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10-03 lecture
• Slides are posted. • The lecture will be taped tomorrow (Thurs) and posted thereafter. • The lecture will complete c16 • I will proceed with c17.

. including the conversion of alcohols to ketones or aldehydes (an oxidation). • Such reactions are known as oxidation and reduction reactions. but the structural changes in the product are often measured by whether hydrogen or oxygen is gained or lost.2 Chapter 17: Oxidation • A general class of reactions involves the gain or loss of two electrons. • Several functional group exchange reactions are classified as oxidations.

7) • Understand !-covalent bonds. aldehydes and ketones. section 3.4) • Lewis bases and Lewis acids.1.A) • Alkenes undergo oxidative cleavage with ozone. (chapter 9.3. 6.To begin. aldehydes. section 9.5) • The CIP rules for prioritizing substituents. 10. 16.5) • The acid-base properties of alcohols.B) • The general reactions of carbonyl compounds. (chapter 6. sections 10.3 and 16. section 6.2) • Brønsted-Lowry acids and bases. 6. sections 5.7. (chapter 16. (chapter 10. (chapter 5.3) • Understand polarized bonds.5 and 10. sections 102. (chapter 12. ethers and carboxylic acids.3. diols.7.2.5) • The fundamental reactions known for alkenes. ketones. section 10. you should know: • The structure and basic rules of nomenclature for alcohols.9 and chapter 16. (chapter 10. alkenes. 5.3) • Understand "-bonds. section 3. (chapter 3.8) • E2 type reactions. 6. sections 16.3. sections 16. (chapter 10.3 and 12. 10. sections 12. 6. 5.4) • Alkenes are converted to epoxides and to diols. (chapter 3.7) 3 .6. sections 6.2. section 6. (chapter 5. (chapter 6. groups and atoms. (chapter 6. section 5.4.

PDC. or a primary alcohol to an aldehyde. you should know: 4 • Oxidation is defined as loss of electrons or gain of a heteroatom such as oxygen or loss of hydrogen atoms. • Chromium (VI) reagents are powerful oxidants. The reaction of chromium trioxide and pyridine in aqueous HCl leads to pyridinium chlorochromate. . and the product is a ketone. called PCC. Chromium oxidation of an alcohol proceeds by formation of a chromate ester. Oxidation number is a convenient method to track the gain or loss of electrons in a reaction. This is called Collins oxidation. The reaction of a secondary alcohol with chromium trioxide and acid in aqueous acetone is called Jones l•c oxidation. • The oxidation of a secondary alcohol to a ketone or a primary alcohol to an aldehyde using dimethyl sulfoxide (DMSO) with oxalyl chloride at low temperature is called the Swern oxidation. followed by loss of the !-hydrogen to form the C=O unit. Both PCC and PDC can oxidize a secondary alcohol to a ketone.When completed. • Jones oxidation of a primary alcohol leads to a carboxylic acid in most cases. The reaction of chromium trioxide and pyridine in water leads to pyridinium dichromate. • A mixture of chromium trioxide and pyridine gives a reagent that can oxidize a primary alcohol to an aldehyde.

2-diol. you should know: 5 • Oxidation of an alkene with osmium tetroxide or potassium permanganate gives a cis-1. • Oxidation of an alkene with a peroxyacid leads to an epoxide.2-diols with periodic acid or with lead tetraacetate give aldehydes or ketones. • Oxidative cleavage of 1. . with a carboxylic acid as the by-product.When completed. Reductive l•c workup with dimethyl sulfoxide or zinc and acetic acid gives ketones and/or aldehydes. • Oxidative cleavage of an alkene with ozone leads to an ozonide. Oxidative workup with hydrogen peroxide gives ketones and/or carboxylic acids.

usually a heteroatom. . sulfur.Oxidation 6 • An oxidation is formally defined as the loss of one or more electrons from an atom or a group. nitrogen. • Such heteroatoms include oxygen. etc. halogen. but the most common is oxygen. it is possible to associate electron transfer with bond-making and bond-breaking reactions. • The structural changes usually include either loss of hydrogen atoms or the replacement of a hydrogen atom bonded to carbon with a more electronegative atom. • If there are structural changes in the product relative to the starting material.

