Experiment 8: Dehydration of 2-butanol o Pre-Lab Lecture: Reaction mechanism:

Theoretically make a 1:1:1 mole ratio, but in reality they are not. Difference is due to stability.

Least stable (minor) Most stable (major) + HSO4 and H3O regenerates the H2SO4, so effectively, the sulfuric acid is a catalyst for the reaction. Skills learned in this lab: Set up and carry out reaction forming gaseous products. Characterize with gas chromatography Gas Chromatography Instrumental method for separation and identification of volatile organic compounds. A sample is introduced into a heated injector, carried through separating column Separations of volatile organic compounds based on vapor pressure. Stationary phase: a long, thin column with high surface area and chemically inert packing-diatomaceous earth. o Like a very efficient fractional distillation. Mobile phase: an inert gas, mostly helium, that move/push gases through the column. Retention time (TR): time taken for a component of the mixture to reach the detector after introduced into the instrument via the injector part o Each compound has a unique retention time that helps in the identification of a compound. Area under a peak is used to calculate the percent composition of each component in the mixture. ID of compounds: .2mL of mixture of gases will be used Order: 1-butene, trans-2-butene- cis-2-butene o Experimental Procedure: Use 1mL syringe to measure 1.0 mL of 2-butanol into Erlenmeyer flask. Add 7-8 drops of conc H2SO4 Heat. Gas collection reservoir filled with water

Dont let air bubbles enter reservoir Count at least 50 bubbles before inserting Leave gas reservoir inside the beaker with water when you take it for gas chromatography. Obtain gas chromatograph o Pertinent Observations: 2-butanol is clear liquid that smells like rubbing alcohol Solution turned yellow. Gas was clear. o Methods of Analysis Gas chromatography: trans-2-butene should be most abundant, followed by cis-2-butene, and finally 1-butene should have the smallest area. o Summary Questions Reaction mechanism and know what is major product and what is minor product Be able to look at gas chromatograph and know what the major product was, along with the retention time Experiment 9: Williamson Ether Synthesis o Pre-Lab Lecture: Reaction:

Aqueous phase and organic liquid are not going to mix! o Problem with miscibility o Need phase transfer catalyst. Without a PTC, no reaction. Phase transfer catalyst: (C4H9)4N+Bro Four butyls attached to a N o N+ likes to dissolve in water o Butyl groups like to dissolve in organic o Soluble in both organic AND aqueous phase. o Dual solubility. Reaction with PTC:

Diethyl ether = extraction solvent

Organic layer on top IR: should see absence of OH, a C-O between 1300-1000 cm-1, and sp3 CH o Experimental Procedure: Purpose: make p-ethylphenyl methyl ether from 4-ethylphenol and methyl iodide Weigh .165 g 4-ethylphenol into rxn tube. Add .3mL 25% NaOH. Heat and dissolve alcohol. Cool to room temp. Add 20 mg tetrabutyl ammonium bromide, followed by .1 mL methyl iodide. Heat to 60-65 degrees for 10 min. Cool. Add 2mL diethyl ether Transfer aqueous layer to another tube. To this aqueous layer ad another 2mL diethyl ether. Cap, agitate, and vent again. Transfer top organic layer to original organic layer. And 3mL 5% NaOH to combined diethyl ether. Cap, agitate, and vent. Remove aqueous layer. This is crude, wet ether solution. Dry ether solution with sodium sulfate. Purify with column chromatography using polar silica gel. Force diethyl ether through and collect solution that elutes into dry, preweighed 25mL round bottom flask. Rotovap diethyl ether away. Obtain IR. Confirm absence of OH (3650-3200) and presence of ether stretch (1300-1000) o Pertinent Observations: 4-ethyl phenol brownish, clumpy crystalline solid. After adding CH3I and catalyst, 2 layers formed: one brown and one solid wide. Crude product: clear, yellowish brown Final isolated product: bright yellow liquid. o Methods of Analysis: IR spectroscopy: Should see absence of O-H and presence of ether C-O o Summary Questions: Need phase transfer catalyst because two reactants (4-ethylphenol and methyl iodide) exist in separate phases (aqueous and organic, respectively). Polar part of PTC reacts with deprotonated 4-ethylphenol and lets it go into the organic phase, where it reacts, regenerating the catalyst. Silica gel is very polar and separates compounds based on polarity. Know that a primary or methyl alkyl halide is needed in the second step because that is an SN2 process Experiment 10: Substitution Synthesis of a Haloalkane o Pre-Lab Lecture: 1O 1O benzylic

