Reaktion #310114

Reaktionsgleichung

4-(benzyloxy)benzaldehyde

sodium cyanoborohydride

p-toluenesulfonic acid monohydrate

pentafluorophenyl 3-chloro-4-[(1-methylethyl)oxy]benzoate

3-hydrazinopropanenitrile

4-(benzyloxy)benzaldehyde

sodium cyanoborohydride

p-toluenesulfonic acid monohydrate

→

title compound

Ausbeute 61.3%

3-chloro-N′-(2-cyanoethyl)-4-[(1-methylethyl)oxy]-N′-({4-[(phenylmethyl)oxy]phenyl}methyl)benzohydrazide

Ausbeute 61.3%

Lösungsmittel

methanol

Reaktionsbedingungen

Aufarbeitung

1. 1
   Temperaturheated
2. 2
   Temperaturto reflux for 1 h
3. 3
   TemperaturFollowing cooling
4. 4
   workup.STIRRINGthe solution stirred overnight at ambient temperature
5. 5
   SonstigeThe reaction was quenched with 6N aqueous NaOH
6. 6
   workup.ADDITIONdiluted with brine
7. 7
   Extraktionextracted thrice with EtOAc
8. 8
   TrocknenThe organic layer was dried over MgSO4
9. 9
   Filtrationfiltered
10. 10
    Einengenconcentrated in vacuo
11. 11
    SonstigePurification via flash column chromatography (30-80% EtOAc/hexanes)

Vorschrift

A solution of pentafluorophenyl 3-chloro-4-[(1-methylethyl)oxy]benzoate (0.100 g, 0.263 mmol) in methanol (5.0 mL) was treated with 3-hydrazinopropanenitrile (0.023 mL, 0.289 mmol) and heated to reflux for 1 h. Following cooling, 4-(benzyloxy)benzaldehyde (0.067 g, 0.315 mmol), sodium cyanoborohydride (0.020 g, 0.315 mmol), and p-toluenesulfonic acid monohydrate (0.060 g, 0.315 mmol) were added and the solution stirred 30 min. at ambient temperature. Additional 4-(benzyloxy)benzaldehyde (0.067 g, 0.315 mmol), sodium cyanoborohydride (0.040 g, 0.637 mmol), and p-toluenesulfonic acid monohydrate (0.100 g, 0.526 mmol) were added and the solution stirred overnight at ambient temperature. The reaction was quenched with 6N aqueous NaOH, diluted with brine, and extracted thrice with EtOAc. The organic layer was dried over MgSO4, filtered, and concentrated in vacuo. Purification via flash column chromatography (30-80% EtOAc/hexanes) gave the title compound as a white solid (0.077 g; 61%). 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.61 (d, J=2.3 Hz, 1H) 7.45 (dd, J=8.8, 2.2 Hz, 2H) 7.42 (s, 1H) 7.36-7.41 (m, 2H) 7.32 (tt, J=7.0, 1.8 Hz, 1H) 7.28 (s, 1H) 7.17 (br. s., 1H) 6.94 (d, J=8.6 Hz, 2H) 6.88 (d, J=8.6 Hz, 1H) 5.05 (s, 2H) 4.61 (qq, J=6.0 Hz, 1H) 4.22 (s, 2H) 3.39 (t, J=6.6 Hz, 2H) 2.60 (t, J=6.6 Hz, 2H) 1.39 (d, J=6.1 Hz, 6H). MS (ES+) m/e 478 [M+H]+.

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