Chapter 2 Introduction to Hydrocabons Carbon Backbone, Nomenclature, Physical & Chemical Properties.
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Transcript of Chapter 2 Introduction to Hydrocabons Carbon Backbone, Nomenclature, Physical & Chemical Properties.
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Chapter 2
Introduction toHydrocabons
Carbon Backbone, Nomenclature, Physical &
Chemical Properties
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HYDROCARBONS• Compounds composed of only carbon and hydrogen atoms
(C, H). Each carbon has 4 bonds.
• They represent a “backbone” when other “heteroatoms” (O, N, S, .....) are substituted for H. (The heteroatoms give function to the molecule.)
• Acyclic (without rings); Cyclic (with rings); Saturated: only carbon-carbon single bonds; Unsaturated: contains one or more carbon-carbon double and/or triple bond
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HYDROCARBONS• Alkanes contain only single ( ) bonds and have the
generic molecular formula: [CnH2n+2]
• Alkenes also contain double ( + ) bonds and have the generic molecular formula: [CnH2n]
• Alkynes contain triple ( + 2) bonds and have the generic molecular formula: [CnH2n-2]
• Aromatics are planar, ring structures with alternating single and double bonds: eg. C6H6
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Types of Hydrocarbons
Each C atom is trigonal planar with sp2 hybridized orbitals.There is no rotation about the C=C bond in alkenes.
Each C atom is tetrahedral with sp3 hybridized orbitals. They only have single bonds.
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Types of Hydrocarbons
Each C atom is linear with sp hybridized orbitals.
Each C--C bond is the same length; shorter than a C-C bond: longer than a C=C bond.The concept of resonance is used to explain this phenomena.
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Propane
It is easy to rotate about the C-C bond in alkanes.
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Naming AlkanesNaming AlkanesCC11 - C - C10 10 : the number of C atoms present in the chain.
Each member CC33 - C - C1010 differs by one CH2 unit. This is called a homologous series.
Methane to butane are gases at normal pressures.Pentane to decane are liquids at normal pressures.
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Nomenclature of Alkyl Substituents
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Examples of Alkyl Substituents
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Constitutional or structural isomers have the same molecular formula, but their atoms are linked differently. Naming has to account for them.
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A compound can have more than one name, but a name must unambiguously specify only one compound
C7H16 can be any one of the following:
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Alkanes (Different types of sp3 carbon atoms)
• Primary, 1o, a carbon atom with 3 hydrogen atoms: [R-CH3]
• Secondary, 2o, a carbon atom with 2 hydrogen atoms: [R-CH2-R]
• Tertiary, 3o, a carbon atom with 1 hydrogen atom: [R-CH-R] R
• Quaternary, 4o, a carbon atom with 0 hydrogen atoms: CR4
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Different Kinds of sp3 Carbons and Hydrogens
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Nomenclature of Alkanes
1. Determine the number of carbons in the parent hydrocarbon
CH3CH2CH2CH2CHCH2CH2CH3
CH3
12345678
CH3CH2CH2CH2CHCH2CH3
CH2CH2CH3
45678
123
CH3CH2CH2CHCH2CH2CH3
CH2CH2CH2CH3
1234
5 6 7 8
2. Number the chain so that the substituent gets the lowest possible number
CH3CHCH2CH2CH3
CH3
1 2 3 4 5
2-methylpentane
CH3CH2CH2CHCH2CH2CH2CH3
CHCH3
CH3
1 2 3 4 5 6 7 8
4-isopropyloctane
CH3CHCH2CH2CH3
CH3
common name: isohexanesystematic name: 2-methylpentane
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3. Number the substituents to yield the lowest possible number in the number of the compound
CH3CH2CHCH2CHCH2CH2CH3
CH3 CH2CH3 5-ehtyl-3-methyloctanenot
4-ethyl-6-methyloctanebecause 3<4
