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Outline efficient syntheses of each of the following alkynes from acetylene and any necessary organic or inorganic reagents: (a) 1-Heptyne (b) 2-Heptyne (c) 3-Heptyne

Short Answer

Expert verified
1-Heptyne: Acetylene + 1-bromohexane. 2-Heptyne: Acetylene + 1-bromo-3-methylbutane, partial hydrogenation. 3-Heptyne: Acetylene + 1-bromo-2-pentene, reorganization.

Step by step solution

01

Understanding Acetylene Derivation

Acetylene, with the formula \(C_2H_2\), is a basic alkyne that can be used to synthesize longer carbon chains. By using appropriate reagents, we can elongate this molecule to form various heptyne isomers.
02

Synthesis of 1-Heptyne

For 1-Heptyne (鈭扖鈮鈭扖_5H_{11}), we need to create a terminal alkyne with a straight chain. First, react acetylene with sodamide to form the acetylide ion. Then, use a primary bromide like 1-bromohexane in a nucleophilic substitution reaction to attach the hexyl group, forming 1-Heptyne. This would be represented as: \[ \text{HC鈮H} + \text{NaNH}_2 \to \text{HC鈮}^- \text{Na}^+ \ + \text{NH}_3 \] followed by \[ \text{HC鈮}^- \text{Na}^+ \ + \ \text{Br-C}_6\text{H}_{13} \to \text{HC鈮-C}_6\text{H}_{13} \text{(1-Heptyne)} \]
03

Synthesis of 2-Heptyne

To create 2-Heptyne (鈭扖鈮鈭扖_4H_9鈭扖H_3), we perform a sequence of reactions where acetylene undergoes alkynylation. First, extend the carbon chain by initiating the sequence with 1-bromo-3-methylbutane. Add the acetylide ion from acetylene prepared by reacting it with sodamide. The process is similar to that of 1-Heptyne.\[ \text{HC鈮}^- \text{Na}^+ \ + \ \text{Br-C}_5\text{H}_{11} \to \text{HC鈮-C}_5\text{H}_{11} \text{(intermediate)} \] followed by selective hydrogenation.
04

Hydrogenation to Convert Intermediate

The synthetic intermediate can undergo partial catalytic hydrogenation using Lindlar's catalyst to convert the intermediate to 2-Heptyne, favoring internal triple bonds and stopping at the desired alkyne.
05

Synthesis of 3-Heptyne

Creating 3-Heptyne (鈭扖鈥怌鈭扖鈮鈭扖H_2鈭扖_2H_5) involves forming a central alkyne within the chain. Begin with 1-bromo-2-pentene and the acetylide ion from acetylene. Use lithium diisopropylamide (LDA) for dehydrohalogenation to achieve the structural reorganization: \[ \text{(CH}_3\text{)_2CLi} \ + \ \text{I-C}_5\text{H}_{11} \to \text{C}_7\text{H}_{12} \text{(3-Heptyne)} \] with similar initial steps followed by selective treatments.

