반응 #5472

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sodium hydride oil dispersion

4-amino-5-chloro-2-hydroxybenzoic acid

(2-chloroethyl)methyl sulfide

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product

수율 57.0%

4-Amino-5-chloro-2-[2-(methylthio)ethoxy]benzoic acid

수율 57.0%

용매

dimethylformamide

반응 조건

후처리

1. 1
   온도A cooled
2. 2
   온도heated to 100° C. for 18 hours
3. 3
   온도The solution is cooled
4. 4
   농축concentrated in vacuo
5. 5
   workup.ADDITIONadded to water (25 mL)
6. 6
   추출The aqueous solution is extracted with ether
7. 7
   건조the extract is dried (MgSO4)
8. 8
   농축concentrated in vacuo
9. 9
   workup.ADDITIONtreated with potassium hydroxide (5.0 g)
10. 10
    온도refluxed for one hour
11. 11
    농축The mixture is concentrated
12. 12
    workup.ADDITIONdiluted with water to 75 mL total volume
13. 13
    추출extracted with ether
14. 14
    여과The precipitate is filtered
15. 15
    세척washed with water, air
16. 16
    기타dried
17. 17
    기타recrystallized from ethyl acetate

실험 절차

A cooled (5° C.) suspension of 60% sodium hydride oil dispersion (0.52 g, 13 mmoles) in anhydrous dimethylformamide (15 mL) under nitrogen was treated in portions with 4-amino-5-chloro-2-hydroxybenzoic acid (0.94 g, 5 mmoles), stirred for 15 minutes at 25° C., treated with (2-chloroethyl)methyl sulfide (1.66 g, 15 mmoles), and heated to 100° C. for 18 hours. The solution is cooled, concentrated in vacuo, and added to water (25 mL). The aqueous solution is extracted with ether, and the extract is dried (MgSO4), concentrated in vacuo, taken up in 50% aqueous ethanol (50 mL), treated with potassium hydroxide (5.0 g), and refluxed for one hour. The mixture is concentrated, diluted with water to 75 mL total volume, extracted with ether, and acidified to pH 3 with concentrated HCl. The precipitate is filtered, washed with water, air dried, and recrystallized from ethyl acetate to afford 0.74 g (57%) of product as fine voluminous white needles, mp 137.5°-139.5° C.

출처