CHM 1022

1 1
Dr. Kellie Tuck Prof. Steven Langford
School of Chemistry, Monash University School of Chemistry, Monash University
Room 111C/B19, PH: 9905 4510 Room 128C/B19, PH: 9905 4569
Email: Kellie.Tuck@monash.edu Steven.Langford@monash.edu
CHM1022 Lecture 1 (Introduction to Organic
Structures)
CHM 1022
2 2
CHM1022 Lectures: Organic Chemistry
Resources
Textbook
Prescribed: Allan Blackman, Steven E. Bottle,
Siegbert Schmid, Mauro Mocerino and Uta Wille
Chemistry
2011 (2
nd
edition), Wiley [540 B629C]
Recommended: William H. Brown
An Introduction to Organic Chemistry
3
rd
Edition, Wiley Publishing, [547 B881.I]
Your lecture notes and powerpoint slides
Form a study group, visit the Resource Centre
Companion Web-sites
Past exam papers
CHM 1022
3
Syllabus
This section of the course comprises 12 lectures on organic
chemistry following the textbook Chemistry (2nd Edition) by
Blackman et al.. References to this edition of the text are made
throughout the lecture slides. The first edition may also be used in
this course.
Use your syllabus book for more detail on the
course and deadlines
To assist you:
Learning objectives - Given at the beginning of a lecture
Revision slides Used throughout to cement concepts
Summary of Objectives - Given at the end of a lecture
Recommended Problems - The problems selected are representative
of those which you should be able to answer in the end of semester exam
Tutorials
Laboratory exercises to aid in concept transfer
CHM 1022
4
After thIs lecture your should be able to:
- Fecall basIc functIonal groups (FCs)
- dentIfy FCs wIthIn a complex molecule
- 8egIn to realIse the relatIonshIp between FCs
- 8ecome famIlIar wIth the fIve reactIon types
covered In thIs course
Lecture 1
Learning Objectives
CHM 1022
5
Introduction
Organic Chemistry
Food Household
Proteins Soaps, detergents
Carbohydrate Carpets, furniture
Flavouring
Colouring Agriculture
Preservatives Fertilizers
Packaging Pesticides
Growth promoters
Ripening agents
Health
Medicine, antibiotics, drugs Polymers
Artificial joints, hearts, arteries Plastics, paint
Cell membranes Fibers
Disinfectants Wrapping, packages
Anaesthetics
Introduction to Organic Structures
CHM 1022
6
Revision CHM1011 slide
FunctIonaI Croup
"An atom or group of atoms wIthIn a molecule
that shows a characterIstIc set of physIcal and
chemIcal propertIes"
Compounds may have more than one type of
functIonal groups present In theIr structure
Hydrocarbons provIde the scaffold as well as
some reactIvIty
Introduction to Organic Structures
CHM 1022
Introduction to Organic Structures 7
Blackman 16.1
Hydrocarbons
are the form
for function
Hydrocarbons
are the form
for function
Revision CHM1011 slide
Hydrocarbons
CHM 1022
Introduction to Organic Structures 8
Functional Groups
Alkanes
Alkenes
Alkynes
Alcohols
Alkyl Halides
Amines
e.g. butane
e.g. 2-butene
e.g. 2-butyne
e.g. 1-butanol
e.g. 1-chlorobutane
e.g. 1-butylamine
Blackman last page (cover) Revision CHM1011 slide
CHM 1022
Introduction to Organic Structures 9
Functional Groups
Aldehydes
Ketones
Carboxylic Acids
Esters
Amides
e.g. butanal
e.g. butanone
e.g. butanoic acid
e.g. butyl butanoate
e.g. ethyl butanamide
Revision CHM1011 slide Blackman last page (cover)
CHM 1022
Introduction to Organic Structures 10
Multiple Functional Groups
PacIItaxeI
a mItotIc InhIbItor used In cancer
chemotherapy.
PacIItaxeI
a mItotIc InhIbItor used In cancer
chemotherapy.
CHM 1022
Introduction to Organic Structures 11
Multiple Functional Groups
Alcohol
CHM 1022
Introduction to Organic Structures 12
Multiple Functional Groups
O
O
OH
NH O
O
O
O
O
O
O
OH
O
O
Ester
CHM 1022
Introduction to Organic Structures 13
Multiple Functional Groups
Ether
CHM 1022
Introduction to Organic Structures 14
Multiple Functional Groups
Amide
CHM 1022
Introduction to Organic Structures 15
Multiple Functional Groups
Ketone
CHM 1022
Introduction to Organic Structures 16
Multiple Functional Groups
Alkene
Aromatic rings
CHM 1022
Introduction to Organic Structures 17
Interconversion
55
Reaction types
covered
in this
course
*
CHM 1022
18
Addition Reactions
An AddItIon PeactIon
"s one where an atom or group of atoms Is
added (formally or Informally) to a molecule
wIthout the loss of any other atom or group of
atoms"
Occurs typically
in multiple bonds
Occurs typically
in multiple bonds
Introduction to Organic Structures
CHM 1022
19
Substitution Reactions
A SubstItutIon PeactIon
"s one In whIch an atom or group of atoms Is
replaced by a dIfferent atom or groups of
atoms"
Introduction to Organic Structures
CHM 1022
20
Elimination Reactions
An EIImInatIon PeactIon
"s one In whIch an atom or group of atoms Is
elImInated from a molecule wIthout replacement."
0suclly lecds to the ]ormcton o] multple bonds 0suclly lecds to the ]ormcton o] multple bonds
Introduction to Organic Structures
CHM 1022
21
Oxidation Reactions
An DxIdatIon PeactIon
"Dccurs formally wIth the loss of electrons from
an atom or molecule"
n DrganIc ChemIstry however, we can generalIse
thIs statement as the addItIon of oxygen to
(typIcally) a molecule
Introduction to Organic Structures
CHM 1022
22
Reduction Reactions
A PeductIon PeactIon
"Dccurs formally wIth the gaIn of electrons from an
atom or molecule"
n DrganIc ChemIstry however, we can generalIse thIs
statement as the addItIon of two hydrogen atoms to
(typIcally) an unsaturated hydrocarbon, aldehyde,
ketone or carboxylIc acId derIvatIve
Introduction to Organic Structures
CHM 1022
23
Green Chemistry
Applying fundamental knowledge of chemical processes and products to
achieve elegant solutions with the ultimate goal of hazard-free, waste-free,
energy efficient synthesis of non-toxic products without sacrificing efficacy of
function. Anastas & Warner
Green chemistry is the design of chemical products and processes that
reduce or eliminate the use and generation of hazardous substances.
Anastas & Kirchoff
reactive
risk management
remediation (end of pipe)
regulation
unproductive and expensive
unsustainable
proactive
risk reduction
design (start of pipe)
innovation
productive
sustainable
Green Chemistry
Environmental Chemistry

Introduction to Organic Structures
CHM 1022
24
Use of Renewable Feedstock
Fossil Fuels
Chemical
Products
Ancient Biomass
?
Living Biomass
Introduction to Organic Structures
CHM 1022
25
Green Chemistry
An example:

Polyethylene terephthalate (PET) - A plastic for applications such as
magnetic tape, soft drink bottles and polyester fibre
See oxidation in Lecture 9
Introduction to Organic Structures
CHM 1022
26
1. PreventIon t Is better to prevent waste than to treat or clean up waste after It
Is formed.
2. Atom Economy SynthetIc methods should be desIgned to maxImIse the IncorporatIon
of all materIals used In the process Into the fInal product.
3. Peduce Hazard Whenever practIcable, synthetIc methodologIes should be desIgned
to use and generate substances that possess lIttle or no toxIcIty to
human health and the envIronment.
4. Safer 0esIgn ChemIcal products should be desIgned to preserve effIcacy of the
functIon whIle reducIng toxIcIty.
5. Peduce AuxIIIarIes The use of auxIlIary substances (solvents, separatIon agents, etc.)
should be made unnecessary whenever possIble and, when used,
Innocuous.
6. Energy EffIcIency Energy requIrements should be recognIzed for theIr envIronmental
and economIc Impacts and should be mInImIsed. SynthetIc methods
should be conducted at ambIent temperature and pressure.
Paul T Anastas, John C Warner, Green Chemistry: Theory and Practice, Oxford University Press, New York, 1998.
12 Principles of Green Chemistry
Introduction to Organic Structures
CHM 1022
27
7. PenewabIe haterIaIs A raw materIal or feedstock should be renewable rather than
depletIng whenever technIcally and economIcally practIcal.
8. Peduce 0erIvatIves Unnecessary derIvatIsatIon (blockIng group,
protectIon/deprotectIon, temporary modIfIcatIon of
physIcal/chemIcal processes) should be avoIded whenever
possIble.
. Use CataIysIs CatalytIc reagents (as selectIve as possIble) are superIor to
stoIchIometrIc reagents.
10. 0esIgn for 0egradatIon ChemIcal products should be desIgned so that at the end of theIr
functIon they do not persIst In the envIronment and Instead break
down Into Innocuous degradatIon products.
11. PeaI-tIme AnaIysIs AnalytIcal methodologIes need to be further developed to allow
for realtIme Inprocess monItorIng and control prIor to the
formatIon of hazardous substances.
12. AccIdent PreventIon Substance and the form of a substance used In a chemIcal process
should be chosen so as to mInImIse the potentIal for chemIcal
accIdents, IncludIng releases, explosIons, and fIres.
Paul T Anastas, John C Warner, Green Chemistry: Theory and Practice, Oxford University Press, New York, 1998.
12 Principles of Green Chemistry
Introduction to Organic Structures
CHM 1022
28
Chemicals: Are they safe? Are they toxic?
Plastics: Can they be recycled?
Sustainability for Chemists
Materials
or
Technologies
Materials or technologies certainly should be environmental benign but also they
should be produced in environmental benign way. And the chemists are the
group who can focus on both sides.
?
Introduction to Organic Structures
CHM 1022
Introduction to Organic Structures 29
Summary
Fecall basIc functIonal groups (FC's)
- Alkanes, alkenes, alcohols and esters
0IstInguIsh FC's wIthIn a complex molecule
- PaclItaxel example 0o others
8egIn to realIse the relatIonshIp between FC's
- nterconversIon thIs wIll be a recurrIng theme!
