Spin-spin coupling

The source of spin-spin coupling

The ¹H-NMR spectra that we have seen so far (of methyl acetate and para-xylene) are somewhat unusual in the sense that in both of these molecules, each set of protons generates a single NMR signal.  In fact, the ¹H-NMR spectra of most organic  molecules contain proton signals that are 'split' into two or more sub-peaks.  Rather than being a complication, however, this splitting behavior actually provides us with more information about our sample molecule. 

Consider the spectrum for 1,1,2-trichloroethane.  In this and in many spectra to follow, we show enlargements of individual signals so that the signal splitting patterns are recognizable.

The signal at 3.96 ppm, corresponding to the two H_a protons, is split into two subpeaks of equal height (and area) – this is referred to as adoublet.  The H_b signal at 5.76 ppm, on the other hand, is split into three sub-peaks, with the middle peak higher than the two outside peaks - if we were to integrate each subpeak, we would see that the area under the middle peak is twice that of each of the outside peaks.  This is called a triplet.

The source of signal splitting is a phenomenon called spin-spin coupling, a term that describes the magnetic interactions between neighboring, non-equivalent NMR-active nuclei. In our 1,1,2 trichloromethane example, the H_a and H_b protons are spin-coupled to each other. Here's how it works, looking first at the H_a signal: in addition to being shielded by nearby valence electrons, each of the H_a protons is also influenced by the small magnetic field generated by H_b next door (remember, each spinning proton is like a tiny magnet). The magnetic moment of H_b will be aligned with B₀ in (slightly more than) half of the molecules in the sample, while in the remaining half of the molecules it will be opposed to B₀.  The B_eff ‘felt’ by H_a is a slightly weaker if H_b is aligned against B₀, or slightly stronger if H_b is aligned with B₀.  In other words, in half of the molecules H_a is shielded by H_b (thus the NMR signal is shifted slightly upfield) and in the other half H_a isdeshielded by H_b(and the NMR signal shifted slightly downfield).  What would otherwise be a single H_a peak has been split into two sub-peaks (a doublet), one upfield and one downfield of the original signal.  These ideas an be illustrated by a splitting diagram, as shown below.

Now, let's think about the H_bsignal.  The magnetic environment experienced by H_b is influenced by the fields of both neighboring H_aprotons, which we will call H_a1 and H_a2.  There are four possibilities here, each of which is equally probable.  First, the magnetic fields of both H_a1 and H_a2 could be aligned with B₀, which would deshield H_b, shifting its NMR signal slightly downfield.  Second, both the H_a1 and H_a2 magnetic fields could be aligned opposed to B₀, which would shield H_b, shifting its resonance signal slightly upfield.  Third and fourth, H_a1 could be with B₀ and H_a2 opposed, or H_a1opposed to B₀ and H_a2 with B₀.  In each of the last two cases, the shielding effect of one H_aproton would cancel the deshielding effect of the other, and the chemical shift of H_b would be unchanged.

So in the end, the signal for H_b is a triplet, with the middle peak twice as large as the two outer peaks because there are two ways that H_a1and H_a2 can cancel each other out.

Now, consider the spectrum for ethyl acetate:

We see an unsplit 'singlet' peak at 1.833 ppm that corresponds to the acetyl (H_a) hydrogens – this is similar to the signal for the acetate hydrogens in methyl acetate that we considered earlier.  This signal is unsplit because there are no adjacent hydrogens on the molecule.  The signal at 1.055 ppm for the H_c hydrogens is split into a triplet by the two H_b hydrogens next door.  The explanation here is the same as the explanation for the triplet peak we saw previously for 1,1,2-trichloroethane.

The H_bhydrogens give rise to a quartet signal at 3.915 ppm – notice that the two middle peaks are taller then the two outside peaks.  This splitting pattern results from the spin-coupling effect of the three H_c hydrogens next door, and can be explained by an analysis similar to that which we used to explain the doublet and triplet patterns.

http://newdrugapprovals.org/ DRUG APPROVALS BY DR ANTHONY MELVIN CRASTO

By now, you probably have recognized the pattern which is usually referred to as the n + 1 rule: if a set of hydrogens has n neighboring, non-equivalent hydrogens, it will be split into n + 1 subpeaks. Thus the two H_b hydrogens in ethyl acetate split the H_c signal into a triplet, and the three H_c hydrogens split the H_b signal into a quartet.  This is very useful information if we are trying to determine the structure of an unknown molecule: if we see a triplet signal, we know that the corresponding hydrogen or set of hydrogens has two `neighbors`.  When we begin to determine structures of unknown compounds using ¹H-NMR spectral data, it will become more apparent how this kind of information can be used.

