Benzyl chloroformate → 5-Bromo-2-(Cbz-amino)pyridine

HRID 613743Notes

Reaction equation

HRID 613743 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][N:3]=1.C(N(C(C)C)CC)(C)C.Cl[C:19]([O:21][CH2:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)=[O:20]>C(Cl)(Cl)Cl>[CH2:22]([O:21][C:19](=[O:20])[NH:1][C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][N:3]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Participants

5

Reactant 3

HCID 10387Benzyl chloroformateHCID 706222-Amino-5-bromopyridineHCID 81531Diisopropylethylamine

Product 1

HCID 105908245-Bromo-2-(Cbz-amino)pyridine

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent2×

Procedure

A solution of 2-amino-5-bromopyridine (6.92 g, 40 mmol) and 6.22 g (48 mmol) of diisopropylethylamine in 50 mL of chloroform was added dropwise to a solution of 8.19 g (48 mmol) of benzyl chloroformate in 20 mL of chloroform at about 0° C., with stirring. A voluminous white precipitate formed. After about 15 minutes, the mixture was filtered and the precipitate was washed three times with chloroform and dried to give 2.70 g of the title product, mp 184° C. (dec) (recrystallization solvent=2-propanol). 1H nmr (dimethylsulfoxide-d6): δ=10.48 (br s, 1 H), 8.37 (d, 1 H), 7.98 (d of d, 1 H), 7.81 (d, 1 H), 7.40 (m, 5 H), 5.17 (s, 2 H); ms (NH3Cl): m/z=307, 309 (MH+).

Workup

  1. customA voluminous white precipitate formed
  2. filtrationthe mixture was filtered
  3. washthe precipitate was washed three times with chloroform
  4. customdried
  5. customto give
  6. custom2.70 g of the title product, mp 184° C. (dec) (recrystallization solvent=2-propanol)

Sources & evidence

ORD record
ord-2331d59e7c71481d8c468f077dcd16ba
Source dataset
uspto-grants-1999_12
Patent number
US06008361

Reaction notes

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