2-Methyl-2-butene → 1-(2-Bromopyridin-4-yl)cyclopropane-1-carboxylic acid

HRID 1423069Notes

Reaction equation

HRID 1423069 reaction equation
Cl([O-])=O.[Na+].[OH2:5].P([O-])(O)(O)=O.[Na+].[Br:12][C:13]1[CH:18]=[C:17]([C:19]2([CH:22]=[O:23])[CH2:21][CH2:20]2)[CH:16]=[CH:15][N:14]=1.CC(=CC)C>O.C(O)(C)(C)C>[Br:12][C:13]1[CH:18]=[C:17]([C:19]2([C:22]([OH:5])=[O:23])[CH2:20][CH2:21]2)[CH:16]=[CH:15][N:14]=1

Participants

7

Reactant 4

HCID 105532-Methyl-2-buteneHCID 516949Sodium Phosphate, Monobasic, MonohydrateHCID 23668197Sodium ChloriteHCID 866727561-(2-Bromo-4-pyridinyl)cyclopropanecarboxaldehyde

Product 1

HCID 717432461-(2-Bromopyridin-4-yl)cyclopropane-1-carboxylic acid

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6386tert-ButanolSolvent

Procedure

A solution of sodium chlorite (368 mg, 3.26 mmol) and sodium dihydrogen phosphate monohydrate (449 mg, 3.26 mmol) in 5 mL of water is added dropwise to a solution of crude 1-(2-bromopyridin-4-yl)-cyclopropanecarboxaldehyde (566 mg, 2.50 mmol) and 2-methyl-2-butene (1.73 mL, 16.3 mmol) in t-butanol (12 mL), and the resulting reaction mixture is stirred at room temperature. After 18 hours, the mixture is concentrated in vacuo, acidified to pH 2 with 1 M aqueous HCl, diluted with brine (25 mL) and extracted with EtOAc (3×50 mL). The combined organic layers are dried over Na2SO4, filtered and concentrated to afford crude 1-(2-bromopyridin-4-yl)-cyclopropanecarboxylic acid which is used without purification.

Workup

  1. customthe resulting reaction mixture
  2. concentrationthe mixture is concentrated in vacuo
  3. additiondiluted with brine (25 mL)
  4. extractionextracted with EtOAc (3×50 mL)
  5. dry with materialThe combined organic layers are dried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-2f52ecc95e7145a5b7755525fa9d037f
Source dataset
uspto-grants-2015_01
Patent number
US08927550B2

Reaction notes

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