Documente Academic
Documente Profesional
Documente Cultură
– 379 –
SHAPES OF ORGANIC MOLECULES
• The arrangement of atoms bonded to a carbon atom follows VSEPR
theory.......
– 380 –
• Carbon occurs as three allotropes, with three different
structures.
• The incredible hardness of diamond results from a three-
dimensional network of C—C bonds; it is in fact a single giant
molecule; each carbon is bonded to four other carbons.
– 381 –
Structural Classification of Organic Compounds
• Most organic compounds fall into a small number of groups.
• Within each of these groups, all compounds have similar chemical
and physical properties and can be synthesized by similar reactions.
• So....... we can concentrate on learning the characteristics of these
groups, or families without discussing individual compounds in detail.
Hydrocarbons
aliphatic aromatic
acyclic cyclic
– 382 –
• We begin with the hydrocarbons, compounds containing only C and H
atoms.
• The first subdivision is the aliphatic hydrocarbons, which may be
divided into acyclic compounds (having no rings of C atoms) and
cyclic compounds (having rings of C atoms).
• When all of the C atoms are linked by single bonds only, the
compound is said to be saturated, and is called an alkane.
• The first eight members of the acyclic alkane family are:
– 383 –
• A particularly important characteristic of any such homologous
series of compounds is that it can be represented by a general
molecular formula.
• The general formula for acyclic aliphatic hydrocarbons is CnH2n+2
(where n = 1,2,3.... the number of Carbon atoms).
– 384 –
ISOMERISM IN ALKANES
Structural Isomerism
• When the differences between isomers arise from a difference in
which atoms are bonded to which other atoms, the isomers are
termed structural isomers.
• If one looks at compounds of C and H, it becomes apparent that
three of the simplest compounds, CH4, C2H6 and C3H8, can have only
one bonding arrangement.
• Each C atom forms 4 bonds; each H atom 1 bond.
– 385 –
• For C4H10, we saw that two non-equivalent bonding arrangements are
possible, depending upon how the C atoms are linked.
A B
• Each isomer has its own unique physical and chemical properties,
which can differ greatly.
• For the two isomers of C4H10, the only way that isomer A could
possibly be converted into isomer B would be if two single bonds
were broken, CH3 and H were to exchange positions, and two new
bonds were to form. (This does not happen under normal
conditions.)
• Because the energy required to break many single bonds is about
300!400 kJ molG1 at ordinary temperatures, structural isomers are
normally stable and distinct chemical species.
• When you are drawing structural isomers you must remember that
one or more bonds must be broken to change one bonding
arrangement into another.
• This is characteristic of all structural isomers.
– 386 –
Drawing Structural Isomers
C6H14
C4H9CR
– 387 –
• The number of structural isomers possible for large molecules can
be enormous, as the following data show:
EXAMPLE:
Hexane is C6H14:
– 388 –
ORGANIC CHEMISTRY SHORTHAND
• The most common method for depicting rings is by simple polygons,
in which each corner is a C atom.
• Hydrogen atoms are not shown; the number of H’s at each corner C
is the difference between 4 and the number of line-bonds shown.
• Also, each line bond is assumed to terminate in a C atom.
8 3
2
7 4
1
5
– 389 –
• Each type of ring system is classified also according to the number
of rings (mono- vs poly-cyclic) and, more importantly, the degree of
unsaturation (discussed later).
CH2 CH2
or CH3 or
CH2 CH2
C4H8
C6H12
– 390 –
Bond Rotation and Conformers
• In addition to structural isomers, differing short-lived
arrangements of atoms in a molecule, termed conformations, can
result by rapid rotation of atoms, or groups of atoms, around single
bonds.
• When two atoms are connected by a single bond, the atoms are free
to spin about the bond axis.
• For simple molecules such as HCR, this rotation of the two atoms
with respect to the bond axis has no effect on the molecular
geometry, and has no structural consequences.
• For a bond to persist, overlap between orbitals must be maintained.
Rotation about the H —CR bond ( a σ-bond ) does NOT break the
overlap.
• For molecules containing more than two atoms, however, the
rotation about a single bond axis may change the molecular
geometry.
