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B GIO DC V O TO

TRNG I HC KINH T - K THUT BNH DNG


KHOA K THUT CNG NGH





HA HU C

CAO NG DC
Bnh Dng, thng 12 nm 2013
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MC LC
CHNG 1. ALCOL, PHENOL ................................................................................................... 5
1.1.Alcol ...................................................................................................................................... 5
1.1.1. Mt s khi nim chung ................................................................................................ 5
1.1.2. Danh php ................................................................................................................. 5
1.1.3. iu ch alcol ........................................................................................................... 7
1.1.4. Tnh cht vt l ....................................................................................................... 10
1.1.5. Tnh cht ha hc .................................................................................................... 10
1.1.6. ng dng ................................................................................................................ 13
1.2. Phenol ................................................................................................................................. 14
1.2.1. Khi nim .................................................................................................................... 14
1.2.2. Danh php .................................................................................................................... 14
1.2.3. iu ch phenol ........................................................................................................... 14
1.2.3. Tnh cht vt l ............................................................................................................ 15
1.2.4. Tnh cht ha hc ........................................................................................................ 15
1.1.4. ng dng ..................................................................................................................... 19
BI TP CHNG 1 .................................................................................................................. 20
CHNG 2. ALDEHYD, CETON, QUINON ............................................................................ 21
2.1. Gii thiu chung ................................................................................................................. 21
2.2. Aldehyd v ceton ................................................................................................................ 21
2.2.1. Danh php ca aldehyd ................................................................................................ 21
2.2.2. Danh php ca ceton .................................................................................................... 22
2.2.3. iu ch aldehyde v ceton ......................................................................................... 23
2.2.4. Tnh cht vt l ............................................................................................................ 24
2.2.5. Tnh cht ha hc ........................................................................................................ 24
2.2.6. Mt s ng dng ca aldehyd v ceton ....................................................................... 30
2.3. Quinon ................................................................................................................................ 30
2.3.1. GI TN: .................................................................................................................... 30
2.3.2. IU CH ................................................................................................................... 31
2.3.3. ng dng ..................................................................................................................... 31
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BI TP CHNG 2 .................................................................................................................. 32
CHNG 3. ACID CARBOXYLIC V CC DN XUT ...................................................... 33
3.1. ACID CARBOXYLIC ....................................................................................................... 33
3.1.1. Cu to ......................................................................................................................... 33
3.1.2. Danh php .................................................................................................................... 33
3.1.3. Phng php iu ch ................................................................................................. 35
3.1.4. Tnh cht vt l ............................................................................................................ 36
3.1.5. Tnh cht ha hc ........................................................................................................ 36
3.2. Cc dn xut ca acid carboxylic ....................................................................................... 38
3.2.1. Ester ............................................................................................................................. 39
3.2.2. Anhydrid acid .............................................................................................................. 41
3.2.3. Ceten ............................................................................................................................ 42
3.2.4. Halogenid acid (acyl halogenid) .................................................................................. 42
3.2.5. Amid ............................................................................................................................ 43
3.2.6. Nitril (R-CN) ............................................................................................................ 43
BI TP CHNG 3 .................................................................................................................. 44
CHNG 4. AMIN, HP CHT KHC CHA NIT, HP CHT C LU HUNH V
PHOSPHO .................................................................................................................................... 45
4.1. Amin ................................................................................................................................... 45
4.1.1. Cu to ......................................................................................................................... 45
4.1.2. Danh php .................................................................................................................... 45
4.1.3. iu ch ....................................................................................................................... 46
4.1.4. Tnh cht vt l ............................................................................................................ 48
4.1.5. Tnh cht ha hc ........................................................................................................ 48
4.2. HP CHT KHC CHA NIT .................................................................................... 50
4.3. Hp cht c lu hunh, phosphor ...................................................................................... 50
4.3.1. Hp cht hu c c lu hunh .................................................................................... 50
4.3.2. Hp cht hu c cha phosphor .................................................................................. 52
BI TP CHNG 4 .................................................................................................................. 54
CHNG 5. HP CHT D VNG........................................................................................... 55
5.1. PHN LOI DANH PHP ............................................................................................ 55
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5.1.1. PHN LOI ................................................................................................................ 55
5.1.2. DANH PHP .............................................................................................................. 56
5.1.3. Tnh cht ha hc ca d vng c tnh thm ............................................................... 60
5.2. Hp cht d vng 5 cnh 1 d t v nhiu d t .................................................................. 62
5.2.1. Hp cht d vng 5 cnh 1 d t ................................................................................... 62
5.2.2. Hp cht d vng 5 cnh nhiu d t ............................................................................ 65
5.3. Hp cht d vng 6 cnh mt d t v hai d t .................................................................. 67
5.3.1. Hp cht d vng 6 cnh mt d t .............................................................................. 67
5.3.2. Hp cht d vng 6 cnh 2 d t ................................................................................... 69
5.4. HP CHT D VNG 7 CNH V D VNG NGNG T ........................................ 74
5.4.1. D vng 1 d t ............................................................................................................. 74
5.4.2 D vng 2 d t .............................................................................................................. 74
5.4.3. D vng ngng t ......................................................................................................... 75


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CHNG 1. ALCOL, PHENOL
1.1.Alcol
1.1.1. Mt s khi nim chung
Alcol l nhng hp cht hu c c nhm hydroxyl (-OH) gn trc tip vi C lai ha
sp
3

ca gc hydrocarbon. Cng thc tng qut R-OH
C nhiu cch phn loi alcol khc nhau:
- Da vo cu to gc hydrocarbon c cc loi: alcol no, alcol cha no, alcol mch
vng, alcol thm
- Da vo s lng nhm OH trong phn t c cc loi: monoalcol (ru n
chc), polyalcol (ru a chc). S lng nhm OH trong phn t khng gii hn,
song trong phn t mi nguyn t C ch c kh nng lin kt bn vi mt nhm
OH
- Da vo bc ca nguyn t C c gn nhm OH, c cc loi alcol bc 1 (v d
CH
3
CH
2
OH), bc 2 (v d CH
3
CH
2
CH(CH
3
)OH), bc 3 (v d (CH
3
)
3
C-OH)
1.1.2. Danh php
a. Danh php IUPAC
Cc alcol c tip v ng l ol (Tn hydrocarbon tng ng + ol).
Cch gi tn c thc hin ln lt nh sau:
- Chn mch C di nht c nhm OH lm mch chnh
- nh s trn mch chnh sao cho C mang nhm OH c s v tr nh nht
- Cc nhm th khc nhau c sp xp theo th t ca bng ch ci. Nu c nhiu
nhm th ging nhau, dng tip u ng nh di (2), tri (3), tetra (4), t trc
tn cc nhm th
- Khi mt cht cha nhiu loi nhm chc khc nhau th mc u tin th t cc
nhm th khc nhau trong h danh php IUPAC nh sau: -COOH > -CHO > C=O
> -OH > -NH
2
> -Cl, Br
- Trng hp c nhiu nhm OH trong phn t, cch gi tn tng t nh trn,
thm cc t di-, tri-, tetra- trc tip v ng -ol ch s lng nhm OH trong
phn t.
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V d:

b. Danh php thng thng
i vi monoalcol, cch gi tn thng thng nh sau: Alcol (hoc ru) +tn
gc hydrocarbon tng ng +ic
Sau y l tn gi ring ca mt s gc hydrocarbon
- Gc bc 1:

- Gc bc 2:

- Gc bc 3

- Gc khng no:
CH
2
=CH- : vinyl CH
2
=CH-CH
2
- : allyl CHC-CH
2
-: propagyl
- Cc gc khc
benzyl
V d:
Tn thng thng ca mt s monoalcol nh sau:

2,3-dimethyl-2,3-butandiol

hay isoamyl hay amyl
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CH
2
=CH-CH
2
-OH: Alcol allylic C
6
H
5
-CH
2
-OH: Alcol benzylic
(CH
3
)
3
C-OH: Alcol tert-butylic CH
3
OH: Alcol methylic
CHC-CH
2
OH: Alcol propagylic
Danh php thng thng ca mt s polyalcol nh sau:

c. Danh php carbinol
i vi monoalcol, alcol metylic c gi l carbinol. Cc alcol n gin khc xem l
dn xut th ca carbinol
V d:

1.1.3. iu ch alcol
C rt nhiu phng php iu ch alcol
a.Thy phn dn xut halogen trong mi trng kim
RX + NaOH ROH + NaX
V d: C
2
H
5
Br + NaOH C
2
H
5
OH + NaBr
b.Hydrat ha alken
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R-CH
2
=CH
2
+ H
2
O

R-CH
2
OH-CH
3

Qui tc Markovnikov: trong phn ng cng hp vi tc nhn khng i xng HX (H-
OH, H-Cl,), H c cng vo C ni i c cha nhiu nguyn t H hn, X c cng
vo C cn li ca ni i
V d: CH
3
-CH
2
=CH
2
+ H
2
O

CH
3
-CH
2
OH-CH
3
(sn phm chnh)
c.Kh hp cht aldehyde, ceton
Kh ha hp cht carbonyl bng nhiu phng php khc nhau: H
2
/Ni, Na/C
2
H
5
OH,
LiAlH
4
, NaBH
4
,..

