Acetic Acid → 5-(3-Chloropropyl)-10,11-dihydro-5H-dibenz[b,f]azepine

HRID 363309

Reaction equation

HRID 363309 reaction equation
[Cl:1][CH2:2][CH2:3][C:4]([N:6]1[C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][C:11]=2[CH2:10][CH2:9][C:8]2[CH:17]=[CH:18][CH:19]=[CH:20][C:7]1=2)=O.[BH4-].[Na+].C(O)(=O)C.O>O1CCCC1>[Cl:1][CH2:2][CH2:3][CH2:4][N:6]1[C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][C:11]=2[CH2:10][CH2:9][C:8]2[CH:17]=[CH:18][CH:19]=[CH:20][C:7]1=2

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 962WaterHCID 606961HCID 606961, compoundHCID 4311764Sodium borohydride2×

Product 1

HCID 2867795-(3-Chloropropyl)-10,11-dihydro-5H-dibenz[b,f]azepineYield 38.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 3-chloro-1-(10,11-dihydro-5H-dibenz[b,f]azepin-5-yl)-1-propanone (14.0 g, 0.044 mol) in tetrahydrofuran (150 ml) at 0° C., sodium borohydride (6.66 g, 0.176 mol) was added, followed by dropwise addition of glacial acetic acid (10.0 ml). The resulting mixture was stirred at room temperature overnight and then heated at reflux temperature for 2 h. More sodium borohydride (6.50 g, 172 mmol) and then borontrifluoride diethyl etherate (20.0 ml, 0.163 mol) were added and heating at reflux temperature was continued for 20 h. Water (350 ml) was cautiously added and the phases were separated. The aqueous phase was extracted with toluene (3×100 ml). The combined organic phases were washed with brine (3×100 ml), dried (MgSO4) and concentrated in vacuo. The residue was purified by flash chromatography on silica gel (100 g) using a gradient of heptane and ethyl acetate (10:0→10:2), to give 4.58 g (38%) of 5-(3-chloropropyl)-10,11-dihydro-5H-dibenz[b,f]azepine as an oil.

Workup

  1. temperatureheated
  2. temperatureat reflux temperature for 2 h
  3. temperatureheating
  4. temperatureat reflux temperature
  5. waitwas continued for 20 h
  6. customthe phases were separated
  7. extractionThe aqueous phase was extracted with toluene (3×100 ml)
  8. washThe combined organic phases were washed with brine (3×100 ml)
  9. dry with materialdried (MgSO4)
  10. concentrationconcentrated in vacuo
  11. customThe residue was purified by flash chromatography on silica gel (100 g)

Sources & evidence

ORD record
ord-943a4bf634e54b0b94c84c125de361c2
Source dataset
uspto-grants-1999_02
Patent number
US05874428

Linked notes

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