Tabela de Deslocamentos Químicos de Prótons RMN - Compostos Orgânicos

SPECTROMETRIC IDENTIFICATION OF ORGANIC COMPOUNDS SEVENTH EDITION Robert M Silverstein Francis X Webster David J Kiemle CHART A1 CHEMICAL SHIFTS OF PROTONS ON A CARBON ATOM ADJACENT α POSITION TO A FUNCTIONAL GROUP IN ALIPHATIC COMPOUNDS MY I M methyl 8 M methylene M methine APPENDIX A Continued OTS is CHART A2 CHEMICAL SHIFTS OF PROTONS ON A CARBON ATOM ONCE REMOVED β POSITION FROM A FUNCTIONAL GROUP IN ALIPHATIC COMPOUNDS MCY M methyl 8 M methylene M methine MCCH2 MCCC MCCC MCPh MCF MCCl MCB r MCI MCOH MCOR MCOPh MCOCOR MCOCOPh MCOCOCF3 MCCOH MCCOR MCCOPh MCCOOR MCCONR2 MCCN MCNR2 MCNPhR MCNR3 MCNHCOR MCNO2 MCSH MCSR EFFECT ON CHEMICAL SHIFTS BY TWO OR THREE DIRECTLY ATTACHED FUNCTIONAL GROUPS groups Note that chemical shifts of methyl protons can be calculated by using the constant for H 034 For example HCH2Br is equivalent to CH3Br The chemical shift of a methylene group attached to two functional groups can be calculated by means of the substituent constants σ values in Table B1 Schoolerys rule states that the sum of the constants for the attached functional groups is added to δ 023 the chemical shift for CH4 δ YCH2Z 023 σY σZ The chemical shift for the methylene protons of C6H5CH2Br for example is calculated from the σ values in Table B1 023 σPh 185 σBr 233 δ 441 Found δ 443 Shoolerys original constants have been revised and extended in Table B1 The observed and calculated chemical shifts for 62 of the samples tested were within 02 ppm 92 within 03 ppm 96 within 04 ppm and 99 within 05 ppm Table B1 contains substituent constants Friedrich and Runkle 1984 for the more common functional Shoolery JN 1959 Varian Technical Information Bulletin Vol 2 No 3 Palo Alto CA Varian Associates Data from Friedrich EC and Runkle KG 1984 J Chem Educ 61 830 198663 127 TABLE B1 Substituent Constants for Alkyl Methylene and Methyl Protons Y or Z Substituent Constants σ Y or Z Substituent Constants σ H 034 CH3 068 C 132 CC 144 Ph 183 CF2 112 CF3 114 F 330 Cl 253 Br 233 I 219 OH 256 OR 236 OPh 294 OCOR 301 OCOPh 327 COR 150 COPh 190 COOR 146 CONR2H2 147 CN 159 NR2H2 157 NHPH 204 NHCOR 227 N3 197 NO2 336 SRH 164 OSO2R 313 Tables B2a B2b and B2c Chemical Shift Correlations for Methine Protons Table B2a gives the substituent constants to be used with the formulation δ CHXYZ 250 σX σY σZ which is satisfactory if at least two of the substituents are electronwithdrawing groups In other words only a single substituent may be an alkyl group R Within these limits the standard error of estimate is 020 ppm For example the chemical shift of the methine proton in OEt CH3CHOEt is calculated from Table B2a as follows δ 250 114 114 000 478 The found value is 472 Tables B2b and B2c are used jointly for