Julia Carlstad

1230835
Chem 463 A
TA: Brice Jurban
I.

Unknown #2: Morita

Given data and known spectral parameters

The unknown was a white crystalline solid. It was semi-soluble in most solvents, especially
Acetonitrile and methylene chloride, but was not readily soluble in water or CDCl3.
IR was taken using two different methods, to obtain different parts of the spectrum. The thin film
method was done by dissolving a small amount of compound in methylene chloride and allowing
it to evaporate on the salt plate, leaving behind a thin layer of solid compound. This produced
spectral definition of the region above 1500 cm-1, the functional group region. A KBr press was
used to obtain the fingerprint region of the spectrum. This was done with 2 mg of unknown in
200 mg KBr.
CNMR was taken with 16.4 mg in 0.5 mL of DMSO using the method file 13CTran463 and the
pulse program zgpg. HNMR was run using the same concentration and method file proton.
COSY was run using method file JuliaCOSY with 16.4 mg in 0.75 mL DMSO. HMQC and
DEPT 45, 90, 135 were taken by Brice using a concentrated sample and carefully prepared
method files using their respective pulse programs.
UV-Vis was taken with 2.6mg in Acetonitrile diluted to 0.0026 molality using an ocean optics
instrument with a deuterium discharge lamp for the UV range and a tungsten-iodide incandescent
lamp for the visible range. The neutral solution was acidified with 0.5 mL 3M HCl and a separate
neutral sample was basified with 0.5 mL of NaOH. The integration time was set to 2300
seconds, boxcar smoothing was set to 10 and 7 spectra were averaged.
GC-MS was taken using the BRICE463LONG program with 1.7 mg unknown in 1.5 mL
methylene chloride. The instrument uses electron impact MS and was set in positive mode.
II.

Annotated Spectra

See attached pages

III.

Initial Spectra Analysis

GC-MS
The structure eluted from the GC at a time of 16.551 minutes with 100% abundance. The
molecular ion peak can be seen to be at 235.9 m/z which rounds to 236 m/z and has an
abundance of 13445. This indicates that the structure has an even number or zero nitrogens. The
[M+1]+. abundance is 1577/13445 or 11.7% of the molecular ion. There is a very strong [M+2]+.
peak as well, with an abundance of 12831/13445 or 95.4% of the molecular ion. This
immediately indicates that the structure contains a halide, and with such a strong peak, it is most

likely a bromine atom. There is also a larger [M+1]+. peak than would be anticipated for a carbon
and hydrogen structure, which indicates the presence of another heteroatom, a nitrogen or
oxygen.
The initial molecular formulas were determined to be C11H9NBr with an index of hydrogen
deficiency (IHD) of 7 and a molecular weight of 234 amu or C11H9OBr with an IHD of 7 and a
molecular weight of 236 amu.
The base peak can be observed at 114 m/z, which indicates that this is the most stable fragment
of the molecule. While the molecular ion peak is strong, the structure at 114 m/z must also be a
very stable structure in order to produce such high abundance. This can be seen to be a loss of
the bromine from the structure at 192.9 m/z. The structure at 192.9 m/z is the loss of a CH3 first
producing the peak at 220.9 m/z followed by a successive loss of CO from the structure.
Fragmentation pattern shows noticeably lacking structures, such as the lack of a tropylium ion
fragment and a lack of a charged benzene fragment. This indicates that the molecule does not
contain a six-membered aromatic ring that is easily fragmented, such as a substituted benzene.
Other notable peaks include the peak at 15.2 m/z which has a large abundance of 4368,
indicating a rapid loss of a methyl group. Also, the peak at 126.0 m/z indicates two fused
benzene rings, such as a structure like naphthalene. The peak at 157.0 is not highly abundant, but
is due to the loss of a bromine from the molecular ion.
IR
The first key feature that can be noted in the IR spectra is the presence of an aromatic system.
This can be observed in the peaks at 1626 cm-1 (C=C stretch), 1587.9 cm-1 and 1498.6 cm-1 (C-C
aromatic), 902.2 cm-1, 853.6 cm-1, and 816.3 cm-1 (CH out-of-plane bending in an aromatic).
Additional features of note are a small amount of sp3 C-H alkane stretch at 2718.9 cm-1, and a CO stretch at 1065.9 cm-1 and 1032.0 cm-1. The peak at 1266.0 cm-1 could indicate a C-X bonding,
but is hard to differentiate from the aromatic C-C stretching. Additionally of note are the features
between 500-800 cm-1 which can be indicative of C-Br stretching or the bending of a fused
aromatic ring system.
There is no hydroxyl, acid, or amine group in this complex because of the lack of broad
stretching above 3000 cm-1 in the Nujol IR. In the KBr spectrum this can be attributed to an
acetone or water impurity in the sample. There is also a complete lack of any carbonyl functional
group, which would show a strong peak around 1700-1800 cm-1 or any triply bonded system
which would show a peak at 2200-2400 cm-1.

