Triethylamine → Tert-butyl 4-(methylsulfonyloxymethyl)piperidine-1-carboxylate

HRID 423617Notes

Reaction equation

HRID 423617 reaction equation
[C:1]([N:8]1[CH2:13][CH2:12][CH:11]([CH2:14][OH:15])[CH2:10][CH2:9]1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].CCN(CC)CC.[CH3:23][S:24](Cl)(=[O:26])=[O:25]>C(Cl)Cl>[CH3:23][S:24]([O:15][CH2:14][CH:11]1[CH2:12][CH2:13][N:8]([C:1]([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2])[CH2:9][CH2:10]1)(=[O:26])=[O:25]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 2764081Tert-butyl 4-(hydroxymethyl)piperidine-1-carboxylate

Product 1

HCID 2765838Tert-butyl 4-(methylsulfonyloxymethyl)piperidine-1-carboxylateYield 102%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A mixture of N-Boc-4-piperidinemethanol (1.0 g, 4.51 mmol), Et3N (1.30 mL, 9.01 mmol) in CH2Cl2 (20 mL) at 0° C. was treated dropwise with methanesulfonyl chloride (0.39 mL, 4.96 mmol). The reaction mixture was stirred at 0° C. to 5° C. for 1.5 h, was diluted with CH2Cl2 (100 mL) and washed with 1M NaH2PO4 (50 mL×2) and brine (25 mL). The CH2Cl2 layer was dried over Na2SO4, filtered, and the filtrate was concentrated to a brown oil, which solidified upon cooling to give 1.35 g (100%) of 1,1-dimethylethyl 4-{[(methylsulfonyl)oxy]methyl}-1-piperidinecarboxylate as a brown solid, which was used without further purification. 1H NMR (400 MHz, CDCl3): δ 4.20-4.10 (m, 2H), 4.04 (d, 2H, J=6.5 Hz), 2.99 (s, 3H), 2.75-2.60 (m, 2H), 1.95-1.85 (m, 1H), 1.75-1.65 (m, 2H), 1.43 (s, 9H), 1.30-1.10 (m, 2H).

Workup

  1. washwashed with 1M NaH2PO4 (50 mL×2) and brine (25 mL)
  2. dry with materialThe CH2Cl2 layer was dried over Na2SO4
  3. filtrationfiltered
  4. concentrationthe filtrate was concentrated to a brown oil, which
  5. temperatureupon cooling

Sources & evidence

ORD record
ord-afbcdc34d75b4abca2e96e0dde121861
Source dataset
uspto-grants-2012_01
Patent number
US08101634B2

Reaction notes

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