Matthew Ellis Student ID: 1124829 Section B TA: Derek Church Unknown #3: Smaug I.

Given Data and Spectral Parameters Appearance: Smaug is a transparent liquid at room temperature. The unknown has a fruity odor with a hint of mint.
1

H-NMR:

Dissolved 1 drop of Smaug in 0.5 mL CDCl3 Spectral width: 0.0-14.0 ppm CDCl3 used as reference peak at 7.26 ppm Instrument: Bruker DPX 200 Parameter set: proton.462 Dissolved 1 drop of Smaug in 0.5 mL CDCl3, added two drops of D2O and mixed Spectral width: 0.0-14.0 ppm CDCl3 used as reference peak at 7.26 ppm Instrument: Bruker DPX 200 Parameter set: proton.462 Dissolved 5 drops of Smaug in 0.5 mL CDCl3 Spectral width: 0-220 ppm CDCl3 used as reference peak at 77 ppm Instrument: Bruker DPX 200 Parameter set: carbon Sandwiched 1 drop of Smaug between NaCl plates; neat Empty sample chamber used to acquire background (air) Spectral width: 4440-500 cm-1, 4 scans Instrument: Perkin-Elmer FTIR Dissolved 1 drop of Smaug in 20.0 mL DCM Instrument: Agilent 6890 Series GC system & Agilent 5973 Network Mass Selective Detector Method: chem463 Dissolved 32 mg of Smaug in 10.0 mL Methanol using volumetric glassware. Concentrations: 3.2 mg/mL, 1.6 mg/mL, 0.8 mg/mL Acidic/Basic spectra obtained at 0.8 mg/mL with addition of a few drops of 1.0 N HCl/NaOH; pH verified with litmus paper Instrument: DT-MINI-2-GS/USB2000+UV-Vis configuration using Ocean Optics Spectra Suite software Spectral width: 180-400 nm Blank: MeOH

D2O shake:

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C-NMR:

IR:

MS:

UV:

II. Annotated Spectra See attached spectra III. Initial Spectral Feature Analysis Mass Spectrometry: Presence of molecular ion peak at 152 m/z, indicating the molecular weight of structure. The fragment at 137 m/z could indicate loss of a methyl group from structure as at M-15 m/z. This would point to an easily dissociated terminal methyl group, perhaps branched off from the general structure. The M+1 peak analysis (11.16% of M+) leads to 10 carbon atoms being present in the molecular formula, leaving 32 amu available after carbon subtraction. The M+2 peak analysis (0.867% of M+) after carbon contribution (0.554%) subtraction is 0.313%, indicating the presence of other isotopic contributors in the molecular formula, most likely an oxygen atom due to the high remaining abundance and the typical contribution from 18O. This would leave 16 hydrogen atoms in the molecular formula, leading to the formula C10H16O with an index of hydrogen deficiency of 3, indicating the presence of double bonds, rings or carbonyls in the structure of the unknown, each of which would contribute a deficiency of one. NMR Spectroscopy: 1H-NMR shows a multiplet of integral 2 at = 4.730 ppm, and no other peaks above = 2.6 ppm. This downfield shift is indicative of an alkene with magnetically inequivalent protons attached as the shifts of the two protons are the same but the splitting is different. The spectrum also shows various multiplets of integral 1 ranging for = 1.327 to 2.145 ppm, as well as a multiplet of integral 4 at = 2.334 ppm. Upfield shifts such as these with the complex splitting displayed are indicative of a cyclohexane ring with the various equatorial and axial positions behaving differently in the magnetic field. The spectrum also shows a singlet of integral 3 at = 1.729 ppm indicating an isolated methyl group nearby some electronegative group due to its presence in the spectrum relatively downfield of a standard methyl group shift. At = 1.022 ppm there is a doublet of doublets of integral 3 perhaps indicating another methyl group nearby two inequivalent protons. D2O shake spectrum shows no notable difference from the 1H-NMR spectrum, indicating no protons in the structure are easily exchangeable. COSY spectrum shows correlation between the protons at = 4.730 ppm, indicating that these may be magnetically inequivalent as they split one another, as well as correlation between these protons and the singlet at = 1.729 indicating that these shifts are in close proximity. COSY spectrum also shows correlation between upfield multiplet proton shifts indicating that these protons split both other protons at the same shift and nearby protons in multiplets at different shifts.
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C-NMR shows 10 unique carbon atoms overall in structure, one at = 212.510 ppm indicative of a ketone due to this highly downfield shift, and two at = 147.477 and 109.496 ppm both within the range for alkenyl carbon atoms, with the more downfield shift likely more substituted as this peak is shorter after broadband decoupling. The other 7 shifts fall in the aliphatic carbon range, 5 of which are attached to electronegative groups due to their relatively downfield shifts; = 30.648 to 46.908 ppm compared to = 14.247 and 20.378 ppm, respectively.

