Triethylamine → HCID 59829174, compound

HRID 2061411Notes

Reaction equation

HRID 2061411 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([C:19](=O)[CH:20]=[CH2:21])[CH:5]=[C:6]([Br:18])[C:7]=1[O:8][CH2:9][C:10]1[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[CH:12][CH:11]=1.O.[NH2:24][NH2:25].[Br:26][C:27]1[CH:28]=[C:29]([CH:33]=[CH:34][C:35]=1[Cl:36])[C:30](Cl)=[O:31].C(N(CC)CC)C>C(O)C.ClCCl>[Br:26][C:27]1[CH:28]=[C:29]([C:30]([N:24]2[CH2:21][CH2:20][C:19]([C:4]3[CH:3]=[C:2]([Br:1])[C:7]([O:8][CH2:9][C:10]4[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[CH:12][CH:11]=4)=[C:6]([Br:18])[CH:5]=3)=[N:25]2)=[O:31])[CH:33]=[CH:34][C:35]=1[Cl:36]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 24654Hydrazine hydrate (1:1)HCID 202297303-Bromo-4-chlorobenzoyl chlorideHCID 59829207HCID 59829207, compound

Product 1

HCID 59829174HCID 59829174, compoundYield 35%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
85 °C

Procedure

To a stirred mixture of 1-(3,5-dibromo-4-(4-methoxybenzyloxy)phenyl)prop-2-en-1-one (E) (0.1003 g, 0.235 mmol) in ethanol (2 mL) was added hydrazine monohydrate (19.4 μL, 0.400 mmol) and the mixture was heated at 85° C. for 1 h. After cooling, the mixture was partitioned between dichloromethane (15 mL) and water (10 mL). The aqueous layer was extracted further with dichloromethane (15 mL) and the combined organic extracts were washed with brine (10 mL), dried (Na2SO4), and nitrogen was bubbled through the solution for a few minutes. The solution was concentrated to 10 mL in vacuo with no heat and then added by syringe to a stirred mixture of 3-bromo-4-chlorobenzoyl chloride (59.8 mg, 0.236 mmol) in dichloromethane (1 mL) under nitrogen. Triethylamine (34.4 μL, 0.247 mmol) was then added dropwise and the resulting solution was stirred at room temperature for 64 h. The mixture was diluted with dichloromethane (10 mL) and successively washed with water (10 mL), 10% aqueous citric acid (10 mL), 1 N aqueous NaOH (10 mL), water (10 mL) and brine (10 mL). The remaining organic layer was dried (Na2SO4) and evaporated. The residue was purified by flash chromatography (silica gel, 40% EtOAc/pet. ether) to give 54.1 mg (35%) of the title compound as a yellow solid. 1H NMR δ (ppm) (CDCl3): 3.23 (2 H, t, J=10.04 Hz), 3.83 (3 H, s), 4.26 (2 H, t, J=10.05 Hz), 5.02 (2 H, s), 6.93 (2 H, d, J=8.32 Hz), 7.51 (2 H, d, J=8.18 Hz), 7.55 (1 H, d, J=8.38 Hz), 7.83 (2 H, s), 7.86 (1 H, dd, J=8.43, 2.07 Hz), 8.28 (1 H, d, J=2.02 Hz).

Workup

  1. temperatureAfter cooling
  2. customthe mixture was partitioned between dichloromethane (15 mL) and water (10 mL)
  3. extractionThe aqueous layer was extracted further with dichloromethane (15 mL)
  4. washthe combined organic extracts were washed with brine (10 mL)
  5. dry with materialdried (Na2SO4), and nitrogen
  6. customwas bubbled through the solution for a few minutes
  7. concentrationThe solution was concentrated to 10 mL in vacuo with
  8. temperatureno heat
  9. washsuccessively washed with water (10 mL), 10% aqueous citric acid (10 mL), 1 N aqueous NaOH (10 mL), water (10 mL) and brine (10 mL)
  10. dry with materialThe remaining organic layer was dried (Na2SO4)
  11. customevaporated
  12. customThe residue was purified by flash chromatography (silica gel, 40% EtOAc/pet. ether)

Sources & evidence

ORD record
ord-08fd1388806a4b349381e99df33b6839
Source dataset
uspto-grants-2012_10
Patent number
US08283351B2

Reaction notes

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