Water → HCID 86693520, compound

HRID 575457Notes

Reaction equation

HRID 575457 reaction equation
[CH2:1]([O:5][C:6]1[CH:11]=[CH:10][C:9]([I:12])=[CH:8][C:7]=1[NH:13][N:14]=[C:15](Cl)[C:16]([O:18][CH2:19][CH3:20])=[O:17])[CH2:2][C:3]#[CH:4].C(N(CC)CC)C.O.C(OCC)(=O)C>C1(C)C=CC=CC=1>[I:12][C:9]1[CH:10]=[CH:11][C:6]2[O:5][CH2:1][CH2:2][C:3]3[N:13]([N:14]=[C:15]([C:16]([O:18][CH2:19][CH3:20])=[O:17])[CH:4]=3)[C:7]=2[CH:8]=1

Participants

6

Reactant 4

HCID 962WaterHCID 8471TriethylamineHCID 8857Ethyl AcetateHCID 86693518HCID 86693518, compound

Product 1

HCID 86693520HCID 86693520, compoundYield 74%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
125 °C

Procedure

To a solution of ethyl 2-{2-[2-(but-3-yn-1-yloxy)-5-iodophenyl]hydrazin-1-ylidene}-2-chloroacetate (3.9 g, 9.27 mmol) in toluene (800 ml) was added triethylamine (13 ml, 9.32 mmol) and the mixture was then stirred under reflux (heating block at 125° C.) for 18 hours. After cooling to ambient temperature water (100 ml) and ethyl acetate (100 ml) were added and the mixture was transferred into a separation flask. The organic layer was separated, washed with brine (200 ml), dried over MgSO4, filtered and pre-absorbed onto a small amount of silica. Purification by FCC (silica, 0-20% ethyl acetate in heptane) provided 2.63 g (74%) of the title compound as crystalline solid. 1H NMR (500 MHz, CDCl3) δ ppm 1.43 (3H, t, J=7.17 Hz), 3.09 (2H, t, J=6.03 Hz), 4.45 (2H, q, J=7.17 Hz), 4.53 (2H, t, J=6.10 Hz), 6.81 (1H, s), 6.93 (1H, d, J=8.54 Hz), 7.61 (1H, dd, J=8.54, 2.14 Hz), 8.28 (1H, d, J=2.14 Hz);); M+1=385

Workup

  1. temperatureunder reflux
  2. additionwere added
  3. customthe mixture was transferred into a separation flask
  4. customThe organic layer was separated
  5. washwashed with brine (200 ml)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. custompre-absorbed onto a small amount of silica
  9. customPurification by FCC (silica, 0-20% ethyl acetate in heptane)

Sources & evidence

ORD record
ord-834fa10fa3bd40498e7158f0574cd5a9
Source dataset
uspto-grants-2015_05
Patent number
US09034866B2

Reaction notes

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