1 Compiled by mr Isabirye David. [email protected] 0703732102/0784863664 The diazonium salt can be converted to any of the aromatic halides as shown below.
Cl Conc HCl CuCl
N+ NCl Conc HBr
Br CuBr
I KI(aq) warm
Qn. Explain why Bromobenzene does not easily react with sodium hydroxide solution while Bromoethane easily react with sodium hydroxide solution. Explaination; Bromobenzene does not easily react with sodium hydroxide solution. This is because the lone pair of electrons on the bromine atom interacts (associates) with the delocalised pi-electrons of the benzene ring. This leads to the formation of a partial double bond between the carbon atom of the benzene ring and the bromine atom. The carbon bromine bond is therefore made stronger and not easily broken. Bromoethane easily reacts with sodium hydroxide solution. This is because the carbon-bromine bond is polar since the bromine atom is more electronegative than the carbon atom. The bromine atom pulls the electrons of the bond more towards itself. This weakens the carbon-bromine bond creating a partial positive charge on the carbon atom and so it is easily attacked by the hydroxide ion.
N.B The same explaination applies for Chlorobenzene and any alkyl halide containing the chloride atom e.g Chloroethane and Iodobenzene with any alkyl halide containing the iodide atom e.g Iodobutane but while explaining, use the corresponding halide.
2 Compiled by mr Isabirye David. [email protected] 0703732102/0784863664 Reactions of aromatic halides The following reactions involve replacement of the halogen atom with another group. 1. Conversion to a phenol.(C6H5OH)
Qn. Name the reagent(s) that can be used to distinguish between the following pairs of compounds. In each case state what is observed when each member of the pair is treated with the named reagent(s) and write an equation (s) for the reaction that takes place. Cl (a) and CH3CH2Cl
Br (b) and CH3CH2Br
I (c) and CH3CH2I
CH3 CH2Br Br (d) and
Cl Cl (e) and
(f) HC≡CH and HC≡CBr
4 Compiled by mr Isabirye David. [email protected] 0703732102/0784863664 Reagent(s) Hot Sodium hydroxide solution followed by acidified silver nitrate solution. (Hot Sodium hydroxide solution followed by dilute nitric acid followed by silver nitrate solution). Observation(s) Cl (a) ; No observable change.
7 Compiled by mr Isabirye David. [email protected] 0703732102/0784863664 Reactions of Grignard reagents (importance of Grignard reagents in Organic synthesis) 1. Conversion to an alkane. Hydrolysis of a Grignard reagent forms an alkane.
H+ / H2O RMgX RH + Mg(OH)X Example H+ / H2O CH3CH2MgBr CH3CH3 2. Conversion to a primary alcohol. When a Grignard reagent is treated with methanal (HCHO) and the product hydrolysed,a primary alcohol is formed.i.e O + RMgX + HCH dry ether RCH2OMgX H / H2O RCH2OH + Mg(OH)X Example (i) HCHO / dry ether CH3CH2MgI CH3CH2CH2OH (ii) H+ / H2O
HCHO / dry ether H+ / H2O
CH3CH2CH2OMgI N.B This reaction increases the length of the carbon chain. Qn. Synthesise CH3Br to CH3CH2OH Solution Mg (i) HCHO / dry ether CH3Br CH3MgBr CH3CH2OH dry ether (ii) H+ / H2O
3. Conversion to a secondary alcohol.
When a Grignard reagent is treated with other aldehydes and then the product hydrolysed, a secondary alcohol is formed.i.e
Tertiary alcohols are formed when Grignard reagents are reacted with ketones and the products formed hydrolysed.i.e
O RI + RI RCR / dry ether H / H2O RIMgX RCOMgX RCR + Mg(OH)X R OH Example O CH3 (i) CH3CCH3 / dry ether CH3MgBr CH3CCH3 (ii) H+ / H2O OH
5. Conversion to a carboxylic acid .
A carboxylic acid is formed when a Grignard reagent is reacted with carbon dioxide and the product formed hydrolysed.i.e
CO2 / dry ether H+ / H2O
RMgX RCO2 MgX RCOOH + Mg(OH)X Example (i) CO2 / dry ether CH3CH2MgI CH3COOH (ii) H+ / H2O
6. Conversion to ketones. A ketone is formed when a Grignard reagent is reacted with an acid chloride.e.g O O dry ether CH3MgCl +CH3CCl CH3CCH3 + MgCl2
