c6 derivati cu azot ai acizilor carboxilici
DESCRIPTION
CO3TRANSCRIPT
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Derivati cu azot ai acizilor carboxilici
Amide, imide si nitrili
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1. Amide si imide
CR
O
NH2
CR
O
NH R'
CR
O
NR'2
amide primare amide secundare amide tertiare
Amide ciclice = imide
Nomenclatura amidelor: numele acidului in care se inlocuieste sufixul ic sau oic cu amida de exemplu:
- acid acetic => acetamida - acid benzoic => benzamida
Nomenclatura imidelor: numele acidului in care se inlocuieste sufixul ic sau oic cu imida de exemplu:
- acid ftalic => ftalimida - acid succinic => succinimida
CCH3
O
NH2
C
O
NH2
NH
O
O
NH
O
O
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Caracterul acido-bazic al amidelor si imidelor
a) Amide: grupa NH2 este implicata intr-o conjugare interna => amidele sunt baze slabe.
b) Imide: grupa NH este implicata intr-o dubla conjugare interna => imidele au caracter acid.
R C NH2
O
+ H R C NH2
O
H
R C NH2
O
H
R C NH2
O
H
.
.
.
.+
+ +
+. ...
+
CH2
CH2
C
C
O
O
NHCH2
CH2
C
C
O
O
NH
CH2
CH2
C
C
O
O
NH
Atomul de hidrogen este acidifiat
CH2
CH2
C
C
O
O
N H + KOH
CH2
CH2
C
C
O
O
NCH2
CH2
C
C
O
O
N K
+ +
..
+..
.
_
._
_
_H2O
_
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Sinteze de amide
1. Acilarea amoniacului
RCOCl
(RCO)2O
RCOOR'
RCONH2
HCl
R'OH
NH3+
RCOO NH4
RCOOH H2O
creste
reactivitatea
cel mai putin reactiv (necesita T = 200oC)
2. Hidroliza partiala a nitrililor
R C N + H2OH2SO4
RCONH2
Sinteze de imide
+ NH3O
O
O
- H2O
NH
O
O
T
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Sinteza de amide ciclice – transpozitia Beckmann a oximelor - sinteza -caprolactamei
H+i
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Proprietati chimice ale amidelor
Reactia de hidroliza
Reactia de deshidratare
Degradarea Hofmann => amine
RCONH2 + H2O RCOOH + NH3toC
acizi sau baze
- H2O
P2O5R C NR C
O
NH2
toC
- H2O
CH3 C N + H2Oacid sau baza
CH3 C
O
NH2
acid sau bazaCH3 C
O
OH
+ H2O
P2O5
NH3,
RCONH2 + NaOBr RNH2 + CO2
NaOH + Br2
hipobromit de sodiu
CH3 C
O
NH2
+ NaOBr CH3 NH2
acetamida metilamina
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Poliamide
naturale => peptide si proteine
sintetice => fibre poliamidice
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Nylon 6 si Nylon 6,6
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Nylon 6,6
Nylon 6
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Utilizari ale nylon-ului
… de azi sau …
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… de ieri!
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Reciclarea nylon-ului
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Consumul mondial de nylon
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Kevlar - prima fibră polimerică organică adecvată utilizării în compozite avansate
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Utilizari ale kevlar-ului
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Nitrili R C N
Nomenclatura
numele acidului in care se inlocuieste sufixul ic sau oic cu nitril + intermediar “o”
in special pentru: - acid acetic => acetonitril - acid benzoic => benzonitril
numele alcanului cu acelasi nr. de atomi C+ nitril
cand CN este considerat ca si substituent => ciano
CH3 C N C N
Metode de sinteza
a) Derivati halogenati cu reactivitate normala sau marita si KCN
RX + KCN RCN + KX X: Cl, Br, I
CH3CH2CH2CH2C N pentan nitril
CN COOCH3 p- cianobenzoat de metil
CH3 CH
Br
C N
2-brompropan nitril
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CH3 CH2 Cl + KCN CH3 CH2 C N + KCl
BrCH2CH2CH2Br + 2 NaCN N C CH2CH2CH2 C N
pentandinitril
propan nitril
c) Compusi carbonilici si acid cianhidric
b) Saruri de diazoniu aromatice si CuCN (reactia Sandmeyer)
Pt. nitrili aromatici
R CH O + HCNCN
_
R CH OH
C N
H+
R CH OH
COOH
cianhidrina -hidroxiacid
H2O/
C6H5 CH O + HCNCN
_
C6H5 CH OH
C N
2-hidroxi-2-fenilacetonitril
(mandelonitril)
H+
H2O/C6H5 CH OH
COOH
acid 2-hidroxi-2-fenilacetic(acid mandelic)
Pt. α -hidroxiacizi
+ CuCN Ar C N N2Ar N N] Cl ++ _
- CuCl
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Reactii ale nitrililor
Reducerea – cu LiAlH4
Hidroliza
CH3 CH2 C N + H2O
acid sau baza
CH3 CH2 CO
NH2acid sau baza
+ H2OCH3 CH2 C
O
OH
+ 2 H2O
acid sau baza
N C (CH2)3 C NLiAlH4
CH2 (CH2)3 CH2H2N NH2
1,5-pentandiamina (cadaverina)
C
O
NH
CH3
C6H5
LiAlH4CH3 CH2 NH
C6H5acetanilida N-etilanilina
C6H5 CH2 CO
OHacid fenilacetic
LiAlH4 C6H5 CH2 CH2OH
2-feniletanol
C6H5 CO
OC2H5
LiAlH4C6H5 CH2OH + C2H5OH
benzoat de etil alcool benzilic
etanol
Acizii carboxilici si ceilalti derivati functionali pot fi de asemenea redusi cu LiAlH4
+ H2ON C CH2CH2CH2 C NH+
HOOC (CH2)3 COOH
acid glutaric- NH3
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Acrilonitril
Obtinere:
Procedeul Sohio – amonoxidarea propenei
CH2 CH C N
CH CH + HCNCuCl / NH4Cl
H2C CH
CN
CH3 CH O + HCN CH3 CH CN
OH
H3PO4 H2C CH
CNH2O-
H2C CH
C N
H2C CH CH3 + 2 NH3 + 3 O22 2 + 6 H2OBiPMo12O40
400-500oC
Alte procedee:
Proprietati
Lichid foarte inflamabil si toxic; potential cancerigen
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H2C CH
CN
CH2 CH
C6H5
n mH2C CH
CN
+ CH2 CH
C6H5
n mcopolim.
Copolimerizarea acrilonitrilului => materiale plastice; cauciucuri sintetice
Copolimer stiren - acrilonitril (SAN)
SAN SAN - utilizari similare cu ale polistirenului
Polimerizarea acrilonitrilului => poliacrilonitril (PNA)
H2C CH
CN
npolimerizare
H2C CH
CN
n
- fibre sintetice (Orlon, Melana) - precursor pentru fibre de C de calitate inalta
PNA
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Copolimer butadiena – acrilonitril (Buna –N)
n mCH2 CH CH CH2 CH2 CH
CNManusi chirurgicale sau de protectie
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Imbunatatire a cauciucului acrilonitril-butadiena (“Nitrile Butadiene Rubber (NBR)”) - cauciucul acrilonitril-butadiena carboxilat (“Carboxylated Nitrile Butadiene Rubber (XNBR)”)
Cu sau fara punti de sulf
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Copolimer butadiena – acrilonitril – stiren
n mCH2 CH CH CH2 CH2 CH
CN
CH2 CH
C6H5
p
(ABS)