反応 #4382

反応方程式

hydrogen chloride

n-BuLi

2-iodo-5-methoxy-N,N-dimethylbenzeneethanamine

1-hexyne

→

2-(1-hexynyl)-5-methoxy-N,N-dimethylbenzeneethanamine hydrochloride

収率 27.0%

溶媒

Water

tetrahydrofuran

tetrahydrofuran

反応条件

後処理

1. 1
   workup.ADDITIONwas added slowly via syringe through a serum
2. 2
   その他cap
3. 3
   その他After the 20 minutes
4. 4
   温度The second flask was cooled to 0° C
5. 5
   workup.STIRRINGThis solution was stirred for 20 minutes
6. 6
   workup.STIRRINGwas stirred overnight at room temperature under nitrogen
7. 7
   その他the organics were evaporated in vacuo
8. 8
   ろ過the solid catalyst was filtered off
9. 9
   その他the methanol was evaporated in vacuo
10. 10
    workup.ADDITIONMethylene chloride was added to the aqueous residue
11. 11
    洗浄the organic layer was washed with sodium bicarbonate solution, water, brine solution
12. 12
    乾燥dried over potassium carbonate
13. 13
    その他The organics were evaporated in vacuo
14. 14
    その他to give a red oil
15. 15
    その他gave white crystals which
16. 16
    その他upon recrystallization from acetonitrile

実験手順

A solution of 2.7 ml (0.027 mole) 1-hexyne in 10 ml dry (4 A sieves) tetrahydrofuran was cooled to 0° C. in an ice bath. Argon was passed over the solution 10.4 ml (0.027 mole) 2.69 M n-BuLi was added slowly via syringe through a serum cap. The resulting solution was stirred 20 minutes under argon. During this time, a second flask containing 3.2 g (0.027 mole) anhydrous zinc chloride was attached to the first flask via cannula. After the 20 minutes the contents of the first flask was transferred to the second flask via cannula. The second flask was cooled to 0° C. This solution was stirred for 20 minutes, then 5 g (0.016 mole) 2-iodo-5-methoxy-N,N-dimethylbenzeneethanamine in 20 ml dry tetrahydrofuran was added via syringe. 0.32 g (mole 1%) tetrakis(triphenylphosphine) palladium was added to the reaction mixture which was stirred overnight at room temperature under nitrogen. Water was added to the reaction mixture and the organics were evaporated in vacuo. The residue was taken up in methanol, the solid catalyst was filtered off and the methanol was evaporated in vacuo. Methylene chloride was added to the aqueous residue, the organic layer was washed with sodium bicarbonate solution, water, brine solution and dried over potassium carbonate. The organics were evaporated in vacuo to give a red oil. Addition of ethereal hydrogen chloride gave white crystals which upon recrystallization from acetonitrile gave 1.27 g (27% yield) of 2-(1-hexynyl)-5-methoxy-N,N-dimethylbenzeneethanamine hydrochloride, mp 145.5°-147.5° C.

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