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01 STRUCTURAL ISOMERISM
01 STRUCTURAL ISOMERISM
&
Structural Isomerism
Contents
Topic Page No.
Theory 01 - 07
Exercise - 1 08 - 23
Exercise - 2 24 - 26
Exercise - 3 26 - 28
Exercise - 4 29 - 31
Answer Key 32 - 33
Syllabus
Hybridisation of carbon; Sigma and pi-bonds; Shapes of simple organic molecules
& structural isomerism, IUPAC nomenclature of simple organic compounds (only
hydrocarbons, mono-functional and bi-functional compounds);
IUPAC Nomenclature :
Groups :
Atom or a group of atoms which possess any 'charge' on it or any 'free valency' are called as Groups.
Alkyl group : When a hydrogen is removed from saturated hydrocarbon then alkyl group is formed. It is
represented by R & its general formula is CnH2n + 1. A bond is vacant on alkyl group on which any functional
group may come.
CH4 H CH3 – Methyl
CH3
(b) C4H9 has following four structures :
CH3
CH3
(iv) Tertiary butyl (1,1-dimethyl ethyl) CH3–C–
CH3
Alkenyl group :
CH2 = CH – Ethenyl
CH3 – CH = CH – Propenyl(1-propenyl)
Alkynyl group :
CH C– Ethynyl
Retained Name :
Normal group :
(c) Free bond will come either on 1st carbon atom or on last carbon atom.
n-butyl C–C–C–C–
n-propyl C–C–C–
Iso group :
It is represented by following structure C–C–
C
Neo group :
(a) When two methyl group are attached to second last carbon atom group is named as neo group.
(b) It is represented by following structure -
Number of
Name
Carbon Atoms
1 Methane
2 Ethane
3 Propane
4 Butane
5 Pentane
6 Hexane
7 Heptane
8 Octane
9 Nonane
10 Decane
11 Undecane
12 Dodecane
13 Tridecane
14 Tetradecane
15 Pentadecane
16 Hexadecane
17 Heptadecane
18 Octadecane
19 Nonadecane
20 Eicosane
21 Heneicosane
22 Docosane
23 Tricosane
30 Triacontane
31 Hentriacontane
40 Tetracontane
50 Pentacontane
60 Hexacontane
70 Heptacontane
80 Octacontane
90 Nonacontane
100 Centane or Hectane
6. R–C–X
Alkanoyl halide – oyl halide (carbonyl halide) halo carbonyl
||
O
7. R – C – NH2
Alkanamide – amide (carboxamide) Carbamoyl
||
O
9. R–C–H
Alkanal – al (carbaldehyde) formyl
||
O
Isomerism
Organic compounds having same molecular formula but differing from each other at least in some physical or
chemical properties or both are known as isomers (Berzelius) and the phenomenon is known as isomerism.
The difference in properties of isomers is due to the difference in the relative arrangements of various atoms
or groups present in their molecules. Isomerism can be classified as follows:
CH3
|
(ii) C5 H12 : (Three) CH3 CH2 CH2 CH2 CH3 , CH3 CH CH2 CH3 , CH3 C CH3
| |
n Pentane
CH3 CH3
Isope ntane
Neop entane
Except alkynes chain isomerism is observed when the number of carbon atoms is four or more than four.
Chain isomers differ in the nature of carbon chain, i.e., in the length of carbon chain.
The isomers showing chain isomerism belong to the same homologous series, i.e., functional group,
class of the compound (Cyclic or open) remains unchanged.
Chain and position isomerism cannot be possible together between two isomeric compounds. If two
compounds are chain isomers then these two will not be positional isomers.
(2) Position isomerism : It is due to the difference in the position of the substituent atom or group or an
unsaturated linkage in the same carbon chain.
C 3 H6 Cl2 : CH3 CCl2 CH3 , CH3 CH2 CHCl2 , CH3 CH CH 2 , CH2 CH2 CH2
2,2 Dichloro propane, 1,1Dichloro prop ane | | | |
(gemdihalide ) (gemdiha lide) Cl Cl Cl Cl
1,2 Dichloro propane 1,3 Dichloro propane
(, -dihali de)
(Vicdih alid e)
Aldehydes, carboxylic acids (and their derivatives) and cyanides do not show position isomerism.
Monosubstituted alicylic compounds and aromatic compounds do not show position isomerism.
Structural isomers which differ in the position of the functional group are called regiomers.
