반응 #4382

반응 방정식

hydrogen chloride

n-BuLi

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

1-hexyne

→

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

수율 27.0%

용매

Water

tetrahydrofuran

tetrahydrofuran

반응 조건

후처리

1. 1
   workup.ADDITIONwas added slowly via syringe through a serum
2. 2
   기타cap
3. 3
   기타After the 20 minutes
4. 4
   온도The 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
   기타the organics were evaporated in vacuo
8. 8
   여과the solid catalyst was filtered off
9. 9
   기타the methanol was evaporated in vacuo
10. 10
    workup.ADDITIONMethylene chloride was added to the aqueous residue
11. 11
    세척the organic layer was washed with sodium bicarbonate solution, water, brine solution
12. 12
    건조dried over potassium carbonate
13. 13
    기타The organics were evaporated in vacuo
14. 14
    기타to give a red oil
15. 15
    기타gave white crystals which
16. 16
    기타upon recrystallization from acetonitrile

실험 절차

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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