Diethyl Ether → HCID 178492145, compound

HRID 1607171Notes

Reaction equation

HRID 1607171 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([N:9]=[C:10]=S)=[CH:5][CH:4]=1.[NH2:12][C:13]1[CH:14]=[C:15]2[C:19](=[CH:20][C:21]=1[NH2:22])[NH:18][C:17](=[O:23])[C:16]2([CH3:25])[CH3:24].C(N(CC)CC)C.C(OCC)C>ClCCl.C(O)C>[CH3:24][C:16]1([CH3:25])[C:15]2[C:19](=[CH:20][C:21]3[NH:22][C:10]([NH:9][C:6]4[CH:7]=[CH:8][C:3]([O:2][CH3:1])=[CH:4][CH:5]=4)=[N:12][C:13]=3[CH:14]=2)[NH:18][C:17]1=[O:23]

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 8471TriethylamineHCID 752934-Methoxyphenyl isothiocyanateHCID 135892372H-Indol-2-one, 5,6-diamino-1,3-dihydro-3,3-dimethyl-

Product 1

HCID 178492145HCID 178492145, compound

Reagents, catalysts & solvents 2

HCID 702EthanolSolvent2×HCID 6344DichloromethaneSolvent

Conditions

Temperature
60 °C

Procedure

3 ml. 4-Methoxyphenyl isothiocyanate are added dropwise to a solution of 3.8 g. 5,6-diamino-3,3-dimethylindolin-2-one in 20 ml. dry ethanol. The reaction mixture is stirred for 3 hours at 60° C., the solvent is removed in a vacuum, the residue is suspended in water and extracted with dichloromethane. The organic phase is dried over anhydrous sodium sulphate, filtered and the solvent removed in a vacuum to give 7.5 g. of residue, 6.8 g. of which are dissolved in 1 liter dichloromethane. 8 ml. Triethylamine and 16 g. mercurous chloride are added thereto and the reaction mixture boiled under reflux for 3 days. The solvent is removed in a vacuum, the residue is suspended in 100 ml. ethanol and 30 ml. concentrated hydrochloric acid are added thereto, followed by saturation with hydrogen sulphide. The reaction mixture is heated under reflux and the precipitated mercury sulphide is filtered off and then washed with hot ethanol. The filtrate is evaporated to dryness in a vacuum, the residue is dissolved in 100 ml. water, insoluble components are filtered off, the filtrate is rendered alkaline with 2N ammonia solution, the base is filtered off with suction and then washed with water. The product is purified over a silica gel column (elution agent 1,1,1-trichloroethane/methanolic ammonia 15:1 v/v). The appropriate fractions are evaporated in a vacuum, the oil obtained is taken up in hot ethanol, diethyl ether is added thereto until turbidity commences and then left to crystallise. There are obtained 2.8 L g. of the title compound; m.p. 286°-288° C.

Workup

  1. customthe solvent is removed in a vacuum
  2. extractionextracted with dichloromethane
  3. dry with materialThe organic phase is dried over anhydrous sodium sulphate
  4. filtrationfiltered
  5. customthe solvent removed in a vacuum
  6. customto give 7.5 g
  7. temperatureunder reflux for 3 days
  8. customThe solvent is removed in a vacuum
  9. additionconcentrated hydrochloric acid are added
  10. temperatureThe reaction mixture is heated
  11. temperatureunder reflux
  12. filtrationthe precipitated mercury sulphide is filtered off
  13. washwashed with hot ethanol
  14. customThe filtrate is evaporated to dryness in a vacuum
  15. dissolutionthe residue is dissolved in 100 ml
  16. filtrationwater, insoluble components are filtered off
  17. filtrationthe base is filtered off with suction
  18. washwashed with water
  19. customThe product is purified over a silica gel column (elution agent 1,1,1-trichloroethane/methanolic ammonia 15:1 v/v)
  20. customThe appropriate fractions are evaporated in a vacuum
  21. customthe oil obtained
  22. waituntil turbidity commences and then left
  23. customto crystallise
  24. customThere are obtained 2.8 L

Sources & evidence

ORD record
ord-fd57a75eeef346e2adc3f982ac00d87d
Source dataset
uspto-grants-1989_09
Patent number
US04863945

Reaction notes

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