(substituents are listed in alphabetical order)
4. Assign the lowest possible numbers to all of the substituents
CH3CH2CHCH2CHCH3
CH3CH3
2,4-dimethylhexane
CH3CH2CH2C
CH3
CH3
CCH 2CH 3
CH3
CH3
3,3,4,4-tetramethylheptane
CH3CH2CHCH2CH2CHCHCH2CH2CH3
CH2CH3
CH2CH3 CH2CH3
CH3
3,3,6-triethyl-7-methyldecane
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5. When both directions lead to the same lowest number for oneof the substituents, the direction is chosen that gives the lowest possible number to one of the remaining substituents
CH3CHCH2CHCH3
CH3
CH3 CH3
2,2,4-trimethylpentanenot
2,4,4-trimethylpentanebecause 2<4
CH3CH2CHCHCH2CHCH2CH3
CH3
CH3 CH2CH3
6-ethyl-3,4-dimethyloctanenot
3-ethyl-5,6-dimethyloctanebecause 4<5
6. If the same number is obtained in both directions, the firstgroup receives the lowest number
CH3CH2CHCH2CHCH2CH3
CH3
CH2CH3
3-ethyl-5-methylheptanenot
5-ethyl-3-methylheptane
CH3CH2CHCH3
Cl
Br
2-bromo-3-chlorobutanenot
3-bromo-2-chlorobutane
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7. In the case of two hydrocarbon chains with the same number ofcarbons, choose the one with the most substituents
CH3CH2CHCH2CH2CH3
CHCH3
CH31
2
3 4 5 6
3-ethyl-2-methylhexane (two substituents)
CH3CH2CHCH2CH2CH3
CHCH3
CH3
1 2 3 4 5 6
3-isopropylhexane (one substituent)
8. Certain common nomenclatures are used in the IUPAC system
CH3CH2CH2CH2CHCH2CH2CH3
CHCH3
CH3
4-isopropyloctaneor
4-(1-methylethyl)octane
CH3CH2CH2CH2CHCH2CH2CH2CH2CH3
CH2CHCH3
CH3
5-isobutyldecaneor
5-(2-methylpropyl)decane
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CCnnHH22nn
Cycloalkane Nomenclature
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Cycloalkanes• Cycloalkanes are alkanes that contain a
ring of three or more carbons.• Count the number of carbons in the ring,
and add the prefix cyclo to the IUPAC name of the unbranched alkane that has that number of carbons.
CyclopentaneCyclopentane CyclohexaneCyclohexane
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EthylcyclopentaneEthylcyclopentane
CHCH22CHCH33
• Name any alkyl groups on the ring in the usual way. A number is not needed for a single substituent.
Cycloalkanes
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• Name any alkyl groups on the ring in the usual way. A number is not needed for a single substituent.
• List substituents in alphabetical order and count in the direction that gives the lowest numerical locant at the first point of difference.
3-Ethyl-1,1-dimethylcyclohexane3-Ethyl-1,1-dimethylcyclohexane
CHCH22CHCH33
HH33CC CHCH33
Cycloalkanes
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For more than two substituents,
CH3CH2CH2
H3C CH2CH3
4-ethyl-2-methyl-1-propylcyclohexanenot
1-ethyl-3-methyl-4-propylcyclohexanebecause2<3
not 5-ethyl-1-methyl-2-propylcyclohexane
because 4<5
CH3
CH3
CH3
1,1,2-trimethylcyclopentanenot
1,2,2-trimethylcyclopentanebecause1<2
not1,1,5-trimethylcyclopentane
because 2<5
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2.17Physical Properties of
Alkanesand Cycloalkanes
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Crude oilCrude oil
Refinery gasRefinery gasRefinery gasRefinery gas
CC11-C-C44
Light gasolineLight gasoline(bp: 25-95 °C)(bp: 25-95 °C)
Light gasolineLight gasoline(bp: 25-95 °C)(bp: 25-95 °C)
CC55-C-C1212
NaphthaNaphtha(bp 95-150 °C)(bp 95-150 °C)
NaphthaNaphtha(bp 95-150 °C)(bp 95-150 °C)
KeroseneKerosene(bp: 150-230 °C)(bp: 150-230 °C)
KeroseneKerosene(bp: 150-230 °C)(bp: 150-230 °C)
CC1212-C-C1515
Gas oilGas oil(bp: 230-340 °C)(bp: 230-340 °C)
Gas oilGas oil(bp: 230-340 °C)(bp: 230-340 °C)
CC1515-C-C2525
ResidueResidueResidueResidue
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Fig. 2.15
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Example of Intramolecular Forces: Protein Folding
10-40kJ/mol
700-4,000kJ/mol
150-1000kJ/mol
0.05-40kJ/mol
Ion-dipole(Dissolving)40-600kJ/mol
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Ion-Dipole Forces (40-600 kJ/mol)• Interaction between an ion and a dipole (e.g. NaOH and
water = 44 kJ/mol)• Strongest of all intermolecular forces.
