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312 112 Basic Organic Chemistry312 112 Basic Organic Chemistry
Atomic Structures Chemical Bondings
Hybridizations Acids-Bases
Hydrocarbons (Alkanes, Alkene, Alkynes)
Alkylhalides
Instructor: Chanokbhorn Phaosiri
e-mail: [email protected]
office: Sc4502-3
(Pharmacy English Program)(Pharmacy English Program)
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Organic ChemistryOrganic ChemistryThe study of the compounds of carbonOver 10 million organic compounds have
been identifiedabout 1000 new ones are discovered or
synthesized and identified each day!C is a small atom it forms single, double, and triple bondsit is intermediate in electronegativity (2.5)it forms strong bonds with C, H, O, N, and
some metals
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HOH H
OCH3
H
Estrone(Female Steroidal Hormone)
O
H3CO
H3CO
N CH3
Morphine(Analgesic)
OCH3
H3C
HOCH3
H3C
3
Vitamin E
OCH2 CHN
O
N
S
OCO2H
Penicillin V
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COOH
O CH3
O
2-Acetyloxybenzoic acid(Aspirin, Bayer Aspirin)
OH
HNC
O
CH3
N-(4-Hydroxyphenyl)acetamide(Acetaminophen, Tylenol)
H3C
O
OH
2-[4-(2-Methylpropyl)-phenyl]propanoic acid
(Ibuprofen)
The Painkillers
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1s22s22px12py
12pz1N(7)
1s22s22px12py
1C(6)
1s22s22px1B(5)
Electron Configurations
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To write the electron configuration for Cl -
but Cl- has one more electron
Cl-
1s22s22p63s23px23py
23pz1
1s22s22p63s23px23py
23pz2
Cl (17)
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To write the electronic structure for Na+
1s22s22p63s1Na (11)
Na+ 1s22s22p6
but Na+ has one less electron
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Classification of Chemical Bonds
Difference in Electronegativity Between Bonded Atoms Type of Bond
less than 0.50.5 to 1.9
greater than 1.9
nonpolar covalentpolar covalent
ionic
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Electronegativity (EN)
ElectronegativityElectronegativity: a measure of the force of an
atom’s attraction for the electrons it shares in a chemical bond with another atom
Pauling scale increases from left to right within a period
increases from bottom to top in a group
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H Cl2.1 3.0
+ -A Polar Covalent Bond
Na F
N H
C Mg
C Cl
N O
C H
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Lewis Structures
H ydrogen chloride
M ethane Ammonia
Water
H O
H
H
H NH C
H
H
H Cl
HH
H 2O (8)
N H 3 (8)CH 4 (8)
H Cl (8)
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Lewis Structures
Carbonic acidMethanal
Acetylene
Ethylene
HC C
H
C C HH
HO
CC
H OH
OH
HH
O
C2H4 (12)
C2H2 (10)
CH2O (12) H2CO3 (24)
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Draw Lewis Structures, showing all valence electrons, for these molecules
H2O2
CH3OH
CH3Cl
C2H2
(CH3CH2)2CO
CH3CN
CH3COOH
CH2NNH2
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Draw Lewis Structures, showing by charges which bonds are ionic and by lines which bond are covalent.
NaOH
KHCO3
CH3ONa
CH3COONa
NH4Cl
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Formal Charge# of valence electrons in
unbonded atom
all unsharedelectrons
one half of all shared
electrons+Formal
charge=
H
H N HNitrogen valences electrons = 5
Nitrogen nonbonding electrons = 2
Nitrogen bonding electrons = 6
Formal Charge = 5- 2-(6/2) = 0
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Nitrogen valences electrons = 5
Nitrogen nonbonding electrons = 0
Nitrogen bonding electrons = 8
Formal Charge = 5- 0-(8/2) = +1
NH4 ?
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if the number assigned to the bonded atom is less than that
assigned to the unbonded atom, the atom has a positive
formal charge.
if the number is greater, the atom has a negative formal
charge.
NH4+ CH3 NH3
+
HCO3- CO3
2-OH-
CH3 CO2-CH3
-
CH3 OH2+
BF4-
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Assign formal charge in each structure as appropriate.
HOCO2
CH3CH2O
CH3CH2
NH3CH2CO2
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Molecular Shapes
4 regions of e - density(tetrahedral, 109.5°)
••••
•• ••
••
••
••
••
HH
NH
C
H H H
H
HC C
H
O C
H
C
HH
OH
CH C HO
3 regions of e - density(trigonal planar, 120°)
2 regions of e - density(linear, 180°)
••
HH
O
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Polar & Nonpolar Molecules
Bond Dipole Moments
H3C CH3 H3C NH2
H3C OH H3C Cl
C OO
OHH
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Molecular Dipole Moments
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Which of these molecules are polar? Indicate the direction of their polarity.
1. H2O
2. NH3
3. CH2Cl2
4. CH2=CH2
5. CH2=CHCl
6. CH3C N
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Molecular Representations
(Line-Angle Formula)
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Provide line-angle formula for these compounds.
2
2
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Shapes of Atomic Orbitals All s orbitals have the
shape of a sphere, with its
center at the nucleus. Of
the s orbitals, a 1s is the
smallest, a 2s is larger,
and a 3s is larger still.
x
y
z
a pz orbital
xy
z
an s orbital
A p orbital consists of two
lobes arranged in a straight
line with the center at the
nucleus.
