11 Asam Karboksilat Dan Turunannya
11 Asam Karboksilat Dan Turunannya
11 Asam Karboksilat Dan Turunannya
O O O
R C
R-C R C OH
H R
ALDEHID KETON ASAM KARBOKSILAT
O O
O O R C O C R O
R C R C R C
OR Cl
NH
ESTER HALIDA ASAM ANHIDRIDA ASAM KARBOKSILAT AMIDA 2
SENYAWA KARBONIL
• Tata nama : IUPAC dan TRIVIAL
• Reaksi-reaksi
• Manfaat
ASAM KARBOKSILAT &
TURUNANNYA
• Strukturnya : O
R C
OH
ASAM KARBOKSILAT
O O
O O R C O
R C R C O C R R C
OR Cl
NH2
ESTER HALIDA ASAM ANHIDRIDA ASAM KARBOKSILAT AMIDA
Asam Karboksilat
• Struktur :
O
R C
OH
ASAM KARBOKSILAT
Cl 2-Chloropentanoic acid
-Chlorovaleric acid
Penamaan
O
2-Methylpropanoic acid
O 4-Aminobutanoic Acid
H2N CH2 CH2 CH2 C -Aminobutyric Acid
“GABA”
OH
m o
More Naming
3 2
O
1
p 4 C OH
5 6 Benzoic acid
m o Benzenecarboxylic acid
C OH
O Cyclohexanecarboxylic acid
Penamaan Trivial
O O O
H C OH CH3 C OH CH3 CH2 C OH
Formic acid Acetic Acid Propionic Acid
O O
CH3 CH2 CH2 C OH CH3 CH2 CH2 CH2 C OH
Butyric Acid Valeric Acid
O
CH3 CH2 CH2 CH2 CH2 C OH
Caproic Acid
O
H3C C C C C C C OH
Reaksi-reaksi Asam Karboksilat
• Reaksi Pembuatan
Oksidasi
Oksidasialkohol
alkoholprimer
primerdan
danaldehid
aldehid
[O] [O] [O] [O]
• R - CHR2OH
- CH2OH R- CHOR- CHO R - COOH
R - COOH
• alkohol
alkohol primerprimer aldehid
aldehid asamasam karboksilat
karboksilat
• K2Cr2O7
K2Cr2O 7
• CH3CH CH3CH2OH + 2 [O] CH3COOH + H2O
2OH + 2 [O] CH3COOH + H 2O
•
etanoletanol H2SOH2SO4
4 asam asam asetat
asetat
• K2Cr2O7
K Cr O
• CH3CHO + [O] 2 2 7 CH3COOH
• CH3CHO + [O]
asetaldehid H2SO4 CH3COOH
asam asetat
asetaldehid H2SO4 asam asetat
Oxidation of Primary Alcohols
with KMnO4
O
KMnO4
R CH2 OH R C H
heat
KMnO4
two -hydrogens
heat
O
R C OH + MnO2
precipitate
Oxidation of Primary Alcohols
with K2Cr2O7
K2Cr2O7 O
R CH2 OH R C H
H2SO4
K2Cr2O7
H2SO4
O
R C OH + Cr3+
Oxidation of Side Chains
O
R C OH
KMnO4
heat + n CO2
Example O
CH2 CH3 C OH
KMnO4
O CH3 O CH3
Carbonation of Grignard Reagents
( or Alkyllithium Compounds )
O
+
R MgX + CO2 R C O MgX
ether
( R-Li )
H3O+
O
R C OH
+ MgX(OH)
Formation of Nitriles and Hydrolysis
_ DMSO
R CH2 Cl + : C N: R CH2 C N + Cl
H2SO4 H 2O
SN2 heat
O
+
R CH2 C OH + NH4
SYNTHESIS OF CARBOXYLIC ACIDS
( DUE TO LACK OF SPACE REACTION CONDITIONS ARE ABBREVIATED)
( benzene = R
R C C R R' sidechain = R’ )
R R
KMnO4
KMnO4
R CH2 OH
H H KMnO4
CrO3
or KMnO4
H2SO4
O O
CrO3 H2O
R C H R C OH R C N
H2SO4 H2SO4
DIBAL or
NaCN
Rosenmund H2O CO2 KMnO4 acetone
O
H2SO4 R Li R X SOCl2
Li or
R C Cl H2O or Mg R OH
Chap 19 O R Mg X
R R
R C OR
H H
This is all stuff you know! OH OH
b. Reaksi Haloform
• Hidrogen α pada metil keton dioksidasi
dengan X menghasilkan asam karboksilat
Contoh :
O O O
_ _ Cl2 _ NaOH _ _ - +
R C CH3 R _ C CCl3 R C O Na + CHCl3
O Na _ karboksilat
Cl2
CH3CH2CCH3 CH3CH2COONa + CHCl3
etil-metil keton NaOH Na-propionat kloroform
c. Hidrolisa Ester
• Ester dihidrolisa akan menghasilkan asam
karboksilat :
HCl/
R COOR' + H2O RCOOH + R'OH
H2SO4
O
2. Substitusi Hα
H/ Cl
H3C u.v.
