Kuliah Aromatis 1

senyawa bensena atau senyawa yang mempunyai sifat kimia seperti bensena.
Benzene is a colorless compound, m.p. 6o C and b.p. 80o C, discovered in 1825 by Michael Faraday.
It is a six membered ring, with the formula C6H6 indicating three double bonds and a ring. The structure of benzene was a puzzle for chemists in the 19th century as its formula indicated a high degree of saturation, like alkenes. However, it did not give addition reactions as did alkenes.
The first structure of benzene was proposed by August Kekul in 1865. He proposed that benzene was composed of three double bonds in a six-membered ring. These double bonds, he hypothesized, shift back and forth rapidly such that the two possible forms cannot be separated.
Theorie of the Structure of Benzene

Benzene
Structures I and II are equal resonance contributors to the real structure of benzene
The Resonance Explanation of the Structure of
Benzene is particularly stable because it has two equivalent and important resonance structures Each carbon-carbon bond is 1.39 , which is between the length of a carbon-carbon single bond (1.47) and a carbon-carbon double bond (1.33 ) Often the hybrid is represented by a circle in a hexagon (III)
Benzene is much more stable than would be expected based on calculations for cyclohexatriene
THE STABILITY OF BENZENE
A reasonable prediction for the heat of hydrogenation of hypothetical cyclohexatriene is -360 kJ mol-1 (3 times that of cyclohexene, -120 kJ mol-1 )
The experimentally determined heat of hydrogenation for benzene is -280 mol-1, 152 kJ mol-1 more stable than hypothetical cyclohexatriene This difference is called the resonance energy
KESTABILAN BENSENA
Tidak seperti senyawa-senyawa yang mengandung ikatan rangkap lainnya, bensena lebih mudah mengalami reaksi substitusi daripada adisi. Hal ini dapat dilihat dari data berikut.
Reagen KMnO4 encer Sikloheksena Terjadi Oksidasi, cepat Bensena Tidak bereaksi
Br2/CCl4 (dlm gelap) HI H2 + Ni
Terjadi Adisi, cepat
Tidak bereaksi
Terjadi Adisi, cepat Terjadi hidrogenasi, 25oC, 20 lb/in.2
Tidak bereaksi Terjadi hidrogenasi, lambat, 100-200oC, 1500 lb/in.2
Hckels criteria for aromaticity are as follows:

1. The compound must be cyclic. 2. It must have one p orbital on each atom of the ring. 3. It should be planar or nearly planar so that there is continuous or nearly continuous overlap of all p orbitals. 4. It must have a closed loop of (4n+2) p electrons in the cyclic arrangement of p orbitals.
Note: n adalah bilangan bulat
AROMATISITAS MENURUT ATURAN HUCKEL

H H H H H H
H H
H H
H H
Kation siklopentadienil 4 elektron p
Radikal siklopentadienil 5 elektron p
Anion siklopentadienil 6 elektron p Aromatis H H H H H H
H H
H H H
H H
H H H
H H H
Kation sikloheptatrienil 6 elektron p Aromatis
Radikal sikloheptatrienil 7 elektron p
Anion sikloheptatrienil 8 elektron p
TATANAMA DERIVAT BENSENA

1. menambahkan awalan gugus substituen diikuti nama bensena, misal : klorobensena, bromobensena, nitrobensena, dll 2. beberapa derivat bensena mempunyai nama spesifik yang mungkin tidak menunjukkan nama dari substituen yang terikat pada bensena, misal : metilbensena dikenal sebagai toluene, aminobensena sebagai aniline, dll 3. Apabila bensena mengikat lebih dari satu substituen, maka nama substituen dan letak substituen harus dituliskan. Ada 3 (tiga) isomer yang mungkin untuk bensena yang tersubstitusi oleh 2 gugus. Penamaan digunakan nama orto (1,2-); meta (1,3-); para (1,4-) 4. Apabila 2 atau lebih substituen yang terikat pada bensena berbeda, maka penamaannya diawali dengan nama substituen berturut-turut dan diikuti dengan nama bensena atau diberi nama khusus/spesifik.
In molecules containing other functional groups, the phenyl group and others are named as substituents.
CH3 benzene phenyl group, Phtoluene H2 C benzyl group, Bn-
ELECTROPHILIC AROMATIC SUBSTITUTION

