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Prof.N.D.Phupate
 Phenols.
 Acidity of phenols.
 Effect of substituent
on acidity.
 Qualitative test.
 Structure and uses of
 Phenol
 Cresol
 Resorcinol
 Napthols
 Phenol are compound containing –OH group
attached directly to benzene ring.
 Differ from alcohol
 As like alcohol they may be mohydric or
polyhydric consist of formula C6H5OH.
 Methyl phenol given special name cresol.
 Phenol are classified as monohydric phenols
,dihydric phenols,trihydric phenols
 Monohydric Phenol:-
 Dihydric Phenol:-
 Trihydric Phenol:-
Hydro quinol pyrogallol Phloroglucinol
 Similar to alcohol
 Resonance interaction takes place between a lone
pair of electron on oxygen and benzene ring
 C-O bond acquires double bond become shorter
and stronger than C-O bond in alcohol
 O acquirs slight +ve charge due to which it attracts
electron pair in O-H bond become more polar than
alcohol
 Colourless liquid or solid ( red tint when
oxidation)
 Carbolic odour,slightly water soluble,
 B.P of Phenol higher than alcohol.
 Strong intermolecular H bonding.
 Extra OH group at Para position on ring
increase B.P
 Substitution at ortho position leads greater
vilocity (intramolecular H bonding)
 Dissolve in NaOH but not in Na2CO3.
 More acidic than alcohol but less than carboxylic
acid ,Phenol acidic due to formation of Phenoxide
ion in aq solution.
 -ve charge spread throughout benzene ring which
delocalizing factor in the phenoxide ion ,no
resonance possible for alkoxide ion (Pka 10,17
benzene)
 Stability of Phenoxide ion depends upon
stability of reactant and product
 Any factor which stabilize the phenoxide ion
more than phenol increase acidity & vice
versa
 Factor affecting substitution
A)Nature of substituent B)Position of substituent
1) Electron withdrawing substituent's
2) Electron releasing substituent's.
 Electron Withdrawing
group-
 No2, CN,-x(Cl,Br,I)on
arom. Ring acid
strength.
 Enable to withdraw
electron from phenoxy
oxy.
 Stabilize Phenoxide ion
result stroger acid.
 P-Nitrophenol more
stronger than phenol
 Electron realeasing
substituents-
 NH2,OH,R,CH3 on arom.
Ring acid strength
 This destabilize
Phenoxide ion result
weaker acid.
 P-Cresol less acidic than
phenol
 Electron withdrawing & releasing group more pronounced at
ortho and para position than meta ( resonance effect).
 P-nitrophenol>o-nitro phenol>m-nitro phenol
 m-cresol>P-cresol>o-cresol
Qualtative test:-
 Formation of salt:-
C6H5OH + NaOH C6H5ONa + H2O
2[C6H5OH] + 2Na 2[C6H5ONa] + H2
Phenol weaker acid than carboxylic acid (no reaction with
Na2CO3,NaHCO3)
 Reaction With FeCl3:-
3[C6H5OH] + FeCl3 Fe3+ [C6H5O]3 purple complex.
Phenol, Sulphur salicylic acid , water soluble.
2-Napthol, Salicylic acid ,Gallic acid are water ethanol soluble.
2-Napthol- green, Gallic-black, Salicylic acid- violet 1,2,3
hydroxy benzene –brown colour
c
c
c
 Libermon nitrous test
Initially get green/blue colour after dilution it become red and after addition of NaOH blue
colour reapers.
 Bromine water test
White ppt
 Litmus test
Weakly acidic in aqueous solution after application on litmus paper it leads blue litmus red.
