Diethylaminoethyl chloride → Etonitazene 6-nitro isomer

HRID 2074459노트

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HRID 2074459 반응식
[H-].[Na+].[CH2:3]([O:5][C:6]1[CH:24]=[CH:23][C:9]([CH2:10][C:11]2[NH:15][C:14]3[CH:16]=[CH:17][C:18]([N+:20]([O-:22])=[O:21])=[CH:19][C:13]=3[N:12]=2)=[CH:8][CH:7]=1)[CH3:4].Cl[CH2:26][CH2:27][N:28]([CH2:31][CH3:32])[CH2:29][CH3:30]>O1CCOCC1>[CH2:3]([O:5][C:6]1[CH:24]=[CH:23][C:9]([CH2:10][C:11]2[N:12]([CH2:26][CH2:27][N:28]([CH2:31][CH3:32])[CH2:29][CH3:30])[C:13]3[CH:19]=[C:18]([N+:20]([O-:22])=[O:21])[CH:17]=[CH:16][C:14]=3[N:15]=2)=[CH:8][CH:7]=1)[CH3:4]

참가 물질

5

반응물 3

HCID 13364Diethylaminoethyl chlorideHCID 24758Sodium hydride2회HCID 178466243HCID 178466243, 화합물

생성물 1

HCID 59799752Etonitazene 6-nitro isomer수율 13.6%

시약·촉매·용매 1

HCID 312751,4-Dioxane용매3회

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온도
65 °C

실험 절차

To a small, argon purged flask fitted with a condenser and magnetic stirbar is charged Sodium Hydride (60 wt %, 74 mg, 1.850 mmol) and anhydrous dioxane (5 mL) and stirring begun. A solution of 2-(4-Ethoxy-benzyl)-5-nitro-1H-benzimidazole 42 (550 mg, 1.850 mmol) in anhydrous dioxane (10 mL) was added dropwise to the suspension of sodium hydride and the mixture heated to 65° C. for 90 minutes at which time a solution of (2-Chloroethyl)-diethyl-amine (251 mg, 1.850 mmol) in anhydrous dioxane (5 mL) is added dropwise to the hot solution. After 60 minutes at 65° C. the mixture is cooled to room temperature, filtered and solvent removed under reduced pressure to afford crude. The product was purified using dry silica gel column chromatography eluting with 25 mL portions of solvent system (1.25% 2M NH3 in methanol/98.75% dichloromethane to 2.5% 2M NH3 in methanol/97.5% dichloromethane). The enriched fractions were further purified using silica gel column chromatography eluting with 50% ethyl acetate/50% hexanes to 70% ethyl acetate/30% hexanes to afford a pale yellow-colorless solid 43 {2-[2-(4-Ethoxy-benzyl)-6-nitro-benzoimidazol-1-yl]-ethyl}-diethyl-amine Yield: 100 mg (13.6%). 1H NMR (DMSO) δ: 0.70 (t, 6H, J=7.1), 1.30 (t, 3H, J=6.9), 2.39 (q, 4H, J=7.1), 2.50 (m, 2H), 3.98 (q, 2H, J=6.9), 4.28-4.36 (s, 2H; m, 2H) 6.87 (d, 2H, J=8.7), 7.20 (d, 2H, J=8.6), 7.72 (d, 1H, J=9.0), 8.06 (dd, 2H, J=8.9, 2.1), 8.51 (d, 1H, J=2.1); MS (ESI): 397 (MH+, 100%).

후처리

  1. customTo a small, argon purged flask fitted with a condenser
  2. additionis added dropwise to the hot solution
  3. filtrationfiltered
  4. customsolvent removed under reduced pressure
  5. customto afford crude
  6. customThe product was purified
  7. washeluting with 25 mL portions of solvent system (1.25% 2M NH3 in methanol/98.75% dichloromethane to 2.5% 2M NH3 in methanol/97.5% dichloromethane)
  8. customThe enriched fractions were further purified
  9. washeluting with 50% ethyl acetate/50% hexanes to 70% ethyl acetate/30% hexanes

출처 및 근거

ORD 기록
ord-6255660cac294a18915ef2769ab34b8e
출처 데이터셋
uspto-grants-2011_04
특허 번호
US07919510B2

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