Professional Documents
Culture Documents
Name
Functional Group
Structure
Example Compound
alcohol
methanol
(methyl alcohol)
-ol endings
phenol
phenol
(phenol)
-ol endings
Alcohols
A hydroxyl group is a hydrogen bonded to an oxygen that is covalently bonded to
the rest of the molecule. Just as with alkenes, alkynes, and ketones, the location of
the hydroxyl group is made by numbering the molecule such that the hydroxyl
group has the lowest number possible.
is 2-pentanol
Alcohols are subdivided by examining the carbon to which the hydroxyl group is
bonded. If this carbon is bonded to one other carbon atom, it is a primary (1 o)
alcohol. If this carbon is bonded to two other carbons, it is a secondary (2 o) alcohol.
If it is bonded to three other carbons, it is a tertiary (3 o) alcohol.
is 1o
is 2o
is 3o
Phenols
When the hydroxyl group is bonded directly to a benzene ring, the compound is
classified as a phenol. Naming phenols can be done in many ways.
is resorcinol.
Phenol, also known as carbolic acid, is an organic compound with the formula C6H5OH. It is a
white crystalline solid that is volatile. The molecule consists of a phenyl group (-C6H5) bonded to
a hydroxyl group (-OH). It is mildly acidic, but requires careful handling due to its propensity to cause
burns.
Phenol was first extracted from coal tar, but today is produced on a large scale (about 7 billion
kg/year) from petroleum. It is an important industrial commodity as a precursor to many materials and
useful compounds.[4] Its major uses involve its conversion to plastics or related materials. Phenol and
its chemical derivatives are key for
building polycarbonates, epoxies, Bakelite, nylon,detergents, herbicides such as phenoxy herbicides,
and numerous pharmaceutical drugs.
acetals:*
Compounds having the structure R C(OR') (R' not equal to H) and thus diethers of
geminal diols. Originally, the term was confined to derivatives of aldehydes (one R
= H), but now it applies equally to derivatives ofketones (neither R = H). NOC
Rule C-331, GNOC Recom. R-5.6.4.1. Mixed acetals have different R' groups. See
also acetonides, ketals. Cf. acylals, hemiacetals.
2
acyloins:*
-Hydroxy ketones, RCH(OH)C(=O)R. NOC Rule C-333. So named from the fact
that they are formally derived from reductive coupling of carboxylic acyl groups.
See also ketones.
aldehydes:*
Compounds RC(=O)H, in which a carbonyl group is bonded to one hydrogen atom
and to one R group. NOC Rule C-301.1.
carbonyl compounds:
1. Compounds containing the carbonyl group, C=O. The term is commonly used in
the restricted sense of aldehydes and ketones, although it actually
includes carboxylic acids and derivatives. See under oxo compounds.
2. Metal carbonyls, in which carbon monoxide is a formal ligand.
diosphenols:
Cyclic -diketones, which exist predominantly in an enolic form.
dypnones:
hemiacetals:*
Compounds having the general formula R C(OH)OR' (R' not equal to H). NOC
Rule C-331.4. GNOC Recom. R-5.6.4.2. See also lactols, hemiketals.
2
hemiketals:*
Hemiacetals having the structure R C(OH)OR (R not equal to H), derived
from ketones by formal addition of an alcohol to the carbonyl group. This term,
once abandoned (NOC Rule C-331.4, footnote) has been reinstated as a subclass
of hemiacetals. GNOC Recom. R-5.6.4.2.
2
ketals:*
Acetals derived from ketones by replacement of the oxo group by two
hydrocarbyloxy groups: R C(OR) (R not equal to H). This term, once abandoned
(NOC Rule C-333.1), has been reinstated (GNOC Recom. R-5.6.4.1) as a subclass
of acetals.
2
ketenes:*
Compounds in which a carbonyl group is connected by a double bond to
an alkylidene group: R C=C=O. NOC Rule C-321.
2
quinhydrones:
Molecular complexes of one equivalent amount of a quinone with one equivalent
amount of the corresponding hydroquinone.
quinomethanes:
Methylidenecyclohexadienones and dimethylidenecyclohexadienes, formally
derived from quinones by replacement of one or both of the quinone oxygens by
methylidene groups. (The diradical, triplet state of quinodimethanes can also be
called o- or p-xylylenes).
p-quinomethane,
p-quinodimethane
11.1 Classification
The classification of compounds makes their study systematic and hence
simpler. Therefore, let us first learn how are alcohols, phenols and ethers
classified?
11.1.1 Mono, Di, Tri or Polyhydric Compounds
Alcohols and phenols may be classified as mono, di, tri- or polyhydric
compounds depending on whether they contain one, two, three or many
Primary, secondary and tertiary alcohols: In these three types of alcohols, the
OH group is attached to primary, secondary and tertiary carbon atom,
respectively as depicted below:
11.1.2 Ethers
Ethers are classified as simple or symmetrical, if the alkyl or aryl groups
attached to the oxygen atom are the same, and mixed or unsymmetrical, if
the two groups are different. Diethyl ether, C H OC H , is a symmetrical ether
whereas C H OCH and C H OC H are unsymmetrical ethers.
