Amides are named by replacing the suffix -oic acid in the carboxylic acid name with -amide. Nitriles are named by adding the suffix -nitrile to the alkane name. The nitrile carbon is assigned position 1. α-Hydrogen atoms of carbonyl compounds are acidic due to stabilization of the resulting enolate anion. This allows for halogenation and reactions involving enolate intermediates, such as aldol condensations.
Indole is an aromatic heterocyclic organic compound. It has a bicyclic structure, consisting of a six-membered benzene ring fused to a five-membered nitrogen-containing pyrrole ring. Compounds that contain an indole ring are called indoles.
N-BROMOSUCCINAMIDE A REAGENT USED IN THE SYNTHESIS, IT IS ALSO A SYNTETIC REAGENT AND HERE IN THIS PRESENTATION THE MOLECULAR FORMULA ITS ALTERNATE NAME APLLICATION ARE DISCUSSED.
Aldehydes and ketones are organic compounds which incorporate a carbonyl functional group, C=O. The carbon atom of this group has two remaining bonds that may be occupied by hydrogen or alkyl or aryl substituents. If at least one of these substituents is hydrogen, the compound is an aldehyde.
Benzene has 6π electrons delocalized in 6p orbitals that overlap above and below the plane of the ring. Because benzene’s six pie electrons satisfy Huckel’s rule, benzene is especially stable. Reaction that keep the aromatic ring intact are therefore favoured
this ppt include introduction synthesis, physical ,chemical properties, and uses of pyrrole furan and thiophene
also include introduction of 5 membered heterocyclic compound and fused heterocyclic compounds
Chemical methods of reduction can take place by addition of electrons to the unsaturated compound followed by transfer of protons or can take place by addition of hydride ion followed by protonation.
Reductions that follow the first path are generally effected by metal, the source of the electrons, and a proton donor, which may be water, an alcohol or an acid. However, in the absence of proton source, it can undergo dimerization or polymerization.
THIS SLIDE HAVE GOOD CONTENT. THIS SLIDE CONTAIN INTRODUCTION, STRUCTURE, RESONANCE, AROMATICITY, PHYSICAL AND CHEMICAL PROPERTIES, SYNTHESIS AND APPLICATION OF QUINOLINE.
The combination of a carbonyl group and a hydroxyl on the same carbon atom is called a carboxyl group. Compounds containing the carboxyl group are called carboxylic acids. The carboxyl group is one of the most widely occurring functional groups in organic chemistry.
Aromatic Carboxylic acids: Carboxylic acids have an aryl group bound to the carboxyl group is known as aromatic carboxylic acids. The general formula of an aliphatic aromatic carboxylic acid is Ar-COOH.
Acidity of carboxylic acid:
A carboxylic acid may dissociate in water to give a proton and a carboxylate ion. Dissociation of a carboxylic acid involves breaking an O-H bond gives a carboxylate ion with the negative charge spread out equally over two oxygen atoms, compared with just one oxygen atom in an alkoxide ion. The delocalized charge makes the carboxylate ion more stable therefore; dissociation of a carboxylic acid to a carboxylate ion is less endothermic.
Preparation Methods:
1. Oxidation:
The oxidation of aldehyde with oxidizing agents such as CrO3 to forms carboxylic acids containing the same numbers of carbon atoms with a oxidizing agents like chromic acid, chromium trioxide. The silver oxide (Ag2O) in aqueous ammonia solution (Tollen’s reagent) is mild reagent give good yield at room temperature. E.g. Acetaldehyde reacts with CrO3 in aqueous acid to give acetic acid.
2. Grignard reagents (from CO2):
Carboxylic acid can be prepared by the reaction of Grignard reagent (alkyl magnesium halide) with carbon dioxide (CO2) in presence of dry ether. Grignard reagents react with carbon dioxide to forms a magnesium carboxylates which on hydrolysis by dilute HCl produces carboxylic acids.
3. Hydrolysis of nitrile:
The hydrolysis of nitrile or cyanide in presence of dilute acid to forms a carboxylic acid. In this reaction –CN group is converted to a –COOH group.