methine protons that are substituted by at least two alkyl groups Bell HM Bowles DB and Senese F 1981 Org Magn Reson 16 285 With permission TABLE B2a Substituent Constants for Methine Protons Group σ F 159 Cl 156 Br 153 NO2 184 NH2 064 NH3 134 NHCOR 180 OH OR 114 OAr 179 OCOR 207 Ar 099 CC 046 CC 079 CN 066 COR COOR COOH 047 CONH2 060 COAr 122 SH SR 061 SO2R 094 R 0 TABLE B2b Observed Methine Proton Chemical Shifts of Isopropyl Derivatives CH32CHZ CH32CHZ Z δ ppm obs Z δ ppm obs H 133 HO 394 H3C 156 RO 355 R 150 C6H5O 451 XCH2 185 RHCOO 494 RHCO 254 C6H5COO 522 C6H5CO 358 F3CCOO 520 RHOCO 252 ArSO2O 470 R2H2NCO 244 RHS 316 C6H5 289 RSS 263 R2H2CCRH 262 F 450 RHCC 259 Cl 414 NC 267 Br 421 R2H2N 307 I 424 RHCONH 401 O2N 467 or other groups of low polarity Friedrich and Runkle proposed the relationship δCHXYZ δCH32CHZ xy in which the X and Y substituents are alkyl groups or other groups of low polarity The Z substituent covers a range of polarities xy is a correction factor The relationship states that the chemical shift of a methine proton with at least two lowpolarity groups is equivalent to the chemical shift of an isopropyl methine proton plus correction factor The substituent constants for a Z substituent on an isopropyl methine proton are given in Table B2b The xy correction factors are given in Table B2c The following example illustrates the joint use of Tables B2b and B2c with CH3 CHCH2 and C6H5 as substituents The most polar substituent is always designated Z Z Z C6H5 δXCHY δ CH3CHCHCH2 δ CH3CHCH3 xy TABLE B2c Correction Factors for Methine Substituents of Low Polarity OpenChain Methine Proton Systems Cyclic Methine Proton Systems Z Δxy Z Δxy CH3CHCH3 000 Z H 10 CH3CHR 020 H 040 RCHR 040 Z H 020 CH3CHCH2X 020 monosub 020 H axial H 045 CH3CHCHCH2 040 equat H 025 CH3CHC6H5 115 Z H 000 RCHC6H5 090 Z H 000 C6H5 From Table B2b δ 289 for CH3CHCH3 From Table B2c xy 000 for CH3 xy 040 for CHCH2 Therefore δ CH3CHCHCH2 289 000 040 329 Found δ 344 APPENDIX C CHEMICAL SHIFTS IN ALICYCLIC AND HETEROCYCLIC RINGS TABLE C1 Chemicals Shifts in Alicyclic Rings 022 196 151 144 154 178 165 196 303 206 222 238 230 18 18 152 152 TABLE C2 Chemical Shifts in Heterocyclic Rings 254 7 185 272 473 375 151 352 162 003 238 223 354 159 275 201 150 150 274 184 227 193 223 CH3 190 317 343 282 300 370 H S S O2 O2 R O 3941 590 475490 168 470 380 355 301 208 438 162 162 406 231 227 CHEMICAL SHIFTS IN UNSATURATED APPENDIX D AND AROMATIC SYSTEMS are calculated Ha C6H5 gem 135 525 ORtrans 128 007 007 δ 532 Hb ORgem 118 525 C6H5 trans 010 108 108 δ 633 See Table D1 Rc is H C C Rtrans Rgem δH 525 Zgem Zcis Ztrans For example the chemical shifts of the alkene protons in C6H5 OC2H5 C C Ha Hb TABLE D1 Substituent Constants Z for Chemical Shifts of Substituted Ethylenes