BENZENE its Aromaticity M ARULSELVAN Syllabus Benzene and

BENZENE & its Aromaticity M. ARULSELVAN

Syllabus Benzene and Aromaticity 4. 1 Concept of aromaticity: -Huckel's rule for aromaticity, -identification of aromatic, -Non-aromatic and anti aromatic systems based on planarity, conjugation and Huckel's rule.

Syllabus 4. 2 Electrophilic Aromatic Substitution: -Reactions of benzene (with mechanism and structures of intermediate/s involved) like -nitration, -sulphonation, -protonation, -halogenations, -Friedel‐Crafts alkylation and Acylation. -Classification and influence of substituent groups on orientation and reactivity, orientation in disubstituted benzenes.

Syllabus 4. 3 Nucleophilic Aromatic Substitution: -Bimolecular displacement mechanism with evidence, -Reactivity and orientation in -Nucleophilic aromatic substitution, -Elimination ‐Addition mechanism.

Benzene • Benzene (C 6 H 6) is the simplest aromatic hydrocarbon (or arene). • Benzene has four degrees of unsaturation, making it a highly unsaturated hydrocarbon. • Whereas unsaturated hydrocarbons such as alkenes, alkynes and dienes readily undergo addition reactions, benzene does not. 5

The Criteria for Aromaticity—Hückel’s Rule Four structural criteria must be satisfied for a compound to be aromatic. [1] A molecule must be cyclic. To be aromatic, each p orbital must overlap with p orbitals on adjacent atoms. 6

[2] A molecule must be planar. All adjacent p orbitals must be aligned so that the electron density can be delocalized. Since cyclooctatetraene is non-planar, it is not aromatic, and it undergoes addition reactions just like those of other alkenes. 7

[3] A molecule must be completely conjugated. Aromatic compounds must have a p orbital on every atom. 8

[4] A molecule must satisfy Hückel’s rule, and contain a particular number of electrons. Hückel's rule: Benzene is aromatic and especially stable because it contains 6 electrons. Cyclobutadiene is antiaromatic and especially unstable because it contains 4 electrons. 9

Note that Hückel’s rule refers to the number of electrons, not the number of atoms in a particular ring. 10

Considering aromaticity, a compound can be classified in one of three ways: 1. Aromatic—A cyclic, planar, completely conjugated compound with 4 n + 2 electrons. 2. Antiaromatic—A cyclic, planar, completely conjugated compound with 4 n electrons. 3. Not aromatic (nonaromatic)—A compound that lacks one (or more) of the following requirements for aromaticity: being cyclic, planar, and completely conjugated. 11

Note the relationship between each compound type and a similar open-chained molecule having the same number of electrons. 12

Examples of Aromatic Rings • Completely conjugated rings larger than benzene are also aromatic if they are planar and have 4 n + 2 electrons. • Hydrocarbons containing a single ring with alternating double and single bonds are called annulenes. • To name an annulene, indicate the number of atoms in the ring in brackets and add the word annulene. 13

• [10]-Annulene has 10 electrons, which satisfies Hückel's rule, but a planar molecule would place the two H atoms inside the ring too close to each other. Thus, the ring puckers to relieve this strain. • Since [10]-annulene is not planar, the 10 electrons can’t delocalize over the entire ring and it is not aromatic. 14

• Two or more six-membered rings with alternating double and single bonds can be fused together to form polycyclic aromatic hydrocarbons (PAHs). • There are two different ways to join three rings together, forming anthracene and phenanthrene. • As the number of fused rings increases, the number of resonance structures increases. Naphthalene is a hybrid of three resonance structures whereas benzene is a hybrid of two. 15

Which of these is aromatic? A) Is aromatic. Count the number of pi bonds in the outer ring. A has 5 which means 10 pi electrons, 4(2)+2=10. While B has 6 pi bonds and 12 pi electrons, 4(3)=12. Doesn’t meet the Huckel rule requirements for aromaticity. 16

Is this compound aromatic or antiaromatic? Antiaromatic – cyclic, planar, conjugated , but does not meet Huckel’s rule. 4 doulbe bonds and 2 triple bonds so 4(2) + 2(4)=16 pi electons. 4 n+2 or 4 n? 4(4)=16 17

Indicate which of the following are aromatic and antiaromatic? C is aromatic 4(3)+2=14 A is antiaromatic 4(2)=8 18

Which of the following is aromatic? C is aromatic 10 pi electrons, 4(2)+2=10 and completely conjugated b/c lone pair is in a p orbital. Which are antiaromatic? 19

Which of these is antiaromatic? B 8 pi electrons 4(2)=8 C and D as well, 8 and 4 respectively 20

Physical Properties • Melting points: More symmetrical than corresponding alkane, pack better into crystals, so higher melting points. • Boiling points: Dependent on dipole moment, so ortho > meta > para, for disubstituted benzenes. • Density: More dense than nonaromatics, less dense than water. • Solubility: Generally insoluble in water.

