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

X
Preparare

1. Halogenarea direct
+ Cl2 + Cl2 + Cl2
CH3 COOH ClCH2 COOH -HCl
Cl2CH COOH Cl3C COOH
-HCl -HCl
Acid cloroacetic Acid dicloroacetic Acid tricloroacetic
Conditii: Temp. sau h - mecanism homolitic

Pt. 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 halogenrii n poziia este determinat de vecintatea grupei COBr

3. Adiia de acizi halogenai la acizi carboxilici nesaturai

HOOC CH CH COOH + HBr HOOC CH CH2 COOH

Acid fumaric (sau maleic) Br Acid bromosuccinic

CH3 CH CH COOH + HBr CH3 CH CH2 COOH

Acid crotonic Br Acid 3-bromobutiric
 Reactivitate 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
SN2
CH3 CH COOH CH3 CH COOH
- HCl
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
HO CH2 COOH CH3 CH COOH HOOC CH2 CH COOH
OH OH
Acid glicolic Acid lactic Acid malic

COOH COOH COOH

C6H5 CH COOH H C OH HO C H H C OH
OH HO C H H C OH H C OH
Acid mandelic COOH COOH COOH

CH2 COOH Acid (+) tartric Acid (-) tartric Acid mezo-tartric

HO C COOH Acid (+) si (-) tartric, cristale, optic

activi cel (+) este natural
CH2 COOH racemicul acestor forme este mai
rar ntlnit n natura
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 de(z)aminare a aminoacizilor

HONO
CH3 CH COOH CH3 CH COOH + N2 + H2O
NH2 OH
-Alanina
4. Adiia acidului cianhidric la aldehide i cetone; r.cu epoxizi

HCN H2O
C6H5 CH O C6H5 CH CN C6H5 CH COOH + NH3
H
OH OH
Benzaldehida Nitril mandelic Acid mandelic

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. 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
6. Metode biochimice

Fermentatie de zaharuri cu diverse tulpini de Lactobacillus

si Streptococcus lactis

Acid (S)-(-)- lactic

Fermentatie de zaharuri cu Aspergillus niger

Acid citric
 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 (prin distilare sau incalzire cu H2SO4 dil.)

HO CH2 CH2 COOH CH2 CH COOH

-H2O
Acid -hidroxipropionic Acid acrilic

CH3 CH CH2 COOH H3C CH CH COOH

-H2O
OH Acid crotonic
Acid -hidroxibutiric

HOOC CH CH2 COOH HOOC CH CH COOH

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

Acid 1-ciclohexenilacetic Acid ciclohexilidenacetic

 - i -hidroxiacizi - formare de lactone (f.usor, din sol.apoase acidulate)

-lactonele sunt mai stabile dect -lactonele

Aroma de piersica Aroma de cocos

 acidul 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

Distilare uscata

CH2 COOH CH COOH CH2 CH CO

-CO2 O
HO C COOH C COOH C CO
-H2O -H2O O + C CO
CH2 COOH CH2 COOH CH2 CO CH3
Acid citric Acid aconitic Anhidrida Anhidrida
itaconica citraconica
 In organismele aerobe ciclul acidului citric (ciclul Krebs) este o parte a
cii metabolice de conversie a carbohidratilor, proteinelor si grasimilor
la CO2 si apa
 OH
OH
COOH

COOH
Acid orto-hidroxibenzoic
(Acid salicilic) Acid para-hidroxibenzoic

OH O
HO OH COOH O

OH
COOH COOH
Acid galic Acid 3-hidroxi-2-naftoic Acid piperonilic
1. Sinteza Kolbe-Schmidt
Preparare
K

OH

Mecanism

O O
O-Na+

O-K+
+ CO2

O
+ CO2

C
125oC
6 at.

O
OH

o
220 C
6 at.

O
COO-Na+

OH

COO- K

H
COO
HCl
OH

OH

COOH

OH O
HCOOH

Acid 2-hidroxibenzoic
(acid salicilic)

COO -
 COO-Na+
O-Na+ OH o
OH
CO2 220 C
o
120 C
COO-Na+
acid 3-hidroxi-2-naftoic
(intermediar pt. colorantii azoici)

NH2 NH2 NH2 NH2

NaOH topire CO2

alcalina p;t
SO3H SO3Na OH OH
COOH

PAS
p-Aminosalicilat de
sodiu - medicament
anti TBC
 Aplicaii
Medicamente
OH OH OH O COCH3
CONH2 COOCH3 COOH COOH
NH3 CH3OH Ac2O
- CH3OH
H
Salicilamida Salicilat de metil Acid salicilic Acid acetilsalicilic
(Aspirina)
Propriet. analgezice Subst. de aroma Analgezic, antipiretic
si antipiretice antinflamator (Bengay) Anti-inflamator nesteroidian
antiseptic (Listerine)

Conservanti

O Parabenii (p-hidroxibenzoatii de alchil)

C
OR
CH3 Activitatea antimicrobian depinde de
lungimea catenei ataate, crescnd n ordinea:
R= C 2H 5 metil < etil < propil < butil
C3 H 7
C4H9
OH