a reaction in which a small molecule, such as H2O or HCl, is removed from an organic molecule
of Halogenoalkanes
removed molecule is HX
ethanolic NaOH
OHminus act as base
The original 2-bromopropane molecule has lost an H atom and a Br atom. We can think of it as HBr
being eliminated from the halogenoalkane. The ethanolic OH– ion acts as a base, accepting an H+
from the halogenoalkane to form water. The C Br bond breaks heterolytically, forming a Br– ion and
leaving an alkene as the organic product
dehydration of alchols
H2O is removed
alkene+water
alcohol vapor
Al2O3 or SiO2or H2SO4
substitution
Nota:
eaction that involves the replacement of one atom, or group of atoms, by another.
ree-radical substitution the reaction in which halogen atoms substitute for hydrogen atoms in alkanes. The mechanism involves steps in which reactive free radicals are produced (initiation), regenerated (propagation) and consumed (termination)
Alkanes(free radical substitution
homolytic fission
mechanism
termination
only free radicle react
they form a molecule
propagation
free radicles are very reaxtive
free radicles hits the normal molecule >CH3radicle
intiation
energy is put in to break
the bonds,
only 2 free
radicles formed
halogenoalkane
with alkali(OHminus)Aq
Nota:
The halogen atom in the halogenoalkane
is replaced by an OH, hydroxyl group, so the organic
product formed is an alcohol
gives alcohol
wtih cyanide ion,CN- in ethanol
heated in reflux with the halogenoalkane
extra carbon atom is added
CH3CH2Br + CN->CH3CH2CN + Br–
with NH3
If a halogenoalkane is heated
with an excess of ammonia
dissolved in ethanol under
pressure, an amine is formed.
CH3CH2Br + NH3--> CH3CH2NH2 + HBr
amine is formed
Mechanism of nucleophilic substitution
in halogenoalkanes
Nota:
nucleophiles are donors of an electron pair and
are attracted to electron-deficient atoms
primary SN2(heterolytic)
when C is boned to X and one CH3(+2H)
SN1 Tertiary
Nota:
The Br– ion forms again, as in the SN2 mechanism,
but in this mechanism a carbocation ion forms. This
does not happen with primary halogenoalkanes. This
is because tertiary carbocations are more stable than
primary carbocations due to the inductive effect of the
alkyl groups attached to the carbon atom bonded to
the halogen. Alkyl groups tend to release electrons
to atoms attached to them. So a tertiary carbocation
has three alkyl groups donating electrons towards the
positively charged carbon atom, reducing its charge
density. This makes it more stable than a primary
carbocation, which just has one alkyl group releasing
electrons
the C bonded to X is also bonded to 3C(s) or CH3(s)
of alcohols forms halogenoalkanes
hydrolysis
Nota:
the breakdown of a compound by water, which is often speeded up by reacting with acid or alkali.
nucleophilic hydrolysis of halogenoalkane
CH3CH2Br+H2O(IN AgNO3)-->CH3CH2OH+H-PLUS+Br MINUS
reflux
oxidation
Nota:
crease in Oxidation nu#
losss of e
gain of oxygen
loss of hydrogen
alkene
alkene converted to diol
cold
dilute acidified KMnO4
CO2 or aldehyde.carboxylic and or keton
hot
conc. MNslo
reduction
Nota:
decrease in Oxidation nu#
losss of e
gain of oxygen
loss of hydrogen
Addition
Nota:
an organic reaction in which two
reactant molecules combine to give a single
product molecule.
c=c broken and eache carbon makes a new segma bond
alkene[C=C is broken]
H2->>alkane
Ni(finely powdered catalyst
140 degree C
steam->> alcohol
gaseous alkene
6mega pa
330 degree C
catalyst
phosphoric
tungestic
dilute H2SO4
mechanism of electrophilic
HX->> halogenoalkane
conc.sol. of HX(HF,HCl... ROOM TEP
when not symetric ^ markovnikov alkene will decolorise
Nota:
When a compound HX is added to an unsymmetrical alkene, the hydrogen becomes attached to the carbon with the most hydrogens attached to it already.
electrophile can easily attact the c=c
Nota:
electrophile acceptor of e
H+
HX is polar due to electronegativity
the only difference is in how fast the reactions happen with the different hydrogen halides. The rate
of reaction increases as you go from HF to HCl to HBr to HI.
Nota:
The reason for this is that as the halogen atoms get bigger, the strength of the hydrogen-halogen bond falls. Bond strengths (measured in kilojoules per mole) are:
H-F
568
H-Cl
432
H-Br
366
H-I
298
c=c will polarize the nonpolar br-br
Nota:
Bromine as an electrophileThe bromine is a very "polarisable" molecule and the approaching pi bond in the ethene induces a dipole in the bromine molecule. If you draw this mechanism in an exam, write the words "induced dipole" next to the bromine molecule - to show that you understand what's going on.