Chapter 14

Br Bensene ; C 6H6 C6H5Y 1 isomer Br Br Br

C6H4XY 3 isomer

Hhydrogenation, Hcomb for Benzene are lower than expected (~ 36 kcal/mole) Fig 14.1

substitution rxn rather than addition rxn (Table on p497)

C C ; 1.34 A C C in CH3CH3 ; 1.53 A in CH3CH=CH 2 ; 1.50 A in CH2=CHCH=CH 2 ; 1.48 A all C C in benzene ; 1.39 A resonance energy = 36 kcal/mol hybrid of &

aromatic properties sp2 sp2 bond sp2 s bond H

substitution rather than addition to retain the ring system

6 eletrons are delocalized.

electrons are loosely held

electrophilic substitution

aromatic character ? experimentally

a high degree of unsaturation electrophilic sybstitution rxn insted of addition rxn. low Hhydrogenation , low Hcomb cyclic, flat.

theorerically

cyclic clouds of delocalized p electrons above and below the molecular plane (4n + 2) electrons 4n + 2 rule or Huckel rule ex) benzene 6 electrons (aromatic sextet)

II

III III & IV have unsually high stability.

IV

VI

p ka = 15

p ka = 45

Br
+

behave like R Br

m.p.

200 C

Fe

electrophilic substitution rxn

water soluble insoluble in nonpolar solvent + AgNO3(aq)

AgBr

108

128.5

a small deviation from 120o (a small angle strain)

good overlap of p orbitals How about 2, 10, 14 ... electrons ? not as stable as bezene due to angle strain or poor overap of p orbitals but more stable than their relatives.

aromaticity X NO2 CH3 NH2 OH

halobenzene

nitrobenzene

toulene

aniline

phenol

COOH

SO3H

Br

ortho ; o-dibromobenzene metha ; m-dibromobenzene para ; p-dibromobenzene Br

benzoic acid CH3 O2N

benzenesulfonic acid

NO2

2,6-dinitrotoluene

Polynuclear aromatic hydrocarbon

8 7 6 5

2 3

anthracene phenanthrene

naphthalene

electrophilic substitution rather than addition rxn Hcomb : 61 kcal lower, cyclic, flat 6 electrons 2 a pair is shared 10 electrons

diamond : polycyclic aliphatic graphite : planar (CC : 1.42 A , layers : 3.4 A , lubricant) C60 (buckminster)fullerene : 20 6-membered rings + 12 5-membered rings Quantitative elemental analysis for N ; Dumas method (N) CuO Cu N2 OH

Kjeldahl method

(N)

conc. H2SO4 H2O2 or HNO3

(NH4)2SO4

NH3

for S ;

Carius method

(S)

SO4

BaSO4