Problem 245 OK

The hydrocarbon compound of C14H18 consists of 6 DBE numbers without significant absorption
from its IR spectrum. The molecular ion peak is determined as base ion peak (m/z = 186) and
another fragment from [M+ - C2H4] (m/z = 158). The carbon NMR spectrum gives two types of
methylene at higher field followed by aromatic methine and quaternary carbon. Considering
these data, the proposed structure to fit all of these interpretations is octahydroanthracene.
Thus, the proton NMR gives three signals for methylene proton as triple triplet (Ha, 8H) and
triplet (Hb, 8H). As predicted, a singlet signal around 6.9 ppm belongs to aromatic methine (2H).

Problem 246 OK

The molecule with 11 DBE numbers has absorption for ketone which considerably shifted to
lower field due to conjugation ability. Its mass spectrum gives molecular ion peak as base ion
peak (m/z = 208) and other fragments might be from [M+ - CO] (m/z = 180) and [M+ - 2CO] (m/z
= 152) respectively. The carbon NMR obtained carbonyl ketone at the lowest field followed by
quaternary carbon between two methine signals. Since the proton NMR only gives two signals
indicated for aromatic methine, the best arrangement to fulfill those interpretations is
anthraquinone. Thus, those signals are assigned as double doublet after long range coupling.

Problem 247 OK

The molecule of C18H24 contains 7 DBE numbers without helpful information from its IR
spectrum. The base ion peak is simply obtained from molecular ion peak (m/z = 240). Looking at
carbon NMR spectrum, the signals appear as two types of methylene and quaternary carbon.
Moreover, the proton NMR spectrum occurs by giving two separated signals at higher field. If
the arrangement is made as dodecahydrotriphenylene, the signal around 1.8 ppm should appear
as triple triplet and the next one as triplet. However, the characterization using 100 MHz might
not be able to give a clear splitting pattern.

Problem 248 OK

The molecule with 13 DBE numbers also comes without worthwhile adsorption to be assigned.
The mass spectrum gives no other fragment except molecular ion peak as base ion peak (m/z =
228). The carbon NMR gives three signals as quaternary carbon and two types of methine. The
predicted structure leads to triphenylene. Two methine signals must be obtained as double
doublet at expected range of aromatic proton.
Problem 249 OK

The molecule of C5H11NO with 1 DBE number has three fragments from its mass spectrum that
can be interpreted. They are molecular ion peak (m/z = 101), a fragment from [M + - NHCH3]
(m/z = 71) and -CH2NCH3 (m/z = 43) as base ion peak. The carbon off-resonance decoupled
NMR gives methyl signal which shifted at lower filed as it is previously assign next to nitrogen
atom. Two types of methylene must be allocated adjacent to nitrogen and oxygen atom within
ring structure as well. Thus, these interpretations bring the structure as N-methylmorpholine.
Moving to proton NMR, the methyl signal which obviously comes as singlet appeared close to
methylene signal adjacent to nitrogen atom as double double doublet. The other methylene will
occur at lower field with same splitting pattern.

If two hydrogens of a methylene are inequivalent, a couple of ddd should be observed: totally 16
lines. When you cannot assign the coupling pattern, it is OK to indicate as a multiplet. If you can
measure coupling constants, you should analyze the coupling pattern even though it is a complex
signal.

Problem 250 OK

The given molecule with 2 DBE numbers has noticeable O-H broad absorption from its IR
spectrum at 3250 cm-1. Moreover, the weak absorption at 1685 cm-1 might come from C=N. The
mass spectrum gives molecular ion peak (m/z = 99), a fragment after losing hydroxy group (m/z
82) and base ion peak proposedly from -CNOH (m/z 55). When carbon NMR spectrum gives
quaternary signal and four signals from methylene, the structure is easily arranged as
cyclopentanone oxime. The oxygen atom from hydroxy can donate its lone pair electron
allowing conjugation of double bond. Hence, it caused the adjacent methylenes to quaternary
carbon are being electron rich than the other. Following this rule, the methylene signals at lower
field should belong to Hc and Hd as triplet followed by Hb and He with same coupling pattern.