Intermolecular ForcesIntermolecular Forces
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Ion-Dipole & Dipole-Dipole Interactions: like dissolves like
• Polar compounds dissolve in polar solvents & non-polar in non-polar
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Dipole-Dipole Forces
(permanent dipoles)
Intermolecular ForcesIntermolecular Forces
5-25 kJ/mol
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Dipole-Dipole Forces
Intermolecular ForcesIntermolecular Forces
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Boiling Points &
Hydrogen Bonding
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Hydrogen Bonding
• Hydrogen bonds, a unique dipole-dipole (10-40 kJ/mol).
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QuickTime™ and aSorenson Video 3 decompressorare needed to see this picture.
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Hydrogen Bonding
Intermolecular ForcesIntermolecular Forces
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DNA: Size, Shape & Self Assemblyhttp://www.umass.edu/microbio/chime/beta/pe_alpha/atlas/atlas.htm
Views & Algorithms
10.85 Å10.85 Å
QuickTime™ and aAnimation decompressorare needed to see this picture.
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London or Dispersion Forces• An instantaneous dipole can induce another dipole in an
adjacent molecule (or atom).• The forces between instantaneous dipoles are called
London or Dispersion forces ( 0.05-40 kJ/mol).
Intermolecular ForcesIntermolecular Forces
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van der Waals Forces
The boiling point of a compound increases with the increase in van der Waals force..and the Gecko!
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Gecko: toe, setae, spatulae6000x Magnification
http://micro.magnet.fsu.edu/primer/java/electronmicroscopy/magnify1/index.html
Geim, Nature Materials (2003) Glue-free Adhesive100 x 10 6 hairs/cm2
Full et. al., Nature (2000)5,000 setae / mm2
600x frictional force; 10-7 Newtons per seta
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Boiling Points of Alkanes
• governed by strength of intermolecular attractive forces
• alkanes are nonpolar, so dipole-dipole and dipole-induced dipole forces are absent
• only forces of intermolecular attraction are induced dipole-induced dipole forces
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Induced dipole-Induced dipole Attractive Forces
++––++
––
• two nonpolar molecules• center of positive charge and center
of negative charge coincide in each
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++––++
––
• movement of electrons creates an instantaneous dipole in one molecule (left)
Induced dipole-Induced dipole Attractive Forces
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++––++––
• temporary dipole in one molecule (left) induces a complementary dipole in other molecule (right)
Induced dipole-Induced dipole Attractive Forces
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++––++ ––
• temporary dipole in one molecule (left) induces a complementary dipole in other molecule (right)
Induced dipole-Induced dipole Attractive Forces
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++––++ ––
• the result is a small attractive force between the two molecules
Induced dipole-Induced dipole Attractive Forces
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++–– ++ ––
• the result is a small attractive force between the two molecules
Induced dipole-Induced dipole Attractive Forces
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Boiling Points
•Increase with increasing number of carbons
• more atoms, more electrons, more opportunities for induced dipole-induceddipole forces
•Decrease with chain branching
• branched molecules are more compact withsmaller surface area—fewer points of contactwith other molecules
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London Dispersion Forces
Intermolecular ForcesIntermolecular Forces
Which has the higherattractive force?
