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BG Hidrocacbon
BG Hidrocacbon
BG Hidrocacbon
Tc gi
CHNG 1. HIROCACBON NO
Hirocacbon l tn chung ca tt c cc hp cht hu c m thnh phn phn t
ch cha hai loi nguyn t l cacbon v hiro. Hirocacbon l nhng hp cht hu c
n gin nht.
Da trn c s cu to ho hc, c th phn hirocacbon thnh nhng loi sau:
- Khi mch hirocacbon l mch h, ta c cc loi hirocacbon no (ankan),
hirocacbon cha no cha cc lin kt i (anken), hidrocacbon cha no cha cc lin
kt ba (ankin).
- Khi mch hirocacbon l mch vng, ta c cc loi hirocacbon vng no
(xyclo ankan), hirocacbon cha no cha lin kt ba (xyclo ankin), hp cht thm
cha nhn benzen trong phn t (aren).
1.1. Ankan, gii thiu metan
1.1.1. Dy ng ng metan, ng phn
1) Dy ng ng metan
Ankan thuc loi hirocacbon mch h, trong phn t ch c cc lin kt CC,
CH nn gi l hirocacbon no hay cn gi l parafin (do c t i lc trong cc phn
ng ho hc).
Cng thc chung l: CnH2n+2 hay H(CH2)nH.
Khi
n = 1, l hirocacbon n gin nht: CH4 c gi l metan.
n = 2: ta c etan C2H6.
n = 3: propan C3H8
n = 4: butan C4H10.
Nh vy, mi khi tng n thm mt n v, ta c mt hirocacbon no mi ch
khc cht ng trc mt nhm CH2 gi l nhm metylen.
Ton b cc hirocacbon no mch h khc nhau trong thnh phn phn t bi
mt bi s cc nhm metylen hp thnh dy ng ng ca metan.
2) ng phn
a)Cu trc ca ankan
-Cng thc phng:
Trong phn t ankan, cc nguyn t cacbon u c lai ho sp3 nn phn t c
biu din bng ng ziczc.
H2
C
H 3C
H2
C
CH3
C
H2
H 3C
H2
C
C
H2
CH3
C H 3C H 2C H 2C H 2C H 2C H 2C H 3
n _ h e p ta n
Cc ankan c nhnh cng c biu din tng t.
3 e ty l h e c x a n
2 ,2 _ d im e ty l h e p ta n
Cl
2 _ c lo _ 3 _ m e ty l b u ta n
Cl
2 ,2 _ d ic lo p e n ta n
C
H
H
H
H 3C
H2
C
n _ b u ta n
H
C
CH3
H 3C
H
C
CH3
CH
iz o b u ta n
S nguyn t cacbon:
S ng phn:
1 2 3 4 5 6 7 8
1 1 1 2 3 6 9 18
- ng phn cu dng:
Ngoi cc ng phn cu to trn, ankan c ng phn cu dng l do kh nng
quay xung quanh lin kt C-C. Cc ng phn cu dng thng c biu din m
hnh lp th: phi cnh v newman.
Do kh nng quay xung quanh lin kt CC vi cc gc quay khc nhau nn c v
s ng phn. Song ngi ta ch quan tm ti hai dng: ng phn che khut c nng
lng cao nht v ng phn xen k c nng lng thp nht.
-Cng thc phi cnh: biu din s phn b nhm th hai nguyn t cacbon
chn theo hng ng cho t tri sang phi.
CH3
H
H
CH3
CH3
H
CH3
H
Nu cc nhm th trng nhau ta c dng che khut, nu nhm th sau nm gia hai
nhm th trc ta c dng xen k.
- Cng thc chiu Newman: phn t c nhn dc theo lin kt CC. Cacbon sau
che khut cacbon trc biu din bng ng trn cn cacbon trc l giao im ca
cc nhm th. Cc nhm th trng nhau l che khut, cn cc nhm th gia gc ca
nhau gi l xen k hay km hm.
CH3
H 3C C H 3
H
H
H
H
H
CH3
C5H12: pentan
C7H16: heptan
C9H20: nonan
C6H14: hecxan
C8H18: octan
C10H22: ecan
C2H5: etyl.
2) Danh php hp l
- Chn nguyn t cacbon c bc cao nht trong cu to phn t lm cacbon trung
tm mang tn mtan. Ln lt gi tn cc gc chung quanh nguyn t cacbon , gc
nh trc, gc ln sau v cui cng l mtan.
H 3C
H
C
H 3C
CH
H
C
CH3
T rim e ty l m e ta n
H
C
C 2H
H2
C
CH
m e ty l e ty l- n -p ro p y lm e ta n
-i khi, c th chn nguyn t cacbon trung tm mtan khng nht thit phi l
nguyn t cacbon c bc cao nht.
H 3C
CH
H2
C
CH3
d i iz o p r o p y lm e t a n
CH
H 3C
CH3
CH3
H 3C
CH3
CH3
h e c x a m e ty l e ta n
CH3
13
H2
C
12
H2
C
11
H2
C
10
H2
C
H2
C
H
C
C
H
H2
C
H2
C
H2
C
H2
C
H
C
H2
C
CH3
H2
C
H2
C
CH3
CH
H 3C
CH3
5 _ iz o p r o p y l _ 7 ( 1 ,2 _ d i m e t y l p e n ty l ) tr i d e c a n
T trng ca cc ankan tng ln khi phn t lng tng nhng khng qu 0,8 g/cm3.
trng thi kt tinh, mch cacbon ca cc ankan thng c dng zizc, cc nguyn
t cacbon nm trn mt mt phng cn gc ho tr th gn bng gc ca t din u.
Trong tinh th, cc phn t ny sp xp song song thnh tng b cch nhau mt
khong cch nh.
1.1.4. Cc phng php iu ch
Thng thng, cc phng php iu ch cc hp cht hu c c chia lm 2 loi:
phng php cng nghip v phng php phng th nghim. Hai phng php ny c
nhng im khc nhau sau y:
- Phng php cng nghip: thng thu nhn mt khi lng ln hp cht vi gi
thnh thp trong khi phng php phng th nghim cn tng hp mt vi trm
gam, mt vi gam hoc t hn v khng quan tm ti gi thnh sn phm v thi gian
tng hp.
- Phng php cng nghip thng chn cch thu nhn hp cht sao cho tin li v
vic tn dng dy chuyn cng ngh v thit b. V vy, phng php cng nghip ch
c ngha vi cch thu nhn mt hp cht nht nh. Tri li, phng php phng th
nghim quan tm n vic s dng cho c mt lot hp cht cng loi vi nhau.
1) Phng php cng nghip.
a) Ngun thu nhn chnh ca ankan l kh thin nhin v du m
Tri qua hng triu nm, cc cht hu c phc tp ca ng vt v thc vt
chuyn ho thnh hn hp ankan c thnh phn t 1 cho n 30, 40 nguyn t cacbon.
Kh thin ch cha nhng ankan nh (c phn t lng b) 75% mtan, 15% tan,
5% propan, phn cn li l cc ankan cao hn v nhiu cht khc. Du m c thnh
phn ankan phc tp hn. Bng phng php chng ct du m, ngi ta tch loi
ankan ra khi nhau v c ng dng rng ri trong i sng cng nh cng nghip.
Cc ankan l kh c s dng lm cht t, ankan lng dng lm nhin liu cho
cc ng c, ankan cao hn dng du dng lm cht bi trn, nha ng, cc ankan
rn dng lm nn.
T cc ankan cao, c th iu ch ankan thp bng cc phn ng cracking.
C nH 2n+2
C r a c k in g
C m H 2m +2
C (n -m )H 2 (n -m )
nC O
(2 n + 1 )H 2
C nH 2n+ 2
nH 2O
C n H 2 n -2
C nH 2n
H 2 ,P t ( P d ,N i)
C nH 2n+2
H 2 ,P t (P d ,N i)
C nH
2n+2
Zn
+ H+
RH +
Zn2+ +
X-
2HI
+
6HI
RH +
HX
RCH3
+
+
I2
2H2O +
3I2
Mg
CnH2n+1MgBr
CnH2n+2
+
MgBr(OH)
NaOH
RH +
Na2CO3
2Na
RR +
2NaX
+ 6Na RR + RR + RR + 6NaX
[ R C O O ] -N a +
anot
RCOO
c a to t
-e
-e
N a.
-C O
H 2O
N a O H + 1 /2 H
R.+ CO2
R.+ R.
+ 12H2O
4Al(OH)3 + 3CH4
-T sunfua cacbon:
CS2 + 2H2S + 8Cu
CH4
+ 4Cu2S
-T axtat natri:
CH3COONa + NaOH
CH4
+ Na2CO3
RH
HNO3
1 1 0 -1 4 0 0C , P c a o
NO2
H 2O
C H 3C H 2C H 2N O 2 + (C H 3)2N O 2 + C H 3C H 2N O 2 + C H 3N O 2
10%
40%
25%
15%
c) Phn ng sunfo ho
10
H 3C
H2
C
CH3
H 2S O
H 3C
H2
C
CH3
CH3
H 2O
CH3
Trong thc t, ngi ta thng khng dng sunfo ho trc tip bng H2SO4 c m
hay dng phn ng sunfo clo ho hoc sunfo oxi ho.
d) Phn ng sunfo- clo ho
Khi cho SO2 v clo cng tc dng ln ankan 20 300C c chiu sng bng n t
ngoi hoc c mt cht khi mo l peoxit ta s thu c sn phm l ankan.
C l2
R
AS
2 C l.
H +
R.
C l2
R. +
SO
SO
+
R
C l2
HCl
S O 2.
O2
S
C l + C l.
O2
S
Cl
2N aO H
S O 3N a
H 2O
NaCl
+ SO2 +
O2
S O 3H
S sunfo oxi ho cng c th tin hnh khi c mt anhydric axetic nhng phi tin
hnh nhit 450C v di p sut 1518 at.
2) Cc phn ng thuc lin kt CC
a)Phn ng t chy v oxy ho
11
nhit thng, oxi v cc cht oxi ho khc (c nhng cht oxi ho mnh nh
axit crmic v kali pemanganat) u khng tc dng vi hirocacbon no.
nhit cao, hirocacbon no chy trong khng kh to nhit v pht sng.
Phng trnh phn ng t chy hon ton nh sau:
2 C nH 2n+2 +
(3 n + 1 )O 2
2nCO 2 +
2 (n + 1 )H 2O
2Q
CH4
2H 2
Khi CH4 i qua thch anh nung ti 100012000C trong thi gian ngn 0,3s
s thu c sn phm: axetilen, tilen, butaien, nhit ln hn 12000C ch thu
c l axetilen:
12
C 2H 2
2C H 4
3H 2
-9 1 k c a l
C H 2N 2
H2
C
H2
C
H2
C
H2
C
N2
V d:
H 3C
H2
C
H2
C
H2
C
AS
C H 3 + C H 2N 2
H 3C
H2
C
H
C
+ H 3C
H2
C
CH3
CH3
H 3C
H2
C
CH3 + N2
H2
C
H
C
H2
C
CH3
CH3
CH4 +
2H2O
1 2 0 0 0 C H (1 ,2 5 % ) + it e ta n + C H
4
2 2
C + 2H 2
Khi tng p sut th s tng hiu sut thu CH4. Khi c mt xc tc v nhit thp
hn:
13
CH4
H2
3000C, cn bng hu nh dch chuyn sang phi (90% CH4) v 8000C cn bng
li dch chuyn sang tri (4,4% CH4).
b) Kh cacbon oxit v kh cacbonic
Cho hn hp kh gm cacbon oxit v hiro hoc cacbonic v hiro i qua xc tc
bt niken 2504000C:
CO
CO2
+
+
3H2
4H2
CH4
CH4
+
+
H2 O
2H2O
12H2O
3CH4 +
4Al(OH)3
Ngoi ra, c th thu phn cacbua kim loi khc nh: cacbua berili, thori, urani,
mangan.
d) i t cacbon isunfua v ng kim loi
Bng cch cho hn hp kh hiro sunfua, hi cacbon sunfua i qua Cu nung s
thu c kh mtan v ng I sunfua.
CS2
2H2S +
8Cu
CH4
4Cu2S
e) i t axetat natri v vi ti xt
un nng hn hp axetat natri vi vi ti xt c th thu c kh CH4:
CH3COONa +
NaOH
CH4
Na2CO3
CH4
2H 2
Cl2
CH3Cl
metyl clorua
CH2Cl2
metylen clorua
CHCl3
clorofom
CCl4
tetraclorua cacbon
CH3OH
ru etylic
O2
CH4
V 2O5 , 3000C
NH3 + O2
HCHO
formandehyt
HCN
axit xyanhydric
C
mc in, ch ho cao su
H2
NH3
XY
RX
HY
Cl2
AS hay 200-4000C
2Cl.
(1)
Cl2
Cl:Cl
Cl
Cl.
R.
R. +
RH
HCl
RCl + Cl
X2
(2)
(3)
Phn ng c th tip din cho n khi to thnh sn phm th hon ton cc nguyn
t hidro ca ankan.
- Giai on tt mch:
Tuy nhin, cc qu trnh trn y xy ra khng phi l vnh cu v s va chm ca
cc gc t do vi nhau, tuy rt t nhng vn c th xy ra v c th dn n s mt i
ca gc t do:
X.
X.
X2
(4 )
R.
R.
R2
(5 )
R.
X.
RX
(6 )
16
[R XX]*
S chuyn t R n trng thi chuyn tip l thu nhit nhng t trng thi
chuyn tip n sn phm l to nhit mnh. Do , giai on ny l to nhit.
Giai on tt mch cng l giai on to nhit.
1.2.3. nh hng ca cu to n phn ng th SR
Trong phn ng vi propan ca clo, gc n-propyl c to thnh khi tch i 1
hydro bc , izo propyl c to thnh khi tch i mt H bc 2. Ta nhn thy rng trong
phn t propan c 6 H bc 1 v 2 H bc 2 nn xc sut va chm ca Cl vi cc loi
hiro ny l 6:2 (3:1) c ngha l n-propyl clorua: izo-propyl clorua l 3:1. Nhng
trong thc t t l ny l 1:1 (45:55). iu ny c ngha l kh nng phn ng ca
izopropan gp 3 ln n-propan. V ch c gii thch bng nng lng hot ho Ea
dng tch H bc 3 nh hn rt nhiu so vi H bc 1. V ngi ta i n kt lun
rng kh nng tham gia phn ng halogen ho ca cac nguyn t H c thay i theo
dy sau:
H bc 1 < H bc 2 < H bc 3
Kh nng tham gia phn ng khc nhau ca cc loi H trong phn ng halogen ho
c gii thch da vo trng thi nng lng v bn ca cc gc t do trung gian
hnh thnh. V phn ng theo c ch gc nn t izopentan hnh thnh cc gc t do:
H3C
CH
H3C
C
H
H3C
CH2.
C
H3C
C.
H
C
H
H
C
C.
C
H
CH3
CH2
C 6H 5
CH2
1 ,0
4 ,0
0 ,3 1
I2
3 H 2O
3 I2
18
Trong iu kin thng, phn ng c khuynh hng chuyn dch v pha tri ti
to ankan. Mun cho phn ng chuyn dch v pha phi to ra dn xut iot cn dng
cc cht oxy ho mnh nh axit iodic HIO3 tch HI ra khi hn hp phn ng:
5H I
H IO 3
3H 2O
+ 3 I2
F2
HF
+ 1 0 3 k c a l/m o l
19
H2
C
CH3
H2
C
H2
C
CH3
1 - c y c lo p r o p y l b u t a n
m e t y l c y c l o p e n ta n
-Vi xycloankan mang nhm th ankyl, C1 c chn l cacbon mang nhm th,
cc nhm th cn li c nh s theo nguyn tc tng cc s th t l nh nht.
CH3
CH3
1
6
5
H 3C
H 3C
C 2H 5
CH3
2
CH3
6
7
2 - e ty l- 1 , 4 - d i m e ty l c y c lo h e p ta n
C 2H 5
6
1
3
1
1 ,5 - d i m e ty l x y c l o h e c x a n ( s a i)
2
H 3C
C 2H 5
CH3
CH3
4
1 ,3 - d im e ty l c y c lo h e c x a n
5
6
1 - e ty l - 2 ,6 - d im e t y l c y c l o h e p ta n
( s a i)
CH3
3
4
6 - e ty l - 1 ,5 d i m e t y l c y c lo h e p t a n
( s a i)
-Khi c nhiu nhm th ankyl khc nhau c cng cch nh s th s u tin theo
mu th t A, B, C.
CH3
CH3
1
2
C 2H 5
3
4
2 -e ty l-1 -m e ty l c y c lo p e n ta n
( s a i)
C 2H 5
5
4
1 - e ty l - 2 - m e t y l c y c l o p e n t a n
-Nu c s hin din ca halogen, coi chng nh nhm ankyl trong cch nh s
th t.
