Keto-enol tautomer 16% keto tautomer 84% enol tautomer 445 9 9 ° wary oso | i I Fost I HacS¢"ScHy = Hac“ Sc*ScHs = Hac“ C7 cH 224 He 224 ho 208 2.08 3.60 silo 2,4-pentanedione (neat liquid) TMS 145 Jt T I T T T Yr «a T T TS 9 8 7 6 ppm © 4 gi 2 1 0 Scanned with CamScannerAmine N-H protons Amine NH Protons. NH; protons of primary alkyl amines typically appear as a somewhat broadened signal at 5 1-2 in CDCI, The broadening is in part due rapid intermolecular exchange, and in part because of partially coalesced ‘coupling to the quadrupolar “N nucleus (/ = 1), which usually has a short T;. In the example below, the CH, group bonded to amino (5 2.82) shows no sign of coupling to the NH. protons. 300 Miz 'HNMIR spectum in CDCI, ‘Source: Arch NUR Library i} Note: = I I oF E Ep 5 ppm 4 3 2 1 Scanned with CamScannerPartial 'H NMR Spectrum of Menthol in CDCI, see UA myeg x a l ANNA | a Ju T T T TT Tt T mT TT T 36 34 3.2 30 28 26 24 22 2.0 18 16 14 ppm Scanned with CamScannerMagnetic Anisotropy There can be both shielding and deshielding effects from electron motion in other parts of the molecule. We refer to such interactions as magnetic anisotropy effects, since they are caused by anisotropic electron circulation Nonlocal Fields + Groups that have appreciably different currents induced by By resulting from different orientations in space are said to have diamagnetic anisotropy + Just as the local effect can result in shielding (electron donation) or deshielding (electron withdrawal) the nonlocal effect can result in either permutation + Regions of shielding are indicated by (+) and deshielding (-) FIGURE 3-4. Shielding geometry for a benzene ring. Scanned with CamScannerThe Chemical Shift Ring Current Shifts The six electrons in an aromatic benzene ring circulate in the external magnetic field creating a ring current The magnetic field reinforces the applied magnetic field for the bonded protons Thus the protons feel a stronger magnetic field and resonates at a higher frequency. The are said to be de-shielded and are shifted downfield. i — \ A, 3 2 1 Scanned with CamScanner2.23 GHs 2.23 7.24 CHs 7.05 7.24 7.08 7 a 1 0 PPM Scanned with CamScanner249 CH3 7.01 7.01 7.01 7.01 CH3 2.19 PPM Scanned with CamScannerHO O° 1H-NMR Assignment for salicylic acid HO Hy H, H, H, J | Scanned with CamScannerAnisotropy of Nitro groups. The NO2 group may have a a small anisotropic effect similar to that of C=O groups, with a deshielding (+8) region in the plane of carbonyl group. The ortho protons of nitrobenzenes are strongly downfield, in part due to this interaction. For example the proton H, between the NO, and Br groups (the small downfield doublet) has a very similar electronic environment in the two compounds whose spectra are shown below. The upper one has this proton upfield in part because the ortho-methyl group tums the nitro group out of the plane. Of course, turning the nitro group also causes reduced resonance interactions, which causes a shift in the same direction, as seen from the change in the proton ortho to the Me group (H,).. 300 MHz 'H NMR spectra Source: Aldrich Spectra Viewer ures ra [ae No, Scanned with CamScanner767 7.67 7.32 7.32 7.32 7.32 767 7.67 PPM Scanned with CamScanner6.11 6.11 U\ 6.67 6.67 N CH; 3.60 PPM Scanned with CamScanner7.75 “OC” 859 Syy7 8.59 N Scanned with CamScanner7.43 7.61 N77 881 8.05 10 PPM Scanned with CamScannerAH AD Scanned with CamScannerScanned with CamScanner> Ass-character of carbon atom increases, the electronic cloud is held morecloserto the carbon and provides less electron density for shielding of protons, and thus the chemical shift, 5, increases (shifted downfield). > According to the above reasoning, the following trend for the chemical shiftis expected: —H > —=¢— yy > —C—H1 -. 