2
Intext Questions
11.1 Classify the following as primary, secondary and tertiary alcohols:
11.2 Identify allylic alcohols in the above examples.
11.2 Nomenclature
(a) Alcohols: The common name of an alcohol is derived from the common
name of the alkyl group and adding the word alcohol to it. For example,
CH OH is methyl alcohol.
According to IUPAC system (Unit 12, Class XI), the name of an alcohol is
derived from the name of the alkane from which the alcohol is derived, by
substituting e of alkane with the suffix ol. The position of substituents are
indicated by numerals. For this, the longest carbon chain (parent chain) is
numbered starting at the end nearest to the hydroxyl group. The positions of
the OH group and other substituents are indicated by using the numbers of
carbon atoms to which these are attached. For naming polyhydric alcohols,
the e of alkane is retained and the ending ol is added. The number of OH
3
groups is indicated by adding the multiplicative prefix, di, tri, etc., before ol.
The positions of OH groups are indicated by appropriate locants e.g., HO
CH CH OH is named as ethane1, 2-diol. Table 11.1 gives common and
IUPAC names of a few alcohols as examples.
2
COMPOUND
COMMON NAME
I U PAC N A M E
CH -OH
Methyl alcohol
Methanol
n-Propyl alcohol
propan-1-ol
Isopropyl alcohol
propan-2-ol
n-Butyl alcohol
Butan-1-ol
sec-Butyl alcohol
Butan-2-ol
Isobutyl alcohol
2-methylpropane-1-ol
tert-Butyl alcohol
2-Methylpropan-2-ol
Glycerol
Propane-1,2,2-triol
(c) Ethers: Common names of ethers are derived from the names of alkyl/aryl
groups written as separate words in alphabetical order and adding the word
ether at the end. For example, CH OC H is ethylmethyl ether. If both the
alkyl groups are the same, the prefix di is added before the alkyl group. For
example, C H OC H is diethyl ether.
According to IUPAC system of nomenclature, ethers are regarded as
hydrocarbon derivatives in which a hydrogen atom is replaced by an OR or
OAr group, where R and Ar represent alkyl and aryl groups, respectively. The
larger (R) group is chosen as the parent hydrocarbon. The names of a few
ethers are given as examples in Table 11.2.
3
COMPOUND
COMMON NAME
I U PAC N A M E
CH OCH
Dimethyl ether
Methoxymethane
Diethyl ether
Ethoxyethane
C H OC H
2
CH OCH CH CH
Methyl n-propyl
ether
C H OCH
Ethylphenyl
ether(Phenetole)
C H OCH CH
6
C H O(CH ) -CH
6
Ethoxybenzene
1-Methoxypropane
Methyl isopropyl
ether
2-Methoxypropane
Phenylisopentyl
ether
3Methylbutoxybenzene
1,2-Dimethoxyethne
2-Ethoxy-1,1dimethylcyclohexane
Solution
(i) 4-Chloro-2,3-dimethylpentan-1-ol
(ii) 2-Ethoxypropane
(iii) 2,6-Dimethylphenol
(iv) 1-Ethoxy-2-nitrocyclohexane
Intext Question
11.3 Name the following compounds according to IUPAC system.
Mechanism
The mechanism of the reaction involves the following three steps:
Step 1: Protonation of alkene to form carbocation by electrophilic attack of
HO .
HO + H HO
3
2
The addition of borane to the double bond takes place in such a manner that
the boron atom gets attached to the sp carbon carrying greater number of
hydrogen atoms. The alcohol so formed looks as if it has been formed by the
addition of water to the alkene in a way opposite to the Markovnikovs rule. In
this reaction, alcohol is obtained in excellent yield.
2
(ii) By reduction of carboxylic acids and esters: Carboxylic acidsv are reduced
to primary alcohols in excellent yields by lithium aluminium hydride, a strong
reducing agent.
The overall reactions using different aldehydes and ketones are as follows:
You will notice that the reaction produces a primary alcohol with methanal, a
secondary alcohol with other aldehydes and tertiary alcohol with ketones.
Example 11.2
Give the structures and IUPAC names of the products expected from the
following reactions:
(a) Catalytic reduction of butanal.
(b) Hydration of propene in the presence of dilute sulphuric acid.
(c) Reaction of propanone with methylmagnesium bromide followed by
hydrolysis.
Solution
4. From cumene
Phenol is manufactured from the hydrocarbon, cumene. Cumene
(isopropylbenzene) is oxidised in the presence of air to cumene
hydroperoxide. It is converted to phenol and acetone by treating it with dilute
acid. Acetone, a by-product of this reaction, is also obtained in large
Intext Questions
11.4 Show how are the following alcohols prepared by the reaction of a
suitable Grignard reagent on methanal ?
It is interesting to note that boiling points of alcohols and phenols are higher
in comparison to other classes of compounds, namely hydrocarbons, ethers,
haloalkanes and haloarenes of comparable molecular masses. For example,
ethanol and propane have comparable molecular masses but their boiling
points differ widely. The boiling point of methoxymethane is intermediate of
the two boiling points.