4. Hydrolysis Reactions:
All the carboxylic acid derivatives can be hydrolyzed into the carboxylic acid in the acidic or basic media; the hydrolysis reaction is fast and occurs in presence of water with no acid or base catalyst.
1. From Ester (Hydrolysis of ester): Ester can be hydrolyzed in either acidic or basic medium to yield carboxylic acid. The ester is heated with an excess of water contains strong acid or base catalyst.
Properties of Carboxylic Acids:
1. Low molecular weights carboxylic acids are colourless liquid at room temperature i.e. lower member ate liquid up to C9 and have characteristic odors whereas higher members are solid.
2. Carboxylic acids are polar organic compound. Low molecular weight carboxylic acids (first four members) are soluble in water whereas solubility in water decrease as molecular weight and chain lengthing increases.
3. Aromatic acids are insoluble in water.
4. Carboxylic acids have higher melting and boiling point due to their capacity to readily form stable hydrogen-bonded dimers.
Indole is an aromatic heterocyclic organic compound. It has a bicyclic structure, consisting of a six-membered benzene ring fused to a five-membered nitrogen-containing pyrrole ring. Compounds that contain an indole ring are called indoles.
N-BROMOSUCCINAMIDE A REAGENT USED IN THE SYNTHESIS, IT IS ALSO A SYNTETIC REAGENT AND HERE IN THIS PRESENTATION THE MOLECULAR FORMULA ITS ALTERNATE NAME APLLICATION ARE DISCUSSED.
Aldehydes and ketones are organic compounds which incorporate a carbonyl functional group, C=O. The carbon atom of this group has two remaining bonds that may be occupied by hydrogen or alkyl or aryl substituents. If at least one of these substituents is hydrogen, the compound is an aldehyde.
Benzene has 6π electrons delocalized in 6p orbitals that overlap above and below the plane of the ring. Because benzene’s six pie electrons satisfy Huckel’s rule, benzene is especially stable. Reaction that keep the aromatic ring intact are therefore favoured
this ppt include introduction synthesis, physical ,chemical properties, and uses of pyrrole furan and thiophene
also include introduction of 5 membered heterocyclic compound and fused heterocyclic compounds
Chemical methods of reduction can take place by addition of electrons to the unsaturated compound followed by transfer of protons or can take place by addition of hydride ion followed by protonation.
Reductions that follow the first path are generally effected by metal, the source of the electrons, and a proton donor, which may be water, an alcohol or an acid. However, in the absence of proton source, it can undergo dimerization or polymerization.
THIS SLIDE HAVE GOOD CONTENT. THIS SLIDE CONTAIN INTRODUCTION, STRUCTURE, RESONANCE, AROMATICITY, PHYSICAL AND CHEMICAL PROPERTIES, SYNTHESIS AND APPLICATION OF QUINOLINE.
The combination of a carbonyl group and a hydroxyl on the same carbon atom is called a carboxyl group. Compounds containing the carboxyl group are called carboxylic acids. The carboxyl group is one of the most widely occurring functional groups in organic chemistry.
Aromatic Carboxylic acids: Carboxylic acids have an aryl group bound to the carboxyl group is known as aromatic carboxylic acids. The general formula of an aliphatic aromatic carboxylic acid is Ar-COOH.
Acidity of carboxylic acid:
A carboxylic acid may dissociate in water to give a proton and a carboxylate ion. Dissociation of a carboxylic acid involves breaking an O-H bond gives a carboxylate ion with the negative charge spread out equally over two oxygen atoms, compared with just one oxygen atom in an alkoxide ion. The delocalized charge makes the carboxylate ion more stable therefore; dissociation of a carboxylic acid to a carboxylate ion is less endothermic.
Preparation Methods:
1. Oxidation:
The oxidation of aldehyde with oxidizing agents such as CrO3 to forms carboxylic acids containing the same numbers of carbon atoms with a oxidizing agents like chromic acid, chromium trioxide. The silver oxide (Ag2O) in aqueous ammonia solution (Tollen’s reagent) is mild reagent give good yield at room temperature. E.g. Acetaldehyde reacts with CrO3 in aqueous acid to give acetic acid.
