Carbonil Compounds :

ALDEHYDES and KETONES

1
Nama & Struktur Gugus-gugus Alkil yang Sering Dijumpai

NAMA STRUKTUR NAMA STRUKTUR

Metil -CH3 CH3

Etil CH2CH3 Tersier butil C CH3

Propil CH2CH2CH3 CH3

H
Isopropil C CH3 n-pentil CH2CH2CH2CH2CH3

CH3
Isopentil CH2CH2CHCH3
Butil CH2CH2CH2CH3
H2 H CH3
Isobutil C C CH3
CH3

CH3 H2
Neopentil C C CH3
H H2
Sekunder butil C C CH3

CH3
CH3

Gugus Alkil : alkana yang kehilangan satu atom H

 Aldehydes and Ketones general
formula

O O
atau RCHO atau RCOR'
C C
R H R R'

R = alkil, aril, H R, R' = alkil, aril

aldehida keton

3
 IUPAC Nomenclature of Aldehydes
• Nama aldehida diturunkan dari nama alkana
induknya dengan mengubah huruf akhir –a
menjadi –al.
• Atom karbon pada –CHO diberi nomor 1,
tetapi nomor tidak perlu dicantumkan.
O O
O
CH3CHCH CH3CH CHCH
CH3CH
Cl
etanal 2-butenal
2-kloropropanal

4
• in the IUPAC system, cyclic and aromatic al
dehydes are named by adding the word carb
aldehyde to the name of the ring system.

5
 Common Name
• Aldehida: diberi nama menurut nama trivial
asam karboksilat induknya dengan mengubah
imbuhan asam –oat atau asam -at menjadi
akhiran –aldehida.
• Posisi lain dalam molekul dirujuk dengan
huruf Yunani.

O O

H OH H H

asam format/asam metanoat formaldehida

6
7
 IUPAC Nomenclature for Ketones
• Nama keton diturunkan dari alkana induknya,
huruf akhir –a diubah menjadi –on. Bila perlu
digunakan nomor.
O O O
O
CH3CCH2CH2CH3 CH3CCH2CCH3

sikloheksanon 2-pentanon 2,4-pentanadion

8
In the IUPAC system, aromatic ketones are considered
benzenesubstituted aliphatic ketones.

9
• Many aromatic compounds retain their com
mon names in the IUPAC system. Followin
g are two such examples:

10
 Common Name
• In the common system, ketones names are created
by naming the groups attached to the carbonyl car
bon and then adding the word ketone. Following a
re several examples:

11
 Nama IUPAC vs. Nama Trivial
O
O O
CH3CHCH
HCH CH3CH
Br
IUPAC: metanal etanal 2-bromopropanal
Trivial: formaldehida asetaldehida -bromopropionaldehida

O O O

CH3CCH3 CH3CCH2CH3 (CH3)2CHCC(CH3)3

IUPAC: propanon butanon 2,2,4-trimetil-3-pentanon
Trivial: aseton metil etil keton isopropil t-butil keton

12
 Structure of the Carbonyl Group

C O
 Hybridization of the carbonyl carbon is sp2.
 Geometry of the carbonyl carbon is trigonal planar
 Attack by nucleophiles will occur with equal ease from
either the top or the bottom of the carbonyl group.
 The carbonyl carbon is prochiral. That is, the carbonyl
carbon is not the center of chirality, but it becomes chiral
as the reaction proceeds.
Prochiral
Nu

C OH
R'
:Nu R
These two products
R'
are enantiomers.
C O
R
:Nu R
R' In general, both
C OH enantiomers are
formed in equal
Nu amount.
Consequences polar carbonyl group :
• Weak associations occur between the molecules of
aldehydes and ketones  higher boiling point than
the equivalent alkane.
But aldehydes and ketones can not form hydrogen
bonds with each other  lower boiling point than
the alcohol equivalent.

CH3 O OH

CH3CHCH3 CH3CCH3 CH3CHCH3

td. -12 oC td. 56 oC td. 82,5 oC

15
Consequences polar carbonyl group :
• Aldehydes and ketones can hydrogen bond with
other molecules  Aldehydes and ketones in water-
soluble low BM.
O H O

CH3CCH3 H

• Aldehydes and ketones limitly solvate ions.

