Ethyl Acetate → HCID 14012376, compound

HRID 1650653Notes

Reaction equation

HRID 1650653 reaction equation
[C:1]([C:3](=[N:10][NH:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[C:4]([NH:6][CH2:7][CH2:8][CH3:9])=[O:5])#[N:2].[Cl-].[Al+3].[Cl-].[Cl-].C(OCC)(=O)C>C1(C)C=CC=CC=1>[NH2:2][C:1]1[C:17]2[C:12](=[C:13]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[CH:14]=[CH:15][CH:16]=2)[N:11]=[N:10][C:3]=1[C:4]([NH:6][CH2:7][CH2:8][CH3:9])=[O:5]

Participants

5

Reactant 3

HCID 8857Ethyl AcetateHCID 6451240Aluminum(III) ChlorideHCID 86743917HCID 86743917, compound

Product 1

HCID 14012376HCID 14012376, compoundYield 94%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

To a suspension of the product of Example A (9.50 g) in dry toluene (150 ml) was added aluminum chloride (14.44 g). The mixture was stirred under nitrogen at reflux (110°) for three hours. The reaction mixture was then cooled to room temperature, and the toluene was decanted from the dark, oily layer into a flask. The oily layer was chilled to 0°, and aqueous sodium hydroxide (1 Liter of 20% w/v solution) was slowly added with stirring to produce a yellow suspension which was stirred with the previously decanted toluene and ethyl acetate (1 Liter) until the precipitate dissolved. The organic layer was separated and the aqueous layer was extracted two times with ethyl acetate (500 ml each time). The extracts were combined, washed with water (1 Liter) and saturated NaCl (500 ml), dried, and evaportated in vacuo to provide 8.92 g (94% yield) of a yellow solid. The solid was purified by flash chromatography over silica gel. Elution with dichloromethane/acetonitrile (95:5) provided the title compound as 7.70 g (81% yield) of an off white solid. Recrystallization from toluene/hexane provided 6.43 g (68% yield) of white crystals m.p. 153°-155°. A second recrystallization from toluene/hexane provided the title compound as white crystals, m.p. 153°-155°. 1H NMR (CHCl3 -d, characteristic peaks only): 1.00 (t, 3H), 1.66 (sextet, 2H), 3.46 (q, 2H), 7.43-7.54 (m, 3H), 7.69-7.88 (m, 5H), 8.60 (br.t, exchangeable, 1H).

Workup

  1. temperatureat reflux (110°) for three hours
  2. customthe toluene was decanted from the dark, oily layer into a flask
  3. temperatureThe oily layer was chilled to 0°
  4. additionaqueous sodium hydroxide (1 Liter of 20% w/v solution) was slowly added
  5. stirringwith stirring
  6. customto produce a yellow suspension which
  7. dissolutiondissolved
  8. customThe organic layer was separated
  9. extractionthe aqueous layer was extracted two times with ethyl acetate (500 ml each time)
  10. washwashed with water (1 Liter) and saturated NaCl (500 ml)
  11. customdried

Sources & evidence

ORD record
ord-c4552d25f2bc416d938f86adb0b5d92a
Source dataset
uspto-grants-1990_05
Patent number
US04925844

Reaction notes

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