Organic Chemistry AC 003

LECTURE 03 Conformers; Reactions; Alkanes: Isomers, Nomenclature and Physical Properties

1

ASC0302-1-Gas Liquid Solid 1

Ya Allah! Bukakanlah dan Tambahkanlah Rahmat daripada KahazanahMu itu kepada kami. Ya Tuhan, yang Maha Pengasih lagi Maha Penyayang.

Tip for the Day

Pastikan Bacaan Al-Fatihah anda sempurna terutama dalam Solat anda. Setiap sehari semalam, anda membaca minimum 17 kali al-Fatihah sekiranya anda orang beriman.

Who are You ?

What Do We Need To Be The Best? Desire Study Skills Exam Strategy Effort

Ujian 1
JADUAL PELAKSANAAN UJIAN 1, SEMESTER KETIGA KURSUS ASM0403 ASA0103 ASP0503 TARIKH 13.2.2012 14.2.2012 15.2.2012 HARI ISNIN SELASA RABU MASA 8.15 - 10.00 8.15 - 10.00 8.15 - 10.00 TEMPAT KAE 1-20 KAE 1-20 KAE 1-20

ASC0303 ASB0203 ASM0402

16.2.2012 KHAMIS 8.15 - 10.00 20.2.2012 21.2.2012 ISNIN SELASA 8.15 - 10.00 8.15 - 10.00

KAE 1-20 KAE 1-20 KAE 1-21

How Prepared Are You? Prelecture Quiz 2

Lecture Group: 1

Matric No.:

Name:

The formula for a substituted alkane is shown below.

In the IUPAC system what is the root or base name of this compound? How many alkyl substituents are attached to the longest chain? In numbering the chain, which carbon is #1? Give the IUPAC name for this compound.
8

LO
Conformers butane and cyclohexane Types of reactions in organic chemistry (describe) Nucleophile, Electrophile (define, identify) Homolytic and Heterolytic Cleavage (describe) Hydrocarbons
Alkanes (open chain and cyclic)
Isomers Nomenclature Physical Properties
9

Materials

Materials: Ball and Stick Molecular Model Prelecture Quiz Question Lecture understanding test

10

Conformational Analysis and Conformers

In chemistry, conformational isomerism is a form of stereoisomerism in which the isomers can be interconverted exclusively by rotations about formally single bonds. Such isomers are generally referred to as conformational isomers or conformers and specifically as rotamers when the rotation leading to different conformations is restricted (hindered) rotation, in the sense that there exists a rotational energy barrier that needs to be overcome to convert one conformer to another. Conformational isomers are thus distinct from the other classes of stereoisomers for which interconversion necessarily involves breaking and reforming of chemical bonds. The rotational barrier, or barrier to rotation, is the activation energy required to interconvert rotamers.
11

Important Examples in ASC 0303

Some important examples of conformational isomerism include: Linear alkane conformations with staggered, eclipsed and gauche conformers, and

Ring conformation Cyclohexane conformations with chair and boat conformers.

12

Conformers of butane
Newman projection: The two gauche as well as the anti form are staggered conformations Butane has three rotamers: two gauche conformers, which are enantiomeric and an anti conformer, where the four carbon centres are coplanar. The three eclipsed conformations with dihedral angles of 0,120 and 240 are not considered to be rotamers, but are instead transition states.
13

Eclipsed Butane
The calculated energy difference between (a) the non-energy-minimized and (b) the energy-minimized eclipsed conformations is 5.6 kJ (0.86 kcal)/mol.

