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8/18/2019 2.BAB II.2. ALKANOAT
1/46
ASAM KARBOKSILAT
( ALKANOAT )
O O O
R – C R – C R – C
O – H O – H O – H
datar Polar Elektron
menyendiri
....
....
. .
. .
. .
. .
δδ
δδ
δδ
δδ
++
++
– –
– –
8/18/2019 2.BAB II.2. ALKANOAT
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Aam Kar!okilat Biolo"i # Komeril
O
OCCH$
CO%H
Aam aetil aliilat
&i – CH$(CH%)'CH CH(CH%)'CO%H
Aam oleat (Aam lemak)
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O (CH%))CO%H
OH H
C C (CH%)*CH$
H H C
H OH Prota"landin E+ (P,E+)
(S-at- moderator akti.ita /ormon)
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KEASAMAN
Se!a"ai aam lema/
RCOOH 0 COOH OH 0 ROH O
CH$C 1 H%O
OH
O O
CH$C – O CH$C O 1 H$O
Terta!ilkan e&ara reonani
.
. .
.
....
....
....
.
.
.
. – –
– – .
. .
.
.
. .
.
....
....
.
.
.
. ++
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O
R – C – R – C
O
Pandan"an am2in" yan" men-n3-kkan t-m2an"tindi/ o2!ital 24
(Lone 2air e–
tidak dit-n3-kkan)
OO
OO
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TATA NAMA ASAM KARBOKSILATCl
HCO%H CH$CH%CHCO%H Aam Metanoat % – Kloro!-tanoat
HO%CCH%CO%H H$C CO%H Aam 2ro2anadioat Aam 25tol-at
CO%H
CO%H CO%H
Aam 2talat aam iklo/ekana
kar!okilat
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8/18/2019 2.BAB II.2. ALKANOAT
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O
CH% CHCO%H RC
O
Aam akrilat "-"- ailoki
CH$CH%CO%H Br
CH$CH%CHCO%H
al.a !romo !-tanoat
O O
R – C – CH$C –
,-"- ail "-"- aetil(A&5)
ββ αα
8/18/2019 2.BAB II.2. ALKANOAT
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O O
C – CH$CO –
"-"- !en6oil "-"- aetoki
(B6 –) (A&O –)
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SI7AT 7ISIS ASAM KARBOKSILAT
O 8 H – OCH$ C C CH$
O – H 8 OS-at- dimer ole/ ikatan /idro"en
O8 HCH$C O
O H
Ikatan /idro"en den"an H%O
Makin !anyak atom C9 titik didi/ makin tin""i4
..
..
....
.
.
.
.
.
.
.
.
HH
8/18/2019 2.BAB II.2. ALKANOAT
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PEMB:ATAN ASAM KARBOKSILAT
I4 HidroliiO O
CH$COCH%CH$ 1H%O CH$C 1 HOCH%CH$
OHEtil aetat eter aam aetat etanol
:m-m
O
R – C 1 H%O RCO%H 1 HOR;
O – R;
H /OHH /OH++ – –
8/18/2019 2.BAB II.2. ALKANOAT
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Amida
O
R – C 1 H%O RCO%H 1 HNR;% N – R;%
An/idrida
O ORC– O –C –R; 1 H%O RCO%H 1 HO%CR;
Halida aam
OR – C< 1 H%O RCO%H 1 <
H /OHH /OH++ – –
H /OHH /OH++ – –
H /OHH /OH++ – –
8/18/2019 2.BAB II.2. ALKANOAT
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Nitril
RC N 1 H%O RCO%H 1 NH$
O O O O O
RC–OR; R –C –< R–C –NH% R–C–O –C–R;
,-"- elektrone"ati.
O 8 O O8
R–C–< R–C–< R– C 1 < 8N- N- N-
8 N- H%O = < ,-"- elektrone"ati.
H1 ata- OH – e!a"ai katali (/al4+%)
H /OHH /OH++ – –
.
. .
.
.
. .
.
.... – –
(1)(1)
adisiadisi
(2)(2)
eliminasieliminasi
8/18/2019 2.BAB II.2. ALKANOAT
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Mekanime Hidrolii
O O
CH$C< 1 H%O CH$– C – < 1OH%
O O
CH$– C 1 < CH$ – C 1 H
1OH%
OH
.
