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25th March 2013 @ 04:15
Mnr: MNR81-90

Synthesis of near neighbour analog MNR82-2 from pyrrole AEW45-1 and thiazolidinone PMY13-1

As for - Synthesis of Near Neighbour Analog MNR82-1

Starting materials from - Synthesis of 2,5-dimethyl-1-(4-nitrophenyl)-1H-pyrrole-3-carbaldehyde (AEW 45-1)

Preparation of 2-phenyliminothiazolidin-4-one (PMY 13-1)

 

Hazard Assessment

HIRAC MNR82.pdf

Procedure

Thiazolidinone PMY13-1 (0.094 g, 0.49 mmol) was dissolved in ethanol (7 mL) and piperdine (0.07 mL, 0.74 mmol) was added. AEW45-1 (120 mg, 0.49 mmol) was added to the mixture, and the resulting solution was heated to 60 °C. After 5 hours, TLC showed consumption of AEW45-1 and a precipitate had formed.  The reaction was allowed to cool to room temperature, was filtered and the precipitate washed with EtOH to yield a dark orange solid (0.147 g, 0.35 mmol, 72 %)

NMR

mnr82-2_1H.pdf
mnr82-2_filter.zip

Conclusion

 Similr result to before s taken on to the next step, the reduction of the nitro group.

Strings

Starting Materials

InChI=1S/C13H12N2O3/c1-9-7-11(8-16)10(2)14(9)12-3-5-13(6-4-12)15(17)18/h3-8H,1-2H3

InChI=1S/C10H9NOS/c12-9-7-13-10(11-9)6-8-4-2-1-3-5-8/h1-6H,7H2,(H,11,12)/b10-6-

Product

InChI=1S/C22H18N4O3S/c1-14-12-16(15(2)25(14)18-8-10-19(11-9-18)26(28)29)13-20-21(27)24-22(30-20)23-17-6-4-3-5-7-17/h3-13H,1-2H3,(H,23,24,27)/b20-13-

 

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30th January 2013 @ 06:22
Mnr: MNR81-90

Synthesis of near neighbour analog MNR90-1 from pyrrole AEW50-1 and thiazolidinone PMY13-1

 

Hazard Assessment

HIRAC MNR82.pdf

Procedure

Thiazolidinone PMY13-1 (0.067 g, 0.35 mmol) was dissolved in ethanol (5 mL) and piperdine (0.05 mL, 0.52 mmol) was added. AEW50-1 (0.070 g, 0.35 mmol) was added to the mixture, and the resulting solution was heated to 60 °C overnight.  The reaction was then allowed to cool to room temperature but no precipitate formed.  THe reaction mixture was concentrated then dissolved in DCM (5 mL) and washed with water (5 mL).  The water was then washed with DCM (5 mL x 2), the organic layers were combined, dried over magnesium sulphate, filtered and concentrated to give the crude as brown oil (0.144 g).  Column, not very succesful and no clean product recovered, further purification not attempted.  The reaction should be repeated if this compound is required in the future

NMR

 

Conclusion

Purification not very succesful and no clean product recovered, further purification not attempted.  The reaction should be repeated if this compound is required in the future

Strings

Starting Materials

InChI=1S/C12H12N2O/c1-9-7-11(8-15)10(2)14(9)12-5-3-4-6-13-12/h3-8H,1-2H3

InChI=1S/C10H9NOS/c12-9-7-13-10(11-9)6-8-4-2-1-3-5-8/h1-6H,7H2,(H,11,12)/b10-6-

 

Product

InChI=1S/C22H19N3OS/c1-15-12-18(16(2)25(15)20-10-6-7-11-23-20)14-19-22(26)24-21(27-19)13-17-8-4-3-5-9-17/h3-14H,1-2H3,(H,24,26)/b19-14-,21-13-

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24th January 2013 @ 00:16
Mnr: MNR81-90

Synthesis of (Z)-2-((4-hydroxyphenyl)imino)thiazolidin-4-one (MNR88-1) from commercially available N-(4-Hydroxyphenyl)thiourea

Prep from ZYH14-1 As for MNR70-1

 

 

Hazard Assessment

HIRAC MNR70.pdf

Procedure

Reaction on at 1100, 24/01/13

To a mixture of  N-(4-Hydroxyphenyl)thiourea (1.03 g, 6.12 mmol) and sodium acetate trihydrate (0.83 g, 6.12 mmol) in ethanol (6 mL) was added ethyl bromoacetate (0.68 ml, 6.12 mmol) dropwise and the mixture was heated to 60 °C for 20 hours.  The reaction was allowed to cool to room temperature then ice was added at which point a a light brown precipitate formed.  This was filtered and washed with water and dried under vacuum.