Example : NaI soluble in aceton.

16
 Physical properties of some aldehydes
Boiling solubility in
Common name Structure point water
(oC) (g/100mL)
formaldehyde HCHO -21 absolutely

acetaldehyde CH3CHO 20 absolutely

propionaldehyde CH3CH2CHO 49 16

butiraldehyde CH3CH2CH2CHO 76 7

benzaldehyde C6H5CHO 178 partially

17
 Physical properties of some ketones

Boiling solubility in
Common name Structure point water
(oC) (g/100mL)
aceton CH3COCH3 56 absolutely

ethyl methil CH3COCH2CH3 80 26

ketone
acetofenone C6H5COCH3 202 Not soluble

benzophenone C6H5COC6H5 306 Not soluble

18
 Relative reactivity: aldehydes > ketones
Aldehydes are usually more reactive toward nucleophilic substitutions
than ketones because of both steric and electronic effects

(1) Steric effects : differences obstruction space (due to the size

of the R group in ketones more blocking than H)
Nu
Nu

In aldehydes, the relatively small hydrogen atom is attached to

one side of the carbonyl group, while a larger R group is affixed
to the other side. In ketones, however, R groups are attached to
both sides of the carbonyl group. Thus, steric hindrance is less in
19
aldehydes than in ketones.
Relative reactivity: aldehydes > ketones
(2) electronic effects : differences in the stability of a partial
positive charge (R pushing more electrons than H, so C of the
carbonyl ketone is less positive than aldehyde)

-
O - O
 
R H R R'
aldehydes have only one R group to supply electrons toward the
partially positive carbonyl carbon, while ketones have two
electron‐supplying groups attached to the carbonyl carbon. The
greater amount of electrons being supplied to the carbonyl carbon,
the less the partial positive charge on this atom and the weaker it
will become as a nucleus.
20
 Relative Reactivity of Aldehydes
Aliphatic aldehydes >>> Aromatic aldehydes
The electon-donating resonance effect of the aromatic ring
makes the carbonyl group less electrophilic than the carbonyl
group of the aliphatic aldehyde.
The carbocation intermediate
H H  The positive charge character on
O O carbon makes this an excellent site
for attack by Lewis bases
C C (nucleophiles).

 Nucleophile attacks the electrophilic C=O carbon from a

direction ~45˚ to the plane of the carbonyl group
 At the same time: Rehybridization of the carbonyl carbon from
sp2 to sp3 occurs.
 α hydrogens and α carbon
• In addition to nucleophilic additions, aldehydes and ketones
show an unusual acidity of hydrogen atoms attached to carbo
ns alpha (adjacent) to the carbonyl group. These hydrogens a
re referred to as α hydrogens, and the carbon to which they a
re bonded is an α carbon.
• In ethanal, there is one α carbon and three α hydrogens, whil
e in acetone there are two α carbons and six α hydrogens.

23
 Reactivity of α Hydrogens
• Why hydrogen is positioned α (H-α) to the c
arbonyl group are acidic ????
1. C-α atom adjacent to one or more C atoms are partially
positive. C-α was also took part this positive charge (the
electron-withdrawing inductive effect), so the CH bond
becomes weakened.

O O
H2
C C C

24
 Lanjutan.....
2. Resonance stability of the enolate ion, is the anion formed
when the protons apart.
Of resonance structures, it appears that the negative charge
carried by the oxygen-oxygen carbonyl and the α carbon. This
charge delocalization stabilizes the enolate ion and encourage
formation

Berdekatan dengan 1 gugus karbonil :

O O

H
C C C C
H
Berdekatan dengan 2 gugus karbonil :
O O O O O O
H
C C C C C C C C C
H H
25
26
Synthesis of aldehydes
1. Oxidation of primary alcohol
PCC
CH2OH CHO
CH2Cl2
Sitronelol Sitronelal (82%)

