Chapter 17 Hydroxyl Compound SMK Sacred Heart, Sibu

1. Preparation of hydroxyl compound

Reduction of C=O bond
Alkaline hydrolysis of haloalkanes, R-X + NaOH(aq)
Hydration of alkenes, C=C
Reaction of Grignard reagent
(i) LiAlH4 in dry ether, (ii) H3O+,
Na in C2H5OH
H2, Ni, 180oC ,(Not suitable for aromatic compounds)
(i)NaBH4, ethanol (ii)H3O+, (For aldehyde & ketone)
+H2O(g), conc H3PO4, 300oC, 60atm
(i) Conc H2SO4, rtp (ii)H2O,
RMgX + H2C=O
RMgX + RCH=O
RMgX + RRC=O

2. Reactions of Aliphatic alcohol 2. Reactions of Aromatic alcohol (Phenol)

n e o w +HX SCl i +NaOH(aq) ONa
+Na ONa
n Na metal, r.t.p
R-OH + Na R-ONa + H2 +RCOCl OCOR
e Esterification
(a) RCOOH, , conc H2SO4
(b) RCOCl, rtp
-OH group is Ortho and Para director
Remove H2
o A)Oxidation +Cl2, dry AlCl3
C-OHC=O
Insert O btw C-H Conc H2SO4,
KMnO4/H+
+RX, dry AlCl3
1o RCOOH
2o RCOR +RCOCl, dry AlCl3
3o No reaction +HNO3
Remove H2
B) Dehydrogenation
C-OHC=O
Cu, 300oC
dilute Concentrated
1o RCHO
2o RCOR OH OH OH
3o C=C (Remove H2O) NO2 O 2N NO2
-w Dehydration +
(a) Conc H2SO4, 180oC Remove H2O
(b) Al2O3, C-OHC=O
NO2 NO2
+HX Lucas reagent (Conc HCl, ZnCl2)
(a) Conc H2SO4, 180oC Chemical test for phenol
(b) Al2O3,
R-OH + HCl R-Cl + H2O Add Br2(aq) or Cl2(aq)
1o no cloudiness at rtp Observation: White solid
OH
2o cloudiness after 5 min
Br Br
3o cloudiness immediately
SCl Cl substitution (Conc HCl, ZnCl2)
(a) PCl5 / SOCl2 R-OH R-Cl
i Iodoform test (I2 in NaOH(aq), warm) Br
H
R C OH R C O Fission of RO-H bond neo
CH3 ONa Fission of R-OH bond -w +HX SCl i