Sulfuric Acid → HCID 14209962, compound

HRID 1196888Notes

Reaction equation

HRID 1196888 reaction equation
S(=O)(=O)(O)O.[CH3:6][C:7]1([CH3:22])[C:16]2[C:11](=[CH:12][C:13]([NH2:20])=[C:14]([N+:17]([O-])=O)[CH:15]=2)[C:10](=[O:21])[NH:9][CH2:8]1>[N+]([O-])(O)=O>[CH3:6][C:7]1([CH3:22])[C:16]2[CH:15]=[C:14]3[NH:17][C:15]([C:16]4[CH:11]=[CH:10][N:9]=[CH:8][CH:7]=4)=[N:20][C:13]3=[CH:12][C:11]=2[C:10](=[O:21])[NH:9][CH2:8]1

Participants

4

Reactant 2

HCID 1118Sulfuric Acid2×HCID 14209955HCID 14209955, compound

Product 1

HCID 14209962HCID 14209962, compound

Reagents, catalysts & solvents 1

HCID 944Nitric AcidSolvent

Conditions

Temperature
25 °C

Procedure

45 g. (186 mmole) of the above compound were nitrated in 300 ml. concentrated sulphuric acid at 0° C. by dropping in nitration acid (8.5 ml. 96% nitric acid +30 ml. concentrated sulphuric acid). After completion of the addition, the reaction mixture was further stirred for 3 hours at 25° C., poured on to ice, filtered off with suction and recrystallized from 400 ml. glacial acetic acid. The crystallizate contained the false isomer (24 g.). The filtrate was evaporated and the residue boiled with 200 ml. ethanol and 40 ml. concentrated hydrochloric acid for 20 hours, evaporated, mixed with water, neutralized, extracted with methylene chloride, dried and evaporated. The residue was purified by column chromatography (silica gel, elution agent: ethyl acetate/methylene chloride; 1:10 v/v to 1:1 v/v) to give 11 g. (25% of theory) 4,4-dimethyl-6-nitro-7-amino-1,2,3,4-tetrahydroisoquinolin-1-one; m.p. 231°-234° C.

Workup

  1. customat 0° C.
  2. additionAfter completion of the addition
  3. additionpoured on to ice
  4. filtrationfiltered off with suction
  5. customrecrystallized from 400 ml
  6. customThe filtrate was evaporated
  7. waitconcentrated hydrochloric acid for 20 hours
  8. customevaporated
  9. additionmixed with water
  10. extractionextracted with methylene chloride
  11. customdried
  12. customevaporated
  13. customThe residue was purified by column chromatography (silica gel, elution agent: ethyl acetate/methylene chloride; 1:10 v/v to 1:1 v/v)
  14. customto give 11 g

Sources & evidence

ORD record
ord-99b4b45a6a664985ab99c99722f6cf42
Source dataset
uspto-grants-1992_05
Patent number
US05116843

Reaction notes

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