derivatives of carboxylic acids - kfupmfaculty.kfupm.edu.sa/chem/ajhamdan/chem202/chapter 15.pdf ·...
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Chapter 15
Derivatives Of Carboxylic Acids
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• Derivative Of Carboxylic Acid is a compound that yields a carboxylic acid upon reaction with water
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The typical reaction of an aldehyde or ketone is addition, or an addition followed by loss of water.
COMPARISON OF CARBONYL COMPOUNDSCOMPARISON OF CARBONYL COMPOUNDS
CO
CO
H
NuR
CNuRCNu
R
enamine
imine
NuR
NuR
acetal:Nu-R
-H2O
hemiacetal
Acid derivatives (acyl compounds) undergo substitutionreactions.
R CX
O
R CNu-R
O
:Nu-R
+ :Xa leaving group
displacement
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1): :
R C YO
+ Nu:
slow:..
:R C Y
O
Nu
2)
:..
:R C Y
O
Nu
: :R C
O
Nu
+ Y:
NucleophilicNucleophilic AcylAcyl SubstitutionSubstitution
-
-
-
SIMPLIFIED VIEW
addition ofnucleophile
elimination ofleaving group
most aren’t this simple, protontransfers are usually required
carbonyl groupforms again
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REACTIVITY IS ALSO REFLECTED IN REACTIVITY IS ALSO REFLECTED IN THE STABILITY OF THE LEAVING GROUPTHE STABILITY OF THE LEAVING GROUP
(not considering acid catalysis)
MOSTREACTIVE
R C ClO
RCO
R C OO
R C OO
R'
R C NH2
O
RCO
O
O-R’
NH2
Cl
STRONGESTBASE
-
-
-
-
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carboxylic acid
acid halide or acid anhydride
ketone ester amide
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Spectroscopic Properties of Acid derivatives• IR Spectra
– The carbonyl stretching frequency varies according to the type of carboxylic acid derivative present
– O-H stretching vibrations of the carboxylic acid give a broad band at 2500-3100 cm-1
– N-H stretching vibrations of amides appear at 3140-3500 cm-1
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1H NMR Spectra•The α hydrogens of carboxylic acids and their derivatives appear at δ 2.0-2.5
•The carboxyl group proton appears downfield at δ10-12
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Nomenclature Of Acid Chloride
• Acid chlorides are named by dropping the -ic acid from the name of the carboxylic acid and adding -yl chloride
CO
ClCH3CH2CH2 CO
ClCH3 C
O
Cl
butanoyl chloride
butyryl chloride
ethanoyl chloride
acetyl chloride
benzoyl chloride
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PREPARATION OF PREPARATION OF ACID CHLORIDESACID CHLORIDES
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• Acid chlorides are made from carboxylic acids by reaction with thionyl chloride, or phosphorus trichloride.
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Examples
CH3CH2COH
O
SOCl2+ CH3CH2CCl
O
+ SO2 + HClPropanoyl chloride
Cl
O
+ H3PO2
CO2H PCl3
Benzoyl chloride
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REACTIONS OF REACTIONS OF ACID CHLORIDESACID CHLORIDES
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NucleophilicNucleophilic AcylAcyl SubstitutionSubstitutionSimplified Mechanism
RC
O
Cl
Nu
RC
O-
Cl
Nu
1) addition
RC
O
Nu2) elimination
+ Cl-
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1) Hydrolysis
• Reaction with water
RC
O
OH + HClRC
O
Cl + H2OMechanism
RC OH2
O-
Cl
+RC
O
OH2+
Cl-+- H+
RC
O
OH
RC
O
Cl + H2O
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2- Reaction With Alcohols
General reaction ESTER
RCCl
OR'OH RCOR'
O
HCl+ +
Usually HCl is removed using tertiary amine
CH3CCl
O(CH3)3COH+ + (CH3CH2)3N
CH3COC(CH3)3
O(CH3CH2)3NH Cl-+