• When a rotation around a single bond does result in a change in the
molecular geometry, the structures which can be drawn are called
conformations, and the molecules are conformers.
– 391 –
• The concept of a preferred conformation is simply illustrated using
ethane, C2H6:
A B C
H H
H H H H
H C C H H C C
C C
H H H
H H H H H H
• Figure B shows ethane in 3-D (recall the wedges indicate the bond
coming forward and the dotted line indicate the bond going away).
– 392 –
H H H
H
H H H
H
H H
H H
Eclipsed Staggered
– 393 –
• All other conformations are intermediate in geometry and energy
between these two extremes.
Cl Cl H Cl
H H
H H H Cl H
H
Cl H Cl
H H H
– 394 –
Conformations of Cyclic Compounds
• There many compounds, both naturally-occurring and synthetic,
which contain rings of atoms.
• The cyclic structure limits the rotation about the bonds linking the
ring atoms, and has extremely important consequences for the
conformations and hence the shapes of a molecule.
– 395 –
• In order to avoid these unfavourable bonding angles, many rings
larger than 3-membered are not planar, and, more significantly, if
the ring contains six C atoms, the tetrahedral bond angle can be
exactly achieved by adoption of a non-planar conformation.
Cyclohexane, C6H12
• This molecule is unique in that it can adopt two basic conformations
in which all bond angles are perfectly tetrahedral, referred to as
the "chair" and "boat" conformations.
A B
– 396 –
• If we look at the geometry of 6-membered ring systems more
closely, two important characteristics of the chair become
evident.......
• Despite its non-planar nature, the ring approximates a planar
system having 'top' and 'bottom' sides with one of the two H atoms
on each C atom on top and the other on the bottom. (Structure B).
• Of the twelve H atoms, six lie close to the average plane of the
ring, and are described as equatorial, while the other six lie above
and below the plane, and are called axial hydrogen atoms.
– 397 –
ALKENES AND ALKYNES [MH5; 22.2]
• When one or more multiple bonds (C=C or C/C) are present, the
molecule is said to be unsaturated because such compounds always
contain fewer H atoms than the saturated analogs, the alkanes.
• You may have noticed that for each multiple bond introduced, two H
atoms are lost from the fully saturated alkane parent....
Ethene (ethylene)
Ethyne (acetylene)
– 398 –
• 2 H atoms = one degree of unsaturation.
• How else can a compound “lose” 2 H atoms??
• When it forms a ring; as we saw with cyclohexane.
CH3(CH2)4C/CCH3
2-octyne 1,3-octadiene
• Shown in the figures above are some of the methods used to depict
– 399 –
the structural formula of a compound.
• In the condensed structural formula, the H atoms (or other
atoms/groups of atoms) are written on the right hand side of the
C to which they are attached (e.g. CH3CH2CH2CH3).
• You may also see:
(CH3)2CHCH2CH3 or CH3(CH2)4CH3
– 400 –
Decalin
H
O S O O N
hetero-atoms, usually N, O and S, as depicted below for a number of
heterocyclic species
-401-
Cis Trans
-402-
• There is no rotation at room temperature about a double bond, so
conversion of cis to trans would require that bonds be broken and
reformed.
• Because there is no rotation, the isomers do not interconvert and a
mixture of them can be separated because of their differing
physical and chemical properties.
• Therefore, they are not conformations, but are actually different
compounds.
• Geometric isomers exist only when the two carbon atoms of the
double bond each bear two different groups.
• For example, the molecule 1,1 - dichloroethene, CH2= CCR2 (a
structural isomer of 1,2-dichloroethene) does not have geometric
isomers...
1,1-dichloroethene
-403-
• As a further example, the formula CH3CH=CHCH3 has geometric
isomers, but (CH3)2C=CHCH3 does not.......
CH3CH=CHCH3
geometric isomers
(CH3)2C=CHCH3
no geometric isomers
-404-
• So for compounds containing two double bonds, a maximum of four
geometric isomers can result; for the formula
CH3CH=CH-CH=CHCH2CH3..............
-405-
Geometric Isomerism in Cyclic molecules
• The presence of a ring of atoms in a molecule can also give rise to
geometric isomers.
