Nitric Acid → Benzyl 4-(benzyloxy)-5-methoxy-2-nitrobenzoate

HRID 2263471Notes

Reaction equation

HRID 2263471 reaction equation
[CH2:1]([O:8][C:9]1[CH:24]=[CH:23][C:12]([C:13]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)=[O:14])=[CH:11][C:10]=1[O:25][CH3:26])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.ClCCl.S(=O)(=O)(O)O.[N+:35]([O-])([OH:37])=[O:36]>C(O)(=O)C.O>[CH2:1]([O:8][C:9]1[C:10]([O:25][CH3:26])=[CH:11][C:12]([C:13]([O:15][CH2:16][C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)=[O:14])=[C:23]([N+:35]([O-:37])=[O:36])[CH:24]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 944Nitric AcidHCID 1118Sulfuric AcidHCID 6344DichloromethaneHCID 22070405Benzyl 4-(benzyloxy)-3-methoxybenzoate

Product 1

HCID 10894498Benzyl 4-(benzyloxy)-5-methoxy-2-nitrobenzoate

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent

Conditions

Temperature
10 °C

Procedure

Benzyl 4-(benzyloxy)-3-methoxybenzoate (78 g) was mixed with dichloromethane (580 ml), water (72 ml) and glacial acetic acid (288 ml). The mixture was cooled to 10° C. Concentrated sulfuric acid (108 ml) was added in a controlled manner maintaining the is temperature of the reaction mixture below 25° C. Concentrated nitric acid (17.5 ml) was then added keeping the temperature of the reaction mixture below 20° C. The reaction mixture was then stirred at 20° C. for 23 hours. The lower aqueous layer was removed and the organic layer was washed with water (290 ml). The organic layer was separated and distilled to 270 ml at atmospheric pressure. Isopropanol (750 ml) was added to the reaction mixture at 45° C. The reaction mixture was then heated to 40° C. and stirred at this temperature for 15 minutes. The resulting suspension was then cooled to 20° C., then to 5° C. and held at this temperature for one hour. The product (benzyl 4-(benzyloxy)-5-methoxy-2-nitrobenzoate) was isolated by filtration, washed with isopropanol (200 ml) and dried at less than 25° C. Yield: 78.4 g, 89.6%;

Workup

  1. temperaturemaintaining the is temperature of the reaction mixture below 25° C
  2. customthe temperature of the reaction mixture below 20° C
  3. customThe lower aqueous layer was removed
  4. washthe organic layer was washed with water (290 ml)
  5. customThe organic layer was separated
  6. distillationdistilled to 270 ml at atmospheric pressure
  7. additionIsopropanol (750 ml) was added to the reaction mixture at 45° C
  8. temperatureThe reaction mixture was then heated to 40° C.
  9. stirringstirred at this temperature for 15 minutes
  10. temperatureThe resulting suspension was then cooled to 20° C.
  11. waitto 5° C. and held at this temperature for one hour

Sources & evidence

ORD record
ord-ad6e6e81d0984d6fafb7a70fbdae27a9
Source dataset
uspto-grants-2010_12
Patent number
US07851623B2

Reaction notes

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