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Grignard reagents, such as \(\mathrm{CH}_{3} \mathrm{MgI}\), often add to the triple bond of nitriles, \(\mathrm{RC} \equiv \mathrm{N}\), to give adducts that, on hydrolysis, yield ketones, \(\mathrm{RCOCH}_{3}\). Show the possible steps involved.

Short Answer

Expert verified
Grignard reagent adds to nitrile, forms imine salt, which hydrolyzes to ketone \(\mathrm{RCOCH}_{3}\).

Step by step solution

01

Formation of the Grignard Reagent

The Grignard reagent, \(\mathrm{CH}_{3}\mathrm{MgI}\), is prepared by reacting methyl iodide (\(\mathrm{CH}_3\mathrm{I}\)) with magnesium (\(\mathrm{Mg}\)) in an appropriate solvent such as diethyl ether. This results in the formation of the Grignard reagent, \(\mathrm{CH}_{3}\mathrm{MgI}\), which is a highly reactive organometallic compound.
02

Nucleophilic Addition to the Nitrile

The nucleophilic carbon atom in the Grignard reagent \(\mathrm{CH}_{3}\mathrm{MgI}\) attacks the electrophilic carbon atom of the nitrile \(\mathrm{RC} \equiv \mathrm{N}\). This reaction forms an intermediate imine salt, represented as \(\mathrm{RC(MgI)=NMgI}\).
03

Hydrolysis of the Imine Salt

The imine salt \(\mathrm{RC(MgI)=NMgI}\) is hydrolyzed in an aqueous acidic solution. During this step, water reacts with the imine salt to form the ketone \(\mathrm{RCOCH}_{3}\) by cleaving the \(\mathrm{C-N}\) bond and forming a carbonyl group \(\mathrm{C=O}\).
04

Final Product

The final product obtained from the hydrolysis is a ketone, specifically \(\mathrm{RCOCH}_{3}\), where the original alkyl group \(\mathrm{R}\) from the nitrile is retained. This ketone is formed as a result of the Grignard addition and subsequent hydrolysis.

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Organometallic Chemistry
In organometallic chemistry, which merges organic and inorganic chemistry, a key role is played by compounds comprising bonds between carbon and metal atoms. These compounds are significant because of their reactivity and their ability to act as intermediates in various chemical reactions. Grignard reagents, named after Victor Grignard, are an important class of such organometallic compounds. They are formed by the reaction of alkyl or aryl halides with magnesium in a solvent like diethyl ether.
These reagents are denoted as RMgX, where R is a hydrocarbon group and X is a halide. The Grignard reagent developed from methyl iodide, ext(CH}_3 ext{I} , and magnesium is a classic example of how such organometallic compounds are prepared. Due to the polar nature of the carbon-metal bond, Grignard reagents act as nucleophiles, enabling a variety of valuable reactions, including nucleophilic additions to form new carbon-carbon bonds.
Nucleophilic Addition
Nucleophilic addition is a fundamental process in organic chemistry where nucleophiles bind to positively charged or electron-deficient sites in molecules. The Grignard reaction exemplifies nucleophilic addition, where the nucleophilic carbon in the organometallic compound attacks an electrophilic carbon.
In the given exercise, the Grignard reagent ext{CH}_3 ext{MgI} acts as a nucleophile when it encounters the nitrile group ext{RC} ext{=} ext{N} . The electron-rich carbon forms a bond with the carbon of the nitrile, which is electron-deficient. This initial attack results in the formation of an intermediate, called an imine salt, noted for having a ext{C=N} bond.
This step is crucial as it sets the stage for subsequent hydrolysis that transforms this imine into a more stable ketone.
Hydrolysis of Nitrile
Hydrolysis of nitriles is a key step that often follows the initial attachment of a Grignard reagent. In this reaction, the intermediate compound formed after nucleophilic addition, specifically the imine salt, undergoes hydrolysis. Hydrolysis involves the reaction of water, or an acidic aqueous solution, with this imine salt, leading to the breaking of the bond between carbon and nitrogen.
During this process, the nitrile group undergoes conversion into a carbonyl group ( ext{C=O}). This step is critical in the production of more usable organic compounds from nitriles, ultimately resulting in the formation of ketones, such as ext{RCOCH}_3 , as illustrated in the exercise. The ability to transform a nitrile into a ketone via hydrolysis expands the versatility of nitrile chemistry, offering pathways to numerous organic products.
Ketone Formation
Ketone formation in this context serves as the ultimate goal of the Grignard reaction with nitriles. Once the imine salt undergoes hydrolysis, the ketone is formed. Ketones are characterized by their carbonyl group ( ext{C=O}) bonded to two hydrocarbon groups, distinguishing them from other carbonyl-containing compounds like aldehydes.
Ketones are valuable in both academic and industrial chemistry due to their roles in further chemical synthesis and as solvents and intermediates in the manufacture of various products.
Through the step-by-step transformation from nitrile to ketone using a Grignard reagent, this exercise demonstrates how precise chemical manipulations lead to specific and necessary compounds in organic chemistry. Understanding these transformations allows chemists to selectively synthesize desired molecules with wide applications.

