ORGANIC CHEMISTRY

Lesson 1/midterms/08-03-2021
Alkenes and Alkynes - The parent name is that of the longest chain that
- Alkene: a hydrocarbon that contains one or more contains the C=C.
carbon-carbon double bonds. - Number the chain from the end that gives the lower
o ethylene is the simplest alkene. numbers to the carbons of the C=C.
- Alkyne: a hydrocarbon that contains one or more - Locate the C=C by the number of its first carbon.
carbon-carbon triple bonds. - Use the ending -ene to show the presence of the
o acetylene is the simplest alkyne. C=C
- Branched-chain alkenes are named in a manner
H H
C C H-C C-H
similar to alkanes; substituted groups are located and
H H named.
Ethylene
(an alkene)
Acetylene
(an alkyne) Alkenes - IUPAC Names
Structure of Alkenes • Examples
- Valence Shell Electron Repulsion (VSEPR) model 5
4
3
2
1

predicts bond angles of 120° about each carbon of a 6 4 2 6 4 2

5 3 1 5 3 1

double bond. CH3 CH2 CH3

- In ethylene, the actual angles are close to 120°. CH3 CH2 CH2 CH2 CH=CH2 CH3 CH2 CHCH2 CH=CH2 CH3 CH2 CHC=CH2
CH2 CH3
- In substituted alkenes, angles about each carbon of 1-Hexene 4-Methyl-1-hexene 2,3-Diethyl-1-pentene
the double bond may be greater than 120° because of Alkynes - IUPAC Nomenclature
repulsion between groups bonded to the double • follow the same rules as for alkenes, but use the
bond. ending -yne to show the presence of the triple bond.
1
124.7°
1 CH3 3 4
121.7° 4
2 2 5
H H H3 C H CH3 CHC CH 3 CH3 CH2 C CCH2 CCH3 6 7

C C C C
CH3 CH3
H H H H 3-Methyl-1-butyne 6,6-Dimethyl-3-heptyne
Ethylene Propene
Common Names
• VSEPR theory assumes that each atom in a • Common names are still used for some alkenes and
molecule will achieve a geometry that alkynes, particularly those of low molecular weight.
minimizes the repulsion between electrons in the CH3
valence shell of that atom. CH2 =CH2 CH3 CH= CH2 CH3 C=CH2
• The five compounds shown in the figure below IUPAC name: Ethene Propene 2-Methylpropene
can be used to demonstrate how the VSEPR Common name: Ethylene Propylene Isobutylene
theory can be applied to simple molecules. HC CH CH3 C CH CH3 C CCH3
IUPAC name: Ethyne Propyne 2-Butyne
Common name: Acetylene Methylacetylene Dimethylacetylene

Cycloalkenes
• To name a cycloalkene:
- number the carbon atoms of the ring double
bond 1 and 2 in the direction that gives the
lower number to the substituent encountered
first.
- number and list substituents in alphabetical
order.
Alkenes 4
6
1
3 5
Cis-trans isomerism 5
4
- because of restricted rotation about a carbon-carbon 1 2 3
2

double bond, an alkene with two different groups on 3-Methylcyclopentene 4-Ethyl-1-methylcyclohexene

each carbon of the double bond shows cis-trans (not 5-methylcyclopentene) (not 5-ethyl-2-methylcyclohexene)
isomerism. Dienes, Trienes, Polyenes
H H H CH3 • Alkenes that contain more than one double bond
C C
H3 C CH3 H3 C
C C
H
are named as alkadienes, alkatrienes, and so on.
cis-2-Butene trans-2-Butene • Those that contain several double bonds are
mp -139°C, bp 4°C mp -106°C, bp 1°C referred to more generally as polyenes (Greek:
Alkenes - IUPAC Nomenclature poly, many).
• To name an alkene:
 ORGANIC CHEMISTRY
Lesson 1/midterms/08-03-2021

