Bes oe Nodeax Magnetic Retonamce (> * Th Qnduced ield opposes the apphied eld, the proton in said to be shielded, Shielding shitts the absorption upfield amd $ value will be Dowered. : * th the induced eld —abpoees reinfpreea the applied freld the proton feels a higher field strength amd cudh a’ proton, an sald fo be dechielded. Dechielding shtks the absorption downfield to get am ekective ~feld strength necessary tor absorption. Greater the Aeshielding Of protons , Larger will be the value of S. : | Highly inde sind gt a | ——> pe chielded Signals Downed Sit torr * Presence of the clecro negative dlibms or Groups Cause reducton dn electron density around the proton (cleshielding) mck thus absorption ia shifted downtield (& increases). | 2 TE hoa been sfpumd that the absorption cepercls upon the wmanner in whidh the a electvme circulate under the Anfuence of the applied field, * Prtns adjacent tp Nic ave very ctungly deslialdled Rete ge So cle w 0: ear eS one power fully s , Vovinus aspects of Aim FA) Nor OF Semake:- tells how many dliftt linda of proton ia there b) pesition of signal tell ua cometting lst elechonic enviroment | around each prow | ce) Totensity obsignal > nook protons oh each kind { ca} Sites ot Sevel ervemensd ot en eeeTAD He NV} Adkenea!- iP APS sctig rr _ WS shielding )_ Bengere | w decal sb Shidetnpe— dechiclding iv) Six_membered_vins ~ 4 shielding Sexpiteriol > pe § aval > Svalues!- ggch > Rut 7 RHZChewical shift t- )» = Hc cn, ii) Primary R-CH, ti) vinylic cacon W) Peetyleinic C=c—H Vv} Promate Ar-H Mi) pluoride Hoc-F vil) Mertdes -c-d ~ vii) alah & W-c-on Ik) Ethers H-cor *) Esters Wy Ack n—c- aon xi) Pldehydes RCHO xiii) Hydroxy R-OH XW) Phendic — Ay—on MTEnte C2 ch xvi) Garboxyhic — ReooH H- C—cooR Svollues od O98 46-S8 Q-35 6-3-0 4-4-5 3-4 3-4-4 33-4 R->2 B25 9-40 4-55 412 415-47 40-5~49 e8Some. points regarding the volue of Chemica) chitt > Svolue 4or methine > Methylene > methyl © > Gresley the electronegativity of substituent, greater 4s valve of. > whic of S depends upon the type of hybrid orbital hetding proton ve sp? > Sp> spe. 3 For the aldehydic protons , & value are 9-2 or aboye > Ss volue Jor protons in acyclic compd +2 aloays Lower than thot of amy other proton. > The chemical Shift of protons in o-h groupe omd abso in —NH_ growp defend upon remperature, solvent, con® omd@ he neighbouring group. > The absorption due te —Coort group appears ot 40-5-42 S. > TE two Singlets ore observed then there ore tro kinda of protons amd to carbon clams carving 400 sels of protons ove rot the adjacent covbons, > Formation of too triplets must be due to tro methylene groups whose protons are in ditherent Chemical enviroments X— chy- cH Y@® ] Hydrogen Bonehing = . sHtording proton being coched fo a highly elechonegative dbo Wilk have smaller electron dencity around th. Being Jers shielded , the teld felt by such a proton adh be move amd hence resonamce vot ocony cloonfield, | So high hydiogen bonding —> move S volue. ® Ttexmaeculay md intramkecwWey hydrogen boncling com be covly distinguished i. > Trtamdeculay Heboncling 44 conch independent here as Tuter melecuav h—bonding 2a Cone” dependent & Svolue increases with ® in concentration, Spin- Spin Coupling :— *spliting of Sgnol ta clue 4 the different envionment Of the absorbing proton votth respect to the rearby protons, The relative intensities of the individual Lned of a mudtiplet Covveapond to the mule mumerical coefficient the Vines of the binomiol x ponsion of ara)”, a b Foren: hich chy aay fapplied aan field Signa qyon”s__ ‘a! protons Spin dntuence of proton'p! hy <—— 11 N Tapblied field Ho . = ms as ee Spin Antluence of protons Sa’, + Thus a set of n expivalent prone splits up a signal (due to neighboring group) into a groub of (+4) peaks multiplet,@ Tt sa important to remember, that no “spuuing aoeaty TJ the protons din a mitecule are equivalent . For ex, benzene, cy cobuame. My a set of