reactions of organic compounds
DESCRIPTION
Reactions of Organic Compounds. The Alkanes. homologous series with the general formula C n H 2n+2 . have trends in physical properties e.g. density and m.p. and b.p. all increase with M r . all undergo similar chemical reactions. - PowerPoint PPT PresentationTRANSCRIPT
Reactions of Organic Compounds
The Alkanes homologous series with the general formula CnH2n+2.
have trends in physical properties e.g. density and m.p. and b.p. all increase with Mr. all undergo similar chemical reactions.
SATURATED HYDROCARBONS. i.e. they contain only single C to C bonds and are made up of C and H atoms only.
Alkanes are obtained from crude oil by fractional distillation.They are mainly used as fuels.The large Mr alkanes do not ignite easily so there is little demand for them as fuels so they are CRACKED to make smaller more useful alkanes and alkenes.Apart from combustion alkanes undergo few chemical reactions. This is for two main reasons:
• The bonds in alkanes are relatively strong.• The bonds have a relatively low polarity as the
electronegativity of C and H is similar.As a consequence alkanes can be used as lubricating oils, although they do degrade over time.
1. Similar for all alkanes2. Not very reactiveReasons:3. C-H and C-C covalent bonds essentially
non-polar, unlikely to attract polar molecules or ions.
4. Strong C-C and C-H bonds require a lot of energy to break.
Chemical Properties of Alkanes
Smaller alkanes burn easily in air when ignited If the combustion is complete, products formed are
CO2 and H2O.
CH4 + 2O2 CO2 + H2O H = -890kJ/mol
Reaction is exothermic - a result of the high relative strength of the C=O in CO2 and O-H in H2O
molecules. The large amount of heat energy released in making these bonds means the reaction is strongly exothermic.
The combustion of Alkanes
Write equations for the complete combustion of butane and octane.
If the combustion is incomplete, products formed are CO, C (soot) and H2O.
2C H4 + 3O2 2CO + 4H2O CH4 + O2 C + 2H2O
What problems do the gases released on combustion of alkanes cause?
In the presence of ultraviolet light, methane can combine with chlorine to give a mixture of products (chloroalkanes)
Light energy is used to start the reaction (by providing the energy to break the covalent bond between the chlorine atoms in Cl2.
The chlorine atom(radical) produced then reacts with alkane by substituting the hydrogen atom.
Reactions of Alkanes with halogens – Substitution reactions
Free radical = species with an unpaired electron.Free radicals are formed by homolytic fission of bonds. In homolytic fission one electron from the shared pair goes to each atom.So
ClCl
ClCl +
or Cl2 2Cl.
unpaired electron
Heterolytic fission of Cl – Cl would result in the formation of Cl+ and Cl-.There are three steps in the mechanism: initiation, propagation and termination
CH4 + Cl2 CH3Cl + HCl
Overall reaction equation
Conditions
ultra violet light (breaks weakest bond)
excess methane to reduce further substitution
i.e. homolytic breaking of covalent bonds
Free radical substitution
chlorination of methane
CH4 + Cl CH3 + HCl
Cl2 Cl + Cl
CH3 + Cl2 CH3Cl + Cl
CH3ClCH3 + Cl
initiation step
propagation steps
termination step
UV Light
CH3CH3CH3 + CH3
Free radical substitution mechanism
Also get reverse of initiation step occurring as a termination step.
Cl2 Cl + Cl
CH3Cl + Cl2 CH2Cl2 + HCl
Overall reaction equations
Conditions
CH2Cl2 + Cl2 CHCl3 + HCl
CHCl3 + Cl2 CCl4 + HCl
ultra-violet light
excess chlorine
Further free radical substitutions
Details of free radical substitution Page 435
general formula CnH2n. unsaturated hydrocarbons containing C =
C.
Much more reactive than alkanes.
Industrial importance of alkenes:
1. Making polymers (plastics)
2. Hydrogenation of vegetable oils to make margarine
3. Hydration of ethene to make ethanol.
The Alkenes
When naming alkenes have to include position of double bond, for example:
CH3CH=CHCH3 is but - 2 - ene andCH3CH2CH=CH2 is but -1- ene
Alkenes undergo ADDITION reactions. Two substances combine to form one new substance. Unsaturated molecules are converted to saturated molecules.
More than 1 C=C bond
Page 440
1. Similar for all alkenes2. More reactive than alkanes
Reasons:3. C=C covalent bonds (4 electrons) represents
a region of high electron density, therefore attracts electrophile ( + ion / + end of dipole )
4. Ä bond in C=C can break easily – allow other atoms to join to the carbon atoms resulting in an addition reaction.
Chemical Properties of Alkenes
Alkenes burn in an excess air to form CO2 and H2O.
C2H4 + 3O2 2CO2 +2H2O H = -1322kJ/mol
Reaction is exothermic.