+
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MORE EXAMPLES
+CH3CH2OH Cl
O
+ N
pyridine
OCH2CH3
O
NH Cl-++
Ethyl benzoate
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3- Reaction with ammonia and amines
primary
secondary
tertiary
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Examples
CH3CCl
ONH3 CH3CNH2
O+HCl
NH3NH4
+ Cl-
+CH3CCl
O
CH3NH22 CH3CNHCH3
OCH3NH3
+ Cl-+
CH3CCl
O+ 2(CH3)2NH CH3CN(CH3
O
)2 (CH3)2NH2+ Cl-+
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Schotten-Baumann Reaction
• NaOH is added to remove HCl if the acid chloride is not very reactive
CCl
O
+HN OH-
C
O
N
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4- CONVERSION TO ANHYDRIDE
Reaction with carboxylate ion
CH3CH2COCCH3
O OCH3CH2CCl
OCH3CO- Na+
O
+
ethanoic propanoicanhydride
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5- Conversion to Aryl Ketone
Friedel-Crafts acylation
CH3CH2C
OCH3CH2CCl
O
+AlCl3
1-phenyl-1-propanone
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6- Reaction with Grignard Reagents
Acid chloride react with two moles of a Grignardreagent to yield a tertiary alcohol
RC R
O a ketone
RC
O
Cl + R MgX RC
O-
Cl
R RMgX
RC
O-
R
R
MgXH+
H2ORC
OH
R
RTertiary Alcohol
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ExamplesOH
CH3
CH3Cl
O
1) 2 CH3MgBr
2) H+, H2O
CH3CH2C(C6H5)2
OH
CH3CH2CCl
O1) C6H5MgCl
2) H+, H2O
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LITHIUM DIALKYLCUPRATESLITHIUM DIALKYLCUPRATES
R2CuLi Made by treating analkyllithium compoundwith copper (I) iodide.
R X R Li
R Li Cu
R
R
Li
2 + CuI0°C
etherLi
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7- Reaction with Cuprates
An acid chloride can be coupled with a dialkylcuprate to yield a ketone
R C Cl
O
R'2CuLi R C R'
O
+
KETONEACID CHLORIDE
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Examples
CH3CH2CC6H5
OCH3CH2CCl
O(C6H5)2CuLi
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8a- Reduction with LiAlH4
1) Acid chloride + LiAlH4 primary alcohol
Cl
O
2) H+, H2O1) LiAlH4
CH2OH
CH3CH2CCl
O
2) H+, H2O1) LiAlH4 CH3CH2CH2OH
Primary alcohol
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8b- Reduction with LiAlH[OC(CH3)3]3
2) Acid chlorides react with lithium tri-tert-butoxyaluminum hydride to give aldehydes
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9- Alpha halogenation
• Acid chloride undergo tautomerism alpha halogenation.
CH3CCl
OCH2 CCl
OH
Keto form enol form
Cl2 CH2 CCl
OH
Cl Cl
- HCl
CH2 CCl
O
Cl
An α-halo acid chloride
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Examples
CH3CH2COH
OPBr3CH3CH2CBr
OBr2 CH3CHCBr
O
Br
(CH3)2CHCO2H Br2PBr3
+ (CH3)2CCBr
O
Br
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Hell-Volhard-Zelinesky Reaction
If PBr3 is used as a catalyst, halogenationproduce α-halo acid
R2CCO2H
X+ X2
PX3 catalystR2CHCO2H
(CH3)2CCOH
O
Br
(CH3)2CHCO2H Br2PBr3
+ catalyst
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EVERYTHING CAN BE MADE FROM THE ACID (CHLORIDE)
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NaOH
RMgX + CO2
SOCl2
NH3NR’2H
H2O
R’OH“ACID DERIVATIVES”
Na+
…. or the anhydride
R CH2 OH
R C OH
R C N
R C OHO
R C OO
R' R C OO
R C ClO
R C NH2
O
RCO
R C OO
R C NR'2
O
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Acid Chloride Reactions ( summary)
LAH = LiAlH4
R2CHC OH
OH2O
R2CHC X
O
R'OH
R2CHC OR'
O
R'2NH
R2CHC NR'2
O
R'CO2-
R2CHC O2CR'
O
ArHAlX3
R2CHC Ar
O
1) R'MgX2) H+, H2O
R2CHC R'
OH
R'
R'2CuLi
R2CHC R'
O
1) LAH2) H+,H2O
R2CHCH2OH
1) LiAlH[OC(CH3)3]3
2) H+, H2O
R2CHC H
O
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Anhydrides of Carboxylic Acids
