HYDROCARBON THM - AREN

Lin kt

Benzen l h/c c tnh thm c bn nht.

Nhng phn t hoc ion l nhn thm khi tha k:
- c cu to vng phng, cha no v lin hp
- c s electron p to h thng lin hp tha cng thc Huckel 4n + 2
vi n l s t nhin (n = 0, 1, 2, 3)
n = 0 (2e)

n=1 (6e)

N = 2 (10e)

2. DANH PHP V NG PHN.

V tr nhnh + Tn nhnh + Benzen

Toluen

Ethylbenzen

n-propylbezen
iso-propylbenzen
(Cumen)

isobutylbenzen
Tert-butylbenzen

 Nu cc ng ng c 2 gc alkyl gn vo nhn benzen th 2 nhm

ny c th cc v tr khc nhau. Chng l cc p ca nhau.

1,2-dimethylbenzen
o-xylen

V tr:

Ortho (o-)
1,2

1,3-dimethylbenzen
m-xylen

Meta (m-)
1,3

1,4-dimethylbenzen
p-xylen

Para (p-)
1,4

 Hp cht c 3 nhm th trn vng

Vicinal (vic-)
1, 2, 3

Asymmetrical (as-)
1, 3, 4

Symmetrical (s-)
1, 3, 5

Danh php cc gc

Phenyl

o-phenylen
1,2-phenylen

o-tolyl

m-phenylen
1,3-phenylen

m-tolyl

p-tolyl

p-phenylen
1,4-phenylen

Benzyliden
benzal

Benzyl

Benzo
7

3. IU CH
3.1. hydro ha cc cycloalkan

Decalin
(perhydronaphtalen)

3.2. Pp trimer ha

Mesitylen

3.3. Pp wurtz - Fittig

3.4. Pp alkyl ha theo Friedel Crafts:

- tc nhn p RX,
- xt AlCl3 hoc 1 s acid Lewis, acid proton khc BF3, HF, H3PO4

P kh dng g to n alkyl. trnh a alkyl ha th dng lng

d benzen.
* Nu dng alkyl halogenid mang nhiu halogen th sp c th cha
nhin nhn benzen

10

3.5. Kh ha hp cht cha no

3.5.1. Kh ha carbonyl bng Zn(Hg)/HCl hoc NH2-NH2/HO-.
-Trnh c s a alkyl ha v c th to alkylbenzen vi mch
nhnh di thng

3.5.2. Hydro ha dy nhnh cha no gn trn nhn benzen

11

3.6. iu ch alkenylbenzen
Tch loi HX hoc H2O t dn xut halogen hoc alcol

allylbenzen

12

4. TNH CHT HA HC CA HYDROCARBON THM:

- P/ th i in t vo nhn benzen (SE)
- P/ cng vo vng benzen
- P/ oxy ha
4.1. Phn ng th i in t:
P/ qua 2 g:
g/1: to tc nhn i in t E+
g/2: E+ ttc vi vng benzen to phc phc

Phc

s/phm

Phc

13

Cc loi p/ th i in t
4.1.1. Phn ng halogen ha: xt AlCl3, FeCl3, FeBr3, CuCl2

14

4.1.2. Phn ng nitro ha

m-dinitrobenzen

1,3,5-trinitrobenzen
o-nitrotoluen

p-nitrotoluen
15

C ch p/ nitro ha:

16

4.1.3. Phn ng sulfonic ha:

Tc nhn: H2SO4, H2SO4 + SO3 (oleum)
P/ c t/c thun nghch. Cc acid arensulfonic l acid mnh, mui
sulfonat d tan trong nc

Acid p-toluensulfonic

Acid -naphtalensulfonic

Acid -naphtalensulfonic

17

4.1.4. Alkyl ha theo Friedel-Crafts.

Tc nhn p/ l RX, xt l acid Lewis nh AlCl3, FeCl3, FeBr3, CuCl2

C ch

Benzen khng cho p alkyl hoa nu trn vng mang nhm ht in t +

NR3, -NO2, -CN, -SO3H, -CHO, -COCH3, -COOH,- COOR hoc cc nhm
amino nh -NH2, -NHR, -NR2
18

