Ammonia → HCID 19972882, compound

HRID 2260651Notes

Reaction equation

HRID 2260651 reaction equation
[N:1]1[CH:2]=[CH:3][N:4]2[CH:9]=[C:8]([C:10]3([C:17](=[S:20])[NH:18][CH3:19])[CH2:15][CH2:14][CH2:13][CH2:12][C:11]3=O)[CH:7]=[CH:6][C:5]=12.[C:21]1([S:31]([NH:34][CH:35](N)[CH3:36])(=[O:33])=[O:32])[C:30]2[C:25](=[CH:26][CH:27]=[CH:28][CH:29]=2)[CH:24]=[CH:23][CH:22]=1.[NH3:38]>ClCCl.[Ti](Cl)(Cl)(Cl)Cl>[C:21]1([S:31]([NH:34][CH2:35][CH2:36][NH:38][CH:11]2[CH2:12][CH2:13][CH2:14][CH2:15][C:10]2([C:8]2[CH:7]=[CH:6][C:5]3[N:4]([CH:3]=[CH:2][N:1]=3)[CH:9]=2)[C:17](=[S:20])[NH:18][CH3:19])(=[O:33])=[O:32])[C:30]2[C:25](=[CH:26][CH:27]=[CH:28][CH:29]=2)[CH:24]=[CH:23][CH:22]=1

Participants

6

Reactant 3

HCID 222AmmoniaHCID 15290094HCID 15290094, compoundHCID 19972904HCID 19972904, compound

Product 1

HCID 19972882HCID 19972882, compound

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

600 m of 1-(imidazo[1,2-a]pyridin-6-yl)-N-methyl-2-oxocyclohexanecarbothioamide and 2.09 g of 1-naphthalenesulfonylaminoethylamine were dissolved in ml of dichloromethane to form a solution. 2 ml of a 1M solution of titanium tetrachloride in dichloromethane was added to this solution in 30 minutes at room temperature. The obtained mixture was stirred overnight, followed by the addition of 1 ml of concentrated aqueous ammonia. The crystal thus precipitated was filtered out, followed by the washing with 10% methanol/dichloromethane. The filtrate was concentrated in a vacuum, followed by the addition of 10 ml of methanol. 200 mg of sodium cyanoborohydride was added to the mixture at room temperature. The obtained mixture was stirred for one hour and concentrate, in a vacuum, followed by the addition of a saturated aqueous solution of sodium hydrogencarbonate. The resulting mixture was extracted with chloroform. The chloroform phase was dried over anhydrous sodium sulfate and concentrated in a vacuum. The residue was purified by silica gel column chromatography (solvent: a 10:10:1 dichloromethane/ethyl acetate/methanol mixture) to give 280 mg of a lower-polarity diastereomer (L-form) and 350 mg of a higher-polarity diastereomer (M-form) each as a pale-yellow crystal.

Workup

  1. customto form a solution
  2. customThe crystal thus precipitated
  3. filtrationwas filtered out
  4. concentrationThe filtrate was concentrated in a vacuum
  5. additionfollowed by the addition of 10 ml of methanol
  6. addition200 mg of sodium cyanoborohydride was added to the mixture at room temperature
  7. stirringThe obtained mixture was stirred for one hour
  8. concentrationconcentrate, in a vacuum
  9. additionfollowed by the addition of a saturated aqueous solution of sodium hydrogencarbonate
  10. extractionThe resulting mixture was extracted with chloroform
  11. dry with materialThe chloroform phase was dried over anhydrous sodium sulfate
  12. concentrationconcentrated in a vacuum
  13. customThe residue was purified by silica gel column chromatography (solvent
  14. customa 10:10:1 dichloromethane/ethyl acetate/methanol mixture) to give 280 mg of a lower-polarity diastereomer (L-form) and 350 mg of a higher-polarity diastereomer (M-form) each as a pale-yellow crystal

Sources & evidence

ORD record
ord-bd95a90952904efcb8d143750b6c1866
Source dataset
uspto-grants-1995_12
Patent number
US05478839

Reaction notes

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