HALOGENOACIZI

CH

COOH

X = F, Cl, Br, I

Preparare
1. Halogenarea direct

CH3 COOH

+ Cl2
-HCl

ClCH2 COOH
Acid cloroacetic

+ Cl2
-HCl

Temp. sau h - mecanism homolitic

Omologi - amestecuri

Cl2CH COOH
Acid dicloroacetic

+ Cl2
-HCl

Cl3C COOH
Acid tricloroacetic

2. Reacia Hell-Volhard-Zelinski
H2O

R CH2 COOH

+ Br2
Prosu

R CH COBr
Br

-HBr
R'OH
-HBr

R CH COOH
Br
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

R HC

COOR
COOR

Br2
- HBr

R C

COOR

Br COOR

+ H2O

COOH
R C

-CO2

Br COOH

R CH COOH
Br

4. Oxidarea aldehidelor halogenate

Cl3C CH O

HNO3

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

HOOC CH CH COOH + HBr

Br Acid 3-bromobutiric
HOOC CH CH2 COOH

Br Acid bromosuccinic

Acid fumaric (sau maleic)

7. Metode speciale

Cl2C CH Cl

1/2 O2

Cl2C CH Cl
O

izomerizare

Cl2CH COCl

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

H2O

HC

OH

H3O+

O-

Constante de aciditate ale acizilor acetici clorurai:

Acidul
Formula chimic
Acetic
CH3-COOH
Cloroacetic
ClCH2-COOH
Dicloroacetic
Cl2CH-COOH
Tricloroacetic
Cl3C-COOH

pKa
4.74
2.85
1.48
0.77

Constante de aciditate ale acizilor halogeno-acetici:

Acidul
Formula chimic
Iodoacetic
I-CH2COOH
Bromoacetic
Br-CH2COOH
Cloroacetic
Cl-CH2COOH
Fluoroacetic
F-CH2COOH

pKa
3.10
2.90
2.85
2.65

Reacia de hidroliz
Cl-CH2COOH
Acid cloroacetic

+ H2O
- HCl

CH3 CH COOH
Cl

+ H2O
- HCl

Acid cloropropionic

HO CH2 COOH
Acid glicolic

CH3 CH COOH

SN2

OH
Acid lactic

Stereochimie
Inversia configuraiei n substituia nucleofil la carbonul saturat.
Inversia Walden(1895)
SN2
R1

R1
Nu

R2
R3

Nu

C
R2

R1
X

Nu

C
R2

R3

R3

Hidroliza enantiomerilor acidului clorosuccinic

H
C COOH

(-) HOOC CH2

Cl
H
C COOH

Ag2O

(-) HOOC CH2

Acid malic (-) OH

KOH
PCl5
PCl5
KOH

OH
Inversia
(+) HOOC CH2 C COOH
configuratiei
Acid malic (+)
H
Ag2O Cl
(+) HOOC CH2 C COOH
H

Pastrarea
configuratiei

O
C

H
H2C

Cl

COOH

-Cl

O
C

H HC
2

OH

COOH

-Lactona

Prima inversie

C
H
OH
H2C
COOH
A doua inversie

Hidroxiacizi
HO CH2 COOH

CH3 CH COOH

HOOC CH2 CH COOH

OH

OH
Acid glicolic

C6H5 CH COOH C6H5 CH COOH

OH

Acid mandelic

Acid malic

Acid lactic

CH2OH

Acid tropic

COOH

CH2 COOH

H C OH HO C COOH
H C OH
CH2 COOH
COOH
Acid mezo-tartric

Acid citric

Preparare
1. Hidroliza halogenoacizilor

Cl-CH2COOH
Acid cloroacetic

+ H2O
- HCl

CH3 CH COOH
Cl

HO CH2 COOH
Acid glicolic

+ H2O

CH3 CH COOH

- HCl

OH

Acid cloropropionic

Acid lactic

2. Reducerea acizilor aldehidici i cetonici

CH3 C COOH

2 [H]

