Sodium Hydroxide → 2-Allyloxy-4-nitrophenol

HRID 362245

Reaction equation

HRID 362245 reaction equation
[OH-].[Na+].[CH2:3]([O:6][C:7]1[CH:8]=[C:9]([N+:15]([O-:17])=[O:16])[CH:10]=[CH:11][C:12]=1[O:13]C)[CH:4]=[CH2:5]>CS(C)=O>[CH2:3]([O:6][C:7]1[CH:8]=[C:9]([N+:15]([O-:17])=[O:16])[CH:10]=[CH:11][C:12]=1[OH:13])[CH:4]=[CH2:5]

Participants

4

Reactant 2

HCID 14798Sodium HydroxideHCID 120822023-Allyloxy-4-methoxynitrobenzene

Product 1

HCID 120822032-Allyloxy-4-nitrophenol

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
65 °C

Procedure

To one liter of dimethyl sulfoxide was added 750 ml of 2N aqueous sodium hydroxide and the mixture was heated to 65° C. The pale yellow solid 3-allyloxy-4-methoxynitrobenzene prepared above was added in portions over a 30 minute period and then the temperature was raised to 95° C. and maintained for 3 hours, after which time the starting material had been consumed. The mixture was allowed to cool and poured into a mixture of 1 L ice and 1 L 2N HCl. 73 Grams of crude but homogeneous (by tlc 1:1 CH2Cl2 /hexane) desired product was isolated as a light brown solid by filtration. This material was subsequently dissolved in 1:1 hexane/methylene chloride and filtered through silica gel to give 68 g of pale yellow solid, which, when recrystallized from ethyl/acetate/hexane, gave m.p. 61°-62 ° C. The aqueous mother liquors from the initial crystallization above were extracted with 2 L of ethyl acetate. This was dried over sodium sulfate, filtered and evaporated to a dark oil. Column chromatography on silica with 1:1 CH2Cl2 /hexane gave an additional 12 g of the title compound as a yellow solid. Elution with 2% MeOH in CHCl3 gave 12 g of a dark oil which slowly crystallized in vacuum. This proved to be the Claisen product, 3-allyl-4-nitrocatechol.

Workup

  1. additionabove was added in portions over a 30 minute period
  2. temperaturethe temperature was raised to 95° C.
  3. temperaturemaintained for 3 hours
  4. customafter which time the starting material had been consumed
  5. temperatureto cool
  6. additionpoured into a mixture of 1 L ice and 1 L 2N HCl

Sources & evidence

ORD record
ord-6a424ad56a1a44dabd58708256831cd0
Source dataset
uspto-grants-1999_02
Patent number
US05869490

Linked notes

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