UV-Vis

UV-Vis Spectrum of Unknown #2

1.8
1.6
1.4
1.2
1
Absorbance

0.8

Unknown #2

Base

0.6
0.4
0.2
0
200

220

240

260

280

300

320

340

360

380

400

Wavelength (nm)
Figure 1: UV-Vis spectra of Unknown #2 in Acetonitrile. Blue shows the diluted sample in Acetonitrile, while red
shows the basification with 0.5 mL of NaOH of this original sample. The max is at 230.74 nm with an Absorbance of
0.804. Two other smaller peaks are observed at 271.99 nm (A=0.091) and at 334.55 nm (A=0.049).

The UV-Vis shows a major peak at 230.74 nm [=309 m-1cm-1] with an absorbance of 0.804 and
two smaller peaks at 271.99 nm [35.0 m-1cm-1] and 334.44 nm [18.8 m-1cm-1] with absorbance
values of 0.091 and 0.049 respectively. These peaks are indicative of a conjugated chromophore,
such as an aromatic ring, but they do not align with many of the standard aromatics, such as a
benzene group, which has major peaks at 184 nm, 204 nm, and 254 nm. This could mean that the
compound has a more complicated pi bonding system than a standard aromatic complex.
Acidification with HCl and basification with NaOH showed minor changes that were only due to
the addition of volume and thus change in concentration of the sample. With the addition of acid
and base the wavelength shifted to 230.37 nm, a negligible change from 230.74 nm in a neutral
solution. This indicates that the compound must not have a group that can change protonation
such as an amine or a hydroxyl group.
NMR
Initial analysis of the HNMR notes two large singlet peaks in the alkane region that are bonded
to an electronegative substituent, such as an oxygen because they have chemical shifts of 3.437
ppm and 3.927 ppm. These peaks must be isolated from other spin systems because they are
singlets and both integrate to three protons, meaning that they must be methyl groups.

Next, it can be observed that there is a complicated splitting pattern in the aromatic region of the
spectrum between 7.268 ppm and 8.156 ppm. There are a total of six hydrogens in the aromatic
region based on integration values of the peaks. These peaks also have a large range of chemical
shift, with the most downfield proton at 8.156 indicating that there is an electronegative
substituent on the aromatic ring. There is evidence of long range coupling based on the fact that
the peaks at 8.155 ppm and at 7.405 ppm are essentially singlets and have very small coupling
constants of 1.0 Hz and 2.2 Hz respectively. The peak at 7.850 ppm initially appears to be a
triplet, however it is actually an overlapping pair of doublets. This can be determined from the
fact that there are two different coupling constants (8.8 Hz and 6.8 Hz) for these peaks. This can
also be determined from the peak height analysis, where a triplet should show a 1:2:1 ratio of
peak heights. These peaks do not show this ratio, only slight differences in height between the
inner and outer peaks. This is significant because it could indicate that the molecule has
symmetry that induces a similarity in chemical shifts for two protons. The peak height analysis is
shown pictorially below.

