2-Bromo-4-nitrotoluene → 4-(2-Methyl-5-nitro-phenyl)-piperazine-1-carboxylic acid tert-butyl ester

HRID 1926579Notes

Reaction equation

C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Br[C:48]1[CH:53]=[C:52]([N+:54]([O-:56])=[O:55])[CH:51]=[CH:50][C:49]=1[CH3:57].[N:58]1([C:64]([O:66][C:67]([CH3:70])([CH3:69])[CH3:68])=[O:65])[CH2:63][CH2:62][NH:61][CH2:60][CH2:59]1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:67]([O:66][C:64]([N:58]1[CH2:63][CH2:62][N:61]([C:48]2[CH:53]=[C:52]([N+:54]([O-:56])=[O:55])[CH:51]=[CH:50][C:49]=2[CH3:57])[CH2:60][CH2:59]1)=[O:65])([CH3:70])([CH3:68])[CH3:69]

Participants

Conditions

Temperature: 70 °C

Procedure

In a first flask 0.135 g of palladium acetate (0.135 g, 0.602 mmol) and BINAP (2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) (0.375 g) were suspended in 5 mL of toluene and stirred at 70° C. for 30 min. In a second flask, 2-bromo-1-methyl-4-nitrobenzene (1 g, 4.63 mmol), tert-butyl piperazine-1-carboxylate (1.12 g, 6.02 mmol and sodium tert-butoxide (1.068 g, 11.11 mmol) were added to 5 mL of toluene and stirred for 30 min. at 60° C. To this mixture was added the contents of the first flask, and stirring was continued for 3 h at 60° C. The solvent was evaporated, the residue purified via silica gel chromatography with dichloromethane-methanol (0 to 100%) to yield the title compound (0.145 g).

Workup

stirringstirred for 30 min. at 60° C
additionTo this mixture was added the contents of the first flask
stirringstirring
waitwas continued for 3 h at 60° C
customThe solvent was evaporated
customthe residue purified via silica gel chromatography with dichloromethane-methanol (0 to 100%)

Sources & evidence

ORD record: ord-c48c4773b233401eb1e2513e59c0eadd
Source dataset: uspto-grants-2012_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08183237B2

Reaction notes

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