PCC = piridinium klorokromat N H CrO3Cl

Mekanisme:
H CrO3
O O O
CrO3 Reaksi
2-
C C E2 C + CrO3
H H

27
Synthesis Mechanism

Oxidation of 1˚ alcohols
:Base
O
O
O O
Cr O
H O O O Cr
O H + Cr O
O O
O C
C R H
C C R H
R H R H H
H H
:Base
Synthesis of aldehydes
2. Oxidative cleavage of double bond which containing
hydrogen vinilik (ozonolysis of alkenes)
CH3 O O
1. O3

2. Zn, CH3COOH H3C H

H
1-Metilsikloheksena 6-Oksoheptanal (86%)

Mekanisme (Ingat kembali pelajaran tentang alkena)

O C O
O O O O
O3 Zn
C C C C +
o C C CH3COOH/H2O
CH2Cl2, -78 C O
O C
molozonida ozonida

29
Synthesis Mechanism
O
O
O
O O
H + O O
O O
H R R
C C
R H H R R H
H R

CH3COO-
CH 3COO H
O H
+
O O O O
+ R O O H
R H H R
R H H R
H O R
Synthesis of aldehydes
3. Reduction of certain carboxylic acid derivatives.

O O
H
+ Y
R Y R H

O O
o
1. DIBAH, toluena, -78 C
CH3(CH2)10COCH3 CH3(CH2)10CH
+
2. H3O
Metil dodekanoat Dodekanal (88%)

DIBAH = Diisobutilaluminium hidrida

H

(H3C)2HCH2C Al CH2CH(CH3)2
31
32
 Synthesis of Ketones
1. Oxidation alkohol sekunder
Reagent : Jones reagent (CrO3/aq.H2SO4),
PCC, Natrium dikromat/aq. AcOH.

PCC
(H3C)3C OH (H3C)3C O
CH2Cl2

4-ter-Butilsikloheksanol 4-ter-Butilsikloheksanon (90%)

33
Synthesis Mechanism
Oxidation of 2° alcohols w/ PCC and base

:Base
O
O O O O
H Cr Cr Cr
O O H + O
O O O O
O

C C R
C C
R H R H H R R
R R R
:Base
Synthesis of ketones
2. Oxidative cleavage of alkenes one / two
unsaturated carbon atom is disubstituted
(ozonolysis of alkenes)

R R 1. O3 R R
O + O
R R 2. Zn/H3O+ R R

O O
1. O3
CH2 O
2. Zn/H3O+ + CH2O
CH3 CH3
(70%)
35
Ozonolysis of alkenes, if one of the unsaturated carbon
atoms is disubstituted.
O CH 3COO H

O O
O + O O O O
O O
O
R R O
C C R R R
R
R R

CH3COO-

O H
O O + O
O
+
R R R R R R R R
Synthesis of ketones
3. Aryl ketones prepared by Friedel-Crafts acylation
reaction of aromatic rings with hydrochloric acid using
a catalyst AlCl3. O
O
AlCl3 CH3
+
CH3CCl 
Asetil
Benzena klorida Asetofenon (95%)

Mekanisme: (ingat kembali pelajaran tentang senyawa aromatis)

O
AlCl3
C R C O R C O + AlCl4
R Cl O O
R

+ R H CH3
C O
+ HCl
Cl 37
Synthesis of ketones
4. Methyl ketones are made from the terminal alkyne
hydration catalyst mercuric ion.
O
H3O+
H3C(H2C)3C CH CH3(CH2)3C CH3
Hg(OAc)2
1-Heksuna 2-Heksanon (78%)

Mekanisme: (Ingat kembali kuliah tentang alkuna)

H
H H
Hg2+SO42- OH2 H O
R C C H R C C C C
alkuna Hg+SO42- R Hg+SO42-
kation vinil
-H+
O
C H HO H H3O+ HO H
R C
C C C C
keton H H R H R Hg+SO42-
38
Synthesis of ketones
5. Ketones can be made of certain carboxylic acid
derivatives.
O O
-
R'
C C + Y-
R Y R R'

