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Structural: representation of molecule showing how the atoms are bonded to each other.
Full structural formula graphic formula showing every bond and atom. Usually 90 and 180
angles are used to show the bonds because this is the clearest representation on a 2-
dimensional page, although it is not the true geometry of the molecule. (MUST DRAW Hs!)
Condensed structural formula often omits bonds where they can be assumed, and groups
atoms together. It contains the minimum information needed to describe the molecule
unambiguously.
Stereochemical formula attempts to show the relative position of atoms and groups around
carbon in three dimensions. The convention is that a bond coming out of the page is shown as
a solid, enlarging wedge; a bond sticking behind the page is shown as a dotted line; a bond in
the plane of the paper is a solid line.
o Examples: methanol, CH3OH ethene, C2H4
molecular
full structural
condensed
structural
IUPAC: International Union of Pure and Applied Chemistry
International, non-governmental organization that is best known for its system of nomenclature, which is now
recognized as the world authority in this field.
# of C-atoms in longest chain Stem in IUPAC name Example (C2H2n+2 for alkanes)
1 meth- CH4, methane
b) If two chains have equal lengths, pick the one with more branch points.
Note: in cyclic and aromatic (benzene derivatives) compounds, no number needed if only one substituent.
Rule #3: Identify the functional group and attach appropriate suffix
Note: the name for the stem/root is derived from the longest carbon chain, which may include the carbon of
the functional group.
alkene -ene
alkyne -yne
alcohol -anol
nitrile -anenitrile
aldehyde -anal
ketone -anone
ester* -anoate
amine* -anamine
amide* -anamide
Ester functional group*: organic salts where the alkyl group of the alcohol has replaced the hydrogen of the
carboxylic acid. Their name puts the alkyl group first, followed by the name of the acid anion.
Example: C2H5COOCH3
Amine functional group*: primary amines have an NH2 group which can undergo substitution by alkyl groups,
giving rise to secondary and tertiary amines. These are named using N- to show the position of the
substituents.
Example 1: (primary amine)
Example 2: (secondary amine)
Amide functional group*: acid derivatives where the OH of the acid has been replaced by N<
Example 1: (primary amide)
Indicating position of the functional group: shown by a number inserted before the functional group ending.
The number refers to the carbon atom to which the functional group is attached when the chain is numbered
starting at the end that will give the smallest number to the group.
Example 1: Example 2:
Sometimes a functional group can only be in one place, and in these cases we do not need to give a number to
show its position.
Example 1: Example 2:
EXAMPLES:
PART 2: Physical Properties & Isomerism (Structural- v. Stereo-)
Homologous series
Same general formula with neighboring members of the series differing by CH 2.
Examples:
Alkanes: CnH2n+2 Alcohols: CnH2n+1OH
Boiling points
Length of carbon chain
Structural isomers
Solubility in water
Determined by polarity
Stereoisomerism
1) Geometrical isomerism: occurs when rotation about a bond is restricted or prevented
Example: asymmetric non-cyclic alkenes
cis-2-butene v. trans-2-butene
Stereoisomerism
2) Optical isomerism: shown by all compounds containing at least one asymmetric or chiral carbon atom within a
molecule (one that contains for different atoms or groups bonded to it).
o Two isomers are known as enantiomers and are mirror images of each other (like your right and left hand).
Example:
o Enantiomers are optically active with plane polarized light (both rotate plane-polarized light)
o Normal light consists of electromagnetic radiation vibrating in all planes when passed through a polarizing
filter the transmitted waves only vibrate in one plane and the light is said to be plane-polarized.
Enantiomers
o Apart from behavior toward plane-polarized light, enantiomers have identical physical properties.
o Chemical properties of enantiomers are also identical except when they interact with other optically active
substances.
o Often the case in the body, where different enantiomers can have completely different physiological
effects.
o Optical activity of enantiomers can be detected and measured by an instrument called a polarimeter.
o A polarimeter consists of a light source, two polarizing lenses, and between the lenses a tube to hold the sample
of the enantiomer.
o Diagram:
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Unit 10: Organic Chemistry IB Topics 10 & 20 AP Chapters (Zumdahl): 21.4, 22(all) & beyond!
AP Chapters 1-5
o If the analyzer has to be rotated clockwise, the enantiomer is said to be dextrorotatory (from the Latin, dexter,
meaning right).
o If it has to be rotated counterclockwise, the enantiomer is said to be laevorotatory (from the Latin, laevus,
meaning left).
o One enantiomer is thus known as the d-form and the other is the l-form.
o If both enantiomers are present in equal amounts, the two rotations cancel each other out, and the mixture
appears to be optically inactive. Such a mixture is known as a racemic mixture.
o Ex: gasoline
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Unit 10: Organic Chemistry IB Topics 10 & 20 AP Chapters (Zumdahl): 21.4, 22(all) & beyond!
