Name: cyclohexane ring flipping in variable-temperature nmr
Uploaded: 2024-12-05T18:32:25.000Z
Duration: 1 min 15 s
Channel: JoVE

The variable-temperature NMR technique helps distinguish between the two types of protons in cyclohexane - axial and equatorial.
To prevent the spin-spin coupling between the adjacent protons, eleven of the twelve protons are replaced by deuterium &#8212; the remaining proton switches between the axial and equatorial positions.
This sample is labeled cyclohexane-d11, and the corresponding proton NMR spectrum is recorded at various temperatures.
At room temperature, the rapid chair-chair interconversion produces a single sharp peak. However, the reduced rate at &#8722;60&#176;C results in peak broadening. Further lowering of the temperature continues to broaden the peak &#8212; first, to form a saddle, which then splits into two peaks.
Below &#8722;89&#176;C, two sharp, well-resolved peaks are formed at &#948; 1.62 and 1.14, corresponding to the equatorial and axial protons. At this temperature, NMR detects the two sets of protons due to the significantly low rate of chair-chair interconversion.

&sup1;h nmr of conformationally flexible molecules: variable-temperature nmr

&sup1;H NMR of Conformationally Flexible Molecules: Variable-Temperature NMR

The axial and equatorial protons in cyclohexane can be distinguished by performing a variable-temperature NMR experiment. In this process, except for one proton, the remaining eleven protons are replaced by deuterium. The deuterium substitution avoids the possible peak splitting caused by the spin-spin coupling between the adjacent protons. The remaining proton flips between the axial and equatorial positions.
<img alt="Chromatography method; detector response vs. retention time graph; peak separation analysis." src="/files/ftp_upload/13016/13016-PT_Figure_1.svg" style="text-align: center; height: 480px;" data-altupdatedat="1761830439000" data-alt="Figure1" />
Figure 1. The temperature-dependent proton NMR spectra of cyclohexane.
Figure 1 depicts the proton NMR spectrum of the deuterium substituted sample, recorded at various temperatures. At room temperature, the rapid ring flipping of cyclohexane results in a single sharp peak. As the temperature is lowered to &#8722;60&#176;C, the rate of chair-chair interconversion reduces, resulting in the broadening of the peak.
Further lowering of the temperature broadens the peak, forming a saddle that splits into two peaks. On reaching a temperature lower than &#8722;89&#176;C, two sharp, well-resolved peaks corresponding to the equatorial and axial protons are formed. The peaks corresponding to the equatorial and axial protons occur at &#948; 1.62 and 1.14, respectively. At such low temperatures, the rate of chair-chair interconversion is reduced significantly, enabling the detection of the two distinct sets of protons on the NMR time scale.

The axial and equatorial protons in cyclohexane can be distinguished by performing a variable-temperature NMR experiment. In this process, except for one ...

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Analytical Chemistry

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Advanced Nuclear Magnetic Resonance Spectroscopy

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KEY TERMS AND CONCEPTS

cyclohexane ring flipping in variable-temperature nmr

Cyclohexane ring flipping can be tracked with variable-temperature NMR. The experiment helps distinguish the axial and equatorial protons in a deuterium-substituted cyclohexane sample. Deuterium is used to replace eleven of the twelve protons. This reduces possible peak splitting from spin-spin coupling between neighboring protons.

The remaining proton shifts between the axial and equatorial positions as the chair form of cyclohexane changes. At room temperature, ring flipping is very fast, so the proton NMR spectrum shows one sharp peak. When the temperature drops to −60°C, chair-chair interconversion slows down and the peak broadens.

Lowering the temperature even more makes the broad peak widen into a saddle shape that then splits into two peaks. Below −89°C, the spectrum shows two sharp, well-resolved peaks. These peaks match the equatorial and axial protons, at δ 1.62 and 1.14, respectively. At this low temperature, chair-chair interconversion is slow enough that the two proton environments can be seen on the NMR time scale.

Cyclohexane Ring Flipping in Variable-Temperature NMR

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&sup1;h nmr of conformationally flexible molecules: temporal resolution

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¹H NMR Ring Flips and Signal Averaging

¹H NMR can show how fast molecular motion changes the signals we see. In cyclohexane, the chair form flips rapidly between two equivalent chair conformers at room temperature. This happens about 10^5 times per second, and the two shapes stay in equilibrium. During ring flipping, an axial proton becomes equatorial, and an equatorial proton becomes axial. These changes are too fast to detect on the NMR timescale. As a result, the NMR spectrometer cannot tell the axial and equatorial protons...

Cyclohexane ring flipping can be tracked with variable-temperature NMR. The experiment helps distinguish the axial and equatorial protons in a deuterium-substituted cyclohexane sample. Deuterium is used to replace eleven of the twelve protons. This reduces possible peak splitting from spin-spin coupling between neighboring protons. The remaining proton shifts between the axial and equatorial positions as the chair form of cyclohexane changes. At room temperature, ring flipping is very fast, so...

