Introduction of poly-cyclic compounds, resonance, molecular orbital structure, physical properties, preparation, reaction and uses of napthalene, anthracene, phenanthrene, napthaquinone, napthol, napthylamine, 9,10 anthraquinone and phenanthrequinone.
Heterocyclic compounds-II
Nucleophilic ring opening reactions of aziridines
Three Membered Heterocyclic Compounds with One Hetero Atom, Chemical Properties
Mechanism,
Ring-Opening Reactions, azacyclopropane, Aziridine has often been called azacyclopropane or more common derivative of a parent alkene, ethylenimine.
Introduction of poly-cyclic compounds, resonance, molecular orbital structure, physical properties, preparation, reaction and uses of napthalene, anthracene, phenanthrene, napthaquinone, napthol, napthylamine, 9,10 anthraquinone and phenanthrequinone.
Heterocyclic compounds-II
Nucleophilic ring opening reactions of aziridines
Three Membered Heterocyclic Compounds with One Hetero Atom, Chemical Properties
Mechanism,
Ring-Opening Reactions, azacyclopropane, Aziridine has often been called azacyclopropane or more common derivative of a parent alkene, ethylenimine.
I hope You all like it. I hope It is very beneficial for you all. I really thought that you all get enough knowledge from this presentation. This presentation is about materials and their classifications. After you read this presentation you knowledge is not as before.
Introduction to benzene, orbital picture, resonance in benzene, Huckel‟s rule
Reactions of benzene - nitration, sulphonation, halogenation- reactivity, Friedel- Craft‟s alkylation- reactivity, limitations, Friedel-Craft‟s acylation.
Substituents, effect of substituents on reactivity and orientation of mono substituted benzene compounds towards electrophilic substitution reaction.
I hope You all like it. I hope It is very beneficial for you all. I really thought that you all get enough knowledge from this presentation. This presentation is about materials and their classifications. After you read this presentation you knowledge is not as before.
To study the properties, nomenclature and the physical as well chemical reactions of aliphatic and alkyl benzene. Might as well as the usage of benzene in our daily life routine
Substitution Reactions of Benzene and Other Aroma.pdfajitdoll
Substitution Reactions of Benzene and Other Aromatic Compounds The
remarkable stability of the unsaturated hydrocarbon benzene has been discussed in an earlier
section. The chemical reactivity of benzene contrasts with that of the alkenes in that substitution
reactions occur in preference to addition reactions, as illustrated in the following diagram (some
comparable reactions of cyclohexene are shown in the green box). A demonstration of bromine
substitution and addition reactions is helpful at this point, and a virtual demonstration may be
initiated by clicking here. Many other substitution reactions of benzene have been observed, the
five most useful are listed below (chlorination and bromination are the most common
halogenation reactions). Since the reagents and conditions employed in these reactions are
electrophilic, these reactions are commonly referred to as Electrophilic Aromatic Substitution.
The catalysts and co-reagents serve to generate the strong electrophilic species needed to effect
the initial step of the substitution. The specific electrophile believed to function in each type of
reaction is listed in the right hand column. Reaction Type Typical Equation Electrophile E(+)
Halogenation: C6H6 + Cl2 & heat FeCl3 catalyst ——> C6H5Cl + HCl Chlorobenzene Cl(+) or
Br(+) Nitration: C6H6 + HNO3 & heat H2SO4 catalyst ——> C6H5NO2 + H2O Nitrobenzene
NO2(+) Sulfonation: C6H6 + H2SO4 + SO3 & heat ——> C6H5SO3H + H2O Benzenesulfonic
acid SO3H(+) Alkylation: Friedel-Crafts C6H6 + R-Cl & heat AlCl3 catalyst ——> C6H5-R +
HCl An Arene R(+) Acylation: Friedel-Crafts C6H6 + RCOCl & heat AlCl3 catalyst ——>
C6H5COR + HCl An Aryl Ketone RCO(+) 1. A Mechanism for Electrophilic Substitution
Reactions of Benzene A two-step mechanism has been proposed for these electrophilic
substitution reactions. In the first, slow or rate-determining, step the electrophile forms a sigma-
bond to the benzene ring, generating a positively charged benzenonium intermediate. In the
second, fast step, a proton is removed from this intermediate, yielding a substituted benzene ring.