Creen ChemIstry has purpose In today's envIronment
8enIgn by desIgn
CHM 1022
30 30
Dr. Kellie Tuck Prof. Steven Langford
School of Chemistry, Monash University School of Chemistry, Monash University
Room 111C/B19, PH: 9905 4510 Room 128C/B19, PH: 9905 4569
Email: Kellie.Tuck@monash.edu Steven.Langford@monash.edu
CHM1022 Lectures 2-4 (Chemical Detective)
CHM 1022
31 31
You should be able to:-
Use mass spectrometry to derive a molecular formula
Use IR spectroscopy to identify functional groups
Understand the origin of the integration and chemical shift of a
NMR signal
Apply the spectroscopy techniques of NMR, IR, adsorption
spectroscopy and MS spectrometry to solve chemical structures
Chemical Detective
At the end of these 3 lectures:-
CHM 1022
The Chemical Detective 32
Learning Objectives
After thIs lecture your should be able to:
- Use mass spectrometry to derIve a moIecuIar formuIa
- Calculate a moIecuIar formuIa from
Its mIcroanalysIs result
- Use F spectroscopy
to IdentIfy functIonaI groups
Lecture 2
CHM 1022
The Chemical Detective 33
Mass Spectrometry
EIectron Impact IonIzatIon (EI) hass Spectrometry
- E mass spectrometry Is routInely used to determIne the moIecuIar
weIght of a compound.
- The output from the detector Is called a mcss spectrum, plot of
sIgnal IntensIty agaInst mass:charge (m/z) ratIo.
For ion with z = 1, the m/z value
corresponds to the molecular
mass, M
r
. Most intense signal
assigned value of 100%
For ion with z = 1, the m/z value
corresponds to the molecular
mass, M
r
. Most intense signal
assigned value of 100%
E
(s)
E
(g)
E + e
-
E
+
+ 2e
-
12
C
Molecular
ion (M
+
)
Blackman 20.2
CHM 1022
The Chemical Detective 34
Mass Spectrometry
HIgh- and Low-PesoIutIon hass Spectra
- HIghresolutIon gIves accurate masses up to fIve decImal places.
e.g. LowresolutIon CD m/z = 28 N
2
m/z = 28
HIghresolutIon CD m/z = 27.99491 N
2
m/z = 28.00614
Hyhresoluton MS s mportcnt ]or dstnyushny
comound comostons oj smlar masses.
Hyhresoluton MS s mportcnt ]or dstnyushny
comound comostons oj smlar masses.
Blackman 20.2
CHM 1022
The Chemical Detective 35
Mass Spectrometry
Isotope 0IstrIbutIons
- ChlorIne occurs as a mIxture of 75.77
J5
Cl and 24.2J
J7
Cl. ThIs Is
shown In the |S of atomIsed chlorIne.
- LIkewIse wIth 8r. The 1:1 ratIo of
79
8r:
81
8r Is shown In the |S of
atomIzed 8r.
35
Cl:
37
Cl
79
Br:
81
Br
Blackman 20.2
CHM 1022
The Chemical Detective 36
Microanalysis
0educIng the hoIecuIar FormuIa of an DrganIc Compound
CombustIon of a compound provIdes the percentage of C, H, N contaIned.
hoIecuIar formuIa can then be determIned, normally wIth the use of the
mass spectrum.
Worked ExampIe:
|S IndIcates m/z = 108 and mIcroanalytIcal; C, 78, H, 7.4, D = 14.6.
0etermIne the molecular formula of the unknown.
C (mass) : H (mass) : D (mass) = 78 : 7.4 : 14.6
C
n
: H
n
: D
n
= 78/12 : 7.4/1 : 14.6/16
= 6.5 : 7.4 : 0.92
= 7 : 8 : 1
SInce C
7x
H
8x
D
1X
= 108 If X=1 the moIecuIar formuIa Is C
7
H
8
D
C (mass) : H (mass) : D (mass) = 78 : 7.4 : 14.6
C
n
: H
n
: D
n
= 78/12 : 7.4/1 : 14.6/16
= 6.5 : 7.4 : 0.92
= 7 : 8 : 1
SInce C
7x
H
8x
D
1X
= 108 If X=1 the moIecuIar formuIa Is C
7
H
8
D
Blackman 20.1
CHM 1022
The Chemical Detective 37
Index of hydrogen defIcIency (aIso know as doubIe bond
equIvaIents)
nformatIon about the presence of rIngs or unsaturatIon can be obtaIned from
the moIecuIar formuIa.
ndex of hydrogen defIcIency = H
reference
- H
moIecuIe
For excmple:
C

H
12
= (14 - 12)/2 = 1 (1 rny)
C

= (14)/2 = 4 (1 rny and 3 alkenes)

The Chemical Detective
C
6
H
12
C
6
H
6
The molecular jormula oj the
rejerence hydrocarbon wth
sx carbon atoms s C
6
H
14
The molecular jormula oj the
rejerence hydrocarbon wth
sx carbon atoms s C
6
H
14
Blackman 20.1
2
CHM 1022
The use of IR Spectroscopy as an analytical tool
The Chemical Detective 38
IR Spectroscopy
The absorption of infrared radiation provides information regarding
functional groups in a molecule.
For a bond to be IR active it must be have a dipole moment.
Blackman 20.3 and 20.4
Stretching frequencies in the
region 1550 - 3800 cm
-1
are
the most informative.
Stretching frequencies in the
region 1550 - 3800 cm
-1
are
the most informative.
Below 1400 cm
-1
is a complex
section of limited use due to its
complexity.
Below 1400 cm
-1
is a complex
section of limited use due to its
complexity.
CHM 1022
The Chemical Detective 39
IR Spectroscopy
The use of IR Spectroscopy as an analytical tool
Stretching frequencies in the
region 1550 - 3800 cm
-1
are
the most informative.
Stretching frequencies in the
region 1550 - 3800 cm
-1
are
the most informative.
Below 1400 cm
-1
is a complex
section of limited use due to its
complexity.
Below 1400 cm
-1
is a complex
section of limited use due to its
complexity.
Blackman 20.3 and 20.4
CHM 1022
The Chemical Detective 40
IR Spectroscopy
OH
Blackman 20.4
CHM 1022
The Chemical Detective 41
IR Spectroscopy
- StretchIng of C=D double bond gIves rIse to strong absorptIon
-1700 cm
1
The excct ]requency depends on strenyth oj bond The excct ]requency depends on strenyth oj bond
Blackman 20.4
CHM 1022
The Chemical Detective 42
IR Spectroscopy
The use of IP Spectroscopy as an anaIytIcaI tooI
Phenol
Blackman 20.4
CHM 1022
The Chemical Detective 43
IR Spectroscopy
The use of IP Spectroscopy as an anaIytIcaI tooI
Aniline
Blackman 20.4
CHM 1022
The Chemical Detective 44
Unknown
- dentIfy the functIonal groups In the spectra below.
IR Spectroscopy
Blackman 20.4
CHM 1022
The Chemical Detective 45
Summary
Understand and apply mass spectrometry
-Electron mpact onIzatIon (E) |ass Spectrometry, low
resolutIon, hIgh resolutIon, Isotope composItIon
Calculate an unknowns molecular formula from its
microanalysis
Empirical formula and molecular formula determination
Use F Spectroscopy as an analytIcal tool
to IdentIfy functIonal groups
-FunctIonal group IdentIfIcatIon; C=D, DH, NH, etc.
CHM 1022
The Chemical Detective 46
Learning Objectives
After thIs lecture your should be able to:
-Understand the orIgIn of the chemIcaI shIft of a N|F
sIgnal
-Understand the orIgIn of the IntegratIon of a N|F sIgnal
-Interpret sImple
1
H and
1J
C N|F spectra.
Lecture 3
CHM 1022
The Chemical Detective 47
NMR Spectroscopy
- Nuclear |agnetIc Fesonance (N|F) spectroscopy Is a powerful
technIque that gIves us three types of InformatIon
-FunctIonaI Croups
-Number of dIfferent groups
-ConnectIvIty of dIfferent groups
- After thIs lecture you wIll be able to use
1
HN|F spectroscopy to gaIn
InformatIon about the dIfferent types of hydrogen nucleI wIthIn a
molecule and how they are connected.
- You wIll also gaIn InformatIon on the carbons present In a molecule by
usIng
1J
CN|F spectroscopy
Blackman 20.5
CHM 1022
The Chemical Detective 48
NMR Spectroscopy
NucIeI : resonance frequencIes, Isotope abundances
Not all Atoms are NMR actve Not all Atoms are NMR actve
Blackman 20.5
CHM 1022
The Chemical Detective 49
NMR Spectroscopy
NhP Spectrometer
Blackman 20.5
CHM 1022
The Chemical Detective 50
NMR Spectroscopy
NucIear SpIns In a hagnetIc FIeId
- A spInnIng charge creates an assocIated magnetIc fIeld.
- f a nucleus of
1
H Is placed In a strong external magnetIc fIeld (8
o
Tesla, 1T = 104 Causs), Its magnetIc moment wIll lIne up wIth fIeld.
- The moment can be parallel or antIparallel to the fIeld.
Blackman 20.5
CHM 1022
The Chemical Detective 51
NMR Spectroscopy
NucIear SpIns In a hagnetIc FIeId
- For
1
H and
1J
C, only two orIentatIons are allowed.
- AbsorptIon of rcdo]requency radIatIon of the approprIate energy flIps the
nuclear spIn
Blackman 20.5
CHM 1022
The Chemical Detective 52
NMR Spectroscopy
ChemIcaI ShIft
- To standardIse reportIng of N|F data, chemIsts have adopted a
quantIty called ChemIcal ShIft ()
- Expressed as parts per mIllIon whIch Is derIved from a dIfference In
frequency from a standard (tetramethylsIlane, T|S) as well as the
magnetIc fIeId of the spectrometer.
Si
CH
3
CH
3
H
3
C
H
3
C
TMS
Blackman 20.5
CHM 1022
The Chemical Detective 53
NMR Spectroscopy
Nuclear Spins in a Magnetic Field
For NMR spectroscopy to be useful different nuclei in a molecule
need to absorb at different frequencies.
Fortunately they do. Each nucleus generates a unique magnetic field
(B
N
) that means each nuclei is in a different environment (B
L
).
CHM 1022
The Chemical Detective 54
NMR Spectroscopy
NucIear SpIns In a hagnetIc FIeId
- The degree of effect that 8
N
has on 8
L
Is defIned as descrIbed Is Its shIeIdIng
effect. f 8
N
Is large then 8
L
wIll be decreased and Iess energy wIll be
needed to excIte the nucleI.
CHM 1022
The Chemical Detective 55
NMR Spectroscopy
13
C NhP Spectroscopy
- The sample Is dIssolved In a solvent, most commonly C0Cl
J
or 0
2
D
and then analysed.
