HALOGENOACIZI

R CH COOH X = F, Cl, Br, I

Preparare
1. Halogenarea direct

+ Cl2 + Cl2 + Cl2

CH3 COOH ClCH2 COOH -HCl
Cl2CH COOH Cl3C COOH
-HCl -HCl
Acid cloroacetic Acid dicloroacetic Acid tricloroacetic

Temp. sau h - mecanism homolitic

Omologi - amestecuri
2. Reacia Hell-Volhard-Zelinski

H2O
R CH COOH
+ Br2 -HBr
R CH2 COOH R CH COBr Br
Prosu
R'OH
Br -HBr R CH COOR'
Br
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 (SO2Cl2), brom sau iod i acid iodic

COOR Br2 COOR COOH

+ H2O -CO2
R HC R C R C R CH COOH
- HBr
COOR Br COOR Br COOH Br
4. Oxidarea aldehidelor halogenate
HNO3
Cl3C CH O Cl3C COOH

5. Reacii de dublu schimb

Cl3C COOH + 3 NaF F3C COOH + 3 NaCl

6. Adiia de acizi halogenai la acizi carboxilici nesaturai

CH3 CH CH COOH + HBr CH3 CH CH2 COOH

Acid crotonic Br Acid 3-bromobutiric
HOOC CH CH COOH + HBr HOOC CH CH2 COOH
Acid fumaric (sau maleic) Br Acid bromosuccinic

7. Metode speciale
1/2 O2 izomerizare
Cl2C CH Cl Cl2C CH Cl Cl2CH COCl
O
 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
O O
X HC C + H2O X HC C + H3O+
OH O-

Constante de aciditate ale acizilor acetici clorurai:

Acidul Formula chimic pKa
Acetic CH3-COOH 4.74
Cloroacetic ClCH2-COOH 2.85
Dicloroacetic Cl2CH-COOH 1.48
Tricloroacetic Cl3C-COOH 0.77

Constante de aciditate ale acizilor halogeno-acetici:

Acidul Formula chimic pKa
Iodoacetic I-CH2COOH 3.10
Bromoacetic Br-CH2COOH 2.90
Cloroacetic Cl-CH2COOH 2.85
Fluoroacetic F-CH2COOH 2.65
 Reacia de hidroliz

+ H2O
Cl-CH2COOH HO CH2 COOH
- HCl
Acid cloroacetic Acid glicolic
+ H2O
CH3 CH COOH CH3 CH COOH
- HCl SN2
Cl OH
Acid cloropropionic Acid lactic

Stereochimie

Inversia configuraiei n substituia nucleofil la carbonul saturat.

Inversia Walden(1895)
SN2
R1 R1
R1

Nu + C X Nu C X Nu C
R2 R2
R3 R2
R3 R3
 Hidroliza enantiomerilor acidului clorosuccinic
H OH
KOH Inversia
(-) HOOC CH2 C COOH (+) HOOC CH2 C COOH
PCl5 Acid malic (+)
configuratiei
Ag2O
Cl H
H PCl5
Ag2O Cl

(-) HOOC CH2 C COOH (+) HOOC CH2 C COOH

KOH
Acid malic (-) OH H
Pastrarea
configuratiei

O O O O O
C C C
O
C C C
H -Cl OH H
Cl H HC OH
H2C 2 H2C
COOH COOH COOH
-Lactona

Prima inversie A doua inversie

 Hidroxiacizi

HO CH2 COOH CH3 CH COOH HOOC CH2 CH COOH

OH OH
Acid glicolic Acid lactic Acid malic

C6H5 CH COOH C6H5 CH COOH COOH CH2 COOH

OH CH2OH H C OH HO C COOH
H C OH CH2 COOH
COOH
Acid mandelic Acid tropic Acid mezo-tartric Acid citric
 Preparare
1. Hidroliza halogenoacizilor
+ H2O
Cl-CH2COOH HO CH2 COOH
- HCl
Acid cloroacetic Acid glicolic
+ H2O
CH3 CH COOH CH3 CH COOH
- HCl
Cl OH
Acid cloropropionic Acid lactic
2. Reducerea acizilor aldehidici i cetonici
2 [H]
CH3 C COOH CH3 CH COOH
O OH
Conditii normale de reducere amestec racemic
Catalizatori sau agenti de reducere optic activi- reducere enantioselectiva

