NMR Project

Sample 35 and 40

Chemical Engineering

Chemical Analysis

Aim The two samples are 35 and 40. Analytical techniques are vital in everyday science and so NMR procedure is an absolute essential to deduce compounds and chemical structures; this assignment requires the identification of two samples using an NMR software program. Background NMR spectroscopy is a well established method for structure determination of various organic molecules ranging from small molecules all the way up to large bio-molecules such as proteins, DNA and polysaccharides. The chemical environment surrounding each atom as well their proximity to other atoms in a molecule can be studied with various experiments, enabling high-resolution 3D-structure determinations as well as verification of the chemical structure. NMR spectroscopy is well suited for wood characterization, both in solution and in the solid-state.

Sample Number # 40 Sample 40 has been provided with sample information stating; an Infrared reading of 3350 / 1040 cm-1, a boiling point ranging between +107C and +109C, Figure 1: Sample spectrum Parameters:

Frequency = 100MHz

Accumulation = 20

Because there is a need to report the location of an NMR signal/peak in a spectrum relative to a reference signal from a standard compound added to the sample, we use tetramethylsilane, (CH3)4Si, usually referred to as TMS. TMS is unreactive and easily removed from the sample after the measurement. By zooming in on peak E, we see that this signal has a chemical shift at 0ppm; therefore this is just the TMS signal, which doesnt need to be analysed.

Spectrum was not clear; in order to view the spectrum in more detail changed the parameters.

Figure 2: sample NMR spectrum at higher frequency Parameters:

Frequency= 400MHz Accumulations = 80

C D B

From the information given about this sample, it has an i.r band at 3350 cm -1 and 1040cm-1. Comparing with literature value, i.r band of 3200 3400 cm-1 (broad) suggest that it has an O H bond. But this is however just an early assumption. Keeping this in mind, more detail analysis of each peak will be made to obtain a correct compound. Therefore the sample 33 should contain the following below bonds. Ir reading 3350cm-1 1040cm-1 Literature value 3400-3200cm-1 10401060cm-1 Bond O-H C-O

E.g. Or

Integration:

D B

Table 2: Peak A B C D Peak Height cm 2 4 2 12 Integration ratio 6 1 2 1 No of protons 1H 2H 1H 6H

Sample 33 has an Integration Ratio of 6:1:2:1 giving a total of 10 protons. The area under the peak is proportional to the number of protons that the peak represents. The integral measures the area of the peak and so the integral gives the relative ratio of the number of H for specific peak. In general, the more protons the more intense the peak / signal so I will now integrate my sample and simply measure the heights of the integral. I have a 6:1:2:1 ratio as seen below, although the integrals look too large to be 12:2:4:2 so this is most likely 6:1:2:1 as it is just the smallest simplest ratio it could be. Peak D

The integral ratio of peak D is 6:1, therfore an enviroment around 1 of the Carbon, within the compound is attached to 6 protons One way that this could exist is that of symmetrical branches or 2 branches. This may be a starting chain for my compound however the chain cannot be purely based on this as it is a ratio and so any scale factor could change the number of protons in that enviroment. E.g.

Chemical Shift The chemical shift (ppm) of each signal is tabulated in Table 1:

Peaks A B C D

Splitting Pattern Doublet Nonet Doublet Singlet

Chemical Shift (ppm) 0.89 1.7 3.31 4.33

A singlet suggests a proton is attached to an electronegative (Oxygen, Nitrogen or Halogen), or a proton is more than 3 sigma bonds away from the next influential proton. Looking at my Infrared data, there is no C N / C X bond present. As I only have 1 singlet, a proton must be attached to a C O bond, making an Alcohol group. An early guess can be made that peak D is responsible for this hydrogen environment as it is within the range of chemical shift of a proton bonded to an oxygen atom. Peak B also show a broad signal compared to the others.

I.e.

There are 2 doublets, it means that our CH group, if any, will couple other protons or may be partly responsible for coupling a proton.

There are no triplets which suggests that there is no presence of a CH2 group inbetween 2 non-equivalent protons nor will there be 2 CH2 groups adjacent to one another. Finally there was a nonet, which suggests a proton signal with peaks caused by 8 protons evenly or unevenly distributed adjacent the absorbing proton.

