反応 #315523

反応方程式

cyclopentene oxide

tyramine

→

title compound

4-[2-(2-Hydroxycyclopentylamino)ethyl]phenol

溶媒

EtOAc

NaOH

反応条件

後処理

1. 1
   workup.WAITat 100° C. for 18 hours
2. 2
   その他Quench
3. 3
   その他the reaction with saturated aqueous NH4Cl (40 mL)
4. 4
   その他Separate the layers
5. 5
   workup.STIRRINGafter shaking
6. 6
   洗浄Wash the organic layer with H2O and brine (50 mL each)
7. 7
   抽出Back-extract the aqueous layers with CH2Cl2, EtOAc and CH2Cl2 (50 mL each)
8. 8
   濃縮concentrate
9. 9
   その他decant off the supernatant
10. 10
    workup.DISSOLUTIONDissolve the residual solid in H2O
11. 11
    抽出extract it with 10:40:50 2.0 M NH3 in MeOH/CH2Cl2/EtOAc (100 mL) and 10:90 2.0 M NH3 in MeOH/CH2Cl2
12. 12
    濃縮concentrate
13. 13
    workup.DISSOLUTIONDissolve the residue in a small amount of MeOH
14. 14
    その他purify by flash chromatography
15. 15
    洗浄eluting with 10:40:50 2.0 M NH3 in MeOH/CH1CL2/EtOAc

実験手順

Stir a mixture of cyclopentene oxide (482.0 mg, 5.73 mmol) and tyramine (943.2 mg, 6.88 mmol) in 1.0 N NaOH (20 mL) at room temperature for 64 hours, at 45-55° C. for 6 hours, and at 100° C. for 18 hours. Quench the reaction with saturated aqueous NH4Cl (40 mL) and take it up in EtOAc (50 mL). Separate the layers after shaking. Wash the organic layer with H2O and brine (50 mL each). Back-extract the aqueous layers with CH2Cl2, EtOAc and CH2Cl2 (50 mL each). Adjust the pH of the combined aqueous layers to alkaline and concentrate. Suspend the residue in 10:40:50 2.0 M NH3 in MeOH/CH2Cl2/EtOAc and decant off the supernatant. Dissolve the residual solid in H2O and extract it with 10:40:50 2.0 M NH3 in MeOH/CH2Cl2/EtOAc (100 mL) and 10:90 2.0 M NH3 in MeOH/CH2Cl2. Combine all the organic layers and concentrate. Dissolve the residue in a small amount of MeOH and purify by flash chromatography, eluting with 10:40:50 2.0 M NH3 in MeOH/CH1CL2/EtOAc to afford the title compound as a 1:3 cis/trans isomeric mixture (566 mg, 45%): MS ES+ 222.0 (M+H)+, HPLC [YMC-Pack Pro C-18 (150×4.6 mm, S-5 microm), acetonitrile in water containing 0.01% concentrated HCl at 1.0 mL/min, 5-95% over 19 min], tR=4.72 min, 76% and 6.52 min, 24%.

出典