13
C NMR spectrum, 25 MHz
Blackman 20.5
CHM 1022
The Chemical Detective 56
NMR Spectroscopy
13
C NhP spectra: chemIcaI envIronments
240 200 160 120 100 60 40 0
Chemical shift ( )
Ester/Amide/
Aldehyde/ Ketone/
Carboxylic Acid
Vinylic
X = O, N, halide
Unsat.
C-H
Saturated
C-H
C H
C H
X
C C C H
C H
C
O
Aromatic
H
Chemcal shjt related to the 8
L
whch s determned by the
hybrdzaton oj the carbon centre cnd the yrous attached.
Chemcal shjt related to the 8
L
whch s determned by the
hybrdzaton oj the carbon centre cnd the yrous attached.
Blackman 20.5
CHM 1022
The Chemical Detective 57
NMR Spectroscopy
hoIecuIar Symmetry
- f a molecule has a plane of symmetry It sImpIIfIes the NhP spectrum.
- The two halves are IdentIcal and we only need to examIne one half to
determIne the N|F spectrum.
- e.g - how many sIgnals would you expect In the
1J
C N|F of the molecules
below:
Blackman 20.5
CHM 1022
The Chemical Detective 58
NMR Spectroscopy
13
C NhP Spectroscopy
13
C NMR spectrum, 25 MHz
Blackman 20.5
CHM 1022
The Chemical Detective 59
NMR Spectroscopy
13
C NhP spectrum of phenoI
Blackman 20.5
CHM 1022
The Chemical Detective 60
Review Questions
- The
1J
C N|F spectrum has sIgnals at J0.7 and 199.5 ppm.
AssIgn the spectrum to one of the compounds below and assIgn
the peaks.
CHM 1022
The Chemical Detective 61
NMR Spectroscopy
1
H NhP Spectroscopy
- Three key features of
1
H N|F spectroscopy that gIve InformatIon
about a molecule
1. ChemIcaI ShIft (d) - provIdes InformatIon about neIghbourIng
functIonal groups (same ruIes as
13
C NhP)
2. IntegratIon- the relatIve areas of a sIgnal Is proportIonal to the
number of hydrogens
3. SpIIttIng- (or multIplIcIty) measured In hertz (Hz), the couplIng
constant (1) can be used to determIne the connectIvIty of a
molecule
Blackman 20.5
CHM 1022
The Chemical Detective 62
NMR Spectroscopy
1
H NMR spectra: chemical environments
240 200 160 120 100 60 40 0
Chemical shift ( )
Ester/Amide/
Aldehyde/
Ketone/
Carboxylic Acid
Vinylic
X = O, N, halide
Unsat.
C-H
Saturated
C-H
C H
C H
X
C C C H
C H
C
O
Aromatic
H
Blackman 20.5
Also see Blackman Tables
20.9-20.12 and 20.13
Chemical shift ( )
8 7 6 5 4 3 2 1 0
Aromatic Vinylic
X = O, N, halide
Unsat.
C-H
Saturated
C-H
H
C H
C H
X
C C C H
C H
CHM 1022
The Chemical Detective 63
NMR Spectroscopy
1
H NhP spectra: chemIcaI envIronments
DH cnd NH
2
protons ccn yve brocd
syncls due to exchanye rocesses
DH cnd NH
2
protons ccn yve brocd
syncls due to exchanye rocesses
1
H NMR spectrum, 100 MHz
Blackman 20.5
CHM 1022
The Chemical Detective 64
NMR Spectroscopy
1
H NhP spectra: chemIcaI envIronments
- e.g - how many sIgnals would you expect In the
1
H N|F of the
molecules below:
Blackman 20.5
CHM 1022
The Chemical Detective 65
NMR Spectroscopy
1
H NhP spectra: IntegratIon
- ntegratIon Is the area under a curve and Is proportIonaI to the
equIvaIent number of hydrogens.
lnteyraton s the
roton count.
lnteyraton s the
roton count.
Blackman 20.5
CHM 1022
The Chemical Detective 66
NMR Spectroscopy
1
H NhP spectra: IntegratIon
- EquIvalent hydrogens: have the same chemIcal envIronment.
CH
J
CH
2
CH
J
2 sIgnals (6:2)
CH
J
CH
2
CH
2
CH
J
2 sIgnals (6:4)
(CH
J
)
J
C(C=D)DCH
J
2 sIgnals (J:9)
Blackman 20.5
CHM 1022
The Chemical Detective 67
NMR Spectroscopy
1
H NhP spectra: chemIcaI envIronments
- e.g - what ratIo would you expect for the Integrals In the
1
H N|F of
the molecules below:
Blackman 20.5
O
2 signals
OH
4 signals
CHM 1022
The Chemical Detective 68
Learning Objectives
After thIs lecture your should be able to:
- nterpret a
1
H N|F spectrum, understand and apply the
key feature of spectroscopy spInspIn splIttIng
- Apply the spectroscopy technIques of N|F, F,
adsorptIon spectroscopy and |S spectrometry
to solve chemIcal structures
Lecture 4
CHM 1022
The Chemical Detective 69
1
H NhP spectra: NucIear spIn-spIn coupIIng
- When two or more hydrogen nucleI are close enough there magnetIc
fIelds result In splIttIng.
- ChemIcally equIvalent protons show no splIttIng
All protons equIvalent
no splIttIng
- A proton wIth n equIvalent neIghbours wIll be splIt Into n+1 lInes
wIth couplIng constant 1.
- Two groups of protons coupled wIth each other wIll have IdentIcal
couplIng constants 1.
NMR Spectroscopy
Blackman 20.5
CHM 1022
The Chemical Detective 70
NucIear spIn-spIn coupIIng
NMR Spectroscopy
Blackman 20.5
CHM 1022
The Chemical Detective 71
DrIgIns of CompIex spIIttIng
-
effect on H
a
NMR Spectroscopy
Total magnetIc effect (8
L
) due to H
b
I.e.
L
=
o
+
Hb
B
0
H
a
is split into n+1 peaks H
a
is split into n+1 peaks
n = 1
n = 2
C C
H
a
C C
H
b
H
a
C C
H
b
H
b
H
a
CHM 1022
The Chemical Detective 72
PascaI's trIangIe
NMR Spectroscopy
6ves the relctve nteyraton o]
the multlet synals.
6ves the relctve nteyraton o]
the multlet synals.
0
1
2
3
4
5
6
7
No of adj. H
Blackman 20.5
CHM 1022
The Chemical Detective 73
NMR Spectroscopy
Blackman 20.5
CHM 1022
The Chemical Detective 74
Summary
Recognise and interpret a NMR spectrum
Identify the difference between
1
H and
13
C NMR spectra
nterpret N|F spectra of molecules wIth one envIronment
and molecules wIth more than one envIronment
- Understand how N|F can be used to 'count' the number
of envIronments
Interpret a
1
H NMR spectrum, understand and apply the
key features of spectroscopy, chemical shift and the
number of protons
- ShIeldIng - Influence on chemIcal shIft, IntegratIon -
number of equIvalent hydrogens
CHM 1022
The Chemical Detective 75
Review Questions
- PredIct the number of
1
HN|F sIgnals, the IntegratIon of each
proton and the splIttIng pattern of each of these compounds.
(a) CH
3
CCH
2
CH
3
(c) CH
3
CCH(CH
3
)
2
(b) CH
3
CH
2
CCH
2
CH
3
O
O
O

CHM 1022
The Chemical Detective 76
Chemical Detective
ProbIem 1
CHM 1022
The Chemical Detective 77
Chemical Detective
ProbIem 1
2H, q
3H, s
3H, t
CHM 1022
The Chemical Detective 78
Chemical Detective
ProbIem 1 - Answer
IR C=O, 1741
Hydrogen deficiency
= (10 8)/2
= 1
CHM 1022
The Chemical Detective 79
Chemical Detective
ProbIem 1 - Answer
2H, q
3H, s
3H, t
3H, t CH
2
CH
3
2H, q CH
2
CH
3
3H, s -CH
3
4 different C
Environments
1x C=O
3 sp
3
hybridised C
downfield
CHM 1022
The Chemical Detective 80
Chemical Detective
ProbIem 1 - Answer
Ethyl acetate
1.2 3H, t CH
2
CH
3
4.2 2H, q CH
2
CH
3
2.0 3H, s O=C-CH
3
15 CH
2
CH
3
20 CH
3
60 CH
2
170 C
(quat)
CHM 1022
The Chemical Detective 81
Chemical Detective
ProbIem 2
CHM 1022
The Chemical Detective 82
Chemical Detective
ProbIem 2
1H, q
3H, d
CHM 1022
The Chemical Detective 83
Chemical Detective
ProbIem 3
CHM 1022
The Chemical Detective 84
Chemical Detective
ProbIem 3
5H, m
1H, br s
2H, t
2H, t
CHM 1022
The Chemical Detective 85
Chemical Detective
ProbIem 4
CHM 1022
The Chemical Detective 86
Chemical Detective
ProbIem 4
4H, q
6H, t
CHM 1022
The Chemical Detective 87
Summary
nterpret a
1
H N|F spectrum, understand and apply the
key features of spectroscopy, spInspIn splIttIng
- CouplIng constant (1), Pascal's trIangle
Know how to apply the Index of hydrogen defIcIency to
solvIng chemIcal structures
- Problems 1,2,J and 4
Apply the spectroscopy technIques of N|F spectroscopy,
F spectroscopy, adsorptIon spectroscopy and |S
spectrometry to solve chemIcal structures
- Problems 1,2,J and 4
CHM 1022
Chemical Detective
At the end of these 3 lectures Can you now
answer all of these questions? And Blackman et al. questions in
Chapter 20?
Understand and apply mass spectrometry Electron Impact
Ionization (EI) Mass Spectrometry, low resolution, high resolution,
isotope composition
Calculate an unknowns molecular formula from its microanalysis
Empirical formula and molecular formula determination
Use IR Spectroscopy as an analytical tool to identify functional
groups Functional group identification
Interpret a
1
H NMR spectrum, understand and apply the key
features of spectroscopy, spin-spin splitting
CHM 1022
89 89
Dr. Kellie Tuck Prof. Steven Langford
School of Chemistry, Monash University School of Chemistry, Monash University
Room 111C/B19, PH: 9905 4510 Room 128C/B19, PH: 9905 4569
Email: Kellie.Tuck@monash.edu Steven.Langford@monash.edu
CHM1022 Lectures 5-8 (Alkenes, Alkynes and
Reactivity)
CHM 1022
90 90
You should be able to:-
Draw hybrid orbitals and be able to identify C as sp
3
, sp
2
or sp
Understand the rules for writing a mechanism
Recognise aromatic compounds and understand the pK
a
values
of phenol and aniline
Understand several addition reactions and be able to draw
mechanisms to show product formation
Alkenes, Alkynes and Reactivity
At the end of these 4 lectures:-
CHM 1022
91
Learning Objectives
Lecture 5
After thIs lecture your should be able to:
Understand the hybrIdIsatIon of alkenes and
alkynes and how thIs affects reactIvIty.