CH3
CH3
1
2
1
Br
1 - b r o m o - 2 - m e ty l c y c l o b u t a n
Br
1 - m e t y l - 2 - b r o m o c y c lo b u t a n ( s a i )
Me
Me
Br
H
C i s - 1 ,3 - d i m e t y l x y c l o b u t a n
Et
tra n s -1 -b ro m o -3 -e ty l x y c lo p e n ta n
d e c a l in
N o rb o rn a n
b a s k e ta n
cuban
Gi tn theo IUPAC:
-Xc nh s vng: s vng c suy ra t s ni i CC phi ct t thu c
hp cht mch h. Lc danh php s bt u bng bixyclo, trixyclo, tetra
b ix y c lo
trix y c lo
te tr a x y c lo
21
10
Cl
3
4
4
6
7
4
5
b ix y c lo [ 3 .1 .0 ] h e c x a n 8 - c lo r o b i x y c lo [ 4 .2 .0 ] o c ta n
6
7
5
8
4 - b r o m o - 9 - m e ty l tr ix y c lo [ 5 .3 . 0 1 ,7 .0 2 ,6 ] d e c a n
5
4
6
8
7
7
4
7
5
6
Br
8
4
2
b ix y c l o [ 2 .2 .2 ] o c ta n
3
2
1
1
6
2
tr ix y c lo [ 2 .2 .1 .0 2 ,6 ] h e p t a n
13
10
12
11
te tr a x y c l o [ 7 .3 .1 .0 3 ,1 3 .0 7 , 1 3 ] tr i d e c a n
1.3.2. ng phn
Mt hp cht vng gm cc loi ng phn sau y:
1) ng phn do s thay i s nguyn t cacbon ca vng
V d: C5H10
CH3
CH3
CH3
H 3C
CH3
C 2H 5
C
H
CH3
CH3
22
R'
CH3
R
R
H 3C
CH3
R'
R
R'
CH3
4) ng phn hnh hc
CH3
CH3
CH3
c is
tra n s
CH3
5) ng phn quang hc
Xut hin khi trong phn t c cacbon bt i.
6) ng phn cu dng
CH2
Br
)
C
H2
C H 2C l
2N a
n(H 2 C
Br
2N aB r
CH2
H2
C
2N a
H2
C
+ 2N aC l
CH2
Cl
+ Zn
H2C
C
H2
+ ZnCl2
H2C
CH2
Cl
+ C H 2N 2
N
N
C u ,t 0
C
CH2
+ N2
C
H2
c)Phn ng quang ho
as
C
HC
C
H
HC
C
H
CO
O
HC
CHR
HC
CHR
as
24
H 2C
2H 2C
CH2
H 2C
CH2
H 2C
CH2
H 2C
CH2
CH2
H 2C
OO
C
Ca
H
C
H 2C
C
OO
H 2C
H2
C
H 2C
C
H 2C
H2
C
H 2C
4 [H ]
C aC O 3
C
H2
Z n /H g + H C l
(H 2 /N i)
C
H2
H2
C
H 2C
CH2 +
H 2C
H 2O
C
H2
C 6H 6
N i ,1 9 0 0 C , 2 5 a t
3H 2
g) iu ch xyclopropan
Xyclopropan l cht kh, c kh nng gy m, c dng rng ri trong gii phu,
khng c hi cho c th v khng li hu chng. c sn xut bng phn ng
Gustabcon:
Cl
H2
C
Cl
H2
C
C
H
H2
C
CH2
HBr
H2
C
Br
+ Zn
Cl
H2
C
H2
C
H2
C
Br
+ Z n B rC l
25
B r2
H2
C
Br
H2
C
H2
C
Br
H 2C
HI
H2
C
H 3C
H2
C
H 2C
N i,8 0 0 C
2
H
C
H 3C
CH
A l2O 3,1 0 0 0
H 3C
C
H
CH3
+ H2
N i, 1 2 0 0
H 3C
H2
C
H2
C
CH3
26
H
C
H 2C
H
C
H 2C
CH2
OH
a x it o x a lic
H2
C
HC
CH2
HC
C
H2
H 2O
x y c lo p e n te n
A lC l3
3 0 -8 0 0C
Phn ng khng tin hnh mt chiu hon ton v pha phi. Phn ng t trng
thi cn bng khi thu c 75% xyclo hecxan v 25% metyl xyclo hecxan. Ngc lai,
nu i t metyl xyclopentan ta cng thu c hn hp tng t nh vy. Vy, khi c
mt nhm halogenua, gia hai hirocacbon ny thit lp mt trng thi cn bng. Cc
cn bng ho hc khng ph thuc vo cht xc tc v c ch phn ng m ch ph
thuc vo tnh bn nhit ng ca c hai thnh phn. Hn hp cn bng thu c
chng t rng vng 5 v 6 cnh c tnh bn gn nh ng nht.
Kt lun ny vn ng vi trng hp cn bng gia metyl xyclo hecxan v imetyl
xyclo pentan v xyclo heptan li chuyn hon ton thnh hn hp cn bng.
CH
H 3C
CH3
Tng t nh trn, xyclooctan chuyn hon ton thnh imetyl hecxan cn etyl
xyclo butan th chuyn thnh hn hp cn bng xyclo hecxan v metyl xyclo pentan.
T , ta kt lun rng cc vng 5 v 6 cnh l bn vng nht trong tt c cc vng.
Cc vng 5 6 cnh cng d c to thnh hn nhiu so vi cc vng nh v to. V
vy, trong thin nhin thng gp nhiu dn xut ca xyclohecxan v xyclopentan,
cn rt t gp cc dn xut ca cc xycloankan khc.
Khi tc dng vi halogenua, cc xyclo ankan loi vng 5, 6 cnh cng nh cc vng
ln hn khng b v vng m ch tham gia phn ng th.
27
C l2
Cl
HCl
109 0 28'
2
l gc a din u ca vng.
3
24044
4
9044
5
0044
6
-5016
7
-9033
8
-12046
9
-36016
1
6
3
4
a
e
e
e
a
a
a
CH3
e
e
e
a
a
a
a
e
H 3C
a
a
e
e
a
31
CU HI V BI TP
Bi 1. Nu c tnh ha hc ca ankan (minh ha bng cc phn ng) v nguyn nhn
dn ti c tnh , gii thch?
Bi 2. So snh tnh cht ha hc ca ankan v xicloankan. Gii thch v sao c s
ging nhau v khc nhau gia chng?
Bi 3. Nhit nng chy v nhit si ca cc ankan bin i theo cu trc phn t
ca chng nh th no, cho v d minh ha?
Bi 4. V sao nhit si v nhit nng chy ca xicloankan u cao hn hn so
vi n-henxan?
Bi4. Ion kiu metoni v cabocation ging v khc nhau nh th no (cu trc v
chuyn ha)?
Bi 6. Nhng yu t no (sc cng no) nh hng n bn xiclan? Cho v d?
Trong dy xiclan (CH2)n n = 313, v sao k hi n = 6 th entapi hnh thnh i vi mt
nhm CH2 l nh nht?
Bi 7. Tm quan trng ca ankan v xiclo ankan trong th gii ngy nay?
Bi 8. a) Vit cng thc cu to, gi tn theo danh php thng v danh php IUPAC
cc hidrocacbon ng phn c cng cng thc C4H10 v cc gc ankyl c cng cng
thc C4H9 .
b) Vit cc phng trnh phn ng tng hp ra n-butan t:
- Than v vi
- 2 butin
- 2 Iotbutan
- Axit valeric CH3 CH2 CH2 CH2 COOH
- Axit propionic CH3 CH2 COOH
c) Cho bit ti sao phn ng ha hc c trng ca ankan l phn ng th theo
c ch gc. Vit phng trnh phn ng xy ra khi cho clo tc dng vi n-butan c
chiu sng.
Bi 9. a)Vit cng thc cu to ca tt c cc hidrocacbon c cng thnh phn nguyn
t C5H12 v gi tn chng theo danh php thng v IUPAC. Cho bit bc ca tng
nguyn t cacbon tng ng.
b) T metan v cc hp cht v c cn thit hy tm cc phng php iu ch
ra izopentan.
Bi 10. a)T ru metylic v cc cht v c cn thit hy iu ch ra 2-metylpropan
v 2,2,4-trimetylpentan.
b) Trn 2-metylpropan vi clo theo t l 1:1 v th tch v tin hnh phn ng
khi un nng. Cc sn phm ca phn ng l 2-clo-2-metylpropan v 1-clo-2metylpropan c to ra theo t l phn t gam l 1:2. Cho bit nguyn t hidro
cacbon bc nht hay bc ba d phn ng hn.
Vit cng thc cu to ca cc dn xut monoclo sinh ra khi clo ha 2,2,4trimetylpentan.
Bi 11. a) Vit cng thc v gi tn cc ng phn cu to v ng phn lp th ca
nhng hp cht c cng thnh phn C5H8(CH3)2.
32
33
34
H2
C
C
H
CH2
e t y l e t il e n
CH3
d im e ty l e ty le n d o i x u n g
H 3C
C
H
C
H
H 3C
CH2
d im e ty l e tile n k h o n g d o i x u n g
CH3
H 3C
H
C
CH3
H2
C
C
H
C
H
CH3
5 - m e ty l- 2 - h e c x e n
H 3C
C
H
C
H
H2
C
H 2C
C
H
H2
C
H2
C
3 - b u te n y l
2 -b u te n y l
H 2C
H 2C
C
H
C
H
H2
C
H 2C
izo p ro p e n y l
a ly l
v in y l
CH3
2.1.3. ng phn
1) ng phn cu to
Ngoi ng phn v mch cacbon nh i vi ankan, cc anken cn c cc ng
phn v v tr ca lin kt i, do s ng phn cu to ca anken nhiu hn ca
ankan c cng s nguyn t cacbon.
V d: buten C4H8 c 3 ng phn trong khi butan C4H10 ch c 2 ng phn,
penten C5H10 c 5 ng phn trong khi pentan C5H12 ch c 3 ng phn, hecxen
C6H12 c 12 ng phn trong khi hecxan C6H14 c 5 ng phn.
S nguyn t cacbon trong phn t cng tng th s chnh lch v s ng phn cu
to gia anken v ankan tng ng cng nhiu.
2) ng phn hnh hc hay ng phn cis trans
S c mt ca lin kt i trong anken lm xut hin mt loi ng phn lp th,
l ng phn hnh hc hay ng phn cis trans. c im ca ng phn ny l hai
nhm th nh hai cacbon mang ni i v cng mt pha hoc khc pha vi ni
i, thc cht l cng pha hoc khc pha i vi mt phng ca lin kt i. Khi
hai nhm th cng pha ta c ng phn cis, khi hai nhm th khc pha cho dng
ng phn trans.
V d: 2-buten cho hai dng ng phn cis trans nh sau:
H
H 3C
CH3
c is - 2 -b u te n
H 3C
CH3
tra n s -2 - b u te n
36
Cl
Cl
Cl
Cl
t r a n s - d i c lo e t il e n
c i s - d i c l o e ti le n
Nhit si 0C
Nhit nng chy 0C
60,2
-80,5
1,289
1,89
d 15
4
Momen lng cc
48,3
-50
1,265
0
V tnh cht ha hc, ta thy s khc nhau r rt gia axit maleic (cis) v axit
fumaric (trans). Khi ung nng ch c axit maleic mi chuyn thnh dng anhiric:
H
H
C
C
COOH
COOH
a x it m a le ic
150 C
-H 2O
O
C
HOOC
COOH
O
H
C
O
a n h i d r ic m a le i c
a x it f u m a r i c
Ni chung l dng trans bn hn dng cis do trng thi nng lng thp hn.
2.1.4. Tnh cht vt l
Ba cht u tin trong dy ng ng nhit thng l cc cht kh, cc anken
trung bnh l nhng cht lng, cc anken cao hn l cc cht rn. Nhit si ca cc
anken gn vi nhit si ca cc ankan c cng s nguyn t cacbon trong phn t.
T khi ca cc anken hi cao hn so vi t khi ca cc ankan tng ng.
Tnh cht vt l c ngha quan trng ca anken l khc x phn t MR. MR c
tnh cht cng tnh, ngha l khc x ca phn t bng tng s khc x cc
nguyn t c trong phn t y. Cho nn MR ca cc ankan bng tng s khc x
ca cc nguyn t C v H c trong thnh phn phn t. Tuy nhin, trong trng hp
cc anken, MR c xc nh bng thc nghim (theo cng thc Lorentz-Lorenz) ln
hn tr s tnh l thuyt khi ch da vo khc x nguyn t. Do , i vi cc
anken c mt i lng b sung gi l s gia k hiu l F th hin c im cu to ca
anken l s c mt ca lin kt i trong phn t. Trung bnh, s gia F i vi mt lin
kt i bng 1,7 1,9.
Nh vy, bng cch so snh khc x phn t MR thc nghim vi khc x
phn t MR tnh theo l thuyt c th khng nh s c mt hay khng ca lin kt i
trong phn t.
37
Ph hng ngoi ca cc anken cho vch hp th gn 1650 cm-1, c trng cho dao
ng ho tr ca lin kt i C=C. Tuy nhin, cng v v tr ca vch ny cn ph
thuc vo cu to phn t ca anken, n thay i vi phn nhnh lin kt i v
vi s c mt ca lin kt cha no th hai lin hp vi lin kt i th nht.
2.1.5. Cc phng php iu ch
1) Tch nc ra khi ancol
Khi tch H2O ra khi ancol no, s thu c anken. C th tin hnh vic tch H2O
bng hai phng php:
a) Trong pha lng
un nng ancol vi axit mnh nh axit sunfuric hoc axit photphoric hoc vi kali
sunfat axit. Axit s tng tc vi ancol trc ht to ra este (este v c), sau b
phn hu s cho anken. S chung nh sau:
H2
C
H2
C
O H + H 2S O 4 d
H2
C
H2
C
t0c
H2
C
R
R
S O 3H
H2
C
C
H
CH2
S O 3H
+ H 2O
H 2S O 4
H 3C
OH
H O S O 3H
H 2O
C H 2O S O 3H
H 2C
H 3C
H 3C
CH2
C H 2O S O 3H
+
H 2S O
H
C
H
C
OH
R'
A l2 O 3
3 0 0 -4 0 0 0C
C
H
C
H
R'
H 2O
38
H
C
CH2
OH
C 6H 5
C
H
CH2
+ H 2O
s tir e n
p h e n y l m e ty l c a c b i n o l
H2
C
H 3C
H2
C
H 3C
C H 2O H
C
H
H2
C
C H 3 + H 3C
C
H
C
H
CH2
CH2
dd K O H , ancol
CH2
HX
CH3
H
C
H
C
R'
Zn
C
H
C
H
R'
ZnX2
C
H
C
H
COOH
t0 C
C 6H 5
C
H
CH2
CO
5) hiro ho ankan
Trong cng nghip cc anken thng iu ch bng cch ehiro ho cc ankan
di tc dng xc tc ca crm trioxit 4500C. Bng phng php ny, c th iu
ch c cc buten i t n-butan v izobutilen t izobutan.
Cc anken cng c to thnh khi nhit phn cc ankan v cc hirocacbon khc
trong phn ng cracking.
2.1.6. Tnh cht ho hc
1) Bn cht, c im ca lin kt i C=C
Lin kt i C=C c to nn bi hai nguyn t cacbon trng thi lai ho sp2, tc
l kiu lai ho tam gic. Trong lin kt i c mt lin kt do s xen ph trc ca
hai electron lai ho v mt lin kt do s xen ph bn ca hai electron p. Tt c cc
nguyn t ni vi hai cacbon mang lin kt i u nm trn cng mt mt phng vi
hai cacbon gi l mt phng phn t v gc ho tr mi cacbon mang lin kt i
bng 1200. Hai trc ca hai electron p song song vi nhau to thnh mt phng
thng gc vi mt phng ni trn. Thc cht ca lin kt to thnh l obitan lin kt
c mt electron bao ph c pha trn v pha di hai nguyn t cacbon mang ni
i.
Lin kt i c di bng 1,34 A, ngn hn so vi lin kt n (1,54 A). Nng
lng lin kt i C=C bng 145,8 kcal/mol, trong khi nng lng lin kt n
CC bng 82,6 kcal/mol. Gi thit nng lng lin kt trong lin kt i bng nng
lng ca lin kt n th nng lng ca lin kt bng 145,8 82,6 = 63,2
kcal/mol. Nh vy, nng lng lin kt ln hn nng lng lin kt , chnh
lch vo khong 20 kcal/mol, iu ny gii thch tnh km bn ca lin kt v kh
nng phn ng cao ca lin kt i. So vi ankan, anken c kh nng phn ng ln
hn nhiu. Cc phn ng c trng ca anken thng tp trung vo lin kt i, do
ni i c coi l trung tm phn ng ca cc anken.
Cc phn ng quan trng nht i vi anken l phn ng cng, phn ng oxi ho v
phn ng trng hp.
40
2) Phn ng cng
Cc phn ng cng c trng nht i vi anken l phn ng cng vo lin kt i.
