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19th July 2017 @ 16:24

Scheme:

AcetylScheme.png

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, 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.  

AcetylTLC.jpg

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 mmol26 % yield).  

Product was crystallized from methanol and placed in the freezer overnight to yield white crystals (0.0845 g, 0.36 mmol, 14% yield).  

JS_LTDaraprimAcetylS3Crystals_PROTON_cdcl3_01.jpeg

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:

Derivatization1.png

The GC-MS showed an mpeak at 378 and an [m-15]peak at 363. 

GCMS2.png
 
GCMS.png



Attached Files
AcetylScheme.png
AcetylTLC.jpg
JS_LTDaraprimAcetylS3Crystals_PROTON_cdcl3_01.jpeg
Derivatization1.png
GCMS.png
GCMS2.png