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Most popular questions from this chapter

Compound X, of formula \(\mathrm{C}_{3} \mathrm{H}_{5} \mathrm{Br}_{3}\), with methyllithium formed bromocyclopropane and 3-bromopropene. The NMR spectrum of \(\mathrm{X}\) showed a one-proton triplet at \(5.9 \mathrm{ppm}\), a two-proton triplet at \(3.55 \mathrm{ppm}\), and a complex resonance centered at \(2.5\) ppm downfield from TMS. What is the structure of \(X\) ? Account for the products observed in its reaction with methyllithium.

From the nature of the carbon-metal bonds in organometallic compounds, predict the products of the following reactions. Give your reasoning. a. \(\mathrm{CH}_{3} \mathrm{MgCl}+\mathrm{ICl}\) b. \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{Li}+\mathrm{CH}_{3} \mathrm{OH}\) c. \(\mathrm{CH}_{3} \mathrm{Li}+\mathrm{HC} \equiv \mathrm{CH}\) d. \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{Li}+\mathrm{CuI}\)

The rate of addition of dimethylmagnesium to excess diphenylmethanone (benzophenone) in diethyl ether initially is cleanly second order, that is, first order in ketone and first order in \(\left(\mathrm{CH}_{3}\right)_{2} \mathrm{Mg}\). As the reaction proceeds, the rate no longer follows a strictly second-order rate overall. Suggest how the apparent specific rate could change as the reaction proceeds.

Both 2,4-D and 2,4,5-T are herbicides that have been used for weed control and as defoliating agents in jungle warfare. Apart from the arguments for or against the use of chemicals for such purposes, there have been reports of serious dermatitis among the industrial workers who produce these substances. The cause finally was traced to \(2,3,7,8\) -tetrachlorodibenzo-p-dioxin (TCDD), which is produced as an impurity in the manufacture of 2,4,5-T. This substance (TCDD) is very toxic. In addition to the dermatitis in produces, it is a potent teratogen (induces birth abnormalities). The lethal does is less than \(10^{-6} \mathrm{~g}\) for guinea pigs. Its presence in 2,4,5-T can be eliminated, but the conditions by which it is formed are pertinent to our present discussion. The production of 2,4,5-T involves the substitution of one chlorine of 1,2,4,5-tetrachlorobenzene with hydroxide ion to give 12. This is followed by a second displacement reaction, this time on chloroethanoate by the sodium salt of 12 : If the temperature of the first step exceeds \(160^{\circ}\), then two molecules of 12 react in a double nucleophilic displacement to give TCDD. a. Write reasonable mechanisms for the steps by which two molecules of 12 are converted to TCDD. b. Would you expect TCDD to be formed in the preparation of 2,4-D from 1,2,4-trichlorobenzene? Explain.

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