Peak A

Characteristic of Peak A: It shows two peaks which is known as doublet. This is the result of spin spin splitting due to interaction or coupling with the spin of nearby nuclei. Therefore the number of peak will tell us how many Hydrogen there is in the adjacent carbon. This can be obtain be using the n + 1 rule where n = number of hydrogen in the adjacent carbon. Number of peak = n + 1 2=n+1 n = 1 (therefore the adjacent carbon has 1 hydrogen) The chemical shift of peak A is within the range of (0.86 0.9). This suggests that peak A is attached to a methyl group as looking at the sheet given in lectures, which shows types of protons that more specific chemical shifts can represent; we see that this peak most relates to being attached to a Carbon group with a methyl branch.

There are many possibilities of where this bond could be within the compound as it consists of a R CH3. We will only know where after analysis more data.

Peak B

Characteristic of Peak B: It shows 9 peaks which is known as nonet. This is the result of spin spin splitting due to interaction or coupling with the spin of nearby nuclei. Therefore the number of peak will tell us how many hydrogen are there in the adjacent carbon. This can be obtain be using the n + 1 rule where n = number of hydrogen in the adjacent carbon. Number of peak = n + 1 9=n+1 n = 8 (therefore the adjacent carbon has 8 hydrogen in its environment) Peak B is a nonet however the oxygen molecule which is bonded to the CH2 causes peak B to move downfield to chemical shift 1.7, this is due to the fact that oxygen is very electronegative, and the proton is deshielded by the oxygen atom. This suggests that peak B was initially around 2.0, we see that from data below, this peak most relates to a proton being attached to a Carbon group which has 3 other Carbon groups attached to it, be it CH3 or CH2.

The suggested proton placement for peak B is:

Peak C:

Characteristic of Peak C: It shows a peak known as a doublet. The number of peak will tell us how many hydrogen are there in the adjacent carbon. This can be obtain be using the n + 1 rule where n = number of hydrogen in the adjacent carbon. Number of peak = n + 1 2=n+1 n = 1 (therefore the adjacent carbon has 1 hydrogen) Following my previous e.g. of what my structure will look like, and knowing that peak C shows that its adjacent Carbon only has 1 hydrogen, it leads to me believe that the structure may look something like this:

Peak D:

Characteristic of Peak D It shows one peak which is known as singlet. The number of peak will tell us how many hydrogen are there in the adjacent carbon. This can be obtain be using the n + 1 rule where n = number of hydrogen in the adjacent carbon. Number of peak = n + 1 1=n+1 n = 0 (therefore the adjacent carbon has no hydrogen) The chemical shift of peak C is 4.32 which are close to the range of an alcohol group (2.5 5). This suggests that peak D is due to the hydrogen from the O H group. As suggested earlier from the Infrared band at 3350 cm-1, peak C also show a broad signal which support the suggestion made earlier for it to have an O H group. The suggested hydrogen for peak D is:

Possible Structure of compound / sample :

Number of protons = 10.

Decoupling If a carbon having one proton A splits proton B into doublet, then by decoupling, the effect of the spins of proton A onto proton B can be eliminated and the peak due to proton B will appear as a singlet. From this we can conclude that proton A and proton B are located next to each other. This is the process of removing the spin spin splitting between spins; called decoupling. The effect of decoupling peak A on the other peaks in sample 44:

Analysis on the effect of decoupling peak A on the other peaks: Decoupling of the CH3 group proton (0.9) would reduce the CH group proton signal (1.7) from a nonet to a triplet. This shows that peak B is affected by peak A. This tells us that peak B is split into a triplet by the spin spin effect of peak A. Peak C does not show any changes in both spectrums. It has a doublet peak in full spectrum and also show a doublet peak in decouple spectrum. Therefore peak C is not affected by peak A. Peak A proton, methyl group on each clears as same environment. Peak B proton is next to a CH2 causing a triplet.

The effect of decoupling peak B on the other peaks in sample 44:

C B

Analysis on the effect of decoupling peak B on the other peaks: Originally peak A appears to be a doublet. After decoupling of peak B, it appears to be a singlet. This shows that peak A is affected by peak B. This tells us that peak A is split into a double by the spin spin effect of peak B. In its absence, the proton of the CH3 group has no adjacent Hydrogen proton anymore and so shows a singlet. Peak C also shows changes in its spectrum. It has a doublet peak in full spectrum and now shows a singlet peak in decouple spectrum. Therefore peak C is also affected by peak B. In its absence, the proton of the CH2 group has no adjacent Hydrogen proton, just an alcohol group and so shows a singlet. Peak A Proton

Peak C Proton

Peak B Proton decoupled causes the Ch3 attached to form a singlet.