Finally, coupling can be observed based on calculated coupling constants and also correlated to
the COSY data. From this determination it can be seen that coupling occurs between peaks at
7.268 ppm and 7.850 ppm with a coupling constant of 8.9 Hz. Based on COSY it can be
observed that the other large coupling occurs between the peaks at 7.617 and 7.850 ppm with a
coupling constant of 6.8 Hz. Finally, long range coupling can be seen to exist between 8.156 ppm
and 7.617 ppm with 1 Hz coupling and between 7.406 ppm and 7.268 ppm with 2.2 Hz coupling.
This important connectivity information shows that there are multiple spin systems in this
molecule that are not fully interacting. This will be key in finding the ultimate connectivity of the
molecule when combining all spectral data.
There are eleven unique carbon signals in the CNMR, and all but one appears in the aromatic
region of the spectrum. Notable in the carbon NMR are the nine peaks clustered together at
downfield chemical shifts, ranging from 105.937-157.557 ppm which indicates the presence of
an aromatic ring complex. The highest field carbon, at 55.124 ppm is not in the region of an alkyl
chain, but rather is bonded to an electronegative element such as a halide or oxygen atom. The
DEPT data shows that this carbon is the sole primary carbon, which indicates that it must be
bonded to an oxygen rather than a halide. The DEPT data shows that there are four quaternary
carbons in the aromatic region at 116.169 ppm, 129.597 ppm, 132.851 ppm, and 157.557 ppm,
signifying that there must be four bonding locations to the aromatic. The similarity in chemical
shift of the carbons from 128ppm-130 ppm could mean that this compound has a high amount of
symmetry that causes the carbons to be in similar chemical environments, such as a para

substitution with different types of substituents. Finally, the downfield nature of the carbon at
157.557 ppm indicates that it must be attached to an electron-rich substituent.
HMQC data must be analyzed using the peak picking values shown in the following table.
HMQC peak data for C-H correlation
HNMR shift
CNMR shift
Intensi
(ppm)
(ppm)
ty
3.976
55.772
4.415
7.284
120.135
0.556
7.38
106.208
2.021
7.629
129.454
0.432
7.798
128.967
0.939
7.906
129.362
0.751
8.197
129.652
0.747

From this data it can immediately be observed that the high field carbon is connected to the three
hydrogen peak that is high field in the HNMR. Another important first conclusion from this data
is the lack of coordination of the first hydrogen peak at 3.437ppm. This must be due to solvent
effects or impurity in the sample because it is shown to not have any connectivity to any carbon
in the structure. It can also be observed that the doublet of doublets at 7.2678 ppm is connected
to the carbon at ~120 ppm. The hydrogen singlet peak at ~7.4 is connected to the carbon at ~105
ppm. After careful structure elucidation the remainder of the peaks will be used to determine and
identify each carbon and hydrogen connectivity.
IV.

Logical Structure Elucidation

Based on the number of carbons in CNMR and hydrogens in HNMR, combined with the
functional groups observed in IR and the fragmentation pattern observed in MS, the chemical
formula can be determined to be C11H9OBr which has an IHD of 7.
IR, CNMR, HNMR, and UV-Vis all show strong indication of an aromatic ring system, but one
that involves 10 carbons and 6 hydrogens. The UV-Vis and MS show that this complex is not a
benzene ring because of the significant difference between literature values for wavelengths and
significant fragmentation patterns. The DEPT shows that there are four quaternary carbons in
the system, which could indicate that there is a fused ring system, such as a naphthalene
backbone. This aligns with the CNMR because a naphthalene system involves ten carbons
bonded in a pi system. This would also provide a large and strongly interacting electron system
for analysis in UV-Vis. Further evidence of this system comes from the MS, which shows a
naphthalene peak at 126.0 m/z, and smaller fragments that align with the literature fragmentation
pattern for this compound, such as the peak at 63 m/z. The IHD of 7 also matches with a
naphthalene backbone with no extra unsaturation. The chemical shifts of the unknown are on the
order of a literature studied naphthalene complex, which can have values between 6.9-8.9 ppm
depending on substitution. More indicative of a naphthalene backbone in this complex are the
coupling constants between protons in the structure. In literature, a naphthalene has coupling
constants of 8.28 Hz, 6.85 Hz, 0.74 Hz, and 1.24 Hz. These values, especially 8.28 Hz and 6.85

