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Wurtz-Fittig reaction
Equal moles of aryl halide and alkyl halide dissolved in dry ether when reacts with Na
+ 2NaCl
dry ether
R-R + 2NaX
When phenyl magnesium bromide/iodide reacts with methyl bromide/iodide in dry ether produces toluene
MgBr Dry ether + CH3Br CH3 + MgBr2
Friedel-Crafts Alkylation
In Friedel-Crafts alkylation, treatment of benzene with an alkyl halide and a Lewis acid (AlCl3) forms an alkyl benzene( when R = -CH3, toluene forms)
CH3 + CH3Cl Anh AlCl3
CH3 H3PO2
CH3
N=NCl
Physical properties
1.Insoluble in water
4.Used as solvent
Chemical properties-chlorination
Cl
p-chloro toluene
Ring chlorination should be done at ordinary temperature in pr of halogen carrier I2 or anh AlCl3 7 or FeCl3 of Fe dust
Bromination
CH3 Br +
CH3
Br
Sidechain chlorination
CCl3
Benzyl chloride on hydrolysis gives benzylalcohol, benzalcloride gives benzaldehyde and benzo tri chloride gives benzoic acid.
CH2Cl + NaOH CH2OH
CHO
- H 2O
COOH
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CH2Br
11
Nitration of toluene
NO2
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Preparation of TNT
Sulphonation
Heat
SO3H
Ortho product predominates at lower temp but para product predominates at higher temperature.
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Oxidation of toluene
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Oxidation of toluene
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Oxidation of toluene
CH3
+ MnSO4 + H2O
If acid is concentrated and temperature is high , the product of the above reaction will be benzoic acid.
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Oxidation of toluene
K2Cr2O7 + H2SO4
We can also use air passed over V2O5(cat) at 3000C with 19 toluene vapour produces benzoic acid
Hydrogenation of toluene
CH3
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preparation of chlorobenzene
In presence of Fe or FeCl3 at ordinary temperature, benzene reacts with chlorine gas to form chlorobenzene
Cl Cl2 Fe or FeCl3 + HCl
In industry, chlorobenzene is prepared by passing a mixture of benzene vapour, HCl and air over Cu2O as catalyst at 2500C
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Benzene diazonium chloride disolved in HCl when heated with cuporus chloride produces chlorobenzene
NH2 NaNO3+ HCl 00C N=N-Cl CuCl/HCl Cl + N2 + HCl
Other preparations:
OH + PCl5
Cl + POCl3 + HCl
Cl + HOCl H+ + H2O
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The Low Reactivity of Halobenzenes The p orbital on the carbon atom of the benzene ring side-way overlaps with the p orbital of halogen atom form a delocalized bonding system
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The Low Reactivity of Halobenzenes The CX bond of halobenzenes is stronger than that of haloalkanes partial bond character Breaking of the CX bond requires a larger amount of energy substitution reactions of halobenzenes are difficult to occur
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Replacement by OH group
At 3000C and 300 atm pressure chlorobenzene reacts with NaOH to form sodium phenate which on acidification produces phenol
Cl + 2NaOH 3000C 300 atm ONa dil HCl OH
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Cl
NH2.HCl NaOH
NH2
+ 2NH3
+ CuCl
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Nitration reaction
At 1000C chlorobenzene react with a mixture of conc HNO3 and conc H2SO4 to form a mixture of o-and pchloronitrobenzene
Cl conc HNO3 conc H2SO4 1000C NO2 Cl NO2 + Cl
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Cl Cl +
Cl
600C
O- and p- chlorobenzene sulphonic acid
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COCH3
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Preparation of DDT
DDT is produced when a mixture of chlorobenzene and chloral is heated with conc H2SO4
Cl H 2 + O=C-CCl3 Cl H C CCl3
Cl DDT
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Preparation of biphenyl
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Wurtz-Fittig reaction
Equal moles of aryl halide and alkyl halide dissolved in dry ether when reacts with Na
+ 2NaCl
ether medium CO2 H3O+ C6H5COOH CH3CN H3O+ C6H5COCH3 CH3CHO H3O
+
O CH2
+ ,H3O CH2
C6H5-CH OH CH3
C6H5CH2CH2OH
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Lab method
Nitrobenzene is obtained by the action of a mixture of Conc HNO3 and conc H2SO4 on benzene at 50-600C. At
+ H2O
In place of nitrating mixture,we can use (a) conc HNO3 of sp gr 1.5 (b)Fuming nitric acid( containing 6-12% NO2) (c) Nitronium tetrafluoroborate ( NO2+BF4-) (d) Acetyl nitrate ( CH3COONO2)
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Other preparation
C6H5N=N-Cl
HNO2 Cu2O
C6H5NO2
HBF4
C6H5N2+BF4-
C6H5NO2
C6H5NH2 + 3CF3COOOH
C6H5NO2 + 3CF3COOH
Chemical properties
Nitrobenzene is very stable compound not easily attacked by acids or alkalis but it is easily reduced.
nucleus
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Nitrobenzene when heated with Sn or Zn with conc HCl or Fe dust + conc HCl or SnCl2/HCl, it is reduced to
aniline.
NH2 Sn /HCl(C) + 2H2O
NO2
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Nitrobenzene when warmed with powdered Zn and NaOH( in methanol) converted to azoxy benzene.
NO2 + O 2N Zn methanolic NaOH + N=N O
Azoxy benzene is further reduced to azobenzene with conc methanolic NaOH solution
+ N=N O
Zn methanolic NaOH
N=N
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Nitrobenzene is reduced to hydrazo benzene when treated with Zn dust and hot aq NaOH solution
NO2 +
O2N
HH Zn aq NaOH N- N
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Nitrobenzene is reduced to phenyl hydroxylamine when it is warmed with Zn dust and an aq solution of
NHOH + H2O
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The presence of NO2 can be confirmed using this test.The compound is heated with Zn + 50% aq ethanolic solution of NH4Cl.After cooling it is reacted with Tollens reagent and formation of grey or black ppt of metallic Ag confirms NO2 gr.
NO2 Zn NH4Cl NHOH + H2O
Other reductions :
NO2 Catalytic hydrgenation : raney Ni + H2 heat + 2H2O NH2
NH2
NO2 + 4H+ + 4e
NHOH
OH
46 p-aminophenol
Selective reduction
If we want to reduce one nitro gr of m-dinitrobenzene, the reducing agent to be used : NH4HS or aq Na2S or
NO2
NH2 m-nitroaniline
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Substitution reactions
NO2 Cl2 Fe powder NO2 Br2 Fe Br NO2 conc HNO3 conc H2SO4 900C fuming sulphuric acid heat SO3H
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NO2
Cl
NO2 NO2
Nucleophilic substitution
NO2 OH +
NO2
OH
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