Substituent R Z gem cis trans Substituent R Z gem cis trans H 0 0 0 H Alkyl 044 026 029 CO 103 097 121 Alkylringa 071 033 030 CH2O CH2I 067 002 007 N CH2S 053 015 015 CO 137 093 035 CH2Cl CH2Br 072 012 007 Cl CH2N 066 005 023 CO 110 141 099 CC 050 035 010 OR R aliph 118 106 128 CN 023 078 058 OR R conjb 114 065 105 CC 098 004 021 OCOR 209 040 067 CC conjb 126 008 001 Aromatic 135 037 010 CO 110 113 081 Cl 100 019 003 CO conjb 106 101 095 Br 104 040 055 COOH 100 135 074 R COOH conjb 069 097 039 NR aliph 069 119 131 R COOR 084 115 056 NR conjb 230 073 081 R COOR conjb 068 102 033 SR 100 024 004 SO2 158 115 095 a Alkyl ring indicates that the double bond is part of the ring R C C b The Z factor for the conjugated substituent is used when either the substituent or the double bond is further conjugated with other groups Source Pascual C Meier J and Simon W 1966 Helv Chim Acta 49 164 TABLE D2 Chemical Shifts of Miscellaneous Alkenes R COOCH3 R COCH3 R OCOCH3 673 H R 197 212 206 165 H3C R H3C R H3C R H3C H598 193 184 562 173 195 186 597 165 667 CH2 392 H5C2 H 619 435 H H 597 200 H3C CH2 OSiMe3 H490 OSiCH33 H5C2 OSiCH33 565 502 R CH2 601 716 455 257 560 R CH2 H3C C 171 608 562 OC2H5 092 595 190 228 570 H 650 N 238 230 361 640 202 771 688 215 592 165 650 290 736 559 196 642 266 610 580 764 642 213 300 O CH3 317 343 227 190 CH3 370 282 193 S 223 578 253 482 190 465 266 483 615 763 675 672 420 622 397 637 616 683 492 O 0 0 0 0 0 0 0 CH2Ph 694 589 560 590 590 453 728 772 753 642 750 732 710 piperitone linalool αterpinene TABLE D3 Chemical Shifts of Alkyne Protons HCCR 173188 HCCCCR 195 HCCPh 271337 HCCCOH 223 HCCH 180 HCCCHCR2 260310 TABLE D4 Chemical Shifts of Protons on Fused Aromatic Rings 781 760 800 761 864 746 789 765 788 767 764 831 791 774 869 781 913 879 739 765 801 873 802 775 CHEMICAL SHIFTS OF PROTONS ON MONOSUBSTITUTED BENZENE RINGS 9 8 6 4 2 8 8 6 4 2 7 8 6 4 2 6 δ Benzenea CH3 omp CH3CH2 omp CH32CH omp CH33C omp CCH2 omp CCH o mp Phenyl o m p CF3 omp CH2Cl omp CHCl2 omp CCl3 o mp CH2OH omp CH2OR omp CH2OCOCH3 omp CH2NH2 omp F mpo Cl omp Br o pm I opm OH mpo OR m op OClOCH3 mpo OTSb mp o CHOopm COCH3 o mp COOH o p m COOR o p m COCl o p m CN omp NH2 mpo NCH32 mop NHCOR omp NH3 o mp NO2 opm SR omp NCO omp 9 8 6 4 2 8 8 6 4 2 7 8 6 4 2 6 δ a The benzene ring proton is at δ 727 from which the shift increments are calculated as shown at the end of Section 34 b OTS ptoluenesulfonyloxy group TABLE D5 Chemical Shifts of Protons on Heteroaromatic Rings TABLE D6 Chemical Shifts of HCO HCN and HCO3 Protons RCHO 970 HCOOR 805 RCHNOH cis 725 PhCHO 998 HCONR2 805 RCHNOH trans 665 RCHCHCHO 978 HCOR3 500 PROTONS SUBJECT TO HYDROGENBONDING EFFECTS APPENDIX E PROTONS ON HETEROATOMSa δ 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 Proton Class OH Carboxylic