Three important points need to be emphasized here.  First, signal splitting only occurs between non-equivalent hydrogens – in other words, H_a1 in 1,1,2-trichloroethane is not split by H_a2, and vice-versa. 

Second, splitting occurs primarily between hydrogens that are separated by three bonds.  This is why the H_a hydrogens in ethyl acetate form a singlet– the nearest hydrogen neighbors are five bonds away, too far for coupling to occur.

Occasionally we will see four-bond and even 5-bond splitting, but in these cases the magnetic influence of one set of hydrogens on the other set is much more subtle than what we typically see in three-bond splitting (more details about how we quantify coupling interactions is provided in section 5.5B). Finally, splitting is most noticeable with hydrogens bonded to carbon.  Hydrogens that are bonded to heteroatoms (alcohol or amino hydrogens, for example) are coupled weakly - or not at all - to their neighbors.  This has to do with the fact that these protons exchange rapidly with solvent or other sample molecules.

Below are a few more examples of chemical shift and splitting pattern information for some relatively simple organic molecules. 

http://newdrugapprovals.org/ DRUG APPROVALS BY DR ANTHONY MELVIN CRASTO

Coupling constants

Chemists quantify the spin-spin coupling effect using something called the coupling constant, which is abbreviated with the capital letterJ.  The coupling constant is simply the difference, expressed in Hz, between two adjacent sub-peaks in a split signal.  For our doublet in the 1,1,2-trichloroethane spectrum, for example, the two subpeaks are separated by 6.1 Hz, and thus we write ³J_a-b = 6.1 Hz.

The superscript 3 tells us that this is a three-bond coupling interaction, and the a-b subscript tells us that we are talking about coupling between H_a and H_b. Unlike the chemical shift value, the coupling constant, expressed in Hz, is the same regardless of the applied field strength of the NMR magnet.  This is because the strength of the magnetic moment of a neighboring proton, which is the source of the spin-spin coupling phenomenon, does not depend on the applied field strength.

When we look closely at the triplet signal in 1,1,2-trichloroethane, we see that the coupling constant - the `gap` between subpeaks - is 6.1 Hz, the same as for the doublet. This is an important concept!  The coupling constant ³J_a-b quantifies the magnetic interaction between the H_a and H_b hydrogen sets, and this interaction is of the same magnitude in either direction. In other words, H_a influences H_b to the same extent that H_b influences H_a. When looking at more complex NMR spectra, this idea of reciprocal coupling constants can be very helpful in identifying the coupling relationships between proton sets.

Coupling constants between proton sets on neighboring sp³-hybridized carbons is typically in the region of 6-8 Hz.  With protons bound to sp²-hybridized carbons, coupling constants can range from 0 Hz (no coupling at all) to 18 Hz, depending on the bonding arrangement. 

For vinylic hydrogens in a trans configuration, we see coupling constants in the range of ³J = 11-18 Hz, while cis hydrogens couple in the ³J= 6-15 Hz range. The 2-bond coupling between hydrogens bound to the same alkene carbon (referred to as geminal hydrogens) is very fine, generally 5 Hz or lower.  Ortho hydrogens on a benzene ring couple at 6-10 Hz, while 4-bond coupling of up to 4 Hz is sometimes seen between meta hydrogens.

Fine (2-3 Hz) coupling is often seen between an aldehyde proton and a three-bond neighbor. Table 4 lists typical constant values.

Complex coupling

In all of the examples of spin-spin coupling that we have seen so far, the observed splitting has resulted from the coupling of one set of hydrogens to just one neighboring set of hydrogens. When a set of hydrogens is coupled to two or more sets of nonequivalent neighbors, the result is a phenomenon called complex coupling. A good illustration is provided by the ¹H-NMR spectrum of methyl acrylate:

First, let's first consider the H_c signal, which is centered at 6.21 ppm.  Here is a closer look:

With this enlargement, it becomes evident that the Hc signal is actually composed of four sub-peaks. Why is this? H_c is coupled to both H_aand H_b , but with two different coupling constants.  Once again, a splitting diagram can help us to understand what we are seeing.  H_a istrans to H_c across the double bond, and splits the H_c signal into a doublet with a coupling constant of ³J_ac = 17.4 Hz. In addition, each of these H_c doublet sub-peaks is split again by H_b (geminal coupling) into two more doublets, each with a much smaller coupling constant of²J_bc = 1.5 Hz.