Trng hp mch C ca gc R trong hp cht carbonyl khng no th cc tc nhn
H
2
/Ni, Na/C
2
H
5
OH s kh lun cc lin kt bi trong mch C .
Kh ha bng LiAlH
4
tin hnh trong dung mi ether. Cc aldehyd, ceton, acid, ester
v clorid acid u b kh ha to alcol, trong trng hp ny nu hp cht cha no th
ni i C=C khng b kh ha

NaBH
4
l tc nhn kh ha c tnh chn lc cao, ch kh cc aldehyd, ceton,
halogenid acid.
Kh ha ester ca acid carboxylic
- Cht kh l Na/C
2
H
5
OH:
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- Hydro ha ester c xc tc l hn hp CuO v Cr
2
O
3
:

d.T hp cht c magne RMgX
- Vi aldehyde, ceton (xem thm trong phn ha tnh ca aldehyde, ceton)

- Vi ester

- Oxy ha hp cht c magne, sau thy phn

e.Thy phn ester
Ester b thy phn trong mi trng kim hoc acid to alcol
RCOOR + H
2
O

RCOOH + ROH
Ngoi ra cn c nhiu phng php iu ch alcol khc.
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1.1.4. Tnh cht vt l
tan ca alcol: Phn t alcol gm 2 phn: phn R ha tan trong cc dung mi
khng phn cc, phn OH ha tan trong dung mi phn cc, v d nc. Do s ha
tan ca alcol ph thuc vo kch thc ca R so vi OH.
Nhng alcol c R cng ngn th cng d tan trong nc, R cng di th ha tan
cng km i. Alcol ha tan c trong nc l do to lin kt H lin phn t gia nhm
OH vi nc
Nhit si v nhit nng chy ca alcol: Cc alcol c s carbon thp dng
lng c mi v v c trng. Cc alcol c s carbon cao dng rn, khng mi.
Cc alcol c nhit si cao hn cc hydrocarbon tng ng v alcol to c lin
kt H lin phn t. Tng t cc hp cht khc, nhit si ca alcol cng tng theo
phn t lng
1.1.5. Tnh cht ha hc
Ha tnh ca alcol (R-OH) bao gm ha tnh ca gc hydrocarbon R v ca nhm
chc -OH.
Ta xt ha tnh ca nhm OH. C 2 loi phn ng ty vo s ct ni C-O hoc O-H

1.1.5.1. Phn ng do s t ni C-O
Phn ng tch H
2
O to alken
- un nng alcol vi acid v c H
2
SO
4
hoc H
3
PO
4


Qui tc Zaicep: Nhm OH b tch u tin cng nguyn t H C bc cao hn
- Cho hi alcol i qua nhm oxit un nng

1.1.5.2. Phn ng do s t ni O-H
a. Tnh acid-baz
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Ging nh H
2
O, alcol va c tnh acid yu, va c tnh baz yu.
- Tnh acid ca alcol rt yu, yu hn c nc: alcol bc 3 < alcol bc 2 < alcol bc
1 < H
2
O
Phn ng th hin tnh acid ca alcol
ROH + Na RONa + H
2

ROH + NaNH
2
RONa + NH
3

ROH + NaH RONa + H
2

- Tnh baz ca alcol rt yu, nhng mnh hn nc. N c th b proton ha bi
cc acid mnh

b. Phn ng to ether
- Hai phn t alcol

- Cc alcolat l tc nhn i nhn mnh tc dng vi RX to ether
R-ONa + R-I R-O-R + NaI
c. Phn ng to ester
Alcol tc dng vi acid hu c, anhydrid acid, halogenid acid to thnh ester

Phn ng ester ha l phn ng thun nghch, v vy to nhiu ester ngi ta s
dng cc cht lm gim nng nc, acid to thnh. Cc cht thng s dng l acid
v c (H
2
SO
4
, H
3
PO
4
,..), baz (pyridine)
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Acid sunfuric m c va ng vai tr xc tc (cung cp proton H
+
) phn ng xy
ra nhanh hn, va c tc dng ht nc phn ng chuyn dch v pha to nhiu ester.
Alcol tc dng vi acid v c to ester v c:

Mui natri alkylsulfat ca alcol t C
10
-C
20
nh natri lauryl sulfat C
12
H
25
OSO
3
Na c
s dng lm cht nh ha trong dc phm, v trong mt s cht c tc dng ty ra.
1.1.5.3.Phn ng oxi ha alcol
Alcol bc 1 b oxy ha thnh aldehyde, sau thnh acid
Alcol bc 2 b oxy ha thnh ceton
Cc cht oxy ha thng s dng l CuO, CrO
3
, (K
2
Cr
2
O
7
+ H
2
SO
4
), KMnO
4
,
Cc alcol cha no b oxy ha bi K
2
Cr
2
O
7
+ H
2
SO
4
to hp cht carbonyl m lin kt
pi trong mch Carbon khng b oxy ha, nhng khi oxy ha bi KMnO
4
th lin kt pi
trong mch Carbon to ru a chc

V d:
3CH
3
CH
2
OH + K
2
Cr
2
O
7
+ 4H
2
SO
4
3CH
3
CHO + K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 7H
2
O
3CH
3
CH(OH)-CH
3
+ K
2
Cr
2
O
7
+ 4H
2
SO
4
3CH
3
COCH
3
+ K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 7H
2
O

1.1.5.4.Mt s phn ng khc
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Vi cc Polyalcol c cc nhm OH xa nhau: tnh cht ha hc tng t monoalcol
Polyalcol c nhm OH cnh nhau: nh hng ca nhiu nhm OH lm polyalcol c
tnh acid mnh hn monoalcol. V vy polyalcol c tnh cht ring l ha tan c
Cu(OH)
2
to dung dch mu xanh lam

Cc alcol vng c th b oxy ha thnh ceton vng

1.1.6. ng dng
Trong thin nhin tn ti nhiu alcol cha no, c s C cao nh citronellol, geraniol,
linalol, pharnezol, phytol c nhiu ng dng trong cng nghip hng liu v dc
phm.
Mt s alcol vng c nhiu ng dng. Menthol c trong tinh du bc h c ng
dng nhiu trong y dc. Hp cht 1,2,3,4,5,6-cyclohexahexanol c nhiu ng phn,
trong ch c ng phn Inositol c ng phn quang hc v c ng dng trong dc
phm

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1.2. Phenol
1.2.1. Khi nim
Phenol l hp cht c nhm OH gn trc tip vi nhn benzene.
Cng thc tng qut ca phenol thng gp
- Monophenol Ar-OH
- Polyphenol Ar(OH)
n

1.2.2. Danh php
Hu ht cc phenol c trong t nhin u c tn thng thng
Xem C
6
H
5
OH l phenol. Gi tn cc phenol khc nh l dn xut ca phenol


1.2.3. iu ch phenol
a. Thy phn chlorobenzen
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b. Phng php kim chy
Sn xut phenol t benzen:
C
6
H
6
+ H
2
SO
4
C
6
H
5
SO
3
H (acid benzensulfonic)
2C
6
H
5
SO
3
H + 2NaOH

