12.12: ¹³C NMR Spectroscopy and DEPT

Distortions Enhancement by Polarization Transfer (DEPT)

DEPT is used for distinguishing between a CH₃ group, a CH₂ group, and a CH group. The proton pulse is set at 45°, 90°, or 135° in the three separate experiments. The different pulses depend on the number of protons attached to a carbon atom. Fig 11. is an example about DEPT spectrum.

Fig 11. DEPT spectrum of n-isobutlybutrate

While broadband decoupling results in a much simpler spectrum, useful information about the presence of neighboring protons is lost. However, another modern NMR technique called DEPT (Distortionless Enhancement by Polarization Transfer) allows us to determine how many hydrogens are bound to each carbon. For example, a DEPT experiment tells us that the signal at 171 ppm in the ethyl acetate spectrum is a quaternary carbon (no hydrogens bound, in this case a carbonyl carbon), that the 61 ppm signal is from a methylene (CH₂) carbon, and that the 21 ppm and 14 ppm signals are both methyl (CH₃) carbons. The details of the DEPT experiment are beyond the scope of this text, but DEPT information will often be provided along with ¹³C spectral data in examples and problems.

Below are two more examples of ¹³C NMR spectra of simple organic molecules, along with DEPT information.

Example 13.5.2

Give peak assignments for the ¹³C-NMR spectrum of methyl methacrylate, shown above.

Solution

One of the greatest advantages of ¹³C-NMR compared to ¹H-NMR is the breadth of the spectrum - recall that carbons resonate from 0-220 ppm relative to the TMS standard, as opposed to only 0-12 ppm for protons. Because of this, ¹³C signals rarely overlap, and we can almost always distinguish separate peaks for each carbon, even in a relatively large compound containing carbons in very similar environments. In the proton spectrum of 1-heptanol, for example, only the signals for the alcohol proton (H_a) and the two protons on the adjacent carbon (H_b) are easily analyzed. The other proton signals overlap, making analysis difficult.

In the ¹³C spectrum of the same molecule, however, we can easily distinguish each carbon signal, and we know from this data that our sample has seven non-equivalent carbons. (Notice also that, as we would expect, the chemical shifts of the carbons get progressively smaller as they get farther away from the deshielding oxygen.)

This property of ¹³C-NMR makes it very helpful in the elucidation of larger, more complex structures.

Example 13.5.3

¹³C-NMR (and DEPT) data for some common biomolecules are shown below (data is from the Aldrich Library of ¹H and ¹³C NMR). Match the NMR data to the correct structure, and make complete peak assignments.

• spectrum a: 168.10 ppm (C), 159.91 ppm (C), 144.05 ppm (CH), 95.79 ppm (CH)
• spectrum b: 207.85 ppm (C), 172.69 ppm (C), 29.29 ppm (CH₃)
• spectrum c: 178.54 ppm (C), 53.25 ppm (CH), 18.95 ppm (CH₃)
• spectrum d: 183.81 ppm (C), 182. 63 ppm (C), 73.06 ppm (CH), 45.35 ppm (CH₂)

Solution

¹³C NMR Chemical Shifts

The Carbon NMR is used for determining functional groups using characteristic shift values. ¹³C chemical shift is affect by electronegative effect and steric effect. If an H atoms in an alkane is replace by substituent X, electronegative atoms (O, N, halogen), ?-carbon and ?-carbon shift to downfield (left; increase in ppm) while ?-carbon shifts to upfield. The steric effect is observed in acyclic and clyclic system, which leads to downshifted chemical shifts. Figure 9 shows typical ¹³C chemical shift regions of the major chemical class.

Figure 9: ¹³C Chemical shift range for organic compound

Spin-Spin splitting

Comparing the ¹H NMR, there is a big difference thing in the ¹³C NMR. The ¹³C-¹³Cspin-spin splitting rarely exit between adjacent carbons because ¹³C is naturally lower abundant (1.1%)

• ¹³C-¹H Spin coupling: ¹³C-¹H Spin coupling provides useful information about the number of protons attached a carbon atom. In case of one bond coupling (¹J_CH), -CH, -CH₂, and CH₃ have respectively doublet, triplet, quartets for the ¹³C resonances in the spectrum. However, ¹³C-¹H Spin coupling has an disadvantage for ¹³C spectrum interpretation. ¹³C-¹H Spin coupling is hard to analyze and reveal structure due to a forest of overlapping peaks that result from 100% abundance of ¹H.
• Decoupling: Decoupling is the process of removing ¹³C-¹H coupling interaction to simplify a spectrum and identify which pair of nuclei is involved in the J coupling. The decoupling ¹³C spectra shows only one peak(singlet) for each unique carbon in the molecule(Fig 10.). Decoupling is performed by irradiating at the frequency of one proton with continuous low-power RF.

Fig 10. Decoupling in the ¹³C NMR

Contributors

• Prof. Steven Farmer (Sonoma State University)

• Organic Chemistry With a Biological Emphasis by Tim Soderberg (University of Minnesota, Morris)

• Chris P Schaller, Ph.D., (College of Saint Benedict / Saint John's University)