The following four-part illustration shows this mechanism for the bromination reaction. Also, an
animated diagram may be viewed. Bromination of Benzene - An Example of Electrophilic
Aromatic Substitution There are four stages to this slide show. These may be viewed
repeatedly by continued clicking of the \"Next Slide\" button. To see an animated model of this
reaction using ball&stick models . This mechanism for electrophilic aromatic substitution
should be considered in context with other mechanisms involving carbocation intermediates.
These include SN1 and E1 reactions of alkyl halides, and Brønsted acid addition reactions of
alkenes. To summarize, when carbocation intermediates are formed one can expect them to react
further by one or more of the following modes: 1. The cation may bond to a nucleophile to give
a substitution or addition product. 2. The cation may transfer a proton to a base, g.
Seminar of U.V. Spectroscopy by SAMIR PANDASAMIR PANDA
Spectroscopy is a branch of science dealing the study of interaction of electromagnetic radiation with matter.
Ultraviolet-visible spectroscopy refers to absorption spectroscopy or reflect spectroscopy in the UV-VIS spectral region.
Ultraviolet-visible spectroscopy is an analytical method that can measure the amount of light received by the analyte.
(May 29th, 2024) Advancements in Intravital Microscopy- Insights for Preclini...Scintica Instrumentation
Intravital microscopy (IVM) is a powerful tool utilized to study cellular behavior over time and space in vivo. Much of our understanding of cell biology has been accomplished using various in vitro and ex vivo methods; however, these studies do not necessarily reflect the natural dynamics of biological processes. Unlike traditional cell culture or fixed tissue imaging, IVM allows for the ultra-fast high-resolution imaging of cellular processes over time and space and were studied in its natural environment. Real-time visualization of biological processes in the context of an intact organism helps maintain physiological relevance and provide insights into the progression of disease, response to treatments or developmental processes.
In this webinar we give an overview of advanced applications of the IVM system in preclinical research. IVIM technology is a provider of all-in-one intravital microscopy systems and solutions optimized for in vivo imaging of live animal models at sub-micron resolution. The system’s unique features and user-friendly software enables researchers to probe fast dynamic biological processes such as immune cell tracking, cell-cell interaction as well as vascularization and tumor metastasis with exceptional detail. This webinar will also give an overview of IVM being utilized in drug development, offering a view into the intricate interaction between drugs/nanoparticles and tissues in vivo and allows for the evaluation of therapeutic intervention in a variety of tissues and organs. This interdisciplinary collaboration continues to drive the advancements of novel therapeutic strategies.
Multi-source connectivity as the driver of solar wind variability in the heli...Sérgio Sacani
The ambient solar wind that flls the heliosphere originates from multiple
sources in the solar corona and is highly structured. It is often described
as high-speed, relatively homogeneous, plasma streams from coronal
holes and slow-speed, highly variable, streams whose source regions are
under debate. A key goal of ESA/NASA’s Solar Orbiter mission is to identify
solar wind sources and understand what drives the complexity seen in the
heliosphere. By combining magnetic feld modelling and spectroscopic
techniques with high-resolution observations and measurements, we show
that the solar wind variability detected in situ by Solar Orbiter in March
2022 is driven by spatio-temporal changes in the magnetic connectivity to
multiple sources in the solar atmosphere. The magnetic feld footpoints
connected to the spacecraft moved from the boundaries of a coronal hole
to one active region (12961) and then across to another region (12957). This
is refected in the in situ measurements, which show the transition from fast
to highly Alfvénic then to slow solar wind that is disrupted by the arrival of
a coronal mass ejection. Our results describe solar wind variability at 0.5 au
but are applicable to near-Earth observatories.
What is greenhouse gasses and how many gasses are there to affect the Earth.moosaasad1975
What are greenhouse gasses how they affect the earth and its environment what is the future of the environment and earth how the weather and the climate effects.
Nutraceutical market, scope and growth: Herbal drug technologyLokesh Patil
As consumer awareness of health and wellness rises, the nutraceutical market—which includes goods like functional meals, drinks, and dietary supplements that provide health advantages beyond basic nutrition—is growing significantly. As healthcare expenses rise, the population ages, and people want natural and preventative health solutions more and more, this industry is increasing quickly. Further driving market expansion are product formulation innovations and the use of cutting-edge technology for customized nutrition. With its worldwide reach, the nutraceutical industry is expected to keep growing and provide significant chances for research and investment in a number of categories, including vitamins, minerals, probiotics, and herbal supplements.