The high boiling points of alcohols are mainly due to the presence of
intermolecular hydrogen bonding in them which is lacking in ethers and
hydrocarbons.
Solubility
Solubility of alcohols and phenols in water is due to their ability to form
hydrogen bonds with water molecules as shown. The solubility decreases with
increase in size of alkyl/aryl (hydro- phobic) groups. Several of the lower
molecular mass alcohols are miscible with water in all proportions.
The above reactions show that alcohols and phenols are acidic in nature. In
fact, alcohols and phenols are Brnsted acids i.e., they can donate a proton to
a stronger base (B:).
(ii) Acidity of alcohols: The acidic character of alcohols is due to the polar
nature of OH bond. An electron-releasing group (CH , C H ) increases
electron density on oxygen tending to decrease the polarity of O-H bond. This
decreases the acid strength. For this reason, the acid strength of alcohols
decreases in the following order:
3
Alcohols are, however, weaker acids than water. This can be illustrated by the
reaction of water with an alkoxide.
This reaction shows that water is a better proton donor (i.e., stronger acid)
than alcohol. Also, in the above reaction, we note that an alkoxide ion is a
better proton acceptor than hydroxide ion, which suggests that alkoxides are
stronger bases (sodium ethoxide is a stronger base than sodium hydroxide).
Alcohols act as Bronsted bases as well. It is due to the presence of unshared
electron pairs on oxygen, which makes them proton acceptors.
(iii) Acidity of phenols: The reactions of phenol with metals (e.g., sodium,
aluminium) and sodium hydroxide indicate its acidic nature. The hydroxyl
group, in phenol is directly attached to the sp hybridised carbon of benzene
ring which acts as an electron withdrawing group. Due to this, the charge
distribution in phenol molecule, as depicted in its resonance structures,
causes the oxygen of OH group to be positive.
2
The reaction of phenol with aqueous sodium hydroxide indicates that phenols
are stronger acids than alcohols and water. Let us examine how a compound
in which hydroxyl group attached to an aromatic ring is more acidic than the
one in which hydroxyl group is attached to an alkyl group.
The ionisation of an alcohol and a phenol takes place as follows:
COMPOUND
FORMULA
o-Nitrophenol
7.2
m-Nitrophenol
8.3
Phenol
C H -oH
10.0
o-Cresol
o-CH -C H - OH
10.2
m-Cresol
m-CH C H -OH
10.1
p-Cresol
p-CH -C H -OH
10.2
Ethanol
C H OH
15.9
PKA
From the above data, you will note that phenol is million times more acidic
than ethanol.
Example 11.4
Arrange the following compounds in increasing order of their acid strength:
Propan-1-ol, 2,4,6-trinitrophenol, 3-nitrophenol, 3,5-dinitrophenol,phenol, 4methylphenol.
Solution
Propan-1-ol, 4-methylphenol, phenol, 3-nitrophenol, 3,5-dinitrophenol,2,4, 6trinitrophenol.
2. Esterification
Alcohols and phenols react with carboxylic acids, acid chlorides and acid
anhydrides to form esters.
The reaction with carboxylic acid and acid anhydride is carried out in the
presence of a small amount of concentrated sulphuric acid. The reaction is
reversible, and therefore, water is removed as soon as it is formed. The
reaction with acid chloride is carried out in the presence of a base (pyridine)
so as to neutralise HCl which is formed during the reaction. It shifts the
equilibrium to the right hand side. The introduction of acetyl (CH CO) group in
alcohols or phenols is known as acetylation. Acetylation of salicylic acid
produces aspirin.
3
they form the halides easily. Primary alcohols do not produce turbidity at
room temperature.
2. Reaction with phosphorus trihalides: Alcohols are converted to alkyl
bromides by reaction with phosphorus tribromide (Refer Unit 10, Class XII).
3. Dehydration: Alcohols undergo dehydration (removal of a molecule of
water) to form alkenes on treating with a protic acid e.g., concentrated
H SO or H PO , or catalysts such as anhydrous zinc chloride or alumina (Unit
13, Class XI).
2
Secondary and tertiary alcohols are dehydrated under milder conditions. For
example
Thus, the relative ease of dehydration of alcohols follows the following order:
Tertiary > Secondary > Primary
The mechanism of dehydration of ethanol involves the following steps:
Mechanism
Step 1: Formation of protonated alcohol.
Step 2: Formation of carbocation: It is the slowest step and hence, the rate
determining step of the reaction.
The acid used in step 1 is released in step 3. To drive the equilibrium to the
right, ethene is removed as it is formed.
4. Oxidation: Oxidation of alcohols involves the formation of a carbonoxygen double bond with cleavage of an O-H and C-H bonds.
become electron rich due to the resonance effect caused by OH group. The
resonance structures are shown under acidity of phenols.
Common electrophilic aromatic substitution reactions taking place in phenol
are as follows:
(i) Nitration: With dilute nitric acid at low temperature (298 K), phenol
yields a mixture of ortho and para nitrophenols.
The ortho and para isomers can be separated by steam distillation. oNitrophenol is steam volatile due to intramolecular hydrogen bonding while pnitrophenol is less volatile due to intermolecular hydrogen bonding which
causes the association of molecules.
