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:O:
R C R' ketone
: O:
C
carbonyl group
q The simplest aldehyde is formaldehyde (CH2O). It is the only aldehyde without an alkyl group attached to the carbonyl C.
: O:
H C H formaldehyde
All other aldehydes, such as acetaldehyde (CH3CHO), have one alkyl group and one H attached to the carbonyl C.
: O:
CH3 C H acetaldehyde
: O:
CH3
H3C
: O:
CH2CH3
CH3
Nu:
alkoxide
: O:
3
..
C
sp2
sp
Nu
The weak bond breaks as the Nu:- adds, so that C remains tetravalent ( 5 bonds).
qThe alkyl group and the H atom bonded to the carbonyl are not leaving groups. They are not displaced because hydride (H:-) and alkanides (R:-) are extremely strong bases. qpKb H:-= -21 and pKb :CH3- = -40! (:CH3- = methide).
3
.. O ..
: O:
C R
: O:
R C R
: O:
R C
.. OH ..
N:
acid chloride acid anhydride aldehyde ketone ester carboxylic acid amide nitrile carboxylate
: O:
R C
.. Cl : ..
: O:
R C H
most reactive
:O:
R C
:O:
R C
.. O ..
..
N
H H
:O:
R C
.. _ O: ..
least reactive
4
Nu:
: O:
HSO4R
: O+
C
H R
R
C
E+
R
: O:
C
qThe + charge is shared with the carbonyl C by resonance forming a carbocation a very good E+. qEven weak Nu:-s (like H2O and ROH) will donate electrons to an aldehyde or ketone in the presence of a strong acid catalyst, e.g., H2SO4 or HCl.
: O:
R C R
HSO4R
: O:
C
: O:
R .. CH3CH2OH ..
C
+
R
5
CH3CH2OH ..
H H H
:O :
C
-hydrogens pKa = ca. 17 in aldehydes pKa = ca. 19 in ketones H The carbonyl H of an aldehyde is not acidic. It's pKa is ca. 50.
qThe -hydrogens can be removed by strong bases because the carbanion that forms is stabilized by resonance with the adjacent carbonyl oxygen forming an enolate.
H H H C H C H
:O :
C H OHH
H C H
H C ..
:O :
C H
H H H C
H C
:O :
C H
..
enolate
Boiling Points and Solubility of Aldehydes and Ketones qThe carbonyl group is strongly polar but does not produce hydrogen bonding (It has no polar hydrogens). As a result, the boiling points of aldehydes and ketones are higher than the nonpolar hydrocarbons and the alkyl halides but lower than those of alcohols. qFormaldehyde is a gas at room temperature (b.p. = -21 C) but heavier aldehydes are liquids. Acetone, the simplest ketone, is a liquid at room temperature (b.p. = 56 C). qLower molecular weight aldehydes and ketones are water soluble. Acetone, formaldehyde and acetaldehyde are miscible in water.
OH
5
4 3 2
O
1
2
O CH2C H
1
CH3CHBrCH2C H
3 2 1
CH3CHCH2CH2C H
3-bromobutanal
4-hydroxypentanal
2-phenylethanal
qThe parent chain must contain the CHO- group, and this group is numbered as carbon 1 (because it is always at a chain end). Aldehydes: attached to rings: ring+carbaldehyde ringcarbaldehyde
O C H O C H HO CHO
benzenecarbaldehyde
3-hydroxycyclopentanecarbaldehyde cyclohexanecarbaldehyde
8
methanoic acid ethanoic acid propanoic acid butanoic acid pentanoic acid hexanoic acid
formic acid acetic acid propionic acid butyric acid valeric acid caproic acid
qSubstituents locations are given using Greek letters (, , , , , .) beginning with the carbon next to the carbonyl carbon, the -carbon.
O CH3CHBrCH2C H OH O O CH2C H CH3CHCH2CH2C H
-bromobutyraldehyde
-hydroxyvaleraldehyde
-phenylacetaldehyde
10
O4 5 CH3 CHCCHCH3
1 2
Cl
CH3
2-butanone
2-chloro-4-methyl-3-pentanone
1-phenyl-1-butanone
qKetones are just below aldehydes in nomenclature priority. qA ketone group is named as an oxo substituent in an aldehyde.