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Sigma Bonding
Electron density lies between the nuclei.
A bond may be formed by s-s, p-p, s-p, or hybridized orbital overlaps.
The bonding Molecular Orbital (MO) is lower in energy than the original atomic orbitals.
The antibonding MO is higher in energy than the atomic orbitals.
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Cl2: p-p overlap
Constructive overlap along the same axis forms a sigma bond.
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Pi Bonding Pi bonds form after sigma bonds.
Sideways overlap of parallel p orbitals.
bonding MO
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If all bonding occurred between s- and p-orbitals, then all bond angles would be 90o.
We know that isn’t true!
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Hybridization
Linus Pauling
Atominc orbitals on the same atom combine to
form hybrid atomic orbitals. Why?
Hybrid orbitals are more directional, so they
have more effective bonding interctions.
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2p
2s
Ground electron state of carbon
Higher-energy electronic state of carbon
sp3 hybrid state of carbon
2p
2s
2sp3
SS PP
+
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4sp3
Conservation of orbitals
Tetrahedron
sp3 Hybridization
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sp3 Hybrid Orbitals
each sp3 hybrid orbital has two lobes of
unequal size.
the four sp3 hybrid orbitals are directed
toward the corners of a regular
tetrahedron at angles of 109.5°.
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sp3 CH4 (4 sigma bonds)Tetrahedron Bond angle 109.5o
bonds (H) - sp3 (C)
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sp3 carbon sp3 carbon
+
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sp3- sp3 sigma bond
6(s- sp3) sigma bonds
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2p
2s
2p
2s2sp2
2p
sp2 Hybridization
3sp2
Trigonal Planar
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each sp2 hybrid orbital has two lobes
of unequal size.
the three sp2 hybrid orbitals are
directed toward the corners of an
equilateral triangle at angles of 120°.
the unhybridized 2p orbital is
perpendicular to the plane of the sp2
hybrid orbitals .
sp2 hybrid orbitals
unhybridized2p orbital
sp2 Hybrid Orbitals
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+
+ 4s of H
sp2- sp2 sigma bond
4(s- sp2) sigma bonds
sp2 carbons
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1 + 1
p orbitals that remain on carbons overlap to form bond
C(2p)-C(2p) bond
H
H
H
HCC
H
H
H
HCC
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2p
2s
2p
2s
2sp
2p
sp Hybridization
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sp Hybrid Orbitals
– each sp hybrid orbital has two
lobes of unequal size.
– the two sp hybrid orbitals lie in a
line at an angle of 180°(linear).
– the two unhybridized 2p orbitals
are perpendicular to each other
and to the line through the two sp
hybrid orbitals.
x
yz
sp hybridorbitals
unhybridized 2p orbitals lie on the y and z axes
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sp carbons
+
+ 2s of H
1 + 2
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Multiple Bonds
• A double bond (2 pairs of shared electrons) consists of a sigma bond and a pi bond.
• A triple bond (3 pairs of shared electrons) consists of a sigma bond and two pi bonds.
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• We study three types of hybrid atomic orbitals
spsp33 (1 s orbital + 3 p orbitals -> four sp3 orbitals)
spsp22 (1 s orbital + 2 p orbitals -> three sp2 orbitals)
spsp (1 s orbital + 1 p orbital -> two orbitals)
• Overlap of hybrid atomic orbitals can form two types of
bonds, depending on the geometry of the overlap
s bonds s bonds are formed by “direct” overlap
p bonds p bonds are formed by “parallel” overlap
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Hybrid OrbitalsHybrid-ization
Types of Bonds to Carbon Example
sp3 four sigma bonds
sp2 three sigma bondsand one pi bond
sp two sigma bondsand two pi bonds
H H
H H
H- C C- H
H
C C
H
H H
H- C- C- H Ethane
Ethylene
Acetylene
Name
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State the hybridization of each carbon atom.
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3 Sigma bonds and one lone pair
:NH3
N
H HH
sp3 hybrid nitrogen
2p
2s
2p
2s
2sp3
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2 sigma bonds and 2 lone pair
O
HH
sp3 hybrid oxygen H2O
2s 2s
2p 2p2sp3
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sp2 hybrid oxygen
trigonal planar : 120o bond angles
2p
2s
2p
2s2sp2
2p
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sp hybrid nitrogen
2p
2s
2p
2s
2sp
2p
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Functional Groups
Functional groupFunctional group: an atom or group of atoms within a molecule that shows a characteristic set of physical and chemical properties.
Functional groups are important for three reason; they are
the units by which we divide organic compounds into classes.
the sites of characteristic chemical reactions.
the basis for naming organic compounds.
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Hydrocarbons
Alkane/ Cycloalkane: single bonds.
Alkene/ Cycloalkene: double bonds.
Alkyne: triple bonds.
Aromatic: contains a benzene ring.
