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ALCOHOLS
Tertiary Alcohols (30): In these alcohols the –
SYNOPSIS
OH group is attached with tertiary carbon atom
Alcohols are the hydroxyl derivatives of They posses a general formula R3C-OH
hydrocarbons i.e., obtained by the replacement CH 3
of one or more H atoms R-H -H
+OH
R-OH
C2 H5 - C - OH
The compound in which a hydroxyl group is Eg: Tert. amyl alcohol
attached to a saturated carbon atom are called CH 3
e
r
t
.
a
m
y
l
a
l
c
o
h
o
l
T
alcohols.
Allyl alcohols: In these alcohols the –OH group
Eg:- 1)CH 3OH 2)C2 H 5OH is attached a sp3 hybridized carbon atom next to
The compounds in which hydroxyl group is the carbon – carbon double bond i.e. to an allylic
attached to an unsaturated carbon atom of a carbon.
double bond are called ‘enols’.Eg;- H 2C=CH-OH
Classification: Alcohols are classified
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according to the number of hydroxyl groups Eg: H 2C = CH-CH 2 -OH
present in their molecules. Allyl alcohol But-3-en 2-ol
up
Monohydric alcohols contain one –OH group, Benzyl Alcohols: In these alcohols, the –OH
dihydric two and trihydric three, respectively. group is attached to sp3 hybridised carbon next
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Monohydric alcohols are further classified to an aromatic ring.
H
according to the hybridization of carbon atom
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CH2OH C – OH C – OH
to which the –OH group is attached.
Compounds containing Csp -OH bond:
3 Eg:- CH3 CH3
sp3 hybridised carbon atom of an alkyl group. Hence, allylic and benzylic alcohols may be
Sa
OH
CH3CH2OH Ethyl alcohol OH
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naming the alcohols. Unsaturated alcohols and carbonyl compounds
are tautomers.
Common system: In this system alcohols are
up
named as alkyl alcohols i.e., the word alcohol CH3 –C=CH 2 and CH3 –C–CH 3
OH O
are tautomers.
is added to the name of alkyl group.
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In higher members, it is always indicated Alcohols containing chiral centres can exhibit
whether the –OH group is attached to primary, optical isomerism.
secondary or tertiary carbon atom by prefixing The simplest monohydric alcohol that can
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‘n’ for primary, sec for secondary and tert for exhibit enantiomerism is butan–2–ol.
tertiary.
H
nj
m
e
t
h
y
l
2
b
u
t
a
n
o
l
2
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The product obtained in this reaction seems to Reduction of Aldehyde and Ketone:
follow anti markownikoff’s addition of water Aldehyde on reduction with LiAlH 4 gives
over alkene.
up primary alcohol, whereas ketones gives
Hydroboration is regioselective. secondary alcohols.
With unsymmetrical alkenes, the boron atom
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bonds to the less substituted carbon atom. H H3O R – CH – OH
R – CH – O
R – C = O 2
BH
H 3C CH CH 2
3
CH 3 CH CH 2
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H H
| | Primary
Aldehyde alcohol
H BH 2
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C6 H 5 CH 2 CH 2 CH 2 OH
carbon – carbon bond.
Hydrolysis of Ester: Esters on hydrolysis Absolute alcohol is 99.6 to 100% pure ethyl
gives acid and alcohol. alcohol.
RCOOR1 + H 2 O H
R-COOH + R1 - OH
+
From Starch: A suspension of starch is made
or HO-
by heating with water at 50°C.
Alcohols being more volatile than acid an hence Germinated barley called malt is added. Malt
it can easily be separated by distillation. contains diastase, which converts starch to
Ester hydrolysis involves the cleavage of C–O
maltose.
– C – OR
1 2(C6H10O5)n + nH2O DIASTASE
nC12H22O111
bond of The mixture is cooled to 30°C and yeast is
O added. An enzyme, maltase produced by yeast
By Fermentation:Decomposition of large converts maltose into glucose.
compounds into simple compounds by enzymes C12H22O11 + H2O MALTASE
2C6H12O6
derived by mirco organisms like yeast is called
Zymase converts glucose to ethyl alcohol.
fermentation.
