Chemistry
Chemistry
10th Edition
ISBN: 9781305957404
Author: Steven S. Zumdahl, Susan A. Zumdahl, Donald J. DeCoste
Publisher: Cengage Learning
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I need help calculating the theoretical yield of the product(s) for this experiment. I’m not sure if I only need the theoretical yield for Flavone 4 or if I need to find it for 1, 2, 3, and 4, so if it’s possible please calculate it for all 4. Also please specify the limiting reagent! The experiment information is in the photos.
Experiment 1: Synthesis of a Flavone
This experiment will illustrate a multistep synthetic sequence and will constitute a three-step process. The first
step of the synthesis will involve a simple benzoylation of 2-hydroxyacetophenone. The second step is a
Baker-Venkataraman rearrangement to provide the ß-diketone 3, which upon treatment with acid leads to
cyclization to form the target molecule 4. Note that the final compound is a heterocycle.
Reaction Sequence:
&=&==
KOH
heat
●
OH O
2-Benzoyloxyacetophenone (2):
Things to know:
●
●
1
●
Ph CI
pyridine
Acylation mechanism
● Büchner funnel-vacuum filtration
Things to know:
●
Ph
2
recrystallization from MeOH (hot; cold)
Structural Determination (m.p. IR, GC-MS and NMR)
Dissolve 2-hydroxyacetophenone (1) (2.72 g, 20.0 mmol) in pyridine (5 mL), add benzoyl chloride (4.22 g, 30,0
mmol) by Pasteur pipette and then fit the flask with a calcium chloride drying tube. Swirl the flask and some
heat will be evolved. Allow the reaction to stand for 20 min, or until no further heat is evolved, and then pour
the entire contents of the flask into a mixture of 3% HC1¹ (~120 mL) and crushed ice (~40 g). Once all the ice
has melted, collect the precipitated solids by vacuum filtration. Wash the product with ice-cold methanol (~5
mL) and then water (~5 ml). Dry at the pump for 20 min² and then recrystallize the crude product from
methanol (~5 mL). Record a mp, IR, GC-MS and NMR spectrum on the product.
● Pyridine's role?
Enolate & Acyl transfer mechanism
OH OO
● Büchner funnel-vacuum filtration
Structural Determination (Crude ¹H NMR and m.p.)
3
Ph
o-Hydroxydibenzoylmethane (3):
Dissolve 2 (2.40 g, 10 mmol) in pyridine (8 mL) in a 50 mL beaker and heat the solution to 50 °C on a steam
bath. Add crushed KOH pellets (~0.85 g) and stir the resulting mixture with a glass rod. During this time a
yellow precipitate of the potassium salt of 3 should form. Cool the mixture to room temperature and
cautiously add 10% aqueous acetic acid solution (15 mL). Collect the product by suction filtration and dry at
the pump for a few minutes. Record the yield, a ¹H NMR spectrum and the melting point. Use the crude
product directly in the next step.
