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31st January 2013 @ 17:27

Sodium 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-sulfonate was synthesised (1.38 g, 47% yield) to be used in sulfonamide formation.

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Synthesis of sodium 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-sulfonate with reduced sulfur trioxide pyridine complex.

Reaction start time: 12:30 AM EST 30/1/13

AEW 1-1 (2.0 g, 10 mmol, 1 equiv. ) and Sulfur trioxide pyridine (1.71 g, 10 mmol, 1 equiv.) were refluxed in toluene (16 mL) for 16 hours. Reaction was concentrated under reduced atmosphere followed by addition of water and heating to 100° C, the boiling reaction was then neutralised with sodium carbonate (approx. 1 g). Water was then removed under reduced pressure. A 90:10 ethanol:water mix (20 mL) was added to the residue and the solution heated to 90° C then filtered. The product was then concentrated to give the final product (1.38 g 4.7 mmol, 47% yield).

 

See also: Method used from this paper Synthesis of sodium 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-sulfonate (MD 6-1) Synthesis of sodium 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-sulfonate (MD 6-2)

Risk and Hazard assessment: Same as Synthesis of sodium 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-sulfonate (MD 6-1)

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31st January 2013 @ 17:13

Could only isolate starting material, reaction is to be redone with AEW 1-1.

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Synthesis of sodium 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-sulfonate with reduced sulfur trioxide pyridine complex.

Reaction start time: 12:30 AM EST 26/1/13

MD 22-1 (3.25 g, 10 mmol, 1 equiv) and Sulfur trioxide pyridine (2.6 g, 10 mmol, 1 equiv) were refluxed in toluene (6 mL) for 16 hours. Reaction was concentrated under reduced atmosphere followed by addition of water and heating to 100° C, the boiling reaction was then neutralised with sodium carbonate (approx. 3 g). Water was then removed under reduced pressure. A 90:10 ethanol:water mix (20 mL) was added to the residue and the solution heated to 90° C then filtered. Only starting material was isolated, possibly due to the 4-fluoroaniline contamination mentioned in MD 22-1.

See also: Method used from this paperSynthesis of sodium 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-sulfonate (MD 6-1) Synthesis of sodium 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-sulfonate (MD 6-2)

Risk and Hazard assessment: Same as Synthesis of sodium 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-sulfonate (MD 6-1)

31st January 2013 @ 17:10

Reaction scheme MD 22-1"

 

 

Reaction start time: 5:00 PM EST 21/1/13
4-fluoroaniline (8.8 mL, 93 mmol, 1 equiv.) and 2,5-hexanedione (10 mL, 93 mmol, 1 equiv.) were mixed and heated to 110 °C and left overnight. In the morning, the reaction was cooled to room temperature. The mixture was dissolved in hot EtOH (15 mL) after which a mixture of EtOH (10 mL) and aqueous solution of 10% citric acid (10 mL) was added. Reaction was cooled in an ice bath. The resulting brown crystals contained contaminated black crystals. The crystals were re-dissolved in hot EtOH (10 mL) and a mixture of EtOH (10 mL) and aqueous solution of 10% citric acid (10 mL) were added and the mixture cooled. The resulting crystals were filtered and washed with water. Black contaminate (thought to be 4-fluoroaniline) still remained, product was used in next reaction without further purification.

See also:Synthesis of 1-ethoxy-1-oxopropan-2-yl 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-carboxylate through ester synthesis (MD 17-1)

Risk and Hazard assessment: Same as Synthesis of Ethyl 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-carboxylate (MD 1-1)

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31st January 2013 @ 15:29

Reaction start time: 12:00 AM EST 17/1/13

MD 1-2 (5.2 g, 22 mmol) was dissolved in EtOH (10 mL). 20% NaOH(aq) (32 mL) was added to the solution. Reaction was heated to 90°C and left over night. 11:30 AM TLC showed reaction had completed.

5 M HCL (10 mL) was used to acidify the solution so that light brown crystals formed. The crystals were filtered and washed with H2O (40 mL) and EtOH (20 mL) then concentrated under reduced atmosphere to give the final product (3.7 g, 15 mmol, 68% yield).

See also:Hydrolysis of Ethyl 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-carboxylate (PMY 8-2) Hydrolysis of Ethyl 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-carboxylate (PMY 8-4) Hydrolysis of Ethyl 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-carboxylate (JRC 2-1)

Risk and Hazard assessment: Same as Hyrdolysis of Ethyl 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-carboxylate (MD 2-1)

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31st January 2013 @ 15:19

Ethyl 1-(4-fluorophenyl)-2,5-dimethyl-1<em>H</em>-pyrrole-3-carboxylate was synthesised with a yield of 7.7g, progressed to hydrolysis.

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Reaction Start time: 11:00 AM EST 15/1/13

Potassium carbonate (11.2 g, 81 mmol, 1.3 equiv.) and sodium iodide (10.1 g, 68 mmol, 1.1 equiv. ) were stirred in acetonitrile (50 mL) and cooled in an ice bath. Ethyl acetoacetone (8.0 mL, 62 mmol, 1 equiv.) followed by chloroacetone (6.4 mL, 80 mmol, 1.3 equiv.) were added dropwise. The mixture was heated to 90 °C and left overnight. At 10:00 AM the next day, the mixture was filtered then concentrated under reduced pressure. The concentrated mixture was then washed with water (2 × 20 mL) and with brine (2 × 20 mL). The product was dried then concentrated under reduced atmosphere giving a brown oil (6.4 g) which was used in the second step without further purification.

4-fluoroaniline was added at 4:00 PM and the reaction was heated to 90 °C and left overnight. The reaction was cooled and dissolved with ethyl acetate (25 mL) then washed with water (2 × 20 mL), followed by brine (1 × 20 mL). The mixture was then concentrated under reduced pressure to give a brown liquid, which was recrystallised with EtOH (40 mL) and 40% EtOH (20 mL). Brown crystals formed (7.7 g, 29 mmol, 47% yield).

 

See also: Synthesis of Ethyl 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-carboxylate (MD 1-1) Upscaled Synthesis of Ethyl 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-carboxylate (JRC 1-1) Synthesis of ethyl 2-acetyl-4-oxopentanoate intermediate. (LMW 7-1) Synthesis of Ethyl 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-carboxylate (PMY 6-1)

 

Risk and Hazard Assessment:
Same as Synthesis of Ethyl 1-(4-fluorophenyl)-2,5-dimethyl-1H-pyrrole-3-carboxylate (MD 1-1)

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