• If one of the H atoms in cyclopentane, A, is replaced by another
atom/group (e.g. CH3 or F), there is no difference between it being
on the top, B or the bottom side C. Structures B and C are
identical.
H F F
F H F
A B C D
-406-
• But if the second F atom is bonded to a different Carbon atom,
then the possibility of geometric isomerism arises; the second F
atom can be on the same side of the ring, E, or on the opposite side,
structure F, from the first.
F F F
E
F
E: cis!1,2!difluorocyclopentane
F: trans!1,2!difluorocyclopentane
-407-
Optical Isomers
• Optical isomers are another example of stereoisomerism.
• Optical isomers occur when a carbon atom in a molecule is bonded to
four different atoms or groups.
• This type of bonding arrangement always results in two different
forms of the molecule, and the forms are mirror images of each
other.
• The carbon atom in such molecules is called the chiral centre ( or
sometimes the stereocentre) ; and these molecules are said to be
chiral.
• The two different forms of the molecule are called enantiomers.
• Chiral molecules have no plane of symmetry; molecules that do have
a plane of symmetry therefore cannot be chiral.
• A molecule may have more than one chiral centre, in this case, there
will be more than one pair of enantiomers.
• Stereo isomers which are not mirror images of each other are
called diastereomers.
-408-
• Because molecules that exist as pairs of enantiomers have the same
tetrahedral structure and bonded groups, they exhibit nearly
identical chemical properties.
• However, they may behave differently when they react with other
chiral molecules....
• Most biochemical reactions involve chiral molecules (some with
several chiral centres) and the “fit” between molecules is crucial.
• So, if chiral molecules exist as pairs of enantiomers, how do we tell
them apart ?
• A characteristic of chiral molecules is their ability to rotate a plane
of polarized light; one isomer will rotate the light clockwise (to the
right) and the other isomer will rotate the light counter clockwise
(or to the left).
• The direction of rotation must be determined experimentally.
• We often label these molecules “R” (right handed) and “S” (left
handed); this designation has to do with the orientation of the
various groups bonded to the chiral carbon.
EXAMPLES:
-409-
Finding chiral carbons (or the chiral centres) in a molecule:
OH H H
l l l
H3C - CH2 - C - CH = CH2 H3C - C - CH2 - C - CH2CH3
l l l
CH2CR OH CH2CH3
CH3 CH3
OH
OH
CH3
CH3
OH H3C
CH2OH
H O H
H
OH H
OH OH
H OH
-410-
Aromatic Hydrocarbons or Arenes
• When rings are highly unsaturated their chemical behaviour is
different from the corresponding saturated compounds, so their
chemistry is usually treated separately.
• Since most of the examples first identified had distinctive smells
or aromas, they became known as aromatic compounds.
• The simplest (and probably most discussed!!) arene, benzene, C6H6
was discovered in 1825 by Michael Faraday.
• All aromatic compounds are cyclic by definition.
C 6 H 6 benzene C 12 H 10 biphenyl
OH
Oil of wintergreen naphthalene
C OOC H3
-411-
• Now that we know all (!!??) about the structural skeletons of
organic molecules, we will look at what happens when one or more H
atoms of a hydrocarbon is replaced by other atoms or groups of
atoms.
• These other atoms/groups - the functional groups - are what
determine both the chemical and the physical properties of the
"families" of compounds.
• A tabular summary of some common functional groups arranged
according to the heteroatoms involved follows on page 415 - 416.
-412-
• Water, H - O - H and an alcohol, R - O - H
C O
-413-
• If the second atom is a C the compound is a ketone.
C O
C O
• The other families form a sub-set in that the second atom attached
to the carbonyl C atoms is a heteroatom (i.e. N, O, X).
• When that second atom is the O atom of a hydroxy group, the
ombination is called a carboxyl group.
C O
-414-
• The other members of this sub-set (carboxylate salts and esters)
are referred to as acid derivatives because they each can be
derived from carboxylic acids.