14

Conformers: Cyclohexane Derivatives

Substituents found on cyclohexane adopt cis and trans formations and cannot be easily switched by simple single sigma bond rotation as with linear molecules. Cis formation means that both substituents are found on the same side of the 2 substituent placements on the carbon, while trans would mean that they were on opposing sides. Despite the fact that carbons on cyclohexane are linked by a single bond, the ring remains rigid, in that switching from cis to trans would require breaking the ring. The nomenclature for cis is dubbed (Z) while the name for trans is (E) to be placed in front of the IUPAC name.
15

16

Substituents in Cyclohexane
For di-substituted cyclohexane rings (i.e. two groups on the ring), the relative orientation of the two substituents affect the energy of the possible conformations. For 1,2- and 1,4-di-substituted cyclohexane, a cis configuration leads to one axial and one equatorial group. This configuration can undergo chair flipping. For 1,2- and 1,4-di-substituted cyclohexane, a trans configuration leads to either both groups axial or both equatorial. In this case, the diaxial conformation is effectively prevented by its high steric strain (four gauche interactions more than the diequatorial). For 1,3-di-substituted cyclohexanes, the cis form is diequatorial and the flipped conformation suffers additional steric interaction between the two axial groups. Trans-1,3-di-substituted cyclohexanes are like cis-1,2- and cis-1,4- and can flip between the two equivalent axial/equatorial forms.
17

Note: 1,3 diaxial interaction which engenders the steric effect which destabilises the axial conformation

18

Note: 1,3 diaxial interaction which engenders the steric effect which destabilises the axial conformation
19

Organic Reaction
Organic reactions are chemical reactions involving organic compounds. The basic organic chemistry reaction types are substitution, elimination, addition and rearrangement reactions. In organic synthesis, organic reactions are used in the construction of new organic molecules. The production of many man-made chemicals such as drugs, plastics, food additives, fabrics depend on organic reactions.

20

21

Substitution Reaction
In a substitution reaction, a functional group in a particular chemical compound is replaced by another group. In organic chemistry, the electrophilic and nucleophilic substitution reactions are of prime importance. Organic substitution reactions are classified in several main organic reaction types depending on whether the reagent that brings about the substitution is considered an electrophile or a nucleophile. A good example of a substitution reaction is the photochemical chlorination of methane forming methyl chloride.

22

Elimination Reactions
An elimination reaction is a type of organic reaction in which two substituents are removed from a molecule in either a one or two-step mechanism. Either the unsaturation of the molecule increases (as in most organic elimination reactions) or the valence of an atom in the molecule decreases by two, a process known as reductive elimination. An important class of elimination reactions are those involving alkyl halides, or alkanes in general, with good leaving groups, reacting with a Lewis base to form an alkene in the reverse of an addition raection. The one and two-step mechanisms are named and known as E2 reaction and E1 reaction, respectively. Example:

23

Addition Reaction
An addition reaction, in organic chemistry, is in its simplest terms an organic reaction where two or more molecules combine to form a larger one Addition reactions are limited to chemical compounds that have multiply bonded atoms, such as molecules with carbon-carbon double bonds, i.e., alkenes, or with triple bonds, i.e., alkynes. Also included are molecules containing carbon - hetero double bonds like those with carbonyl (C=O) groups or those with imine (C=N) groups. There are two main types of polar addition reactions: electrophilic and nucleophilic addition. One non-polar addition reaction exists as well called free radical addition.
24

Addition Reaction
There are two main types of polar addition reactions: electrophilic addation and nucleophilic addition. One nonpolar addition reaction exists as well called free radical addition.
Addition reactions general overview. Top to bottom: electrophilic addition to alkene, nucleophilic addition of nucleophile to carbonyl and free radical addition of halide to alkene

Examples:
25

Rearrangement Reaction
A rearrangement reaction is a broad class of organic reactions where the carbon skeleton of a molecule is rearranged to give a structural isomer of the original molecule. Often a substituent moves from one atom to another atom in the same molecule. In the example below the substituent R moves from carbon atom 1 to carbon atom 2:

26

Electrophile and Nucleophile

An electrophile (literally electron-lover) is a reagent attracted to electrons that participates in a chemical reaction by accepting an electron pair in order to bond to a nucleophile. Because electrophiles accept electrons, they are Lewis acids. Most electrophiles are positively charged, have an atom that carries a partial positive charge, or have an atom that does not have an octet of electrons. The electrophiles attack the most electron-populated part of a nucleophile. The electrophiles frequently seen in the organic synthesis are cations such as H+, and NO+, polarized neutral molecules such as HCl, alkyl halides and carbonyl compounds, polarizable neutral molecules such as Cl2 and Br2, chemical species that do not satisfy the octet rule such as radicals.