For example, (i) CH3 CH2 CH2 OH (ii) CH3 CH CH3
|
OH
(iii) Acids, esters and hydroxy carbonyl compounds …etc. (Cn H2 n O2)
C2 H4 O2 : CH3 COOH ; HCOOCH3
Acetic a cid Methyl forma te
O
||
C3 H6 O2 : CH3 CH2 COOH ; CH3 COOCH3 ; H3C CH CHO ; CH3 C CH2 OH
Prop ionic a cid Methyl a cetate 1 Hydroxy propan-2-o ne
OH
2-Hydroxypr opanal
O
C2 H5 NO2 : C2H5 N ; C2H5 O N O
Ethyl ni trite
O
Nitro ethane
If same polyvalent functional group is there in two or more organic compounds, then chain or position
isomerism is not possible, there will be metamerism e.g.,
(a) CH3 C CH2 CH2 CH3 ; CH3 CH2 C CH2 CH3 are metamers and not position isomers.
| | ||
O O
(Pe n tan 2 one ) (Pen tan 3 on e)
(b) CH3 C CH2CH2CH3 ; CH3 C CH CH3 are metamers and not chain isomers.
|| || |
O O CH3
(Pentan 2 one) (3-Methylbutan-2-one)
A-2. How many secondary carbon atoms does methyl cyclopropane have?
(A) None (B) One (C) Two (D) Three
A-3. Which of the following is the first member of ester homologous series ?
(A) Ethyl ethanoate (B) Methyl ethanoate (C) Methyl methanoate (D)Ethyl methanoate
A-4. How many carbons are in simplest alkyne having two side chains ?
(A) 5 (B) 6 (C) 7 (D) 8
A-5. How many 1º carbon atom will be present in a simplest hydrocarbon having two 3º & one 2º carbon atom?
(A) 3 (B) 4 (C) 5 (D) 6
A-8. The total number of secondary H-atoms in the structure given below are :
(CH3)2CHCH2C2H5
(A) 1 (B) 4 (C) 3 (D) 2
A-12. An organic compound has molecular formula C9H18. It is a saturated hydrocarbon and its all hydrogen
atoms are identical. Its structural formula can be :
(A) (B)
(C) (D)
B-2. As per IUPAC rules, which one of the following groups, will be regarded as the principal functional group?
HC CH HC COOH HC CH HC CH
(A) | (B) | (C) | (D) |
HC CH HC COOH HC CH HC CH
C-2. The IUPAC name of the compound Br(Cl) IC. CF3 is:
(A) 2-bromo-2-chloro-2-iodo1,1,1-trifluoroethane
(B) 1,1,1-trifluoro-2-bromo-2-chloro-2-iodo ethane
(C) 2-bromo-2-chloro-1,1,1-trifluoro-2-iodo ethane
(D) 1-bromo-1-chloro-1-iodo-2,2,2-trifloro ethane
C-3. The IUPAC name of the following structure is [CH3CH(CH3)]2 C(CH2CH3)C(CH3) C(CH2CH3)2
(A) 3,5-diethyl-4,6-dimethyl-5-[1-methylethyl]-3-heptene
(B) 3,5-diethyl-5-isopropyl-4,6-dimethyl-2-heptene
(C) 3,5-diethyl-5-propyl-4,6-dimethyl-3-heptene
(D) None of these
F Cl
C-4. The IUPAC name of this compound is : | |
CH3 C CH2 C CH3
(A) 2-fluoro-4-chloro-2,4-diethyl pentane
| |
(B) 3-fluoro-5-chloro-3-methyl-5-ethyl hexane CH 2 CH 3 CH 2CH3
C-8. In the structure of 4-Isopropyl-2, 4, 5-trimethylheptane, number of 1°, 2° & 3° H's are respectively :
(A) 18, 5, 4 (B) 21, 4, 3 (C) 18, 4, 3 (D) 21, 5, 4
D-1. The IUPAC name of the compound having the formula is:
CH 3
|
H 3C C CH CH 2
|
CH 3
(A) 3,3,3-trimethyl-1-propene (B) 1,1,1-trimethyl-2-propene
(C) 3,3-dimethyl-1-butene (D) 2,2-dimethyl-3-butene
CH3 – C C – CH3
| |
C2H5 C2H5
D-7. The molecular formula of the first member of the family of alkenynes and its name is given by the set
(A) C3H2, alkene (B) C5H6, 1-penten-3-yne
(C) C6H8, 1-hexen-5-yne (D) C4H4, butenyne
