5 1H NMR Spectroscopy 5.1 Alkanes 5.1.4. Chemical Shifts 1H Chemical Shifts and Coupling Constants (6 in ppm, J in Hz) CH, 0.23 CH, 086 2p Tem “124 cH, CH, 089 Ahic i pum \ Hc “cH, Hc: GH 091 jc TA CHa O91 My, 73 fein dap rar tered oa be bi oan gross oe ghar ba In long-chain alkanes, the methyl groups at 8 ea. 0.8 ppm typically show distorted triplets due to second- order effects:158 1H Chemical Shifts of Monosubstituted Alkanes (8 in ppm) 5 1HNMR Substituent| OH ~O-alkyl OCH=CH, —O-phenyl -OcOcH, -OCO-phenyl ~08(0),-Holyl NH, -NHCH,, NCH), -NHCOCH, “No, « xc SH Salkyl -SS-alkyl -S(0)CH, -S(0),CH, CHO ~COCH, CO-phenyl COOH -COOCH, ~CONH, COC Methyl 2.30 2.50 2.84 2.20 247 255 2.10 201 2.02 2.66, -cHy 06 2.00 2.16 2.63 455 347 3.37 3.16 a1 337 3.66 3.98 442 437 407 2.66 2.32 3.26 437 238 339 244 249 2.67 2.94 2.46 244 2.92 236 2.32. 223 293 Ethyl -CHy 086 1,00 Lis 121 135 133 1.66 1.88 124 Las 121 138 126 138 130 LL 1.06 14 158 131 128 131 125 135) 2.80 13 1.06 Las. 116 Las 13 124 -cHy, 091 2.02 2.10 2.59 430 347 3.35 3.16 3.59 3.27 3.86 4.02 425 3.94 2.65 3.18 428 2.34 2.50 2.43 2.63 2.37 2.40 2.86 231 2.22 219 287 T-Propyt -My 133 143) 150 1.65 1.68 181 189 1.88 159 155 1.70 1.65 176 1.60 146 155 201 1.70 1.63 159 171 164 1.60 172 1.68 1.65 1.68 174 cH; 091 091 097 095 097 1.06 1.06 1.03 094 093 105 095 107 095 091 096 1.03 1.08, 099 098. 1.03 097 093 102 1.00 098 099 1.00S.1 Alkanes 1H Chemical Shifts of Monosubstituted Alkanes (8 in ppm, contd.) ‘Substituent| HH ~CH=CH, ~cac_ ~pheayl + -OCO-phenyl -OS(0),+Htolyl NH, -NHCOCH, oO: =COCH, =CO-phenyl ~COOH ~COOCH, ~CONH3 =coc | 2Propyl -cH =CHy 133 091 259 115 289 1.25 484 134 Ald 155 421 173 424 189 402 121 355 1.08 406 1.23 451131 499 1.23 522.137 470 1.25 3.07 1.03 401 1.13 444 153 267 135 387 143 3.16 134 293 125 3.13, 141 239 113 288 111 358 1.22 256 121 256 1.17 244 118 297131 =CH, 091 2.06 218 261 4nd 342 342 3.20 3.64 3.40 3.68 3.94 4.06 403 269 321 447 2 252 249 269 242 295 235 231 222 2.88 mBuryl CH, ~CHy 131131 s15 =12 152 141 160 1.34 65 168 141 1841.46 180 142 156 139 154138 161 139 176 147 160 139 162 136 143135 149135 207 150 163 150 159 143 156 142 164 142 159 135 17214 162 139 16 133 160 137 167140 -CHy 091 0.90 0.92, 0.93 095 092 0.93 0.93 0.94 092 0.94 097 0.94 088: 0.92 0.92 107 0.96 092 092 0.93 0.93 0.96 0.93 0.92 0.93 093 CH, 089 102 124 132 134 1.60 176 195 126 124 145 158 Las 1.28 139 137 144 143 139 132 144 1.08) 13 123 120 122 159 vert Butyl160 5 1HNMR Estimation of "H Chemical Shifts of Substituted Alkanes (8 in ppm) CHy CH, cH Bouya! = 086424 Bayy=1BT#EZ + BZ, Boy = 1504 EZ, + 22, Bowsclnae = 086 + ‘Substituent, CH3 cH cH BURR) Ze Zp Za Zp Za Zp C= 000005000006 0.17 —-0.01 085 020 063 0.00 0.68 0.03 094 032 070 0.13 1.08 131 122 029 128038 3a 276 0.16 183 027 220 063 205 024 «198031 183 083 197 046 244 OAL 130 102 180053 2460.15 253 025 220 O15 «1.78 0.08 Borce 025 204 013185 032 ~0C=C= 64 036 © 263 033 200 030 ~O-phenyl 287-047-261 0.38 2.20050 0-CO- 281 044 283024247059 N -n< 161 0.14 132 022.13. 023 Ne 244 039 191 040178056 188 03 163 022 210 082 343 065 308 OSB 2.31 112 04s 108 0331.00 251 054 220 036 «1.94 0.60 Ss Tid 045 123 026 © 105 0.31 =s-co- 141 037 154 063 © 131 019 S(0- 164 036 © 124 030 125 S0)- 198 042 208 052 150 040 =ScN 175 066 162 16 QO ~cHo 134 0211.07 029-086 0.22 y) 123 020112024 =CooH 122 023 090 023087032 © ~ Jig always holds for given substituents. ‘Typical ranges: Iygq, ~4 10. 4 Ky 4t012 Trang M410 195.2 Alkenes 165 Coupling Over More than Three Bonds in Alkenes (Long-Range In acyclic systems, the coupling constants range from ca. -0.8 to -1.8 Hand, usually, Ulgoid #8 larger thant Ulgangoig- ThE magnitudes of the coupling constants depend fon the conformation. Largest absolute values are observed if the C-H bond of the substituents overlaps with the st electrons of the double bond (¢ = 0 or 180°) Allylic Coupling 9 Stay o 30 90 +18 180° “30 z10° 0.0 Homoallylic Coupling cisoid: — (I,y10-3 ransoid: (I, 0-3 He he values of homoallytic coupling constants between methyl groups and of allylic ones are comparable: Mv. HC=C-CHy In acyclic systems, Usisoil trans yaas*—! USI In desivaives 144 In derivatives: au a "5 1010 Bae 81013 Ngan S 0 10 Acie Yan 2068 Hyg 12 “Seqeq 2405 H., 1.60 Generally: ol In derivatives: © 3 3, 15t020 an Be 10 aint Oe a OS to1S 257 Age 03 he $555 ang 128 yy 23 £643 413 hy Ld Oi: Since 93 reais 24 Dus pel Tye 20 % abarans 5:7 Dye rans 3-0 Me 5.0 My LO 179 Wpemp 161 Teg 58 34, 23 10653 My, 51 My, -02 yy =10 oh My 6.235 05 thy 04 b 5.69 a 15. Shag 14 Tye 2.0 ci a 4. 