C COOH + Cl2 H3C C COOH + HCl
H H
asam / -kloro propionat
Reaksi-reaksi lain Asam karboksilat
1. Esterifikasi
Contoh : HCl/H2SO4
CH3COOH + CH3OH CH3COOCH3 + H2O
asam asetat metanol metil asetat
O metal -oate
CH3CH2CH2CH2 C - +
O Na
sodium pentanoate
O
- +
O K
potassium benzoate
potassium benzenecarboxylate
The Fatty Acids
O O O
CH3 (CH2)10 C OH CH3 (CH2)12 C OH CH3 (CH2)14 C OH
O
CH3 (CH2)4 CH CH CH2 CH CH (CH2)7 C OH
Linoleic acid
O
CH3 CH2 CH CH CH CH CH2 CH CH (CH2)7 C OH
Linolenic acid
Carboxylic Acid Derivatives:
Nucleophilic Acyl Substitution
SOME ACYL COMPOUNDS
ACID DERIVATIVES
O carboxylic O O O
acid
R C OH R C NH R C NH R C N R''
2
O R' R'
acid
primary secondary tertiary
R C Cl chloride
amides
O O O
ester anhydride
R C OR' R C O R'
2)
.. - elimination of
:O: leaving group : O:
R C Y R C + Y: -
carbonyl group Nu Nu
forms again
most aren’t this simple, proton
transfers are usually required
REACTIVITY OF CARBONYL COMPOUNDS
most reactive least reactive special case
( acidic H )
-I +I +R
O O O O
..
R C Cl R C H R C O R' R C OH
..
O O O O OH-
..
R C O C R R C R' R C NH2
O
no catalyst R C O
acid catalyst acid catalyst
required
required required acid required
Not acid with weak (base may be (in the conjugate
derivatives; nucleophiles used for base C=O is
different only hydrolysis) deactivated)
chemistry.
REACTIVITY IS ALSO REFLECTED IN (not considering
THE STABILITY OF THE LEAVING GROUP acid catalysis)
MOST
REACTIVE
O
R C Cl Cl
-
O O O
R C O C R
-O C R
O
R C O R' - O-R’
O
-
R C NH2 NH2
STRONGEST
BASE
EVERYTHING CAN BE MADE FROM THE ACID (CHLORIDE)
R CH2 OH R C N
RMgX + CO2
R C O
O
H
R C OH
NaOH
O O
R C O R' H2O SOCl2 R C O
Na+
O
R’OH
“ACID R C Cl
DERIVATIVES”
O NH3
R C NH2 NR’2H O O
O R C O C R
R C NR'2
…. or the anhydride
ESTER
• Struktur
O O
R-C atau R-C atau R - COOR' atau R - CO - OR'
OR' O - R'
isopropyl benzenecarboxylate
isopropyl benzoate
O CH3
CH2 C O C CH3
CH3
tert-butyl phenylethanoate
ESTERS
H
O
C
O CH
3
methyl cyclohexanecarboxylate
Reaksi-reaksi Ester
• Esterifikasi
R-COOH +R’OH/H+ RCOOR’ +H2O + H+
+
O OH OH
CH3C OH + H
+
CH3 - C - OH CH3 - C - OH
H3CO H
CH3O: +
H
+
O OH : OH
+
- H +
CH3 - C - OCH3 CH3 - C - OCH3 - -
CH3 C OH
2
+ H2O H3CO
Fischer Esterification
+
O H O
R C OH + R OH R C O R
EQUILIBRIUM
+ O
The equilibrium position H H
is usually about 50/50
unless shifted by using
an excess of a reactant
or removing water.
ECONOMICS: use an
excess of the cheaper
starting reactant.
Fischer Esterification
MECHANISM
O Na+ _ O Na+
R C O R + OH R C O + R O H
heat
Acidic Solution
O H2SO4 O
R C O R + H2O R C OH + R O H
heat
excess
O
.. _ ..
:
.. + H O
R C O .. R'
Hydrolysis of an Ester in Acid
+ H2SO4 / H2O
H3 O+ H O: ..
..
R C O H O:
.. R' slow
..
R C O .. R'
.. +
H O.. H
H O
.. H
+
H-OH2 + .. ..
..
H O: H O H H O:
proton .. .. .. +
R C O .. R' R C O .. R' R C O R'
transfers + :
H O.. H H O.. : H O
.. H
OH2
.. + ..
