HALOGENOACIZI

R CH
X
COOH
X = F, Cl, Br, I
Preparare
1. Halogenarea direct
CH
3
COOH
+ Cl
2
ClCH
2
COOH
-HCl
Cl
2
CH COOH Cl
3
C COOH
Acid cloroacetic
Acid dicloroacetic
Acid tricloroacetic
+ Cl
2
-HCl
+ Cl
2
-HCl
Temp. sau h - mecanism homolitic
Omologi - amestecuri
2. Reacia Hell-Volhard-Zelinski
R CH
2
COOH
P
rosu
+ Br
2
R CH
Br
COBr
H
2
O
R'OH
-HBr
-HBr
R CH
Br
COOH
R CH
Br
COOR'
Orientarea n poziia a a halogenrii este determinat de vecintatea grupei COBr
3. Halogenarea esterului malonic i a derivaillor si alchilai
Conditii: clorur de sulfuril (SO
2
Cl
2
), brom sau iod i acid iodic
Br
2
- HBr
R HC
COOR
COOR
R C
COOR
COOR
Br
+ H
2
O
R CH
Br
COOH
-CO
2
R C
COOH
COOH
Br
4. Oxidarea aldehidelor halogenate
Cl
3
C CH O
HNO
3
Cl
3
C COOH
5. Reacii de dublu schimb
Cl
3
C COOH 3 NaF
F
3
C COOH 3 NaCl +
+
6. Adiia de acizi halogenai la acizi carboxilici nesaturai
CH
3
CH CH COOH
+ HBr CH
3
CH
Br
CH
2
COOH
Acid 3-bromobutiric Acid crotonic
HOOC CH CH COOH
+ HBr HOOC CH
Br
CH
2
COOH
Acid fumaric (sau maleic) Acid bromosuccinic
7. Metode speciale
Cl
2
C CH Cl Cl
2
CH COCl
1/2 O
2
Cl
2
C CH Cl
O
izomerizare
Aciditatea halogeno-acizilor
aciditatea halogenoacizilor este mai mare dect a acizilor carboxilici corespunztori
- efectul inductiv, atrgtor de electroni al halogenului
-. Efectul cel mai puternic l produce atomul de fluor
Constante de aciditate ale acizilor acetici clorurai:
Acidul Formula chimic pKa

Acetic CH
3
-COOH 4.74
Cloroacetic ClCH
2
-COOH 2.85
Dicloroacetic Cl
2
CH-COOH 1.48
Tricloroacetic Cl
3
C-COOH 0.77
Constante de aciditate ale acizilor halogeno-acetici:
Acidul Formula chimic pKa
Iodoacetic I-CH
2
COOH 3.10
Bromoacetic Br-CH
2
COOH 2.90
Cloroacetic Cl-CH
2
COOH 2.85
Fluoroacetic F-CH
2
COOH 2.65
X
HC C
O
OH
HC C
O
O
-
X
+ H
2
O
+ H
3
O
+
Reacia de hidroliz
Cl-CH
2
COOH
HO CH
2
COOH
- HCl
CH
3
CH
Cl
COOH
+ H
2
O
CH
3
CH
OH
COOH
Acid glicolic
Acid lactic
+ H
2
O
Acid cloroacetic
Acid cloropropionic
- HCl
Stereochimie
C X
R
1
R
3
R
2
Nu +
C X
R
1
R
3
R
2
Nu C
R
1
R
3
R
2
Nu
Inversia configuraiei n substituia nucleofil la carbonul saturat.
Inversia Walden(1895)
SN2
SN
2

(-) HOOC CH
2
C COOH
Cl
H
KOH
PCl
5
(+) HOOC CH
2
C COOH
OH
H
(-) HOOC CH
2
C COOH
OH
H
(+) HOOC CH
2
C COOH
H
Cl
KOH
PCl
5
Ag
2
O
Ag
2
O
Acid malic (-)
Acid malic (+)
Hidroliza enantiomerilor acidului clorosuccinic
Inversia
configuratiei
Pastrarea
configuratiei
-Cl
OH
C
C
O O
Cl
H
2
C
COOH
H
C
C
O
O
H
2
C
COOH
H
C
C
O O
H
2
C
COOH
H
OH
-Lactona
A doua inversie Prima inversie
Hidroxiacizi
HO CH
2
COOH
Acid glicolic Acid lactic
HOOC CH
2
CH COOH
OH
Acid malic
CH
3
CH
OH
COOH
C
6
H
5
CH
OH
COOH
Acid mandelic
C
6
H
5
CH
CH
2
OH
COOH
Acid tropic
COOH
C OH H
C OH H
COOH
Acid mezo-tartric Acid citric
C HO COOH
CH
2
COOH
CH
2
COOH
Preparare
1. Hidroliza halogenoacizilor
Cl-CH
2
COOH
HO CH
2
COOH
- HCl
CH
3
CH
Cl
COOH
+ H
2
O
CH
3
CH
OH
COOH
Acid glicolic
Acid lactic
+ H
2
O
Acid cloroacetic
Acid cloropropionic
- HCl
2. Reducerea acizilor aldehidici i cetonici
CH
3
CH
OH
COOH CH
3
C COOH
O
2 [H]
Conditii normale de reducere amestec racemic
Catalizatori sau agenti de reducere optic activi- reducere enantioselectiva
3. Reacia de desaminare
CH
3
CH
OH
COOH
CH
3
CH
NH
2
COOH
HONO
N
2
H
2
O
-Alanina
+ +
4. Adiia acidului cianhidric a aldehide i cetone

