Concept:
Haloform Reaction:
The general reaction scheme is given as follows
R-COCH3 + X2/OH(hydroxide) = RCOO- + CHX3 (halo form)
\(\begin{array}{{20}{c}} {\rm ,,,,,,O}\ {,,,,,,||}\ {\rm C{H_3} - C - R } \end{array} \begin{matrix} {} \\ {} \\ \xrightarrow{\rm 3NaOH} \end{matrix} \ \ \begin{array}{{20}{c}} {\rm ,,,,,,O}\ {,,,,,,||}\ {\rm C{H_3} - C - R } \end{array} \begin{matrix} {} \\ {} \\ + \ \ \rm 3NaOH \end{matrix} \)
\(\begin{array}{*{20}{c}} {\rm ,,,,,,O}\ {,,,,,,||}\ {\rm C{X_3} - C - R } \end{array} \begin{matrix} {} \\ {} \\ \rm \xrightarrow{NaOH} \underset{haloform}{CHX_3} + RCOONa \end{matrix} \)
Explanation:
Criteria for giving positive haloform test:
Step I (oxidation step)
\(\begin{array}{{20}{c}} {\rm C{H_3} - CH - R + {I_2}}\ {|,,,,,,,,,,}\ {\rm OH,,,,,,} \end{array} \begin{matrix} \begin{array}{{20}{c}} {\rm \ \ \ \ \ O,,,,,,,}\ { \ \ \ \ \ ||,,,,,,,}\ {\longrightarrow \rm C{H_3} - C - R + 2HI} \end{array} \\ {} \\ {} \\ {} \\ {} \end{matrix}\)
2.Halogenation.
\(\begin{array}{{20}{c}} {\rm O,,,,,,,}\ {||,,,,,,,}\ {\rm C{H_3} - C - R + 3{I_2}} \end{array} \begin{array}{{20}{c}} {\rm \ \ \ \ O,,,,,,,}\ { \ \ \ \ ||,,,,,,,}\ {\longrightarrow \rm C{I_3} - C - R + 3{HI}} \end{array} \)
- Hydrolysis
\(\begin{array}{{20}{c}} {\rm C{I_3} - C - R + {NaOH}}\ {||, \ \ \ \ \ \ \ \ \ \ ,,,}\ {\rm O,,,,,, \ \ \ \ \ \ \ \ } \end{array} \begin{matrix} \begin{array}{{20}{c}} {\rm \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ O,,,,,,,}\ { \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ ||,,,,,,,}\ {\longrightarrow \rm \underset{Iodoform}{C{HI_3}} + R - C - ONa } \end{array} \\ {} \\ {} \\ {} \\ {} \end{matrix}\)
Thus, both the groups \(\begin{array}{{20}{c}} {\rm O,, \ \ ,,,,,,,}\ {|| \ \ ,,,,,,,,,,}\ { - \rm C - C{H_3}} \end{array}\) and \(\begin{array}{{20}{c}} {\rm OH,,,,,, \ \ \ ,,}\ {|,,,,,,,,, \ \ \ \ ,,,,}\ { - \rm{CH - CH}_3} \end{array}\)will give the haloform test.
Hence, (CH3)2CHOH will give a positive iodoform test.