Using 1H NMR Spectroscopy for Structure Determination

Example #1 Deduce the structure of a compound with the formula C3H7Br that has the following 1H NMR spectrum: 3.1 ppm (triplet; integral = 1), 1.7 ppm (sextet; integral = 1), and 1.0 ppm (triplet; integral = 1.5). To Start: calculate the number of double bond equivalents. DBE = C - (H/2) + (N/2) + 1 = 3 - (7 + 1)/2 + 0/2 + 1 = 0. We conclude that the molecule has no rings or pi bonds.
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H-NMR Analysis Chemical Shift 3.1 ppm 1.7 ppm 1.0 ppm Splitting triplet sextet triplet Totals Integral 1 1 1.5 3.5 # of H Implications

Step 1: summarize the 1H-NMR data in a table.

Step 2: The total of the integrals is 1 + 1 + 1.5 = 3.5. Because there are seven hydrogens, we conclude that each unit of the integral corresponds to two hydrogens. Chemical Shift 3.1 ppm 1.7 ppm 1.0 ppm
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Splitting triplet sextet triplet Totals

Integral 1 1 1.5 3.5

# of H 2H 2H 3H 7H

Implications

Step 3: For each H-NMR signal, use the number of hydrogens to decide if each signal corresponds to a CH3, CH2, CH, OH, NH, etc. For example, a three hydrogen signal might arise from a CH3, 3 x CH, or 3 x OH. OH is possible only when there is enough oxygen in the formula, if the IR does not rule it out, and if the 1H-NMR signal is not split. Chemical Shift 3.1 ppm 1.7 ppm 1.0 ppm Splitting triplet sextet triplet Totals Integral 1 1 1.5 3.5 # of H 2H 2H 3H 7H Implications CH2 CH2 CH3

Step 4: Use the n+1 rule and the observed splitting patterns to determine all the possibilities that would give the observed 1H-NMR signals. Example: The 2H triplet at 3.1 ppm could be due to a CH2, or 2 CH groups. The CH2 or 2 x CH groups must have two neighbors, as the observed splitting pattern is a triplet. Keeping things simple, it would appear that the CH2 group has another CH2 group next to it; this accounts for the triplet. The sextet at 1.7 ppm must arise from a total of five neighboring hydrogens. Since a single carbon cant have five hydrogens, there must be two different sets of hydrogens that sum to five; lets use a CH3 and a CH2 group. We make record of this in the table. (In this table the underlined hydrogens correspond to the given chemical shift.) The triplet at 1.0 ppm is determined accordingly. . Chemical Shift 3.1 ppm 1.7 ppm 1.0 ppm Splitting triplet sextet triplet Totals Integral 1 1 1.5 3.5 # of H 2H 2H 3H 7H Implication CH2 in CH2CH2 CH2 in CH2CH2CH3 CH3 in CH3CH2

Step 5: We now sum up the atoms that are underlined. We do this as a check to make sure we have used all the hydrogens and to look for atoms that do not show up in the 1H-NMR spectrum, such a COO portion of an ester. Chemical Shift 3.1 ppm 1.7 ppm 1.0 ppm Splitting triplet sextet triplet Totals Integral 1 1 1.5 3.5 # of H 2H 2H 3H 7H Implication CH2 in CH2CH2 CH2 in CH2CH2CH3 CH3 in CH3CH2 CH2 + CH2 + CH3 = C3H7

Step 6: Atom Check. Look for unused atoms. Given formula - atoms from 1H-NMR or other sources such as IR = unused atoms. For this example: C3H7Br C3H7 = Br. Therefore 1H-NMR data accounts for all of the atoms in the formula except the bromine. This bromine atom must be included when assembling the pieces. Step 7: DBE Check. Look for unused DBEs. DBEs calculated from formula DBE accounted for (by 1H-NMR, etc.) = unused DBEs. In this example the formula has no DBEs and the 1HNMR data does not require any DBEs, so there are no left over DBEs to consider when assembling the pieces. Step 8: List and assemble the pieces. At this point youve done 90% of the work. Now we assemble the pieces to come up with the final structure. The pieces suggested by the 1H-NMR data are: CH2 in CH2CH2 CH2 in CH2 CH2CH3 CH3 in CH3CH2 Br 2