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CH3CH2 C
O
H
CH3 C
O
CH3
H3C OH R OH Alcohols
RCHO Aldehydes
RCOR Ketones
Compounds Containing Oxygen
H3C O CH2CH3 R O R Ethers
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Carboxylic Acid: RCOOH
Compounds Containing Oxygen
or or
O
CH3 - C-O- H CH3 COOH CH3 CO2 H
Acid Chloride: RCOCl Ester: RCOOR' Amide: RCONH2
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C
O
OH
C
O
ClC
O
OCH3C
O
NH2
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Compounds Containing Nitrogen
Amines: RNH2, RNHR', or R3N
Amides: RCONH2, RCONHR, RCONR2
Nitrile: RCN
N
O
CH3 CH3 C N
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HOH H
OCH3
H
Estrone(Female Steroidal Hormone)
O
H3CO
H3CO
N CH3
Morphine(Analgesic)
OCH3
H3C
HOCH3
H3C
3
Vitamin E
OCH2 CHN
O
N
S
OCO2H
Penicillin V
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Chemical Reactions
What? Change in electron configuration.Bonds broken/ Bonds formed.
Why? Attain a stable state.
How? Collisions between atoms, molecules, ions.
1) Sufficient kinetic energy.2) Proper orientation.
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Energy
Reaction Time
A + B
(Reactants)
(Intermediate)
[A-B]# (Transition State)
C(Product)
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Classifications of Reactions
addition
elimination
substitution
2
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rearrangement
oxidation
reduction
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Reaction Mechanism
Overall description of how a reaction occurs.
Which bonds are broken and formed.
Free Radical : Movement of one electron,
usually proceeds by chain reaction.
Polar : Movement of electron pairs from areas of high
electron density to areas of low electron density.
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Ways to Form and Break Covalent Bonds.
1. Symmetrical (one electron goes to each atom in the bond).
Homolytic cleavage (Radical Mechanism)
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2. Unsymmetrical (both electrons go to one atom in the bond).
Heterolytic cleavage (Polar Mechanism)
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Acids and BasesAcids and Bases
Lewis Acids and Bases
Lewis base(donates an
electron pair)
Lewis acid(accepts an
electron pair)
-+ O-H H- OH
+ H- O-H
H
H O H
C H 3 - C +H
C H 3
+ C l - C H 3 - C - C lH
C H 3A carbocation(a Lewis acid)
Chloride ion(a Lewis base)
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Lewis Acid(Accepts electron pair)
If H+ is doing the accepting
acid
If atom other than H+ is doing the accepting
electrophile
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Lewis Base(Donates electron pair)
If donate electron pairto H+
base
If donates electron pair to atom other than H+
nucleophile
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Complete the following Lewis acid-base reactions.
3 3
3 3
3
3
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AlkanesAlkanesandand
CycloalkanesCycloalkanes
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StructureHydrocarbonHydrocarbon: a compound composed only of carbon and
hydrogen.
Saturated hydrocarbonSaturated hydrocarbon: a hydrocarbon containing only
single bonds.
AlkaneAlkane: a saturated hydrocarbon whose carbons are
arranged in a chain.
Aliphatic hydrocarbonAliphatic hydrocarbon: another name for an alkane.
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Nomenclature
• IUPAC system
International Union of Pure and Applied Chemistry
(IUPAC)
Prefix tells the number of carbon atoms
Suffix -aneane specifies an alkane
• Common names
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undec-dodec-
tetradec-pentadec-hexadec-heptadec-
nonadec-eicos-
tridec-
11121314151617
octadec- 181920
Prefixmeth-eth-prop-but-pent-hex-
oct-non-dec-
1234567hept-89
10
Carbons
CarbonsPrefix
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Alkanes have the general formula CnH2n+2
Condensed Structural Formula
Molecular FormulaName
heptane
hexane
pentanebutane
propaneethanemethane CH4 CH4
C2 H6 CH3 CH3C3 H8 CH3 CH2 CH3C4 H10 CH3 (CH 2 ) 2 CH3C5 H12 CH3 (CH 2 ) 3 CH3C6 H14 CH3 (CH 2 ) 4 CH3C7 H16 CH3 (CH 2 ) 5 CH3
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Nomenclature1. The general name of an open-chain saturated
hydrocarbon is alkane.
2. For a branched-chain hydrocarbon, the alkane
corresponding to the longest chain is taken as the
parent chain and its name is the root name.
3. Groups attached to the parent chain are called
substituents.
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Alkyl groups (R-)
isopropyl
propyl
ethyl
methyl
CondensedStructural FormulaName
CH3
- CH2 CH3
- CH3
- CH2 CH2 CH3
- CHCH3
4. If there is one substituent, number from the end of the
chain that gives it the lower number.
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CH3CH2CH2CH2CHCH2CH2CH3
CH3
123456784-methyloctane
2-methylpentane
4-ethyloctane
4-propyloctane
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n-octane
5-ethyl-3-methyloctane
2,2-dimethyl-4-methylpentane
6-ethyl-3,4-dimethyloctane
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CH3CH2CHCH2CHCH3
CH3 CH3
2,4-dimethylhexane
CH3CH2CH2C
CH3
CH3
CCH2CH3
CH3
CH3
3,3,4,4-tetramethylheptane
CH3CH2CHCH2CH2CHCHCH2CH2CH3
CH2CH3
CH2CH3 CH2CH3
CH3
3,3,6-triethyl-7-methyldecane
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5. Certain common nomenclatures are used in the IUPAC system.