2C
6
H
5
OH + Na
2
SO
3
+ H
2
O
c. Oxy ha cumen

d.Thy phn mui diazoni

e. Oxy ha hp cht aryl magne halogenid

1.2.3. Tnh cht vt l
S c mt ca nhm OH gn trc tip vi vng benzen quyt nh tnh cht ca
phenol. Do tng tc vi nhn benzene, lin kt O-H b phn cc mnh hn lin kt OH
trong alcol. Lin kt hydro trong phenol bn hn lin kt hydro trong alcol
Phn ln phenol dng rn, kh tan trong nc v t bay hi.
1.2.4. Tnh cht ha hc
a. Tnh acid
Phenol c tnh acid mnh hn alcol, do cp in t trn O ca nhm OH lin hp vi
vng benzene khin H ca nhm OH tr nn linh ng hn
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Tnh acid: H
2
CO
3
> phenol > H
2
O > alcol
Cc phn ng chng minh tnh acid ca phenol mnh hn alcol v yu hn acid cacbonic

b. Phn ng th nhm OH
Nhm OH phenol c th b thay th bi Cl hay NH
2
khi tc dng vi PCl
5
hoc NH
3

xc tc AlCl
3



c. Phn ng ester ha
Phenol tc dng trc tip vi acid carboxylic hiu sut rt thp. Phn ng xy ra kh
khn hn s ester ha ca alcol. Phn ng xy ra d dng hn khi dng clorid acid,
anhydride acid c xc tc baz hoc acid
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Ester ca phenol tham gia phn ng chuyn v Fries to ceton thm khi c mt AlCl
3


d.Phn ng to ether ca phenol
ArONa + RX ArOR + NaX
V d:


Di tc dng ca nhit , ether cha no allylphenylether tham gia chuyn v
Claisen

e.Phn ng tng hp Kolbe

Acid Salicylic
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Thng p dng phn ng ny sn xut acid salicylic quy m cng nghip
T acid salicylic c th tng hp nn thuc Aspirin

f. Phn ng vi aldehyde
Phenol tc dng vi aldehyde formic trong mi trng baz to hn hp ng phn
alcol v tr orthor v para

Cc alcol to thnh tng tc vi nhau tng t phn ng trng ngng to thnh
polymer gi l bakelit
Trong mi trng acid

g. Cc loi phn ng th i in t khc

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h. Phn ng to mu vi FeCl
3

Vi dung dch FeCl
3
phenol to hp cht C
6
H
5
OFeCl
2
dung dch mu tm , crezol
to dung dch mu xanh, phenol khc to dung dch mu vng
Phn ng ny cng c dng trong nh tnh acid salicylic
mu tm
1.1.4. ng dng
Phenol c nhiu ng dng. T phenol c th tng hp c cc cht chng oxy ha
bo qun sn phm du m thc phm hay m phm nh BHT, BHA. Phenol c th
tng hp nn acid salicylic ng dng trong sn phm dit trng v dit nm, ng thi n
cng l nguyn liu iu ch thuc aspirin
Nhiu dn xut phenol trong t nhin nh eugenol, thymol, c hot tnh sinh hc,
c s dng trong sn xut dc phm hoc trong y hc

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BI TP CHNG 1
Alcol
1. Vit cng thc cu to ca cc cht sau:
a. Alcol tert- butylic ; b. Alcol isoamylic ; c.sec-Butylethylmethylcarbinol
d. 2-Propanol ; e. 2,2-dimethyl-2-pentanol f. Alcol allylic.
g.2,3-Dimethyl-2,3-butadiol; h. Alcol propagylic i. phenylacetylcarbinol
2. Nhng alcol no c to thnh khi thy phn bng dung dch kim t cc hp cht
halogen sau:
a. Isobutylbromid; b. sec-butylbromid; c. 1-Brom-2-buten ;
3. Vit phn ng xy ra trong cc trng hp di y
a. Hydrat ha propylen; trimethylethylen; isobutylen; 2,2-dimethyl-3-hexen.
b. Phn ng tch nc ca hp cht (CH
3
)
2
C(OH)CH
2
CH
2
CH
2
OH.
c. Oxy ha cc alcol n-butylic, sec-butylic bng hn hp K
2
Cr
2
O
7
v H
2
SO
4
.
4. Cho phn ng chng minh polyalcol c tnh acid mnh hn monoalcol
5. V sao polyalcol d tan trong nc hn monoalcol
Phenol
6. Vit cng thc cu to cc cht sau
a. m-Cresol; b. p-Ethylphenol; c. 2,4- Dinitrophenol;
d. o-Nitrophenol; e. Acid picric; f. Acid 2,4-Phenoldisulfonic
g. Acid salicylic h. Aspirin i. 2-amyl-5-metylphenol
7. Vit s phn ng trong cc trng hp sau:
a. Tng hp acid salicylic t phenol
b. Tng hp aspirin t phenol
c. Thc hin s chuyn v Fries hp cht p-hydroxyphenolacetat

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CHNG 2. ALDEHYD, CETON, QUINON
2.1. Gii thiu chung
Aldehyd, ceton, quinon l nhng hp cht c cha nhm carbonyl C=O.
Tng qut


Ty thuc vo cu to ca cc gc R
1
, R
2
, R m aldehyde, ceton c cc loi no, cha
no, thm, hoc vng
Nhm chc CHO gi l chc aldehyde hay nhm formyl
Nhm carbonyl C=O trong ceton gi l chc ceton hay nhm oxo
Quinon l sn phm oxy ha cc diphenol. Quinon phi l mt h thng lin hp. Do
tn ti 1,2-quinon hoc 1,4-quinon. Khng c 1,3-quinon

2.2. Aldehyd v ceton
2.2.1. Danh php ca aldehyd
a. Danh php IUPAC
Tn hydrocarbon tng ng + al
nh s 1 t C ca nhm CHO
V d:

b. Tn thng thng
O
O
1,2-hay orto-quinon
O O
1,4- hay para-quinon
H C
O
H
aldehyd formic
R H C
O
Aldehyd
R
1
C
O
R
2
Ceton
O O
Quinon
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22

Gi tn thng thng theo tn acid tng ng, thay ch acid bng aldehyde
Aldehyd + tn acid tng ng hoc tn gc acyl R-CO- + aldehyde
V d

Aldehyd cinnamic CHC-CH
2
-CHO: Aldehyd propagylic
2.2.2. Danh php ca ceton
a. Danh php IUPAC
Tn hydrocarbon tng ng + on
Chn mch chnh l mch C di nht c cha nhm C=O. nh s t u gn nhm
C=O nht
V d

b. Tn thng thng
Tn cc gc hydrocarbon + ceton
V d:
Methylphenylceton
Diphenylceton hay Benzophenon
Methylphenylceton hay Acetophenon
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23

Methyl,tert-Butylceton hay Pinacolin
2.2.3. iu ch aldehyde v ceton
Aldehyde v ceton u c nhm carbonyl, v vy phng php iu ch gn ging
nhau.
a.Ozon ha alken


b. Hydrat ha acetilen v alkyn
CHCH + H
2
O CH
3
CHO
R-CC-R + H
2
O R-CO-CH
2
-R
c. Oxi ha alcol
Oxi ha alcol (xem ha tnh alcol)
Alcol bc 1

Aldehyd Alcol bc 2

Ceton
d.Nhit phn mui ca acid carboxylic
Khi nhit phn cc mui Canxi, Bari, Natri,.. ca acid carboxylic nhit khong
300
o
C s to thnh ceton (phn ng Perrier)
(RCOO)
2
Ca

R-CO-R + CaCO
3

Nu s dng hn hp 2 mui, trong c mui ca acid formic s thu c aldehyde

e.Phn ng Acyl ha vo nhn thm theo Friedel-Crafts
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24


Acyl ha c th xy ra trong ni phn t to ceton vng

i. Cc phn ng iu ch khc
Phn ng ca ester vi thuc th Grignard: ty vo cu to ester m sn phm to
thnh c th l aldehyd hoc ceton
RCOOR + RMgX R-CO-R + RO-MgX
HCOOR + RMgX R-CHO + RO-MgX
Phn ng Stephen: kh ha hp cht nitril R-CN bng thic clorid SnCl
2
trong mi
trng acid
R-CN + SnCl
2
+ 2HCl R-CH=NH + SnCl
4