eqpivalent protons co not have amsthey set of protons odtached with the adjacent carbon olem . Rr ex: Chg Hy CO CHa « Ex) cH- paper here one will get 3 signals, hick corresponds to ‘three hon ~eqpivalert Protons oA hous a here H2omd HP also cause splitting a SNA Ser ‘ of ‘signals omd ead, appears ad es n clublet. + The adjacent distonce between tne centres of two adjacent beaks tn 0 par tcwlar wudliplet ia shown by the value. of “T awd is called Coupling Corstomb, > separation of peaks in o Anplet ts exactly the Same as thot observed in the doublet Some Hines the heights of the peaks in a particular woultiplet ave not alioays symmetrical, Tt 4s due to the eck tho the Separatin between the 420 signals tot very Marge velative to the Separation of peaks within 4, fears mal tiphet, . yh oy here wi lA uader the intlaence of = & sets of protone with ditterent Chemtol environments.: | Chemical &xChomge!- (proton exchange) ® * TE O protom shuttles bet” two magnetic envivoments ata wate which a much foater in Comparison coith the nmr transitions times then the vewnance observed por that protan. will be simply thob of the avg! ell én the tu envirnments. Anhydrous > pore ional Hat 0h => S Signals ave observed amd a triplet wilt be observed for on, ~ ethyl aleohel containing waler, the oH signal appears a4 q Singlet amd its coupling with adjacent —ch,— does not take place. > proton exchange becomes fester ay the waler content is thoreaied | > proton exchange Coes hot occur | Vif Sompbe ia pure : Ti) the sample in vecorded of a Yow temberatare, and “i) If the cumple din cliseelved in a highby polar calvent Like climethyh Sulphoxide . 7 & Proton undergoing chemical exchange does not show Spin- spin coupling > Proton exchange adso ocairs rapid ly im Some other compa dn which hydrogen a adtached with nitrogen, culbhar Oma oxygen (carboxylic acids, thiols, mines ete.) and hence ho coupling as obsewed between the protons of these functional groups with the protone on the adjacent carbon albsims,> The Austunce beth the centre: of too adjacent peaks ina wultiplet aa usually constant ond iis cabhed coupling constont, > ds indebendent 64 the external field. > Vuti- Ha or dn chs 3 Generally beth 09 2043 > Spectrum of O porticular corsbound ob dlittevent vradio~freq the Separation of two adjacent peaks in o multiplet vemains always constont. > From the value of coupling canctawt, one can distinguith loetuween the two singlets and one cloublet. Poot . + TL the separation beth the fines Lie value obs) aD bot Chomge While Changing the vodio- freqpencics then the signal da a loublet otheruise it isilh be tao etngleh > Tha sigabia split duc to the intbience of t100 dittemt sets of — protens| protons with ditjerent chemical shifts } Aten the peak Separations in the wubtiplet observed wh not be eapidistert. ex- cfg BH, day 1 here Sab=62 CPS, Ipc =73 CPS > J clependa partly on the vo: of covalent confor, bonds Meough which protons moy -intevact oma also upen the clructuvah vellationships between the coupllect protrs. ') Gerninal Gubling = . protons attached oh the Same carbon having dittevert chemical environment, of a Satuvaded | combo the value of J will dleperd upon aye Ahe bord angle (— ech #5 value increased with Jneveade tn bonol : ome (increases in $= drowactey) ree rae 18 sth oan chechomgtivity of ecto , the value of To the value of T decreases if an electronegative eubstiuent wrthdvaue electrons rom the Tr-bonds,+ Gsiikal coupling Conckants for olefins are quite simall, + Por mono-subshtuted olefins Strons 7 Scie > Sgem + + For isomeric vileting it is sound thot for gem cis protons 4a too-thivd of the value of gem trans protons, for exs- ® 3 a 4 a yh Seis (Hy HP) = 10-6 cps coy cng H Doan Ae, HD aney cps Tgem (Hr, WS gs cps VW) Vieinad Couphirg. *- +S varies with the dihedral omg he. * mox J value, when dihedral angle ay & or Lev" min 3 value Cobig ely ve] when dihedral ongle i4 95. * Dvokue fey