Spectroscopy Data Tables Infrared Tables (short summary of commot sorption frequencies) The values given in the tables that follow are typical values. Specific bands may fall over a range of wavenumbers, cm". Specific substituents may cause variations in absorption frequencies. Absorption intensities may be stronger or weaker than expected, often depending on dipole moments. Additional bands may confuse the interpretation. In very symmetrical compounds there may be fewer than the expected number of absorption bands (it is even possible that all bands of a functional group may disappear, i.e. a symmetrically substituted alkyne!). Infrared spectra are generally informative about what functional groups are present, but not always. The 'H and '*C NMR’s are often just as informative about functional groups, and sometimes even more so in this regard. Information obtained from one spectroscopic technique should be verified or expanded by consulting the other spectroscopic techniques. IR Summary - All numerical values in the tables below are given in wavenumbers, em™ Bonds to Carbon (stretching wave numbers} sp).CX single bonds ; Af Ty \ / { \ | | 1000-1350, 1050-1150 1100-1350 not used aotveryasefal alkoxy C-0 not very usfi 1250 acyl and phenyl C-0 ‘GX double bonds \ ‘GX triple bonds 1640-1810 expanded able . 1600-1680 1640-1690 eect pues 2100-2280 2240-2260 ‘Stronger dipoles produce more iniense IR bands and weaker dipoles produce les intense IR bands (sometimes none) Bonds to Hydrogen (stretching wave numbers) | cy \ = \ | | 3000.3100 t sp C-H 3300 2700-2760 sp! CH pattems below) (sp C-H bend = 620) (two bands) am eon oy RSH J™ t 3100%500 310000 0. primary NH, secondary SH 3200-3400 rsonsavo GSD AS (two bands) fone ban alcohol O-H acid O-H thiol S-H_ ides = 0nd mines = weak Zfles\closses\ spectroscopy \Wypical spectra charts DOCSpectroscopy Data Tables 2 Carbonyl Highlights (stretching wave numbers) i i i AN I I, Ae R 4 RoR Ro R 0 ‘saturated = 1725. saturated = 1715 saturated = 1735 saturated = 1715 aromatic = 1700 aromatic = 1690 aromatic = 1720 aromatic = 1690 Amides Anhydrides: Acid Chlorides 1 nitro, — i fj i ll — — oO Ide ! i eR ao R war saturat 0 saturated = 1760, 1820 saturated = 1800 + oe urate 1680 conjogaed—1733,1785 | SaumedS MM conjugated = 164 aromatic = 1725, 1785 eee ato | asymmetric = 1500-1600 700 1745 4 arom ring 5 atom ring ~ 1785, 1865 ‘Very often there is a very weak C=O overtone at approximately 2 x'v (=3400 car), 3 atom ring = 1850 ‘Sometimes this is mistaken for an OH or NH peak, ‘sp? C-H bend patterns fr alkenes sp C-H bend patterns for aromatics sbsoepon absorption atkenesubstiuion ——deseriptive —grequeaces ca) [aromatic sbsizton descriptive equnses (62) ate aiken eh hen ‘ot aromtctem greene teas 5 \ monosubstituted 985-1000 monosubstituted } ‘tkene 300-920 x ‘somatic S010 ; x Nad wmtgaims somm | i’ K | ‘meta disubstituted 680-725, R R Aromatic compounds have characteristic weak overtone bands \_/ vena thorsow Sten 6502000). Some Dake roe Po \ tetasbeinted ——gege picts or comparison nates). A song C=O peak wl Zfles\closses\ spectroscopy \Wypical spectra charts DOC cover up most ofthis regionSpectroscopy Data Tables 3 4900000 200 1780 tszo ato 130 1200 80 1090 