Pyridine → (4-Nitrophenyl)methyl 2-bromo-2-methylpropanoate

HRID 653306Notes

Reaction equation

HRID 653306 reaction equation
[N+:1]([C:4]1[CH:11]=[CH:10][C:7]([CH2:8][OH:9])=[CH:6][CH:5]=1)([O-:3])=[O:2].N1[CH:17]=[CH:16][CH:15]=CC=1.[Br:18]C(Br)C(C)C.CC[O:26][CH2:27]C>>[Br:18][C:16]([CH3:15])([CH3:17])[C:27]([O:9][CH2:8][C:7]1[CH:6]=[CH:5][C:4]([N+:1]([O-:3])=[O:2])=[CH:11][CH:10]=1)=[O:26]

Participants

5

Reactant 4

HCID 1049PyridineHCID 3283Diethyl EtherHCID 116631,1-Dibromo-2-methylpropaneHCID 692754-Nitrobenzyl alcohol

Product 1

HCID 15058101(4-Nitrophenyl)methyl 2-bromo-2-methylpropanoate

Procedure

In 250 ml of dry ether is dissolved 15.3 g of p-nitrobenzyl alcohol, followed by addition of 8.90 ml of pyridine under ice-cooling and stirring. Then, 25.3 g of α-bromoisobutylbromide is added dropwise over 50 minutes. The mixture is stirred at room temperature for 5 hours and the resulant crystalline precipitate is separated by filtration and washed with ether. The filtrate and washings are combined and 150 ml of ethyl acetate is added. The mixture is washed with dilute hydrochloric acid, water, aqueus sodium hydrogen carbonate and aqueous sodium chloride in this order, and dried over anhydrous magnesium sulfate. The solvent is then distilled off under reduced pressure and the residue is chromatographed on a silica gel column [silica gel: 600 g; eluent:chloroform-hexane (1:1)] to give 29.6 g of p-nitrobenzyl α-bromoisobutyrate as a yellow oil. This product solidifies on standing under cooling.

Workup

  1. temperaturecooling
  2. stirringThe mixture is stirred at room temperature for 5 hours
  3. customthe resulant crystalline precipitate is separated by filtration
  4. washwashed with ether
  5. addition150 ml of ethyl acetate is added
  6. washThe mixture is washed with dilute hydrochloric acid, water, aqueus sodium hydrogen carbonate and aqueous sodium chloride in this order
  7. dry with materialdried over anhydrous magnesium sulfate
  8. distillationThe solvent is then distilled off under reduced pressure
  9. customthe residue is chromatographed on a silica gel column [silica gel: 600 g; eluent:chloroform-hexane (1:1)]

Sources & evidence

ORD record
ord-456a23c6152a475995072306d0be4dd9
Source dataset
uspto-grants-1987_06
Patent number
US04675397

Reaction notes

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