Cyanoethylation

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Cyanoethylation is a process for the attachment of CH2CH2CN group to another organic substrate. The method is used in the synthesis of organic compounds. [1]

Cyanoethylation entails addition of protic nucleophiles to acrylonitrile. Typical protic nucleophiles are alcohols, thiols, and amines. Two new bonds form: C-H and C-X (X = carbon, nitrogen, sulfur, phosphorus, etc):

The β-carbon atom that is furthest from the nitrile group is positively polarized and therefore binds the heteroatom on the nucleophile. Acrylonitrile is a Michael acceptor. [2] The reaction is normally catalyzed by a base. [3]

Tris(cyanoethyl)phosphine is produced by the cyanoethylation of phosphine. P(C2CN)3.svg
Tris(cyanoethyl)phosphine is produced by the cyanoethylation of phosphine.

Cyanethylation is used to prepared numerous commercial chemicals. Detailed laboratory procedures are available for several variants of this reaction.

An alternative method for cyanoethylation entails alkylation of the substrate with 3-chloropropionitrile.

De-cyanoethylation

Cyanoethyl is a protecting group. It is removed by treatment with base:

RNuCH2CH2CN + OH → RNu + CH2=CHCN + H2O

This methodology is popular in the synthesis of oligonucleotides. [10]

Related Research Articles

Acrylonitrile is an organic compound with the formula CH2CHCN and the structure H2C=CH−C≡N. It is a colorless, volatile liquid although commercial samples can be yellow due to impurities. It has a pungent odor of garlic or onions. In terms of its molecular structure, it consists of a vinyl group linked to a nitrile. It is an important monomer for the manufacture of useful plastics such as polyacrylonitrile. It is reactive and toxic at low doses. Acrylonitrile was first synthesized by the French chemist Charles Moureu (1863–1929) in 1893.

<span class="mw-page-title-main">Imine</span> Organic compound or functional group containing a C=N bond

In organic chemistry, an imine is a functional group or organic compound containing a carbon–nitrogen double bond. The nitrogen atom can be attached to a hydrogen or an organic group (R). The carbon atom has two additional single bonds. Imines are common in synthetic and naturally occurring compounds and they participate in many reactions.

In organic chemistry, an acyl chloride is an organic compound with the functional group −C(=O)Cl. Their formula is usually written R−COCl, where R is a side chain. They are reactive derivatives of carboxylic acids. A specific example of an acyl chloride is acetyl chloride, CH3COCl. Acyl chlorides are the most important subset of acyl halides.

<span class="mw-page-title-main">Acyl halide</span> Oxoacid compound with an –OH group replaced by a halogen

In organic chemistry, an acyl halide is a chemical compound derived from an oxoacid by replacing a hydroxyl group with a halide group.

The Hofmann rearrangement is the organic reaction of a primary amide to a primary amine with one fewer carbon atom. The reaction involves oxidation of the nitrogen followed by rearrangement of the carbonyl and nitrogen to give an isocyanate intermediate. The reaction can form a wide range of products, including alkyl and aryl amines.

<span class="mw-page-title-main">Trimethylaluminium</span> Chemical compound

Trimethylaluminium is one of the simplest examples of an organoaluminium compound. Despite its name it has the formula Al2(CH3)6 (abbreviated as Al2Me6 or TMA), as it exists as a dimer. This colorless liquid is pyrophoric. It is an industrially important compound, closely related to triethylaluminium.

In organic chemistry, the Mannich reaction is a three-component organic reaction that involves the amino alkylation of an acidic proton next to a carbonyl functional group by formaldehyde and a primary or secondary amine or ammonia. The final product is a β-amino-carbonyl compound also known as a Mannich base. Reactions between aldimines and α-methylene carbonyls are also considered Mannich reactions because these imines form between amines and aldehydes. The reaction is named after Carl Mannich.

The Ullmann condensation or Ullmann-type reaction is the copper-promoted conversion of aryl halides to aryl ethers, aryl thioethers, aryl nitriles, and aryl amines. These reactions are examples of cross-coupling reactions.

<span class="mw-page-title-main">Phenyllithium</span> Chemical compound

Phenyllithium or lithobenzene is an organometallic agent with the empirical formula C6H5Li. It is most commonly used as a metalating agent in organic syntheses and a substitute for Grignard reagents for introducing phenyl groups in organic syntheses. Crystalline phenyllithium is colorless; however, solutions of phenyllithium are various shades of brown or red depending on the solvent used and the impurities present in the solute.

<span class="mw-page-title-main">Trimethylsilyl chloride</span> Chemical compound

Trimethylsilyl chloride, also known as chlorotrimethylsilane is an organosilicon compound (silyl halide), with the formula (CH3)3SiCl, often abbreviated Me3SiCl or TMSCl. It is a colourless volatile liquid that is stable in the absence of water. It is widely used in organic chemistry.

<span class="mw-page-title-main">Dakin oxidation</span>

The Dakin oxidation is an organic redox reaction in which an ortho- or para-hydroxylated phenyl aldehyde or ketone reacts with hydrogen peroxide in base to form a benzenediol and a carboxylate. Overall, the carbonyl group is oxidised, whereas the H2O2 is reduced.

In chemistry, dehydrohalogenation is an elimination reaction which removes a hydrogen halide from a substrate. The reaction is usually associated with the synthesis of alkenes, but it has wider applications.

Pivalic acid, also known as neovaleric acid, is a carboxylic acid with a molecular formula of (CH3)3CCO2H. This colourless, odiferous organic compound is solid at room temperature. A common abbreviation for the pivalyl or pivaloyl group (t-BuC(O)) is Piv and for pivalic acid (t-BuC(O)OH) is PivOH. It is an isomer of valeric acid, the other two isomers of it are 2-Methylbutanoic acid and 3-Methylbutanoic acid.

Organophosphines are organophosphorus compounds with the formula PRnH3−n, where R is an organic substituent. These compounds can be classified according to the value of n: primary phosphines (n = 1), secondary phosphines (n = 2), tertiary phosphines (n = 3). All adopt pyramidal structures. Organophosphines are generally colorless, lipophilic liquids or solids. The parent of the organophosphines is phosphine (PH3).

<span class="mw-page-title-main">Benzyl cyanide</span> Chemical compound

Benzyl cyanide (abbreviated BnCN) is an organic compound with the chemical formula C6H5CH2CN. This colorless oily aromatic liquid is an important precursor to numerous compounds in organic chemistry.

Phenylphosphine is an organophosphorus compound with the chemical formula C6H5PH2. It is the phosphorus analog of aniline. Like other primary phosphines, phenylphosphine has an intense penetrating odor and is highly oxidizable. It is mainly used as a precursor to other organophosphorus compounds. It can function as a ligand in coordination chemistry.

In nitrile reduction a nitrile is reduced to either an amine or an aldehyde with a suitable chemical reagent.

<span class="mw-page-title-main">Diethylphosphite</span> Chemical compound

Diethylphosphite is the organophosphorus compound with the formula (C2H5O)2P(O)H. It is a popular reagent for generating other organophosphorus compounds, exploiting the high reactivity of the P-H bond. Diethylphosphite is a colorless liquid. The molecule is tetrahedral.

in organic chemistry, vinylation is the process of attaching a vinyl group to a substrate. Many organic compounds contain vinyl groups, so the process has attracted significant interest, especially since the reaction scope includes substituted vinyl groups. The reactions can be classified according to the source of the vinyl group.

4-Chlorobutyronitrile is the organic compound with the formula ClCH2CH2CH2CN. With both chloro and cyano functional groups, it is a bifunctional molecule. It is a colorless liquid.

References

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