isokuinolin (isoquinoline)
TRANSCRIPT
![Page 1: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/1.jpg)
GUSTIA NINGSIH1010412037
^___^
![Page 2: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/2.jpg)
Isoquinoline
N
1
2
3
45
6
7
8
cincin benzenoid bersifat seperti
naftalen
cincin piridin
![Page 3: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/3.jpg)
Struktur Hibrid Isoquinoline
N N N
NN
![Page 4: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/4.jpg)
Sehingga,
N
Tersubstitusi oleh Nukleofil (Nu-)
![Page 5: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/5.jpg)
NaftalenParsial
negatif, sehingga
tersubstitusi oleh
Elektrofil (E+)
![Page 6: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/6.jpg)
Posisi a
Posisi b
Pada naftalen ini
substitusi elektrofil lebih
suka pada posisi a.
Karena bentuk resonansi
pada posisi a lebih
banyak dari posisi b
![Page 7: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/7.jpg)
Contoh:
Br2
Br
Br
atau
??????
Br tersubstitusi
pada posisi a
Br tersubstitusi
pada posisi b
![Page 8: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/8.jpg)
Pada posisi a
Br2
Br BrH
Untuk mengetahui posisi mana yang lebih
disukai, maka dibandingkan berdasarkan
jumlah bentuk resonansi dari intermediet
intermediet
![Page 9: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/9.jpg)
Bentuk resonansi:Br H Br H
Br H
Br HBr HBr H
Br H
7 bentuk resonansi
![Page 10: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/10.jpg)
Pada posisi b
Br2
Br
H
Br
intermediet
![Page 11: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/11.jpg)
Bentuk resonansi:
H
Br
H
Br
H
Br
H
Br
H
Br
H
Br
6 bentuk resonansi
![Page 12: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/12.jpg)
Jadi,
N
Mengalami substitusi
Elektrofilik yaitu pada
atom C5 dan C8
Mengalami Substitusi
Nukleofilik yaitu pada atom
C1 dan C3
![Page 13: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/13.jpg)
Isoquinoline Synthesis
1. Bischler Napierlaski
NH
O
R
POCl3
N
R
Dihydroisoquinoline
![Page 14: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/14.jpg)
Mekanisme:
NH
O
R
PCl
O
Cl
Cl
NH
R OPOCl2
N
R OPOCl2
H
H
N
R
![Page 15: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/15.jpg)
2. Pictet - Spengler
NH2
O
R H
NH
R
Tetrahydroisoquinoline
![Page 16: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/16.jpg)
Mekanisme:
NH2
O
R H
H+
NH H
R
H
OH
N H
R
H
OH
N H
RH
N
R
H
N
R
H
NH
R
![Page 17: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/17.jpg)
3. Pomeranz - Fritsch
RO
H
O
H2NCH2CH(OEt)2
RO
N
![Page 18: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/18.jpg)
Mekanisme:
RO
H
O
H2NCH2CH(OEt)2
RO
H
N
RO
H
N
H
OEt OEt
RO
H
N
H
OEt
H
H+
RO
H
N
OH
OEtEtO
H
H
RO
H
N
OH
OEtEtO
H
RO
H
N
OEtEtO
H
![Page 19: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/19.jpg)
Reaksi pada Isoquinoline
Substitusi Nukleofilik (pada
cincin piridin)
Substitusi Elektrofil (pada
cincin benzenoid)
![Page 20: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/20.jpg)
Elektrofil
Nukleofil
H-, BH4-, HSO3
-, HO-, RS-, CN-, RCO2-, RC C -,
-CH(CO2Et)2, O, N, S, RMgBr, RLi
H+, H3O+, NO2, NO+, PhN2+, R3C+,
SO3, CO2, BF3, AlCl3, I Cl, Br2, O3
![Page 21: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/21.jpg)
Substitusi Nukleofilik
Reaksi Chichibabin
N
1
2
NaNH2
N
NH2
1.
![Page 22: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/22.jpg)
N
Cl
Cl
CH2(CO2Et)2
NaNH2 N
CH(CO2Et)2
Cl
2.
![Page 23: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/23.jpg)
3.N
N
n-BuLi
Li
H Bu
H2O
NH
H Bu
oksidasi
N
Bu
![Page 24: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/24.jpg)
Substitusi Elektrofilik
N
H2SO4 + HNO3
N N
NO2
NO2
+
major
N
Br2 + AlCl3
N N
Br
Br
+
![Page 25: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/25.jpg)
Namun, nitrasi (substitusi elektrofilik NO2)dapat
terjadi pada cincin piridin dari isokuinolin pada atom
C4 yaitu dengan menggunakan asam nitrat dan asetat
anhidrida. Hal ini terjadi pada kondisi ekstrim (suhu
tinggi).
N
HNO3 + Ac2O
N
NO2
![Page 26: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/26.jpg)
Oksidasi Isoquinoline
N KOH
225oC
N
H OHK+
-H2
N
OK
NH
O
![Page 27: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/27.jpg)
Reduksi Isoquinoline
N
Et2AlH
Na-EtOH
NH
NH
![Page 28: Isokuinolin (isoquinoline)](https://reader030.vdokumen.com/reader030/viewer/2022012405/55a1ea5e1a28ab74358b4786/html5/thumbnails/28.jpg)
THANK
YOU
^__^