acids Sulfonic acids Phenols Phenols intramolecular H bond Alcohols Enols cyclic αdiketones Enols βdiketones Enols βketoesters Waterb Oximes NH2 and NHR Alkyl and cyclic amines Aryl amines Amides Urethanes Amines in trifluoroacetic acid SH Aliphatic mercaptans Thiophenols δ 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 a Solvent CDC13 Chemical shifts within a range are a function of concentration b See Section 3612 APPENDIX F PROTON SPINCOUPLING CONSTANTS Type Jab Hz Jab Typical Type Jab Hz Jab Typical 030 1215 612 10 CHaCHb free rotation 68 7 03 12 CHaCCHb 01 0 410 7 axax 614 810 03 15 axeq 05 23 03 2 eqeq 05 23 913 10 3 member 0520 cis 510 4 member 2540 trans 510 5 member 5170 6 member 88110 cis or trans 7 member 913 8 member 1013 cis 412 23 trans 210 23 cis 713 trans 49 410 5 CHaOHb no exchange 13 23 6 1320 3138 01 12 01 12 01 0 1 1 1 58 6 J ortho 610 9 J meta 13 3 J para 01 0 J 23 56 5 J 34 79 8 J 24 12 15 J 35 12 15 J 25 01 1 J 26 01 0 cis or trans cis or trans 03 02 23 23 01 0 15 25 4 Type Jab Hz Jab Typical Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb CHa CHb CHa CHb CHa CHb CHa CHb CHa CHb CHa CHb CHa CHb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb C CH H H C CH Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb Ha Hb CCHa CH CHa CH Hb Hb Hb CHa CH Hb CHa CC Ha Hb CHa CH Hb 05 23 05 23 1218 17 03 02 APPENDIX F Continued Type Jab Hz Jab Typical Type Jab Hz Jab Typical J 23 4962 54 ProtonCarbon13 J 34 3450 40 See Tables 517 518 J 24 1217 15 ProtonFluorine J 25 3237 34 4481 J 13 23 325 J 23 23 04 J 34 34 J 24 12 J 25 1525 J 45 46 J 25 12 J 24 01 J 46 23 J 45 34 18 J 24 0 J 25 12 1240 o 610 m 56 p 2 aγ 43 βγ 48 ProtonPhosphorus 630707 27 134 05 HCCP 137 HCP 119 HCCP 163 HCP 1013 1520 10512 88 95 Source Complied by Varian Associates Absolute values Reproduced with permission CHEMICAL SHIFTS AND MULTIPLICITIES OF RESIDUAL PROTONS IN COMMERCIALLY AVAILABLE DEUTERATED SOLVENTS MERCK CO INC Compounda Molecular Weight δH multiplet Compounda Molecular Weight δH multiplet Acetic acidd4 1153 1 Nitromethaned3 433 5 64078 203 5 64059 Acetoned6 204 5 Isopropyl alcohold8 512 1 64117 389 br Acetonitriled3 193 5 110 br 44071 871 br Benzened6 715 br Pyridined5 755 br 84152 84133 719 br Chloroformd 726 1 Tetrahydrofurand8 358 br 120384 80157 173 br Cyclohexaned12 138 br Toluened8 709 m 96236 100191 700 br Deuterium oxide 463 ref DSSc 698 m 20028 467 ref TSPc 209 5 12Dichloroethaned4 372 br Trifluoroacetic acidd 1150 1 102985 115030 Diethyld10 ether 334 m 222Trifluoroethyl alcohold3 502 1 84185 107 m 103059 388 4 x 3 Diglymed14 349 br 148263 340 br 322 5 N NDimethylformamided7 801 br 80138 291 5 274 5 Dimethyld6 sulphoxide 249 5 84170 pDioxaned8 353 m 96156 Ethyl alcohold6 anh 519 1 52106 355 br 111 m 340 m Glymed10 322 