Alkohol dan Eter

Ikatan tunggal Karbon ke Oksigen Ikatan tunggal Karbon ke Oksigen

Tata Nama: AlKohol
OH ditunjukkan oleh akhiran ol
Rantai induk adalah rantai terpanjang Rantai induk adalah rantai terpanjang
yang mengandung C-OH
K b di i d i j t i Karbon dinomori dari ujung rantai yang
terdekat OH
C h Contoh
C H
3
CH
2
CH CH
2
CHCH
3
OH
OH
CH
3
F
CH
3
5-methyl-3-hexanol
(1R 3S 4S)3 fl 4 th l l h l
O H
OH
(1R,3S,4S)3-fluoro-4-methylcyclohexanol, or
(1R,3S,4S)3-fluoro-4-methyl-1-cyclohexanol
3 (1 methylpropyl) 2 heptanol
hex-5-en-2-ol or
5-hexen-2-ol
3-(1-methylpropyl)-2-heptanol
(Note that the OH takes precedence over
the pi bond in detemining the numbering.)
Tata Nama: Eter
Eter sederhana :
nama dua gugus karbon sebagai nama dua gugus karbon sebagai
substituen, diikuti dengan eter
Si t tik Sistematik:
nama sebagai alkoksi alkana
C h Contoh
CH
3
CH
2
O CH
2
CH
3
dieth l ether or
O
diethyl ether or
ethyl ether
(If both alkyl groups are the
same the "di" is often not used ) same, the di is often not used.)
O
CH -CH
phenoxycyclopentane or
cyclopentyloxybenzene
CH
2
-CH
3
5-ethoxy-2-methylheptane
G i l lk h l Gugus Fungsional Alkohol
Tiga lokasi dimana reaksi kimia bisa terjadi
O
H
.
.
.
.
H
Lokasi kaya elektron?
Lokasi miskin elektron? Lokasi miskin elektron?
Th Eth F ti l G The Ether Functional Group
Same as Alcohols but no O-H Same as Alcohols, but no O-H
O
C
O
C
Reaksi pada ikatan C-O Reaksi pada ikatan C O
Does this happen? pp
O
H
.
.

.
.
+
Nuc:
+ OH
-
+
Nuc
+ OH
The C-Ois inert toward heterolytic cleavage The C O is inert toward heterolytic cleavage.
Why?
OH
-
terlalu basa untuk menjadi gugus lepas
Ikatan C-O putus pada kondisi asam
O
H
.
.

.
.
H
+
Br
+ H
2
O
Br
+
H
+
Substitution
OH
H
H
+
+
O H
2
Elimination
Kenapa ikatan C-O putus pada
k di i ? kondisi asam?
H
H
H
O
H
H OSO
3
H :
..
H
O
+
H
H
..
+
HSO
4
-
H
O
H
H OSO
3
H :
.. O
+
H
H
..
+
HSO
4
-
4
Alkohol adalah basa lemah bereaksi dengan asam Alkohol adalah basa lemah, bereaksi dengan asam
kuat (Bronsted or Lewis).
C-O dari alkohol terprotonasi
bisa putus
O
H
.
.

.
.
+
-
O
+
H
.
.
H
+
HA
O
+
H
.
.
+
A
-
O
H
O
H
+
+
O H
2
slow
+
+
A
A
_
Suatu reaksi substitusi nukleofilik
Air sebagai gugus lepas
S
N
2 jika primer uncrowded S
N
2 jika primer uncrowded
S
N
1 (seperti terlihat)
Substitution of the Hydroxyl Hydrogen
Ether Chemistry is C-OChemistry Ether Chemistry is C O Chemistry
--J ust Like Alcohol C-O Chemistry
O
H
O
H H-X
X
H
O
H
+
+
O
H-X
X
H
O
+ +
H-X O
+ +
Identical Mechanisms, Too.
Protonation of the O, then Nucleophilic Substitution
O
H
H-X
X
+
H
O
H
O
+
H
H
X
H
H
O
H-X
O
H
+
X
X
+
H
O
Prediksi Produk
Pemutusan Ether tidak selalu selektif; kedua
set produk pemutusan diharapkan. p p p
Dalam metil eter, X lebih menyukai
menyerang gugus metil.
Dalam HX berlebih, kedua C-O diputus,
menghasilkan air dan dua ikatan C-X.
Dalam fenil eter, cincin benzena tidak
diserang, walaupun dalam HX berlebih.
Eth Cl R ti Ether Cleavage Reactions
CH
3
CH
CH
3
O CH
2
CH
3
H-I
+
excess
H I
+
O
CH
3
H-I
+
O
H-I
+
excess
O
one equivalent
O
H-I
+
H-I
O
+
excess
excess
excess
Reaksi Alkohol yang tidak
melibatkan pemutusan C-O
Electron-rich oxygen Electron-rich oxygen
The O-H
Reactions of the O-H
Water has the same functional group
O
H
.
.