Hz are almost exactly matching with the experimental values of 6.8 Hz and 8.9 Hz. This is very
strong evidence for the presence of a naphthalene aromatic system in this unknown.
There must be substituents on this ring, based on the DEPT NMR that shows that there are four
carbons that are quaternary and only two are created in a naphthalene compound. The structure
of the substituents can be concluded from a number of different spectroscopic sources. First, the
MS shows strong indication of a bromine based on the large [M+2]+ peak, which matches very
closely with the isotopic ratios of bromine, especially in comparison to any other heteroatom.
The IR shows some evidence of C-X and C-Br stretches around 1200 cm-1 and 500 cm-1. This
must be directly bonded to the aryl ring system because there are no primary or secondary
carbons in the alkyl region as one would expect for a Ar-C-Br complex.
The second substituent must involve the remaining carbon that is only primary based on DEPT
analysis. This CNMR chemical shift is not indicative of a methyl attached to an aryl ring,
because it is too far downfield. Rather, the methyl must be attached to an electron withdrawing
group, such as an ether. This is aligned with the HNMR chemical shift, where an ether gives a
much higher hydrogen chemical shift than other common heteroatoms. Additional evidence is
shown in the IR, where a C-O stretch is observed. Finally, the MS fragmentation pattern matches
that of a methoxy group because of the peak at 220.9 m/z, which signifies the loss of a methyl
from the molecular ion, and then the further change from this peak to 192.9 m/z, which
corresponds to the loss of a CO (28 m/z) from a naphthalene derivative.
After determining the naphthalene backbone and substituents corresponding to a bromide and
methoxy ether, the substitution pattern on the rings must be determined. To do this the splitting
patterns, coupling constants, and chemical shifts must be determined and assigned to each
carbon, hydrogen, and substituent location. This was done utilizing literature data for substituent
effects on an aromatic ring. It is known that methoxy is an electron donating group to a ring, so it
will activate and shield the ortho and para locations to its substitution, and somewhat deshield
the meta position. The bromine is somewhat less electron donating, and will have a smaller effect
on the chemical shift of the protons on the ring.
The splitting pattern shows two singlet peaks with long range coupling, but these singlets have
very different chemical shifts. This means that these two protons must not have three bond
coupling to another proton, but must also be near the two different substituents. The singlet that
is more downfield (8.155 ppm) must be the one next to the bromine, since this has less shielding
effects than the methoxy group. This means that the other singlet (7.4055 ppm) must be adjacent
to the methoxy substituent.
Next, there are four total sets of doublets, with one set overlapping in chemical shift. These four
hydrogens must be in two different spin systems and are splitting one and other. The downfield
hydrogen must be ortho to the methoxy group because this would provide the most shielding.
The next downfield doublet must be that ortho to the bromine because it feels less shielding
effect since the bromine is less electron donating than a methoxy, but is still more shielded than
the meta position. Finally, the overlapping doublets must be the hydrogens meta to the
substituents, with the methoxy being slightly more upfield than the bromine hydrogen. This is
corroborated by the fact that these hydrogens are similar based on molecular symmetry, which

would cause them to have a similar chemical shift. These assignments match with the coupling
constants seen in a substituted naphthalene ring, where the two hydrogens with three bond
coupling near the bromine should have coupling constants of approximately 8 Hz and the
hydrogens near the methoxy should have approximately 9 Hz coupling. Similarly, the protons
that are isolated should have coupling constants of 1.0-1.5 Hz. This placement also matches with
a synthetic method that one would take to create this compound, where the methoxy would first
be added to the aryl ring and then would activate through resonance to the location of bromine
attachment. Taking into account the symmetry of the molecule in addition to expected coupling
constants, splitting patterns, and chemical shifts the substituent location can be assigned.
The final structure of this compounds is 2-bromo-6-methoxy naphthalene.

