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Introduction
Ethers
Alcohols Phenols
* Inert solvent for many
* Ethanol = Wood polish * Adhesive
reactions
* In pe rfume rv
* Menthol - Flavour to food * Antise ptic
* Was used as surgical
* Solvent for many organic co mpounds * Disinfectant
anaesthetic
Alcohols I
Alcohol s are h ydroxy d erivatives of a lkan es in which one or more H-atoms are replaced by - OH group . They
have general form ula C 11 H 2 11 , 1 OH .
Classification of Alcohols
Alcohols
I
J
Alcohols containing Alcohols containing
Cs 3 - OH bond Cs 2 -OH bond
(-OH gr attached to sp3 (-OH gr attached to sp 2 hybridised
(hybridized ca rbon atom) carbon atom)
J
l J
e.g. CH 2 = CH - OH (Vinyl alcohol)
( 1- Phenylethanol)
(510)
~ Phenols and Ethers
AfcoIio I.. 511
j:IC:Nomenclature of ~
Accordi n g to IUPAC s vstem I
' a coho! a . II '
Sr. re ca ed a lka nol s', by replacin g ' e' of alkane by ' ol'
No. Alcohol Common name IUPAC name
1. CH3 - CH2 - CH - CH (Alkyl alcohol) (Alkanol)
2 2 - OH
2. CH3 - CH - CH n -Butyl alcohol Butan - 1-ol
I 2 - OH
CH 3 iso-Butyl alco hol 2-Methyl butan - 1-ol
3. CH 3 - CH - CH
I 2 - CH 3
OH sec-Butyl alcohol Butan -2-ol
4. CH 3
I t-Butyl alcohol
CH 3 - C - OH 2- Methyl propan-2-ol
I
CH 3
5. CH 3
I neo-Pentyl alcohol
CH3 - C - CH2 - OH 2, 2-Dimethyl propan-1-ol
I
CH 3
6. OH
-
7.
QCH
CH 3 CH
3
CH CH 3
3-Methyl cyclohexanol
I I - Butane-2 , 3-diol
OH OH
Preparation of Alcohols \
• Alcohols are generally prepared by -
(1) Hydrolysis of alkyl halides:
!:,
RX + aq . KOH ~ ROH + KX
(2) Hydration of alkenes:
CH 3
Hp I
RCH = CH 2 + H2SO4 ~ R - TH - HSO4 R-CH-OH
boil
(Alkene) (Alcohol)
CH 3
(3) Hydroboration-oxidation of alkenes:
BH 3 3HP2
3CH 3 CH = CH 2 THF (CH 3 CH 2CH 2hB Olf' l 3CH 3 CH 2 CH 20H + H 3B0 3
(Propene) (Propanol)
(4) Reduction of carbonyl compounds:
Ni or Pt or Pd catalyst
RCHPH
RCHO + 2H NaBH 4 or LiAIH 4 or Na/C 2 HsOH
H"'
H/ i
~
108 .90 H
pm
•
•
So - OH group attached to carbon by a -bond (overlap of sp C and sp 0) .
Bond angle C - 0 - H is slightly less than tetrahedral as oxygen atom cames two
lon e pairs of e·, so repulsion between these lone pair e· occurred. .
H • H _ o bond in alcohols is polar covalent bond and hydrogen carnes a partial
(Structure of methanol) I'>+ &--
positive charge (H - 0 )
- _ : _ - - - - - - - 1 Alcohols (R - OH)
t
, (1'1 aeactions involving (B) Reactions involving
breaking of O - H bond breaking of C - 0 bond:
Na or K
i{
~
MgorCa
Al
RO- Na+ H 2
(ROJiCa + H 2
HX / Anhyd. Zn C12
11
R-X+Hp
(ROb Al + H2
1
R-OH 7 RCOOH / H. PX5
RO- COR + H 2 o 1 - - - - - - - ~R - X + POX3 + HX
-~ { RCOCI / Pyridine
i.;:: RO - COR + HCl
·c::11)
t, (RC0) 2 0 / ff SOCl2
~ RO - COR + RCOOH ~, t - - -- - -- ~ RCl + SO 2 i + HCI
~ Pyridine
Cone. H 2 S0 4
-4_3_ K _ _~
i - - -4 ) c = c( + Hp
[OJ fO]
'---~ RCHO --~)RCOOH
L--_ _ C_u~/_S_73_K
_ ___,, RCHOorRCOR
•u@
*
Phenols / . .