• Oxidation state is a number is assigned to the carbon atoms involved in the transformation. and the formal rules for determining oxidation state are: (1) The oxidation state of a carbon is taken to be zero. NaOH (0) (0) OH OH H3C H 1 CH3 H2 O H3C 2 CH3 3 (-1) 4 . (3) Every heteroatom attached to a carbon is assigned a value of +1.Oxidation Number 7 • There is a method that identifies the so-called oxidation state of atoms that is useful for identifying whether electrons are gained or lost during the transformation. aq. OH (0) CrO3 . (2) Every hydrogen atom attached to a carbon is given a value of –1. H+ O (+2) (-1) KMnO4 .

and it has two bonds to oxygen. H+ O (+2) H3C H 1 CH3 H2O H3C 2 CH3 . • The conversion of 1 to 2 involves the loss of two electrons. since electrons are negatively charged particles. • To go from zero to +2 requires that two electrons be lost. C2 is bonded to two carbon atoms. • The oxidation state of C2 = 0 + 0 –1 + 1 = 0 (zero for each carbon. OH (0) CrO3 . The oxidation state of C2 in 2 is calculated by 0 + 0 + 1 + 1 = +2. and +1 for the oxygen). C2 is attached to two carbon atoms. • In the final product. • A comparison of the oxidation state of the pertinent carbon atoms in 1 and in 2 reveals that conversion of 1 to 2 involves a transfer of two electrons. –1 for the hydrogen. 2.Oxidation Number 8 • In alcohol 1. one hydrogen atom. and it is an oxidation. and one oxygen.

6). • When chromium trioxide is dissolved in water. a complex equilibrium is established that includes not only 5. where the “n” is an integer signifying the number of repeating CrO3 units. • There are several other reagents that also involve chromium(VI). including chromic acid (HCrO4. • Chromium trioxide is usually written as the monomer (the single unit) CrO3.Oxidation of Alcohols with Chromium (VI): Chromium trioxide 9 • Chromium(VI) is a powerful oxidizing agent and there are several inorganic reagents characterized by the presence of chromium(VI). 7) and potassium dichromate (K2Cr2O7. but also chromic acid (6) and the protonated form of the dichromate ion (Cr2O7-2). sodium dichromate Na2Cr2O7. • The most common is chromium trioxide (CrO3). which probably exits in a polymeric form [(CrO3)n]. O O Cr 5 HO O O Cr O 6 O Na O O Cr O 7 O Cr O O Na O KO O Cr O 8 O Cr O OK O . with the structure shown for 5. 8).

10 OH 9 Na2Cr2O7 . and the reaction of this mixture with an alcohol is called Jones oxidation. • In a typical experiment using Na2Cr2O7 in sulfuric acid. • This is called the Jones reagent. • The acetone moderates the reaction and helps to solubilize the various reactions found in this oxidation. water 12 O . in the presence of an acid such as H2SO4. acetone H+ . 3-pentanol (9) is converted to 3-pentanone (12) in 57% yield.Oxidation of Alcohols with Chromium (VI): Jones Oxidation • Alcohols are oxidized by a solution of chromium trioxide in aqueous acetone (2). allows the use CrO3 as the active oxidizing agent to look at a simplified mechanism. • Recognition that in aqueous solution CrO3 is in equilibrium with Cr3O7–2.

a carbonyl (C=O). • This mechanism predicts that the secondary alcohol (9) will be converted to 3-pentanone (12). Note the similarity of the oxidation of an alcohol to the elimination reaction of 11 via an E2 reaction (shown in the box) for conversion of an alkyl halide to an alkene. which is an oxidation. • Formation of the chromate ester makes the hydrogen atom on the !-carbon acidic (marked in red in 11).HCrO3 O . • Removal of that hydrogen by water is an acid-base reaction that leads to loss of the chromium(III) leaving group. 11. If the chromium unit is viewed as a leaving group.H3O+ H H H H O 12 9 10 11 H HO– H E2 reaction + HO H + Br– Br . then the hydrogen !. • Transfer of the acidic proton of the oxonium salt in 10 to the chromate oxygen (the base) leads to a so-called chromate ester.Oxidation of Alcohols with Chromium (VI): Jones Oxidation 11 • The oxygen of the alcohol (a Lewis base) donates two electrons to chromium (Cr is a Lewis acid) to form oxonium salt 10.to the oxygen is lost to water and the leaving group is CrO3H. O O H Cr OH O O H Cr O O O CrO3 O . which is an elimination reaction that forms a new "-bond.

