Sodium cyanoborohydride → 1-[2-(4-Nitrophenyl)ethyl]-4-{2-[4-nitro-3-(trifluoromethyl)phenyl]ethyl}piperazin-2-one

HRID 1466119Notes

Reaction equation

HRID 1466119 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([CH2:10][CH:11]=O)=[CH:6][C:5]=1[C:13]([F:16])([F:15])[F:14])([O-:3])=[O:2].[N+:17]([C:20]1[CH:25]=[CH:24][C:23]([CH2:26][CH2:27][N:28]2[CH2:33][CH2:32][NH:31][CH2:30][C:29]2=[O:34])=[CH:22][CH:21]=1)([O-:19])=[O:18].C([BH3-])#N.[Na+]>CC(C)[O-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].C(O)C>[N+:17]([C:20]1[CH:25]=[CH:24][C:23]([CH2:26][CH2:27][N:28]2[CH2:33][CH2:32][N:31]([CH2:11][CH2:10][C:7]3[CH:8]=[CH:9][C:4]([N+:1]([O-:3])=[O:2])=[C:5]([C:13]([F:16])([F:15])[F:14])[CH:6]=3)[CH2:30][C:29]2=[O:34])=[CH:22][CH:21]=1)([O-:19])=[O:18]

Participants

6

Reactant 3

HCID 5003444Sodium cyanoborohydrideHCID 89524879[4-Nitro-3-(trifluoromethyl)phenyl]acetaldehydeHCID 895248911-[2-(4-Nitrophenyl)ethyl]piperazin-2-one

Product 1

HCID 895335101-[2-(4-Nitrophenyl)ethyl]-4-{2-[4-nitro-3-(trifluoromethyl)phenyl]ethyl}piperazin-2-one

Reagents, catalysts & solvents 2

HCID 11026Titanium isopropoxideCatalystHCID 702EthanolSolvent

Procedure

A solution of 1-nitro-4-(prop-2-en-1-yl)-2-(trifluoromethyl)benzene in methanol and cooled to −78° C. Ozone was bubbled through the solution until it turned blue. Excess ozone was removed by bubbling nitrogen through the solution, followed by addition of triphenylphosphine (1.1 g, 4.3 mmol). The mixture was warmed up naturally. TLC showed formation of the desired product. The crude material was adsorbed onto silica gel, and purified by flash chromatography to afford the desired [4-nitro-3-(trifluoromethyl)phenyl]acetaldehyde. The aldehyde (20 mg, 0.070 mmol) was treated with 1-[2-(4-nitrophenyl)ethyl]piperazin-2-one (16 mg, 0.070 mmol) and titanium(IV) isopropoxide (0.20 mL). After stirring the mixture for 15 minutes, ethanol (2 mL) and sodium cyanoborohydride (44 mg, 0.70 mmol) was added into the reaction. The mixture was allowed to stir for 4 hours. LC showed formation of the desired product. The reaction was diluted with ethyl acetate, washed with brine, dried over sodium sulfate, and concentrated to give the crude product. The crude product was purified by mass-directed reverse phase HPLC (AcCN-Water with 0.1% TFA). LC-MS (IE, m/z): 467 [M+1]+.

Workup

  1. stirringto stir for 4 hours

Sources & evidence

ORD record
ord-0ee1b14967644b409bdb7f1b86df1301
Source dataset
uspto-grants-2015_04
Patent number
US08999990B2

Reaction notes

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