0escrIbe covalent bond formIng/breakIng
- 0escrIbe reactIons mechanIstIcally
- 8e able to IdentIfy electrophIles and nucleophIles
Alkenes, Alkynes and Reactivity
CHM 1022
92
Hybridisation - Previously seen in CHM1011
lion + tiger = liger
So too with orbitals..
Blackman 5.6
Alkenes, Alkynes and Reactivity
Hybrd Drbtcls Hybrd Drbtcls
CHM 1022
93
Revision
Alkanes
- Alkane: a saturated hydrocarbon whose carbons are arranged In a chaIn
(alIphatIc) or In a rIng (cycloalkane)
- SuffIx ane specIfIes an alkane
- Electron confIguratIon of carbon 1s
2
2s
2
2p
2
- 7alence orbItals are 2s and 2p orbItals
- They are mIxed to form a new hybrId orbItal (see next slIde) sp
J
orbItals are
s In character and p In character
Alkenes, Alkynes and Reactivity
Blackman 5.6
CHM 1022
94
Revision
Alkanes
Methane forms from orbital overlap between the hydrogen 1s orbitals and the sp
3
hybrid orbital of carbon atom
Alkenes, Alkynes and Reactivity
Blackman 5.6
Shae - tetrahedral about carbon
all bond angles are approxImately
109.5r
CHM 1022
95
Hybridisation-Alkene
Alkenes
- Alkene: a unsaturated hydrocarbon whIch contaIns a double bond (C=C)
- SuffIx ene specIfIes an alkene
Alkenes, Alkynes and Reactivity
Blackman 5.6
Hybrdse 2 x p cnd 1 x s = J x sp
2
Also hcve c unhybrdsed p orbtcl, remember the electron
con]yurcton o] ccrbon s 2s
2
2p
2
CHM 1022
96
Hybridisation-Alkene
Ethene
Alkenes, Alkynes and Reactivity
Blackman 5.6
Shae - trIgonal planar about carbon
all bond angles are approxImately
120r
Each carbon has 3 sp
2
+ 1 p
framework
CHM 1022
97
Hybridisation-Alkyne
Alkynes
- Alkyne: a unsaturated hydrocarbon whIch contaIns a trIple bond (C=C)
- SuffIx yne specIfIes an alkyne
Alkenes, Alkynes and Reactivity
Blackman 5.6
Hybrdse 1 x p cnd 1 x s = J x sp
2
Also hcve two unhybrdsed p orbtcls, remember the electron
con]yurcton o] ccrbon s 2s
2
2p
2
CHM 1022
98
Hybridisation-Alkyne
Ethyne
Alkenes, Alkynes and Reactivity
Blackman 5.6
Shae - lInear about carbon
all bond angles are approxImately 180r
Each carbon has 2 sp + 2 p
framework
CHM 1022
Alkenes, Alkynes and Reactivity 99
Bond Lengths and Bond Strength
Blackman 5.5 and 8.4
C-C bond length 154 pm
C=C bond length 133 pm
C=C bond length 120 pm
C-C bond enthalpy 348 kJ mol
-1
C=C bond enthalpy 612 kJ mol
-1
C=C bond enthalpy 960 kJ mol
-1
The p bond s wecker
thcn the bond
The p bond s wecker
thcn the bond
CHM 1022
100
Revision Questions
(a) 0raw the LewIs structure of H
2
D
(b) 0raw the structure of benzene (C
6
H
6
) showIng all orbItals
Involved In bondIng - use hybrId orbItals, where applIcable.
Alkenes, Alkynes and Reactivity
CHM 1022
101
Organic Reactions
How do we descrbe reactons
ut what's actually haenny
Alkenes, Alkynes and Reactivity
CHM 1022
102
Mechanism
The reacton
mechansm descrbes
the jormaton and
breakaye oj bonds.
Alkenes, Alkynes and Reactivity
Blackman 2.2
CHM 1022
103
valence
bond theory
valence
bond theory
Mechanism
A snyle covalent bond
s ]ormed by the
overlcp o] two snyle
electron orbtcls
A B
Alkenes, Alkynes and Reactivity
CHM 1022
104
Mechanism
REAKlNC 0N0S (Lytc)
HomoIytIc bond cIeavage
Neutral products wIth an
UnpaIred electron
PadIcaI
HeteroIytIc bond cIeavage
Charged products wIth
paIred electrons
"FIsh Hook" arrow
movement of 1 eIectron
"NormaI" arrow
hovement of 2 eIectrons
Alkenes, Alkynes and Reactivity
CHM 1022
105
Mechanism
MAKlNC 0N0S (Cenc)
HomogenIc bond formatIon
1 eIectron from each
startIng materIal
HeterogenIc bond formatIon
2 eIectrons from one
startIng materIal
In usIng curved arrows, there are two common types of eIectron
redIstrIbutIon:
from a bond to an adjacent atom
from an atom to an adjacent bond
Alkenes, Alkynes and Reactivity
CHM 1022
106
Mechanism-Heterogenic Reactions
HeterogenIc bond formatIon
also known as PDLAP PEACTIDNS.
Electrons go from an eIectron-rIch atom
to an eIectron-poor atom.
electronpoor atom "lIkes electrons"
ELECTPDPHILE.
electronpoor atom "lIkes electrons"
ELECTPDPHILE.
electronrIch atom "lIkes
nucleI"
NUCLEDPHILE.
electronrIch atom "lIkes
nucleI"
NUCLEDPHILE.
c.f. common bases c.f. proton, H
+
Alkenes, Alkynes and Reactivity
CHM 1022
107 107
Electronegativity
PauIIng eIectronegatIvIty of some eIements
Blackman 5.1
X = halogen, OH, NR
2
Alkenes, Alkynes and Reactivity
CHM 1022
108
Review Question
Whch oj the jollowny act as electrohles, whch act as nucleohles
CN
-
Alkenes, Alkynes and Reactivity
CHM 1022
109
Curved Arrow Notation
Electrons go from an eIectron-rIch atom
to an eIectron-poor atom.
Rules
AII acceptabIe eIectron redIstrIbutIons (bond breaklmake) must:
1. have the same number of vaIence eIectrons
2. obey the ruIes of covaIent bondIng
3. dIffer onIy In dIstrIbutIon of vaIence eIectrons
4. have the same number of paIred and unpaIred eIectrons
5. Have a charge baIance foIIowIng the redIstrIbutIon
Alkenes, Alkynes and Reactivity
CHM 1022
Alkenes, Alkynes and Reactivity 110
Mechanism of Something Familiar
Carbonyl carbons are
electronpoor especIally
wIth neIghbourIng halIdes!
-
+
|eDH Is electron rIch
Break a bond Make a bond
CHM 1022
Alkenes, Alkynes and Reactivity 111
Mechanism of Something Familiar
CHM 1022
Alkenes, Alkynes and Reactivity 112
Summary
0raw sp
J
, sp
2
and sp hybrIdIsed orbItals
Through drawIng bondIng InteractIons
0escrIbe covalent bond formIng/breakIng
Through curves arrows, number of electrons In a
bond
0escrIbe reactIons mechanIstIcally
Through curves arrows
8e able to IdentIfy electrophIles and nucleophIles
Electron () lovIng, nucleus (+) lovIng
CHM 1022
Alkenes, Alkynes and Reactivity 113
Learning Objectives
After thIs lecture your should be able to:
- FecognIse benzene and understand how Its structure was
dIscovered
- dentIfy aromatIc compounds and apply the Huckel rule
- Know the dIfference and sImIlarItIes of phenol and anIlIne
- 8e able to descrIbe the reasons for theIr pK
a
values
Lecture 6
CHM 1022
Alkenes, Alkynes and Reactivity 114
Benzene/Resonance/Aromaticity
Michael Faraday (1791-1867)
Discovered and described
Benzene in 1825
photograph by John Watkins, British Library
Michael Faraday (1791-1867)
Discovered and described
Benzene in 1825
photograph by John Watkins, British Library
August Kekul (1829-1896)
Proposed the first structure for
Benzene in 1872
published by the Deutsche Post der DDR
August Kekul (1829-1896)
Proposed the first structure for
Benzene in 1872
published by the Deutsche Post der DDR
Blackman 16.7
CHM 1022
Alkenes, Alkynes and Reactivity 115
Structure of Benzene
Benzene - Kekul structure
Discovered in 1825 by Faraday from coal tar distillation.
Formula established as C
6
H
6
.
The first structure for benzene was proposed by Kekul in 1872.
This structure did not account for the chemical reactivity or equal bond
lengths of benzene.
This structure did not account for the chemical reactivity or equal bond
lengths of benzene.
Blackman 16.7
CHM 1022
Alkenes, Alkynes and Reactivity 116
Structure of Benzene
Benzene Structural Determination
In 1900s diffraction methods confirmed the equivalence of the
C-C bonds.
Molecule is planar and the C-C bonds are 140 pm in length.
Between values for C-C single (154 pm) and double (134 pm)
bonds.
Blackman 16.7
CHM 1022
Alkenes, Alkynes and Reactivity 117
Structure of Benzene
Thermochemical Evidence for non-triene-
like nature
Evidence suggests benzene should not be described as a triene
with localised single and double C-C bonds
Benzene is more stable than the triene model suggests! Benzene is more stable than the triene model suggests!
(for triene)
Blackman 16.7
Cyclohexene Cyclohexane
Benzene Cyclohexane
H = -360 kJ mol
-1
CHM 1022
Structure of Benzene
Blackman 16.7
118 Alkenes, Alkynes and Reactivity
CHM 1022
Alkenes, Alkynes and Reactivity 119
Structure of Benzene
Chemical Evidence Reactivity
Alkenes undergo facile addition reactions (e.g. addition of Br
2
)
Benzene only reacts with Br
2
in the presence of a catalyst.
0oesn't react lIke an alkene!
SubstItutIon rather than addItIon.
0oesn't react lIke an alkene!
SubstItutIon rather than addItIon.
