1.bab i.2.aldehid keton
DESCRIPTION
PRESENTASITRANSCRIPT
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RENCANA PROGRAM KEGIATAN
PEMBELAJARAN SEMESTER
JURUSAN KIMIA
FAKULTAS MATEMATIKA DAN ILMU PENGETAHUAN ALAM
UNIVERSITAS GADJAH MADA
2007
KIMIA ORGANIK DASAR II (MKS – 2402, Semester II)
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BAB I
ALDEHIDA DAN KETON
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PENDAHULUAN
Cara mudah mempelajari ilmu kimia
organik
1. Harus memahami prinsip dasar
NUKLIOFILIK DAN ELEKTROFILIK
2. Pemutusan ikatan heterolitik dari gugus
karbonil ( )
3. Prinsip reaksi kimia adalah patuh pada
konsep berpasang-pasangan.
C
O
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(
ALKANAL)
1.1 PENDAHULUAN ALDEHID DAN KETON
aldehid aromatik
aldehid siklik
H C H
OC H
O
C H
O
ALDEHIDA C
O
GUGUS FUNGSI KARBONIL
R C H
O
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KETON (ALKANON )
O
R – C keton alifatik
R
O
R – C aril alkil keton
Ar
O keton siklik
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1.2 TATA NAMA ALDEHIDA DAN KETON
Dalam sistem IUPAC tatanama aldehid
dan keton diturunkan dari nama alkana
dengan mengubah huruf akhir (a) pada
nama induk alkana menjadi akhiran al.
Gugus aldehida (CHO) selalu diberi nomor
satu (1). Berarti penomoran pada senyawa
aldehida selalu dimulai dari gugus CHO
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1.2 TATA NAMA ALDEHID DAN KETON
ALDEHIDA (ALKANAL)
# Akhiran a (alkana) al (aldehida)
CH3CH3 etana
O
CH3 – C etanal (asetaldehid)
H
CH3CH2CH3 propana
O
CH3 CH2 – C propanal (propionaldehid)
H
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#Penomoran dimulai dari C karbonil
O
CH3– CHCH2CH2C 4-metilpentanal
CH3 H
O
CH3– CH=CH – C 2-butenal
H
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# Rantai utama siklik diberi akhiran
karbaldehid
O
C siklobutanakarbaldehid
H
O
C benzenakarbaldehid
H (benzaldehid)
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KETON # Akhiran a (alkana) on (keton)
O O
CH3– C – CH3 CH3– CH2– C – CH2– CH3
propanon (aseton) 3-pentanon (dietil keton)
O O
CH2=CH – C – CH3 C
CH3
3-buten-2-on asetofenon
(metil fenil keton)
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HUBUNGAN NAMA TRIVIAL ALDEHIDA DAN ASAM KARBOKSILAT
Asam karboksilat Aldehida
CH3COH asam asetat
OCH3CH asetaldehid
O
CH3CH2COH asam propionat CH3CH2COH propionaldehid
O O
CH3CH2CH2COH asam butirat CH3CH2CH2CH butiraldehid
O O
CH
O
C
O
OH asam benzoat benzaldehid
OO
HCOH asam format HCH formaldehid
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CH3-CH2-CH2-CHO
karbon ϒ karbon β karbon α
CH3COCH2COCH3
Suatu β diketon
CH2 CH2 CH
OCH3CH2CH
O
3-fenilpropanal
β fenilpropionaldehida
2-bromopropanal
α- bromopropionaldehida
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1.3 ALDEHID DAN KETON YANG
SERING DIJUMPAI
O
1. Formaldehid HC
H
Kat Ag
- Pembuatan : 2CH3OH 2 HCOH 600-700°
- Bentuk gas, karsinogen
- Disimpan dalam bentuk formalin (37%) ; sebagai dissinfektan
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2. Asetaldehid
- Pembuatan :
Pd - Cu O
2 CH2=CH2 + O2 2 CH3 C
200-300° H
O
3. Aseton CH3 C
CH3
- Pembuatan : oksidasi isopropil alkohol
- Sebagai pelarut
CH3 C H
O
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1.4. ALDEHID DAN KETON DI ALAM
O CH3 O O
C HO C
H H
benzaldehid vanilin
CH3 CH3
CH3 O
kamfer
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PEMBUATAN ALDEHIDA DAN KETON
CH3(CH2)5OH+CrCO3 piridina CH3(CH2)5CHO
CH3
OH
CH
H3C CH3
+ H2CrO460o
CH3
O
CHH3C CH3
menton ( 84%)
HC
H3C
H3C
CH3 + CH3COCl HC
H3C
H3C
CH3
C
O
CH3
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PEMBUATAN ALDEHID KETON MELALUI
REAKSI OKSIDASI ALKENA
C C
R1
R2
R3
R4
C O C O
R1
R2
R3
R4
+
RCCl
O1.LiAlH(C (C H3) 3) 3
2.H2O,H+
RCHO
RCCl
OR2Cd
RCR
O
R2CHOH
alkohol sekunder
R C R
O
keton
RCH2OH
alkohol primer
R C H
O
2.