CH3CH2CH2CHCH2CH2CH2CH3
CHCH3
CH3
4-isopropyloctane
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Common Names Isobutane, “isomer of butane”
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CH3CH2CH2CH2CHCH2CH2CH2CH2CH3
CH2CHCH3
CH3
5-isobutyldecaneor
5-(2-methylpropyl)decane
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CycloalkanesGeneral formula CnH2n
Ring sizes from 3 to 30 and more are known
five- and six-membered rings are the most common
Line-angle drawingseach line represents a C-C bondeach angle represents a C
CC C
CC
CC
CH2 C
H2 C CCH
C
CH
H2
H2 CH 3
CH 3
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Nomenclature of Cycloalkanes
1. No number is needed for a single substituent on a ring.
CH3
methylcyclopentane
CH2CH3
ethylcyclohexane
CH2CH2CH2CH2CH3
1-cyclobutylpentane
2. Name the two substituents in alphabetical order.
H3CCH2CH2CH3
1-methyl-2-propylcyclopentane
H3CH2C
CH3
1-ethyl-3-methylcyclopentane
CH3
CH3
1,3-dimethylcyclohexane
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3. If there are 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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Physical Properties
Low-molecular-weight alkanes (methane....butane)
are gases at room temperature
Higher-molecular weight alkanes (pentane, decane,
gasoline, kerosene) are liquids at room temperature
High-molecular weight alkanes (paraffin wax) are
semisolids or solids at room temperature
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Physical Properties
Solubility: hydrophobic
Density: less than 1 g/mL
Boiling points increase with increasing
carbons (little less for branched chains).
Melting points increase with increasing carbons.
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Sources of alkanesNatural gas 90-95% methane
Petroleum
C1-C2: gases (natural gas)
C3-C4: liquified petroleum (LPG)
C5-C8: gasoline
C9-C16: diesel, kerosene, jet fuel
C17-up: lubricating oils, heating oil
Origin: petroleum refining
Coal
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Reactions of AlkanesCombustion/Oxidation
CH3CH2CH2CH3 + O2 CO2 + H2Oheat
8 10132
long-chain alkanes catalystshorter-chain alkanes
CH4 + Cl2 CH3Cl + CH2Cl2 CHCl3 CCl4+ +heat or light
Cracking and hydrocracking (industrial)
Halogenation
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Alkanes are very unreactive compounds because they have
only strong s bonds and atoms with no partial charges.
However, alkanes do react with Cl2 and Br2
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Chlorination of Methane
Requires heat or light for initiation.
The most effective wavelength is blue, which is absorbed
by chlorine gas.
Lots of product formed from absorption of only one
photon of light (chain reaction).
C
H
H
H
H + Cl2heat or light
C
H
H
H
Cl + HCl
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Free-Radical Chain Reaction
Initiation generates a reactive intermediate.
Propagation: the intermediate reacts with a stable
molecule to produce another reactive intermediate (and
a product molecule).
Termination: side reactions that destroy the reactive
intermediate.
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Initiation Step
A chlorine molecule splits homolytically into chlorine
atoms (free radicals).
Cl Cl + photon (h) Cl + Cl
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Propagation Step (1)
The chlorine atom collides with a methane molecule and
abstracts (removes) a H, forming another free radical and
one of the products(HCl).
C
H
H
H
H Cl+ C
H
H
H
+ H Cl
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Propagation Step (2)
The methyl free radical collides with another chlorine
molecule, producing the other product (methyl chloride)
and regenerating the chlorine radical.
C
H
H
H
+ Cl Cl C
H
H
H
Cl + Cl
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Overall Reaction
C
H
H
H
H Cl+ C
H
H
H
+ H Cl
C
H
H
H
+ Cl Cl C
H
H
H
Cl + Cl
C
H
H
H
H + Cl Cl C
H
H
H
Cl + H Cl
Cl Cl + photon (h) Cl + Cl
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Termination Steps
Collision of any two free radicals
Combination of free radical with contaminant or collision
with wall.
C
H
H
HCl+ C
H
H
H
Cl
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Consider the relative stabilities of alkyl radicals,
The stable alkyl radical is formed faster, therefore 2-chlorobutane is formed faster.
3 2 2 3 2
3 2 2 2
3 2 3
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Reactions of Cyclic Compounds
Page 106
Chlorofluorocarbons remain very stable in the atmosphere
until they reach the stratosphere.
C ClFCl
F
hCFCl
F+ Cl
The chlorine radicals are ozone-removing agents.
Cl + O3 ClO + O2
ClO + O3 Cl + 2 O2
Page 107
Hydrocarbons containing double bonds.
Alkenes
Noncyclic alkene: CnH2n
Cyclic alkene: CnH2n–2
CH3CH2=CH2
Page 108
Physical PropertiesLow boiling points, increasing with mass.
Branched alkenes have lower boiling points.
Less dense than water.
Slightly polar
Pi bond is polarizable, so instantaneous dipole-dipole
interactions occur.
Alkyl groups are electron-donating toward the pi bond,
so may have a small dipole moment.
Page 109
Polarity Examples
= 0.33 D = 0cis-2-butene, bp 4°C
C CH
H3C
H
CH3
trans-2-butene, bp 1°C
C CH
H
H3C
CH3
Page 110
Common Names
Usually used for small molecules.