 Reaction with zinc dust
 Reaction with ammonia
C6H5OH + NH3 Anhy.ZnCl3 C6H5NH2+ H2O
675K
 From chlorobenzene (Dow process)
 From cumene
 From diazonium salt
 From Grignard reagent
 From coal tar
C6H5OH + NaOH C6H5ONa + H2O
2[C6H5OH] + CO2 + H2O 2[C6H5OH] + Na2CO3
Reaction of Phenol:
Reaction on OH group
 Formation of ester (use aqueous alkali – phenyl ether)
C6H5OH + Na2CO3 C6H5ONa+CH3COCl C6H5OCOCH3
 Formation of ether:(s)(ethoxy benzene )
C6H5OH + NaOH C6H5ONa + CH3CH2Cl C6H5OCH2CH3
Reaction on benzene ring
 Halogenations:
C6H5OH + 3Br2 H2O 2,4,6 tribromo phenol +3HBr
 Nitration:
C6H5OH + dil HNO3 O & P nitrophenol
Con. HNO3 2,4,6 trinitrophenol (picric acid)
c
c
c c
c c
c
c
c
 Halogination
C6H5OH + 3H2 Cyclohexanol
 Sulphonation
C6H5OH + Conc.H2SO4 o-Phenol sulphonic acid(200c)
p-Phenol sulphonic acid(800c)
 With formaldehyde
Ni
433k
c
 Klobe reaction:
 With phthalic anhydride
 Reimer Thiemann reaction:
C6H5OH + CHCl3 + 3NaOH O & P hydroxybenzaldehyde
 Phenol- Colourless liquid or white solid at R.T.,highly
toxic caustic
 Uses-
 antiseptic in soap and lotion,
 cosmetic industry sunscreen, skin lightning, hair colouring
 cosmetic surgery exfoliate remove dead skin
 Manufacture of drug salicylic acid, aspirin (picric acid explo.)
 preservative ink, vaccine
 synthesis plastic ,backlite resin.
 Extraction of nucleic acid,
 High con.for ingrown tow, fingernail., herbicides detergent
nylons temporary for Pharyngitis.
 Cresols:-
 Structure:-
 Known methyl phenol,colourless expo in air yellow/brown red tint,similar
odour,three isomer(o,m,p) mixture of three -tricrisols . Extracted from coal
tar or synthetically by methylation high conc. Cause irritation ,burning throat,
vomiting, liver kidney.
 Uses-
 Synthetic intermediate for plastic,pestcide,p’ceutcal & dye
 O-Cresol on chlorination gives MCPA use herbicide.
 O-Cre. Synthesis of mephenesin ( muscle relaxant)
 P-Cre. Synthesis of BHT (antioxident)
 P-Cre synthesis of Bupranalol ( non selective beta blocker)
 Chlo.m –cre. use house hold disinfetant
 M-cre precursor for
vit E,preservative in Insulin,pesticide,amyl m-cre as
anticeptic,solvent for polymer.
 Resorcinol-
 Structure-
 Colourless,less water more alcohol, ether insoluble chloroform & CS2
 Undergoes nucleophilic electrophilic substitution,pink on exposure or
contact with iron,sweet test,on exposure irritation skin or mucous membrane
 Uses-
 Use as anticeptic,disinfectant
 2% solution for hay fever & in cough
 Use in antidandruff shampoo & cosmetic ( sunscreen)
 Treatment of gastric ulcer, bactericidal effect.
 Use reagent for ketoses determination, anticancer agent.
 Use for characterization of Zn,lead (colorimetric method)
 Use as preservative in cosmetic,ointment for psoriasis
 Use parent molecule for holding target molecule in proper
alignment.
 Napthols:-
 Structure:-
 Consist of two isomers 1 & 2
 Aromatic consist of alternate double single bond,Electronigitivity highly polar
 1 napthol-white,fluorescent soluble alcohol ether chloroform
 2 napthol-colourless or yellow rs
 Uses:-
 1napthol-molisch ingredient for carbohydrate.
 1n. Precursor for insecticide like carbonyl.
 1n. Is use to detect arginin in protin(Sakaguchi test)
 1n. Use to detect breakdown of glucose in acetoin ( Voges Proskauer
test)
 2n. Precursor for Sudan dye
 Use for synthesis of BINOL used as legand. Antiseptic in perfumes.
