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Dr. Ralph C. Gatrone Department of Chemistry and Physics Virginia State University
Spring, 2011
Chapter Objectives
Nomenclature Preparation Reactions Spectroscopy
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Nomenclature
Aldehydes Identify the alkane Parent alkane must contain the CHO
group CHO group C is numbered 1 Replace the e with al
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Examples
O
4 1 H
1 H
4-butyloctanal
3-phenylbutanal
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Nomenclature
Aldehydes Aldehyde carbon is bonded to ring Suffix used is carbaldehyde
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Examples
O H O H
benzenecarbaldehyde
cis-2-methylcyclopentanecarbaldehyde
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Common Names
O H O H3C H acetaldehyde O H O CH3CH2
O
formaldehyde
O
valeraldehyde
acrolein
propionaldehyde
O H crotonaldehyde
butyraldehyde
H
O H H benzaldehyde cinnamaldehyde
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Nomenclature
Ketones Identify the alkane Parent alkane The longest chain containing the carbonyl group The carbonyl C gets the lowest number possible Replace the e with one
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Examples
O O
3-heptanone
(E,E)-nona-5,7-dien-2-one
O O
1,2-cyclohexandione
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2-cyclohexenone
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Nomenclature
If present with another functional group Prefix oxo is used
O
4-oxohexanal
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Common Names
O O O
acetone
acetophenone
benzophenone
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As a Substituent
When R-C=O is used as a substituent Referred to as an acyl group Ending yl is used
O O
acetyl
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benzoyl
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Preparation
[O] of primary ROH
PCC/CH2Cl2
OH O
[H] of RCO2H
o OH 1. DIBAH/toluene/-78 C
2. H3O+
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Preparation
Ozonolysis of Alkenes
R H 1. O3 2. Zn/HOAc must have one H R O H
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Hydration of Alkynes
Hydration of terminal alkynes in the presence of
Hg2+ (catalyst)
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Preparation
From Organometallics
O R Cl R2CuLi from RLi and CuCl O R Cl R2Cd from RLi and CdCl2 R2Cd R O R R2CuLi R O R
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Preparation
Friedal-Crafts Acylation
O R AlCl3 Cl O R
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Reactions
Oxidation of Aldehydes
O R H [O] R O OH
Reactions
O O +
Resonance contribution Carbon is electrophilic Oxygen is nucleophilic
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Nucleophilic Addition
O O -
Nu
Nu:
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-H2O R
Nu R
Nucleophile = Water
Product is a 1,1-diol, a gem-diol, a hydrate Reaction is equilibrium process Position of equilibrium depends upon structure Reaction is readily reversible
O R R
HO R
OH R
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Equilibrium Process
O R H H2O R OH OH H
O R R
H2O R
OH R OH
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Nucleophile = Y in HY
Reaction of C=O with H-Y, where Y is
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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
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Grignard reagent
Effectively a carbanion
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Grignard Additions
O R H R R' MgX R' O H H3O+ MgX+ R R' secondary alcohol OH H
O R'
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Nucleophile = Hydride
Reduction of Carbonyl compounds Can use NaBH4 or LiAlH4
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Hydride Addition
Convert C=O to CH-OH LiAlH4 and NaBH4 react as donors of hydride ion Source of H-1 (not real but useful formally) Protonation after addition yields the alcohol
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Primary and Secondary amines react Tertiary amines do not react with carbonyls
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Derivatives of Imines
Hydroxylamine (NH2OH)
O R R' NH2OH H+ NOH R R' oxime
Hydrazine (NH2NH2)
O R R' NH2NH2 H+ NNH2 R R' hydrazone
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Uses of Oximes
Beckmann rearrangement Synthesis of Nylon
NHOH H+ H N O Nylon
caprolactam
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Reduction under basic conditions Ketone or Aldehyde into an alkane Originally carried out at high temperatures but
with dimethyl sulfoxide as solvent takes place near room temperature
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TsNHN
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Nucleophile = Alcohol
Two equivalents of ROH and acid catalyst Acetal formation
O ROH/H+ H3O+ HO O OH H3O+
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OR OR
H+
O O
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)
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Uses of Acetals
Thioacetals Prepared in same manner as acetals Reduction under neutral conditions
HS acid
SH
Raney Ni S
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CH2OH
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Glucopyranoses
OH HO HO OH H
-D-Glucose -D-Glucose
OH O OH HO HO
O OH H OH
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Glucose
-D-glucopyranose mp = 146 oC and [] = +112.2o -D-glucopyranose mp = 148 - 155 oC and [] = +18.7o
Dissolve either in water, mutarotation occurs Alpha become beta, beta becomes alpha Equilibrium mixture results (37:63 :)
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X-
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Phosphorus Chemistry
Positive charge on P stabilizes negative charge that can
form on an alpha carbon (must have a H atom)
R R P + base R XR R P + R
CH2R
- CHR an ylid
alpha carbon
+
R3P=O
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trisubstituted alkenes but not tetrasubstituted alkenes For comparison, addition of CH3MgBr to cyclohexanone and dehydration with, yields a mixture of two alkenes
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Aldehydes and ketones react with Nu sp3 intermediate forms Intermediate may
Brief Review
Reverse to give SM Accept proton to form addition product Eliminate water to form new Nu=C species If derivative of carboxylic acid, also may
O R X
Nu: R
X R
O Nu
Nu
See details of this chemistry in Chapter 16 Elimination of X does not occur when X = H or R
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gamma H
H alpha H H beta O
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conjugate addition,
or 1,4 addition
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Conjugate Addition
Resonance explains conjugate addition
O O + + positive charge designates electrophilic site O -
Certain Nu: will add in 1,2 manner Other Nu: add 1,4 manner
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diorganocopper reagent gives 1,4 addition Diorganocopper (Gilman) reagents from by reaction of 1 equivalent of cuprous iodide and 2 equivalents of organolithium 1, 2, 3 alkyl, aryl and alkenyl groups react but not alkynyl groups
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Other Additions
Grignards add 1,2 and 1,4 to , unsaturated ketones Organo lithium reagents add 1,2 to , unsaturated ketones Cyanide ion adds 1,4 to , -unsaturated ketones
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Summary of Reactions
Aldehydes - from oxidative cleavage of alkenes, oxidation of 1
alcohols, or partial reduction of esters Ketones - from oxidative cleavage of alkenes, oxidation of 2 alcohols, or by addition of diorganocopper or organocadmium reagents to acid halides . Aldehydes and ketones - reduced to yield 1 and 2 alcohols , respectively React with Grignard reagents giving alcohols Addition of HCN yields cyanohydrins 1 amines add to form imines, and 2 amines yield enamines Reaction with hydrazine gives hydrazones Reduction of hydrazone in base yields an alkane Reduction of hydrazone in acid/Zn yields an alkane Alcohols add to yield acetals Phosphoranes add to aldehydes and ketones to give alkenes (the Wittig) -Unsaturated aldehydes and ketones are subject to conjugate addition (1,4 addition)
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Infrared Spectroscopy
C=O Strong absorption 1660 1770cm-1 See next two spectra
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NMR Spectroscopy
The aldehyde H resonates at 10d Coupling is observed with adjacent H J = 3Hz H adjacent to C=O are slightly deshielded Resonate near 2.0 to 2.3d Methyl ketones are distinctive (2.1d) See next spectrum
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NMR Spectroscopy
C=O carbons resonate between 190
215d See next spectra
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Mass Spectrometry
A g H leads to McClafferty rearrangement
Mass Spectrometry
cleavage is also observed
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