C
6
H
5
CH O
HCN
C
6
H
5
CH CN
OH
H
2
O
H
C
6
H
5
CH
OH
COOH + NH
3
Nitril mandelic Acid mandelic Benzaldehida
CH
2
C O
CH
2
Cl
Cl
HCN 2 KCN
H
2
O
C HO CN
CH
2
Cl
CH
2
Cl
C HO CN
CH
2
CN
CH
2
CN
Acid citric
C HO COOH
CH
2
COOH
CH
2
COOH
CH
2
CH
2
O
HCN
HO CH
2
CH
2
CN
H
2
O
CH
2
COOH CH
2
HO
-Hidroxipropionitril
Acid -hidroxipropionic
5. Reacia Reformatsky- -hidroxiacizi
CH
2
COOR Br
Zn
BrZnCH
2
COOR
O
BrZnCH
2
COOR
O
CH
2
COOR
ZnBr
H
2
O
OH
CH
2
COOR
-Zn(OH)Br
+
6. Oxidarea acizilor carboxilici nesaturai
KMnO
4
2 HO
C
C
COOH
COOH
H OH
HO H
COOH
C HO H
C H OH
COOH
C
C
COOH
H
H
HOOC
Acid fumaric Acid (+)-tartric Acid (-)-tartric
KMnO
4
2 HO
C
C
COOH
COOH
H OH
H OH
COOH
C HO H
C HO H
COOH
C
C
COOH
COOH
H
H
Acid maleic Acid mezo-tartric
7. Metode biochimice
Fermentatie de zaharuri cu diverse tulpini de Lactobacillus
si Streptococcus lactis
Acid (S)-(-)- lactic
Fermentatie de zaharuri cu Aspergillus niger
Reactivitate
1. Eliminare de ap

- -hidroxiacizi
CH
3
CH OH
COOH
HOOC CH CH
3
OH
O
O
CH
3
H
3
C O
O
Acid lactic Lactida
- Formare de polimeri- acid polilactic- biodegradabil

- -hidroxiacizi
HO CH
2
CH
2
COOH CH
2
CH COOH
-H
2
O
Acid -hidroxipropionic Acid acrilic
HOOC CH CH COOH HOOC CH
OH
CH
2
COOH
CH
3
CH
OH
CH
2
COOH
-H
2
O
H
3
C CH CH COOH
-H
2
O
Acid malic Acid fumaric
Acid -hidroxibutiric Acid crotonic
-H
2
O
OH
CH
2
COOH
CH COOH CH
2
COOH
Acid ciclohexilidenacetic
Acid 1-ciclohexenilacetic
-H
2
O
Acid 1-ciclohexanol
acetic
- i -hidroxiacizi - formare de lactone
-lactonele sunt mai stabile dect -lactonele
Aroma de piersica
Aroma de cocos
acid citric
Acid citric
C HO COOH
CH
2
COOH
CH
2
COOH
H
2
SO
4
-HCOOH
C
CH
2
COOH
CH
2
COOH
O C
CH
3
CH
3
O
-2 CO
2
Acid acetondicarboxilic Acetona
Acid citric
C HO COOH
CH
2
COOH
CH
2
COOH
-CO
2
-H
2
O
-H
2
O
C COOH
CH
2
COOH
CH COOH
C CO
CH
2
CO
CH
2
O C CO
CH
3
CH CO
O
Acid aconitic
Anhidrida
itaconica
Anhidrida
citraconica
+ Distilare
uscata
In organismele aerobe ciclul acidului ciclic este o parte a caii metabolice de
conversie a carbohidratilor, proteinelor si grasimilor si genereaza CO
2
si apa
Acizi fenolici
OH
COOH
O
O
COOH COOH
OH
OH HO COOH
OH
Acid salicilic Acid piperonilic Acid galic Acid 3-hidroxi-2-naftoic
Preparare
1. Sinteza Kolbe-Schmidt.
OH
COOH
CO
2
HCl
O
-
Na
+
OH
COO
-
Na
+
+
125
o
C
6 at.
Mecanism
CO
2
O
OH
COO
O O
H
COO
CO
2
O
-
Na
+
OH
COO
-
Na
+
OH
COO
-
Na
+
220
o
C
120
o
C
Coloranti azoici
acid 3-hidroxi-2-naftoic
CO
2 2 NaOH topire
alcalina
NH
2
SO
3
H
NH
2
SO
3
Na
NH
2
OH
NH
2
OH
COOH
PAS
p;t
Medicament anti TBC
Ac
2
O
OH
COOH
O
COOH
COCH
3
Aspirina Acid salicilic
CH
3
OH
H
OH
COOCH
3
Salicilat de metil
NH
3
- CH
3
OH
OH
CONH
2
Salicilamida
Aplicatii
Medicamente
Conservanti
Parabenii
Activitatea antimicrobian depinde de lungimea
catenei ataate crescnd n
ordinea: metil < etil < propil < butil