Sulfuric Acid → 4H-Thieno[3,2-e]-1,2-thiazin-4-one, 6-chloro-2,3-dihydro-2-(3-methoxypropyl)-, 1,1-dioxide

HRID 129926노트

반응식

HRID 129926 반응식
[Cl:1][C:2]1[S:10][C:9]2[S:8](=[O:12])(=[O:11])[N:7]([CH2:13][CH2:14][CH2:15][O:16][CH3:17])[CH2:6][CH:5]([OH:18])[C:4]=2[CH:3]=1.[Cr](O[Cr]([O-])(=O)=O)([O-])(=O)=O.[Na+].[Na+].S(=O)(=O)(O)O.[Cr](O)(O)(=O)=O>COC(C)(C)C.O>[Cl:1][C:2]1[S:10][C:9]2[S:8](=[O:12])(=[O:11])[N:7]([CH2:13][CH2:14][CH2:15][O:16][CH3:17])[CH2:6][C:5](=[O:18])[C:4]=2[CH:3]=1

참가 물질

7

반응물 4

HCID 1118Sulfuric AcidHCID 24425Chromic AcidHCID 25408Sodium DichromateHCID 111097216-chloro-3,4-dihydro-2-(3-methoxypropyl)-2H-thieno[3,2-e]-1,2-thiazin-4-ol 1, 1-dioxide

생성물 1

HCID 108705954H-Thieno[3,2-e]-1,2-thiazin-4-one, 6-chloro-2,3-dihydro-2-(3-methoxypropyl)-, 1,1-dioxide

시약·촉매·용매 2

HCID 962Water용매HCID 15413tert-Butyl methyl ether용매

실험 절차

243 g of alcohol 5 were dissolved in 1.56 L t-butyl methyl ether and charged into a 4-L three necked flask fitted with a reflux condenser and a thermometer. With stirring and cooling with an ice bath a mixture consisting of 155 g of sodium dichromate and 206 g sulfuric acid dissolved in 546 mL of water was added. The temperature was maintained below 20° C. during the addition. After the addition of chromic acid, the biphasic mixture was stirred for further 90 min at 25° C. until the TLC indicated complete consumption of the racemic alcohol 5. Then the aqueous layer was separated and 4× extracted with 390 mL of t-butyl methyl ether. The combined etheral solutions were successively washed with 624 mL of saturated sodium bicarbonate and sodium chloride solution, respectively. After drying with sodium sulfate and filtration the solvent was evaporated. Crystallization of the residual oil was induced by addition of a few crystals of authentic ketone 6 and about 25 mL of diethyl ether. To complete the crystallization 400 mL of n-hexane were added. An analytical sample was recrystallized from diethyl ether, mp: 48°-52° C., yield: 194 g (80%).

후처리

  1. customfitted with a reflux condenser
  2. temperaturecooling with an ice bath a mixture
  3. additionwas added
  4. temperatureThe temperature was maintained below 20° C. during the addition
  5. stirringthe biphasic mixture was stirred for further 90 min at 25° C. until the TLC
  6. customconsumption of the racemic alcohol 5
  7. customThen the aqueous layer was separated
  8. extraction4× extracted with 390 mL of t-butyl methyl ether
  9. washThe combined etheral solutions were successively washed with 624 mL of saturated sodium bicarbonate and sodium chloride solution
  10. dry with materialAfter drying with sodium sulfate and filtration the solvent
  11. customwas evaporated
  12. customCrystallization of the residual oil
  13. additionwas induced by addition of a few crystals of authentic ketone 6 and about 25 mL of diethyl ether
  14. customthe crystallization 400 mL of n-hexane
  15. additionwere added
  16. customAn analytical sample was recrystallized from diethyl ether, mp: 48°-52° C., yield: 194 g (80%)

출처 및 근거

ORD 기록
ord-d75ba70ff4b24dcba0125cf606e9f805
출처 데이터셋
uspto-grants-1995_11
특허 번호
US05470973

반응 노트

불러오는 중…