O O

CH3(CH2)4CCl + (CH3)2CuLi CH3(CH2)4CCH3

Litium
Heksanoil klorida 2-Heptanon (81%)
dimetilkuprat

39
40
 Oxidation of aldehydes and ketones
Oxidation : process of oxygen binding and release of hydrogen

ada hidrogen tidak ada

O O O hidrogen
[O]
C C C tidak reaktif kecuali
R H R OH R R' pada kondisi sangat
Aldehida Keton kuat

Pereaksi:
• HNO3 hot
• KMnO4
• Jones reagents (CrO3 in H2SO4/H2O)  paling umum
• Tollens reageents (Ag2O in NH4OH/H2O)  anal. kualitatif
41
 Oxidation of Aldehydes & Ketones

1. Conversion of aldehydes to carboxylic acids

2. Oxidation of aromatic aldehydes / ketones to benz
oic acid derivatives
3. Haloform reaction of methyl carbonyls
4. Periodic acid cleavage of vicinal dials/diketones
 Aldehyde / Ketone Oxidations
+
A g ( N3)2H
1. R C H or A r C H RCO O H( A r CO O H
( To l l e n s r e a ge nt )
O O

2. C H

O
KM n O4 o r 2Cr
K 2O 7
or CO O H
²
C R

O
X2 -
3. CH 3 C R - H CX3 + RCO O
O H / 2O
H
O
R C C H + H CO O +HH I 3O
RCO O H
4. H I 4O
O O
Example

44
• Baeyer‐Villiger oxidation is a ketone oxida
tion, and it requires the extremely strong oxi
dizing agent peroxybenzoic acid. For examp
le, peroxybenzoic acid oxidizes phenyl met
hyl ketone to phenyl acetate (an ester).

45
 The oxidation mechanism of aldehydes
• Oxidation takes place through the intermediate 1,1-diol.
O H2O OH CrO3 O
C C
R H R OH H3O+ R OH
H
aldehida hidrat as. karboksilat

Oxidation of ketones
• Inert against oxidizing ketones in general.
• Ketones react slowly with KMnO4 in alkaline hot  event of
termination of bond.
O 1. KMnO4, H2O,
NaOH COOH

2. H3O+ COOH

Sikloheksanon Asam heksanadioat (79%) 46

  Reduction of aldehydes produce primary alcohol
 Reduction of ketones give secondary alcohols

47
 Reduction Reactions of Aldehydes & Ketones
1. Alcohol formation
a. Hydrogenation
b. Hydride reduction
2. Alkane formation
a. Clemmensen reduction
b. Wolff-Kishner reduction
H 2 / Pt
R C H R CH 2O H
O
Li A l 4H H 2O
R C H R CH 2O H
et her H+
O

R C H c onc . H Cl R CH 3
Zn( H g)
O
N H2N H2
R C H - R CH 3
OH / H 2O
O
• Reducing agent lithium aluminum hydride (LiAlH4) is often used and N
atrium borohydrida (NaBH4).
• Basically is also a nucleophilic addition involving a hydride ion (H-).

O AlH3
  H2O
OH
C O Li
C C
H+
H H

H AlH3 Li Aluminium alkoksida Alkohol

Product initially is aluminium alkoxide, which is subsequently hydrolyzed by
water and acids to produce alcohols. The end result is the addition of hydrogen to
carbon double bond -oxygen.

H
1. LiAlH4
O
2. H+, H2O
OH
Sikloheksanon Sikloheksanol 49
50
Reaction of the Carbonyl Group
H
1. O O
+ H+
C C

O O

2. C C

+ B

B:

  Nu:- Nu
C O + H+ C OH C OH C OH

karbokation terstabilkan resonansi

Nucleophilic Addition to Carbonyl: General
Mechanism
+
1. : O: :OH
fast
+
+ H C
C

..
+ : OH
: OH
slow
+ :Nu C
C
Nu
 .. _
: O:
2. :O :
slow
+ :Nu C
C
Nu

.. _ ..
: O: : OH
fast
C + H2O C

Nu Nu
 Once we have the
intermediate, what
happens to it?
Case 1: The Addition Product is Stable.

