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Aldehydes and Ketones

Based on McMurry’s Organic Chemistry, 6th edition
©2003 Ronald Kluger
Department of Chemistry
University of Toronto

Based on McMurry, Organic Chemistry, Chapter 1
19, 6th edition, (c) 2003

Carbonyl Compounds

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Based on McMurry, Organic Chemistry, Chapter
19, 6th edition, (c) 2003

1

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Aldehydes and Ketones
n Aldehydes and ketones are characterized by the the
carbonyl functional group (C=O)
n The compounds occur widely in nature as
intermediates in metabolism and biosynthesis
n They are also common as chemicals, as solvents,
monomers, adhesives, agrichemicals and
pharmaceuticals

Based on McMurry, Organic Chemistry, Chapter 3
19, 6th edition, (c) 2003

1. Naming Aldehydes and Ketones

n Aldehydes are named by replacing the terminal -e of
the corresponding alkane name with –al
n The parent chain must contain the ¾ CHO group
n The ¾ CHO carbon is numbered as C1

Based on McMurry, Organic Chemistry, Chapter 4
19, 6th edition, (c) 2003

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Nomenclature of Aldehydes

Based on McMurry, Organic Chemistry, Chapter 5
19, 6th edition, (c) 2003

Naming Ketones
n Replace the terminal -e of the alkane name with –one
n Parent chain is the longest one that contains the
ketone group
n Numbering begins at the end nearer the carbonyl
carbon

Based on McMurry, Organic Chemistry, Chapter 6
19, 6th edition, (c) 2003

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Nomenclature of Ketones

Based on McMurry, Organic Chemistry, Chapter 7
19, 6th edition, (c) 2003

Naming Aldehydes and Ketones

Based on McMurry, Organic Chemistry, Chapter 8
19, 6th edition, (c) 2003

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4/26/2016 Ketones with Common Names Based on McMurry. CHO: formyl. C6H5CO: benzoyl n The prefix oxo. 6th edition. Organic Chemistry. Chapter 9 19. (c) 2003 Ketones and Aldehydes as Substituents n The R–C=O as a substituent is an acyl group is used with the suffix -yl from the root of the carboxylic acid n CH3CO: acetyl. 6th edition. (c) 2003 5 . Chapter 19. Organic Chemistry.is used if other functional groups are present and the doubly bonded oxygen is labeled as a substituent on a parent chain 10 Based on McMurry.

and more polar than C=C bond in alkenes. Organic Chemistry. Chapter 11 19. (c) 2003 6 . Chapter 12 19. 6th edition. Based on McMurry. 4/26/2016 Carbonyl Structure n Carbon is sp2 hybridized. 6th edition. (c) 2003 Based on McMurry. n C=O bond is shorter. stronger. Organic Chemistry.

Organic Chemistry. (c) 2003 Based on McMurry. 6th edition. 4/26/2016 Based on McMurry. 6th edition. Chapter 13 19. Organic Chemistry. Chapter 14 19. (c) 2003 7 .

Organic Chemistry. 4/26/2016 Based on McMurry. (c) 2003 8 . (c) 2003 Based on McMurry. Organic Chemistry. 6th edition. 6th edition. Chapter 16 19. Chapter 15 19.

Organic Chemistry. (c) 2003 9 . Chapter 17 19. Preparation of Aldehydes and Ketones n Preparing Aldehydes n Oxidize primary alcohols using pyridinium chlorochromate n Reduce an ester with diisobutylaluminum hydride (DIBAH) 18 Based on McMurry. 6th edition. Chapter 19. Organic Chemistry. (c) 2003 2. 6th edition. 4/26/2016 Based on McMurry.

Organic Chemistry. 4/26/2016 Preparing Ketones n Oxidize a 2° alcohol n Many reagents possible: choose for the specific situation (scale. and acid/base sensitivity) Based on McMurry. 6th edition. Chapter 20 19. cost. 6th edition. Organic Chemistry. Chapter 19 19. (c) 2003 10 . (c) 2003 Ketones from Ozonolysis n Ozonolysis of alkenes yields ketones if one of the unsaturated carbon atoms is disubstituted Based on McMurry.

