CHAPTER 8: ALKYL HALIDES

Learning objectives
Name of alkyl halides State the alkyl halides Explain the reaction of alkyl halides

Learning outcomes
Students will be able to
Name the alkyl halides Understand the synthesis of alkyl halides Addition of HX to alkenes Chlorination of alkenes Reaction of alcohols with HCl, SOCl2 and PBr3. Understand the reaction of alkyl halides Grignard reagents Nucleophilic substitution reactions Eliminations

Alkyl halide: compound with a halogen atom bonded to a saturated carbon atom

Organohalides: compounds that contain one or more halogen atoms

Naming Alkyl Halides

Alkyl halides can be named by following three steps
1. 2. Find the longest chain, and name it as the parent Number the carbons of the parent chain beginning at the end nearer the first substituent, whether alkyl or halo

3. Write the name. 4. List all substituents in alphabetical order and use one of the prefixes di, tri, tetra and so on

Functional group is an alkane, therefore suffix = -ane The longest continuous chain is C3 therefore root = prop The substituent is a chlorine, therefore prefix = chloro

Preparing Alkyl Halides

Reactions of HX and X2 with alkenes in electrophilic addition reactions The hydrogen halides HCl, HBr, and HI react with alkenes by a polar mechanism to give the product of Markovnikov addition When alkene reacts with bromine and chlorine to give 1,2dihalogenated products

Preparing Alkyl Halides

Preparing alkyl halides from alcohols Many common methods have been developed to transform alcohols into alkyl halides Treat the alcohol with HCl, HBr, or HI Simplest method The reaction works best with tertiary alcohols, R3COH Primary and secondary alcohols react slowly and at higher reaction temperatures

Preparing Alkyl Halides

The reaction of HX with a tertiary alcohol is so rapid that it is often carried out simply by bubbling the pure HCl or HBr gas into a cold ether solution of the alcohol Conversion of 1-methylcyclohexanol into 1-chloro-1methylcyclohexane

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Preparing Alkyl Halides

Primary and secondary alcohols are best converted into alkyl halides by treatment with either thionyl chloride (SOCl2) or phosphorus tribromide (PBr3) These reactions normally take place in high yield

phosphorous Acid

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Reactions of Alkyl Halides: Grignard Reagents

Grignard Reagents: Alkylmagnesium halide, RMgX, produced from reaction of alkyl halides, RX, with magnesium metal in ether solvent The products are examples of organometallic compounds because they contain a carbon-metal bond

Halogens

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Reactions of Alkyl Halides: Grignard Reagents

The Grignard reagents are synthesized from the corresponding organobromide with magnesium

Organic halide

Grignard Reagent

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Discovery of the Nucleophilic- Substitution Reaction

Each step involves the substitution of one nucleophile (chloride ion, Cl-, or hydroxide ion, HO-) by another

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Characteristics of the SN2 Reaction

The nucleophile reacts with a substrate (R-X) and substitutes for a leaving group (X:-) to yield the product (R-Nu) Any species either neutral or negatively charged that has an unshared pair of electrons If negatively charged, the product is neutral

If neutral, the product is positively charged

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Characteristics of the SN2

Reaction

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The SN2 Reaction

Essential features of the SN2 Reaction Takes place in a single step without intermediates Incoming nucleophile reacts with the alkyl halide from a direction opposite the group that is displaced (the leaving group)

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The SN2 Reaction

[a] rate of reactions In chemical reaction, there is a direct relationship between the rate at which the reaction occurs and the concentrations of the reactants

At a concentration of reactants, the substitution occurs at a certain rate If concentration of OH- doubles, the frequency of collision between the two reactants doubles and we find that the reaction rate also doubles. If concentration of CH3Br doubles, the reaction rate again doubles Thus, the 2 in SN2 is said to be bimolecular because the rate of the reaction depends on the concentrations of two substances.

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The SN2 Reaction

As the incoming nucleophile attacks the substrate and begins pushing out the leaving group on the opposite side

In the transition state, the new Nu-C bond is partially forming and old C-X bond is partially breaking The negative charge is shared by both the incoming nucleophile and outgoing leaving group

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 Steric effects arise from the fact that each atom within a molecule occupies a certain amount of space.
Steric hindrance occurs when the size of groups within a molecule prevents chemical reactions that are observed in related smaller molecules. Although steric hindrance is sometimes a problem (it prevents the SN2 reactions with tertiary substrates from taking place).
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Characteristics of the SN2 Reaction

The Substrate: Steric Effects in the SN2 Reaction
The ease with which a nucleophile can approach a substrate to carry out an SN2 reaction depends on steric accessibility to the halide-bearing carbon. Bulky substances, in which the halide-bearing carbon atom is difficult to approach, react much more slowly than those in which the carbon is more accessible.

Bromomethane is readily accessible, resulting in a fast SN2 reaction

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Characteristics of the SN2 Reaction

Alkyl branching next to the leaving group slows the reaction [secondary halides]. Halts the reaction for tertiary halides This lack of reactivity is due to the steric hindrance.

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Characteristics of the SN2 Reaction

SN2 reactions occur only at relatively unhindered sites Relative reactivities for some different substrates are as follows:

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Characteristics of the SN2 Reaction

Vinylic halides (R2C=CRX) and aryl halides are unreactive toward SN2 reaction

This is due to steric hindrance

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Characteristics of the SN2 Reaction

The Leaving Group The best leaving groups are those that give the most stable anions (anions of strong acids) A halide ion (I- , Br- and Cl ion) is the most common leaving group. while strong bases such as OH and NH2 make poor leaving groups

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Elimination Reaction
When a nucleophile reacts with an alkyl halide two kinds of reactions can occur Substitution where a nucleophile can react at carbon to substitute for the halide

Elimination where a nucleophile can react at a neighboring hydrogen to cause elimination of HX

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Elimination Reaction
Elimination reactions almost always give mixtures of alkene products . Zaitsevs rule In the elimination of HX from an alkyl halide, the more highly substituted alkene product predominates Used to predict major products The alkene with the larger number of alkyl substituents on the double bond

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Elimination Reaction
The second complication is that eliminations can take place by several different mechanisms E1, E2, and E1cB reactions Differ in the timing of C-H and C-H bond breaking All three mechanisms occur in laboratory E1cB predominates in biological pathways

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Elimination Reaction

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Elimination Reaction

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The E2 Reaction

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Checking outcomes
Name the alkyl halides

Understand the synthesis of alkyl halides

Addition of HX to alkenes Chlorination of alkenes Reaction of alcohols with HCl, SOCl2 and PBr3.

Understand the reaction of alkyl halides

Grignard reagents Nucleophilic substitution reactions Eliminations
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Thank you

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