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

HRID 4286

반응식

HRID 4286 반응식
[CH:1]#[C:2][CH2:3][CH2:4][CH2:5][CH3:6].[Li]CCCC.I[C:13]1[CH:18]=[CH:17][C:16]([O:19][CH3:20])=[CH:15][C:14]=1[CH2:21][CH2:22][N:23]([CH3:25])[CH3:24].[ClH:26]>O1CCCC1.[Cl-].[Zn+2].[Cl-].[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O>[ClH:26].[C:1]([C:13]1[CH:18]=[CH:17][C:16]([O:19][CH3:20])=[CH:15][C:14]=1[CH2:21][CH2:22][N:23]([CH3:25])[CH3:24])#[C:2][CH2:3][CH2:4][CH2:5][CH3:6]

참가 물질

9

반응물 4

HCID 313Hydrochloric AcidHCID 127321-HexyneHCID 14025500HCID 14025500, 화합물HCID 178418339Butyllithium

생성물 1

HCID 201523392-(1-hexynyl)-5-methoxy-N,N-dimethylbenzeneethanamine hydrochloride수율 27%

시약·촉매·용매 4

HCID 3007855Zincchloride촉매HCID 11979704Tetrakis(triphenylphosphine)palladium촉매HCID 962Water용매HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
0 °C

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.

후처리

  1. additionwas added slowly via syringe through a serum
  2. customcap
  3. customAfter the 20 minutes
  4. temperatureThe second flask was cooled to 0° C
  5. stirringThis solution was stirred for 20 minutes
  6. stirringwas stirred overnight at room temperature under nitrogen
  7. customthe organics were evaporated in vacuo
  8. filtrationthe solid catalyst was filtered off
  9. customthe methanol was evaporated in vacuo
  10. additionMethylene chloride was added to the aqueous residue
  11. washthe organic layer was washed with sodium bicarbonate solution, water, brine solution
  12. dry with materialdried over potassium carbonate
  13. customThe organics were evaporated in vacuo
  14. customto give a red oil
  15. customgave white crystals which
  16. customupon recrystallization from acetonitrile

출처 및 근거

ORD 기록
ord-c233d3f7474f4b86a95a4c7f7873d8ec
출처 데이터셋
uspto-grants-1988_02
특허 번호
US04725602

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