13 eg OL HOH S89 Vy 20 a b579 3 2567 yy o7 My 2.087 65.79 4 1.0 62.12 We 37 eg EL 150 w Bho 5174 S 1HNMR © 6.09, 08 a 67 2.11 The 3:7 was HH 134 HoH 112 HoH Ban Bova L 1.50” 1.50 HOW 123 4.60” 6.63 be Po b In condensed alicyclics, couplings over four bonds are often observed. Such long- range couplings are particularly large if the arrangement of the bonds between the ‘wo protons is W-shaped (ef. Jue VS. Jug and Thy Below left and Jyg VS. Jpg below right). Owing to the rigid arrangement, vicinal coupling constants (33) may’ assume unusually small values when the torsional angles are close to 90° (J,, below right. zr be 23 0.1 ou a7SA Alieyelies 175 1H Chemical Shifts and Coupling Constants of Monosubstituted Cyclopro- panes (8 in ppm, J in Hz) Ha Ha Hy Fw Tan The 020 020 020 90 36 43 G 1.00 035 0.15 1.14 040 030 135 064 034 82 49 93 62 183 089 065 95 63 95 52 x 432 069 027 59 24 67 108 77 120 255 087 074 70 36 60 103 71 106 283 096 O81 7.1 38 -6.1 102 70 105 231 1.04 076 75 44 99 66 100 O on 335 040 048 62 29 -S4 103 68 109 No-NH, 223 032 020 66 36 97 62 99 =Nin* 1.06 052 0.34 “No, 421 113 160 70 34 -S5 101 83 113 -C=N 129 096 101 84 51 47 92 71 95 © -cHo 179 099 103 80 46 45 88 70 96 yy cots 183 077 093 79 46 35 92 70 95 =CO- -NHCHO (rans to 0) -NHCHO (cis to 0) -N(CH3)CHO, -NHCOCH, -NHCSNH, “0.17 0.14 0.13, 0.05, 0.19 0.85 -0.07 0.08, 0.16 0.16 0.20 0.22 073 “031 -0.01 ous 036 -051 “0.44 “0.45 033 -0.26 -0.12 0.05 -0.67 073 -0,60 0.26 072 0.25 -0.20 0.16 ous ould ents on "H Chemical Shifts of Monosubstituted Benzenes (in 0.05 0.08 0.04 0.07 0.07 0.07 0.02 0.00 0.01 0.04 0.06 0.09 0.03 0.06 0.12 24 0.10 0.05 0.13 0.02 0.03 0.10 0.07 0.20 0.16 0.10 0.10 0.40 0.03 021 007 0.02 007o=0 ‘Substituent R -NHNH,, N=N-phenyl (O)-CH=CH, (O)-pheny! (O}.CHg -S(0),0CH, -8(0),C1 -S(O),NH =cHO =COCH, =COCH CH, =CO-phenyl =CO-2-pyridy!) =COOH =COOCH, -COOCH(CHs), =COO-phenyl -CONH, =COF =cocl -coBr 0 “li -MgBr ~Mg-phenyl -Si(CH), -Si(pheny!), -SiCl, ~Piphenyl), -P(O)(OCH,), -Pb' (phenyl) Cr ~Zn-phensl renyl {phenyl 5.5 Aromatic Hydrocarbons 0.20 0.29 0.26 oud 0.04 0.16 -0.10 -0.20 -0.05 ous: 0.09 037 0.26 0.27 0.28 019 2 ol 2 ol ould 0.09 oul og. oul 021 ous, os: 0.24 0.26 0.19 ous. 0.00 0.07 0.20 00 outa 049 0.02. 0.10. O55 0.20 035 039 0.28 0.02 02 024 026 0.10 ous 0.13 oal 0.28, 037 024 029 0.22 021 0.23 0.20 0.28 021 0.20 030 0.19 038 035 032 024 029 026 025 0.00 0.12 020 00 0.22 O61 0.05 0.10 179180 S 1HNMR 1H-IH Coupling Constants in Selected Monosubstituted Benzenes (\J] in Hz) Substituent R OCH, ~O-phenyl z -S(0),0CH =cHO -COCH; COOH -COOCH, -CONH) Coc! o9=0 —MeBr Piphenyl)» -PO(OCHS)» Zo-phenyl He-phenyl 15 Jas 06 06 06 06 oa os os os os oa os os os os os o7 06 06 06 06 06 06 06 06 08 07 06 06 07 06 Ta Jas 15 15 13 14 18 7 18. 18 7 18 17 7 16 15 15 13 15 14 13 13 14 13 13 14 13 14 14 14 1s 1s5S Aromatic Hydrocarbons 181 1H Chemical Shifts and Coupling Constants of Condensed Aromatic- Alicyclic Hydrocarbons (6 in ppm, J in Hz) 740 7.98 2.91 2 e339 y, 55 791 285 hy SS 6.93 OO OD i 8 CI" 7.19 655 SI, 0.7 77 8 688 ye 19 7.84 391 731 287 73 738 7.19 { ) ae OO» 23340 Sy 1S a 7s 4h, 0 Ce ren es Co TUL aa 05 CO 790 Sha © ee 67 sg le 7 le 731 jibe © 758 jt Ng 12 Athy 0.6 ¥ st 5. a me Ye 8.1 ore Meg 8 403 [| on 14s CY 223,291182 S 1HNMR Effect of Substituents in Position 1 on the 'H Chemical Shifts of Monosubstituted Naphthalenes (in ppm) R FOrRIM Bin Diag Sts Dugg = 784 Binge Sys Bigs Oty = TAB TH _W3_H4 WS He a7 _A® “020 -0.14 -0.17 -003 -003 0.00 0.12 0.15 0.08 -0.15 002 001 021 0.09 0.23 -0.23 0.13 -003 0.52 0.10 -0.18 -O.11 005 0.02 0.22 051 -001 001 007 0.13 0.35, -0.07 -0.10 0.09 0.02 001 0.18 “0.14 0.13 0.14 0.07 -003 0.10 0.22 0.14 -01 0.05 OSI “0.11 -0.04 -0.06 0.13 -0.07 -0.02 035-010 -0.23 005 0.03 027 0.06 0.14 -0.12 002 0.09 0.42 0.29 0.25 -0.04 0.04 0.11 039 0.20 046 0.13 0.09 -002 0.18 075 022 942 003-001 032 oct OM 025 085 018 012 013 Zope a3) into) azz (oma (oad (oan “cot, “31. 