RCOH
O
HOCR'
O
RCOCR'
O O- H2O
An anhydride
Anhydride means “without water”
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Nomenclature of anhydride
• Anhydrides are named after the parent carboxylic acid followed by the word anhydride
CH3COCCH3
O OCH3CH2COCCH2CH3
O O
ethanoic anhydride (IUPAC)
Acetic anhydride (trivial)
Propanoic anhydride (IUPAC)
Propionic anhydride (trivial)
CH3COCCH2CH3
O Oethanoic propanoic anhydride
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Preparation of Anhydride
1. From acid chloride
RC
O
Cl -OCR'
O
+ RC
O
OCR'
O
An acid chloride
A carboxylateion
An anhydride
C
O
Cl -OCCH3
O
+ C
O
OCCH3
O
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2-From carboxylic acids
RCOH
O
2 + CH3COCCH3
O ORCOCR
O O
CH3COH
O
2+
CH3COCCH3
O O+
CO2H
COC
O O
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Reactions of Anhydrides
RC
O
OCR
O
Nu
RC
O-
OCR
Nu
O2) elimination
RC
O
Nu
-OCR
O
+
1) addition
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1- Hydrolysis
• Anhydrides react with water Carboxylic acid
CH3COCCH3
OOH2O CH3COH
O
2
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2- Reaction with Alcohols and Phenols
• Anhydride with alcohol or phenol in the presence oh acid Ester
CH3COCCH3
OO CH3OH CH3COH
O
CH3COCH3
O+
An ester
CH3COCCH3
OOOH
OH
H2SO4+CH3CO OCCH3
O O
+ 2 CH3CO2H
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• Phenyl ester can prepared under basic conditions
OCCH3
O
+ CH3CO2-Na+
OH
NaOH
O- Na+
CH3COCCH3
OO
O
O
O
CH3CH2OH
O
O
OCH2CH3OH
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3- Reaction with Ammonia and amines
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Examples
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Esters of Esters of carboxylic carboxylic
acidsacids
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carboxylic acid
ester
acid anhydride acid halide
different ester
alcohol
amide
carboxylic acid
polyester
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Nomenclature of Esters
SALTS OF ACIDSSALTS OF ACIDS
sodium pentanoate
potassium benzoate
Change -ic acid to -oateESTERSESTERS
ethyl pentanoate
CH3CH C O CH3
CH3
O
methyl 2-methylpropanoatemethyl isobutyrate
CH3 CH2 CH2 CH2 C O CH2 CH3
OCH3CH2CH2CH2 C
O
O Na- +
O
O K- +
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ESTERS
C OO
CH CH3
CH3
isopropyl benzenecarboxylateisopropyl benzoate
CH2 C O C CH3
CH3
CH3
O
tert-butyl phenylethanoate
H
CO CH3
O
methyl cyclohexanecarboxylate
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Preparation of EstersPreparation of Esters
1) From Carboxylic acids and Alcohols
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2) Esters from Acid Chlorides and alcohols
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3) Esters from Carboxylic Acid Anhydrides and alcohols
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Example
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4) Esters from carboxylate ions and alkyl halide
RCO2- + R’-X RCO2R’ + X-
CH2OCCH3
O
CH3CO-
O CH2Cl+
Benzyl acetate
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Summary of Ester Preparation
RC
O
OR'
RC
O
OH
R'OH, H+
RC
O
Cl
R'OH
RC
O
OCR
OR'OH
RC
O
O-
R'X
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Reactions of Esters
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AcidAcid--Catalyzed Catalyzed NucleophilicNucleophilic AcylAcyl SubstitutionSubstitution
2)
+ Nu:
slow:..
R C OR'O
Nu
H
3): :
R CO
Nu+
1)
R C OR'O: :
R C OR'
O H:+
R C OR'
O H:+
:..
R C OR'
O
Nu
H
+ H3O+R'O-
SIMPLIFIED
OH
H: ..
