反応 #81541

反応方程式

N-methylbis (2-chloroethyl)amine hydrochloride

3-nitroaniline

Sodium carbonate

→

piperazine

収率 50.3%

3-(N-Methyl-N'-piperazinyl)-1-nitrobenzene

収率 50.3%

溶媒

1-butanol

反応条件

後処理

1. 1
   温度was heated
2. 2
   温度at reflux for 60 h
3. 3
   温度the mixture heated
4. 4
   温度at reflux for a further 18 h
5. 5
   温度cooled to 0° C.
6. 6
   ろ過filtered
7. 7
   その他The solid was collected
8. 8
   洗浄washed with anhydrous ether
9. 9
   その他then partitioned between dichloromethane (200 ml) and sodium hydroxide solution (1M, 150 ml)
10. 10
    その他The organic layer was separated
11. 11
    洗浄the aqueous phase washed once more with dichloromethane (200 ml)
12. 12
    乾燥The combined organic layers were dried (K2CO3)
13. 13
    その他evaporated in vacuo
14. 14
    その他The resultant residue was chromatographed on silica gel
15. 15
    その他to afford an orange oil
16. 16
    その他The oil crystallised
17. 17
    その他the resultant solid was triturated with petrol (60/80)

実験手順

A mixture of N-methylbis (2-chloroethyl)amine hydrochloride (9.8 g) and 3-nitroaniline (7.0 g) in 1-butanol (100 ml) was heated at reflux for 60 h then cooled to room temperature. Sodium carbonate (2.8 g) was then added and the mixture heated at reflux for a further 18 h, then cooled to 0° C. and filtered. The solid was collected, washed with anhydrous ether then partitioned between dichloromethane (200 ml) and sodium hydroxide solution (1M, 150 ml). The organic layer was separated and the aqueous phase washed once more with dichloromethane (200 ml). The combined organic layers were dried (K2CO3) and evaporated in vacuo. The resultant residue was chromatographed on silica gel, using dichloromethane:methanol (96:4) as the eluant, to afford an orange oil. The oil crystallised on standing and the resultant solid was triturated with petrol (60/80) to give the desired piperazine (5.64 g). 1H NMR (360 MHz, CDCl3) δ2.37 (3H, s), 2.58 (4H, t, J=5 Hz), 3.30 (4H, t, J=5 Hz), 7.18 (1H, dd, J=9 and 3 Hz), 7.35 (1H, t, J=8 Hz), 7.64 (1H, dd, J=9 and 2 Hz), 7.71 (1H, d, J=2 Hz). MS (CI, NH3) 222 (M+1).

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