Benzosuberone → HCID 68772034, compound

HRID 2382176Notes

Reaction equation

HRID 2382176 reaction equation
[CH2:1]1[CH2:12][C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:4](=O)[CH2:3][CH2:2]1.[CH3:13][C@@H:14]1[CH2:19][NH:18][CH2:17][CH2:16][NH:15]1.[BH4-].[Na+].C(Cl)Cl.CO>CO.CC(C)[O-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-]>[CH3:13][C@H:14]1[NH:15][CH2:16][CH2:17][N:18]([CH:4]2[C:6]3[CH:7]=[CH:8][CH:9]=[CH:10][C:11]=3[CH2:12][CH2:1][CH2:2][CH2:3]2)[CH2:19]1

Participants

7

Reactant 4

HCID 70003BenzosuberoneHCID 4311764Sodium borohydrideHCID 73304342-Methylpiperazine, (R)-HCID 21226129Dichloromethane methanol

Product 1

HCID 68772034HCID 68772034, compoundYield 70.2%

Reagents, catalysts & solvents 2

HCID 11026Titanium isopropoxideCatalystHCID 887MethanolSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 1-benzosuberone (0.803 ml, 5.01 mmol), (R)-2-methylpiperazine (1.505 g, 15 mmol) in titanium (4+) isopropoxide (4.399 ml, 15 mmol) was heated at 80° C. overnight. After cooling to RT, the reaction mixture was diluted with 30 mL of MeOH and sodium borohydride (0.529 ml, 15 mmol) was slowly added. After stirring at rt for 20 min, the solvent was evaporated to dryness. The residue was redissolved in 50 mL of EtOAc and to this solution was added 10 g of NaHCO3 and 0.5 mL of water to generate a white slurry. After stirring at rt for 2 h, the mixture was filtered with the help of excess EtOAc and the filtrate was evaporated to dryness. Column chromatography (SiO2, DCM/MeOH=100:5 to 100:10 to 100:15 to 100:20) gave (3R)-3-methyl-1-(6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-yl)piperazine (860 mg, 70% yield) as an off white gum.

Workup

  1. temperatureAfter cooling to RT
  2. additionwas slowly added
  3. customthe solvent was evaporated to dryness
  4. dissolutionThe residue was redissolved in 50 mL of EtOAc and to this solution
  5. additionwas added 10 g of NaHCO3 and 0.5 mL of water
  6. stirringAfter stirring at rt for 2 h
  7. filtrationthe mixture was filtered with the help of excess EtOAc
  8. customthe filtrate was evaporated to dryness

Sources & evidence

ORD record
ord-206daf58f0b0432389e685906095908e
Source dataset
uspto-grants-2012_09
Patent number
US08258306B2

Reaction notes

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