. .
.
.
. .
.
.... .
. .
.
....
....
– –
. . . .
....
....
++........
.
. .
.
eliminasieliminasi
LepasnyaLepasnya
protonproton – –
8/18/2019 2.BAB II.2. ALKANOAT
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II4OKSI>ASI
Alko/ol 2rimer 8 RCH%OH RCO%H
O
Alde/id 8 RCH 1 ?O@ RCO%H
Alkena 8 RCHCR % RCO%H 1 R %CO
Alkil Arena 8 Ar – R ArCO%H
O
Metil keton 8 RCCH$ 1
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Okidai alko/ol
5 Okidator /ar- k-at (H%CrO*)
5 Tak !ole/ ada "-"- yan" terik-t diokidai4
Okidai alkena
5 Okidator lema/ (A"1)
Okidai alkena
HO%CCH%CH%CH%CH%CO%H
Siklo/ekana Aam /ekanadionat(aam adi2at)
okidator k-at
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Okidai alkil!en6ena
NO% NO%
O%N CH$ O%N COOH
NO% NO%%9$9 – trinitrotol-en aam %9*95trinitro!en6oat
alkil 2en"ara/ o92 5 C 2en"ara/ meta
,ri"nard R< RCO%H
R< 1 M" RM"< RCO%H
OO
1.1. Mg, eter Mg, eter
2. CO2. CO22. H. H22O, HO, H
++
eter eter COCO22
HH22O, HO, H++
HH22CrOCrO!!
"alor "alor
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7AKTOR AN, MEMPEN,AR:HI K:AT ASAM
A4 Keelektrone"ati.an
C N O 7
Meni"katnya keeletrone"ati.an -n-r
R $C – H R $N – N RO – H 7 – H
Naiknya k-at aam
R $C – R %N RO 7
Naiknya k-at !aa dari !aa kon3-"ai
– – – – – – – –
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B4 :k-ran
7 Cl Br I
Bertam!a/nya 3ari53ari ion
H7 HCl HBr HI
2Ka $9* 5' 5 59
Naiknya k-at aam
– – – – – – – –
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C4 Hi!ridiai
2$ 2% 2
5 Karakter or!ital /i!rid !ertam!a/5 Kelektrone"ati.an C !ertam!a/
5 Polarita C – H !ertam!a/
5 K-at aam !ertam!a/
CH$CH$ CH% CH% CH CH
2Ka D D* D%
Naiknya k-at aam
CH$CH% CH%CH CH C
Naiknya k-at !aa (!aa kon3-"ai)
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>4 E.ek Ind-ki
CH$CO%H ClCH%CO%H
2Ka *9' aam kloroaetat 2Ka %9F+
O O
Cl CH% – C Cl CH%– COH O
m-atan G 1 !erdekatan !erdekatan
mendeta!ilkan aam menta!ilkan anion
O O
CH$C ClCH%C
OH OH
##
## ## ## – – ##++
– –
– –++ ++
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CH$– H – CH%CH – C)HB–
HO – CH$O – I – Br – Cl –
Naiknya daya menarik elektron
CH$CH%CO%H CH$CO%H CH%CHCH%CO%H
C)HBCH%CO%H HNOCH%CO%H ClCH%CO%H
Bertam!a/ k-at aam
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E4 Sta!ilita Reonani
ROH ArOH RCO%H ArCOOH
2Ka + – + + *9%K-at aam die!a!kan ta!iliai
Reonani anion
RO m-atan ne"ati. tidak didelokalkan
O
RC m-atan ne"ati. di!a"i ama rata ole/ % atom O
O
O m-atan ne"ati. e!a"ian die!arkan
(delokal) ole/ aan π arokatik (men"-ran"i k-at aam)
– –
– –
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74 SolJai
Molek-l 2elar-t menta!ilkan anion den"an &ara
menye!ar m-atan ne"ati. leat antaraki di2ol5di2ol4
>era3at olJai anion α k-at aam
H%o9 CH$CH%OH
Naiknya olJai (ion dalan air 0 etanol)
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,4 Pen"ar-/ S-!tit-en Pada A Ben6oat
Ben6oat 8 O O
C – O C O
7enol 8
O O
O O
....
