ETHER

Total number of Questions in Ether are :

(i) In chapter Examples. . . . . . . . . . . . . . . . . . 4
(iii) Solved Examples . . . . . . . . . . . . . . . . . . . 10
Total no. of questions . . . . . . . . . . . . . . . . . 14
 (c) For better yield, the alkyl halide should be
1 GENERAL POINTS primary and alkoxide should be secondary or
tertiary.This method is not applicable to
(a) It is dialkyl derivative of water or alkoxy tertiary alkyl halides, because the alkoxide
derivative of alkane or monoalkyl derivative of ions being both powerful nucleophiles and
alcohols. bases would bring dehydrohalogenation of the
(b) Their general formula is C n H 2n+2 O or tertiary alkyl halides to f orm alkenes
CnH2n+1O preferentially.
(c) Hybridisation state of oxygen is sp3 and bond
Mechanism : (SN2)
angle is 110º due to counter balance repul-

sion of alkyl groups. C2H5 ONa C2H5O¯ + Na
Slow
(d) If both alkyl groups are similar then these C2H5O¯ + C2H5  
are called as simple ether, if different they C2H5O .......... C2H5 ........... – 
– Fast

are called as mixed ether. C2H5OC2H5 + ¯
(e) Carbon oxygen bond length is 1.42 Aº. 
Na + ¯ Na 
(f) Ether shows chain, position metamerism and
functional isomerism. Ethers are functional 2.3 Alkoxy mercuration – demercuration :
isomers of alcohols.
+ R – OH + Hg (OOCCF3)2 
(g) In IUPAC system ethers are called as
‘Alkoxy alkane’. An alkene Mercuric trifluoroacetate

2 METHODS OF PREPARATION I I Na BH4 I I

C C    C C
I I I I
2.1 Dehydration of alcohals : OR HgOOCCF 3 OR H

(a) With conc. H2SO 4 at 140ºC : Ether

Conc. H SO 4
2.4 Heating alkyl halides with silver oxide (dry)
R– OH + H–OR  º2  ROR + H O
2
140 C Heat
2 RX + Ag2O   R – O – R + 2 Ag X
Lower ether are prepared industrially by this
2.5 Action of diazomethane on alcohols : Methyl
method.
ethers are formed by this method.
NOTE: This reaction is mainly applicable for the
R – OH + CH2N2 B F3
dehydration of primary alcohols. Secondary and   ROCH3 + N2
tertiary alcohols form alkenes mainly. diazomethane
(b) With Al2O3 at 250ºC : 2.6 Addition of alcohols to alkenes :
H2 SO4
CH2 = CH2 + ROH 
Al O3
2 ROH 2 
  R – O – R + H O   CH2CH2OR
º
250 C 2
Alcohol Ether
2.2 Williamson synthesis : Heating of alkyl halides Mechanism : The intermediate is carbonium ion.
with sodium or potassium alkoxides. This is a 
very good method for the preparation of simple CH2 = CH2 + H CH3 CH 2
and mixed ethers.

R – O Na + R' X  R O R' + Na X CH3 –  CH3 CH2  O  R
I
(a) Order of reactivity of primary halides is : H
CH3 X > CH3CH2 X > CH3CH2CH2 X H


 CH3 CH2 –O–R
CH3 –CH2
(b) Tendency of alkyl halides to undergo
elimination is : 3º > 2º > 1º
 (a) This method is very useful for preparing mixed 4. CHEMICAL PROPERTIES
ethers. 4.1 Halogenation : –
(b) In higher cases, there can be 1, 2 – hydride (a) In dark : -
or 1, 2 – methyl shift to form more stable Halogen reacts with ether in dark and substitutes
carbonium ion.  and ’ hydrogen atoms.
' '  
CH3  CH2  O  CH2  CH3  Cl  Cl
Methods of Preparation of Ether
Cl
|
Ex.1 Ethyl iodide reacts with moist Ag2O to form–  CH3  CH  O  CH  CH3
|
(A) Ether (B) Alcohol Cl
(C) Alkene (D) Alkane Ans.(B) , ’ -dichlorodiethyl ether
(b) In Light : -
Sol. CH2 – CH2 – I + Ag – O – Ag + I – CH2 – CH3 CH3 – CH2 – O – CH2 –CH3 + 10Cl2
  CH3 – CH2 – O – CH2 – CH3 + 2AgI h
 CCl 3 – CCl 2 – O – CCl2 – CCl3 + 10HCl
Ex.2 Ethyl iodide reacts with sodium ethoxide to perchloroether
form – The reactivity order of halogen in halogenation is-
(A) Ethene (B) Ethoxy ethane F2 > Cl2 > Br2 > I2
(C) Alcohol (D) None
4.2 Oxidation : –
Ans. (B)
When ether is left open in air, it reacts with
atmospheric oxygen and forms peroxide.
Sol. Ethers are formed when ethyl iodide reacts
with sodium ethoxide .
1
CH3 – CH2 – I + Na – O – CH2 – CH3 + O 
2 2
 CH3–CH2–O–CH2–CH3 + NaI

