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Transcript of Chapter 17 Aldehydes and Ketones: Copyright © The McGraw-Hill Companies, Inc. Permission required...
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Chapter 17Chapter 17Aldehydes and Ketones:Aldehydes and Ketones:
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
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Classes of Carbonyl Compounds
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 33
Resonance
• The first resonance is better because all atoms complete the octet and there are no charges.
• The carbonyl carbon has a partial positive and will react as an electrophile.
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 44
Aldehydes Nomenclature
• The aldehyde carbon is number 1.• IUPAC: Replace -e with -al.• If the aldehyde group is attached to a ring, the suffix
carbaldehyde is used.
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when named as a substituent
formyl group carbaldehyde orcarboxaldehyde
when named as a suffix
C H
O
IUPAC Nomenclature of Aldehydes
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 66
Ketone Nomenclature
• Number the chain so that the carbonyl carbon has the lowest number.
• Replace the alkane -e with -one.
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 77
Cyclic Ketone Nomenclature
• For cyclic ketones, the carbonyl carbon is assigned the number 1.
• When the compound has a carbonyl and a double bond, the carbonyl takes precedence.
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Functional Class IUPAC Nomenclature of Ketones
CH3CH2CCH2CH2CH3
O O
CH2CCH2CH3
CH CH2
O
H2C CHC
List the groups attached to the carbonyl separately in alphabetical order, and add the word ketone.
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CH3CH2CCH2CH2CH3
O
ethyl propyl ketone benzyl ethyl ketone
divinyl ketone
O
CH2CCH2CH3
CH CH2
O
H2C CHC
Functional Class IUPAC Nomenclature of Ketones
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Structure and Bonding:Structure and Bonding:The Carbonyl GroupThe Carbonyl Group
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planar
bond angles: close to 120°
C=O bond distance: 122 pm
Both C and O are sp2 hybridizes.
Structure of Formaldehyde
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The half-filled2p orbitals oncarbon andoxygen overlapto form a bond.
Bonding in Formaldehyde
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1-butene propanal
The Carbonyl Group O
dipole moment = 0.3D dipole moment = 2.5D
very polar double bond
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2475 kJ/mol
2442 kJ/mol
Alkyl groups stabilize carbonyl groups the sameway they stabilize carbon-carbon double bonds,carbocations, and free radicals.
heat of combustion
Carbonyl Group of a Ketone is MoreStable than that of an Aldehyde
O
O
H
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Nucleophiles attack carbon; electrophiles attack oxygen.
Resonance Description ofCarbonyl Group
C
O •• ••
C
O
+
–•••• ••
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Physical PropertiesPhysical Properties
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boiling point
–6°C
49°C
97°C
Aldehydes and Ketones have Higher Boiling Pointsthan Alkenes, but Lower Boiling Points than Alcohols
More polar than alkenes, but cannot form intermolecular hydrogen bonds to other carbonyl groups.
O
OH
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Sources of Aldehydes and KetonesSources of Aldehydes and Ketones
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from alkenes
ozonolysis
from alkynes
hydration (via enol)
from arenes
Friedel-Crafts acylation
from alcohols
oxidation
Table 17.1 Synthesis of Aldehydes and Ketones
A number of reactions alreadystudied provide
efficient syntheticroutes to
aldehydes and ketones.
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 2020
Ozonolysis of Alkenes
• The double bond is oxidatively cleaved by ozone followed by reduction.
• Ketones and aldehydes can be isolated as products under these conditions.
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 2121
Friedel–Crafts Reaction
• Reaction between an acyl halide and an aromatic ring will produce a ketone.
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 2222
Hydration of Alkynes
• The initial product of Markovnikov hydration is an enol, which quickly tautomerizes to its keto form.
• Internal alkynes can be hydrated, but mixtures of ketones often result.
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 2323
Grignards as a Source for Ketones and Aldehydes
• A Grignard reagent can be used to make an alcohol, and then the alcohol can be easily oxidized.
