H2 CHEMISTRY 9647

TUTORIAL 10: INTRODUCTION TO ORGANIC CHEMISTRY

FORMATIVE ASSESSMENT: Each carbon atom can form 4 covalent bonds. Carbon needs to form equivalent orbitals of same shapes and energies by a process known as hybridisation before bonding can occur.

Classification: Aliphatic molecules contain open (straight or branched) chains of carbon skeletons. Alicyclic molecules consist of closed rings of carbon atoms, which may contain single or multiple bonds. Aromatic molecules contain at least 1 benzene ring (ring of 6 carbon atoms where electrons in p-orbitals are delocalized). Functional Groups & Homologous Series: Functional Group consists of an atom or groups of atoms or bond common to a series or family of compounds and it governs the principal chemical properties of the series. A series of compounds containing the same functional group is called a homologous series. Formulae: Empirical formula gives the simplest ratio of the atoms of each element present. Molecular formula gives the actual number of atoms of each element present. Condensed structural formula shows how the constituent atoms are joined together. Full-structural or Displayed formula shows both the relative placing of atoms and the number of bonds between them. Nomenclature:

(position prefix substituent) Parent

Indicates the position of the Indicates the number Longest, continuous Arrange in substituent on the carbon of the same carbon chain alphabetical order chain. substituent. (functional group) Number should be as small as possible.

Reactions of Organic Compounds: (I) Types of reagent:

(a) Nucleophiles are negative ions (e.g. OH-, CN-) and compounds in which an atom has a
lone pair of electrons (e.g. NH3).

(b) Electrophiles are reagents (e.g. NO2+) which attack a region where the electron density is
high. (II) Types of reactions:

(a) Substitution: involves replacing an atom (or a group of atoms) by another atom
(or groups of atoms).

(b) Addition: (c) Elimination: (d) Hydrolysis:

involves two molecules joining to form a single new molecule. involves the removal of a molecule from a larger molecule. involves breaking covalent bonds by reaction with water.

(e) Oxidation / Reduction (III) Types of bond fission:

(a) Homolytic fission: when the bond breaks, each of the bonded atoms takes one
electron. Free radicals, which are atoms or groups of atoms with unpaired electrons, are formed. They are electrically neutral but highly reactive.

(b) Heterolytic fission: When the bond breaks, one of the atoms take both of the bonding
electrons to form an anion. The rest of the molecule becomes a cation. Isomerism: Isomers are compounds with the same molecular formula but different arrangement of the atoms in the molecule. ISOMERISM

Structural same molecular formula different structural formula i.e. different arrangement of atoms

Stereoisomerism same molecular formula same structural formula but different spatial arrangement of atom

Chain

Positional

Functional Group

Geometric (cis-trans)

Optical isomerism

DISCUSSION QUESTIONS: 1 Give the IUPAC name for each of the following structures. (a)

CH3CH CHCH3 CH3 CH3

(b)

CH3CHCH=CH2 CH3

(c)

CH3CHCO2H CH3

(d)

Br Cl CH3C CCH3 CH3 CH3

(e)

CH3 C CH CH3 3 CH=CH2

(f)

(CH3)2CHCCl=CH2

(g) CH3C(CH3)2CHClCH3

Q1a 2,3-dimethylbutane

Q1e

3,3-dimethylbut-1-ene
H H HH C H H C H CH3 C CH3 C C H H

Q1b 3-methylbut-1-ene Numbering starts from the carbon with the double bond.

Q1f

Functional group: alkene 2-chloro-3-methylbut-1-ene

Cl H H C H H C CH3 C C H H

Q1c 2-methylpropanoic acid Functional group: carboxylic acid

Functional group: alkene Q1g 3-chloro-2,2-dimethylbutane

CH3 H3C H C Cl CH3

C
CH3

2-chloro-3, 3-dimethylbutane does not give the smallest overall number assigned to the compound. Q1d 2-bromo-3-chloro-2,3dimethylbutane

* Substitutents arranged in alphabetical order

2. For each of the following compounds, i. Give the IUPAC name of the compound ii. Predict the hybridization and geometry of the carbon atom (marked with an asterix *) iii. Indicate whether the bonds involved are or bonds (a) CH3CH2C*Br2CH3 (b) CH3CH2CH=C*HCH3

* H3C
(c)

Cl Note: There are two asterixes

ai) 2, 2-dibromobutane ii) carbon is sp3 hybridized (bonded to 4 atoms) tetrahedral iii) All bonds involved are bonds. bi) pent-2-ene ii) Carbon is sp2 hyridized (bonded to 3 atoms) trigonal planar iii) double bond consists of a and bond. c) i) 3-chloromethylbenzene (Note: Numbering of carbon atoms in ring can be clockwise or anticlockwise. Assign lowest number to substituents by alphabetical order) ii) Carbon on methyl group is sp3 hybridized (bonded to 4 atoms) tetrahedral Carbon in benzene ring is sp2 hyridized (bonded to 3 atoms) trigonal planar iii) Carbon in methyl group only has bonds. Carbon in benzene ring has 3 bonds and 1 electron in a delocalized cloud.

