ALKOHOLOK S SZRMAZKAIK

Levezets

R OH
alkohol

O R
ter

OH

Elnevezs
Nyltlnc, teltett alkoholok
ltalnos nv: alkanol
alkil-alkohol

CH3OH
metanol
metil-alkohol

CH3CH2OH
etanol
etil-alkohol

CH3CH2CH2OH
propn-1-ol
propil-alkohol

CH3CHCH3
OH
propn-2-ol
izopropil-alkohol

CH3CH2CH2CH2OH

CH3CH2CHCH3

butn-1-ol
butil-alkohol

OH
butn-2-ol
szek-butil-alkohol
CH3

CH3CHCH2OH
CH3
izobutil-alkohol

CH3

OH

CH3
terc-butil-alkohol

Teltetlen alkoholok
CnH2n-1OH "alkenol"
CnH2n-3OH "alkinol"
CH2

CH2OH

CHCH2OH

CH2

vinil-alkohol
(nem ltkpes)

CH

CCH2OH

propargil-alkohol

allil-alkohol

Tbbrtk alkoholok

OH

OH

OH OH

geminlis

vicinlis

H2C

HO CH2 OH
metndiol
(nem ltkpes)

C
OH

H2C

CH2

CH

OH OH

C
OH

diszjunkt

CH2 CH2

OH

OH OH
etilnglikol
H2C

OH

propn-1,3-diol

CH2
OH

glicerin
Szrmazkok
CH2

CH2COOH

OH
3-hidroxi-propionsav

CH3

CHCOOH
CH2OH

2-hidroximetil-propionsav

Csoportnevek
R

OH

R O
alkoxi

C2H5O
etoxi

CH3O
metoxi

Sk
R

CH3O- Na+
ntrium-metoxid

R Oalkoxid ion

OH

terek
CH3 O CH3
dimetil-ter

C2H5

C2H5

CH3 O C2H5
etil-metil-ter

dietil-ter

O
O

etiln-oxid

trimetiln-oxid

tetrahidrofurn

OR
C

OR
OH

flacetl

O
dioxn

OR

acetl

hidroperoxid

peroxid

AZ ALKOHOLOK S TEREK SZERKEZETE

104
H
H
O

105
O

110
O

O
O
analg szerkezetek

AZ ALKOHOLOK FIZIKAI TULAJDONSGAI

Molekulatmeg

Forrspont (C)

CH3OH

32

65

CH3CH3

30

-89

CH3CH2OH

46

78

CH3OCH3

46

-24

CH3CH2CH3

44

-42

HOCH2-CH2OH

62

200

CH3CH2CH2CH3

58

-1

HOCH2-CHOH-CH2OH

92

290

CH3(CH2)4CH3

86

69

Hidrognkts
180 pm 100 pm
O

ktsi energia

R
20 kJ/mol

476 kJ/mol

Olvadspont
CH3
OH

CH3

OH

CH3
-90 C

26 C

AZ ALKOHOLOK SAV-BZIS TULAJDONSGAI

Savi jelleg
H

H
R
H

O + H

MeOH

H2 O

EtOH

15.5

15.7

15.9

pKa

O
+

Me3COH
18

aciditsi sorrend
H2O > ROH > RC

CH > H2 > NH3 > RH

bzicitsi sorrend
R- > NH2- > H- > RC

C- > RO- > HO-

C2H5OH + HO-

C2H5O- + H2O

C2H5OH + NH2-

C2H5O- + NH3

C2H5OH + Na

C2H5O- Na+ + 1/2 H2

Bzicits
+

OH + HA

OH2 + A-

OR + HA

OH

+ A-

AZ ALKOHOLOK KMIAI TULAJDONSGAI

Az alkoholok alkilezse; Williamson terszintzis
R

H +

1. Primer Q-X

+ HX

SN2

Plda
CH3CH2CH2O-Na+ + H-H

CH3CH2CH2OH + NaH
-

CH3CH2CH2O Na + CH3CH2I

2. Tercier Q-X

SN 2

CH3CH2CH2OCH2CH3 + NaI

SN1, E1

CH3

Plda
EtOH
-H+

CH3
CH3

C
CH3

CH3
Br

EtOH
-

-Br

CH3

CH3

OCH2CH3

CH3

C+
CH3

CH2

-H

CH3

C
CH3

Az alkoholok acilezse. Kzvetlen szterests.

R

H + R'

OH

O
C2H5OH

R' + H2O

O
K~4

+ CH3COOH

C2H5O-CO-CH3 + H2O

Savkatalizlt szterests
a) Primer alkoholok reakcija
+

O
R

OH

C
OH

H
O R'

OH
R

OH

OR'

OH

-H

OH H

OR'

OH
H+

O
R

+
-H

OR'

OR'

OH

-H2O

OR'

+OH

acil-O kapcsolat
C2H518OH + CH3COOH

C2H518O-CO-CH3 +

H2O

b) Tercier alkoholok reakcija

R'

H+

OH

-H2O

R'

OH2

R'
O
R C OH

R'

-H+

R'

alkil-O kapcsolat
(CH3)3C-18OH + CH3COOH

(CH3)3C-O-CO-CH3 + H218O

Egyb acilez reagensek

O
R

OH

R'

O
Cl

R' + HCl

karbonsav-klorid
O
R'
R

OH

O
R'

O
karbonsav-anhidrid

R' + R'COOH

Szulfonsavak szterei
O
R

OH

R'

Cl

O
szulfonil-klorid

R'