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Key Concepts

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

Acetylene Derivation
Acetylene, a small molecule consisting of just two carbon atoms joined by a triple bond, is an essential building block in organic chemistry. Its formula is simple: \(C_2H_2\). This molecule can act as a precursor for synthesizing longer carbon chains, specifically alkynes, which have one or more carbon-carbon triple bonds.
Acetylene's reactive nature makes it ideal for extension into longer molecules. By using various chemical reactions, such as nucleophilic substitution, this molecule serves as the starting point for deriving larger structures, like heptyne isomers. Through strategic manipulation, chemists can elongate acetylene's simple two-carbon setup into the desired multi-carbon alkynes.
Nucleophilic Substitution Reaction
Nucleophilic substitution reactions play a pivotal role in extending acetylene into desired alkyne chains. In this process, a nucleophile鈥攁 chemical species that donates an electron pair to form a bond鈥攔eplaces a leaving group in an organic substrate.
In the context of alkyne synthesis, acetylene is first converted into an acetylide ion with the help of a strong base like sodamide (\(\text{NaNH}_2\)). This ion acts as the nucleophile. For instance, in the synthesis of 1-Heptyne, the acetylide ion interacts with a primary bromide, such as 1-bromohexane.
  • The acetylide ion is highly reactive and successfully replaces the halide ion (bromide) on the 1-bromohexane.
  • This results in 1-Heptyne, depicted as \(\text{HC鈮-C}_6\text{H}_{13}\).
The efficiency of the substitution is significant due to the strength of the acetylide ion as a nucleophile, allowing for successful carbon chain elongation.
Catalytic Hydrogenation
Catalytic hydrogenation is a process where hydrogen gas is added to multiple bonds, typically using a catalyst. This is crucial for controlling the saturation level of organic compounds.
In alkyne synthesis, hydrogenation can selectively add hydrogen molecules, transforming alkynes into alkenes, and ultimately into alkanes. However, to maintain a triple bond, chemists use Lindlar's catalyst. This allows for partial hydrogenation, specifically reducing alkynes to alkenes without affecting the triple bond further, thereby converting intermediates into desired internal alkynes like 2-heptyne.
  • Using Lindlar's catalyst, the reaction is controlled and stops at the alkyne stage.
  • It is key to producing compounds with internal triple bonds, ensuring that the partial reduction is selective without over-reacting.
By carefully monitoring the reaction, chemists can skillfully obtain the desired hybrid structure.
Dehydrohalogenation
Dehydrohalogenation is a chemical reaction that involves the removal of a halogen and a hydrogen atom from adjacent carbon atoms, forming multiple bonds. This reaction is essential for creating internal alkyne arrangements from simpler precursors.
For example, in the synthesis of 3-Heptyne, lithium diisopropylamide (LDA) is used as a strong base to initiate dehydrohalogenation. By promoting the removal of hydrogen and halogen, LDA leads to the formation of an internal alkyne position within the heptyne chain.
  • The reactant, often a halide like 1-bromo-2-pentene, undergoes a transformation to create a double or triple bond configuration.
  • This method is effective for introducing triple bonds at specific locations within a larger carbon framework, like in 3-Heptyne.
Through careful selection of bases and mild conditions, dehydrohalogenation allows for strategic bond formation.

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Most popular questions from this chapter

Write the structure of the major organic product isolated from the reaction of 3 -hexyne with (a) Hydrogen ( 2 mol ), platinum (e) Chlorine (1 mol) (b) Hydrogen (1 mol), Lindlar palladium (f) Chlorine \((2 \mathrm{~mol})\) (c) Hydrogen chloride (1 mol) (g) Aqueous sulfuric acid, mercury(II) sulfate (d) Hydrogen chloride ( 2 mol) (h) Ozone followed by hydrolysis

Show by writing appropriate chemical equations how each of the following compounds could be converted to 3 -hexyne: (a) 1-Butene (b) 1,1 -Dichlorobutane (c) Acetylene

Diphenylacetylene can be synthesized by the double dehydrohalogenation of 1,2 -dibromo-1,2-diphenylethene. The sequence starting from \((E)-1,2\) -diphenylethene consists of bromination to give the dibromide, followed by dehydrohalogenation to give a vinylic bromide, then a second dehydrohalogenation to give diphenylacetylene.

An unknown acetylenic amino acid obtained from the seed of a tropical fruit has the molecular formula \(\mathrm{C}_{7} \mathrm{H}_{11} \mathrm{NO}_{2} .\) On catalytic hydrogenation over platinum, this amino acid yielded homoleucine (an amino acid of known structure shown here) as the only product. What is the structure of the unknown amino acid?

When 1,2 -dibromodecane was treated with potassium hydroxide in aqueous ethanol, it yielded a mixture of three isomeric compounds of molecular formula \(\mathrm{C}_{10} \mathrm{H}_{19} \mathrm{Br}\). Each of these compounds was converted to 1 -decyne on reaction with sodium amide in dimethyl sulfoxide Identify these three compounds.

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