Experiment No. 7 The Iodoform Reaction I.

Objectives At the end of this activity, we should be able to (1) identify the organic compounds that will give a positive test and as well those organic compounds that will give a negative test using iodoform reaction. (2) Also to identify the reason why such organic compounds give a positive test to iodoform reaction. (3) And to identify the reason why such organic compounds give a negative test to iodoform reaction. II. Materials -Vials (6)

-Droppers (8)

-Organic compounds

III. Procedure (Three trials) Prepare 6 vials. 1

Ethanol

2
N-butanol

4
Tert-butyl

5
Iso-butyl

6
Formalin Acetone

Place 5 drops of each organic compounds in each of the vials. 1 vial=1 compound

15 drops of 1 M NaOH

Put 15 drops of 1 M NaOH to each of the vials.

Shake. Observe.
25 drops of KI-I2

Add 25 drops of KI-I2 to each of the vials.

Shake. Wait for 2-3 minutes. Observe.

Wait for another minutes. Observe.

5-10

IV. Data and Results

Organic Compound Ethanol

N- butanol

15 drops of NaOH + 25 drops of KI-I2 T1 T2 T3 Very cloudy or turbid; Cloudy or turbid; pale Cloudy or turbid; pale pale yellow yellow precipitate yellow precipitate precipitate formed at formed at the bottom formed at the bottom the bottom of the vial of the vial of the vial the solution was oily; the solution was oily; the solution was oily; very cloudy or turbid; cloudy or turbid; pale very cloudy or turbid; pale yellow yellow precipitate pale yellow precipitate formed at formed at the bottom precipitate formed at the bottom of the vial of the vial the bottom of the vial No changed Cloudy or turbid; pale yellow precipitate formed at the bottom of the vial No changed Pale yellow precipitate formed at the bottom of the vial; it is very turbid or cloudy No changed Very cloudy or turbid; pale yellow precipitate formed at the bottom of the vial No changed Pale yellow precipitate formed at the bottom of the vial; it is very turbid or cloudy No changed Very cloudy or turbid; pale yellow precipitate formed at the bottom of the vial No changed Pale yellow precipitate formed at the bottom of the vial; it is very turbid or cloudy

Tert-butyl

Iso-butyl

Formaldehyde

Propanone

Organic Compound Ethanol N-butanol Ter-butyl Iso-butyl Formaldehyde Propanone

Smell It has a bad odor Smell like hospital/s Smell like acetone Smell like hospital/s It has a bad odor Smell like hospital/s

V. Discussions or Questions Q1. What do you observe after 2-3 and after 5-10 minutes? Prepare a table like the one below. TABLE 1: TESTING OF VARIOUS COMPOUNDS WITH HYPOIODITE (I2/KI NaOH) SOLUTION APPEARANCE OF WELL PRECIPITATE (CHI3(s)) COMPOUND CONTENTS AFTER 2 TO 3 MINUTES Ethanol N-butanol Tert-butyl Iso-butyl Formaldehyde Propanone Turbid/ Cloudy Turbid/ Cloudy; Oily No changed Turbid/ Cloudy No changed Turbid/ Cloudy FORMATION? (After 5-10 minutes) Precipitate was formed Precipitate was formed No changed Precipitate was formed No changed Precipitate was formed

Q2. What do you notice in the vials where turbidity was observed earlier? Weve noticed that after 3-5 minutes the solution became cloudy or turbid and after 5-10 minutes there was precipitate forming at the bottom of the vial. Q3a. What do you see? We saw precipitate forming at the bottom of the vials. Q3b. What do you notice? Weve noticed that the color of the precipitate formed was pale yellow. And when we leave it, the precipitate will settle at the bottom of the vial and also if we do not shake it well they will not be dispersed or be carried. Q4. Describe the odour/ smell. The smell was like the smell of the hospitals. Q5. Examine the structures of propanone and cyclohexanone along side. What is the difference in structure between these two ketones, besides the fact that one ketone is cyclic and the other aliphatic?

Propanone has CH3 attached to CO

Cyclohexanone has CH2 attached to CO

It is easier for propanone to bond with other compounds than cyclohexanone because of its structure.

Q6. Based upon your answer to question 1 and the observations made in this experiment, how does the iodoform test help to distinguish methyl ketones from non-methyl ketones? Methyl ketones can be distinguished from non- methyl ketones by their reaction with iodine in a basic solution to yield iodoform (CHI3) as a pale yellow colored precipitate. Q7. The reaction of a methyl ketone with iodine solution in the presence of aqueous sodium hydroxide is shown in the equation below: RCOCH3(l) + 3I2(aq) + 4NaOH(aq) RCOONa(aq) + CHI3(s) + 3NaI(aq) + 3H2O(l) (where R = H, alkyl or aryl group) i. Which part of the ketone molecule has been involved in the formation of an iodoform molecule? The part of the ketone molecule has been involved in the formation of an iodoform molecule is the CH3 molecule. ii. Use your answer to i to explain why cyclohexanone gives a negative reaction in the iodoform test. Cyclohexanone gives a negative reaction in iodoform test because it doesnt have methyl group that will undergo in reaction. Q8. Formaldehyde gives a negative result in the iodoform test. Do you think that the iodoform test could be used to distinguish methyl ketones from all aldehydes? Explain your answer with reference to the equation given in question 3. I dont think that iodoform test could be used to distinguish methyl ketones from all aldehydes because ethanal is an alddehyde that gives a positive test to iodoform test.