The effect of decoupling peak C on the other peaks in sample 44: Analysis on the effect of decoupling peak C on the other peaks:

A B B

A C B

Decoupling peak C only shows changes to Peak B. Therefore in the compound, the proton at peak C only has effect on the proton at B. Peak B goes from a nonet into a septet, this is because in the CH2 absence, the proton of the CH group has 6 adjacent Hydrogen protons, creating a septet. From this it can be concluded that proton in peak C is not located close to proton in peak A.

Peak C Proton

Peak B Proton forms a septet as adjacent Carbons have 6 protons within its environment.

The effect of decoupling peak D on the other peaks in sample 44:

Analysis on the effect of decoupling peak D on the other peaks: Decoupling peak D does not show any changes to both peak A and B and C. From this it can be concluded that proton in peak D is not located close to proton in peak A and peak B and C, or that it may be an OH proton as OH protons are not involved with coupling.

Coupling constant, J for peak A and B:

Figure 10 shows the distance of the doublet peak for A and B:

The difference in frequency between the two peaks of the doublet is called the coupling constant, J (measured in Hz). The coupling constant, JA for peak A: JA = (0.898 - 0.882) x 400 Hz = 6.4 Hz The coupling constant, JB for peak B: JB = (1.716 1.7) x 400 Hz = 6.4 Hz The coupling constant value for peak A and peak B is equal, therefore this confirm the suggestion that they couple each other.

Final Analysis : The boiling point of Sample 40 has been givin, within the Sample information, stating a a boiling point ranging between +107C and +109C. The integral plot of the Samples NMR shows a proton ratio of 6:1:2:1, showing that there is a minimum of 10 protons within the compound. As Peak A had a ratio of 6:1 , it showed that its same enviroment had 6 protons. At this stage we assumed that a bond may exist such as CH3 C CH3. The Infrared analysis shows that there is a C O / O H bond present within the structure however we couldnt tell wether the ompound was a primary / secondary / tertiary alcohol at this stage. The chemical shift data showed which bonds existed within the sample, looking at the data, each peak showed a different bond and in some respects what it was attached to; the main thing we accomplished from this was that the coumpound was a Primary Alcohol.

Therefore sample 40 is Iso-Butanol:

Weve been given a boiling point ranging between +107C and +109C. According to the reference below, it states that Isobutanol boils at +107C to +108C and so the molecule fits this criteria.

http://www.chemicalland21.com/petrochemical/ISO-BUTANOL.htm

Sample Number # 35 Sample 35 has been provided with sample information stating; an Infrared reading of 1725 / 1300-1155 / 1034 cm-1. It has also provided that there is a mass spec parent ion at 172 amu. Figure 1: Sample spectrum Parameters: Frequency = 100MHz Accumulation = 20

Because there is a need to report the location of an NMR signal/peak in a spectrum relative to a reference signal from a standard compound added to the sample, we use tetramethylsilane, (CH3)4Si, usually referred to as TMS. TMS is unreactive and easily removed from the sample after the measurement. By zooming in on peak E, we see that this signal has a chemical shift at 0ppm; therefore this is just the TMS signal, which doesnt need to be analysed.

Spectrum was not clear; in order to view the spectrum in more detail I changed the parameters.

Figure 2: sample NMR spectrum at higher frequency Parameters: Frequency= 400MHz Accumulations = 80

Infrared Ir reading 1155-1300cm-1 1034cm-1 1725 cm-1 Literature value 11001300 cm1 10301060cm-1 1725 cm-1 Bond C=O C-O Aldehyde or Ketone

From the information given about this sample it suggests that the compound most likely has an aldehyde / ketone bond, as all 3 show a C-O. However this is just an early assumption, as a C O could be an Alcohol, so keeping this in mind more detail analysis of each peak will be made to obtain a correct compound. Therefore the sample 33 should contain some of the following below bonds. E.g.

