Chapter 5 Alkyl Halides
Chapter 5 Alkyl Halides
Chapter 5 Alkyl Halides
Objective
Ability to explain the relationship between the structure, physical and chemical properties of the different bonds and functional group in organic compounds.(CO2) Ability to explain each of functional group activity. (CO3)
Outcome
The student should be able to: Name alkyl halides. Explain alkyl halides properties. Predict, draw and name the products of functional groups reactions. Draw the mechanistic pathway.
BACKGROUND
The functional group of alkyl halides is a carbon-halogen bond, the common halogens being fluorine, chlorine, bromine and iodine. With the exception of iodine, these halogens have electronegativities significantly greater than carbon. This functional group is polarized so that the carbon is electrophilic and the halogen is nucleophilic, as shown in the drawing on the right.
In alkyl halides this polarity causes the carbon to become activated to substitution reactions with neucleophiles. Carbon-halogen bonds get less polar, longer and weaker in going from fluorine to iodine. Classes of halides :i. Alkyl : Halogen, X, is directly bonded to sp3 carbon ii. Vinyl : X is bonded to sp2 carbon of alkene. iii. Aryl : X is bonded to sp2 carbon on benzene ring.
H H H C C Br H H alkyl halide
H C C
H Cl vinyl halide
aryl halide
REVIEW
IUPAC SYSTEM
An alkyl halide is named as an alkane with a halogen substituent-that is , as a halo alkane. To name a halogen substituent, change the ine ending of the name of the halogen to the suffix o (chlorine -> chloro) The halogen is treated as a substituent.
8
6 7
5 6 4
3 2
1
1 3
7 5
4
2 bromo-5-methylheptane
1-chloro-5,5-dimethylhexane
4-bromo-2-chloro-1-methylcyclohexane
Br
Cl
Cl
Example
How to name an alkyl halide Using the IUPAC System 1. Give the IUPAC name of the following alkyl halide :
STEP 1 :- Find the parent carbon chain containing the halogen. STEP 2 :- Apply all other rules of nomenclature. a. Number the chain b. Name and number the substituents c. Alphabetize
Common Names
Common names for alkyl halides are used only for simple alkyl halides. To assign a common name: - Name all the carbon atoms of the molecule as a single alkylgroup. - Name the halogen bonded to the alkyl group. To name the halogen,change the ine ending of the halogen name to the suffix ide; for example, bromine -> bromide. - Combine the names of the alkyl group and halide, separating the words with a space.
tert-butyl iodide
ethyl chloride
nucleop ile
hali e ion
2.
C C X H alkyl hali e
(-HX)
C C alkene
R-X
:X
: :
: :
There are two fundamental events in these substitution reactions: i. formation of the new bond to the nucleophile ii. breaking of the bond to the leaving group Depending on the relative timing of these events, two different mechanisms are possible: 1. Bond breaking to form a carbocation preceeds the formation of the new bond : SN1 reaction 2. Simultaneous bond formation and bond breaking : SN2 reaction
SN1 Mechanism
Two step reaction with carbocation intermediate. Rate is first order in the alkyl halide, zero order in the nucleophile
STEP 1 :
(CH3)3C Br
(CH3)3C
+ Br
.
STEP 2 : (CH3)3C+
+ H O H
(CH3)3C O H H
(CH3)3C O H + H3O
+
(CH3)3C O H + H O H H
SN2 Mechanism
Rate is first order in each reactant. (one-step reaction with no intermediate Concerted reaction: new bond forming and old bond breaking at same time.
H H O C Br H H
H HO C Br H H HO C
H + H H Br
-
N cleo - + I RRRRRRRRR+ + +
-
ile
p p p p p p p p p
-
Class of Prod ct k l li lc et er t i l t i et er l
R'
+ R' + N + N + +
-
| -R' |N
R- | -R' R- |N -R' R-
+ R-
SN2
SN2
Primary or methyl Strong nucleophile ( Strong Lewis base) Polar aprotic solvent (DMF, DMSO) Rate = k[halide][Nuc] Inversion at chiral carbon No rearrangements
vs
SN1
SN1
Tertiary
Weak nucleophile (Weak Lewis base) Polar protic solvent, (alcohol and water) Rate = k[halide] Racemization of optically active compound Rearranged products
Leaving Group :- for both SN1 and SN2 ( the weaker the base the group departs, the better the leaving group)
The two most important methods are: Dehydration (-H2O) of alcohols, and Dehydrohalogenation (-HX) of alkyl halides. There are three fundamental events in these elimination reactions: i. removal of a proton ii. formation of the CC p bond iii. breaking of the bond to the leaving group Depending on the relative timing of these events, different mechanisms are possible: i. Loss of the LG to form a carbocation, removal of H and formation of C=C bond : E1 reaction ii Simultaneous H removal, C=C bond formation and loss of the LG : E2 reaction iii. Removal of H to form a carbanion, loss of the LG and formation of C=C bond (E1reaction)
E1 Reaction
Unimolecular elimination Two groups lost (usually X- and H ) Nucleophile acts as base) Also have SN1 products (mixture SN1 and E1 have common first step. E1 Mechanism
H Br H C C CH3 H CH3 H H O H H
H H C C CH3 H CH3
Halide ion leaves, forming carbocation
H C C CH3 H CH3
E2 Reaction
Bimolecular elimination Requires a strong base Halide leaving and proton abstraction happens simultaneously - no intermediate
E2 Mechanism
H Br H H O H C C CH3 H CH3 H C C
CH3 CH3
+ H2O + Br
How do we determine whether a reaction will go via an elimination or a substitution and whether it will be first or second order?
Primary (1) carbons Normally react by an SN2 pathway. With good nucleophiles such as Br-, I-, CN-, RS-, or NH3 get only SN2 reactions. However, with strong base (hydroxide or alkoxide) get some competition by E2 reaction, though SN2 still predominates. Secondary (2) carbons Go by either SN2 or E2: - With good nucleophiles get mostly SN2. - With strong base E2 predominates. Tertiary (3) carbons Go by SN1, E1, or E2: - SN1 and E1 are both favored by acid conditions, but acidic nucleophiles such as HCl, HBr, and HI favor SN1, while sulfuric acid favors E1 - E2 is favored by strong base again.
Substitution or Elimination
Control of the reaction pathway between substitution and elimination is generally accomplished by careful choice of the reactants; strong, sterically hindered bases tend to favor elimination, while weak, unhindered nucleophiles tend to favor substitution. The choice for a "strong, hindered base" is generally tert-butoxide
TRY THIS..
Formation of Alcohol
Example 1
60oC
CH3
Br
OH
H2O
CH3 O
Br
H H O C Br H H
H HO C Br H H HO C
H + H H Br
-
Example 2
(CH3)3C Br
(CH3)3C
+
(CH3)3C
+ Br
+ H O H
(CH3)3C O H H (CH3)3C O H
+ H3O
+
(CH3)3C O H + H O H H
Example
CH3CH2CH2OH
Propyl alcohol
NaH
CH3CH2CH2O Na
Sodium propoxide
H H
CH3CH2I CH3CH2OCH2CH2CH3
Ethyl propyl ether
Na I
The alkyl halide ( alkyl sulfonate) should be primary to avoid E2 reaction. Substitution favored over elimination at low tempertaure.
2 Na
dry (CH2H5)2O
2 NaX
R-Na ( an intermediate compound) is so reactive that is attacks RX itself, thus the method can only be used to prepare symmetrical alkane. The reaction is limited in its preparation, giving only low yields with haloalkanes of low relative molecular mass, although much better yields are obtained with those of higher relative molecular mass. A more versatile coupling reaction of this type is the Corey-House reaction involving the haloalkane and a lithium dialkylcopper.
RX
R2'CuLi
R'
R'Cu
LiX
Suggest.