If the combustion is incomplete, products formed are CO, C (soot) and H2O. C2H4 + O2 2C + 2H2O C2H4 + 2O2 2CO + 2H2O
More soot (C) is produced compared to the corresponding alkane, due to higher percentage by mass of carbon.
The combustion of Alkenes
How can you tell whether the reaction is complete or incomplete?
R : alkyl group or H
Addition Reactions
C =CR
R R
R+ X-Y R – C – C – R
X Y
R R
Hydrogenation (with hydrogen) Addition of hydrogen (hydrogenation)
Alkenes react with hydrogen in the presence of a nickel catalyst at 150 °C to form an alkane. e.g.
H – C – C – H C =CH
H H
H+ H2
H H
H H
C2H4 + H2 C2H6
ethene ethane
Ni / 1500C
Hydrogenation is used in margarine industry to convert oils containing unsaturated hyrocarbon chains into saturated compounds with higher melting points.
Margarine is a solid at room temperature
Hydrogenation
Addition of halogens (halogenation) Halogens react with alkenes at room
temperature and pressure in a non-polar solvent to form a dihalogenoalkane.
Halogenation (with halogens,X2)
C =CH
H H
H+ Cl2 H – C – C – H
Cl Cl
H H
C2H4 + Cl2 C2H4Cl2
ethene 1,2-dichloroethaneWrite the equation when propene reacts with chlorine.
C =CH
H H
H+ HBr H – C – C – H
H Br
H H
C2H4 + HBr CH3CH2Br
ethene bromoethane
With hydrogen halides (H-X) Alkenes react with hydrogen halides (HCl,
HBr etc.) to solvent to form a dihalogenoalkane.
The reaction occurs at room temperature and pressure. e.g.
C =CH
H H
H+ H2O
OH
H – C – C – H
H
H H
Hydration (with water) Hydration reaction can be done in 2 ways:
addition of concentrated sulfuric acid at room temperature and warm with water to produce an alcohol.
Conc. H2SO4
heat
ethanol
Bromine water is used as a test for unsaturation.In the presence of an alkene, bromine water turns from red brown to colourless. Alkanes do not react with bromine water.
C =C – C – C –
Br Br
+ Br2(aq)
colorless orange colorless
Test for Unsaturation – bromine water test for alkenes
heat
monomer polymer
A large number of monomers are joined together into a polymer.
Addition Polymerisation
C =CR
R R
R
–C – C–
R R
R R
n
n
ethene poly(ethene)
Poly(ethene)
C =CH
H H
H
–C – C–
H H
H H
n
n
2000C, 2000 atm
O2 / peroxide
ethene poly(chloroethene)
Poly(vinylchloride)
C =CH
H H
Cl
–C – C–
H Cl
H H
n
nrepeating unit
ethene poly(ethene)
Poly(propene)
C =CH
H H
CH3
C – C
H CH3
H H
n
n
repeating unit
monomer repeating unit polymer typical uses
CH2=CH2 - CH2 – CH2 - poly(ethene)polythene
film, bags
poly(propene)polypropylene
Moulded plastic, fibres
poly(phenylethene)polystyrene
packaging,insulation
CH2=CHCH3 - CH2 – CH -
CH3
CH2=CHC6H5 - CH2 – CH -
C6H5
monomer repeating unit
polymer typical uses
pipes, flooringCH2=CHCl - CH2 – CH -
Cl
poly(chloroethene)polyvinylchloridePVC
Poly(tetrafluoroethene)PTFE
CF2=CF2 - CF2 – CF2 - Non-stick coating (Teflon)
Practice questions Page 446
1. To make margarine2. To make alcohols, used as antifreeze and
solvents3. To make plastic (polymers) like
poly(ethene), PVC4. Used in agriculture (in low concentration)
to help hasten the ripening of fruits like bananas.
Uses of Alkenes
2CH3OH(l) + 3O2(g) 2CO2(g) + 4H2O(l) ΔH = -726kJ/mol
C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l) ΔH = -1371kJ/mol
In countries such as Brazil, ethanol is mixed with petrol and used to power cars. Ethanol is less efficient as a fuel than petrol as it is already partially oxidised but does make the country less reliant on supply of petrol. As it can be produced by fermentation of sugar beet, many consider ethanol a carbon neutral fuel.
The combustion of Alcohols
OHH
H
C
H
H
C
H
+ H2OO
H
H
C
H
CH
ethanol ethanal
The oxidation reactions of Alcohols Primary alcohols are oxidised first to
aldehydes. A suitable oxidising agent is acidified potassium dichromate(VI)
Cr2O72-
/H+
heat
An aldehyde still has one hydrogen atom attached to the carbonyl carbon, so it can be oxidised one step further to a carboxylic acid.
OH
H
C
H
CH
OH
H
C
H
COH
ethanal ethanoic acid
Cr2O72-
/H+
10 alcohol aldehyde carboxylic acid Cr2O7
2- /H+
Cr2O72-
/H+
Inductive reasoning – applicable to another 10 alcohol Page 450
heat
heat heat
In practice, a primary alcohol such as ethanol is dripped into a warm solution of acidified potassium dichromate(VI).