-415-
The Functional Group Classification
Alkanes : or C C C
C C C
Alkenes: or C C
or C C
Alkynes:
Arenes: Alcohols: R OH
O
Ethers:
R R'
O O
Aldehydes: or
C
R H R H
-416-
O
O
Ketones: or
C
R R' R R'
O
O
Carboxylic Acids: or
C
R OH R OH
O
O
Esters: C
R' or R'
R O R O
R"
O O
Amides:
R' or C R'
R N R N
H H
-417-
• You can see that in several of the functional groups there are
oxygen atoms, some of which are double bonded, or a nitrogen atom.
• Determination of degrees of unsaturation is trickier when there are
heteroatoms in the formula of a molecule......
EXAMPLE: C5H12O
EXAMPLE: C4H8O
-418-
• Halogen atoms, F, CR, Br, and I : When a halogen atom is present
it is considered to have replaced a H atom, and therefore the
number of halogen atoms and H atoms must be added to arrive at
the 'base hydrocarbon'.
EXAMPLE: C4H5Br3
EXAMPLE: C5H9N
-419-
REACTIVITY of ORGANIC COMPOUNDS
• Most reactions of organic compounds involve a second reactant,
called a reagent.
• For a reaction to take place usually two species must collide and do
so in such a way that one or more covalent bonds are broken and/or
one or more bonds are made.
• These reactions occur typically through a number of separate and
discrete steps.
• Reaction mechanism is the term applied to the description of the
detailed course of the overall reaction - any mechanism must
explain and account for all observable, experimental facts.
• These include such things as reaction conditions (heat, light,
catalysts), formation of intermediates or of by-products through
side reactions, and ultimately, why these changes occur.
• When a covalent bond breaks it can do so in two ways which differ
in the fate of the shared electron pair...........
-420-
ELECTRONEGATIVITIES OF SOME ELEMENTS
H C N O F
2.1 2.5 3.0 3.5 4.0
Si P S CR
1.8 2.1 2.5 3.0
l
— C — CR º CR +
l C
CARBOCATION
— C— H + :B º HB + C:
l
CARBANION
• Many of the reactions involve a conversion of one functional group
into another while the C skeleton remains intact and unchanged.
• Most of the reactions we will consider in the sections which follow
can be classified in one of three categories:
-421-
Substitution
• An atom or group of atoms is substituted for another atom or group
of atoms attached to a C atom, without any change in the number of
double or triple bonds if any are present.
H Br
Br2
FeBr3
Addition
• Atoms or groups of atoms are added to the compound without any
loss of atoms from it.
• There is an increase in the number of atoms attached to at least
one C atom:
Pd catalyst
CH3CH 4 CH2 + H2 ! CH3CH2CH3
• Here 2 H atoms are added, one to each of the two C atoms of the
C = C group.
-422-
Elimination
• Atoms or groups of atoms are eliminated, or removed from the
compound without any atoms being added to it.
• There is a decrease in the number of atoms attached to at least
one C atom, with a corresponding increase in the number of double
or triple bonds.
H2SO4 catalyst
CH3CH2CH2—OH ! CH3CH 4 CH2 + H2O
-423-
Oxygen
• The most important use of alkanes is as fuels.
• When initiated (e.g. with a spark), alkanes burn in an excess of oxygen
according to the combustion equations discussed in earlier parts of
the course...
Chlorine
• When illuminated with ultraviolet light, or heated to 300!400EC, a
mixture of methane and chlorine gases reacts vigorously to form
chloromethane and hydrogen chloride:
-424-
• The CH3CR formed can then undergo a second substitution reaction to
form dichloromethane, CH2CR2, which in turn can form CHCR3
(chloroform), and yet again to yield carbon tetrachloride, CCR4....
-425-
Alkenes and alkynes
• In contrast to alkanes, unsaturated aliphatic hydrocarbons react
readily with the halogens, acidic reagents and a variety of oxidizing
and reducing agents.
• Reaction is characterized by addition of reagent X—Y to the double
or triple bond.......
-426-
• Once addition to an alkene has occurred the product is saturated, so
further addition is not possible.
• The most common alkene addition reactions of practical importance
are outlined below.
• Alkynes react in the same way; often the only essential difference is
that further addition can occur since after one addition to an alkyne,
the product is an alkene........
H2
CH3C/CH !
Pd
Hydrogen, H2
• The addition of hydrogen converts an alkene to an alkane.
• This saturation or hydrogenation of the double bond is an important
reaction both in the research laboratory and in commercial
applications.