2. Chapter 17 2
Electrophilic Aromatic
Substitution
Although benzene’s pi electrons are in a stable aromatic
system, they are available to attack a strong electrophile to give
a carbocation.
This resonance-stabilized carbocation is called a sigma
complex because the electrophile is joined to the benzene ring
by a new sigma bond.
Aromaticity is regained by loss of a proton.
5. Chapter 17 5
Mechanism for the
Bromination of Benzene: Step
1
Before the electrophilic aromatic substitution can take
place, the electrophile must be activated.
A strong Lewis acid catalyst, such as FeBr3, should
be used.
Br Br FeBr3 Br Br FeBr3
+ -
(stronger electrophile than Br2)
6. Chapter 17 6
H
H
H
H
H
H
Br Br FeBr3
H
H
H
H
H
H
Br
+ FeBr4
-
H
H
H
H
H
H
Br
FeBr4
-
Br
H
H
H
H
H
+ FeBr3 + HBr
Step 2: Electrophilic attack and formation of the sigma complex.
Step 3: Loss of a proton to give the products.
Mechanism for the
Bromination of Benzene: Steps
2 and 3
8. Chapter 17 8
Chlorination and Iodination
Chlorination is similar to bromination.
AlCl3 is most often used as catalyst, but
FeCl3 will also work.
Iodination requires an acidic oxidizing
agent, like nitric acid, to produce iodide
cation.
H+
+ HNO3 + ½ I2 I+
+ NO2 + H2O
9. Chapter 17 9
Predict the major product(s) of bromination of p-chloroacetanilide.
The amide group (–NHCOCH3) is a strong activating and directing group because the nitrogen atom
with its nonbonding pair of electrons is bonded to the aromatic ring. The amide group is a stronger
director than the chlorine atom, and substitution occurs mostly at the positions ortho to the amide. Like
an alkoxyl group, the amide is a particularly strong activating group, and the reaction gives some of the
dibrominated product.
Solved Problem 1
Solution
10. Chapter 17 10
Nitration of Benzene
Sulfuric acid acts as a catalyst, allowing the reaction
to be faster and at lower temperatures.
HNO3 and H2SO4 react together to form the
electrophile of the reaction: nitronium ion (NO2
+
).
HNO3
H2SO4
NO2
+ H2O
12. Chapter 17 12
Reduction of the Nitro Group
NO2
Zn, Sn, or Fe
aq. HCl
NH2
Treatment with zinc, tin, or iron in dilute acid
will reduce the nitro to an amino group.
This is the best method for adding an amino
group to the ring.
13. Chapter 17 13
Sulfonation of Benzene
Sulfur trioxide (SO3) is the electrophile in the reaction.
A 7% mixture of SO3 and H2SO4 is commonly referred
to as “fuming sulfuric acid”.
The —SO3H groups is called a sulfonic acid.
SO3H
+ SO3
H2SO4
14. Chapter 17 14
Mechanism of Sulfonation
Benzene attacks sulfur trioxide, forming a sigma
complex.
Loss of a proton on the tetrahedral carbon and
reprotonation of oxygen gives benzenesulfonic acid.
15. Chapter 17 15
Desulfonation Reaction
Sulfonation is reversible.
The sulfonic acid group may be removed
from an aromatic ring by heating in dilute
sulfuric acid.
HSO3H
+ H2O
H+
, heat
+ H2SO4
16. Chapter 17 16
Mechanism of Desulfonation
In the desulfonation reaction, a proton adds
to the ring (the electrophile) and loss of sulfur
trioxide gives back benzene.
17. Chapter 17 17
Nitration of Toluene
Toluene reacts 25 times faster than benzene.
The methyl group is an activator.
The product mix contains mostly ortho and
para substituted molecules.
18. Chapter 17 18
Ortho and Para Substitution
Ortho and para attacks are preferred because their
resonance structures include one tertiary carbocation.
20. Chapter 17 20
Meta Substitution
When substitution occurs at the meta position, the
positive charge is not delocalized onto the tertiary
carbon, and the methyl groups has a smaller effect
on the stability of the sigma complex.
21. Chapter 17 21
Alkyl Group Stabilization
CH2CH3
Br2
FeBr3
CH2CH3
Br
CH2CH3
Br
CH2CH3
Br
+ +
o-bromo
(38%)
m-bromo
(< 1%)
p-bromo
(62%)
Alkyl groups are activating substituents and ortho,
para-directors.