008 027 O14 023-009-001 NOME 7 022 055 007 008 008 008 out sue 00791030) ons)lons erm 135 co om 96 02 091 ono 009 O30 Te0oH om Olt 034 020 013 020 109 C “coc, «06S 08 08 00S 002 00 Loo Teoes 1s 095 022 062 047 O17 O885.5 Aromatic Hydrocarbons 183, Effect of Substituentsin Position 2.0n the 1H Chemical Shifts of Monosubstituted Naphthalenes (in ppm) Subsiwent ir C -ls 024 =CH,CH, 022 =CH(CH,), 024 -CF; 028 =CHOH 013 =CH=CH, “ou 0.19 020 0008 o.t4 on 076 053 030 093 “107 033 0.90 040 od oad 058 =CO-phenyl oa ~COOH 083 =COOCH, 0.66 =cocl 0.85 z aQ=0n * interchangeable; ® interchangeable for: H Tes “0.18 0.14 0.15 14 0.08 4 0.04 025 0.08 0.05 -0.39 0.33 0.22 0.27 0.62 0.49 0.02 0.70 013 0.19 04s 051 046 057 050 058 14 “0.11 0.08 0.12 0.06, 0.07 0.06 0.05 0.06, 0.10 0.16 0.10 0.14 0.01 0.04 023 0.30 0.10 0.05 0.08 0.17 0.05 001 0.09, 020 0.08 022 814, ity Pity Org = Bit Bigs Sigs ty is 0.06 0.05 0.10 0.10 0.05 0.06 0.03 ool 0.05 0.12 0.09 0.10 0.02 0.04 0.19 0.29 0.11 o.0s 0.06 0.11 0.03 0.01 0.06 0.9 0.07 032 16 -0.09 0.08 0.12 0.09 0.04 -0.06 002 0.02 0,03 0.02 0.16 0.14 0.08 0.04 027 0.39 0.09 0.19 0.19 009 oud 0.08 013 0.20 001 0.17 17 -0.05 0.06 0.10 0.06 0.03 0.04 0.02 0.02 0.01 0.00 0.06 0.06 0.04 0.02 O15 024 0.06 ous 03 0.06 0.08, 0.03 0.06 016 0.05 021 84 TES 0.10 0.08 -0.10 0.10 0.08 0.06 0.03 0.05 0.128 0.06 0.18 0.14 0.15 -0.08 027 033 0.09 out 0.06 0.19 02 ool 0.06 031 0.00 0.20184 S 1HNMR 5.6 Heteroaromatic Compounds 5.6.1 Non-Condensed Heteroaromatic 1H Chemical Shifts and Coupling Constants (0 in ppm, |J| in Hz) 2 638 yy 18 e b 6.23 yy 26 Vin 208 OY ah ts 7.09 Uy, 48 erat te 10 Tas 15 ag 2 s ad 3iy 34 Heat, Uy, 26 Ie 35 broad 34,, 3.5 My 2.6 Yo OS ew rss Ya 2 wos ae to ne 5 La 5 te Oo 7A TB ay 10 4 3h 17 Aye 03 aie LS 31, 47 775 - ee mM aes Ow CBars we HO=12 ° N-N A 858 6758 414 ONe MN ois lk Ours eens crSolvent: DCI, DMSO 2859 BSR b725 7.38 © 7627.78 31, 49 27.56 a 35 922 sf 39 Bye BA 5 3}, 5.0 as NON 9738 the 25 all Dass hu 0 oat N 1s O 8.63 56 Heteroaromatics 185 Solvent: My, 60 cDcl,* DMSO" 4. 1.6 49.00 8.98 51,08 »797 814 TL e843 867 3,79 * ptoluylsulfonate “oa 1+ *HSO,- B24 Boe ° N. C yen de 08 zg ing 06 a\yeasad get 1 ° 3, 68 fo on Ang 16 ah 2 1843 4g 20 Te 49 Sips 1.0 41 Ihe 04186 S 1HNMR Effect of Substituents on the 'H Chemical Shifts of Monosubstituted Furans Gn ppm TAL+ Zig 38 +Zix 38+ Zig bys= 7424 Zs Ms a i, Hs Substituent in position? or 5 in position 3 or 4 Zs ky hs tn ku bs ty ty ty tis Zu Zn Cc -ci, “OAS 01S 017-025 -0.17 012 —CHCH 0M 0.12 014 —CH,OH 0.12 007 005-007 000-006 —CHSH 022 -0.09 009 =CHSCH, 021 -0.09 008 CH=CHCOCH, (rans) 0.29 0.11 0.08 X 023 -0.17 0.17 4 0.04 021-005 -0.17 -004 -026 O -ocn, -126 0.14 057-050 -036 -041 N No, 113, 047 047 ae 048 002 -004 041 0.14 -0.06 S -sch, 0.05 001 0.13 -022 -0.13 -0.19 -SCN’ 032 002 006 0.15 0.11 -001 O -cHo 092 025 031 092 047 0.19 || cocts O81 016 018 042 028 -016 G ~£2C0-21 126 027 037 COOH 097 019 024 070 040 0.03 ~COOCH, 081 014 0.18 060 037 0.01 —coci 114 032 046 M -Pfury), 0.254 -0.128 0.03" —-0.16 0.10 -0.09% =P(OV-x-furyl)) 0.76% 0.15 030° 0.14 0.19 031° PS\ExfuryDy O7F 0.128 027 — 0.10> 0.18 030° PCH )@-furyDy 153. 0490.77 -Hgcl +009 0.02 025 x=5.6 Heteroaromaties 187 Effect of Substituents on the 1H Chemical Shifts of Monosubstituted Pyrroles (in ppm Su dy2= 8.71 + Zn 843702347 8442 9.23 + by.s= 6-71 4Z5 8, broad, solvent-dependent Hy ‘Substituent| © a, 589636033 O=0 ZO) -COCH, -COOCH, Hy Substituent in position 1 312 Substitwentin position 1 712 ai, “013 —CH,CH, 0.16 ~CH,CHCN 0.05 —CH,-phenyl 0.12 phenyl 036 N(CH,), ol ~COCH, 056 ~CO-phenyl 0s7 (CH(CHS))3 0.08 i Hy in position 2 or 5 a Za Las sa 2s Zs 572 589 636 TAL 629 7.05 688 628 7.13, 623 6.10 6.72 653 61S 6.90 701 634 7.18 693 626 7.06 684 6.18 691 Hy Zs Zig AT on ‘007 “oot ol 19 012 os 0.08 HO, He in postion 3 or 4 Zn Zu Zas a5 has Zan 16 026 1.05 024 043 083 023 51 018 005 90.10 048 0.10 028 078 oll 087 070 003 035 079 013 029188 S 1HNMR Effect of Substituents on the 1H Chemical Shifts of Monosubstituted Thi phenes (in ppm) Substituent Cc -cx, y ~phenyl 2-thienyl ~2-pyridyl wel Br 4 © -on “oct, N NH) -NO, SCH, S(0),CH3 S(0),C1 =SCN f] ~coct =CO-phenyl =COOH -COOCH, ~CONHNH, =COCL keto form Oy2=731+Z2 4.3 =7.09 + Zia 344-7094 Zig Oysa731+Zs OH He OH, OH iy in postion 2 or 5 in postion 3 oF 4 Zs 2m Los ty ty Ls Zsa sy Lis ay Zan 034-020-024 045-022-015 002 -029 ‘023 0.11 028 005 008 -009 0.11 048 001 006 078-054 086 080 -040 -031 030 (035 039-025 “0.17 -009 095 023 010-023-021 -021 0.11 034 001 005 0.13 -030 085 044 321 093 041 082-10 -036 -017 SK -096 +136 +066. -0.36 069 0.16 0.19 084 047 -008 034 013 017 052 007 0.04 013 033 018 033 033-021 016 031 0.16 044 023-014 090 007 068 085 035 035 060 007 034 0.17 0.18 017 0.14 -008 -006 069 013 047 081 044 006 060 003 032 074 045 001 055 006 040 067 005 029 093 048 003 070 000 022 067 034 -0.16 0.63 o4L 731 799 -7.31 0.75 0.33 om5.6 Heteroaromaties 189 Effect of Substituents on the 'H Chemical Shifls of Monosubstituted Pyridines (in ppm, Hy Substituent in position 2 or 6 Cc -cH; =CH,CH, ~CHy-phenyl =CH,OH =CH=CH, =phenyl =2-pyridyl X + -cl oO: -COOH -COOCH, ~CONH, ~CH=N-NH-2-pyridyl (CH), * Keto form 2-pyridone) “OM 0.09 0.03, out -0.07 042. 127 -0.30 0.09 0.26 049 0.63 051 0.76 -087 0.77 “055 1.00 021 093 052 0.34 0.73 0.80 o8t 087 91 0.98 0.76 ous: By.s= 725+ Zs ou. 594Zig Hs 2 das Zea Zo “0.08 -0.15 oor -o.15 0.06 0.04 0.03 0.08 0.14 023 002-009 004 0.1 0.16 005 002 0.00 0.06 0.03 029 004 0.13 093 010-041 024 063 022 069 023.073 017-058 009 0.19 001-042 044 04s 026 035 020-042 026 031 022 024 027 025 ol y 028 024 00s 0.22 Zag 2s “0.17 0.03 -0.04 0.14 0.12 0.07 0.00 0.36 0.10 0.23 023 “117 0.43 054 052 0.44 0.48 -0.32 0.36 0.00 ous -091 21 0.10 03 017 ou7 -0.01 -0.03 0.99190 S 'HNMR cn Substituent in positon 3 or 5 in positon 4 Zy Ty ts te tn Za Zs Tsu Zu Zs Zan Zas C cH, “0.15 -0.16 -007 017-013 -0.13 =CH,CH, “0.13 0.14 -006 017 0.12 0.14 ~CHiy- phenyl “008 0.18 -004 0.14 0.00. -0.15 ~phenyl 025 020 008 -003 CH=CH, 0.12 0.08 -005 -021 004 0.13 -0.07 -0.03 =ci 0.09 000 005 -005 0.00 os Br 009 0.18 -004 007 009 0s -ont 0.31 029 006 050 ~ocH, 1027 037 004 040 0.16 -0.42 Hooch, “015-015 008 -0.13 N -Niy “051-065 -0.20 060 0.158 074 =N(CHi)a “038 07 -NHCOCH, 037 050 006 016 019 0.16 =c=N 032 038 025 026 024 032 S -Sopheny! 005 -0.16 =8(0),0H 070 114 081 070 O cho 052 058 030 028 031 049 f] coc 058 061 020 020 021 050 =CO-phenyl 023 035 © “cou 054 057 020 024 020 os =Coocy 061 067 016 019 019 Ost =COO-phenyl 024 075 “CONE, 049 050 015 0.5 —CSNH, 068 067 024 026 035 068 =CH=-NOH 039 043 0.19 O15 006 032 =Si(CHy) 0.08 0.00 -0.21-0.11 08 0.015.6 Heteroaromatics 191 5.8.2 Condensed Heteroaromatic Rings 1H Chemical Shifts and Coupling Constants (6 in ppm, \J| in Hz) 33, 25 m $6095 Sty 09 7208 Vazsa 479 725 ¢ o 4g 12 t Ty 08 vat a 93 Ba 08 Jemical shits in CDC ef My 84 cooningeensaaia og 08 {all other cou acetone) Mae Tl pling constants iy 13 sects) ay 81 tats cov pling conan reatetie 182 By 55 179 51,02 2 ab ab 7364 Ae O84 A chet Nara 30,80 Sia gio Shs 04 qae ¢ at 7348 o 5 00 t 515 0.9 « Me 82 788 59 758 tg LO Ba 19 chemical shifts in CDCI, ee 0? Mg 8.0 teuplingconsanisin ded 74 (alotercot- eee) st 12 pling constants Aye 83 weatenie 730 ge 82 794 Sty, 0.1 4 op . N ald gi y Ne 02 728 esos Syo7 75! Yager the 04 7264 N Mey 71-746 a s Sue 0.1 | {all other cou © 8h, 82 750 125+ Hlingeownns 8.14 rani reliibe) se 06 (chemical shitsincDC,—§ *in DMSO ‘coupling constants in Jeg 72 acetone), 4y. Ld192 S 'HNMR 778 Sy 08 78 8.10 le . 3h, 78 Ibe Td3¢ \, sig 12 7364 HY Tye 1.0 © eR 3g 7.0 758 4 12 fin DMSO) “Ie 79 (alether cou pling constants eglgible) 795 5 191 yy 89 A ‘yy 83 a a N sb - 7.39 bj Sy Se 10 753», 5 09 nN yg 0.9 . sy UL 67 @ H=16 ye 7.0 a (chensca shite in CDCI, coupling constants in 861 yy, 84 921 3 ‘uy bo or 5 08 +870 se 7.0 so Ny % hey 10 Raiss 4 lea 79 (in DMSO) 768 AN ‘Tg 07 owrare pr 77 is 99 oss eb NY st a3 f 39760 Sy 13 soos a 6s Age 13 Ny 68 (a ttc pling constants negligible) {all ether cou Plingconstanis negligible5.6 Heteroaromatics 193 10 os 92 1 1 64 09 3g TL (al oer eou- pling constants vests) 632 Ao. Bay 79 ony 57 sin ts ° 5h 04 rr a. 79 746 7,70 34,4 96 A Neg 7.7 7aT© ay. 74 TO Oa Ld 72 3 8d (alot cone pling coms west) 782 8.12 ty 42 a fe a 5 41. 18 1556 Syo739 jhe uy, 82 ame 22892 08 € 3, 8.2 sis sa SI, 07 My 69) eg 12 ee 3p 8S pling constants sect) 6974 6.02 «! 