Exercise 2 OXIDATION OF A SECONDARY ALCOHOL STEVENS-CHAPMAN REACTION Cyclohexanone from cyclohexanol Inorganic oxidation and reduction processes are

readily recognized as the loss and gain of electrons, respectively. It is often less clear whether electrons are being gained or lost in a reaction with organic compounds. Thus, more useful definitions were used to define oxidation and reduction in other terms. Oxidation is a process that adds electronegative atoms such as halogen or oxygen to or removes hydrogen from a molecule. On the other hand, reduction is the removal of halogen or oxygen or the addition of hydrogen (Vollhardt and Schore, 2011). Oxidation of organic compounds normally involve transfer of electron but since the valence of carbon remains at four, it is more convenient to define it as either loss of hydrogen atoms or addition of oxygen to the other electronegative atoms. Conversely, reduction of organic compounds results in gain of electron density of the carbon atom, bond formation between a carbon and a less electronegative atom or the bond breaking between a carbon and a more electronegative atom. Oxidation of an alcohol yields a carbonyl compound which may be an aldehyde, a ketone, or a carboxylic acid. This depends on the alcohol and the oxidizing agent used. Primary alcohols are oxidized resulting either to an aldehyde or to a carboxylic acid. Secondary alcohols are oxidized to ketones while tertiary alcohols have no hydrogen on their hydroxyl-bearing carbon and do not usually undergo oxidation reaction readily (Carey and Giuliano, 2011). The most commonly used oxidizing agents to synthesize ketones from secondary alcohols are H2CrO4 or KMnO4. However, NaOCl in acetic acid, an alternative oxidizing agent was introduced by Stevens, Chapman, and Willer in 1980. This reagent oxidizes secondary alcohols rapidly and gives high yield. It is also less toxic and costly. It can be disposed through the sink unlike the traditional oxidizing agents that contains heavy metals which causes problems in handling and waste disposal. In this experiment, cyclohexanone, a ketone, will be synthesized from the oxidation of cyclohexanol, a secondary alcohol. The general equation is: OH + ClO+ 2H+ ---- > O + H3O + Cl-

The oxidation number of chlorine of the hypochlorite is +1 while the chloride ion is -1. Thus, 2 moles of electrons were involved in going from ClO - to Cl-. Chlorine is reduced.

The mechanism involved in the reaction is (1) Formation of alcohol hypochlorite (2) Elimination of HCl

Glacial acetic acid, a weak acid, is used as a catalyst in the dissolution of cyclohexanol. This is done to control the formation of Cl 2 gas and avoid a vigorous reaction. Cl-O+ 2H+ ----- > Cl-O+H2 + Cl- ---- > Cl2 + H2O

The hypochlorite oxidant needs a proton as a catalyst. It is not advisable to use strong acids such as HCl or H2SO4 since it causes the formation of Cl2, causing green coloration of the reaction mixture. In the experiment, sodium bisulfate (NaHSO 3) is added in the preparation of the cyclohexanone from cyclohexanol and acts as a reducing agent. It reacts with excess Ca(ClO)2. HSO3 + ClO--- > HSO4- + Cl-

To neutralize the acidic distillate, NaHCO3 was used since with the use of this reagent, neutralization usually stops when the bubbles formation stops. HCO3+ H3O+ --- > H2O + CO2

Addition of sodium chloride (NaCl) aids in the isolation of the product to be obtained through salting-out technique. This technique allows the separation of layers in the distillate from steam distillation. (show reaction here)

The ion-dipole interaction between NaCl and water is stronger than the dipole-dipole interaction between water and cyclohexanone. Therefore, the solubility of the compound in water decreases. Chemical tests will be performed to compare the product obtained and the starting material. Jones test is a rapid method for distinguishing primary and secondary alcohols from tertiary alcohols. It is a suspension of chromic anhydride (CrO 3) in concentrated H2SO4 in water. The reaction involved is (show reaction here)

A positive result for this is the production of an opaque suspension with blue green color. Another test is the reaction with warm, dilute, neutral KMnO 4. Formation of brown precipitate and disappearance of purple color indicates a positive result. (show reaction here)

Derivatization of cyclohexanone was performed to confirm if the desired product was successfully synthesized using 2,4-dinitrophenylhydrazine. The reaction involved is (show reaction here)

In the synthesis, the possible side reactions are: 1. Ether formation. This side reaction can be minimized by mixing the reaction mixture thoroughly and also the use of a weak acid. (show reaction here) 2. Enol formation. This side reaction is prevented by using a weak acid catalyst. This is also minimized during distillation since acetic acid is being distilled off and also, by neutralizing the product with NaHCO3. (show reaction here) 3. Dehydration of alcohol. This is minimized at lower temperature and with the use of a weak acid catalyst. (show reaction here) 4. Ester formation. This is not favored since the mixture is slightly acidic. (show reaction here)

In this experiment, the student should be able to: (1) synthesize cyclohexanone from cyclohexanol using , (2) to apply the different techniques for the isolation and purification of the product, (3) to perform different tests for the comparison of the product and the starting material, and (4) perform derivatization.