O CH3CH2CCH2CHO 5 4 3 2 1
3-oxopentanal
H3C
:O:
CH3CCH2CHCH3
O CH3CHCCHCH3
OCH3
Cl
CH3
C CH2CH2CH2
O C
C CH3
acetophenone
benzophenone
benzaldehyde
12
Nomenclature Practice
qName these in IUPAC and, where possible, common nomenclature.
O CH2 C CH3 F O C H O C H
qDraw the structures of the following compounds. butanedial bromomethyl -bromoethyl ketone 2,4-pentanedione
O O
BrCH2 O C CH2CH2Br
H3C O C CH2 O O C CH3
HCCH2CH2CH
qAnd these:
CH3CH CH
O C H
CH2 CH
CH3
(I) 2-butenal
13
O HC
O CH
.. Cl : ..
..
-78C 1equiv.
R 1 DIBAH + 2 H3O
: O:
C H aldehyde
: O:
R C
OR ..
N:
Only 1 equivalent of very cold DIBAH is used to avoid further reduction of the aldehyde to an alcohol.
14
: O:
C
OH
mild oxidation
CrO3 in N or PCC in CH2Cl2
1 alcohol
OH ..
..
carboxylic acid
1 LiAlH4 + 2 H3O
qIn non aqueous media, moderate to strong oxidants become mild, oxidizing 1 alcohols only as far as the aldehyde. qCarboxylic acids can be reduced to 1 alcohols with LiAlH4, but no reagent has been found that will stop the reduction at the aldehyde.
15
+ Al
CH3 CH2CHCH3
H:
qDIBAH is weaker than LiAlH4. DIBAH is neutral; LiAlH4 is ionic. qDIBAH is similar to AlH3 but is hindered by its bulky isobutyl groups. qOnly one mole of H:-is released per mole of DIBAH. q
16
propanal CH3CH2
O C H + CH3OH CH3CH2C N
HCl
_ NH 3
propanenitrile
qWrite equations showing the preparation of: a)pentanal from 1-pentanol b)butanal from an ester
CH3CH2CH2CH2CH2OH
O
CH3CH2CH2CH2CH
O CH3CH2CH2CH
CH3CH2CH2COCH3
-78C 1equiv.
O C H
1 DIBAH + 2 H3O
17
(CH3 )3 C
4-t-butylcyclohexanone
2.Friedel Crafts Acylation of Aromatics: yields ketones when an acid chloride is used as the electrophile.
O C
O HO + CH3CH2 C Cl AlCl3 EAS
HO
CH2CH3
propanoyl chloride
1-(4-hydroxyphenyl)propanone
3.Hydration of Alkynes: with Hg+2 and H3O+ yields an enol, that tautomerizes to a ketone.
Hg(OAc)2 CH3 (CH2)3 C 1-hexyne CH H3O+
O CH3 (CH2)3 C an enol H CH H
H CH H
CH3 (CH2)3 C
2-octanone
18
hexanoyl chloride
2-heptanone
qRecall that a stronger reducing reagent, such as a Grignard (RMgBr) will also reduce an acid chloride to a ketone, but reduction cannot be stopped here. The ketone is further reduced to an alcohol. ..
: O:
R C
.. Cl : ..
CH3MgBr
: O:
R C CH3 ketone
CH3MgBr
R
:O:
C CH3
+ 2 H3O
..
:O
CH3
acid chloride
alkoxide CH3
3 alcohol CH3
19
O CH3CH2C 3-hexanone
O C
H CCH2CH3 H
O C CH3
3-hexyne
Hg , H3O
+2
b)benzene m-bromoacetophenone
: O:
H3C
.. Cl : ..
AlCl3
CH3
FeBr3 Br2
Br
c)bromobenzene acetophenone
Br Mg in ether
acetyl chloride
HBr
acetophenone
: O: MgBr
H C CH3
:O:
CH CH3
H3O+
..
: OH
CH CH3 Cr+6, H+
O C CH3
..
m-bromoacetophenone
d)1-methylcyclohexene 2-methylcyclohexanone
CH3
1 BH3, THF 2 NaOH, H2O2, pH8 CH3 OH
acetophenone
Cr , H
+6
CH3 O
20
o- and pdirecting Br
Reactivity
Reactivity
OH
O NH C CH3 activators
Cl deactivators
O COCH3
O C CH3
C N
N+R3
deactivators
21