Reaktion #5471

Reaktionsgleichung

water

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

sodium hydride

allyl bromide

→

pale tan solid

Ausbeute 62.2%

4-Amino-5-chloro-2-(2-propenyloxy)benzoic acid

Ausbeute 62.2%

Lösungsmittel

dimethylformamide

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.STIRRINGThe mixture was stirred at 95°±5° C. for one hour
2. 2
   Temperaturcooled to room temperature
3. 3
   SonstigeThe solid was removed by filtration
4. 4
   Extraktionthe filtrate was extracted with ether (2×100 mL)
5. 5
   workup.ADDITIONtreated with potassium hydroxide (10 g)
6. 6
   Temperaturrefluxed for 45 minutes
7. 7
   SonstigeThe ethanol was removed in vacuo
8. 8
   Extraktionthe aqueous solution was extracted with ether (50 mL) and petroleum ethers (30°-60°, 50 mL)
9. 9
   Temperaturcooled (0° C.)
10. 10
    FiltrationThe suspension was filtered
11. 11
    Sonstigedried
12. 12
    workup.DISSOLUTIONdissolved in methylene chloride (150 mL)
13. 13
    workup.ADDITIONcontaining a little methanol
14. 14
    Trocknendried (Na2SO4)
15. 15
    Einengenconcentrated in vacuo
16. 16
    SonstigeTrituration from cold ether/petroleum ethers (30°-60°) and recrystallization from ethyl acetate/hexane (2 crops)

Vorschrift

A suspension of 60% sodium hydride/oil dispersion (1.52 g, 38 mmol) in anhydrous dimethylformamide (50 mL) under nitrogen was treated in portions with 4-amino-5-chloro-2-hydroxybenzoic acid methyl ester (6.05 g, 30 mmol), stirred at room temperature for 30 minutes, and treated with allyl bromide (4.60 g, 38 mmol). The mixture was stirred at 95°±5° C. for one hour, cooled to room temperature, and added to water (250 mL). The solid was removed by filtration and saved, and the filtrate was extracted with ether (2×100 mL). The concentrated ethereal extracts were combined with the filtered solid, taken up in 20% aqueous ethanol (100 mL), treated with potassium hydroxide (10 g), and refluxed for 45 minutes. The ethanol was removed in vacuo and the aqueous solution was extracted with ether (50 mL) and petroleum ethers (30°-60°, 50 mL), cooled (0° C.), and acidified to pH 4 with concentrated hydrochloric acid (17 mL). The suspension was filtered and the solid was air dried, dissolved in methylene chloride (150 mL) containing a little methanol, dried (Na2SO4), and concentrated in vacuo. Trituration from cold ether/petroleum ethers (30°-60°) and recrystallization from ethyl acetate/hexane (2 crops) afforded 4.25 g (62.2%) of a pale tan solid; mp 136°-137° C.

Quelle