Or

Or

Or

Integration:

Table 2: Peak A B C Peak Height cm 9 6 3 Integration ratio 3 2 1 No of protons 3H 2H 1H

Sample 33 has an Integration Ratio of 3:2:1 giving a total of 6 protons. The area under the peak is proportional to the number of protons that the peak represents. The integral measures the area of the peak and so the integral gives the relative ratio of the number of H for specific peak. In general the more protons there are the more intense the peak / signal so achieved by integrating the sample and simply measuring the heights of the integral. I have a 3:2:1 ratio as seen above, this is the smallest simplest ratio it can be however as it is just a ratio, and scale factor could change how many protons the compound has.

Peak A and B Peak A and B show an integral ratio of peak 3:2, this ratio means how many protons there are in each enviroment compared to the other. This shows the structure could be started with a simple CH3 CH2 bond. This may be a starting chain for my compound however the chain cannot be purely based on this as it is a ratio and so any scale factor could change the number of protons in that enviroment. E.g.

Chemical Shift The chemical shift (ppm) of each signal is tabulated in Table 1:

Peaks A B C

Splitting Pattern Triplet Quartet Singlet

Chemical Shift (ppm) 1.3 4.25 6.8

A singlet suggests a proton is attached to an electronegative (Oxygen, Nitrogen or Halogen), or a proton is more than 3 sigma bonds away from the next influential proton. Looking at my Infrared data, there is no C N / C X bond present. As I only have 1 singlet, a proton must be attached to a C O bond, making an Alcohol group, or Aldehydye or Ketone. I.e. Or Or Or

There are no doublets, it means that our CH group, if any, will not couple other protons nor be partly responsible for coupling a proton. There is a triplet which suggests that there is a presence of a CH2 group in-between 2 non-equivalent protons or will there be 2 CH2 groups adjacent to one another.

Finally there was a quartet, which suggests a proton signal with peaks caused by a triplet; 3 protons evenly or unevenly distributed adjacent the absorbing proton.

Peak A Characteristic of Peak A:

It shows three peaks which is known as triplet. This is the result of spin spin splitting due to interaction or coupling with the spin of nearby nuclei. Therefore the number of peak will tell us how many Hydrogen there is in the adjacent carbon. This can be obtain be using the n + 1 rule where n = number of hydrogen in the adjacent carbon. Number of peak = n + 1 3=n+1 n = 2 (therefore the adjacent carbon has 2 hydrogen) The chemical shift of peak A is within 1.3. This suggests that peak A is attached to a CH2 group, looking at the sheet given in lectures which shows types of protons that more specific chemical shifts can represent; we see that this peak most relates to being attached to a CH2 group.

There are many possibilities of where this bond could be within the compound as it consists of a R CH2. We will only know where after analysing more data. Peak B

Characteristic of Peak B: It shows 4 peaks which is known as quartet. This is the result of spin spin splitting due to interaction or coupling with the spin of nearby nuclei. Therefore the number of peak will tell us how many hydrogen are there in the adjacent carbon. This can be obtain be using the n + 1 rule where n = number of hydrogen in the adjacent carbon. Number of peak = n + 1 4=n+1 n = 3 (therefore the adjacent carbon has 3 hydrogen in its environment) The chemical shift value of 4.2 suggesting that peak B is related to a Ester group, looking at the sheet given in lectures which shows types of protons that more specific chemical shifts can represent; we see that this peak most relates to being double bonded and single bonded to an Oxygen atom. This is backed up by evidence from what the Infrared shows; that a C=O / C-O bonds are present. However the shift value of 4.2 also shows a double bond existing between two CH2 groups. A double existing as well as an Ester group would mean the molecule wouldnt require many protons, explaining the low ratio and few amount of peaks.

The suggested proton placement for peak B is:

Peak C:

Characteristic of Peak C: It shows a peak known as a singlet. The number of peak will tell us how many hydrogen are there in the adjacent carbon. This can be obtain be using the n + 1 rule where n = number of hydrogen in the adjacent carbon. Number of peak = n + 1 1=n+1 n = 0 (therefore the adjacent carbon has 0 hydrogen) Peak C is a singlet however its proton may be near an oxygen molecule which is bonded to the Carbon atom in its environment causing peak C to move upfield to chemical shift 6.8, this is due to the fact that oxygen is very electronegative, and the proton is deshielded by the oxygen atom. This suggests that peak B was initially around 5.0, we see that from data below, this peak most relates to a proton being attached to a Carbon group which is double bonded to another C atom.