7.60 © sit 744 658 15 05 oN sh 08 pa730 Se Na fey 89 ¥ 839 821 0 r 147 72 155 a: {alter cou pling constanis negligbe) yp so 3a! OF Tye 58 ZN Sieg 09 Ye 786 922 Slag 08 My 69 4, 12 eg ai 83 (al other oot ling constants negligible)194 5 'HNMR 790777 My 6a A ‘ AI. 1.0 168 AYE 8s 1I9e DPasss Igy 09 . y ug 82 877 oO Nye 1.2, SIyy 03 (all otber cou “Yeg 7-2 pling constants “Sg 14 rE Re Bol 88 Uy 50 eg O8 186474 929 Heo ros nats rN STy O08 844 Mae 69 hyp 13 My 8.6 BB ag 84 14 mr St a . (7 *B85 Aye 69 a Ay 8.0 N. ann 18 SpA 758 pe 41 tio e By 84 NAYES cog Hae 16 ] £914 S09 smb A Ao ro7 a2 vo so tn sis pling constants ‘egligible) 72 168 AA 44, 17 a S ab 7.608 ¢ gn yy 0 719 878 * assignment uncertain 798 9.41 444, 00 NA Shy 05 793 4 Sy NSS 767 Ae oas Hes rN 5 09 8.06 My 70 * Hp 13 assignment uncertain at 1 193 94 04 S 382 7a No al . ZN N06 ry 4g, 68 793 yy 82 AY Ns coi0 8 826 (AAS) <920 S09 NAA 0792 Meal on Ay 60 928 828 ty 09 aller cow pling conta seeks) 3 82 NON, a 20 ANS NS 9.13. 3p ] he 43 SAA 0750 821\ \ / \ U 7196 Ff Se 735 2? 746 787 B16 a Nye 745 Bras 788 80 Age Ll Sigg 07 Bye 72 yg 12 8 Sig 8.0 5.6 Heteroaromaties J \ J \ / \ y Y 786 a BONS 07.43 Z 8.22 8.08 Sya7.24 Ben voX = 742 8.03 779 a Sos b 7.48 sow ios oO 797 baat 9 827 ‘ee 2174 NO S787 1170 195 ae 0.7 Bye 8.1 10 o7 12 79 7 07 75 1 16 oa 19 oa 70 82199 S 'HNMR 5.7 Halogen Compounds 5.7.1 Fluoro Compounds '9F (natural abundance 100%) has a spin quantum number I of 1/2. The signals of "A atoms are split by coupling to '9F up toa distance of about four bonds. 1H Chemical Shifts and Coupling Constants (8 in ppm, J] in Hz) 47 sas 625 CHE yp 464 CHF, yyy 50.2 CHF, ye 79.2 2a 1.56 * Y yp 25.2 3p 20.9 057 430 436 Hy 69 F S945), 45 Be 1a a F Hb OF yp 874 3g, 128 Tr S={ hp 201 3, 47 Ho Ny Age S24 Ay 32 3 403° 617 027 2p 649 Fi 4 449 A a ore 128 4 163 . ck soi i eH F 3y 1.65, 1358 i J, 59 tf wr Hass : “4, ae 24 HW 215 H 2.03 (gy The 67 az go 142 Lae as Has 3Tq 108 (in benzene/CFCl,) Joe 77 31, 120 : : Fy Mp 08 3,79 F Sup 89 My 8A She 08 412 $e 57 Ae LA GS 153 Nop 07 515 06 ° 07.03 Np 02 Ig 04 al 727 47, 2.0 a b 7.31 Bye 27 Y ‘Iye 7.6 © gine 75 734 Nya 13 73 iy 185.7 Halogen Compounds 197 CH, Couplings Hy OF F with CHy sul Bhp 107 Sup te 25 751 a 713 Aig SA Zo Im 00 an is 73 b 7.38 p 5hye22 784 761 5.7.2. Chloro Compounds 1H Chemical Shifts and Coupling Constants (5 in ppm, J in Hz) 3.06, sm 1225 i ae eae a, 8 ot ay 2 Lv cl 3g C1 Pe cl 092 1ss cl cl 361 3368 . . ‘ fieres >See as Ts an 135 1.60 5 70 3.88 36 133 7H \77 a 4 ii 60 168 175 103 tit, Ropes ° 7 Hd 2.00 H LISHTR4H 158 12644 554176 106 5 4 i st an e 2733 Sas OS * 2789 Sa OS all Dy 728 thee 23 all Dy 727 ta 24 oN rs OX ORE 722 ha 725 “E 198 S 'HNMR sar ¢l 377 Aye LO TR 16S oy 5 aed Vy,02 TATE 748 t 8749 S78 Ay 68 Tas‘ 7.40 Tade 728 5,07 41,06 70" 754 ue S81 Wy 78 ‘t+; assignment 734. 78s e +: assignments interchangeable 5.7.3. Bromo Compounds 1H Chemical Shifts and Coupling Constants (8 in ppm, J in Hz) 2.68 494 682 Les CH,8r CHB, CHB, \8r 386 247 3.63 189 093 184 Yoae! 84 ae aN SN 1386 104 356 Me 342 584 4 ‘a Br Hy Br yy 14.9 Me TL 4.20 ae ES 173 1.76 He 597 644 081 409 A 135 4 1.79 Br i is Hi 17 , 178 “ft it FiBS3 i Hi 4st : H ; HT 2.08 Hi 122H180H175 1244!) 60 H181 0.96 5 Br Br nee 819) TPB 198 pe sos 751 TN 748 Sa 749 Sas 05 Sh eS h22 714 721 7.46 753 ay 74 77 770 772 768 © 4 as Ug 185.7 Halogen Compounds 199 5.7.4 lodo Compounds 1H Chemical Shifts and Coupling Constants (3 in ppm, J in Hz) 2.16 390 491 cist CHa CHl, 296 ya 1.86 NG e™ ~! 154 1.04 3.16 657 ‘E 1 He | Uy 159 4.24 or Y={ he 78 H Ube “1S 189 19s Me 623 633 48 136 4H im | i it 180 173 RAT Ries " ff 206 1a0H'LerH 197 26H" 6 His3 ' 8.02 a0 746 768 Cur ns 1 782 797 732200 Ss 'HNMR 5.8 Alcohols, Ethers, and Related Compounds 5.8.1 Alcohols 1H Chemical Shifts and Coupling Constants (0 in ppm, J in Hz) Aliphatic and alicyclic alcohols: dg, Phenols: 801 5-300 (in DMSO: 4-6) ppm (0-8.0 (in DMSO: 8-12) ppm. Hydrogen bonds strongly deshield hydroxyl protons. The position of the signal may depend heavily on the experimental conditions including the concentration of the sample, Ifa compound contains several kinds of hydroxyl protons (~OH, COOH, H,0), in general only one signal at an average position is seen because of rapid exchange. In dimethyl sulfoxide (DMSO) as solvent, this exchange in most cases is so slow that isolated signals are oblained. In this case, the chemical shifts of hydroxyl protons are characteristic. However, i the sample contains strong acids or ‘amine bases, the exchange rate increases and, also in DMSO, a single signal at an average position is observed. Frequently, intermediate exchange rates lead to very broad signals extending over several ppm