OH

R C R

Nu

The reaction stops here. This happens most often when

the nucleophilic atom is carbon, oxygen, or sulfur.
Case 2: Addition-Elimination

OH
R R
R C R C + O
H H
Nu Nu
H

The addition product is unstable with respect to loss

of a molecule of water. This is observed most often
when the nucleophilic atom is nitrogen or
phosphorus.
Case 3: Loss of Leaving Group

O O

R C X R C + X

Nu Nu

This process is observed when X is a potential

leaving group. In this case we have nucleophilic
acyl substitution.
Nucleophil
HO (ion hidroksida)

H (ion hidrida)
Nukleofil bermuatan negatif R3C (karbanion)
Nu
RO (ion alkoksida)

N C (ion sianida)

HOH (air)

Nukleofil netral ROH (alkohol)

Nu H H3N (amonia)

RNH2 (amina) 58
59
 Tautomerisation of Aldehydes & Ketones
• Aldehydes and ketones can be in the form of the equilibrium mixtu
re of two forms, called keto and enol forms.

H O OH

C C C C

bentuk keto bentuk enol

 Lanjutan.....

• Carbonyl compounds which do not have the H-α can not form
the enol and keto forms are only in. For example :

O O

O C C
H
C
H H
formaldehida
benzaldehida benzofenon
 Lanjutan.....
• Most simple aldehyde or ketone exists in the keto form.
• Enol form, especially there on the phenol, is due to mainta
ined stability of the structure due to resonance.

OH O

62
 ALDOL CONDENSATION
• Nucleophilic addition of carbonyl compounds to aldehydes or ket
ones resulted in an aldol (aldehida-alkohol).
• Aldol condensation reaction catalyzed by bases. Because of the p
olarization of the carbonyl group, H-α an aldehyde or ketone is m
ore acidic than the more distant hydrogen, so it can be pulled by a
base to give an enolate anion that is nucleophiles.

O O O

: OH C C C C C C
R R R
H
Struktur resonansi anion enolat

63
 Example of Aldol condensation
O O OH O
HO- H2
H3C C H + H3C C H H3C C C C H
H
Asetaldehida 3-hidroksibutanal
O O

Langkah 1 : H3C C H + HO- H2C C H + H2O
Anion enolat
O O O O
 H2
Langkah 2 : H3C C H + H2C C H H3C C C C H
H
Nukleofili Ion Alkoksida

O O OH O
H2 H2
Langkah 3 : H3C C C C H + H2O H3C C C C H + HO-
H H 
3-hidroksibutanal
(suatu aldol)
 Assignment

• Write the aldol condensation rea

ction of butanal with alkaline ca
talyst ?

65
 Cross-aldol condensation

• An aldol condensation between two differen

t aldehydes produces a cross‐aldol condensa
tion
• Example: aldol formation of ethanal with be
nzaldehyde followed by alkaline catalyst fol
lowing reaction :

66
 O
OH
C O
H CH
H O
 C C
H C C H2 H
H
H

Benzaldehida Etanal 3-Hydroxy-3-phenyl-propionaldehyde

kalor - H2O

H O
C
C C
H H

Sinamaldehida
(Cita rasa dari kayu manis)

• Because benzaldehyde has no α-hydrogen, i

t can not form an enolate anion.
67
 Tugas
• How to synthesize 2-etilheksan-1,3-diol (a
mosquito repellent active ingredient) of buta
nal aldol condensation followed by reductio
n ???? Write the reaction mechanism !

68
 Ketonic aldol condensation
• Aldol condensation reaction similar cross, but one of the
m is a ketone, then called the Claisen-Schmidt reaction.

O
OH
C O O
-
CH
H OH C C
H3C C CH3 H2 CH3
100°C
Propanon (aseton)
Benzaldehida
H
OH
O
O C
CH - H2O C C
C C CH3
H2 CH3 Panas
H

Reaction 2 occurs spontaneously because it is more stable

69
and because the reaction conditions
 Cyclizations via aldol condensation
• Internal aldol condensations (condensations where
both carbonyl groups are on the same chain) lead t
o ring formation.