OH
CH3 OH
CH2 = CHCH2 CH=CH2 CH2 =CCH=CH2
1,4-Pentadiene 2-Methyl-1,3-butadiene 1,3-Cyclopentadiene Farnesol Vitamin A (retinol)
(Isoprene) (Lily-of-the valley)
Physical Properties Reactions of Alkenes
- Alkenes and alkynes are nonpolar compounds. • The most common reaction is addition
- The only attractive forces between their molecules Reaction Descriptive Name(s )
are London dispersion forces. H Cl
- Their physical properties are similar to those of C C + HCl C C hydrochlorination

alkanes with the same carbon skeletons. H OH

- Alkenes and alkynes are insoluble in water but C C + H2 O C C hydration

soluble in one another and in nonpolar organic Br Br

liquids. C C + Br2 C C bromination

- Alkenes and alkynes that are liquid or solid at room H H

temperature have densities less than 1.0 g/mL; they C C + H2 C C hydrogenation
(reduction)
float on water.
Most alkene addition reactions are exothermic.
Ethene, an alkene, is a gas with sweetish odor and the • The products are more stable (lower in energy)
most important raw material in organic chemical than the reactants.
industry. • Just because they are exothermic doesn’t mean that
• It is obtained from the refining of petroleum alkene addition reactions occur rapidly.
• It is used in making plastic polyethylene • Many alkene addition reactions require a catalyst.
• Also produced by plants which causes the H H H H
are replaced by
change in fruit color that occurs as fruits ripen C C + H H H C C H + heat
• Used by producers to produce proper ripe color H H H H
Ethyne, an alkyne, is better known by its common name one double bond three single bonds
acetylene. and one single bond
• Acetylene burns with oxygen in the Addition of HX
oxyacetylene torch to produce a very hot flame Addition of HX (HCl, HBr, or HI) to an alkene gives a
(about 3000 to 5400 OC that is used for cutting haloalkane.
and welding metals • H adds to one carbon of the C=C and X to the
• A very reactive gas that is also an important other.
starting material in the production of plastics and H Cl
synthetic rubber CH2 =CH2 + HCl CH2 -CH2
Terpenes Ethylene Chloroethane
(Ethyl chloride)
• Terpene: a compound whose carbon skeleton
• reaction is regioselective.
can be divided into five-carbon units identical
• Markovnikov’s rule: H adds to the less
with the carbon skeleton of isoprene.
CH3 head C tail substituted carbon and X to the more substituted
CH2 =C-CH=CH2
1 2 3 4
C-C-C-C
carbon.
Cl H H Cl
2-Methyl-1,3-butadiene Isoprene unit
(Isoprene) CH3 CH=CH2 + HCl CH3 CH-CH2 CH3 CH-CH2
•Terpenes illustrate an important principle of the Propene 2-Chloropropane 1-Chloropropane
(not formed)
molecular logic of living systems; Markovnikov's Rule: describes the outcome of some
in building large molecules, small subunits are
Alkenes ‘addition reactions
bonded together by a series of enzyme-catalyzed
• the acid hydrogen (H) becomes attached to
reactions and then chemically modified by additional
the carbon with more hydrogen substituents,
enzyme-catalyzed reactions.
forming this and the halide (X) group becomes attached to
head bond makes the carbon with more alkyl substituents.
OH the ring
• Alternatively, the rule can be stated that the
tail
OH hydrogen atom is added to the carbon with
the greatest number of hydrogen atoms while
Myrcene Geraniol Limonene
(Bay oil) (Rose and (Lemon
Menthol
(Peppermint)
the X component is added to the carbon with
other flowers) and orange) the least number of hydrogen atoms
 ORGANIC CHEMISTRY
Lesson 1/midterms/08-03-2021
• Chemists account for the addition of HX to an – reaction is generally carried out using pure
alkene by a two-step reaction mechanism. reagents, or mixing them in a nonreactive organic
• We use curved arrows to show the solvent
Br Br
repositioning of electron pairs during a CH3 CH=CHCH3 + Br2 CH3 CH-CHCH3
chemical reaction. 2-Butene
CH2 Cl2
2,3-Dibromobutane
• The tail of an arrow shows the origin of Br
the electron pair (either on an atom or in + Br2
CH2 Cl2
the double bond). Br
Cyclohexene 1,2-Dibromocyclohexane
• The head of the arrow shows its new
position. – addition of Br2 is a useful qualitative test for the
• Curved arrows show us which bonds presence of a carbon-carbon double bond
break and which new ones form. – Br2 has a deep red color; dibromoalkanes are
colorless.
Addition of HCl to 2 Butene
Step 1: Addition of H2 – Reduction
– reaction of the carbon-carbon double bond with • Virtually all alkenes add H2 in the presence of a
H+ gives a secondary (2°) carbocation transition metal catalyst, commonly Pd, Pt, or Ni.
H3 C H
intermediate. C C + H2
Pd
CH3 CH2 CH2 CH3
+
H 25°C, 3 atm
CH3 CH=CHCH3 + H+ CH3 CH-CHCH3
H CH3 Butane
A 2° carbocation intermediate
trans-2-Butene