H+
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NucleophilicNucleophilic Acyl Sunstitution In Alkaline Conditions
RC
O
OR
Nu
RC
O-
OR
NuRC
O
Nu1) addition
2) elimination
+ -OR
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11-- Hydrolysis of EstersHydrolysis of EstersBasic Solution
OCR O R
OCR O+ OH
_+ R O H
OCR O R
OCR OH+ + R O HH2O
H2SO4
Acidic Solution
excess
heat
heat
Na+ Na+
Hydrolysis in acid is reversible ,but in base it is irreversible.
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:....
..
..
OCR O R'
H
H O H
:....
OCR O R'OH
H
H
..
..
slow
..
..
OCR O R'OH H
H..
..
..
..
OCR O R'O
H
H
H..
..
..OCR O R'O H
H
H
..
..:
+
: ..OCR O R'O H
H
H
..
.. :
+:
..OCROH
H
.. :O R'H
:+
+
+
:
:
:
+
+
+ :OCR O H
......
Hydrolysis of an Ester in AcidHydrolysis of an Ester in Acid
protontransfers
H3O+
+ H3O+
H-OH2
+
OH2
H2SO4 / H2OMechanism
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Base-Promoted Hydrolysis of Esters: Saponification
Mechanism
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Examples
CH3CH2COH
O+ C6H5CH2OHCH3CH2COCH2C6H5
O+ H2O H+
excess
C6H5COCH2CH3
O
H2OOH-
H+
C6H5CO-
O+ CH3CH2OH
C6H5COH
O
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C6H5COC
O CH2CH3
HCH3 H2O
OH-
(R)
C6H5CO-
O+ C
CH2CH3
HCH3
HO
(R) 2-butanol
suggest: RC
O
O R'
If this bond cleaved racemization or inversion of configuration is produced
This bond is cleaved
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SAPONIFICATIONSAPONIFICATION
CCC
HOCRO C R
O C R
OO
O SOAPSOAP
CH2
CCH2
HOH
OHOHONaCR
O NaO C RO
NaO C RO
NaOH
“SOAP”
heat
(lye)fat = triglyceride
glycerol
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22-- TransesterificationTransesterificationOCR O R
OCR O RR OH
OH R
+
+
H+
mechanism is similar toEsterification
EXAMPLE
OC O CH3
OC O CH
CH3
CH3+ +H+
CH OHCH3
CH3
CH3 OH
excess
heat
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3- Reaction with Ammonia
• Esters + ammonia or amines amides
C6H5COCH2CH3
ONH3 C6H5CNH2
O
+ CH3CH2OH
CH3CH2CNHC6H5
O
+ CH3OH
CH3CH2COCH3
O H2N+
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4- Reduction
• Esters are reduced to primary alcohols
To a primary alcohol
To the other alcohol
RC
O
OR'red.
RCH2OH + HOR'
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1) Reduction using sodium metal in ethanol.
CH3(CH2)4COCH3
ONa
CH3CH2OH
CH3(CH2)4CH2OH + CH3OH
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2) Reduction using catalytic Hydrogenation
CH3OC(CH2)4COCH3
OOH2, CuCr2O4 catalyst
2oo atm, 250 Co
HOCH2(CH2)4CH2OH + CH3OH2
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3) Reduction using LiAlH4
C2H5OC(CH2)2COC2H5
OO1) LiAlH4
2) H+, H2O
HOCH2(CH2)2CH2OH + C2H5OH2
1) LiAlH4
2) H+, H2OOO
OH
OH
Cyclic ester
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5- Reaction with Grignard Reagents
• Esters react with two moles of a Grignardreagent to yield a tertiary alcohol
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Example
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HCOC2H5
O 1) CH3MgBr
2) H+, H2OHC
OH
CH3
CH3 Secondary alcoholA formateester
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Lactonesγ- or δ-Hydroxyacids undergo acid catalyzed reaction to give cyclic esters known as γ- or δ-lactones, respectively
CH2O
CH2CH2
CO
OHHH+
O O+
H2O
CH2OH
O
OH H+O
O +H2O
4-hydroxybutanoic acid lactone
( γ-bytrolactone)
5-hydroxypentanoic acid 5-hydroxypentanoic acid lactoneδ-lactone
4-hydroxybutanoic acid
γ-hydroxy acid
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Reactions of Lactones• Lactones are cyclic esters and they undergo
same reactions of esters
O
O
NH3
O
OH
NH2
O
O
1) CH3MgBr (escess)2) H+, H2O
HO CH3
CH3OH
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Polyesters By Transesterification
COCH2CH2OHHOCH2CHOC
OO+ CH3OH2
COCH2CH2OC
OO
x
H+dimethyltrephthalate 1,2-ethanediol
OH groups can react with more dimethyltrephthalate
COCH3CH3OC
OO+ HOCH2CH2OH2
Dacron
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Nomenclature of Amides• Amides with no substituents on nitrogen are
named by replacing -ic acid or –oic acid in the name with amide.