Your drawing resonance structure is incorrect.

When electrons move to the adjacent C-C bond, C-C double bond should be formed, but the
carbon have five bonds. When electrons move on the carbon, three membered ring should be
formed, but the carbon also should have five bonds.
Problem 251

This molecule also has 2 DBE numbers with noticeable O-H broad absorption from its IR
spectrum. The molecular ion peak is still assigned for base ion peak (m/z = 113) along with a
fragment which might be formed after losing hydroxy group (m/z = 96). When carbon DEPT
NMR spectrum gives quaternary signal, which is obviously not from carbonyl, the plausible
source is sp2 carbon adjacent to nitrogen atom. By these up of interpretations, the proposed
structure leads to cyclopentanone oxime. Thus, four downward signals indicated four different
types of methylene appeared close to each other at higher field. The proton signal for hydroxy
obtained at the lowest field followed by methylene adjacent to sp2 carbon as triplet signal (4H).
The next methylene occurs as triple triplet and central methylene as quintet.

Four protons of H-c are not inequivalent because of E- and Z-isomers of oxime. Indeed, five methylene
signals are observed in the 13C NMR. So, you should assign H-d as triple triplet instead of quintet.

Problem 252 1-aza-2-cycloheptanone or caprolactam OK

The molecule has 2 DBE numbers and carbonyl amide absorption is observed at 1658 cm -1
beside N-H bond at 3212 cm-1. Some fragments are obtained as molecular ion peak (m/z = 113),
a fragment from [M+ - CO] (m/z = 85) and base ion peak proposedly from [M + - CH2CONH]
(m/z = 55). Since carbon DEPT NMR only provides quaternary carbon and five types of
methylene, the best arrangement will form ring character namely 1-aza-2-cycloheptanone or
caprolactam. The order of methylene carbons from lower field comes as: Cf, Cb, Ce, Cd and
Cc. The signal for methylene next to nitrogen atom obtained at lower field which should be
double double doublet similar with methylene next to carbonyl atom. Meanwhile, the most
upfield signal seems a combined one from the rest methylene proton (6H) giving multiplet.

Problem 253 OK

With zero DBE number, the molecule of C 5H13NO2 has O-H broad absorption at 3297 cm -1. The
base ion peak is proposedly from -CH2N(CH3)2 (m/z = 58) and another fragment as [M + -
CH2OH] (m/z 88). The carbon DEPT NMR showed methyl signal with high intensity and shifted
to lower field after being adjacent with nitrogen atom, two types of methylene and one methine
at the lowest field. The plausible arrangement from these up interpretations gives N,N-dimethyl-
2,3-dihydroxy-1-propylamine. Each methylene proton from the structure is inequivalent, thus
the geminal coupling is permitted. From the proton NMR, the obvious singlet signal from two
methyl groups appears followed by methylene proton adjacent to nitrogen atom at 2.22-2.50 ppm
as double doublet. Next, the methylene proton adjacent with hydroxy group also appears as
double doublet at 3.49-3.66. Finally, the methine proton should appears as dddd but obtained as
6 lines giving sextet alike signal.

Problem 254 OK
The molecule of C10H15NO has 4 DBE numbers and significant absorption to tell the existence of
O-H and N-H bonds at expected range. Two fragments from its mass spectrum are assigned for
base ion peak proposedly form -CCH3NHOH (m/z = 58) and a fragment after molecular ion peak
cut the previous fragment (m/z = 105). Since the carbon DEPT obtained three upward signals
where two of them is methine, aromatic methine and quaternary carbon, the structure is arranged
as 2-hydroxyamino-1-phenylpropanol. From proton NMR, the doublet signal which belongs to
methyl proton appears at the highest field followed by hydroxy proton (2H) after D 2O
exchanged. Next, the signal with low intensity around 2.5 ppm must be from methine proton
adjacent to nitrogen atom and obtained as double quartet. The other methine proton adjacent to
aromatic appears as doublet at 4.2 ppm and the rest signal from aromatic proton at expected
range assign as multiplet respectively.