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C
O
R OH
aldehydes from carboxylic acids
RCH2OH
1. LiAlH4
2. H2OPDC, CH2Cl2
HC
O
R
What About..?
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Benzaldehyde from benzoic acid COH
O CH
O
1. LiAlH4
2. H2OPDCCH2Cl2CH2OH
(81%) (83%)
Example
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C
O
R H
Ketones from aldehydes
R'RC
O
PDC, CH2Cl21. R'MgX
2. H3O+
RCHR'
OH
What About..?
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C
O
CH3CH2 H
3-heptanone from propanal
H2CrO4
1. CH3(CH2)3MgX
2. H3O+
CH3CH2CH(CH2)3 CH3
OH
O
CH3CH2C(CH2)3 CH3
(57%)
Example
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Industrial Importance
• Acetone and methyl ethyl ketone are common industrial solvents.
• Formaldehyde is used in polymers like Bakelite and many other polymeric products.
• Also used as flavorings and additives for food.
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Reactions of Aldehydes and Reactions of Aldehydes and Ketones:Ketones:
A Review and a PreviewA Review and a Preview
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
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Already covered in earlier chapters:
Reduction of C=O to CH2
Clemmensen reduction
Wolff-Kishner reduction
Reduction of C=O to CHOH
Addition of Grignard and organolithium reagents
Table 17.2 Reactions of Aldehydes and Ketones
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 3131
Catalytic Hydrogenation
• Widely used in industry• Raney nickel is finely divided Ni powder
saturated with hydrogen gas.• It will attack the alkene first, then the carbonyl.
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 3232
Deoxygenation of Ketones and Aldehydes
• The Clemmensen reduction or the Wolff–Kishner reduction can be used to deoxygenate ketones and aldehydes.
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Clemmensen Reduction
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 3434
Wolff–Kishner Reduction
• Forms hydrazone, then heat with strong base like KOH or potassium tert-butoxide
• Use a high-boiling solvent: ethylene glycol, diethylene glycol, or DMSO.
• A molecule of nitrogen is lost in the last steps of the reaction.
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 3535
Sodium Borohydride
• NaBH4 can reduce ketones and aldehydes, but not esters, carboxylic acids, acyl chlorides, or amides.
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 3636
Lithium Aluminum Hydride
R R(H)
OH
HR R(H)
OLiAlH4
ether
aldehyde or ketone
• LiAlH4 can reduce any carbonyl because it is a very strong reducing agent.
• Difficult to handle
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Principles of Nucleophilic Addition:Principles of Nucleophilic Addition:
Hydration of Aldehydes and Hydration of Aldehydes and
KetonesKetones
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 3838
• In an aqueous solution, a ketone or an aldehyde is in equilibrium with its hydrate, a geminal diol.
• With ketones, the equilibrium favors the unhydrated keto form (carbonyl).
Hydration of Ketones and Aldehydes
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 3939
Acid-Catalyzed Hydration of Carbonyls
• Hydration occurs through the nucleophilic addition mechanism, with water (in acid) or hydroxide (in base) serving as the nucleophile.
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 4040
• The hydroxide ion attacks the carbonyl group. • Protonation of the intermediate gives the hydrate.
Base-Catalyzed Hydration of Carbonyls
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 4141
Cyanohydrin Formation
• The mechanism is a base-catalyzed nucleophilic addition: Attack by cyanide ion on the carbonyl group, followed by protonation of the intermediate.
• HCN is highly toxic.
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2,4-Dichlorobenzaldehydecyanohydrin (100%)
Example
Cl Cl CH
OCl
Cl CHCN
OHNaCN, water
then H2SO4
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Example
CH3CCH3
ONaCN, water
then H2SO4
CH3CCH3
OH
CN
(77-78%)
Acetone cyanohydrin is used in the synthesis of methacrylonitrile.