CH CH3
||
HC C C C C CH2 CH3 is :
(A) 5-ethyl- 5-heptene-1, 3- diyne (B) 3-ethyl- 2-heptene-4, 6- diyne
(C) 5-ethenyl-1, 3- heptatriyne (D) 3-ethenyl-4, 6-heptatriyne
is -
C2H5
CH3
is -
(A) Spiro [5.3] nonane (B) Spiro [3.5] nonane (C) Spiro [5.4] nonane (D) Spiro [4.5] nonane
Ph
|
F-2. The IUPAC name of the compound is CH 3 CH CH NH 2
|
CH 3
(A) 6-oxo-1,2,2- trimethyl bicyclo [2,2,1] heptane (B) 1,7,7-trimethyl bicyclo [2,2,1] heptan-2-one
(C) 1,5,5-trimethyl bicyclo [2,1,1] hexan-2-one (D) 1,7,7-trimethyl bicyclo [2,1,2] heptan-2-one
HO C O CH 3
| |
G-3. The IUPAC name of compound CH 3 C C — C H is:
| |
NH 2 Cl
H 2 N CH CH CHO
| |
HOOC COOH
(A) 3-amino-2-formyl butane-1, 4-dioic acid (B) 3-amino-2, 3-dicarboxy propanal
(C) 2-amino-3-formyl butane-1, 4-dioic acid (D) 1-amino-2-formyl succinic acid
G-12. is named as :
H-2. One among the following is the correct IUPAC name of the compound
H
|
CH 3CH 2 N CHO
(A) N-Formyl aminoethane (B) N-Ethyl formyl amine
(C) N-Ethyl methanamide (D) Ethylamino methanal
H 3COOC CH COOCH 3
|
CH 2OH
(A) methyl 2-hydroxymethylpropandioate (B) Methyl methyl-2-hydroxypropandioate
(C) dimethyl-2-hydroxy methyl propandioate (D) 2-hydroxy methyl-dimethyl propandioate
(A) CH 3 C O CH CH 3 (B)
|| |
O CH 3
(C) CH3 C O CH 2 CH 2 (D) H C O CH CH 3
|| | || |
O CH 3 O CH 3
J-2. Which of the following is the first member of ester homologous series?
(A) Ethyl ethanoate (B) Methyl ethanoate (C) Methyl methanoate (D) Ethyl methanoate
(A) Chain isomers (B) Position isomers (C) Functional isomers (D) Identical
J-12. Which of the given set of molecules have similar molecular formula :
(A) Nonane, 2-methylheptane (B) 3-Isopropylcyclopent-1-ene, 3-methylhexane
(C) 3-Methylcyclopent-1-ene, penta-1, 3-diene (D) Ethylcyclohexane, oct-2-ene
COOH
OCOH
J-16. & functional isomer
OMe OEt
Et
& metamers
Me
& metamers
Me – N – Me CH2 – NH – CH3
Me Me Me
Me Me
Me Me
O – Me O–Me
OH OH
I II III IV
K-2. How many positional isoemrs are possible for 3-ethylpentane (including it self)
(A) 1 (B) 2 (C) 3 (D) 4
K-3. The total number of unsaturated cyclic structure possible for a compound with the molecular formula C4H6
is:
(A) 3 (B) 4 (C) 5 (D) 6
K-7. The number of primary, secondary and tertiary amines possible with the molecular formula C3H9N
respectively:
(A) 1, 2, 2 (B) 1, 2, 1 (C) 2, 1, 1 (D) 3, 0, 1
Comprehensions Type :
Comprehension
The international group IUPAC has developed a detailed. system of nomenclature that we call the IUPAC
rule. Which are accepted throughout the world as the standard method for naming organic compounds. In
this system Alkyl groups are named by replacing the ‘-ane’ suffix of alkane name with ‘-yl’ like methyl ethyl
etc. complex alkyl groups are named. by a systematic method using the longest alkyl chain as the base
alkyl group. The base alkyl group is numbered beginning with the carbon atom bonded to the main chain.
The substitutes on the base alkyl group are listed with appropriate number and parentheses are used to
set off the name of the complex alkyl group.