The result of this `double splitting` is a pattern referred to as a doublet of doublets, abbreviated `dd`.

The signal for H_a at 5.95 ppm is also a doublet of doublets, with coupling constants ³J_ac= 17.4 Hz and ³J_ab = 10.5 Hz. 

The signal for H_b at 5.64 ppm is split into a doublet by H_a, a cis coupling with ³J_ab = 10.4 Hz. Each of the resulting sub-peaks is split again by H_c, with the same geminal coupling constant ²J_bc = 1.5 Hz that we saw previously when we looked at the H_c signal.  The overall result is again a doublet of doublets, this time with the two `sub-doublets` spaced slightly closer due to the smaller coupling constant for the cisinteraction.  Here is a blow-up of the actual H_bsignal:

http://newdrugapprovals.org/ DRUG APPROVALS BY DR ANTHONY MELVIN CRASTO

When constructing a splitting diagram to analyze complex coupling patterns, it is usually easier to show the larger splitting first, followed by the finer splitting (although the reverse would give the same end result).

When a proton is coupled to two different neighboring proton sets with identical or very close coupling constants, the splitting pattern that emerges often appears to follow the simple `n + 1 rule` of non-complex splitting.  In the spectrum of 1,1,3-trichloropropane, for example, we would expect the signal for H_b to be split into a triplet by H_a, and again into doublets by H_c, resulting in a 'triplet of doublets'.

H_a and H_c are not equivalent (their chemical shifts are different), but it turns out that ³J_ab is very close to ³J_bc.   If we perform a splitting diagram analysis for H_b, we see that, due to the overlap of sub-peaks, the signal appears to be a quartet, and for all intents and purposes follows the n + 1 rule.

For similar reasons, the H_c peak in the spectrum of 2-pentanone appears as a sextet, split by the five combined H_b and H_d protons. Technically, this 'sextet' could be considered to be a 'triplet of quartets' with overlapping sub-peaks.

http://newdrugapprovals.org/
DRUG APPROVALS BY DR ANTHONY MELVIN CRASTO

In many cases, it is difficult to fully analyze a complex splitting pattern.  In the spectrum of toluene, for example, if we consider only 3-bond coupling we would expect the signal for H_b to be a doublet, H_d a triplet, and H_c a triplet.

In practice, however, all three aromatic proton groups have very similar chemical shifts and their signals overlap substantially, making such detailed analysis difficult.  In this case, we would refer to the aromatic part of the spectrum as a multiplet.

When we start trying to analyze complex splitting patterns in larger molecules, we gain an appreciation for why scientists are willing to pay large sums of money (hundreds of thousands of dollars) for higher-field NMR instruments.  Quite simply, the stronger our magnet is, the more resolution we get in our spectrum.  In a 100 MHz instrument (with a magnet of approximately 2.4 Tesla field strength), the 12 ppm frequency 'window' in which we can observe proton signals is 1200 Hz wide.   In a 500 MHz (~12 Tesla) instrument, however, the window is 6000 Hz - five times wider.  In this sense, NMR instruments are like digital cameras and HDTVs: better resolution means more information and clearer pictures

TAKE A TOUR

Austral Islands

• Austral Islands – Wikipedia, the free encyclopedia

  en.wikipedia.org/wiki/Austral_Islands

  The Tuha’a Pae or Austral Islands (French: Îles Australes or Archipel des Australes) are the southernmost group of islands in French Polynesia, an overseas …
  

Tubuai is in the Austral Archipelago. These island chains are spread out over an area the size of Europe with 120 islands in all, 25 of which that are …

////////

1H NMR VERSUS 13C NMR

 

 

 

 One of the greatest advantages of ¹³C-NMR compared to ¹H-NMR is the breadth of the spectrum - recall that carbons resonate from 0-220ppm 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.

3,3'''-dioctyltetrathiophene.