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•Increase with increasing number of carbons
• more atoms, more electrons, more opportunities for induced dipole-induceddipole forces
HeptaneHeptanebp 98°Cbp 98°C
OctaneOctanebp 125°Cbp 125°C
NonaneNonanebp 150°Cbp 150°C
Boiling Points
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•Decrease with chain branching
• branched molecules are more compact withsmaller surface area—fewer points of contactwith other molecules
Octane: bp 125°COctane: bp 125°C
2-Methylheptane: bp 118°C2-Methylheptane: bp 118°C
2,2,3,3-Tetramethylbutane: bp 107°C2,2,3,3-Tetramethylbutane: bp 107°C
Boiling Points
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•All alkanes burn in air to givecarbon dioxide and water.
2.18Chemical Properties:
Combustion of Alkanes
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4817 kJ/mol4817 kJ/mol
5471 kJ/mol5471 kJ/mol
6125 kJ/mol6125 kJ/mol
654 kJ/mol654 kJ/mol
654 kJ/mol654 kJ/mol
HeptaneHeptane
OctaneOctane
NonaneNonane
Heats of Combustion
What pattern is noticed in this case?
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•Increase with increasing number of carbons
• more moles of O2 consumed, more moles
of CO2 and H2O formed
Heats of Combustion
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5471 kJ/mol5471 kJ/mol
5466 kJ/mol5466 kJ/mol
5458 kJ/mol5458 kJ/mol
5452 kJ/mol5452 kJ/mol
5 kJ/mol5 kJ/mol
8 kJ/mol8 kJ/mol
6 kJ/mol6 kJ/mol
Heats of Combustion
What pattern is noticed in this case?
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8CO8CO22 + 9H + 9H22OO
5452 kJ/mol5452 kJ/mol5458 kJ/mol5458 kJ/mol
5471 kJ/mol5471 kJ/mol
5466 kJ/mol5466 kJ/molOO22++ 2525
22
OO22++ 2525
22 OO22++ 2525
22 OO22++ 2525
22
Figure 2.17Figure 2.17
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•Increase with increasing number of carbons
• more moles of O2 consumed, more moles
of CO2 and H2O formed
•Decrease with chain branching
• branched molecules are more stable(have less potential energy) than theirunbranched isomers
Heat of CombustionPatterns
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•Isomers can differ in respect to their stability.
•Equivalent statement:
–Isomers differ in respect to their potential energy.
Important Point
Differences in potential energy can be measured by comparing heats of combustion. (Worksheet problems)
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2.19Oxidation-Reduction in Organic
ChemistryOxidation of a carbon atom corresponds to an increase in the number of bonds to the carbon atom and/or a decrease in the number of hydrogens bonded to the carbon atom. See examples on the board.
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increasing oxidation increasing oxidation state of carbonstate of carbon
-4-4 -2-2 00 +2+2 +4+4
HH
HH
HH
CC HH
HH
HH
HH
CC OOHH
OO
CCHHHH
OO
CCOOHHHH
OO
CCOOHHHHOO
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increasing oxidation increasing oxidation state of carbonstate of carbon
-3-3 -2-2 -1-1
HCHC CHCH
CC CC
HH
HH HH
HH
CC CC HH
HHHH
HH HH
HH
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• But most compounds contain several (or many)carbons, and these can be in different oxidationstates.
CHCH33CHCH22OHOH CC22HH66OO
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• But most compounds contain several (or many)carbons, and these can be in different oxidationstates.
• Working from the molecular formula gives the average oxidation state.
CHCH33CHCH22OHOH CC22HH66OO
Average oxidationAverage oxidationstate of C = -2state of C = -2
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• How can we calculate the oxidation stateof each carbon in a molecule that containscarbons in different oxidation states?
CHCH33CHCH22OHOH CC22HH66OO
Average oxidationAverage oxidationstate of C = -2state of C = -2
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Table 2.5 How to Calculate Oxidation Numbers
• 1. Write the Lewis structure and include unshared electron pairs.