CH3CH2CH2CNH2
O
Butanamide
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• Groups on the nitrogen are named as substitutents and are given the prefix N- or N,N-
N-Ethylethanamide
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Preparation of amides
RCCl
O
R'2NH
RCOCR
O O
R'2NH RCOR'
O
R'2NH
RCNR'2
O
Amide
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Reactions of Amides• Amides are not basic.
CH3NH2 + HCl CH3NH3+Cl-
CH3CNH2
O+ HCl
Methyl amine Methylammoniumchloride ( salt)
No reaction
CH3 C
O
NH2 CH3C NH2
O-
+
Positive N not basic
Due to resonance
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Evidence for resonance participation
H C
O
N(CH3)2 C NH
O CH3
CH3
-+
The two methyl groups are not equivalent NMR shows two singlets
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11-- Hydrolysis of AmidesHydrolysis of AmidesBasic Solution
Acidic Solution
excess
heat
heat
Na+ Na+
Hydrolysis requires strong acid or base and heating under reflux.
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: :..
:....
_
OCR NH2
O H
: :.. _
..
: ..
R C NH2
O
O H
: :.. _
..
: ..
R C NH2
O
O H
: :
: ..
+ NH2:.._O
CRO H
OCR OH
: :.... + NH2:
.._ OCR O
: :.... :
_+ NH3
..
BaseBase--Promoted Hydrolysis of a AmidePromoted Hydrolysis of a AmideMECHANISM
stronger basethan OH-, butthis step doesn’treverse becauseof the next one
once ina while
most often this step reversesbecause OH- is a better leaving group than NH2-
accumulates
NaOH
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AcidAcid--catalyzed Hydrolysis of a Amidecatalyzed Hydrolysis of a Amide:..+OCR NH2
H
OH H
OCR NH2
H
O HH
:
:..
+
OCR NH2
H
O HH
:
:..
+
OCR NH2
H
O H
H
:
:
..
+ OCR NH2
H
O HH
:
:..
+
..
OCR NH3
H
O H:
:..
+
..
OCR OH
H
..
..
OCR OH + NH4
+
:+
:NH3+
....MECHANISM
1)
2)
3)
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Examples
CH3CH2CN(CH3)2
O
+ H2OH+
CH3CH2CO2H + (CH3)2NH2+
N,N-dimethylpropanamidePropanoicacid
Dimethylammonium ion
NHCH3
O
OH-CO2
-
+ CH3NH2
methylamineBezoate ion
N-methylbenzamide
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Reduction
RCNR'2
O1) Li AlH4
2) H+, H2ORCH2NR'2
General
An amide An amine
example
CH3(CH2)4CNHC2H5
O1) Li AlH4
2) H+, H2O CH3(CH2)4CH2NHC2H5
N-ethylhexanamide N-ethyl hexylamine
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Reduction Mechanism
RCNR'2H
O-
RC
H
O AlH3
NR'2RCNR'2
O+ H AlH3
- AlH3
RC NR'2H
+Al H
H
H
O- +R C
H
H
NR'2- OAlH2
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Polyamides
HOC(CH2)4COH
OO+ H2N(CH2)6NH2x x
Hexanedioic acid 1,6-hexanediamine
C(CH2)4CNH(CH2)6NH
O O
xnylon 6,6polyamide
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Compounds Related to amides
NH
O
CNC
O O
NH
O
OLactam = cyclic amide
imide
NCN
OH2NCNH2
O
NCO
OH2NCOCH3
O
Carbamate, or urethane
UREA
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Carbamates are prepared from isocyanates and alcohols
N C O+
HONHCO
O
Phenyl isocyanate
phenolPhenyl N-phenyl carbamatepolyurethanes
N C O
NCO
HOCH2CH2OH + xx
CH2CH2OCNH
O
NHCO
O
x
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Barbiturates
• Reaction of diethyl malonate with urea in the presence of sodium ethoxide produces barbituric acid