3 PHYSICAL PROPERTIES
 O C2H5–O–O–C2H5
(a) Ethers are colourless with specific smell
liquid. These are highly volatile liquid due to
When ether is exposed to air for a long time then
low boiling point.
the above peroxide changes into another peroxide
(b) These are insoluble in water although they which is called as ‘Epoxy ethyl hydroperoxide’
have oxygen atom, but their oxygen atom is and is explosive in nature.
neutral due to steric hindrance of both alkyl
1
groups. C2H5 – O – O – C2H5 + O
2 2
(c) Ether is also called as inert solvent of
aliphatic chemistry, due to inertness of C 2H 5–O–CH–CH 3
                    |
oxygen. O–O–H
(d) Due to inertness of oxygen, it is best solvent epoxy ethyl hydroperoxide
for preparation of highly reactive compounds
Note :
such as G.R.
When ether is oxidised with acidic K2Cr2O7 then
(e) It is used as an anesthetic.
it forms aldehyde.
(f) Boiling point of diethyl ether is 34.5 ºC.
4.3 Reaction with HX : –
 (a) If HX is cold : -
Na / liq. NH
3
CH3 – CH2 – O – CH2 – CH3 + H – X (cold) C2H5 – O – C2H5 + 2H   

              CH3 – CH2 – X + C2H5OH C2H6 + C2H5 – OH
CH3 – O – CH2 – CH3 + HX (cold)
4.8 Reaction with H2SO 4 :-
               CH3 – X + C2H5OH
Note : If we take unsymmetrical ether with cold (a) With conc. H2SO 4 :-
H–X then smaller alkyl group forms alkyl CH3 – CH2 – O – CH2 – CH3 + H – SO 4 – H
halide.
  (conc.)
(b) If HX is hot : -
              CH3 – CH2 – SO4H + C2H5OH
CH3 – CH2 – O – CH2 – CH3 + 2 H–X
(hot) (b) With dil. H2SO4 :-

                 2CH3 –CH2–X + H2O CH3 – CH2 – O – CH2 – CH3 + H – OH
CH3 – O – CH2 – CH3 + 2 H–X
dil. H2SO 4
(hot)    2CH3 – CH2 – OH


                  CH3 – X + C2H5 X + H2O
4.9 Dehydration :-
Note : When vapours of ether are passed on heated
The above reaction is called ‘Ziesel’s Method of alumina then by the elimination of water alkene
Alkoxy group estimation’. If we take is formed.
unsymmetrical ether with hot H – X then we get
two different types of alkyl halide and by the test
of both alkyl halide we can confirm alkoxy group
of ether.
2CH2 = CH2 + H2O
4.4 Reaction with PCl5 : –
C2H5 – O – C2H5 + PCl5  2C2H5Cl + POCl3

4.5 Reaction with Acetyl Chloride : –

C2H5 – O – C2H5 + Cl – – CH3 4.10 Preparation of Oxonium Salt :-

Oxygen of ether has lone pair of electron so it
can form salt with mineral acid or lewis acid by
forming coordinate bond with it. Such type of salt
            CH3– –O – C2H5 + C2H5Cl
is called Oxonium Salt.

4.6 Reaction with Carbon monoxide :– 


C2H5 – C– C2H5 + C O 
 
 
C2H5– –O C2H5   Cl–
 
 

diethyl oxonium chloride

Note : In the case of unsymmeterical ether, CO-
group attaches with the bigger alkyl group.

