R-X
(X = F, Cl, Br, I)
RCH2-X
1o
R2CH-X
2o
R3C-X
3o
Tata nama:
Trivial: nama alkil + halida
CH3CHCH3
n-butil bromida
isopropil chlorida
1-bromobutana
2-chloropropana
1o
2o
CH3
CH3CHCH2CHCH3
Br
2-bromo-4-metilpentana
2o
CH3
Cl-CHCH2CH3
sec-butil chlorida
2-chlorobutana
2o
CH3
CH3CCH3
I
tert-butil iodida
2-iodo-2-metilpropana
3o
Tidak larut air krn tdk dpt mbtk ikt.hidrogen. Larut dlm
pelarut organik tertentu.
Uses: pestisida, refrigerants (freons), pelarut,
intermediate sintetik.
Contoh: CH3Br
CClF3
CCl4
1. Dari alkohol
a) HX
b) PX3
5. Pertukaran halida
1. Dari alkohol.
#1 synthesis!
a) Dengan pereaksi HX
R-OH
HX
R-X
H2O
i) HX = HCl, HBr, HI
(HBr)
n-butil bromida
1-butanol
CH3
CH3CCH3
OH
1-bromobutana
tert-butil alkohol
2-metil-2-propanol
CH3-OH
metil alkohol
metanol
CH3CH2CH2CH2-Br
HCl
CH3
CH3CCH3
Cl
tert-butil klorida
2-chloro-2-metilpropana
HI, H+,heat
CH3-I
metil iodida
iodometana
CH3CH2-OH
+ P, I2 CH3CH2-I
etil alkohol
etil iodida
etanol
iodoetana
CH3
CH3CHCH2-OH
isobutil alkohol
2-metil-1-propanol
+ PBr3
CH3
CH3CHCH2-Br
isobutil bromida
1-bromo-2-metilpropana
+ X2, or h
R-X
+ HX
CH3
CH3CCH3
CH3
+ Cl2, heat
neopentana
2,2-dimetilpropana
CH3
CH3CCH2-Cl
CH3
neopentil chlorida
1-chloro-2,2-dimetilpropana
+ NaI, acetone
R-I + NaX
CH3CH2CH2-Br
n-propil bromida
n-propil idodida
1-bromopropana
1-idodopropana
ROH
HX
NaI
aseton
PX3
RX
X2, or h
RH
Soal :
1.Sintesis senyawa alkil halida dibawah ini dengan
metode/pereaksi yang berbeda dalam skala laboratorium:
1-bromobutana
neopentil chlorida
n-propil iodida
tert-butil bromida
CH3
CH3
CH3CCH3 + Cl2, heat CH3CCH2-Cl
CH3
CH3
CH3CH2CH2-Br + NaI, aseton CH3CH2CH2-I
CH3
CH3
CH3C-OH + HBr CH3C-Br
CH3
CH3
a. H3C-CH2-CH2-CH2-Br
b.
H3C-CH2-C(CH3)2 I
+ :Z-
R-Z
+ :X-
2. Dehidrohalogenasi (Eliminasi)
3. Pembentukan Pereaksi Grignard
R-X
+ Mg
RMgX
RMgX
4. Reduksi
R-X
+ Mg
R-X
+ Sn, HCl
R-H
+ H2O
R-H
Substitusi Nukleofilik
R-X
substrat
:Znukleofil
R-Z
produk substitusi
:Xgugus pergi
R-X + :OH-
ROH
+ :X-
alkohol
R-X + H2O
ROH
+ HX
alkohol
R-X + :OR-
R-O-R + :X-
ether
R-CCR + :X-
alkuna
R-X + :I-
iodida
R-X + :CN-
R-CN
+ :X-
nitril
R-X + :NH3
+ HX
amina primer
R-X +
-:CCR
R-I
R-NH2
+ :X-
R-SH
R-X + :SR
+ :X-
R-SR + :X-
amina sekunder
thiol
thioether
Etc.
Lebih baik bila R-X adalah CH3- halida or alkil halida 1o !
CH3CH2CH2-Br
KOH
CH3CH2CH2-OH
CH3CH2CH2-Br
HOH
CH3CH2CH2-OH + HBr
CH3CH2CH2-Br
NaCN
CH3CH2CH2-Br
NaOCH3
CH3CH2CH2-Br
NH3
CH3CH2CH2-Br
KBr
CH3CH2CH2-CN + NaBr
CH3CH2CH2-OCH3 + NaBr
CH3CH2CH2-NH2 + HBr
SN2
RDS
Z:
C W
Z C
:W
+ NaOH
CH3OH
NaBr
SN2 stereokimia
CH3
CH3
Br +
NaOH
HO
(kondisi SN2 )
C6H13
(S)-(-)-2-bromooktana
C6H13
(R)-(+)-2-oktanol
100%
Alasannya:
Z:
C W
Z C W
Z C
:W
CH3
CH3CCH3
Br
+ OH-
CH3
CH3CCH3
OH
+ Br- + alkena
1)
RDS
C W
:W
carbocation
2)
:Z
C Z
Stereokimia SN1
CH3
CH3
Br +
NaOH
HO
CH3
H +
OH
(kondisi SN1)
C6H13
(S)-2-bromooktana
C6H13
(R)-2-oktanol
C6H13
(S)-2-oktanol
R+
Br-
CH3Br
H = 219 Kcal/mole
CH3+
CH3CH2Br
H = 184 Kcal/mole
1o
CH3CHBr
CH3
H = 164 Kcal/mole
2o
H = 149 Kcal/mole
3o
CH3
CH3CBr
CH3
RDS in SN1:
RW R+
RX
[ R---------X ]
+
-
:W-
R+
+ X-
--CC-+
H
[1,2-H]
--CC
+
H
[1,2-CH3]
--CC-
--CC
+
+
CH3
CH3
CH3
CH3CHCHCH3 + NaCN (kondSN1 conditions)
Br
CH3
CH3CHCHCH3
+
2o Karbokation
CH3
CH3CCH2CH3
CN
[pergeseran 1,2-H ]
CH3
CH3CCH2CH3
+
3o Karbokation
CN-
?????
SN1
RDS
C W
Z C
C W
:Z
:W
C Z
:W
SN2
SN1
stereokimia
Rasemisasi Parsial
(1:1)
Kinetika, order
Rate = k[RX][Z-]
Order dua
Rate = k[RX]
Order satu
Penataan Ulang
Tidak ada
Mungkin ada
Rates CH3,1o,2o,3o
CH3>1o>2o>3o
3o>2o>1o>CH3
Rates RCl,RBr,RI
RI>RBr>RCl
RI>RBr>RCl
Kebasaan /Nukleofil
Harus kuat
Solven
Tahapan Reaksi
1 tahap
2 tahap
CH3
1o
2o
3o
- SN1
SN2 faktor sterik CH3 > 1o > 2o > 3o
SN1 stabilitas karbokation 3o > 2o > 1o > CH3
Mechanisms
SN2
RDS
Z:
SN1
RDS
C W
Z C
C W
:Z
:W
C Z
:W