70
The mechanism for cyclization via an aldol proceeds through an
enolate attack on the aldehyde carbonyl.
1. The hydroxy ion removes a hydrogen ion α to the ketone carbonyl.

2. The enolate ion attacks the aldehyde carbonyl, closing the ring.

71
3. The alkoxide ion abstracts a proton from water in an acid‐base reaction.

4. The base removes a hydrogen ion to form a resonance‐stabilized molecule.

72
 HALOGENATION OF KETONES
• Hydrogen α can be substituted by a halogen ketones thr
ough the formation of an enolate anion and activated eit
her by acidic or alkaline.

O O
H2
OH H C C CH3 H2C C CH3

O O
H2
Br Br H2C C CH3 Br C C CH3 + Br-

73
 Haloform formation reaction
• In alkaline, methyl ketones will react with halogens rep
eatedly to produce haloform (CHX3). This is because th
e H-α becomes more acidic with the inclusion of haloge
n, so that all the hydrogen methyl substituted into trihal
oketon.
• With the presence of a base as a nucleophile that attacks
the C-carbonyl ketones, causing interruption trihalomet
hyl fairly stable anion (negative charge distributed three
halogen) followed by proton transfer produces halofor
m and carboxylic acids.
74
Lanjutan......
O O
O H
H
H
- Br Br C Br
OH C
C H + Br-
H H
H

• Halogenated reaction as above take place until all H further

substituted, thus generated:
O O
O
Br
Br C Br
C
C -
OH C Br
C Br O H
+ C Br
OH
Br
Br Br

O O
Br
C Br C
O H C Br
+ C Br
+
O H
Br
Br 75
bromoform
 Cannizzaro reaction
• Only applicable for aldehydes that do not have the H
atom on the C atom next to the cluster that group
(formaldehyde and benzaldehyde derivatives).
• Ketones not react

CHO CO2H CH2OH

1. -OH, H2O
+
2. H3O+

Benzaldehyda Benzoic acid Benzil alcohol

76
 Mechanism of Cannizzaro reaction
O
O C
OH
C
O O H H
C C 1. (teroksidasi)
H OH OH
+
2. H3O+ H H
C
Intermediat OH
tetrahedral

(tereduksi)

Substitusi asil nukleofilik pada turunan asam karboksilat :

O O O
+ Nu + Y
C R C Nu C
R Y Y R Nu
77
Formaldehyde is the most easily oxidized aldehyde. When
mixed with another aldehyde that doesn’t have any alpha-
hydrogens and conc. NaOH, all of the formaldehyde is
oxidized and all of the other aldehyde is reduced.
Crossed Cannizzaro:

CH=O CH2OH

conc. NaOH
+ H2C=O + HCOO-
OCH3 OCH3
OH OH
vanillin
Conjugate addition in ,b-unsaturated carbonil group
- O O O
b
 C  C C C C C
C C C
pusat elektrofilik

Adisi langsung (adisi 1,2):

2
O O OH
+
Nu H3O
C C C
1 Nu Nu

Adisi konjugat (adisi 1,4):

4
O O O +
O
Nu H3O
3C C C C C C C C
C 1 C Nu C Nu C Nu
2
H
intermediat ion enolat 79
Nucleofilic addition of H2O: Hidration

O OH
H2O
R R' R OH
R'
suatu geminal diol

O OH
H2O
H3C CH3 H3C OH
H3C
Aseton (99,9%) Aseton hidrat (0,1%)

O OH
H2O
H H H OH
H
Formaldehida (0,1%) Formaldehida hidrat (99,9%)
80
 Hidration Mechanism
(1) Base catalyzed

O O OH
OH H OH
OH
OH OH

(2) Acid catalyzed

O OH OH OH
H OH2
H2O H2O
H H3O+
O OH
H

81
 Nucleofilic addition of HCN: Cianohidrin

O OH
HCN
R R' R CN
R'
suatu sianohidrin

• With pure HCN reaction is very slow

• With the addition of slightly alkaline or cyanide ion fast reaction

O O HO
CN CN
C N HCN
H H H C N

Benzaldehida Mandelonitril (88%)