and, therefore, sometimes not discernible in routine spectra As a consequence of fast intermolecular exchange of the hydroxyl protons, their coupling with the protons on the adjacent carbon atoms is usually not observed. However, in very pure (acid-free) solutions or in DMSO, the exchange is suffi- ciently slow so that the H-O-C-H couplings become visible, Their dependence on. the conformation is analogous to that shown by the H-C-C-H couplings (Chapter 5.1.2). In ease of fast rotation: SFyocy = 5 Hz. In eyclohexanols, the vicinal cou- pling constants for axial hydroxyl protons (3.042 Hz) are lower than those of ‘equatorial ones (4.2-5.7 Hz). boa © on < oh CHOH NH owt ¥ cy CDCI; DMSO DO CDC; DMSO DO CDCI; DMSO _D,0 a 113" 4.05 a isl 431 a isl 431 b 349 317 334 b 371 344 365 B359 334 361 3p 52 6126 106 LIT 6 159142157 Sy 48 2094 084 089 3.6.9cpl, DMSO a 136° 430 b 404 3.78 © 122 104 51, ay 62 5.8 Alcohols, Ethers, and Related Compounds 201 (in DMSO) 034 a oH = HY a 1 OHa — CDCI; DMSO 3, 8.0 9 469 eg SP» 683 el dec 724 4693 NAW 0H ‘OH wy b{O CDCI, BMSO.D;0 Eb, DMSO D,0 ao $361 338 36 8128 LI 128 My 1S6 140151 * 0a! 087 091 s6 6a cv-on coon L, , «indMS0) (inbMso) Ay 62 Bye 7.0 Mey 23 3. 29 8heg 81 Ay 5.2 ae Sa ie 0 yy 104 Ayg 103, Nye Ld Bye 9.7 aye 68. Aeg-l10 Ay, -09 31, 109 Nee 79 Nyy 0 3hgp-11.0 Los ase cocy, bMso SS kpe in DMSO. Bor dyydoas 432 409 085 HH ag Son dOss Tse tas 0st 78 op Few 176 161 Ky DRS Derivatives 186 144 H4.03 BPMS Fe so 342 os ih Joon 3 0-42 OH ILL OH 10.57 No, 929 Ig Ld 696 716 675 I, 05 81d TAS Nye 22 8 sere 676 Ig 74 NO, 47,18 inDMSO in CDCI;202 § 'HNMR 1H Chemical Shifts and Coupling Constants of Enols (6 in ppm, Jin Hz) 6 Iss H Hl oto sa oo WS hon no Sony 790 hy 2 20s 208 5.60 552 {in CDCI, partly enol- ized; for the keto form, see Chapter 5.11.2) 166 162 6 fi oO oO oO oO as F 0 A HoT SoH, SoH, [ ° 2d gL 24 ho 28 OV os oie 200 T {in CDCI, pay enolized) 5.8.2 Ethers 1H Chemical Shifts and Coupling Constants ( in ppm, J in Hz) 3a a8 BAL 3g 093 No ecm “10.6 roo ie Non 20 159 3.65 das 340.138 say Jone ak, o oN No sa 092 6.4 Hy 41, 03 355 343 3.60 oa a 2A TPP RR RT 24 2.05.8 Alcohols, Ethers, and Related Compounds 203 1H Chemical Shifts and Coupling Constants of Cyclic Ethers (3 in ppm, Jin Hz) ° Orsa In derivatives: 3.07 HE Beem 6 : ua as Be Jeans 3-1 a Throughout i Seis > Sirans led cpch, DMSO » 4374) 3.60 6 185176 ©. CPC, PMSO D,0 CJ 3m 3873.15 o” 3ncis 83 ‘pn '02 he 2S Mey 26 Shy 26 0, By, 6.2 3.96 e PJaoat 41,0 20 1854 b4ot My 38 < hg 06 1.98 Ox 0. Say 5.0 ye 277 tae 24 638 A Jo 643 Sha 12 Y ye 63 756 hg LS 3g 94 278 Hi 2 oH 147 H, 3.34 27 Ba gum “58 52 2 gem “HLO 42 BT 33 Trans 8 42 Hd <03 cpcl; DMso 1365) 353 bovis? 1a? Oe et 158 °. °. 367 3.88 287 237 y s Mie 3, 1.6 2463 425 41, Ta Oy sg0 Satcn Waa trans 46 Be 63 0°, 4, 7.0 eff rent the 17 4 b463 Aye 1S © Spe 34 266 0. 344, 6.0 op a7 sok clea 837 Mn. Ld 8204 ~S 'HNMR 1H Chemical Shifts and Coupling Constants of Aromatic Ethers (3 in ppm, J in Hz) F375 Say=0.8 3.98 1.38 1 jb 6.90 sy he 1296" 97 694 4 18 1) Stay 723s o 4 5 Tai" aa ‘o. Fete art a Jor af * assignment uncertain © 7.09 83 Li os 26 Ta 17 1H Chemical Shifts and Coupling Constants of Acetals, Ketals, and Ortho Esters (3 in ppm, J in Hz) im 4g a0 9320 of & oo wg Wis Ki ve \ ma TS Sagem “75 Nees 73 Fate jrans 6.0 sat 132 oo 681 OO Or ssl 162 OF A s00 gem mK oo : gem 1S y in 329 pS 002 Lo oH, os. x 3.58 _/ > po 8 se ON ro oN™5.9 Nitrogen Compounds — 205 5.9 Nitrogen Compounds 5.9.1 Amines Amine and Ammonium Protons (5 in ppm, |J| in Hz) Chemical shifts of amine protons lie around 0.56 ppm depending on solvent, con centration, and hydrogen bonding. Those of ammonium protons are found between ca. 7 and 12 ppm. Neighboring H bond acceptors lead to deshielding in all cases, incbcl, in DMSO Amines: Oyu» Oyu aliphatic <2 24 ‘aromatic a 447 Ammonium: Axyss*>Oyag*s Ox aliphatic Tl Tl aromatic a2 812 Coupling of amine protons with vicinal H atoms is usually not seen in aliphatic amines because of their rapid intermolecular exchange. However, for ~C-NH-CH moieties (enamines, aromatic amines, amides, ete.) the exchange rate is slower and spliting (orline broadening a intermediate rates) i often observed. The H-C-N-H. coupling depends on the conformation in a similar way as the H-C-C-H coupling (Gee Chapter 5.1.2). For N-CH, and NCH gr0Ups: Sen = 5-6 Hz In acidic media (eg. in trifluoroacetic acid as solvent, the exchange of the am- ‘onium protons is slowed down to such an extent that the vicinal coupling HN" C-H generally becomes observable. In other media signals are usually broad owing to intermediate exchange rates. The signals of amine and especially of ammonium protons are often broad- ened additionally because the 'SN-IH coupling is only party eliminated by the quadrupole relaxation of '4N (spin quantum number, I= 1; natural abundance, 99.6%; ‘yy, = 60 Hz). This line broadening has no effect onthe vicinal H-C-N-H coupling so that sharp multiplets ean be observed for neighboring H atoms even when the NH proton exhibits a broad signal. In ammonium compounds of high symmetry, the quadrupole relaxation is slow and the coupling with '4N leads to triplets of equal intensity forall thee lines NH Myyy 52.8208 S 'HNMR 1H Chemical Shifts and Coupling Constants of Amines and Ammonium Salts (3 in ppm, J in Hz) 247 sity ai, on A 274 135° 269 i vo 1109 099 (CH,).NH NN DH 266 282 263 2.22 103 252 (CHonN ‘Ny ot ia Byeg “117 N aaa a 129 238 321 (in D0) 102145 (CHy.N - 127.327 3.40 a7 Me or 168 Nar 3.46 in CDCL) a (Cl)eN" AcO™ in ,0) a \ . oss Lo to tts os #8 110104 Mf Lo b NU N. NO aw aay me oan sf ta © Lea 187 {020 GHA Mie 159 asp Ton 222 (neat) Ln 137 4 NA, wo 3a eS 128" V'g2 155 * assignment uncertain5.9 Nitrogen Compounds 207 366 283 298 NH, 3.61 M80 HN 382 SN Iq, 84 ae an a" 1.0 ° 2667 y05 © 4661 S104 © 96.74 Shay 04 al Derg me 25 all ors te25 al agg he 28 Y 474 373 M73 6.75 ANyg 16 6.70 AIgg 17 6.72 ha 18 pati DMSO:4.94 yy in DMSO: 5.52 3.70 462 Hy 24 Sy S10 NCH), or 653 659 8.08 8.09 8.09 764 759 No. No, Gin DMSO) ya in DMSO:732 1H Chemical Shifts and Coupling Constants of Cyclic Amines (0 in ppm, J in Hz) 09 ee 208 H 201 y 21s 3y, 63 3.63 275 2.79 his 363 Ariage 3 O 23 ae obcns Ms (neat) 133 | 223 H259 | | 226 N N N N 233 286 232 237 159 367 362 288 ° ° N Mm Nin 5.9.2 Nitro and Nitroso Compounds 1H Chemical Shifts and Coupling Constants (8 in ppm, J in Hz) 434 1588 201 CH.NO, Qn02 sie 74 NNO 433 103 428 183 107 2.07 159 Nog SAN No, 444 130 47208 «Ss 'HNMR 438 No, iH No, 491 HO | fas 2.26, 2.12 1.67 H; HNO? nA 223 2.60 1.88, 1.70 128 OM gs h ied 185 162 3, 84 No 3,79 No, 587 712, rani a3 4 ype «A aga7 Tyo & 9784 51,06 3g 146 a Sha A760 tae 24 5 ® 7 No, he Lt oh Aors7 the29 te thes 763 hel 5.9.3 Nitrites and Nitrates 1H Chemical Shifts (8 in ppm) 32 1.06 439 Us " 1a OTN: er Ne 137 ‘O-NO, 5.94 Nitrosamines, Azo and Azoxy Compounds 1H Chemical Shifts (8 in ppm) ‘Owing to hindered rotation around the N-NO bond, corresponding protons in cis and trans positions have different chemical shifts in the neighborhood of the group. In general: cjg <3yan, for O-CH,, -CHy, and f-CH, > Dang For a-CH Bcis® Stans 2 a ye yo? oo7 17s | 17s 093 i 12S Ns oN 1287, Yas ANAL 376 96 1% 207 3% 1%5.9 Nitrogen Compounds 209 Mi tan ete hg i N CO ” 750 74 46 ‘Sy Ons Nes 2 we Sas reK, ° 7.39 5.9.5 Imines, Oximes, Hydrazones, and Azines 1H Chemical Shifts (8 in ppm) 34 7.46 739 720-738 / S014 ras € Noun) 122 S40 85 In aldoximes and ketoximes, the chemical shift difference between syn and anti protons at the a-CH group, Ad = djyq = Dyqiv depends on the dihedral angle, pcan , Se ee £ 115° 10.18 OH N A 2a CY 225 1%9 150 166 164 (in DMSO) 69 70 OH OH N N 230210 S 'HNMR 793 828 136 7.94 8.29 1102 aia 757 NP He 10d om-orn tno, | Ome No, 9.10 Ss 230 209 1.00 2.66 My, 75 We Ld 54 0.5 1.01157 4, 2.0 3758 se ye 7.2. 27 294 184 aR 16 9 (CHS tu © a TAT (in DMSO) yf al Do 729 724 5.10.4 Sulfoxides and Sulfones 1H Chemical Shifts and Coupling Constants (3 in ppm, J in Hz) ° ° ° ° for 24 4 s i gfe 8 g S57 Z a “ H L£A\242 288 262 261 2 5 4 12 243 Gn DMSO) on net 2.50 205 cw cw, wr si SP a7 es Po 284 fe " 280 294 La i Z O= $n 3.06 Aas5.10 Sulfur-Compounds 215 5.10.5 Sulfonic, Sulfurous, and Sulfuric Acids and Deriv ives 1H Chemical Shifts and Coupling Constants (5 in ppm, J in Hz) 142 3.17 1a 2.36 CH,-CH,—So, —OH 3.02 391 278 CH,-S0,—0-C) CH, -S0, Apparently lower 3x “CH; valves in DMSO due to fast exchange with HO 370 507. 