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CNMRspectroscopyworksheet(30points)
AI:

due2/24/11inlecture

Name

1. (18points)ProvideviablestructuresforthefollowingNMRsbasedonthefollowingmolecularstructures.Giventhe molecularformula,itwouldbesmarttostarttheproblembycalculatingthedegreeofunsaturationfirst.Labelyour structureappropriatelyonyourstructureandtheNMRclearlysothatyourAIcangradeiteasily.

e
a b c d

OH

a. C5H10O2(inCDCl3):
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pentanoic acid

CNMRsignals:181,34,27,22,4ppm
c
Cl

1-chloro-2,2- dimethyl propane b

a b

Cl

b. C5H11Cl(inCDCl3):
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acceptable answer, but b too deshielded

CNMRsignals:57,33,27ppm

c b a
Accetpable answers:
O

b c a
OH

a b

c. C5H10O(inCDCl3):
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CNMRsignals:69,31,19ppm (Asignallike19ppmissignificantlydifferentthan31suchthatitwould needtobeamethylversusamethylene.)

d c

b
O O O O

d. C8H12O4(inCDCl3):
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diethyl cis-butenedioate

CNMRsignals:165,131,61,14ppm

(cisortransstructurecouldbeprovidedabove)

Onceyoufigureoutthestructure,proposewhatthesmallimpurityat167ppmmightbe:
O

Thestereoisomer(cisortrans)istheimpurity.

a b

c
d

OH

methacrylic acid
O

a d c
OH

e. C4H6O2(inCDCl3):
13

b accetpable answer

CNMRsignals:174,136,128,18ppm
O

c b d e f

b&c

a acetophenone
O

a
b

c d e
H

f e d
f

a partial credit, except not two ipso carbons would be observed in the NMR

f.

C8H8O(inCDCl3):
13

CNMRsignals:198,137,133,128.7,128.4,26ppm

2. (6 points) The two 13C NMR spectra match two of the compounds below. Determine which isomer fits the each NMRbelowandthenassignthepeaks.(Generatedspectrashownosolventpeaksbelow.)

For this top spectrum, you need seven signals, no aliphatic CO signals (i.e. alkoxides), an ipso carbon attached to an oxygen and an ethyl group that gives signals that provide aliphatics that are around 30 and 10 ppm. This leads you to thebottomtwoleftcompounds.However,thefinalpiecethatleadsyoutothephenolicketoneisthatthearenesignals havealargerdisparityduetothephenolicOHbeingelectrondonatingandplacingmoreelectrondensityontothering. TheketoneandthephenolicOHhaveoppositeeffects:electronwithdrawinganddonating,leadingtodisparatearene signals.

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CNMR:200,163,130,129,116,32,8ppm

13

CNMR:172,151,129,125,121,27,10ppm

3. (4 points) Compare the expected 13C signals between carbons A and B on the following structure. Use structures to provide a good answer. Then, compare expected signals for carbonsCandD.Finally,comparesignalsEandF. Carbon F is next to an electron withdrawing group, O, which places it around 6080 ppm. By comparison, E is next a less electronwithdrawing group, C=O, where one would expect it to comearound30ppm. Carbon C is attached is an electronwithdrawing substituent (ketone) which would deshield it with respect to an arene; howevercarbon Disattachedtoanelectronnegativeelement, O,whichwould bemore deshielding. CarbonC (ca.140 ppm)versuscarbonD(ca.160ppm). Carbon A is beta is an electron withdrawing group and can participate in resonance which places a partial positive chargeoncarbonA,deshieldingit.CarbonBisbetatoanelectrondonatinggroupwhichplacesapartialnegativeonit, shieldingwithrespecttocarbonA. 4. (2 points) Explain how to make up an NMR sample. Explain why deuterated solvent is used (what is meant by a residualpeak?). Most NMR spectra are recorded for compounds dissolved in a solvent. Therefore, signals will be observed for the solventandthismustbeaccountedforinsolvingspectralproblems.AnNMRsampleismadeupbydissolvingca.20 mg of sample into 0.5 1.0 mL deuterated solvent in an NMR tube, and it is then capped. To avoid spectra dominated bythesolvent signal,most1HNMRspectraarerecordedinadeuteratedsolvent.However, deuteration is not "100%", therefore, signals for the residual protons are observed and used for calibration. In chloroform solvent (CDCl3), this corresponds to CHCl3, so a singlet signal is observed at 7.26 ppm. For methanol solvent, this correspondstoCHD2OD,soasignalisobservedat3.31ppm. 13 C NMR is six thousand times less sensitive than 1H NMR, and a good rule of thumb is to provide as much material aswillgiveasaturatedsolutionifpossible.