反応 #3042

反応方程式

tri-n-butyl tin hydride

AIBN

AIBN

5-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methylene]-3-(ethylmethylamino)-2-thioxo-4-thiazolidinone

hydrochloric acid

→

desired product

収率 29.8%

5-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methylene]-3-(ethylmethylamino)-4-thiazolidinone

収率 29.8%

溶媒

hexane

chloroform

toluene

ethyl acetate

反応条件

後処理

1. 1
   温度to reflux temperature for 30 minutes
2. 2
   温度at reflux temperature for an additional 30 minutes
3. 3
   温度cooled
4. 4
   その他transferred to a separatory funnel
5. 5
   その他separated
6. 6
   洗浄The organic layer was washed with brine
7. 7
   乾燥dried over sodium sulfate
8. 8
   ろ過filtered
9. 9
   その他evaporated
10. 10
    その他to give an orange/red oil which
11. 11
    ろ過filtered
12. 12
    その他The filtrate was chromatographed on a silica gel column
13. 13
    workup.ADDITIONas containing product
14. 14
    その他were evaporated
15. 15
    workup.ADDITIONTo these fractions were added 15 ml of hexane
16. 16
    温度the resultant solution was heated slightly
17. 17
    その他A precipitate formed which
18. 18
    その他The resultant mixture was triturated for about 2 hours
19. 19
    ろ過filtered
20. 20
    洗浄washed with hexane

実験手順

7.02 g of 5-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methylene]-3-(ethylmethylamino)-2-thioxo-4-thiazolidinone (from Example 40D) and 86.3 ml of toluene were stirred and heated to 60° C. under a nitrogen atmosphere. To this was added 18.6 ml of tri-n-butyl tin hydride and 0.43 g of AIBN. The resultant mixture was heated to reflux temperature for 30 minutes. At that time an additional 0.43 g of AIBN was added. The resultant mixture was heated at reflux temperature for an additional 30 minutes, cooled and transferred to a separatory funnel. To this was added 100 ml of 1N hydrochloric acid and 100 ml of ethyl acetate. The resultant mixture was shaken and separated. The organic layer was washed with brine, dried over sodium sulfate, filtered, evaporated and subsequently chased with chloroform to give an orange/red oil which was taken up in 50 ml of chloroform and filtered. The filtrate was chromatographed on a silica gel column using an 8000 ml gradient of 10-40% ethyl acetate in hexane. Those fractions identified as containing product were evaporated and chased with chloroform. To these fractions were added 15 ml of hexane and the resultant solution was heated slightly. A precipitate formed which was diluted to about 25 ml with additional hexane. The resultant mixture was triturated for about 2 hours, filtered and then washed with hexane to yield 1.94 g of the desired product, m.p. 133.5°-135° C.

出典