960 800 790 60 500 Mo wee ye ee § c= — ery pon ad GN = = acyl C-0 seme = = e anyep cauikawon Scweas —=., ary sn ae meat wien set T TI ott txpaton of tan mt CH bed pion =) i po a — = alkene sp? CH — bend = aromatic sp? C: bend roy exponson of earhony (C-O) stretch region ants ~ em") 1700 10 ro i 1890 i mo Cy 7 5 % 5 as Tt TTT moot 10 ’ 8 7 pM 6 5 4 3 1 ° ‘ppieal carbor-13 chemical shifts i 5 —Ts ! | ra i I a onc | — “ hoot i wi wit a 20 220200181] 140 pp 20 tga 20 ° Zfles\closses\ spectroscopy \Wypical spectra charts DOCSpectroscopy Data Tables Cate Fil ton of chemical shifts for protons at p° carbons [Esimation of sp" C-U chemical shifts with multiple substituent parameters for protons within 3 Cs of consideration, GCC — | a = dircetly tached substituent, use these values when the hydrogen and substituent are attached to the same carbon TPT | = once removed substituent, se these values when the hydrogen and substituent are on adjacent (vicinal) carbons +7 = sie removed substituent use these values wien the hydrogen and substituent have 21,3 substation patern X= pistitemt « 5 Surtng value and equations for CH's Re falkvt) a0 00 RC oy) BCH = 09 +a nica RCC. (alkynyD SoH = 09+ G49 J sing) 1O- (aleohat) RO- (ether) “AO= (aroniatie ete) RCO, (ester, oxygen ide), 2 ‘ArCO;- (aromatic ester, oxygen side) R « ‘O;N- (nit) HS- Ahiol.ulte, RS. (oulfde, sults) OHC: (aldehyde RCO- (ketone) ACO- {aromatic ketone), HOsC~ (carboxyl acid) ROC. (ester, carbon side) NC: (oltre) RSO- (sulfoxide), mete is the summation symbol fr all substituents considered tating value and equation for mm Ina similar manner we can calculate chemical shi for methylenes (CH) using the following Formula seo Ere ge isthe summation symbol forall substituents considered Starting value and equation for CLs In a similar manner we can calculate chemical shifts for methines (CH) using the following formula SCH=15+3@ H+) Road OGG rer is the summation symbol forall substituents considered ‘4 methine, methylene \ Ctl Ci A metiyt HOS ae ese a e-methylene # methylene «methyl 2, methine = 1.5 + (1A) + (2.3). + (02) b, methylene = 12+ (1 ©: methyl = 09+ (1.5), =24 ppm actual =2.6 Zfles\closses\ spectroscopy \Wypical spectra charts DOC F methylene = 12 Calculations are generally close to actual chemical shifts for a single substituent, but are less reliable as the numberof substituent factors g0es up. Multiple substituent factors tend to overestimate an actual chemical sti. 4, methyl=0.9 + (0.1). = 10 ppm sctual = 1,0 «¢, methylene = 1.2 +(0.3)q=1.5 ppm sctual = 1.7 (1.7) =2.9 ppm sctual= 2.9Spectroscopy Data Tables Estimated chemical shifts for protons at alkene sp* carbons Substituent © pein on Gums | Substitution relative to calculated "H" H 00 00 00 # Hydrogen c R os oa 7 we \m Ay ee (CoHsCHa- OT “02 a2) B(ppm) = $.2 + 4 gem to cis +O ams Benzyl X-CHy- oF on oo Halomethvl Example Caleulation (HROCH- 06 00 00 calkoxymetbyl gem (H)_/R2NCH2- 06 OT 0.1 i amsinomethy] ROOC! “aT “0 GN oF a 12 Namino Zi a8 19 rr 06 RS TT 5 or Mb onic 1 1 TZ ROC: TT oF oF HO3C- oF Ta Ceacid ROx u8 TH v5 Caster TOC. oa To 05 Camide NC oF oF v8 Nitrik ccharis.00c. ENfles\closses\ spectroscopy \Wpical oe 5 ger B trans 52+ (04) 48 actual = 4.9 (J 73 74.0 52421 actual 14, 6H”) actual = 6.2 (I 18, 11 Hz) s2705 actual 11, 1.4 Hz) actual 64 G= 18, 14 He)Spectroscopy Data Tables Estimated chemical shifts for protons at aromatic sp* carbons Substituen ortho amet para H 00 00 00 Hydrogen “02 “0 “02 Methyl he o0 a oo Cholromethy! 