The characteristic reaction of benzene is electrophilic aromatic substitutiona hydrogen atom is replaced by an electrophile.
Benzene does not undergo addition reactions like other unsaturated hydrocarbons, because addition would yield a product that is not aromatic. Substitution of a hydrogen keeps the aromatic ring intact.
Reaction Coordinate Diagrams for the Two Benzene Reactions
All electrophilic aromatic substitution reactions occur by the same two-step mechanism :
1. addition of the electrophile E+ to form a resonance-stabilized carbocation 2. followed by deprotonation with base, as shown below:
H Y+ + H Y Y H Y
slow
B: fast
-H+
Y
The energy changes in electrophilic aromatic substitution are shown below:
HALOGENATION
In halogenation, benzene reacts with Cl2 or Br2 in the presence of a Lewis acid catalyst, such as FeCl3 or FeBr3, to give the aryl halides chlorobenzene or bromobenzene respectively. Analogous reactions with I2 and F2 are not synthetically useful because I2 is too unreactive and F2 reacts too violently.
Chlorination proceeds by a similar mechanism.
NITRATION and SULFONATION

Nitration and sulfonation introduce two different functional groups into the aromatic ring. Nitration is especially useful because the nitro group can be reduced to an NH2 group.
Generation of the electrophile in both nitration and sulfonation requires strong acid.
Friedel-Crafts Alkylation and Friedel-Crafts Acylation

In Friedel-Crafts alkylation, treatment of benzene with an alkyl halide and a Lewis acid (AlCl3) forms an alkyl benzene.
In Friedel-Crafts acylation, a benzene ring is treated with an acid chloride (RCOCl) and AlCl3 to form a ketone. Because the new group bonded to the benzene ring is called an acyl group, the transfer of an acyl group from one atom to another is an acylation.
In Friedel-Crafts acylation, the Lewis acid AlCl3 ionizes the carbon-halogen bond of the acid chloride, thus forming a positively charged carbon electrophile called an acylium ion, which is resonance stabilized.
The positively charged carbon atom of the acylium ion then goes on to react with benzene in the two step mechanism of electrophilic aromatic substitution.
Three additional facts about Friedel-Crafts alkylation should be kept in mind.

Vinyl halides and aryl halides do not react
Rearrangements can occur (rearrangement of carbocation)
Other functional groups that form carbocations can be used as starting materials : ALKENES & ALCOHOLS
[1]
Vinyl halides and aryl halides do not react in Friedel-Crafts alkylation.
[2]
Rearrangements can occur.
Rearrangements can occur even when no free carbocation is formed initially.
These results can be explained by carbocation rearrangements.
[3] Other functional groups that form carbocations can also be used as starting materials.
Starting materials that contain both a benzene ring and an electrophile are capable of intramolecular Friedel-Crafts reactions.

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senyawa bensena atau senyawa yang mempunyai sifat kimia seperti bensena.

Theorie of the Structure of Benzene

The Resonance Explanation of the Structure of

THE STABILITY OF BENZENE

Br2/CCl4 (dlm gelap) HI H2 + Ni

Terjadi Adisi, cepat

Terjadi Adisi, cepat Terjadi hidrogenasi, 25oC, 20 lb/in.2

Tidak bereaksi Terjadi hidrogenasi, lambat, 100-200oC, 1500 lb/in.2

Hckels criteria for aromaticity are as follows:

AROMATISITAS MENURUT ATURAN HUCKEL

Kation siklopentadienil 4 elektron p

Radikal siklopentadienil 5 elektron p

Anion siklopentadienil 6 elektron p Aromatis H H H H H H

Kation sikloheptatrienil 6 elektron p Aromatis

Radikal sikloheptatrienil 7 elektron p

Anion sikloheptatrienil 8 elektron p

TATANAMA DERIVAT BENSENA

ELECTROPHILIC AROMATIC SUBSTITUTION

Reaction Coordinate Diagrams for the Two Benzene Reactions

The energy changes in electrophilic aromatic substitution are shown below:

Chlorination proceeds by a similar mechanism.

NITRATION and SULFONATION

Friedel-Crafts Alkylation and Friedel-Crafts Acylation

Three additional facts about Friedel-Crafts alkylation should be kept in mind.

Vinyl halides and aryl halides do not react in Friedel-Crafts alkylation.

Rearrangements can occur.

Rearrangements can occur even when no free carbocation is formed initially.

These results can be explained by carbocation rearrangements.

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