2 3 expected to be observed 7 |v ats>7 ——__=— __—_——" - s-character in cs (down field - higher 8) > But in fact, we have the following order: » actually observed | | ats =2-3 > This suggested that other factors than the sp character of carbon might affect the chemical shift in this case. The above discrepancy can be explained by whatis called Magnetic Anisotropic Effect. 15 Scanned with CamScannerMagnetic Anisotropy Figure 7. Components of the B, field produced by the circulation of 1-electrons in alkenes, aromatics, and alkynes asa function of orientation relative to the applied field By. The major anisotropic contribution to the total B, field from circulation of x-electrons adds to (alkene or aromatic) or subtracts from B,, (alkyne). 8 culating electrons 8. ° ae . {Pe 8, subtracts from B, near the proton c> B, adds Pinte SI ieeeen 108, near B, ‘the proton RY Ge? Yr = ' 4 anisotropicinduced_f B, 8, subtracts tromB, above i" ‘magnotic helds. and below the x bor 2-8 Scanned with CamScannerProton Chemical Shift and Structure Unsaturated Aliphatics Alkynes. *Anisotropy of CSC results in a low frequency for terminalH (1.8 - 3.0) 1,73-1.88 2.23 1.95 1.80 2.71-3.37 2.60-3.10 Alkenes. Anisotropy of C=C results in a higher frequency for alkenylic (vinyl}-H Range is very large (4.5 - 7.7) and highly subject to other groups on C=C *Reference value used for ethene is 5.28 Scanned with CamScannerFACTORS THAT INFLUENCE PROTON SHIFTS Local Fields Resonance effects — Donation or withdrawal of e- through resonance will have shielding or deshielding effects, respectively: 55.28 reference H>C=CH, ro BW E10, . H, c=o no foo 41 0CH, OCH, _ — ct! aye! | vc oi!‘ a! ‘a Nw Nu > 38 , resonance donation resonance withdrawal shielding effect deshielding effect Scanned with CamScannerUnsaturated Aliphatics Alkenes. + Conjugation usually increases the observed frequency + Angle strain increases s-character and therefore moves the resonance to higher frequency 5.78 5.94 6.42 + The presence of a C=O group wid electrons by both resonance and induction: oO oO + 6.37 5.93 4.65 — 6.88 + Scanned with CamScannerUnsaturated Aliphatics Alkenes. vos R We net neh es tes ar ne, Hoty ast Naw suction = = a tien “oswcny, wee bsectyy, riperitone Finalool ——e-terpinene Scanned with CamScannerCharge effects with pi-systems Charge effects within x systems are also reflected in proton chemical shift changes (approximately 10 ppm/unit one ome Hoss H 628 CMe." CHaLI you 13.50 Heat H 8.00 6.09 ay a 197 630 oe 045 550 H 103 H 537 Ho 727 Ho917 A®@ 00 Scanned with CamScannerMagnetic Anisotropy * YB “SE ‘Sulfoxide® Nitro* C-C Single Bond —_Cyclohexane Ax-Eq Cyclopropane” Epoxide! Scanned with CamScannerMagnetic Anisotropy + The protons of benzene reside on the periphery of the ring within the deshielding cone + Molecules have been constructed for the purpose of confirming the shielding effect predicted by the model: S H. a CH, -1.06 Scanned with CamScanner‘Magnetic Anisotropy Effect on Chemical Shift in NMR Magnetic Anisotropy 4 4 The applied and induced magnetic fields are opposite and inner hydrogens feel weaker net [18]-Annutene field - lower ppm (upfield). The applied and induced magnetic fields are aligned and outer hydrogens feel stronger net field - higher ppm (downfield). Inner hydrogens: -1.8 magnetic field ier groans: “1-8 BP Applied magnetic field Outer hydrogens: 8.9 ppm -1 ppm: above the ring, shielded A Porphyrin Inner hydrogens: -2 ppm Outer hydrogens: 8 ppm 7 ppm: outside the ring, deshiclded Scanned with CamScannerMagnetic Anisotropy 932 9.82 7 (@J=13Hz) H H (d= 13 Hz) Sia van CLT we | H 8.50 (4, J=7.SHz) VPs Pascal JACS 1987, 6878 Bockehelde JACS 1970, 3511 Makagawa TL1973, 4743 HO HG i 835 toa H (zs) ia Tv 2, ches, 2ehe.. ss 127 H Can S Lae SZ 10x e* Aromatic Nonaromatic we oshe weet 10x e* (aromatic 12x e* (antiaromatic Vogel AC 1964, 145,784 Voge TL. 1086, 685 é ) ( ) Staley JACS 1973, 3384 Scanned with CamScannerAnisotropy for acetylene