R-CH=NH + H
2
O

R-CHO + NH
3

Phn ng Rosenmund: hydro ha hp cht acylclorid vi xc tc Pd/BaSO
4


2.2.4. Tnh cht vt l
Aldehyde v ceton l nhng cht lng hoc rn iu kin thng. Ch c aldehyde
formic l cht kh. Aldehyd formic, aldehyde acetic, aceton l nhng cht tan v hn
trong nc.
Aldehyd v ceton thng c nhit si thp hn alcol tng ng do nhm carbonyl
khng c kh nng to lin kt H lin phn t
2.2.5. Tnh cht ha hc
+ R C
O
Cl
AlCl
3
C R
O
+ HCl
C
O Cl
AlCl
3
O
+
HCl
3-phenylpropanoylclorid Indanon-1
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25

Nhm carbonyl trong phn t lm cho cc hp cht aldehyde, ceton c kh nng tham gia
phn ng c trng nh: phn ng cng hp i nhn vo C=O, phn ng ca cc nguyn
t H C v tr , phn ng oxy ha kh
2.2.5.1. Phn ng cng hp i nhn (A
N
)\

Trong
Hp cht Y-Z c th l H-OH, H-OR, H-CN, H-SO
3
Na, H ca aldehyd
RCH(H

)CHO hay H ca ceton RCH(H

)CO-R (trong mi trng OH


-
), H-NH-R,
XMg-R,
- Nguyn t C trong C=O cng dng, phn ng cng d dng
o Nhm y in t (+C, +I, +H) gim kh nng phn ng
o Nhm ht in t (-C, -I) tng kh nng phn ng
Sau y l mt vi trng hp v phn ng cng hp i nhn ca nhm carbonyl vi
hp cht Y-Z l aldehyd RCH(H

)CHO hay ceton, R-MgX, dn xut ca acid carboxylic


a.Cng vi hp cht c kim R-MgX
Cng vi hp cht c magie

Khi cng vi hp cht c magi ta c ru bc 2 hoc bc 3 (tng ng vi
aldhehyd hay ceton)
b. Cng vi aldehyde hay ceton
Phn ng ngng t aldol

iu kin phn ng aldol: - Hp cht carbonyl c H

.
O R" + MgX
R
C
R'
(H)
OH
H
3
O
+
R
C
R'
(H)
OMgX
R"
R
C
R'
(H)
R"
R CH
2
CHO 2
HO
R CH
2
CH
OH
CH
R
CHO R CH
2
CH CHO C
R
aldehyd aldol

H
2
O
t
0
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26

- Mi trng kim long
C ch:
Giai on 1: to carboanion (xy ra chm)

Giai on 2: carboanion tn cng C
+
, phn ng i nhn (xy ra nhanh)

Giai on 3: proton ha ti to OH
-


Di tc dng nhit cao, xy ra phn ng tch nc (gi l phn ng croton ha)

V d:
Phn ng gia aldehyd v aldehyd


Aldehyd cinnamic
Phn ng gia aldehyde vi ceton

Trng hp aldehyde khng c H (Phn ng Cannizaro)
iu kin: - Aldehyd khng c H , c bit l aldehyd thm.
- Mi trng kim c.
H
OH H
2
O
+
R CHO CH R CHO CH
+
R CH
2
+ CH
R
CHO C
H
O
R CH
2
CH
O
CH
R
CHO
H
2
O
R CH
2
CH
OH
CH
R
CHO CH R
+
HO
H
2
O
R CH
2
CH CHO C
R
R CH
2
CH CHO C
R
R CH
2
CH CHO C
R
t
0
C
6
H
5
CHO + CH
3
CHO
HO
C
6
H
5
CHCH
2
CHO
OH
H
2
O
t
0
C
6
H
5
CH CHCHO
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27

Phn ng to acid v alcol tng ng

C ch:


V d:
2C
6
H
5
CHO


C
6
H
5
COO
-
+ C
6
H
5
CH
2
OH
Phn ng Cannizaro cho: (2 aldehyd khc nhau khng c H

)

c. Phn ng vi cc dn xut ca acid carboxylic.
Phn ng Perkin: Phn ng ca aldehyd thm vi (CH
3
CO)
2
O

d. Phn ng ngng t benzoin
Khi c mt KCN lm xc tc, cc aldehyde thm tham gia phn ng c trng to
hp cht mang chc CH(OH)-CO- gi l phn ng ngng t benzoin

e.Phn ng vi Natrihydrosulfit (NaHSO
3
)
Ar C
O
H
Ar C
O
H
Ar C
O
OH
+
HO
+ Ar CH
2
OH
+ HO Ar C
O
H
Ar C
OH
H
O
Ar C
O
H
( Ar C
OH
H
O
+ Ar C
OH
O
+ Ar CH
2
O Ar C
O
O
+ Ar CH
2
OH
C
6
H
5
CHO HCHO C
6
H
5
CH
2
OH HCOO + +
HO
CHO
(CH
3
CO)
2
O +
CH
3
COONa
CH CH COOH
+
CH
3
COOH
acid cinnamic
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28

Aldehyd v ceton tc dng vi dung dch natrihydrosulfit to thnh sn phm cng
trng thi tinh th gi l hp cht hydrosulfitic. Hp cht hydrosulfitic d b thy phn
trong mi trng acid to hp cht carbonyl ban u v SO
2
. V vy phn ng ny c
dng tch aldehyd hoc ceton ra khi hn hp.


f. Phn ng cng hp vi hp cht c chc amin NH
2


Trong phn t hydrazon c nhm NH
2
t do c th phn ng vi nhm carbonyl to
hp cht azin

2.2.5.2. Phn ng kh

* Tc nhn kh: Cc hydrid kim loi (LiAlH
4
, NaBH
4
), H
2
/xc tc,..
Khi dng tc nhn kh l H
2
c xc tc kim loi th tt c lin kt i, ba, v nhm
carbonyl u b kh
V d:
RCH O
[H]
RCH
2
OH
aldehyd alcol ba c 1
R C R'
O
[H]
R CH R'
OH
ceton alcol bac 2
-H
2
O
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29


Cc tc nhn kh l hydrid kim loi c tnh chn lc cao, ch kh ha chc carbonyl
m khng kh ha cc ni i, ni ba khc trong mch carbon (nh C=C, CC)
V d:

2.2.5.3. Phn ng oxy ha
Oxy ha bng cc tc nhn v c

Cc tc nhn [O] l: - AgNO
3
/NH
4
OH (Thuc th Tollens)
- Cu(OH)
2
(Thuc th Fehling)
- H
2
O
2
, KMnO
4
, CrO
3

Nhng phn ng ny c dng nh tnh hp cht c chc aldehyde

Ceton ch b [O] bng cc cht oxy ha mnh, mch carbon b ct t thnh cc acid.

2.2.5.4. Phn ng th. Phn ng halogen ha
a. Tc dng PCl
5
, PBr
3
: To gem-dihalogen
R CH O
[O]
R COOH
aldehyd acid
CHO Ag
2
O +
H
2
O
THF
COOH + 2Ag
O
HNO
3
V
2
O
5
HOOC(CH
2
)
4
COOH
cyclohexanon acid adipic
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30


2-butanon 2,2-dichloroethan

3-methylbutanal 1,1-dichloro-3-methylbutan
b. Tc dng vi halogen

Phn ng ch xy ra i vi hydro v tr .
2.2.6. Mt s ng dng ca aldehyd v ceton
a. Tng hp vitamin A t Citral (3,7-dimethyl-2,6-octadienal)
Citral tham gia phn ng ngng t aldol vi aceton to sn phm -ionon l sn phm
trung gian trong cng nghip tng hp vitamin A


b. Aldehyd cinnamic: l thnh phn ch yu ca tinh du qu
aldehyde cinnamic
2.3. Quinon
2.3.1. GI TN:
+ + CH
3
CH
3
C
O
C PCl
5
POCl
3
Cl
CH
3
CH
2
CH
3
CH
2
Cl
+ + PCl
5
POCl
3
(CH
3
)
2
CHCH
2
CHO (CH
3
)
2
CHCH
2
CHCl
2
R
O
C CH
3
+ Br
2

h
R C
O
CH
2
Br + HBr
CH
3
COCH
3
+
HO
BF
3
CH
3
CH
3
CH
3
O
CH
3
CH
3
CH
3
CHO
CH
3
CH
3
CH
3
CH
3
O
CH
3
citral Ionon
CH
3
CH
3
CH
3
CH
3
CH
3
CH
2
OH
Retinon ( vit A
1
)
CH CH CHO
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31