Orange,
aqueous solution
Ethene
1,2-Dibromoethane
(Colourless)
Benzene Bromobenzene
Blackman 16.7
CHM 1022
Alkenes, Alkynes and Reactivity 120
Structure of Benzene
Benzene Structural Determination
We often represent benzene as a hybrid of two equivalent Kekul
structures.
Each makes an equal contribution to the hybrid, and thus the C-C
bonds are neither double nor single, but something in between.
Resonance
C-C bonds are neither
double nor single, but
something in between
Resonance
C-C bonds are neither
double nor single, but
something in between
Representations of benzene indicate the structure
Blackman 16.7
CHM 1022
Alkenes, Alkynes and Reactivity 121
Structure of Benzene
Delocalized Bonding Model
- HybrIdIzatIon of atomIc orbItals and the of resonance theory, developed In
the 19J0s, provIded the fIrst adequate descrIptIon of benzene's structure and
reactIvIty.
the carbon skeleton Is a regular hexagon, wIth all CCC and HCC bond
angles 120r (78 model).
Each carbon Is sp
2
hybrIdIsed wIth one p orbItal contaInIng one electron.
Dverlap of the sIx parallel 2p orbItals forms a "donutshaped" contInuous
pI cloud.
Each carbon Is sp
2
hybrIdIsed wIth one p orbItal contaInIng one electron.
Dverlap of the sIx parallel 2p orbItals forms a "donutshaped" contInuous
pI cloud.
Blackman 16.7
CHM 1022
Alkenes, Alkynes and Reactivity 122
Aromaticity and the Hckel rule
AromatIcIty
- SpecIal character assocIated wIth the planar rIng systems wIth a
delocalIsed psystem.
- Allows reactIvIty and structure of benzene and related structures
to be understood
Hckel rule
A compound with a planar ring system and a
delocalized -system containing
(4n + 2) -electrons, where n is an integer
Includes neutral molecules, anions and cations
is AROMATIC
Hckel rule
A compound with a planar ring system and a
delocalized -system containing
(4n + 2) -electrons, where n is an integer
Includes neutral molecules, anions and cations
is AROMATIC
Blackman 16.7
CHM 1022
Alkenes, Alkynes and Reactivity 123
Aromaticity and the Hckel rule
CHM 1022
Alkenes, Alkynes and Reactivity 124
Review Questions
Draw the resonance structures of benzene
Is the following compound aromatic?
Cyclooctatetraene
CHM 1022
Alkenes, Alkynes and Reactivity 125
Phenol and Aniline
Aromatics attract cockroaches
Phenol and naphthol attract male cockroaches of one particular
species.
Phenol 1-Naphthol
Blackman 19.3
CHM 1022
Alkenes, Alkynes and Reactivity 126
Phenol and Aniline
PhenoI (hydroxybenzene)
- "Phenols" are compounds In whIch an DH group Is attached
drectly to an aromatIc rIng.
Phenol s colourless crystcllne sold. Soluble n wcter cnd
wde rcnye o] orycnc solvents
Phenol s colourless crystcllne sold. Soluble n wcter cnd
wde rcnye o] orycnc solvents
pK
a
= 9.99, more acIdIc than alIphatIc alcohols
Blackman 19.3
CHM 1022
Phenol (hydroxybenzene)
Alkenes, Alkynes and Reactivity 127
pK
a
= 9.89, more acIdIc than alIphatIc alcohols
Phenol and Aniline
The phenoxde on s delocclsed over the cromctc rny The phenoxde on s delocclsed over the cromctc rny
Blackman 19.3
Fesonance Is alternate locatIons of electrons.
f a molecules electrons are "resonance delocalIsed" they are spread
over the molecule.
CHM 1022
Alkenes, Alkynes and Reactivity 128
o-Nitrophenol
(2-Nitrophenol)
p-Nitrophenol
(4-Nitrophenol)
Phenol and Aniline
PhenoI - PeactIons
- The DH group pushes electron densIty onto the ortho- and
ara- posItIons.
Undergoes electrophilic
substitution more readily
than benzene.
Undergoes electrophilic
substitution more readily
than benzene.
-NO
2
deactivating
No double nitration
-NO
2
deactivating
No double nitration
CHM 1022
Alkenes, Alkynes and Reactivity 129
Phenol and Aniline
PhenoI - PeactIons
- The DH group Is stronyly cctvctny and ortho and pcrc
dIrectIng.
Hcloyenctons cre rcpd cnd multple substtuton s common Hcloyenctons cre rcpd cnd multple substtuton s common
CHM 1022
Alkenes, Alkynes and Reactivity 130
Phenol and Aniline
AnIIIne (amInobenzene)
- Aromctc prImary amIne behaves as a very weak base
Anlne s
colourless, oly
lqud. Slyhtly
soluble n wcter
Anlne s
colourless, oly
lqud. Slyhtly
soluble n wcter
Weck bcse cs
resoncnce
"sprecds" the
electron densty
Weck bcse cs
resoncnce
"sprecds" the
electron densty
Blackman 19.7
pK
a
= 4.63
CHM 1022
Alkenes, Alkynes and Reactivity 131
Phenol and Aniline
Aniline - Reactions
The NH
2
group is highly activating and ortho- and para-
directing.
Electrophilic substitution with halogens occurs readily
and multi-substituted products are obtained
Electrophilic substitution with halogens occurs readily
and multi-substituted products are obtained
CHM 1022
Alkenes, Alkynes and Reactivity 132
Green Chemistry
Traditional Route Traditional Route
Green Route Green Route
waste
CHM 1022
Alkenes, Alkynes and Reactivity 133
Use of Renewable Feedstocks
Renewable Raw Materials Biocatalytic synthesis from Glucose
New biocatalytic (enzyme driven) process allows synthesis of catechol from glucose. Glucose may
be obtained from starch and cellulose - renewable agricultural feedstocks.
Catechol: Traditionally synthesised from petrochemical feedstocks
including coal tar and benzene.
Traditional Route Traditional Route
Green Route Green Route
CHM 1022
Alkenes, Alkynes and Reactivity 134
Summary
Recognise benzene and understand how its structure was
discovered
- Kekul structure, CC bonds are neIther double nor
sIngle - theoretIcal and chemIcal evIdence
Distinguish aromatic compounds and apply the Huckel
rule
- Use the 4n + 2 rule to IdentIfy aromatIc compounds
Know the structures of Phenol and Aniline and understand
their pK
a
values
- hydroxybenzene, amInobenzene, resonance
stabIlIsatIon
CHM 1022
Alkenes, Alkynes and Reactivity 135
Learning Objectives
After thIs lecture your should be able to:
Lecture 7
- Understand the mechanIsm of electrophIlIc addItIon to
the alkenes group reactIons.
|arkovnIkov's rule
StereochemIcal control of addItIon reactIons
- 8e able to predIct the mechanIsm and/or outcome of
reactIons wIth new nucleophIles.
CHM 1022
136
Hybridisation-Alkene
Ethene
Alkenes, Alkynes and Reactivity
Blackman 5.6
Each carbon has 3 sp
2
+ 1 p
120r
CHM 1022
Alkenes, Alkynes and Reactivity 137
HBr addition to Ethylene
Blackman 16.5
Alkenes are electronrIch
and react usIng nbond
CHM 1022
Alkenes, Alkynes and Reactivity 138
HBr addition to Ethylene
Blackman 16.5
Alkenes are electronrIch
and react usIng nbond
NUCLEDPHLE.
CHM 1022
Alkenes, Alkynes and Reactivity 139
HBr addition to Ethylene
H8r Is polarIsed and has
an electronpoor "H"
ELECTFDPHLE.
Alkenes are electronrIch
and react usIng nbond
NUCLEDPHLE.
Blackman 16.5
CHM 1022
Alkenes, Alkynes and Reactivity 140
HBr addition to Ethylene
Blackman 16.5
CHM 1022
Alkenes, Alkynes and Reactivity 141
HBr addition to Ethylene
Blackman 16.5
Dont forget the Rules!
AII acceptabIe eIectron redIstrIbutIons (bond breaklmake) must:
1. have the same number of vaIence eIectrons
2. obey the ruIes of covaIent bondIng
3. dIffer onIy In dIstrIbutIon of vaIence eIectrons
4. have the same number of paIred and unpaIred eIectrons
5. Have a charge baIance foIIowIng the redIstrIbutIon
CHM 1022
Alkenes, Alkynes and Reactivity 142
Transition States for HBr addition
1. TransItIon States (TS) are always hypothetIcal
They ccnnot be solcted!
2. TS show formIng and breakIng bonds.
Blackman 16.5
CHM 1022
143
Energy Profile

E
E
ConsIder the followIng
IntermedIate
A B
Blackman 15.5
Alkenes, Alkynes and Reactivity
CHM 1022
Alkenes, Alkynes and Reactivity 144
Energy Diagram for HBr addition
Blackman 16.5
CHM 1022
Alkenes, Alkynes and Reactivity 145
Summary-HBr addition to Ethylene
1. Electrons from nbond
recct (weak bond)
2. A carbocatIonIc
IntermedIate Is formed.
J. Two transItIon states
for the reactIon.
ThIs reactIon Is an example of electrophlc cddton to cn clkene.
Blackman 16.5
CHM 1022
Alkenes, Alkynes and Reactivity 146
HCl addition to Isobutylene
Blackman 16.5
CHM 1022
Alkenes, Alkynes and Reactivity 147
HCl addition to Isobutylene
Blackman 16.5
CHM 1022
Alkenes, Alkynes and Reactivity 148
Markovnikovs Rule
|arkovnIkov's rule
"ProtonatIon wIll be at the
carbon wIth most hydrogens
already"
|arkovnIkov's rule
"ProtonatIon wIll be at the
carbon wIth most hydrogens
already"
Blackman 16.5
CHM 1022
Alkenes, Alkynes and Reactivity 149
Markovnikovs Rule
|arkovnIkov's rule:
The product from the more
stable carbocatIon wIll be
favoured
|arkovnIkov's rule:
The product from the more
stable carbocatIon wIll be
favoured
A reactIon that gIves maInly
one constItutIonal Isomer Is
descrIbed as regIoselectIve.
A reactIon that gIves maInly
one constItutIonal Isomer Is
descrIbed as regIoselectIve.
Blackman 16.5
CHM 1022
Alkenes, Alkynes and Reactivity 150
Review Question
1. When structure A Is treated wIth H8r structure 8 forms
(I) s thIs a TS or an IntermedIate:
(II) 0raw the other carbocatIons that could form:
(III) Why Is thIs carbocatIon formed:
2. Structure 8 then reacts to form Structure C.
(I) ProvIde a mechanIsm showIng It's formatIon.