3.
4.
5.
1
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PEMBUATAN ALDEHID DAN KETON
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1.5. GUGUS KARBONIL
Gugus aktif dari aldehid dan keton
R π
σ 120°
C O 120° C O
R
1. C karbotil sp2 sudut ikatan 120°
2. σ = Csp2 - p Osp2
∏ = p Csp2 - p Osp2
3. O mempunyai 2 orbital terisi 2 pada bidang yang sama dengan C karbonil.
..
..
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4. Panjang ikatan C = O (1,24 Ǻ) lebih kecil dari
C – OH (1,43 Ǻ).
Jadi C = O dianggap “ikatan delokal
C O
Resonansi hibrida :
C O C+ O –
EN O > EN C ikatan C = O polar
Cδ+ O δ- Dipol Td tinggi
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I II III
CH3(CH2)3CH3 CH3(CH2)2CH=O CH3(CH2)3CH2OH
BM = 70 BM = 72 BM = 74
Td = 38° Td = 75° Td = 118°
NO JENIS
SENYAWA
SIFAT IKATAN
I ALKANA NONPOLAR F VAN DER
WAALS
II ALKANAL POLAR F COLOUM
IKATAN
HIDROGEN
III ALKANOL POLAR F COLOUM
IKATAN
HIDROGEN
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FAKTOR STERIK
Reaktifitas raksi adisi terhadap gugus karbonil
dipengaruhi oleh faktor sterik (kesesakan) makin
besar gugus yang terikat pada gugus karbonil
maka sterik disekitar gugus karbonil akan makin
tinggi. (gugus meluah disekitar gugus karbonil
menyebabkan halangan sterik makin besar)
C
R
O
R
kurang terintangi
+ CH3CH2OH R C R
O
OH
CH2CH3
sp2 sp2 lebih terintangi
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H H
R-C=O H – C=O
KETON ALDEHID FORMALDEHID
# Keton BM rendah
- faktor sterik lebih besar dari aldehid dan dapat
membentuk ikatan hidrogen dgn H2O
- sehingga larut dalam air
# Keton BM tinggi
- faktor sterik R makin tinggi tidak membentuk
ikatan hidrogen dengan H2O
- tidak larut dalam air
R
C OR
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FAKTOR INDUKSI TERHADAP
REAKTIVITAS Reaktivitas relatif aldehid dan keton dalam
reaksi adisi disebabkan banyaknya
muatan positif pada karbon karbonil.
Makin besar muatan positif makin besar
Gugus karbonil distabilkan oleh gugus R
didekatnya. Keton dengan 2 R 7kkal/mol
lebih stabil dari aldehid. R adalah induksi
positif ( melepas elektron)
Formaldehid tanpa gugus R adalah yang
paling reaktif.
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Cl bersifat menarik elektron ( induksi
negatif) . Karbon karbonil akan makin
positif dan makin reaktif, bila mengikat
atom Cl
Makin banyak Cl yang diikat makin reaktif
Makin dekat Cl dengan gugus karbonil
makin reaktif
CH3 C H
OCCl3 C H
Oterstabilkan terdestabilkan
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Nama Trivial Struktur tdo Kelarutan air
ALDEHID
formaldehid NCHO -21 Ϩ
asetaldehid CH3CHO 20 Ϩ
propionaldehid CH3CH2CHO 49 16g/100mL
butiraldehid CH3CH2CH2CHO 76 7g/100mL
benzaldehid C6H5CHO 178 sedikit
KETON
aseton CH3COCH3 56 Ϩ
metiletilketon CH3COCH2CH3 80 26g/100mL
asetofenon C6H5COCH3 202 Tak larut
benzofenon C6H5COC6H5 306 Tak larut
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Aldehid dan keton berberat molekul rendah mudah larut
dalam air , karena kemampuannya terjadi ikatan
hidrogen. Tetapi semakin besar gugus R efek sterik
semakin tinggi, sehingga kelarutan semakin sukar
bahkan menjadi tidak larut.