Theo dn xut ca h thm: benzoquinon t benzen, toluquinon t toluen,
naphtoquinon t naphtol.

p-benzoquinon o-benzoquinon 2-methyl-1,4-benzoquinon

2.3.2. IU CH
Oxy ha cc phenol v amin thm

2.3.3. ng dng
Quinon l thnh phn cu to c bn trong cc cht mu
Vitamin K
1
c thnh phn quinon


O
O
1,4-benzoquinon
O
O
1,2-benzoquinon
O
O
CH
3
Toluquinon
O
O
1,4-naphtoquinon
O
O
9,10-anthraquinon
O
O
K
2
Cr
2
O
7
30
0
C
OH
OH
p-benzoquinon Hydroquinon
Na
2
Cr
2
O
7
H
2
SO
4
30
0
C ,
NH
2
Anilin
O
O
vitamin K
1
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32

BI TP CHNG 2
1. Vit cng thc cu to cc hp cht c tn nh sau:
a. 5-Methylhexanal; b. Methylethylceton; c. Methylbenzylceton;
d. Citral e. Acetophenon; f. Benzophenon.
g. Andehit cinnamic
2. Chn cc phng php thch hp iu ch cc cht t cc nguyn liu cho
a. iu ch phenylacetaldehyd t C6H5CH2CH2Cl
b. iu ch aldehyde cinnamic t acetylene v benzaldehyd
c. iu ch methylethylceton t sec-butanol
3. Vit phng trnh phn ng ca benzaldehyd vi cc cht sau:
a. Aldehyd formic/kim c b. Aldehyd acetic/kim long
4. Vit sn phm to thnh khi cho citral phn ng vi cc cht sau:
a. H
2
/Ni b. LiAlH4.
5. Vit cng thc cu to cc cht sau:
a. o-Benzoquinon b. p-Benzoquinon
c. Naphtoquinon-1,4; d. Antraquinon-9,10
6. Vit sn phm to thnh trong cc phn ng di y
a. Benzaldehyd

b/. Acetaldehyd


7. Vit c ch phn ng ngng t aldol 2 phn t acetaldehyde

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33

CHNG 3. ACID CARBOXYLIC V CC DN XUT
3.1. ACID CARBOXYLIC
3.1.1. Cu to
Acid carboxylic l nhng hp cht hu c c nhm carboxyl COOH trong phn t.
C th vit cng thc cu to acid di cc dng sau:

C nhiu cch phn loi acid carboxylic. Da vo gc hydrocarbon, c th phn loi
acid carboxylic thnh acid no, khng no, thm. Da vo s nhm chc COOH c acid
n chc, acid a chc.
3.1.2. Danh php
a. Danh php IUPAC
Phng php 1: dng tip v ng oic
Tn hydrocarbon tng ng + oic
Chn mch di nht cha nhm COOH l mch chnh. nh s bt u t C ca
nhm chc acid (C nhm COOH mang s 1). Hoc dng cc ch ci latinh , ,
ch v tr carbon trong mch chnh (Ch ci bt u t carbon lin k nhm COOH)
V d:

Phng php 2: dng tip v ng carboxylic
Xem acid hu c l dn xut ca hydrocarbon. H c thay th bi chc acid. Chc
acid c tn gi l carboxylic
Tn hydrocarbon tng ng vi gc R + carboxylic
V d:

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34

b. Danh php thng thng
- Danh php thng thng phn nh ngun gc acid
Tn gi ca mt s acid n chc

Tn gi ca mt s acid a chc


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35

3.1.3. Phng php iu ch
Mt s phng php tiu biu
3.1.3.1.Dng tc nhn Grignard
R-X

R-MgX

R-COOH
V d:

3.1.3.2. Phn ng thy phn
- Thy phn dn xut polyhalogen

- Thy phn hp cht nitril

- Thy phn cc dn xut ca acid

3.1.3.3. Carboxyl ha alken

3.1.3.4. Phng php oxy ha
Oxy ha ru bc 1 to aldehyde ri thnh acid (xem bi alcol)

H-Y
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36

Oxy ha hydrocarbon thm

3.1.4. Tnh cht vt l
Vi cu to ca acid carboxylic

Lin kt O-H trong acid phn cc mnh hn trong alcol, do lin kt H acid bn
hn alcol
Tt c acid carboxylic l cht lng hoc cht rn. Acid thm l cht rn. Nhit si
tng dn theo trng lng phn t, cao hn alcol c khi lng phn t tng ng.
R l gc k nc, -COOH l nhm i nc. V vy, R cng ln tan ca acid cng
gim. Cc acid c s C < 4 tan v hn trong nc. Cc acid c s C > 11 hon ton
khng tan trong nc
3.1.5. Tnh cht ha hc
Nhm carboxyl l t hp ca 2 nhm carbonyl (C=O) v nhm hydroxyl (-OH). Hai
nhm ny c nh hng ln nhau, kt qu l C trong nhm carboxyl c + nh hn trong
aldehyde, v nhm O-H phn cc mnh hn trong alcol

Acid carboxylic Aldehyd
C 4 loi phn ng ca acid carboxylic nh sau:

1.t lin kt O-H 2. Phn ng i nhn 3. Tch nhm CO
2
4. Phn ng gc R
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37

3.1.5.1. Phn ng t lin kt O-H
Tnh acid
- Phn ly trong nc

- Phn ng vi kim loi, oxyd kim loi, baz, mui,

- Tnh acid ph thuc vo gc R, R cng ht in t tnh acid cng mnh
3.1.5.2. Phn ng i nhn vo nhm carboxyl
Phn ng ester ha:

C ch phn ng nh sau:

Phn ng th nhm OH bng cc halogen
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38

Acid tc dng vi Thionyl clorid SOCl
2
, Phosphor pentaclorid PCl
5
, Phospho
tribromid PBr
3
,.. to sn phm acylhalogenid RCOX

3.1.5.3. Phn ng decarboxyl ha (tch CO
2
)
Kh nng decarboxyl ha ph thuc vo cu to acid. Acid c nhm ht in t d
b decarboxyl ha hn
Acid acetic rt kh b decarboxyl ha. Mui acetat b decarboxyl ha nhit
cao

Dn xut th ca acid acetic c nhm ht in t d b decarboxyl ha hn:
Cl
3
CCOOH, O
2
N-CH
2
-COOH, NC-CH
2
-COOH, CH
3
COCH
2
COOH,..
V d:

3.1.5.4. Phn ng ca gc hydrocarbon
Phn ng oxy ha
Phn ng oxy ha nh xc tc men to acid -oxocarboxylic ng vai tr quan
trng trong chuyn ha cht bo

Cht oxy ha l SeO
2
to acid -oxocarboxylic

Cc phn ng khc:
Ty thuc gc R l no, khng no, thm, m hp cht c phn ng c trng
ring gc hydrocarbon
3.2. Cc dn xut ca acid carboxylic
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39

Khi thay th nhm OH ca acid carboxylic bng cc nhm th khc ta c dn xut
ca acid carboxylic

Di y l cc loi dn xut ch yu ca acid carboxylic


3.2.1. Ester
L sn phm th nhm OH ca acid RCOOH bng gc RO ca alcol (hay gc C
6
H
5
O
ca phenol)
RCOOH RCOOR
3.2.1.1.Danh php
C th xem ester nh mui ca acid hu c. Cch gi tn ca ester l c tn gc
alkyl ca alcol ghp vi tn ca acid carboxylic tng ng thay vn ic bng at.
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40


V d:

Cc ester ca glycerin vi acid bo gi l cht bo (lipid)

Cc acid bo thng gp

3.2.1.2.iu ch
Phng php ester ha

Phn ng acyl ha alcol bng anhydride acid

Phn ng gia mui ca acid carboxylic vi dn xut halogen
RCOONa + RX RCOOR + NaX
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41

3.2.1.3. Tnh cht vt l
Ester thng c mi thm, t tan trong nc. Ester c trong cc loi tinh du, cht bo
v sp.
3.2.1.4. Tnh cht ha hc
Da vo cu to ca ester, ta thy c ester c ha tnh nh sau: phn ng i nhn
vo C ca C=O, phn ng ca H

v cc phn ng ca gc hydrocarbon tng ng.