2. Grignard reagents (from CO2):
Carboxylic acid can be prepared by the reaction of Grignard reagent (alkyl magnesium halide) with carbon dioxide (CO2) in presence of dry ether. Grignard reagents react with carbon dioxide to forms a magnesium carboxylates which on hydrolysis by dilute HCl produces carboxylic acids.
3. Hydrolysis of nitrile:
The hydrolysis of nitrile or cyanide in presence of dilute acid to forms a carboxylic acid. In this reaction –CN group is converted to a –COOH group.
4. Hydrolysis Reactions:
All the carboxylic acid derivatives can be hydrolyzed into the carboxylic acid in the acidic or basic media; the hydrolysis reaction is fast and occurs in presence of water with no acid or base catalyst.
1. From Ester (Hydrolysis of ester): Ester can be hydrolyzed in either acidic or basic medium to yield carboxylic acid. The ester is heated with an excess of water contains strong acid or base catalyst.
Properties of Carboxylic Acids:
1. Low molecular weights carboxylic acids are colourless liquid at room temperature i.e. lower member ate liquid up to C9 and have characteristic odors whereas higher members are solid.
2. Carboxylic acids are polar organic compound. Low molecular weight carboxylic acids (first four members) are soluble in water whereas solubility in water decrease as molecular weight and chain lengthing increases.
3. Aromatic acids are insoluble in water.
4. Carboxylic acids have higher melting and boiling point due to their capacity to readily form stable hydrogen-bonded dimers.
Aldehydes and ketones are the carbonyl compounds with general formula CnH2nO. Aldehydes have at least one hydrogen atom bonded to the carbonyl group and other group is either hydrogen or an alkyl or aryl group (i.e. Aldehyde has one alkyl or aryl group and one of the hydrogen bonded to the carbonyl carbon) with characteristics functional group -CHO.
Sharpen existing tools or get a new toolbox? Contemporary cluster initiatives...Orkestra
UIIN Conference, Madrid, 27-29 May 2024
James Wilson, Orkestra and Deusto Business School
Emily Wise, Lund University
Madeline Smith, The Glasgow School of Art
This presentation by Morris Kleiner (University of Minnesota), was made during the discussion “Competition and Regulation in Professions and Occupations” held at the Working Party No. 2 on Competition and Regulation on 10 June 2024. More papers and presentations on the topic can be found out at oe.cd/crps.
This presentation was uploaded with the author’s consent.
0x01 - Newton's Third Law: Static vs. Dynamic AbusersOWASP Beja
f you offer a service on the web, odds are that someone will abuse it. Be it an API, a SaaS, a PaaS, or even a static website, someone somewhere will try to figure out a way to use it to their own needs. In this talk we'll compare measures that are effective against static attackers and how to battle a dynamic attacker who adapts to your counter-measures.
About the Speaker
===============
Diogo Sousa, Engineering Manager @ Canonical
An opinionated individual with an interest in cryptography and its intersection with secure software development.
Acorn Recovery: Restore IT infra within minutesIP ServerOne
Introducing Acorn Recovery as a Service, a simple, fast, and secure managed disaster recovery (DRaaS) by IP ServerOne. A DR solution that helps restore your IT infra within minutes.
Have you ever wondered how search works while visiting an e-commerce site, internal website, or searching through other types of online resources? Look no further than this informative session on the ways that taxonomies help end-users navigate the internet! Hear from taxonomists and other information professionals who have first-hand experience creating and working with taxonomies that aid in navigation, search, and discovery across a range of disciplines.
Doctoral Symposium at the 17th IEEE International Conference on Software Test...
amide.pdf
1. Amides
Amides
1
: Nomenclature
IUPAC
An amide has NH2, NHR ,or NR2 group in place of the OH group of a
carboxylic acid.
Amides are named by using the acid name, replacing oic acid or ic acid with
amide. For acids ending with carboxylic acid, ylic acid is replaced with amide.