Example 11.5 Write the structures of the major products expected from the
following reactions:
(a) Mononitration of 3-methylphenol
(b) Dinitration of 3-methylphenol
(c) Mononitration of phenyl methanoate.
Solution
The combined influence of OH and CH groups determine the position of the
incoming group.
3
2. Kolbes reaction
Phenoxide ion generated by treating phenol with sodium hydroxide is even
3. Reimer-Tiemann reaction
On treating phenol with chloroform in the presence of sodium hydroxide, a
CHO group is introduced at ortho position of benzene ring. This reaction is
known as Reimer Tiemann reaction.
The intermediate substituted benzal chloride is hydrolysed in the presence of
alkali to produce salicylaldehyde
5. Oxidation
Oxidation of phenol with chromic acid produces a conjugated diketone known
as benzoquinone. In the presence of air, phenols are slowly oxidised to dark
coloured mixtures containing quinones.
Intext Question
11.6 Give structures of the products you would expect when each of the
following alcohol reacts with (a) HCl ZnCl (b) HBr and (c) SOCl .
(i) Butan-1-ol
(ii) 2-Methylbutan-2-ol
11.7 Predict the major product of acid catalysed dehydration of
(i) 1-methylcyclohexanol and
(ii) butan-1-ol
11.8 Ortho and para nitrophenols are more acidic than phenol. Draw the
resonance structures of the corresponding phenoxide ions.
11.9 Write the equations involved in the following reactions:
(i) Reimer Tiemann reaction
(ii) Kolbes reaction
2
12
In wine making, grapes are the source of sugars and yeast. As grapes ripen,
the quantity of sugar increases and yeast grows on the outer skin. When
grapes are crushed, sugar and the enzyme come in contact and fermentation
starts. Fermentation takes place in anaerobic conditions i.e. in absence of air.
Carbon dioxide is released during fermentation.
The action of zymase is inhibited once the percentage of alcohol formed
exceeds 14 percent. If air gets into fermentation mixture, the oxygen of air
oxidises ethanol to ethanoic acid which in turn destroys the taste of alcoholic
drinks.
Ethanol is a colourless liquid with boiling point 351 K. It is used as a solvent in
paint industry and in the preparation of a number of carbon compounds. The
commercial alcohol is made unfit for drinking by mixing in it some copper
sulphate (to give it a colour) and pyridine (a foul smelling liquid). It is known
as denaturation of alcohol.
Nowadays, large quantities of ethanol are obtained by hydration of ethene
(Section 11.4).
11.6 Ethers
11.6.1 Preparation of Ethers
1. By dehydration of alcohols
Alcohols undergo dehydration in the presence of protic acids (H SO , H PO ).
The formation of the reaction product, alkene or ether depends on the
reaction conditions. For example, ethanol is dehydrated to ethene in the
presence of sulphuric acid at 443 K. At 413 K, ethoxyethane is the main
product.
2
Can you explain why is bimolecular dehydration not appropriate for the
preparation of ethyl methyl ether?
2. Williamson synthesis
It is an important laboratory method for the preparation of symmetrical and
unsymmetrical ethers. In this method, an alkyl halide is allowed to react with
sodium alkoxide.
Better results are obtained if the alkyl halide is primary. In case of secondary
and tertiary alkyl halides, elimination competes over substitution. If a tertiary
alkyl halide is used, an alkene is the only reaction product and no ether is
formed. For example, the reaction of CH ONa with (CH ) CBr gives exclusively
3
2-methylpropene.
It is because alkoxides are not only nucleophiles but strong bases as well.
They react with alkyl halides leading to elimination reactions.
Example 11.6 The following is not an appropriate reaction for the
preparation of t-butyl ethyl ether.
Phenols are also converted to ethers by this method. In this, phenol is used
as the phenoxide moiety.
The large difference in boiling points of alcohols and ethers is due to the
presence of hydrogen bonding in alcohols.
The miscibility of ethers with water resembles those of alcohols of the same
molecular mass. Both ethoxyethane and butan-1-ol are miscible to almost the
same extent i.e., 7.5 and 9 g per 100 mL water, respectively while pentane is
essentially immiscible with water. Can you explain this observation ? This is
due to the fact that just like alcohols, oxygen of ether can also form hydrogen
bonds with water molecule as shown:
Alkyl aryl ethers are cleaved at the alkyl-oxygen bond due to the more stable
aryl-oxygen bond. The reaction yields phenol and alkyl halide.
Ethers with two different alkyl groups are also cleaved in the same manner.
R-O-R + HX -> R- X + R -OH
The order of reactivity of hydrogen halides is as follows:
HI > HBr > HCl. The cleavage of ethers takes place with concentrated HI or
HBr at high temperature.
The reaction of an ether with concentrated HI starts with protonation of ether
molecule.
Step 1:
The reaction takes place with HBr or HI because these reagents are
sufficiently acidic.
Step 2:
Iodide is a good nucleophile. It attacks the least substituted carbon of the
oxonium ion formed in step 1 and displaces an alcohol molecule by S 2
mechanism. Thus, in the cleavage of mixed ethers with two different alkyl
groups, the alcohol and alkyl iodide formed, depend on the nature of alkyl
groups. When primary or secondary alkyl groups are present, it is the lower
alkyl group that forms alkyl iodide (S 2 reaction).
