PHENANTHRENE
• Phenanthrene is a polycyclic aromatic hydrocarbon composed of three fused benzene rings.
• In its pure form, it is found in cigarette smoke and is a known irritant, photosensitizing skin to
light.
• Phenanthrene appears as a white powder having blue fluorescence. Phenanthrene is the
backbone of morphine.
Resonance structure of phenanthrene:
• Like anthracene, phenanthrene is a planar molecule.
• All fourteen carbon atoms are sp2 hybridized.
• The sp2 orbitals overlap with each other and with s orbitals of ten hydrogen atoms to C-Cand
C-H σ bonds.
• Each carbon atom also possesses a p orbital and these are perpendicular to theplane
containing the bonds.
• The lateral overlap of these p orbital produces a π molecular orbital containing ten electrons.
• Phenanthrene shows aromatic properties because the resulting π molecular orbital satisfies the
Huckel`s rule (n=3 in 4n+2).
• Resonance energy=92Kcal/mole.
• Phenanthrene exist in following 5 resonance forms
Preparation of phenanthrene:
(I) Haworth phenanthrene synthesis:
(II) Pschor phenanthrene synthesis:
Reaction of phenanthrene:
1. Reduction: Phenanthrene undergoes reduction with sodium and isopentanol to form 9,10-
dihydrophenanthrene.
Na / C5H11OH
phenanthrene 9,10-dihydrophenanthrene
2. Oxidation: Phenanthrene undergoes oxidation with K2Cr2O7 and Sulphuric acid to form 9,10-
phenanthroquinone which on further oxidation with H2O2 and CH3COOH forms Diphenic acid
O O
HOOC COOH
K2Cr2O 7 H2O 2
H2SO 4 CH3COOH
phenanthrene 9,10 - phenantraquinone Diphenic acid
3. Reaction with Halogens: Phenanthrene react with chlorine in CCl4 to form 9,10 dichloro-9,10-
dihydrophenanthrene. Which on heating loses hydrogen chloride to form 9-bromo phenanthrene
Cl Cl Cl
Cl 2
- HCl
CCl 4
phenanthrene 9,10-dichloro-9,10-dihydrophenanthrene 9-chlorophenanthrene
4. Friedal crafts acylation: Phenanthrene undergoes acylation with acetyl chloride in
presence of AlCl3 to give 9- acetyl phenanthrene.
CH3
O
CH3COCl / AlCl 3
-
phenanthrene 9 acetyl phenanthrene
5. Nitration: Phenanthrene undergoes nitration with conc. Nitric acid and Sulphuric acid to
yield 9-nitrophenanthrene.
O 2N
HNO 3 / H2SO4
phenanthrene 9-nitrophenanthrene
6. Sulphonation: Phenanthrene undergoes Sulphonation with Sulphuric acid at 1200c to
yield mixture of 2-phenanthrene sulphonic acid and 3-phenanthrene sulphonic acid.
H2SO 4
SO 3H
0
120 C
SO 3H
phenanthrene phenanthrene-3-sulfonic acid
phenanthrene-2-sulfonic acid
7. Electrophilic addition versus electrophilic substitution
• The reactivity of the 9- and 10-positions toward electrophilic attack, whether reaction leads to
substitution or addition, is understandable since the initially formed carbocation is the most
stable one, in which aromatic sextets are preserved in two of the three rings.
This carbocation can then either (a) give up a proton to yield the substitution product, or (b)
accept a nucleophile to yield the addition product.
• The tendency for these compounds to undergo addition is due to the comparatively small
sacrifice in resonance energy (12 kcal/ mol for anthracene, 20 kcal/ mol or less for
Phenanthrene).
• Phenanthrene
• Anthracene
Derivatives of phenanthrene:
Medicinal uses of phenanthrene:
1. Anthraquinone is used in the manufacture of alizarin and several other dyes.
2. Dithranol antifungal
3. Steroid moiety contain phenanthrene nucleus.
4. Sex hormones and bile acids.
5. Steroid used as oral contraceptive and anti-inflammatory
6. Cardiac glycosides, morphine, codeine
Diphenylmethane
• Diphenylmethane is an organic compound with the formula(C6H6)2CH2 abbreviated by
(CH2Ph2).
• Thecompound consists of methane where in two hydrogen atoms are replaced by two phenyl
groups. It is a white solid.
Diphenylmethane
Preparation of diphenylmethane:
1. From benzene and benzyl chloride
2. Reduction of Benzophenone
Derivatives of diphenyl methane:
Medicinal uses of diphenylmethane
1.Diphenylmethane is widely used in the synthesis of luminogens for aggregation induced emission.
2.Diphenylmethyl potassium used in the preparation of polymerization.
Triphenylmethane
• Triphenylmethane (C6H6)3CH is the chromogen of a large number of dyes.
• The common chromophore is the p-quinoid structure and the auxochromes are OH,NH2 and
NR2.
• Triphenylmethane dyes are very brilliant intense colors but fade quickly in light.
• Therefore, they are no longer much used on textiles.
• However, they are used in large quantities for coloring paper and typewriter ribbons where
pastness to light is not so important.
Preparation of triphenylmethane:
1. From benzene and chloroform
Derivatives of triphenylmethane:
Medicinal uses of Triphenyl methane
1. Crystal violet used as preparation of detergents , fertilizers, textile dye.
2. Triphenylmethane is used in copying papers, in hectograph and printing inks.