(suatu sianohidrin)
82
 Nucleophilic Addition of Alcohols :
Acetal Formation
• Reactions of aldehydes with alcohols produce either hemiacetals (a
functional group consisting of one —OH group and one —OR group
bonded to the same carbon) or acetals (a functional group consisting of
two —OR groups bonded to the same carbon), depending upon
conditions.
• For example, the reaction of methanol with ethanal produces the
following results:

83
 Acetals and Ketals are formed by reacting two equivalents
of an alcohol with an aldehyde or ketone, in the presence of
an acid catalyst.
 Hemiacetals and Hemiketals are formed by reacting only
one equivalent of alcohol with the aldehyde or ketone in the
presence of an acid catalyst. Further reaction with a second
alcohol forms the acetal or ketal.
 A diol, with two –OH groups on the same molecule, can be
used to form cyclic acetals.
 All steps in acetal/ketal formation are reversible.
 O O H
+
H
C + ROH R C R'
R R'
O R
a hemiacetal

Aldehydes form hemiacetals faster than ketones

O H O R
+
H
R C R' + ROH R C R' + H 2O

O R O R
an acetal
(or ketal)

This reaction is also reversible. But, in this case, the equilibrium can
be driven to the right by an application of Le Châtelier’s Principle.
 OR OR

R H R R
OR OR
asetal ketal

OH OH

R H R R
OR OR
hemiasetal hemiketal
 Mechanism of Acetal Formation:
+ H
: O: H H
Cl :O
O :
+ +
R
O:
aldehyde/ketone
H
.. ..
O
R H .. ..
O
H H

Cl H
H + H
H + R
O :O + OH2 O:
R
O
R +
O+ H3O
.
.
Hemiacetal/
.. .. Hemiketal
O
R H

R
R
O:
O :
R+ +
O
H
R
O
3 +
O:
H Acetal/ .. ..
O Ketal
H H
Example Nucleophilic Addition of Alcohols
1. Formation of 2,2-Dimethoxy-propane
O Dry acid =
CH3 C CH3 O CH3 HCl gas
dry acid HCl in methanol
+ CH3 C CH3 HOTs

2 CH3OH O CH3

+ H2O
2. Formation of a Cyclic Acetal
O CH 2
O
CH 2
dry HCl O
+ H 2O
+

HO CH 2 CH 2 OH a 1,3-dioxolane

Ethylene glycol
1,2-Ethanediol
3. Cyclization of Monosaccharides
Carbohydrates contain the functional groups of alcohols and aldehydes or
ketones in the same molecule. They are polyhydroxyaldehydes or
polyhydroxyketones.
Thus they can form acetal-type products through the intramolecular
interaction of these functional groups.
As a model, consider the reaction:

H OH
O C
H+ CH 2 O
CH 2 CH 2 C
HO CH 2 CH 2 H CH 2 CH 2
CH 2
 O OH
H
1
H C 1C

2 2
H OH H OH

3 3 :O:
HO H HO H

4 4
H OH H OH

5 .. 5
H O H
..
6 H 6
CH 2 OH CH 2 OH

H
: O: O
a pyranose
O OH
ring
H H
6
.. H
O
O: H
H
a furanose
O ring
5 OH
 Addition of Organometallic Reagents
R R
slow
-
"R: " + C O R C O

R' R'
(from R-MgX)

H+
R, R' = H, alkyl, or aryl

R C OH

R'

The products of the addition are always alcohols.

Whatever is attached to the carbonyl group will be attached
to the resulting alcohol carbon.

H H

R M + C O R C OH

(M = Li or MgX) H H
formaldehyde primary alcohol

R R

R M + C O R C OH

H H
other aldehydes secondary alcohol

R R

R M + C O R C OH

R' R'
ketones tertiary alcohol
Nucleophilic Addition of Grignard (R-MgX)

+ MgX R MgX MgX

O O O
R
R

Tetrahedral intermediate

OH2 OH
+ HOMgX
R
An Alcohol
 Addition of Hydride Reagents

O
OH
O
":H-" H3O
C
R R' R C
fr:NaBH4 H R
R' H
R'