As the peak is a singlet is also shows that the proton is next to a Carbon without no protons attached to it, this leads me to believe that near this proton exists a C O / C = O bond as both would cause a singlet peak. Following my previous e.g. of what my structure will look like, and knowing that peak C shows that its adjacent Carbon only has 1 hydrogen, it leads to me believe that the structure may look something like this:

Decoupling If a carbon having one proton A splits proton B into doublet, then by decoupling, the effect of the spins of proton A onto proton B can be eliminated and the peak due to proton B will appear as a singlet. From this we can conclude that proton A and proton B are located next to each other. This is the process of removing the spin spin splitting between spins; called decoupling. The effect of decoupling peak A on the other peaks in sample 35:

B C

A C B

Analysis on the effect of decoupling peak A on the other peaks: Decoupling of the CH2 group proton (1.3) would reduce the CH3 group proton signal (4.3) from a quartet to a triplet. This shows that peak B is affected by peak A. This tells us that peak B is split into a triplet by the spin spin effect of peak A. In its absence, the proton of the CH2 group has no adjacent Hydrogen proton anymore and so shows a singlet. Peak C does not show any changes in both spectrums. It has a doublet peak in full spectrum and also show a doublet peak in decouple spectrum. Therefore peak C is not affected by peak A. Peak A proton.

No adjacent proton after decoupling Peak A shows a singlet forming on Peak B.

The effect of decoupling peak B on the other peaks in sample 44:

Analysis on the effect of decoupling peak B on the other peaks: Originally peak A appears to be a triplet. After decoupling of peak B, it appears to be a singlet. This shows that peak A is affected by peak B. This tells us that peak A is split into a double by the spin spin effect of peak B. In its absence, the proton of the CH2 group has no adjacent Hydrogen proton anymore and so shows a singlet. . Peak A proton

Hydrogen Peak C

The effect of decoupling peak C on the other peaks in sample 44:

A B

A C

Analysis on the effect of decoupling peak C on the other peaks: Decoupling peak D does not show any changes to both peak A and B and C. From this it can be concluded that proton in peak D is not located close to proton in peak A and peak B and C, or that it may be an OH proton as OH protons are not involved with coupling.

Hydrogen Peak B

Hydrogen Peak A

Peak C Proton

Coupling constant, J for peak A and B: Figure 10 shows the distance of the doublet peak for A and B:

The difference in frequency between the two peaks of the doublet is called the coupling constant, J (measured in Hz). The coupling constant, JA for peak A: JA = (1.302 1.286) x 400 Hz = 6.6 Hz The coupling constant, JB for peak B: JB = (4.242 4.225) x 400 Hz = 6.8 Hz The coupling constant value for peak A and peak B is equal, therefore this confirm the suggestion that they couple each other.

Weve been given the Mass spec parent ion of the sample, stated as 172 amu. This data may have been found from a mass spec, the small peak in a mass spec shows the mr; molecular mass of the compound. I will assume that the mr of this compound will be 172. The molecule that i have found so far exists as:

The mr of this molecule adds up to 96, as well as the number of protons it contains is 6. This is exactly half of the molecular mass of the compound, and so it leads me to believe that there is a copy structure on the other side of the molecule. Evidence that this may occur is the existence of a double bond, as shown from my chemical shift pattern. So far I have 6 protons on 1 side, multiplying my proton ratio x 2 makes my proton ratio 6:4:2, giving me 12 protons. Having the existence of a double bond doesnt require many protons as its bonds are used up so the same structure being on the other side of the double bond would give me 6 x 2 = 12 protons. A reason that half the molecule never showed on the NMR is because of the fact that as both sides contain the same structure, its NMR would have overlapped one another and shown as one peak. This is because they exist in the same environment. Final Analysis : The mr of the molecule is given as 172, the molecule adds up to 172. The integral plot of the Samples NMR shows a proton ratio of 3:2:1, showing that there is a minimum of 6 protons within the compound. In my molecule there were 12 protons which fits the proton ratio with a scale factor 2. The Infrared analysis shows that there is a C O / C = O bond present within the structure, my moelcule shows the existance of these. The chemical shift data showed which bonds existed within the sample, looking at the data, each peak showed a different bond and in some respects what it was attached to; the main thing we accomplished from this was where the ester group existed.

Therefore sample 35 is: