2,5-Hexanedione → HCID 722206, compound

HRID 1425633Notes

Reaction equation

HRID 1425633 reaction equation
[NH2:1][C:2]1[CH:3]=[C:4]([C:12]([O:14][CH3:15])=[O:13])[CH:5]=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].[CH2:16]([CH2:20][C:21](=O)[CH3:22])[C:17]([CH3:19])=O>C1(C)C=CC=CC=1.CC1C=CC(S(O)(=O)=O)=CC=1>[CH3:22][C:21]1[N:1]([C:2]2[CH:11]=[C:6]([C:7]([O:9][CH3:10])=[O:8])[CH:5]=[C:4]([CH:3]=2)[C:12]([O:14][CH3:15])=[O:13])[C:17]([CH3:19])=[CH:16][CH:20]=1

Participants

5

Reactant 2

HCID 80352,5-HexanedioneHCID 66831Dimethyl 5-aminoisophthalate

Product 1

HCID 722206HCID 722206, compoundYield 92%

Reagents, catalysts & solvents 2

HCID 6101p-Toluenesulfonic acidCatalystHCID 1140TolueneSolvent

Procedure

To a solution of dimethyl 5-aminoisophthalate (8, 10.5 g, 50 mmol) in toluene (50 mL) was added acetonylacetone (6.18 mL, 52.5 mmol) and p-TsOH (95 mg, 0.5 mmol). The reaction mixture was heated in a Dean-Stark apparatus under reflux for 12 h. After cooling to room temperature, the mixture was concentrated with a rotary evaporator, and the resulting brown oil was purified by flash column chromatography (EtOAc/hexanes, 1:19-1:9) to give 9 (13.2 g, 46 mmol, 92%) as a white solid: 1H NMR (500 MHz, CDCl3) δ2.05 (s, 6H), 3.99 (s, 6H), 5.95 (s, 2H), 8.11 (s, 2H), 8.74 (s, 1H); 13C NMR (125 MHz, CDCl3) δ13.3, 52.9, 106.8, 128.9, 130.0, 132.0, 133.6, 139.9, 165.7; LC-MS (M+H+) calcd for C16H18NO4 288, found 288.

Workup

  1. temperatureThe reaction mixture was heated in a Dean-Stark apparatus
  2. temperatureunder reflux for 12 h
  3. concentrationthe mixture was concentrated with a rotary evaporator
  4. customthe resulting brown oil was purified by flash column chromatography (EtOAc/hexanes, 1:19-1:9)

Sources & evidence

ORD record
ord-5137694d5bdf47b78668b282434d6d22
Source dataset
uspto-grants-2015_01
Patent number
US08932842B2

Reaction notes

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