CH3
CH3 CH CH CH2
CH3
(A) (Di-isohexyl) (B) (2,3-dimethyl butyl) (C) (2,2-dimethyl butyl) (D) (2,-methyl-3-ethylbutyl)
CH2 CH CH2
2. Choose the correct IUPAC name of following alkyl group
OH CH3
(A) (2-methyl-3-Propanoyl) (B) (3-hydroxy-2-methyl propyl)
(C) (2-methyl-3-hydroxy propyl) (D) (1-hydroxy-2-methyl propyl
CH3 CH3
CH3
4. (2-propenyl) group is -
(A) CH2=CH–CH2– (B) CH3–CH=CH–
(C) Both (A) and (B) (D) None of these
Each question has 5 choices (A), (B), (C), (D) and (E) out of which ONLY ONE is correct.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
(E) Statement-1 and Statement-2 both are False.
H
5. Statement-1 : CN is called cyclohexanenitrile.
Statement-2 : : It contains six carbon atoms in the ring and CN as the functional group.
2-ethylprop-2-en-1-ol.
Statement-2 : Ethyl (C2H5) rather than methylene (=CH2) is considered as the substituent group because
‘e’ of ethyl comes first in alphabetically order than ‘m’ of methylene.
Br
|
1. The IUPAC name of CH3 CH CH2 CH2 CH2 C CH3 is
| |
OH Br
(A) 6, 6-Dibromo heptan-2-ol (B) 2, 2-Dibromo heptan-6-ol
(C) 6, 6-Dibromo heptan-2-al (D) None of these
(A) (B)
(C) (D)
5. How many primary amines are possible for the formula C8H11N (only Aromatic structural isomers)
(A) 4 (B) 6 (C) 7 (D) 14
7. How many structural isomers could be obtained from molecular formula C2FCl BrI
(A) Four (B) Five (C) Six (D) Three
and
9. Which of the following compound does not have molecular formula C6H6
(A) Hexa-1, 3-dien-5-yne
(B) 3-(2-cyclopropenyl)cycloprop-1-ene(or Bicyclopropenyl)
(C) Cyclohexa-1, 3-diene-5-yne
(D) Cyclohexa-1, 3, 5-triene
(A) I, II only (B) III, IV only (C) I, II, III (D) All
CH3 Cl
CH3 – CH2 – CH2 – CH2 – Cl CH3 – C – CH3
– CH2 – Cl
Cl
I III IV
II
(A) I & II are chain isomers (B) I & III are functional isomers
(C) II & IV are functional isomers (D) III & IV are chain isomers
1. 2. 3.
4. 5. 6.
CH2 CH2
|| ||
7. 8. CH2=CH– C=CH–CH=CH2 9. CH3 C C C C CH3
|
Br
22.
23. Identify the molecular weight of the compound ‘X’ containing carbon and hydrogen atoms only with 3 and
2 bonds in one molecule.
24. Find the hybridization state of each carbon atoms in following compound.
CH2 = C = CH – CH2 – C C – CH2 – NH2
25. Calculate the molecular weight of the lowest hydrocarbon which contains sp & sp2 hybridised carbon atoms
only.
2. Which of the following represents the given mode of hybridisation, sp2 – sp2 – sp – sp, from left to right?
[JEE-2003]
(A) H2C = CH – C CH (B) CH C – C – C CH
O
||
4. IUPAC name of C 6H5 C Cl [JEE-2006]
(A) Benzoylchloride (B) Benzenecarbonylchloride
(C ) Chlorophenyl ketone (D) phenylchloroketone
7. The total number of cyclic possible for a hydrocarbon with the molecular C4H6 is /are : [JEE-2010]
is -
is –
8. The correct decreasing order of priority for the functional groups of organic compounds in the IUPAC
system of nomenclature is [AIEEE 2008]
(1) –SO3H, –COOH, –CONH2, –CHO (2) –CHO, –COOH, –SO3H, –CONH2
(3) –CONH2, –CHO, –SO3H, –COOH (4) –COOH, –SO3H, –CONH2, –CHO
1. Name the following halides according to IUPAC system and classify them as alkyl, allyl, benzyl (primary,
secondary , tertiary), vinyl or aryl halides :
5. Draw the structures of all isomeric alcohols of molecular formula C5H12O and give their IUPAC names.
8. Write the IUPAC names of the following ketones and aldehydes. Wherever possible, give also common
names:
(i) CH3CO(CH2)4CH3 (ii) CH3CH2CHBrCH2(CH3)CHO
(iii) CH3(CH2)5CHO (iv) Ph–CH=CH–CHO
9. Write IUPAC names of the following compounds and classify them into primary, secondary and tertiary
amines.
