反应 #3042

反应方程式

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

收率 29.8%

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

收率 29.8%

溶剂

hexane

chloroform

toluene

ethyl acetate

反应条件

后处理

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
   其他transferred to a separatory funnel
5. 5
   其他separated
6. 6
   洗涤The organic layer was washed with brine
7. 7
   干燥dried over sodium sulfate
8. 8
   过滤filtered
9. 9
   其他evaporated
10. 10
    其他to give an orange/red oil which
11. 11
    过滤filtered
12. 12
    其他The filtrate was chromatographed on a silica gel column
13. 13
    workup.ADDITIONas containing product
14. 14
    其他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
    其他A precipitate formed which
18. 18
    其他The resultant mixture was triturated for about 2 hours
19. 19
    过滤filtered
20. 20
    洗涤washed with hexane

实验过程

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.

来源