........
.
. .
.
.
. .
.
........ ..
.
.
.... . . . .
– –
....
....
.
.
.
.
..
..
.....
.
.
.
.
.
.
.
. . . .
– –
....
.
.
.
.
. . . .
.
.
.
.
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Aam aetat 8
O O
CH$C – O CH$C O
5 M-atan ne"ati. tidak da2at didelokaliaikan e&ara
e.ekti.45 Cin&in !en6ena tidak men"am!il !a"ian -nt-k ta!ilita
reonani "-"- kar!okilat4
5 S-!tanit-en 2ada &in&in mem2en"ar-/i keaaman ole/
e.ek ind-kti.45 ,-"- 2enarik elektron menaikkan keaaman4
. . .
. . . .
.
............
– –
.
. .
.
.
. .
.
.... – –
.... . . . .
8/18/2019 2.BAB II.2. ALKANOAT
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Cl Cl
CO%H 0 CO%H 0Cl CO%H0Ben6oat
K-at aam men-r-n
< 2ada orto menaikkan k-at aam
O%N CO%H NO% CO%
terdeta!ilkan ole/ terdeta!ilkan ole/
2enarikan elektron 2enarikan elektron
– –δδ ++
δδ ++
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HO CO% HO CO%
HO CO% HO CO%
M-atan ne"ati. !erdekatan
2en-r-nan k-at aam
. . . .
. . . .
– – – –++
. . .
. – –
++
.... . . .
. – – – – ++
.... – –
.
.
..
– –
8/18/2019 2.BAB II.2. ALKANOAT
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Reaki Aam Kar!okilat
HCOOH 1 Na1OH5 HCOO5Na1 1 H%O
Aam 7ormat Na4 .ormat
Aam !aa "aram
NH% NH%
HO%CCH%CH%CHCO%H HO%CCH%CH%CHCO%5 Na1
Aam "l-tamat Monotri-m"l-tamat
Aam amino at 2enyeda2(MS,)
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C)HB
CH$COO 1 CH% – Br C)HBCH%O%CCH$ 1 Br
Ion aetat Ben6il!romida Ben6ilaetat
(N-kleo.il) (S-at- eter)
O O
CH$C 1 HCO$ CH$C 1?H%CO$@ H%O1CO%
OH O
Aetat 0 kar!onat da2at !ereaki
(le!i/ aman)
– – – –
– –
– –
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>alam NaHCO$8
RCO%H RCO% 1 CO% 1 H%O
ArOH dan ROH tidak ada reaki yan" !erarti
>alam NaOH 8
RCO%H RCO% 1 H%O
ArOH ArO 1 H%O
ROH tak ada reaki yan" !erarti
HCOHCO
HCOHCO – –
– –
– –
OHOH – –
OHOH – –
OHOH – –
– –
– –
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ESTERI7IKASI
O O
RC 1 R;OH RC 1 H%O
OH OR; Aam Alko/ol Eter
HH++ , "alor , "alor
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Mekaniame 8
O OH OH
RC – OH RC – OH RC – OH R;O – H
OH OH RC – OH RC – OH%
R;O R O
OH OH O
RC RC RCOR;
R;O R;O
.
.
.
..
.
.
.
....
....
.
.
.
.
....
............
++HH++ $OH$OH
++ ........
....
.....
.
.
.
HH++ ++HH++ % H% H22OO.........
.
.
.........
.....
.
.
.
++
++.
.
.
.
.....
.
.
.
....
.
.
.
.
. . . . ....++
%%HH++
.
.
.
.
.
.
.
.
. . . .
. . . .