.
.
+
:Base
AtomH adalah miskin elektron Atom H adalah miskin elektron
Are alcohols acids?
Learn fromwaters chemistry Learn fromwaters chemistry Learn from water s chemistry Learn from water s chemistry
Keasaman Alkohol
H-O-H pK
a
= 15.7
R-O-H pK =15 to 16 R O H pK
a
= 15 to 16
R-NH
2
pK
a
= 34
CH CH OH
+
O H CH CH O
+
O H CH
3
CH
2
OH
+
O H CH
3
CH
2
O
+
O H
2
CH CH OH
+
N H CH CH O NH CH
3
CH
2
OH
+
N H
2
CH
3
CH
2
O
+
NH
3
Reaksi dengan logamaktif Reaksi dengan logam aktif
2
R O H M R O M
H
2
+
.
+
2
M can be Na or K
K
OH
OK
OH
Na
ON
OH
ONa
Other Ways to Convert the OH to a
Good Leaving Group: Halides
OH OH
+
PBr
3
OH
+
SOCl
2
SOC
2
Reaksi menggunakan pasangan Reaksi menggunakan pasangan
elektron bebas dari oksigen
Basa? Basa?
Nucleophile?
Alcohols and Ethers are o os a d e s a e
Weakly Basic
They are protonated in strong acids.
H
H H
+
O
H
2
SO
4
O
H H
+
+
O
CH
3
H
2
SO
4
O
CH
3
H
+
+
2 4
All oxygenated organic compounds are
t t d b t id protonated by strong acids
Alcohols are Nucleophiles
but not very strong ones.
+
C
X
R O
H
R O
H
C
R O C
C
+
+
With methyl and primart halides, this y p
probably happens by an S
N
2 mechanism
Note that the nucleophile is NOT alkoxide! Like water, alcohols
are not strong acids so there is no R O
-
present The nucleophile are not strong acids, so there is no R-O present. The nucleophile
is the whole alcohol molecule.,
There is no alkoxide (RO
-
) in alcohol!! There is no alkoxide (RO) in alcohol!!
Conversion to Sulfonates
O
SO
2
Cl
Nucleophilic Substitution by Alcohol at Sulfur!!
OH
+
O SO
2
OH
+
O Ts
Ts-Cl
H
C H
3
CH
3
OH
CH
Ts-Cl
+
H
C H
3
CH
3
OTs
CH
3
CH
3
S lf i G d L i Sulfonate is a Good Leaving
Groupp
As good as or better than bromide
OTs
Na-SCH
S-CH
3
O T
+
+
CH
3
Na SCH
3
CH
3
O Ts
+
+
H
C H
3
CH
2
CH
3
OTs
NaI
C H
3
CH
2
CH
3
I
H
O Ts
+
+
Oksidasi alkohol Oksidasi alkohol
Pembuatan ikatan C=O
OH
H
oxidize
O
C
OH
CH
3
CH
2
CH
2
CH
3
HCrO
3
C
H
3 2 2
C
3
CH
2
-OH
CrO
3
idi pyridine
CH
2
-OH
HCrO
3
C O
3
Three Ways to Make the Alcohol
Carbon More Electrophilic Carbon More Electrophilic
OH
X
Convert to a
better leaving group
OH OTs
better leaving group
OH H
O
Oxidize
Elimination Reactions of Alcohols Elimination Reactions of Alcohols
Step (1) The alcohol is protonated by the oxonium
ion fromthe acid solution ion from the acid solution.
Step (2) Heterolytic C-O bond fission occurs to
i h b i d give the carbocation and water.
In Step (3) the carbocation is 'deprotonated' to
give the alkene and oxonium ion.
The double bond is completed from the C-H
bonding pair of electrons 'left' as the proton is
removed. removed.
Alkohol dalam Sintesis o o daa S ess
OTs
Nu:
Nu
TsCl
Nu
OH
X
HX, or
SOCl or PBr
TsCl
Mg
MgX
SOCl
2
or PBr
3
H+, heat
Strong base
oxidize
O
etc.
The three-membered ring of epoxides is highly strained
and undergoes ring-opening reactions with a variety of
nucleophiles, as shown below.