Why is the reactivity of all three classes of alcohols with cone. HCl and ZnCl2 (Lucas reagent) different?
The alcohol combine with HCl to form protonated alcohol. The positive charge on oxygen weakens the C – O bond leading to its cleavage.
The rate determining step in the above mechanism is (ii), which is a slow step reaction. The stability of carbocation will determine the reactivity of the reaction. Since the order of stability of carbocation is: Pri. < sec. < tert. Hence the order of formation of alkyl halide in the above reaction is pri. < sec. < tert.
Assertion (A): Phenols give o-nitrophenol and p-nitrophenol on nitration with cone. HNO3 and H2SO4 mixture.
Reason (R): -OH group in phenol is o-,p-directing.
Assertion (A): Phenol forms 2,4, 6-tribromophenol on treatment with Br2 in carbon disulphide at 273 K.
Reason (R): Bromine polarizes in carbon disulphide.
Write the names of reagents and equations for the preparation of the following ethers by Williamson's synthesis:
(i)1-Propoxypropane
(ii)Ethoxybenzene
(iii)2-Methoxy-2-methylpropane
(iv)1-Methoxyethane
While separating a mixture of ortho and para nitrophenols by steam distillation, name the isomer which will be steam volatile. Give reason.
Ethers can be prepared by Williamson's synthesis in which an alkyl halide is reacted with sodium alkoxide. Di-tert-butyl ether cannot be prepared by this method. Explain.
You are given benzene, cone. H2S04and NaOH. Write the equations for the preparation of phenol using these reagents.
Arrange the following compounds in increasing order of acidity and give a suitable explanation:
Phenol, o-Nitrophenol, o-Cresol
Explain how does the – OH group attached to a carbon of benzene ring activate it towards electrophilic substitution?
Match the starting materials given in Column I with the products formed by these (Column II) in the reaction with HI.
Explain the following with an example
(i) Kolbe's reaction (ii) Reimer – Tiemann reaction –
(iii) Williamson ether synthesis (iv) Unsymmetrical ether
Write the equation of the reaction of hydrogen iodide with (i)1-propoxypropane (ii)methoxybenzene, and (iii)benzyl ethyl ether
Write the structures of the isomers of alcohols with molecular formula C4H10O. Which one of these isomers exhibits optical activity?
Explain why alcohols and ethers of comparable molecular mass have different boiling points.
Assertion (A): Bond angle in ethers is slightly less than the tetrahedral angle. Reason (R): There is a repulsion between the two bulky (-R) groups.
Assertion (A): Like bromination of benzene, bromination of phenol is also carried out in the presence of Lewis acid.
Reason (R): Lewis acid polarizes the bromine molecule.
Assertion (A): o-Nitrophenol is less soluble in water than the m- and p-isomers.
Reason (R): m-Nitrophenol and p-Nitrophenol exists as associated molecules.
Write the reactions of Williamson synthesis of 2-ethoxy-3-methylpentane starting from ethanol and 3-methylpentan-2-ol.
Name the reagents used in the following reactions:
(i)Oxidation of a primary alcohol to carboxylic acid.
(ii)Oxidation of a primary alcohol to aldehyde.
(iii)Brominationofphenolto2,4,6-tribromophenol
(iv)Benzyl alcohol to benzoic acid.
(v)Dehydration of propan-2-oI to propene.
(vi)Butan-2-one to butan-2-oL .
Illustrate with examples the limitations of Willamson synthesis for the preparation of certain types of ethers.
Explain the fact that in aryl alkyl ethers (i) the alkoxy group activates the benzene ring towards electrophilic substitution and (ii) it directs the incoming substituents to ortho and para positions in benzene ring.
When 3-methylbutant 2-ol is treated with HBr, the following reaction takes place:
Give a mechanism for this reaction.
(Hint: The secondary carbocation formed in step II rearranges to a more stable tertiary carbocation by a hydride ion shift from 3rd carbon atom.)
Which of the following are used to convert RCHO into RCH2OH?
(a) H2/Pd
(b) LiAlH4
(c) NaBH4
(d) Reaction with RMgX followed by hydrolysis
Which of the following reagents can be used to oxidize primary alcohols to aldehydes?
(a) CrO3 in anhydrous medium
(b) KMnO4 in acidic medium
(c) Pyridinium chlorochromate
(d) Heat in the presence of Cu at 573 K
Phenol can be distinguished from ethanol by the reactions with ………….
(a) Br2/water (b) Na
(c) Neutral FeCl3 (d) All of these
Give structures of the products you would expect when each of the following alcohol reacts with (a)HCl-ZnCl2 (b)HBrand (c) SOCl2
(i)Butan-1-ol
(ii)2-Methylbutan-2-ol
Write structures of the compounds whose IUPAC names are as follows:
(i)2-Methylbutan-2-ol
(ii)l-Phcnylpropan-2-ol
(iii)3,5-DimethyIhexane-l,3,5-triol
(iv)2,3-Dicthylphenol
(v)1-Ethoxypropane
(vi)2-Ethoxy-3-methylpentane
(vii) Cyclohexylmethanol
(viii) 3-Cyclohexylpcntan-3-ol
(ix)Cyclopcnt-3-en-l-ol
(x)4-ChIoro-3-ethylbutan-l-ol
Alcohols are comparatively more soluble in water than hydrocarbons of comparable molecular masses. Explain this fact.
Give two reactions that show the acidic nature of phenol. Compare its acidity with that of ethanol.