IR Spectroscopy: IR spectrum shows various peaks in the fingerprint range as well as peaks at = 2931.3 and 2967.2 cm-1 indicating sp3 C-H stretches in the structure, and a peak at = 3083.4 cm-1 indicating the presence of sp2 C-H stretched in the structure as well. Very strong peak at = 1715.0 cm-1 is indicative of a carbonyl being present in the structure of the unknown, and peaks at = 1644.9 and 1217.4 cm-1 indicate double bond and single bond carbon stretches, respectively. Peak at high frequency of = 3404.5 cm-1 could indicate a secondary amine or a monomeric alcohol being present in the structure of the unknown. UV/Vis Spectroscopy: UV Spectrum shows two peaks at max = 216.37 nm and 275.79 nm in a 0.8 mg/mL MeOH solution, indicating either a benzene ring or a conjugated carbonyl in the structure of the unknown. The 0 values for these peaks are 131.25 and 28.125 respectively, indicating either a weak interaction between these two chromophores or that they are the result of an impurity due to the relatively low value of molar absorptivity compared to a standard alkene or benzene ring. Acidic and basic spectra at 0.8 mg/mL MeOH showed no marked difference in the max of either peak, indicating no readily ionizable groups in the structure of the unknown. III. Logical Structure Elucidation: From the molecular formula determined through M+1 isotope peak abundance in the mass spectrum, C10H16O, a hydrogen deficiency of 3 was determined. The peak at = 212.510 ppm in the 13C-NMR clearly indicates that this oxygen atom is the element of a ketone, as only this type of functional group shows up so far downfield. This conclusion is in concordance with the infrared spectrum, which shows a very strong peak absorbance at = 1715.0 cm-1, which falls not only at the typical frequency for carbonyl functional groups, but more specifically for ketones. This conclusion also correlates well with UV acidic and basic spectral data as well as the D2O shake data as both show no notable difference from the spectrum at neutral pH or the standard 1H-NMR spectrum. This suggests that no protons in the unknown are easily exchangeable, nor any functional groups easily ionized, as to be expected from a ketone. The downfield shifts in the 1H-NMR at = 4.730 ppm as well as the downfield shifts in the 13C-NMR at = 147.477 and 109.496 ppm indicate the presence of an alkene in the structure of the unknown, as these shifts are typical for both sp2 carbon and hydrogen atoms. The peak in the infrared spectrum at = 3083.4 cm-1 similarly indicates sp2 C-H stretches and the peak at = 1644.9 cm-1 indicates a C=C stretch, further solidifying the presence of an alkene in the structure of the unknown. Accounting for both a carbonyl and an alkene still leaves a hydrogen deficiency of one, and with only hydrocarbon elements remaining, and nothing to suggest further double or triple bonds in any of the spectra, the most logical conclusion is that the structure of the unknown compound contains a ring. The classic upfield multiplet splitting in the 1H-NMR as well as the correlation among these multiplets displayed in the COSY spectrum suggest that the ring is a cyclohexane, with the various axial and equatorial protons behaving differently in the magnetic field. The 2nd order splitting observed in the 1H-NMR spectrum for the peak at = 4.730 ppm suggests that the protons attached to this carbon are geminal and magnetically inequivalent. This is because this particular shift falls in the sp2 C-H range and integrates to two protons which have the same shift, yet displays complex splitting. This indicates that these protons are in a highly similar chemical environment but always split nearby protons differently, as one will be cis