Trong phn ng ny, mt na lin kt i thc cht l lin kt b b gy v kt hp
vi hai nguyn t hoc hai nhm nguyn t mi to ra hp cht no. S chung ca
phn ng cng vo lin kt i:
CH2 +
Br
Br
H 2C
Br
H 3C
CH3 +
Br
Br
H = -2 7 k cal
CH2
Br
2C H 3B r
H = -7 k cal
H2
41
CaCO3, Al2O3 Chng khc pha vi cc cht kh. Chng u khng tan trong mi
trng phn ng (dung mi hu c) v th gi l xc tc d th.
Pd/C xc tc cho s hyro ho anken thnh ankan trong dung dch etanol di p
sut thng, ngay 0200C. Trong iu kin , nhn benzen, nhm C=O, CN
khng b kh. V d:
H
C
H2
C
CH2
CH3
P d /C
H2
2 0 0C
H2
P d /C , 1 a t m
2 0 0C , C 2H 5O H
P d /C
C
H
C
H
COOCH3 +
H2
H2
C
2 0 C , C 2H 5O H
H2
C
COOCH3
Hyro ho dng xc tc Pt thng c tin hnh trong etanol, trong etyl axetat
hoc trong axit axetic di p sut thng, nhit 20500C.
Xc tc Ni c iu ch bng cch cho hp kim Ni-Al tc dng vi dung dch
NaOH nng nhm ho tan ht Al, li Ni dng ht xp, mn. Niken r hn nhiu so
vi cc kim loi qu nh Pd, Pt nhng n hot ng yu hn nn phi tin hnh hyro
ho nhit cao hn, 50 1000C, di p sut 510 atm. Niken hnh thnh theo
phn ng:
2NiAl
2OH- +
2H2O
2Ni
2AlO2-
+ 3H2
CH3
H2
CH3
1 ,2 - d i m e ty l x y c lo h e c x a n
P t/C , 1 a tm
2 0 C , C H 3C O O H
H
CH3
c i s - 1 ,2 - d im e t y l x y c l o h e c x a n
Phn ng hyro ho xc tc d th cng theo kiu syn m khng cng theo kiu anti
l do phn t H2 b hp ph trn b mt kim loi lm cho lin kt HH b yu i.
42
Ni
Ni
H 2C
Ni
CH2
Ni
Ni
H 2C
Ni
Ni
Ni
Ni
CH2
Ni
Ni
Ni
H 3C
Ni
CH3
Ni
Ni
Ni
Ni
Ni
OH
L in a lo o l
43
C a rv o n
H
CH3
C
CH3
D 2 /[(C 6 H 5 )3 P ]3 R h C l
B enzen
C
H
CH3
CH3
+ B r2
C
+ HOCl
+ H 2S O 4
Br
C
Br
C
Cl
OH
+ HCl
H
C
O S O 3H
C
+ H 2O , H +
Cl
OH
44
R 2C
CR2
R 2C
CR2
C ch cng electrphin tin hnh qua 2 giai on: giai on 1, tc nhn electrphin
(phn mang in tch dng ca tc nhn) tin cng vo ni i, kt hp vi cacbon
mang ni i giu electron hn, lm t lin kt v hnh thnh lin kt mi to
ra ion cacboni (cacbocation). Sau , trong giai on 2, cacbocation s kt hp vi
phn cn li ca tc nhn tch in m:
Giai on 1:
+ X
chm
Y
hoc
+ Y
+
X
Giai on 2:
nhanh
H 2C
CH2 +
B r2
+ N aC l
+ N aN O 3
Br
H2
C
H2
C
Br
Br
H2
C
H2
C
Cl
Br
H2
C
H2
C
ONO
45
Thc nghim cho thy rng, phn ng cng to ra nhng sn phm nh trong s
trn, ph hp vi c ch nhiu giai on.
C ch phn ng ny i hi dung mi phn cc, v trng thi chuyn tip v cc
sn phm ca giai on 1 c in tch ion, trong khi tc nhn li khng phn cc.
Br
Br
Br
Br
Br +
Br
C 6H 10 +
dung mi
HBr
C 6H 11B r
H al
H al
+
Hal
H al
Nh vy, phn ng cng electrophin thng xy ra theo kiu trans hay kiu anti.
V d: Khi cho (E)-anken (trans) cng XY cho cp erytr (nu X=Y cho ta c ng
phn mz), cn (Z)-anken (cis) cho cp tre. iu ny chng minh tin trnh cng
anti ca phn ng.
46
X
H
R
X
Y
R
H
R
X
Y
R
H
X
* Mt s phn ng AE ca anken:
- Phn ng cng halogen:
Cc halogen cng vo ni i ca cc anken mt cch d dng to ra dn xut
ihalogen, c hai halogen nh hai nguyn t cacbon cnh nhau.
V d:
H 2C
CH2
C l2
Cl
H2
C
H2
C
Cl
Flo hot ng qu mnh nn khi tng tc vi anken ngay nhit thp cng gy
ra phn ng phn hu anken. It hot ng yu nn phn ng vi anken l thun
nghch v cn bng chuyn hn v pha cc cht u. Phn ng cng ca clo v brm
vo anken vi hiu sut gn 100%. Do phn ng cng vo anken lm mt mu nhanh
dung dch Br2 nn phn ng ny thng c dng nhn bit anken. Ngi ta dng
CCl4 lm dung mi v n ho tan tt c Br2 ln anken nh vy m phn ng nhanh
hn, mu sc bin i r rt hn. Cng c th dng phn ng ny tch anken ra
khi cc hirocacbon khc. Cc hp cht khng no nh ankin, anehyt cng lm mt
mu dung dch nc brm.
- Phn ng cng hyro halogenua:
Cc hyro halogenua (HCl, HBr, HI) cng vo lin kt i ca anken cho cc dn
xut monohalogen. Phn ng xy ra d dng nht vi hyro ioua, kh nht i vi
hyro clorua.
H 2C
CH2
HI
H 3C
H2
C
CH2
HOCl
H O H 2C
H2
C
Cl
e t y l e n c lo h i d r i n
H 2C
CH2
H O S O 3H
H2
C
H 3C
O S O 3H
e ty l s u n fa ta x it
Cc anken lng khng tan trong dung dch axit nhng tan trong H2SO4 m c l
do phn ng cng xy ra. Cc ankyl hirosunfat to thnh d b thu phn khi un
nng vi nc to thnh ancol, chng hn:
C
H
CH2
H O S O 3H
H
C
CH3
H 2O
t0 C
H
C
CH3
OH
O S O 3H
+ H 3O
-H 2O
H 2O
OH
C
-H
H
Cht xc tc axit dng trong phn ng hyrat ho thng l HNO3, H2SO4. Dng
Hhal khng thun tin v bn thn Hhal c th cng vo ni i.
Khi mun hyrat ho nhng anken c t nhm th ni i ngi ta thng
dng H2SO4 m c cng vo ni i, sau thu phn axit alkyl sunfuric thu
c. Nu dng d anken axit alkyl sunfuric c th cng vo ni i to ra sunfat
ialkyl.
V d:
H 2O
H 2C
CH2
+ H 2S O 4
C H 3C H 2O S O 3H
H 2C
C H 3C H 2O H + H 2S O 4
CH2
(C H 3 C H 2O )2S O 2
Ngoi ra, ta cng c th hyro ho gin tip bng phng php hyrobo ho ri sau
xy ho trialkyl bo mi thu c. V d:
6 H 3C
C
H
C H 2 + B 2H 6
2 (C H 3C H 2C H 2)3B
+ 3 H 2O 2
hyrbo ho
oxy ho
NaOH
2 (C H 3 C H 2 C H 2 )3B
3C H 3C H 2C H 2O H
+ H 3B O 3
48
C
H
H
CH2
BH2
H
C
H 3C
CH
H2
C
H 3C
BH2
CH2
BH2
C
H
CH2
BH2
H
C
H 3C
H2
C
BH3
C H 3C H C H 2B H 2
H
C
H 3C
+ BH3
CH2
C H 3C H C H 2B H 2
2 H 3C
C
H
(C H 3 C H 2C H 2)3B
CH2
H
C
C
H
Br
d hn
H
C
H
Br
H
Br
kh hn
H 3C
C
H
CH2+
H 3C
HX
C
C H 2Y
(I)
H 3C
HY
C
C H 2X
(II)
XY
C
H
CH
Khi cho H+Cl- tc dng vi propilen, phn cation ca tc nhn (prton H+) s tn
cng vo cacbon mang in tch m, cn phn anion Cl- s tn cng vo cacbon mang
in tch dng.
- Gii thch theo trng thi ng:
50
H 3C
C
H
CH2
+ H
H 3C
H
C
(I)
CH3
Cl
H 3C
H
C
CH3
Cl
iz o p ro p y l c lo ru a
H 3C
C
H
CH2
+ H
H 3C
H2
C
(II)
CH2
Cl
H 3C
H2
C
H2
C
Cl
n -p ro p y l c lo ru a
51
HBr
cht chng oxy ho
H 3C
C H 2B r
C
chm
cng bnh thng
H 2C
C
H
+ HBr
C H 2B r
p e o x it
H2
C
B rH 2C
nhanh
C H 2B r
C
H
HBr
C
CH3
+ HBr
CH3
p e o x it
H2
C
H 3C
C H 2B r
2 R
+
+
HBr
HBr
ROH + Br.
ROBr + H.
H = -23 kcal
H = +39 kcal
C
H
..
CH2
+ B r.
C H 2B r
..
H 3C
+ HBr
C H 2B r
C H 3C H 2C H 2B r + B r.
H = -5kcal/mol
H = -11kcal/mol
- Giai on tt mch:
R. +
R.
RR
52
H 3C
H
(I)
H
C
H 3C
C H 2B r
(II)
.
CH3
Br
H 3C
H2
C
H
H
+ HX
H 3C
H2
C
H2
C
H
C
CH3
phm phn ng cng khc nhau, tu theo iu kin tin hnh phn ng v c tnh ca
tc nhn.
a)Tc dng ca kali permanganat
Di tc dng ca kali permanganat, trong dung dch trung tnh hoc kim, lin kt
i ca anken s kt hp vi hai nhm hidroxi nh khi cng vi hyro peoxit
HOOH, to ra 1,2-diol.
R
C
H
C
H
+ 2 [O H ]
H
C
H
C
OH
OH
+
C
Mn
O
OH
O-
OH
Mn
O
O
Mn
O-
K M nO 4
OH
Phn ng ny dng trong phn tch nhn ra ni i. Cho anken tc dng vi dung
dch kali pemanganat trong mi trng kim (thuc th Baye) dung dch s mt mu.
Trong iu kin mnh lit hn, dung dch axit v un nng, s xy ra phn ng b gy
phn t ch ni i to ra axit cacboxylic.
b)Tc dng cua axit cromic
Axit cromic c s dng rng ri oxi ho lin kt i hoc di dng dung dch
Cr2O3 trong axit aetic m c c mt H2SO4 hoc khng., hoc di dng dung dch
natri hoc kali bicromat. Phn ng b gy lin kt i to ra xeton hoc axit
cacboxilic. S to thnh xeton chng t s c mt nhm R2C=, cn s to thnh axit
cacboxilic chng t s c mt ca nhm RCH=:
R 2C
C
H
+ 3 [O ]
R 2C
COOH
54
OH
COOH
O -oxit
Axit peaxit dng trong phn ng ny di dng dung dch trong axit axetic v c
tng hp t hiro peoxit v anhiric axetic.
un nng lu nhit cao, ng l thu c anken oxit, ta li thu c sn phm
thu phn ca n, tc l iol.
OH
C
H 2O
OH
Cc diol thu c t anken mch vng l cc trans diol, khc vi cc diol thu
c khi dng tc nhn l permanganat l cc cis diol.
Trong dung dch Hcl pha long cha PdCl2 v ng, etylen b oxy ho n
axetaldehyt:
C2H4 + PdCl2
H2 O
[C2H4PdCl2]
Pd
2CuCl2
2CuCl
PdCl2
+ 1/2O2
2CuCl2 +
H2O
O2
CH3CHO
d)Ozon
Phn ln cc anken tc dng mt cch d dng vi ozon, ngay c khi nhit
thp, lin kt i b b gy, to ra sn phm gi l ozonit. Phn ng tin hnh ht sc
55
C
H
O2
R 2C
CHR
+ H 2O
R 2C
+ RCHO
+ H 2O
CHR
R 2C
+ H2
+ RCHO
+ H 2O
H 3C
C
H 3C
CH2
H 3C
O
CH2
+ O3
H 3C
+ H 2O
O + H C H O + H 2O 2
H 3C
O
C
H
C
H
H2
C
a) Th v tr alyl
Trong nhng iu kin xc nh, tc dng ca clo n anken khng to ra dn xut
diclo m cho sn phm th kiu alyl theo s sau:
H2
C
C
H
C
H
+ C l2
H
C
+ HCl
Cl
CH2
+ C l2
H 2C
H 3C
C H 2C l
+ HCl
CH3
Sn phm ph l 1,2-diclo-2-metyl-propan.
Thc cht c s di chuyn ni i theo c ch phn ng sau y: trc ht c phn
ng cng bnh thng ca cation clo Cl+ vo mt cacbon mang ni i; sau cation
ny hoc s cng vi anion clo Cl- cho sn phm cng bnh thng hoc s tch mt
proton H+ cho sn phm th alyl:
H 3C
C
CH2 +
H 3C
C l :C l
H 3C
C H 2C l
CH3
Cl
+ Cl
H 3C
H 3C
C H 2C l
Sn phm ph
C H 2C l
CH3
-H
CH3
H 2C
Sn phm chnh
C H 2C l
CH3
H 3C
C
H
CH2
+ C l2
5 0 0 -6 0 0 0C
C lH 2 C
C
H
CH2
a ly l c lo r u a
b)Th v tr vinyl
57
H 2C
CH2
+ C l2
2 0 0 -6 0 0 0 C
Cl
C
H
CH2
Phn ng ny dng trong cng nghip sn xut vinyl clorua lm nguyn liu tng
hp mt polime c gi tr l PVC. Hiu sut sn phm phn ng clo ho tng ln (n
90%) nu tin hnh phn ng 250-3500C c mt 0,5% oxi (oxi lm gim phn ng
cng clo).
C ch phn ng clo ho etilen nhit cao cng l c ch gc dy chuyn kiu
nh clo ho ankan.
t0
2 C l.
C l :C l
H 2C
CH2
H 2C
CH.
C l.
+ C l: C l
+
CH.
H 2C
H 2C
+ HCl
C l + C l.
C
H
(A)n
n l h s trng hp.
A l mnme.
V d:
n H 3C
C
H
CH2
H
C
CH2
H2
C
R . + C C l4
.
H 3C
H2
C
H2
C
H 2C
H2
C
C C l3
H2
C
H 3C
+ C C l4
C C l3
H 2C
Cl +
C H 2 + .C C l3
H 2C
R . + C O 2 + .O C O R
Cl
C C l3
C H 2 C H 2 C C l3 +
C C l3
CH2
H2
C
C C l3
+ C C l4
Cl
( C H 2 C H 2 ) 2 C C l3 +
C C l3
v .v ...
Cl(CH2CH2)nCCl3
S to thnh nhng sn phm phn ng khc nhau c cha s gc etilen khc nhau
ph thuc vo iu kin phn ng.
Thu phn dn xut tetracloankan thu c s to ra ankyl cacboxylic.
Cl
( C H 2 C H 2 ) n C C l3
+ 2H 2O
C l( C H 2 C H 2 ) n C O O H +
3H Cl
59
H
H
-H X
-H X
1) C ch phn ng tch
Phn ln nhng phn ng tch quan trng l nhng phn ng nucleophin xy ra
trong dung dch (cc c ch E2, E1, E1cb) v phn ng theo c ch vng (Ei) xy ra
trong tng hi nhit cao.
a) C ch E2
C ch phn ng tch nucleophin lng phn t E2 c nhng nt tng t c ch
phn ng th SN2 v cng l phn ng mt giai on v i qua trng thi chuyn tip l
mt phc hot ng.
Khc vi phn ng SN2, trong phn ng E2, phc hot ng sinh ra do tng tc
gia tc nhn Y- v nguyn t -hyro trong phn t cht p: phc ny tch prton
cng vi Y- v nhm X ng thi to ra sn phm cha no:
H
C
+ YH
+ X
B rH
C
H
H
Br
H 3C
H
C
H
H
H 3C
+ Br
+ C 2H 5O H
C 2H 5O
60
-X
Y
R
-H Y
R
ttct anti
X
H
-H Y
-X
ttct syn
Br
nhanh
-HBr
H
Br
CH
C
Br
Br
Br
chm
-HBr
-Nu so snh nng lng ca cc trng thi chuyn tip th trng thi ng vi s
tch kiu trans n nh hn trng thi ng vi s tch kiu cis v khng c s y nhau
gia cc nhm C. . .H. . . Y v C. . . X .
X
sp 3
sp 3
sp 3
cht u
p
sp 3
sn phm
62
H
H
H 3C
H 3C
i- C 3 H 7
C l i- C 3 H 7
m e n te n -3
75%
(I)
H 3C
i- C 3 H 7
i- C 3 H 7
(III)
25%
H
100% H C
3
Cl
i- C 3 H 7
H
CH3
(II)
Cl
m e n te n -2
S u tin tch theo kiu trans trong phn ng E2 l quy lut c ngoi l. V d,
phn ng E2 ca hyroxit trans-2-phenylxyclohexen tc l tch theo kiu cis.