proton Nonlocal Fields + We say the shift for the terminal acetylene proton experiences magnetic anisotropy. Usual shifts for this H are 5 1.8-3.0. For reference sp? ethane is at 0.86 and sp? ethene at 5.28 Induced magnetic lines of force —™. Circulating a electrons FIGURE 3.20 Shielding of alkyne protons. Scanned with CamScannerAnisotropy of Acetylenes. The magnetic anisotropy of C=C bonds seems to be well-defined. Both the unusual upfield shift of C=C-H signals, and the downfield shifts of protons situated next to a triple bond as in the examples below support a strong diamagnetic affect of electron circulation around the triple bond x system. . +8 3 Lo 3 CH,-CH3 CH=CH HC=CH 7 No) ° 30.90 3525 32.88 +5 H i | H SS 8248 CH, H 83.01 CHy Il Hy 32.52 CHy 45 1.63 ppm 48 0.49 ppm 400 1004, 1823 JOC 1984, 1323 Scanned with CamScannerAnisotropy for sigma bond in cyclohexane Nonlocal Fields * Alkanes do not possess the same degree of electron circulation as alkynes but do exert nonlocal fields on adjacent nuclei * The C—C o-bond shields a proton on its side more than its end, axial proton got shielded due C-C sigma bond anisotropy, again this things were observed at -100 degree when ring flip is frozen Seba p es CH; 0.52 0.62 0.62 NH 0.48 0.12 0.45 HO162 is 47 0.16 0.34 Heas4 ° 0.50 [207] 0.32 At-103°C (Gartisch, Am. S -0.19 0.38 0.50 (Chom. Boe. $268, S0S543), SQ; <0.10 0.17 0.45 Scanned with CamScannerAnisotropy in cyclohexane and others + The result of which is a deshielding of equatorial protons in conformationally locked systems: H127 CHs . hth, Neto Sey — Even simple alkane systems show anisotropy: H H 1.20 Ha Tt ke Le), oo ges on 1 ons a PP ae eo Kw c Cc 4 Methylene Methine deshielded deshielded deshielded by one bond by two bonds by three bonds Scanned with CamScannerAnisotropy of Cyclopropanes. Tho principal magnetic anisotropy of cyclopropane groups appears to be shielding above the ring and deshielcing in the plano of the ring, a ring current effect a Ittio lke that of benzene. an san Ly on war HW H Ly ax ome ACS 1972, 2291 TET 1908, 357 TET, 1866, 2007 TET 1968, 2007 ACS 1972, 2291 JACS 1966. 5272 TET 1998. 337 Hans HSS? OC 1967, 999 Scanned with CamScannerNonlocal Fields » Most common single bonds (C-N, C-O) have shielding properties that parallel those of the bond, although the geometry is more complex than that for the C-C bond. ¢ Lone electron pairs can have a special effect: + In N-methylpiperidine the axial lone pair shields the vicinal H,, by ann > o* interaction without any effect on H,, This way it increases the electron density. As a result, H,, increases to about 1.0 ppm or more in similar systems. Scanned with CamScannerAnisotropy in cyclopropane and others Nonlocal Fields + The highly shielded position of cyclopropane resonances may be attributed either to an aromatic-like ring current or to the anisotropy of the bond that is opposite to a group in the three- membered ring: Again all this data was measured at -103 degree. L Sar ¢ Aw O, * The effect is much larger than the indicated 1.2 ppm , because the cyclopropane carbon orbital to hydrogen ( compared with the orbital in cyclohexane) deshields the proton. * Accyclopropane ring also can shield more distant hydrogens: H,, 1.2 less than Hix Scanned with CamScannerAnisotropy for sigma bond in cyclohexane Nonlocal Fields * Alkanes do not possess the same degree of electron circulation as alkynes but do exert nonlocal fields on adjacent nuclei * The C—Co-bond shields a proton on its side more than its end, axial proton got shielded due C-C sigma bond anisotropy, again this things were observed at -100 degree when ring flip is frozen v ex B H 81.62 Hoas4 t-102°C Gartrscn J Am Chem Sco 1968 90 £43) 5.5, x a B r CH; 052 062 os2 3 5 nH 048 012 045 vA) * NH,” 047 Kors 034 way H ° 0.50 -007 032 “ s 0.19 038 050 " sO. <0.10 017 0.45 Scanned with CamScanner