• Although this addition reaction is strongly exothermic, it is very slow
if no catalyst is used.
Pd catalyst
CH3CH 4 CH2 + H2 !
-427-
Halogens, X2
• In contrast to hydrogen, both CR2 and Br2 react rapidly with alkenes
in the absence of a catalyst.
• The reaction with Br2 is a useful qualitative test for the presence of
a carbon-carbon double or triple bond.
• Solutions of Br2 in most solvents are coloured red-brown; alkenes and
dibromoalkanes are typically colourless.
• The rapid disappearance of the reddish colour of the Br2 solution is a
characteristic reaction of an alkene or alkyne, and provides a simple
visual method of detection.
Water, H2O
• Water adds to alkenes in the presence of an acid (catalyst) to form
alcohols:
H2SO4 catalyst
CH3CH 4 CHCH3 + H - OH !
-428-
• If the alkene is unsymmetrical (the two C atoms of the double bond
do not bear the same groups), addition can lead to two structurally
isomeric products.
H2SO4 catalyst
CH3CH 4 CH2 + HOH !
Hydrogen Halide, HX
• Hydrogen halides (HCR, HBr, HI) add to alkenes to give alkyl halides:
-429-
Arenes, or Aromatic compounds
Br Br Br
Br
Br
Br
-430-
Alcohols
• The system which has been developed for classifying alcohols
specifies the location of the hydroxy group —OH on the C skeleton.
H R’ R’
l l l
R - C - OH R - C - OH R - C - OH
l l l
H H R”
• As water does, alcohols react with the alkali metals (eg. Li, Na, K)
to liberate H2 gas.......
-431-
HOH + Na ! Na+ OHG + ½ H2 (g)
ROH + Na ! Na+ ORG + ½ H2 (g)
RO G + H2O ! ROH + OH G
• Water is not only a very weak acid but also a very weak base.
• In the presence of a strong acid it accepts a proton to form the
hydronium ion, H3O+:
• Similarly, alcohols behave as bases and can react with strong acids
to form oxonium ions, the equivalent of the hydronium ion:
-432-
Oxidation of Alcohols
• Oxidation of alcohols is the first organic oxidation reaction we will
study.
• While we know that oxidation means “loss of electrons”, in organic
chemistry it means other things too......
• Oxidation also means: loss of 2 H’s or gain of O.
• Primary and secondary alcohols oxidize to form carbonyl compounds:
H
l [ O ] \
— C —OH ! C=O + H2 O
l /
O O
ll ll
CH3CH2OH ! CH3 C—H ! CH3 C—OH
Ethanol Acetaldehyde Acetic acid
-433-
• Unless the oxidation is carried out under carefully controlled
conditions, the product isolated from the oxidation of a primary
alcohol is the corresponding carboxylic acid.
• The fact that the alcohol and the aldehyde are being oxidized here
is most easily recognized by drawing analogy to the one-C series
• Add all these numbers together, being sure to keep the signs
straight.
-434-
EXAMPLE:
CH3OH
CH2O
HCOOH
-435-
• Oxidation of a secondary alcohol gives a ketone:
CH3CH — CH3 ! CH3—C—CH3 acetone
l ll
OH O
CH3
l
CH3— C—OH ! NO REACTION
l
CH3
-436-
Reduction of Aldehydes and Ketones
• It should come as no surprise that the oxidation reactions
described above can be reversed with a suitable reducing agent,
converting aldehydes and ketones into alcohols.
• Sodium borohydride, NaBH4 and lithium aluminum hydride, LiAlH4
are commonly used in the laboratory, but H2 gas (with a catalyst) is
used for industrial scale reactions.
• If oxidation reactions lose 2 H atoms, then reduction reactions
must gain 2 H atoms!!
Ethers
• The general formula of an ether is R—O—R’ and they are usually
named by stating the nature of R and R’
symmetrical unsymmetrical
CH3 — O — CH3 C2H5 — O — CH3
dimethyl ether ethyl methyl ether
conc. H2SO4
2 C2H5OH ! C2H5— O — C2H5 + H2 O
heat to 140EC
-437-
• Ethers are quite non-reactive; they do not undergo reduction,
elimination, oxidation, or reaction with bases, so they are popular in
the laboratory as solvents.