H O: H O: O:
..+ .. ..
R C O R' R C + : O R' R C O
.. H
H O : H
.. : H
H O ..
+ H 3O +
Reaksi Transesterifikasi dan
Miscellaneous
1. Transesterifikasi
CH3COOC2H5 + CH3OH CH3COOCH3 + C2H5OH
asam /basa
2. Miscellaneous
O O
basa
CH3- C - Cl + CH3OH CH3- C - OCH3 + HCl
klorida asam metanol metil asetat
O
CH3 - C O
O + CH3OH CH3- C - OCH3 + CH3COOH
CH3 - C metanol metil asetat asam asetat
O
anhidrida
asam asetat
O
CH3COOH + CH2N2 CH3- C - OCH3 + N2
asam asetat diazometana metil asetat
Transesterification
+
O H O
R C O R + R OH R C O R
+ O
mechanism is similar to H R
the Fischer Esterification
EXAMPLE
O O CH3
C O CH3 + C O CH
H CH3
+ +
heat
CH3 CH OH CH3 OH
CH3
excess
SIFAT-SIFAT FISIKA ESTER
• Suku rendah (atom C < 10 ) berupa cairan, berbau
harum, mudah menguap dan biasanya banyak terdapat
dalam buah-buahan
• suku tinggi (atom C>10) berupa padatan seperti lilin dan
tidak berwarna.
• Titik didih etil dan metil ester lebih rendah dibandingkan
dengan asamnya.
• Ester dengan berat molekul kecil larut dengan baik
dalam air. Kelarutan dalam air berkurang dengan
bertambahnya rantai karbon.
• Ester larut dalam pelarut organik seperti etanol, eter,
benzena dll.
SIFAT-SIFAT KIMIA ESTER
1. Terhidrolisa menghasilkan As. Karboksilat
O +
H
CH3 - C - OC2H5 + H2O CH3COOH + C2H5OH
etil asetat asam asetat etanol
O
NaOH
CH3 - C - OC2H5 + H2O CH3COONa + C2H5OH
etil asetat Na-asetat etanol
O OMgX OH
CH3 - C - CH3 CH3 - C- CH3 H2O CH3 - C - CH3
+ CH3MgX
aseton CH3 CH3
t-butanol
Reaction of Esters
with Organometallic Reagents
O 1) ether
R C O R" + 2 R' MgBr
2) H2O, acid
OH
R C R' + MgBr (OR") + MgBr(OH)
R'
cleaves the ether ….
reacts twice !
Reduksi Ester
• Ester direduksi dengan senyawa litium
LiAlH4 akan menghasilkan alkohol
O
LiAlH4
C3H7 - C - OCH3 + 4H C3H7OH + CH3OH
metil butirat n-propanol metanol
Reduction of Esters
O
C R'
4 R O 4 R CH2 OH + 4 R' OH
+ 2 LiAlH4
+ 2 LiOH + 2 Al(OH)3
Reduction of Esters to Aldehydes
O O
DIBALH H2O
R C R C
toluene HCl
O R' -78°C H
+ R' OH
AMIDA (R-CONH2)
• Strukturnya :
O
R - CONH2 amida primer atau R C
NH2
O
R - CONHR' amida sekunder atau R C
NHR'
O
R - CONR2 amida tersier atau R C
NR2
Tata Nama
1. Sistem penamaan IUPAC menyatakan bahwa rantai induk deret
homolog alkana, akhiran “a” diganti dengan “amida”
2. Penamaan trivialnya hampir sama dengan sistem penamaan
pada asam karboksilat yang mana akhiran “at/oat” diganti dengan
amida dan menghilangkan kata asamnya.
3. Bila substituennya ada pada N maka substituen tersebut diberi
notasi N (satu substituen) atau N,N (dua substituen).
Contoh :
O O Cl O
CH3CNH2 CH3CH2CH2CH2CNHCH3 CH3CHCN(CH3)2
aset amida N-metilpentamida N,N-dimetil-2-kloro-
(N-metilvaleramida) propanamida
Reaksi-reaksi Amida
1. Reaksi Pembuatan
RCOOH + NH3 RCONH2 + H2O
CH3COOH + NH3 CH3CONH2 + H2O
CH3COCl + NH3 CH3CONH2 + HCl
2. Reaksi Hidrolisa
RCONH2 + H2O/H+ CH3COOH + NH3
3. CH3NH2 + HCl CH3NH3+Cl-
Hydrolysis of Amides
Basic Solution
O Na+ _ O Na+
R C NH2 + OH R C O + NH3
heat
Acidic Solution
O H2SO4 O
R C NH2 + H2O R C OH + (NH4)SO4
heat
excess
: O: : O:
.. _
.. .. _ ..