This effect is called the inductive effect because
alkyl groups can donate electron density to the ring
through the sigma bond, making them more active.
22. Chapter 17 22
Substituents with Nonbonding
Electrons
Resonance stabilization is provided by a pi bond between
the —OCH3 substituent and the ring.
23. Chapter 17 23
Meta Attack on Anisole
Resonance forms show that the methoxy
group cannot stabilize the sigma complex in
the meta substitution.
24. Chapter 17 24
Bromination of Anisole
A methoxy group is so strongly activating that
anisole is quickly tribrominated without a
catalyst.
25. Chapter 17 25
The Amino Group
Aniline reacts with bromine water (without a
catalyst) to yield the tribromoaniline.
Sodium bicarbonate is added to neutralize
the HBr that is also formed.
27. Chapter 17 27
Activators and Deactivators
If the substituent on the ring is electron donating, the
ortho and para positions will be activated.
If the group is electron withdrawing, the ortho and
para positions will be deactivated.
28. Chapter 17 28
Nitration of Nitrobenzene
Electrophilic substitution reactions for nitrobenzene
are 100,000 times slower than for benzene.
The product mix contains mostly the meta isomer,
only small amounts of the ortho and para isomers.
29. Chapter 17 29
Ortho Substitution on
Nitrobenzene
The nitro group is a strongly deactivating group when
considering its resonance forms. The nitrogen
always has a formal positive charge.
Ortho or para addition will create an especially
unstable intermediate.
30. Chapter 17 30
Meta Substitution on
Nitrobenzene
Meta substitution will not put the positive
charge on the same carbon that bears the
nitro group.
32. Chapter 17 32
Deactivators and Meta-
Directors
Most electron withdrawing groups are
deactivators and meta-directors.
The atom attached to the aromatic ring has a
positive or partial positive charge.
Electron density is withdrawn inductively
along the sigma bond, so the ring has less
electron density than benzene and thus, it will
be slower to react.
33. Chapter 17 33
Ortho Attack of Acetophenone
In ortho and para substitution of acetophenone, one
of the carbon atoms bearing the positive charge is
the carbon attached to the partial positive carbonyl
carbon.
Since like charges repel, this close proximity of the
two positive charges is especially unstable.
34. Chapter 17 34
Meta Attack on Acetophenone
The meta attack on acetophenone avoids
bearing the positive charge on the carbon
attached to the partial positive carbonyl.
36. Chapter 17 36
Nitration of Chlorobenzene
When chlorobenzene is nitrated the main substitution
products are ortho and para. The meta substitution
product is only obtained in 1% yield.
37. Chapter 17 37
Halogens Are Deactivators
X
Inductive Effect: Halogens are deactivating
because they are electronegative and can
withdraw electron density from the ring along
the sigma bond.
38. Chapter 17 38
Halogens Are Ortho, Para-
Directors
Resonance Effect: The lone pairs on the
halogen can be used to stabilize the sigma
complex by resonance.
41. Chapter 17 41
Effect of Multiple Substituents
The directing effect of the two (or more)
groups may reinforce each other.
42. Chapter 17 42
Effect of Multiple Substituents
(Continued)
The position in between two groups in
Positions 1 and 3 is hindered for substitution,
and it is less reactive.
43. Chapter 17 43
Effect of Multiple Substituents
(Continued)
OCH3
O2N
Br2
FeBr3
OCH3
O2N
Br
OCH3
O2N
Br
If directing effects oppose each other, the
most powerful activating group has the
dominant influence.
major products obtained
44. Chapter 17 44
Friedel–Crafts Alkylation
Synthesis of alkyl benzenes from alkyl halides
and a Lewis acid, usually AlCl3.
Reactions of alkyl halide with Lewis acid
produces a carbocation, which is the
electrophile.
46. Chapter 17 46
Protonation of Alkenes
An alkene can be protonated by HF.
This weak acid is preferred because the
fluoride ion is a weak nucleophile and will not
attack the carbocation.
47. Chapter 17 47
Alcohols and Lewis Acids
Alcohols can be treated with BF3 to form the
carbocation.
48. Chapter 17 48
Limitations of Friedel–Crafts
Reaction fails if benzene has a substituent
that is more deactivating than halogens.