Examples:
CH2 CH2
ethylene
CH2 CH CH3
propylene
CH2 C CH3
CH3
isobutylene
Page 111
IUPAC Nomenclature
Parent is longest chain containing the double bond.
-ane changes to -ene. (or -diene, -triene)
Number the chain so that the double bond has the
lowest possible number.
In a ring, the double bond is assumed to be between
carbon 1 and carbon 2.
Page 112
Systematic Nomenclature of Alkenes
Longest continuous chain containing the functional group.
Page 113
Cite the substituents in alphabetical order.
Name with the lowest functional group numberand then the lowest substituent numbers.
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No numbering of the functional group is needed in a cyclic alkene.
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Name These Alkenes
CH2 CH CH2 CH3
CH3 C
CH3
CH CH3
CH3
CHCH2CH3H3C
1-butene
2-methyl-2-butene
3-methylcyclopentene
2-sec-butyl-1,3-cyclohexadiene
3-n-propyl-1-heptene
Page 116
Isomers of Alkene
Page 117
Cis-trans Isomerism
Similar groups on same side of double bond, alkene is cis.
Similar groups on opposite sides of double bond,
alkene is trans.
Cycloalkenes are assumed to be cis.
Trans cycloalkenes are not stable unless the ring has at
least 8 carbons.
Page 118
Name these:
C CCH3
H
H
CH3CH2C C
Br
H
Br
H
trans-2-pentene cis-1,2-dibromoethene
Page 119
An alkene is an electron-rich molecule
Nucleophile: an electron-rich atom or molecule that shares electrons with electrophiles
Examples of Nucleophiles
A nucleophile
Page 120
Nucleophiles are attracted to electron-deficient atoms or molecules (electrophiles)
Examples of Electrophiles
Page 121
Reactivity of C=C
Electrons in pi bond are loosely held.
Electrophiles are attracted to the pi electrons.
Carbocation intermediate forms.
Nucleophile adds to the carbocation.
Net result is addition to the double bond.
Page 122
Curved Arrows in Reaction Mechanisms
Movement of a pair of electrons
Movement of one electron
Page 123
Electrophilic Addition
• Step 1: Pi electrons attack the electrophile.
C C + E +C
E
C +
C
E
C + + Nuc:_
C
E
C
Nuc
• Step 2: Nucleophile attacks the carbocation.
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Addition of Hydrogen Halides
Page 125
What is the product?
Page 126
Addition of HX (1)
Protonation of double bond yields the most
stable carbocation. Positive charge goes to
the carbon that was not protonated.
+ Br_
+
+CH3 C
CH3
CH CH3
H
CH3 C
CH3
CH CH3
H
H Br
CH3 C
CH3
CH CH3
Page 127
Addition of HX (2)
CH3 C
CH3
CH CH3
H Br
CH3 C
CH3
CH CH3
H+
+ Br_
CH3 C
CH3
CH CH3
H+
Br_
CH3 C
CH3
CH CH3
HBr
Page 128
Carbocation Stabilities
Page 129
RegiospecificityMarkovnikov’s Rule: The proton of an acid adds to the
carbon in the double bond that already has the most H’s.
“Rich get richer.”
More general Markovnikov’s Rule:
In an electrophilic addition to an alkene, the electrophile
adds in such a way as to form the most stable intermediate.
HCl, HBr, and HI add to alkenes to form Markovnikov
products.
Page 130
Addition of Halogens
Cl2, Br2, and sometimes I2 add to a double
bond to form a vicinal dibromide.
Anti addition, so reaction is stereospecific.
CC + Br2 C C
Br
Br
Page 131
Mechanism for Halogenation (1)
• Pi electrons attack the bromine molecule.
• A bromide ion splits off.
• Intermediate is a cyclic bromonium ion.
CC + Br Br CCBr
+ Br
Page 132
Halide ion approaches from side opposite the three membered ring.
CCBr
BrCC
Br
Br
Mechanism for Halogenation (2)
Page 133
Test for Unsaturation
Add Br2 in CCl4 (dark, red-brown color) to an alkene
in the absence of light.
The color quickly disappears as the bromine adds to
the double bond.
“Decolorizing bromine” is the chemical test for the
presence of a double bond.
Page 134
Formation of Halohydrin
If a halogen is added in the presence of water,
a halohydrin is formed.
Water is the nucleophile, instead of halide.
Product is Markovnikov and anti.
CCBr
H2O
CC
Br
OH H
H2O
CC
Br
OH
+ H3O+
Page 135
Predict the Product
Predict the product when the given alkene reacts with chlorine in water.
CH3
D
Cl2, H2OOHCH3D
Cl
Page 136
Addition of Hydrogen to Alkenes (Hydrogenation)
Page 137
Alkene + H2 Alkane
Catalyst required, usually Pt, Pd, or Ni.
Finely divided metal, heterogeneous
Syn addition
Page 138
Hydration of Alkenes
Reverse of dehydration of alcohol
Use very dilute solutions of H2SO4 or H3PO4 to drive
equilibrium toward hydration.