AP Chapters 1-5
Incomplete Combustion: If there is an insufficient supply of oxygen, incomplete combustion occurs and carbon monoxide
and carbon are also produced as products.
Substitution Reactions
Alkanes can react with halogens in the presence of UV light to form an acid and a substituted alkane.
o
Ex:
o
Ex:
Free radicals contain an unpaired electron and are highly reactive.
When a chlorine free radicals come into contact with a methane molecule they combine with a hydrogen atom
to produce hydrogen chloride and a methyl radical.
Since a new radical is produced, this stage of the mechanism is called propagation:
The methyl free radical is also extrememly reactive and reacts with a chlorine molecule to form the product and
regenerate another chlorine radical.
Another propagation step:
In theory a single chlorine radical may cause up to 10,000 molecules of chloromethane to be formed.
When two radicals react together, termination occurs:
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Unit 10: Organic Chemistry IB Topics 10 & 20 AP Chapters (Zumdahl): 21.4, 22(all) & beyond!
AP Chapters 1-5
Further substitution can occur when chlorine radicals react with the substituted products.
o
For example:
The substitution can continue even further to produce trichloromethane and then tetrachloromethane.
The overall mechanism is called free radical substitution.
o
Note that in this mechanism hydrogen radicals, H, are not formed.
Reactions of Alkenes
Addition reactions
Bond enthalpies:
o
C-C 348 kJ mol-1
o
C=C 612 kJ mol-1 (less than twice C-C enthalpy)
Thus the C=C bond makes the molecule reactive.
The most important reactions of alkenes are addition reactions, where an unsaturated reactant becomes
saturated.
Addition reactions include the addition of hydrogen, bromine, hydrogen halides and water.
Uses of addition reactions
o
Bromination
Pure bromine is a red liquid, but has a yellow/orange color in soln.
When a soln of bromine is added to an alkene, the product is colorless.
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Unit 10: Organic Chemistry IB Topics 10 & 20 AP Chapters (Zumdahl): 21.4, 22(all) & beyond!
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Test for unsaturation: this decoloriation of bromine solution provides a useful test to indicate the
presence of an alkene group.
o
Hydration
Ethene is an important product formed during the cracking of oil.
Although ethanol can be made from the fermentation of starch and sugars, much industrial
ethanol is formed from the addition of steam to ethene.
o
Hydrogenation
The addition of hydrogen to unsaturated vegetable oils is used industrially to make margarine.
Hydrogenation reduces the number of double bonds in the polyunsaturated vegetable oils
present in the margarine, which causes it to become a solid at room temp (and have a longer
shelf life).
Addition polymerization
Under certain conditions, ethene can also undergo addition reactions with itself to form a long chain polymer
containing many thousands (typically 40,000 to 800,000) of carbon atoms.
These addition reaction scan be extended to other substituted alkenes to give a wide variety of different addition
polymers.
o
Example 1: formation of PVC
o
Example 2: formation of PTFE (Teflon)
Ethanol is used as both a solvent and as a fuel. It combusts completely in excess oxygen to produce carbon
dioxide and water.
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Unit 10: Organic Chemistry IB Topics 10 & 20 AP Chapters (Zumdahl): 21.4, 22(all) & beyond!
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C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l) H=-1371 kJmol-1
Ethanol is already partially oxidized, so it releases less energy than burning and alkane of comparable mass.
However, it can be obtained by the fermentation of biomass; thus, in some countries it is mixed with gasoline to
produce gasohol which decreases dependence on crude oil.
Oxidation of alcohols
Ethanol can be readily oxidized by warming with an acidified soln of potassium dichromate (VI). During the
process, the orange dichromate(VI) ion Cr2O72- is reduced from an oxidation state of +6 to the green Cr 3+ ion.
Breathalyzer test: blow into bag through tube of acidified KCr 2O7 crystals. If orange crystals turn green, this
indicates presence of a lot of ethanol (high BAC).
Ethanol is initially oxidized to ethanal. The ethanal is then oxidized further to ethanoic acid.
To stop rxn at ethanal stage, distill ethanal from the rxn mixture as soon as it is formed.
If complete oxidation to ethanoic acid is desired, heat the mixture under reflux so that none of the ethanal can
escape.
Ethanol is a primary alcohol. The oxidation reactions of alcohols can be used to distinguish between primary, secondary
and tertiary alcohols.
All primary (1) alcohols are oxidized by acidified KCr2O7, first to aldehydes then to carboxyllic acids.
All secondary (2) alcohols are oxidized to ketones, which cannot undergo further oxidation.
Tertiarary (3) alcohols cannot be oxidized by acidified K2Cr2O7 as they have no hydrogen atoms attached directly
to the carbon atom containing the OH group.
It is not true to say that tertiary alcohols can never be oxidized, as they burn readily. However, when this
happens, the carbon chain is destroyed.