while the other is trans to the group in question. If the only two protons attached to the alkene are geminal, then the other carbon in the double bond must have two substituents attached, and also rules out the possibility that this double bond is part of the ring; it would be highly unlikely for two vicinal sp2 protons to display the 2nd order splitting observed in this spectrum as a single peak. This conclusion correlates well with the observed peak height difference for the two peaks at = 147.477 and 109.496 ppm in the 13C-NMR, as the former is much shorter after broadband decoupling, indicating that this is the quaternary carbon atom, showing a similar height to the quaternary substituted ketone carbonyl carbon atom while the other, taller peak has both the alkenyl protons attached, with no other substituents. This leaves 7 unique carbon atoms all in the aliphatic range of the 13C-NMR spectrum and 14 protons in the aliphatic range of the 1H-NMR spectrum. Due to the integration values of 3 for two of the upfield shifts, the logical conclusion is that these shifts arise from terminal methyl groups. The isolated singlet of integral 3 at = 1.729 ppm indicates that the protons responsible for this shift are neighboring no other protons. As a first assumption it is understandable to assume that the structure of the unknown contains a methyl ketone, but as this particular shift is relatively upfield of a standard methyl ketone isolated singlet or integral three, which usually appears around = 2.8 ppm, the isolated methyl group is probably not directly off of the ketone. As there are no peaks in the 1H-NMR at = 2.8 ppm, it is unlikely that a methyl ketone exists in the structure of this unknown. Only two options then remain for the ketone, either it is directly part of the ring (i.e. cyclohexanone) or there is a longer alkyl chain as a substituent. This latter supposition is again unlikely due to the splitting and integration observed in the 1H-NMR; the only two shifts of integral 3 are a singlet and a doublet of doublets, far from any expected ethylmethyl quarter/triplet splitting. However, it is not impossible that the terminal group off of one end of the ketone is the alkene with a methyl group as an additional substituent, either as the isolated singlet or as a doublet of doublets with long-range splitting with the geminal sp2 protons. Clearly, shifts in the 1H-NMR with integral 3 cannot themselves be members of the ring system, as at maximum a carbon atom which is an element of the ring can have two protons attached. Thus, only 8 protons remain as multiplets in the 1H-NMR and 5 unique aliphatic carbon atoms remain after removing the two methyl groups. This indicates that for the unknown to contain a cyclohexane ring, the ketone must itself be an element of the ring. Thus the peak in the IR spectrum at the high frequency of = 3404.5 cm-1 could be the tautomerized enol form of this ketone as a member of the ring. For the five remaining carbon atoms in the ring, for each to have two protons attached, 10 protons would be required, as only 8 protons remain from the chemical formula, two additional substitutions to the ring must be present; these substitutions are accounted for through the two methyl groups as well as the alkene functional group. The 0 values from the UV data can be used to elucidate this structure further. The two peaks at 216.387 and 275.79 nm in a 0.8 mg/mL in methanol solution give values of 131.25 and 28.125 for molar absorptivity, respectively, neither of which is large enough to account for an alkene chromophore. This indicates that it is unlikely for the alkene and carbonyl functional groups to be directly conjugated; the negligible red shift is observed for the ketone absorption also indicates some separation between these groups. Due to the relatively large concentration of sample required to obtain the spectra, 3.2 mg/mL in methanol for an absorbance of 1.205, it is possible that this chromophore is simply the result of an impurity, perhaps through the formation of a conjugated double bond through resonance of elimination, or that the relation between these two groups is from homoconjugation, the slight separation of the pi systems.

Additionally, the COSY spectrum shows a correlation between the isolated singlet at = 1.729 ppm and the sp2 protons at = 4.730 ppm as well as a correlation between the doublet of doublets of integral 3 at = 1.022 ppm and the multiplet at = 2.334 ppm. These data indicate that the doublet of doublets is the result of a methyl group directly attached to the cyclohexane ring system and the isolated singlet is one of the substituents off of the alkene, which the downfield position of the isolated singlet relative to the doublet of doublets similarly suggests. These data then indicate that the structure of the unknown compound is a cyclohexanone ring with a methyl and allylic substituents, the latter of which is connected to the ring through the center carbon atom. There are various substituent positions then these three groups can adopt around the ring, and the empirical calculation for carbon shifts can be used to distinguish among them: Actual Shift (ppm) Candidate 1 Shifts (ppm) Candidate 2 Shifts (ppm) Candidate 3 Shifts (ppm)

212.510 147.477 109.496 46.908 46.750 44.618 34.802 30.648 20.378 14.247

-------2.5+24+9.4+9.4+6 = 46.3 -2.5+20+1+9.1+9.1+9.4 = 46.1 -2.5+24+9.1+9.1+9.4-5 = 44.1 -2.5+9.1+9.1+9.4+9.4+1= 35.5 -2.5-2.5+9.1+6+9.4+9.4= 28.9 -2.5 + 20 = 18.5 -2.5+9.1+9.4+1-2.5 = 14.5