N
However, when one of the alkyl group is a tertiary group, the halide formed is
a tertiary halide.
mechanism.
Therefore the attack by I ion breaks OCH bond to form CH I. Phenols do not
react further to give halides because the sp hybridised carbon of phenol
cannot undergo nucleophilic substitution reaction needed for conversion to
the halide.
3
Example 11.7
Give the major products that are formed by heating each of the following
ethers with HI.
Solution
2. Electrophilic substitution
The alkoxy group (-OR) is ortho, para directing and activates the aromatic
ring towards electrophilic substitution in the same way as in phenol.
Intext Questions
11.10 Write the reactions of Williamson synthesis of 2-ethoxy-3methylpentane starting from ethanol and 3-methylpentan-2-ol.
11.11 Which of the following is an appropriate set of reactants for the
preparation of 1-methoxy-4-nitrobenzene and why?
Summary
Alcohols and phenols are classified (i) on the basis of the number of hydroxyl
groups and (ii) according to the hybridisation of the carbon atom, sp or sp to
which the OH group is attached. Ethers are classified on the basis of groups
attached to the oxygen atom.
Alcohols may be prepared (1) by hydration of alkenes (i) in presence of an
acid and (ii) by hydroboration-oxidation reaction (2) from carbonyl
compounds by (i) catalytic reduction and (ii) the action of Grignard reagents.
Phenols may be prepared by (1) substitution of (i) halogen atom in
haloarenes and (ii) sulphonic acid group in aryl sulphonic acids, by OH group
(2) by hydrolysis of diazonium salts and (3) industrially from cumene.
Alcohols are higher boiling than other classes of compounds, namely
hydrocarbons, ethers and haloalkanes of comparable molecular masses. The
ability of alcohols, phenols and ethers to form intermolecular hydrogen
bonding with water makes them soluble in it.
Alcohols and phenols are acidic in nature. Electron withdrawing groups in
phenol increase its acidic strength and electron releasing groups decrease it.
Alcohols undergo nucleophilic substitution with hydrogen halides to yield alkyl
halides. Dehydration of alcohols gives alkenes. On oxidation, primary alcohols
yield aldehydes with mild oxidising agents and carboxylic acids with strong
oxidising agents while secondary alcohols yield ketones. Tertiary alcohols are
resistant to oxidation.
The presence of OH group in phenols activates the aromatic ring towards
electrophilic substitution and directs the incoming group to ortho and para
positions due to resonance effect. Reimer-Tiemann reaction of phenol yields
salicylaldehyde. In presence of sodium hydroxide, phenol generates
phenoxide ion which is even more reactive than phenol. Thus, in alkaline
medium, phenol undergoes Kolbes reaction.
Ethers may be prepared by (i) dehydration of alcohols and (ii) Williamson
synthesis. The boiling points of ethers resemble those of alkanes while their
solubility is comparable to those of alcohols having same molecular mass.
The CO bond in ethers can be cleaved by hydrogen halides. In electrophilic
3
substitution, the alkoxy group activates the aromatic ring and directs the
incoming group to ortho and para positions.
Execrises
11.1 Write IUPAC names of the following compounds:
11.2 Write structures of the compounds whose IUPAC names are as follows:
(i) 2-Methylbutan-2-ol
(ii) 1-Phenylpropan-2-ol
(iii) 3,5-Dimethylhexane 1, 3, 5-triol
(iv) 2,3 Diethylphenol
(v) 1 Ethoxypropane
(vi) 2-Ethoxy-3-methylpentane
(vii) Cyclohexylmethanol
(viii) 3-Cyclohexylpentan-3-ol
(ix) Cyclopent-3-en-1-ol
(x) 3-Chloromethylpentan-1-ol.
11.3 (i) Draw the structures of all isomeric alcohols of molecular formula
C H O and give their IUPAC names.
(ii) Classify the isomers of alcohols in question
5
12
11.14 Give two reactions that show the acidic nature of phenol. Compare
acidity of phenol with that of ethanol.
11.15 Explain why is ortho nitrophenol more acidic than ortho methoxyphenol
?
11.16 Explain how does the OH group attached to a carbon of benzene ring
activate it towards electrophilic substitution?
11.17 Give equations of the following reactions:
(i) Oxidation of propan-1-ol with alkaline KMnO solution.
(ii) Bromine in CS with phenol.
(iii) Dilute HNO with phenol.
(iv) Treating phenol wih chloroform in presence of aqueous NaOH.
4
11.24 Write the names of reagents and equations for the preparation of the
following ethers by Williamsons synthesis:
(i) 1-Propoxypropane
(ii) Ethoxybenzene
(iii) 2-Methoxy-2-methylpropane
(iv) 1-Methoxyethane
11.25 Illustrate with examples the limitations of Williamson synthesis for the
preparation of certain types of ethers.
11.26 How is 1-propoxypropane synthesised from propan-1-ol? Write
mechanism of this reaction.