Also include pieces suggested by other means such as IR data. There is often many ways to go about assembling the pieces in solving NMR spectroscopy problems. Use the clues provided by the spectra, such as coupling patterns. Sometimes trial and error is all that works. In this case, the middle fragment uses all three of the available carbons and fits with the other fragments as shown below. CH2 in CH2CH2 CH2 in CH2 CH2CH3 CH3 in CH2CH3 The fragments have been reduced to CH3CH2CH2 and Br, which can only be assembled one way: CH3CH2CH2Br Step 9: Check to make sure the proposed structure is consistent with the original data, i.e., chemical shift (use table), splitting, and integration. In this case, examine CH2 next Br: is the chemical shift consistent with what we expect? This process might seem long and unnecessarily complicated for such a simple molecule, but can be very useful in organizing your thoughts for more complex examples. The process becomes much faster with practice and a little bit of experience. Example #2: Deduce the structure of a compound with the formula C9H12 that has the following 1H NMR spectrum: 7.40 7.02 ppm (multiplet, integral = 2.5); 2.57 ppm (triplet, integral = 1); 1.64 ppm (sextet, integral = 1) and 0.94 ppm (triplet, integral = 1.5). To Start: calculate the number of double bond equivalents. DBE = C - (H/2) + (N/2) + 1 = 9 - (12)/2 + 0/2 + 1 = 4. We conclude that the molecule has either four double bonds or four rings, or some combination of the two. Given the number of carbon atoms, we suspect a benzene ring.
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H-NMR Analysis

Step 1: summarize the 1H-NMR data in a table. Chemical Shift 7.40 to 7.02 ppm 2.57 ppm 1.64 ppm 0.94 ppm Splitting multiplet triplet sextet triplet Totals Integral 2.5 1 1 1.5 6 3 # of H Implications

Step 2: The total of the integrals is 1 + 1 + 1.5 + 2.5 = 6. Because there are 12 hydrogens, we conclude that each unit of the integral corresponds to two hydrogens. Chemical Shift 7.40 to 7.02 ppm 2.57 ppm 1.64 ppm 0.94 ppm Splitting multiplet triplet sextet triplet Totals Integral 2.5 1 1 1.5 6 # of H 5 2 2 3 12 Implications

Step 3: Again, for each 1H-NMR signal, use the number of hydrogens to decide if each signal corresponds to a CH3, CH2, CH, OH, NH, etc. Chemical Shift 7.40 to 7.02 ppm 2.57 ppm 1.64 ppm 0.94 ppm Splitting multiplet triplet sextet triplet Totals Integral 2.5 1 1 1.5 6 # of H 5 2 2 3 12 CH2 CH2 CH3 Implications
C6 H5

Step 4: As before, use the n+1 rule and the observed splitting patterns to determine all the possibilities that would give the observed 1H-NMR signals. Example: The 2H triplet at 2.57 ppm is most likely due to a CH2 bonded to another CH2 group, as the observed splitting pattern is a triplet. Determine the rest of table accordingly. Chemical Shift 7.40 to 7.02 ppm 2.57 ppm 1.64 ppm 0.94 ppm Splitting multiplet triplet sextet triplet Totals Integral 2.5 1 1 1.5 6 # of H 5 2 2 3 12 Implications
C6 H 5

CH2 in CH2CH2 CH2 in CH2CH2CH3 CH3 in CH3CH2

Step 5: We now sum up the atoms that are underlined. Check to make sure we have used all the hydrogens and to look for atoms that do not show up in the 1H-NMR spectrum. Chemical Shift 7.40 to 7.02 ppm 2.57 ppm 1.64 ppm 0.94 ppm Splitting multiplet triplet sextet triplet Totals Integral 2.5 1 1 1.5 6 # of H 5 2 2 3 12 Implications
C6 H 5