gauche-Protons Tvalue for anti- protons 4 vorie {rom 5-42 chs T varies trom 5 4 0-4 cpe h 4 iH + Cydopentanes reve ihedyal ongle th cls pratonc da gem so TJ value =~ g chs Th Case of trom , Libedral amgle in gv’ So Tvdue xo | * Cycloheromes ~ From the value of the 3, it iy possible +0 determine | fh the conbiquratio P Hoy a favtioday system, Hn 7? le en sal -eqpitorial capitovial- capi For avial—axial ie ale a Abtedvall angle was abhedwval omgle = 6s c 3x8 chs J~ 2 chs Te acahsBr) ok eo Sveluen {OY vorioud typed of interacting i" on wacker Noe g (Wy vt) Laide gave) = an cps cooK ° “3 (, WP) (Vicind anti) = 1-1 chs slit, ¥) (Gem) = ano obs > tmpovtant pants fer vicinal coupling * J ww always positivs In olefinic combds Strona as more than Jes Vii) Long vomge. Coupling: sno coubhing ih distance beth twee absorbing move tham three covalent elem bon ds . «Bot in unsaturated and aw blaovo campounda ,appreciab le coupling 4a observedeven ib Concerned nuclei are three bola apart. eo nachel isCoupling Constomt due Fume on Noa Bo shy, (agen) Bese. a th” Wicirat) ne if Vee (yamay pee 4: Page, H-c=ec-h cra 4 7H to geminal omd vicinak groupe J value [in cps) 0-25 depending upon the decronegati of the attached groups 2-9 — debenda upon dlihedral omple, 0-5-3-0 43-18 1) ortho = 6-9 Hy meta = 41-3 Ti} para = 0-4 a asPp Mestions of nme Shectw stoby ') Tdentication > Struchnall comers - Orly a ay Nae orts (5 sereds) A (2 signals) i) Detection of He boroling !~ + Tnteymaecoay hydrogen bonding Slatts the absorption ter a concerned proton downtild. the extent of hydrogen, bending varies gzsie ah ss temperature + anbomeecday hebording Ja conch independent, WY Detection of avomaticity > * aromatic chavoctey of the combd Gan be imveatigated . W) Detection bet” Cic_trame isomers A_Qniprmerc’'— *The cisand troms isomers of @ combd com be eani distinguished aa the aorcerned frotonc having clitterent Chemical shitts as well ar the coupling constants, c , Hp. ‘sae Sane Nac é a x A Sa Ho Ry 4 b (eis) (froma ) Ze 42 cps eis cps : Siwavy the Various conformations of a eonpnind , the orich and equitorial postions can be distinguished 4rom theiy Aifterert values of the coupling con clams , V) Detection o4 eleckronegative otsm or grou 2 Predence of on electronegative cain causes dle shielding nd the signal ia shitted down field.Wi) detection Of some double bond character due to veaorances> + Tn some compounds the mec acqpives a tte clouble bond chavacter cue 40 vedonance, Bue to tus, wo signals can be expected or apparently equivalent protons nb on ne 2 Nc ER a” z= Nae Zee ae fan Bes (Sec signal) (three Signa) Here presence ot double borcl seibricts rotation ancl “oo meth{> groups rerain no Longer eqpivalent. Vil) Treporbomce Gs Quolita tive sic’ . Squilibvivm mixture can be omalyged when the proton siqndls of ‘the Semporents are woes xabed. 5 eet tg a a OES rch ace eee ts pred ter on proton but when weéller ia odded tn aleohat then due to proton ex : triplet collopces to a Sitghe*. The position of thin singlet depends upon the wafer comtent in alcchth, From the yalues of Chemical shipt the vatio of wakey and alors com be estimaled by Comparing with known results, Vii) Keto -entt ‘Content '~ Keto -endt toutomerian can be chulied in the Same manner, b ‘eae ° a ‘OH 5 yj ! ny een 28 nas ey, - b—ehy—e - cH, = ay—t= Cem C=C Oe 7-BCT a= BRST at eight protons b= 63ST b= -43T din the endic 4prm spt Sobebo Te are observed at 7 ciiatret eee (Preto ae 7287 T spur signals, Singlet ot 6357 appears de to : ebonic orm So nor OF eno beetons selative to Reto Protons may giveF | a Mise =— e Vol = 1} Pe eealaad fegamt way to simplity om Nm shectrum —anel one tak iy couily understood by Om organic chemict — 4 the use of Deuterium lobeling. Romine Q deutvon bat a much sally “magnet: momest than @ proton, it absorbs at a much higher etd and so @ivet no synal in the Proton NMR spectrum, Fur they move, its Coupling wath & breton