HH
CC
HH
HH
HH
OO
HH
CC HH••••
••••
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Table 2.5 How to Calculate Oxidation Numbers
• 2. Assign the electrons in a covalent bond between two atoms to the more electronegative partner.
HH
OO
HH
CC
HH
HH
HH
CC HH••••••••
••••••••
••••
••••
••••
••••••••
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• 3. For a bond between two atoms of the same element, assign the electrons in the bond equally.
HH
OO
HH
CC
HH
HH
HH
CC HH••••••••
••••••••
••••
••••
••••
••••••••
Table 2.5 How to Calculate Oxidation Numbers
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• 3. For a bond between two atoms of the same element, assign the electrons in the bond equally.
HH
OO
HH
CC
HH
HH
HH
CC HH••••••••
••••••••
••••
••••
••••
•••••••• ••••
Table 2.5 How to Calculate Oxidation Numbers
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• 4. Count the number of electrons assigned to each atom and subtract that number from the number of valence electrons in the neutral atom; the result is the oxidation number.
HH
OO
HH
CC
HH
HH
HH
CC HH••••••••
••••••••
••••
••••
••••
•••••••• ••••
Each H Each H == +1+1C of CHC of CH33 == -3-3
C of CHC of CH22O O == -1-1
O O == -2-2
Table 2.5 How to Calculate Oxidation Numbers
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XX YY
XX less electronegative than carbon less electronegative than carbon
YY more electronegative than carbon more electronegative than carbon
oxidationoxidation
reductionreductionCC CC
Generalization
Oxidation of carbon occurs when a bond between carbon and an atom which is less electronegative than carbon is replaced by a bond to an atom that is more electronegative than carbon. The reverse process is reduction.
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CHCH33ClCl HHClClCHCH44 ClCl22++ ++
OxidationOxidation
++ 2Li2Li LiLiClClCHCH33ClCl CHCH33LiLi ++
ReductionReduction
Examples
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Chapter 4
Alcohols & Halides
Functions, Nomenclature,
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Common Functional GroupsCommon Functional Groups
Class General Formula
Halohydrocarbons RX
Alcohols R
Ethers RR
Amines
R-NH2
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Nomenclature of Alkyl Halides
CH3Cl CH3CH2FCH3CHI
CH3
CH3CH2CHBr
CH3chloromethane fluoroethane2-iodopropane 2-bromobutane
In the IUPAC system, alkyl halides are named as substituted alkanes
CH3CH2CHCH2CH2CH2CH3
CH3
Br
2-bromo-5-methylheptane
CH3CH2CHCH2CH2CH2Cl
CH3
CH3
1-chloro-5,5-dimethylhexane
CH2CH3
I
1-ethyl-2-iodocyclopentane
Br
Cl
CH3
4-bromo-2-chloro-1-methylcyclohexane
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Structures of Alkyl Halides
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Different Kinds of Alkyl Halides
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Nomenclature of Ethers
CH3CHOCHCH2CH3
CH3
CH3
sec-butyl isopropyl ether
CH3CH2CH2CH2O
cyclohexyl isopentyl ether
CH3O
methoxy
CH3CH2O
ethoxy
CH3CH2O
CH3
isopropoxy
As substituents:
CH3CH2CHO
CH3
sec-butoxy
CH3CH2O
CH3
CH3
tert-butoxy
???
