Name: branched alkanes in mass spectra
Uploaded: 2024-12-05T18:32:19.000Z
Duration: 1 min 29 s
Channel: JoVE

The fragmentation of branched alkanes primarily occurs at the branching point, which generates stable secondary or tertiary carbocations.
For instance, consider the mass spectra of 2-methyl butane and 2,2-dimethyl propane. The loss of a methyl radical from 2-methyl butane and 2,2-dimethyl propane molecular ions produces a secondary and tertiary carbocation, respectively.
While the molecular ion peak is visible in the mass spectrum of 2-methyl butane, it is absent in 2,2-dimethyl propane. The increased stability of the tertiary carbocation over the secondary carbocation makes the fragmentation of 2,2-dimethyl propane extensive, leaving no molecular ion to detect.
Here, the increased stability of secondary and tertiary carbocations, in comparison to primary carbocations, drives the fragmentation, leading to a methyl radical, unlike linear alkanes. 
In 2,2-dimethyl pentane, fragmentation on either side of the branching center yields a tertiary carbocation. Here, the stability of the co-produced radical determines the fragmentation pattern. Accordingly, the fragmentation leading to a primary radical rather than a methyl radical is more likely.

mass spectrometry: branched alkane fragmentation

Mass Spectrometry: Branched Alkane Fragmentation

This lesson delves into the mass spectrometry of branched alkane fragmentation. Branched alkanes possess secondary or tertiary carbon atoms, which generate relatively stable carbocations if the cleavage occurs at the branching point. The high stability of carbocations drives the instant fragmentation of branched alkanes. Accordingly, the branched alkane's molecular ion peak is very weak or invisible in the mass spectra, especially in comparison to a linear alkane.
<img alt="Organic reaction mechanism, carbocation rearrangement, chemical equation diagram, SN1 reactions." src="/files/ftp_upload/13041/13041-PT_Figure_1.svg" style="text-align: center; height: 275px;" data-altupdatedat="1761830439000" data-alt="Figure1" />
Figure 1. Fragmentation pathway of 2-methylbutane (top), neopentane (middle), and n-pentane (bottom) molecular ions.
Figure 1 shows the most feasible fragmentation pathway observed in 2-methyl butane, neopentane, and n-pentane molecular ions. 2-methyl butane and neopentane fragment to yield secondary and tertiary carbocations, respectively. The stability of these carbocations drives the fragmentation reaction, even though the co-produced methyl radical is relatively unstable. In contrast, the cleavage of n-pentane leading to the methyl radical is difficult since the stability of a primary carbocation is low.
<img alt="Chemical reaction mechanism; hydrocarbon rearrangement process; organic chemistry diagram." src="/files/ftp_upload/13041/13041-PT_Figure_2.svg" style="text-align: center; height: 105px;" data-altupdatedat="1761830439000" data-alt="Figure2" />
Figure 2. Fragmentation of 2,2-dimethylpentane.
As shown in Figure 2, the fragmentation of 2,2-dimethyl pentane involves the loss of either methyl or propyl radical, resulting in a tertiary carbocation. Here, the stability of the co-produced radical determines the cleaving bond. So, the cleavage that produces a propyl radical is favored, and the signal from the 2-methyl propyl carbocation becomes the base peak.

This lesson delves into the mass spectrometry of branched alkane fragmentation. Branched alkanes possess secondary or tertiary carbon atoms, which ...

mass-spectrometry-branched-alkane-fragmentation

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JoVE Core

Analytical Chemistry

Unit 1

Mass Spectrometry Fragmentation Methods

KEY TERMS AND CONCEPTS

branched alkanes in mass spectra

Branched alkanes in mass spectrometry fragment quickly because branching can create stable carbocations. When cleavage happens at a branching point, a secondary or tertiary carbocation may form. That stability helps explain why the molecular ion peak is often very weak or missing compared with a linear alkane.

