Question

In the presence of light, chlorine can substitute for one (or more) of the hydrogens in an alkane. For the following reactions, draw the possible monochlorination products. a. 2,2 -dimethylpropane \(+\mathrm{Cl}_{2} \stackrel{\mathrm{hv}}{\longrightarrow}\) b. 1,3 -dimethylcyclobutane \(+\mathrm{Cl}_{2} \stackrel{\mathrm{hv}}{\longrightarrow}\) c. 2,3 -dimethylbutane \(+\mathrm{Cl}_{2} \stackrel{\mathrm{hv}}{\longrightarrow}\)

Short answer

The possible monochlorination products are as follows: a. 2,2-dimethylpropane: - \( CH_{3}C(CH_{2}Cl)(CH_{3})_{2} \) - \( CH_{3}C(Cl)(CH_{3})_{3} \) b. 1,3-dimethylcyclobutane: - \( 1-Chloro-1,3-dimethylcyclobutane \) - \( 2-Chloro-1,3-dimethylcyclobutane \) - \( 3-Chloro-1,3-dimethylcyclobutane \) c. 2,3-dimethylbutane: - \( 1-Chloro-2,3-dimethylbutane \) - \( 2-Chloro-2,3-dimethylbutane \) and \( 4-Chloro-2,3-dimethylbutane \) (equivalent positions) - \( 3-Chloro-2,3-dimethylbutane \)

Step-by-step solution

Identify the unique positions for chlorine substitution

Start by drawing the structure of the given alkane, and identify the unique positions where the chlorine can substitute for a hydrogen atom. a. For 2,2-dimethylpropane, there are two unique positions: one on a methyl group (1) and one on the central carbon (2). b. For 1,3-dimethylcyclobutane, there are three unique positions: one on a methyl group (1), one on an unsubstituted carbon directly connected to a methyl group (2), and one on a carbon directly opposite to a methyl group (3). c. For 2,3-dimethylbutane, there are three unique positions along the linear carbon chain: one on a primary carbon atom (1), one on a secondary carbon atom (two possible locations, but they are equivalent, 2), and one on a tertiary carbon atom (3).

Draw the monochlorination products

Replace one hydrogen atom at each unique position with a chlorine atom and draw the new product. Make sure to include the stereochemistry if relevant. a. Monochlorination products for 2,2-dimethylpropane: - At position 1: \( CH_{3}C(CH_{2}Cl)(CH_{3})_{2} \) - At position 2: \( CH_{3}C(Cl)(CH_{3})_{3} \) b. Monochlorination products for 1,3-dimethylcyclobutane: - At position 1: \( 1-Chloro-1,3-dimethylcyclobutane \) - At position 2: \( 2-Chloro-1,3-dimethylcyclobutane \) - At position 3: \( 3-Chloro-1,3-dimethylcyclobutane \) c. Monochlorination products for 2,3-dimethylbutane: - At position 1: \( 1-Chloro-2,3-dimethylbutane \) - At position 2: \( 2-Chloro-2,3-dimethylbutane \) and \( 4-Chloro-2,3-dimethylbutane \) (these are equivalent positions) - At position 3: \( 3-Chloro-2,3-dimethylbutane \) Remember that these are the possible products of monochlorination; all of these products may be formed simultaneously in varying amounts.

Key concepts

Alkane Substitution Reactions

Substitution reactions are pivotal in organic chemistry, forming the backbone for more complex transformations. In the context of alkanes, these reactions involve the replacement of a hydrogen atom with another atom or group, typically a halogen like chlorine. The simplistic beauty of alkane substitution reactions lies in their selectivity—certain positions on the alkane's carbon chain are more reactive, following the principles of chemical reactivity.

Consider regular butane as an analogy to a blank canvas. When chlorine comes into play, each hydrogen atom is a candidate for substitution, but not all hydrogens are equal. Primary, secondary, and tertiary hydrogens possess varying degrees of reactivity due to differences in carbon atom hybridization and surrounding electron density. For a vivid understanding, think of a game where each type of hydrogen represents a different level of difficulty. The rules are simple, as chlorine prefers to replace the 'players' or hydrogen atoms that are easier to access, often resulting in multiple possible substitution products.

• Primary hydrogens, linked to one carbon, are usually the least reactive.
• Secondary hydrogens, connected to two carbons, are of moderate reactivity.
• Tertiary hydrogens, which are bound to three carbons, are the most reactive and favored in substitution.

Understanding these reactivity patterns helps explain why monochlorination of an alkane like 2,2-dimethylpropane might yield two different chloropropanes—one from substitution at a methyl group and another from the central carbon, while an alkane like 2,3-dimethylbutane may provide more diverse outcomes due to its structure offering a variety of reactive sites.

Chlorination Mechanism

The mechanism of chlorination unfurls as a dance of electrons and the creating and breaking of bonds. Envision this as a neat choreography where light (hv) triggers the movement, energizing chlorine molecules to split into two highly reactive chlorine atoms, a process known as homolytic cleavage. These chlorine atoms, now individual reactive species or 'free radicals', seek out alkanes to bond with.

In the chlorination mechanism, there are distinct stages that can be likened to the acts of a play:

Initiation

In the initiation step, light energy initiates the breakage of the diatomic chlorine molecule into two chlorine radicals. Think of it as the starting gun of a race, setting everything into motion.

Propagation

The propagation stage consists of two subplots. First, a chlorine radical abstracts a hydrogen atom from the alkane, creating an alkyl radical and hydrochloric acid. Following this, the alkyl radical reacts with another diatomic chlorine molecule to form a monochlorinated alkane and release another chlorine radical. This newly freed chlorine radical can react with more alkane molecules, perpetuating a chain reaction.

Termination

The final act, termination, occurs when two radicals meet and form a stable bond, halting the chain reaction. This could involve two alkyl radicals coming together or an alkyl radical bonding with a chlorine radical.

The beauty of this mechanism is in its precision—the chlorination reaction selectively replaces a hydrogen atom with a chlorine atom creating various possible products, where the most stable radicals—and thus, the most likely products—are those that form from the tertiary and secondary hydrogens due to their lower bond dissociation energies.

Organic Chemistry Reaction Pathways

The exploration of a reaction's path, known as its mechanism, offers a comprehensive look into the stepwise journey from reactants to products. In organic chemistry, understanding these reaction pathways is akin to reading a map that guides us through a landscape of molecular transformations.

A typical alkane chlorination pathway is fascinating not just for its end products, but for the sequence of steps that unfold. Such pathways reveal the underlying logic of organic chemistry—the more stable an intermediate, the more favored its formation. This logic helps us predict the outcome of reactions, as alkanes with higher degrees of substitution often create more stable reactive intermediates, and thus, preferred chlorination products.

In the case of exercises like the monochlorination of alkanes, the student must exercise their detective skills. By considering the structure of the alkane, one can envision where the chlorine atom is most likely to insert itself. The pathway logic suggests multiple scenarios based on the alkane's unique structure—each promising a slightly different tale in the grand narrative of organic synthesis. For example:

• Less substituted alkanes tend to give a variety of monochlorination products due to the presence of multiple similar positions for chlorine substitution.
• Alkanes with more complex geometry may form products with different stereochemistry, adding another layer of intricacy to the puzzle.

By appreciating these pathways and the stability of intermediates involved, students can predict the major and minor products of reactions, and understand the elegance and predictability of organic chemistry.