Oleh adanya pasangan elektron bebas pada atom
oksigen , gugus karbonil dapat membentuk ikatan
hidrogen dengan H2O. Sehingga manjadi semakin
mudah larut dalam air.
Contoh di bawah ini terjadi kenaikan titik didih
CH3 CH CH3
CH3
CH3 C CH3
O
CH3 CH CH3
OH
t.d.-12 t.d. 560 t.d. 82,5
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1.6 ADISI NUKLEOFILIK PADA
GUGUS KARBONIL
_
C = O C+ – O
Nu _
Nu : + C = O C – O
sp2 sp3
zat antara tetrahedral
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Nu SOH Nu
C – O C – OH Pelarut
Kekuatan nukleofil
NuI + – C – X – C – Nu + X –
NuII + – C – X – C – Nu + X – NuI lebih kuat dari pada NuII
Kekuatan muatan parsial
EN F = 4 – Cδ++ ––– F δ--
Cl = 3,5
C = 2,5 – Cδ+ ––– Cl δ-
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Reaktifitas aldehid dan keton
R R O -
I. Nu: + C = O C
H H Nu
R R O -
II. Nu: + C = O C
R R Nu
Sterik II >Strerik I
Jadi Aldehid lebih reaktif daripada keton
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1.7 ADISI ALKOHOL TERHADAP
ALDEHID - KETON
R R – O
R – OH + C=O R` – C – OH
H H Hemiasetal
Untuk alkohol Berlebih
R – O H + R – O
R` – C – OH + ROH R’ – C – H + H2O
H R O
Asetal
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Reaksi asetaldehid dan etanol
CH3 CH3 + CH3 +
C=O + H+ C=OH C – OH
H H H
H
CH3 + CH3 +OC2H5
CH3CH2OH + C – OH C
H H OH
-H +
CH3 OC2H5
C
H OH Hemiasetal
..
..
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Untuk etanol berlebihan :
CH3 OC2H5 H+ CH3 OC2H5
C C
H OH H +OH
Hemiasetal H
– H2O
CH3 OC2H5
C +
H
..
.. ..
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CH3 OC2H5 CH3 OC2H5
C2H5OH + C + C
H H +OC2H5
H
- H+
CH3 OC2H5
C
H OC2H5
(Asetal)
..
.. ..
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Reaksi Keton Dengan Alkohol
R H+ R OH
R` – OH + C = O C hemiketal
R R OR`
R OH H+ R OR`
C + R` – OH C + H2O
R OR` R OR`
Ketal
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Fakta : Hidrolisis asam terhadap ketal > eter
H
R OR′ H + R + OR′ R R
C C C C + +R’OH
R OR′ R OR′ R OR′ R OR′
Ketal
H
R OR′ H + R + OR′ R
C C C + R’OH
R R′ R R′ R R
Eter
R
Jadi C – O lebih stabil daripada C
R R
+
+
+
+
..
..
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1.8 ADISI AIR ; HIDRASI ALDEHID - KETON
H HO
C = O + H – OH C – OH
H H H Asetaldehid hidrat
Cl O Cl OH
Cl – C – C + HOH Cl – C – C – OH
Cl H Cl H Kerapatan elektron C-karbonil rendah karena tarikan Cl
CH3 CH3
C = O + HOH CH3 – C – OH
CH3 OH
..
..
..
..
..
..
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1.9 ADISI PEREAKSI GRIGNARD
DAN ASETILIDA
R R
C = O + RMgX C – OMgX C-OH + Mg2+ + Cl-
Mekasnisme :
A. Adisi nukleofilik
R – MgX R - + MgX
R - + C = O R – C – O
R – C – O + +MgX R – C – O – MgX
– + eter H2O
HCl magnesium
alkoksida
+
..
.. –
..
.. – ..
..
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B. Hidrolisis
R – C – O – MgX + H – O – H R –C –OH + OH +MgX
Mg X+ Mg2+ + X
OH + HCl H2O + Cl
HCl mencegah endapan Mg(OH)2
Cara membuat CH2OH dari senyawa
karbonil dan pereaksi Grignard
MgX + +MgX
..
.. .. ..
–
–
alkohol –
–
–
–
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O O
R – C + R – C – H + MgX
H
H H
OH + R – C – OH R – C - O MgX
alkohol sekunder
–
–
+
– – + H2O
HCl
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1.10 ADISI HIDROGEN SIANIDA
NC
C = O + HCN – C – OH
sianohidrin
Mekanisme :
HCN + OH C N + H2O
NC
C = O + C N – C – O
NC NC
– C – 0 + HCN – C – OH + CN
OH –
– –
– .. ..
