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

HRID 2172965Notes

Reaction equation

HRID 2172965 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-bromo-pyridin-4-yl)-cyclopropanecarbaldehyde (566 mg, 2.50 mmol) and 2-methyl-2-butene (1.73 mL, 16.3 mmol) in tert-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 1M aqueous solution of HCl, diluted with brine (25 mL) and extracted with ethyl acetate (3×50 mL). The combined organic layers are dried over Na2SO4, filtered and concentrated to afford crude 1-(2-bromo-pyridin-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 ethyl acetate (3×50 mL)
  5. dry with materialThe combined organic layers are dried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-894c9cbae3ce4e32a02f16eef2964d4d
Source dataset
uspto-grants-2015_06
Patent number
US09056858B2

Reaction notes

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