Isolation of Caffeine

Overview

Liquid/Liquid Extraction of Caffeine from Vivarinan, an over-the-counter

An aqueous Vivarin/Sodium Carbonate mixture is extracted with Dichloromethane (Methylene Chloride)

The solution is evaporated to dryness and the mass and % recovery of the product are determined. Confirmation of product is verified by Melting Point

References: Pavia: pp. 24, 73 84 Note: These pages are not in the GMU version of the Pavia text sold in the book, only in the primary text that we do not use anymore.
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Background Caffeine is a bitter, white crystalline alkaloid (derivative of Xanthine) that acts as a stimulant drug

Caffeine is synthesized in plants from the purine nucleotides AMP, GMP, and IMP. These in turn are transformed into xanthosine and then theobromine, the latter being the penultimate precursor of caffeine
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The two Amide groups exist as zwitterionic resonance structures where the Nitrogen and Carbon atoms are double bonded to each other so that both of the Nitrogen atoms are essentially planer (in sp2 orbital hybridization) A zwitterion is a neutral molecule with a positive and a negative electrical charge (not dipoles) at different locations within that molecule Zwitterions are sometimes also called inner salts The fused ring system therefore contains a total of ten pi () electrons and hence according to Huckels rule is aromatic

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Zwitterionic Resonance

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Chemical Properties

Caffeine acts as a general nervous system stimulant, warding off drowsiness

Caffeine is considered a psycho active substance, but is generally legal and unregulated Caffeine is found in varying quantities in the seeds, leaves, and fruit of some plants, acting as a natural pesticide by paralyzing and killing insects
Sources for human use include coffee plants, tea leaves, and kola nuts
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Procedure

Obtain 2 Vivarin tablets noting % of active ingredient Determine the mass of the tablets Obtain and determine mass of approximately 8 g of Sodium Carbonate Crush the tablets with a pestal & mortor

Add the crushed sample to a 150 mL beaker

Add 60 mL Distilled Water Sodium Carbonate (Na2CO3) to solution Add Teflon boiling chip Heat solution to boiling on a hot plate maintain boiling point for 2 minutes
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Procedure (Contd)

Allow the hot mixture to settle slightly - some solid particles will remain undissolved

Obtain a glass funnel containing a small amount of glass wool packed lightly into the upper part of the stem. Note: use moistened finger tips
Place glass funnel through a clay triangle sitting on an iron ring attached to a ring stand Obtain a 125 mL Separatory funnel and secure the stopcock from leakage by tightening the nut (not too tight) Place the end of the Separatory funnel through a clay triangle sitting on another iron ring attached to the ring stand below the glass funnel
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Procedure (cont)

Decant the sample solution into the glass funnel allowing the liquid to drain into the 125 mL Separatory Funnel Rinse the beaker with a small amount of distilled water and pass the water through the glass funnel to the separatory funnel Allow the filtrate in the Separatory Funnel to cool to room temperature

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Liquidliquid Extraction, also known as solvent extraction and partitioning, is a method to separate compounds based on their relative solubilities in two different immiscible liquids, usually water and an organic solvent. It is an extraction of a substance from one liquid phase into another liquid phase utilizing a separatory funnel Use the following steps to extract the Caffeine into the Methylene Chloride solvent You will do three (3) extractions
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Procedure (Contd)

Add 8.0 mL of Dichloroethane (Methylene Chloride) to the mixture in the separatory funnel Place the stopper in the top opening and make sure it is secure, i.e. wont leak

Invert the funnel pointing the stopcock end away from your face
Use gentle swirling (avoids formation of an emulsion) for 10-15 seconds Slowly open the stopcock to relieve any pressure
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Close the stopcock and continuing swirling with venting every 15 seconds until no more gas is released (two or three times should be sufficient)

Continue the swirling for a total of 5 minutes

Replace the separatory funnel in the ring stand and allow the mixture to settle for a few minutes

Remove the stopper from the Separatory Funnel

Open the stopcock slowly and collect the clear bottom layer into a clean 150 mL beaker Repeat the extraction process two more times with new 8.0 mL aliquots of Methylene Chloride, but reduce the total swirling time to 2 minutes Each time, add the clear bottom layer to the 150 mL beaker
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Procedure (Contd) With the help of the instructor, add Anhydrous Sodium Sulfate as a drying agent Leaving the particles settled on the bottom of the beaker, slowly pour (decant) the liquid into a clean, dry, 50 mL beaker Rinse the beaker containing the drying agent particles on the bottom with one additional small portion of Dichloromethane and add to the sample beaker Evaporate the mixture to dryness in the hood Note: Set hot plate setting to about 3 Note: Crude yield at this point is roughly 90%
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Procedure (Contd)

Recrystallization Process (only if directed by instructor)

Dissolve the dried product in 12-15 mL cold Acetone (from ice/water bath)

Heat solution gently on hot plate If solution is incomplete, remove beaker from hot plate and add more acetone in 2 mL increments Up to 20 mL of additional Acetone may be required until a clear pale-yellow solution is obtained

Remove solution from hot plate and allow to cool slightly

Add Petroleum Ether, drop by drop, with swirling from a full plastic pipet until the first appearance of pervasive cloudiness throughout the solution
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Procedure (Contd)

Continue cooling until crystallization is complete Note: Maximum yield is obtained when the addition of Petroleum Ether is stopped at the first appearance of a pervasive cloudiness throughout the solution

Separate the crystals from the solution by Vacuum Filtration rinsing the beaker and crystals in the funnel with small amounts of Petroleum Ether

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Isolation of Caffeine

Air-dry the sample from the evaporation procedure or the vacuum filtration procedure on a pre-weighed weighing tray for one week

Compute the mass of the purified sample

Compute the percent recovery from the original mass of the tablets

If available, use the percentage of active ingredient from the tablet bottle to compare your experimentally determined content with the actual content
Determine melting point - 236 oC Note: Decomposition of this crude material occurs beginning at 236oC over a range of 5oC or so

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