Mt s phn ng tiu biu
a. Phn ng thy phn
- Trong mi trng acid: phn ng thun nghch

- Trong mi trng baz: cn gi l phn ng x phng ha

C ch phn ng trong mi trng baz

b. Phn ng chuyn i ester
Khi un ester vi alcol c xc tc acid hoc natri alcolat xy ra phn ng trao i
ester

c. Phn ng ca H (Phn ng ngng t Claisen)

3.2.2. Anhydrid acid
Hai phn t acid b loi nc to thnh anhydride acid. Cng thc chung: (RCO)
2
O
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42


Anhydrid acid l tc nhn acyl ha

3.2.3. Ceten
C th xem Ceten l sn phm loi 1 phn t nc ca 1 acid (nhm OH vi H)

Cch gi tn: Xem CH
2
=C=O l ceten, cc ceten khc c gi tn nh l dn xut
th H ca ceten. Tn gc hydrocarbon + ceten

3.2.4. Halogenid acid (acyl halogenid)
Khi thay th nhm OH trong acid bng halogen (X) thu c halogenid acid
RCOOH RCOX
Cch gi tn: thay tip v ng ic hoc oic trong acid bng yl hoc oyl + tn
halogenid
V d:

Halogenid acid l tc nhn acyl ha to ceton, ester
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43


3.2.5. Amid
Thay th nhm OH trong acid bng nhm NH
2
thu c amid

3.2.6. Nitril (R-CN)
Nitril c cu trc R-C v Ar-C
Danh php nitril
- Danh php IUPAC: c tn hydrocarbon tng ng + nitril
- Danh php thng thng: Gi tn gc acyl c s carbon tng ng + nitril hoc
tn gc hydrocarbon tng ng + cyanid
V d:

a s hp cht nitril c c cao

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44

BI TP CHNG 3
1.Gi tn cc cht sau:
a- ClCH2CH2CH2CH2COOH c- CH3CH2CH(CH3)CH2CHCOOH
b- (CH3)3CCH2CH2CH2COOH d- CH2=CH-CH=CHCOOH
2.Thc hin cc chuyn ha sau
a- (CH3CH2CH2)3CBr (CH3CH2CH2)3CCOOH
b-HOCH2CH2CH2CH2CH2CH2Br HOCH2CH2CH2CH2CH2CH2COOH
c- CH3CH2CH2CH2CH=CH2 CH3CH2CH2CH2CH2COOH
3. Vit phng trnh phn ng gia hexanoic acid vi
a-Etanol c mt H
2
SO
4
m c b-Thioyl clorid
4.T cc acid sau hy vit cng thc anhydride, ceten, acylclorid tng ng v gi tn
cc cht
a- CH3CH2CH2CH2CH2COOH b- (CH3)2CHCH2CH2COOH
c- CH2=CHCH2CH2COOH d- BrCH2CH2COOH
5. Hon thnh phng trnh phn ng sau
a. Benzen + Acetylclorid


b. Isopropylbenzoat + NaOH

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45

CHNG 4. AMIN, HP CHT KHC CHA
NIT, HP CHT C LU HUNH V PHOSPHO
4.1. Amin
4.1.1. Cu to
Amin l nhng hp cht c gc alkyl, gc aryl lin kt trc tip vi nguyn t Nit.
C th xem amin l dn xut th H ca amoniac NH
3

Da vo s nguyn t H b thay th bi gc hydrocarbon, amin c chia thnh 3
loi:
- Amin bc 1. R-NH
2

- Amin bc 2. R-NH-R
- Amin bc 3. RRRN
Trng hp N lin kt 4 gc R ta c ion amoni R
4
N
+

Cu trc khng gian ca amin

4.1.2. Danh php
a. Danh php gc-chc
Tn gc hydrocarbon + amin

b. Danh php IUPAC
Tn hydrocarbon tng ng + amin
Hoc -NH
2
c xem nh nhm th, c tn gi l amino
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46

amino + tn hydrocarbon tng ng
V d:


Tn ca mt s amin thm


Nu hp cht cha nhiu nhm chc, s c mt nhm chc chnh, cc nhm cn li
xem nh nhm th.
Th t u tin nhm chnh l COOH > -CHO > >C=O > -OH > -NH
2


4.1.3. iu ch
Mt s phng php iu ch tiu biu
a. Alkyl ha amoniac v cc amin khc
- Alkyl ha bng alkyl halogenua
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47

Khi alkyl ha amoniac v cc amin khc bng alkyl halogenua s thu c hn hp
amin cc bc khc nhau

V d:

- Mun thu c amin bc 1 khng ln amin cc bc khc, dng phn ng tng
hp Gabriel, xut pht t phtalimid, alkyl halogenid s thu c alkyl amin bc
mt

- Alkyl ha bng alcol

b. Kh hp cht cha nit
- Kh ha hp cht nitro: y l phng php thng s dng iu ch cc amin
thm

- Kh ha hp cht nitril (C ) trong mi trng ete

- Kh ha hp cht imin (R-CH=NH): xut pht t aldehyd hoc ceton v amoniac
thu c hp cht imin. Imin to thnh khng bn d b kh thnh amin
RCHO + NH
3
RCH=NH + H
2
O
RCH=NH + H
2


RCH
2
NH
2
- Kh ha hp cht amid: RCONH
2
RCH
2
NH
2

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48

4.1.4. Tnh cht vt l
Cc amin l nhng cht khng mu, tan trong nc. Cc amin t 3C tr ln dng
lng. tan trong nc gim khi phn t lng tng. Cc amin thm l cht lng hoc
rn khng mu. B ha en hoc nu khi tip xc khng kh
Gia cc phn t amin c lin kt H (yu hn alcol). V vy nhit si ca amin cao
hn hydrocarbon v thp hn alcol c khi lng phn t tng ng.
Gia cc ng phn amin bc 1, 2, 3 th amin bc 1 c nhit si cao nht do n d
to lin kt H nht
4.1.5. Tnh cht ha hc
a. Tnh baz
Trn nguyn t N cn cp in t t do, nn amin c tnh baz (theo Lewis) ging
alcol. V N c m in nh hn O nn amin c tnh baz ln hn alcol
Trong dung dch nc, amin c cn bng

Tnh baz ca amin ph thuc cc nhm th v hiu ng khng gian. Nhm th cng
y in t th tnh baz cng mnh
b. Phn ng alkyl ha (phn iu ch amin)
c. Phn ng acyl ha to amid

X c th l HO-, Halogen, RCOO-
V d:

d. Phn ng vi arylsulfonylclorid to sulfonamid
- Vi amin bc 1: to sn phm tan trong dung dch kim
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- Vi amin bc 2: to sn phm khng tan trong dung dch kim

- Amin bc 3 khng tham gia phn ng
S dng phn ng ny phn bit cc amin c bc khc nhau v to cc sulfamid c
nhiu ng dng trong dc phm
e. Phn ng cng hp vi hp cht c nhm carbonyl
R-NH
2
+ O=C< R-N=C< + H
2
O
V d:
C
6
H
5
NH
2
+ CH
3
CHO C
6
H
5
N=CH-CH
3
+ H
2
O
f. Phn ng vi acid nitr HNO
2
Acid nitr kh tn ti iu kin bnh thng. V vy c acid nitr phi s dng
hn hp mui nitrit v acid (NaNO
2
+ HCl)
- Vi amin bc 1
Amin bo bc 1 to mui diazoni khng bn, phn hy thnh alcol v N
2
.
R-NH
2
+ NaNO
2
+ 2HCl

[RNN]
+
Cl
-


R-OH + N
2
+ HCl
Amin bc 1 mui diazoni alcol
Amin thm bc 1 phn ng vi acid nitr to mui diazoni < 5
o
C

- Vi amin bc 2: c amin bo v amin thm u to hp cht N-nitroso amin

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50


- Vi amin bc 3: cc amin bo khng tham gia phn ng, cn amin thm tham gia
phn ng th i in t vo nhn benzene