11.7
(i) 1-Methylcyclohexene
(ii) A Mixture of but-1-ene and but-2-ene. But-1-ene is the major product
formed due to rearrangement to give secondary carbocation.
11.10
11.11 (ii)
(i) A, B, C, D
(ii) A, D
(iii) B, C
(iv) A
7. Give IUPAC name of the compound given below.
(i) 2-Chloro-5-hydroxyhexane
(ii) 2-Hydroxy-5-chlorohexane
(iii) 5-Chlorohexan-2-ol
(iv) 2-Chlorohexan-5-ol
8. IUPAC name of m-cresol is ___________.
(i) 3-methylphenol
(ii) 3-chlorophenol
(iii) 3-methoxyphenol
(iv) benzene-1,3-diol
is ______________.
10. Which of the following species can act as the strongest base?
(i) OH
(ii) OR
(iii) O C H
11. Which of the following compounds will react with sodium hydroxide
solution in water?
(i) C H OH
(ii) C H CH OH
(iii) (CH ) COH
(iv) C H OH
6
(i) H /Pd
(ii) LiAlH
(iii) NaBH
(iv) Reaction with RMgX followed by hydrolysis
2
19. Which of the following reagents can be used to oxidise primary alcohols
to aldehydes?
(i) CrO in anhydrous medium.
(ii) KMnO in acidic medium.
(iii) Pyridinium chlorochromate.
(iv) Heat in the presence of Cu at 573K.
3
20. Phenol can be distinguished from ethanol by the reactions with _________.
(i) Br /water
(ii) Na
(iii) Neutral FeCl
(iv) All the above
2
25. Name the factors responsible for the solubility of alcohols in water.
26. What is denatured alcohol?
27. Suggest a reagent for the following conversion.
28. Out of 2-chloroethanol and ethanol which is more acidic and why?
29. Suggest a reagent for conversion of ethanol to ethanal.
30. Suggest a reagent for conversion of ethanol to ethanoic acid.
31. Out of o-nitrophenol and p-nitrophenol, which is more volatile? Explain.
32. Out of o-nitrophenol and o-cresol which is more acidic?
33. When phenol is treated with bromine water, white precipitate is obtained.
Give the structure and the name of the compound formed.
34. Arrange the following compounds in increasing order of acidity and give a
suitable explanation.
Phenol, o-nitrophenol, o-cresol
35. Alcohols react with active metals e.g. Na, K etc. to give corresponding
alkoxides. Write down the decreasing order of reactivity of sodium metal
towards primary, secondary and tertiary alcohols.
36. What happens when benzene diazonium chloride is heated with water?
37. Arrange the following compounds in decreasing order of acidity.
H O, ROH,
2
38. Name the enzymes and write the reactions involved in the preparation of
ethanol from sucrose by fermentation.
39. How can propan-2-one be converted into tert- butyl alcohol?
40. Write the structures of the isomers of alcohols with molecular formula
C H O. Which of these exhibits optical activity?
4
10
45. Why is the reactivity of all the three classes of alcohols with conc. HCl and
ZnCl (Lucas reagent) different?
46. Write steps to carry out the conversion of phenol to aspirin.
47. Nitration is an example of aromatic electrophilic substitution and its rate
depends upon the group already present in the benzene ring. Out of benzene
and phenol, which one is more easily nitrated and why?
48. In Kolbes reaction, instead of phenol, phenoxide ion is treated with
carbon dioxide. Why?
49. Dipole moment of phenol is smaller than that of methanol. Why?
50. Ethers can be prepared by Williamson synthesis in which an alkyl halide is
reacted with sodium alkoxide. Di-tert-butyl ether cant be prepared by this
method. Explain.
51. Why is the COH bond angle in alcohols slightly less than the
tetrahedral angle whereas the COC bond angle in ether is slightly
greater?
52. Explain why low molecular mass alcohols are soluble in water.
53. Explain why p-nitrophenol is more acidic than phenol.
54. Explain why alcohols and ethers of comparable molecular mass have
different boiling points?
55. The carbon-oxygen bond in phenol is slightly stronger than that in
methanol. Why?
56. Arrange water, ethanol and phenol in increasing order of acidity and give
reason for your answer.
2
58. Match the starting materials given in Column I with the products formed
by these (Column II) in the reaction with HI.
(i)
Column II
Neutral ferric
(a) chloride
(ii)
(b) Glycerol
(iii)
(c) Methanol
(iv)
Wood spirit
(d) Phenol
(v)
(e) Ethleneglycol
(vi)
(f)
Ethanol
(i)
(ii)
Column II
Methanol
(a Conversion of phenol to o)
hydroxysalicylic acid
Kolbes reaction
(b
)
Ethyl alcohol
(c
)
Conversion of phenol to
salicylaldehyde
Conversion of 2 alcohol to (d
(iv) ketone
)
Wood spirit
(e
)
Heated copper at 573K
(vi) Fermentation
; Propane-1,2,3-triol
23. (A) 3-Ethyl-5-methylhexane-2,4-diol, (B) 1-Methoxy-3-nitrocyclohexane
24. 3-Methylpent-2-ene-1,2-diol
25. (i) Hydrogen bonding (ii) Size of alkyl/aryl group.
