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Jo Blackburn Richland College, Dallas, TX Dallas County Community College District 2003,Prentice Hall
Carbonyl Compounds
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Chapter 18 2
Carbonyl Structure
Carbon is sp2 hybridized. C=O bond is shorter, stronger, and more polar than C=C bond in alkenes.
=>
Chapter 18 3
Examples
O CH3 C CH CH3
Br O
CH3 3-methyl-2-butanone
O CH3 C CH CH2OH CH3
3-bromocyclohexanone
4-hydroxy-3-methyl-2-butanone =>
Chapter 18 5
Naming Aldehydes
IUPAC: Replace -e with -al. The aldehyde carbon is number 1. If -CHO is attached to a ring, use the suffix -carbaldehyde.
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Chapter 18 6
Examples
CH3 CH3 CH2 CH CH2 O C H
3-methylpentanal
CHO
2-cyclopentenecarbaldehyde
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Chapter 18 7
Name as Substituent
On a molecule with a higher priority functional group, C=O is oxo- and -CHO is formyl. Aldehyde priority is higher than ketone.
COOH
O CH3 C
CH3 CH CH2
O C H
CHO
3-methyl-4-oxopentanal
3-formylbenzoic acid
Chapter 18
=>
8
O C CH3
acetophenone
benzophenone =>
Chapter 18 10
Boiling Points
More polar, so higher boiling point than comparable alkane or ether. Cannot H-bond to each other, so lower boiling point than comparable alcohol.
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Chapter 18 12
Solubility
Good solvent for alcohols. Lone pair of electrons on oxygen of carbonyl can accept a hydrogen bond from O-H or N-H. Acetone and acetaldehyde are miscible in water.
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Chapter 18 13
Formaldehyde
Gas at room temperature. Formalin is a 40% aqueous solution.
H H O H C O O heat H C H H2O HO OH H C H
C C H O H H
formalin =>
14
IR Spectroscopy
Very strong C=O stretch around 1710 cm-1. Conjugation lowers frequency. Ring strain raises frequency. Additional C-H stretch for aldehyde: two absorptions at 2710 cm-1 and 2810 cm-1.
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Chapter 18 15
1H
NMR Spectroscopy
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Chapter 18 16
13C
NMR Spectroscopy
Chapter 18
17
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MS for 2-Butanone
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Chapter 18 18
MS for Butyraldehyde
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Chapter 18 19
McLafferty Rearrangement
Loss of alkene (even mass number) Must have -hydrogen
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Chapter 18 20
UV Spectra, *
C=O conjugated with another double bond. Large molar absorptivities (> 5000)
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Chapter 18 21
UV Spectra, n *
Small molar absorptivity. Forbidden transition occurs less frequently.
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Chapter 18 22
Industrial Importance
Acetone and methyl ethyl ketone are important solvents. Formaldehyde used in polymers like Bakelite. Flavorings and additives like vanilla, cinnamon, artificial butter.
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Chapter 18 23
Synthesis Review
Oxidation
2 alcohol + Na2Cr2O7 ketone 1 alcohol + PCC aldehyde
Ozonolysis of alkenes.
H C C R R'' R' 1) O3 2) (CH3)2S H C O R + O C R''
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Chapter 18 24
R'
O C
CH2CH3
CH2CH3
Chapter 18 26
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O C CH2CH3
CH2CH3
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Chapter 18 27
O C CH3
C OH _ H2O CH3
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Chapter 18 28
O C CH2CH3
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Chapter 18 29
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Chapter 18 30
(CH3CH2CH2)2CuLi
O CH3CH2C CH2CH2CH3
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Chapter 18 31
Nucleophilic Addition
A strong nucleophile attacks the carbonyl carbon, forming an alkoxide ion that is then protonated. A weak nucleophile will attack a carbonyl if it has been protonated, thus increasing its reactivity. Aldehydes are more reactive than ketones.
Chapter 18
32
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Wittig Reaction
Nucleophilic addition of phosphorus ylides. Product is alkene. C=O becomes C=C.
Chapter 18
33
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Phosphorus Ylides
Prepared from triphenylphosphine and an unhindered alkyl halide. Butyllithium then abstracts a hydrogen from the carbon attached to phosphorus.
