Carbon tetrabromide → tert-Butyl 4-(bromomethyl)piperidine-1-carboxylate

HRID 1883164Notes

Reaction equation

HRID 1883164 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH:11]([CH2:14]O)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(Br)(Br)(Br)[Br:36]>C1COCC1>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH:11]([CH2:14][Br:36])[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 11205Carbon tetrabromide2×HCID 11776TriphenylphosphineHCID 2764081Tert-butyl 4-(hydroxymethyl)piperidine-1-carboxylate

Product 1

HCID 15512811tert-Butyl 4-(bromomethyl)piperidine-1-carboxylateYield 75.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To 3.4 g of 4-hydroxymethyl-piperidine-1-carboxylic acid tert-butyl ester (15.79 mmol) in 80 ml of THF, cooled in an ice/water bath, was added 4.76 g triphenylphosphine (18.16 mmol) and then 6.05 g total of carbon tetrabromide (18.16 mmol) in two portions. The reaction was stirred to room temperature over 16 hours. 1.2 g carbon tetrabromide (3.6 mmol) was added twice more over 24 hours before the reaction mixture was filtered. Approximately 240 ml of diethyl ether was added and the resulting mixture was filtered and evaporated. The residue was purified by chromatography on silica gel in 5-10% ethyl acetate/hexanes to give 3.3 g 4-bromomethyl-piperidine-1-carboxylic acid tert-butyl ester (MS: M+H=263/265).

Workup

  1. filtrationwas filtered
  2. additionApproximately 240 ml of diethyl ether was added
  3. filtrationthe resulting mixture was filtered
  4. customevaporated
  5. customThe residue was purified by chromatography on silica gel in 5-10% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-6374f4adccc246deb7692523fa3c4ff2
Source dataset
uspto-grants-2004_07
Patent number
US06759428B2

Reaction notes

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