(c) 2003 11 . Chapter 22 19. Organic Chemistry. 6th edition. 4/26/2016 Aryl Ketones by Acylation n Friedel–Crafts acylation of an aromatic ring with an acid chloride in the presence of AlCl3 catalyst Based on McMurry. Chapter 21 19. 6th edition. Organic Chemistry. (c) 2003 Methyl Ketones by Hydrating Alkynes n Hydration of terminal alkynes in the presence of Hg2+ (catalyst) Based on McMurry.

(c) 2003 12 . in aqueous ammonia (Tollens’ reagent) oxidizes aldehydes (no acid) 23 Based on McMurry. Chapter 24 19. 6th edition. 4/26/2016 3. Organic Chemistry. Oxidation of Aldehydes and Ketones n CrO3 in aqueous acid oxidizes aldehydes to carboxylic acids efficiently n Silver oxide. 6th edition. Organic Chemistry.1-diols (“hydrates”) n Reversible addition of water to the carbonyl group n Aldehyde hydrate is oxidized to a carboxylic acid by usual reagents for alcohols Based on McMurry. (c) 2003 Hydration of Aldehydes n Aldehyde oxidations occur through 1. Ag2O. Chapter 19.

(c) 2003 4. Chapter 19. Nucleophilic Addition Reactions of Aldehydes and Ketones n Nu. 4/26/2016 Ketones Oxidize with Difficulty n Undergo slow cleavage with hot. alkaline KMnO4 n C–C bond next to C=O is broken to give carboxylic acids n Reaction is practical for cleaving symmetrical ketones Based on McMurry. (c) 2003 13 . Organic Chemistry. 6th edition. 6th edition. Organic Chemistry.approaches 45° to the plane of C=O and adds to C n A tetrahedral alkoxide ion intermediate is produced 26 Based on McMurry. Chapter 25 19.

Chapter 27 19. (c) 2003 5. 6th edition. Organic Chemistry. Chapter 28 19. Organic Chemistry. 6th edition. 4/26/2016 Nucleophiles n Nucleophiles can be negatively charged ( : Nu-) or neutral ( : Nu) at the reaction site n The overall charge on the nucleophilic species is not considered Based on McMurry. (c) 2003 14 . Relative Reactivity of Aldehydes and Ketones n Aldehydes are generally more reactive than ketones in nucleophilic addition reactions n The transition state for addition is less crowded and lower in energy for an aldehyde (a) than for a ketone (b) n Aldehydes have one large substituent bonded to the C=O: ketones have two Based on McMurry.

stabilizing the C=O carbon inductively 29 Based on McMurry. 4/26/2016 Electrophilicity of Aldehydes and Ketones n Aldehyde C=O is more polarized than ketone C=O n As in carbocations. (c) 2003 Reactivity of Aromatic Aldehydes n Less reactive in nucleophilic addition reactions than aliphatic aldehydes n Electron-donating resonance effect of aromatic ring makes C=O less reactive electrophilic than the carbonyl group of an aliphatic aldehyde 30 Based on McMurry. more alkyl groups stabilize + character n Ketone has more alkyl groups. Organic Chemistry. 6th edition. (c) 2003 15 . Organic Chemistry. 6th edition. Chapter 19. Chapter 19.

formaldehyde consists is 99. 4/26/2016 6. 6th edition. Nucleophilic Addition of H2O: Hydration n Aldehydes and ketones react with water to yield 1. Organic Chemistry. (c) 2003 Relative Energies n Equilibrium generally favors the carbonyl compound over hydrate for steric reasons n Acetone in water is 99.9% ketone form n Exception: simple aldehydes n In water. 6th edition.1- diols (geminal (gem) diols) n Hydration is reversible: a gem diol can eliminate water Based on McMurry. Chapter 31 19. (c) 2003 16 . Chapter 19.9% hydrate 32 Based on McMurry. Organic Chemistry.

