تفاعل #7496

معادلة التفاعل

methanesulfonic acid

ethyl 4-oxocyclohexanecarboxylate

sodium bicarbonate

sodium azide

→

ester

المردود 70.0%

ethyl 7-oxo-4-azepanecarboxylate

المردود 70.0%

المذيبات

CHCl3

ظروف التفاعل

المعالجة

1. 1
   درجة الحرارةwith reflux condenser, magnetic stirrer
2. 2
   workup.DISSOLUTIONdissolved in 20 ml of over 30 min
3. 3
   درجة الحرارةThe mixture was heated
4. 4
   درجة الحرارةto reflux for 1 hour
5. 5
   أخرىthe mixture decanted
6. 6
   استخلاصthe aqueous phase extracted with 3×150 ml of CHCl3
7. 7
   تجفيفthe combined organic phases were dried over magnesium sulfate
8. 8
   ترشيحfiltered
9. 9
   تركيزconcentrated to dryness
10. 10
    أخرىThe residue was purified by PrepLC (800 g SiO2, CH2Cl2/MeOH, 97/3)
11. 11
    أخرىto give 5.1 g of crude compound
12. 12
    أخرىIt was crystallised from 40 ml of diethylether

الإجراء التجريبي

In a 250 ml three necked flask fitted with reflux condenser, magnetic stirrer and dropping funnel under inert atmosphere, 5.6 ml (5.98 g, 34 mmoles, 1 eq) of ethyl 4-oxocyclohexanecarboxylate 27 were dissolved in 50 ml of CHCl3. 6.65 g (102 mmole, 3 eq) of sodium azide were added, followed by 22.1 ml (32.8 g, 341 mmoles, 10 eq) of methanesulfonic acid dissolved in 20 ml of over 30 min. The mixture was heated to reflux for 1 hour and cooled down to 10° C. 200 nl of saturated sodium bicarbonate solution were added, the mixture decanted and the aqueous phase extracted with 3×150 ml of CHCl3, the combined organic phases were dried over magnesium sulfate, filtered and concentrated to dryness. The residue was purified by PrepLC (800 g SiO2, CH2Cl2/MeOH, 97/3) to give 5.1 g of crude compound. It was crystallised from 40 ml of diethylether to give 4.41 g of pure ester 28, 70% yield.

المصدر