Phenols are the aromatic hydroxyl compounds m which one or more
(- OH) groups are directly attached to the I
e.g. (QJ
OH
00
OH
e.g.
J:oH
LSJ
J
~ OH
e.g.
HO@OH
OH
(fCH,
OH
I
o-Cresol 2-Methylphenol
~
(fNH,
I
OH
o-Aminophenol 2-Aminophenol
~
*
Q-o/.
- OH gr is attached to sp 2 hy bridised C-atom
* C - O bond Jen th in henol is less than in menthol alcohol
. Phl'llo/s and Ethers
,4/tll/,OI., .
515
,·~ parti a. l ~. bond ch aracter
-- -on- - - - -- _
electrons of aromatic nng a nd sp2 h b . . account of the conJugation of un sh ,d -_-
- ---:------....:.._ Y nd1sed state f
~aratlon of Phenols
b
J are e pair of oxyg
o ca r on to which oxygen IS bonded.
.
,,n With n-
@+ 2Na0H
6 13 K
300atm . ➔
6
LgJ dil. HCI
@ +H 20
Ca3(P04)2
698K
6
l9J +
HCI
(Chlorobenzene) (Phenol)
(31 From Benzene sulphonic acid:
ONa•
~ ,H ~ ;Na•
(Benzene
sulphonic acid)
+ NaOH
Neutralization
2 NaOH
fused/573K ©
ONa• OH
2@ + H 2 S0 4 ~
(di!. )
2@ + N32S0 4
(Phenol)
(41 From aniline (Diazotization) :
+
N = NCI- OH
~2 +
HN0 2 + HCI
273 -278K © ©
(Phenol)
+ N2i + HCl
(Aniline)
; {51 From cumene fCommercial method):
CH 3
OH
©
I
3
\.,.p Reacti~~Phenoi]
OH
S03'-I
Br * OH Br
3 Br21oq1
Cone. H SO4 ~ (p~Phcnol sulphonic acid)
< - - - - ----1 Room temp .
S0 3H
Br
(2 ,4 ,6-Tribromo phenol)
OH OH Na or ~ a (Sodium phenoxide)
NaOH
Br 2 in CS 2
0
~
Br
(major)
' l~ Br 273 K
1---_
N<Li---"'Cr
H2SO 4
--_,_P~1--;> rb
y1
(Benwquinone)
Phenol 0
OH NO (oxidation)
~.
2
dil . HN03
OH
298 K ONa
(major) NaOH ~ (i) CO 2 , 400K, 4-7 atm
& COOH
N0 2
l8J (ii)H '
(minor)
(Kolbe's reaction) (Salicylic acid)
OH
0 2N* Q N02 / one. HN0 3
cone. H2 N0 4 '~ -..-i'--,_..-~©f
ONa CHO-~- ~ CHO
HCl3 (i) H' -
N02 aq. NaOH (ii) H,0
340 K
(Picric acid) (Salicylaldehyde)
(Reimer-Tiemann
rea ction)
Drugs-Salicylic acid,
salol, aspirin Antiseptic - Dettol
~ phenols and Ethers
,4/cOI10I· ·
51 7
~thers . . --
Ethers a re denvat1ves of h ydroca rb . .
• ons in which a h ct .
(- OAr) group . Y rogen Atom 1s re placed by a n ::i lkoxy (- OR) or a n ary loxy
They have generaJ formu la C H. 0 h .
•
. 211, 2 w e re 11 is ulways grcutc r th a n I .