5 100184 Hexafluroacetone deuterate 526 1 198067 HMPTd18 253 2 x 5 197314 Methyl alcohold4 478 1 36067 330 5 Methylene chlorided2 532 3 86945 Nitrobenzened5 811 br 128143 767 br 750 br a Purity Atom D up to 9996 100 for several solvents b The residual proton consists of one proton of each kind in an otherwise completely deuterated molecule For example deuterated acetic acid has two different kinds of residual protons CD2HCOOD and CD3COOH The CD2H proton coupled to two D nuclei is at δ 203 with a multiplicity of 5 ie 2n1 1 2 x 2 x 1 1 5 The carboxylic proton is a singlet at δ 1153 c DSS is 3trimethylsilyl1propane sulfonic acid sodium salt TSP is sodium3trimethylpropionate2233d4 Both are reference standards used in aqueous solutions CHEMICAL SHIFTS OF COMMON LABORATORY SOLVENTS AS TRACE IMPURITIES proton mult CDCl3 CD32CO CD32SO C6D6 CD3CN CD3OD D2O solvent residual peak 726 205 250 716 194 331 479 H2O s 156 284a 333a 040 213 487 acetic acid CH3 s 210 196 191 155 196 199 208 acetone CH3 s 217 209 209 155 208 215 222 acetonitrile CH3 s 210 205 207 155 196 203 206 benzene CH s 736 736 737 715 737 733 tertbutyl alcohol CH3 s 128 118 111 105 116 140 124 OHc s 419 155 218 tertbutyl methyl ether CCH3 s 119 113 111 107 114 115 121 OCH3 s 322 313 308 304 313 320 322 BHTb ArH s 698 696 687 705 697 692 OHc s 501 665 479 520 ArCH3 s 227 222 218 224 222 221 ArCCH33 s 143 141 136 138 139 140 chloroform CH s 726 802 832 615 758 790 cyclohexane CH2 s 143 143 140 140 144 145 12dichloroethane CH2 s 373 387 390 290 381 378 dichloromethane CH2 s 530 563 576 427 544 549 diethyl ether CH3 t 7 121 111 109 111 112 118 117 CH2 q 7 348 341 338 326 342 349 356 diglyme CH2 m 365 356 351 346 353 361 367 CH2 m 357 347 338 334 345 358 361 OCH3 s 339 328 324 311 329 335 337 12dimethoxyethane CH3 s 340 328 324 312 328 335 337 CH2 s 355 346 343 333 345 352 360 dimethylacetamide CH3CO s 209 197 196 160 197 207 208 NCH3 s 302 300 294 257 296 331 306 NCH3 s 294 283 278 205 283 292 290 dimethylformamide CH s 802 796 795 763 792 797 792 CH3 s 296 294 289 236 289 299 301 CH3 s 288 278 273 186 277 286 285 dimethyl sulfoxide CH3 s 262 252 254 168 250 265 271 dioxane CH2 s 371 359 357 335 360 366 375 ethanol CH3 t 7 125 112 106 096 112 119 117 CH2 q 7d 372 357 344 334 354 360 365 OH scd 132 339 463 247 ethyl acetate CH3CO s 205 197 199 165 197 201 207 CH2CH3 q 7 412 405 403 389 406 409 414 CH2CH3 t 7 126 120 117 092 120 124 124 ethyl methyl ketone CH3CO s 214 207 207 158 206 212 219 CH2CH3 q 7 246 245 243 181 243 250 318 CH2CH3 t 7 106 096 091 085 096 101 126 ethylene glycol CH se 376 328 334 341 351 359 365 greasef CH3 m 086 087 092 086 088 CH2 br s 126 129 136 127 129 nhexane CH3 t 088 088 086 089 089 090 CH2 m 126 128 125 124 128 129 HMPAg CH3 d 95 285 259 253 240 257 264 261 