4.2. HP CHT KHC CHA NIT
Ngoi amin cn c nhiu hp cht khc cha Nit

4.3. Hp cht c lu hunh, phosphor
4.3.1. Hp cht hu c c lu hunh
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51


a.Thiol v sulfid
- Thiol c cng thc chung R-SH
Ty theo R l gc alkyl ta c Thioalcol hay R l gc thm ta c Thiophenol
Nhm SH gi l chc thiol hay mercaptan
Danh php: gi tn hydrocarbon tng ng v thm thiol hoc gi tn gc
hydrocarbon tng ng v thm mercaptan
V d:

- Sulfid c th xem nh eter, trong thay th nguyn t O bng S c cng thc R-
S-R
Danh php: gi tn cc gc hydrocarbon tng ng v thm sulfid
V d:
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52


Cc hp cht thiol v sulfid c nhiu ng dng trong y dc, nng nghip v cng
nghip.
b. Acid sulfonic
C cha nhm chc SO3H.
Danh php: c tn hydrocarbon tng ng v thm sulfonic
Cc phn ng ca hp cht sulfonic c ng dng trong tng hp ha dc
Tng hp cc loi sulfamid trn c s phn ng

Trong sulfamid, nguyn t H trong NH hay NH
2
c th thay th cc nguyn t khc
lm tng kh nng ng dng ca sulfamid trong nhiu lnh vc khc nhau.
Cloramin T v Dicloramin T c tc dng st trng

4.3.2. Hp cht hu c cha phosphor
Cc hp cht hu c cha phospho nh l dn xut ca cc hp cht sau:
Phosphin PH
3

Phosphoran PH
5

Acid phosphinic H
3
PO
2
HOH
2
P=O
Acid phosphonic H
3
PO
3
(HO)
2
HP=O
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53

Acid phosphor H
3
PO
3
(HO)
3
P
Acid phosphoric H
3
PO
4
(HO)
3
P=O
Acid pyrophosphoric H
4
P
2
O
7
(HO)
2
PO-O-OP(OH)
2

Ngi ta chia hp cht hu c cha phospho thnh 2 nhm:
- Hp cht c nguyn t P lin kt trc tip vi C P-C
- Hp cht c nguyn t P khng lin kt trc tip vi C P-O-C
a. Phosphin
Ging amin, phosphin c 3 loi:

C th iu ch triphenylphosphin t hp cht c magi

b. Cc alkyl ca acid cha phospho
- Acid dialkylphosphinic v acid alkylphosphonic

c.Cc ester ca acid phosphor


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54

BI TP CHNG 4
1. Vit phng trnh phn ng khi cho Anilin phn ng ln lt vi cc cht
a. Acid acetic
b. Acetylbromid
c. Benzensulfonylclorid
2. Vit phng trnh phn ng khi cho benzaldehyde phn ng vi
a. o-toluidin
b. tert-butylamin
c. Phenylhydrazin
3. Vit s iu ch sec-butylamin t sec-butylclorid bng phng php Gabriel







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55

CHNG 5. HP CHT D VNG
D vng l nhng hp cht vng. Trong vng ngoi cha nguyn t carbon cn c cc d
t khc nh oxy, nit, lu hunh,Cc nguyn t ny gi l d t.
5.1. PHN LOI DANH PHP
5.1.1. PHN LOI
Da vo cu to c th chia lm 2 loi chnh: d vng thm v d vng khng thm
D vng thm: c cu trc in t ph hp cng thc (4n+2) e
V d: pyridin, furan, pyrrol
D vng khng thm: no hoc khng no
Trong cc hp cht d vng th d vng thm l quan trng.
Phn loi d vng thm nh sau:
a. D vng 5,6,7 cnh 1 d t


b. D vng 5,6 cnh nhiu d t


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56



c. Cc d vng ngn t vi nhau

5.1.2. DANH PHP
a. Danh php thng thng
Xut pht t ngun gc hoc tnh cht ca mt hp cht c trong thin nhin
Danh php thng thng ca hn 60 hp cht d vng c quy c nh l danh php
quc t

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57


nh s d vng theo quy c:
- Bt u t d t v theo chiu ca d vng
- i vi hp cht a vng th nh s bt u t nguyn t cnh vng kt hp
b.Danh php h thng ca hp cht n vng
Danh php Hantzsh-Widman
Tn gi gm 2 phn: tip u ng + phn thn
- Tip u ng ch tn cc d t:
O: oxa S: thia N: aza P:phospha
- Phn thn: ch khung vng, ln vng no hoc cha no c s ni i ln
nht

- Nguyn tc nh s:
o Nhiu d t khc loi: nh s theo chiu u tin O>S>N>P
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58

o Nhiu d t cng loi: bt u t d t cao nht, thm tip u ng di, tri,
tetra,..ch s lng d t
o Khi h thng vng c s ni i cc i c no ha dn: v tr ca
nguyn t bo ha c nh s km theo tip u ng H v gi tn ca
d vng cha no tng ng
V d:


c.Danh php h thng vng ngng t:
Dng tn thng thng ca cc n vng, nu khng c th dng danh php h thng.
Vng ln c tn gi thng thng quy c s c chn u tin. Tn gi ca d vng
ngng t c hai thnh phn:
Thnh phn th hai + thnh phn c s
- Thnh phn c s chn theo nguyn tc sau
o D vng cha nit, nu d vng ch c 1 thnh phn nit N
o Nu khng c nit th chn vng c d t c u tin cao hn
o Nu vng ngng t c s vng ln hn hai vng chn s vng ln nht
o Nu vng c ln khc nhau chn vng ln
o Nu vng c s d t khc nhau chn vng c s d t nhiu nht, hay s
th t ln nht

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59



- Thnh phn th hai nh l tip u ng ca thnh phn c s, thm ch o
vo sau tn d vng th hai
Mt vi ngoi l:

K hiu v cch gi tn:
Cc cnh ca vng trong thnh phn c s c k hiu bng cc ch ci a, b, c, d,
etheo chiu nh s. Cc nguyn t to vng ca thnh phn th hai c nh s bng
cc ch s 1, 2, 3Cnh chung ca c 2 vng c gi theo ch s ca thnh phn th 2
v ch ci ca thnh phn c s (tt c t trong du mc vung)
Cch nh s trn d vng ngng t
Bt u t nguyn t cnh nguyn t u cu (nguyn t chung cho c 2 vng) i theo
chiu sao cho cc d t c s nh nht. Nu khng tha mn iu kin ny th d t c
u tin nh s b nht

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60




d. Danh php th
Xem hp cht d vng l hp cht vng hydrocarbon m mt hay nhiu nguyn t
carbon c thay th bi cc d t.
- Tn d t nh l tip u ng v tn hydrocarbon vng tng ng

Danh php th t thng dng vi hp cht d vng.
5.1.3. Tnh cht ha hc ca d vng c tnh thm
a. Tnh thm ca d vng
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61

Vng c to thnh do s xen ph ca nguyn t carbon lai ha sp
2
v cc orbital
ca cc d t. H thng in t ca d vng thm l h lin hp v s in t trong vng
ph hp vi cng thc Huckel (4n+2) in t .
Cc d vng thm c h thng lin hp cho nn cc d vng c s phn b mt
in t trn cc nguyn t. C th minh ha cc cng thc trung gian ca mt s d vng
nh sau:
- D vng thm 5 cnh:

Nhn xt: ti cc v tr c in tch (-) d xy ra phn ng th i in t v tr 2 v 3.
Vng thm 5 cnh c h thng dien lin hp nn th hin tnh cht ca hydrocarbon cha
no. C cc phn ng cng hp, phn ng cng Diels-Alder, phn ng oxy ha.
- D vng thm 6 cnh:
Cc cng thc cu to v cng thc trung gian c th c ca d vng pyridin

Nhn xt: in tch m tp trung trn d t. Pyridin c tnh base
in tch dng xut hin carbon 2, 4, 6. Phn ng th i nhn xy ra cc v tr
ny. d vng thm 6 cnh, phn ng th i in t xy ra kh khn ti v tr 3, 5. D
vng thm 6 cnh c cu trc nh benzen nn nhn d vng kh b oxy ha. Cng nh
cc ng ng ca benzen, d vng ch b oxy ha mch nhnh.
b. Tnh cht ca d t
D t c in tch m hoc c cp in t khng lin kt nn d vng c tnh base. Cp
in t ca d t trn d vng thm 5 cnh tham gia h thng thm cho nn tnh base
ca d vng thm 5 cnh yu hn tnh base ca d vng thm 6 cnh. Tnh base ca
pyridin mnh hn pyrrol l do cp in t t do trn nit khng tham gia h thng thm.
Pyridin th hin tnh base nh mt amin bc 3.
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62