4. 2 Electrophilic Aromatic Substitution Electrophile substitutes for a hydrogen on the benzene ring. Chapter 17 22

Mechanism Step 1: Attack on the electrophile forms the sigma complex. Step 2: Loss of a proton gives the substitution product. Chapter 17 23

Nitration of Benzene 24

Sulfonation of Benzene Chapter 15 25

Sulfonation of Benzene 26

Halogenations of Benzene 27

Halogenations of Benzene 28

Nitration of Toluene • Toluene reacts 25 times faster than benzene. The methyl group is an activating group. • The product mix contains mostly ortho and para substituted molecules. Chapter 17 29

Sigma Complex Intermediate is more stable if nitration occurs at the ortho or para position. => Chapter 17 30

Energy Diagram Chapter 17 31

Activating, O-, P-Directing Substituents • Alkyl groups stabilize the sigma complex by induction, donating electron density through the sigma bond. • Substituents with a lone pair of electrons stabilize the sigma complex by resonance. 32

Substitution on Anisole 33

The Amino Group Aniline, like anisole, reacts with bromine water (without a catalyst) to yield the tribromide. Sodium bicarbonate is added to neutralize the HBr that’s also formed. 34

Summary of Activators 35

Deactivating Meta-Directing Substituents • 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. • Meta-directors deactivate all positions on the ring, but the meta position is less deactivated. 36

Ortho Substitutionon Nitrobenzene 37

Para Substitution on Nitrobenzene 38

Meta Substitution on Nitrobenzene 39

Energy Diagram Chapter 17 40

Structure of Meta-Directing Deactivators • The atom attached to the aromatic ring will have a partial positive charge. • Electron density is withdrawn inductively along the sigma bond, so the ring is less electron-rich than benzene. 41

Summary of Deactivators 42

More Deactivators 43

Halobenzenes • Halogens are deactivating toward electrophilic substitution, but are ortho, para-directing! • Since halogens are very electronegative, they withdraw electron density from the ring inductively along the sigma bond. • But halogens have lone pairs of electrons that can stabilize the sigma complex by resonance. 44

Sigma Complex for Bromobenzene Ortho and para attacks produce a bromonium ion and other resonance structures. No bromonium ion possible with meta attack. 45

Energy Diagram Chapter 17 46

Summary of Directing Effects 47

Multiple Substituents The most strongly activating substituent will determine the position of the next substitution. May have mixtures. 48

Friedel-Crafts Alkylation • Synthesis of alkyl benzenes from alkyl halides and a Lewis acid, usually Al. Cl 3. • Reactions of alkyl halide with Lewis acid produces a carbocation which is the electrophile. • Other sources of carbocations: alkenes + HF, or alcohols + BF 3. 49

Examples of. Carbocation Formation 50

Formation of Alkyl Benzene + 51

Limitations of Friedel. Crafts • Reaction fails if benzene has a substituent that is more deactivating than halogen. • Carbocations rearrange. Reaction of benzene with n-propyl chloride and Al. Cl 3 produces isopropylbenzene. • The alkylbenzene product is more reactive than benzene, so polyalkylation occurs. 52

Friedel-Crafts. Acylation • Acyl chloride is used in place of alkyl chloride. • The acylium ion intermediate is resonance stabilized and does not rearrange like a carbocation. • The product is a phenyl ketone that is less reactive than benzene. 53

Mechanism of Acylation 54

Nucleophilic Aromatic Substitution • Aryl halides with electronwithdrawing substituents ortho and para react with nucleophiles • Form addition intermediate (Meisenheimer complex) that is stabilized by electron-withdrawal • Halide ion is lost to give aromatic ring 55

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. 56

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. 57

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. 58

Benzyne Reaction: Elimination. Addition • Reactant is halobenzene with no electronwithdrawing groups on the ring. • Use a very strong base like Na. NH 2. 59

Benzyne Mechanism • Sodium amide abstract a proton. • The benzyne intermediate forms when the bromide is expelled and the electrons on the sp 2 orbital adjacent to it overlap with the empty sp 2 orbital of the carbon that lost the bromide. • Benzynes are very reactive species due to the high strain of the triple bond. 60

Nucleophilic Substitution on the Benzyne Intermediate 61

Q. P 1 Mark: a) Complete the following reactions 2 Marks: a) Explain how does the –NH 2 group in C 6 H 5 NH 2 influence the orientation of the benzene ring towards electrophilic aromatic substitution b) Mechanism for Nitration of Benzoic acid 62

Q. P c) Explain how –OCH 3 groups behaves as ortho, para director in Electrophilic Substitution reaction? d) Write the mechanism of sulphonation of toluene ? e) Identify A, B in the given reaction 3 Marks: a) Explain in detail about Mechanism for Nucleophilic Subsitution Reaction of benzene? * b) Briefly discuss the Elimination Addition mechanism for Nucleophilic Aromatic substitution. Give two evidence to support the same? c) Identify A, B, C in the given reaction 63

Q. P 4 Marks: a) Identify Aromatic/Non Aromatic/Anti-Aromatic 64