• 1-Propanol is oxidized to propanal. • When a primary alcohol such as 1-pentanol (15) reacts with chromium trioxide and aqueous sulfuric acid. a carboxylic acid is formed as a second product or even the major oxidation product rather than the aldehyde. in only 49% yield. . with formation of chromate ester 16. • Very often. for example. it follows the same mechanistic pathway as 9. and to obtain the product requires a short reaction time. • Experiments show that the yields of aldehyde from primary alcohols can be very low. • It is known that aldehydes are easily oxidized to carboxylic acids.Oxidation of Alcohols with Chromium (VI): Aldehydes 12 • Jones oxidation is such a powerful oxidizing medium that unwanted products are possible due to over-oxidation. even by oxygen in the air.

H3 O+ H O CrO3 . OH CrO3 . aq. • In general.Oxidation of Alcohols with Chromium (VI): Aldehydes 13 • Formation of an aldehyde such as 17 in the presence of a powerful oxidizing agent such as chromium(VI). is usually followed by rapid oxidation of 17 to the corresponding carboxylic acid. Jones oxidation of simple aldehydes usually gives the carboxylic acid as the major product. over-oxidation to the carboxylic acid is even more rapid. H2 O H+ OCrO3H . • If the reaction mixture is heated. H+ H2O heat OH O 18 15 16 17 .HCrO3 . aq. pentanoic acid (18).

• This means that cold temperatures and short reaction times favor the aldehyde.Oxidation of Alcohols with Chromium (VI): Aldehydes 14 • When acetone is used as a solvent the rate of oxidation of aldehyde to acid is relatively slow. Acetic acid (ethanoic acid) serves a similar role in many oxidations. assume that oxidation of a secondary alcohol with chromium (VI) leads to a ketone and oxidation of a primary alcohol leads to an aldehyde if temperature and time are controlled. • The reaction of 19 with CrO3 in sulfuric acid and aqueous acetic acid for several hours and then heated to 100°C gives carboxylic acid 20 was isolated in 82% yield.3 CrO3 . • If the number molar equivalents of oxidizing agent is diminished. H2SO4 aq. CH3COOH 0-5°C heat (10 minutes) 82% 20 19 .3 • In general. CHO OH 1. CH3COOH 25°C (overnight) 100°C (1 h) COOH 59% 21 aq. H2SO4 2.1 CrO3 . aldehyde 21 is isolated in 59% yield. but long reaction times and heat favor formation of the acid. and the temperature is keep low with a short reaction time.

Oxidation of Alcohols with Chromium (VI): Steric Effects 15 • Alcohol 22 (2-methyl-3-pentanol) is oxidized faster than alcohol 24 (2.4-tetramethyl-3-pentanol). so it is more difficult for the base (water) to approach that hydrogen.2. OH OCrO3H FAST H 22 OH H 23 OH2 OCrO3H SLOW H 24 H 25 OH2 very sterically hindered so it is difficult for OH2 to collide with H O O .4. • Note that the chromate ester is formed in both cases. • The !-hydrogen in 23 is relatively unhindered and is easily removed by the base. and the steric hindrance to oxidation occurs in the chromate ester and not in the alcohol. • The steric hindrance in the chromate ester makes it more difficult for the water to react with the !proton. the !-hydrogen (marked in red) must be removed in each case to give the ketone. • The surrounding methyl groups in 25 create significant steric hindrance around the !-hydrogen. • If both alcohols are converted to the corresponding chromate ester (23 and 25 respectively). so the rate of oxidation is relatively fast for 23 but slower for 25 due to steric hindrance in the chromate ester.

CrO3 is in equilibrium with H2Cr2O7. CrO3Cl N H 31 N H 32 2 Cr2O7 -2 . and pyridine reacts with both acidic hydrogen atoms to produce PDC. 32). which reacts with HCl to form HCrClO3. • In dilute solution. and the HCl is omitted. • If the reaction conditions are modified to increase the amount of pyridine in the water solution. Pyridine then reacts as a base with this acidic proton to form PCC. 31) that is isolated and purified. in aqueous HCl generates a specific compound known as pyridinium chlorochromate (PCC. • The CrO3 forms HCrO4 (6) in dilute aqueous acid. the reaction generates pyridinium dichromate (PDC.Oxidation of Alcohols with Chromium (VI): PCC & PDC 16 • The reaction of chromium trioxide (5) with pyridine. presumably by reaction of an excess of pyridine with H2Cr2O7.