Enzymes are biocatalysts which are non living C6H12O6 ZYMASE
2CH3CH2OH + 2CO2
nitrogenous compounds. Methyl alcohol is prepared from water gas
They catalyse reactions taking place in living enriched with H 2 in presence of oxides of
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organism and act as specific catalysts. Yeast is chromium and zinc. It is also prepared by the
a single cell microorganism. partial oxidation of methane.
up
From Molasses: Molasses is the mother liquor CO + 2H2
ZnO, Cr2 O3 , 200atm,600K
CH3OH
left after seperation of sugar from sugar cane
2CH3OH
0
2CH4 + O2 Cu, 250 C,100atm
juice.
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It is black and viscous and still contains 20-40% Mineralised methylated spirit : 90%
sucrose. rectified spirit +9% methyl alcohol +1%
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It is diluted with water so that the percentage of petroleum oil and a purple dye.
sugar in it is 10%. Industrial methylated spirit : 95% rectified
Then H2SO4 is added to maintain the pH at 4.
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added and the mixture is taken and retained in alcohol is also made unfit for drinking by adding
large wooden tank for 2–3 days at 30°C – 40°C. methyl alcohol.
An enzyme, invertase produced by yeast
converts sucrose into glucose and fructose. W.E-3:How acetylene is converted to ethyl alcohol?
C12H22O11 + H2O INVERTASE
C6H12O6 + Sol. Acetylene on hydration gives acetaldehyde,
C6H12O6 which on reduction gives ethanol.
Another enzyme, zymase converts glucose and HC CH + H 2 O
HgSO4
CH3 - CHO
LiAlH 4
C2 H5OH
H 2SO4
fructose into ethyl alcohol.
C6H12O6 ZYMASE
2CH3CH2OH + 2CO2 W.E-4:How benzyl alcohol is obtained from benzyl
The fermented solution contains 6–10% ethyl chloride ?
alcohol and is called wash or wort. Sol. Benzyl chloride on base hydrolysis gives benzyl
This dilute solution on fractional distillation alcohol.
gives rectified spirit containing 93-95% alcohol.
Generally 95-96% alcohol is called as Rectified CH2Cl CH2OH
spirit (or) industrial alcohol.
aq.NaOH
It is converted to absolute alcohol by drying on
treating with quick lime and then over calcium.
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In case of alcohols with same alkyl group, and hydrogen tends to separate as a proton.
boiling point decreases with increasing
up Hence in O – H cleavage, the order of
branching. reactivity is Primary > Secondary > Tertiary
Eg. n–Butyl alcohol > Iso butyl alcohol > tert. and in C – O cleavage the order of reactivity
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Butyl alcohol. is Tertiary > Secondary > Primary.
Alcohols are soluble in water due to hydrogen During O – H cleavage proton is given out
bonding between molecules of alcohol and
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Reaction with Metals: Alcohols react with W.E-6:Assertion (A): Dehydration of alcohols can be
metal to form metal alkoxide and evolve H2. carried out with Conc H 2SO4 but not with
This reaction is acid – base reaction. conc.HCl.
1 Reason (R) : H2SO4 is dibasic while HCl is
R - OH + M R - OM + H 2 (M = Na, K etc)
2 monobasic.
1
1) Both A and R are true and R is the correct
Eg: C 2 H 5OH + K C 2 H 5OK + H 2 explanation to A
2
2) Both A and R are true and R is not the correct
Metal hydrides react with alcohol and evolve
explanation to A
H2 gas.
3) A is true but R is false
R-OH + MH R - OM + H2 (M = Na, K etc) 4) A is false but R is true
Dehydration of Alcohols: Alcohols when Sol. ‘2’
heated in presence of conc. W.E-7:Hydroboration-Oxidation of CH 3CH CH 2
0
H2SO4 (170 – 180 C) or H3PO4, Al2O3 or P2O5 produces.
undergoes dehydration to form alkene.
1. CH 3CH 2CH 2OH 2. CH 3CH OH CH 3
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Eg: CH 3 - CH 2 - OH H 2 C = CH 2 + H 2O
0
H SO ,160 C
2 4
CH 3
CH 3 CH CH 2OH CH 3 C OH
OH > OH> OH 1.
