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14th November 2013 @ 17:07

Synthetic scheme

1-(4-iodophenyl)-2,5-dimethyl-1H-pyrrole: 4-iodoaniline (2.19 g, 10 mmol), 2,5-hexanedione (1.4 mL, 12 mmol) and sulfamic acid (50 mg, 0.5 mmol, 5 mol%) combined in capped tube.  Solution crystallized completely within ~1 hr. Solid recrystallized from hot ethanol to give 1.72 g (55%) peach-colored needles.

1-(4-iodophenyl)-2,5-dimethyl-1H-pyrrole-3-carbaldehyde: DMF (1.0 mL) and phosphoryl chloride (0.118 mL, 1.27 mmol, 1.9 equiv.) were stirred for 25 minutes in an ice bath under a nitrogen atmosphere. The reaction was removed from the ice bath and the pyrrole (203 mg, 0.684 mmol, 1.0 equiv.) dissolved in DMF (1.0 mL) was added. Continuing to stir, the reaction was complete by TLC after 45 minutes. The reaction was poured over ice (10 mL), stirred, and 10% NaOH was added dropwise until a pH of 11 was achieved. Subsequent suction filtration yielded the pyrrole as a sticky beige solid (>100% due to residual solvent). m.p.=135.6°C-138.2°C; FTIR (neat) 3387, 1641 cm-1; 1H-NMR (400 MHz, CDCl3) δ 9.86 (s, 1H), 7.86 (d, J = 8.4 Hz, 2H), 6.96 (d, J = 8.8 Hz, 2H), 6.38 (d, J = 1.2 Hz, 1H), 2.28 (s, 3H), 1.99 (s, 3H).

Knoevenagel condensation of 1-(4-iodophenyl)-2,5-dimethyl-1H-pyrrole-3-carbaldehyde (IDPCA): (Z)-2-((3-phenyl)imino)thiazolidin-4-one (70 mg, 0.347 mmol, 1.00 equiv.) was dissolved in ethanol (5.0 mL). Piperidine (0.051 mL, 0.521 mmol, 1.50 equiv.) and the aldehyde (113 mg, 0.347 mmol, 1.0 equiv.) were added to the mixture, and the solution was monitored by TLC and refluxed at 60°C overnight. The reaction was let cool to r.t., washed with ethanol (1.0 mL), and filtered to give the thiazolidinone pyrrole as a yellow powder (106 mg, 0.21 mmol, 61%): m.p.=309 °C (dec.); FTIR (neat) 3057, 2947, 2776, 1699, 1640 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.83 (m, 2H), 7.70 (s, 1H), 7.41 (t, 2H), 7.21 (t, 1H), 7.15 (br s, 2H), 6.93 (d, 2H), 6.12 (s, 1H), 2.14 (s, 3H), 1.98 (s, 3H); 13C NMR (400 MHz, CDCl3) δ 138.78, 137.31, 135.04, 129.78, 129.44, 125.05, 121.74, 105.66, 12.71, 11.09.

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16th August 2013 @ 01:35

Synthesised using direct method but also see Hydrolysis of acyl-iminothiazolidinone PMY 14-1 (PMY 16-1) for reference.

(PMY 13-1) (135 mg, 0.70 mmol, 1.02 equiv.) was dissolved in ethanol (10 mL) and combined with piperidine (0.11 mL, 1.11 mmol, 1.61 equiv.). AEW 2-3 (150 mg, 0.627 mmol, 1.00 equiv.) was dissolved in ethanol (5 mL) and added to the mixture, and the resulting clear brown solution was heated to 60 °C for 2.5 h 


AEW 80-1
AEW 80-1.pdf

Hazard and Risk Assessment:

See Synthesis of (2Z,5Z)-5-((2,5-dimethyl-1-(p-tolyl)-1H-pyrrol-3-yl)methylene)-2-(phenylimino)thiazolidin-4-one (AEW 76-1, OSM-S-37)

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16th August 2013 @ 01:12

For original synthesis see here. Resynthesised for characterisation and possible submission to new assay.

Going to start at 4.30pm

AEW 76-1 (50 mg, 0.13 mmol, 1 equiv.) was dissolved partially in toluene (~5 mL) and stirred under a nitrogen atmosphere. Pyridine (~20 μL, 0.25 mmol, 1.9 equiv.) was added, followed by acetic anhydride (~40 μL, 0.4 mmol, 3 equiv.). The mixture was heated to 80 °C and left stirring overnight under nitrogen.

Hazard and Risk Assesment:

See Acetylation of para-trifluoromethyl near neighbour analogue (ZYH 12-1)

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13th August 2013 @ 08:02

Resynthesis of OSM-S-37, See ZYH 5-1 for original expt.

2-phenyliminothiazolidin-4-one (PMY 13-1) (123 mg, 0.640 mmol, 1.02 equiv.) was dissolved in ethanol (10 mL) and combined with piperidine (0.100 mL, 1.01 mmol, 1.61 equiv.). 2,5-dimethyl-1-(4-methylphenyl)-1H-pyrrole-3-carboxaldehyde (LMW 5-1) (145 mg, 0.627 mmol, 1.00 equiv.) was dissolved in ethanol (5 mL) and added to the mixture, and the resulting clear brown solution was heated to 60 °C for 2.5 h then removed from the heat and stirred at room temperature o/n. Reaction mixture cooled and stirred in an ice bath and then filtered to yield a yellow solid. First filtration, solid passed through and blocked sinter. Re-filtered using fine grade filter paper to give a bright yellow solid that was dried at the high vac (x mg). Sinter funnel washed with EtOAc and the illuminous yellow mother liquors were concentrated to yield

Hazard and Risk Assessment:

See Synthesis of p-methyl arylpyrrole based near neighbour (ZYH 5-1)

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11th April 2013 @ 06:41
Mnr: MNR121-130

 Starting material from Synthesis of Near Neighbour Analog MNR82-2 

also Synthesis of Near Neighbour Analog MNR82-1

Procedure as for Example 6 step b

Hazard Assessment



To MNR82-2 (0.040 g, 0.1 mmol) in MeOH (2.4 mL) and DMF (0.6 mL) was added a catalytic amount of Palladium on charcoal (10%) and the reaction was stirred under an atmosphere of hydrogen overnight.  The reaction was then filtered through celite and concentrated.  Crude NMR showed DMF was still present but the crude mixture was soluble in CDCl3.  

Crude NMR


Colum 5% MeOH/CHCl3

2013-04-12 15.42.04.jpg


Frac 9 -  as a yellow oil, upon adding DCM a solid formed.  DCM removed and dried.


Frac 10-17 -






Starting Materials




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