is weak and its ordinary broadens, but does rot split, a proton's signal, = AS a veault , then , the veplacement db a proton by @ cleutron vemoves trom am NMR spectrum both the signal produced {rom that proton and the splitting by rt OF Signds of ther protons. Ga— CH, — 3 Shd oH Triplet Quartet Triplet — Triple: 3H ah aH ay 7 Ore Can use deuterium Rabeling to Yind out Which Signa is broduced by which proton oy rotons: one Observes the olinabbearance of a particalay Signal Dhen a Proton in a Rnoton Mocation 48 vebhaced by deuterium, 2) _Diarterestypic_protonss> Dieuterectopic protons, are ron- sapivlent and no vetation toll Change tus . Thass dasterectopic will produce ditterent Sgnale, & ae Here 3 signals wilt be observed. Os OS a my co ar HyEx) the two Protons of 4-2, dichbooprobame chic dh cH, oh 6 are dunstgestspic; em " a | Here rotation gam not Ankerconvert | w= Re clinsteren isomers por com TE pi mel make the protons Ha amd Hb j ivolert. Tin hone of the conformations oy (2, Tomd TE) is the exivonment of | the two rotons ave Some, ns cs) 3 Ha Hy a Hg 4 ) | he oF vw i" A Bk 8 oh b Ha = @ 2S > ha thing hota good, whether the cornpoumndl ee optically active or inactive; the presence or absence of an enatiomeric molecule haa ro effect on the environment of a proton tn omy individual molecule. Ex) yebherea ee o ee a ee” We have one NMR sgnah for all twelve, cnce thelr avg environments are identical: halt equiteral , halt arial. Rowever Hy we replace a proton by, sou bromine , the picture Chom ges. 7 ? Ha By Pe a 4 4 Wy BY Now the axiol and equitoriah protuns on cach Carbon are diastexeotopic protons.clam Frotons Hy and Hy, have ditteremt environments, Por they mire the stabilities and hence populations of the +00 conformations WL, in generoh, be ditterend ancl Ha amd hy, will cbend Obtferent eackons of thelr Hine in oxic and equitorial pocttors, . Concebt- By Jowexing the temberature — Wwe could oatticien’ Stow clown whations about Single bonda oe would expect an NMR specu tha vetlects the inctantameaud Environments Of protons in each combormation, For ex. Tfe arlshexane cooled dow , the single Sharp peak cr Observed ab voom temperature ia seen to broaden Omd then jot about —me'c to split into two peaks, whic, ak 40sec ave early separated’ One peak is due to Oxiak protons amd the other peak is dhe t eqpiteria protons, Note'— By study of the broadening of peak jor of the Et coallercerce of the tuo peaks it is boccible ‘to eatimete the Bact tor rotation. me By Enatiotopic Protong os es ie ay cs Sas ba Zine — = 3, =e 5 ch a a Heve veplacement ot either Df tu methylene probonc pair of cnatiomers, coh bors of Protons ave cated enatiotopie brotans the envivonmerte thee too protons are miryor images of each other; in an | SIE medi tus phic Aeheeee e Ona we see ye Ore NMR Signal for ead pair 1 would give one of oP The Sp carbin of the clubbe bond hos Ligh s—character omd abtrarts electrons , there by removing elecbrns trom the vichuky of the Pycroges ond leshivtling it, Thus tne range tor postion of TEESE Gh bhene OD ee | ¥ - 6 He gy% When a substituent in Q monosubstituted — Dengene is - uN wv au ok pe ae Se elertroboitive yelative to caren, the ortho, meta and para hydrogens have significant dy ligt Chemica shitts. * the alkenic protens of cyclohexene haa s velue = 5.57 but 1 may vary with the substituent in the ring Ex) pose? e Ba ove ® or" a the clectronic fpctor ds not only factor lich determines dhe chemical gli{t. These are other tncters adgo whic determines the S- valued Hs — Sa 23 ppm. eng pecans 3 $= og—42 bhm 5 s—valae= 46 xeon the other hemd Darge Chong ah chemical sbitts ave seen 4or protons diyertly dtacked to double bonds. i 5578 yeser? Ore nsec rv E: ‘> grediey S-cheracter in nr sf orbit and greater leebronegatity OF sf hybeidited carbon may actount for the downdield Slitt of protons in case ot T® > the probawgylic methy) Gres (= cac~ cH, ) ave forme ob higher