....... 13 c nmr



 Mp. 55-56°C. Yield 19%. 
¹H-NMR (270 MHz, CDCl ₃, ppm), 7.15 (2H, d), 7.10 (2H, d), 7.0 (2H, d), 7.0 (2H, d), 6.90 (2H, d), 2.78 (4H, t,a-CH₂), 1.65 (4H, m, b-CH₂), 1.24 (20H, m, CH₂), 0.88 (6H, t, CH₃). The UV max in CHCl₃ was 456.6 nm.

 http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0366-16442000000100008&lng=en&nrm=iso&ignore=.html

The UV-visible absorption of the alkylthiophene tetramer (3), l_max = 456.6 nm (CHCl₃) is related with the conjugation length of the oligomer. For non-substituted thiophene oligomers this absorption increases from bithiophene to sexithiophene from 300 to 434 nm (CHCl₃), the tetrathiophene oligomer absorbs at 416 nm (CHCl₃)⁸⁾. The alkyl side chain lead to increased steric interaction between the conjugated backbones and thus reduces p-p interactions between the molecules in solid state. The presence of the side alkylchain increases the solubility alkylthiophene in aromatic and chlorinated hydrocarbons allowing a full characterization. As a result of the steric influence of the alkyl side chain, the substituted thiophene rings are rotated so the alkyl groups lie on opposite side facilitating the conjugation length through the rings and thus shifting the absorption to a lower energy.

Figures 2 and 3 show FT-IR, and ¹³C-NMR spectra of 3,3'''-dioctyltetrathiophene respectively. The infrared spectrum, Figure 2, shows three main regions, between 2850-2950 cm^-1 the C-H stretching vibration due to othe alkyin, between 1500-1400 cm^-1 which corresponds to the C=C stretching vibration and between 900-450 cm^-1, the -H bending (out of plane) vibrations. The absorption near 1490 cm^-1 (C=C) asymetric is characteristic of thiophene oligomers and increases in intensity from bithiophene to sexithiophene⁸⁾. The strong band at 798 cm^-1corresponds to the C-H bending and is characteristic of 2,5-substituted thiophene ring⁹⁾.

The ¹³C-NMR spectrum is shown in Figure 3, a completed assignment of the aromatic carbon chemical shift has been achieved and is presented on the structure. The spectrum shows the 8 carbon signals due to the octyl alkyl group, betwen 13 and 31 ppm, which is normal for this region. Between 122 and 139 ppm are the absorption of the aromatic carbon of thiophene rings. The non-substituted tetrathiophene has absorptions between 123 and 134 ppm.⁸⁾

The a,a'-coupled carbon has at 136-137 ppm signals. The a carbons which are not coupled absorb at 122.9 ppm, while the b carbons present two different signals depending of their position. The ones which are on the extreme positions absorb at 129.1 ppm and the inner ones have signals between 124.5-125.5 ppm. The carbons carrying the alkyl chain absorb upfield at 138.9 ppm. This signal is observed at 143.2 ppm with the 3-octyl thiophene.

FIG. 2. FT-IR spectrum of 3,3''-dioctyltetrathiophene.

FIG. 3. ¹³C-NMR spectrum of 3,3''-dioctyltetrathiophene. 
________________________________ 
*To whom correspondence should be addressed.

REFERENCES

1. F. Garnier, G. Horowitz, D. Fichou. Synth. Met., 28, C705 (1989).         [ Links ]

2. T. Zhao, M. Samoc, B. Singh, P. Prasad. J. Phys. Chem., 93, 7916 (1989).         [ Links ]

3. J. Roncali. J. Chem. Rev., 92, 71 (1992).         [ Links ]

4. M. Sato, H. Mori. Macromolecules, 24, 1196 (1991).         [ Links ]

5. M. SAto, S. Tanaka, K. Kaeriyama. J. Chem. Soc. Chem. Commun., 873 (1986).         [ Links ]

6. K. Jen, G. Miller, R. Eisenbaumer. J. Chem. Soc., Chem. Commun., 1346 (1986).         [ Links ]

7. K. Tamao, S. Kodama, I. Nakajima, M. Kudama. Tetrahedron, 38, 3347 (1982).         [ Links ]

8. F. Martínez, R. Voelkel, D. Naegele, H. Naarmann. Mol. Cryst. Liq. Cryst., 167, 227 (1998).         [ Links ]


DRUG APPROVALS BY DR ANTHONY MELVIN CRASTO
http://newdrugapprovals.org/