Science of college, Dep. of Chem., Lecturers in Organic chemistry by Dr.Ihmood .

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Alkyl halide

CH3 H2 H
F C C CH3
CH3CH2 Cl CH3CH2CH2CH2Cl
Ethyl Chloride C CH3 CH3
Butyl Chloride H
Isopropyl 1-fluoro -2-methyl propane
CH3CH2 Cl CH3CH2CH2CH2Cl CH3
chloroethane 1-chlorobutane
Cl CH
CH3
2-chloropropane

Physical properties:

Alkyl halides have higher boiling point than alkane of the number of
carbon because the greater M.wt., Also iodide compound have higher b.p
than Br > Cl > F

They are insoluble in water in spite of their polarity soluble in most

organic solvent.

Iodo , bromo, poly chloro compound are more dense than water .

Industrial source:-
Science of college, Dep. of Chem., Lecturers in Organic chemistry by Dr.Ihmood .kh
.jebur// 2020 //class 2

Certain important halides are prepared industrially.

Preparation:

1- from alcohol by reaction of alcohol with hydrogen halide some

time the reaction require catalyst for least reactive hydrogen halide
with 1 and 2 alcohol

In this method rearrangement be occur, this can be minimized by using

phosphoro halide.
Science of college, Dep. of Chem., Lecturers in Organic chemistry by Dr.Ihmood .kh
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2- halogenation of contain hydrocarbon

3- Addition of hydrogen halide to alkenes.

C C HX C C + HX= HCl, H Br, HI

H X

peroxides
CH3CHBrCH3 Markonikov`s addition
H H
2- bromo propane
HBr or isopropylbromide
CH3 C C H

CH3CH2CH2Br
no peroxides
1- bromo propane anti Markonikov`s addition
or n-propylbromide

4- Addition of halogens to alkenes and alkynes :

5- Halide exchange
Science of college, Dep. of Chem., Lecturers in Organic chemistry by Dr.Ihmood .kh
.jebur// 2020 //class 2

Alkyl iodide is often prepared from the corresponding bromide or

chloride by treatment with a solution iodide in acetone.

C C C C C C

H benzylic hydrogen X benzyl halide

C C

H Allylic hydrogen X Allylic halide

Reactions:

1- Nucleophilic substitution

Halide ion is weak base, so the hydrogen can be readily displaced as

halide ion by other stronger bases. These bases possess an un shared pair
of electron and seeking the positive site (nucleus) . Electron rich reagents
are called nucleophilic reagents. The typical reactions of alkyl halides are
the nucleophilic substitution.

R:X+:Z R:Z+X Nucleophilic substitution

Nucleophilic reagent (strong base) leaving group ,The nucleophilic

reagents are either bearing negative charge like OH , CN , RO or neutral
bases like ammonia and water which contain unshared pair of electrons .
Science of college, Dep. of Chem., Lecturers in Organic chemistry by Dr.Ihmood .kh
.jebur// 2020 //class 2

1- Elimination Reaction : Dehydrogenation previously discussed .

Science of college, Dep. of Chem., Lecturers in Organic chemistry by Dr.Ihmood .kh
.jebur// 2020 //class 2

HX
C C C C

X H

2- Preparation of Grignard reagents

4- Reduction

Nucleophilic aliphatic substitution: Second order and first order

kinetics.

For example reaction of methyl bromide with sodium hydroxide to

produce Methanol.

The reaction is carried out in aqueous ethanol is order to soluble all

compound if the reaction result from collision between hydroxide ion and
methyl bromide molecule , then the rate will depend on the conc. of both
of those two reactant .i.e.

Rate α conc of CH3 Br x conc . of OH as the conc increase the rate will be
increase
Science of college, Dep. of Chem., Lecturers in Organic chemistry by Dr.Ihmood .kh
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Rate = K[CH3 Br][ OH-]

K is the rate constant . for a particular reaction K value is constant at a

given temperature and a given solvent

Therefore this reaction is second order reaction because the rate depends
on conc of two substances. Now the reaction of tetra – butyl bromide with
hydroxide ion .The rate of reaction depend only on the conc . of alkyl
halide and if we change the conc . Of OH the rate always the same.

Rate α cone of tetra butyl bromide

H3C H3C

H3C C Br OH- H3C C OH Br

H3C H3C

Rate = K [Rx] .

This reaction is first order reaction because it depend on the conc of only
one substant.

Now why reaction

1- depend on conc . of OH while reaction 2- independence on conc . of

OH

From the order of reaction we can say that the two nucleophilic
substitutions proceed by two different mechanisms.

The SN2 reaction Mechanism and kinetics:

For the reaction

CH3Br OH CH3OH Br

Rate = K[CH3 Br][ OH-]

Science of college, Dep. of Chem., Lecturers in Organic chemistry by Dr.Ihmood .kh
.jebur// 2020 //class 2

The rate depends upon the conc of both reactions i.e. the reaction occur
by the collision between a hydroxide ion and methyl bromide molecule.

The OH attack CH3Br from the side back side for away from bromide i.e.
attacks the molecule from the rear.

C2H5 C2H5 H CH3

H C Br HO C Br H Br
HO C
OH
H3C C2H5
CH3

SN2

The HO- C bond form simultaneously with breaking of C- Br bond and

the C- Br bond in the T.S is not completely and the C- OH is not
completely formed and each group have partially negative charge. the –
OH and – Br are located is for apart as possible .

1- This mechanism is called bimolecular nucleophilic substitution (SN2)

which is follows second order kinetics particles (SN2 substitution
nucleophilic bimolecular).

Bimolecular is used because the r.d.s. involves collision of two particles.

This mechanism is consistent with the kinetics of reaction.