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Acetal FormationAcetal Formation
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
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Some reactions of aldehydes and ketones progressbeyond the nucleophilic addition stage
Acetal formation
Imine formation
Enamine formation
Compounds related to imines
The Wittig reaction
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Recall Hydration of Aldehydes and Ketones
HOH
C••O ••
HO C O H••
••
••
••
R
R'
R
R'
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Alcohols Under Analogous Reactionwith Aldehydes and Ketones
R”OH
C••O ••
R
R'
R"O C O H••
••
••
••
R
R'
Product is called a hemiacetal.
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Product is called a hemiacetal.
R”OH, H+
Hemiacetal reacts further in acid to yield an acetal
R"O C O H••
••
••
••
R
R'
R"O C OR”••
••
••
••
R
R'
Product is called an acetal.
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HCl
2CH3CH2OH+
+ H2O
Benzaldehyde diethyl acetal (66%)
Example
CH
O CH(OCH2CH3)2
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HOCH2CH2OH+CH3(CH2)5CH
O
p-toluenesulfonic acid
benzene
+ H2O
(81%) H (CH2)5CH3
H2C CH2
O O
C
Diols Form Cyclic Acetals
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In general:
Position of equilibrium is usually unfavorablefor acetal formation from ketones.
Important exception: Cyclic acetals can be prepared from ketones.
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HOCH2CH2OH+
O
p-toluenesulfonic acid
benzene
+ H2O
H2C CH2
O O
C(78%)
C6H5CH2CCH3
CH3C6H5CH2
Example
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 5353
Mechanism for Hemiacetal Formation
• Must be acid-catalyzed.• Adding H+ to carbonyl makes it more reactive
with weak nucleophile, ROH.
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Acetal Formation
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CR R'
O
2R"OH+
OR"
R R'C
OR"
+ H2O
mechanism:
reverse of acetal formation;hemiacetal is intermediate
application:
Aldehydes and ketones can be "protected" as acetals.
Hydrolysis of Acetals
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Acetals as Protecting GroupsAcetals as Protecting Groups
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The conversion shown cannot be carried outdirectly...
CHCH3CCH2CH2C
O
CCH3CH3CCH2CH2C
O
1. NaNH2
2. CH3I
Example
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because the carbonyl group and thecarbanion are incompatible functionalgroups.
C:CH3CCH2CH2C
O–
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1) protect C=O
2) alkylate
3) restore C=O
Strategy
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HOCH2CH2OH+
p-toluenesulfonic acid
benzene
H2C CH2
O O
C
CH3
CH3CCH2CH2C
O
CH
CH2CH2C CH
Example: Protect
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H2C CH2
O O
C
CH3CH2CH2C CH
1. NaNH2
2. CH3I
H2C CH2
O O
CCH3
CH2CH2C CCH3
Example: Alkylate
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H2C CH2
O O
C
CH3CH2CH2C CCH3
H2O
HCl
HOCH2CH2OH
(96%)
CCH3CH3CCH2CH2C
O
+
Example: Deprotect
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Reaction with Primary Amines:Reaction with Primary Amines:
IminesImines
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© 2013 Pearson Education, Inc.© 2013 Pearson Education, Inc. Chapter 18Chapter 18 6464
Formation of Imines
• Ammonia or a primary amine reacts with a ketone or an aldehyde to form an imine.
• Imines are nitrogen analogues of ketones and aldehydes with a C═N bond in place of the carbonyl group.
• Optimum pH is around 4.5.
