Sulfuric Acid → 5-(2-dimethylaminoethyl)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene-5-carbaldehyde

HRID 1935325Notes

Reaction equation

HRID 1935325 reaction equation
[CH3:1][N:2]([CH3:22])[CH2:3][CH2:4][C:5]1([C:20]#N)[C:11]2[CH:12]=[CH:13][CH:14]=[CH:15][C:10]=2[CH2:9][CH2:8][C:7]2[CH:16]=[CH:17][CH:18]=[CH:19][C:6]1=2.[H-].C([Al+]CC(C)C)C(C)C.[Cl-].[NH4+].S(=O)(=O)(O)[OH:36]>C(Cl)Cl>[CH3:1][N:2]([CH3:22])[CH2:3][CH2:4][C:5]1([CH:20]=[O:36])[C:11]2[CH:12]=[CH:13][CH:14]=[CH:15][C:10]=2[CH2:9][CH2:8][C:7]2[CH:16]=[CH:17][CH:18]=[CH:19][C:6]1=2

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 25517Ammonium ChlorideHCID 21225700DiisobutylaluminumhydrideHCID 22464000HCID 22464000, compound

Product 1

HCID 224639665-(2-dimethylaminoethyl)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene-5-carbaldehyde

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a solution of 5-(2-dimethylaminoethyl)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene-5-carbonitrile (101) (4.15 g, 14.3 mmol) in 50 mL of CH2Cl2 stirred at −78° C. and maintained under a nitrogen atmosphere was added diisobutylaluminum hydride (20.6 mL of a 1.0M solution in CH2Cl2; 20.6 mmol) dropwise. The mixture was stirred at −78° C. for 30 minutes, warmed to 0° C. and left stir an additional 4 hours. The solution was poured into 35 mL of saturated aqueous ammonium chloride. The resulting gelatinous mixture was stirred vigorously for 15 minutes, then 65 mL of 1.5N sulfuric acid was added and the mixture stirred overnight. The mixture was extracted with CH2Cl2 (3×), and the combined organic layers were washed with saturated aqueous sodium bicarbonate and brine, dried the over sodium sulfate, filtered, and evaporated do dryness. The resulting oil was purified by chromatography on silica gel with 96/4/0.4 of methylene cloride/methanol/ammonium hydroxide. The product fractions were evaporated to dryness to yield the title product as an oil.

Workup

  1. temperaturemaintained under a nitrogen atmosphere
  2. temperaturewarmed to 0° C.
  3. waitleft
  4. stirringstir an additional 4 hours
  5. stirringThe resulting gelatinous mixture was stirred vigorously for 15 minutes
  6. stirringthe mixture stirred overnight
  7. extractionThe mixture was extracted with CH2Cl2 (3×)
  8. washthe combined organic layers were washed with saturated aqueous sodium bicarbonate and brine
  9. dry with materialdried the over sodium sulfate
  10. filtrationfiltered
  11. customevaporated
  12. customThe resulting oil was purified by chromatography on silica gel with 96/4/0.4 of methylene cloride/methanol/ammonium hydroxide
  13. customThe product fractions were evaporated to dryness

Sources & evidence

ORD record
ord-7a5eba3ad6634b43891ce9a09c178e67
Source dataset
uspto-grants-2002_05
Patent number
US06387893B1

Reaction notes

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