COSY

There is a two-nucleus (2D) NMR experiment called a COSY that evaluates proton-toproton interactions. Coupling in the 1D 1H-NMR experiment also gives information about proton-to-proton interactions but the COSY experiment has many advantages. Identification of coupling partners in complex structures is generally easier in a COSY than in a standard PMR spectrum. COSY spectra can often allow for assignment of coupling relationships in non-first order spectra. Many people find interpretation of COSY to be easier than the interpretation of 1D PMR spectra. In a COSY experiment, the 1D PMR spectrum is plotted along both the x and y axis. There is also a diagonal line in a COSY that represents the 1D spectrum. It is the peaks that are recorded off of the diagonal line, known as off-diagonal peaks, that indicate coupling relationships. You look on the x-axis for the chemical shift of a particular proton signal. Once located, any other signals that appear off-diagonal are then traced back to the coupling peak along the y-axis. The connection of the off-diagonal peaks to the x and y axis intersects generates a box about the diagonal line. Peaks on the diagonal line that are boxed-off are coupling to each other. Begin by examination of Figure 9.29, page 400 of Solomons. The red lines that are drawn between signals on the diagonal line indicate the coupling interactions. The diagonal line represents the 1D spectrum. Peaks on the diagonal line which are connected to each other by a box, are coupling. Each off diagonal intersection of two red lines indicates a different coupling interaction. Hb couples to three different protons: Ha, Ha and Hc. Why? Because Hb is vicinal to Hc, Ha, and Ha. Ha couples to Ha and Ha couples to Hb, but Ha does not couple to Hc. Why? Because Ha and Ha, although geminal, are not chemical shift equivalents (so they can couple with each other) and both (Ha and Ha) are vicinal to Hb, but neither (Ha nor Ha) is vicinal to Hc. The explanation for coupling of Ha is the same as that applied to Ha. Hc should only couple to its vicinal neighbor, Hb, as is indicated by the COSY spectrum. To fully understand the foregoing rationalizations, you will probably have to pull out a pencil and map out each of the relationships to be sure that you understand what you are reading. As another example, consider the predicted COSY spectra of 1-nitropropane (CH3CH2CH2NO2) shown in Figure 2DNMR2-1, below. Compare this COSY to the 1D spectra on page 390 of Solomons (Figure 9.24). You should be able to identify all coupling interactions from the COSY (Figure 2DNMR2-1). Protons are labeled a, b, c to follow the assignments in the Solomons text. Only protons Hb should couple to two other protons (Ha and Hc) and the protons closest to the nitro group (Hc) should be the most downfield.

4 ppm

3 ppm

2 ppm

1 ppm

a 1 ppm

b b-a 2 ppm

3 ppm

c-b

4 ppm

Figure COSY-1. Predicted COSY Spectrum of 1-nitropropane CH3CH2CH2NO2. a b c QCOSY-1. What signals should exhibit COSY cross peaks in the compound para-ethylanisole? QCOSY-2. Fill in the cross peaks (as dots) on the ACOSY-1. The signal for Ha + Ha should show a cross peak to the signal for Hb + Hb. The COSY that you would expect to see in the signal for the benzylic methylene should have a compound para-ethylanisole. cross peak to its vicinal methyl proton neighbors.

Hb H 3C H 2C

Ha CH3 O

Hb'

Ha'

QCOSY-3. Identify the coupling partners based on the COSY shown below.
A B C D

ACOSY-2.

ACOSY-3. A D, B C, C D