(II) Could another product form: (HInt: AlternatIve nucleophIle)
CHM 1022
Alkenes, Alkynes and Reactivity 151
Summary
- HybrIdIsatIon of alkenes and alkynes affects reactIvIty.
- The mechanIsm of electrophIlIc addItIon to alkenes
follows
|arkovnIkov's rule
StereochemIcal control of addItIon reactIons
Reyoselectvty
- PredIctIng the mechanIsm and/or outcome of other
addItIon reactIons follows same approach.
CHM 1022
Alkenes, Alkynes and Reactivity 152
Learning Objectives
-Have a better understandIng of resonance structures
and how to draw a resonance hybrId structure.
-Understand the mechanIsm of electrophIlIc addItIon to
alkenes.
HydratIon
8romInatIon
HalohydrIn
After thIs lecture your should be able to:
Lecture 8
CHM 1022
Alkenes, Alkynes and Reactivity 153
Hydration of Alkenes
Alkenes are electronrIch
and react usIng nbond
NUCLEDPHLE.
H
J
PD
4
Is polarIsed
(also resonance stabIlIsed anIon)
ELECTFDPHLE.
H
2
SD
4
also works In thIs regard
Blackman 16.5
CHM 1022
Alkenes, Alkynes and Reactivity 154
Hydration of Alkenes
Blackman 16.5
CHM 1022
Alkenes, Alkynes and Reactivity 155
Hydration of Alkenes
Blackman 16.5
CHM 1022
Alkenes, Alkynes and Reactivity 156
Resonance
Fesonance Is alternate locatIons of electrons.
f a molecules electrons are "resonance delocalIsed" they are spread
over the molecule.
CHM 1022
Alkenes, Alkynes and Reactivity 157
Br
2
Addition to alkenes
A reactIon that gIves maInly one stereoIsomer Is
descrIbed as stereoselectIve. (CH|1011)
A reactIon that gIves maInly one stereoIsomer Is
descrIbed as stereoselectIve. (CH|1011)
ConstItutIonal: ConnectIvIty of atoms
Stereo: Arrangement of atoms In space.
ConstItutIonal: ConnectIvIty of atoms
Stereo: Arrangement of atoms In space.
Blackman 16.5
CHM 1022
Alkenes, Alkynes and Reactivity 158
Br
2
Addition to alkenes
Blackman 16.5
CHM 1022
Alkenes, Alkynes and Reactivity 159
Br
2
Addition to alkenes
AddItIon to opposIte face of an
alkene Is cnt addItIon.
Same face Is syn cddton.
AddItIon to opposIte face of an
alkene Is cnt addItIon.
Same face Is syn cddton.

Blackman 16.5
CHM 1022
Alkenes, Alkynes and Reactivity 160
Br
2
Addition to alkenes
Blackman 16.5
CHM 1022
Alkenes, Alkynes and Reactivity 161
Br
2
Addition to alkenes
8rIdged bromonIum IntermedIate supported by IsolatIon
of adamanyl bromonIum shown.
8rIdged bromonIum IntermedIate supported by IsolatIon
of adamanyl bromonIum shown.
Blackman 16.5
CHM 1022
Alkenes, Alkynes and Reactivity 162
Halohydrin Formation
8r electronegatIvIty
=2.8
N electronegatIvIty
=J.0
ELECTFDPHLC source
of 8r.
A halohydrin
CHM 1022
Alkenes, Alkynes and Reactivity 163
Halohydrin Formation
CHM 1022
Alkenes, Alkynes and Reactivity 164
Halohydrin Formation
CHM 1022
Alkenes, Alkynes and Reactivity 165
Summary-Halohydrin
1. NUCLEDPHLC alkene attacks the ELECTFDPHLC bromIne of N8S.
2. SuccInImIde anIon Is stabIlIsed and nonnucleophIlIc
J. Water adds as NUCLEDPHLE.
4. WATEF acts as base
1. NUCLEDPHLC alkene attacks the ELECTFDPHLC bromIne of N8S.
2. SuccInImIde anIon Is stabIlIsed and nonnucleophIlIc
J. Water adds as NUCLEDPHLE.
4. WATEF acts as base
WhIle synthetIcally less
useful 8r
2
can replace
N8S
WhIle synthetIcally less
useful 8r
2
can replace
N8S
CHM 1022
Alkenes, Alkynes and Reactivity 166
Summary- Alkenes with Electrophiles
Step 2
Some nucleophIle attacks the carbocatIon IntermedIate.
Step 1
An alkene attacks an electrophIle gIvIng a carbocatIon.
CHM 1022
Alkenes, Alkynes and Reactivity 167
Summary- Alkenes with Electrophiles
Step 2
Some nucleophIle attacks the carbocatIon IntermedIate.
Step 1
An alkene attacks an electrophIle gIvIng a carbocatIon.
What types of
nucleophIles have
we seen:
What types of
nucleophIles have
we seen:
Every reactIon we have
seen so far follows the
rules below!
Every reactIon we have
seen so far follows the
rules below!
CHM 1022
Alkenes, Alkynes and Reactivity 168
Review Question
HydratIon of alkene A gIves dIol 8.
(I) 0raw the carbocatIonIc IntermedIate en route to 8.
(II) 0raw the bromonIum brIdged resonance contrIbutor.
(III) When water was left out of the reactIon a new product formed, draw
that product:
CHM 1022
Alkenes, Alkynes and Reactivity 169
Summary
A mechanIsm of electrophIlIc addItIon to alkenes was
developed for
HydratIon
8romInatIon
HalohydrIn
Can you draw mechanIsms for the above reactIons:
CHM 1022
Alkenes, Alkynes and Reactivity
At the end of these 4 lectures Can you now
answer all of these questions? And Blackman et al. relevant
questions in Chapters 16 and 19?
Draw bonding interactions, using hybrid orbitals where
required, for simple organic compounds.
Identify nucleophiles and electrophiles, and draw mechanisms
for a number of addition reactions
Use Markovnikovs rule to predict the major product
Have a good knowledge of benzene, why it is aromatic and how
to identify other aromatic compounds
CHM 1022
171 171
Dr. Kellie Tuck Prof. Steven Langford
School of Chemistry, Monash University School of Chemistry, Monash University
Room 111C/B19, PH: 9905 4510 Room 128C/B19, PH: 9905 4569
Email: Kellie.Tuck@monash.edu Steven.Langford@monash.edu
CHM1022 Lectures 9-10 (Alcohols and Amines)
CHM 1022
172 172
You should be able to:-
Describe the general properties of alcohols and amines
Describe how to convert an alcohols to an alkyl halide
Discuss how alkyl halides can undergo substitution or elimination
reactions
Understand and use Zaitsevs rule to predict the major product
from an elimination reaction
Alcohols and Amines
At the end of these 2 lectures:-
CHM 1022
Alcohols and Amines 173
Learning Objectives
Lecture
After thIs lecture your should be able to:
- 0escrIbe the general propertIes of alcohols and
amInes
- 0raw a mechanIsm for the dehydratIon of alcohols
- Use ZaItsev's rule to predIct the major product
- Understand how alcohols can be oxIdIsed
CHM 1022
174
Alcohols and Amines
There are three classes of alcohols each has a
dIfferent reactIvIty:
Blackman 2.3 and 19.1
So...
Alcohols and Amines
CHM 1022
175
Alcohols and Amines
SImIlarly, there are three classes of amInes each
has a dIfferent reactIvIty based prImarIly on sterc
hndrance:
Blackman 19.6 and 19.7
All amInes act as weak 8rnsted bases (pK
a
= 1011)
Alcohols and Amines
CHM 1022
176
Alcohols and Amines
AmInes are further dIvIded Into aIIphatIc,
aromatIc, and heterocycIIc amInes:
aIIphatIc amInes: amInes In whIch nItrogen Is bonded
onIy to aIkyI groups
aromatIc amInes: amInes In whIch nItrogen Is bonded
to one or more aryI groups
AromatIc aIcohoIs: aIcohoIs In whIch oxygen Is bonded to
one or more aryI groups are caIIed phenoIs
Blackman 19.6
Alcohols and Amines
CHM 1022
177
Haloalkanes, Alcohols and Amines
ElectronegatIvIty of the halogens (represented generally as
X), oxygen and nItrogen play a large role In the reactIvIty
and propertIes of alkyl halIdes (FX), alcohols (FDH) and
amInes (FNH
2
) respectIvely
C
2.6
N
3.0
F
4.0
S
2.6
Cl
3.2
Br
3.0
I
2.7
H
2.2
O
3.4
X = halogen, OH, NR
2
Alcohols and Amines
CHM 1022
178
Alcohols and Amines
Small alcohols (FDH) and amInes
(FNH
2
) are able to hydrogen bond
extensIvely and so are mIscIble In
water.
AmInes are approx. 1000 tImes
stronger bases than alcohols whIch
have pK
a
's sImIlar to water
Blackman 19.1
Properties
Q: What happens
to the solubIlIty
wIth IncreasIng
molecular weIght:
Q: What happens
to the solubIlIty
wIth IncreasIng
molecular weIght:
Alcohols and Amines
CHM 1022
179
Amines
All amInes, whether soluble or Insoluble In water,
react quantItatIvely wIth strong acIds to form
watersoluble salts
Blackman 19.6
Alcohols and Amines
CHM 1022
180
Industrial Synthesis
CD + 2H
2
CH
J
DH
150 bar, 670K
ZnD catalyst
CO = Heating wood in
absence of air
CO = Heating wood in
absence of air
Yeast
2 CH
J
CH
2
DH + 2CD
2
glucose
Alcohols and Amines
Blackman 19.1
CHM 1022
181
Revision Question
Can you thInk of any other ways to synthesIse alcohols:
Blackman 19.1
WrIte the UPAC name for thIs alcohol:
C
CH
2
OH
H
3
C
H
CH
2
CH
3
Alcohols and Amines
CHM 1022
182
Alcohols and Alkyl Halides
Alkyl halides include chlorinated organic
solvents. Many of these are still in common
use, despite being chemicals of
environmental concern, including:
Chloroform
Dichloromethane (DCM)
Carbon Tetrachloride
1,2-Dichloroethane
Alcohols are generally less toxic, and therefore
are preferable as solvents. They also tend to
biodegrade more rapidly.
Common alcohol solvents include:
Ethanol
Methanol
Isopropanol
Volatile Organic Compounds (VOCs) include some Alcohols and Alkyl Halides of low molecular weight.