4/26/2016 Base-Catalyzed Addition of Water n Addition of water is catalyzed by both acid and base n The base-catalyzed hydration nucleophile is the hydroxide ion. Organic Chemistry. Chapter 33 19. 6th edition. (c) 2003 17 . 6th edition. (c) 2003 Acid-Catalyzed Addition of Water n Protonation of C=O makes it more electrophilic 34 Based on McMurry. which is a much stronger nucleophile than water Based on McMurry. Chapter 19. Organic Chemistry.

(c) 2003 18 . Chapter 36 19. Organic Chemistry. 4/26/2016 Addition of H-Y to C=O n Reaction of C=O with H-Y. Chapter 35 19. RCH(OH)CºN Based on McMurry. 6th edition. Nucleophilic Addition of HCN: Cyanohydrin Formation n Aldehydes and unhindered ketones react with HCN to yield cyanohydrins. gives an addition product (“adduct”) n Formation is readily reversible Based on McMurry. 6th edition. (c) 2003 7. Organic Chemistry. where Y is electronegative.

generating nucleophilic cyanide ion. Organic Chemistry. 6th edition. Chapter 38 19. Chapter 37 19. (c) 2003 19 . (c) 2003 Uses of Cyanohydrins n The nitrile group (¾ CºN) can be reduced with LiAlH4 to yield a primary amine (RCH2NH2) n Can be hydrolyzed by hot acid to yield a carboxylic acid Based on McMurry. 4/26/2016 Mechanism of Formation of Cyanohydrins n Addition of HCN is reversible and base-catalyzed.to C=O yields a tetrahedral intermediate. Organic Chemistry. 6th edition. which is then protonated Based on McMurry. CN n Addition of CN.

Organic Chemistry. Chapter 40 19. Chapter 39 19. 4/26/2016 Next…………… Based on McMurry. 6th edition. (c) 2003 20 . 6th edition. Organic Chemistry. (c) 2003 Based on McMurry.

4/26/2016 Based on McMurry. Organic Chemistry. (c) 2003 Based on McMurry. (c) 2003 21 . 6th edition. Chapter 42 19. 6th edition. Chapter 41 19. Organic Chemistry.

(c) 2003 Mechanism of Addition of Grignard Reagents n Complexation of C=O by Mg2+. 6th edition. 43 Based on McMurry. 4/26/2016 8. Chapter 44 19.MgX +. or carbanion. protonation by dilute acid yields the neutral alcohol n Grignard additions are irreversible because a carbanion is not a leaving group Based on McMurry. so a Grignard reagent reacts for all practical purposes as R : . A carbon–magnesium bond is strongly polarized. Chapter 19. Nucleophilic addition of R : -. 6th edition. Organic Chemistry. Nucleophilic Addition of Grignard Reagents and Hydride Reagents: Alcohol Formation n Treatment of aldehydes or ketones with Grignard reagents yields an alcohol n Nucleophilic addition of the equivalent of a carbon anion. (c) 2003 22 . Organic Chemistry.

Chapter 45 19. Nucleophilic Addition of Amines: Imine and Enamine Formation RNH2 adds to C=O to form imines. R2N¾ CR=CR2 (after loss of HOH) (ene + amine = unsaturated amine) Based on McMurry. 6th edition. (c) 2003 23 . Organic Chemistry. Organic Chemistry. Chapter 46 19. (c) 2003 9. R2C=NR (after loss of HOH) R2NH yields enamines. 6th edition. 4/26/2016 Hydride Addition n Convert C=O to CH-OH n LiAlH4 and NaBH4 react as donors of hydride ion n Protonation after addition yields the alcohol Based on McMurry.

