Dichloromethane → HCID 58494891, compound

HRID 925187Notes

Reaction equation

HRID 925187 reaction equation
Cl.[NH:2]1[C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][C:7]=2[CH:6]=[CH:5][CH:4]=[CH:3]1.C(Cl)Cl.Cl[C:17]([O:19][CH2:20][CH3:21])=[O:18]>Cl>[CH2:20]([O:19][C:17]([N:2]1[CH2:3][CH2:4][C:5]2[CH:6]=[CH:7][CH:12]=[CH:11][C:10]=2[CH2:9][CH2:8]1)=[O:18])[CH3:21]

Participants

5

Reactant 3

HCID 6344DichloromethaneHCID 10928Ethyl chloroformateHCID 19991712HCID 19991712, compound

Product 1

HCID 58494891HCID 58494891, compoundYield 92.2%

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidSolvent

Conditions

Temperature
0 °C

Procedure

To a stirred solution of benzazepine hydrochloride (5.0 g, 27.2 mmol) in DCM (˜50 ml) diisopropyl ethylamine (10.4 ml, 59.8 mmol) was added at 0° C., followed by dropwise addition of ethyl chloroformate (2.86 ml, 29.9 mmol). The reaction was stirred at 0° C. for 1 hour and then allowed to warm to room temperature over 2 hours. LCMS indicated reaction was complete, and 1N HCl (˜100 ml) was added to the reaction. The layers were separated and the aqueous layer was extracted with additional DCM (2×). The combined DCM extracts were washed with brine and dried over Na2SO4. The solvent was evaporated in vacuo and the residue purified by silica-gel chromatography (gradient elution: 0 to 40% EtOAc in hexanes) to provide the sub-title product as an oil (5.5 g). 1HNMR (CDCl3) δ 7.14 (s, 4H), 4.18 (q, J=7.2 Hz, 2H), 3.61 (bs, 4H), 2.92 (bs, 4H), 1.29 (t, J=7.2 Hz, 3H); MS: ESI (positive): 220 (M+H).

Workup

  1. temperatureto warm to room temperature over 2 hours
  2. customreaction
  3. customThe layers were separated
  4. extractionthe aqueous layer was extracted with additional DCM (2×)
  5. washThe combined DCM extracts were washed with brine
  6. dry with materialdried over Na2SO4
  7. customThe solvent was evaporated in vacuo
  8. customthe residue purified by silica-gel chromatography (gradient elution: 0 to 40% EtOAc in hexanes)

Sources & evidence

ORD record
ord-1cb9d8d80f8f430a9d354e721c4ff3e3
Source dataset
uspto-grants-2016_03
Patent number
US09284277B2

Reaction notes

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