Download - KIMIA ORGANIK FISIK
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KIMIA ORGANIK FISIK
CARBON-CARBON BOND FORMATION
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Pembentukan Ikatan C-C
1. Melalui reaksi radikal bebas
C C C C
Tidak terkendali, dapat melakukan reaksi berantai (tidak digunakan dalam sintesis)
2. Melalui reaksi antara C+ dengan C-
C C C C
Lebih terkendali, (digunakan dalam sintesis)
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FREE RADICAL C-C BOND FORMATION
A. DIMERISATIONS CH3. + CH3. CH3 – CH3
POLYMERISATION ALKENES
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5
Chain branching occurs by abstraction of a hydrogen atom on the same chain and continuation of growth from the main chain
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SERANGAN C NUCLEOFIL (C-) PADA KARBOKATION (C+)
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Sumber C elektrofil
1. Alkil halida
2. Alkil sulfonat
3. Senyawa karbonil
4. Alkena yang berkonjugasi dengan EWG
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Sumber C nukleofil
1. Organo logam
2. Karbanion alkinil
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Carbanion Alkylation
Carbonyl Reaction
1,4- Adition (Michael)
Alkenes & Alkynes Rxn
C+ C+ C+ C+C- C- C- C-
O
R
R C C
N C
R-Mg-X
R2CuLi
R-X
O
R-CH-PPh3
O
R C C
N C
R-Mg-X
R2CuLi
R
O
RO
O O
RR
R
O
H
O
R R
R-Mg-X
R2CuLi
O O
RR
O R2C:
CLASSIFICATION OF C-C FORMATION
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Pembentukan Ikatan C-Ca) Carbanion Alkylation
i) Alkylation of enolate ions
ii) Alkylation of acetylide or cyanide
iii) Organometallic alkylation
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b) Carbonyl Addition And Carbonyl Substitution Reactionsi) Aldol and related reactions (Addn)
ii) Claisen condensation and related reactions (Subn)
iii) Organometallic reactions (Addn)
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iv) Acetylide/cyanide addition
v) Wittig reaction (Addn)
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c) Conjugate Addition Reactions - ‘Michael’ (1,4 Addition)
d) Reaction Of Alkenes, and Alkynes i) Addition of carbenes to alkenes
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Electrocyclic reactions
Sigmatropic reactions
ii) Pericyclic reactions:Cycloadditions
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Suatu reaksi yang melibatkan keadaan transisi berupa siklik yang menyerupai karakter aromatis
Rearrangement Cope /Sigmatropik
Reaksi Elektrosiklik
Reaksi Diels Alder
REAKSI PERISIKLIK
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REARRANGEMENT COPE/SIGMATROPIK
Yaitu migrasi dari suatu ikatan sigma pada sistem elektron phi ke suatu posisi baru.Contoh rearrangement tingkat [3,3], ikatan sigma pada karbon no 3 bermigrasi ke posisi baru yang berjarak 3 karbon
Melibatkan keadaan transisi berkarakter aromatis
300oC
keadaan transisiberkarakter aromatis
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Claisen Rearrangement
OO O
Htautomerisasi
H
O
keadaan transisiberkarakter aromatis
panas
Bila posisi ortho telah terisi, maka migrasi dapat berlanjut ke posisi para
O O200oC
O O OH
tautomerisasi
12
3
33
3
3
2
2
22
1
111
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REAKSI ELEKTROSIKLIKadalah suatu sikloadisi intramolekuler, dengan suatu ikatan tunggal terbentuk di antara dua atom karbon terminal dari sistem elektron phi terkonyugasi (atau sebaliknya)
12
34
12
3 4panas
Karakteristik reaksi elektrosiklik: Mekanismenya tidak melibatkan intermediet radikal atau ionik Ikatan-ikatan yang dibentuk atau diputuskan dalam tahap serempak
dan melibatkan keadaan transisi yang siklik memerlukan panas atau cahaya untuk inisiasi Reaksi bersifat stereospesifik
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Dalam reaksi elektrosiklik, pembentukan ikatan sigma baru dapat berlangsung secara:
Conrotatori :rotasi orbital p berlangsung dengan arah sama
Disrotatori: rotasi orbital p berlangsung dengan arah berbeda
H3CH
HCH3
CH3CH3
H H
panasconrotatori
CH3H
HH3C HH
CH3 CH3
conrotatoripanas
H3CH
HCH3 CH3
CH3
H
H
disrotatori
CH3
HH
H3C
H
H
CH3
CH3disrotatori
hv
hv
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Aturan Woodward-Hoffman untuk Reaksi Perisiklik
Jumlah elektron phi Kondisi Rotasi4n termal conrotatori4n fotokimia disrotatori
4n + 2 Termal disrotatori4n + 2 fotokimia conrotatori
HCH3
H CH3
hv
hvH3C H
CH3H
?
?
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Reaksi Diels-Alder
BA
Y Z
A
Y
B
Z
+
diena dienofil sikloheksenaDiels-Alder adduct
Suatu reaksi sikloadisi
(stereospesifik)
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Reaksi Diels-Alder A. Mechanisme
Reaksi Pericyclic :concerted reaction that proceeds througha cyclic array of electrons in the TS
+
cyclic array of6 p e–s
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The Diels-Alder ReactionDienes and dienophiles
Works best with electron-poor dienophiles (A,B,Y,Z = C=O, CN):
O
H+H
O
O
O
O
+ O
O
O
acrolein
maleic anhydride
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The Diels-Alder ReactionB. Dienes and dienophiles
C
C
CO2CH3
CO2CH3
+
CO2CH3
CO2CH3
dimethyl acetylenedicarboxylate
CO2CH3+
CO2CH3
methyl acrylate
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The Diels-Alder ReactionB. Dienes and dienophiles
+
+CN
CN
O
O
O
O
2
acrylonitrile
p-quinone
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The Diels-Alder ReactionC. Stereospecificity
+
CO2CH3
CO2CH3
CO2CH3
CH3O2C
CO2CH3
CO2CH3
CO2CH3
CO2CH3
dimethyl maleate
dimethyl fumarate
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The Diels-Alder ReactionD. Stereoselectivity
O
+
O
HO
H
+
endo(major)
exo(minor)
O
additionaloverlap
stabilizesTS
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The Diels-Alder Reaction
Question . Draw the structure of the Diels-Alder adduct in each of the following reactions.
CO2CH3
+
CN
CN
+
+
O
O
Check Answer
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The Diels-Alder Reaction
Answer Draw the structure of the Diels-Alder adduct in each of the following reactions.
CO2CH3
+
CN
CN
+
+
O
O
H
HH
CO2CH3
CN
CN
O
O
H
H
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The Diels-Alder ReactionQuestion 10-6. What diene and dienophile would be used to make each of the following compounds?
CO2CH3
CO2CH3
O
O
O
O
O
Check Answer
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The Diels-Alder ReactionAnswer What diene and dienophile would be used to make each of the following compounds?
CO2CH3
CO2CH3
O
O
O
O
O
C
C
CO2CH2
CO2CH3
+
+
O
O
+
+ O
O
O
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Tunjukkan 2 cara mensintesis aldrin
ClCl
Cl
Cl
Cl Cl
H
H
aldrininsektisida