C C + H2OH+
C
H
C
OH
alkene alcohol
Page 139
Mechanism for Hydration
+C
H
C+
H2O C
H
C
O H
H+
+ H2OC
H
C
O H
H+
C
H
C
OH
H3O++
C C OH H
H
++ + H2OC
H
C+
Page 140
Orientation for Hydration
• Markovnikov product is formed.
+CH3 C
CH3
CH CH3 OH H
H
++ H2O+
H
CH3CH
CH3
CCH3
H2OCH3 C
CH3
CH CH3
HOH H
+
H2OCH3 C
CH3
CH CH3
HOH
Page 141
Hydroboration
Borane, BH3, adds a hydrogen to the most
substituted carbon in the double bond.
The alkylborane is then oxidized to the alcohol which
is the anti-Mark product.
C C(1) BH3
C
H
C
BH2
(2) H2O2, OH-
C
H
C
OH
Page 142
Addition of Borane (Hydroboration–Oxidation)
Anti-Markovnikov’s rule in product formation
Page 143
Anti-Markovnikov Addition of an OH Group
Page 144
Epoxidation
Alkene reacts with a peroxyacid to form an epoxide
(also called oxirane).
Usual reagent is peroxybenzoic acid.
CC + R C
O
O O H CCO
R C
O
O H+
Page 145
Mechanism
One-step concerted reaction.
Several bonds break and form simultaneously.
OC
O
R
H
C
C
OOH
OC
O
RC
C
+
Page 146
Opening the Epoxide Ring
Acid catalyzed.
Water attacks the protonated epoxide.
Trans diol is formed.
CCO
H3O+
CCO
H
H2O
CC
O
OH
H H H2O
CC
O
OH
H
Page 147
Syn Hydroxylation of Alkenes
• Alkene is converted to a cis-1,2-diol,
• Two reagents:
– Osmium tetroxide (expensive!), followed by hydrogen
peroxide or
– Cold, dilute aqueous potassium permanganate, followed by
hydrolysis with base
Page 148
Mechanism with OsO4
Concerted syn addition of two oxygens to form a cyclic ester.
C
COs
O O
OO
C
CO O
OO
Os
C
C
OH
OH+ OsO4
H2O2
Page 149
Oxidative Cleavage
Both the pi and sigma bonds break.
C=C becomes C=O.
Two methods:
Warm or concentrated or acidic KMnO4.
Ozonolysis
Used to determine the position of a double bond in
an unknown.
Page 150
Example
CCCH3 CH3
H CH3 KM nO4
(warm, conc.)C C
CH3
CH3
OHOH
H3C
H
C
O
H3C
H
C
CH3
CH3
O
C
O
H3COH
+
Page 151
Cleavage with MnO4-
Permanganate is a strong oxidizing agent.
Glycol initially formed is further oxidized.
Disubstituted carbons become ketones.
Monosubstituted carbons become carboxylic acids.
Terminal =CH2 becomes CO2.
Page 152
General formula: CnH2n–2 (acyclic); CnH2n–4 (cyclic)
Alkynes
Page 153
Structure of Alkynes
1. The functional group is a triple bond.
a. The triple bond is composed of two π bonds anda σ bond.
i. The π bonds are oriented perpendicular to eachother.
ii. The two π bonds are electron-rich, theyundergo electrophilic addition like alkenes.
b. The general formula is: CnH2n-2
C C RR R = H, alkyl
Page 154
The Structure of Alkynes
Page 155
Acetylene
(Ethyne)H C C H
1.20 Å
* The strength of the carbon-carbon triple bond is about 837 kJ/mol.
* It is the strongest and the shortest known carbon-carbon bond.
Page 156
Nomenclature: The alkynes are named according to 2 systems
1. They are considered to be derived from acetylene by replacement
of one or both hydrogen atoms by alkyl groups.
H C C C2H5
Ethylacetylene
H3C C C CH3
Dimethylacetylene
H3C C C CH(CH3)2Isopropylmethylacetylene
2. For more complicated alkynes, the IUPAC names are used.
Page 157
IUPAC names for Alkynes
1. The rule are exactly the same as for the naming of alkenes, except
that the ending -yne replaces -ene.
2. The parent structure is the longest continuous chain that contains
the triple bond.
3. Numbering provides the lowest number for the triple bond.
H3C C C CH1 2 3 4 CH3
CH3
5
4-Methyl-2-pentyne
Page 158
CH3CHCHC
Cl Br
CCH2CH2CH31 2 3 4 5 6 7 8
3-bromo-2-chloro-4-octyne
A substituent receives the lowest number if there is no functional group suffix,
or if the same number for the functional group suffix is obtained in both directions.
CH3CHC
CH3
CCH2CH2Br123456
1-bromo-5-methyl-3-hexyne
Page 159
4-Bromo-2-hexyne
CH2 CHCH2CH2 CH
4-Penten-1-yne
CH2 C CHCCH3
H3CCH3
CH2 C CHCOH
H3CCH3
* Triple bonds have priority over double bonds.
* An -OH (hydroxyl group) has priority over the triple bond.
4,4-Dimethyl-1-pentyne 2-Methyl-4-pentyn-2-ol
Page 160
Physical Properties of Alkynes1. The alkynes have physical properties that are essentially the same
as those of the alkanes and alkenes.
2. They are insoluble in water but quite soluble in the usual organic
solvents of low polarity.