C 6H 5
C 6H 5
H H
HO
N (C H 3 )3
Br
IB r +
R
IB r +
C
H
Br
H
C
+ Br
R
I2 + B r
b)C ch E1
C ch phn ng tch n phn t E1 tng t c ch n phn t SN1 v giai on
chm to ra cacbocation, nhng giai on sau th khc ca phn ng. Trong phn
ng E1 cacbocation tch prton to ra sn phm cha no.
63
chm
nhanh
+ X
+ H
X : C l , B r , I , O S O 2 R , S R 2 , O H 2 . ..
(C H 3)3C
Br +
sol
(C H 3)3C so l
(C H 3)3C so l
(C H 3)2C H
+
CH2
B r so l
+
H sol
64
+ Y
+ YH
+ X
O
C
H2
C
-H 2O
O
C
-H 2O
-N H 2
O
C
C
H
C
H
C
H
OH
H2
C
C
OH
O
C
H2
C
C
NH2
CF3
N aO D
-H
C C l2
CF3
C l2 D C
CF3
C l2 C
CF2
-F
C 6H 5
C 6H 5
NO
N OO2 C O C H 3
N OC2 6 H 5
(I I)
(I)
E1
cc c ch
trung gian
E2
E1cb
d)C ch Ei
C ch Ei thng gp trong cc phn ng nhit phn ankyl axetat (to ra anken v
CH3COOH), ankyl xantogenat (to anken, CH3SH v COS), oxit amin bc 3 (to
anken v hyroxylamin) V d:
C H 3C H 2C H 2O C O C H 3
C H 3C H 2C H 2O C S S C H 3
C H 3C H 2C H 2(C H 3)2N O
5 0 0 0C
H 3C H C
CH2
C H 3C O O H
H 3C H C
CH2
COS +
H 3C H C
CH2
(C H 3)2N O H
300 C
15 0 0C
C H 3S H
Phn ng Ei l phn ng mt giai on, i qua trung tm chuyn tip vng kiu
perixilic. V d:
O
O
C
O
O
O
HO
C
R
C
R
66
E1
C H 3H C
CHCH3
H 2C
C H C H 2C H 3
chnh
OH
C H 3C H C H 2C H 2C H 3
E1
H 2C
C H C H 2C H 3 +
C H 3H C
C H C H 2C H 2C H 3
chnh
OH
H
C
H 3C
ph
(C H 3)2 S
E1
CHCH3
H 3C H C
chnh
CH3
ph
CCH3
CHCHCH3
H 2C
ph
CH3
CH3
E2
C 2H 5O
C H 3H C
chnh
CHCH3
H 2C
ph
C H C H 2C H 3
Br
HO
E2
C H 3H C
ph
CHCH3
H 2C
C H C H 2C H 3
chnh
67
C H 3C H C H 2C H 2C H 3
bazo
E2
C H 3H C
ph
C H C H 2C H 3 +
H 2C
chnh
C H C H 2C H 2C H 3
S O 2C H 3
I
80
20
Penten-2
Penten-1
Br
75
25
Cl
64
36
F
18
82
C
H
X
C
69
Br
Br
C
HO
H 3C H C
C H 2C H 3
C
H
CH2
H 3C
HO
Br
CH3
HO
HO
-H 2O
-H 2O
-B r
-B r
H 3C H 2C
b u te n -1
H 3C
CH3
b u te n -2
(bn hn) 80%
O
H
H
H
Et
Et
Me
Me
HO
Me
Me
NM e3
cu dng km bn
N M e3
TZ
Et
Me
Me
-H O H
-N M e3
Sn phm Zaixep
70
O
H
P r-i
Pr
-H O H
-N M e3
HO
Me
Me
NM e3
N M e3
cu dng bn
P r-i
Me
TH
Sn phm Hopman
S
H
(II)
(I)
C
CH3
H2
C
C
CH3
CH3
CH3
CH3
Cl
E1
H 3C
H2
C
C
CH3
C
CH3
an k en -1 8 1 %
C H 2 + H 3C
CH3
C
H
C
CH3
CH3
a n k e n -2 1 9 %
71
H 3C
H 3C
H
C
H
C
CH3
S (C H 3 )2
H
C
H
C
CH3
CH3
CH3
H
H
H 3C
H
C
C
CH3
H 3C
H 3C
H 3C
91%
CH3
Anken bn hn
(H 3C )2 H C
(H 3C )2H C
9%
Anken km bn
72
H
C 6H 5
C 6H 5
C 6H 5
C 6H 5
C 6H 5
Cl
(I)
C 6H 5
H
Cl
Cl
(II)
(III)
O
H
C 6H 5
HO
C 6H 5
C 6H 5
Cl
(I)
C 6H 5
-H O H
-C l
H
C l
C 6H 5
C 6H 5
HO
H
C 6H 5
C 6H 5
C 6H 5
C l
Cl
tra n s- stilb e n
O
H
C 6H 5
C 6H 5
C 6H 5
-H O H
-C l
(II)
c is -stilb e n
Gin nng lng ca hai qu trnh trn c trnh by hnh sau. So snh
cc gin , nht l so snh cc nng lng hot ho ta thy hng to thnh transstilben thun li hn hng to thnh cis-stilben. Thc nghim xc nhn lp lun
trn l ng.
i vi cc phn ng E1, nu cacbocation trung gian sinh ra t quay t do c
th bt k hai dng hnh hc ca cht u nh th no, trng thi bn ca ion cng s l
trng thi m trong nhm ln hn ca cp nhm th L-N s i din vi nhm nh
hn ca cp nhm th L-N (L: ln, N: nh).
N'
N'
L
L'
L
N
hay
L
H
N
HO
C
H 2C
H2
Br
HO
C
H2
Br
75
CH3
CH3
CH3
H 3C
H 3C
Br
HO
SN1
H 3C
C
CH3
OH
H 3C
CH3
-B r
CH3
CH3
HO
E1
C
H2
-H O H
OH
CH3
CH3
HO
H 2C
CH3
C
CH3
CH3
KOH
KOH
C 2H 5O K
t- C 4 H 9 O K
HOH
C 2H 5O H
C 2H 5O H
t- C 4 H 9 O H
d) nh hng ca nhit
i vi mt cht hu c nht nh, hai phn ng song song v cnh tranh nhau
thng khc nhau v nng lng hot ho.
Theo phng trnh Areniut k BZe E / RT , mt nhit nht nh, nng lng hot
ho cng ln phn ng s cng chm nhng nu nhit tng vn tc ca phn ng
no c nng lng hot ho ln hn s tng nahnh hn. Cho nn, c th c nhng
phn ng nhit phng th xy ra chm (Ea ln) nhng nhit cao li xy ra rt
nhanh.
Cc phn ng tch v th nucleophin thuc loi nhng phn ng song song v cnh
trnah nhau. Phn ng tch thng c nng lng hot ho ln hn phn ng th
2 1kcal / mol . V d cc phn ng lng phn t gia bromua izopropyl v etylat natri
c nng lng hot ho ln lt l SN2: 20,8 kcal/mol; E2: 22,1 kcal.mol.
V l do ny, khi tng nhit phn ng ln th t l gia cc sn phm tch v th
E/S cng tng ln tc l tng hiu sut anken.
V d: un EtOH vi axit sunfuric m c nhit < 1400C tao c Et2O l
chnh, nng nhit ln th hiu sut ete gim, hiu sut etylen s tng, ti >1800C th
sn phm chnh l etylen.
a
H 3C
C H 2O H
H 3C
C H 2O H
+ H 2S O 4 d d
t0 > 1 7 0 0 C
A l2 O 3 , 3 5 0 0 C
H 2C
CH2 +
H 2O
H 2C
CH2 +
H 2O
CH
H2
Ni
H 2C
CH2
CH2 +
C l2 + H O H
H 2C
Cl
KOH
CH2
H 2C
CH2
O
OH
e t y le n c l o h y d r i n
e t y le n o x it
+ H 2C
CH2
H2
C
A lC l3
e ty lb e n z e n
CH3
C
H
-H 2
CH2
s tire n
H 3C
C H 2O H
ru etylic
+H OH
H 3C
C H 2C l
Etyl clorua
+ HCl
H2
C
Br
H2
C
Br
dibrometan
cht chng chy n cho xng
+ B r2
H 2C
CH2
H2
C
Cl
H2
C
Cl
Diclo etan
Dng iu ch cao su polisunfua,
dng iu ch etylen diamin
+ C l2
H2
C
Cl
H2
C
OH
e ty l e n c l o h id r in
+ HOCl
H 2C
CH2
O
e t y le n o x it
+ O 2, xt
+ C 6H 6, x t
C 6H 5
C 2H 5
e t y lb e n z e n
C 6H 5
C
H
CH2
s ir e n
Trng hp
H2
C
H2
C
p o li e t y le n
2.2. Ankadien-tecpenoit
2.2.1. Ankadien
1) Cu to v gi tn
Cc hirocacbon cha no cha nhiu ni i trong phn t gi chung l polien hoc
poliolefin.
Tu theo v tr tng i ca cc ni i trong mch cacbon, c th chia thnh ba
loi polien chnh sau y:
+ Polien c ni i cch bit:
78
C
CH3
C
H
H2
C
(C H 2 C
CH3
C
H
H2
C
H2
C
C
H
CH3
CH3
H
C
H
H
C
H
s to thnh lin kt
trong phn t 1,3-butadien
H 2C
C
H
C
H
CH2
H 2C
C
H
C
H
CH2
C
C
C
C
H
H
C
C
s - c i s - b u t a d i e n - 1 ,3
s - t r a n s - b u t a d i e n - 1 ,3
C
H
CH3
is o p re n
2 - m e t y l - 1 ,3 - b u t a d i e n
CH2
x ic lo p e n ta d ie n
x ic lo -1 ,3 -p e n ta d ie n
H 3C
C
H
H2
C
CH2
C
H 2C
CH2
8
7H
m irx e n
6 - m e t y l e n - 2 - m e t y l - 2 ,7 - o c t a d i e n
81
H 3C
C
CH3
CH3
CH3
H
CH3
H 3C
(S )-1 ,3 -d im e ty la lle n
H 3C
CH3
H
H
(R )- 1 ,3 -d im e ty la lle n
H 3C
CH3
C
c i s - 2 , 3 ,4 - h e c x a t r i e n
tra n s -2 ,3 ,4 -h e c x a trie n C H 3
2) Tnh cht vt l
a)Tnh cht vt l thng thng
S bin i cc tnh cht vt l thng thng ca polien cng tun theo nhng quy
lut nh i vi anken v ankan. V d:
Polien:
0 0
s
t , C
t 0nc , 0 C
d,g/ml
CH2=C=CH2
-34,3
CH2=C=CH=CH3
-10,8
-146
-136
0
0,662 (-35 C)
CH2=CHCH=CH2
-4,7
-108,9
0,667 (0 C)
0,650 (-60C)
b)Tnh cht ph
Ph electron ca cc polien lin hp c nghin cu kh k v rt c ch trong
vic xc nh cu to ca cc polien lin hp thin nhin cng nh tng hp. Khi mch
lin hp ko di, c max v max u tng mnh. Cc nhm th gn vo h lin hp
lm tng max theo nhng gia s ring c tnh cht cng tnh. Chng hn, mi nhm
ankyl lm tng max thm 5nm, mi nhm RO lm tng 6nm, nhm RS lm tng
ti 30nm.
Gi tr CC ca cc polien lin hp nh hn CC polien thng cng nh CC
anken. Tt c chng u nm trong vng 1600-1650 cm-1. CC ca allen th ln ti
1950 cm-1 tc l nm trung gian gia anken v ankin (2100-2300 cm-1). Dao ng ho
82
tr ca lin kt Csp2H polien thng v polien lin hp ging nh anken (30003100 cm-1).
chuyn dch ho hc ca proton gn vi Csp2 polien thng v polien lin hp
khng khc my so vi anken (khong 4,5-6 ppm) cn ca proton allen th thp hn
hn (khong 4-5 ppm).
3) Cc phng php iu ch v ng dng
Butadien l mt trong nhng nguyn liu quan trng nht tng hp cao su nhn
to v c iu ch bng nhng phng php khc nhau.
a)Nhit phn du m
Khi nung nng mt s phn on du m n 700-8000C, s thu c butadien vi
hiu sut 3-4%.V vy, khi cracking du m trong cc kh cracking thu c, thng
lun c cha mt lng nh butadien.
Mt s hirocacbon b nhit phn cho butadien vi hiu sut cao. Chng hn, khi
cho xiclohecxen trng thi kh i qua mt dy kim loi nung bng dng in s
cho butadien v etylen. (phng php Zelinski).
CH2
CH2
+
CH2
CH2
C
H
C
H
CH3
H 2C
C
H
C
H
CH2
+ H2
Do phn ng lm tng th tch nn tin hnh trong iu kin p sut thp s thun
li hn. trnh phn ng trng hp c th xy ra ng thi, xc tc c ph mt
lp cacbon mng. Xc tc mi c bit hot ng l canxi niken photphat kp
Ca8Ni(PO4)6 c hot ho bi crom oxit cho hiu sut 87%.
Vic ehydro ho n-butan thc hin qua hai giai on. Trc ht, n-butan b
ehydro ho trong iu kin nh nhng thnh cc n-buten; cc n-buten c tch ra
khi hyro v cc hirocacbon C3 v C2, sau cc n-buten b ehydro ho thnh
butadien nh m t trn.
c) i t axetylen
T axetylen, c th iu ch butadien bng nhiu cch khc nhau:
-Trng hp thnh vinylaxetilen ri hyro ho.
HCCH
HCCH
CH2=CHCCH
CH2CHCH=CH2
83
-Cng HOH qua axetandehyt, qua andol, qua butilen glicol ri thnh butadien.
HC
CH
+H O H
H 3C
C H 3C H O
H2
C
CHOH
+KOH
H 3C
H
C
CHOH
C H 2O H
H 2C
C
H
CHO
C
H
CH2
HC
CH
+2H CH O
H O H 2C
-H 2O
-H 2O
+H 2
C H 2O H
H 2C
C
H
H O H 2C
C
H
H2
C
H2
C
C H 2O H
CH2
te tr a h y d r o f u r a n
d)i t etanol
- Phng php Ostromlensli: cho hn hp etanol v axetandehyt i qua nhm oxit
300-4000C:
CH3CH2OH
CH3CHO
CH2=CHCH=CH2 +
2H2O
4) Tnh cht ho hc
Tnh cht ho hc ca polien thng (polien bit lp) hon ton tng t nh anken.
Do c im cu trc electron, tnh cht cc allen khc hn cc anken v c phn no
ging vi cc ankin. Cn polien lin hp th v c bn tng t nh anken nhng n
cng c nhng nt c o ring.
Polien lin hp, nht v ien lin hp c ngha thc t v l thuyt quan trng hn
c, v th trong chng ny ch yu xem xt cc phn ng ca chng.
Butadien l mt cht kh, izopren v dimetyl butadien l nhng cht lng nhit
thng.
nh hng lin hp th hin r kh nng phn ng tng ln trong cc phn ng
cng v c bit l cc phn ng cng 1,4. Loi phn ng vo cc u mch ny
khng gii hn trong cc dien m cn th hin trong nhiu hp cht hu c khc c
cha h ni i lin hp. Ngoi ra, cc ankadien c ni i lin hp cn rt d tham
gia phn ng trng hp thnh cc polime dng ch cao su nhn to.
a) bn ca dien lin hp
bn ca cc dien lin hp c xc nh bng nhit hyro ho cc dien. Kt qu
thc nghim cho thy rng nhit hyro ho ca cc anken nh sau:
RCH=CH2
~30 kcal/mol
R2C=CH2
~28kcal/mol
RCH=CHR
~28kcal/mol
R2C=CHR
~27kcal/mol
CH2=CHCH=CH2
30 + 30 = 60 kcal/mol
57 kcal/mol
CH3CH=CHCH=CH2
28 + 30 = 58 kcal/mol
54 kcal/mol
So snh cc kt qu tnh ton theo l thuyt v thc nghim ta thy cc dien lin
hp bn hn cc ien khng lin hp.
b)Phn ng cng
- Cng brom.
Khi cho butadien tc dng vi brom s thu c sn phm cng 1,4 l 1,4dibrombuten v mt lng nh 3,4-dibrom-1-buten l sn phm phn ng cng vo
ni i:
Cho butadien cng vi clo trong dung dch cacbon disunfua s thu c sn
H 2C
C
H
C
H
CH2 +
B r2
Br
H
C
C
H
C
H
1 ,4 - d i b r o m 2 - b u t e n
C H 2B r + B r
H2
C
H
C
C
H
Br
3 ,4 - d i b r o m 1 - b u t e n
CH2
Trc y, Thil gii thch phn ng cng 1,4 bng thuyt ho tr d: Thil
cho rng trong butadien mi nguyn t cacbon c mt ho tr d, cc ho tr d C2
v C3 kt hp vi nhau cn cc ho tr d C1 v C4 trng thi t do nn d kt hp
vi cc nguyn t khc cho sn phm cng 1,4. Gi thuyt ca Thil gii thch c
phn ng cng 1,4 nhng khng gii thch c s hnh thnh sn phm cng 1,2.