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Using D2O to Identify OH Protons

Deuterium substitution can help identify labile protons in ¹H NMR spectra. Labile protons are hydrogens that can be replaced by another hydrogen isotope. In this lesson, deuterium is used to simplify the spectrum of ethanol. Deuterium, or ²H, is one of the three isotopes of hydrogen. Its nucleus contains one proton and one neutron. When D₂O is added to a pure dry ethanol solution, the labile proton on the –OH group is replaced by deuterium. A proton NMR spectrum does not show signals from...

nuclear overhauser enhancement (noe)

Using NOE to Map Nearby Nuclei

Nuclear Overhauser enhancement, or NOE, shows how irradiation of one spin-active nucleus can change the signal of nearby nuclei. These nuclei do not have to be chemically bonded or connected through J-coupling. The effect comes from through-space interactions between nuclear spins. NOE gets weaker as the distance between nuclei increases. It is generally not observed beyond about 4 angstroms. Dipole-dipole interactions between neighboring spin-active nuclei transfer nuclear spin polarization,...

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NMR Signal Boosting with INEPT Pulses

INEPT is an NMR method that boosts weak signals from low-abundance nuclei. It is used to detect nuclei such as carbon-13 and nitrogen-15 in small molecules. The goal is to make these hard-to-see nuclei easier to observe in an NMR spectrum. The technique works by transferring polarization from a more abundant nucleus, usually hydrogen-1, to the nucleus of interest. Hydrogen-1 has higher receptivity, so it can provide the starting signal boost. Spin coupling then helps move that polarization to...

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Spin Decoupling in NMR Spectroscopy

Spin decoupling is a key use of double resonance in nuclear magnetic resonance (NMR) spectroscopy. It uses two radiofrequency pulses or frequencies at the same time to act on two different nuclear spins. This makes the spectrum simpler and easier to read. In spin decoupling, one type of nucleus is selectively suppressed while the signal from another nucleus is observed. The radiofrequency pulse sequence removes the coupling with one nuclide and can greatly improve resolution. As a result, the...

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2D NMR Spectra and Signal Mapping

Two-dimensional (2D) NMR helps make sense of crowded NMR data from large and complex molecules, such as natural products. A 1D NMR spectrum can have overlapping signals and complicated splitting patterns. 2D NMR adds a second frequency axis, which helps show the coupling information between nucleus A and nucleus B in a molecule. 2D spectra are built in four steps. First is the preparation period, when nucleus A is excited with a radiofrequency pulse. Next is the evolution, or wait, period t1.

2d nmr: overview of homonuclear correlation techniques

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2D NMR Correlation Paths in Molecules

2D NMR homonuclear correlation techniques show how nuclei of the same type connect within a molecule. In nuclear magnetic resonance (NMR) spectroscopy, these methods reveal scalar couplings, which are interactions between nearby nuclei through bonds. That information helps identify which atoms are linked and how a molecule is put together. COSY is the main homonuclear correlation experiment. COSY90 is the standard 2D COSY method and uses a second 90-degree pulse to improve sensitivity and...

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Reading Proton Coupling with COSY Maps

COSY is a 2-dimensional NMR method that shows which protons are coupled to each other. It is used to spot geminal and vicinal coupling in a sample. This makes it helpful for reading proton relationships in complex spectra. The ethyl acetate example shows how COSY is built from the 1D proton NMR spectrum. The same chemical shift scale appears on both the vertical and horizontal axes. The peaks along the diagonal are called diagonal peaks, and they match the three peaks seen in the 1D proton...

2d nmr: overview of heteronuclear correlation techniques

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2D NMR Correlation Peaks and Bond Links

Heteronuclear correlation spectroscopy is a 2D NMR method that links different nuclei, usually a proton and an X-nucleus such as carbon-13 or nitrogen-15. It helps scientists study the structure and composition of complex chemical compounds. In a heteronuclear correlation spectrum, one axis shows X-nucleus chemical shifts and the other axis shows the proton spectrum. Cross-peaks mark which protons are connected to which X-nuclei. The main heteronuclear correlation experiments are HETCOR, HSQC,...

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HSQC NMR Maps Carbon-Proton Connections

HSQC NMR maps the direct links between hydrogen atoms and the carbons they are attached to. It is a 2D NMR method, so it shows the data on two axes instead of one. The experiment is similar to heteronuclear correlation spectroscopy, or HETCOR, but HSQC is more sensitive. In an HSQC spectrum, the proton chemical shift appears on the horizontal F2 axis. The 13C chemical shift appears on the vertical F1 axis. The spectrum also includes the matching proton and 13C spectra. The contour plot does...

key terms and concepts

See how variable-temperature 1H NMR reveals cyclohexane ring flipping, peak broadening, and the separation of axial and equatorial protons at low temperature.

Cyclohexane Ring Flipping in Variable-Temperature NMR | JoVE K12

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Cyclohexane Ring Flipping in Variable-Temperature NMR

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