methanol CH3 sh 349 331 316 307 328 334 334 OH sgh 109 312 401 216 nitromethane CH3 s 433 443 442 294 431 434 440 npentane CH3 t 7 088 088 086 087 089 090 CH2 m 127 127 127 123 129 129 2propanol CH3 d 6 122 110 104 095 109 150 117 CH sep 6 404 390 378 367 387 392 402 APPENDIX H Continued proton mult CDCl3 CD32CO CD32SO C6D6 CD3CN CD3OD D2O pyridine CH2 m 862 858 858 853 857 853 852 CH3 m 729 735 739 666 733 744 745 CH4 m 768 776 779 698 773 785 787 silicone greasel CH3 s 007 013 029 008 010 tetrahydrofuran CH2 m 185 179 176 140 180 187 188 CH2O m 376 363 360 357 364 371 374 toluene CH3 s 236 232 230 211 233 232 CHop m 717 7172 718 702 7173 716 CHm m 725 7172 725 713 7173 716 triethylamine CH3 t7 103 096 093 096 096 105 099 CH2 q7 253 245 243 240 245 258 257 a In these solvents the intermolecular rate of exchange is slow enough that a peak due to HDO is usually also observed it appears at 281 and 330 ppm in acetone and DMSO respectively In the former solvent it is often seen as a 111 triplet with 2JHD 1 Hz b 26Dimethyl4tertbutylphenol c The signals from exchangeable protons were not always identified d In some cases see note a the coupling interaction between the CH2 and the OH protons may be observed J 5 Hz e In CD3CN the OH proton was seen as a multiplet at δ 269 and extra coupling was also apparent on the methylene peak f Longchain linear aliphatic hydrocarbons Their solubility in DMSO was too low to give visible peaks g Hexamethylphosphoramide h In some cases see notes a d the coupling interaction between the CH3 and the OH protons may be observed J 55 Hz i Polydimethylsiloxane Its solubility in DMSO was too low to give visible peaks APPENDIX I PROTON NMR CHEMICAL SHIFTS OF AMINO ACIDS IN D2O Alanine Ala A Arginine Arg R Asparagine Asn N Aspartic Acid Asp D Cysteine Cys C Glutamic Acid Glu E Glutamine Gln Q Glycine Gly G Histidine His H Isoleucine Ilue I Leucine Leu L Lysine Lys K Methionine Met M Proline Pro P Phenylalanine Phe F Serine Ser S Threonine Thr T Tryptophan Trp W Tyrosine Tyr Y Valine Val V APPENDIX A THE 13C CHEMICAL SHIFTS COUPLINGS AND MULTIPLICITIES OF COMMON NMR SOLVENTS Structure Name δppm JCDHz Multiplicity a CDCl3 Chloroformd1 770 32 Triplet CD3OD Methanold4 490 215 Septet CD3SOCD3 DMSOd6 397 21 Septet DCNCD32 DMFd7 301 21 Septet 352 21 Septet 1677 30 Triplet C6D6 Benzened6 1280 24 Triplet THFd8 252 205 Quintet 674 22 Quintet Dioxaned8 665 22 Quintet Pyridined5 1235 C35 25 Triplet 1355 C4 245 Triplet 1492 C26 275 Triplet Acetoned6 298 methyl 20 Septet 2065 carbonyl 1 Septet b CD3CN Acetonitriled3 13 methyl 32 Septet 1182 CN 1 Septet b CD3NO2 Nitromethaned3 605 235 Septet CD3CD2OD Ethanold6 158 C2 195 Septet 554 C1 22 Quintet Etherd10 134 C2 19 Septet 643 C1 21 Quintet HMPAd18 358 21 Septet CD3CO2D Acetic acidd4 202 C2 