Step 2: Pd
+ H2
– reaction of the carbocation intermediate with 25°C, 3 atm
chloride ion completes the addition. Cyclohexene Cyclohexane
:

: Cl :
- +
Polymerization
: :

: Cl : + CH3 CHCH2 CH3 CH3 CHCH2 CH3

Chloride 2° Carbocation 2-Chlorobutane • From the perspective of the organic chemical
ion intermediate industry, the single most important reaction of
Addition of H2O alkenes is polymerization:
• Addition of water is called hydration – polymer: Greek: poly, many and meros, part
– hydration is acid catalyzed, most commonly by – monomer: Greek: mono, single and meros,
H2SO4. part
– hydration follows Markovnikov’s rule; H adds to initiator
nCH2 =CH2 CH2 CH2 n
the less substituted carbon and OH adds to the (polymerization)
more substituted carbon. Ethylene Polyethylene
OH H • Show the structure of a polymer by placing
H2 SO4
CH3 CH=CH2 + H2 O CH3 CH-CH2
Propene 2-Propanol
parentheses around the repeating monomer unit.
CH3 CH3 • Place a subscript, n, outside the parentheses to
H2 SO4
CH3 C=CH2 + H2 O CH3 C-CH2 indicate that this unit repeats n times.
HO H
2-Methylpropene 2-Methyl-2-propanol • The structure of a polymer chain can be reproduced
by repeating the enclosed structure in both
• Step 1: directions.
+ H • following a section of polypropene (polypropylene)
CH3 CH=CH2 + H+ CH3 CHCH2 monomer units shown in red
A 2° carbocation
intermediate
• Step 2: n
H H CH3
CH3 CH3 CH3 CH3
:

+ O+
CH2 CH-CH2 CH-CH2 CH-CH2 CH CH2 CH n
:

CH3 CHCH3 + :O-H CH3 CHCH3

H An oxonium ion Part of an extended polymer chain The repeating unit
• Step 3:
H H
:

O+ : OH
CH3 CHCH3 CH3 CHCH3 + H+
2-Propanol

Addition of Cl2 and Br2

• Addition takes place readily at room temp.
 ORGANIC CHEMISTRY
Lesson 1/midterms/08-03-2021
Monomer Common Polymer Name(s) and
Formula Name Common Uses
CH2 =CH2 ethylene polyethylene, Polythene;
break-resistant containers
CH2 =CHCH3 propylene polypropylene, Herculon;
textile and carpet fibers
CH2 =CHCl vinyl chloride poly(vinyl chloride), PVC;
construction tubing
CH2 =CCl2 1,1-dichloro- poly(1,1-dichloroethylene);
ethylene Saran Wrap is a copolymer
with vinyl chloride
CH2 =CHCN acrylonitrile polyacrylonitrile, Orlon;
acrylics and acrylates
CF2 = CF2 tetrafluoro- polytetrafluoroethylene, PTFE;
ethylene Teflon, nonstick coatings
CH2 =CHC6 H5 styrene polystyrene, Styrofoam; insulation
CH2 =CHCOOC2 H5 ethyl acrylate poly(ethyl acrylate); latex paints
CH2 =CCOOCH3 methyl poly(methyl methacrylate), Lucite,
CH3 methacrylate Plexiglas; glass substitutes

Polyethylene
Low-density polyethylene (LDPE):
• a highly branched polymer; polymer chains do not
pack well and London dispersion forces between
them are weak.
• softens and melts above 115°C.
• approximately 65% used for the production of films
for packaging and for trash bags.
High-density polyethylene (HDPE):
• only minimal chain branching; chains pack well and
London dispersion forces between them are strong.
• has higher melting point than LDPE and is stronger
• can be blow molded to squeezable jugs and bottles.
Codes for Plastics
Code Polymer Common Uses
1 PET poly(ethylene soft drink bottles, household
terephthalate) chemical bottles, films, textile fibers
2 HDPE high-density milk and water jugs, grocery bags,
polyethylene squeezable bottles
3 V poly(vinyl shampoo bottles, pipes, shower curtains,
chloride), PVC vinyl siding, wire insulation, floor tiles
4 LDPE low-density shrink wrap, trash and grocery bags,
polyethylene sandwich bags, squeeze bottles
5 PP polypropylene plastic lids, clothing fibers, bottle caps,
toys, diaper linings
6 PS polystyrene styrofoam cups, egg cartons, disposable
utensils, packaging materials, appliances
7 all other plastics various