Solvents
A soIvent Is a lIquId that dIssolves another compound (solId, lIquId or gas) to form a solutIon.
Water Is a common nontoxIc solvent, but It wIll only dIssolve polar compounds.
To dIssolve non-poIar compounds we use voIatIIe organIc compounds (VDCs).
Alcohols and Amines
CHM 1022
AcIdcatalyzed alcohol dehydratIon and alkene
hydratIon are competIng processes
large amounts of water favor alcohol formatIon
scarcIty of water or experImental condItIons where water Is
removed favor alkene formatIon
183
Dehydration of Alcohols
Blackman 19.2
Alcohols and Amines
CHM 1022
184
Dehydration of Alcohols
Note reactivity differences
Blackman 19.2
Major product
Alcohols and Amines
CHM 1022
185
Dehydration of Alcohols
Note reactivity differences
Blackman 19.2
Alcohols and Amines
CHM 1022
186
Dehydration of Alcohols
|ore substItuted
double bond Is
formed In preference
|ore substItuted
double bond Is
formed In preference
Zaitsevs Rule
Blackman 19.2
Alcohols and Amines
CHM 1022
187
Alcohols and Amines
|ore substItuted
double bond Is
formed In preference
|ore substItuted
double bond Is
formed In preference
Zaitsevs Rule
Blackman 19.2
Alcohols and Amines
CHM 1022
188
Dehydration of Alcohols
The relatIve ease of dehydratIon parallels the
relatIve stabIlIty of carbocatIon formatIon
Blackman 19.2
Alcohols and Amines
CHM 1022
189
Revision Question
The dehydration of 1-methylcyclohexanol can lead to
two products. What are they?
Which is formed in preference? Why?
Alcohols and Amines
CHM 1022
190
Alcohols
Alcohols react wIth LI, Na, K, and other actIve metals
to lIberate hydrogen gas and form metal alkoxIdes
Blackman 19.2
Alcohols and Amines
CHM 1022
191
Oxidation of Alcohols
K
2
MnO
4
K
2
Cr
2
O
7
PCC
K
2
MnO
4
K
2
Cr
2
O
7
PCC
K
2
MnO
4
K
2
Cr
2
O
7
Blackman 19.2
Alcohols and Amines
CHM 1022
192
Revision Question
UsIng only ethanol as a startIng materIal, devIse a
synthesIs for ethyl acetate
Alcohols and Amines
CHM 1022
193
Learning Objectives
Lecture 10
After thIs lecture your should be able to:
- 0escrIbe how to convert an alcohols to an alkyl
halIde
- 0Iscuss how alkyl halIdes can undergo substItutIon
or elImInatIon reactIons
- 0escrIbe several reactIons that can be used to form
amInes
Alcohols and Amines
CHM 1022
194
Alcohols to Alkyl halides
ConversIon of an alcohol to an alkyl halIde Involves
substItutIon of halogen for DH. The most common
reagents for thIs purpose are the halogen acIds, HX, and
thIonyl chlorIde, SDCl
2
Blackman 19.2
Alcohols and Amines
CHM 1022
J r Alcohols react very rapIdly wIth HCl, H8r, and H.
LowmolecularweIght 1r and 2r alcohols are unreactIve under these
condItIons
195
Alcohols to Alkyl halides
Blackman 19.2
Alcohols and Amines
CHM 1022
196
Alcohols to Alkyl halides
mechanism
Alcohols and Amines
CHM 1022
197
Haloalkanes
Alkyl halides (R-X) are susceptible to nucleophiles
NucIeophIIIc substItutIon: any reactIon In whIch one
nucIeophIIe Is substItuted for another
Blackman 18.1
Alcohols and Amines
CHM 1022
198
Haloalkanes
Blackman 18.2
Alcohols and Amines
CHM 1022
Revision and Introduction to Organic Chemistry 199
S
N
2 mechanIsm
SImultaneous bond breakIng and formIng
Fate of reactIon = k[haloalkane][nucleophIle]
Blackman 18.2
CHM 1022
Energy profile of an S
N
2 reaction
Revision and Introduction to Organic Chemistry 200
Blackman 18.2
CHM 1022
201
-Elimination
ElImInatIon: removal of atoms or groups of atoms
(e.g. HX) from adjacent carbons to form a carbon
carbon double bond
Blackman 18.3
Alcohols and Amines
|ore substItuted
double bond Is
formed In preference
|ore substItuted
double bond Is
formed In preference
Zaitsevs Rule Zaitsevs Rule
CHM 1022
202
-Elimination
Strong base, e.g. sodium ethoxide in ethanol is required.
Blackman 18.3
Alcohols and Amines
CHM 1022
203
Review Question
H
3
C
Br
CH
3
Na
+
OCH
2
CH
3
CH
3
CH
2
OH
CH
3
What is the major organic product from the
following reaction?
Alcohols and Amines
CHM 1022
204
Formation of Amines
AromatIc amInes can be prepared by the reductIon
of aromatIc nItro compounds by hydrogenatIon over
a nIckel catalyst.
Blackman 19.6
Alcohols and Amines
CHM 1022
205
Amines
AmInes can be formed by reactIon of haloalkanes wIth
ammonIa.
8ut further reactIon also leads to
Blackman 19.6
Alcohols and Amines
CHM 1022
206
Amines
FeductIve amInatIon Is a better approach
1
o
and 2
o
amInes can aIso be
used In thIs reactIon.
1
o
and 2
o
amInes can aIso be
used In thIs reactIon.
Blackman 21.5
Alcohols and Amines
CHM 1022
207
Amines
AmInes can also be synthesIsed from nItrIles by reductIon
Alcohols and Amines
CHM 1022
208
Amines
Amines react with carboxylic acids to form amides
One of the most important
reactions
Will be discussed in the next
section (Carbonyl Chemistry)
Alcohols and Amines
Blackman 21.5
CHM 1022
209
Summary
0Ifferences and sImIlarItIes between alcohols and amInes
SolubIlIty, basIcIty, classIfIcatIons
Alcohols are an important class of compound
Can manipulate to form alkenes, ketones, aldehydes
and alkyl halides
Amines are basic and nucleophilic
React with acids to form water soluble ammonium salts
Formed by a variety of methods
Alkylation, amination, reduction of RCN
Alkyl halIdes are susceptIble to nucleophIles and bases
LeadIng to substItutIon or elImInatIon
Alcohols and Amines
CHM 1022
Alcohols and Amines
At the end of these 2 lectures Can you now
answer all of these questions? And the relevant Blackman et al.
questions in Chapter 18 and 19?
Describe how to convert alcohols to alkenes, ketones, aldehydes
and alkyl halides
Explain how amines can be synthesized
Express how alkyl halides are susceptible to attack by
nucleophiles and bases. Use Zaitsevs rule to determine the major
product of an elimination reaction.
CHM 1022
211 211
Dr. Kellie Tuck Prof. Steven Langford
School of Chemistry, Monash University School of Chemistry, Monash University
Room 111C/B19, PH: 9905 4510 Room 128C/B19, PH: 9905 4569
Email: Kellie.Tuck@monash.edu Steven.Langford@monash.edu
CHM1022 Lectures 11-12 (Carbonyl Chemistry)
CHM 1022
212 212
You should be able to:-
Name ketone, aldehydes, carboxylic acids and amines
Describe why the carbonyl group is reactive
Become proficient in drawing reactions for nucleophilc attack on
a carbonyl group
Know how to convert carbonyl containing compounds
Carbonyl Chemistry
At the end of these 2 lectures:-
CHM 1022
213 Carbonyl Chemistry 213
Learning Objectives
After thIs lecture your should be able to:
Lecture 11
- FecognIse and name carbonyl contaInIng functIonal groups.
- Understand the orIgIn of the carbonyl groups reactIvIty.
- Understand the mechanIsm of nucleophIlIc addItIon to the
carbonyl group reactIons.
- 8e able to predIct the mechanIsm/outcome of reactIons wIth
new nucleophIles.
CHM 1022
214 Carbonyl Chemistry 214
Naming Ketones and Aldehydes
AIdehyde (Su]]x = aI)
carbonyl wIth one
hydrogen and one
carbon substItuent.
hethanaI
EthanaI
Ketone (Su]]x = one)
carbonyl wIth two
carbon substItuent.
Propanone
(Acetone)
Pentan-2-one
Blackman 21.2
CHM 1022
215 Carbonyl Chemistry 215
Naming Acids and Derivatives
AcId ChIorIdes
(Su]]x = oyI chIorIde
Esters
(Frst ncme = P',
Su]]x = oate)
CarboxyIIc AcIds
(Su]]x = oIc acId)
PropanoIc acId
enzoyI chIorIde
EthyI propanoate
Blackman 23.2
CHM 1022
216 Carbonyl Chemistry 216
Naming Amides
PrImary AmIde
(Su]]x = amIde) Secondary AmIde TertIary AmIde
Blackman 23.2
CHM 1022
217 Carbonyl Chemistry 217
Reactivity of the Carbonyl Group
A C=0 bond s 720 kJ/mol
C-0 bond s 350 kJ/mol.
Why Is It reactIve!
A C=C bond s 598 kJ/mol
C-C bond s 346 kJ/mol.
The -bond Is weak.
Blackman 16.3 and 21.1
CHM 1022
218 Carbonyl Chemistry 218
Reactivity of the Carbonyl Group
A double bond between cn sp
2
hybrdsed 0 cnd cn sp
2
C.
E-neg. 2.5 3.5
Blackman 21.1
CHM 1022
219 Carbonyl Chemistry 219
Hydrogen Bonding of Carbonyl
Carbonyl compounds due to theIr polarIty form
hydrogen bonds readIly.
CHM 1022
Blackman 6.8 and 21.3
CHM 1022
220 Carbonyl Chemistry 220
Boiling Point of Carboxylic Acids
Blackman 23.3
CHM 1022
221 Carbonyl Chemistry
Summary of reactions
- NucIeophIIIc AddItIon
- NucIeophIIIc SubstItutIon
Blackman 21.5 and 23.5
Y= Cl, OR, OCOR, NHR
CHM 1022
222 Carbonyl Chemistry 222
Nuc Addition- Hydrates
n practIce hydrates are only observed In "specIal" cases.
AcId catalysts can be used to help theIr formatIon.
n practIce hydrates are only observed In "specIal" cases.
AcId catalysts can be used to help theIr formatIon.
CHM 1022
223 Carbonyl Chemistry 223
Nuc Addition- Hydrates
CHM 1022
224 Carbonyl Chemistry 224
Formaldehyde
13
C NhP of a carbonyI Is 150-200 ppm (dependIng on the soIvent)
So formaIdehyde In water Is 100X as the hydrate.
