Morpholine → (+/-)-1-[3-(Benzhydrylidene-amino)-4-cyano-benzyl]-6-oxo-piperazine-2-carboxylic acid methyl ester

HRID 1433009Notes

Reaction equation

HRID 1433009 reaction equation
[CH3:1][O:2][C:3]([CH:5]1[N:10]([CH2:11][C:12]2[CH:17]=[CH:16][C:15]([C:18]#[N:19])=[C:14]([N:20]=[C:21]([C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=3)[C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)[CH:13]=2)[C:9](=[O:34])[CH2:8][N:7](C(OCC=C)=O)[CH2:6]1)=[O:4].N1CCOCC1>C(Cl)Cl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:1][O:2][C:3]([CH:5]1[CH2:6][NH:7][CH2:8][C:9](=[O:34])[N:10]1[CH2:11][C:12]1[CH:17]=[CH:16][C:15]([C:18]#[N:19])=[C:14]([N:20]=[C:21]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[C:28]2[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=2)[CH:13]=1)=[O:4]

Participants

5

Reactant 2

HCID 8083MorpholineHCID 54080225(+/-)-4-[3-(Benzhydrylidene-amino)-4-cyano-benzyl]-5-oxo-piperazine-1,3-dicarboxylic acid 1-allyl ester 3-methyl ester

Product 1

HCID 54153171(+/-)-1-[3-(Benzhydrylidene-amino)-4-cyano-benzyl]-6-oxo-piperazine-2-carboxylic acid methyl esterYield 97%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

Tetrakis(triphenylphosphine)palladium(0) (237 mg, 0.2 mmol) is added to a solution containing (±)-4-[3-(benzhydrylidene-amino)-4-cyano-benzyl]-5-oxo-piperazine-1,3-dicarboxylic acid 1-allyl ester 3-methyl ester (1.10 g, 2.05 mmol) and morpholine (894 mg, 10.2 mmol) in CH2Cl2 (30 mL). After ˜5 min, the reaction mixture is absorbed onto silica gel and chromatographed (CH2Cl2 to 10% MeOH/CH2Cl2) to provide 900 mg (97%) of the title compound as a viscous yellow oil. 1H NMR (300 MHz, CDCl3) δ1.83 (br s, 1H), 2.95 (dd, J=13.5, 4.3 Hz, 1H), 3.27 (br d, J=13.5 Hz, 1H), 3.46-3.72 (m, 4H), 3.73 (s, 3H), 5.40 (d, J=15.3 Hz, 1H), 6.57 (br s, 1H), 6.83 (dd, J=8.0, 1.2 Hz, 1H), 7.17-7.50 (m, 9H), 7.75-7.77 (m, 2H) ppm; MS (ion spray): m/z 453 (M+H).

Workup

  1. customthe reaction mixture is absorbed onto silica gel
  2. customchromatographed (CH2Cl2 to 10% MeOH/CH2Cl2)

Sources & evidence

ORD record
ord-e41695355e784d4ea4800f5e40d535ce
Source dataset
uspto-grants-2009_11
Patent number
US07612075B2

Reaction notes

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