CH 3
2.
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CH 3
Rearrangement in the Alicyclic ring: Primary alcohols are oxidized to either aldehyde or
In case of cyclic alcohols whenever a to carboxylic acids by replacing either one or two
carbocation is formed outside the next carbon C – H bonds by C – O bonds.
atom of a ring, ring expansion may takes place.
Examples of ring expansion: R - CH 2 -OH
[O]
R-CHO
[O]
R-COOH
Secondary
2 alcohols
6
are oxidized to ketones by
2 + + + one C – H bond by a C – O bond.
replacing
3
H 3 1 1
OH 6
R 2 - CH 5- OH R2- C = O
H2O Bond breaks at C1 and C5 [O]
4 5 New bond forms at C5 and C6 4
–
1° Carbocation
Tertiary alcohols have no H atom on the carbon
2° Carbocation
2 6
2 + + 3
+
3 1 1
OH
H
6
Bond breaks at C1 and C5
R
H2O
4 5 New bond forms at C5 and C6 4 5 Cyclo hexene
O
– 2° Carbocation
R – C – OH No reaction
1° Carbocation
–H+
R
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Cyclo hexene
hydrogens
Reaction with HX: The reaction of alcohols
with HX (X = Cl, Br) is a general method to Oxidation with Ceric ammonium nitrate (CAN)
up
prepare primary, secondary and tertiary alkyl is a very selective reagent for the mild oxidation
halide. of primary alcohol. The reagent also oxidise
aromatic methyl group into – CHO.
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CH 3 - CH 2 - OH
HBr
CH 3CH 2 Br + H 2 O
CH 3 - CH 2 - OH
CAN
CH 3 - CHO
More substituted alcohols usually react more
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Tertiary > Secondary > Primary. Manganese dioxide (MnO2) is selective and
Primary alcohols form R – X by SN2 reaction mild oxidant. It is specific for allylic and
Sa
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Uses of Ethanol: propane HBr 3 2 2
|
(iii) C 2 H5 MgCl + H C O
MISCLLANEOUS SOLVED EXAMPLES ethyl magnesium methanal
chloride
W.E-9:Draw the structures of all isomeric alcohols
H H
of molecular formula C5H12O and give their OH
H 2O
H – C – OMgCl H – C – OH + Mg
IUPAC names. Classify them as primary,
secondary and tertiary alcohols. C2H5 C2H5
Cl
Sol. The structures, IUPAC names and the propan-l-ol
classification of all isomeric alcohols of
molecular formula C5H12O are : CH3
|
(iv) CH3 C O + CH3 MgBr ether
Pentan-1-ol CH3 -CH 2 -CH 2 -CH 2 -CH 2OH Primary propanone methyl magnesium
(acetone) bromide
Lucas reagent Does not form turbidity Turbidity is formed in 5 Turbidity is formed
Testing with a mixture of at room temperature to 10 minutes immediately
conc. HCl and anhyd. (turbidity is obtained
ZnCl2 only upon heating)
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RCHO RCOR RCOR of
permanganate or carbon
dichromate solution) atoms)
RCOOH
up Two acids Two acids
(same number of carbon (with less number of (with less number of
atoms in the three carbon atoms) carbon atoms under drastic
compounds) conditions)
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Victor Meyer test Nitrolic acid gives red Pseudonitrol gives blue No colour is obained
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colour colour
Alcohol
HI RCH2OH R2CHOH R3COH
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HI HI HI
Alkyl iodide
AgNO2 RCH2I R2CHI R2CI
Sa
NO NO
NaOH
R–C–NO2 Blue colour
NOH
NaOH
R–C–NO2
– +
NONa
Red colour
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3) dry ZnCl2 / con. HCl 4) alk.KMnO4 1) Propane 2) Ethanol 3) Ethyne 4) Ethylene
5. Ethyl alcohol is the hydrolysis product of 18. A compound (X) of molecular formula C3H8O
1) C2H5Cl 2) CH3CHO 3) C2H4 4) C2H5 MgI
upcan be oxidized to a compound of molecular
PROPERTIES formula C3H6O2 (Y), (X) is most likely an
6. 95% ethyl alcohol can be converted to 1) Aldehyde 2) Alcohol
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100% ethyl alcohol by the following 3) Ether 4) Both 2 and 3
1) Magnesium chloride 2) Calcium oxide 19. Which of the following gives Iodo form test
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19. CH 3CO group is present 3) 2 - Butanol 4) 1 - Butanol
11. If the boiling point of ethanol (molecular
20. X= RCH 2OH ; Y= R2CHOH
up weitht = 46) is 780 C , the boiling point of di-
ethyl ether (molecular weight = 74) is
LEVEL-I (H.W)
1) 1000 C 2) 780 C 3) 86 0 C 4) 34 0 C
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1. Which of the following is a tertiary alcohol 12. The percentage of C2 H 5OH in wash is
1) Ethyl alcohol 2) Isopropyl alcohol (approximatly)
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alcohol ?
