Chemistry Elimination Reactions and Reactions with Metals

Topics Covered :

● Elimination Reactions
● Reaction with Metals
● Wurtz Reaction

Elimination reactions :

`=>` When a haloalkane with `color{red}(β)`-hydrogen atom is heated with alcoholic solution of potassium hydroxide, there is elimination of hydrogen atom from `color{red}(β)`-carbon and a halogen atom from the `color{red}(α)`-carbon atom.

● As a result, an alkene is formed as a product.

● Since `color{red}(β)`-hydrogen atom is involved in elimination, it is often called `color{red}(β)`-elimination. See fig.

`=>` If there is possibility of formation of more than one alkene due to the availability of more than one `color{red}(α)`-hydrogen atoms, usually one alkene is formed as the major product.

● Alexander Zaitsev (also pronounced as Saytzeff) in 1875 formulated a rule summarised as “In dehydrohalogenation reactions, the preferred product is that alkene which has the greater number of alkyl groups attached to the doubly bonded carbon atoms.”

● Thus, 2-bromopentane gives pent-2-ene as the major product.

`color{red}(undersettext{pent -2- ene (81 %) } (H_3C-CH_2-CH= CH- CH_3) overset{ overset(-) OH } ← undersettext(2- Bromopentane) ( H_3C - CH_2-CH_2- overset( overset(Br)(|))CH - underset(underset(H)(|))CH_2) overset{ overset(-)OH } → undersettext{Pent -1- ene (19 % ) } (H_3C- CH_2-CH_2-CH = CH_2))`
Q 3261245125

Explain Saytzeff rule .

Solution:

● “In dehydrohalogenation reactions, the preferred product is that alkene which has the greater number of alkyl groups attached to the doubly bonded carbon atoms.”

● Thus, 2-bromopentane gives pent-2-ene as the major product.

`undersettext{pent -2- ene (81 %) } (H_3C-CH_2-CH= CH- CH_3) overset{ overset(-) OH } ← undersettext(2- Bromopentane) ( H_3C - CH_2-CH_2- overset( overset(Br)(|))CH - underset(underset(H)(|))CH_2) overset{ overset(-)OH } → undersettext{Pent -1- ene (19 % ) } (H_3C- CH_2-CH_2-CH = CH_2)`

Elimination versus substitution :

`=>` A chemical reaction is the result of competition; it is a race that is won by the fastest runner.

`=>` A collection of molecules tend to do, by and large, what is easiest for them.

`=>` An alkyl halide with `color{red}(α)`-hydrogen atoms when reacted with a base or a nucleophile has two competing routes : substitution (`color{red}(S_N1)` and `color{red}(S_N2)`) and elimination.

● Which route will be taken up depends upon the nature of alkyl halide, strength and size of base/nucleophile and reaction conditions.

● Thus, a bulkier nucleophile will prefer to act as a base and abstracts a proton rather than approach a tetravalent carbon atom (steric reasons) and vice versa.

● Similarly, a primary alkyl halide will prefer a `color{red}(S_N2)` reaction, a secondary halide - `color{red}(S_N2)` or elimination depending upon the strength of base/nucleophile and a tertiary halide - `color{red}(S_N1)` or elimination depending upon the stability of carbocation or the more substituted alkene.

Reaction with metals :

`color{green}("Organometallic Compounds ")` : Most organic chlorides, bromides and iodides react with certain metals to give compounds containing carbon-metal bonds. Such compounds are known as organo-metallic compounds.

● An important class of organo-metallic compounds discovered by Victor Grignard in 1900 is alkyl magnesium halide, `color{red}(RMgX)`, referred as `color{green}("Grignard Reagents")`.

● These reagents are obtained by the reaction of haloalkanes with magnesium metal in dry ether.

`color{red}(CH_3CH_2 Br + Mg oversettext(dry ether )→ undersettext(Grignard reagent )(CH_3CH_2 MgBr))`

`=>` In the Grignard reagent, the carbon-magnesium bond is covalent but highly polar, with carbon pulling electrons from electropositive magnesium; the magnesium halogen bond is essentially ionic.

`color{red}(overset(delta-)R - overset(delta+)Mg overset(delta-)X)`

`=>` Grignard reagents are highly reactive and react with any source of proton to give hydrocarbons.

● Even water, alcohols, amines are sufficiently acidic to convert them to corresponding hydrocarbons.

`color{red}(RMgX +H_2O → RH + Mg (OH) X)`

`=>` It is therefore necessary to avoid even traces of moisture from a Grignard reagent.

`=>` On the other hand, this could be considered as one of the methods for converting halides to hydrocarbons.



Q 3271245126

What are Grignard reagents .

Solution:

●Grignard Reagents are an important class of organo-metallic compounds (Most organic chlorides, bromides and iodides react with certain metals to give compounds containing carbon-metal bonds. Such compounds are known as organo-metallic compounds) discovered by Victor Grignard in 1900 is alkyl magnesium halide `RMgX`,
● These reagents are obtained by the reaction of haloalkanes with magnesium metal in dry ether.

`CH_3CH_2 Br + Mg oversettext(dry ether )→ undersettext(Grignard reagent )(CH_3CH_2 MgBr)`

● In the Grignard reagent, the carbon-magnesium bond is covalent but highly polar, with carbon pulling electrons from electropositive magnesium; the magnesium halogen bond is essentially ionic.

`overset(delta-)R - overset(delta+)Mg overset(delta-)X`

● Grignard reagents are highly reactive and react with any source of proton to give hydrocarbons.

● Even water, alcohols, amines are sufficiently acidic to convert them to corresponding hydrocarbons.

`RMgX +H_2O → RH + Mg (OH) X`

`=>` It is therefore necessary to avoid even traces of moisture from a Grignard reagent.

Wurtz reaction :

Alkyl halides react with sodium in dry ether to give hydrocarbons containing double the number of carbon atoms present in the halide. This reaction is known as Wurtz reaction.

`color{red}(2RX + Na → R R +NaX)`


 
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