Problem 266 OK

The molecule has 5 DBE numbers and O-H broad absorption is observed ad 3517 cm -1. Some
fragments are recognized from molecular ion peak as base ion peak (m/z = 164), a fragment from
[M+ - CH3] (m/z = 149) and benzyl. Its carbon DEPT NMR showed nine signals to be assigned
for each atom carbon from C10H12O2. Since the methylene carbon signal appeared at higher field
than methyl, it can be predicted that this methyl is an ethoxy group and the methylene might be
adjacent to benzene ring. When proton NMR showed aromatic methine as three separated signals
with 1,2,4-trisubstituted pattern, we can assign the substituents as methoxy, hydroxy and another
one as allyl. After considering some plausible arrangements, the result is 4-allyl-2-
methoxyphenol (although 3-allyl-4-methoxyphenol can’t be excluded either). Thus, the proton
NMR from higher field come as follows: Hh (doublet, with long range coupling should be ddd),
Ha (singlet), Hj (double doublet), Hi (double double triplet) and aromatic proton which obtained
as Hd (doublet, coupling constant about 2 Hz), Hf (double doublet, with two ortho coupling
around 9 Hz and meta aroung 2 Hz) and the last signal as doublet (Hg).

Problem 267 OK

The given molecule with 7 DBE numbers only has one weak absorption to be identified from
alkyne group at 2204 cm-1. Thus, the sharp peak around 3000 cm-1 must be form terminal
hydrogen from alkyne as well. The mass spectrum gives molecular ion peak (m/z = 218/220) and
base ion peak after cutting methyl group (m/z = 203/205) where each of these fragments has 1:1
ratio. The other fragment is surely from [M+- CH3 – Cl] (m/z = 183). The carbon DEPT NMR has
ten signals to accommodate C14H15Cl molecule, thus the methyl signal is predicted bearing three
carbon atoms and the molecule assign as 1,4-disubstitued benzene (because aromatic methine
carbon is shown by two signals). Moving to its proton NMR, methyl signal from tert-butyl
appears at higher field as singlet followed by two methine protons which each comes as doublet.
Methine signal adjacent to chlorine obtained at higher field than the one adjacent to sp3 carbon.
We can assume that the well separated doublet signals are resulted from trans configuration.
Hence, the structure will be named (E)-1-chloro-4-(4-tert-butylphenyl)-1-but-en-3-yne.

It is sure that there are tert-butyl, ethenyl, ethynyl and chloro groups in this compound. However,
the sequence is not sure. So, you should consider all possibilities.
Problem 268 OK

The molecule of C6H9NO5 has 3 DBE numbers and a broad O-H absorption can be seen easily
followed by carbonyl absorption which might be come from carbonyl carboxylic (1701 cm-1).
The base ion peak is assigned from acylium ion peak (m/z = 43). After seeing the carbon DEPT
NMR where three signals for quaternary carbons indicating carbonyl appeared around 177 ppm
along with other carbon signals as methyl, methylene and methine, the plausible structure is N-
acetylaspartic acid. Since the methylene protons are inequivalent due to intramolecular
hydrogen bonding prevent free rotation, the doublet looks signal at 3.0 ppm should appear as
double doublet doublet. Futhermore, the methine signal which obtained as 3 lines is the result of
doublet double doublets signal with similar coupling.

Problem 269 OK

This molecule has one addition of carbon atom from previous problem, which is mean the
methylene carbon becomes two. The fragments can be identified as [M + - COOH] (m/z = 144),
[M+ - COOH- COCH3] (m/z = 102), base ion peak after the previous fragment lose hydroxy
group (m/z = 84) and acylium ion peak. From proton NMR, the centered methylene gives a
signal around 2.0 ppm as dddd (although it is easily assigned as multiplet) followed by
methylene adjacent with two inequivalent protons where each should be ddd but looks like
triplet due to similarity of coupling constant. The methine signal will be assigned as ddd after
coupling with N-H proton and adjacent methylene resulting 4 lines since two different types of
coupling constant occurred. Nevertheless, the molecule of C 7H11NO5 will be named N-
acetylglutamic acid.

Two protons of H-e are separately observed at 2.0 and 1.85 ppm, which indicates they are
inequivalent. With regard to H-f, two protons seem to be equivalent. Thus, H-f is observed as a
dd, H-e as a ddt, H-e’ as a ddt, and H-d as a dd. Although an N-H proton of an amide function
sometimes shows coupling with adjacent proton, it is not observed in this case because the
spectrum is measured using D2O as a solvent.