3. Which of the following enzyme converts 1) Ethylene 2) Isobutylene
maltose to glucose 3) Propylene 4) 1 - Butene
1) Invertase 2) Zymase 3) Maltase 4) Diastase 14. Which one of the following gases is liberated
4. Absolute alcohol is prepared from rectified when ethyl alcohol is heated with methyl
spirit by magnesium iodide ?
1) Steam distillation 2) Fractional distillation 1) Methane 2) Ethane
3) distillation with CaO &Ca 3) Carbondioxide 4) Propane
4) Simple distillation 15. Identify A and B in the following reaction
5. Reaction, CO 2 H 673 k ,300 atm ,/ Cr2O3 zno
2 g C2 H 5 Cl A
C2 H 5OH B
C2 H 5Cl
may be used for manufacture of : 1) A = aqueous KOH; B = moist Ag2O
1) HCHO 2) CH3COOH 2) A = alcoholic KOH ; B = aqueous NaOH
3) HCOOH 4) CH3OH
3) A = aqueous NaOH ; B = AgNO2
PROPERTIES
6. When wine is exposed to air it become sour 4) A = AgNO2 ; B = KNO2
due to 16. 23g of sodium will react with methanol to give
1) Oxidation of C2H5OH into CH3COOH 1) One mole of oxygen 2) 1/2 Mole of hydrogen
2) Bacteria 3) Virus 4) Formic acid formation 3) One mole of hydrogen 4) 1/4 Mole of oxygen
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20. Which is formed when ethanol reacts with ace-
tic acid up
1) CH 3COOC2 H 5 2) C2 H 5OC2 H 5
3) CH 3OCH 3 4) CH 3CH 2CHO
LEVEL -I (H.W) - KEY
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1) 4 2) 3 3) 3 4) 3 5) 4 6) 1 7) 4
8) 1 9) 2 10) 3 11) 4 12) 2 13) 2 14) 1
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CH 2 OH
|
H-C-OH
2. |
is glycerol
CH 2 OH
NOMENCLATURE 3) CH3—CH2—CH2—CH2—OH
1. Which one of the following pairs of 4) CH 3 CH CH 2 OH
compounds are functional isomers of each |
OH
other
1) CH 3CH 2CH 2OH , CH 3CHOHCH 3 11. Compound A reacts with Na metal to give B.
A also reacts with PCl5 to give C. B and C
2) CH 3CH 2CH 2OH , CH 3 2 CHCH 2OH reacts with each other to give dimethyl ether.
3) CH 3CH 2 CH 2 OH , CH 3CH 2 CH 2 Cl Then A, B and C respectively are
4) CH 3CH 2CH 2OH , CH 3OCH 2CH 3 1) CH3OH, CH3ONa, CH3COCl
2. Primary alcoholic group is 2) CH3OH, CH4, CH3Cl
3) CH3OH, CH3ONa, CH3Cl
4) CH3Cl, CH4, CH3OH
1) -CH2OH 2) C OH 3) >CHOH 4) >C=O 12. Two organic compounds A and B react with
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sodium metal and release H2 gas. A and B
PREPARATION up react with each other to give ethyl acetate.