Ph3P + CH3CH2Br + Ph3P _ CH2CH3 Br
+ Ph3P
CH2CH3
BuLi
Chapter 18
+ Ph3P
ylide
_ CHCH3
=>
34
_ CHCH3
H3C C O Ph
Ph3P O
Ph3P H C
C CH3 CH3 Ph
Ph3P H H3C C O C CH3 Ph
35
H C C CH3 CH3 Ph
H C C CH3 CH3 Ph
Chapter 18
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Addition of Water
In acid, water is the nucleophile. In base, hydroxide is the nucleophile. Aldehydes are more electrophilic since they have fewer e--donating alkyl groups.
O H C + H2O H
O CH3 C + H2O CH3
HO H
HO CH3
Chapter 18
OH C H
OH C CH3 K = 0.002
36
K = 2000
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Addition of HCN
HCN is highly toxic. Use NaCN or KCN in base to add cyanide, then protonate to add H. Reactivity formaldehyde > aldehydes > ketones >> bulky ketones.
O CH3CH2 C HO CH3 + HCN CH3CH2 C CH3
37
CN
Chapter 18
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Formation of Imines
Nucleophilic addition of ammonia or primary amine, followed by elimination of water molecule. C=O becomes C=N-R
H3C RNH2 C O Ph R _ C H2N O + Ph CH3 R CH3 N C OH H Ph
CH3
CH3 N C Ph
N C OH H Ph
Chapter 18
=>38
pH Dependence
Loss of water is acid catalyzed, but acid destroys nucleophiles. NH3 + H+ NH4+ (not nucleophilic) Optimum pH is around 4.5
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Chapter 18 39
Other Condensations
Chapter 18
40
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Addition of Alcohol
=>
Chapter 18 41
Mechanism
Must be acid-catalyzed. Adding H+ to carbonyl makes it more reactive with weak nucleophile, ROH. Hemiacetal forms first, then acidcatalyzed loss of water, then addition of second molecule of ROH forms acetal. All steps are reversible. =>
Chapter 18 42
OH + HOCH3
Chapter 18
43
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Hemiacetal to Acetal
HO H+ OCH3 + HO H OCH3 + + HOH OCH3
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Chapter 18 44
Cyclic Acetals
Addition of a diol produces a cyclic acetal. Sugars commonly exist as acetals or hemiacetals.
O + CH2 HO CH2 OH CH2 CH2 O O
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Chapter 18 45
CH2 OH
+
C O
=>
46
HO
CH3
C O
=>
Chapter 18 47
Oxidation of Aldehydes
Easily oxidized to carboxylic acids.
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Chapter 18 48
Tollens Test
Add ammonia solution to AgNO3 solution until precipitate dissolves. Aldehyde reaction forms a silver mirror.
O R C H + 2
+ Ag(NH3)2
_ + 3 OH
O H2O 2 Ag + R C O
_ + 4
+ NH3)2
_ + 3 OH
O H2O 2 Ag + R C O
Chapter 18
_ + 4 NH3 + 2 H2O
=>
49
Reduction Reagents
Sodium borohydride, NaBH4, reduces C=O, but not C=C. Lithium aluminum hydride, LiAlH4, much stronger, difficult to handle. Hydrogen gas with catalyst also reduces the C=C bond.
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Chapter 18 50
Catalytic Hydrogenation
Widely used in industry. Raney nickel, finely divided Ni powder saturated with hydrogen gas. Pt and Rh also used as catalysts.
O OH Raney Ni H
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Chapter 18 51
Deoxygenation
Reduction of C=O to CH2 Two methods:
Clemmensen reduction if molecule is stable in hot acid. Wolff-Kishner reduction if molecule is stable in very strong base. =>
Chapter 18 52
Clemmensen Reduction
O C CH2CH3 Zn(Hg) HCl, H 2O CH2CH2CH3
O CH2 C H
Zn(Hg) HCl, H 2O
CH2
CH3
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Chapter 18 53
Wolff-Kisher Reduction
Form hydrazone, then heat with strong base like KOH or potassium t-butoxide. Use a high-boiling solvent: ethylene glycol, diethylene glycol, or DMSO.
CH2 C H O H2N NH2 CH2 C H NNH2 KOH heat CH2 CH3
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Chapter 18 54
End of Chapter 18
Chapter 18
55