3. Nitriles
Nitriles
3
: Nomenclature
IUPAC
They are considered carboxylic acid derivatives because they react with water
to form carboxylic acids. Nitriles are named by adding the suffix -nitrile to the
alkane name. The nitrile carbon is assigned position 1
***Ethanenitrile is usually called acetonitrile
5. Amides
5
: Preparation
1) From Acyl Chlorides
Ammonia, 1ry or 2ry amines react with acid chlorides to form amides.
An excess of amine is added to neutralize the HCl formed in the
reaction.
Carboxylic acids can be converted to amides via the corresponding
acid chloride
6. Amides
6
: Preparation
2) From Carboxylic Anhydrides
Anhydrides react with 2 equivalents of amine to produce an
amide & ammonium carboxylate
7. Amides
7
: Preparation
2) From Carboxylic Acids & Ammonium Carboxylates
Direct reaction of carboxylic acids & ammonia yields ammonium salts
Some ammonium salts of carboxylic acids can be dehydrated to the amide at
high temperatures .This is generally a poor method of amide synthesis
11. Amides
11
: Reaction
1) Amides react with water or alcohol if the reaction is
heated in presence of an acid
Hydrolysis of Amides
Heating an amide in
concentrated aqueous
acid or base causes
hydrolysis
12. Amides
12
: Reaction
2) 1ry amides can be dehydrated to nitriles. Dehydrating
reagents such as P2O5, POCl3, SOCl2 can be used.
14. Lactams
14
Cyclic amides are called lactams. The size of the lactam ring is designated by
Greek letters in a way that is analogous to lactone nomenclature
• γ-Lactams and δ-lactams often form spontaneously from γ- and δ-amino acids.
• β-Lactams, however, are highly reactive; their strained four-membered rings open
easily in the presence of nucleophilic reagents.
19. Tautomerism
19
Tautomerism
keto and enol forms of carbonyl compounds are constitutional isomers,
but of a special type. Because they are easily interconverted by proton
transfers in the presence of an acid or base. Interconvertible keto and
enol forms are called tautomers, and their interconversion is called
tautomerization
enol form
keto form
C
OH
C
C C
O
H
The keto form is usually predominant with few exceptions.
20. 20
The keto form is usually predominant with few exceptions.
2,4-Pentanedione
Enol form (76%)
Tautomerism
21. Decarboxylation of Carboxylic Acids
21
Loss of CO2 from a carboxyl group = Decarboxylation
• Carboxylic acids undergo thermal decarboxylation, when heated to a very high
temperature and most carboxylic acids are resistant to moderate heat.
• Exceptions are carboxylic acids that have a carbonyl group β to the carboxyl group
(β-ketoacids undergo decarboxylation readily on mild heating).
22. Decarboxylation of Carboxylic Acids
22
Loss of CO2 from a carboxyl group = Decarboxylation
• There are two reasons for this ease of decarboxylation:
1. When the acid itself decarboxylates, it can do so through a six-membered
cyclic transition state:
This reaction produces an enol (alkene-alcohol) directly and avoids an anionic
intermediate. The enol then tautomerizes to a methyl ketone.
23. Decarboxylation of Carboxylic Acids
23
Loss of CO2 from a carboxyl group = Decarboxylation
• There are two reasons for this ease of decarboxylation:
2. When the carboxylate anion decarboxylates, it forms a resonance-stabilized
anion:.
This type of anion is much
more stable than simply
RCH2:−, the anion that would
have been produced by
decarboxylation in the absence
of a β-carbonyl group. It is
known as an enolate.
24. Decarboxylation of Carboxylic Acids
24
Loss of CO2 from a carboxyl group = Decarboxylation
• β-Dicarboxylic acids (1,3-dicarboxylic acids, also called malonic acids)
decarboxylate readily for reasons similar to β-keto acids.