Tnh base ca d vng khng ph thuc vo s lng d t c trong vng. Yu t phn
b mt in t v yu t lp th nh hng mnh n tnh base

5.2. Hp cht d vng 5 cnh 1 d t v nhiu d t
5.2.1. Hp cht d vng 5 cnh 1 d t

a. Nhm Furan
- Tng hp nhn furan:
o Dehydrat ha hp cht 1,4-dicarbonyl

o Ngng t -halogenoceton vi ester ca -ceton acid

- Tnh cht ha hc: tnh thm yu, th hin tnh cht ca dien-1,3, tham gia
phn ng cng hp, trong mi trng acid c furan b polymer ha, trong mi
trng acid long phn ng m vng
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63



Tnh thm yu: tham gia phn ng th i in t trong iu kin rt nh nhng

- Dn xut quan trng ca Furan
+ Furfural: (furan-2-aldehyd) c th c trch ly t li ng hoc tru
Hp cht 5-nitrofurfural ngng t vi cc cht semicarbazid, thiosemicarbazid
to thnh cc cht semicarbazon v thiosemicarbazon c tc dng khng nm

Furfural c tnh cht ca aldehyde thm, tham gia phn ng Cannizaro to acid
v ru tng ng

+ Benzofuran (Coumaron)

+ Mt s dc cht c nhn furan


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b.Nhm Pyrrol
- Tng hp pyrrol


- Dn xut ca pyrrol
+ L thnh phn chnh to thnh khung cho clorophyl, pheophorbid


+ Benzopyrol (Indol)
Mt s acid amin cha khung indol

c.Nhm Thiophen
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65

- Tng hp

- Tnh cht ha hc: tng t c phn ng th i in t, phn ng cng hp,
- Dn xut ca thiophen
o Benzothiophen (Thionaphthen)
Thiophen, Furan, Pyrrol c th chuyn ha ln nhau:

5.2.2. Hp cht d vng 5 cnh nhiu d t
a.Nhm oxazol (O, N)
- Tng hp: c nhiu cch


- Tnh cht: oxazol th hin tnh thm yu, th hin tnh cht dien tham gia phn
ng cng hp

- ng dng tng hp dn xut ca pyridine nh vitamin B6
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b.Nhm thiazol (S, N)
- Tng hp


- ng dng
Nhn thiazol c trong hp cht t nhin nh penicillin, vitamin B, beta-lactam
c.Nhm imidazole (1,3)

- Tng hp

- Mt s dc phm c vng imidazole nh 2-nitroimidazol, metronitrazol,
bifonazol, clotrimazol
-
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d.Nhm pyrazol (1,2)
- Tng hp

5.3. Hp cht d vng 6 cnh mt d t v hai d t
5.3.1. Hp cht d vng 6 cnh mt d t
a.Pyridin
- Tng hp:
Pyridin c trong nha than . Khi chng ct than thu c hn hp pyridine,
metylpyridin (picolin), dimetylpyridin (lutidin), trimetylpyridin (colidin).

- Tnh cht
Cht lng khng mu, mi hi c trng
Tnh cht ha hc tng t nitrobenzen
+ Phn ng th i in t: km hn benzene, u tin th vo v tr 3,5
+ Phn ng th i nhn: u tin vo cc v tr 2,4,6
+ Phn ng oxy ha

+ Phn ng kh

+ Tnh baz
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- Mt s hp cht cha d vng pyridine
o Picolin: metylpyridin
D b oxy ha thnh acid pyridine carboxylic
Cc amid, hay hydrazid ca acid ny c ng dng nhiu trong dc
phm nh:

o Quinolin: benzopyridin
o Isoquinolin
o Acridin: dibenzopyridin
Cc hp cht 3,6-nitroacridin hay 9-nitroacridin c tc dng khng
khun

b. Pyran

Pyran khng tn ti dng t do. Khung pyran ch tn ti trong hp cht, thng gp
nh pyron hay cromon
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Mui pyrilium thng gp dng benzopyrilium c trong cu to ca cht mu thc vt
cyanin

Khung coumarin c trong cu to ca hp cht varfarin c tc dng chng ng mu

Trong cc hp cht flavonoid c cha vng -cromon

5.3.2. Hp cht d vng 6 cnh 2 d t
5.3.2.1. Hai d t l N
a. Pyridazin

- Tng hp:
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70

Ngng t hydrazine vi hp cht 1,4-dicarbonyl

- Tnh cht: Pyridazin l cht lng. C tnh bazo yu. Phn ng th i in t v phn
ng th i nhn xy ra yu. Vng b ph v khi tc dng vi cht oxy ha mnh
- Hp cht cha vng pyridazin
o Phtalazin: benzo[d]pyridazin

b. Pyrimidin

- Tng hp:
Ngng t ur hoc thiour vi hp cht 1,3-dicarbonyl

T acid barbituric

- Tnh cht:
Pyrimidin nng chy 22,5
o
C, si 124
o
C.
Tnh baz yu hn pyridazin v pyridine.
Phn ng th i in t xy ra kh khn, u tin v tr 5
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71

Phn ng th i nhn xy ra d hn v tr 2,4 (ch yu l 4)
- Cc dn xut ca pyrimidin

Nhiu dng thuc c cha vng pyrimidin
Vitamin B1 (thiamin)

Acid barbituric

Khung acid barbituric l dn xut ca mt s dc phm nh: Veronal v Luminal l
cc thuc gy ng

Quinazolin, quinazolon:

Mt s cht hu c thuc dy quinazolon-4 c tc dng gy ng nh metaqualon
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72


c.Pyrazin

- Tng hp
T ngng t -aminoceton

Ngng t gia hp cht 1,2-diamino vi 1,2-dicarbonyl

- Tnh cht
Tnh baz yu hn pyrimidin v pyridine
Phn ng th i in t xy ra rt chm. Phn ng th i nhn xy ra nhanh hn
Phn ng cng hp vi hydro to piperazin (l thuc tr giun)

5.3.2.2. Hai d t l N v S
Dn cht quan trng l phenothiazine hay dibenzo-p-thiazin
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73


Phenothiazin l khung ca mt lot phm nhum, trong c xanh metylen

Dy hp cht phenothiazine c nhn amino alkyl ha v tr 10 v nhm th v tr 2
thng c tc dng gim p trn h thn kinh trung ng, dng lm thuc an thn, khng
histamine, chng nn


5.3.2.3. Hai d t l N v O
Dn cht quan trng l phenoxazin

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74

ng dng: Xanthommatin (cht mu trong nm, a y, bm bm), actinomycin c
nhiu trong chng Streptomyces: tc nhn ngng bo trong tr liu ung th
5.2.3.4. Hai d t l O


5.4. HP CHT D VNG 7 CNH V D VNG NGNG T
5.4.1. D vng 1 d t

5.4.2 D vng 2 d t
Dn xut ca h thng 1,4-diazepin l quan trng v c nhiu cht thuc loi ny l
thuc cha bnh.

Nhm benzodiazepine l thnh phn trong cc loi thuc ng
Tng hp:

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5.4.3. D vng ngng t
Purin: Imidazo[4,5-d]pyrimidin

Purin l khung c bn trong nhiu hp cht thin nhin c trong ng vt v thc vt
nh acid uric, xanthin, hypoxanthin v adenine


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76

TI LIU THAM KHO
L Ngc Thch, Ha hu c, NXB H Quc gia Tp.HCM, 2001
Nguyn Ngc Sng, C s l thuyt Ha hu c, NXB H Quc gia Tp.HCM, 1997
Trng Th K (ch bin), Ha hu c (Hp cht hu c n chc v a chc) tp 1 v
tp 2, (Sch dng o to dc s i hc), NXB Y hc HN, 2006
Nguyn Minh Tho, Ha hc cc hp cht d vng, NXB Gio dc HN, 2004

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