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19492095N-benzoylation of rac-PZQamine (MW58-1)
Experiments
profiles.google.com-micha.wolfleMichael Wolfle high vac [u]Yield:[/u] 4.10 g (13.4 mmol, 84%) - filtrate evaporated, remaining orange solid recrystallized a second time from toluene (20 mL) [u]Yield:[/u] 520 mg (1.70 mmol, 11%) [b]Result:[/b] Over-all yield: 4.62 g (15.1 mmol, 94%) [b]Analytical data:[/b] Rf (ethyl acetate, 100%) = 0.45. m.p. 157-158.5°C (recrystallized from toluene) (lit. 158-160°C (acetone) [1]) 1H NMR (CDCl3, 200 MHz): δ = 2.74-3.10 (m, 4H), 4.02-4.10 (m, 1H), 4.40 (br m, 1H), 4.80-5.00 (m, 2H), 5.19 (br m, 1 H), 7.21 (m, 4H), 7.48 (m, 5H). 13C NMR (CDCl3, 50.3 MHz): δ = 28.8, 39.0, 45.8 (br), 51.5 (br), 54.9 (br), 125.4 (br), 127.0, 127.4 (br, 2 C), 127.5, 128.8 (2 C), 129.5, 130.7, 132.5 (br), 134.4 (br), 135.0, 164.4, 170.3. IR (neat): nu = 1786 cm-1, 1611, 1420, 1289, 1247, 1212, 1036, 760, 718, 698, 656. MS (ESI (+)) m/z (%): 635 (100, [M2+Na]+), 329 (28, [M+Na]+). HRMS (ESI (+)) Calcd. for [C19H18N2O2+Na]+: 329.12605, found: 329.12619. HPLC: Chiralcel OD-H, hexane/iso-propanol/Et3N = 60/40/0.1, 0.7 ml/min flow rate, RT: 24.8 min, 31.5 min.[data=text]1107[/data] HPLC: Chiralcel OD-H, hexane/iso-propanol/Et3N = 70/30/0.1, 0.7 ml/min flow rate, RT: 30.2 min, 38.3 min. [data=text]1110[/data] [data]1095[/data][data]1071[/data][data]1077[/data][data]1105[/data] Starting material for: [*] [url=http://www.ourexperiment.org/enantio_hydgen/1962]Oxidation of N-benzoyl-PZQ by sulfur (MW59-1 to MW59-6)[/url] [*] [url=http://www.ourexperiment.org/enantio_hydgen/1993]Scale-up: Oxidation of N-benzoyl-PZQ by sulfur (MW59-7)[/url] [b]References:[/b] [url=http://onlinelibrary.wiley.com/doi/10.1002/ardp.19893221104/abstract][1] Spectral and Chemical Properties of Pyrazino-[2,1-a]-isoquinolin-4-one Derivatives, K. Kiec'-Kononowicz, [i]Arch. Pharm.[/i] [b]1989[/b], [i]322[/i],795-799. DOI: 10.1002/ardp.19893221104.[/url]]]>
Scheme MW58.png


Hazard and Risk Assessment:
HRAF MW57.pdf


Start time: 6:30 PM 14/04/2011
End time: 9:15 AM 15/04/2011

To an ice-cooled solution of rac-PZQamine (3.23 g, 16.0 mmol, M.W. = 202.3 g/mol) and triethylamine (2.43g, 24.0 mmol,3.35 mL, 1.5 eq., M.W. 101.2, d=0.726 g/mL) in DCM (60 mL) was added benzoyl chloride (3.38 g, 24.0 mmol, 2.80 mL, 1.5 eq., M.W. = 140.6 g/mol, d=1.21 g/mL) at 0°C and stirred at room temperature for 15 h.
The reaction was quenched with water and stirred for a further 30 min. The mixture was neutralized with sodium hydrogen carbonate solution and the layers were separated. The organic layer was washed with sodium hydrogen carbonate solution and dried over magnesium sulfate. After evaporation of the solvent a yellow solid remained.
- crude yield: 6.42 g (21.0 mmol, 131%) [M.W. 306.4 g/mol]
TLC (ethyl acetate, stain: ninhydrin, KMnO4)
TLC MW58-1a.jpg


- recrystallized from toluene (70 mL), filtered, dried under vac.: yield: 4.69 g (15.3 mmol, 96%) colourless solid, still toluene impurities -> high vac
Yield: 4.10 g (13.4 mmol, 84%)

- filtrate evaporated, remaining orange solid recrystallized a second time from toluene (20 mL)
Yield: 520 mg (1.70 mmol, 11%)

Result:
Over-all yield: 4.62 g (15.1 mmol, 94%)

