Benzophenone → HCID 23121897, compound

HRID 1713500Notes

Reaction equation

HRID 1713500 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][N:9]2[CH2:14][CH2:13][N:12]([C:15](OC(C)(C)C)=[O:16])[CH2:11][CH2:10]2)=[CH:4][CH:3]=1.CN(C)CCN(C)C.C([Li])(CC)C.C1CCCCC1.[C:41]([C:49]1[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=1)(=[O:48])[C:42]1[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=1.[Cl-].[NH4+]>O1CCCC1.CCCCCC.C(OCC)(=O)C>[CH3:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:8][N:9]2[CH2:10][CH2:11][N:12]3[C:15](=[O:16])[O:48][C:41]([C:49]4[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=4)([C:42]4[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=4)[CH:13]3[CH2:14]2)=[CH:6][CH:7]=1

Participants

10

Reactant 6

HCID 3102BenzophenoneHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 8078CyclohexaneHCID 25517Ammonium ChlorideHCID 17723848HCID 17723848, compoundHCID 178418400CID 53628100

Product 1

HCID 23121897HCID 23121897, compoundYield 82.8%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

1,1-Dimethylethyl 4-[(4-methylphenyl)methyl]-1-piperazine carboxylate (58 g, 0.2 mol) and N,N,N′,N′-tetramethylethylenediamine (35 g, 0.3 mol) were dissolved in tetrahydrofuran (400 mL), and the mixture was cooled to −78° C. under argon atmosphere. A 1.0 M solution of sec-butyllithium in hexane and cyclohexane (240 mL, 0.24 mol) was added dropwise over 1.5 hours, and the mixture was stirred at −78° C. for 3 hours. Then, the temperature was elevated to −30° C. for 2 hours. After cooling to −78° C. again, a solution of benzophenone (55 g, 0.3 mol) in tetrahydrofuran (200 mL) was added dropwise over 1 hour, and the resulting mixture was stirred overnight while elevating the temperature to room temperature. After ice cooling, an aqueous saturated ammonium chloride solution (300 mL) was added thereto, and the mixture was stirred for 30 minutes with ice cooling. Ethyl acetate (300 mL) was added thereto, and the process of phase separation was performed. The resulting organic layer was washed with water (500 mL) and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and to the residue was added diisopropyl ether-hexane (3:1, v/v, 300 mL). The obtained crystals were collected by filtration and washed with diisopropyl ether-hexane (3:1, v/v) to obtain the title compound (66 g, yield 82%).

Workup

  1. waitThen, the temperature was elevated to −30° C. for 2 hours
  2. temperatureAfter cooling to −78° C. again
  3. stirringthe resulting mixture was stirred overnight
  4. customto room temperature
  5. stirringthe mixture was stirred for 30 minutes with ice cooling
  6. customthe process of phase separation
  7. washThe resulting organic layer was washed with water (500 mL)
  8. dry with materialdried over magnesium sulfate
  9. distillationThe solvent was distilled off under reduced pressure
  10. additionto the residue was added diisopropyl ether-hexane (3:1, v/v, 300 mL)
  11. filtrationThe obtained crystals were collected by filtration
  12. washwashed with diisopropyl ether-hexane (3:1

Sources & evidence

ORD record
ord-fdd73a3363bb4bf59e4c3a268afafda8
Source dataset
uspto-grants-2010_09
Patent number
US07795267B2

Reaction notes

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