The lesson uses 2-methylbutane, neopentane, and n-pentane to show how this pattern appears in mass spectra. 2-methylbutane and neopentane break apart to form secondary and tertiary carbocations, respectively. Even though the methyl radical that is lost is not very stable, the carbocation stability drives the fragmentation.

n-Pentane behaves differently because cleavage that would form a methyl radical is less favorable. The reason is that the matching primary carbocation is not very stable. The lesson also shows 2,2-dimethylpentane, where loss of either a methyl or a propyl radical can produce a tertiary carbocation.

In that example, the stability of the radical that leaves helps decide which bond breaks. The pathway that forms a propyl radical is favored. As a result, the 2-methyl propyl carbocation gives the base peak in the mass spectrum.

Branched Alkanes in Mass Spectra

mass spectrometry: long-chain alkane fragmentation

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Mass Spectra of Linear Alkane Chains

Mass spectra of linear alkanes show a clear fragmentation pattern. The molecular ion often breaks at a carbon-carbon bond away from the end of the chain. This cleavage forms a stable carbocation and a stable radical, so the middle of the mass-to-charge plot usually has the strongest signals while the ends are weaker. As each bond breaks, a methyl group is lost and the main peaks in the spectrum appear 14 u apart. Smaller peaks near each main signal can also appear. These come from secondary...

Branched alkanes in mass spectrometry fragment quickly because branching can create stable carbocations. When cleavage happens at a branching point, a secondary or tertiary carbocation may form. That stability helps explain why the molecular ion peak is often very weak or missing compared with a linear alkane. The lesson uses 2-methylbutane, neopentane, and n-pentane to show how this pattern appears in mass spectra. 2-methylbutane and neopentane break apart to form secondary and tertiary...

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Cycloalkane Ions and Mass Peaks

Cycloalkane ions in mass spectrometry often give strong peaks because the ring structure helps stabilize the molecular ion. Compared with linear or branched alkanes, this added stability changes how the molecule breaks apart. As a result, cycloalkanes can produce prominent signals in the mass spectrum. Cyclohexane is a clear example. Its molecular ion has an m/z of 84, and this peak is often stronger than the signal from hexane, a linear alkane. The closed ring helps hold the ion together,...

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Alkene Ion Fragmentation Patterns

Alkene ion fragmentation patterns in mass spectrometry begin when the molecule loses one electron from the unsaturated π bond. This ionization forms a stable molecular ion. The ion can then break apart by three main reaction pathways. The most common pathway is cleavage at the allylic position, which is the carbon next to the double bond. This produces an allylic carbocation that is stabilized by resonance. In terminal alkenes, this fragment appears at a mass-to-charge ratio of 41. In internal...

mass spectrometry: cycloalkene fragmentation

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Cycloalkene Side-Chain Cleavage in Mass Spectra

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Alkyne Mass Spectra and Key Peaks

Alkyne mass spectra often show strong peaks from two main fragmentation paths. One path breaks the carbon-carbon bond between the alpha and beta carbons of the alkyne bond. This produces a 3-propynyl cation, also called a propargyl cation. In terminal alkynes, this is the only fragmentation path that gives the 3-propynyl cation. The unsubstituted 3-propynyl cation appears at a mass-to-charge ratio of 39. In internal alkynes, the 3-propynyl cation is substituted. For example, 2-pentyne forms a...

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Alcohol Fragmentation Patterns in Mass Spectra

Alcohols fragment in mass spectrometry in predictable ways. When an alcohol, written as R-OH, ionizes, it can lose one non-bonded electron from the oxygen atom. That forms a molecular ion, but the molecular ion peak is often weak or may not appear because alcohols break apart quickly. Two main fragmentation routes are important for alcohols: β-cleavage and dehydration. In β-cleavage, the bond at the β-position next to the hydroxyl group breaks. This gives a resonance-stabilized cation and a...

