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19th July 2017 @ 16:24
Scheme: [data]20984[/data] SM/P  (Z)-2-(4-chlorophenyl)-3-methoxybut-2-enenitrile  Guanidine chloride  Sodium methoxide  5-(4-chlorophenyl)-6-methylpyrimidine-2-diamine    mw  207.66  95.53  54.02  234.69   Equiv  1.00  3.00  3.00  1.00    mmol  2.72  8.16  8.16  2.72    g  0.565  0.78  0.44  0.6   mL            g/mL      1.059    Procedure: 7/17/17 Guanidine hydrochloride (0.78 g, 8.16 mmol, 3 eq) and sodium methoxide (0.44 g, 8.16 mmol, 3 eq) were dissolved in ethanol (5.8 mL) and stirred for 5 min. A solution of (Z)-2-(4-chlorophenyl)-3-methoxy-3-phenylacrylonitrile (0.565 g, 2.72 mmol, 1 eq) in ethanol (1.9 mL) was added to the cloudy, white solution. The reaction mixture was heated under reflux for 6 hours. Some starting material was lost from syringe during transfer.   [data]20986[/data] 30:70 EtOAc: Hexanes, silica gel plate. Starting material gone after 6 hours of reflux. 7/18/17 The reaction mixture was diluted with dichloromethane. Saturated NaCl was added and the mixture was extracted with dichloromethane and then washed with saturated NaCl. Organic extracts were dried over MgSO4. Solvent was removed under reduced pressure to yield a white/yellow solid (0.157 g,0.67 mmol, 26 % yield).   Product was crystallized from methanol and placed in the freezer overnight to yield white crystals (0.0845 g, 0.36 mmol, 14% yield).   [data]20988[/data] 7/20/17 Product was derivitized in order to run GC-MS. A small sample of the crystals (1 mg) was placed in a microcentrifuge tube and a 40 mg/mL solution of methoxyamine hydrochloride in pyridine (10 μL) was added. The tube was heated to 30°C for 90 minutes in a standard heatblock. After 90 minutes, N-methyl-N-trimethylsilyltrifluoroacetamide (90 μL) was added and the samples were heated at 37°C for 30 minutes. (Fiehn, O.; Kind, T. Metabolomics 2009, 3–18.) This added TMS groups as shown: [data]21034[/data] The GC-MS showed an m+ peak at 378 and an [m-15]+ peak at 363.  [data]21038[/data] [data]21036[/data]
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