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30th January 2012 @ 10:39
Condensation of PMY 13-1 and propionaldehyde (ZYH 24-1)

reactionscheme24-1.jpg

Experiment start time: 10:50 EST 30/01/2012
PMY 13-1 was dissolved in ethanol (15 mL) and propionaldehyde was added dropwise. The mixture was heated to 60 °C and turned a darker orange-brown colour but no precipitate was observed. After four hours the reaction was complete by TLC and was cooled to room temperature but the products remained in solution. After evaporating the ethanol off under reduced pressure, the orange-brown oil was dissolved in ethyl acetate and washed with water (3 x 10 mL) and brine (15 mL). The organic layer was then dried over magnesium sulfate and evaporated under reduced pressure to give a brownish-orange solid powder. After an hour or so of exposure to air the solid became tacky, suggesting ready absorption of moisture from the air. The solid was dried again under high vacuum and placed in a sealed container in the fridge. TLC and H NMR suggested a mixture of products and the experiment was put aside for the present.

High resolution mass spectrometry:
HRMS (ESI (+)) Calcd. for [C12H12N2OSH+]: 233.0743, found: 233.0736.

TLC (10% methanol in dichloromethane) visualised using UV and vanillin:
TLC at 4 hrs


Hazard and risk assessment:
Refer to: Synthesis of phenyliminothiazolidinone-substituted arylpyrrole (ZYH 3-1)
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30th January 2012 @ 10:20
Condensation of benzaldehyde and PMY 13-1

reactionscheme23-1.jpg

Experiment start time: 10:10 EST 30/01/2012
PMY 13-1 was dissolved in ethanol (15 mL) and benzaldehyde was added dropwise. The mixture was heated to 60 °C. A yellow precipitate was first observed after half an hour and the reaction was complete by TLC after four hours. The mixture was cooled to room temperature and the precipitate was filtered off to give a very fine, brownish-yellow powder (170 mg, 51% yield).

Data summary table:
Yield % Melting point °C 1H NMR 13C NMR19F NMR IR Mass spec
ZYH 23-1 51 260-261Yes (1H + 13C NMR pdf, can't find data file) Not assignedNAYes (pdf, .dx) ESI 303 M+Na; 583 2M+Na (.raw)


Comparison with literature
The product is a known compound (CAS: 38771-64-1 or 851429-54-4 or 1082659-12-8, depending on stereochemistry) with IR, mass and H NMR spectra available for the record with the E/Z isomerism of the phenyl substitution uncharacterised.

TLC (10% methanol and dichlormethane) visualised using UV and vanillin:
TLC at 4 hrs


Hazard and risk assessment:
Refer to: Synthesis of phenyliminothiazolidinone-substituted arylpyrrole (ZYH 3-1)
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25th January 2012 @ 06:53
Arylpyrroles:
ZYH 1 product
ZYH 8 product
ZYH 9 product

Blog entries: ZYH 1-1; ZYH 8-1, ZYH 9-1

Aldehydes:
ZYH 2 product
ZYH 4 product
ZYH 11 product
ZYH 13 product

Blog entries: ZYH 2-1, 2-2; ZYH 4-1, 4-2, 4-3; ZYH 11-1; ZYH 13-1

Near neighbours:
ZYH 3 product
ZYH 5 product
ZYH 6 product
ZYH 7 product
ZYH 10 product
ZYH 12 product
ZYH 15 product
ZYH 18 product
ZYH 19 product
ZYH 17 product
ZYH 22 product

Blog entries: ZYH 3-1, ZYH 5-1, ZYH 6-1, ZYH 7-1, 7-2, ZYH 10-1, ZYH 12-1, 12-2, ZYH 15-1, ZYH 17-1, ZYH 18-1, ZYH 19-1

Modified thiazolidinone:
ZYH 23 product


Thiazolidinone precursor:
ZYH 20 product

Blog entries: ZYH 20-1
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24th January 2012 @ 21:35
Synthesis of cyclopentane substituted near neighbour analogue from ZYH 6-2

reactionscheme22-3.jpg

Experiment start time: 10:00 EST 25/01/2012
Sodium hydride (27 mg, 0.68 mmol, 1.5 equiv.) was combined with DMF (2 mL) and stirred under a nitrogen atmosphere on an ice bath. ZYH 6-2 (200 mg, 0.45 mmol, 1 equiv.) was combined with DMF (8 mL) and added in portions over 3 minutes and frothing was observed. The mixture was left stirring for 10 minutes and then cyclopentylbromide (60 uL, 0.56 mmol, 1.2 equiv.) was added dropwise. No change was observed by TLC after one hour and the mixture was heated to 60 °C. No reaction was observed at the end of the day and the mixture was left at 60 °C under nitrogen over two nights. In the morning, TLC showed three new spots, two visible under UV, as well as starting material. The reaction was quenched by dropwise addition of water which resulted in precipitation of a brownish-yellow solid which was filtered off and washed with water (~20 mL) then dried under high vacuum. TLC still showed starting material and two products, one more and one less polar, and the mixture was purified by column chromatography (2-8% ethyl acetate in hexane on silica) to extract the least polar fraction as a brownish yellow solid. H NMR and C NMR were consistent with the desired product.

Data summary table:
Yield % Melting point °C 1H NMR 13C NMR19F NMR IR Mass spec
ZYH 22-3 25 *MP*Yes (pdf, data from 300 MHz .zip, data from 400 MHz .zip) Extra peaks (pdf)Yes (pdf)Yes (pdf, .dx) HRMS ESI 510 M+H (can't find low res)


Comparison with literature:
No reference to the product was found in the literature.

High resolution mass spectrometry:
HRMS (ESI (+)) Calcd. for [C28H26F3N3OSH+]: 510.1821, found: 510.1820.

X-ray crystallography:
Single crystal x-ray showed the expected product (.docx, .cif) with the the cyclopentyl substituent attached to the ring nitrogen of the thiazolidinone.

ZYH_22-3.jpg

TLC (50% ethyl acetate in hexane), visualised using UV and Vanillin:
TLC at 45 min
TLC at 2 days
TLC before column


Hazard and risk assessment:
Refer to: Synthesis of acetonitrile substituted p-trifluoromethyl near neighbour analogue (ZYH 10-1)
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24th January 2012 @ 05:21
Synthesis of cyclopentane substituted near neighbour analogue from ZYH 6-2

reactionscheme22-2.jpg

Experiment start time: 17:15 EST 24/01/2012
Sodium iodide (75 mg, 0.4 mmol, 1.1 equiv.) was combined with acetonitrile (~5 mL) and stirred under a nitrogen atmosphere. Triethylamine (0.1 mL, 0.6 mmol, 1.5 equiv.) was added, followed by cyclopentylbromide (0.06 mL, 0.45 mmol, 1.1 equiv.). ZYH 6-2 (200.0 mg, 0.4 mmol, 1 equiv.) was combined with acetonitrile (~10 mL) and added in portions. No change was observed. The mixture was then heated to reflux, with the solid ZYH 6-2 remaining largely undissolved, and left refluxing under nitrogen overnight. In the morning no reaction had taken place by TLC and the mixture was removed from the heat.

Conclusions
Reaction conditions were ineffective so the experiment will be reattempted using sodium hydride as the base.

Hazard and risk assessment:
Hazard and risk assessment
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