Example: H+ and Br2

27

Electrophile and Nucleophile

A nucleophile is an electron-rich chemical reactant that is attracted to electron-deficient compounds. Examples of nucleophiles are anions such as Cl, or a compound with a lone pair of electrons such as NH3 (ammonia). Nucleophiles may take part in nucleophilic substitution, whereby a nucleophile becomes attracted to a full or partial positive charge.

28

Homolytic and Heterolytic Cleavage

Homolysis or homolytic fission is chemical bond dissociation of a neutral molecule generating two free radicals. That is, two electronsn that are involved in the bond are distributed one by one to the two species. Each of the two covalently shared electrons are withdrawn by the bonded atoms. AB A + B Such reactions can be induced by irradiation in the UV region, diffused sunlight or peroxide. High temperatures in the absence of oxygen (pyrolysis) can also induce homolytic elimination of carbon compounds. Heterolysis or heterolytic fission is chemical bond cleavage of a neutral molecule generating a cation and an anion. In this process the two electrons that make up the bond are assigned to the same fragment. The more electronegative fragment receives both electrons.

A:B

A+ + B29

Q and A on Alkanes
Gas Cylinders in Restaurants / Kitchens Petrol Pump Stations in Malaysia

30

What is RON ?

What is RON 92, 95, 97?

RON (Research Octane Number) is a rating of petrol. It determines a petrols anti-knock quality or resistance to pre-ignition or detonation as it burns in the combustion chamber. Knocking is an abnormal combustion and should be prevented as it is damaging to the engine.

What are the gases used for cooking?

Propane is replacing wood and other traditional fuel sources in such places, where it is now sometimes called "cooking gas". The cooking gas we use is actually a mixture of propane and butane. The warmer the country, the higher the butane content, commonly 50/50 and sometimes reaching 75% butane. 31

Hydrocarbons
Hydrocarbons Saturated

Unsaturated

Class

Alkanes (Chapter 2)

Alkenes (Chapters 5-6) One or more carbon-carbon double bonds

Alkynes (Chapter 7) One or more carbon-carbon triple bonds

Arenes (Chapter 21-22) One or more benzenelike rings

Carbon- Only carboncarbon carbon single bonding bonds

Example
Name

HH H- C-C- H

H H
Ethane

H H C C H H
Ethene (Ethylene)

H- C C-H
Ethyne (Acetylene Benzene
32

Alkanes
General Formula: CnH2n+2 Saturated Contain only single bonds ( bonds)

33

Structure
Shape
tetrahedral about carbon (sp3 hybridised) all bond angles are approximately 109.5

109.5

34

Drawing Alkanes
Line-angle formulas:
an abbreviated way to draw structural formulas. each vertex and line ending represents a carbon.
Ball-and stick mod el Line-an gle formula Structu ral formu la CH3 CH2 CH3 Propane CH3 CH2 CH2 CH3 Butan e CH3 CH2 CH2 CH2 CH3 Pentan e
35

Constitutional Isomerism
Constitutional isomers: Compounds with the same molecular formula but a different connectivity of their atoms.
example: C4H10

CH3 CH2 CH 2 CH3 Butane (bp -0.5C)

CH3 CH3 CHCH3 2-Methylpropane (bp -11.6C)