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Mass Spectra of Benzene and Toluene

Mass spectra of aromatic compounds show a strong molecular ion peak. In ionization, the molecule becomes a molecular ion, which appears as a prominent peak in the spectrum. Benzene gives a molecular ion at m/z 78, and toluene gives one at m/z 92. Benzene’s molecular ion is especially stable. It does not fragment readily because breaking the aromatic benzene ring requires a large amount of energy. Alkyl-substituted benzenes behave differently in mass spectrometry. Toluene can lose a hydrogen...

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Amines in Mass Spectra: Nitrogen Rule

Amines can be identified in mass spectrometry by their fragmentation patterns and by the nitrogen rule. The molecular ions of amines often break apart through β-cleavage, which cuts a carbon-carbon bond next to the nitrogen. This process forms an alkyl radical and a resonance-stabilized nitrogen-containing cation. The nitrogen rule helps predict the mass of the molecular ion. A compound with one nitrogen atom, or any odd number of nitrogen atoms, gives a molecular ion with an odd molecular...

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Mass Spectra of Alkyl Halides

Mass spectra of alkyl halides show clear isotope patterns from the halogen atom. Chlorine has two common isotopes, 35Cl and 37Cl, in a 3:1 ratio. Bromine has two common isotopes, 79Br and 81Br, in a 1:1 ratio. These isotope ratios create two molecular ion peaks, [M] and [M + 2], with relative heights that match the halide abundance. This pattern is easy to see in examples such as 2-chloropropane and 1-bromopropane. 2-Chloropropane gives peaks in a 3:1 ratio. 1-Bromopropane gives peaks in a 1:1...

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Carbonyl Fragment Patterns in Mass Spectra

Aliphatic aldehydes and ketones break apart in mass spectrometry through a few key carbonyl fragment patterns. The main pathways are alpha-cleavage, inductive cleavage, and the McLafferty rearrangement. These patterns help chemists read the mass spectrum and spot a carbonyl group. Alpha-cleavage is a common break next to the carbonyl group. The bond beside the carbonyl splits, and this forms an alkyl radical and an acylium cation. The acylium cation is often seen in the spectrum because it is...

mass spectrometry: carboxylic acid, ester, and amide fragmentation

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Mass Spectra of Carboxylic Compounds

Mass spectra of carboxylic acids, esters, and amides often show two key fragmentation routes: β-cleavage and McLafferty rearrangement. In β-cleavage, the carbon-carbon bond at the β-position next to the carboxylic group breaks. This produces a neutral radical and a cation. Long-chain compounds can also fragment by McLafferty rearrangement if they have a hydrogen on the γ-carbon. The γ-carbon is the third carbon away from the carboxylic group. This rearrangement gives a radical cation and a...

chemical ionization (ci) mass spectrometry

Using Reagent Gas in CI Mass Spectrometry

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electrospray ionization (esi) mass spectrometry

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How ESI Turns Biomolecules Into Ions

Electrospray ionization, or ESI, is a mass spectrometry method used to detect biomolecules that are too large or nonvolatile for conventional electron impact ionization. These molecules may break down before they can ionize or evaporate. ESI helps prevent rapid fragmentation and lets scientists record a mass signal for the whole biomolecule. ESI uses electrical energy to move ions from the liquid phase into the gas phase. The analyte biomolecule is mixed with an ionic liquid, which is a...

matrix-assisted laser desorption ionization (maldi)

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How MALDI Turns Samples Into Ions

Matrix-assisted laser desorption ionization (MALDI) is a mass spectrometry technique that turns biomolecules into ions for analysis. It is used to identify and characterize proteins, peptides, nucleic acids, and carbohydrates. Because of this, it is common in biological and medical research, as well as pharmacology and biochemistry. In MALDI, the analyte of interest is mixed with a matrix material. The matrix is usually an organic compound, such as a small organic acid or a crystalline...

key terms and concepts

Learn how branched alkanes fragment in mass spectrometry, why molecular ion peaks can be weak, and how carbocation stability shapes key peaks.

Branched Alkanes in Mass Spectra | JoVE K12

analytical chemistry

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Branched Alkanes in Mass Spectra

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