Write the structural formula for each of the following compounds.

(a) (c)

1-chloropropan-2-ol 3-chloro-3-ethylpentane

(b) (d)

1-bromo-2-methylbutane 2-methylbut-2-ene

a) 1-chloropropan-2-ol
H Cl H C H O C H H

b) 1-bromo-2-methylbutane
Br H
C H H

H C C H

H C H H

H C H H

C HH

* To show all bonds and arrangement of atoms in compounds. CH2ClCH(OH)CH3 c) 3-chloro-3-ethylpentane

H H C H H C HH H Cl C C C H H C HH H H

CH2BrCH(CH3)CH2CH3

d) 2-methylbut-2-ene
H H C H H H H C H C C C H H C H H H

CH3CH2CCl(C2H5)CH2CH3

CH3CHC(CH3)2

4. (a) What do you understand by the term structural isomerism? (b) Draw and name the full structural formulae for all possible isomers of (i) (ii) (iii) (iv) (v) C3H7Cl C3H6Br2 C4H9Br C3H8O C8H10 (Hint: this structure contains a benzene ring)

a) Structural isomerism arises due to different arrangement of atoms in organic compounds (different structural formulae) but they have the same molecular formula.

b) i) C3H7Cl CH3CH2CH2Cl
H H C H H C H Cl H

CH3CHCl CH3
H C H Cl C H H C H H

Positional isomers

C H

1-chloropropane (ii) C3H6Br2 CH3CH2CHBr2 Positional isomers

H H C H H C H Br C Br H H

2-chloropropane

CH3CBr2CH3
H C H Br H C C H

CH2BrCHBrCH3
Br Br H H C H C H C H H

CH2BrCH2CH2Br
H H C H C Br C H H

Br H

Br H

1,1dibromopropane

2,2dibromopropane

1,2dibromopropane

1,3dibromopropane

No chain isomers or functional group isomers possible for 3bi and 3bii (iii) C4H9Br CH3CH2CH2CH2Br
H H C H H C H H C H H H

CH3CHBrCH2CH3
H C H H C Br H C H H C H H

Positiona l isomers

C Br

1-bromobutane CH2BrCH(CH3)2
H CH3 H C H C H H H

2-bromobutane CH3CBr(CH3)2
H C H CH3 H C Br C H H

Chain isomers

C Br

1-bromo-2-methylpropane (iv) C3H8O CH3CH2CH2OH (alcohol)

2-bromo-2-methylpropane

CH3OCH2CH3 (ether) 6

Functional group isomers

H H C H

H C H

H C H OH H

H C H O

H C H

H C H H

Propan-1-ol CH3CH(OH)CH3
H H C H C H

Methoxyethane

Positional isomers

C H

OH H

Propan-2-ol (v) C8H10

CH3

H CH3 C H

H C H H

Chain isomers

1,2-dimethylbenzene
CH3
CH3

ethylbenzene

Positiona l isomers
CH3
CH3

1,3dimethylbenzene

1,4dimethylbenzene

5. (a) What do you understand by the term stereoisomerism? (b) Name the two types of stereoisomerism and explain briefly how they arise.

(c) Which of the following structures will have cis-trans isomers? (i) CH2=C(CH3)2 (iii) CH3CH=CHCH3 (v) CH2=CHCH2CH=CH2 (d) Mark the chiral carbons (if any) with an asterisk (*). (i) (ii) (iii) (ii) (iv) CH3BrC=CCl2 C6H5CH=CHCO2H

OH OH CH3 C OH

H C NH CH3 2 CO2H

H C N OH CH3
H2NCH2CO2H

(iv) (CH3)2CHCHBrCH3 (e)

(v)

(vi)

CH3CHBrCHBrCH2CH3

Draw the optical isomers for the organic compounds in parts d (i) and d (iv).

a) Stereoisomerism arises due to different arrangement of atoms in space in organic compounds with the same molecular and structural formula. b) Geometric isomerism arises to the restriction of rotation about the C=C double bond & when 2 different substituents are attached to each C across the double bond. Optical isomerism arises when compounds do not exhibit a plane of symmetry and forms mirror images which are non-superimposable.

c) (i) (ii) (iii)

H C H3C C CH3 H3C H H C C H CH3

Does not display cis-trans as 2 similar groups (CH3) are attached to the same carbon atom. Does not display cis-trans as 2 similar groups (Cl) are attached to the same carbon atom.

cis-but-2-ene (iv)

trans-but-2-ene

H C H3C C

H C H3C

CO2H CH3
C H

CO2H
CH3

cis-isomer

trans-isomer

(v)

Does not display cis-trans as 2 similar groups (H) are attached to the same carbon atom.
H H

C
H

C CH2CH=CH2

d) (i)
H3C

H C

H
NH2

H C CH3

C H3C

CO2H

NH2 CO2H

H2N HO2C

Mirror (ii) (iii)

OH H C OH H3C C H3C OH HO H C CH3

No chiral carbon

OH

HO

OH

Mirror

(iv)

H C CH(CH3)2

* (CH3)2CHCHBrCH3
(H3C)2HC

Br CH3

Br

Mirror

H3C

(v) (vi)

No chiral carbon 2 chiral carbons CH3CHBrCHBrCH2CH3 * CH3CHBrCHBrCH2CH3 *

H H3C C Br CHBrCH2CH3 H3CBrHC

H C Br CH2CH3

6.