R C OH + : NH2 R C O : + NH3
.. ..
accumulates
Acid-catalyzed Hydrolysis of a Amide
+ .. ..
:O H :O H +
.. .. H-OH2
4) R C NH2 R C NH2
+ :O H
..
O
H .. H H
OH2
.. H ..
:O H + :O H
:O H +
5) R C NH2 R C NH2 H
+ :O H R C NH2
:O H
:O ..
H .. H
.. +
:O H :O H
+ R C OH + :NH3
6) R C NH3
:O
.. H
O
+
R C OH + NH4
Manfaat Amida
Obat-obatan sulfa merupakan Sulfonamida yang mana
nitrogen terikat pada suatu gugus sulfonil. Suatu sulfonil dibuat
dengan mereaksikan suatu arilsulfonilklorida pada amonia primer
atau sekunder :
ArSO2Cl + R2NH ArSO2NR2 + HCl
Benzenasulfonil Sulfonamida
IUPAC
O
an acyl group
R C -oyl
Common
“oh-wheel”
O
ethanoyl -yl
CH3 C acetyl
“eel”
O
O O
C
CH3CH2CH2 C CH3 C Cl
Cl Cl
butanoyl chloride ethanoyl chloride benzoyl chloride
butyryl chloride acetyl chloride
Preparation of an Acid Chloride
O benzene O
R C OH + SOCl2 R C Cl + O S O
or “neat”
+ H Cl
thionyl chloride
( a liquid )
Hydrolysis
O O
R C Cl + H2O R C OH + H Cl
Acid
O O
R C Cl + R OH R C O R + H Cl
Ester
O R O R
R C Cl + H N
+
+ R2NH2 Cl
-
R C N
R R
2 equivalents Amide
ACID CHLORIDES
..
-
- .. O
O: : O:
R C .. R C .. +
Cl : + Cl: R C
.. O ..
.. R' ..
H Cl
R' O
.. H very reactive
no catalyst needed
water or alcohol
.. ..
O: O: .. -
R C .. R C .. : Cl
.. :
O
.. R' + O R'
H
H .. - ..
: .. : O R'
O + R' Cl H ..
H ..
Anhidrida Asam Karboksilat
• Tata Nama
Anhidrida yang gugus asilnya sama (simetris) diberi nama dengan
menambahkan kata anhidrida di depan nama asam karboksilat
induknya.
CH3COOOCCH3 CH3CH2COOOCCH2CH3
CH3COOOCCH2CH3
IUPAC : anhidrida etanoat propanoat
TRIVIAL : anhidrida asetat propionat
Preparations of an Acid Anhydride
best
O O method O O
R C Cl + R C O Na R C O C R
NaOH
O P 2 O5 heat
R C OH
O
The acid chloride and the acid
may be reacted directly to form 2 R C OH
the anhydride, but the reaction
usually gives a better yield if This method works
the carboxylate salt is used best with small MW
(shown above). liquid acids or
O O diacids that can
R C O C R make a cyclic
anhydride.
+ HCl
Formation of Cyclic Anhydrides
O O
OH heat
O + H2O
OH
Geometry is
O O important in
forming cyclic
phthalic acid phthalic anhydride anhydrides.
O O
heat Linear anhydrides
OH are usually not
O + H2O
OH made by this
maleic method.
O cis O maleic
acid anhydride
O
trans OH
fumaric
acid HO no reaction
heat
O
ACID ANHYDRIDES
ARE ALMOST AS REACTIVE AS ACID CHLORIDES
NO CATALYST REQUIRED
2 equivalents
O O Hydrolysis O
O
R C O C R + H-OH + HO C R
R C
OH
Acid
O O O
O
R C O C R + R’-OH + HO C R
R C
OR'
Ester
O O R O R O
.. ..
R C O C R + H N R C N + -O C R
R R +
R2NH2
2 equivalents Amide
Reaksi-reaksi
• Reaksi Pembuatan
• Reaksi Hidrolisis
• Reaksi dengan Alkohol
• Reaksi dengan Amina/amonia
Reaksi Pembuatan
• Pembuatan anhidrida biasanya tidak bisa
langsung mempergunakan 2 molekul asam
karboksilat akan tetapi dipergunakan suatu
turunan asam karboksilat dengan asam
karboksilat/ion karboksilat.
RCO-OH + H-OOCR’ RCOOOCR’+ H2O
(reaksi di atas jarang terjadi)
RCOCl + -OOCR’ RCO-OOCR’ + Cl-
CH3COCl + -OOCCH3 CH3CO-OOCCH3+Cl-
(reaksi di atas sangat mudah terjadi)
Reaksi Hidrolisis