-------2.5+9.1+9.1+(3)(9.4)+6-2.5-2= 45.4 -2.5+24+9.1+(2)(9.4)-(2)(2.5)= 44.4 -2.5+20+(2)(9.1)+1+9.4-(2)(2.5)= 41.1 -2.5+24+9.1-2.5+9.4-2.5+6= 41 -2.5+(3)(9.1)+9.4+1-(2)2.5-0.5= 29.7 -2.5+9.1+9.4+9.4-2-2.5 = 20.9 -2.5 + 20 = 18.5

-------2.5+20+24+9.1+9.4-2.5= 57.5 -2.5+9.1+9.1+24= 39.7 -2.5+(2)(9.1)+(2)(9.4)+1-2.5= 33

-2.5+(2)(9.1)+(2)(9.4)-(2)(2.5)-2= 27.5

-2.5+(2)(9.1)+9.4-2(2.5)+1+6 = 27.1 -2.5 + 20 = 18.5 -2.5+9.1+9.4+1- 2.5 = 14.5

The empirically determined shifts for the aliphatic carbon atoms from Candidate 1 can be matched with every peak <47 ppm in the 13C-NMR spectrum, each close to or within 1 ppm unit of the experimental value from the unknown compound. This makes Candidate 1 the most likely choice for the structure of the unknown and the final structure elucidated is:

IV. Final Spectral Assignments: UV/Vis Spectroscopy: pH Concentration (mg/mL) 3.2 3.2 1.6 1.6 0.8 0.8 0.8 0.8 0.8 0.8 max (nm) 223.27 284.48 219.44 278.06 216.387 275.79 215.98 275.41 219.05 274.28 Absorbance 1.205 0.656 1.059 0.611 0.890 0.420 0.886 0.383 1.106 0.432
0

Transition * n* * n* * n* ---------

Identification C=C C=O C=C C=O C=C C=O ---------

Neutral

Acidic Basic

131.25 28.125 131.25 28.125 131.25 28.125 ---------

Mass Spectrometry: m/z 154 153 152 137 109 95 82 67 Assignment M+2 (0.867% of 152) M+1 (11.16% of 152 [calculated for C10H16O]) M+ M-15 [loss of CH3] M-43 [serial loss of CH2CH2 from fragment at 137] M-57 [serial loss of CH2 from fragment at 109] M-70 [loss of CH2COCHCH3] M-85 [serial loss of CH3 from fragment at 82]

Mechanisms:

m/z: 137

m/z: 109

m/z: 95

m/z: 82

m/z: 67

Infrared Spectroscopy: (cm-1) 3404.5 3083.4 2967.2 2931.3 1715.0 1644.9 1449.5 1376.3 1217.4 892.0 Intensity w w s v.s v.s m s m m s Assignment Tautomerized enolic OH stretch sp2 C-H stretch sp3 C-H stretch sp3 C-H stretch C=O stretch, ketone Alkenyl C=C stretch C-H bending C-H rock Alkyl C-C stretch sp2 C-H bending

NMR Spectroscopy:
1

H-NMR: (ppm) 4.730 2.334 2.121 1.907 1.729 1.628 1.391 1.022 7.26 # of Hs 2 4 1 1 3 1 1 3 ----Multiplicity m m m m s m m dd ----Coupling (Hz) ------------------Identification H-1, H-2 H-3, H-4, H-5, H-6 H-7 H-8 H-9 H-10 H-11 H-12 CDCl3 solvent peak COSY Coupling H-1, H-2, H-9 H-3, H-4, H-5, H-6, H-12 H-7, H-11 H-8, H-10 H-1, H-2, H-9 H-8, H-10 H-7, H-11 H-6, H-12 ---

D2O shake: (ppm) 4.724 2.323 2.103 1.884 1.716 1.618 1.380 1.009 7.26 # of Hs 2 4 1 1 3 1 1 3 ----Multiplicity m m m m s m m dd ----Coupling (Hz) ------------------Identification H-1, H-2 H-3, H-4, H-5, H-6 H-7 H-8 H-9 H-10 H-11 H-12 CDCl3 solvent peak

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C-NMR: (ppm) 212.510 147.477 109.496 46.908 46.750 44.618 34.802 30.648 20.378 14.247 77 Identification C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 CDCl3 solvent peak

Structure: