blessie mae r. encila iv-b.s chemistry for teachers advance organic chemistry
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Blessie Mae R. EncilaIV-B.S Chemistry for TeachersAdvance Organic Chemistry
NITRILER-CN
WINTERTemplateNitrile
History
Nomenclature
01
• A nitrile is any organic compound that has a -C≡N functional group.
• The prefix cyano- is used interchangeably with the term nitrile in industrial literature.
• Nitriles are found in many useful compounds, including– methyl cyanoacrylate
• used in super glue– nitrile butadiene rubber
• a nitrile-containing polymer used in latex-free laboratory and medical gloves.
Nitrile
• Organic compounds containing multiple nitrile groups are known as cyanocarbons.
• Inorganic compounds containing the -C≡N group are not called nitriles, but cyanides instead.
• Though both nitriles and cyanides can be derived from cyanide salts, most nitriles are not nearly as toxic.
Nitrile
Nitrile• C.W. Scheele in 1782
-He synthesized the first compound of the homolog row of nitriles, which is the nitrile of formic acid, and hydrogen cyanide.
• J. L. Gay-Lussac in 1811
-He was able to prepare the very toxic and volatile pure acid.
• Friedrich Wöhler and Justus von Liebig
-They prepared the nitrile of benzoic acids, but due to minimal yield of the synthesis neither physical nor chemical properties were determined nor a structure suggested.
History
Nitrile• Théophile-Jules Pelouze in 1834
-He synthesized propionitrile suggesting it to be an ether of propionic alcohol and hydrocyanic acid.
• Hermann Fehling in 1844
-The synthesis of benzonitrile, by heating ammonium benzoate, was the first method yielding enough of the substance for chemical research. He determined the structure by comparing it to the already known synthesis of hydrogen cyanide by heating ammonium formate to his results. He coined the name nitrile for the newfound substance, which became the name for the compound group.
History
NitrileTwo systems have been adopted by IUPAC:
1. Nitriles derived from open-chain alkanes are named by adding –nitrile as a suffix to the alkane name, with the nitrile carbon numbered C1:
CH3 5 43
2
CH3
CN1
CH3 6 54
CH3
CH3
32
CN1
4-Methylpentanenitrile4,5-dimethylhexanenitrile
Nomenclature
NitrileTwo systems have been adopted by IUPAC:
2. Nitriles are named as derivatives of carboxylic acids by replacing the –ic acid or –oic acid with –onitrile, or replacing –carboxylic acid with -carbonitrile.
Acetonitrile Benzonitrile
CH3C
N C N
3
4
2
5
1
6
CH3
CH3NC
3,3-Dimethylcyclohexanecarbonitrile
Nomenclature
02
NitrileGeneral Reactions of Nitrile
Chem
istry
of N
itrile
s
General Reactions of Nitriles
Nitrile
Amine
Amide Carboxylic Acid
Ketone
R N
O
H2R OH
O
RC
N
HH
H2 R R'
O
R
C
N
H2O
H2O
LiAlH4 R’MgX
Chem
istry
of N
itrile
s
A nitrile can be hydrolyzed in either basic or acidic aqueous solution to yield a carboxylic acid and ammoniz or an amine
Hydrolysis: Conversion of Nitriles into Carboxylic Acids
H3O+
Basic hydrolysis of a nitrile
Amide
C NROr NaOH, H2O
R OH
O
+ NH3
C NR
RC
N-
OH
RC
N
OH
H
+--OH
NH
RC
O
H
--OH
RC
N
O-
O-
H2
RC
N
OHO-
H2+
H2O
O-
RC
O+NH2
-
Carboxylate
--OH
OH H
Dianion
Chem
istry
of N
itrile
s
A nitrile can be reduced with LiAlH4 to give a primary amine
Reduction: Conversion of Nitriles into Amines
R C NLiAlH4
etherR
CH
N-
LiAlH4
etherH2O
RC
N
HH
H2RC
N2-
HH
Nitrile Imine anion Dianion Amine
Chem
istry
of N
itrile
s
A nitrile can add a Grignard reagent to give an intermediate imine anion that is further hydrolyzed by water to yield a ketone:
Reaction of Nitriles with Organometallic Reagents
R C N:R’- +MgX H2O
Nitrile Imine anion Ketone
R'RC
N-
RC
R'
O
+ NH3
03
NitrileApplication
• Over 30 nitrile-containing pharmaceuticals are currently marketed for a diverse variety of medicinal indications with more than 20 additional nitrile-containing leads in clinical development.
Nitrile
• Structure of periciazine, an antipsychotic studied in the treatment of opiate dependence.
Nitrile
• Structure of citalopram, an antidepressant drug of the selective serotonin reuptake inhibitor (SSRI) class.
• Structure of cyamemazine, an antipsychotic drug.
Nitrile
• Structure of fadrozole, an aromatase inhibitor for the treatment of breast cancer.
• Structure of letrozole, an oral non-steroidal aromatase inhibitor for the treatment of certain breast cancers.
Nitrile
04
NitrileJournal
Nifurtimox Activation by Trypanosomal Type I
Nitroreductases Generates Cytotoxic
Nitrile MetabolitesBelinda S. Hall, Christopher Bot, and Shane R. Wilkinson
From the School of Biological and Chemical Sciences, Queen Mary University of London, United Kingdom
• The aim of this work was to determine the role of NTRs (trypanosomal type I nitroreductase) in nifurtimox action.
05
Thank You!
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