HCl

O
alkil-szulfont

Pldk
O
C2H5

OH +

CH3

O
Cl

C2H5

O
metnszulfonil-klorid

CH3 + HCl

O
etil-metnszulfont
O

C2H5OH

CH3

Cl

O
p-toluol-szulfonil-klorid
tozil-klorid

O
CH3

S
O
etil-tozilt

OC2H5

Szulfontok felhasznlsa SN2 reakcikban

O
Nu-

RCH2

O
R'

SN 2

Nu

CH2R +

O-

R'

j tvoz csoport

Plda
C6H5CH2CHCH3
OH

p-CH3-C6H5-SO2Cl

C6H5CH2CHCH3

-HCl

O-SO2-C6H5-p-CH3
C2H5OH

C6H5CH2CHCH3
O-C2H5

Alkoholok szervetlen savakkal kpzett szterei

Saltromossav szterek
R

OH

HONO

alkil-nitrit
Saltromsav szterek
R

OH

HONO2

CH2 OH
CH

OH

O NO2
alkil-nitrt

CH2 ONO2
+ HONO2

CH

CH2 OH

ONO2

CH2 ONO2
glicerin-trinitrt

Knsav szterek
R

CH3OH

OH + OH

H2SO4

SO2 OH

RO SO2 OH
alkil-hidrogn-szulft
deszt.

CH3O SO2 OH
metil-hidrogn-szulft

Foszforsav szterek
3R

OH + POCl3

CH3O SO2 OCH3

dimetil-szulft

O
RO

OR

OR
trialkil-foszft

Alkil-halogenidek ellltsa alkoholokbl

R

OH +

HX

CH3CH2CH2CH2OH + HBr

CH3CH2CH2CH2Br

CH3
CH3

CH3

OH +

H2O

CH3

HCl

CH3

Cl

CH3

Mechanizmus
a)

CH3CH2CH2CH2

OH

CH3CH2CH2CH2

OH2

Br

Br-

S N2

CH3

b)
CH3

OH

Cl

CH3

CH3

OH2

CH3

CH3CH2CH2CH2Br + H2O

OH2

CH3

CH3
C

OH2

CH3

CH3

CH3

CH3CH2CH2CH2

-H2O

CH3

C+
CH3

Cl

CH3

S N1

CH3

Cl

CH3

Egyb halognez reagensek

OH + PBr3
foszfor-tribromid

Br + H3PO3

OH + SOCl2
tionil-klorid

Cl + SO2 + HCl

Lucas reagens; cc. HCl + ZnCl2

+ ZnCl2

Cl

O
H

ZnCl2

ZnCl2

Cl

R + [Zn(OH)Cl2]

Az alkoholok dehidratlsa

HA

OH

OH

HA

C C
alkn

HO

ter

Pldk
H2SO4
180 C

CH2

CH2

CH3CH2OH
H2SO4
140 C

OH

CH3CH2OCH2CH3

85% H3PO4
170 C

CH3
CH3

OH

CH3

CH2
20% H2SO4
85 C

CH3

C
CH3

H 2O

+ H 2O

Mechanizmus

OH + H2SO4

C
E
-H+
-H2O

HO

+
OH2 + OSO2OH

OH2

SN

H
SO2 O

HO

-H2O
-H+

1. Primer alkohol

ter (SN2), alkn (E2)

(hmrskletfggs)

2. Szekunder alkohol

alkn, ter

3. Tercier alkohol

alkn (E1)

Az alkoholok oxidcija
O

O
R CH2OH
primer alkohol
R

OH
karbonsav

H
aldehid
R

CH

OH

R
szekunder alkohol

C O
R
keton

oxidlszerek: CrO3, Na2Cr2O7, KMnO4

3 (CH3)2CH-OH + 2CrO3 + 6H+ = 3(CH3)2CO + 2Cr3+ + 6H2O

izopropil-alkohol
aceton

A krm-trioxidos oxidci mechanizmusa

1.

CH

OH + CrO3

CH3

CH3
CH3

C
H

CH3

O Cr OH

CH3

O
H

O Cr OH

CH3

2.

CH3

CH3

C
+

Cr

O +

OH

O
H

H
3H2CrO3 + 6H+ = CrO3 + 2Cr3+ + 6H2O

kinetikai izotpeffektus
CH3

CH3

CH OH
CH3
krel

CD3

CD OH
CH3

CH OH
CD3

0.16

Az terkts hastsa

Nu +

Nurossz tvoz csoport

CH3CH2OCH2CH3 + 2 HBr

2 CH3CH2Br + H2O

Mechanizmus

1. CH3CH2OCH2CH3 + HBr

CH3CH2O

CH2CH3 + Br-

2. CH3CH2O

CH2CH3 + Br-

CH3CH2OH + CH3CH2Br

3.

CH3CH2OH

HBr

CH3CH2Br

H2 O

Epoxidok (oxirnok)
Elllts
CH2

CH2

OH

Cl

HO- (-H2O)

CH2

CH2

O-

Cl

-ClSNi

CH2

CH2

Az epoxidok hastsa
A) Bzikus kzeg

CH3
CH3

CH2

CH3
+

CH3O-

CH3OH

CH3

CH2OCH3

OH

Mechanizmus (SN2)
CH3
CH3

CH2

CH3
OCH3

CH3

C
O

CH2 OCH3
CH3OH

CH3
CH3O + CH3

C
OH

CH2OCH3

A) Savas kzeg
CH3
CH3

CH3

CH2

HA

CH3OH

CH3

CH2OH

OCH3

Mechanizmus (SN1)
CH3
CH3

CH3

CH2 + H+

CH3

CH3
C

CH2

+OH

CH3

CH2OH

OCH3

CH3

-H

CH3OH

CH3

C
+

CH2OH