urea
Used as sedatives
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Sulfonamides or Sulfa drugs
S
O
O
Cl + R2NH S
O
O
NR2 + HCl
Benzenesulfonylchloride
An amine a sulfonamide
Nitrogen is attached to sulfonylgroup
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NITRILESNITRILES
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Nomenclature
CH3C N
IUPAC: The alkane name is suffixed with nitrile
CN
ethanenitrilebenzenecarbonitrile
Trivial:
acetonitrile Trivial: benzonitrile
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Preparation of Preparation of NitrilesNitriles
1) SN2 Reaction
R CH2 Cl R CH2 C N +_
: : +C N Cl
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2) Aryl nitriles from diazonium salts
NH2NaNO2HCl
0 CoN2
+Cl-
CuCN, KCN
CN
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3) Nitriles from the Dehydration of Amides
Anitrile can be formed by reaction of an amide with SOCl2,phosphorous pentoxide (P2O5)or boiling acetic anhydride
RC NH2
OSOCl2, P2O5, or (CH3CO)2O
- H2O RC NA nitrile
CH3(CH2)3C NH2
OSOCl2 CH3(CH2)3C N
pentanenitrile
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Reactions of Nitriles
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1)1) Hydrolysis of Hydrolysis of NitrilesNitrilesACID SOLUTION
R CH2 C N R CH2 C OHO
+ H2O + NH4+
H2SO4
heat
Acid or Base
R CH2 C N R CH2 C OO
+ H2O + heat
NaOH:NH3Na+
-
BASIC SOLUTION
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BaseBase--Promoted Hydrolysis of a Promoted Hydrolysis of a NitrileNitrileMECHANISM NaOH
C N R
:....
_O H
slow :.. _
C NRO H: ..
.._
CRN
OH
:
..
:
+ H2O CRNH
OH
: .... + OH
_
CRNH
OH
:.... CR
NH2
O
: ....
1)
2)
3) amide
Tautomerism….. continued
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: :..
:....
_
OCR NH2
O H
: :.. _
..
: ..
R C NH2
O
O H
: :.. _
..
: ..
R C NH2
O
O H
: :
: ..
+ NH2:.._O
CRO H
OCR OH
: :.... + NH2:
.._ OCR O
: :.... :
_+ NH3
..
BaseBase--Promoted Hydrolysis of a AmidePromoted Hydrolysis of a AmideMECHANISM
4)
5)
6)
NaOH
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AcidAcid--catalyzed Hydrolysis of a catalyzed Hydrolysis of a NitrileNitrileMECHANISM
C N R +fast
H+ + +
C NR H+
OHH
slow ..
:+C NR HOH
H
..
:+
C NR HOH
H
..
:C NROH
HH:
+
C NR H C NR H..
..
..
protonatedamide
H-OH2+
H2SO4 / H2O
Amide may be isolated as the product of the reaction under mild conditions
1)
2)
3)
….. continued
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AcidAcid--catalyzed Hydrolysis of a Amidecatalyzed Hydrolysis of a Amide
:..+OCR NH2
H
OH H
OCR NH2
H
O HH
:
:..
+
OCR NH2
H
O HH
:
:..
+
OCR NH2
H
O H
H
:
:
..
+ OCR NH2
H
O HH
:
:..
+
..
OCR NH3
H
O H:
:..
+
..
OCR OH
H
..
..
OCR OH + NH4
+
:+
:NH3+
OH2
.... H-OH2
+
4)
5)
6)
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Examples
CH2CN +H2O H2SO4 (40%)reflux CH2COH
O
CH2CN +H2O HCl (40%)
40 Co CH2CNH2
O
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2) Reduction• Nitriles can be reduced to primary amines
(RCH2NH2 ) by Hydrogenation or LiAlH4
CH2CNH2, Niheat, p
CH2CH2NH2
CH3CH2CH2C N 1) LiAlH4
2) H+, H2O CH3CH2CH2CH2NH2
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