CH2 in CH2CH2 CH2 in CH2CH2CH3 CH3 in CH3CH2 C6H5 + CH2 + CH2 + CH3 = C9H12

Step 6: Atom Check. Given formula - atoms from 1H-NMR or other sources such as IR = unused atoms. For this example: C9H12 C9H12 = nothing. Therefore 1H-NMR data accounts for all of the atoms in the formula. Step 7: DBE Check. For this example the formula has 4 DBEs and the 1H-NMR data accounts for 4 DBE. No additional DBE. Step 8: List and assemble the pieces. The pieces suggested by the 1H-NMR data are: CH2 in CH2CH2 CH2 in CH2 CH2CH3 CH3 in CH3CH2

The fragments have been reduced to CH3CH2CH2 and mono-substituted benzene ring with a total of two open valences (places to make a bond). There is only one way to assemble pieces. Final structure is propylbenzene.

CH2 CH2 CH3

Step 9: Check to make sure the proposed structure is consistent with the original data, i.e., chemical shift (use table), splitting, and integration, and IR data (if given).

Example #3: Deduce the structure of a compound with the formula C4H8O2 that has the following 1H NMR spectrum: 3.67 ppm (singlet, integral = 1.5); 2.32 ppm (quartet, integral = 1); 1.15 ppm (triplet, integral = 1.5).

To Start: calculate the number of double bond equivalents. DBE = C - (H/2) + (N/2) + 1 = 4 - (8)/2 + 0/2 + 1 = 1. The molecule has either one double bond or one ring.
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H-NMR Analysis Splitting singlet quartet triplet Totals Integral 1.5 1 1.5 4 # of H 3 2 3 8 Implications CH3 CH2 in CH2CH3 CH3 in CH3CH2 CH3 + CH2 + CH3 = C3H8

Chemical Shift 3.67 ppm 2.32 ppm 1.15 ppm

Atom Check: C4H8O2 (given formula) C3H8 (from 1H-NMR) = CO2. DBE Check: The 1H-NMR data does not account for the one DBE. Now suspect an ester functional group, since have CO2 remaining and one DBE. Being able to make inferences like this is very important and requires practice. 6

List and Assemble the Pieces:

CH3 CH2 in CH2CH3 CH3 in CH3CH2 O C O ester

We have an ethyl group and a methyl group, each with an empty valence. Since there are two empty valences on the ester functional group, the ethyl and methyl groups can go on either end of the ester; thus, there are two possible ways to assemble the fragments: O C H3C A O CH2CH3 CH3CH2 B O C O CH3

Use chemical shift and splitting patterns to distinguish between these. Compound A would have a singlet integrating for three at ~2.2 ppm for the CH3 group bonded to the carbonyl carbon. Compound A would also have a quartet at ~3.8 ppm for the CH2 group bonded to the ether oxygen. Our NMR data is not consistent with these predicted chemical shifts and splitting patterns. We conclude, therefore, that compound B is the correct answer.
Predict: quartet @ 3.8 ppm Observe quartet @ 2.32 ppm Predict: quartet @ 2.2 ppm

O C H3C A O CH2CH3 CH3CH2

O C O B CH3

Predict: singlet @ 2.2 ppm

Predict: triplet @ ~0.9 ppm Observe: triplet @ 1.15 ppm

Predict: singlet @ 3.8 ppm Observe: singlet @ 3.67 ppm

Final Check for Consistency: Compound B should have a singlet integrating for 3 protons at about 3.8 ppm; we have a singlet at 3.67 ppm. We should have a quartet integrating for two protons at ~2.2 ppm; we have such a signal at 2.32. We predict a triplet integrating for three protons at 0.9; we observe a triplet at 1.15 ppm. The data is consistent with the proposed structure; it is not consistent with compound A.