– –
–
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1.11 REAKSI ADISI DAN ELIMINASI DARI ALDEHID DAN KETON
(REAKSI DENGAN AMONIA DAN AMINA PRIMER)
Nukleofil nitrogen : NH3
NH2 R
NH2OH
OH
C = O + NH2 – R C C = NR
NHR
O OH
N H2 C HN – C
+ H
Hasil adisi
tetrahedral
imin
– H2O
H
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REAKSI WITTIG
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1.12 ADISI HIDROGEN (REDUKSI)
Merupakan reaksi reduksi (pembentukan ikatan
C – H)
a.Hidrida logam : LiAlH4 ; NaBH4
Mekanisme :
LiAlH4 Li + AlH4
H H
H – Al – H H – Al + H
H H
H + C = O H – C – O
+ _
_ ..
..
..
.. –
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H – C – O + Li+ H – C – O Li+
H – C – O Li H – C – OH + Li OH
Contoh :
O
CH2–CH=CH – CH CH3CH=CH–CH2OH
(2-buten-1-ol)
litium alkoksida
alkohol
H
H2O
– – + +
LiAlH4
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b. Reduksi dengan Hidrogenasi Katalik
H
C = O + H – H – C – OH
O OH
C – CH3 + H2 CH
CH3
O H
C C
Reduksi +Adisi
Ni , Cr
Ni
H2
Ni
OH
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OH
CH3CH = CH – CH – CH2
LiAlh4 ; H+ / H2O
0
H3 CCH=CHC – CH3
H2,Ni
OH
CH3CH2 – CH2 CH– CH3
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OH
CH3CH = CH – CH – CH2
LiAlH4 ; H+ / H2O
0
H3CH=CHC – CH3
H2,Ni
OH
CH3CH – CH – CH3
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c. Reduksi Wolff – Kishner
O OH NNH2
CCH3 CCH3 CH2 CH3
Asetofenon Etilbenzena (73%)
Reduksi Clemensen
O
CCH3 CH2 CH3
(45%)
H+
NH2NH2 KOH
Zn/HJ
HCl
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d. Aminasi Reduksi
O
CH CH = NH CH2NH2
Benzaldehid suatu Imina Benzilamina (85%)
O NCH3
CH3 CH2 CCH3 CH3 CH2 CCH3
Butanon Suatu imina
NHCH3
CH3 CH2 CHCH3
N-Metil-2-butilamina (69%)
NH3
- H2O
H2 , Ni
CH3NH2
- H2O
H2 /Pt
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1.13 OKSIDASI SENYAWA KARBONIL
Reaksi Oksidasi = reaksi terbentuk ikatan C – O
(reaksi penambahan atom oksigen)
O O
R – C – H R – C – OH
aldehid asam karboksilat
[O]
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Identifikasi Gugus Aldehid
1. Pereaksi Tollens
O
R – C – H + 2 Ag (NH3)2+ +3 OH
aldehid ion kompleks
perak amoniak
O
R – C – O + 2Ag + 4 NH3 + 2 H2O
cermin
perak
–
–
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2. Pereaksi Fehling
O
R – C – H + 2 Cu2+ + 5 OH
biru
O
R – C – O + Cu2O + 3 H2O
merah bata
–
–
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3. Pereaksi Benedict
kompleks Cu2+ + asam sitrat
endapan merah bata Cu2O
Keton sulit harus memutus ikatan gugus
karbodil dengan gugus alkil
O O
R – C – R R – C – OH + RH [O]
sulit
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TAUTOMERISASI
Syarat
Harus dalam lingkungan basa
Mempunyai H alfa ( α )
H α adalah H yang terikat pada C α
C α adl atom C yg terikat pada karbonil
H α bersifat asam sehingga dapat lepas
dan menghasilkan karbanion
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KESETIMBANGAN
KETO-ENOL
Syarat 1. dalam lingkungan basa
2. mempunyai H alfa
H alfa adalah H yang terikat pada C alfa
yaitu C yang terikat pada gugus karbonil
C
H
C
O C COH
KETOENOL
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1.14 TAUTOMERI KETO-ENOL
H O OH
– C – C – C = C ; H = hidrogen
Keto enol
Fakta : I II
H O H H OH H
H – C – C – C – H C = C – C – H
H H H H 99,9997% 0,0003%
Tinjau :
O O – H
H C C – – C C – σ1 1 2
Eσ1+1 < Eσ2+2
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Jadi bentuk keto lebih stabil daripada enol.