11
1
Genera l formula = c n H2n +2 0
I j•@ Classification of Ethers
I
J
Simple/ Symmetrical ether
l
Mixed/Unsymmetrical ether
(Both - R or -Ar group attached to oxygen
(-R or -Ar group attached to oxygen are
are same)
different)
e.g. CH 3 - 0 - CH 3
e.g. CH 3 - 0 - C 2 H 5
(Dimethyl ether)
Eth I meth I ether
:- Nomenclature of Phenol
If#
• M
Metamerism I
I c mula but diffe re nt a lkyl groups a ttac hed on either side of the oxygen
. .
etamers: They have same mo Iecu ar or
atom.
e.g. Metamers of C 4 H JOO are given below :
(1) Diethyl ether C 2H 5 - 0 - C 2H s
(2) Methyl n -propyl ether CH 3 - 0 - CH 2CH 2CH 3
(3) lsopropyl methyl ether CH 3 - CH - 0 - CH 3
I
CH 3
~I X t J11om ·.1 Ml /7'-( 'FT (Ow1111 111:v)
l1omerJ1m In Ether
J l
Funotlonal laomeriam
Chain laomerlam
I iJI diffi·rc nl
Su m c 11 H<v l 141Ol1p 011 c·11 lw1 s 1dC' ol oxyg(' n Snuw 111 ok1 ·1tl111 for ,nu I11 1 .
but ciilk1 111 nri 11 11 gt·1n t· 111 nl e n , l>on chri , 11 , ,111•1 '1 · ll w1 nnd monuliydrir: ulcoho l)
I 11
I 111 11'111 ,, . \ J
e.g. Cll 0 Cll }.' 11 1 C' ll 1 11 11d ( 'II () e ll (dirn cllly l e the r) 1Jnc
1 «,,g, I I
c11 1
B1111 Methods of Preparation of Ethers
~
J, t (3) From Alcohol and
( 1) From Alcohol (2) From Alkyl halide
Diazomethane
(Willi amson's sy nth es is )
(De hydrnt1o n)
2 R - OH
(Alcohol)
co n e . H)S0,1
4 13 K l ,:d~~:a:\t:;;' ~l
a lkoxide) ha li de)
R - OH + CH 2 N2
(Alcohol) (Di azomet han e)
R - 0 - CH 3 + N2 i
R - 0 - R + H2 0 R - 0 - It + NaX (Eth er)
I
1
•
(Eth er)
Limitation• of preparation methods:
(a} From alcohol:
(El her)
.
( J) As temperature in creases, formation of alkenes predominates.
O
(2) Ethers can be obtained using J alcohols, 2° and 3° alcohols from alkenes .
(3) On ly simple ether can be obtained .
(b} From alkyl halide: ( J) Best yie ld of un symm etri cal eth er wh en 1° R - X and 3° R - ON a are used .
(2) But if 3° R - X and 1° R - ON a u sed th en 3° (Tertiary) alkyl halides
und ergoes elimination and form aJkenes .
(c} From R - OH and CH 2 N 2 : On ly methyl eth ers are obta in ed.
OCH 3 OCH 3
,,....__ / CH ,
CH Cl ~ -1/"
3
-:--:---:--"---~
Anhyd . AlC1 / CS3
> '
2
y I, ~
'V -
2- Methoxy toluene
CH 3 (M inor)
&-
4-Methoxy toluene
(Major)
OCH 3
(Anisole)
--.-:-C.:-H-;3C~O-:--;C~l; ----~
Anhyd . AlC1 3
) !iH
y, ~ COCH 3
~
2-Methox:,· acetophe none
COCH 3
(Minor)
4- Methoxy acetophenone
(Major)
OCH ,
+ (f
2- Nitroanisole
I
~ O--
N0 2 (Minor)
4-Nitroanisole
(Major)
fM Uses of Diether
J
"
Industrial solvent Solvent in reaction Refrigerant Natalite
of Grignard Reagent lfuel-substitute of petrol)
mix. of dietl1y\ ethe r and
C:H 50H
(5) Th
ions or NH 4
ion by co-ordination through oxygen .
ey are used to increase the solubility of ionic salts or
organic solvent.
lo) They are used to separate readioactive elements from
1v V O
O
l
0 -1 O>..')'gen atoms
• - CH~- groups
I
I
radioactive waste.
18
crown-6-ethers are used to extract Cesium and Strontium .
000
I