Tc nhn alkyl ha c th l alken, alcol khi c H2SO4, H3PO4 lm x/t

Sn phm alkyl ha c th l mch thng hoc phn nhnh do tc

nhn i in t c th b ch/v c carbocation bn vng

19

4.1.5. Phn ng acyl ha:

Thay H ca nhn thm bng nhm RCO
Tc nhn : RCOX, (RCO)2O
Xc tc AlCl3 khan (p/ Friedel-Crafts), AlBr3, GaCl3, FeCl3, SbCl3,
SnCl4, BCl2

Alkylphenylceton

20

Acetylchlorid
Anhydrid acetic

Acetophenon

P/ acyl ha thng tin hnh trong dm CS2, nitrobenzen. Lng xt

AlCl3 phi dng nhiu hn v gia sp v xt c th to phc cht.

21

4.1.6. Mt s phn ng th i in t
Phn ng Gatterman:

Phn ng Gatterman Koch:

Phn ng th hydro ca hydrocarbon thm bng nhm CH2Cl

22

4.2. Phn ng cng hp ca hydrocarbon thm

Xy ra kh khn v benzen l 1 h lin hp
4.2.1. Cng hp vi hydro:

cyclohexan

O-xilen

methylcyclohexan

Cis-1,2-dimethylcyclohexan (90%)
Hoc H2/Pt,2000psi, 25oC

Trans-1,2-dimethylcyclohexan (10%)

23

Nu trn nhn benzen c cc nhm chc ald, ceton hoc ni i th

cc nhm chc v ni i b cng trc tin

24

4.2.2. Phn ng cng halogen

4.2.3. Phn ng oxy ha:

Nhn benzen bn vng vi cc tc nhn oxy ha mnh nh: KMnO4,
K2Cr2O7
Anhydrid maleic

Anhydrid phtalic

25

Phn ng ch xy ra ti C (dy nhnh) cn mang hydro

26

5. S nh hng trong phn ng th i in t-Qui tc Holleman

Khi nhn thm c sn 1 hay nhiu nhm th th nhng nhm ny
/h n v tr th tip theo vo nhn thm:
Nhm th loi 1: nh hng nhm th mi vo v tr ortho v para
ca vng benzen
X: nhm th tng hot (loi I)
h/ /t
CH3, C2H5, C3H7
NH2, NR2, -NHCOR, -O, OH, OCH3, OR, OCOR
F, Cl, Br, I

Do
+ I, H
- I, +C
- I, +C

o-bromoanisol (4%)

p-bromoanisol (96%)
27

Nhm th loi 2: nh hng nhm th mi vo v tr meta ca vng

benzen
X: nhm th gim hot (loi II)
NO2, SO3H, COOH, CN, CHO, COOR, COR
COCl, CONH2, CN, CCl3, CF3, +NH3, +NHR2

Do h/ /t
- I, - C
- I, - C

Acid m-bromobenzoic

m-nitrobenzaldehyd
28

Nu nhn thm c sn 2 nhm th th nhm th ba vo nhn thm

theo nhng qui tc:
- Nhm tng hot quyt nh s nh hng
- Nu 2 nhm th cng tng hot th u tin nhm mnh hn
- Hiu ng lp th c vai tr quan trng trong vic x/ v tr nhm
th th ba

29

30

V d:

Khi tin hnh p/ SE vo nhn thm thng thu c h/hp sp c t l khc nhau

31

32

L thuyt v s nh hng
Nu trn vng benzen c nhm th loi (I) th mt e tng. V tr
orto v para c mt e cao hn v p/ SE ch yu xy ra y

Khi vng benzen c nhm th loi (II), mt e gim. CTCH c/m

gim nhiu nht v tr orto v para, p/ SE xy ra v tr meta

33

Cch gii thch khc da vo bn ca trung gian carbocation

( ca phc )

34

35

36