Analytical data:
Rf (ethyl acetate, 100%) = 0.45.
m.p. 157-158.5°C (recrystallized from toluene) (lit. 158-160°C (acetone) [1])
1H NMR (CDCl3, 200 MHz): δ = 2.74-3.10 (m, 4H), 4.02-4.10 (m, 1H), 4.40 (br m, 1H), 4.80-5.00 (m, 2H), 5.19 (br m, 1 H), 7.21 (m, 4H), 7.48 (m, 5H).
13C NMR (CDCl3, 50.3 MHz): δ = 28.8, 39.0, 45.8 (br), 51.5 (br), 54.9 (br), 125.4 (br), 127.0, 127.4 (br, 2 C), 127.5, 128.8 (2 C), 129.5, 130.7, 132.5 (br), 134.4 (br), 135.0, 164.4, 170.3.
IR (neat): nu = 1786 cm-1, 1611, 1420, 1289, 1247, 1212, 1036, 760, 718, 698, 656.
MS (ESI (+)) m/z (%): 635 (100, [M2+Na]+), 329 (28, [M+Na]+).
HRMS (ESI (+)) Calcd. for [C19H18N2O2+Na]+: 329.12605, found: 329.12619.

HPLC: Chiralcel OD-H, hexane/iso-propanol/Et3N = 60/40/0.1, 0.7 ml/min flow rate, RT: 24.8 min, 31.5 min.Data: HPLC MW58-1 (40_60_01).jpg
HPLC: Chiralcel OD-H, hexane/iso-propanol/Et3N = 70/30/0.1, 0.7 ml/min flow rate, RT: 30.2 min, 38.3 min. Data: HPLC MW58 (30_70_01).jpg

1H NMR MW58-1.pdf
13C NMR MW58-1 (lb_2).pdf
13C NMR MW58-1 (lb=6).pdf
IR MW58-1.pdf


Starting material for:
  • Oxidation of N-benzoyl-PZQ by sulfur (MW59-1 to MW59-6)
  • Scale-up: Oxidation of N-benzoyl-PZQ by sulfur (MW59-7)


    References:
  • [1] Spectral and Chemical Properties of Pyrazino-[2,1-a]-isoquinolin-4-one Derivatives, K. Kiec'-Kononowicz, Arch. Pharm. 1989, 322,795-799. DOI: 10.1002/ardp.19893221104.
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    19497075N-benzoylation of rac-PZQamine (MW58-1)
    Experiments
    profiles.google.com-micha.wolfleMichael Wolfle high vac [u]Yield:[/u] 4.10 g (13.4 mmol, 84%) - filtrate evaporated, remaining orange solid recrystallized a second time from toluene (20 mL) [u]Yield:[/u] 520 mg (1.70 mmol, 11%) [b]Result:[/b] Over-all yield: 4.62 g (15.1 mmol, 94%) [b]Analytical data:[/b] Rf (ethyl acetate, 100%) = 0.45. m.p. 157-158.5°C (recrystallized from toluene) (lit. 158-160°C (acetone) [1]) 1H NMR (CDCl3, 200 MHz): δ = 2.74-3.10 (m, 4H), 4.02-4.10 (m, 1H), 4.40 (br m, 1H), 4.80-5.00 (m, 2H), 5.19 (br m, 1 H), 7.21 (m, 4H), 7.48 (m, 5H). 13C NMR (CDCl3, 50.3 MHz): δ = 28.8, 39.0, 45.8 (br), 51.5 (br), 54.9 (br), 125.4 (br), 127.0, 127.4 (br, 2 C), 127.5, 128.8 (2 C), 129.5, 130.7, 132.5 (br), 134.4 (br), 135.0, 164.4, 170.3. IR (neat): nu = 1786 cm-1, 1611, 1420, 1289, 1247, 1212, 1036, 760, 718, 698, 656. MS (ESI (+)) m/z (%): 635 (100, [M2+Na]+), 329 (28, [M+Na]+). HRMS (ESI (+)) Calcd. for [C19H18N2O2+Na]+: 329.12605, found: 329.12619. HPLC: Chiralcel OD-H, hexane/iso-propanol/Et3N = 60/40/0.1, 0.7 ml/min flow rate, RT: 24.8 min, 31.5 min.[data=text]1107[/data] HPLC: Chiralcel OD-H, hexane/iso-propanol/Et3N = 70/30/0.1, 0.7 ml/min flow rate, RT: 30.2 min, 38.3 min. [data=text]1110[/data] [data]1095[/data][data]1071[/data][data]1077[/data][data]1105[/data] Starting material for: [*] [url=http://www.ourexperiment.org/enantio_hydgen/1962]Oxidation of N-benzoyl-PZQ by sulfur (MW59-1 to MW59-6)[/url] [*] [url=http://www.ourexperiment.org/enantio_hydgen/1993]Scale-up: Oxidation of N-benzoyl-PZQ by sulfur (MW59-7)[/url] [b]References:[/b] [url=http://onlinelibrary.wiley.com/doi/10.1002/ardp.19893221104/abstract][1] Spectral and Chemical Properties of Pyrazino-[2,1-a]-isoquinolin-4-one Derivatives, K. Kiec'-Kononowicz, [i]Arch. Pharm.[/i] [b]1989[/b], [i]322[/i],795-799. DOI: 10.1002/ardp.19893221104.[/url]]]>
    Scheme MW58.png