Give the structural formulae for each of the following compounds (including geometrical isomers, if any). (a) (c) hex-1-ene 2-methylbut-1-ene (b) (d) hex-2-ene 1-chlorobut-2-ene

H C C

(a) No geometric isomers1 (b)

C3H7 C H C

C4H9

CH3

H C C

CH3

C3H7

cis-hex-2-ene

trans-hex-2-ene

To express C2H5 as CH2CH3, C3H7 as CH2CH2CH3 and C4H9 as CH2CH2CH2CH3 when representing solutions to students.

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H3C C C

(c) No geometric isomers (d)

H3C C H C

C2H5

CH2Cl

H C C

CH2Cl

H3C

cis-1-chlorobut-2-ene

trans-1-chlorobut-2-ene

7. A monocarboxylic acid P occurs in goats milk. P has the following composition by mass: C, 62.1%; H, 10.3%; O, 27.6%. Neutralisation of a sample of 0.10 g of P requires 8.6 cm 3 of 0.10 mol dm-3 sodium hydroxide. Calculate the empirical and the molecular formulae of P. (Ans: C3H6O; C6H12O2)

% by mass Ar No of moles Simplest mole ratio Empirical formula: C3H6O

C H O 62.1 10.3 27.6 12.0 1.0 16.0 5.18 10.3 1.73 1 3 6

Let molecular formula be (C3H6O)n Mr of carboxylic acid = (36.0+6.0+16.0)n = 58.0n

8 .6 0.10 = 8.60 10 4 1000 Since the acid is a monocarboxylic acid, NaOH acid

No. of moles of NaOH =

No. of moles of acid = 8.60 x 10-4 0.10 = 8.60 10 4 58.0n 58.0n = 116.28 n = 1.99 2

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 Molecular formula of acid = C6H12O2

ASSIGNMENT QUESTIONS 8. (a) A carboxylic acid of the formula C3H5O2Br is optically active. What is its structure? (b) Give the structure of the lowest-molecular-mass alcohol (containing only C, H and O) that is chiral. (c) A solution of 2-hydroxypropanoic acid isolated from a natural source rotated polarised light to the right, whereas a solution of 2-hydroxypropanoic acid synthesised from ethanol did not rotate polarised light. Why is this so?

a)

A carboxylic acid with formula C3H5O2Br has two possible structural formulae as shown below:
Br H C H H C H C OH O H H C H Br C H O C OH

3-bromopropanoic acid 2-bromopropanoic acid However only 2-bromopropanoic acid is optically active (b)*
C2H5 OH C H CH3

* Note: Ans to 8(b) should be OH HCCCCH3 H Lowest molecular mass alcohol (containing only C, H and O) that is chiral. (c) A racemic mixture containing an equal amount of both 2-hydroxypropanoic acid enantiomers is formed when the acid is synthesised from ethanol. When 2hydroxypropanoic acid is isolated from the natural source, only one of the pair of enantiomers is obtained, thus the acid is able to rotate polarised light.

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9. A hydrocarbon (containing 14.3% by mass of hydrogen) is a gas of density 2.50g dm-3 at s.t.p. (a) (b) (c) Calculate its empirical formula. Calculate its molecular formula. Draw three possible structural formulae for the compound.

(a) % by mass Ar No of moles Simplest mole ratio Empirical formula: CH2 (b) Molar gas volume at s.t.p = 22400 cm3 At s.t.p, 1 mole of the hydrocarbon has a volume of 22.4 dm3 Mass of 1 mole of hydrocarbon = 22.4 2.50 = 56.0g Let molecular formula of hydrocarbon be (CH2)n Mr of hydrocarbon = 14.0n
14.0n = n=4 56.0 1

C H 85.7 14.3 12.0 1.0 7.14 14.3 1 2

Molecular formula of hydrocarbon = C4H8 (c) CH2CH2CH2CH2 CH3CH2CHCH2

H C2H5 C H C H H

CH3CHCHCH3
H3C C C H H CH3 H

CH2C(CH3)2
CH3 C C CH3

Structural isomers cyclobutane

But-1-ene

But-2-ene

2-methylpropene

ADDITIONAL QUESTIONS (ON ISOMERISM) 1) Nov 2004 P3 Q6 (a) 2) Nov 2002 P2 Q5 (a)

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3) Nov 2000 P2 Q4 (a) 4) Jun 2000 P1 Q6 (a)

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