Hexane → tert-butyl 4-(5-bromo-1-methyl-1H-1,2,4-triazol-3-yl)piperidine-1-carboxylate

HRID 1749665Notes

Reaction equation

HRID 1749665 reaction equation
[Br:1][C:2]1[NH:6][N:5]=[C:4]([CH:7]2[CH2:12][CH2:11][N:10]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:9][CH2:8]2)[N:3]=1.[N+](=[CH:22][Si](C)(C)C)=[N-].CCCCCC>C1(C)C=CC=CC=1.CO>[Br:1][C:2]1[N:6]([CH3:22])[N:5]=[C:4]([CH:7]2[CH2:12][CH2:11][N:10]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:9][CH2:8]2)[N:3]=1

Participants

6

Reactant 3

HCID 8058HexaneHCID 167693TrimethylsilyldiazomethaneHCID 178451823HCID 178451823, compound

Product 1

HCID 86727653tert-butyl 4-(5-bromo-1-methyl-1H-1,2,4-triazol-3-yl)piperidine-1-carboxylateYield 55.3%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 1140TolueneSolvent

Procedure

To a stirred suspension of tert-butyl 4-(5-bromo-1H-1,2,4-triazol-3-yl)piperidine-1-carboxylate (26 g, 78.50 mmol) in toluene (200 mL) and methanol (50 mL) was added dropwise (diazomethyl)trimethylsilane 2M solution in hexane (43.2 mL, 86.35 mmol) under N2, keeping temperature around 20° C.: gas evolution and a small exotherm were observed. The yellow solution obtained was stirred at room temperature for 1 h. The solvent were evaporated and the resulting oil was purified on silica, eluting with 40% EtOAc in petroleum ether to afford tert-butyl 4-(5-bromo-1-methyl-1H-1,2,4-triazol-3-yl)piperidine-1-carboxylate (15.00 g, 55.3%) as an oil: 1H NMR Spectrum; (CDCl3) 1.46 (9H, s), 1.65-1.78 (2H, m), 1.90-2.01 (2H, m), 2.68-3.02 (3H, m), 3.83 (3H, s), 3.94-4.31 (2H, m); Mass Spectrum [M+H]+=no mass ion.

Workup

  1. customtemperature around 20° C.
  2. customThe yellow solution obtained
  3. customThe solvent were evaporated
  4. customthe resulting oil was purified on silica
  5. washeluting with 40% EtOAc in petroleum ether

Sources & evidence

ORD record
ord-bb1d46d9a16046688602cd6eefadca44
Source dataset
uspto-grants-2015_10
Patent number
US09156831B2

Reaction notes

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