    Hazard and Risk Assessment:
    HRAF MW57.pdf


    Start time: 6:30 PM 14/04/2011
    End time: 9:15 AM 15/04/2011

    To an ice-cooled solution of rac-PZQamine (3.23 g, 16.0 mmol, M.W. = 202.3 g/mol) and triethylamine (2.43g, 24.0 mmol,3.35 mL, 1.5 eq., M.W. 101.2, d=0.726 g/mL) in DCM (60 mL) was added benzoyl chloride (3.38 g, 24.0 mmol, 2.80 mL, 1.5 eq., M.W. = 140.6 g/mol, d=1.21 g/mL) at 0°C and stirred at room temperature for 15 h.
    The reaction was quenched with water and stirred for a further 30 min. The mixture was neutralized with sodium hydrogen carbonate solution and the layers were separated. The organic layer was washed with sodium hydrogen carbonate solution and dried over magnesium sulfate. After evaporation of the solvent a yellow solid remained.
    - crude yield: 6.42 g (21.0 mmol, 131%) [M.W. 306.4 g/mol]
    TLC (ethyl acetate, stain: ninhydrin, KMnO4)
    TLC MW58-1a.jpg


    - recrystallized from toluene (70 mL), filtered, dried under vac.: yield: 4.69 g (15.3 mmol, 96%) colourless solid, still toluene impurities -> high vac
    Yield: 4.10 g (13.4 mmol, 84%)

    - filtrate evaporated, remaining orange solid recrystallized a second time from toluene (20 mL)
    Yield: 520 mg (1.70 mmol, 11%)

    Result:
    Over-all yield: 4.62 g (15.1 mmol, 94%)

    Analytical data:
    Rf (ethyl acetate, 100%) = 0.45.
    m.p. 157-158.5°C (recrystallized from toluene) (lit. 158-160°C (acetone) [1])
    1H NMR (CDCl3, 200 MHz): δ = 2.74-3.10 (m, 4H), 4.02-4.10 (m, 1H), 4.40 (br m, 1H), 4.80-5.00 (m, 2H), 5.19 (br m, 1 H), 7.21 (m, 4H), 7.48 (m, 5H).
    13C NMR (CDCl3, 50.3 MHz): δ = 28.8, 39.0, 45.8 (br), 51.5 (br), 54.9 (br), 125.4 (br), 127.0, 127.4 (br, 2 C), 127.5, 128.8 (2 C), 129.5, 130.7, 132.5 (br), 134.4 (br), 135.0, 164.4, 170.3.
    IR (neat): nu = 1786 cm-1, 1611, 1420, 1289, 1247, 1212, 1036, 760, 718, 698, 656.
    MS (ESI (+)) m/z (%): 635 (100, [M2+Na]+), 329 (28, [M+Na]+).
    HRMS (ESI (+)) Calcd. for [C19H18N2O2+Na]+: 329.12605, found: 329.12619.

    HPLC: Chiralcel OD-H, hexane/iso-propanol/Et3N = 60/40/0.1, 0.7 ml/min flow rate, RT: 24.8 min, 31.5 min.Data: HPLC MW58-1 (40_60_01).jpg
    HPLC: Chiralcel OD-H, hexane/iso-propanol/Et3N = 70/30/0.1, 0.7 ml/min flow rate, RT: 30.2 min, 38.3 min. Data: HPLC MW58 (30_70_01).jpg

    1H NMR MW58-1.pdf
    13C NMR MW58-1 (lb_2).pdf
    13C NMR MW58-1 (lb=6).pdf
    IR MW58-1.pdf


    Starting material for:
  • Oxidation of N-benzoyl-PZQ by sulfur (MW59-1 to MW59-6)
  • Scale-up: Oxidation of N-benzoyl-PZQ by sulfur (MW59-7)


    References:
  • [1] Spectral and Chemical Properties of Pyrazino-[2,1-a]-isoquinolin-4-one Derivatives, K. Kiec'-Kononowicz, Arch. Pharm. 1989, 322,795-799. DOI: 10.1002/ardp.19893221104.
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