Theo quan im hin i, c ch phn ng cng brom tin hnh theo hai giai
on nh khi cng brom vo mt lin kt i ring bit. Phn ng cng brom l mt
phn ng cng electrophin, khi cation Br+ tin li gn butadien s gy ra s phn cc
trong phn t butadien v Br+ tn cng vo mt u ca h lin hp to ra mt ion
cacboni trung gian:
H 2C
C
H
C
H
CH2 +
Br
H 2C
C
H
C H 2B r
H 2C
C
H
H 2C
C H 2B r
C
H
C
H
C H 2B r
H 2C
C
H
C
H
C H 2B r
Br
H
C
Br
H2
C
Br
C
H
H
C
C
H
C H 2B r
C
H
CH2
Br
Trc khi thit lp cn bng, cc sn phm cng 1,2 v 1,4 d dng chuyn ho ln
nhau. Hn hp cn bng cha khong 80% sn phm cng 1,4. S ng phn ho tin
hnh nh s phn li ca ion Br-. Trong s phn li , c hai dn xut dibrom u cng
cho mt cation alyl l sn phm trung gian ca phn ng cng brom, l cation c nng
lng thp v bn vng hn c.
T l cc sn phm cng 1,2 v 1,4 cng cn ph thuc vo iu kin tin hnh
phn ng. Trong dung mi phn cc nh trong axit axetic nhit 400C t l sn
phm cng 1,4 t khong 70-80%,
- Cng hyro clorua.
86
Cho butadien tc dng vi hyro clorua cng to ra hai sn phm cng 1,2 v 1,4
nhng trong trng hp ny sn phm cng 1,2 t ti t l 75-80% cn sn phm
cng 1,4 ch chim t l 20-25%.
H2
C
Cl
H 2C
C
H
C
H
C H 2B r
H 2C
C
H
C
H
CH3
C
H
Cl
C
H
CH3
2 0 -2 5 %
H
C
H 3C
C
H
CH2
C l 7 5 -8 0 %
- Hyro ho.
Phn ng cng hyro vo butadien thng tin hnh bng cch dng hyro mi
sinh do tc dng ca kim loi vi dung mi proton ha c nh nc, ru hoc axit.
Khi kim loi cho phn t butadien hai electron ng thi chuyn thnh ion trong
dung dch, phn t butadien b phn cc ho v ln lt nhn hai proton t dung dch.
Phn ng hyro ho tin hnh theo s sau:
2e
H 2C
C
H
C
H
CH2
..
H 2C
C
H
C
H
CH3
H 3C
C
H
C
H
CH3
C
H
C
H
C
H
C
H
C 6H 5
H
2e
d ip h e n y lb u ta d ie n
C 6H 5
H2
C
C
H
H2
C
C
H
C 6H 5
1 ,4 d ip h e n y l-2 -b u te n
HC
O
C
+
HC
O
HC
CH2
O
C
C
O
a n h y d ric m a le ic
C
O
b u ta d ie n
87
CH2
HC
O
C
HC
C
O
HC
CH
x y c l o p e n ta d ie n
H
H
O
OC
a n h y d r ic m a le i c
OC
n H 2C
C
H
C
H
CH2
Na
H2
C
C
H
C
H
p o lib u ta d ie n
H2
C
NaCH2CH=CHCH2CH2CH=CHCH2Na
v.v
Phn ng tip tc din ra nh trn n khi to ra polime c phn t lng cao. Cng
c th to ra polime c cu to phn nhnh do phn ng xy ra va theo kiu 1,4 va
1,2:
88
N aH 2C
C
H
C
H
C H 2N a +
N a H 2C
CH
H 2C
C
H
H2
C
C
H
H2
C
CH
CH
CH2
CH2
H 2C
C
H
C
H
CH2
N aH 2C
C
H
CHNa
C
H
H2
C
H2
C
H
C
H2
C
C
H
C
H
C H 2N a
CH
CH2
H2
C
C
H
CH3
H2
C
C
CH3
C
H
H2
C
H2
C
C
CH3
C
H
H2
C
H2
C
C
H
H2
C
.. .
CH3
90
...
H2
C
C
C H 3O
H2
C
H
C
H2
C
C H 3O
H2
C
H
C
H2
C
H2
C
H
C
C H 3O
...
H 2C
C
H
CH2
n H 2C
H2
C
CH2
H 2C
C
CH3
C
H
H2
C
H2
C
C
CH3
C
H
CH2
CH3
CH3
CH3
...
C
H
C
H
H2
C
H2
C
C
H
H2
C
. ..
CH3
91
H2
C
H 3C
C
CH
C
H2
H2
C
C
C
H2
H 3C
CH
H 3C
CH
CH
C
H2
9 ,1 A
cu hnh ca phn t cao su (dng cis)
H2
C
H 3C
C
H 3C
CH
C
H2
H2
C
C
CH
C
H2
5 ,0 A
H 3C
C
H2
5 ,0 A
92
Hin tng ny c xc tin khi un nng v nht l khi chiu sng v khi c mt
ca mt s cht xc tc nh ng v.v
S t oxy ho l mt phn ng dy chuyn, tng t phn ng t oxi ho cc olefin.
Ngi ta nhn thy giai on cm ng rt di (ti vi nm) cao su th, nhng rt
nhanh cao su c x l vi dung mi tch mt s cht km hm thin nhin (cc
cht phn oxi ho). Sn phm u tin l peoxit, cht ny c th nhn ra nh phn ng
vi kali iodua. C l nhm CH2 b tn cng s hot ho cc lin kt i bn cnh.
Trc ht, to ra nhm >CHOOH, sau chuyn thnh cc nhm >CHOH v
>CO, ng thi xy ra s b gy i phn t, iu ny gii thch s gim bn, gim
h s trng hp v lm thay i cc tnh cht c l ca cao su.
Ti sao cao su c tnh n hi?
Ta bit rng mch cao su c phn t ln. Mt khc, do cc nguyn t cacbon c gc
lai ho l 109028 cng vi s quay t do cc lin kt cacbon-cacbon to thnh v
s cu dng khc nhau nhng v tr ni i trong phn t khng thay i. mt phn
t ln, s xp t ca mch phn t s khng iu ho m rt tu tin v cu dng. Khi
b ko mnh nhng ch sp xp khng trt t b ko ra lm cho mch cao su b gin.
Nu b lc ko n li tr v trng thi bnh thng.
e)Cao su tng hp
Cao su tng hp l polibutadien. thay i tnh cht ca n, cao su tng hp
thng s dng cc phn ng ng trng hp: butadien vi styren, acrilonitrin
H 2C
C
H
C
H
CH2
H 2C
C
H
C
H
CH2
+ H 2C
CH
H 2C
C
H
C
H
CH2
C 6H 5
xt
...
H2
C
C
H
C
H
H2
C
C
H
C
H
H2
C
H2
C
H
C
H2
C
C
H
C
H
H2
C
.. .
C 6H 5
c a o s u b u t a d ie n s t y r e n ( b u n a S )
93
2.2.2. T ecpenoic
T c xa xa, loi ngi u thch v quan tm ti du thm tch ra t thc vt.
Tuy nhin, mi n u th k XIX mi c nhng nghin cu u tin v thnh phn
ho hc ca tinh du. V vo nm 1818 ngi ta xc nh c rng t l nguyn t
C: H tinh du l 5:8. Tip theo , mt s hirocacbon khng no, khng vng hoc
c vng c tch ra. Chng c cng thc chung l (C5H8)n (n2) v c gi l
tecpen. Khi n=2 ta c cng thc l C10H16 l monotecpen thng gi gn l
tecpen; khi n=3 ta c C15H24 l setkitecpen, n=4 c C20H32 l ditecpen, n=6 c
C30H48 l tritecpen v.v
T nm 1887, Otto Wallach nhn thy c im chung trong cu trc ca tcpn
l gm cc mt xch ging nh isopren hp thnh. Sau , nh nhng nghin cu tng
kt cc tecpen bit, L.Rugiska nu ra quy tt isopren ni rng tecpen dng nh
c to thnh do isopren kt hp vi nhau theo kiu u ni vi ui. V d:
C5H8, isopren
C10H16, Oximen
C10H16, Silvestren
C15H24, Xingiberen
Trong a s trng hp, c ngha quan trng trong thc t khng phi l cc
hirocacbon loi tecpen m l dn xut cha oxi ca chng nh cc ancol, andehyt,
xeton, este. Tecpen v cc dn xut ca n c gi chung l tecpenoit. Tecpen v
tecpenoit i khi cn c gi l isoprenoit nhn mnh rng n gm cc mt xch
c khung cacbon ging vi isopren.
Ngi ta cng tm thy nhiu hp cht thin nhin m b khung cacbon gm t
cc mt xch ging isopren nhng c ch kt hp vi nhau khng theo kiu u ni
vi ui nhng cng vn c xp vo loi tecpen. V d:
C30H50 squalen
C loi tch ra t v nh cam, chanh, qut, bi. C loi tch ra t g ca thn, cnh
cy nh tinh du long no. C loi tch ra t c nh tinh du gng, ring. C loi ly
ra t r nh hng lau, pmu. C loi tch ra t nha cy nh tinh du thng v.v
Tinh du c mt s c tnh chung, khc vi du bo p t cc ht qu thc vt
nh sau:
- Tinh du si nhit kh cao (thng trong khong 150-2500C) nhng li
d bay hi to mi thm d chu. Nh mt git tinh du ln mt giy thy xut hin vt
trong m nh khi nh git du bo nhng vt ca git tinh du th bin i kh nhanh,
mt giy tr li bnh thng trong khi vt m ca git du bo th tn ti mi.
- Tinh du thng khng tan hoc t tan trong nc, tan nhiu trong cc dung
mi hu c nh ru, ete, benzen v.v a s tinh du nh hn nc nh s, bc h
v.vcng c loi tinh du nng hn nc nh qu, inh hng v.v Tinh du
thng khngmu hoc mu vng nht nhng lu mu sc tinh du thng thay i
do mt s thnh phn trong tinh du b oxi ho trong khng kh v bin mu.
- Tinh du thng l mt hn hp phc tp gm hng chc cht khc nhau, mi
cng nh gi tr tinh du do mt s thnh phn trong quyt nh. Tinh du c nhiu
ng dng quan trng trong nhiu ngnh kinh t nh dc phm, thc phm, m phm
v hng phm. Do , n l loi sn phm thin nhin c gi tr kinh t cao.
1) Monotecpen
Cc tecpen c thnh phn C10H16 c th chia thnh hai nhm ln:
- Nhm th nht l cc tecpen mch h khng vng.
- Nhm th hai l cc tecpen mch vng: gm cc tecpen mt vng v hai vng.
a)Tecpen mch h v nhng dn xut ca chng
Cc tecpen mch h t gp trong thin nhin v ngi ta tm c hai
hirocacbon loi monotecpen khng vng (axiclicmonotecpen) l mirxen v oximen.
Chng c ba lin kt i trong phn t.
H 3C
C
H
CH3
H 2C
C
CH3
H2
C
H2
C
H2
C
o x im e n
C
H
CH2
C
H
CH2
CH2
m irx e n
H2
C
C
H
C
CH3
C H 2O H
C H 2O H
C H 2O H
C H 2O H
N ero l
g e ra n io l
Nerol c dng cis v n khp vng nhanh hn 10 ln so vi geraniol cho tecpineol. C th thu nhn c nerol khi un nng geraniol vi etylat natri.
Geraniol l thnh phn chnh tinh du hoa hng, tinh du s v cng c trong
nhiu tinh du khc. Geraniol v nerol c hng thm mi hoa hng.
Xitronelol C10H20O cng l ru bc nht c cha mt ni i l hn hp ca
hai ng phn izopropyliden v izopropenil.
C H 2O H
C H 2O H
X it r o n e l o l
OH
L in a lo l
96
p - x im e n
m e n ta n
97
OH
Trong thin nhin thng gp dng mentol quay tri. Cht ny l thnh phn
chnh ca tinh du bc h (mentha piperita); c th tch ra d dng t loi tinh du ny
(-) mentol kt tinh, nng chy 430C, si 2160C, [ ]D = -490.
Mentol c cha ba nguyn t cacbon bt i trong phn t v vy c 8 ng
phn quang hc vi 4 cp i quang v 4 bin th raxemic ( ). Chng c tn: ( )
mentol, ( ) neomentol, ( ) izomentol v ( ) neoizomentol.
Mentol c nhiu ng dng trong i sng v y hc: ch thuc nh rng, lm
bnh ko, thuc ho v.v
Tecpineol C10H18O l ancol bc ba cha mt ni i gm cc ng phn:
OH
OH
OH
OH
-tecpineol
-tecpineol
1-tecpineol
4-tecpineol
Nhm pinan
Nhm camphan
98
- Nhm pinan:
Cht tiu biu chnh ca nhm ny l -pinen. cng l tecpen ph bin nht
trong thin nhin. N c mt trong nhiu tinh du cng vi -pinen, ch yu trong
tinh du thng, c khi chim ti 70-90% thnh phn tinh du.
-pinen
-pinen
C H 2O H
F a rn e z e n (C 15H 24)
F a rn e z o l (C 15H 24)
H2
C
C
H
CH3
H 3C
C
H
CH3
O
C
H
H2
C
F arn ero l
H2
C
CH3
A x e to n
H2
C
H2
C
C
H
H2
C
O3
OH
Z n /H C l
CH3
C
CH3
C
H
H2
C
H2
C
O +
C
H
C H 2O H
CH3
A n d e h y t g lic o lic
A n d e h y t l e v u l i n o ic
Cedren
Bisabolen
Cadinen
Copaen
Selinen
100
O
O
Cedrol
Xantonin
-Cadinol
3) Cc tecpen khc
a)Dictecpen (iso-C5)4
C gi tr quan trng l hai ancol ditecpen: phitol (C20H39OH) v retinol
(C20H29OH). Phitol dng este to thnh mt nhnh ca clorophin c trong cht dip
lc ca cy xanh. Retinol hay vitamin A c trong lng trng, du gan c
CH2OH
CH2OH
Retinol (vitamin A)
Phitol
CHO
Poli-trans-Retinal
11-cis-retinal
CHO
squalen
101
HO
Fridelin (C30H50O)
Fridelanol (C30H52O)
H
-H2O
C30H50 (55%)
102
CH2
H3C
H2
C
H
CH2
H3C
H
H2 C
120 pm
H
106 pm
sp 2
r( C
sp 3
H
C
H
C
X
H2
C
R'
2 K O H /r u o u
2 K O H /ru o u
CHX2
+ 2H X
R'
CH
+ 2H X
C
H
CH2
+ B r2
H 3C
2 K O H /ru o u
H
C
CH2
Br
Br
-2 H B r
H 3C
CH
Phn ng tch hyro bromua c th tin hnh qua hai giai on. V d, dn xut
dibromphenyl d b tch mt phn t hyro bromua to thnh bromstiren, sau li
tch phn t hyro bromua th hai, giai on ny kh khn hn giai on trc to ra
phenylaxetylen:
105
C 6H 5
C
H
CH2
+ B r2
+ B r2
C 6H 5
2 K O H /ru o u
H
C
CH2
Br
Br
C 6H 5
S ti r e n
C
H
CH
Br
b r o m s t ir e n
1 ,2 - d ib r o m p h e n y le t a n
2 K O H /ru o u
C 6H 5
CH
p h e n y l a x e t y le n
2) i t dn xut tetrahalogen
Cho dn xut tetrahalogen c bn halogen nh vo hai cacbon lin nhau tc dng
vi bt km cng to ra c lin kt ba.
X
X
R' + 2Zn
R
X
+ 2ZnX 2
R'
3) iu ch ng ng ca axetylen i t axetylen
Nh kh nng c th chuyn ho axetylen thnh dn xut c kim (dn xut natri)
nn c th tng hp c cc ng ng cao ca axetylen khi cho dn xut ny tc
dng vi dn xut halogen theo s sau:
HC
CH
+ Na
HC
IR
Na
HC
H2
C
Br
Na
CH
H 3C
H2
C
CH
4) iu ch axetylen
Trong dy ng ng ankin, axetylen l thnh phn u tin, ng thi cng ng
vai tr quan trng nht trong thc t nn c sn xut vi qui m ln trong cng
nghip.
a)i t canxi cacbua
Phng php quan trng nht v thng dng nht trong cng nghip cng nh trong
phng th nghim l thu phn canxi cacbua, thng gi l t n. Cho canxi cacbua
tip xc vi nc s gii phng kh axetylen bay ln:
CaC2
2H2O
HCCH
+ Ca(OH)2
Trong cng nghip s thu phn c th tin hnh theo phng php t (c) hoc
theo phng php kh (mi). Phng php t dng nhiu nc. Phng php kh
106
dng t nc hn, ch cn lng nc bng 1/10 lng nc dng trong phng php
t. Trong l phn ng theo phng php kh, ngi ta cho nc vo canxi cacbua,
phn ng pht nhit v lm cho ton khi nng ln ti 1150C, nc d cng bay hi
ch cn li khi vi rn. Hi nc ln vi kh axetylen bay ra s c ngng t trong
thp ngng.