The aldehyde, ethanal, is formed and immediately distils off, thereby preventing further oxidation to ethanoic acid, because the boiling point of ethanal
(23 °C) is much lower than that of either the original alcohol ethanol (78 °C) or of ethanoic acid (118 °C). Both the alcohol and the acid have higher boiling points because of hydrogen bonding.
If oxidation of ethanol to ethanoic
acid is required, the reagents must
be heated together under reflux to
prevent escape of the aldehyde before
it can be oxidised further.
H
H
C
H OH
H
C
H
H
C H
propan-2-ol
H
H
C
H O
H
C
H
C H
propanone
Secondary alcohols are oxidised to ketones. These have no hydrogen atoms attached to the carbonyl carbon and so cannot easily be oxidised further.
Tertiary alcohols are resistent to oxidation
Cr2O72-
/H+
heat
Distinguishing between 1°, 2° and 3° alcohols
When orange acidified potassium dichromate(VI) acts as an oxidising agent, it is reduced to green chromium(III) ions.
1° and 2° alcohols both turn acidified dichromate(VI) solution from orange to green when they are oxidised, and this colour change can be used to distinguish them from 3° alcohols.
3° alcohols are not oxidised by acidified dichromate(VI) ions, so they have no effect on its colour, which remains orange. Practice Page 452
An aldehyde can be oxidised by heating with acidified potassium dichromate(IV) to carboxylic acid.
OH
H
C
H
CH
OH
H
C
H
COH
ethanal ethanoic acid
Cr2O72-
/H+
heat
Reactions of aldehydes and ketones
The + carbon atom is susceptible to attack by NUCLEOPHILES.
A nucleophile is a species with a lone pair of electrons. E.g. OH-, NH3, CN-.
When attack by a nucleophile occurs, the carbon – halogen bond breaks releasing a halide ion.
A suitable nucleophile for experimentation is OH- from an aqueous solution of an alkali such as sodium hydroxide.
Nucleophilic substitution reactions
CH3CH2CH2X + OH- CH3CH2CH2OH + X-
OH has replaced the X so overall we have NUCLEOPHILIC SUBSTITUTION
X = Cl, Br or I.
H
Br
C
H H
H
C
H
H
C H H
OH
C
H H
H
C
H
H
C HNaOH(aq)
heat
1-bromopropane Propan-1-ol
A nucleophile is a molecule / negatively charged ion with a lone pair of electrons which is attacted to a more positively charged region in a molecule and donates a lone pair of electrons to form a covalent bond.
Mechanisms for nucleophilic substitution
SN1 = unimolecular nucleophilic substitution (only one species in the slow step of the mechanism, rate determining step)
SN2 = bimolecular nucleophilic substitution (two species in the slow step of the mechanism, rate determining step)
Use of curly arrows:
Curly arrows are used in reaction mechanisms to show the movement of electron pairs.
to forma lone pairof electrons
X
eithera bond pairof electrons
or a lone pairof electrons
eithernext to an atom
TAILS come from
HEADS point
to form a bond pair of electrons
orat an atom
X
-OH
CH3
H
OHC
H
Br-
CH3
H
BrC
H
CCH3
H
H
+ +
CCH3
H
H
+
slow
fast
SN1
Intermediate carbocation
Heterolytic fission of C – Br bond
Page 461
-OH
HO
H
CH3C
H
Br-
BrC
CH3
H
H
+
C
H
CH3 H
HO Br
-
SN2
Transition state
Page 460
Which is best? SN1 or SN2?
For primary halogenoalkanes – SN2For tertiary halogenoalkanes – SN13° halogenoalkanes cannot undergo the SN2 mechanism as 5 bulky groups would not fit around the C in the transition state - steric hindrance.1° halogenoalknes are less likely to undergo SN1 as this would involve the formation of a primary carbocation as an intermediate. Alkyl groups push electron density to the C atom they are attached to (positive inductive effect) which stabilises the positive charge. More alkyl groups mean a more stable carbocation.
2° halogenoalkanes react via a mixture of SN1 and SN2. The mechanism predominating depends upon the nature of the alkyl groups and the nature of the solvent.
Reaction pathways
alkane
halogenoalkane
alcohol
ketone
dihalogenoalkane
alkene
aldehyde
poly(alkene)
carboxylic acid
trihalogenoalkanetetrahalogenoalkane
M1
M2
M1 and M2 : You should know the mechanisms for these reactions
The flow chart above enables you to convert 2-bromobutane into butanoneusing a two-step synthetic route
2-bromobutane butan-2-ol butanone reflux with NaOH reflux with H+/Cr2O7
Page 482-486
Devise two-step syntheses of the following products from the starting material. Include any experimental conditions.
(a) Ethanoic acid from ethene(b) Butan-1-ol from butane(c) Propanal from 1-bromopropane
Example