CHM 1022
225 Carbonyl Chemistry 225
Chloral and Chloral Hydrate
CHM 1022
226 Carbonyl Chemistry 226
Nuc Addition- Hemiacetal
HemIacetaI formatIon Is lIke hydrate formatIon wIth alcohol. HemIacetaI formatIon Is lIke hydrate formatIon wIth alcohol.
|ost commonly hemIacetaIs are IntermedIates In the
formatIon of acetaIs.
|ost commonly hemIacetaIs are IntermedIates In the
formatIon of acetaIs.
Protonaton makes the
carbonyl more
reactIve towards
the nucIeophIIe
Protonaton makes the
carbonyl more
reactIve towards
the nucIeophIIe
AII steps are under
equIIIbrIum controI
AII steps are under
equIIIbrIum controI
Blackman 21.5
CHM 1022
227 Carbonyl Chemistry 227
Nuc Addition- Acetal
Acetal formatIon generally
requIres:
-acId catalyst to "speed up the
reactIon" (kInetIcs).
-a "drIvIng force"
(thermodynamIcs).
Acetal formatIon generally
requIres:
-acId catalyst to "speed up the
reactIon" (kInetIcs).
-a "drIvIng force"
(thermodynamIcs).
Blackman 21.5
CHM 1022
228 Carbonyl Chemistry 228
Review Question
ProvIde a
hechanIsm.
ProvIde the condItIons
and startIng materIaI.
ProvIde the startIng
materIaI.
CHM 1022
229 Carbonyl Chemistry 229
Reduction of Carbonyls
PeductIon of a carbonyI can be consIdered to be
nucIeophIIIc addItIon of H
-
.
PeductIon of a carbonyI can be consIdered to be
nucIeophIIIc addItIon of H
-
.
Blackman 21.5
CHM 1022
230 Carbonyl Chemistry 230
Protection of Carbonyls
Chemstry n Context Chemstry n Context
CHM 1022
231 Carbonyl Chemistry 231
Chemoselective Reduction
SodIum orohydrIde Is an
exampIe of a chemoseIectIve
reducIng agent.
-Is It better to use
chemoseIectIve agents or to
rotect!
SodIum orohydrIde Is an
exampIe of a chemoseIectIve
reducIng agent.
-Is It better to use
chemoseIectIve agents or to
rotect!
Chemstry n Context Chemstry n Context
CHM 1022
232 Carbonyl Chemistry 232
Summary
FecognIse carbonyl compounds
- Ketones and aldehydes
Understand theIr structure and hybrIdIsatIon
- sp
2
hybrIdIsatIon, dIpole
0evelop an understandIng of general reactIvIty
- nucleophIlIc addItIon/substItutIon
CHM 1022
233 Carbonyl Chemistry 233
Learning Objectives
After thIs lecture your should be able to:
Lecture 12
- Understand the mechanIsm of nucleophIlIc substItutIon to the
carbonyl group reactIons.
- 8e famIlIar wIth the conversIon of carbonyl contaInIng
compounds.
TransesterIfIcatIon
CarboxylIc AcId to Ester
AcId ChlorIde/AnhydrIdes to Ester/AmIde
Ester to AmIde
- Understand the use of 8IodIesel as a green fuel.
CHM 1022
234 Carbonyl Chemistry 234
Forming Alcohols
host common reactIon of a carbonyl group Is addItIon of
a nucIeophIIe to form an ALCDHDL
Blackman 21.5
Nu
-
= H
-
(Reduction), R (Grignard), H
2
O (Hydrate), ROH (Acetal)
CHM 1022
235 Carbonyl Chemistry 235
Grignard reagents
VIctor CrIgnard,
NobeI PrIze wInner, 112,
wIth PauI SabatIer
PauIIng eIectronegatIvIty of some eIements
Blackman 21.5
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236 Carbonyl Chemistry 236
Grignard Addition to Carbonyls
CrIgnard Feagents react wIth aldehydes to gIve 2
o
alcohols CrIgnard Feagents react wIth aldehydes to gIve 2
o
alcohols
CrIgnard Feagents react wIth ketones to gIve J
o
alcohols CrIgnard Feagents react wIth ketones to gIve J
o
alcohols
When a CrIgnard Feagents reacts wIth formaldehyde (H
2
C=D)
what type of alcohol would form:
When a CrIgnard Feagents reacts wIth formaldehyde (H
2
C=D)
what type of alcohol would form:
Blackman 21.5
CHM 1022
237 Carbonyl Chemistry 237
Grignard Addition to Carbonyls
When a CrIgnard Feagents reacts wIth formaldehyde (H
2
C=D)
what type of alcohol would form:
When a CrIgnard Feagents reacts wIth formaldehyde (H
2
C=D)
what type of alcohol would form:
When a CrIgnard Feagents reacts wIth Carbon 0IoxIde (CD
2
)
what would form:
When a CrIgnard Feagents reacts wIth Carbon 0IoxIde (CD
2
)
what would form:
Blackman 21.5
CHM 1022
238 Carbonyl Chemistry 238
Revision Question
2phenyl2butanol can be synthesIzed by three
dIfferent combInatIons of a CrIgnard reagent and a
ketone. Show each combInatIon.
Blackman 21.5
CHM 1022
239 Carbonyl Chemistry 239
Summary
So far we have only dIscussed nucIeophIIIc addItIon to carbonyIs.
We have talked about two mechanIsms.
WhIch nucIeophIIes have we seen react by the fIrst pathway:
WhIch nucIeophIIes react vc the second pathway:
So far we have only dIscussed nucIeophIIIc addItIon to carbonyIs.
We have talked about two mechanIsms.
WhIch nucIeophIIes have we seen react by the fIrst pathway:
WhIch nucIeophIIes react vc the second pathway:
Reducton, Crynard Reducton, Crynard
Acetal jormaton Acetal jormaton
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240 Carbonyl Chemistry 240
Esters from Acids and Alcohols
EsterIfIcatIon between a carboxylIc acId and an alcohol Is a
nucIeophIIIc substItutIon reactIon you have seen before.
EsterIfIcatIon between a carboxylIc acId and an alcohol Is a
nucIeophIIIc substItutIon reactIon you have seen before.
Blackman 23.5
CHM 1022
241 Carbonyl Chemistry 241
Esters from Acids and Alcohols
EsterIfIcatIon between a carboxylIc acId and an alcohol Is a
nucleophIlIc substItutIon reactIon you have seen before.
EsterIfIcatIon between a carboxylIc acId and an alcohol Is a
nucleophIlIc substItutIon reactIon you have seen before.
Blackman 23.5
CHM 1022
242 Carbonyl Chemistry 242
Hydrolysis of Esters
HydrolysIs can be achIeved usIng the same condItIons, however
pushIng equIIIbrIum to the left.
-How can ths be acheved
HydrolysIs can be achIeved usIng the same condItIons, however
pushIng equIIIbrIum to the left.
-How can ths be acheved
SaponIfIcatIon can also be achIeved under basIc condItIons, In thIs
case the base Is not catalytIc. Why
SaponIfIcatIon can also be achIeved under basIc condItIons, In thIs
case the base Is not catalytIc. Why
Blackman 23.5
CHM 1022
243 Carbonyl Chemistry 243
Esters from Acid Chlorides
Same key steps as before.
AcId ChlorIde Is more reactIve. Why:
WhIle H
2
D Is a nucleophIle and can reverse the reactIon HCl Is not.
Blackman 23.5
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244 Carbonyl Chemistry 244
Amides from Acid Chlorides
8ut thIs reactIon
makes HCl
Need 2 eq. of amIne
1st to react
2nd to react wIth the
HCl
8ut thIs reactIon
makes HCl
Need 2 eq. of amIne
1st to react
2nd to react wIth the
HCl
Blackman 23.5
CHM 1022
245 Carbonyl Chemistry 245
Amides from Acid Chlorides
AddItIon of a base aIIows equImoIar amounts of amIne
and acId chIorIde to be used.
Blackman 23.5
CHM 1022
246 Carbonyl Chemistry 246
Esters from Anhydrides
- Commonly a base Is added to "mopup" the acId produced commonly
that base Is pyrIdIne.
EsterIfIcatIon from anhydrIdes Is EXACTLY the same mechanIsm.
Blackman 23.5
CHM 1022
247 Carbonyl Chemistry 247
Nucleophilic Substitution and LG
Blackman 23.5
CHM 1022
248 Carbonyl Chemistry 248
Summary
- The mechanIsm of nucIeophIIIc addItIon to the carbonyl group
was dIscussed.
Crynard, hydrde, amne
- 8e famIlIar wIth the conversIon of carbonyl contaInIng
compounds.
CarboxylIc AcId to Ester
AcId ChlorIde/AnhydrIde to Ester
AcId ChlorIdes to AmIde

CHM 1022
249 Carbonyl Chemistry 249
Biodiesel
CHM 1022
250 Carbonyl Chemistry 250
Use of Renewable Feedstock
Fossil Fuels
Chemical
Products
Ancient Biomass
?
Living Biomass
CHM 1022
251 Carbonyl Chemistry 251
Biodiesel
transesterification
with
methanol
+
triglyceride triglyceride
alkyl esters of fatty acids alkyl esters of fatty acids
glycerol glycerol
CHM 1022
252 Carbonyl Chemistry 252
Biodiesel
Methyl Linoleate
Produced from soybean oil using methanol.
The types of molecule found in biodiesel depends on the vegetable oil, and the
alcohol used to perform the transesterification.
Ethyl Stearate
Produced from soybean oil using ethanol.
head
ethyl ester
tail stearic acid
(octadecanoic acid)
head
methyl ester
tail linoleic acid
(cis, cis-9,12-octadecadienoic acid)
CHM 1022
253 Carbonyl Chemistry 253
Issues
DII seed productIon
LImItatIons of agrIcultural productIon
- LImIted arable land
- Loss of food productIon
- 0eforestatIon
IodIeseI productIon
- TransesterIfIcatIon has poor atom economy.
- For every J molecules of bIodIesel, we also get 1 molecule of gIyceroI.
- ChemIstry challenge: convert glycerol to other useful materIals.
CHM 1022
Carbonyl Chemistry
At the end of these 2 lectures Can you now
answer all of these questions? And Blackman et al. questions in
Chapter 23?
Understand the structure and hybridisation of the carbonyl group
Draw mechanisms for nucleophilic substitution reactions at the
carbonyl group
Identify Grignard reagents and describe how they react with
aldehydes and ketones