 2n. Synthesis of fungicide & antioxident for rubber
 Detection of 1& 2n. In urine for pesticide content in body.
phenol ppt 7718.pptx

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phenol ppt 7718.pptx

  • 2.  Phenols.  Acidity of phenols.  Effect of substituent on acidity.  Qualitative test.  Structure and uses of  Phenol  Cresol  Resorcinol  Napthols
  • 3.  Phenol are compound containing –OH group attached directly to benzene ring.  Differ from alcohol  As like alcohol they may be mohydric or polyhydric consist of formula C6H5OH.  Methyl phenol given special name cresol.  Phenol are classified as monohydric phenols ,dihydric phenols,trihydric phenols
  • 4.  Monohydric Phenol:-  Dihydric Phenol:-  Trihydric Phenol:- Hydro quinol pyrogallol Phloroglucinol
  • 5.  Similar to alcohol  Resonance interaction takes place between a lone pair of electron on oxygen and benzene ring  C-O bond acquires double bond become shorter and stronger than C-O bond in alcohol  O acquirs slight +ve charge due to which it attracts electron pair in O-H bond become more polar than alcohol
  • 6.  Colourless liquid or solid ( red tint when oxidation)  Carbolic odour,slightly water soluble,  B.P of Phenol higher than alcohol.  Strong intermolecular H bonding.  Extra OH group at Para position on ring increase B.P  Substitution at ortho position leads greater vilocity (intramolecular H bonding)  Dissolve in NaOH but not in Na2CO3.
  • 7.  More acidic than alcohol but less than carboxylic acid ,Phenol acidic due to formation of Phenoxide ion in aq solution.  -ve charge spread throughout benzene ring which delocalizing factor in the phenoxide ion ,no resonance possible for alkoxide ion (Pka 10,17 benzene)
  • 8.  Stability of Phenoxide ion depends upon stability of reactant and product  Any factor which stabilize the phenoxide ion more than phenol increase acidity & vice versa  Factor affecting substitution A)Nature of substituent B)Position of substituent 1) Electron withdrawing substituent's 2) Electron releasing substituent's.
  • 9.  Electron Withdrawing group-  No2, CN,-x(Cl,Br,I)on arom. Ring acid strength.  Enable to withdraw electron from phenoxy oxy.  Stabilize Phenoxide ion result stroger acid.  P-Nitrophenol more stronger than phenol  Electron realeasing substituents-  NH2,OH,R,CH3 on arom. Ring acid strength  This destabilize Phenoxide ion result weaker acid.  P-Cresol less acidic than phenol
  • 10.  Electron withdrawing & releasing group more pronounced at ortho and para position than meta ( resonance effect).
  • 11.  P-nitrophenol>o-nitro phenol>m-nitro phenol  m-cresol>P-cresol>o-cresol Qualtative test:-  Formation of salt:- C6H5OH + NaOH C6H5ONa + H2O 2[C6H5OH] + 2Na 2[C6H5ONa] + H2 Phenol weaker acid than carboxylic acid (no reaction with Na2CO3,NaHCO3)  Reaction With FeCl3:- 3[C6H5OH] + FeCl3 Fe3+ [C6H5O]3 purple complex. Phenol, Sulphur salicylic acid , water soluble. 2-Napthol, Salicylic acid ,Gallic acid are water ethanol soluble. 2-Napthol- green, Gallic-black, Salicylic acid- violet 1,2,3 hydroxy benzene –brown colour c c c
  • 12.  Libermon nitrous test Initially get green/blue colour after dilution it become red and after addition of NaOH blue colour reapers.  Bromine water test White ppt
  • 13.  Litmus test Weakly acidic in aqueous solution after application on litmus paper it leads blue litmus red.  Reaction with zinc dust  Reaction with ammonia C6H5OH + NH3 Anhy.ZnCl3 C6H5NH2+ H2O 675K