3. Ethyl alcohol containing 9.5% methyl alcohol The A and B are
and 0.5% pyridine is called 1) CH3COOH and C2H5OH
1) Spirit 2) Denaturated spirit 2) HCOOH and C2H5OH
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3) Rectified spirit 4) Absolute alcohol 2) CH3COOH and CH3OH
4. Breaking of big organic molecules in the 4) CH3COOH and HCOOH
presence of enzymes is called
13. Which one of the following reagents is useful
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1) Cracking 2) Pyrolysis
in converting 1-butanol to 1-bromobutane?
3) Fermentation 4) Oxidation
1) CHBr3 2) Br2 3) CH3Br 4) PBr3
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20. The alcohol which gives the most stable
the given alcohols with acids like conc. H 2 SO4
carbonium ion on dehydration is:
is 30 20 10
1) (CH3)2 CHCH2OH 2) (CH3)3 C - OH
up
3) CH3 CH2CH2 CH2 OH 4) CH3-CH-CH2CH3 18. The reaction occur with rearrangement as
21. Which of the following reactions will yield 20 carbocation is more stable than 10 carbo
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propan-2-ol? cation.
1) CH CH CH HOH H 19. Correct order or reactivity is
2 3
CH 3OH CH 3CH 2OH CH 3 2 CHOH
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2) CH 3 CHO
CH MgBr / HOH
3
Neutral KMnO4
4) CH 2 CH CH 3 to give a secondary alcohol
Sa
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16. Which of the following is most suitable
3) 2,2,2-Trifluoroethanol 4) 2-Chloroethanol.
method for removing the traces of water from
8. R OH HX R X H 2O .
up ethanol ?
In this reaction, the reactivity of alcohols is 1) Heating with Na metal
1) Tertiary > Secondary > Primary 2) Passing dry HCl through it
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2) Tertiary < Secondary < Primary 3) Distilling it with CaO 4) Reacting with Mg
3) Tertiary > Primary > Secondary 17. Which of the following compound gives
4) Secondary > Primary > Tertiary ethylmethyl ketone on oxidation ?
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1. C
2
OH—CHOH—CH2OH is glycerol.
H
OH PREPARATION
4. Ethyl alcohol is manufactured from ethylene
Sa
CHCl3 by
Product 1) Permanganate 2) Catalytic oxidation
NaOH
3) Absorption into Conc. H2SO4 followed by
CHO OH hydrolysis 4) Reduction
CHO 5. Which of the following pairs of the compounds
can be used as starting materials in the synthesis
1) 2) of 2-phenyl-2-pentanol?
1) CH 3 CH 2 3 Br and PhCOOH
OH CO2H 2) CH 3 2 CHCH 2 Br and PhCOCH 3
CO2H
3) PhBr and CH 3CH 2CH 2COCH 3
3) 4) 4) PhBr and CH 3 2 CHCH 2COCH 3
6. An enzyme which brings about the
2. X Y
Benzoquinone . Identify X and Y in conversion of starch into maltose is known
as
this reaction
1) Diastase 2) Zymase 3) Maltase 4) Invertase
7. Which is the catalyst in the conversion of water
gas and hydrogen into methyl alcohol?
1) MnO 2) raney Ni 3) Fe 4) ZnO-Cr2O3
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liquid A is
1) C2H5Cl 2) C2H5CHO 3) C2H6 4) C2H5OH 1) Oxidation of CH 4 by steam at 900 0 C
11. A compound reacts with sodium and liberates
up 2) Reduction of HCHO using LiAlH 4
hydrogen and on oxidation gives ketone. The 3) Reaction HCHO with a solution of NaOH
formula of the compound could be.
1) CH3CH2OH 2) CH3CHOHCH3 4) Reduction of CO using H 2 and ZnO Cr2O3
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12. Iodoform cannot be prepared from This reaction takes place through
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18. Diethyl ether produces.
19. based on the structure 1. CH 3CH 2CH 2OH 2. CH 3CH OH CH 3
20. from CO and H2
up
21. E1 mechanism 3. CH 3CH OH CH 2OH 4. CH 3COCH 3
9. The compound which gives the most stable
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LEVEL-IV
carbonium ion on dehydration.