20 Septet 1784 C1 1 Septet b CD2Cl2 Dichloromethaned2 531 29 Quintet Methylene chlorided2 a Triplet intensities 111 quintet 12321 septet 1367631 b Unresolved longrange coupling Source Breitmaier E and Voelter W 1987 Carbon13 NMR Spectroscopy 3rd ed New York VCH p 109 with permission Also Merck Co Inc APPENDIX B Continued nhexane CH3 1414 1434 1388 1432 1443 1445 CH22 2270 2328 2205 2304 2340 2368 CH23 3164 3230 3095 3196 3236 3273 HMPA CH3 3687 3704 3642 3688 3710 3700 3646 methanol CH3 5041 4977 4859 4997 4990 4986 4950 nitromethane CH3 6250 6321 6328 6116 6366 6308 6322 npentane CH3 1408 1429 1328 1425 1437 1439 CH22 2238 2298 2170 2272 2308 2338 CH23 3416 3483 3348 3445 3489 3530 2propanol CH3 2514 2567 2543 2518 2555 2527 2438 CH 6450 6385 6492 6423 6430 6471 6488 pyridine CH2 14990 15067 14958 15027 15076 15007 14918 CH3 12375 12457 12384 12358 12776 12553 12512 CH4 13596 13656 13605 13528 13689 13835 13827 silicone grease CH3 104 140 138 210 tetrahydrofuran CH2 2562 2615 2514 2572 2627 2648 2567 CH2O 6797 6807 6703 6780 6833 6883 6868 toluene CH3 2146 2146 2099 2110 2150 2150 Ci 13789 13848 13735 13791 13890 13885 CHo 12907 12976 12888 12933 12994 12991 CHn 12826 12903 12818 12856 12923 12920 CHp 12533 12612 12529 12568 12628 12629 triethylamine CH3 1161 1249 1174 1235 1238 1109 907 CH2 4625 4707 4574 4677 4710 4696 4719 13C CHEMICAL SHIFTS of COMMON LABORATORY SOLVENTS APPENDIX B as TRACE IMPURITIES CDCl3 CD32CO CD32SO C6D6 CD3CN CD3OD D2O solvent signals 7716 006 2984 001 3952 006 12806 002 132 002 4900 001 20626 013 11826 002 acetic acid CO 17599 17231 17193 17582 17321 17511 17721 CH3 2081 2051 2095 2037 2073 2056 2103 acetone CO 20707 20587 20631 20443 20743 20967 21594 CH3 3092 3060 3056 3014 3091 3067 3089 acetonitrile CN 11643 11760 11791 11602 11826 11806 11968 CH3 189 112 103 020 179 085 147 benzene CH 12837 12915 12830 12862 12932 12934 tertbutyl alcohol C 6915 6813 6688 6819 6874 6940 7036 CH3 3125 3072 3038 3047 3068 3091 3029 tertbutyl methyl OCH3 4945 4935 4870 4919 4952 4966 4937 ether C 7287 7281 7204 7240 7317 7432 7562 CCH3 2699 2724 2679 2709 2728 2722 2660 BHT C1 15155 15251 15147 15205 15242 15285 C2 13587 13819 13912 13608 13813 13909 CH3 12555 12905 12797 12852 12961 12949 C4 12827 12603 12485 12583 12638 12611 CH3Ar 2120 2131 2097 2140 2123 2138 CH3C 3033 3161 3125 3134 3150 3115 C 3425 3500 3433 3435 3505 3536 chloroform CH 7736 7919 7916 7779 7917 7944 cyclohexane CH2 2694 2751 2633 2723 2763 2796 12dichloroethane CH2 4350 4525 4502 4359 4554 4511 dichloromethane CH2 5352 5495 5484 5346 5532 5478 diethyl ether CH3 1520 1578 1512 1546 1563 1546 1477 CH2 6591 6612 6205 6594 6632 6688 6642 diglyme CH3 5901 5877 5798 5866 5890 5906 5867 CH2 7051 7103 6954 7087 7099 7133 7005 CH2 7190 7263 7125 7235 7263 7292 