25. Decarboxylation of Carboxylic Acids
25
Loss of CO2 from a carboxyl group = Decarboxylation
• COOH group at o-or p-position to OH group is easily replaced by Br or NO2 group
27. 27
Enolate formation
• The pKa values for the α hydrogens of most simple aldehydes or ketones
are of the order of 19–20 that are more acidic than hydrogen atoms of
ethyne (pKa = 25), and ethene (pKa = 44) or of ethane (pKa = 50).
• The carbonyl group is strongly electron withdrawing, and when a carbonyl
compound loses an α proton, the anion that is produced, called an
enolate, is stabilized by delocalization.
The Acidity of the α Hydrogens
of Carbonyl Compounds
28. 28
Carbonyl compounds bearing an α hydrogen can undergo halogen
substitution at the α carbon in the presence of acid or base.
The Acidity of the α Hydrogens
of Carbonyl Compounds
Halogenation at the α Carbon
+ H2O
+
Br -
C
CH3
O
CH2Br
Br2 / OH -
C
CH3
O
CH3
+ HBr
C
CH3
O
CH2Br
Br2 / H+
C
CH3
O
CH3
29. 29
Carbonyl compounds bearing an α hydrogen can undergo halogen
substitution at the α carbon in the presence of acid or base.
The Acidity of the α Hydrogens
of Carbonyl Compounds
Halogenation at the α Carbon
(multiple halogenations can occur) Ex: Haloform reaction
30. 30
The Acidity of the α Hydrogens
of Carbonyl Compounds
Halogenation at the α Carbon
31. 31
The Acidity of the α Hydrogens
of Carbonyl Compounds
Halogenation at the α Carbon
32. 32
The Acidity of the α Hydrogens
of Carbonyl Compounds
Halogenation at the α Carbon
α-Halo Carboxylic Acids: The Hell–Volhard–Zelinski Reaction
Carboxylic acids bearing α hydrogen atoms react
with bromine or chlorine in the presence of
phosphorus (or a phosphorus halide) to give α-
halo carboxylic acids through a reaction known as
the Hell–Volhard–Zelinski (or HVZ) reaction.
α-Iodo acyl chlorides can be obtained by using molecular iodine in a similar reaction.
33. 33
The Acidity of the α Hydrogens
of Carbonyl Compounds
Halogenation at the α Carbon
34. 34
The Acidity of the α Hydrogens
of Carbonyl Compounds
Reactions of carbanion
Aldehydes or ketones containing α-H's, in the presence of alkali, give carbanion.
35. 35
The Acidity of the α Hydrogens
of Carbonyl Compounds
Reactions of carbanion
Aldol condensation:
Aldehydes or ketones containing α-H's, in the presence of alkali, give carbanion.
The resulting carbanion attacks the carbonyl carbon of a second molecule. e.g.,
aldol condensation:
36. 36
The Acidity of the α Hydrogens
of Carbonyl Compounds
Reactions of carbanion
a- Claisen-Schmidt reaction (crossed aldol):
Condensation between benzaldehyde (which does not contain α-H) and aliphatic
aldehyde or ketone (which contain α-H):
37. 37
The Acidity of the α Hydrogens
of Carbonyl Compounds
Reactions of carbanion
a- Claisen-Schmidt reaction (crossed aldol):
Condensation between benzaldehyde (which does not contain α-H) and aliphatic
aldehyde or ketone (which contain α-H):
38. 38
The Acidity of the α Hydrogens
of Carbonyl Compounds
Reactions of carbanion
b- Claisen reaction (for ester):
Condensation of esters (containing at least 2 α-H's) in the presence of sodium
ethoxide.
N.B. NaOH causes hydrolysis to the ester.
39. 39
The Acidity of the α Hydrogens
of Carbonyl Compounds
Reactions of carbanion
c- Crossed Claisen reaction (for ester):
Aromatic aldehydes (or esters, which do not contain α-H) condense with an ester
(which contains α-H) in the presence of sodium ethoxide.
40. 40
The Acidity of the α Hydrogens
of Carbonyl Compounds
Reactions of carbanion
d- Knoevenagel condensation:
Aromatic aldehydes (or other aldehydes or ketones) condense with esters having
active α- H's in the presence of weak bases (amines).
