HCID 14209963, compound → HCID 14209964, compound

HRID 1031442Notes

Reaction equation

HRID 1031442 reaction equation
[CH3:1][C:2]1([CH3:19])[C:11]2[C:6](=[C:7](Br)[C:8]([NH2:15])=[C:9]([N+:12]([O-])=O)[CH:10]=2)[C:5](=[O:17])[NH:4][C:3]1=[O:18]>[Pd].CO>[CH3:1][C:2]1([CH3:19])[C:11]2[CH:10]=[C:9]3[NH:12][C:10]([C:11]4[CH:6]=[CH:5][N:4]=[CH:3][CH:2]=4)=[N:15][C:8]3=[CH:7][C:6]=2[C:5](=[O:17])[NH:4][C:3]1=[O:18]

Participants

4

Reactant 1

HCID 14209963HCID 14209963, compound

Product 1

HCID 14209964HCID 14209964, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

27 g. (82 mmole) 4,4-dimethyl-6-nitro-7-amino-8- bromo-1,2,3,4-tetrahydroisoquinoline-1,3-dione were hydrogenated in 300 ml. methanol in the presence of 2 g. 10% palladium on charcoal. After separating off the catalyst, the filtrate was evaporated, the residue was mixed with 500 ml. methylene chloride and 50 ml. triethylamine and, while cooling, 24 g. isonicotinic acid chloride hydrochloride slowly introduced. After 4 hours, the methylene chloride was evaporated off, the residue was worked up with water, filtered off with suction and the moist residue heated under reflux for 20 hours in 500 ml. ethanol and 200 ml. concentrated hydrochloric acid. The evaporation residue was subsequently mixed with water, neutralised and purified by column chromatography (silica gel, elution agent: methylene chloride/ methanol saturated with ammonia; 10:1 v/v). After recrystallisation from ethanol/water, there were obtained 12.2 g. (51% of theory) of the title compound; m.p. above 300° C.

Workup

  1. customAfter separating off the catalyst
  2. customthe filtrate was evaporated
  3. additionthe residue was mixed with 500 ml
  4. temperaturetriethylamine and, while cooling
  5. additionisonicotinic acid chloride hydrochloride slowly introduced
  6. customthe methylene chloride was evaporated off
  7. filtrationfiltered off with suction
  8. temperaturethe moist residue heated
  9. temperatureunder reflux for 20 hours in 500 ml
  10. additionThe evaporation residue was subsequently mixed with water
  11. customneutralised and purified by column chromatography (silica gel, elution agent: methylene chloride/ methanol saturated with ammonia; 10:1 v/v)
  12. customAfter recrystallisation from ethanol/water
  13. customthere were obtained 12.2 g

Sources & evidence

ORD record
ord-62132942ca6540589ff6a201deb2a224
Source dataset
uspto-grants-1990_09
Patent number
US04954498

Reaction notes

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