36

Constitutional Isomerism
The ability of carbon to form strong bonds with other carbon atoms results in a staggering number of constitutional isomers.
Mole cular Formula CH 4 C5 H1 2 C1 0 H2 2 C1 5 H3 2 C2 5 H5 2 C3 0 H6 2 Constitutional Is ome rs 1 3 75 4,347 36,797,588 4,111,846,763
37

World population is about 6,000,000,000

Nomenclature - IUPAC
Suffix -ane specifies an alkane, e.g. ethane. Prefix tells the number of carbon atoms.
Pre fix methethpropbutpenthexheptoctnondecNumber of carbons 1 2 3 4 5 6 7 8 9 10 Number of Pre fix carbons unde c11 dodec12 tride c13 te tradec14 pentadec- 15 hexadec16 heptadec- 17 octade c18 nonadec19 eicos 20
38

Nomenclature - IUPAC
1.The name of a saturated hydrocarbon with an unbranched chain consists of a prefix and suffix. 2. The parent chain is the longest chain of carbon atoms. 3. Each substituent is given a name and a number. Use a hyphen to connect the number to the name. 4. If there is one substituent, number the chain from the end that gives it the lower number.
CH3 CH3 CHCH3
1 2 3

2-Methylprop ane

CH3 CH3 CH2 CH2 CHCH3

4 5

3 2

2 1 1

3 4

2-Methylpentane

(not 4-methylpentane)
39

Nomenclature - IUPAC
5. If there are two or more identical substituents, number the chain from the end that gives the lower number to the substituent encountered first. Indicate the number of times the substituent appears by a prefix di-, tri-, tetra-, etc. Use commas to separate position numbers.
4 2 3 5

2,4-Dimethylhexane

(not 3,5-dimethylhexane)

40

Nomenclature - UPAC
6. If there are two or more different substituents, list them in alphabetical order. number from the end of the chain that gives the substituent encountered first the lower number.

3-Ethyl-5-methylheptane

(not 3-methyl-5-ethylheptane)

41

Nomenclature - IUPAC
7. Alphabetize the names of substituents first and then insert the prefixes indicating the number of each substituent. (The prefixes di-, tri-, tetra-, etc. are not included in alphabetization)

4-Ethyl-2,2-dimethylh exane (not 2,2-dimethyl-4-ethylhexane)

42

Nomenclature - IUPAC
Alkyl groups (substituents)
Name methyl ethyl propyl Conde nsed Structural Formula - CH 3 - CH 2 CH3 - CH 2 CH2 CH3 Name butyl 2-methylpropyl (isobutyl) 1-methylpropyl (sec- butyl) Conde nsed Structural Formula - CH 2 CH2 CH2 CH 3 - CH 2 CHCH3 CH3 - CH CH 2 CH3 CH3 CH3 1,1-dimethylethyl - CCH3 (tert- butyl) CH3

1-methylethyl - CH CH 3 (isopropyl) CH3

43

Nomenclature - Common
The number of carbons in the alkane determines the name. All alkanes with four carbons are butanes, those with five carbons are pentanes, etc. iso- indicates the chain terminates in -CH(CH3)2; neothat it terminates in -C(CH3)3.
CH3 CH3 CH2 CH2 CH3 Butane CH3 CHCH3 Is ob utane CH3 CH3 CH2 CH2 CH2 CH3 CH3 CH2 CHCH3 Pentan e Is op entane CH3 CH3 CCH3 CH3 N eopentan e
44

Systematic vs Trivial name

Common prefixes of alkanes
Trivial name isopropyl Systematic prefix 1-methylethyl 2-methylpropyl 1-methylpropyl 1,1-dimethylethyl 2,2-dimethylpropyl 3-methylbutyl
45

Draw their C-skeleton

sec-butyl tert-butyl neo-pentyl iso-pentyl

Cycloalkanes
General formula CnH2n Five- and six-membered rings are the most common. Structure and nomenclature Add the prefix cyclo- to the name of the open-chain alkane containing the same number of carbons. If only one substituent, no need to give it a number. If two substituents, number from the substituent of lower alphabetical order. If three or more substituents, number to give them the lowest set of numbers and then list substituents in alphabetical order.