3. They are less dense than water.
4. Their boiling points show the usual increase with the increasing
carbon number.
Page 161
Preparation of Alkynes
Dehydrohalogenation of alkyl dihalides.
Treatment of a dihalide with strong base, leads to
elimination of HX (X = Cl, Br).
Just like alkene synthesis.
The reaction can take place twice with a dihalide to
form an alkyne.
C C
ClCl
HH KOH C C
Page 162
H3CHC CH2Br2
H3CHC CH2
Br Br
H3CHC CHBr
KOH
+ KBrNaNH2
H3CC CH- KBr
+ H2O- H2O
Page 163
Reaction of Alkynes
1. Addition Reactions
1.1 Addition of Hydrogen (Reduction to Alkenes)
RC CR'YZ RC CR'
Y Z
YZ RC CR'Y Z
Y Z
RC CR'
Na, NH3(liq)C C
H
R
R'
H
C CR
H
R'
H
H2
Lindlar catalyst
Anti
Syn
Page 164
The trans alkene can be obtained by using Li or Na / liquid NH3 as the reducing agent.
1. When lithium or sodium are dissolved in liquid ammonia an intensely blue solution results.
2. These solutions are composed of the metal cations anddissolved electrons which produce the blue color.
3. When an alkyne is added to this solution, an electron adds to one of the π bonds to produce a radical anion.
C C RR C C RRe
(Li)+ Li+
Page 165
4. The radical anion abstract a hydrogen from the solvent,ammonia leading to a radical.
C C RR NH2H C CR
HR
5. The radical then reacts with a second dissolved electron to form an anion which again abstracts a hydrogen to give thefinal product.
C CR
HR eC C
R
HR
C CR
HRC C
R
HR
HNH2H
+ NH2-
Page 166
* The cis alkene can be obtained by using Lindlar’s catalyst.
* Lindlar’s catalyst is a form of Palladium (Pd) that has been
deactivated by treatment with leadacetate and quinoline.
Surface of metal catalyst
+ H2
H H
* When a Platinum (Pt) catalyst is used, the alkyne generally
react with two molar equivalents of hydrogen to give an alkane.
Page 167
1.2 Halogenation
Mechanism
C CX2
C CX
X2C CX X
X X
(X = Cl, Br)
X
C CX2
(X = Cl, Br)C C
X
X
C CX
X
Page 168
1.3 Hydrohalogenation
C CHX
C CX
HXC CH X
H X
(X = Cl, Br, I) H
Mechanism
C C H C CXH
X
C CH X
AlkenylAlkenyl CarbocationCarbocation
Page 169
The second carbocation, with the halogen atom attached, is stabilized by the lone electrons on halogen atom.
The charge on the alkenyl carbocation is centered in an sp2 orbital, this is relatively high energy.
These two factors lead to the fact that the second hydrogen attack occurs faster than the initial attack.
H C C C CH X
H XX
H
X
C CH X X
Carbocation
Page 170
1.4 Hydration
C C RHHgSO4
H2SO4H2O
C C RH
OH
H
* Terminal alkynes
* Other alkynes
C C RCH3HgSO4
H2SO4H2O
C C RCH3
OH
H
C C RR
OH
HH2OH2SO4
HgSO4C C RR
C C RCH3
HO
H
Page 171
• Markovnikov product is found for the hydration with the OH group
adding to the more highly substituted carbon and the H
attaching to the less highly substituted carbon.
* The intermediate in the reaction, a vinyl alcohol, then rearranges to
a ketone in a process called tautomerism.
C CO
H
Enol tautomer(less favored)
C CO H
Keto tautomer(more favored)
Page 172
Mechanism
C C
C CO H
HRH
R HHg+SO4
2-C CR
HOH2
Hg+SO42-
C CR
HOHH
-H+
Hg+SO42-
C CR
HOH
H3O+
HC C
R
HOH
Page 173
1.5 Hydroboration/ Oxidation
2) H2O2, OHC C HCH3
OH
H
1) BH3, THFC C HCH3
* Hydroboration of symmetrically substituted internal alkynes gives
vinylic boranes.
* The vinylic boranes are oxidized by basic hydrogen peroxide to
yield ketones (via enols)
* The reaction occurs in anti-Markovnikov fashion.
Page 174
2. Reactions as Acids
C CR H + Na C CR Na
Sodium acetylide
2 2 2 + H2
C CR H + LiNH2 C CR Li
Lithium acetylide
+ HNH2
C CR H + Ag+
Precipitate
C CR Ag
+ HNO3
C CR H + Ag+
Page 175
Table 1. Acidity of Simple Hydrocarbons
Type Example Ka pKa
Alkyne 10-25 25
Alkene 10-44 44
Alkane 10-60 60
HC CH
H2C CH2
H3C CH3
Stronger acid
Weaker acid
Page 176
Reactions of metal acetylides with primary alkyl halides
* Lithium or sodium acetylides can react with primary alkyl
halides
* The alkyl group becomes attached to the triply bonded carbon,
and a new, larger alkynes has been generated.