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B-kti den"an Ioto2
O OH
COH 1 CH$OH C OH
OCH$
O
C – OCH$ 1 H%O
1&1&
1&1&
'"atan C – O tida" pts'"atan C – O tida" pts
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Kereakti.an Alko/ol >an Aam Kar!okilat
R
R – C –OH R –CH –OH R –CH%OH CH$OH
R R
Bertam!a/nya kereakti.an
R $CCOOH R%CHCOOH RCH%COOH
CH$COOH HCOOH
Bertam!a/nya Kereakti.an
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Red-ki Aam Kar!okilat
CH$CO%H CH$CH%OH
aam aetat etanol
CO%H CH%OH
Aam Ben6oat
O
5 Sem-a "-"-kar!onil – C da2at tered-ki
5 Tidak !ia den"an 2ered-ki !iaa
5 Aam kar!okilat !erada 2ada okidai tertin""i
1. LilH1. LilH!!
2. H2. H22O, HO, H
++
1. LilH1. LilH!!
2. H2. H22O, HO, H++
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Aam Kar!okilat Poli.-n"ional A4 Keaaman Aam >i!aa
HO%CCH%CO%H 1 H%O HO%CCH% 1 H$O1
Aam malonat
2K + %9F$
HO%CCH%CO% 1H%O O%CCH%CO% 1H$O1
2K + 9Ion H1 2ertama le!i/ m-da/ le2a
– –
– – – – – –
B P ! k A /id id
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B4Pem!ent-kan An/idrida
O O O O
RC – OH 1 HO – CR RC – O – C – R 1 H%O
Aam mono !aa
CH%C O O
1 CH$C–O– C– CH$
CH%C
OO
OHOHOO
OHOH
sam s"sinat sam s"sinat
*oliasa*oliasa
nidrida s"sinat nidrida s"sinat
(-)(-)
O
O
O
+ CH3 CH
O
2
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C4>ekar!okilai (β5keto dan β5di aam)
O O O
RCCH%COH RCCH$ 1 CO%
Aam β5keto keton
H O C CH2 C OH
OOCH3 C OH
O
Beta dwi asam
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Mekanime
H H O
O O O O OH CRC CO RC CO RC O
C C CH%
O
R – CCH$
O O OH – OC – CNCOH CH$CH%CH%COH 1 CO%
CH%CH$
Aam etilmalonat Aam !en6oat
.
. .
.
. . . .
.
.
.
.
. . . . ....
.
.
.
.
....
.
.
.
.
. . . .
. . . .
. . . .
. . . . .
.
.
.
. . . .
enolenol .
. . .
. . .
.
. .
. .
.
.
.
.
0eadaan transisi0eadaan transisi
ββ%iasa%iasa
HH22 HH22
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>ekar!okilai Aam α5Kar!onil
O O
HOC – COH HCO%H 1 CO%
Aam okalat Aam .ormat
O O O
CH$C – C – OH CH$CH 1 CO%
Aam 2ir-.at Aetalde/id
5 Biaa den"an en6im katali
en3imen3im
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>4 Aam Kar!olilat Tak en-/ α9 β
O O
C N 1 CH%CH– C –OH NCCH%CHCOH
O
NCCH%CH%CO
Reaki adii +9*
H CO%H NH$
NH$ 1 C C O%CCHCH%CO%H
HO%C H
.... ....
.
.
.
..
.
.
.
enolenol
. . . . . .
. .
.
. .
.
.
. .
.
.... – –
.
.
.
..
.
.
.
....
....
.
.
.
. – –
++
– –4H4H
!!ClCl
1&51&5
sam 6marat sam 6marat sam aspartat sam aspartat
(asam amino)(asam amino)
> i. t A K ! k il t
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>eri.at Aam Kar!okilat 8
Adala/ enyaa yan" da2at men"/ailkan AamKar!okilat !ila !ereaki den"an air4
O O
CH$COCH%CH$ 1 H%O CH$COH 1 HOCH%CH$Etil aetat ↑ Aam aetat
O
CH$CONH% 1 H%O 1 H1 CH$COH 1 NH*1
Aetamida ↑ Aam aetat
O O O O O
R5C5OR R5C5Cl R5C5NH% R5C5O5C5R RCN
HH++
7gs 8le"tronegati6 7gs 8le"tronegati6
! k l
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>eriJat Aam Kar!okilat Aromati
O
CO%CH$ CO – Cl CNH%
eter Halida aam Amida
CH$
O
( CO)%O O O CN
O
CH$ An/idrida an/idrida ikli Kantaridin Nitril
(pada lalat 9payol)(pada lalat 9payol)
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