2- Another evidence for SN2 is the stereochemistry. In which the reaction

yield a product whose configuration is opposite to that of reactant.

3- i.e. the SN2 reaction proceeds with complete inversion of

configuration. Evidence

The rate of SN2 reaction depends on size of groups attached by the

reaction center. The increase of the group’s size will decrease bulk of
substitution the rate of SN2 reaction. i.e. the differences in rate between
Science of college, Dep. of Chem., Lecturers in Organic chemistry by Dr.Ihmood .kh
.jebur// 2020 //class 2

two SN2 reactions seem to be due chiefly to steric factors and not to
electronic factors .

In SN2 reactions the order of reactivity of Rx is CH3X > 1º > 2º > 3º

The SN1 reaction Mechanism, kinetic, relative reactivity.

The reaction between tert – butyl bromide and hydroxide ion to yield tert
– butyl alcohol follows first order kinetic , i.e. the rate depends upon the
conc.of only one reactant , tert – butyl bromide .

C2H5 C2H5
OH
H C Br H C
H3C
H3C

The rate is consistent with the following mechanism:

The first step is the slow dissociation of t- butyl bromide to bromide ions
and tert– butyl alcohol. then the carbonium ions combine rapidly (syep2)
with hydroxide ions to yield tert- butyl alcohol .The rate of reaction is
determined by the slow step (breaking of C – Br bond) r.d.s : A single
step whose rate determines the overall rate of a stepwise reactions . The
energy require for breaking of C- Br bonds coming from the formation of
ion – dipole bonds between the two kinds of ions and the solvent.

This mechanism called SN1 substitutes unimoleculer nucleophilic

substitution.

Evidence

1- The mechanism is consistent with the first order kinetics. i.e. SN1
reaction follows first order kinetics. Therefore the rate of reaction
determines by the rate of ionization of alkyl halides, that is , depend only
on the conc of alkyl halide .
Science of college, Dep. of Chem., Lecturers in Organic chemistry by Dr.Ihmood .kh
.jebur// 2020 //class 2

3-The SNI reaction Stereo chemistry:

H2O

C6H13 b
H

CH

x
CH3
a
b

C6H13

C6H13
H
HO C OH

H C

CH3

H3C
Enantiomers

SNI reaction proceeds with racemization. The carbonium ion has a flat
–
structure , then the nucleophilic reagent OH attached itself to the
carbonium ion either face of this flat ion .

3- The reactivity, In SN1 mechanism is face carbonium ion 'is formed then
any group stabilize the carbonium ion will increase the rate of reaction .
therefore the order of reactivity of alkyl halides in SN1 reaction is the
same order of stability of carbonium ions .In SN1 reactions the order of
reactivity of R x is alkyl, benzyl > 3º > 2º> 1º

The rate of SN1 reaction is affected largely by electric factors, i.e. the
ability of substituent’s to release or with draw electrons.

4- Rearrangement:
Science of college, Dep. of Chem., Lecturers in Organic chemistry by Dr.Ihmood .kh
.jebur// 2020 //class 2

If the SN mechanism involves formation of carbonium ion , then we

expect occurrence of rearrangement to more stable carbonium ion .

CH3
C2H5O-
H3C C CH2OC2H5 NO rearranagment
SN1
CH3
Neo pentyl ethyl ether
CH3
H3C C CH2Br CH3
CH3 H3C C CH2CH3
OC2H5
C2H5OH Tert-pentyl ethyl ether Rearranagment

SN1 CH3
H3C C CHCH3
2-methyl -2-butene

Also SN1 reaction is accompanied by elimination reaction.

2- Elimination reaction:

Also there are two mechanisms for elimination. E2 (bimolecular

elimination) and E1 (unimoleculer elimination).

E2 involve single step , base pulls a hydrogen ion a way from carbon ,
and simultaneously a halide ion separates .

E2 (bimolecular elimination

C C X C C H:B

H B

An this mechanism the r.d.s. involves two molecules . Some time alkyl
halide particularly tert – alkyl halide can carried out by two , dissociation
step of alkyl halides into halide ions and carbonium ions in slow step ,
Science of college, Dep. of Chem., Lecturers in Organic chemistry by Dr.Ihmood .kh
.jebur// 2020 //class 2

than the carbonium ion loss proton to base to form alkene in the second
step .

E elimination

C C slow
C C X

H Carbanion
H

C C C C H:B fast

H
B

The r.d.s (slow step) involve one molecule which the first step .

The order of reactivity of alkyl halide toward E2 or E1 is the same. 3º >

2º > 1º .

Evidence of E1 mechanism

1- Follow first – order kinetics.

2- The reaction accompanied by rearrangement.
Evidence for E2 mechanism

1- Follow second – order kinetics.

2- Are not accompanied by rearrangement.
Science of college, Dep. of Chem., Lecturers in Organic chemistry by Dr.Ihmood .kh
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X X

C C C C H:B

H
Carbanion
B
X

C C X C C

orientation of elimination :-

The formation of more stable alkene is called saytzelf orientation

according to substituted alkenes.

Elimination as substitution

There is competition between substitution and elimination both reactions

result from attack by the same nucleophilic reagent : attack at carbon
causes substitution , attack at hydrogen causes elimination .

C C E2 , SN2

Z:

The speed of elimination of alkyl halides depend chiefly upon the

stability of the alkene formed . text – alkyl halides which yield highest
branched (more stable) alkenes , undergo elimination fastest and
substitution slowest primary halides , undergo substitution fastest and
elimination slowest .
Science of college, Dep. of Chem., Lecturers in Organic chemistry by Dr.Ihmood .kh
.jebur// 2020 //class 2

Reaction of others ethers are un reaction compounds. They are star

towards bases oxidizing and reducing agents ethers undergo just one k of
reaction, which is cleavage by acids>