RC CR'X
Li RC C R' + LiBr
HC CCH3CH2Br
Li HC C CH2CH3 + LiBr
Page 177
3. Oxidative cleavage
C C +
An internal alkyne
R'RKMnO4 or O3
CRO
OH CR'O
OH
A terminal alkyne
C C +HRKMnO4 or O3
CRO
OH CO O
Page 178
Organic Synthesis* Prepare octane from 1 pentyne
1). NaNH2, NH3
2). BrCH2CH2CH3, THF
H2/Pt in Ethanol
* Prepare cis-2-hexene from 1 pentyne1). NaNH2, NH3
2). CH3Br, THF
H2/Pd in Ethanol
Page 179
Designing a Synthesis
CH3CH2C CH CH3CH2CCH2CH2CH3
O?
Problem 1
Problem 2
Page 180
Alkyl Halides
1. Aliphatic Alkyl Halides
2. Aromatic Alkyl Halides
Methyl halide
H C
H
X
H
1oalkyl halide
R C
H
X
H
R C
H
X
R
2oalkyl halide
R C
R
X
R
3oalkyl halide
X
Page 181
Br CH3
CH3
CH3 CH3
Br
Cl
Cl
CH3
Br
Cl
CH3
CH3
Br
CH3ICl
Page 182
Br X
C C
X
Br
Cl
C O C
halothane
F
C
H
F
H
Cl
F
H
H
C C F
Br
H
Cl
F
Fenflurane
Page 183
Halomethane Dipole Moment, (D)
CH3F 1.82
CH3Cl 1.94
CH3Br 1.79
CH3I 1.64
+ +
Page 184
ElectrophilicElectrophilic Substitution ReactionsSubstitution Reactions
Page 185
+ NaCNI + NaICN
H Br
+ NaN3
N3 H
+ NaBr
Page 186
C Br
C3H7
C2H5H3C
+ H2O C OH
C3H7
C2H5H3C
CHO
C3H7
C2H5CH3
+ HBr
C Cl
CH3
H3C
CH3
+ CH3OH C
+ HCl
CH3
H3C
CH3
OCH3
Page 187
1. S1. SNN1 (1 (UnimolecularUnimolecular MechnismMechnism))
- Rate of the reaction depends on a concentration of a reagent.
C Br
C3H7
C2H5H3C
C
C3H7
C2H5 CH3
+ Br
ElectrophilicElectrophilic Substitution ReactionsSubstitution Reactions
- The first step is a cleavage of a leaving group.
CarbocationCarbocation
Page 188
C
C3H7
C2H5 CH3+ H2O
C
C3H7
C2H5H3C
OH
H
C
C3H7
C2H5H3C
OH
+ Br
+ H2O
C
C3H7
C2H5CH3
OH
H
+ Br
CHO
C3H7
C2H5CH3
+ HBr
- The second step is a bond formation of carbocation and nucleophile.
Page 190
2. S2. SNN2 (Bimolecular Mechanism)2 (Bimolecular Mechanism)
Transition StateTransition State
+ NaN3
BrH
Br
H
N3+ NaBr
HN3
ElectrophilicElectrophilic Substitution ReactionsSubstitution Reactions
Rate of the reaction depends on the conc. of a reagent and a substrate.
A cleavage of a leaving group and nucleophilic attack occurs in one step.
Page 192
SSNN1 Mechanism 1 Mechanism
1. Rate of the reaction: tertiary > secondary > primary alky halides
2. Weak nucleophiles
3. Good leaving groups
HS- > CN- > I- > CH3O- > HO- > Cl- > NH3 > H2O
I- > Br- > Cl- > F-
Page 193
SSNN2 Mechanism2 Mechanism
1. Rate of the reaction: primary/ secondary alky halides
2. Good nucleophiles.
3. Weak leaving groups.
+ NaCNCCH2Br
H CH3
+ NaBr
CCH2CN
H CH3
Page 194
Elimination ReactionsElimination Reactions
Page 195
Elimination ReactionsElimination Reactions
1) E11) E1
C Br
H3C
H3CH
C
CH3
H3C H
+ Br
- Rate of the reaction depends on a concentration of a reagent.
- The first step is a cleavage of a leaving group.
Page 196
- Base will react with hydrogen.
C
H2C
H3C H
OHH
+ HOHC CH2
H3C
H
Br
CH3NaOH
CH2 CH3
+ HOH NaBr
Page 197
2) E22) E2
A hydrogen atom and a halide will be removed.
OH
H
Br
HH
H
H
+ HOH
Elimination ReactionsElimination Reactions
Rate of the reaction depends on conc. of a reagent and a strong base.
Page 200
Acid Formula pKaConjugate Base
ethanolwaterbicarbonate ionammonium ioncarbonic acidacetic acid
sulfuric acidhydrogen chloride
10.3315.715.9
4.766.369.24
-5.2-7
CH3 CH2 OH CH3 CH2 O-
H2 O HO-
HCO 3- CO3
2-
NH 4+ NH 3
H2 CO3 HCO 3-
CH3 CO2 H CH3 CO2-
H2 SO4 HSO4-
HCl Cl -
Page 201
CH3CH2OHC Br
CH3
H3C
CH3
C OCH2CH3
CH3
H3C
CH3 (80%)
CH3CH2ONaC Br
CH3
H3C
CH3
C
CH2
H3C CH3 (97%)
Page 202
BrNaCN
HBr
NaSCH3
Cl H
NaOH
CN SN2
SCH3
HSN2
E2