• Because they do not have the — OH functional group, ethers
molecules do not hydrogen bond to each other; this results in quite
low boiling points. (For diethyl ether, the b.p. is 35o C)
-438-
Acid/Base Properties of Carboxylic Acids [MH5; 13.4]
• The most distinctive chemical property of these compounds is their
acidity.
• All are weak acids undergoing partial ionization in water to give
weakly acidic solutions:
-439-
• As there are two contributing structures; each O atom has a formal
charge of !½.
• Since this delocalized structure is of lower energy than a localized
one, equilibrium for the formation of the carboxylate lies farther
to the right than that for the formation of an alkoxide ion.
• Carboxylic acids are strong enough acids to liberate CO2 gas from
bicarbonate salts (e.g. NaHCO3).
-440-
Formation of Carboxylic Acid Derivatives
• Carboxylic acids can be converted into a number of structurally
related derivatives, compounds in which the —OH group is replaced
by other groups.
• One important derivative is the ester.
Esters
• When a carboxylic acid and an alcohol are heated in the presence of
an acid catalyst (usually conc. HCR or conc. H2SO4) an equilibrium is
established with an ester and water:
O O
ll ll
CH3 C—OH + HO - CH3 º CH3 - C—O—CH3 + H2O
acetic acid methanol methyl acetate
-441-
• Volatile esters generally have pleasant odours, and are of
importance in the perfume industry and as artificial flavourings.
Amines
• Amines are derivatives of ammonia and are classified as primary,
secondary or tertiary according to the number of C atoms attached
to the nitrogen atom...........
H-N-H R-N-H R - N - R’ R - N - R’
l l l l
H H H R”
• Note that the terms primary, secondary and tertiary are applied to
amines in a different way than they are applied to alcohols.
• As is the case for ethers and ketones, the R groups may be the
same or different, and the nitrogen atom may be part of a ring of
atoms.
-442-
Basicity of Amines [MH5; 13.5]
• Like ammonia, amines are weak bases and their aqueous solutions
are basic:
-443-
Amides
• Amides are compounds formed from the reaction of a carboxylic
acid with an amine.
• In these compounds, the —OH of the carboxylic acid is replaced by
—NH2 or —NHR or —NRR'.
• So, an amide contains a carbonyl group linked to an amino group....
1)
-444-
2)
-445-
ORGANIC POLYMERS [MH5;22.6]
• Polymers are giant molecules (from the Greek, 'many parts' poly
meros ) made by joining many small molecules often referred to as
monomers.
• Polymer molecules can have molecular weights ranging from
thousands to millions.
-446-
• Heating ethylene to 100-250EC at 1000-3000 atmospheres in the
presence of a catalyst gives polymers with molar masses of several
million.
• A polymer with molar mass of one million would contain almost
36,000 ethylene molecules!!!!
branched (LDPE),
-447-
or cross-linked (CLPE)
• HDPE is dense,
hard and strong, due to the close packing formed by the long, linear
chains.
• LDPE is soft and flexible; it has a lower density due to the
branching of the polymer chains.
• CLPE is rigid and inflexible; the cross linking adds to the rigidity of
the polymer.
• Teflon is polytetrafluoroethylene:
C C
-448-
• Condensation polymers such as polyesters and polyamides are made
by elimination reactions.
• The reaction between terephthalic acid and ethylene glycol gives
the polymer PETE, polyethylene terephthalate, by elimination of a
water molecule.
HO O
C C + HOCH 2CH 2OH
O OH
OH O
+ H 2O
C C
HOCH2CH2 O O
C C
O OCH2CH2O O
C C
OH
O
-449-
• Nylon is a polyamide prepared by elimination of H2O in the reaction
of adipic acid and hexamethylenediamine:
O H
H
OH + N
N
HO H
O H
H
O
N H
HO N
O
H
H
H O O
N N OH
N N
H
O O
H H
-450-
Natural Polymers: Polypeptides and Proteins
• Proteins contain an amide linkage formed by elimination of a water
molecule in a condensation reaction between two amino acids.
• Amino acids (with one exception) are chiral molecules......
-451-