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CH3NH2CH
O
+
CH=NCH3 + H2O
N-Benzylidenemethylamine (70%)
Example
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CH3NH2CH
O
+
CH=NCH3 + H2O
N-Benzylidenemethylamine (70%)
Example CH
OH
NHCH3CH3
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© 2013 Pearson Education, Inc. Chapter 18 67
Mechanism of Imine FormationAcid-catalyzed addition of the amine to the carbonyl compound group
Acid-catalyzed dehydration
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© 2013 Pearson Education, Inc. Chapter 18 68
Other Condensations with Amines
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CH3(CH2)5CH + H2NOH
O
CH3(CH2)5CH + H2O
NOH
(81-93%)
Example
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+ H2NNH2
+ H2O
(73%)
Example OC NNH2
C
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CCH3
Example O
+ H2NNH
phenylhydrazine
+ H2O
CCH3
NNH
a phenylhydrazone (87-91%)
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CH3(CH2)9CCH3
O
H2NNHCNH2
O
+
H2OCH3(CH2)9CCH3
NNHCNH2
O
+
Example
semicarbazide
a semicarbazone (93%)
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17.11Reaction with Secondary Amines:
Enamines
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R2NH••
+ H2O
(enamine)
C••R2N
C
Enamine Formation
••C
••OR2N H
H C
••C O
••
H C
••
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+
(heat in benzene)
Example O NH
viaviaOOHH
N
(80-90%)
N
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© 2013 Pearson Education, Inc. Chapter 18 76
The Wittig Reaction
The Wittig reaction converts the carbonyl group into a new C═C double bond where no bond existed before.
A phosphorus ylide is used as the nucleophile in the reaction.
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© 2013 Pearson Education, Inc. Chapter 18 77
Preparation of Phosphorus Ylides
Prepared from triphenylphosphine and an unhindered alkyl halide.
Butyllithium then abstracts a hydrogen from the carbon attached to phosphorus.
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© 2013 Pearson Education, Inc. Chapter 18 78
Mechanism of the Wittig ReactionBetaine formation
Oxaphosphetane formation
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© 2013 Pearson Education, Inc. Chapter 18 79
Mechanism for Wittig
The oxaphosphetane will collapse, forming alkene and a molecule of triphenyl phosphine oxide.
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Retrosynthetic Analysis
There will be two possible Wittig routes toan alkene.
Analyze the structure retrosynthetically.
Disconnect the doubly bonded carbons. One will come from the aldehyde or ketone, theother from the ylide.
C C
R
R'
A
B
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Retrosynthetic Analysis of Styrene
C6H5CH CH2
HCH
O
+(C6H5)3P CHC6H5
+ –
••
C6H5CH
O
+ (C6H5)3P CH2
+ –
••
Both routesare acceptable.
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© 2013 Pearson Education, Inc. Chapter 18 82
Oxidation of Aldehydes
Aldehydes are easily oxidized to carboxylic acids.
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© 2013 Pearson Education, Inc. Chapter 18 83
Infrared (IR) Spectroscopy
Very strong C═O stretch around 1710 cm-1 for ketones and 1725 cm-1 for simple aldehydes
Additional C—H stretches for aldehyde: Two absorptions at 2710 cm-1 and 2810 cm-1
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© 2013 Pearson Education, Inc. Chapter 18 84
IR Spectra
Conjugation lowers the carbonyl stretching frequencies to about 1685 cm-1.
Rings that have ring strain have higher C═O frequencies.
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© 2013 Pearson Education, Inc. Chapter 18 85
Proton NMR Spectra
Aldehyde protons normally absorb between 9 and 10.
Protons of the α carbon usually absorb between 2.1 and 2.4 if there are no other electron-withdrawing groups nearby.
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© 2013 Pearson Education, Inc. Chapter 18 86
1H NMR Spectroscopy
Protons closer to the carbonyl group are more deshielded. The , and protons appear at values of that decrease with
increasing distance from the carbonyl group.
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© 2013 Pearson Education, Inc. Chapter 18 87
Carbon NMR Spectra of Ketones
The spin-decoupled carbon NMR spectrum of 2-heptanone shows the carbonyl carbon at 208 ppm and the α carbon at 30 ppm (methyl) and 44 ppm (methylene).
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© 2013 Pearson Education, Inc. Chapter 18 88
Mass Spectrometry (MS)
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© 2013 Pearson Education, Inc. Chapter 18 89
MS for Butyraldehyde