Problem 270 OK

The molecule with 6 DBE numbers showed some significant absorption which can be assigned
for carbonyl amide (1659 cm-1), carbonyl ester (1722 cm-1), a broad O-H bond and N-H bond
(3547 cm-1) respectively. The base ion peak is proposedly from [M + - NH2COCH3] (m/z = 192)
and continue lose ethoxy group giving a peak at m/z = 147. The next peak with secondary
highest intensity is from hydroxybenzyl fragment (m/z = 107). We can be sure the molecule is
1,4-disubtituted benzene after see the methine signals form carbon and proton NMR. Now, the
carbonyl ester will appear at lower field than carbonyl amide followed by quaternary atom
adjacent to hydroxy. The aromatic methine signals are separated with another quaternary carbon
adjacent to methylene. However, the methylene appeared around 60 ppm is from ethoxy group
which then followed by methine adjacent to nitrogen. Two types of methyl also obtained at
higher field among all carbon atoms. By these up interpretations, the molecule is arranged as
ethyl 2-acetamido-3-(4-hydroxyphenyl)propanoate. The proton signal for methylene adjacent
to phenyl appeared around 3.0 ppm as two double doublet signals from its inequivalent protons
respectively. Meanwhile, the methylene from ethoxy is obviously gives quartet signal at 4.2
ppm. Next, the methine adjacent positioned between carbonyl and nitrogen atom appeared at 4.9
ppm as ddd and the aromatic methines give doublet at expected range.

It is similar in this case. Two protons of H-e appear independently as a dd, respectively (2.98 and
3.07 ppm). This spectrum is measured using CDCl 3 as a solvent, H-d shows a coupling with N-
H, hence, it is observed as a ddd.

Problem 271 OK

This molecule has 2 DBE number which later fits to assign as one double bond and a ring
character. The absorptions from IR spectrum can be predicted form C=C (2851 cm- 1) and C-O
(1077 cm-1). Since the carbon proton decoupled NMR obtained simply giving methylene which
come at lower field due to adjacent with electronegative oxygen atom and methine signals, the
plausible structure is 2,5-dihydrofuran. Thus, the singlet looks like signal for methylene with
equivalent protons should be doublet followed by the other singlet which must be triplet. The
splitting pattern might not obtain clearly by using 200 MHz NMR spectrum.

Problem 272 OK

This molecule is isomer from Problem 271. The arrangement that could give two types of
methine and methylene signal is strongly 2,3-dihydrofuran. The absorption from IR spectrum at
1620 cm-1 can be assigned for enol ether (-C=O-OR). The signal for each methine proton (Ha and
Hb) has long range coupling with expected methylene resulting double double doublet signal and
ended up giving quartet looks like signal since all of the coupling constant are the same. The
methylene adjacent to oxygen atom will have dddd with overlapping of signal resulting triplet
looks at 4.25 ppm. Futhermore, the centered methylene with 2 inequivalent proton has ddddd.

This spectrum is somewhat strange because vicinal coupling constant between H-c and H-b is
almost similar to that of long range coupling between H-c and H-a. Anyway, two prptons of Hd
and H-c are equivalent. Thus, H-d is observed as triplet, H-c as a ddt, H-b as a dt, and H-a as a
dt.
Problem 273 OK

This molecule has 8 DBE numbers and carbonyl carboxylic absorption at 1697 cm -1. The
fragments can be identified as [M+ -OH] (m/z = 198) followed by peak after losing carboxylate
group (m/z = 154) and another peak as base peak ion after continue losing -CO (m/z = 126).
Since carbon DEPT NMR only tells the existence of quaternary carbons for carbonyl and
aromatic along with aromatic methine, the predicted structure will be 2,3-naphthalene-
dicarboxylic acid. Centered methine proton will appear as singlet at low field followed by two
signals which supposed to be double doublet.

Problem 274 OK

This molecule of C11H9NO3 contains 8 DBE numbers and a look of nitro group absorption is
observed at expected range. The only recognized fragment is molecular ion peak as base ion
peak. The carbon off resonance NMR gives two separated quaternary carbon from aromatic
which is predicted adjacent to different substituent. Since the methyl signal is obtained shift to
higher chemical shift, firstly assumed it is form methoxy group. Now, the quaternary adjacent to
methoxy is indeed appear at lowest field compare to the one adjacent with nitro group. If the
molecule is once again bearing naphthalene ring, these up interpretations will give 1-methoxy-4-
nitronaphthalene as the proposed structure. Thus, two doublet signals are easily recognized for
methine with ortho or meta position of each substituents respectively. In the terms to identify the
naphthalene methine, the expansion using 400 MHz NMR spectrum is used.

Notes:

1. For Problem 274, I still don’t get how come the coupling from aromatic naphthalene
becomes so complex while they are only four chemically inequivalent proton even after
considering long range coupling for each of those methine. Could you explain it more
about this.

Since electron-donating methoxy and electron-withdrawing nitro groups are attached, electron
density on the benzene ring is biased, which is confirmed by large difference of chemical shifts
of H-c and H-d. Similarly, electron density on the other benzene ring is also influenced by these
substituents. As you can see the resonance structure, C-g, k, i are electron rich, and C-f, h, j are
electron poor. In this case, long range coupling between para-hydrogens (H-h and H-k) is also
observed. Hence, each four protons H-h~k is observed as a ddd. Signals of H-h and H-k are
doublet like, and those of H-I and H-j are triplet like, of which edges are overlapped.