Canxi cacbua c iu ch t than v vi sng trong l in nhit gn
25000C:
CaO + 3C
CaC2 + CO
15000C
C 2H 2
+ 3H 2
Tnh ton nhit ng cho thy rng iu kin cn bng lm thun li cho s to
thnh axetylen nng trn 12000C. Tuy nhin, nhit ny, axetylen li d b
phn hu thnh cacbon v hyro. Mt khc, di 12000C c mt hyro axetylen cng
khng bn v mt nhit ng. V vy, cn lm lnh ngay hn hp kh sau khi ra khi
khu vc phn ng. nhit di 1000C, axetylen khng ph phn hu nh tnh tr
ca phn t.
Phn ng nhit phn metan lm tng th tch, v vy, s tin hnh phn ng di p
sut thp thun li cho s to thnh axetylen.
Phn ng ny c p dng trong cng nghip vi nhiu phng php tin hnh
c th khc nhau. Chng hn, ngi ta cho metan i vo l di p sut thng, cho
bt tia la in gia hai in cc kim loi trong mt thi gian ngn (bng mt phn
giy), sau lm lnh ngay hn hp kh i ra bng nc. Kh thu c cha 12-15%
axetylen (v l thuyt c th t ti 25%), axetylen li c tch ra bng cch ho tan
trong nc di p sut cao. Sn phm ph l diaxetylen C4H2 c tnh n d dng.
Cng c th dng phng php t chy tng phn bng cch cho hn hp metan
v oxi i qua nhng ngn la c bit. Nhit to ra do phn ng t chy dng
cung cp cho phn ng nhit phn thu nhit. Trong hn hp kh to thnh, ngoi 810% axetylen, cn c H2, CO, CO2.
107
H2
C2H2
Phn ng din ra trong vng cung la in gia hai in cc bng than. Tnh
ton nhit ng chng t rng, cn bng ch lch v pha phi nhit rt cao (trn
30000C). Do , phn ng ny khng c p dng trong thc t v ch c ngha v
mt l thuyt.
5) ng dng
a)Lm nhin liu
Khi axetylen chy trong oxi nhit ngn la c th t ti 30000C v th n
x axetylen-oxi c dng hn v ct kim loi. Ngun cp axetylen cho n x c
th l mt thng phn ng n gin thu phn canxi cacbua k thut (gi l t
n) hoc c th l cc bnh thp cha cht xp v axeton ho tan axetylen p sut
12 n 15 at ( p sut 1 th tch axeton ho tan c 300 th tch axetylen).
Axetylen chy trong khng kh cho ngn la sng chi. V th trc kia ngi
ta dng canxi cacbua k thut np vo bnh thp c van cho nc nh xung t t ri
t kh axetylen sinh ra thp sng. Canxi cacbua k thut cha nhiu tp cht c
mu en nn c gi l t n.
Khi t n phn ng vi nc, ngoi C2H2 cn to ra H2S, PH3, NH3 chng
to ra mi hi gi l mi t n.
b) Lm nguyn liu cho cng nghip tng hp hu c
Trc nhng nm nm mi ca th k 20, cng nghip tng hp hu c da trn
nguyn liu chnh l axetylen. T axetylen ngi ta iu ch c axetandehyt (cng
nc), vinyl clorua (cng HCl), vinyl axetylen (dime ho) ri butadien v cloropren,
acrilonitril (cng HCN), vinyl axetat (cng CH3COOH), ankyl vinyl ete (cng
ancol) Cc cht ny dng sn xut ho cht hu c c bn khc v quan trng
hn l tng hp cc polime sn xut ra cc cht do v cao su tng hp.
Ngy nay, nh s pht trin vt bc ca cng ngh ho du, cc ho cht hu c
c bn trn u c sn xut t etylen hoc t cc hirocacbon thu c khi cracking
du m bng cc phng php kinh t hn v t nh hng n mi trng hn.
c)Tng hp cc hp cht c hot tnh sinh hc
Nu nh ngnh cng nghip ho hc trn c s axetylen ngy ny hu nh b
thay th bi cng nghip ho hc trn c s etylen th vic tng hp cc hp cht c
hot tnh sinh hc t axetyeln li c nhng bc pht trin mnh m v thu c
nhng thnh tu to ln.
Dn chng tiu biu l vic tng hp cc pheromon. l cc hp cht ha hc do
sinh vt tit ra thng tin cho nhau. Pheromon c tnh cht hp dn, li cun ng
loi khc gii gi l pheromon hay l cht d dn gii. S dng cht dn d gii ngi
108
C (C H 2 )10 O H
1 ) ( x ic lo - C 6 H 1 1 ) 2 B H
0
2 )C H 3C O O H , 0 C
C 5H 5N H C rO 3C l
H 3C H 2C H C
H 3C H 2C H C
C
H
C
H
C
H
C
H
C H (C H 2)10O H
C H (C H 2 )9C H O
Lai
ho
CH3CH3
CH2=CH2
CHCH
sp3
sp2
sp
m
in ca
C (eV)
2,50
2,69
2,75
Bn knh
nguyn t C
(A0)
0,722
0,74
0,69
di lin
kt CH
(A0)
1,102
1,081
1,064
Momen
lng cc
(D)
0,307
0,692
1,05
Hng s
phn li
axit Ka
<10-40
10-40
10-22
109
H2
xt
R'
C
H
C
H
H2
xt
R'
H2
C
H2
C
R'
H 3C H 2C H C (H 2C )4
C 2H 5
H
C
(C H 2 )4 C
( C H 2 ) 6C H 2 O H
H 2 / x t L a n d la r
2 0 0C , C 2H 5O H
CH3
H
CH3
H 3C H 2C H C (H 2C )4
C rO 3 , C 5 H 5 N , H C l
C H 2C l2, 2 0 0C
(C H 2)6C H 2 O H
(C H 2)6C H
9 2 % c is
CH3
H
9 2 % c is
cht d dn b ry
H
C 6H 5
C 6H 5
P d /C , q u i n o l i n
C 6H 5
c is-S tilb e n C 6H 5
C 3H 7
N a /N H 3 lo n g
C 3H 7
+ N aN H 2
-3 3 0 C
H
97%
C 3H 7
110
NH3 (lng)
Na+(NH3)m
e-(NH3)n
..
H
R
NH2
.
R
+ N H 2-
-N a (s o l)
gc vinyl
Dng cis v dng trans ca gc vinyl c th chuyn i cho nhau qua trng thi
chuyn tip m nguyn t cacbon mang electron c thn trng thi lai ho sp.
Cng ging nh anken, gc dng trans bn hn:
R
H
R
C
H
gc trans-vinyl
gc cis-vinyl
e -( s o l) N a + ( s o l)
R
C
-N a (so l)
H
..
C-
R
H
+ NH2
NH2
H
b)Cng halogen
Cng nh phn ng hyho, phn ng cng halogen xy ra theo hai giai on. V d,
khi cho brom cng vo axetylen, giai on u s cho trans-1,2-dibrometylen v giai
on sau cho 1,1,2,2-tetrabrometan:
111
HC
CH
+ B r2
Br
B r2
B r2H C
C H B r2
1 ,1 , 2 ,2 - t e t r a b r o m e t a n
Br
tra n s -1 ,2 -d ib ro m e ty le n
CH
H 2C
+ HF
C
H
H 3C
CHF2
1 ,1 -d iflo e ta n
v in y l flo ru a
CH
+ HCl
H gSO 4
H 2C
C
H
Cl
v in y l c lo ru a
d)Cng nc
Phn ng cng HOH vo axetylen v ng ng ca n c Kucherop nghin cu
nm 1881. Phn ng tin hnh bng cch cho ankin i vo dung dch axit sunfuric
long c cha thu ngn sunfat ng vai tr xc tc. Phn ng qua giai on trung
gian l dng enol khng bn nn n ng phn ho thnh hp cht cacbonyl theo s
chung sau:
+ HOH
H gSO 4
C
H
C
OH
dng enol
H2
C
C
O
dng cacbonyl
Nu i t axetylen, giai on trung gian l ancol vinylic khng bn, cui cng ta
c axetandehyt:
112
HC
CH
H gSO
+ HOH
H 2C
CH
H 3C
C
H
OH
andehyt axetyic
H 3C
CH
+ HOH
H gSO 4
H 3C
H 3C
CH2
CH3
O a x e to n
OH
+ H gSO 4
Hg
SO
Sau , hp cht phc ny b thu phn, cho hp cht cacbonyl v li gii phng
thu ngn sunfat:
C
Hg
H 2O
SO2
C
H
-H g S O 4
OH
H2
C
C
O
HOC2H5
H2C=CHOC2H5
CHCH
HOOCCH3
H2C=CHOCOCH3
vinyl axetat
113
CH
HC
HC
CH
HC
CH
HC
CH
CH
CH
C
H
CH3
CH3
HC
H 3C
HC
CH
H 3C
CH3
CH
CH
CH3
C
H
HC
H
C
CH
CH
CH
CH
HC
CH
CH
CH
HC
CH
HC
CH
C
H
C
H
+ HC
CH
CH
H
C
H
CH
v in y la x e ty le n
+
+
Na
NaNH2
HCCNa
HCCNa
+
+
1/2H2
NH3
115
[A g (N H 3 )2 ]
CH
Ag
Ag
Cng tng t, khi cho axetylen i qua dung dch ng clorua trong amonic s to
ra kt ta v nh hnh mu gch ca ng axetylenua Cu2C2.
HC
[C u (N H 3)2]
CH
Cu
Cu
2C
2Ag
87 kcal
H 3 C (H 2C )3C
H 3 C (H 2C )3C
CH
CH
+ HBr
+ HBr
(C 2H 5)4N B r
C H 2 C l2
8 m o l p e o x it
0 -5 0 C , 1 h
H 3C (H 2C )3 C
CH2
89%
Br
H 3 C (H 2C )3H C
CH
74%
Br
b) Cng bohidrua
Hydrobo ho ankin xy ra tng t nh hydrobo ho anken. im khc bit l sau
khi ch ho vi H2O2/HO- th khng thu c enol m thu c xeton.
116
3 R
R + BH3
THF
(R C H
H 2 O 2 /O H -
C R )3B
CR
RCH
OH
R
C H 2R
c) Cng nucleophin
Do nguyn t cacbon mang ni ba trng thi lai ho sp c m in ln hn
Csp2 v vy, khc vi anken ankin c phn ng cng theo kiu nucleophin (AN) khi
c tc nhn Nucleophin tn cng giai on quyt nh tc phn ng. V d phn
ng ca axetylen vi ancolat kim loi kim nhit cao to ra vinyl ete.
CH + RONa
HC
2 0 0 0C
RO
ROH
C
H
ROH
CH
RO
C
H
CH2
v i n y l e te
CCH3 +
R SH
SR
N aO H
C 2H 5O H
CH3
Phn ng cng amin vo ankin hot ho nh nhm ht electron cng thuc loi
cng nucleophin. V d:
C 6H 5
O
C
CH
+ (C 2 H 5)2 N H
C 6H 5
O
C
C
H
C
H
N (C 2H 5)2
6) Phn ng oxi ho
a) Oxi ho gi mch v ct mch cacbon.
Ankin lm mt mu tm ca dung dch KMnO4 ging nh anken. u tin c l to
ra vixinal dienol. Nhng phi nhit thp v mi trng trung tnh phn ng mi
dng li giai on to thnh -dixeton (gi nguyn mch cacbon). Cn nu khng
khng ch pH ca mi trng v khng lm lnh th mch cacbon b ct ti ch c lin
kt ba to ra axit cacboxylic. V d:
0 0 C , p H 7 ,5
H 3C C
C C H 2C H 3
H 3C
K M nO 4
H 2O
t0
H 3C
COOH
C H 2C H 3
+ C H 3C H 2C O O H
117
H 3 C 3(H 2C )
CH3
1 ) O 3 , C C l4 , 0 0 C
2) H 2O
C H 3(C H 2)3C O O H + C H 3C O O H
Phn ng oxi ho ct mch bng KMnO4 cng nh phn ng ozon phn c dng
xc nh v tr ca lin kt ba trong mch cacbon. V d, khi oxi ho mt hp cht
thin nhin c cng thc phn t l C18H32O2 ngi ta thu c axit laurinic v axit
adipic. Suy ra hp cht l axit octadeca-6-inoic:
H 3 C (H 2 C )1 0 C
C (C H 2 )4 C O O H
K M nO 4
H 2O
C H 3(C H 2)1 0C O O H
a x i t la u r in i c
H O O C (C H 2 )4C O O H
a x it a d ip i c
C 6H 5C
NH3
C u 2C l2
C 2H 5O H
CH +
C 4H 9C
C 6H 5C
C u 2C l2 + O 2
Cu
C 5H 5N
O2
C 4H 9C
600C
C 6H 5C
C 2H 5O H
C C 6H 5
C C 4H 9
C
H
( C H 2 ) 4C
CH + HC
C u (I)
O2
C (C H 2 )7 C O O H
H 2C
C
H
( C H 2 ) 4C
C (C H 2 )7C O O H
CH2
CH
CH
C u (C H 3 C O O )2
C 5H 5N
c) Phn ng chy
118
Ankin chy hon ton to thnh CO2 v H2O to nhit mnh (H < 0).
CnH2n-2
CHCH
3n 1
2 O 2
5
O2
2
nCO2 +
2CO2 +
(n-1)H2O
H2 O
5/2 O2
2CO2 + H2O
O2
2CO +
H2
119
H 2C
CH2
e ty le n
+ C l2
C l2 H C
C H C l2
1 , 1 ,2 ,2 - t e t r a c l o e t a n
+ HCl
H 2C
C
H
Cl
C
H
CN
v in y l c lo ru a
+ HCN
H 2C
a c rilo n itrin
+ HOH
HC
H 3C
CH
C
H
a x e ta n d e h y t
+ R
COOH
H 2C
C
H
OCOR
e ste v in y lic
+ CO + ROH
H 2C
C
H
COOR
a c rila t a n k y l
HC
+ HCHO
C H 2O H
a n c o l p ro p a c g ilic
H O H 2C
C H 2O H
1 ,4 - b u t i n d i o l
+ HC
CH
H 2C
C
H
CH
v in y la x e ty le n
120
CU HI V BI TP
Cu 1. Nhm chc ca anken, ankin, ankadien l nhm nguyn t no? Trnh by cu
trc v c tnh ca chng (cu trc electron, cu trc khng gian, nng lng, di
v gc lin kt, bn nhit ng)?
Cu 2. So snh tnh cht ha hc ca anken, ankin v ankadien?
Cu 3. Hy a ra bng chc thc nghim chng t rng lc axit ca axetylen,
etilen, etan v amonic c sp xp nh sau: CH CH > NH3 > CH2=CH2 > CH3
CH3. Gii thch?
Cu 4. Hy lp s ni ln mi quan h gia ankan, anken, ankin v ankadien?
Cu 5. Hy nu phng php thc nghim phn bit ankan, anken, ankin v
ankadien (phng php ho hc v phng php vt l)?
Cu 6. Hy dng 3 s phn ng vi axetilen, etilen v metan ln lt l trung
tm gii thch th no l nn cng nghip ho cht hu c da trn axetilen, da
trn etilen v da trn metan?
Cu 7. Tecpen l g? Phn loi tecpen?
Hy pht biu quy tt isopren v minh ho bng cc trng hp sau: -pinen,
camphen, cedren, xantonin v vitamin A?
Cu 8. Hy trnh by s sinh tng hp tecpenoit v cho bit giai on no ging
vi phn ng trong phng th nghim, giai on no khc?
Cu 9. Khi dn hi ru n-propilic qua Al2O3 nhit 3000C thu c anken.
Cho anken tc dng vi dung dch brm c cha kali clorua v natri nitrat.
Cho bit nhng sn phm no c hnh thnh? Vit cc phng trnh
phn ng xy ra v gii thch?
Cu 10. Xut pht t cc cht u l etilen, propilen, izobutilen v cc cht v c
thch hp hy vit cc phng trnh phn ng tng hp ra nhng hp cht sau:
a) (CH3)3C OH
d) CH3 CH2 CH2OH
b) (CH3)2CH CH2Br
e) ClCH2 C(CH3)2 CH2 CH(CH3)2
c) CH3 CH(OH) CH2Br
f) (CH3)3C CH2 C(CH3)2I
Cu 11. a) Cho bit ti sao cc ankadien lin hp c kh nng tham giai phn ng
cng 1,2 v 1,4.
b) Vit phng trnh phn ng cng gia 1,3-butadien vi tng tc nhn sau
(theo t l 1:1 v phn t gam): Br2, HCl, Icl, CH2 = CH CN
c) Khi oxy ha (trong iu kin thch hp) sn phm cng hai nguyn t
brm vo 1,3-butadien thu c axit bromaxetic (BrCH2-COOH). Hy cho bit
hng ca phn ng cng xy ra?
Cu 12. Mt ankadien c cng thc phn t C6H10, sau khi ozon ha ri thy phn
ozonit to thnh thu c mt trong cc sn phm l andehyt sucxinic (O=CH-CH2CH2-CH=O). Hy suy ra cu to ca ankadien ban u.
Cu 13. Hai hidrocacbon u lm mt mu dung dch nc brm v u c kh nng
tc dng vi ozon. Khi thy phn ozonit ca chng thy t mt phn t gam ozonit
ca A cho mt phn t gam CH3-CO-CH=O v hai phn t gam CH2=O; t mt phn
t gam ca B cho mt phn t gam O=CH-CH=Obitan v hai phn t gam CH2=O.
Xc nh cu to ca A v B. Vit cc phn t phn ng ha hc xy ra.
121
122
123
2NaOH
C6H6 +
Na2CO3 + H2O
H
H
124
H 3C C
CCH3
H 2C
C
H
CH2
H
C
H
CH2
X
X
X
X
Tuy nhin khi nghin cu chi tit cu trc ca Kekule th thy c kh nng c hai
ng phn th 1,2. gii quyt vn ny, Kekule cho rng phn t benzen lun
lun chuyn ho v trong mt trng thi cn bng khng th phn chia.
X
X
X
X
X
2) S n nh ca vng benzen
Cn li mt s vn m cu trc ca Kekule khng gii quyt c. Chng hn,
cu trc ny th hin s khng no rt ln, ngha l n phi d dng tham gia phn ng
cng v kh tham gia phn ng th nh anken. Nhng ngc li, benzen tng i tr
vi cc tc nhn oxi ho, thc hin phn ng th d dng nhng rt kh tham gia phn
ng cng. Ngoi ra, ngi ta cn xc nh vng benzen bn vng hn nhiu so vi
nhng g d on t xiclohecxatrien. Nhit hyro ho ca xiclohecxen l 118 kJ/mol,
ca xyclohecxadien-1,3 l 231 kJ/mol, ngha l ln hn hai ln. Vy, i vi
xyclohecxatrien phi l 358 kJ/mol, song hyro ho benzen ch to ra 208 kJ/mol, t
hon 150 kJ/mol theo d on. iu c ngha l benzen bn hn xiclohecxatrien 150
kJ/mol.
3) di lin kt trong benzen
125
C
H
C
C
S to thnh lin kt
trong phn t benzen
Cc obitan 2p trong
phn t benzen
126
CH3
CH3
CH3
CH3
1 ,2 -d im e ty l b e n z e n
(o c to -x ile n )
1 ,3 -d im e ty l b e n z e n
( m e ta -x ile n )
CH3
1 ,4 -d im e ty l b e n z e n
(p a ra -x ile n )
2) Danh php
a)Tn benzen l tn ring c IUPAC lu dng v l hyrua nn gi tn
cc ng ng v dn xut khc theo danh php thay th. Nhiu ankyl v
ankenylbenzen c tn ring:
Hp cht
C6H5CH3
Tn thay th
Metylbenzen
Etylbenzen
Tn thng
Toluen*
Isopropylbenzen
Cumen**
o-dimetylbenzen
1,2-dimetylbenzen
o-Xylen**
C6H5C2H5
C6H5CH(CH3)2
o-C6H4(CH3)2
(ba ng phn o-, m-, p-)
PCH3C6H4CH(CH3)2
(ba ng phn o-, m-, p-)
CH3
H 3C
1,3,5-Trimetyl benzen
Mesitilen**
Siren*
CH3
C 6H 5
C
H
CH2
C 6H 5
CH
Etinylbenzen
127
p-isopropyl toluen
p-C2H5C6H4CH=CH2
p-Etylstiren.
phenyl
C6H4
C6H5CH2
benzyl
C6H5CH=
benzyliden
C6H5C
benzylidin
C6H5CH=CH
stiryl
2,4,6-(CH3)3C6H2
mesityl
(IH )
.
(II)
(III)
(IV )
(V )
(V I)
129
16 kg
2,5 kg
0,3 kg
20 kg
20 60 kg
5 20 kg
300 600 kg.
ankan
Anken
Xiclohecxan
Hidrocacbon thm
H2
C
CH3
H2C
CH3
- H2
H2C
H
C
CH2
H2C
CH2
- 3H2
HC
CH
HC
CH
C
H2
C
H2
C
H
n-hecxan
cyclohecxan
benzen
C6H5C2H5 + 2NaBr
CH3
CH3
Br + 2Na + Br
H3C
H3C
CH
CH
CH3
CH3
p-bromtoluen
ximen
izopropyl bromua
ArR + 2NaX
H +
AlCl3
Ar
R + HX
C2H5
AlCl3
C6H5
C2H5 + HCl
+
+
+
RX
R X
RX
v.v
C6H5R
C6H4(R2)
C6H3(R3)
+
+
+
HX
HX
HX
AlCl3
CH3CH2CH2Cl
n-propyl clorua
H
C
H3C
CH3
C6H6
C6H5
CH
CH3
Cl
izopropyl benzen
izopropyl clorua
CH3
H3C
CH
CH2Cl
AlCl3
H3C
CH3
C6H6
C6H5
C(CH3)3
tecbutyl benzen
H3C
Cl
izobutyl clorua
tecbutyl clorua
H 2C
CH2
AlCl3
C6 H5
C 2H 5
C6H6 +
H3C
C
H
CH2
AlCl3
C6H5
CH
CH3
133
ArH
ArX
Cc phn ng th electrophin vo nhn thm lun lun tin hnh trong iu kin c
mt mt axit mnh hoc mt cht xc tc. Axit mnh hoc cht xc tc c tc dng
chuyn ho tc nhn thnh dng electrophin hot ng, k hiu X . V vy, ta phn ra
thnh hai giai on ln trong phn ng th: giai on u l giai on to ra dng
electrophin hot ng ca tc nhn do kt qu phn ng ca tc nhn vi mi trng
phn ng (vi axit mnh hoc vi cht xc tc); giai on sau mi chnh l giai on
xy ra phn ng th vo nhn.
b) Giai on th vo nhn
Trong giai on th vo nhn, xut hin vn s th vo nhn xy ra theo mt
bc, trong c s trao i trc tip (tng t c ch SN2) qua trng thi chuyn tip
trung gian:
X
Ar
Ar
Ar +
(1)
Ar
Ar
X
H
Ar
Ar
X +
(2)
chm
+ X
X
phc
hoc
phc
nhanh
-H
CH3
CH3
NO2
+ HNO3
+
o-nitro toluen
NO2
p-nitro toluen
137
NO2
NO2
+ HNO3
NO2
m-dinitro benzen
i vi nhm th loi II: N (CH 3 ) 3 > COOH > SO3H > NO2
b) Gii thch quy tt th
* S phn b mt electron trong phn t dn xut th ca benzen (trng
thi tnh)
Khc vi trng hp phn t benzen, trong cc dn xut th ca benzen, mt
electron trong vng benzen phn b khng iu ho na. S ri lon tnh cht i
xng ca my electron trong nhn benzen khi c mt nhm th c sn, c th xy ra
theo hai cch ngc nhau.
-Nu nhm th thuc loi I nh cc nhm NH2, OH, CH3 th mt electron
trong vng benzen ni chung u tng ln v c bit tng nhiu cc v tr octo v
para. S d c s tng mt electron trong nhn l do hiu ng lin hp +C ca nhm
138
H
C
O:
N:
CH3
O
H3C
O
N
O
C
CH3
O:
O:
O:
1/3
1/3
1/3
1/3
1/3
NO2
(I)
1/3
NO2
(III)
(II)
Nh vy, trong trng thi chuyn tip (II), in tch dng c gii to nhiu hn,
nng lng hot ho nh hn so vi trong trng thi chuyn tip (III). Do , trong v
d trn, s nh hng u tin vo v tr octo v para l do kt qu tc dng cng
hng ca cc yu t tnh v cc yu t ng.
Cng do cc nhm th loi I lm tng mt electron ca ton b nhn benzen, c
bit cc v tr octo, para cho nn ta hiu c v sao phn t th electrophin vo cc
hp cht nh anilin, phenol v.v li tin hnh d dng hn so vi bn thn benzen.
- Trng hp dn xut benzen cha nhm th loi II:
Kho st phn ng nitro ho vo nitrobenzen.
Do s phn b mt electron trng thi tnh ca phn t nitrobenzen, s tin li
gn ca tc nhn electrophin vo v tr meta thun li v nng lng hn so vi cc v
tr octo v para (IV).
1/3
(IV)
1/3
1/3
1/3
1/3
NO2
(V)
1/3
NO2
(VI)
Trong cc trng thi chuyn tip, khi th vo octo v para (V), cng nh khi th vo
meta (VI), s san u in tch dng ch xy ra bn trong nhn benzen khng c s
tham gia ca nhm th. Do , nng lng cc trng thi chuyn tip ny l nh nhau.
Trong trng hp ny, s nh hng v c bn do yu t tnh quyt nh c ngha l
nhm th mi s hng vo v tr meta.
Cng do nhm th loi II lm gim mt electron ca vng benzen, v tr meta
tng i gim t cho nn ta hiu v sao phn ng th hngd vo v tr meta v tin
hnh kh khn hn so vi bn thn benzen.
Cc quy tt th electrophin trong nhn benzen c ngha thc tin rt ln. Nh cc
quy tt ny, c th tin on kt qu phn ng ng thi cng cho php chn nhng
con ng hp l nht trong tng hp hu c.
3) Mt s phn ng th electrophin
a)Phn ng halogen ho
Tng tc ca halogen nh clo, brom vi benzen khan nhit thng, c mt
ca xc tc nh bt st hoc cc halogenua kim loi nh FeCl3, FeBr3, AlCl3, AlCl3,
140
SbCl3 hoc iot v.v s xy ra phn ng mnh lit v cho sn phm phn ng l dn
xut halogen thm nh clobenzen, brombenzen:
+ Br
Br
Fe
Br
+ HBr
CH3
CH3
Cl
+ Cl2
FeCl3
+
o-clo-toluen
Cl
p-clo-toluen
Khi khng c cht xc tc v ngoi nh sng mt tri hoc c chiu sng bng
tia t ngoi, nhit si, phn ng th s tin hnh mch nhnh. Tu theo s
nguyn t hidro nhnh c th bng clo, s thu c cc dn xut mono, di v
trihalogen.
C6H5
CH3
+ Cl2
h, t0 cao
C6H5
CH2Cl + HCl
benzyl clorua
0
C6H5
CH2Cl
+ Cl2
h, t cao
C6H5
CHCl2 + HCl
benzyliden clorua
C6H5
CHCl2
+ Cl2
h, t0 cao
C6H5
CCl3
+ HCl
phenyltriclo metan
phenylclorofom
2Fe
2FeBr3
Br
Br + FeBr3
Br
Br
Br +
FeBr3
[FeBr4]
+ Br
chm
nhanh
+ H
brom benzen
[FeBr4]-
FeBr3 +
HBr
Tc dng xc tc ca iot trong phn ng clo ho hoc brom ho nhn thm cng
chnh l iot lm d dng cho s to thnh cc cation clo hoc cation brom:
I2
+
ICl
ClCl
Cl2
I
2ICl
+ Cl
I ICl
+
Cl
Phn ng iot ho benzen nh xc tc Ag+ tin hnh nh sau: khi ho tan iot vo
benzen khng nhn thy c phn ng g. Khi cho thm bc sunfat vo hn hp phn
ng, ri thm sxxit sunfuaric vo, s to ra kt ta bc ioua v iot benzen. Trong bc
iodua cha anion I- nn ch c I+ c th tc dng vi benzen:
II
I+
+
+
Ag+
C6H6
AgI
+ I+
C6H5I + H+
b)Phn ng nitro ho
Nitro ho nhn thm l mt trong nhng phn ng th c nhiu ngha quan trng.
Tng tc ca hn hp axit sunfuric c v axit nitric c vi benzen s xy ra phn
ng nitro ho gn mt nhm nitro NO2 vo nhn benzen cho sn phm l
nitrobenzen:
C6H6 +
HONO2
H2SO4
C6H5
NO2 + H2O
nitrobenzen
142
Khi a nhm NO2 th hai vo nhn, cn phi dng hn hp axit c nng cao
hn v tin hnh nhit cng cao hn, sn phm thu c l dn xut metadinitrobenzen.
Cng c th gn nhm NO2 th ba vo nhn benzen, nhm ny cng vo v tr
meta so vi hai nhm u nhng phi tin hnh trong iu kin mnh lit hn:
NO2
NO2
NO2
NO2
O2N
NO2
CH3
CH3
CH3
CH3
NO2 O2N
NO2
NO2
NO2
NO2
NO2
2,4,6-trinitro toluen
2HNO3
NO 2
H 3O
2NO -
Sau giai on to ra ion nitroni, phn ng ca ion nitroni vi hidrocacbon thm tin
hnh theo hai bc, bc th nht to ra phc trung gian v bc th hai tch
proton theo c ch chung ca s th electrophin vo nhn thm:
143
NO2
O2 N
+ NO2
chm
nhanh
+ H
HOSO3H
ArSO3H
H2 O
Khc vi trng hp nitro ho, phn ng sunfo ho c tnh cht thun nghch. Nc
c gii phng ra, khng nhng lm gim nng axit sunfuric ti gii hn lm
ngng phn ng sunfo ho m cn gy ra phn ng nghch, thu phn sunfoaxit to
thnh:
ArSO3H
H2 O
ArH
H2SO4
HOSO3H
ArSO3H
H2 O
H2SO4
800
SO3H
H2SO4 + SO3
800
SO3H
m-benzendisunfo axit
H2SO4
-naphtalen sunfoaxit
<1000
naphtalen
160
1600
SO3H
-naphtalen sunfoaxit
H +
Cl
Ar
H +
(R
CO)2O
AlCl3
AlCl3
Ar
Ar
R + HCl
O
R + RCOOH
V d:
H
Cl
CH3
AlCl3
Cl
C
O
C6H6
CH3
+ HCl
axetophenol
O axetyl clorua
AlCl3
O
C
+ HCl
benzophenol
145
OH
C
O
1) AlCl3
2) H3O
+
C
O
OH
R H3O
O
C
O
R
AlCl3
OAlCl3
OAlCl2
CR
OH
H3O
C
O
C
R
Do tnh cht electron ca qu trnh chuyn v nn khi trong vng thm c nhm th
y electron, phn ng s tr nn d dng hn.
Phn ng Frai lun lun to ra mt hn hp hai sn phm ng phn; nhit thp
l iu kin thun li cho s to thnh ng phn para, cn nhit cao sn phm
chnh l ng phn octo. V d:
146
OH
COCH3
OCOCH3
OH
0
AlCl3, 165 C
95%
AlCl3, 25 C
80%
CH3
CH3
COCH3
CH3
OCOCH3
COCH3
AlCl3
nitrobenzen
CH3
CH3
C
H
CH2
OH
2000C
CH2CH
CH2
90%
H2C
CH
H2C
CH
OH
CH2
CH2
CH
CH2
H2C
CH
CH2
H 2C
CH
CH2
OH
CH
CH2
HHal
C6H5NHR
HHal
t0
t0
o or p-RC6H4NHR
o or p-RC6H4NH2
HHal
RHal + C6H5NH2
C6H5NH2
+ RHal
RC6H4NH3 Hal
COCH3
HCl
Cl
H
C6H4 N
COCH3
Cl
Ngi ta cho rng trong phn ng trn, clorua hidro tc dng vi cloaxetanilit
sinh ra axetanilit v clo, sau clo tc dng vi vng thm ca axetanilit theo c ch
electrophin:
C6H5N
COCH3
+ HCl
C6H5HN
Cl
COCH3 + Cl2
ClC6H4HN
COCH3 + HCl
NHC6H5
HCl
or C6H5NH2 + HCl
p-H2NC6H4N
NC6H5
148
CH3
p-H3CC6H4N
H
N
CH3
p-CH3C6H4NH2
p-H3CC6H4N
HCl
H2N
Nu thay p-CH3C6H4NH2 bng C6H5NH2 trong phn ng trn ta s c 4metyl-4aminoazobenzen. iu ny cho thy phn ng chuyn v nhm arylazo thuc
loi chuyn v lin phn t.
