Q48 E - Organic Chemistry (Mcmurry)

Question

21-48 Predict the product, if any, of the reaction between propanoyl chloride and the following reagents:

1. $\mathrm{Li}\left(\mathrm{Ph}\right)\mathrm{Cu} \mathrm{in} et\mathrm{her}$
2.   $\mathit{L}\mathit{i}\mathit{A}\mathit{l}{\mathit{H}}_4,\mathit{ }\mathit{t}\mathit{h}\mathit{e}\mathit{n}\mathit{ }{\mathit{H}}_3{\mathit{O}}^{+}$
3.   $\mathit{C}{\mathit{H}}_3\mathit{M}\mathit{g}\mathit{B}\mathit{r},\mathit{ }\mathit{t}\mathit{h}\mathit{e}\mathit{n}\mathit{ }{\mathit{H}}_3{\mathit{O}}^{+}$
4.  ${\mathit{H}}_3{\mathit{O}}^{+}$
5. Cyclohexanol
6. Aniline
7. $\mathit{C}{\mathit{H}}_3\mathit{C}{\mathit{O}}_2^{-}\mathit{N}{\mathit{a}}^{+}$

Step-by-Step Solution

Answer

1. The reaction between propanoyl chloride and the following reagents, is a process, although not a Grignard reaction, uses an organocopper reagent to directly convert an acyl chloride to a ketone, which is impossible in a typical Grignard reaction due to the extreme reactivity of ketones. As a result, the value is created artificially.
2. $LiAe{H}_4$ to reduce an acyl chloride provides a primary i alcohol.
3. An acid chloride is reduced to a $3^o$ alcohol in the Grignard process.
4. An acyl chloride is converted to an ester via the overall acidic catalepsies.
5. The reaction demonstrated the nucleophilic acyl substitution conversion of an acid chloride to an ester.
6. The letter is transformed to an amide by nucleophilic acyl substitution in an aminolysis of an acid chloride.
7. A nucleophilic acyl substitution process has successfully transformed an acyl chloride into an acid anhydride.

Introduction to the Concept

A chemical compound's structural formula is a graphic depiction of the molecular structure (derived by structural chemistry methods) that shows how the atoms might be organised in real three-dimensional space.

Prediction of product of reaction between propanoyl chloride and the reagent L i ( P h ) C u   i n   e t h e r

a)

The diorganocopper anion performs a nucleophilic acyl substitution on the acyl chloride to produce an acyl diorganocopper intermediate, which is followed by the loss of R' Cu and production of the ketone.

The reaction is usually carried out in ether solution at -78°C, with excellent yields.

Only acid chloride carboxylic acids react with lithium diorganocopper reagents; esters, acid anhydrides, and amides do not.

Though not a Grignard reaction, this reaction using an organocopper reagent transforms an acyl chloride to a ketone directly, which is not possible in a regular Grignard reaction due to the strong reactivity of ketones. As a result, the value is synthetic.

Prediction of product of reaction between propanoyl chloride and the reagent L i A l H 4 , t h e n H 3 O +

b)

Acid chloride is reduced by lithium aluminium hydride ${\mathrm{LiAlH}}_4$ ,to produce primary i alcohols.

However, because the parent carboxylic acids are often more easily available and can be reduced by ${\mathrm{LiAlH}}_4$ to generate alcohols, the process is of little practical relevance.

A hydride ion $\left(H{:}^{-},\right)$ attaches to the carboxyl group, generating a tetrahedral intermediate that expels ce in a classic nucleophilic acyl substitution process. The net outcome is a replacement of-ce by -H to produce an aldehyde, which is then fumer reduced by ${\mathrm{LiAeH}}_4$ to create primary alcohol in a second step.

Prediction of the product of the reaction between propanoyl chloride and the reagent C H 3 M g B r ,   t h e n   H 3 O +

c)

The methyl propyl ketone is produced in the first step of the Nucleophilic acyl substitutions, but it is not isolated since ketones are much more inerasable to nucleophiles than acid chlorides. As a result, the intermediate ketone attaches an anomer molecule of the Grignard reagent to the letter, which then undergoes hydrolysis to the reduced 3°, tertiary alcohol. 2-methyl-butan-2Ol.

Prediction of product of reaction between propanoyl chloride and the reagent H 3 O +

d)

The product is formed by the removal of $c{e}^{-}$ and lin of $H^{+}$ from the tetrahedral intermediate.

The reaction is finally catalepsies, acidic, and involved because $H^{+}$ is replenished at the end of the mechanism.

 

To help with the catalepsies at the start, a few drops of $HCl$ acid  could be added.

Prediction of product of reaction between propanoyl chloride and the reagent Cyclohexanol

e)

The reaction is a Nucleophilic acyl substitution at an acyl carbon, and the mechanism is briefly shown below:

The nucleophilic acyl substitution conversion of an acid chloride to an ester was demonstrated in this reaction.

Prediction of product of reaction between propanoyl chloride and the reagent Aniline

f)

Aniline, the animatic amine, causes Ammonolysis via a nucleophilic acyl substitution reaction at the acyl carbon of propanoyl chloride, the acid chloride, in the provided mechanism. The mechanism of the reaction is as follows:

Because $HCl$ is produced during the reaction, two equivalents of the amine, aniline, are required. To generate an ammonium chloride salt, one equivalent reacts with the acid chloride while the other equivalent reacts with the $HCl$ by-product.

Prediction of product of reaction between propanoyl chloride and the reagent

g)

PTO-> is the reaction's mechanistic symbol.

Step 1: The carboxylate anion attacks the acyl carbonyl carbon nucleophilically.

Step 2: Len of $c{e}^{-}$ in the product's elimination step (quick step).