1) Both A and R are true and R is the correct CH3
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explanation to A CH 3 CH CH2OH CH
2) Both A and R are true and R is not the correct 1) 2) 3 C OH
explanation to A CH 3 CH3
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8) 1 9) 2 10) 4 11) 3 12) 4 13) 3 1) II > IV > I > III 2) I > II > III > IV
3) III > I > II > IV 4) IV > III > I > II
LEVEL-IV - HINTS
1. Ammonium phosphate and ammonium sulphate PREVIOUS MAINS KEY : 1) 3
act as food for yeast
2. Both are correct ADDITIONAL QUESTIONS
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3. Ethanol is a associated with water through 1. What is the structure of C4 H10O which can
hydrogen bond. give positive haloform test and evolves
up
4. CaCl2 3C2 H 5OH hydrogen gas with LiAlH 4 .
5. Ethyl alcohol is soluble in polar and non polar
1) CH 3 CH 2 O CH 2 CH 3
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solvents.
6. Both are correct CH 3
7. with HCl R-Cl will form
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CH 3
9. 3 carbanium ion is most stable.
0
CH 3 CH CH 2 CH 3
Sa
10. 3) 4)
CH 3COOH CH 3CH 2COOH OH
CH 3
11. A CH 3CH 2CH OH CH 3 2. The relative rates of reaction with
B CH 3CH CHCH 3 concentrated H 2 SO4 of the following is
O I)
OH
|| OH OH
12.
CH 3 CH 2 C OCH 3
CH 3 MgBr
excess
?
II) III)
13. 11.2 ml of CH 4 at STP is formed by 0.037 g of
R-OH
1) I > II > III 2) II > I > III
22.400 ml CH 4 at STP .......? 3) I > III > II 4) II > III > I
0.037 22, 400 3. Which of the following is the best dehydrating
= = 74g of alcohol agent for 10 alcohols
11.2
1) Con H 2 SO4 2) CaO 3) Al2O3 4) POCl3
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OH OH 4) 1-Chloro-3, 3-dimethylbutane
11. Propylene is subjected to hydroboration
up oxidation reaction. The product formed
would be
1) 2) 1)Propanal 2)1-Propanol 3)2-Propanol 4)Propanone
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12. Ethylene glycol when heated in the presence
CO2H CO2H
of an hydrous ZnCl2 yields.
O O
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3) CH 2 C O C CH3
4) No reaction The compound Y in the above sequence is
CH3 CH3 1) 2-Methyl-2-phenyl-1-propanol
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Cl up 1) OH at C2 is more basic than that of at C5
2) OH at C2 is more acidic than at C5 .
3) 4)
Cl 3) both have same basic strength
21. Glycol on treatment with PI 3 mainly gives 4) both have same acidic strength
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28. Lucas test is used to make distinction between
1) Ethylene 2) Ethylene iodide
3) Ethyl iodide 4) Ethane 10 , 20 and 30 alcohols. This do not show that
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23. Glycerol on treatment with oxalic acid at will give turbidity at fastest rate
1100 C forms 4) alcohol which gives red colour during Victor
1) Allyl alcohol 2) Formic acid Mayor test, will give turbidity ast slower rate
3) CO2 and CO 4) Glyceric acid then those giving blue or white colour during
24. If the starting material is 1-methyl-1, Victor Mayor test.
2-epoxy cyclopentane, of absolute 29. Match the column:
configuration, decide which one compound Column -I Column - II
correctly represent the product of its reaction A) Oxidation of 10
with sodium methoxide in methanol. alcohols in aldehyde P) KMnO4 /
CrO3. .HCl
1) 2) B) Q) Collin’s reagent
OCH3 CH3O CH3
HO CH3 OH N
CrO3.2
3) CH3 4) C) R) Jone’s reagent
OH
CH3O CH3O CH3
N
A) B2 H 6 , H 2O2 / NaOH
CH 3
CH 3 CH CH CH 3
OH
C H 3 C C H 2C H 3
Hg OAc 2 , H 2O / NaBH 4
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C)
CH 3
up
OH
C H 3 C C H 2C H 3
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D) dil. H 2 SO4
CH 3
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1) 3 2) 4 3) 4 4) 3 5) 1 6) 4 7) 4
8) 3 9) 4 10) 1 11) 1 12) 4 13) 2 14) 3
Sa