Fakta :
III IV
O O O O
C C C C
CH3 CH2 CH3 CH3 CH CH3
24% (Keto) 76% (enol)
Tinjau :
O O H – O O
C C C C
C C
H
H
H
H
H
σ3
σ4
3 4
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Struktur Resonansi :
– C = C – C = O – C – C = C – O
EIV = σ4 + 4 - ER
EIII > EIV jadi enol lebih stabil.
Senyawa tidak ada H selalu dalam bentuk “keto”.
Tidak terjadi tautomerisasi
O O
C
H H
formaldehid
benzofenon
..
.. –
+
C H
O
Benzaldehid
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1.15 KESAMAAN HIDROGEN :
Efek Industri
H
H – C – H EN C > EN H
H
H H
H – C – Cl H – C – Cl EN Cl > EN C
H H
H O
– C – C – H bersifat proton
δ - δ +
δ - δ +
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Teori Resonansi
H
– C – – C – + H+
H O O
– C – C – – C – C – + H+
Delokal : C – C – O
O O
Resonansi C – C C = C (muatan terdelokal)
H O H
Jadi Keasaman – C – C > – C –
sp2 (muatan terlokalisasi)
..
..
.. ..
.. –
–
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O O O
CH3CCH3 CH3CCH2COCH2CH3
Aseton Etil aseto asetat
pKa = 20 pKa = 11
O O
CH2CCH3 + Na+ OCH2CH3 Na+ CH2CCH3 + CH3CH2OH
H
tidak disukai
O O
CH3CCHC – OCH2CH3 + Na+ OCH2CH3
O O
CH3CCHCOCH2CH3 + CH3CH2OH
disukai
..
..
.. ..
..
..
..
–
Na+ ..
= terhadap C = O = terhadap dua C=O
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O O O
– CH – C – – CH – C – atau – CH – C –
O O O O O O
– C – CH = C – C – CH – C – – C=C – C –
O O
atau – C – CH – C –
..
..
.. .. –
δ -
δ -
.. ..
.. .. ..
.. ..
..
.. .. ..
δ - δ -
δ -
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1.6 PENYEIMBANG BENTUK
KETO - ENOL
Dengan Katalis Basa
H O O
– C – C + B: – C – C + BH
OH O
B: + – C = C – BH + – C – C –
Atau
H O OH
– C – C – – C = C –
_
_
..
.. ..
B :
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Dengan Kalatis Asam
HCl H + Cl
H O H OH
– C – C + H – C – C –
H OH OH OH
– C – C – + Cl – C – C +HCl – C=C –
Atau:
H O H OH OH
– C – C – C – C C = C
R R R
Keto enol
_ +
enol
– – .. +
Keto
+
+
+
+ H + H
- H - H
+
+
+
+
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1.17 PERTUKARAN DEUTORIUM
DALAM SENYAWA KARBOTIL O O
CH3CH2CH2CH CH3CH2CD2CH
D = deutorium
O O
D D
D D
Bukti Bahwa :
- Adanya bentuk enol / keto
- Yang dapat diganti hanya H-
D+
D2O
NaOCH3
CH3OD
sikloheksanon 2,2,6,6-tetradeutorium
sikloheksanon
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1.18 KONDENSASI ALDOL
O O OH O
CH3CH + CH3CH CH3CH –CH2CH
Asetaldehid 3-hidroksibutanal
(aldol)
OH –
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Mekanisme :
O O
RCH2CH + OH RCHCH + H2O
(enolat)
O O O O
RCHCH + RCH2CH RCH2C – CH – CH
(Nu:) H R (ion alkoksida)
_ –
.. .. –
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O O OH O
RCH2 C – CH– CH + H2O RCH2CH– CHCH+ OH
H R R
atau :
O O OH O
RCH2CH + RCH2CH RCH2CH – CHCH
R
aldol
..
.. ..
–
–
H2O
–
– OH
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1.9 KONDENSASI ALDOL CAMPURAN
(SILANG)
Propanal + Benzaldehid
O O
CH3CH2CH + C – H
O CH3 OH OH
CH – C – C – CH2CH3 + CH3CH – CH
H H C O
H
Buatlah mekanisme reaksinya!!
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1.10 SINTESIS BESAR-BESARAN
MELALUI KONDENSASI ALDOL
Aldol mudah terdehidrasi dibanding alkohol
(C=C terkonjugasi dengan C – karbonil)
O OH O
2CH3CH CH3CHCH2CH
O O
CH3CH = CHCH CH3CH2CH2C (aldehid)
H
CH3CH2CH2CH2OH
OH
- H2O
+
(alkohol)
H2
Kat
OH –
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Nucleophilic Addition to -A,B
Unsaturated
Carboxylic Acid Derivatives
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