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16th January 2013 @ 05:21
Mnr: MNR71-80

Attempted synthesis of  (MNR80-1) from MNR77-1.

Prep from ZYH14-1 

 

Hazard Assessment

HIRAC MNR79.pdf

 

 

 

 

Procedure

To a mixture of crude MNR77-1 (0.75 g, 4.9 mmol) and sodium acetate trihydrate (0.67 g 4.9 mmol, ) in ethanol (5 mL) was added ethyl bromoacetate (0.82 mL, 4.9 mmol) dropwise and the mixture was heated to 60 °C for 16 hours.

TLC

NMR

Conclusion

Strings

Starting materials 

InChI=1S/C6H7N3S/c7-6(10)9-5-1-3-8-4-2-5/h1-4H,(H3,7,8,9,10)

Product 

InChI=1S/C8H7N3OS/c12-7-5-13-8(11-7)10-6-1-3-9-4-2-6/h1-4H,5H2,(H,9,10,11,12)

Attached Files
16th January 2013 @ 05:15
Mnr: MNR71-80

Attempted synthesis of  (MNR79-1) from MNR76-1.

Prep from ZYH14-1 

 

Hazard Assessment

HIRAC MNR79.pdf

 

 

 


Procedure

To a mixture of crude MNR76-1 (1.2 g, 8 mmol) and sodium acetate trihydrate (1.01 g, 8.0 mmol) in ethanol (8 mL) was added ethyl bromoacetate (0.89 mL, 8.0 mmol) dropwise and the mixture was heated to 60 °C for 16 hours.

TLC

NMR

Conclusion

Strings

Starting materials 

InChI=1S/C6H7N3S/c7-6(10)9-5-2-1-3-8-4-5/h1-4H,(H3,7,9,10)

Product 

InChI=1S/C8H7N3OS/c12-7-5-13-8(11-7)10-6-2-1-3-9-4-6/h1-4H,5H2,(H,10,11,12)

Attached Files
13th January 2013 @ 09:43
Mnr: MNR71-80

Synthesis of 1-(pyrimidin-2-yl)thiourea (MNR78-1) from crude MNR74-1 

Ref From Step 4 page 63 of -WO2011119894 (A2) ― 2011-09-29

 

Hazard Assessment

Procedure

To a stirred solution of crude MNR74-1 (2.3 g) in MeOH (60 mL) was added ammonium hydroxide solution (28%) (45 mL) dropwise at 5 C. After addition the reaction was allowed to warm to room temperature and was left to stir overnight (although prep said only 2 hours, reaction had to be left due to time constraints).  TLC in the morning looked promising so the reaction was worked up by removing the MeOH, adding water and the mixture was extracted with EtOAc (50 mL x 3). The organic fractions were combined, washed with brine, dried over MgSO4, filtered and concentrated to give a black oil/solid (0.768 g, 5.0 mmol, 30%)

TLC 

Reaction mixture after 16 hours, ran in 100% EtOAc

 

MNR78_rxn.JPG




TLC shows signs of reaction but not complete, reaction was stil worked up.

NMR 

 

mnr78-1_crude_1H.pdf
mnr78-1_crude_13C.pdf
mnr78-1_crude.zip

 

 

 

 

Looks mainly like product, taken onto the next step without further purification.

Conclusion

Poor yield, probably due to poor solubilty and a messy workup,  taken onto the next step without further purification.

Strings

Starting materials

InChI=1S/C5H3N3S/c9-4-8-5-6-2-1-3-7-5/h1-3H

Product

InChI=1S/C5H6N4S/c6-4(10)9-5-7-2-1-3-8-5/h1-3H,(H3,6,7,8,9,10)

Attached Files
13th January 2013 @ 09:36
Mnr: MNR71-80

Synthesis of 1-(pyridin-4-yl)thiourea (MNR77-1) from crude MNR73-1 

Ref From Step 4 page 63 of -WO2011119894 (A2) ― 2011-09-29

 

Hazard Assessment

Procedure

To a stirred solution of crude MNR73-1 (8.5 g) in MeOH (60 mL) was added ammonium hydroxide solution (28%) (45 mL, XX mmol) dropwise at 5 C. After addition the reaction was allowed to warm to room temperature and was left to stir overnight (although prep said only 2 hours, reaction had to be left due to time constraints).  TLC in the morning was a mees but the reaction was still worked up by removing the MeOH, adding water and the mixture was extracted with EtOAc (50 mL x 3). The organic fractions were combined, washed with brine, dried over MgSO4, filtered and concentrated to give a dark brown oil/solid (0.75 g, unable to calculate yield as starting mass was too high for 100%).

TLC 

Reaction mixture after 16 hours, ran in 100% EtOAc

MNR77_rxn.JPG
 




TLC doesn't look promising but the reaction was stil worked up.

NMR 

 

mnr77-1_crude_1H.pdf
mnr77-1_crude_13C.pdf
mnr77-1_crude.zip

 

 



Looks mainly like product, taken onto the next step without further purification.

Conclusion

Poor yield, probably due to poor solubilty and a messy workup,  taken onto the next step without further purification.

Strings

Starting materials

InChI=1S/C6H4N2S/c9-5-8-6-1-3-7-4-2-6/h1-4H

Product

InChI=1S/C6H7N3S/c7-6(10)9-5-1-3-8-4-2-5/h1-4H,(H3,7,8,9,10)

Attached Files
13th January 2013 @ 09:28
Mnr: MNR71-80

Synthesis of 1-(pyridin-3-yl)thiourea (MNR76-1) from crude MNR72-1 

Ref From Step 4 page 63 of -WO2011119894 (A2) ― 2011-09-29

 

Hazard Assessment

Procedure

To a stirred solution of crude MNR72-1 (2.32 g, 17.04 mmol) in MeOH (60 mL) was added ammonium hydroxide solution (28%) (45 mL) dropwise at 5 C. After addition the reaction was allowed to warm to room temperature and was left to stir overnight (although prep said only 2 hours, reaction had to be left due to time constraints).  TLC in the morning looked promising so the reaction was worked up by removing the MeOH, adding water and the mixture was extracted with EtOAc (50 mL x 3). The organic fractions were combined, washed with brine, dried over MgSO4, filtered and concentrated to give a black oil/solid (1.23 g, 8.-3 mmol, 47%)

TLC 

Reaction mixture after 16 hours, ran in 100% EtOAc

MNR76_rxn.JPG





Looks like a nice spot to spot reaction

NMR 

 

mnr76-1_crude_1H.pdf
mnr76-1_crude_13C.pdf
mnr76-1_crude.zip

 

 

 

 

Looks mainly like product, taken onto the next step without further purification.

Conclusion

Poor yield, probably due to poor solubilty and a messy workup,  taken onto the next step without further purification.

Strings

Starting materials

InChI=1S/C6H4N2S/c9-5-8-6-2-1-3-7-4-6/h1-4H

Product

InChI=1S/C6H7N3S/c7-6(10)9-5-2-1-3-8-4-5/h1-4H,(H3,7,9,10)

Attached Files