263, oui oct cl ni 737 ci ° ¢ " $0, go, $0, $0, $0, 794 802 785 786 7.60 761 758 78 7A 758 7497 inDM50) 397 0 9 oe Q s68 Q kos Apgrt03 se No Bso7 Ao on ee 67 9 ys 126 Wie 6.9 449 264 0.8 QP 394 QP 434 SS Noo Aion oo oa \S sg 5.10.6 Thiocarboxylate Derivatives 1H Chemical Shifts and Coupling Constants (6 in ppm, J in Hz) s ‘ 3, 5.9 $7 a 6A as 70, oy 42945 784 M28 77 09 64 241 HC~ SH 5.09 9.56 HN7 > 2.98 ‘SCH, 227 3.38 Lp 1791.65 2.30 H.C’216 § 'HNMR 5.11 Carbonyl Compounds 5.11.1 Aldehydes 1H Chemical Shifts and Coupling Constants (0 in ppm, J in Hz) ‘alk—CHO 910 Myjc 0-3 alken—CHO 9-10 Aye = ortho-substituted: 10-10.5 ‘meta-, para-substituted: 9.5102 220 9.79 Lis 9.79 167 974 H,c—CHO NwcHo Nw cho (in TMS) * » 246” 097 242° peg! 424 354,3.0 3114 314,20 957 Los 948 "Se cto CHO 093 159 O76 23 » or NA 135. 242 yy Ld 419 652. 637 743 967 He OH, yy 47 ye 10.0 He CHO a1, 78 — ad gi7 — aye 160 Seo Aig 3.56 Hy 31 69 Ny MS He He ge 0.3 ey BB 432Hp Hg 226 yp 05. ° ° ° 3y, 94 4h 1S o7 331 on} 605, 7 yn 631 Thy 13 3 4.09 a16 444 7.10 748 AS AP 733 ge 6 2 <0 © yg 24 ale 2 625 31-4 5.0 5.11.5 Amides and Lactams Amide Protons (5 in ppm, Jin Hz) © 6 ok ke aye y “1 os Ralkorar Realkorar Higher values in DMSO or with H bond acceptors AO 75-10 Roalk or ar in the neighborhood,5.11 Carbonyl Compounds 221 te signals of the NH protons are often broad because the !4N—!H coupling is only partly eliminated by the quadrupole relaxation of !4N (spin quantum number, I = 1; 'Jyq = 60). In primary amides, the hindered rotation around the CO-N bond is another reason for line broadening. At slow rotation, the chemical shifts of the two primary amide protons differ by about 0.41 ppm. Therefore, at intermediate rota- tion rates, line widths of up to 1 ppm may be observed, Due to the slow intermolecular exchange of amide protons, their coupling to ncighboring hydrogen atoms is usually detectable. The splitting of the C-H signal is clearly observed even in those cases where the signal of the NH proton is broad and featureless. The H-N-C-H coupling depends on the conformation in a similar way as the H-C-C-H coupling (see Chapter 5.1.2). For N=CHl, und N-CH groups: Anca =7 He Tertiary Alkylamides he rotation around the CO-N bond is usually so slow that, for identical substituents, ‘wo separate signals are observed for cis and rans positions. With different N- substituents two separate pairs of signals are observed for the two conformers. In general, the following relationships hole: for NCH, NCH,CHy, and NCH(CH) 5.905 pans for NCH(CH,), and NC(CHy); iS for NCH, 8ei1007 Pans 00 rans 100% Pcie 0 Formamides (3 in ppm, J in Hz) In the more stable conformer of monosubstituted formamides, the substituent oceu- pics the cis position relative to the carbonyl oxygen. In the more stable conformer of asymmetrically disubstituted formamides, the larger substituent occupies the trans position relative to the carbonyl oxygen, - Ja det ° ds HE Nite He I, soa |, coc, paso =3%iNCDC, = 10%in CDCI, 297 a 823° 798 CCl, DMSO CDCI, DMSO 44,, =03 580 714 9 819 801» 806 781 tye =07 © 548 741 & 286 259» 294 272 © 555 790 © S86 7.90 ij222 § 'HNMR ° ° ° 32 an Mars H as HO NT HT *N’ gis War a | ° AL 32 WN Lia 8.06 aN 65% yen 10.6 Senn Amides of Aliphatic Carboxylic Acids (3 in ppm, J in Hz) In monosubstituted acetamides, the substituent of the only observable conformer is cis tothe carbonyl oxygen. In disubstituted acetamides, the more stable conformer has the larger substituent cis to the carbonyl oxygen. ° ° ye Ayes a 4 a Sas Hy Hy coc, DMSO Dc, DMSO +208 176 2198178 542, 730 > 353 770 © 542 670 © 280 250 © 326 ° 9 2 3.18 0.96 JL eset mm NaN N’ iss A, nia =o Ns =o My tas at or Hy, 59 3g, 84 ° . 9 9 3.21 135 de aot ye y ea A 128 208 | 7.05 73 2945.11 Carbonyl Compounds 223 9 3 3h, 82 Joe Aer th 2.08 one A, 6732 5405 54 * 218 oH a ‘ye 24 sist ay es . mis assignment uncerisin Lactams (8 in ppm, J in Hz) oO °O oO 9 633 2s, 60g Say Ui 28 282 ~ 331 181 30 34024 339.203 ws Buncn, 08 294 q 9 ° 298 0 4M 635 8 N 237) HN 3.35 HN’ 2.46 'N’ 252 sak Jie ty 321 169 336 1.66 ‘00 Isl 6 Los 1.75 1.65 1.70 ance, 22224 § 'HNMR 5.11.6 Miscellaneous Carbonyl Derivatives Carboxylic Acid Halides (8 in ppm, J in Hz) A, A, AL BU UL 2 282 3.00 23 308 660 663 on el ty 80 og Ke Las too de 12 ; in ws he tS Fhatted Aa IE 625 6.16 Hy . a 749 7S 6.14 635, © ‘yg 14 799 Carboxylic Acid Anhydrides (3 in ppm) o 0° 1.69 o oO 5 4 8.13 AB AKJOW 0 149 oO o 233 ° 8.04 ° "mee Oe Op ° ° ° ° (in DMSO) Carboxylic Acid Imides (3 in ppm, J in Hz) ° 0 "CO 270 54 673 NH BS w\ [ \ Soin