2.bab ii.2. alkanoat

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

++

++

– –

– –


2/46

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)


3/46

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)


4/46

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

.

. .

.

....

....

....

.

.

.

. – –

– – .

. .

.

.

. .

.

....

....

.

.

.

. ++


5/46

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


6/46

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


7/46


8/46

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


9/46

O O

C – CH$CO –

"-"- !en6oil "-"- aetoki

(B6 –) (A&O –)


10/46

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


11/46

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++ – –


12/46

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++ – –


13/46

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


14/46

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 – –


15/46

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


16/46

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


17/46

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


18/46


19/46

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

– – – – – – – –


20/46

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

– – – – – – – –


21/46

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)


22/46

>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

##

## ## ## – – ##++

– –

– –++ ++


23/46

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


24/46

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)

– –

– –


25/46

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)


26/46

,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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.

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..

..

.....

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.

.

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. . . .

– –

....

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.

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. . . .

.

.

.

.


27/46

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

. . .

. . . .

.

............

– –

.

. .

.

.

. .

.

.... – –

.... . . . .


28/46

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 ++


29/46

HO CO% HO CO%

HO CO% HO CO%

M-atan ne"ati. !erdekatan

2en-r-nan k-at aam

. . . .

. . . .

– – – –++

. . .

. – –

++

.... . . .

. – – – – ++

.... – –

.

.

..

– –


30/46

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,)


31/46

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)

– – – –

– –

– –


32/46

>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 – –

– –

– –


33/46

ESTERI7IKASI

O O

RC 1 R;OH RC 1 H%O

OH OR; Aam Alko/ol Eter

HH++ , "alor , "alor


34/46

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.........

.

.

.........

.....

.

.

.

++

++.

.

.

.

.....

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.

.

....

.

.

.

.

. . . . ....++

%%HH++

.

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.

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.

.

. . . .

. . . .


35/46

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


36/46

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


37/46

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++


38/46

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


39/46

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


40/46

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


41/46

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

.

. .

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. . . .

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. . . . ....

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....

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. . . . .

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. . . .

enolenol .

. . .

. . .

.

. .

. .

.

.

.

.

0eadaan transisi0eadaan transisi

ββ%iasa%iasa

HH22 HH22


42/46

>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


43/46

>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


44/46

>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


45/46

>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)


46/46

2.bab ii.2. alkanoat

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