Q.Why are Propan-1-ol and 2-Methylpropan-1-ol not prepared by this method?
Step 1. Recall the method's selectivity. Section 15.2.4 describes cold concentrated H2SO4 adding across an alkene to give an alkyl hydrogen sulfate, which hydrolyses on dilution/heating to the alcohol; this addition follows Markovnikov's rule, so the -OSO3H (and hence eventually -OH) group attaches to the carbon bearing FEWER hydrogens, i.e. the more substituted carbon.
Step 2. Apply this to propene. Propene, CH3-CH=CH2, has one CH (fewer H) and one CH2 (more H) on its double bond; Markovnikov addition puts -OH on the CH carbon, giving propan-2-ol (a secondary alcohol), never propan-1-ol (a primary alcohol, which would need -OH on the terminal CH2).
Step 3. Apply this to 2-methylprop-1-ene. Similarly, 2-methylprop-1-ene, (CH3)2C=CH2, has a fully-substituted carbon and a terminal CH2; Markovnikov addition puts -OH on the more-substituted carbon, giving 2-methylpropan-2-ol (tertiary), never 2-methylpropan-1-ol (primary, needing -OH on the terminal CH2).
Step 4. State the alternative. Making these primary alcohols instead requires the ANTI-Markovnikov hydroboration-oxidation route (diborane/THF, then alkaline H2O2), which specifically places -OH on the less-substituted (terminal) carbon.
Because the H2SO4/water method follows Markovnikov's rule, so -OH always ends up on the more-substituted carbon; propan-1-ol and 2-methylpropan-1-ol are primary alcohols that would need -OH on the LESS-substituted (terminal) carbon, which this route cannot deliver -- the anti-Markovnikov hydroboration-oxidation route (section 15.2.4) is needed instead.
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