Postlab 9

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Texas Tech University *

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3106

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Chemistry

Date

Feb 20, 2024

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docx

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5

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TEXAS TECH CHEM 3106-382 Experiment 9: Preparation of Unknown Derivatives Purpose : Experiment 9 is the third and final part of our unknown analysis. Today we aim to conduct pure organic analysis by preparing and characterize crystalline derivatives. First, we aim to determine which functional groups (from experiments 7 and 8) fit best with IR and functional group test data. Second, we aim to synthesize, isolate, and characterize at least one crystalline derivative from each unknown. Safety : Note that many of the derivatives are extremely hazardous and must be handled properly, under the fume hood. Be sure to wear gloves, goggles, lab coat, and appropriate footwear. Carboxylic Acids—Preparation of an Amide Acid Chloride Intermediate Procedure : Step 1: Preparation of Acid Chloride Intermediate 1. Add 40 mg of carboxylic acid and a boiling chip to a 3.0 mL conical vial. 2. Under the hood, add 8 drops of oxalyl chloride and 1 drop of DMF. 3. Immediately attach air condenser fitted with drying tube and allow the mixture to stand at room temperature. 4. Using a hot plate, gently heat mixture to reflux for 15 minutes. 5. Allow mixture to cool. 6. Add 0.5 mL of CH 2 Cl 2. 1. Anilide Derivative Procedure: 1. Add 10 drops of aniline and ~1 mL of CH 2 Cl 2 to 5mL conical vial. 2. Add a spin vane. 3. Cool in an ice bath. 4. Slowly add (while stirring) crude acid chloride solution. 5. Continue stirring for 10 min.
6. Extract the CH 2 Cl 2 solution with ~mL of water, followed by ~1 mL 5% HCl (aq), followed by ~1 mL 5% NaOH (aq), and finally ~mL of water. The top layer will be aqueous. 7. Transfer to centrifuge tube for easier extraction. 8. Dry organic solution with anhydrous MgSO 4 . 9. Use heat and compressed air to evaporate solvent. 10. Using a shell vial, recrystallize by heating the solid in ~1 mL of ethanol till boiling. 11. Once solid has fully dissolved, slowly add water. 12. Return vial to hot plate. 1. The solid will go in and out of solution. As more water is added, it will take longer for solid to redissolve. 13. Stop adding water when the solid barely dissolves back to solution and lengthy swirling is observed. 14. Allow to cool to room temperature. 15. Using a Hirsch funnel and a 10mm filter paper, use vacuum filtration to isolate your crystals. 16. Find the melting point of unknown crystals. 2. Toluidide Derivative Procedure: 1. This procedure is identical to the Anilide Derivative above, only substitute 50 mg of toluidine (methyl aniline) for aniline. Alcohols Phenylurathane Derivative Procedure: 1. Add ~45 mg unknown alcohol to conical vial. If liquid, preweigh the vial and add alcohol drop wise. 2. Under the hood, add 6 drops of phenyl isocyanate drop wise with swirling. 3. If there is a visible solid, collect using a Hirsch funnel and 10 mm filter. 4. If a solid is not observed, add air condenser and warm on a hot plate for five minutes. Then cool to room temperature and then transfer to an ice bath. 5. If solid is goopy, pipet any remaining liquids and leave the solid in the conical vial. 6. Add 1-2 mL of ligroin and heat vial to extract urethane product. 7. Transfer warm ligroin to shell vial to cool (ice bath may be needed). 8. Collect crystals via vacuum filtration using a Hirsch funnel and a 10mm filter. 9. Find melting point.
Aldehydes and Ketones 2,4-Dinitrophenylhydrazone Derivative Procedure: 1. Liquid: Add 5 drops of unknown liquid to shell vial and ~1 mL of 2,4-DNP reagent solution. Mix and allow solid to form. 2. Solid: Dissolve ~50 mg of unknown in ~1-2 mL of ethanol. Heat to dissolve if needed. 3. Add ~1 mL of 2,4-DNP reagent solution. 4. Collect crystals via vacuum filtration using Hirsch funnel and 10 mm filter. 5. Rinse solid on the Hirsch funnel with ~0.5 mL cold ethanol 6. Obtain melting point. Amines Benzamide Derivative Procedure: 1. Add spin vane to conical vial. 2. Add ~0.5 mL 10% NaOH (aq) and 50 mg of amine (~5-6 drops if liquid). 3. Stir rapidly (under hood) and slowly add 5-6 drops of benzoyl chloride. 4. Allow to stir for 10 min. 5. Use vacuum filtration to obtain crystals, rinsing with ~0.5 mL of dilute HCl (aq) and then ~0.5 mL of water. 6. Obtain melting point.
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