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Structures of Alcohol and Ether
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Nomenclature of Alcohols• In an alcohol, the OH is a functional group
• A functional group is the center of reactivity in a molecule
1. Determine the parent hydrocarbon containing the functional group
CH3CHCH2CH3
OH
1 2 3 4
2-butanolor
butan-2-ol
CH3CH2CH2CHCH2OH
CH2CH3
12345
2-ethyl-1-pentanolor
2-ethylpentan-1-ol
CH3CH2CH2CH2OCH2CH2CH2OH
123
3-butoxy-1-propanolor
3-butoxypropan-1-ol
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2. The functional group suffix should get the lowest number
HOCH 2CH 2CH 2Br
1 2 3
3-bromo-1-propanol
ClCH2CH2CHCH3
OH
1234
4-chloro-2-butanol
CH3CCH 2CHCH 3
CH3
CH3 OH
12345
4,4-dimethyl-2-pentanol
3. When there is both a functional group suffix and a substituent,the functional group suffix gets the lowest number
CH3CHCHCH2CH3
Cl OH
2-chloro-3-pentanolnot
4-chloro-3-pentanol
CH3CH2CH2CHCH2CHCH3
CH3OH
2-methyl-4-heptanolnot
6-methyl-4-heptanol
CH3
OH
3-methylcyclohexanolnot
5-methylcyclohexanol
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4. If there is more than one substituent, the substituents are citedin alphabetical order
CH3CHCH2CHCH2CHCH3
Br
CH2CH3
OH
6-bromo-4-ethyl-2-heptanol
CH2CH3
OHH3C
2-ethyl-5-methylcyclohexanol
CH3
HO
CH3
3,4-dimethylcyclopentanol
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Nomenclature of Amines
CH3CH2CH2CH2NH2
1234
1-butanamineor
butan-1-amine
CH3CH2CHCHCH2CH3
NHCH2CH3
1 2 3 4 5 6
N-ethyl-3-hexamineor
N-ethylhexan-3-amine
CH3CH2CH2NCH 2CH 3
CH3
123
N-ethyl-N-methyl-1-propanamineor
N-ethyl-N-methylpropan-1-amine
• The substituents are listed in alphabetical order and a number or an “N” is assigned to each one
CH3CHCH2CH2NCH 3
Cl
1234
3-chloro-N-methyl-1-butanamine
CH3CH2CHCHCHCH3
NHCH2CH3
CH31 2 3 4 5 6
N-ethyl-5-methyl-3-hexanamine
CH3CHCHCHCH3
NH3C CH3
Br12345
4-bromo-N,N-dimethyl-2-pentanamine
CH2CH3
NHCH2CH2CH3
2-ethyl-N-propylcyclohexanamine
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Structures of Amines
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Naming Quaternary Ammonium Salts
N+
CH3
H3C CH3
CH3
HO-
tetramethylammonium hydroxide
N+
CH3
CH3CH2CH2 CH3
CH3
Cl-
ethyldimethylpropylammonium chloride
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OtherOther Common Functional GroupsCommon Functional Groups
Class General Formula
Aldehydes
Ketones
Carboxylic Acids
Esters
Amides
R-C-HO
R-C-R'O
R-C-OHO
R-C-OR'O
R-C-NO
R
"
R
'
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• The greater the attractive intermoleclar forces between molecules, the higher is the boiling point of the compound, eg. water.
Attractive Forces
van der Waals force
Dipole–dipole interaction
Hydrogen bonds
Covalent bonds
Ionic bonds
Ion-dipoleDispersionForces
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Protein Shape: Forces, Bonds, Self Assembly,Folding (Intramolecular forces)
10-40kJ/mol
700-4,000kJ/mol
150-1000kJ/mol
0.05-40kJ/mol
Ion-dipole(Dissolving)40-600kJ/mol
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• A hydrogen bond is a special kind of dipole–dipole interaction
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Dipole–Dipole Interaction
Dipole–dipole interactions are stronger than van der Waals force but weaker than ionic or covalent bonds
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van der Waals Forces
The boiling point of a compound increases with the increase in van der Waals force
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Ion-Dipole & Dipole-Dipole Interactions: like dissolves like
• Polar compounds dissolve in polar solvents & non-polar in non-polar
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Chapter 3
Alkanes & Cycloalkane
Conformations
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Conformations of Alkanes: Rotation about Carbon–Carbon Bonds
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Conformational AnalysisDrawing Acyclic Molecules
• Newman Projections
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Conformational Analysis Drawing Acyclic Molecules
• Sawhorse Drawings
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• Torsional strain: repulsion between pairs of bonding electrons
• A staggered conformer is more stable than an eclipsed conformer
Different Conformations of Ethane
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Conformations of n-Butane• Steric strain: repulsion between the electron clouds of atoms or groups
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Cycloalkanes: Ring Strain
• Angle strain results when bond angles deviate from the ideal 109.5° bond angle
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The Shapes of Cycloalkanes:Planar or Nonplanar?