3. Reacia de desaminare
HONO
CH3 CH COOH CH3 CH COOH + N2 + H2O
NH2 OH
-Alanina
 4. Adiia acidului cianhidric a aldehide i cetone

CH2 Cl CH2 Cl CH2 CN CH2 COOH

HCN 2 KCN H2O
C O HO C CN HO C CN HO C COOH
CH2 Cl CH2 Cl CH2 CN CH2 COOH
Acid citric

HCN H2O
CH2 CH2 HO CH2 CH2 CN HO CH2 CH2 COOH
O -Hidroxipropionitril Acid -hidroxipropionic
5. Reacia Reformatsky- -hidroxiacizi
Zn
Br CH2 COOR BrZnCH2 COOR
O
O ZnBr H2O OH
+ BrZnCH2 COOR
-Zn(OH)Br
CH2 COOR CH2 COOR

6. Oxidarea acizilor carboxilici nesaturai

COOH COOH COOH

H
C KMnO4 H C OH HO C H
C 2 HO HO C H H C OH
HOOC H COOH COOH
Acid fumaric Acid (+)-tartric Acid (-)-tartric

COOH COOH COOH

H
C KMnO4 H C OH HO C H
C 2 HO H C OH HO C H
H COOH COOH COOH
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
H3C O O
CH3 CH OH HOOC CH CH3
COOH OH O O CH3
Acid lactic Lactida

- Formare de polimeri- acid polilactic- biodegradabil

 - -hidroxiacizi

HO CH2 CH2 COOH CH2 CH COOH

-H2O
Acid -hidroxipropionic Acid acrilic
CH3 CH CH2 COOH H3C CH CH COOH
-H2O
OH
Acid -hidroxibutiric Acid crotonic
HOOC CH CH2 COOH HOOC CH CH COOH
-H2O
OH
Acid malic Acid fumaric

OH
-H2O CH2 COOH
-H2O
Acid 1-ciclohexanol
acetic
CH2 COOH CH COOH

Acid 1-ciclohexenilacetic Acid ciclohexilidenacetic

 - i -hidroxiacizi - formare de lactone

-lactonele sunt mai stabile dect -lactonele

Aroma de piersica Aroma de cocos

acid citric

CH2 COOH CH2 COOH CH3

H2SO4
HO C COOH -HCOOH
C O -2 CO2 C O
CH2 COOH CH2 COOH CH3
Acid citric Acid acetondicarboxilic Acetona

CH2 COOH CH COOH CH2 CH CO

-CO2
C CO O
HO C COOH -H2O C COOH O + C CO Distilare
-H2O
CH2 COOH CH2 COOH CH2 CO uscata
CH3
Acid citric Acid aconitic Anhidrida Anhidrida
itaconica citraconica
In organismele aerobe ciclul acidului ciclic este o parte a caii metabolice de
conversie a carbohidratilor, proteinelor si grasimilor si genereaza CO2 si apa
 Stereochimia acizilor tartrici

Louis Pasteur - prima separare in enantiomeri a sarurilor de

amoniu si sodiu a acizilor tartrici

1951, J. M. Bijvoet, A. F. Peerdeman, si A. J. van Bommel, au stabilit prin difractie de raze X

ca sarea de sodiu si rubidiu a acidului (+) tartric - configuratie R, R
 Acizi fenolici
OH O OH
COOH O HO OH COOH

OH
COOH COOH
Acid salicilic Acid piperonilic Acid galic Acid 3-hidroxi-2-naftoic

Preparare
1. Sinteza Kolbe-Schmidt.
 COO-Na+
O-Na+ OH o
OH
CO2 220 C
Coloranti azoici
o
120 C
COO-Na+
acid 3-hidroxi-2-naftoic

NH2 NH2 NH2 NH2

2 NaOH topire CO2

alcalina Medicament anti TBC
p;t
SO3H SO3Na OH OH
COOH
PAS

Mecanism

O O O OH
H COO
CO2
COO
 Aplicatii

Medicamente

OH OH OH O COCH3
CONH2 COOCH3 COOH COOH
NH3 CH3OH Ac2O
- CH3OH
H
Salicilamida Salicilat de metil Acid salicilic Aspirina

Conservanti

Parabenii
Activitatea antimicrobian depinde de lungimea
catenei ataate crescnd n
ordinea: metil < etil < propil < butil