3O

o o

You cannot prove a mechanism, only disprove If SN1: 3O> 1O Benzylic > 1O If SN2: 1O> 1O Benzylic> 3O Analyze IR spectrum for presence/absence of alcohol bands (C-O and OH) Experimental Procedure: Measure .5 mL of each alcohol in 4.5 mL graded rxn tube. Add 1mL of conc. HCl. Aqueous. First adding HCl: Alcohols can H-bond. Should be homogenous. The alkyl halides cannot H bond with the solvent (HCl) Therefore, the layers do not mix. When alkyl halides form, they make a totally separate layer. The one that goes to completion takes about 10 minutes. 2nd takes about 40 min. Every now and then, shake vigorously. Complete reaction permanent 2nd layer (no more forming) Remove aqueous layer via pipette transfer. Add saturated NaCl (brime) Brime breaks up emulsions. Makes 2 distinct layers. NaCl will settle at the bottom, ignore. Add Na2SO4 to dry product. Isolate and weigh product. Then get IR. Cork isolated product so it doesnt evaporate away. Pertinent Observations: t-butanol and benzyl alcohol started turning cloudy immediately. 1-butanol never turned cloudy. t-butanol took 12 minutes to complete, benzyl alcohol took 47 minutes, and 1butanol did not exhibit any appreciable reaction during the lab period. ~.3-.4 mL of t-butanol and benzyl alcohol evolved. No 1-butanol evolved. After drying, organic layer was clear for both 2-chloro-2-methyl propane nad benzyl chloride. Methods of Analysis: IR spectroscopy: Should have absence of O-H and C-O Summary Questions: Rxn was SN1 Know SN1 precedes through the most stable carbocation intermediate, and thus the reactant the produces the most stable carbocation reacts the fastest. Hammond Postulate: Smaller Ea. In this reaction, tertiary or res-stabilized C+. Know mechanism.

Experiment 11: Alcohols as Nucleophiles Esterification o Pre-Lab Lecture Reaction: Nucleophilic Substitution Reaction One strategy to make a reaction shift to products: Use one of the reactants in excess OR remove one of the products as well. Will shift rxn to the right (Le Chateliers Principle) Acid catalyst: Dowex resin

Strong acid. Makes isolation much easier. This reaction is completely reversible Make it so that any way is possible. How do we know mechanism? Oxygen on Alcohol was isotopically labeled. Cleaving C-O bond on carboxylic acid is where H2O comes from. Experimental Procedure: Rxn run inside a short-neck round bottom flask. Add resin first. Then, dispense reactants into tube, using a syringe. 1mL 1-butanol, .63 mL of acetic acid 3rd arm of 3-ring adapter should slope down. For the first 10 minutes, keep it upright. Reaction is done when volume of water stops increasing. Get IR. Remove product w/ Pasteur pipette and get mass. Pertinent Observations: Catalyst is a sandy, sparkly orange solid. 1-butanol: clear, colorless liquid w/ strong odor. Acetic acid: clear, colorless, smells like vinegar. Water layer clear, organic layer slightly orange. Product (butyl acetate) was clear and colorless, with a very sweet aroma comparable to banana laffy taffy Methods of Analysis: IR spectroscopy All of O-H at ~3300 cm-1 should be gone C=O should still be there. ~1650-1800 cm-1 Csp#-H should still be there. ~ 2850-3000 cm-1 C-O should still be there. 1000-1300 cm-1 Summary Questions: Dean-Stark Apparatus worked by removing water, shifting product to the right. Water, more dense than ether product, went to bottom of collection arm. Wouldnt work if water was less dense. The dowex resin made the isolation of the product significantly easier. Without it, we would have had to do a long processes of product isolation.

Experiment 16: Synthesis of Porphyrin o Pre-Lab Lecture Porphine: unsubstituted porphyrin. Porphyrin: class of organic molecule Ns can act as Lewis bases and donate electron pairs to metal ions. Metal binding ability: Ligand. Heme: iron protoporphyrin IX o Iron binds Oxygen. The mechanism involves sequential acid-catalyzed Friedel-Crafts alkylation reactions. Propionic acid: solvent AND H source Polyperrol = black Porphyriongen: not aromatic Auto-oxidation to make aromatic. All molecules strive to be aromatic (very stable) o Oxygen lost in form of water (condensation) Propionic acid need to be hot because that favors intramolecular ring formation Thermodynamic control. Fluorophore absorbs radiation of shorter wavelength and emits radiation of longer wavelength. o Experimental Procedure: Apply grease to ground glass joins Claisen head converts flask with one opening to a flask with two openings. Heat 12mL propionic acid to reflux before adding reactants. Add .3mL benzaldehyde followed by .2mL pyrrole. Heat to reflux for 30 min. Cool to room temp, then ice bath to form crystals. Vacuum filter using Hirsch funnel. Wash collected solid w/ 2 1mL portions of methanol followed by 2 1mL portions of acetone. Let crystals dry. Determine mass and percent yield. But 1mg of product into dichloromethane. Observe color, fluorescence properties, and determine acid/base properties. Add 3 drops conc HCl and then 6 drops 12M NaOH. o Pertinent Observations: Propionic acid: clear, colorless liquid w/ strong sent like vinegar Benzaldehyde: Dark brown, opaque liquid. Smelled sweet. Pyrrole: dark brown, opaque liquid. No strong odor. No significant change in reaction happened over the 30 min. Crystals: purple and sparkly, crystalline. Color of product + dichloromethane: dark purple/magenta Under long-wave UV: bright pink. Color after adding acid: deep turquoise green. Color after adding base: returned to lighter version of previous color. o Methods of Analysis: Qualitative color analysis.