tert-Butyl piperazine-1-carboxylate → HCID 59441856, compound

HRID 1014254Notes

Reaction equation

HRID 1014254 reaction equation
Br[C:2]1[CH:7]=[C:6]([O:8][CH3:9])[C:5]([N+:10]([O-:12])=[O:11])=[CH:4][C:3]=1[CH3:13].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.[N:56]1([C:62]([O:64][C:65]([CH3:68])([CH3:67])[CH3:66])=[O:63])[CH2:61][CH2:60][NH:59][CH2:58][CH2:57]1>O1CCOCC1>[CH3:13][C:3]1[CH:4]=[C:5]([N+:10]([O-:12])=[O:11])[C:6]([O:8][CH3:9])=[CH:7][C:2]=1[N:59]1[CH2:58][CH2:57][N:56]([C:62]([O:64][C:65]([CH3:68])([CH3:67])[CH3:66])=[O:63])[CH2:61][CH2:60]1

Participants

5

Reactant 3

HCID 143452tert-Butyl piperazine-1-carboxylateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 59441753HCID 59441753, compound

Product 1

HCID 59441856HCID 59441856, compoundYield 38%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
60 °C

Procedure

to a stirred solution of 1-bromo-2-methyl-5-(methyloxy)-4-nitrobenzene (9 g, 36.6 mmol) in 180 mL of Dioxane was added Pd2(dba)2 (2.14 g, 2.34 mmol), XANTPHOS (2.12 g, 3.65 mmol), cesuim carbonte (50 g, 153.6 mmol) and 1,1-dimethylethyl 1-piperazinecarboxylate (13.6 g, 73.15 mmol). The resulting slurry was warmed to 60° C. for 24 hours. The dioxane was removed under reduced pressure and the crude mixture was taken up in ether and filtered to remove cesium carbonate. The ether was, washed with water, dried (Na2SO4), filtered, and rotovaped down. The crude product was purified by flash chromatography to give 1,1-dimethylethyl 4-[2-methyl-5-(methyloxy)-4-nitrophenyl]-1-piperazinecarboxylate (4.83 g, 13.75 mmol, 38%). 1H NMR (400 MHz, CDCl3) δ ppm 7.81 (s, 1 H), 6.56 (s, 1 H), 3.92 (s, 3 H), 3.52-3.63 (m, 4 H), 2.88-2.99 (m, 4 H), 2.25 (s, 3 H), 1.47 (s, 9 H).

Workup

  1. customThe dioxane was removed under reduced pressure
  2. filtrationfiltered
  3. customto remove cesium carbonate
  4. washwashed with water
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. customThe crude product was purified by flash chromatography

Sources & evidence

ORD record
ord-9339f2b5f8064d9b9e5581a8ea712246
Source dataset
uspto-grants-2011_07
Patent number
US07981903B2

Reaction notes

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