  • 14.  From chlorobenzene (Dow process)  From cumene  From diazonium salt  From Grignard reagent
  • 15.  From coal tar C6H5OH + NaOH C6H5ONa + H2O 2[C6H5OH] + CO2 + H2O 2[C6H5OH] + Na2CO3 Reaction of Phenol: Reaction on OH group  Formation of ester (use aqueous alkali – phenyl ether) C6H5OH + Na2CO3 C6H5ONa+CH3COCl C6H5OCOCH3  Formation of ether:(s)(ethoxy benzene ) C6H5OH + NaOH C6H5ONa + CH3CH2Cl C6H5OCH2CH3 Reaction on benzene ring  Halogenations: C6H5OH + 3Br2 H2O 2,4,6 tribromo phenol +3HBr  Nitration: C6H5OH + dil HNO3 O & P nitrophenol Con. HNO3 2,4,6 trinitrophenol (picric acid) c c c c c c c c c
  • 16.  Halogination C6H5OH + 3H2 Cyclohexanol  Sulphonation C6H5OH + Conc.H2SO4 o-Phenol sulphonic acid(200c) p-Phenol sulphonic acid(800c)  With formaldehyde Ni 433k c
  • 17.  Klobe reaction:  With phthalic anhydride
  • 18.  Reimer Thiemann reaction: C6H5OH + CHCl3 + 3NaOH O & P hydroxybenzaldehyde
  • 19.  Phenol- Colourless liquid or white solid at R.T.,highly toxic caustic  Uses-  antiseptic in soap and lotion,  cosmetic industry sunscreen, skin lightning, hair colouring  cosmetic surgery exfoliate remove dead skin  Manufacture of drug salicylic acid, aspirin (picric acid explo.)  preservative ink, vaccine  synthesis plastic ,backlite resin.  Extraction of nucleic acid,  High con.for ingrown tow, fingernail., herbicides detergent nylons temporary for Pharyngitis.
  • 20.  Cresols:-  Structure:-  Known methyl phenol,colourless expo in air yellow/brown red tint,similar odour,three isomer(o,m,p) mixture of three -tricrisols . Extracted from coal tar or synthetically by methylation high conc. Cause irritation ,burning throat, vomiting, liver kidney.  Uses-  Synthetic intermediate for plastic,pestcide,p’ceutcal & dye  O-Cresol on chlorination gives MCPA use herbicide.  O-Cre. Synthesis of mephenesin ( muscle relaxant)  P-Cre. Synthesis of BHT (antioxident)  P-Cre synthesis of Bupranalol ( non selective beta blocker)  Chlo.m –cre. use house hold disinfetant  M-cre precursor for vit E,preservative in Insulin,pesticide,amyl m-cre as anticeptic,solvent for polymer.
  • 21.  Resorcinol-  Structure-  Colourless,less water more alcohol, ether insoluble chloroform & CS2  Undergoes nucleophilic electrophilic substitution,pink on exposure or contact with iron,sweet test,on exposure irritation skin or mucous membrane  Uses-  Use as anticeptic,disinfectant  2% solution for hay fever & in cough  Use in antidandruff shampoo & cosmetic ( sunscreen)  Treatment of gastric ulcer, bactericidal effect.  Use reagent for ketoses determination, anticancer agent.  Use for characterization of Zn,lead (colorimetric method)  Use as preservative in cosmetic,ointment for psoriasis  Use parent molecule for holding target molecule in proper alignment.
  • 22.  Napthols:-  Structure:-  Consist of two isomers 1 & 2  Aromatic consist of alternate double single bond,Electronigitivity highly polar  1 napthol-white,fluorescent soluble alcohol ether chloroform  2 napthol-colourless or yellow rs  Uses:-  1napthol-molisch ingredient for carbohydrate.  1n. Precursor for insecticide like carbonyl.  1n. Is use to detect arginin in protin(Sakaguchi test)  1n. Use to detect breakdown of glucose in acetoin ( Voges Proskauer test)  2n. Precursor for Sudan dye  Use for synthesis of BINOL used as legand. Antiseptic in perfumes.  2n. Synthesis of fungicide & antioxident for rubber  Detection of 1& 2n. In urine for pesticide content in body.