Electrophile

In organic chemistry, an electrophile is an electron pair acceptor. Electrophiles are positively charged or neutral species having vacant orbitals that are attracted to an electron rich centre. It participates in a chemical reaction by accepting an electron pair in order to bond to a nucleophile. Because electrophiles accept electrons, they are Lewis acids (see acid-base reaction theories). Most electrophiles are positively charged, have an atom that carries a partial positive charge, or have an atom that does not have an octet of electrons. They appear to attract electrons as well and seem to behave as though they are partially empty. These partially empty substances thus require an electron rich center, and thus they are filled. Electrophiles can be observed as electron-sensitive or photo-sensitive. In organic chemistry, an electrophile is an electron pair acceptor. Electrophiles are positively charged or neutral species having vacant orbitals that are attracted to an electron rich centre. It participates in a chemical reaction by accepting an electron pair in order to bond to a nucleophile. Because electrophiles accept electrons, they are Lewis acids (see acid-base reaction theories). Most electrophiles are positively charged, have an atom that carries a partial positive charge, or have an atom that does not have an octet of electrons. They appear to attract electrons as well and seem to behave as though they are partially empty. These partially empty substances thus require an electron rich center, and thus they are filled. Electrophiles can be observed as electron-sensitive or photo-sensitive. The electrophiles are attacked by the most electron-populated part of one nucleophile. The electrophiles frequently seen in the organic syntheses are cations such as H+ and NO+, polarized neutral molecules such as HCl, alkyl halides, acyl halides, and carbonyl compounds, polarizable neutral molecules such as Cl2 and Br2, oxidizing agents such as organic peracids, chemical species that do not satisfy the octet rule such as carbenes and radicals, and some Lewis acids such as BH3 and DIBAL. These occur between alkenes and electrophiles, often halogens as in halogen addition reactions. Common reactions include use of bromine water to titrate against a sample to deduce the number of double bonds present. For example, ethene + bromine → 1,2-dibromoethane: This takes the form of 3 main steps shown below; This process is called AdE2 mechanism. Iodine (I2), chlorine (Cl2), sulfenyl ion (RS+), mercury cation (Hg2+), and dichlorocarbene (:CCl2) also react through similar pathways. The direct conversion of 1 to 3 will appear when the Br− is large excess in the reaction medium. A β-bromo carbenium ion intermediate may be predominant instead of 3 if the alkene has a cation-stabilizing substituent like phenyl group. There is an example of the isolation of the bromonium ion 2. Hydrogen halides such as hydrogen chloride (HCl) adds to alkenes to give alkyl halides in hydrohalogenation. For example, the reaction of HCl with ethylene furnishes chloroethane. The reaction proceeds with a cation intermediate, being different from the above halogen addition. An example is shown below: In this manner, the stereoselectivity of the product, that is, from which side Cl− will attack relies on the types of alkenes applied and conditions of the reaction. At least, which of the two carbon atoms will be attacked by H+ is usually decided by Markovnikov's rule. Thus, H+ attacks the carbon atom that carries fewer substituents so as the more stabilized carbocation (with the more stabilizing substituents) will form. This process is called A-SE2 mechanism. Hydrogen fluoride (HF) and hydrogen iodide (HI) react with alkenes in a similar manner, and Markovnikov-type products will be given. Hydrogen bromide (HBr) also takes this pathway, but sometimes a radical process competes and a mixture of isomers may form. In the case of dialkyl-substituted alkynes (e.g., 3-hexyne), the intermediate vinyl cation that would result from this process is highly unstable. In such cases, the simultaneous protonation (by HCl) and attack of the alkyne by the nucleophile (Cl−) is believed to take place. This process is known as the AdE3 mechanism. Because the simultaneous collision of three chemical species in a reactive orientation is improbable, the termolecular transition state is believed to be reached when the nucleophile attacks a reversibly-formed weak association of the alkyne and HCl. Such a mechanism is consistent with the predominantly anti addition of the hydrochlorination product and the termolecular rate law, Rate = k2. In support of the proposed alkyne-HCl association, a T-shaped complex of an alkyne and HCl has been characterized crystallographically.