 

It was unclear from the NMR is the solid was pure product so it was dissolved in MeOH and heated then allowed to cool to room temperature before being filtered to give a light brown solid (0.758 g, 3.6 mmol, 59%)

TLC

NMR

mnr88-1_filter_1H.pdf
mnr88-1_filter.zip
mnr88-1_MeOHwash_1H.pdf
MNR88-1_MeOHwash.zip


1H NMR matches that of compound 3 from http://dx.doi.org/10.1016/j.bmc.2010.05.073

Conclusion


The washing with MeOH stp was not needed as the NMR matches that of the literature.

Strings

Starting materials

InChI=1S/C7H8N2OS/c8-7(11)9-5-1-3-6(10)4-2-5/h1-4,10H,(H3,8,9,11)

InChI=1S/C4H7BrO2/c1-2-7-4(6)3-5/h2-3H2,1H3

Product 

InChI=1S/C9H8N2O2S/c12-7-3-1-6(2-4-7)10-9-11-8(13)5-14-9/h1-4,12H,5H2,(H,10,11,13)

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24th January 2013 @ 00:00
Mnr: MNR81-90

Synthesis of (Z)-2-((2-hydroxyphenyl)imino)thiazolidin-4-one (MNR87-1) from commercially available N-(2-Hydroxyphenyl)thiourea

Prep from ZYH14-1 As for MNR70-1

 

Hazard Assessment

HIRAC MNR70.pdf

Procedure

Reaction on at 1100, 24/01/13

To a mixture of N-(2-Hydroxyphenyl)thiourea (0.99 g, 5.89 mmol) and sodium acetate trihydrate (0.80 g, 5.89 mmol) in ethanol (6 mL) was added ethyl bromoacetate (0.65 ml, 5.89 mmol) dropwise and the mixture was heated to 60 °C for 22 hours.  The reaction was allowed to cool to room temperature then ice was added. Nothing solid precipitated out, only  an oily product. The Reaction mixture was then extracted with EtOAC (20 ml x 3). The organic fractions were combined, dried over MgSO4, filtered and concentrated to give a....

TLC

NMR

Conclusion

Strings

Starting materials

InChI=1S/C7H8N2OS/c8-7(11)9-5-3-1-2-4-6(5)10/h1-4,10H,(H3,8,9,11)

InChI=1S/C4H7BrO2/c1-2-7-4(6)3-5/h2-3H2,1H3

Product 

InChI=1S/C9H8N2O2S/c12-7-4-2-1-3-6(7)10-9-11-8(13)5-14-9/h1-4,12H,5H2,(H,10,11,13)

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22nd January 2013 @ 23:18
Mnr: MNR81-90

Synthesis of near neighbour analog MNR85-1 from pyrrole AEW46-1 and thiazolidinone MNR70-2 

 

Hazard Assessment

HIRAC MNR82.pdf

Procedure

Thiazolidinone MNR70-2 (0.090 g, 0.44 mmol) was dissolved in ethanol (6 mL) and piperdine (0.06 mL, 0.61 mmol) was added. AEW46-1 (0.10 g, 0.44 mmol) was added to the mixture, and the resulting solution was heated to 60 °C.  After 5 hours, a precipitate had formed and the reaction was allowed to cool to room temperature, was filtered and the precipitate washed with EtOH to yield a yellow solid (0.143 g, 0.34 mmol, 78%)

NMR

mnr85-1_1H.pdf
mnr85-1.zip

 Conclusion

Proton NMR looks good and sample is ready to send for testing, further characterisation still needed.

 

Strings

Starting Materials

InChI=1S/C14H15NO2/c1-10-8-12(9-16)11(2)15(10)13-4-6-14(17-3)7-5-13/h4-9H,1-3H3

 

InChI=1S/C10H9NO2S/c12-8-3-1-2-7(4-8)5-10-11-9(13)6-14-10/h1-5,12H,6H2,(H,11,13)/b10-5-

Product

InChI=1S/C24H22N2O3S/c1-15-11-18(16(2)26(15)19-7-9-21(29-3)10-8-19)14-22-24(28)25-23(30-22)13-17-5-4-6-20(27)12-17/h4-14,27H,1-3H3,(H,25,28)/b22-14-,23-13-

 

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