Rearrangements are possible.
The alkylbenzene product is more reactive
than benzene, so polyalkylation occurs.
50. Chapter 17 50
Devise a synthesis of p-nitro-t-butylbenzene from benzene.
To make p-nitro-t-butylbenzene, we would first use a Friedel–Crafts reaction to make t-butylbenzene.
Nitration gives the correct product. If we were to make nitrobenzene first, the Friedel–Crafts reaction to
add the t-butyl group would fail.
Solved Problem 2
Solution
51. Chapter 17 51
Friedel–Crafts Acylation
Acyl chloride is used in place of alkyl chloride.
The product is a phenyl ketone that is less
reactive than benzene.
52. Chapter 17 52
Mechanism of Acylation
Step 1: Formation of the acylium ion.
Step 2: Electrophilic attack to form the sigma complex.
53. Chapter 17 53
Clemmensen Reduction
The Clemmensen reduction is a way to
convert acylbenzenes to alkylbenzenes by
treatment with aqueous HCl and
amalgamated zinc.
54. Chapter 17 54
Nucleophilic Aromatic
Substitution
A nucleophile replaces a leaving group on the
aromatic ring.
This is an addition–elimination reaction.
Electron-withdrawing substituents activate the
ring for nucleophilic substitution.
55. Chapter 17 55
Mechanism of Nucleophilic
Aromatic Substitution
Step 1: Attack by hydroxide gives a resonance-stabilized complex.
Step 2: Loss of chloride gives the product. Step 3: Excess base deprotonates the product.
56. Chapter 17 56
Activated Positions
Nitro groups ortho and para to the halogen
stabilize the intermediate (and the transition
state leading to it).
Electron-withdrawing groups are essential for
the reaction to occur.
57. Chapter 17 57
Benzyne Reaction: Elimination-
Addition
Reactant is halobenzene with no electron-
withdrawing groups on the ring.
Use a very strong base like NaNH2.
58. Chapter 17 58
Benzyne Mechanism
Sodium amide abstract a proton.
The benzyne intermediate forms when the bromide is
expelled and the electrons on the sp2
orbital adjacent
to it overlap with the empty sp2
orbital of the carbon
that lost the bromide.
Benzynes are very reactive species due to the high
strain of the triple bond.
60. Chapter 17 60
Chlorination of Benzene
Addition to the
benzene ring may
occur with excess of
chlorine under heat
and pressure.
The first Cl2 addition is
difficult, but the next
two moles add rapidly. An insecticide
61. Chapter 17 61
Catalytic Hydrogenation
Elevated heat and pressure is required.
Possible catalysts: Pt, Pd, Ni, Ru, Rh.
Reduction cannot be stopped at an
intermediate stage.
CH3
CH3
Ru, 100°C
1000 psi3H2,
CH3
CH3
62. Chapter 17 62
Birch Reduction
H
H
H
H
H
H
Na or Li
NH3 (l), ROH
H
H
H
H
H
H
H
H
This reaction reduces the aromatic ring to a
nonconjugated 1,4-cyclohexadiene.
The reducing agent is sodium or lithium in a
mixture of liquid ammonia and alcohol.
65. Chapter 17 65
Side-Chain Oxidation
Alkylbenzenes are oxidized to benzoic acid by
heating in basic KMnO4 or heating in Na2Cr2O7/H2SO4.
The benzylic carbon will be oxidized to the carboxylic
acid.
CH2CH3
(or Na2Cr2O7, H2SO4 , heat)
CO2H
KMnO4, NaOH
H2O, 100oC
66. Chapter 17 66
Side-Chain Halogenation
CH2CH3
Br2 or NBS
hν
CHCH3
Br
The benzylic position is the most reactive.
Br2 reacts only at the benzylic position.
Cl2 is not as selective as bromination, so
results in mixtures.
69. Chapter 17 69
SN2 Reactions
Benzylic halides are
100 times more
reactive than
primary halides via
SN2.
The transition state
is stabilized by a
ring.
70. Chapter 17 70
Oxidation of Phenols
Na2Cr2O7
H2SO4
OH
Cl
O
Cl
O
2-chloro-1,4-benzoquinone
Phenol will react with oxidizing agents to produce
quinones.
Quinones are conjugated 1,4-diketones.
This can also happen (slowly) in the presence of air.