"R" can be a hydrogen atom or a hydrocarbon group (for example, an alkyl If "R" is hydrogen, then you have the aldehyde ethanal, CH3CHO.

group).

Ethanal is the only aldehyde to give the triiodomethane (iodoform) reaction At this point ethanal can give a positive test to iodoform test because it has what is needed in the reaction.

Q9. The equation for the initial reaction between an alcohol (primary or secondary) and iodine solution in the presence of aqueous sodium hydroxide is: RCH(OH)R.(l) + I2(aq) + 2NaOH(aq) RCOR.(aq) + 2NaI(aq) + 2H2O(l) where R and R. = H, alkyl or aryl group i. According to the equation, which alcohols should react with the hypoiodite solution? The iodoform reaction is given by compounds with a methyl group next to a carbonyl group. Secondary alcohols with a CH3 on the carbon carrying the OH (eg propan-2-ol) that can be oxidized to carbonyl compounds of this type, also give a positive iodoform test. Ethanol is the only primary alcohol which will give a positive test.

The full mechanism for the second and third steps are: Second step

This occurs three times to give CI3CHO Third step

The negative charge on the carbon in the I3C ion is stabilised by the three electronegative iodine atoms. ii. Use the equation to explain why certain alcohols are able to give a positive iodoform reaction. Certain alcohols are able to give a positive iodoform reaction because they have CH3 on the carbon carrying the OH. iii. Why does ethanol give a positive iodoform test but methanol does not? (Hint: look at the reaction equation) Ethanol gave a positive test but methanol doesnt because methanol does not have any H, alkyl or aryl group attached to CH3. Q10. Refer back to Table 1. Write down the reactions taking place for those ketones and alcohols which gave a positive iodoform test. For ethanol:

For secondary alcohols with an adjacent methyl group:.

For Ketone:

Q11. You are working in a company laboratory. You have been asked to use 1-propanol in a particular experiment. You find a cupboard in which there is a shelf for alcohols, but the bottles are not labelled. You know that ethanol and 1-propanol are used often. Explain how you will use the iodoform test to locate a bottle of 1-propanol in the presence of bottles of ethanol. Predict the outcome of your investigation and refer to the structures of the alcohol compounds when necessary. Using iodoform test, ethanol will be more cloudy or turbid than 1-propanol.

VI. Conclusion We therefore conclude that at the end of this activity, we have identified the organic compounds that gave a positive test and as well those organic compounds that gave a negative test using iodoform reaction. The organic compounds that gave a positive test are ethanol, nbutanol, iso-butyl and propanone while the organic compounds that gave a negative test are tertbutyl and formaldehyde. The reason why such compounds gave a positive test is because they contain CH3-CO group in molecule that will undergo in the reaction. The group to which the CH3-CO group is attached can be aryl, alkyl and hydrogen. And the reason why such compounds gave a negative test is because they do not contain CH3-CO group in molecule that will undergo in the reaction and they gave a negative test because R group is a di-ortho substituted aryl group. A positive test is seen when the solution became turbid and a pale yellow precipitate formed at the bottom of the vial and they smell like hospital. The precipitate is called iodoform. A negative test is seen when the solution doesnt have any changes. The iodoform reaction is characteristic for methylketones as well as for alcohols (e.g. ethanol, 2-propanol), that can be oxidized to a methyl carbonyl compounds. The iodoform test is a test for the existence of the CH3-CO group in a molecule. The group to which the CH3-CO group is attached can be aryl, alkyl and hydrogen. Both ethanol and 2-propanol are oxidized by iodine to give ethanale or acetone. (1).

When a-methyl carbonyl compounds react with iodine in the presence of a base, the hydrogen atoms on the carbon adjacent to the carbonyl group (a hydrogens) are subsituted by iodine to form tri iodo methyl carbonyl compounds which react with OH - to produce iodoform and carboxylic acid (2):

Reaction mechanism: The hydrogen atoms on the methyl group are slightly acidic and can be removed with hydroxide. The carbanion formed then react with iodine molecules to give a iodide ion and a monoiodonated methyl carbonyl derivate. Introduction of the first iodine atom (owing to its electronegativity) makes the remaining hydrogens of the methyl group more acidic. Hence a base-catalized iodination of a monohalogenated methyl carbonyl derivate occurs at the carbon that is already substituted. Finally a tri iodo methyl carbonyl derivate is formed.

The next step is a nucleophilic attack by hydroxide on the carbonyl carbon atom. A carboncarbon bond cleavage occurs and a triiodomethanide ion departs. The triiodomethanide ion is unusually stable. Its negative charge is dispersed by the three negative iodine atoms. In the last step a proton transfer takes place between carboxylic acid and triiodomethanide ion to form ultimately carboxylate ion and iodoform.