(i) (CH3)2CHNH2 (ii) CH3(CH2)2NH2 (iii) CH3NHCH(CH3)2
(iv) (CH3)3CNH2 (v) C6H5NHCH3 (vi) (CH3CH2)2NCH3
(vii) m-BrC6H4NH2
10. Write structures of different chain isomers of alkanes corresponding to the molecular formula C6H14. Also
write their IUPAC names.
(i) (ii)
13. Write structures and IUPAC names of different structural isomers of alkenes corresponding to C5H10.
14. Draw cis and trans isomers of the following compounds. Also write their IUPAC names :
(i) CHCl=CHCl (ii) C2H5CCH3=CCH3C2H5
15. Write structures of different isomers corresponding to the 5th member of alkyne series. Also write IUPAC
names of all the isomers. What type of isomerism is exhibited by different pairs of isomers ?
(g)
17. For the following compounds, write structural formulas and IUPAC names for all possible isomers having
the number of double or triple bond as indicated :
(a) C4H8 (one double bond) (b) C5H8 (one triple bond)
G-5. (B) G-6. (B) G-7. (B) G-8. (D) G-9. (B) G-10. (C) G-11. (D)
G-12. (C) H-1. (A) H-2. (C) H-3. (A) H-4. (C) H-5. (D) H-6. (D)
H-7. (B) H-8. (A) H-9. (D) H-10. (D) H-11. (B) I-1. (A) I-2. (A)
I-3. (D) I-4. (B) I-5. (C) J-1. (A) J-2. (C) J-3. (A) J-4. (C)
J-5. (C) J-6. (D) J-7. (A) J-8. (D) J-9. (B) J-10. (A) J-11. (D)
J-12. (D) J-13. (D) J-14. (A) J-15. (C) J-16. (C) J-17. (D) J-18. (A)
K-1. (B) K-2. (A) K-3. (B) K-4. (B) K-5. (B) K-6. (D) K-7. (C)
PART # II
8. (C) 9. (B)
EXERCISE # 2
PART # I
8. (B) 9. (C) 10. (A) 11. (C) 12. (C) 13.* (AD)
PART # II
1. 3-(1-Chloroethyl)-4-methyl-4-phenylpentan-2-one 2. 2-Cyclopropyl-4-ethylhex-1-ene
3. 6-isopropylcyclodec-1-yne 4. 1-Chloro-2, 3-epoxypropane
5. 3-Mercaptobenzoic acid 6. N, N-Diethyl cyclohexanecarboxamide
7. 3–Cyclopropyl-3-methylbutanal 8. 3–Bromohexa–1, 3, 5–triene
9. 2–Methyl–3–methylenehex–1–en–4–yne 10. 3–Methoxy–5, 5–dimethylcyclohex–2–en–1–ol
11. 2–Bromo–1–chloro–3–iodocyclohexane 12. Carbylamineprop-2-ene
13. 1, 1, 1–Trichloro-2, 2-bis(4–chlorophenyl)ethane 14. 1–(3–bromophenyl)–6–phenylhexa–1,3,5–triyne
15. 3–Methyl–2–(3–oxobutyl)cyclohexan-1-one 16. 2, 4, 7-Trioxaoctane
17. 1, 3, 5, 7-Tetraoxacyclooctane 18. 2-Ethoxy-2-methylpropane
EXERCISE # 3
PART # I
5. (C) 6. (B) 7. 5
PART # II
EXERCISE # 4
NCERT QUESTIONS
10. (i) CH3–CH2–CH2–CH2–CH2–CH3 n-Hexane (ii) CH3– CH –CH2–CH2–CH3 2-Methylpentane
|
CH3
CH3
|
(v) CH3– C –CH2–CH3 2, 2-Dimethylbutane
|
CH3
11. (i) 2, 2, 4, 4-Tetramethylpentane (ii) 3, 3-Dimethylpentane (iii) 3, 3-Di-tert-butayl-2, 2, 4, 4-tetramethylpentane
12. (i) 2, 8-Dimethyl-3, 6-decadiene ; (ii) 1, 3, 5, 7 Octatetraene ;
(iii) 2-n-Propylpent-1-ene ; (iv) 4-Ethyl-2, 6-dimethyl-dec-4-ene ;
15. 5th member of alkyne has the molecular formula C6H10. The possible isomers are :