Reaktion #631984

Reaktionsgleichung

N′-(5-ethyl-2,3-dihydro-benzo[1,4]dioxine-6-carbonyl)-hydrazinecarboxylic acid tert-butyl ester

trifluoroacetic acid

NaOH H2O

→

5-ethyl-2,3-dihydro-benzo[1,4]dioxine-6-carboxylic acid hydrazide

Ausbeute 129.9%

Lösungsmittel

water

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.STIRRINGwith stirring, until the acid
2. 2
   SonstigeThe reaction mixture was transferred to a separatory funnel
3. 3
   Extraktionextracted with ethyl acetate
4. 4
   workup.STIRRINGby shaking gently (caution: gas evolution)
5. 5
   ExtraktionThe ethyl acetate extract
6. 6
   Sonstigewas dried
7. 7
   Sonstigeevaporated
8. 8
   Sonstigeto yield 5.51 g of a pale, viscous yellow semi-solid
9. 9
   Sonstigewas then placed in a 50° C.
10. 10
    Sonstigefor about 1 hour

Vorschrift

5.15 g (16 mmol) of N′-(5-ethyl-2,3-dihydro-benzo[1,4]dioxine-6-carbonyl)-hydrazinecarboxylic acid tert-butyl ester were added to a 200 mL round bottom flask. About 20 mL of trifluoroacetic acid were added and the reaction mixture was stirred at room temperature for 24 hours. Then about 40 mL of water were added, followed by the slow addition of cold 10% NaOH/H2O, with stirring, until the acid was neutralized (pH˜14). The reaction mixture was transferred to a separatory funnel and extracted with ethyl acetate by shaking gently (caution: gas evolution). The ethyl acetate extract was dried and evaporated to yield 5.51 g of a pale, viscous yellow semi-solid. The material was then placed in a 50° C. vacuum oven for about 1 hour to yield 4.62 g of 5-ethyl-2,3-dihydro-benzo[1,4]dioxine-6-carboxylic acid hydrazide. The t-Boc cleavage is best accomplished with neat trifluoroacetic acid; use of adjunctive solvents always resulted in much lower yields. 1H NMR (CDCl3, 500 MHz) δ (ppm): 7.0 (br, 1H), 6.83 (m, 1H), 6.71 (m, 1H), 4.28 (br s, 4H), 2.76 (m, 2H), 1.6 (br, 2H), 1.17 (t, 3H).

Quelle