Fekd ham ethe allyhe methyl groips, oe #7 G ae Chen, SS 4-3 bode Anisotropic ettetts- * wndlecular mag: tid induced by the action of applied sel) on pi - electrons, s magnetic field induced by pi aethons are-directional VEs wncymmetrical . © Bras’ the cthects of maint mitecular $olda incluced by Pi electrons ave clirection dependent, thee are, therefore termed anisotropic ete cts, “H The downicard shitt of ovomatic forotine , sheCtrum of Potglene;calkene. prob, omd Ghdelydic pent allan explained by anicotrobic eftect, %# Since Weelectrons are move petarisabhe than O- electrons they ove move free to move in responce to 4 magnetic fiek . * Promatic dechielding g Shielding se <—slidlng Sh l< ng Ho Note’ promatic. protons gereolly give peaks ct s>7 4pm amd benzylic methyl groups ab $aa-4, These being Sritiootly ahitted dowontjeld cielo anisotroby Of the aromatic ings The shot of bengylia protons 41 fers Hon the slatt of aromatic protons bi benaylic protine ave _terther ead the eS et wing BS, Axe. ARE CRTTCTOReattached to the wing. » When aromatic absorptions ave Jarther downfield than those of benzene Ls 737) om cleclron withdvawing substituent Moy be altached . > When upyeld of S737, am electron donating group way be present in te benzene. 7 induced wag Held by alkene a4 ow dn duced mag field by an alddyde. A LO eee afte Ym, ® vn ; “A oe gc desly aa Wen geri e Aue eet. ns ; higher deshielding postion ek a t poe ee | a 1a nator, strong Anducctive t ¢ i dating Li in anissotrop y cay group, Lo ) | sHehtng a : here, clettvons ave mosttree to Grulde eid cxround the symmetry amis of the triple ff Wo takes ey) bond, When however ore considers the madteae aligned I” to the oppiied +R the acetylenic proton is deshielded as 4 So in the case of anatkene bub dlesliedi comporerst ta however smaller cohen compared to shielding beccure electrons ave hot $s te Move dn that direction, * TE protont above the aromatic wings they fed in @ Shielding vegion and so Ngh eld Lbow 8) STL yee SENT es HESa7 [23] - annuleneio * This information 4s used in ehating emicad slit With yelative Canhiguration. The relative Stevenchemictry of diastereomers cay be determined from the chemical! shift data. > CPlonarity sy peor Copdanarity with Of protons with gue She canoremale. ving The position of methylene protons in horbovhene cam be explined by @ the omisotvopy of double bonda, c “4 * =o} = Ee 4 The Syh and endo protons are (629 Mexe positioned over the double bond (in the sbiekding region) and are therefore, more Seah Rendo Shielded than those whichare in the plahe of the double bond. * Using tia information one Can awign steveostructures to Compounds (2 21). gx $2388 on 7 gee = * Tnsyh ésomer (LD the proton (Ha) A@ positioned over the ih ‘ double bond and 4 Z (anti-isomer > az (syn isomer) eae Sr aa aed to protonlHa) th antt Compound, + The anisotvobic etkett of celettrons of c-c bord are cmall compared to the circulating tr-electrons amd the axis of the C-C bond ia the oxic Of the deskielding cone. hax, suede The eqitorial pwoton is ee hey eshiebding abinays fpund deon et NEC, eave Lby about & 0-5 ) than the chelding axda) proton on the same carbon otim , > ) — Hy AY — CA-AY ocH— AY Ss = a7 823-0 sa 23 |> 8 ® The protons on cyclopropyl) wings ave ako dound ob high fel GS OA) due to the cychsbropane ving omdisobrobhy, The chemical shitts of hydgen bonded protons , ve: O-H Protons An alechds Gind N-b pbrolons vin awakned depend on corersbertion. TN cConcentvated sdutions these protons are dechiddded by hydrogen bonded when these absorb at Jower Held ($35 Ommine N= , S$ 45 for an aleahd o-H).When the akeghtl ov : amine ty diluted with a hoh— hydrogen benching solvent ,hydrgen benching becomes Jers imp g consequently thebe redorances are then observed at around § 2.0, O. Bychagen bonding @ broton exchange leads to broadening of Xhe signa Corresponding to the yesonance of & 0-H oy N-h prob», ® bvood peak is ebserved ance taolecule 0 amothey vprotens ave exchanging tran one using PMR redorance, * he chemically cqpivalent protons are chemical Slagt eqpivalent ond @ the Shin~shin cplitiing ia not cbcerved or protons Which ave chemically equivalent Te determine if protons ave eqpnolert, one moy carcyout o © Simple teat. Ohe Angpects the structure amd me, replaces each proton by amcthey obi. Th the veplacenent reaulks ui, only one product ( not Asomers) the protons Ore equivalent, Tf howey er, the replacement giver isomevs , the protons are nat equivalent. 