 g, 95.5 mmole) was cautiously added to the stirred solution with cooling. The pH was adjusted to 4.0 with concentrated hydrochloric acid and the solution was stirred at 25° C. overnight. During the first 8 hrs the pH was readjusted from 6 to 4 on several occasions. The yellow methanol solution was poured into 700 mL of water and extracted with 3×200 mL portions of methylene chloride. The combined organic fractions were washed with 400 mL of saturated sodium bicarbonate and 400 mL of water, dried over magnesium sulfate and evaporated to a pale yellow oil on a rotary evaporator. The oil crystallized (mp=82-83° C.) upon standing and gave 2-carbomethoxy-3-(4-nitrophenyl)propanoic acid methyl ester (p-nitrobenzyl malonate dimethyl ester) in 93 percent yield (21.3 g, 81 mmole).

Workup

  1. custom(mpobs)=133-134° C
  2. customreported in the literature (mplit)=136-137° C
  3. temperaturewith cooling
  4. customDuring the first 8 hrs
  5. extractionextracted with 3×200 mL portions of methylene chloride
  6. washThe combined organic fractions were washed with 400 mL of saturated sodium bicarbonate and 400 mL of water
  7. dry with materialdried over magnesium sulfate
  8. customevaporated to a pale yellow oil on a rotary evaporator
  9. customThe oil crystallized (mp=82-83° C.)

Sources & evidence

ORD record
ord-037470c1caa5479cadc7fd498e645a4a
Source dataset
uspto-grants-1993_12
Patent number
US05274119

Reaction notes

Loading…