Phn ng ca clorua phenyldiazoni vi anilin c th xy ra hai hng khc nhau tu
thuc vo pH ca mi trng:
pH ln hn
C6H5N2Cl +
H2NC6H5
pH nh hn
C6 H5 N
NHC6H5
C6 H5 N
NHC6H5
Da trn cc d kin thc nghim trn ngi ta cho rng s chuyn v nhm
arylazo xy ra qua giai on to thnh ion aryldiazoni s tc dng vo nhn thm ca
amin theo c ch electrophin:
C6H5N
NHC6H5
HCl
C6H5N
C6H5N2 + C6H5NH2
NC6H4
NH2-p
CH3
HCl
H
C6H4 N
o- and p-ON
CH3
NO
CH3
+ H
C6H5N
NO
C6H5N
+ NO
C6H4NHCH3 + H
149
H
N
NH
H2N
NH2
hydrazobenzen
benzidin
NH2
NH2
NH2
diphenylin
H2N
NH2
NH2
N
H
o-benzidin
p-xemidin
N
H
o-xemidin
+ 3H2
benzen
cyclohecxan
CH3
+ 3H2
Ni
metyl cyclohecxan
C6H6 + 3Cl2
C6H6Cl6
hecxaclocylohecxan
Cl
2Cl
Cl
Cl
+ Cl
Cl
Cl
+ Cl
Cl
Cl
Cl
Cl
Cl
Cl
+ Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
+ Cl
Cl
Cl
Cl
Cl
Cl
Cl
C) Phn ng oxi ha
Trong iu kin thng, nhn benzen t ra ht ssc bn vng i vi tc dng ca
cc cht oxi ho, ngay c nhng cht oxi ho mnh nh kali pemanganat, axit cromic
v.v Ch trong iu kin rt mnh lit, nhn benzen mi b oxi ho cho nhiu sn
phm khc nhau.
l iu khc bit nht phn bit hidrocacbon thm vi cc hp cht thng
thng mang ni i.
151
CH3
+ 3 [O]
dd KMnO4
+ H2O
axit benzoic
toluen
COOH
H2
C
H2
C
CH3
+ CH3COOH + H2O
+ 5 [O]
axit benzoic
n-propyl benzen
CH3
COOH
CH
CH3
+ 7 [O]
+ 2HCOOH + H2O
izopropyl benzen
axit benzoic
CH3
CH3
COOH
+ 6 [O]
COOH
+ 2H2O
axitH-phtalic
o-xilen
C6H5
C6H5
H2
diphenyl
152
3O2
O3
O3
+ 3 H3O
CHO
3 OHC
glioxan
triozonit
153
HNO3 + H2SO4
C6H5
Fe + HCl
NO2
C6H5
NH2
C6H5
OH
C6H5
OH
anilin
nitrobenzen
Cl2, FeCl2
C6H5
Cl
phenol
clobenzen
H2SO4
C6H5
SO3H
phenol
benzensunfoaxit
H2C
CH2
C6H5
AlCl3
H2C
C
H
C6H5
C2H5
etylbenzen
C
H
CH2
styren
CH3
CH3
C6H5
C6H5
CH
H3PO4
CH3
benzen
C
H
CH2
styren
izopropylbenzen
CH3COCl
AlCl3
O
C
C6H5
CH3
axetophenon
3Cl2, h
C6H6Cl6
hecxaclocyclohecxan
3H2, Ni
C6H12
cyclohecxan
Pb, 500-6000C
C6H5
C6H5
diphenyl
1
2
7
6
3
5
10
II
III
b)Tnh cht ho hc
* S th electrophin.
Naphtalen cho sn phm vi nhm th v tr 1 hay . V d khi brom ho
naphtalen.
Br
Br2/CH3CO2H
-HBr
155
NO2
HNO3/H2SO4
Br
Br2
CH3COOH/H2O
COCH3
CH3COCl,C6H5NO2
AlCl3
COCH3
+
75%
25%
H2SO4
600C
SO3H
SO3H
H2SO4
1500C
K2Cr2O7
H2SO4
COOH
NO2
COOH
K2Cr2O7
H2SO4
COOH
NH2
COOH
K2Cr2O7
H2SO4
COOH
* Phn ng kh.
156
2) Antraxen v phenantren
Trong phn t antraxen v phenantren, cc v tr c nh s nh sau:
6
7
5
8
6
5
10
4
2
9
1
10
Phenantren
Antraxen
K2Cr2O7, H2SO4
Na, C2H5OH
O
K2Cr2O7, H2SO4
Na, C2H5OH
157
SO3H
t0C
H2SO4d
+ H2O
Cl
H
Cl2
AlCl3
Cl
+
9,10-(trans)-Diclo-9,10-dihidrophenantren
9-clophenantren
Antraxen v phenantren cn tham gia phn ng cng clo hoc brom di tc dng
ca nh sng cho 9,10-dihalogen-9,10-dihidroaren:
Cl2
Cl
Cl
Cl H
H
Cl2
Cl
azulen
annulen
158
:
:
:
cation
xyclopropenyl
anion
xyclopentadienyl
cation
xycloheptatrienyl
(ion tropoli)
dianion
xyclooctatrienyl
..
N
..
..
O
..
pirol
piridin
furan
..
S
..
thiophen
xyclobutadien
cation
xyclopentadien
annulen
xyclohecxadien-1,3
annulen
ditrans-annulen
xyclononatetraen
annulen
A c hai nguyn t cacbon trng thi lai ho sp3, B c cu dng thuyn, C c 4n+
2 electron nhng c hai nguyn t hidro hng vo pha trong vng nn y nhau
lm phn t khng thng. D c mt nguyn t cacbon trng thi lai ho sp3, E c 4n
159
160
CU HI V BI TP
Cu 1. Hy nu c im cu to ca vng benzen. Benzen c tnh cht thm in
hnh, l nhng tnh cht no?
Cu 2. Hy trnh by c ch phn ng electron, hiu ng nhm th v quy tt th trong
vng benzen, gii thch?
Cu 3. Tnh cht khng no ca vng benzen cng biu hin tnh cht bn ca vng?
Cc phn ng no biu hin tnh cht ?
Cu 4. V tr ca ankylbenzen c kh nng phn ng c bit g? Hy gii thch
phn ng th halogen v tr benzylic bng thuyt cng hng?
Cu 5. Hy gii thch ti sao naphtalen kh nng th vo vi tr > ? Trnh by kh
nng phn ng c bit v tr 9 v 10 ca antraxen v phenantren?
Cu 6. T benzen, metan v cc hp cht v c cn thit, hy vit cc phng trnh
phn ng tng hp ra cc hp cht sau:
- 2,6-dibrom-4-nitrotoluen
- Axit 2-nitro-4-brombenzoic
Cu 7. Hy suy ra cng thc cu to ca hai hidrocacbon A v B c cng cng thc
phn t C9H12. Bit khi oxy ha A thu c axit benzoic cn B thu c axit
terephtalic p-HOOC-C6H4-COOH.
Cu 8. Hai hidrocacbon A v B c cng cng thc phn t C6H6. Hidrocacbon A lm
mt mu nhanh dung dch nc brm v dung dch kali permanganat. Hidrocacbon B
khng phn ng c vi hai dung dch trn. C A v B u khng phn ng c vi
bc nitrat trong dung dch amoniac.
Xc nh cng thc cu to ca A v B.
Cu 9. a) Trnh by c im cu to ca naphtalen. C bao nhiu ng phn i vi
dn xut th mt ln ca naphtalen.
b) T naphtalen, hy iu ch ra:
- 4-brom-1-nitronaphtalen
- 5-brom-1-nitronaphtalen
Cu 10. Hidrocacbon A c cng thc phn t C8H10. B c cng thc phn t C10H8.
Khi oxy ha A v B bng oxi khng kh c xc tc V2O5 4000C u cho anhidric
phtalic.
Xc nh cu to ca A v B.
Cu 11. Vit cng thc cu to ca cc hp cht cho di y tha mn cc iu
kin sau:
a) C8H10 khi nitro ha ch cho mt dn xut mononitro
b) C6H3Br3 khi nitro ha cho ba dn xut mononitro.
c) C6H3Cl3 khi nitro ha ch cho mt dn xut mononitro
Cu 12. Mt hp cht hu c A c cng thc phn t C8H6 lm mt mu nc brom,
phn ng vi oxit bc trong NH4OH cho kt ta, khhi oxy ha thu c mt trong cc
sn phm l axit benzoic.
Vit cng thc cu to ca A.
161
162
b)Giai on ch bin s cp
Ch bin s cp l giai on chng ct du m bng nhit thu cc phn on du
m khc nhau. Qu trnh chng ct c tin hnh trong cc thp hnh ng hot ng
lin tc theo nguyn tt chng ct phn on. Nhng phn on tch c c th c
s dng trc tip ch bin thnh cc sn phm tng ng: phn on xng c s
dng sn xut xng t hoc my bay, phn on du ho sn xut nhin liu
cho ng c phn lc hoc du ho dn dng, phn on du diezen sn xut cc
loi du nhn, phn on mazut sn xut cc loi du nhn. Phn cn mazut
(5000C) cn li chin khong 30 45% du th sn xut parafin, atphan.Qu trnh
chng ct phn on du m thu c cc phn on c ghi bng sau:
Cc sn phm du m thu c khi chng ct
Cc sn phm
Nhit si, 0C S nguyn t C
Kh du m
di 20
C1 C4
Ete du ho
20 60
C5 C6
Xng
40 250
C5 C14
Du ho
170 270
C10 C15
Du diezen
220 360
C12 C20
Mazut, cn mazut t 360 tr ln
C20 C60
2) Nhin liu
a)Phn on xng
Xng l nhin liu dng cho ng c t trong c b ch ho kh. Yu cu quan
trng l chy u n v khng b kch n.
- Nguyn nhn ca hin tng kch n c lin quan n cu to ca hidrocacbon
trong xng. Bi v cc hidrocacbon di tc dng nhit ca xi lanh s b oxi ho do oxi
ca khng kh to thnh cc hidro peoxit (ROOH). Hp cht ny khng bn, rt d
b phn hu thnh cc gc t do, to iu kin pht trin nhanh phn ng chy, lm
tng t ngt p sut v kch n trc khi c nh la. Nghin cu hin tng ny
cho thy, cc hidrocacbon khng nhnh (n-parafin) rt d to cc peoxit. Cc naphten
v olefin nm trung gian, cc hidrocacbon thm v cc hidrocacbon c nhnh c kh
nng chng kch n tt. Bi vy, khi s dng xng cn phi quan tm ti tnh chng
kch n ca xng.
- Ch s octan: tnh chng kch n c c trng bng ch s octan. V tr s n
c biu th bng % th tch ca izooctan (2,2,4-trimetylpentan) trong hn hp vi nheptan. Thc t cho thy izooctan chng kch n tt nht, c quy c l 100, cn nheptan l km nht c ch s l 0. Nh vy, mt loi xng c kh nng chng kch n
tng tng vi hn hp gm 70% izooctan v 30% n-heptan th c ch s octan l 70.
Xng thu c t phn on chng ct trc tip du m c ch s octan thp v c
nhiu parafin v naphten, c rt t hidrocacbon thm v izoparafin.
- nng cao ch s octan ca xng, ngi ta phi dng thm cc xng cracking
nhit v cracking xc tc hoc pha thm vo xng cc cu t c ch s octan cao hay
chng chng kch n nh ru etylic, ete diizopropylic, anilin, toluidin v tt hn l
ch tetraetyl (C2H5)4Pb. Ch tetraetyl chng kch n hiu qu nht v ch cn thm vo
xng 0,5% khi lng l lm tng ch s octan ln 12 20 n v. Song tnh c
ca ch cng cn phi lu . Ngi ta phi pha mu hoc xanh vo xng nhn
bit v phng. Hin nay, cm sn xut v s dng cc loi xng c ch, thay vo
165
166
C5H10 + C5H12
C10H22
C2H4
+ C8H8
C10H22
C8H16
+ C2H6
C10H22
C10H20 + H2
C2H4 + C4H8
2C3H6
-H2
-H2
-H2
CH3CH2CH2CH2CH2CH2CH2CH3
.
.
CH3 + CH2CH3
.
.
CH2CH3 + CH2CH3
.
CH2CH2CH2CH2CH2CH3
.
.
CH3 + CH2CH2CH2CH2CH2CH2CH3
.
.
CH3CH2 + CH2CH2CH2CH2CH2CH3
.
.
CH3CH2CH2 + CH2CH2CH2CH2CH3
.
.
CH3CH2CH2CH2 + CH2CH2CH2CH3
CH4 + CH2=CH2
CH3CH2CH2CH3
.
CH3CH2CH2CH2 +
CH2=CH2
167
CH3CH2CH2CH2CH2CH3
-H2A
CH3CHCH2CH2CH2CH3
CH3CH2CHCH2CH2CH3
CH3CCH2CH2CH3
CH3CHCH2CH2CH2CH3
CH3
CH3CH2CCH2CH3
CH3
H2C
CH2
-AH2 A(H )
CH3CCH2CH2CH3
H3C
CH2 + H2C
AH2
CH3
CH3
H3C
AH2
H3C
H
C
CH3
CH3
+ A(H )
CH3
CH3
cracking xc tc. Phng php ny dng ch bin phn on nng nhm thu nhin
liu cho cc l, nhin liu xng hoc nguyn liu cho cc qu trnh cracking tip theo.
b) Nhit phn
Nhit phn l s phn hu cc hidro hoc phn on ca du m di tc dng ca
nhit trn 6500C trong p sut thp (khong p sut ca kh quyn). Nhit phn cho
cc sn phm kh l cc anken v ankan t C1 n C4 cng H2 v sn phm lng trong
cc hidrocacbon thm chim ti 70%. T cc phn on sn phm kh v lng ny,
ngi ta s tch c cc ho cht tinh khit l cc cht u quan trng ca ngnh ho
du.
c)Reforming xc tc
Phng php ny nhm lm thay i cu trc ca hidrocacbon theo hng ng
phn ho (tng ch s octan) m khng gy ra nhng thay i ng k v khi lng
phn t. Nguyn liu l cc phn on xng chng ct c. Qu trnh tin hnh
p sut hidro t 35 n 65 atm, nhit 450 5000C trn cc xc tc a chc nng
nh Pt, Pd, Ir, Ni hoc cc oxit kim loi gn trn cht mang l nhm oxit hoc nhm
silicat.
Khi dng h xc tc platin nhm oxit (Pt/Al2O3) ngi ta gi l phng php
platforming.
Cht xc tc cho reforming phi m nhim c hai chc nng, hidro ho,
ehydro ho v ng phn ho. Nhng cht xc tc ny gip cho phn ng ng phn
ho n-ankan thnh isoankan, vng ho n-ankan thnh naphten, dehidro ho naphten
thnh hidrocacbon thm. Thm vo , cc hp cht cha lu hunh trong xng b
kh ho n H2S bay i.
Ni chung, reforming lm cho ch s octan ca xng tng ln t 50 n 80,
vi platforming c th ln n 90. Mt khc, sau khi reforming ta cng thu c mt
s hidrocacbon thm cho cng nghip ho cht.
C ch phn ng reforming n-ankan: phn ng reforming bt u bng s
dehidro ho ankan thnh anken, sau din ra theo hai hng: hng th nht l ng
phn ho to cc anken mch phn nhnh, hng th hai l vng ho ri thm ho. V
d: reforming n-hecxan:
+
AH
+ CH4
+H2/M
-H+
AH+
+HA
M
-H2
AH+
M/(-H2)
AH+
AH+
+H2/M
-3H2/M
169
Ni
CH4 + H2
171
CO + 2H2
CH2 + H2O
N2
1,3
6,7
H2 S
0,1
0,2
175
CU HI V BI TP
Cu 1. Trn th gii c cc ngun hidrocacbon thin nhin quan trng no? C bao
nhiu cch phn loi du m? Du m Vit Nam thuc loi no?
Cu 2. Phn bit cc khi nim: du th, du gc, ho du, ch s octan v ch s
cetan.
Cu 3. Phn bit cc phn ng cracking, refoming v nhit phn. Cc sn phm chnh
ca cc phn ng trn l g? Th no l phn ng platfoming?
Cu 4. Trnh by c ch cc phn ng cracking nhit, cracking xc tc v refoming?
176
177
MC LC
Trang
Li ni u ............................................................................................................. 1
Chng 1. Hidrocacbon no ...................................................................................
1.1. Ankan, gii thiu metan ...................................................................................
1.1.1. Dy ng ng metan, ng phn ............................................................
1.1.2. Danh php ...............................................................................................
1.1.3. Tnh cht vt l ........................................................................................
1.1.4. Cc phng php iu ch .......................................................................
1.1.5. Tnh cht ho hc ca ankan ....................................................................
1.1.6. Cht tiu biu CH4 ...................................................................................
1.2. Phn ng th theo c ch gc: SR v kh nng phn ng ..................................
1.2.1. c im ca c ch gc SR.....................................................................
1.2.2. C ch phn ng ......................................................................................
1.2.3.nh hng ca cu to n phn ng th SR .............................................
1.2.4. Ho hc lp th ca phn ng SR .............................................................
1.2.5. nh hng ca tc nhn ..........................................................................
1.3. Xycloankan ......................................................................................................
1.3.1. Danh php ...............................................................................................
1.3.2. ng phn ...............................................................................................
1.3.3. Cc phng php iu ch .......................................................................
1.3.4. Tnh cht vt l ........................................................................................
1.3.5. Tnh cht ho hc ....................................................................................
1.3.6. Cc thuyt gii thch v cu to cc hp cht vng ..................................
1.3.7. Xycloankan tiu biu: xyclohecxan..........................................................
Cu hi v bi tp ..............................................................................................
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