6th edition. 4/26/2016 Based on McMurry. Chapter 47 19. Organic Chemistry. which loses proton n Acid is required for loss of OH – too much acid blocks RNH2 Note that overall reaction is substitution of RN for O Based on McMurry. Chapter 48 19. (c) 2003 24 . Organic Chemistry. (c) 2003 Mechanism of Formation of Imines n Primary amine adds to C=O n Proton is lost from N and adds to O to yield a neutral amino alcohol (carbinolamine) n Protonation of OH converts into water as the leaving group n Result is iminium ion. 6th edition.

Chapter 49 19. Organic Chemistry. giving useful. 4/26/2016 Based on McMurry. stable imines n For example. Organic Chemistry.4- dinitrophenylhydrazones Based on McMurry. 6th edition. Chapter 50 19. (c) 2003 Imine Derivatives n Addition of amines with an atom containing a lone pair of electrons on the adjacent atom occurs very readily. 6th edition. (c) 2003 25 .4- dinitrophenylhydrazine readily forms 2. hydroxylamine forms oximes and 2.

Organic Chemistry. Chapter 51 19. (c) 2003 26 . 4/26/2016 Enamine Formation n After addition of R2NH. 6th edition. Chapter 52 19. Organic Chemistry. proton is lost from adjacent carbon R R R R R R R R O O NH H2O N HO + + R2 NH N H N C C + H3 O+ C H C C C C H C H H C C H H H H H Based on McMurry. 6th edition. (c) 2003 Based on McMurry.

6th edition. Organic Chemistry. (c) 2003 27 . (c) 2003 Based on McMurry. Nucleophilic Addition of Hydrazine: The Wolff–Kishner Reaction n Treatment of an aldehyde or ketone with hydrazine. Chapter 54 19. Chapter 19. 6th edition. H2NNH2 and KOH converts the compound to an alkane n Originally carried out at high temperatures but with dimethyl sulfoxide as solvent takes place near room temperature 53 Based on McMurry. 4/26/2016 10. Organic Chemistry.

(c) 2003 28 . R2C(OR¢)2 n These can be called ketals if derived from a ketone Based on McMurry. (c) 2003 11. Organic Chemistry. Chapter 56 19. Nucleophilic Addition of Alcohols: Acetal Formation n Two equivalents of ROH in the presence of an acid catalyst add to C=O to yield acetals. 4/26/2016 Based on McMurry. Chapter 55 19. 6th edition. 6th edition. Organic Chemistry.

6th edition. 4/26/2016 Formation of Acetals n Alcohols are weak nucleophiles but acid promotes addition forming the conjugate acid of C=O n Addition yields a hydroxy ether. 6th edition. R2C=OR+ to which a second alcohol adds to form the acetal Based on McMurry. further reaction can occur n Protonation of the ¾ OH and loss of water leads to an oxonium ion. called a hemiacetal (reversible). Organic Chemistry. Chapter 57 19. to form a cyclic acetal (the reaction goes even more readily) Based on McMurry. (c) 2003 Uses of Acetals n Acetals can serve as protecting groups for aldehydes and ketones n It is convenient to use a diol. Chapter 58 19. Organic Chemistry. (c) 2003 29 .

Organic Chemistry. (c) 2003 30 . 6th edition. (c) 2003 Uses of the Wittig Reaction n Can be used for monosubstituted. Organic Chemistry. disubstituted. Nucleophilic Addition of Phosphorus Ylides: The Wittig Reaction n The sequence converts C=O is to C=C n A phosphorus ylide adds to an aldehyde or ketone to yield a dipolar intermediate called a betaine n The intermediate spontaneously decomposes through a four-membered ring to yield alkene and triphenylphosphine oxide. Chapter 19. yields a mixture of two alkenes 60 Based on McMurry. 4/26/2016 12. Chapter 19. addition of CH3MgBr to cyclohexanone and dehydration with. 6th edition. and trisubstituted alkenes but not tetrasubstituted alkenes The reaction yields a pure alkene of known structure n For comparison. (Ph)3P=O n Formation of the ylide is shown below 59 Based on McMurry.

