Methyl 3,4,5-trimethoxyanthranilate → HCID 178486763, compound

HRID 612146Notes

Reaction equation

HRID 612146 reaction equation
[CH3:1][O:2][C:3]1[C:12]([O:13][CH3:14])=[C:11]([O:15][CH3:16])[CH:10]=[C:5]([C:6]([O:8]C)=O)[C:4]=1[NH2:17]>COC(OC)N(C)C>[OH:8][C:6]1[C:5]2[C:4](=[C:3]([O:2][CH3:1])[C:12]([O:13][CH3:14])=[C:11]([O:15][CH3:16])[CH:10]=2)[N:17]=[CH:12][C:3]=1[C:4]#[N:17]

Participants

3

Reactant 1

HCID 78735Methyl 3,4,5-trimethoxyanthranilate

Product 1

HCID 178486763HCID 178486763, compoundYield 159.2%

Reagents, catalysts & solvents 1

HCID 78373Dimethylformamide dimethyl acetalSolvent

Conditions

Temperature
-78 °C

Procedure

A mixture of 4.82 g of methyl 3,4,5-trimethoxyanthranilate in 20 ml of N,N-dimethylformamide dimethyl acetal was refluxed for 18 hours and concentrated in vacuo. The crude amidine product was used in the next step without further purification. To 25 ml of tetrahydrofuran at -78° C. was added 17.6 ml of 2.5M n-butyllithium in hexanes. Then 2.35 ml of acetonitrile in 45 ml of tetrahydrofuran was added dropwise. The mixture was stirred at -78° C. for 15 minutes. Then a solution of the crude amidine in 30 ml of tetrahydrofuran was added dropwise. The mixture was stirred at -78° C. for minutes, then 5.7 ml of acetic acid was added. The mixture was warmed to room temperature, and 100 ml of water was added. The product was collected, washed with water, and dried to give 4.14 g of 4-hydroxy-6,7,8-trimethoxy-quinoline-3-carbonitrile as a solid, mp 280° C. (decomposed); mass spectrum (electrospray, m/e): M+H 261.2.

Workup

  1. temperaturewas refluxed for 18 hours
  2. concentrationconcentrated in vacuo
  3. customThe crude amidine product was used in the next step without further purification
  4. additionTo 25 ml of tetrahydrofuran at -78° C. was added 17.6 ml of 2.5M n-butyllithium in hexanes
  5. additionThen 2.35 ml of acetonitrile in 45 ml of tetrahydrofuran was added dropwise
  6. additionThen a solution of the crude amidine in 30 ml of tetrahydrofuran was added dropwise
  7. stirringThe mixture was stirred at -78° C. for minutes
  8. addition5.7 ml of acetic acid was added
  9. temperatureThe mixture was warmed to room temperature
  10. addition100 ml of water was added
  11. customThe product was collected
  12. washwashed with water
  13. customdried

Sources & evidence

ORD record
ord-28614f9ba6b84bae900568e9697be248
Source dataset
uspto-grants-1999_12
Patent number
US06002008

Reaction notes

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