Thionyl Chloride → 3-Dichloromethylthio-7-fluoro-1-methyl-4-quinolone

HRID 1823815

반응식

HRID 1823815 반응식
S(Cl)([Cl:3])=O.[Cl:5][CH2:6][S:7]([C:9]1[C:18](=[O:19])[C:17]2[C:12](=[CH:13][C:14]([F:20])=[CH:15][CH:16]=2)[N:11]([CH3:21])[CH:10]=1)=O>N1C=CC=CC=1>[Cl:5][CH:6]([Cl:3])[S:7][C:9]1[C:18](=[O:19])[C:17]2[C:12](=[CH:13][C:14]([F:20])=[CH:15][CH:16]=2)[N:11]([CH3:21])[CH:10]=1

참가 물질

4

반응물 2

HCID 24386Thionyl ChlorideHCID 104685473-Chloromethylsulfinyl-7-fluoro-1-methyl-4-quinolone

생성물 1

HCID 113237793-Dichloromethylthio-7-fluoro-1-methyl-4-quinolone

시약·촉매·용매 1

HCID 1049Pyridine용매

반응 조건

온도
-5 °C

실험 절차

To an efficiently stirred and gently cooled 4.2 ml mixture of thionyl chloride (“SOCl2”) and 1.05 ml of pyridine (“Py”) at −3° C. was added 1.015 g (3.708 mmol) of 3-chloromethylsulfinyl-7-fluoro-1-methyl-4-quinolone (monochloroflosequinan)(Compound 1 of FIG. 21). This addition was made in multiple alloquots over a period of approximately 1 min. During this addition, cooling was applied to keep the temperature in the range 0-5° C. This mixture was then stirred at 0° C. for 8 min and then cooled to −5° C. The mixture was then poured as a thin stream into, stirring, 120 ml of ice-water. After 10 minutes of stirring at 0° C., a solid was filtered off, washed with water, and dried over phosphorus pentoxide under high vacuum. [Yield: 669 mg (61.7%) of a crude product (i.e. Compound 2) that was approximately 94% pure by 1H NMR, CDCl3; d=3.84 s, 3H, N—CH3; 7.11 dd, 1H, J=10.0 & 2.2 Hz, H at C8, 7.19 ddd, 1H, J=8.9, 7.9 & 2.3 Hz, H at C6; 7.24 s, 1H, CHCl2; 8.03 s, 1H, H at C2; 8.47 dd, 1H, J=9.0 & 6.3 Hz, H at C5.]. This product was then, further, purified in Step B described below.

후처리

  1. additionThis addition
  2. additionDuring this addition
  3. temperaturecooling
  4. customin the range 0-5° C
  5. stirringThis mixture was then stirred at 0° C. for 8 min
  6. additionThe mixture was then poured as a thin stream into,
  7. stirringstirring
  8. stirringAfter 10 minutes of stirring at 0° C.
  9. filtrationa solid was filtered off
  10. washwashed with water
  11. dry with materialdried over phosphorus pentoxide under high vacuum
  12. custom[Yield: 669 mg (61.7%) of a crude product (i.e. Compound 2) that was approximately 94% pure by 1H NMR, CDCl3; d=3.84 s, 3H, N—CH3; 7.11 dd, 1H, J=10.0 & 2.2 Hz, H at C8, 7.19 ddd, 1H, J=8.9, 7.9 & 2.3 Hz, H at C6; 7.24 s, 1H, CHCl2; 8.03 s, 1H, H at C2; 8.47 dd, 1H, J=9.0 & 6.3 Hz, H at C5.]
  13. customfurther, purified in Step B

출처 및 근거

ORD 기록
ord-c6e6ce9c75694e3783c39c60659c21c7
출처 데이터셋
uspto-grants-2006_05
특허 번호
US07041677B2

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