(c) 2003 13. The Cannizzaro Reaction: Biological Reductions n The adduct of an aldehyde and OH. Organic Chemistry. Chapter 19. (c) 2003 31 . 6th edition. Organic Chemistry. Chapter 19. 4/26/2016 Mechanism of the Wittig Reaction 61 Based on McMurry. 6th edition.can transfer hydride ion to another aldehyde C=O resulting in a simultaneous oxidation and reduction (disproportionation) 62 Based on McMurry.

Chapter 64 19. (c) 2003 14. lowering the barrier Enzymes are chiral and the reactions are stereospecific. 4/26/2016 The Biological Analogue of the Canizzaro Reaction n Enzymes catalyze the reduction of aldehydes and ketones using NADH as the source of the equivalent of H- n The transfer resembles that in the Cannizzaro reaction but the carbonyl of the acceptor is polarized by an acid from the enzyme. 6th edition. or 1. Organic Chemistry. Based on McMurry. (c) 2003 32 .b- unsaturated aldehyde or ketone (conjugate addition. Organic Chemistry. Conjugate Nucleophilic Addition to a.4 addition) n The initial product is a resonance- stabilized enolate ion.b- Unsaturated Aldehydes and Ketones n A nucleophile can add to the C=C double bond of an a. which is then protonated Based on McMurry. 6th edition. The stereochemistry depends on the particular enzyme involved. Chapter 63 19.

Chapter 65 19. b- unsaturated aldehydes and ketones to yield b-amino aldehydes and ketones Based on McMurry. Organic Chemistry. 6th edition. (c) 2003 33 . Organic Chemistry. 4/26/2016 Conjugate Addition of Amines n Primary and secondary amines add to a. 6th edition. Chapter 66 19. (c) 2003 Based on McMurry.

2°. Chapter 67 19. (c) 2003 34 . an enone n Transfer of an R group and elimination of a neutral organocopper species. R2Cu-. 6th edition. aryl and alkenyl groups react but not alkynyl groups Based on McMurry. Organic Chemistry. b-unsaturated ketone with a lithium diorganocopper reagent n Diorganocopper (Gilman) reagents from by reaction of 1 equivalent of cuprous iodide and 2 equivalents of organolithium n 1°. 3°alkyl. 4/26/2016 Conjugate Addition of Alkyl Groups: Organocopper Reactions n Reaction of an a. Chapter 68 19. (c) 2003 Mechanism of Alkyl Conjugate Addition n Conjugate nucleophilic addition of a diorganocopper anion. Organic Chemistry. 6th edition. RCu Based on McMurry.

(c) 2003 16. Biological Nucleophilic Addition Reactions n Example: Many enzyme reactions involve pyridoxal phosphate (PLP). such as amino acids n The imine undergoes a proton shift that leads to the net conversion of the amino group of the substrate into a carbonyl group Based on McMurry. Organic Chemistry. 4/26/2016 15. Chapter 70 19. Organic Chemistry. (c) 2003 35 . Spectroscopy of Aldehydes and Ketones n Infrared Spectroscopy n Aldehydes and ketones show a strong C=O peak 1660 to 1770 cm-1 n aldehydes show two characteristic C–H absorptions in the 2720 to 2820 cm-1 range. Based on McMurry. 6th edition. 6th edition. as a co-catalyst n PLP is an aldehyde that readily forms imines from amino groups of substrates. a derivative of vitamin B6. Chapter 69 19.

Organic Chemistry. Chapter 19. Chapter 72 19. 6th edition. (c) 2003 36 . Organic Chemistry. J » 3 Hz Based on McMurry. 4/26/2016 Based on McMurry. (c) 2003 C=O Peak Position in the IR Spectrum n The precise position of the peak reveals the exact nature of the carbonyl group 71 NMR Spectra of Aldehydes n Aldehyde proton signals are at d 10 in 1H NMR - distinctive spin–spin coupling with protons on the neighboring carbon. 6th edition.