46

Some common cycloalkanes

47

Cycloalkanes
Line-angle drawings
Each line represents a C-C bond. Each vertices and line ending represents a C.
C C C C C C C C H2 C H2 C CH2 CH2 C8 H1 6 CH3 CH3 CH CH

48

Cycloalkanes
Example: name these cycloalkanes.

(a)

(b)

(c)

(d)

49

Cycloalkanes
Example: name these cycloalkanes.

(a)

(b)

(c)

(d)

(a) (1-methylethyl)cyclopentane (b) 1-(1,1-dimethylethyl)-4-methylcyclohexane (c) 2-ethyl-1,4-dimethylcyclohexane (d) 1-methyl-1-ethylcyclopropane

50

Physical Properties
Low-molecular-weight alkanes (methane to butane) are gases at room temperature. Higher molecular-weight alkanes (pentane, decane, gasoline, and kerosene) are liquids at room temperature. High-molecular-weight alkanes (paraffin wax) are semisolids or solids at room temperature.

51

Physical Properties of Alkanes Parameter Flammability odor color taste toxicity polarity stability reactivity Non poisonous
Insoluble in water, soluble in organic solvents Very strong bonds: C-C = 96-99 kcal/mol & C-H = 83-85kcal/mol Chemically unreactive; good lubricants, backbone for synthesis of other HCs & polymers

Property Burn easily Flammable mild odor colorless tasteless non-toxic Non-polar Stable Inert

52

Solubility
Alkanes are insoluble in H2O, they are non-polar molecules which cannot form H-bonding with H2O molecules. However, alkanes are soluble in non-polar solvents; eg. CCl4, benzene Liquid alkanes (pentane & hexane) are good organic solvents for many org. cpds.
53

Physical Properties
Constitutional isomers have different physical properties.

Name
Hexane

mp ( C) -95 -154 -118 -129 -98

bp ( C) 68.7 60.3 63.3 58.0 49.7

Density (g/mL) 0.659 0.653 0.664 0.661 0.649

2,2-Dimethylbutan e

hexane 2-methylpentane 3-methylpentane 2,3-dimethylbutane 2,2-dimethylbutane

54

Physical properties of alkanes Mol. wt vs m.p./b.p.

200 150
mp and bp ( C)

160 140 120

MW(g/mol)

100 50 0 -50 -100 -150 -200 1 2 3 4 5 6 7 8 9 10 n in normal-CnH2n+2

100 80 60 40 20 0

mp bp MW

Bps & mps for n-alkanes increase with mol. mass. London dispersion forces become greater with increasing mol. size
55

Branching tends to lower the boiling point Branching decreases surface area of the molecule (London dispersion forces are most? pronounced)

Molecular formula
C5H12

Structural formula

Boiling point(oC)
36

28 C5H12 10 C5H12
56

Oxidation of Alkanes
Oxidation is the basis for the use of alkanes as energy sources for heat and power. heat of combustion: The heat released when one mole of a substance in its standard state is oxidized to carbon dioxide and water.
DH 0 kJ (kcal)/mol
+ Methane
C H 3 C H 2 CH 3 CH 4 2 O2 CO 2

+ +

2 H2 O

-890.4 (-212.8)
-2220 (-530.6)

5 O2

3 CO 2

4 H2 O

Propane

57

Heat of Combustion
Heat of combustion for constitutional isomers
Hydrocarbon Octane 2-Methylhep tane 2,2-D imeth ylhexan e 2,2,3,3-Tetramethylbu tane S tru ctural formu la DH 0 [k J (k cal)/mol] -5470.6 (-1307.5) -5465.6 (-1306.3) -5458.4 (1304.6)

-5451.8 (1303.0)
58