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HALOGENOACIZI
R
CH
COOH
X = F, Cl, Br, I
# Preparare
1. Halogenarea direct
CH3 COOH
+ Cl2
-HCl
ClCH2 COOH
Acid cloroacetic
+ Cl2
-HCl
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
R HC
COOR
COOR
Br2
- HBr
R C
COOR
Br COOR
+ H2O
COOH
R C
-CO2
Br COOH
R CH COOH
Br
HNO3
Cloral
Cl3C COOH
Acid tricloroacetic
Acid crotonic
7. Metode speciale
Cl2C CH Cl
Tricloroetilena
1/2 O2
Cl2C CH Cl
O
Epoxid
(intermediar instabil)
izomerizare
Cl2CH COCl
Clorura acida a
acidului dicloroacetic
# Reactivitate
Aciditatea halogeno-acizilor
O
X
HC
H2O
HC
OH
H3O+
O-
pKa
4.74
2.85
1.48
0.77
pKa
3.10
2.90
2.85
2.65
Reacia de hidroliz
Cl-CH2COOH
Acid cloroacetic
+ H2O
- HCl
CH3 CH COOH
Cl
+ H2O
- HCl
HO CH2 COOH
Acid glicolic
SN2
CH3 CH COOH
OH
Acid cloropropionic
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
H
C COOH
Cl
H
C COOH
Ag2O
KOH
PCl5
PCl5
KOH
OH
C COOH
H
Cl
C COOH
Inversia
configuratiei
Pastrarea
configuratiei
O
C
H
H2C
Cl
COOH
-Cl
O
C
H HC
2
OH
COOH
-Lactona
Prima inversie
H
H2C
OH
COOH
A doua inversie
IV.1. Hidroxiacizi
HO CH2 COOH
CH3 CH COOH
OH
Acid glicolic
Acid malic
Acid lactic
CH2OH
COOH
H C OH
H C OH
CH2 COOH
HO C COOH
CH2 COOH
COOH
Acid mandelic
Acid tropic
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
- HCl
Acid cloropropionic
CH3 CH COOH
OH
Acid lactic
CH3 C COOH
2 [H]
CH3 CH COOH
OH
CH3 CH COOH
NH2
-Alanina
HONO
C6H5 CH O
C6H5 CH CN
OH
OH
Acid mandelic
CH2 Cl
CH2 Cl
HCN
Nitril mandelic
Benzaldehida
C O
H2O
HO C CN
CH2 Cl
CH2 CN
2 KCN
H2O
HO C CN
CH2 Cl
CH2 CN
CH2 COOH
HO C COOH
CH2 COOH
Acid citric
CH2 CH2
O
HCN
HO CH2 CH2 CN
-Hidroxipropionitril
H2O
+ BrZnCH2
Zn
BrZnCH2 COOR
O ZnBr
COOR
OH
H2O
CH2 COOR
-Zn(OH)Br
CH2 COOR
HOOC
COOH
COOH
H
C
KMnO 4
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
KMnO 4
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
COOH
H
H3C
OH
Acid citric
# Reactivitate
1. Eliminare de ap
-hidroxiacizi
CH3 CH OH
H3C
CH3
HOOC CH CH3
COOH
OH
Acid lactic
Lactida
-hidroxiacizi
-H2O
-H2O
Acid -hidroxibutiric
CH2 CH COOH
Acid acrilic
H3C CH CH COOH
Acid crotonic
-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
Aroma de piersica
Aroma de cocos
acidul citric
CH2 COOH
HO C COOH
CH2 COOH
Acid citric
H2SO4
-HCOOH
CH2 COOH
C O
CH3
C O
-2 CO2
CH2 COOH
CH3
Acid acetondicarboxilic
Acetona
Distilare uscata
CH2 COOH
HO C COOH
CH2 COOH
Acid citric
CH COOH
-H2O
C COOH
CH2 COOH
Acid aconitic
CH2
-CO2
-H2O
CH CO
CO
CH2 CO
Anhidrida
itaconica
O + C
CO
CH3
Anhidrida
citraconica
COOH
OH
O
O
COOH
COOH
OH
HO
OH
Acid salicilic
COOH
COOH
Acid piperonilic
Acid galic
Acid 3-hidroxi-2-naftoic
OH
acid para-hidroxibenzoic
# Preparare
1. Sinteza Kolbe-Schmidt
O-Na+
+ CO2
OH
125oC
6 at.
OH
COO-Na+
COOH
HCl
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
SO3Na
p;t
OH
COOH
OH
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