6th edition.1 Based on McMurry. Chapter 19. Organic Chemistry. Organic Chemistry. 6th edition. 4/26/2016 Protons on Carbons Adjacent to C=O n Slightly deshielded and normally absorb near d 2.0 to d2.3 n Methyl ketones always show a sharp three-proton singlet near d 2. (c) 2003 13C NMR of C=O n C=O signal is at d 190 to d 215 n No other kinds of carbons absorb in this range Based on McMurry. (c) 2003 74 37 . Chapter 73 19.

Chapter 76 19. Organic Chemistry. (c) 2003 Mass Spectroscopy: a-Cleavage n Cleavage of the bond between the carbonyl group and the a carbon n Yields a neutral radical and an oxygen-containing cation Based on McMurry. 4/26/2016 Mass Spectrometry – McLafferty Rearrangement n Aliphatic aldehydes and ketones that have hydrogens on their gamma (g) carbon atoms rearrange as shown Based on McMurry. (c) 2003 38 . Chapter 75 19. 6th edition. Organic Chemistry. 6th edition.

we get both enantiomers in equal amounts . Organic Chemistry. 4/26/2016 Enantioselective Synthesis n When a chiral product is formed achiral reagents. Chapter 78 19. (c) 2003 39 . Organic Chemistry. oxidation of 1° alcohols. a chiral catalyst can create a lower energy pathway for one enantiomer .the transition states are mirror images and are equal in energy n However.4 addition) Based on McMurry. oxidation of 2° alcohols. gives 97% of the S product and only 3% of the R Based on McMurry. or partial reduction of esters n Ketones are from oxidative cleavage of alkenes. (c) 2003 Summary n Aldehydes are from oxidative cleavage of alkenes. if the reaction is subject to catalysis. respectively n Grignard reagents also gives alcohols n Addition of HCN yields cyanohydrins n 1° amines add to form imines. 6th edition. or by addition of diorganocopper reagents to acid chlorides. n Aldehydes and ketones are reduced to yield 1° and 2° alcohols . and 2° amines yield enamines n Reaction of an aldehyde or ketone with hydrazine and base yields an alkane n Alcohols add to yield acetals n Phosphoranes add to aldehydes and ketones to give alkenes (the Wittig reaction) n ab-Unsaturated aldehydes and ketones are subject to conjugate addition (1. Chapter 77 19. 6th edition.called an enantionselective synthesis n Reaction of benzaldehyde with diethylzinc with a chiral titanium- containing catalyst.

) A nitrogenous base. There have been a lot of wagers on this over the years.] (Chem. the “beta” in “betaine” refers to beets and not a letter in the Greek alphabet. Chapter 79 19. (c) 2003 40 . and also occurring naturally in beet-root molasses and its residues. produced artificially. (Chem. {C17H21NO4}. Chapter 80 19. {C5H11NO2}. Based on McMurry. generic name of the beet. The listed pronunciation indicates it has the exact same emphasis as “cocaine”. n Whatever you say. 6th edition. obtained from the leaves of coca n So – if you say “co-ca-een” (as this dictionary suggests) then you would also say “bee-ta-een”. If you sat “co-cayn” then say “beet-ayn”.) A powerful alkaloid. 6th edition. n. [From beta. (c) 2003 A Note on the Word “Betaines” n The term “betaines” is an extension from a specific substance (betaine) that has permanent + and – charges (as in a zwitterion) that cannot be neutralized by proton transfers (as in normal amino acids). Organic Chemistry. n Cocaine \Co"ca*ine\. Webster's Revised Unabridged Dictionary lists: Betaine \Be"ta*ine\. n. 4/26/2016 Thank You Based on McMurry. Organic Chemistry.