7163 12dimethoxyethane CH3 5908 5845 5801 5868 5889 5906 5867 CH2 7184 7247 1707 7221 7247 7272 7149 dimethylacetamide CH3 2153 2151 2129 2116 2176 2132 2109 CO 17107 17061 16954 16995 17131 17332 17457 NCH3 3528 3489 3738 3467 3517 3550 3503 NCH3 3813 3792 3442 3703 3826 3843 3876 dimethylformamide CH 16262 16279 16229 16213 16331 16473 16553 CH3 3650 3615 3573 3525 3657 3689 3754 CH3 3145 3103 3073 3072 3132 3161 3203 dimethyl sulfoxide CH3 4076 4123 4045 4003 4131 4045 3939 dioxane CH2 6714 6760 6636 6716 6772 6811 6719 ethanol CH3 1841 1889 1851 1872 1880 1840 1747 CH2 5828 5772 5607 5786 5796 5826 5805 ethyl acetate CH3CO 2104 2083 2068 2056 2116 2088 2115 CO 17136 17096 17031 17044 17168 17289 17526 CH2 6049 6056 5974 6021 6098 6150 6232 CH3 1419 1450 1440 1419 1454 1449 1392 ethyl methyl ketone CH3CO 2949 2930 2926 2856 2960 2939 2949 CO 20956 20830 20872 20655 20988 21216 21843 CH2CH3 3689 3675 3583 3636 3709 3734 3727 CH2CH3 786 803 761 791 814 809 787 ethylene glycol CH2 6379 6426 6276 6434 6422 6430 6317 grease CH2 2976 3073 2920 3021 3086 3129 APPENDIX C Continued 220 200 180 160 140 120 100 80 60 40 20 0 20 Acetals Ketals OCO Halides CF13 CCl14 CBr14 CI14 Amines CNR2 Nitro CNO2 Mercaptans Sulfides CSR Sulfoxides Sulfones CSOR CSO2R Aldehydes sat RCHO Aldehydes α βunsat RCCCHO Ketones sat R2CO Ketones α βunsat RCCO Carboxylic acids sat RCOOH Salts RCOO Carboxylic acids α βunsat RCCCOOH Esters sat RCOOR Esters α βunsat RCCCOOR 220 200 180 160 140 120 100 80 60 40 20 0 20 Anhydrides RCO2O Amides RCONH2 Nitriles RCN Oximes R2CNOH Carbarmates R2NCOOR Isocyanates RNCO Cyanates ROCN Isothiocyanates RNCS Thiocyanates RSCN APPENDIX D 13C NMR DATA FOR SEVERAL NATURAL PRODUCTS δ 1129 1459 308 1390 261 1155 1244 1310 171 251 Myrcene 160 1372 587 397 1245 OH 266 1249 1312 174 255 Geraniol 272 244 727 1621 412 1450 OH 226 1113 1246 1303 175 253 Linalool 325 1287 272 CHO 1894 1231 1329 174 253 cisCitral Neral Citral b 238 222 231 217 221 1332 1315 1329 314 316 1208 309 1196 285 1207 309 329 507 348 449 306 280 1165 248 259 236 285 2011 230 713 412 1497 1409 446 OH 1317 499 713 205 1084 340 719 1408 256 159 Limonene αTerpinene αTerpineol Pulegone Menthol 200 195 264 228 261 218 387 466 274 432 380 405 405 236 236 270 519 1518 1059 301 432 313 570 2147 1161 369 301 97 O 315 472 1445 230 Norbornane Camphor αPinene βPinene 188 CH3 358 364 120 565 CH 241 400 225 283 396 228 424 243 280 569 212 194 375 505 CH3 323 316 365 713 H 1412 HO 424 1213 320 βIonone Cholesterol 270 1407 O 1955 326 1347 1307 252 384 1334 175 197 318 414 CH3N 1716 515 CO2CH3 621 352 226 508 1349 689 570 258 359 O 1236 1389 N 1671 1495 403 CH3 654 OC 1336 1291 258 675 1305 1310 Nicotine Cocaine 625 OH 713 HO 774 715 OH HO 775 OH 974 βdGlucose 1652 O 1009 NH 1430 1527 N H Uracil