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•Assumed cycloalkanes were planar Assumed cycloalkanes were planar polygons.polygons.
•Believed distortion of bond angles from Believed distortion of bond angles from 109.5° 109.5° gives angle strain to some cycloalkanes.gives angle strain to some cycloalkanes.
• One for two is great in baseball.One for two is great in baseball.
Adolf von Baeyer (19th century)
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Types of Strain
• • Torsional strain strain that results from eclipsed bonds (measure of the dihedral angle)
• • Van der Waals strain or (Steric strain)strain that results from atoms being too close together.
• • Angle strain results from distortion of bond angles from normal values, for a
tetrahedron 109.5o
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Measuring Strain in Cycloalkanes
•Heats of combustion can be used to compareHeats of combustion can be used to comparestabilities of isomers.stabilities of isomers.
•But cyclopropane, cyclobutane, etc. are not isomers.But cyclopropane, cyclobutane, etc. are not isomers.
•All heats of combustion increase as the numberAll heats of combustion increase as the numberof carbon atoms increase.of carbon atoms increase.
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Measuring Strain in Cycloalkanes
•Therefore, divide heats of combustion by numberTherefore, divide heats of combustion by number of carbons and compare heats of combustion of carbons and compare heats of combustion on a "per CHon a "per CH22 group" basis. group" basis.
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•CycloalkaneCycloalkane kJ/molkJ/mol Per CHPer CH22
•CyclopropaneCyclopropane 2,0912,091 697697•CyclobutaneCyclobutane 2,7212,721 681681•CyclopentaneCyclopentane 3,2913,291 658658•CyclohexaneCyclohexane 3,9203,920 653653•CycloheptaneCycloheptane 4,5994,599 657657•CyclooctaneCyclooctane 5,2675,267 658658•CyclononaneCyclononane 5,9335,933 659659•CyclodecaneCyclodecane 6,5876,587 659659
Heats of Combustion in Cycloalkanes
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•CycloalkaneCycloalkane kJ/molkJ/mol Per CHPer CH22
•According to Baeyer, cyclopentane shouldAccording to Baeyer, cyclopentane should•have less angle strain than cyclohexane.have less angle strain than cyclohexane.•CyclopentaneCyclopentane 3,2913,291 658658•CyclohexaneCyclohexane 3,9203,920 653653
•The heat of combustion per CHThe heat of combustion per CH22 group is group is
•less for cyclohexane than for cyclopentane.less for cyclohexane than for cyclopentane.•Therefore, cyclohexane has less strain Therefore, cyclohexane has less strain thanthan•cyclopentane.cyclopentane.
Heats of Combustion in Cycloalkanes
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•Heat of combustion suggests that angle strain is unimportant in cyclohexane.
•Tetrahedral bond angles require nonplanar geometries.
• The chair and boat conformations.
Conformations of Cyclohexane
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• The chair conformation of cyclohexane is free of strain
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• All of the bonds are staggered and the bond angles at carbon are close to tetrahedral.
Chair is the most stable conformation of
cyclohexane
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• All of the bond angles are close to tetrahedral but close contact between flagpole hydrogens causes strain in boat.
180 pm180 pm
Boat conformation is less stable than the chair
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• Eclipsed bonds bonds gives torsional strain to boat.
Boat conformation is less stable than the chair
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• Less van der Waals strain and less torsional strain in skew boat.
BoatBoat Skew or Twist BoatSkew or Twist Boat
Skew boat is slightly more stable than boat
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•The chair conformation of cyclohexane is themost stable conformation and derivativesof cyclohexane almost always exist in the chair conformation
Generalization
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Axial and Equatorial Bonds in Cyclohexane
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Drawing Cyclohexane
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The 12 bonds to the ring can be divided into two sets of 6.
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Axial bonds point "north and south"Axial bonds point "north and south"
6 Bonds are axial
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The 12 bonds to the ring can be divided into two sets of 6.