06 or Or “OA Ol “OT Hydroxymethyl RyC-CR- or 00 “OI Alkenyl Calls 14 oF oT Phenyl F “05 oo “02 Fluoro. ¢ ow a “OT Chloro Br- 02 “OT 00 Bromo cr 09 Todo HO- “06 OI 05 Hydroxy RO- “05 “OT “04 (DyRN- “08 “02 “07 N-amino RCONE- Or OI 03 N-amide 06 02 03 Aldehyde ROC- 08 Or oD Ketone HO;C oF o2 oS C-acid RO;C- OT or oD Coster HQNOC- 06 al 02 C-amide NC oF 02 os Zfles\closses\ spectroscopy \Wypical spectra charts DOC 8 Substitution relative to calculated "H’ meta ortho para H meta ortho (ppm) = 7.3 + o orto + wets tO para Example Calculation 2 1 1 cH. H SS | He 2H cp H 4 H 1. 8 (CH:)=09 428-37 actual = 3.8 2. 8 2)=73+ 0.5) gato + 0.1) pas 6.7 actual = 68 3. BG)=73 + (0.2) onto * 60.4) pura= 6.7 actual =7.1 4, 8 (CH) = 12+ 0.8)a+ (14a actual 5. 8(5)=52+ 0.) gem = 59 actual = 5.9 6. 86) =5.24 (0.2) tans = 5.0 actual = 5.1 7. BCD =5.24 (2) ey =5.0 actual = 5.1Spectroscopy Data Tables ° Real Examples of Combination Effects on Chemical Shifts anisoirony G8 shielded Shand ceampleioe (cra) 08, shielded 1 shielding cone cm from bond 26 Hi deshielded rt 12 18 Scene and x ond on aT ivaowcn as _ re O-CHCH,CH;CHCHy CHCl CURCH-CL_— CHsCH;CHy-C1_ CHsCH,CH CHCl CH3CHy-R. peeee ob 4 ' 361513 1309 30 1 10 o9 09, ‘multiple substituents Cr cea cen cts cou t ' ' ' t 0.2 qa28—e 3.0 <—yo23—e 535— A=19 72 <— A=? — 2(00ps) “Sibstitaehs at mets] (CHE, methylene (CH) and methine (CH) 2 ? pen CHACHACL (CHY,CHCI njc-&PhH,CH,C~°Ph GC)CH-o~Ph 3.0, 38 41 3.0 35 alkene substituent resonance and inductive effects 09 14-20 © F 1 38 4" 64 Kg sciGt, 189 God u 53 58 aromatic resonance and induct H 7.3 6.6 She abd 1 bond aisotony uo\ ra uo} wo} Produces deshielding Extra electron density via esonance produces Withdrawal of electron density via resonance ffct on aromatic shiciding effect on aromatic protons, expecially produces deshielling effect on aromatic protons, protons. at ortho/para positions. especially at ortho/para positions. ROH alcohol = 1-5 {RN-H amine H 17 HQ y ArO-H phenol t= 410 | o ° PR RS—H thiol H=1-2.5 bore 3 4 ArO—H aromatic thiol H = 3-44 NH O—H acid H= 10-13 Zfles\closses\ spectroscopy \Wypical spectra charts DOCSpectroscopy Data Tables 10 1. One nearest neighbor proton 3 @ st, ete ‘observe a epee Treen » seat 5 Sse ent siay amet ee ma i ne 3 empting content \ cencrgy duc to differing jee eighbor' spin (in H2) neighbors) peaks =N-+1=1=1=2 peaks 5 com) 2, Two nearest neighbor protons (both on same carbon or one each on separate carbons) the ratio of these four populations is about 12:1 @ @ ee bi @ ‘wo equal energy a ‘two neighbor protons are like [#4 PP @ maieeettons rons ye arranged four possible ways M44 (culo Bippinga coin vice) | 4 N+ te =f neighbor) poi nay anneal 3 (opm 3. Three nearest neighbor protos (on same carbon, or two on one and one on another, or one each on Separate carbons) three neighbor . protons observed proton peaks =N+1 3 peaks the ratio ofthese ight popultions is about E331, @ ig three neighbor protons are like OP REE (Mag ay accmtere, (Slr to flipping cin tric) htt idle ranstons HE ® \ \ N41 rule (N= # neigh cutee dpe No 1-41 pee ce 8 opm) Zfles\closses\ spectroscopy \Wypical spectra charts DOC‘common, but not always true} 4 g | Me g etd, & P et, je Ll, Be eich fe tic, Suto he so dk oN dy s. Jenene qn wre Jer -~e ie Ki Na cu | ll ul hi a de « ~~ Secale or exp ws Tosca gle “ Mullet when the N + by + sng tn dome oom " cn So i eat soe ull li Senay Tarwee | point 1g coefficients of variable terms in binomial expansion (x 2135 yP, n= integer rule works al J vals are eg) 5 peak = 100% wel 1p lpsak= 50% 1 peak =28 12 ar ak Islaive sizes of peaks in maiplets ac | peak 6% edge poak shown} 4 ws 1 ue | peak - Isms 6 1 ° ae tpeak= 038% J 1 ae peak = 1.5% 3s 217 ‘Combinations o these are possible. d= doublet of doable; ddd ~ doublet {> tiple of doublets; ete Zfles\closses\ spectroscopy \Wypical spectra charts DOC f doublet of doubles; ddd ~ doublet of doublet of doublet of doublets; dt ~ doublet of ipetsSpectroscopy Data Tables ‘Typical Coupling Constants Range Typical oA 0301 14M hy ‘geminal protons - ean have diferent chemical shins and spitone another if they are diastereotopic Range Typical Ha ts Vicinal protons are on adjacent atoms, when freely rotating coupling averages out to about 7 Hz 6aie THe Range Typical Oz THe depends on dihedral angle, se plot of Karpls equation Range Topical eye Th o-lnz one protons rarely couple through 4 chemical bonds unless ina special, iid shapes (ie. W coupling) Range Typical snd ostz 2H 7 ON sp? geminal coupling ‘Range Lupieal Bee Nad 1Hz 10Hz rN sp cis acyl) coupling (always ond / nicer ost Hy ‘ / oc aot ‘tans / allylic coupling, notice through 4 bonds QE so nf sp? vicinal coupling (Gitfeent » bonds) 7 sp vicinal aldehyde coupling Hf ry —< % sp vicinal aldehyde coupling i cSc-th, I sp! propargylie coupling Range Typical Siz He Range Typical osHz He Range 913Hz 10H 1aHe tHe Tange Typical S8H2 6H Range 23M 2a smaller than the trans isomer) notice through 4 bonds Ky Range Typical Range Typical Nomi i a 5 vas MagH2 1TH ‘ j 25H, 3H Hy sp? trans coupling (always larger than the cs isomer) Range Typical pe bis-propareylic coupling pote through S bonds forte, meta and --> para coupling to Range Typical He PS 410tt2 7H [thisproten ortho 6-102 9 He SoH meta 2382 2H “N Haga aa OL OTe spp! viinal coupling gus When J values are lee han Zfles\closses\ spectroscopy \Wypical spectra charts DOC Ti, eis often dificult resolve them and a peak may merely appear wider and shore.Spectroscopy Data Tables 13, Similar chemical shift information presented in a different format. Remember, proton decoupled carbons appear as singlets. When carbons are coupled to their hydrogens, carbons follow the N+ rule. Methyls = q, methylenes = t, methines = d, and carbons without hydrogen appear as singlets = s. DEPT provides the same information. Carbon chemical shifts are spread out over a larger range than proton chemical shifts (they are more dispersed), so itis less likely that two different carbon] shifts will fall on top of one another. The relative positions of various types of proton and carbon shifts have many parallel trends (shielded protons tend to be on shielded carbons, etc.) | -— : Hy —cH— Simple alkane cH § ty i carbons dA0-30ppm dx 20-40 ppm d 3 30-S0ppm_— d = 30-60 ppm @ ® @ © Ho Ho HERETO ONYEEN 4 59 60 ppm @ d 5 55-80 ppm © gues dx 35-55 ppm G) inex 25-50 ppm sp° carbon CHs-N nextto nitrogen 4g J. 19.50 ppm @ sp? carbon next to bromine or chlorine fre ds 60-80 ppm_d <= 70-90 ppm @ © spe 450-70 ppm dx 50-70 ppm @ © ax x (X= Cl, BY 60-80 ppm 60-80 ppm © @ @ sp carbon (alkynes) —~C=C— sp carbon (nitriles) —ceN 3 5 70-90 ppm 3 5110-125 ppm sp* carbon (alkenes \ P ( ‘ox “a = \ and aromatics) —H wo; < 8 & 100-140 ppm simple sp? carbon resonance donation moves 8 lower, resonance withdrawal moves 8 higher Q x 8 & 140 - 160" ppm sp’ carbon attached to an electronegative atom (X = oxygen, nitrogen, halogen) or Cp carbon conjugated with a carbonyl group ° e x iH 5 180-21 3 & 160-180 ppm carboxyl carbons (acids, esters, amides) ®) values when cor @ Zfles\closses\ spectroscopy \Wypical spectra charts DOC aldehyde carbons, lower 2 —< R 0 ppm 8 & 180-220 ppm ketone carbons, lower values when conjugated (s) njugatedSpectroscopy Dato Tables 4 ulations of all :p* Carbon Chemical Shift Calculations Calculations for sp* carbon !°C chemical shifts of functionalized carbon skeletons can be performed starting from the actual shifts found in the corresponding alkane skeleton, and introducing corrections factors based on the functionality present in the molecule. This assumes that the alkane °C shifts are available, which is why several examples are provided below, Examples of C, alkanes as possible starting points for calculation '°C shifts in ppm. Sterie Corrections for sp* carbon chemical shift ealeulat Approx The caeaited A Be = (2) + 9x(Ha + #B) - 2x(Hy ) + steric corrections, cham | 7 ~\ + primey | seooiey | seniay | gsstemary cy “ ° ut Ba 2-21 9(42)-20)) BaLLSHEISO]=28 tal 340) coy 2 2 3 05-24 9695)-00)+ [85H EISI~€s Gamal =479) qusery a5 a se 250 €5=2+5(12)-20)4(1)=20 acaal= 195) 05=2512)-52)4(2)-14 aca -45) BC shifts fo useful starting points for calculating sp3 carbon chemical shifts ARN ioe re "SAY Zfles\closses\ spectroscopy \Wypical spectra charts DOCSpectroscopy Data Tables Substituent = X x ' NEN X is attached toa terminal carbon atom (ppm) Cq correction Cy correction } C, correction X is attached to an internal carbon atom (ppm) Ca correction C, correction —aor 9 9 2 6 2 —cH,cHs woo 7 2 9 2 HICH 26 4 2 14 OCs 32 i 2 2 20 ‘CH. 20 6 a 15, 5 5 4 2 2 9 2 7 2 X is attached to a terminal carbon atom (ppm) | X is attached to an internal carbon atom (ppm) Substituent=X | C, correction } Cy correction ! C, correction | C,. correction correction, —on ae } wo } 6 44 4 —or 60 7 6 st 6 st 6 6 49 6 28 i 10 24 5 neh 38 8 3 32 4 NCHS). 45 5 i a7 3 4 P : 4 26 7 5 21 5 5 R —no, 62 : 5 5 sf} ENfles\closses\ spectroscopy \Wpical oe (9 enarts DOCSpectroscopy Data Tables 16 X is attached to a terminal carbon atom (ppm) J X is attached to an internal carbon atom (ppm) Substituent = X. Cy correction ! Cy correction correction | C, correction C, correction —- 70 8 Lov 67 oT —a uM wo is 36 Ts er 20 lo f 4 28 rn ) — a nm 2 7 u 2 Pr Tf 30 0O 3 24 3 i LP : : ~* sf 3 26 o i 3 ‘cH r 4 2 2 18, 1 OH i 1 X is attached to a terminal carbon atom (ppm) | X is attached to an intemal earbon atom (ppm) X | C, correction ! Cp correction ‘correction | C, correction “p correction } C, correction és 20 2 fF 38 16 ‘ 3s i oa | 19 2 NH i i —c==N 3 fa 3 3 3 P —~* 3 fo 2} 30 2 $3 ‘a H —su noi wf 3 2 8 i o3 —sr 2 : 8 3 2 $ 6 13 (9 enarts DOC ENfles\closses\ spectroscopy \Wpical oeSpectroscopy Data Tables 28 ppm stating point for benzene carbor 7 9 2 SCHCHACH; 10 SCHACHACHSCH, 1 -CH(CHs} 2 “CICts) 9 CAE ceed cece Scaici 5 Oo “chub s 1 oo Scat Hoa oo ScH,OH Roa oO eB > ca? 2. Branch next to an atom with a lone pair of electrons os , iD Qe oc RRS — wee Xe t N ‘ Tadical can _X lone pir ee tons pally fil in os of electrons at carbocation sit ia esonan is a common fragmentation for any atom that has alone pair of electrons (oxygen ether, ester, nitrogen = amine, amide, sulfur thiol or sulfide, etc). Alcohols often lose water (M-18) and primary amines caa lose ammonia (M-17), 3. Branch next to a carbonyl (C=O) bond....and possible subsequent loss of carbon monoxide, CO 9 lo Roo: ae {in loss of RR, a3 Re ae ‘ “c= ° radical eation R R, orRzcan be ostfiom An oxygen lone par partially fill inthe loss of electrons atthe subsequent loss of CO is possible acids, Carbocation site Via esonance. Ths is common fragmentation after a ragmentation so not oly cat pattem for any carbonjl compound and can occur fom ether you se Toes of enc branch you can ‘de, though some are more cornmon than others fee the mags of an oc branch, 4, McLafferty Rearrangement ee - Positive charge can be on 9 Sita aH of cir fagen. hich Drie Lf Gh Upellyhvean ven mas Reef RO Cy t a= alpha position iN ras lostneural B= Pe# position radical cation sill radical fragment 7 £88 position This is another common fragmentation pattem for carbonyl compounds (and other pi systems as wel: alkenes, aromatic alkynes, nitriles, ete), Ifthe pi bond has at least 3 additional nonhydrogen atoms altached and a hydrogen on the " gama’ atom, the braxch can curve around to a comfortable 6 atom arrangement and the pi bond ean pick up a hydrogen atom and. cut off fragment between the C. and Cp positions. The positive charge can be seen on either fragment and usually the fragments have an even mass (unless there isan odd number of nitrogen atoms) Knowing these few fragmentation pattems will allow you to make many useful predictions and interpretations. Loss of small molecules, via elimination is common: H2O = 18, H2S = 34, CH;OH = 32, CoHsOH = 46, NHy = 17, CH\CO;H = 62, HF = 20, HCl = 36/38, HBr = 80/82, ete, Zfles\closses\ spectroscopy \Wypical spectra charts DOCone ok R cHcHe= 29 GHP! ag | mas 39K Hl Cue 37 S3(R= CH) CH2= 71 61 (RECHCHy) | BSS~ 41. R= HD muss ~ 65 (R= H) mass 91 (R=H) C(HH)8% 85. | also works for $5 (R= CH) 79(R=CH,) 105 (R=CH,) “ ay 69 (Re CH;CH) 93 (R= CH,CH;) 119 (R= CH,CHs) 4 cok aN. a lf % as 29 =H) 43(R=CHs) a ik a HGR) ‘mass = 27 ‘mass = 77 TI(R=CyHy) rmass~ 45(R=H) 105 (R = CoH) Vanissa , 4 @ 9 ° p>CP sesso (fp os — a Sou Ry R variable mass, % ma 41-1) use 28 =H 86(R=C3Hl,) 0(R= Cth) m . Ue per I SS Kh , Fe es ey we PS 4 on LOW i i (i a Son, S R “So, 36 (R= CH) 106 (R= CH,) 54 (R= CH) 55 (R=CH,) 0 (R= CH,CH3) 120 (R= CH,CH3) 68 (R= CH,CH;) 69 (R= CH,CH,) 84 (R= Cs) 14k 1) 82(R= CH) Zfles\closses\ spectroscopy \Wypical spectra charts DOC