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3/1/2012
Aldehydes are named by replacing the terminal -e of the corresponding alkane name with al The parent chain must contain the CHO group
If the CHO group is attached to a ring, use the suffix See Table 19.1 for common names
Based on McMurrys Organic Chemistry, 6th edition
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
Naming Ketones
Replace the terminal -e of the alkane name with one Parent chain is the longest one that contains the ketone group
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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3/1/2012
Preparing Aldehydes Oxidize primary alcohols using pyridinium chlorochromate Reduce an ester with diisobutylaluminum hydride (DIBAH)
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
Preparing Ketones
The prefix oxo- is used if other functional groups are present and the doubly bonded oxygen is labeled as a substituent on a parent chain
Oxidize a 2 alcohol (see Section 17.8) Many reagents possible: choose for the specific situation (scale, cost, and acid/base sensitivity)
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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3/1/2012
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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CrO3 in aqueous acid oxidizes aldehydes to carboxylic acids efficiently Silver oxide, Ag2O, in aqueous ammonia (Tollens reagent) oxidizes aldehydes (no acid)
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Hydration of Aldehydes
Aldehyde oxidations occur through 1,1-diols (hydrates) Reversible addition of water to the carbonyl group Aldehyde hydrate is oxidized to a carboxylic acid by usual reagents for alcohols
Nu- approaches 45 to the plane of C=O and adds to C A tetrahedral alkoxide ion intermediate is produced
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Nucleophiles
Nucleophiles can be negatively charged ( : Nu) or neutral ( : Nu) at the reaction site The overall charge on the nucleophilic species is not considered
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Less reactive in nucleophilic addition reactions than aliphatic aldehydes Electron-donating resonance effect of aromatic ring makes C=O less reactive electrophilic than the carbonyl group of an aliphatic aldehyde
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Aldehydes and ketones react with water to yield 1,1diols (geminal (gem) diols) Hydration is reversible: a gem diol can eliminate water
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Relative Energies
Equilibrium generally favors the carbonyl compound over hydrate for steric reasons
Acetone in water is 99.9% ketone form
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Reaction of C=O with H-Y, where Y is electronegative, gives an addition product (adduct) Formation is readily reversible
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Uses of Cyanohydrins
The nitrile group (CN) can be reduced with LiAlH4 to yield a primary amine (RCH2NH2) Can be hydrolyzed by hot acid to yield a carboxylic acid
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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19.8 Nucleophilic Addition of Grignard Reagents and Hydride Reagents: Alcohol Formation
Nucleophilic addition of the equivalent of a carbon anion, or carbanion. A carbonmagnesium bond is strongly polarized, so a Grignard reagent reacts for all practical purposes as R : MgX +.
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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RNH2 adds to C=O to form imines, R2C=NR (after loss of HOH) R2NH yields enamines, R2NCR=CR2 (after loss of HOH) (ene + amine = unsaturated amine)
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Hydride Addition
Convert C=O to CH-OH LiAlH4 and NaBH4 react as donors of hydride ion Protonation after addition yields the alcohol
Primary amine adds to C=O Proton is lost from N and adds to O to yield a neutral amino alcohol (carbinolamine) Protonation of OH converts into water as the leaving group Result is iminium ion, which loses proton Acid is required for loss of OH too much acid blocks RNH2
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Imine Derivatives
Addition of amines with an atom containing a lone pair of electrons on the adjacent atom occurs very readily, giving useful, stable imines For example, hydroxylamine forms oximes and 2,4dinitrophenylhydrazine readily forms 2,4dinitrophenylhydrazones
These are usually solids and help in characterizing liquid ketones or aldehydes by melting points
Treatment of an aldehyde or ketone with hydrazine, H2NNH2 and KOH converts the compound to an alkane Originally carried out at high temperatures but with dimethyl sulfoxide as solvent takes place near room temperature
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Enamine Formation
After addition of R2NH, proton is lost from adjacent carbon
Two equivalents of ROH in the presence of an acid catalyst add to C=O to yield acetals, R2C(OR)2 These can be called ketals if derived from a ketone
R R R R R R
R R O C C H + R2NH H O C C H C H H C NH HO
H+
H2O C H H
N N C C H C H + H3O+
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Formation of Acetals
Alcohols are weak nucleophiles but acid promotes addition forming the conjugate acid of C=O Addition yields a hydroxy ether, called a hemiacetal (reversible); further reaction can occur Protonation of the OH and loss of water leads to an oxonium ion, R2C=OR+ to which a second alcohol adds to form the acetal
The sequence converts C=O is to C=C A phosphorus ylide adds to an aldehyde or ketone to yield a dipolar intermediate called a betaine The intermediate spontaneously decomposes through a four-membered ring to yield alkene and triphenylphosphine oxide, (Ph)3P=O Formation of the ylide is shown below
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Uses of Acetals
Acetals can serve as protecting groups for aldehydes and ketones It is convenient to use a diol, to form a cyclic acetal (the reaction goes even more readily)
Can be used for monosubstituted, disubstituted, and trisubstituted alkenes but not tetrasubstituted alkenes The reaction yields a pure alkene of known structure For comparison, addition of CH3MgBr to cyclohexanone and dehydration with, yields a mixture of two alkenes
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Enzymes catalyze the reduction of aldehydes and ketones using NADH as the source of the equivalent of HThe transfer resembles that in the Cannizzaro reaction but the carbonyl of the acceptor is polarized by an acid from the enzyme, lowering the barrier
Enzymes are chiral and the reactions are stereospecific. The stereochemistry depends on the particular enzyme involved.
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003 41
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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A nucleophile can add to the C=C double bond of an ,unsaturated aldehyde or ketone (conjugate addition, or 1,4 addition) The initial product is a resonancestabilized enolate ion, which is then protonated Based on McMurry, Organic Chemistry, Chapter
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Conjugate nucleophilic addition of a diorganocopper anion, R2Cu, an enone Transfer of an R group and elimination of a neutral organocopper species, RCu
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Summary
Aldehydes are from oxidative cleavage of alkenes, oxidation of 1 alcohols, or partial reduction of esters Ketones are from oxidative cleavage of alkenes, oxidation of 2 alcohols, or by addition of diorganocopper reagents to acid chlorides. Aldehydes and ketones are reduced to yield 1 and 2 alcohols , respectively Grignard reagents also gives alcohols Addition of HCN yields cyanohydrins 1 amines add to form imines, and 2 amines yield enamines Reaction of an aldehyde or ketone with hydrazine and base yields an alkane Alcohols add to yield acetals Phosphoranes add to aldehydes and ketones to give alkenes (the Wittig reaction) -Unsaturated aldehydes and ketones are subject to conjugate addition (1,4 addition)
Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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Based on McMurry, Organic Chemistry, Chapter 19, 6th edition, (c) 2003
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