EXP286

=Researcher= Matthew McBride =Objective= To synthesize (1E,4E)-1,5-Di(9-phenanthryl)-1,4-pentadien-3-one from phenanthrene-9-carboxaldehyde and acetone via an aldol condensation using NaOH as the catalyst =Procedure= Dissolved phenanthrene-9-carboxaldehyde in methanol and added acetone. Added NaOH as the catalyst and allow the reaction mixture to stir. The yellow crystals obtained were purified by recrystallization from benzene. The following [|Reaction Preparation Sheet] was used to plan this synthesis. =Results= Amount: 0.0834 g [|HNMR] Spectrum Appearance: Yellow powder Purity: This is the crude product and shows some impurity
 * Characterization of Product 286A**

Amount: 0.0242 g Melting point: 264-265°C [|HNMR] Spectrum Appearance: Yellow powder Purity: Very pure with a trace of benzene present
 * Characterization of Product 286B**

Amount: [|HNMR] Spectrum Appearance: Yellow film
 * Characterization of Product 286C**

Amount: [|HNMR] Spectrum Appearance: Yellow Crystals
 * Characterization of Product 286D**

Picture #1: Purified yellow crystals

=Discussion= Product was very insoluble in methanol so could be filtered off. The yield of the synthesis was relatively low at 19%. =Conclusion= (1E,4E)-1,5-Di(9-phenanthryl)-1,4-pentadien-3-one was successfully synthesized in a yield of 19% =Log=

2012-08-09
12:21 Added 0.1249 g (1 pellet) of NaOH to a 25 mL Erlenmeyer flask. 12:50 Added 10 mL of ethanol to the flask with the NaOH. 13:07 Added 10 mL of ethanol to the flask. The pellet was still visible and would not dissolve in. Place the flask on the hot plate to heat. 13:28 The pellet was not dissolving into the ethanol, so the flask was removed from the hot plate. 13:30 Added 0.1307 g (1 pellet) of NaOH to a separate 25 mL Erlenmeyer flask (flask #1). 13:35 Added 10 mL of methanol to the flask #1. Swirled the flask to dissolve the pellet. 13:53 All of the NaOH was observed to have entered the solution in flask #1. 14:10 Added 0.1710 g of acetone to a 25 mL Erlenmeyer flask (flask #2). 14:14 Added 10 mL of methanol to flask #2. 14:28 Added 0.1540 g of phenanthrene-9-carboxaldehyde into a 20 mL test tube. 14:45 Added 15 mL of methanol to the test tube. The crystals were not dissolving into the solution, so the test tube was placed on the shake flask apparatus at 25°C. 15:23 The crystals did not dissolve into the solution. The supernatant in the test tube was poured into a 50 mL Erlenmeyer flask (flask #3). 15 mL of fresh methanol was added to the test tube and it was placed on the shake flask apparatus. 16:01 Some crystals were still visible in the test tube. Poured the supernatant into flask #3 and added 15 mL of fresh methanol and placed the test tube on the shake flask apparatus. 16:16 All but a very tiny bit of crystals had entered the solution. The supernatant from the test tube was poured into flask #3. 1 mL of the acetone solution (flask #2) was added to the reaction mixture (flask #3). 2.5 mL of the NaOH solution (flask #1) was added drop-wise to the reaction mixture (flask #3) as the solution stirred. The flask was let on the stir plate to stir. The solution was clear and colorless.

2012-08-10
8:16 No crystals were visible in the solution. The color of the solution was still clear and colorless. Heat was applied to the solution. 12:28 Added 0.9669 g of NaOH pellets to flask #3 as the solution was stirring. 14:29 Small yellow crystals were visible in the solution. The solution had obtained a yellow color and was cloudy. The heat was turned off, but the solution was left on the stir plate to mix.

2012-08-13
13:20 The solution in the flask was a bright yellow. Took picture #1. 13:34 Filtered the solution using a Buchner funnel and suction filtration. Yellow crystals were captured on the filter paper. The crystals were washed with water and then washed with methanol. The crystals were allowed to sit over the suction to dry. Took picture #2 of the yellow crystals. 14:04 The weight of the empty 5-dram snap cap vial (no cap) was 11.8197 g. 14:11 The yellow crystals (had more of an appearance of a yellow powder) were scrapped off of the filter paper and placed in the 5-dram vial. The weight of the vial was 11.9197 g. This is 0.0834 g of recovered Product A. Approximately 20 mg of Product A was placed in a separate 5-dram vial and CDCl3 was added to the vial. Some of the crystals dissolved into the solution and the solution had a yellowish-green appearance. Using a paster pipette filter (a small piece of kimwipe stuffed into a pipette), the CDCl3 solution was filtered into NMR Tube 1. The sample was then analyzed by 500MHz HNMR. The file of the spectrum was saved as UCEXP286_A.

2012-08-16
13:04 Flask with the crude product weighed 37.2445 g (50 mL Erlenmeyer). Added 2 mL of benzene to the crude product (Product 286A). Placed the flask on the hot plate to boil. 13:31 Added a totally of approximately 8 mL of benzene for a total of 10 mL to the boiling solution. All of the crystals went into the solution. Removed the flask from the hot plate and let cool at room temperature. 13:34 Crystals were first observed to come out of the solution. 14:32 Filtered the solution using suction filtration. Washed the yellow crystals with benzene. Allowed crystals to dry over suction. This is Product 286B. 15:00 Empty 5-dram vial weighed 11.7973 g and vial with the crystals weighed 11.8215. Weighed of recovered product was 0.0242 g. Removed a very small amount of crystals and dissolved in CDCl3. Added solution into an NMR tube and analyzed by 500MHz HNMR. The CDCl3 solution was placed in vial A after taking the NMR and left open to allow the CDCl3 to evaporate.

2012-08-27
13:08 The weight of vial A with the crystals was 11.7768 g. Film of yellow crystals on the bottom of the vial. 14:27 Approximately 1 mL of CDCl3 was added to vial A and all of the crystals were dissolved into the solution. The solution was transferred to a NMR tube and analyzed by 500MHz HNMR. The file of this spectrum was saved as UCEXP286_3. This is product 286C. 14:50 The weight of vial A empty (cleaned without the solution) was 11.7752 g. The solution from the NMR tube was placed back in the vial after being analyzed by NMR.

2012-08-28
10:48 The weight of vial A with the dried yellow film was 11.7762. This means there was a total of 0.0010 g of product in the vial. Placed Product 286B in a 5-dram vial and placed under high vacuum to dry.

2012-08-30
9:52 Vial was removed from high vacuum. The weight of an empty (no cap) 5-dram snap cap vial was 11.8352 g. This is Vial B.  The dried sample was placed in Vial B and then it weighed 11.8503 g.  This is 0.0151 g of Product 286D. 10:27 A small crystal was placed in a new vial and a few drops of DMSO were added to the vial. The crystals were observed to dissolve. 10:30 0.0010 g of Product 286D was placed in a 5-dram snap cap vial and approximately 1 mL of CDCl3 was added to the vial. The crystals were dissolved into the solution and the solution was transferred to an NMR tube. The sample was analyzed by 500MHz HNMR and the file of the spectrum was saved as UCEXP286D. 11:45 The weight of an empty 5-dram snap cap vial was 11.8295 g. The weight of the vial with Product 286D was 11.8315 g.  0.0020 g (2 mg) of product was added to the vial. The vial was sealed with parafilm and submitted to be mailed to Oral Roberts University.