tert-Butyl piperazine-1-carboxylate → HCID 89650458, compound

HRID 1479001Notes

Reaction equation

HRID 1479001 reaction equation
[Br:1][C:2]1[CH:9]=[CH:8][C:7]([F:10])=[CH:6][C:3]=1[CH:4]=O.[C:11]([O:15][C:16]([N:18]1[CH2:23][CH2:22][NH:21][CH2:20][CH2:19]1)=[O:17])([CH3:14])([CH3:13])[CH3:12].C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClCCCl.C(Cl)Cl>[C:11]([O:15][C:16]([N:18]1[CH2:23][CH2:22][N:21]([CH2:4][C:3]2[CH:6]=[C:7]([F:10])[CH:8]=[CH:9][C:2]=2[Br:1])[CH2:20][CH2:19]1)=[O:17])([CH3:14])([CH3:12])[CH3:13]

Participants

6

Reactant 3

HCID 143452tert-Butyl piperazine-1-carboxylateHCID 27733212-Bromo-5-fluorobenzaldehydeHCID 5049666Sodium triacetoxyborohydride

Product 1

HCID 89650458HCID 89650458, compound

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 6344DichloromethaneSolvent

Procedure

A mixture of 2-bromo-5-fluoro-benzaldehyde (3.00 g, 14.8 mmol), piperazine-1-carboxylic acid tert-butyl ester (2.75 g, 14.8 mmol) and sodium triacetoxyborohydride (4.38 g, 20.7 mmol) was prepared in DCE (80 mL) and stirred at RT for 3 hours. The reaction mixture was diluted with DCM (100 mL), and then washed with a mixture of saturated aqueous solution of Na2CO3 (100 mL) and water (50 mL). The aqueous layer was extracted with DCM (100 mL). The organic layers were combined, dried (Na2SO4) and concentrated under vacuum. After purification by filtration through a silica pad (EtOAc), the title compound was obtained as a white powder (5.12 g, 93%). 1H NMR (300 MHz, CDCl3) δ 7.48 (dd, J=8.8, 5.3 Hz, 1H), 7.26 (dd, J=9.6, 3.1 Hz, 1H), 6.85 (ddd, J=8.8, 7.8, 3.1 Hz, 1H), 3.56 (s, 2H), 3.49-3.42 (m, 4H), 2.50-2.42 (m, 4H), 1.46 (s, 9H). HPLC (max plot) 94.1%; Rt 2.73 min. UPLC/MS: (MS+) 373.1 and 375.1 ([M+H]+).

Workup

  1. washwashed with a mixture of saturated aqueous solution of Na2CO3 (100 mL) and water (50 mL)
  2. extractionThe aqueous layer was extracted with DCM (100 mL)
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated under vacuum
  5. customAfter purification
  6. filtrationby filtration through a silica pad (EtOAc)

Sources & evidence

ORD record
ord-f92e927bdc77459eae338a96492f93c0
Source dataset
uspto-grants-2016_08
Patent number
US09403835B2

Reaction notes

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