ACOH
MacBook Pro
H₂SO4
Page <
1 This HCl solution should be made up immediately prior to the lab session in which it will be used.
2 Occasionally use a spatula to break up the filter cake to ensure thorough drying.
O
O Ph
4
1
> of 2
expand button
Transcribed Image Text:Experiment 1: Synthesis of a Flavone This experiment will illustrate a multistep synthetic sequence and will constitute a three-step process. The first step of the synthesis will involve a simple benzoylation of 2-hydroxyacetophenone. The second step is a Baker-Venkataraman rearrangement to provide the ß-diketone 3, which upon treatment with acid leads to cyclization to form the target molecule 4. Note that the final compound is a heterocycle. Reaction Sequence: &=&== KOH heat ● OH O 2-Benzoyloxyacetophenone (2): Things to know: ● ● 1 ● Ph CI pyridine Acylation mechanism ● Büchner funnel-vacuum filtration Things to know: ● Ph 2 recrystallization from MeOH (hot; cold) Structural Determination (m.p. IR, GC-MS and NMR) Dissolve 2-hydroxyacetophenone (1) (2.72 g, 20.0 mmol) in pyridine (5 mL), add benzoyl chloride (4.22 g, 30,0 mmol) by Pasteur pipette and then fit the flask with a calcium chloride drying tube. Swirl the flask and some heat will be evolved. Allow the reaction to stand for 20 min, or until no further heat is evolved, and then pour the entire contents of the flask into a mixture of 3% HC1¹ (~120 mL) and crushed ice (~40 g). Once all the ice has melted, collect the precipitated solids by vacuum filtration. Wash the product with ice-cold methanol (~5 mL) and then water (~5 ml). Dry at the pump for 20 min² and then recrystallize the crude product from methanol (~5 mL). Record a mp, IR, GC-MS and NMR spectrum on the product. ● Pyridine's role? Enolate & Acyl transfer mechanism OH OO ● Büchner funnel-vacuum filtration Structural Determination (Crude ¹H NMR and m.p.) 3 Ph o-Hydroxydibenzoylmethane (3): Dissolve 2 (2.40 g, 10 mmol) in pyridine (8 mL) in a 50 mL beaker and heat the solution to 50 °C on a steam bath. Add crushed KOH pellets (~0.85 g) and stir the resulting mixture with a glass rod. During this time a yellow precipitate of the potassium salt of 3 should form. Cool the mixture to room temperature and cautiously add 10% aqueous acetic acid solution (15 mL). Collect the product by suction filtration and dry at the pump for a few minutes. Record the yield, a ¹H NMR spectrum and the melting point. Use the crude product directly in the next step. ACOH MacBook Pro H₂SO4 Page < 1 This HCl solution should be made up immediately prior to the lab session in which it will be used. 2 Occasionally use a spatula to break up the filter cake to ensure thorough drying. O O Ph 4 1 > of 2
Flavone 4:
Dissolve the crude product 3 (1.20 g, 5 mmol) in glacial acetic acid (7 mL) and add concentrated H₂SO4 (0.25
mL) with stirring. Heat the reaction mixture on a steam bath for 1 h with agitation. Pour the reaction mixture
onto crushed ice (~40 g) and stir with a glass rod. When all the ice has melted, collect the crude solid by
suction filtration and wash with water until it is free from acid.3 Allow the product to dry at the pump for 15
min and then allow to air dry. Recrystallize the residue from petroleum ether (bp 60-80 °C), -40 mL.
Things to know:
● Acid catalyzed cyclo-condensation mechanism
Recrystallization (pet. Ether hot; then cold)
●
Questions and tasks:
1. Obtain and interpret a ¹H NMR, IR, and GC-MS for compound 1.
2. Obtain and interpret mp, ¹H NMR, IR and GC-MS for products 2 and 4.
3. Provide the IUPAC
for flavone 4.
4.
Page <
Provide a reasonable mechanism for the acid catalyzed conversion of 3-4. Note this is acid catalyzed,
and therefore there should not be any negatively charged intermediates or reagents. Report this in
your report discussion.
3 Check the pH of the filtrate coming out of the filter funnel stem with pH paper.
* It is important to ensure that the crude product is as dry as possible otherwise difficulty will be encountered during the
recrystallization step.
MacBook Pro
2
of
expand button
Transcribed Image Text:Flavone 4: Dissolve the crude product 3 (1.20 g, 5 mmol) in glacial acetic acid (7 mL) and add concentrated H₂SO4 (0.25 mL) with stirring. Heat the reaction mixture on a steam bath for 1 h with agitation. Pour the reaction mixture onto crushed ice (~40 g) and stir with a glass rod. When all the ice has melted, collect the crude solid by suction filtration and wash with water until it is free from acid.3 Allow the product to dry at the pump for 15 min and then allow to air dry. Recrystallize the residue from petroleum ether (bp 60-80 °C), -40 mL. Things to know: ● Acid catalyzed cyclo-condensation mechanism Recrystallization (pet. Ether hot; then cold) ● Questions and tasks: 1. Obtain and interpret a ¹H NMR, IR, and GC-MS for compound 1. 2. Obtain and interpret mp, ¹H NMR, IR and GC-MS for products 2 and 4. 3. Provide the IUPAC for flavone 4. 4. Page < Provide a reasonable mechanism for the acid catalyzed conversion of 3-4. Note this is acid catalyzed, and therefore there should not be any negatively charged intermediates or reagents. Report this in your report discussion. 3 Check the pH of the filtrate coming out of the filter funnel stem with pH paper. * It is important to ensure that the crude product is as dry as possible otherwise difficulty will be encountered during the recrystallization step. MacBook Pro 2 of
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