4.7 Reduction :-
 Ex.4 Ether reacts with PCl5 to form –
 (A) Ethyl chloride
(B) Phosphorous oxy trichloride
(C) Both (A) & (B)
 
  (D) None
  H  SO4H–
  Ans.(C)
 

diethyl oxonium hydrogen sulphate


Sol.  2C2H5Cl + POCl3

boron trifluoride etherate

Chemical properties

Ex.3 Ether reacts with halogen in dark and in light

to give –
(A) Same products
(B) Different products
(C) It does not react in light
(D) It does not react in dark
Ans. (B)
Sol. Ether on halogenation, in dark gives , ’ -
dichlorodiethyl ether while in light gives
perchloro ether.
 SOLVED EXAMPLES
Ex.1 An example of a compound with functional Ex.5 When ethyl iodide is treated with dry silver
group — O — is - oxide, it forms -
(A) Acetic acid (B) Methyl alcohol (A) Ag (B) C2H5OC2H5
(C) Diethyl ether (D) Acetone (C) C2H5OH (D) COOH – COOH
(Ans. C) (Ans. B)
Sol. Ethers are R — O — R´ or R — O — R Sol. 2C2H5I + Ag2O  C2H5OC2H5 + 2AgI

Ex.2 An organic compound A reacts with sodium Ex.6 C–O–C bond angle in diethyl ether is about-
metal and forms B. On heating with conc. (A) 180º (B) 110º
H2SO4, A gives diethyl ether. So A and B are (C) 150º (D) 90º
- (Ans. B)
(A) C3H7OH and CH3ONa
(B) CH3OH and CH3ONa Ex.7 On strong oxidation, diethyl ether gives -
(C) C4H9OH and C4H9ONa (A) Ethyl alcohol (B) Acetaldehyde
(C) Acetic acid (D) Methyl alcohol
(D) C2H5OH and C2H5ONa (Ans. D)
(Ans. B)
Sol. C2H5OH (A) reacts with Na to give C2H5ONa [ O]
(B). C2H5OH (A) also reacts with conc. Sol. CH3CH2OCH2CH3  
H O
 2CH3CHO.
2
H2SO 4 to form diethyl ether because of
dehydration. The oxidation may be carried out with
K2Cr2O 7 + conc. H2SO 4 or alkaline KMnO4
Ex.3 In the presence of an acid catalyst, two at elevated temperature.
alcohol molecules will undergo dehydration
Ex.8 The reaction of CH3OC2H5 with HI gives -
to give -
(A) CH3I (B) C2H5OH
(A) Ester
(C) CH3I + C2H5OH (D) C2H5I + CH3OH
(B) Anhydride (Ans. C)
(C) Ether Sol. CH3OC2H5 + HI  CH3I + C2H5OH. In the
(D) Unsaturated hydrocarbon case of mixed ethers such as methyl ethyl
(Ans. C) ether the halogen attaches to a small and
Acid
less complex group. So the products are CH3I
Sol. ROH + HOR   ROR and C2H5OH but not the C2H5I and CH3OH.
H2 O

Ex.4 A carbon compound A forms B with sodium Ex.9 The number of methoxy groups in a compound
metal and again A forms C with PCl5, but B can be determined by treating it with -
and C form diethyl ether. Therefore A, and B (A) HI and AgNO3
and C are - (B) Sodium carbonate
(A) C2H5OH, C2H5ONa, C2H5Cl (C) Sodium hydroxide
(B) C2H5Cl, C2H5ONa, C2H5OH (D) Acetic acid (Ans. A)
(C) C2H5OH, C2H6, C2H5Cl 2
(D) C2H5OH, C2H5Cl, C2H5ONa Sol. CH3OC2H5 + HI — CH3I + C2H5OH
(Ans. A) CH3I + AgNO3 — AgI + CH3NO 3
Sol. C2H5OH (A) + Na  C2H5ONa (B)
C2H5OH (A) + PCl5  C2H5Cl (C) Ex.10 An ether is heated with phosphorous penta
sulphide to give -
C2H5ONa (B) + C2H5Cl (C)  C2H5OC2H5
(A) Alkanthiol (B) Dialkyl sulphide
+ NaCl
(C) Hydrogen sulphide (D) Thioester
(Ans. B)