V.

Final Spectral Assignments

GC-MS
Elution occurred at 16.551 minutes with 100% abundance.
[M]+. = 235.9 m/z ~ 236 m/z with abundance of 13445
[M+1]+. = 1577/13445 = 11.7%
[M+2]+. = 12831/13445 = 95.4%
The large [M+2]+. shows peak the presence of a bromine atom. [M+1]+. indicates an
additional heteroatom that can attributed to the oxygen isotope with a mass of 16 amu.
Molecular formula: C11H9OBr

IHD = 7

MW = 236 amu.

Fragments can be observed due to the initial loss of the methyl at 220.9 m/z, followed by
a loss of the oxygen at 126 m/z. From the 220.9 m/z structure the most stable
fragmentation is the loss of a CO from the aromatic ring, producing the peak at 192.9
m/z. This continues to fragment, losing a bromine and producing the peak at 114 m/z.
Smaller fragments, especially that at 63 m/z are characteristic of a naphthalene, but the
mechanism and structure of fragmentation are not confirmed by literature. The smaller
fragments from these pathways are observed in the methyl peak at 15.2 m/z and the CO
peak at 29.1 m/z. An alternative initial fragmentation that is less abundant can be
observed with the loss of a bromine producing the peak at 157.0 m/z.
See attached page for fragmentation mechanisms.

IR
Wavenumber
(cm-1)
2718.9
1626.0
1587.9
1498.6
1266.0
1211.8
1164.5
1065.9
1032.0
902.2
853.6
816.3
500

Functional
Group
sp3 C-H alkane
C=C
C-C aromatic
C-X

CN/CO
CH oop aromatic

C-Br or fused ring

bend

UV-Vis
UV-Vis peaks at 230.74 nm [=72,900 M-1cm-1], 271.99 nm [8,260 M-1cm-1] and 334.44
nm [ 4,440 M-1cm-1] are all assigned to the extended chromophore of the naphthalene
aromatic ring. This system has no protonated heteroatoms that would be affected by
addition of acid or base which matches with the experimental data. Acid and base
addition shifted the wavelength to 230.37 nm, a negligible change from 230.74 nm in a
neutral solution. There was also no major change in the absorbance upon addition.
HNMR/COSY

3.927 s

Integrati
on [value
used]
1.01 [3]

c
d

7.268 dd
7.406 d

0.31 [1]
0.32 [1]

7.617 dd
Overlappi
ng
7.850 doublets
8.156 d

0.31 [1]

2.6
8.9 f,d
2.2 c
1.6
8.9 g, f

0.67 [2]
0.30 [1]

8.8
6.8 e, c
1 e

Pea
k

f
g

Chemical
Shift (ppm)

Splitting
Pattern

CNMR/DEPT/HMQC

Coupling
Constant, J
(Hz)

COSY
interacti
on
None

Functio
nal
Group
CH-O
Aromati
c

Carbon Number
1
2
3
4
5
6
7
8
9
10
11
VI.

Chemical Shift
(ppm)
55.124
105.937
116.169
119.679
128.519
128.834
129.172
129.304
129.597
132.851
157.557

DEPT
CH3
CH
C
CH
CH
CH
CH
CH
C
C
C

Functional
group
CX X=halide,O
Aromatic

HMQC
Interaction
b
d
None
c
e
f
f
g
None
None
None

References

Lambert, J.B. et al. Organic Structure Spectroscopy, 2nd ed.; Prentice Hall: Boston, 2011.
Reich, H.J. Structure Determination Using NMR. University of Wisconsin[Online] February 11,
2015, (accessed February 10, 2016).
Yinon, J. Mass Spectral Fragmentation processes in nitronaphthalenes: A study using tandem
mass spectrometry and collision-induced dissociation. Rapid Communications in Mass
Spectrometry. 1993, 7, 67-70.