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Aldehyde
O C R H
STRUCTURE
R = H, alkyl, aryl
Ketone
NOMENCLATURE
EXAMPLES
O C CH 3 CH 2
2-Pentanone
CH 2 CH 3
O CH3 CH2 C CH CH2 CH3
4-Ethyl-3-hexanone
CH2 CH3
CH CH3
CH3
3-Isopropylcyclopentanone
KETONES
Diethyl ketone
SPECIAL CASES
O C CH3
acetone
A common laboratory solvent and cleaning agent
O C
CH3
diphenyl ketone
benzophenone
dimethyl ketone
O C CH3
methyl phenyl ketone
acetophenone
KNOW THESE
EXAMPLES
H3C CH2 CH2 CH2
pentanal
C H
Cl
4
CH3
CH
2
CH CH3
C H
2-chloro-3-methylbutanal
RECOGNIZE THESE
O C H
SPECIAL CASES
H
O C H
formaldehyde
O C H CH3
benzaldehyde
acetaldehyde
KNOW THESE
O H
C C C C C C C .
CHO Cl
-chlorocaproaldehyde ( -chlorohexanal )
GENERALIZED CHEMISTRY
.. O:
.. :O :
C
+
Nu:
-:Nu
slow C Nu
an alkoxide ion
.. _ : O: fast C Nu + H2O
.. :O H C Nu
BASIC SOLUTION
.. + O H + C :Nu
.. :O slow C Nu
(+)
Acid catalysis speeds the rate of addition of weak nucleophiles and weak bases (usually uncharged).
CYANOHYDRINS
Addition of Cyanide
Buffered to pH 6-8
:O : _ R C .. _ :O : R C CN R + H2O R R + CN R C CN .. :O C CN
:C N:
.. _ :O : R
H R
a cyanohydrin
In acid solution there would be little CN-, A cyanohydrin and HCN (g) would be a problem (poison).
CYANIDE ION BONDS TO HEMOGLOBIN .. N CYANIDE IS Cyanide bonds IS A POISON (irreversibly) to the C ..
CH3 H3C
N Fe N
N N CH3 CH2CH2COOH
H3C
CH2CH2COOH
HCN is a gas that you can easily breathe into your lungs.
ORGANOMETALLICS
Synthesis of Alcohols
C R
(R-MgBr)
(R-Li)
These reagents cannot exist in acid solution
:R .. :O R C R
H2O + H H R
workup step
M (OH)x
alcohol
etc.
HYDRATES
Addition of Water
O C R R'
aldehyde or ketone favored
+ H
+ H2O R
O H C O H a hydrate
hydrates are unstable and cannot be isolated in most cases
R'
ACID CATALYSIS
RECALL
H O H H .. .. + :O :O H
+
.. :O H
+
Acid catalysis enhances the reactivity of the carbonyl group - nucleophilic addition proceeds more easily.
:Nu
weak nucleophiles can react
WATER ADDS TO THE CARBONYL GROUP OF ALDEHYDES AND KETONES TO FORM HYDRATES
H O H
+
:O
..
..
:O
C
..
:O
C
..
.. O ..
O+ H .. H H
:O ..
H H
+
a hydrate
.. O ..
O H
..
for most compounds the equilibrium favors the starting materials and you cannot isolate the hydrate
MICROREVERSIBILITY: In a reaction where all steps are reversible, the steps in the reverse reaction are the same as those in the forward reaction, reversed!
+ H2O
18
excess
+H2O18
O H R C R
18 O
-H2O
Cl
O Cl H
Cl C Cl H
OH OH
Cl
+Cl
chloral
chloral hydrate
OH
sp3 OH
O
sp2 cyclopropanone
cyclopropanone hydrate
O H H
OH
C C OH H O OH
O Ph C C
O Ph H
phenylglyoxal
C C OH H
ACID CATALYSIS
RECALL
H O H H .. .. + :O :O H
+
.. :O H
+
Acid catalysis enhances the reactivity of the carbonyl group - nucleophilic addition proceeds more easily.
:Nu
weak nucleophiles can react
Addition of Alcohols
TWO MOLES OF ALCOHOL WILL ADD
O R C R' + ROH
addition of second mole
H+
O H R C R' O R
hemiketal
O H R C R' O R + ROH
H+
O R R C R' + H O O R
an aketal
The equilibria normally favor the aldehyde or ketone starting material, but we will show how they can be made.
R C H
OH ROH OR
R C H
OR OR
H aldehyde
hemiacetal
acetal
R C O R
ketone
ROH
R C R
OH ROH OR
R C R
OR OR
(hemiketal)*
*older term
(ketal)*
*older term
..
R OH
+ H 2S O4
R
O H
:O
R C R
..
H O
+
H
..
:O H
R C R
:O
O+
..
R C R H
.. O ..
..
first addition
: R O H :O :O .. ..
H
H
..
R C R
hemiacetal
+ R O+
..
R H O
..
+
H
:O H
R C R
..
O H + R C R
..
.. O ..
:O ..
R C R
SN1
second addition
R C R
:O ..
hemiacetal
:O .. ..
:O +
:O
: R O H
:O R
R C R
: R O H
acetal
..
O R
..
R C R
:O ..
:O ..
AQUEOUS ACID
OR H2SO4 OR
H2O
ROH C O + ROH
AQUEOUS BASE
OR NaOH C OR H2O
no reaction
O C
H2O
HO
OH
hydrate
ALCOHOLS
O C
R-O-H
HO OR
R-O-H
RO OR
H2O
hemiacetal acetal
RO
OR
H+ H2O H2O
O +2 ROH
no reaction
NaOH
REAKSI OKSIDASI
Keton tidak mudah dioksidasi Aldehid sangat mudah dioksidasi, menjadi asam karboksilat
Zat pengoksidasi : KMnO4, H, H2O
Reaksi Reduksi
Reaksi Reduksi
Reduksi aldehid menghasilkan alkohol primer Reduksi keton menghasilkan alkohol sekunder Zat pereduksi: H2, katalis Zn/Hg, HCl
Reaksi Adisi-eliminasi
Reaksi Adisi-eliminasi
Aldehid + Amina Primer Aldehid + Amina sekunder Aldehid + Amina tersier Imina Enamina hidrazon
1. 5-hidroksi-2-heksanon dengan air 2. 1,3,4,5,6-pentahidroksi-2-heksanon dengan air 3. propanal dengan metanol 4. Aseton dengan 1,2,3-propanatriol
1. CH3NH2 2. (CH3)2NH