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Chemical Properties - Nucleophilic Substitution Reactions

The chemical reactions of haloalkanes can be divided into four types:

  • Nucleophilic substitution reactions
  • Dehydrohalogenation
  • Reactions with metals
  • Reduction.
 

Nucleophilic substitution reactions

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In the C-X bond there is a partial positive charge on the carbon atom and negative on the halogen atom. Thus nucleophilies attack the electron deficient carbon resulting in the displacement of the weaker nucleophile, the halide ion. Reactions of alkyl halides are generally nucleophilic substitution reactions.

general representation of nucleophilic substitution reaction

The halide ions are substituted only if the attacking nucleophile is stronger. As the halide ion itself is a very weak nucleophile, the attacking nucleophile should be stronger than it. The order of reactivity of various alkyl halides towards nucleophilic substitution is:

RI > RBr > RCl > RF

This order of reactivity can be explained on the basis of strength of C-X bond. The C-X bond is the weakest in R-I and strongest in R-F.

These reactions take place either by the SN1 and SN2 mechanisms.

Types of nucleophilic substitution reactions

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The nucleophilic substitution reactions can be classified into two types:

First is the SN1 reaction (substitution nucleophilic, first order). This type of reaction proceeds in two steps as:

first step of  substitution nucleophilic first order reaction

second step of substitution nucleophilic first order reaction

The first step is slow and is the rate-determining step. As the nucleophile (Z-) is not involved in the rate-determining step, the reaction depends only upon the concentration of alkyl halide (RX) and is, therefore, a first order reaction.

Rate = k [RX]

The order of reactivity depends upon the stability of carbonium ion formed in the first step. Since the 3° carbonium ion is most stable, the ionization of tertiary alkyl halide is favored. The order of reactivity for SN1 reaction is, tertiary > secondary > primary.

The second type is the SN2 reaction (substitution nucleophilic, second order). This type of reaction occurs in one step through the formation of transition state as:

formation of transition state in substitution nucleophilic second order reaction

Here, the rate of reaction depends upon the concentration of both the alkyl halide and the nucleophile.

Rate = k[RX] [Z-]

The transition state from tertiary alkyl halide is less stable due to steric hindrance i.e., crowding of bulky groups. The order of reactivity is: primary > secondary > tertiary.

Thus the reactivity by SN1 versus SN2 increases as follows:

reactivity by SN1 versus SN2 increases

Factors favouring S

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N1 and SN2 mechanisms

The reaction mechanism of SN1 or SN2 substitutions depends upon a number of factors as follows:

Nature of alkyl halide

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If the alkyl halide is primary, it reacts through SN2 and if it is tertiary, it reacts through SN1 mechanism. 2° Alkyl halide react through both mechanisms.

Nature of nucleophile

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Strong nucleophiles favor SN2 mechanism whereas weak nuclephiles favor SN1mechanism.

Concentration of nucleophile

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High concentration of nucleophile favors SN2, while low concentration favors SN1 mechanism.

Nature of solvent

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Polar solvents favor SN1 mechanism as they can cause dissociation of alkyl halide and thus facilitate the formation of carbocation. Solvents of low polarity favor SN2 mechanism.

Nucleophilic reactions of haloalkanes are:

Replacement by hydroxyl group (Formation of alcohols)

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On treatment with aqueous solution of KOH or moist silver oxide (Ag2O/H2O) haloalkanes give alcohols.

formation of alcohols by nucleophilic reactions of haloalkanes

formation of ethanol by nucleophilic reactions of bromoethane

Replacement by alkoxy group

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(Formation of ethers) - Williamson Synthesis

formation of ethers by Williamson Synthesis reaction

This reaction is called 'Williamson's synthesis' and is quite useful for preparing ethers. Haloalkanes can also be converted into ethers by heating with dry silver oxide.

formation of ethers by Williamson Synthesis reaction
 

Substitution by cyano group

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Haloalkanes react with alcoholic solution of potassium cyanide (KCN) to give alkane nitriles or alkyl cyanides as the major products along with a small amount of alkyl isocyanides.

Substitution by cyano group

preparation of propane nitrile  from ethyl bromide

Alkyl cyanides can further be converted into acid amides, carboxylic acids and primary amines under different conditions. Therefore, they are useful starting materials for these compounds.

The reaction of haloalkanes with alcoholic KCN is important because the product formed has one more carbon atom than the alkyl halide. Therefore, the reaction is a good method for ascending the homologous series (increasing the length of the carbon chain by one carbon atom).

reaction of haloalkanes with alcoholic KCN

Substitution by isocyanide group

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Isocyanides are obtained when haloalkane is treated with alcoholic silver cyanide (AgCN). These are also called carbylamines and have extremely unpleasant smell.

Isocyanides are obtained when haloalkane
(Alkane isonitrile)

preparation of ethyl carbylamine

On reduction with sodium or alcohol, alkyl isocyanides give secondary amines.

alkyl isocyanides give secondary amines

Substitution by amino group (formation of amines)

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A primary amine is formed when haloalkane is heated with alcoholic ammonia solution in a sealed tube at 383 K; the halogen is substituted by -NH2 group.

formation of amines

However, when haloalkane is in excess, a mixture of primary, secondary and tertiary amines is formed, as one or both the hydrogen atoms of the amino alkane (primary amine) are replaced by alkyl groups.

formation of secondary amine from haloalkane

formation of tertiary amine from haloalkane

The tertiary amines which result, can also form quaternary ammonium salt by combining with another molecule of alkyl halide.

tertiary amines  form quaternary ammonium salt

This reaction is called Hoffmann ammonolysis reaction.

Substitution by nitrite group

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The halogen atom of haloalkane gets substituted by nitrite group (-O-N=O) when it is treated with sodium or potassium nitrite and forms alkyl nitrites.

Substitution by nitrite group

The bond between K-O in KNO2 (alkyl nitrites) is ionic and therefore the negative charge on oxygen is the attacking site: it therefore forms nitrites (R-O-N = O).

Substitution by nitro group

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The halogen atom in haloalkane is replaced by nitro group (-NO2) when it is treated with silver nitrite (AgNO2) and give nitroalkanes.

Substitution by nitro group

Substitution by nitro group

The bond between Ag-O is covalent and therefore, the nucleophilic attack here occurs through the lone pair on nitrogen: nitroalkanes (R-NO2) are therefore, formed.

Substitution by carboxyl group (formation of esters)

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When Haloalkanes are heated with an ethanolic solution of silver salt of a fatty acid these form esters.

Substitution by carboxyl group

Substitution by carboxyl group

Substitution by hydrosulphide group

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The formation of thioalcohols or thiols takes place when haloalkane is treated with-sodium or potassium hydrogen sulphide: the halogen atom gets replaced by hydrosulphide (-SH) group.

Substitution by hydrosulphide group

 

Substitution by hydrosulphide group

 

 

Substitution by mercaptide group

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On treatment with mercaptide ion (RS-) haloalkanes give thioethers.

Substitution by mercaptide group

 

Substitution by mercaptide group

 

Thioethers are also formed by heating the haloalkanes with sodium or potassium sulphide.

 

Substitution by  sodium sulphide

 

 

Substitution by alkynyl group (formation of alkynes)

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The formation of higher alkynes occurs when haloalkane is treated with sodium salt of alkynes (sodium alkynides): the halogen atom is replaced by alkyl group (-CC-).

Substitution by alkynyl group

The sodium alkynides needed for the above reaction are formed by the reaction of sodamide (or sodium in liquid NH3) with alkynes containing terminal triple bond.

reaction of sodamide with alkynes


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