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Equatorial bonds lie along the equatorEquatorial bonds lie along the equator
6 Bonds are equatorial
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Conformational Inversion
(Ring-Flipping) in Cyclohexane
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• chair-chair interconversion (ring-flipping)
•rapid process (activation energy = 45 kJ/mol)
•all axial bonds become equatorial and vice versa
Conformational Inversion
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Half-Half-chairchair
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Half-Half-chairchair
SkewSkewboatboat
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Half-Half-chairchair
SkewSkewboatboat
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Half-Half-chairchair
SkewSkewboatboat
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45 45 kJ/molkJ/mol
45 45 kJ/molkJ/mol
23 23 kJ/molkJ/mol
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The Conformations of Cyclohexane and Their Energies
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•most stable conformation is chair
•substituent is more stable when equatorial
Conformational Analysis of
Monosubstituted Cyclohexanes
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Steric Strain of 1,3-Diaxial Interaction in Methylcyclohexane
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5%5% 95%95%
• Chair chair interconversion occurs, but at any instant 95% of the molecules have their methyl group equatorial.
• An axial methyl group is more crowded than an equatorial one.
Methylcyclohexane
CHCH33
CHCH33
axialaxial
equatorialequatorial
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5%5% 95%95%• Hydrogen atoms closer than 2.4 Angstroms will cause
steric strain.• This is called a "1,3-diaxial repulsion" a type of van
der Waals strain or Steric strain.
Methylcyclohexane
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40%40% 60%60%
• Crowding is less pronounced with a "small" substituent such as fluorine.
• Size of substituent is related to its branching.
Fluorocyclohexane
FF
FF
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Less than 0.01%Less than 0.01% Greater than 99.99%Greater than 99.99%
• Crowding is more pronounced with a "bulky" substituent such as tert-butyl.
• tert-Butyl is highly branched.
tert-Butylcyclohexane
C(CHC(CH33))33
C(CHC(CH33))33
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van der Waalsvan der Waalsstrain due tostrain due to1,3-diaxial1,3-diaxialrepulsionsrepulsions
tert-Butylcyclohexane
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Keq = [equatorial conformer]/[axial conformer]
• The larger the substituent on a cyclohexane ring, the more the equatorial substituted conformer will be favored
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Disubstituted Cyclohexanes
Cis-trans Isomerism
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Cyclic Alkanes StereochemistryCis -Trans Isomers
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H
CH3H
CH3 cis-1,4-dimethylcyclohexane
H
H3C
CH3
Hring-flip
The Chair Conformers of cis-1,4-Dimethylcyclohexane
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1,2-disubstituted-cis-cyclohexaneStereochemistry
CH3
CH3
CH3
CH3
CH3
CH3
Mirror
Same
(Rotate to See)
axial axial
equatorialequatorial
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Cyclohexane StereochemistryDrawings: Cis isomers & the need for perspective
CH3CH3
CH3
CH3CH3
CH3
Are the methyl groups axial or equatorial?Are the methyl groups axial or equatorial?What is the actual conformational shape of the cyclohexane ring?What is the actual conformational shape of the cyclohexane ring?
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The Chair Conformers of trans-1,4-Dimethylcyclohexane
H
CH3H3C
Htrans-1,4-dimethylcyclohexane
CH3
H
CH3
Hring-flip
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Cyclohexane StereochemistryTrans isomers
CH3
CH3CH3
CH3 CH3
CH3
No Plane of Symmetry No plane of symmetry
Plane of Symmetry
CH3CH3
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1-tert-Butyl-3-Methylcyclohexane
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Cyclohexane StereochemistryCis -Trans Isomers
Position cis trans
1,2 e,a or a,e e,e or a,a
1,3
1,4
Complete the Table: a = axial; e = equatorial Complete the Table: a = axial; e = equatorial
e,a or a,e e,e or a,a
e,e or a,a a,e or e,a
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Conformations of Fused Rings
• Trans-fused cyclohexane ring is more stable than cis-fused cyclohexane ring