Substitution reactions and reaction pathways
Substitution reactions of halogenoalkanes
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Unit 10: Organic Chemistry IB Topics 10 & 20 AP Chapters (Zumdahl): 21.4, 22(all) & beyond!
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Because of the greater electronegativity of the halogen atom compared with the carbon atom, halogenoalkanes
have a polar bond.
Reagents that have a non-bonding pair of electrons are attracted to the carbon atom in halogenoalkanes and a
substitution rxn occurs.
Such reagents are called nucleophiles.
Because the molecularity of this single-step mechanism is two it is known as an S N2 mechanism
(bimolecular nucleophilic substitution).
o
Primary halogenoalkanes tend to react by an SN2 mechanism.
(bimolecular nucleophilic substitution)
Tertiary halogenoalkanes (three alkyl groups attached to the carbon atom bonded to the halogen).
o
Example: C(CH3)3Br + OH- C(CH3)3OH + Br-
Determined experimentally: rate=k[C(CH3)3Br]
A two-step mechanism is proposed that is consistent with this rate expression.
The 1st step is rate-determining. Because the molecularity is one the mechanism is known as SN1
(unimolecular nucleophilic substitution).
o
Tertiary halogenoalkanes tend to react by an SN1 mechanism.
(unimolecular nucleophilic substitution)
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Unit 10: Organic Chemistry IB Topics 10 & 20 AP Chapters (Zumdahl): 21.4, 22(all) & beyond!
AP Chapters 1-5
What about secondary halogenoalkanes?
o
Proceed by a mixture of SN1 and SN2 mechanisms
You need to be able to deduce rxn pathways given the starting material and the product.
Conversions with more than two stages will not be assessed.
Reagents, conditions and equations should be included.
Example: deduce a reaction pathway for the conversion of 2-butene to butanone can be done in two stages:
Step 1: 2-butene can be heated with steam and a catalyst to form 2-butanol.
Step 2: 2-butanol can then be oxidized by heating with acidified KCr 2O7 to form butanone.
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Unit 10: Organic Chemistry IB Topics 10 & 20 AP Chapters (Zumdahl): 21.4, 22(all) & beyond!
AP Chapters 1-5
+
The nucleophiles are attracted to the carbon atom and substitute the halogen atom in halogenoalkanes.
Primary halogenoalkanes react by an SN2 mechanism.
Tertiary halogenoalkanes react by an SN1 mechanism.
o
Example: bromoethane + NH3
The rxn with KCN provides a means for extending the C-chain length by one C.
The nitrile can then be converted either into amines by reduction using H2 with a Ni catalyst or into carboxyllic
acid by acid hydrolysis.
o
Example:
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Unit 10: Organic Chemistry IB Topics 10 & 20 AP Chapters (Zumdahl): 21.4, 22(all) & beyond!
AP Chapters 1-5
With hot alcoholic NaOH soln (i.e. NaOH dissolved in ethanol), elimination occurs and an alkene
is formed.
In this second rxn, OH- acts as a base. Elimination of HBr can proceed by either a
carbocation or as a concerted process
In the presence of ethanol there will also be some ethoxide ions present.
Ethoxide is a stronger base than OH-, so the equilibrium lies to the left but some
ethoxide ions will be present and these may be the actual species acting as the base.
Condensation rxns
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Unit 10: Organic Chemistry IB Topics 10 & 20 AP Chapters (Zumdahl): 21.4, 22(all) & beyond!
AP Chapters 1-5
Rxns between 2 molecules to form a larger molecule with the elimination of a small molecule such as H2O or
HCl.
o
alcohol + carboxylic acid ester + water
Example:
Esters
Most have distinctive, pleasant, fruity smell
Many uses:
o
Used as natural and artificial flavoring agents in food
o
Used as solvents in perfumes
o
used as plasticizers, substances used to modify the properties of polymers (i.e. PVC) by making them
more flexible.
Phthalate esters (esters of phthalic acid) - Many health concerns!
More condensation rxns
o
Example: Show the general rxn for a carboxylic acid with an amine.
This rxn is important in biological rxns --- amino acids contain an amine group and a carboxylic acid group , thus
amino acids can condense together in the presence of enzymes to form poly(amides).
Condensation polymerization
If each of the reactants in a condensation rxn contains two functional groups that can undergo condensation,
then the condensation can continue to form a polymer.
o
Example: benzene-1,4-dicarboxylic acid + ethane-1,2-diol
o
Example: hexane-1,6-dioic acid + 1,6-diaminohexane
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Unit 10: Organic Chemistry IB Topics 10 & 20 AP Chapters (Zumdahl): 21.4, 22(all) & beyond!
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Example: Propose a process for the conversion of 1-bromopropane to 1-aminobutane (a.k.a. 1-butylamine)
o
Step 1:
o
Step 2:
Example: Propose a process for the conversion ethane into ethylamine
o
Step 1:
o
Step 2:
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