Ethylamine → HCID 14392096, compound

HRID 1607052Notes

Reaction equation

HRID 1607052 reaction equation
[CH3:1][C:2]1([CH3:16])[S:7][C:6]2[S:8][C:9]([S:11]([NH2:14])(=[O:13])=[O:12])=[CH:10][C:5]=2[C:4](=O)[CH2:3]1.[CH2:17]([NH2:19])[CH3:18].[BH4-].[Na+]>O1CCCC1.C1C=CC=CC=1.[Ti](Cl)(Cl)(Cl)Cl>[CH2:17]([NH:19][CH:4]1[CH2:3][C:2]([CH3:16])([CH3:1])[S:7][C:6]2[S:8][C:9]([S:11]([NH2:14])(=[O:13])=[O:12])=[CH:10][C:5]1=2)[CH3:18]

Participants

7

Reactant 3

HCID 6341EthylamineHCID 4311764Sodium borohydrideHCID 14392083HCID 14392083, compound

Product 1

HCID 14392096HCID 14392096, compoundYield 77.1%

Reagents, catalysts & solvents 3

HCID 24193Titanium TetrachlorideCatalystHCID 241BenzeneSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of 5,6-dihydro-6,6-dimethyl-4H-thieno[2,3-b]thiopyran-4-one 2-sulfonamide (3.00 g, 0.011 mol) in dry tetrahydrofuran (40 ml) and benzene (40 ml) was cooled to -10° C. and condensed ethylamine (15 ml, 10.8 g, 0.24 mol) was added rapidly with stirring. Titanium tetrachloride 1.14 g, 0.006 mol) was added over 20 minutes while maintaining the temperature below 0° C. The mixture was stirred at ambient temperature for 2.5 hours, filtered, and the solid was washed with tetrahydrofuran. The combined filtrate and washings were evaporated in vacuo and the residue was suspended in absolute methanol (105 ml). With stirring under nitrogen, sodium borohydride (0.53 g, 0.014 mol) was added portionwise over 15 minutes and the mixture was stirred at ambient temperature for 21 hours. After acidification with concentrated hydrochloric acid, the mixture was concentrated in vacuo. The residue was distributed between water (100 ml) and ethyl acetate (100 ml), and the aqueous layer was separated and extracted with ethyl acetate (2×50 ml). The water layer then was basified with saturated sodium bicarbonate solution and extracted with ethyl acetate (3×250 ml). The combined extracts were washed with water (3×), dried over sodium sulfate, and evaporated in vacuo. The residue was crystallized as the hydrochloride salt from ethanolic hydrogen chloride to afford 2.60 g (69%) of pure product.

Workup

  1. additionwas added rapidly
  2. temperaturewhile maintaining the temperature below 0° C
  3. stirringThe mixture was stirred at ambient temperature for 2.5 hours
  4. filtrationfiltered
  5. washthe solid was washed with tetrahydrofuran
  6. customThe combined filtrate and washings were evaporated in vacuo
  7. stirringWith stirring under nitrogen
  8. stirringthe mixture was stirred at ambient temperature for 21 hours
  9. concentrationAfter acidification with concentrated hydrochloric acid, the mixture was concentrated in vacuo
  10. customthe aqueous layer was separated
  11. extractionextracted with ethyl acetate (2×50 ml)
  12. extractionextracted with ethyl acetate (3×250 ml)
  13. washThe combined extracts were washed with water (3×)
  14. dry with materialdried over sodium sulfate
  15. customevaporated in vacuo
  16. customThe residue was crystallized as the hydrochloride salt from ethanolic hydrogen chloride

Sources & evidence

ORD record
ord-d25c348ae5d14ce2ad1236b5c647b6eb
Source dataset
uspto-grants-1989_09
Patent number
US04863922

Reaction notes

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