26. Alcohol is made unfit for drinking by mixing some copper sulphate and
pyridine in it. This is called denatured alcohol.
27. CrO , pyridine and HCl. (Pyridinium chlorochromate)
28. 2-Chloroethanol, due to I effect of chlorine atom.
29. CrO , Pyridine and HCl (Pyridinium chlorochromate)
3
33.
46.
between oxygen and sp hybridised carbon is more stable than that formed
between oxygen and sp hybridised carbon.
2
3
56. Increasing order of acidity is ethanol < water < phenol. The phenoxide
ion obtained after the removal of a proton is stabilised by resonance whereas
the ethoxide ion obtained after the removal of a proton is destabilised by +I
effect of C H group. Therefore phenol is stronger acid than ethanol. On the
other hand ethanol is weaker acid than water because electron releasing
C H group in ethanol inreases the electron density on oxygen and hence the
polarity of OH bond in ethanol decreases which results in the decreasing
acidic strength. Hence acidic strength increases in the order given above.
2
(i) (d), (ii) (c), (iii) (f), (iv) (a); (v) (g), (vi) (b)
(i) (d), (ii) (e), (iii) (b), (iv) (a)
(i)(e), (ii)(f), (iii)(d), (iv)(c), (v)(a), (vi)(b)
(i) (d), (ii) (a), (iii) (f), (iv) (e); (v) (c), (vi) (b)
Consult
Consult
Consult
Consult
NCERT
NCERT
NCERT
NCERT
textbook
textbook
textbook
textbook
for
for
for
for
Class
Class
Class
Class
XII.
XII.
XII.
XII.
Themes > Science > Chemistry > Organic Chemistry > Determination of
Structure > Organic Compound Identification Using Infrared Spectroscopy
Description
This exercise is intended to familiarize you with the identification of functional groups
in organic compounds using infrared spectra. Before you can use this technique, you
need to have an introduction to infrared spectroscopy and to what an IR spectrum is.
Infrared spectroscopy deals with the interaction of infrared light with matter. The
energy of an infrared photon can be calculated using the Planck energy relation.
E = hn
where h = 6.6 x 10-34 joule second and n = frequency of the photon. This
shows that high energy photons have high frequency.
The frequency, n, and speed of light, c, are related through the relation
c = ln
where c = 3.0 x 108 meter/second and l = wavelength for the light
E = hn = h c
= wavenumber =
; E = hn = h c ;
You can see that both frequency and wavenumber are directly proportional to
energy.
Molecules are flexible, moving collections of atoms. The atoms in a molecule are
constantly oscillating around average positions. Bond lengths and bond angles are
continuously changing due to this vibration. A molecule absorbs infrared radiation
when the vibration of the atoms in the molecule produces an oscillating electric field
Each of these two main types of vibration can have variations. A stretch can be
symmetric or asymmetric. Bending can occur in the plane of the molecule or out of
plane; it can be scissoring, like blades of a pair of scissors, or rocking, where two
atoms move in the same direction.
Different stretching and bending vibrations can be visualized by considering the
CH2 group in hydrocarbons. The arrows indicate the direction of motion. The
stretching motions require more energy than the bending ones.
Note the high wavenumber (high energy) required to produce these motions.
The bending motions are sometimes described as wagging or scissoring motions.
You can see that the lower wavenumber values are consistent with lower energy to
cause these vibrations.
A molecule absorbs a unique set of IR light frequencies. Its IR spectrum is often
The nonlinear horizontal axis has units of wavenumbers. Each wavenumber value
matches a particular frequency of infrared light. The vertical axis shows %
transmitted light. At each frequency the % transmitted light is 100% for light that
passes through the molecule with no interactions; it has a low value when the IR
radiation interacts and excites the vibrations in the molecule.
A portion of the spectrum where % transmittance drops to a low value then rises
back to near 100% is called a "band". A band is associated with a particular vibration
within the molecule. The width of a band is described as broad or narrow based on
how large a range of frequencies it covers. The efficiencies for the different
vibrations determine how "intense" or strong the absorption bands are. A band is
described as strong, medium, or weak depending on its depth.
In the hexane spectrum below the band for the CH stretch is strong and that for the
CH bend is medium. The alkane, hexane (C6H14) gives an IR spectrum that has
relatively few bands because there are only CH bonds that can stretch or bend.
There are bands for CH stretches at about 3000 cm -1. The CH2 bend band appears
at approximately 1450 cm-1 and the CH3 bend at about 1400 cm-1. The spectrum also
shows that shapes of bands can
differ.
Procedure
Every molecule will have its own characteristic spectrum. The bands that appear
depend on the types of bonds and the structure of the molecule. Study the sample
spectra below, noting similarities and differences, and relate these to structure and
bonding within the molecules.