CH3 CH COOH
OH

Conditii normale de reducere amestec racemic

Catalizatori sau agenti de reducere optic activi- reducere enantioselectiva

3. Reacia de desaminare

CH3 CH COOH
NH2
-Alanina

HONO

CH3 CH COOH + N2 + H2O

OH

4. Adiia acidului cianhidric a aldehide i cetone

CH2 Cl

CH2 Cl
HCN

C O

HO C CN

CH2 Cl

CH2 CN
2 KCN

HO C CN

CH2 Cl

CH2 CN

H2O

CH2 COOH
HO C COOH
CH2 COOH
Acid citric

CH2 CH2
O

HCN

HO CH2 CH2 CN
-Hidroxipropionitril

H2O

HO CH2 CH2 COOH

Acid -hidroxipropionic

5. Reacia Reformatsky- -hidroxiacizi

Br CH2 COOR

+ BrZnCH2

Zn

BrZnCH2 COOR
O ZnBr

COOR

OH

H2O

CH2 COOR

-Zn(OH)Br

CH2 COOR

6. Oxidarea acizilor carboxilici nesaturai

HOOC

COOH

COOH

H
C

KMnO4

2 HO

HO C H
COOH

Acid fumaric

Acid (+)-tartric

COOH

COOH

H C OH

COOH
HO C H
H C OH
COOH
Acid (-)-tartric

COOH

KMnO4

H C OH

HO C H

2 HO

H C OH

HO C H

COOH

Acid maleic

COOH

COOH
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
CH3 CH OH

H3C

CH3

HOOC CH CH3

COOH

OH
Acid lactic

Lactida

- Formare de polimeri- acid polilactic- biodegradabil

- -hidroxiacizi

HO CH2 CH2 COOH

Acid -hidroxipropionic

CH3 CH CH2 COOH

OH

-H2O
-H2O

Acid -hidroxibutiric

CH2 CH COOH
Acid acrilic

H3C CH CH COOH
Acid crotonic

HOOC CH CH2 COOH

OH

-H2O

HOOC CH CH COOH

Acid malic

Acid fumaric

OH
-H2O

CH2 COOH
Acid 1-ciclohexenilacetic

CH2 COOH
Acid 1-ciclohexanol
acetic

-H2O

CH COOH
Acid ciclohexilidenacetic

 - i -hidroxiacizi - formare de lactone

-lactonele sunt mai stabile dect -lactonele

Aroma de piersica

Aroma de cocos

acid citric

CH2 COOH
HO C COOH

H2SO4
-HCOOH

CH2 COOH
C O

CH3

CH2 COOH

CH2 COOH

Acid citric

Acid acetondicarboxilic

CH2 COOH
HO C COOH
CH2 COOH
Acid citric

CH COOH
-H2O

C COOH
CH2 COOH
Acid aconitic

C O

-2 CO2

CH3
Acetona

CH2
-CO2
-H2O

CH CO
CO

CH2 CO
Anhidrida
itaconica

O + C

CO

CH3
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 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

OH

O
O

COOH

HO

OH

COOH
OH

Acid salicilic

COOH

COOH

Acid piperonilic

Acid galic

Preparare
1. Sinteza Kolbe-Schmidt.

Acid 3-hidroxi-2-naftoic

COO-Na+
OH

O-Na+

CO2

OH

220 C

Coloranti azoici

120 C

COO-Na+
acid 3-hidroxi-2-naftoic

NH2

NH2

CO2

topire
alcalina

2 NaOH

SO3H

NH2

NH2
p;t

SO3Na

OH

Medicament anti TBC

OH
COOH
PAS

Mecanism

O
CO2

H
COO

OH
COO

Aplicatii
Medicamente
OH

OH

OH

CONH2

COOCH3

NH3

CH3OH

- CH3OH

Salicilamida

Salicilat de metil

COOH

O COCH3
COOH

Ac2O

Acid salicilic

Aspirina

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

Acidul galic si taninurile

Acid galic

Acid hexahidrodifenic HHDP

pentagaloil D-Glucoza

Acid elagic