41. 41
The Acidity of the α Hydrogens
of Carbonyl Compounds
Reactions of carbanion
e- Perkin condensation:
Aromatic aldehydes condense with a carboxylic acid anhydride to give α,b-
unsaturated acid. The reaction is catalyzed by potassium salt of the carboxlic acid.
NaOH should not be used, why ??
Benzaldehyde undergoes another reaction in the presence of NaOH.
In all these aldol-type condensations, the principle involves abstraction of α-H by a
base such as NaOH, NaOC2H5, amines, or salt of carboxlic acid.
42. 42
The Acidity of the α Hydrogens
of Carbonyl Compounds
Reactions of carbanion
Cannizzaro reaction:
Aldehydes that do not contain α-H, in the presence of concentrated NaOH, undergo
selfoxidation-reduction reaction
43. 43
The Acidity of the α Hydrogens
of Carbonyl Compounds
Reactions of carbanion
Crossed Cannizzaro reaction:
A mixture of two aldehydes (with no α-H's), in the presence of concentrated sodium
hydroxide, will give all possible products. If one aldehyde is formaldehyde, the
reaction yields, exclusively sodium formate and the alcohol corresponding to the
other aldehyde
44. 44
The Acidity of the α Hydrogens
of Carbonyl Compounds
Reactions of carbanion
Crossed Cannizzaro reaction:
A mixture of two aldehydes (with no α-H's), in the presence of concentrated sodium
hydroxide, will give all possible products. If one aldehyde is formaldehyde, the
reaction yields, exclusively sodium formate and the alcohol corresponding to the
other aldehyde
C
Ar O
H
OH -
Ar C O-
H
OH
C
Ar O
H
+ Ar C O-
H
OH
Ar C
H
H
O-
+ Ar C
O
OH
H+
- H+
Ar CH2OH Ar COO-
Mechanism
Not methyl alcohol and sodium benzoate are formed.
Because the initial nucleophilic addition of hydroxide
anion is faster on formaldehyde as there are no
electron donating groups on it.
45. 45
The Acidity of the α Hydrogens
of Carbonyl Compounds
Reactions of carbanion
intermolecular cannizzaro
46. 46
The Acidity of the α Hydrogens
of Carbonyl Compounds
Reactions of carbanion
intermolecular cannizzaro
47. 48
a,b-Unsaturated Carbonyl
compounds
1,4-addition
b a
R CH CH C
O
R'
An a,b-unsaturated carbonyl compound has a carbon-carbon double
bond in conjugation with a carbonyl group.
The resonance structures show that the b-carbon, as well as the
carbonyl carbon, carries a partial positive charge, while the
carbonyl oxygen carries a partial negative charge. This can lead to
1,4-addition.
+
CH2 CH C
O-
H
+
CH2 CH C H
O-
CH2 CH C H
O
48. 49
a,b-Unsaturated Carbonyl
compounds
1,4-addition: A) Electrophilic 1,4-Addition
So the Nucleophilic part (CN
-, Cl
-, OH
-) is added to the b-carbon,
which has a partial positive charge.
keto form
enol form
Cl CH2 CH2 C
O
H
CH2 CH C
O
Cl H
H
Cl -
+
CH2 CH C
OH
H
CH2 CH C H
OH+
H+
CH2 CH C H
O
49. 50
a,b-Unsaturated Carbonyl
compounds
1,4-addition: B) Nucleophilic 1,4-Addition
Both carbonyl carbon and b carbon can be attacked by nucleophiles
(CN-, NH2
-, OH-) to give (A) or (B).
(B)
(A)
CH2
CN CH2 C
O
CH3
CH2 CH C
OH
CH3
CN
CN -
CH2 CH C
O
CH3
The mechanism in (A) is the
same as shown in the
formation of cyanohydrin,
but in the formation of (B),
it is 1,4-addition. Both
reactions are possible.
**A highly basic reagents such as, RMgX, attack C=O, while a
weaker bases such as, CN- or R2NH, usually attack C=C.
** Aldehydes, being less hindered than ketones, usually undergo
carbonyl attack.