The spectrum for the alkene, 1-hexene, C6H12, has few strong absorption bands. The
spectrum has the various CH stretch bands that all hydrocarbons show near 3000
cm-1. There is a weak alkene CH stretch above 3000 cm -1. This comes from the
C&emdash;H bonds on carbons 1 and 2, the two carbons that are held together by
the double bond. The strong CH stretch bands below 3000 cm -1 come from carbonhydrogen bonds in the CH2and CH3 groups. There is an out-of-plane CH bend for the
alkene in the range 1000-650 cm-1. There is also an alkene CC double bond stretch
at about 1650 cm-1 .
The spectrum for cyclohexene, (C6H10) also has few strong bands. The main band is
a strong CH stretch from the CH2 groups at about 3000 cm-1. The CH stretch for the
alkene CH is, as always, to the left of 3000 cm -1. The CH2 bend appears at about
1450 cm-1. The other weaker bands in the range 1000-650 cm -1 are for the out of
plane CH bending . There is a very weak alkene CC double bond stretch at about
1650 cm-1.
The IR spectrum for benzene, C6H6, has only four prominent bands because it is a
very symmetric molecule. Every carbon has a single bond to a hydrogen. Each
carbon is bonded to two other carbons and the carbon-carbon bonds are alike for all
six carbons. The molecule is planar. The aromatic CH stretch appears at 3100-3000
cm-1 There are aromatic CC stretch bands (for the carbon-carbon bonds in the
aromatic ring) at about 1500 cm-1. Two bands are caused by bending motions
involving carbon-hydrogen bonds. The bands for CH bends appear at approximately
1000 cm-1 for the in-plane bends and at about 675 cm -1for the out-of-plane bend.
The IR spectrum for the alcohol, ethanol (CH3CH2OH), is more complicated. It has a
CH stretch, an OH stretch, a CO stretch and various bending vibrations. The
important point to learn here is that no matter what alcohol molecule you deal with,
the OH stretch will appear as a broad band at approximately 3300-3500 cm -1.
Likewise the CH stretch still appears at about 3000 cm -1.
The spectrum for the aldehyde, octanal (CH3(CH2)6CHO), is shown here. The most
important features of the spectrum are carbonyl CO stretch near 1700 cm -1 and the
CH stretch at about 3000 cm-1. If you see an IR spectrum with an intense strong
band near 1700 cm-1 and the compound contains oxygen, the molecule most likely
contains a carbonyl group,
The spectrum for the ketone, 2-pentanone, appears below. It also has a
characteristic carbonyl band at 1700 cm-1. The CH stretch still appears at about 3000
cm-1, and the CH2 bend shows up at approximately 1400 cm-1. You can see the
strong carbonyl CO stretch at approximately 1700 cm -1. You can also see that this
spectrum is different from the spectrum for octanal. At this point in your study of IR
spectroscopy, you can't tell which compound is an aldehyde and which is a ketone.
You can tell that both octanal and a 2-pentanone contain C-H bonds and a carbonyl
group.
Carboxylic acids have spectra that are even more involved. They typically have three
bands caused by bonds in the COOH functional group. The band near 1700 cm -1 is
due to the CO double bond. The broad band centered in the range 2700-3300 cm 1
is caused by the presence of the OH and a band near 1400 cm -1 comes from the
CO single bond . The spectrum for the carboxylic acid, diphenylacetic acid, appears
below. Although the aromatic CH bands complicate the spectrum, you can still see
the broad OH stretch between 2700-3300 cm -1. It overlaps the CH stretch which
appears near 3000 cm-1. A strong carbonyl CO stretch band exists near 1700 cm -1.
The CO single bond stretch shows up near 1200 cm -1.
The spectrum for 1-bromobutane, C4H9Br, is shown here. This is relatively simple
because there are only CH single bonds and the CBr bond. The CH stretch still
appears at about 3000 cm-1. The CH2 bend shows up near 1400 cm-1, and you can
see the CBr stretch band at approximately 700 cm -1.
work.
When you analyze the spectra, it is easier if you follow a series of steps in
examining each spectrum.
1. Look first for the carbonyl C::O band. Look for a strong band at 1820-1660 cm-1.
This band is usually the most intense absorption band in a spectrum. It will have a
medium width. If you see the carbonyl band, look for other bands associated with
functional groups that contain the carbonyl by going to step 2. If no C::O band is
present, check for alcohols and go to step 3.
ACID
ESTER
ALDEHYDE
KETONE
3. If no carbonyl band appears in the spectrum, look for an alcohol O-H band.
ALCOHOL
4. If no carbonyl bands and no O-H bands are in the spectrum, check for double
bonds, C::C, from an aromatic or an alkene.
ALKENE
AROMATIC
5. If
none of
the
previous
ALKANE
6. If the
spectrum still cannot be assigned you may have an alkyl bromide.
ALKYL
BROMIDE
In this experiment you will learn about how organic substances can be classified
according to the functional groups they contain. You will then examine the
physical and chemical properties of a number of unknown compounds in order to
determine their identity.
The experiment is composed of four parts (background, prelab, experiment,
postlab) that should be completed in the order listed below.
It would be very time consuming to perform all of the chemical tests on each of the
unknowns you have been assigned. Fortunately, a flow chart can be devised to help
simplify the process. Following the flow chart will help you identify which class of
compound your unknown belongs to. If there is more than one possibility among
the unknowns, you will have to use solubility and boiling point data as well.