7 In vinyh chloride, proton cis tp the ch cbtm ia in o difterest ewironment tham the trons Preton. ae He: thes protons are non-equivalent so we a / ; Cac get three signals, | AF Nye 7% Ee the distinction beth isoprebyl chilovide Gual n-propalichlavicle Som be cmalysed. suing the tase Jis = * res cH CH= CH, C—O —h a ark Signals 3-PMR cignads (250 propyl chloride) ( p—profyh chlovide.}) *Chenicall Shift Gapivoence of Protons veplacemet testt> 1) Homotopic Hydrogen clams + 8 Simp de way to decide i$ or not ‘wo ov rove protons in a given combound ave chemical shift eapiivalent fe. homotopic is to replace each hydrogen for ex! isobutylene (2-methy propene) tio protons ore eqpivalert Wee. ZH replacement Hc. ye ieee A Cmre — mes oe A ae Sh byz Bis Cee ; cael = We etter 2 (chemically eqpivalent protons) NY Enantiotopic hydvogen clincs- In ethyl bromide yeblacement of either of the tuo mettylene protons by a group Z vould after A foir of eratimers, Theretpe of faive of protons ave termed enatiotopic protons. These will give owy one 1H NMR Signal. (Enatiotopic bydvogent may » however, not have the some Chemical shift when dissed tn a Stvent. Since moct Ah Wmk spectra are determined using Adhdvah solvents ond in thease situations enatiotopie Protons have soume chemical shift), [See an the next page) itl) Diaateventopic hydrogen bonding When one vephaces either ving proton by a group Z,one gets compa that ave diasteredros These type of protore ave tewmed dinsterenstopic, volich have. digtevert Chemical Shits amd give +100 Signals J the 4H NMR Spectrum. eroT Sep hoce Zz Beg) oy Sm oe ge ee im a) = A h oe vinyl Chloride (Diastereowevs) Abree hon <4pivalert protons. p i Sh —c—" trenkally bec ey \ replace by Z 1 on, Be 3 (enatiomerc) co only one proton Signal. | | B Crclobatond possemser am ivkerndl mivvor Hone of Syinmetry, . < a as i b +The hydroxyl proton h* Absorbs beth ne : §a-5 depending on Solvent ~ Conch, f He * preter HS and HF ave diacteres topic aml will give diferent signals, TEAM chow cin digrde « brotone HS ave enantictobic amd eqpivobent dn #4 4H mR gpetrum, B So the protons Ht nck only do ckincterenteem diasterestpic protons have dittement Chemica shits but these Otten have clittevent coupling amebnts with neighcouring probs arc this Leads to tarthey complexities tn the nme Spectra, > Spin- Spin Splitking > * the first soley gphiting Oriser bet? protons bn adjacent or on the Some alms , + splitting ocuwys ony betmeen nuclei with ditdevent chemical slitts, thok 4a chemically non - expivolemt protons * The geminal protons ay also murtvally coupled to give g poir o& doublets the Splitting due to geminal coupling cours OW in cH ; ktoo protene are cliastereptobic, ssang, da i. oo oe oe rans Se doublet > 9S =C Coy vs= Goch jproxon 4h a: Syccemp ig eer are protone appears at a set of four peak (unequal coupling ~D -TWwO VICINOK pty Ly RE nt tet! re pur peaks are not every spaced and do hot have relative antensitia of 4:3: 3246 * the Splitting dud to vicinal protos Hy and hy having chitkerent chvivon ment Lt | 3 doubher ; yale: roo diboe ape jy ontiadtd ae ~>| Sab : i Se Sh | > srereouing applied field oF WE triplet 4 - Signal dn absence | 0} protons HL Protons of Hb, Spit the signa) > ante 4.214 triple —_—_ Snexeaning Ho ~> Some times the doublete ave distorted (Ve: Skewed ) the Antenci wotio of peaks ain neither of the doublets ia 4:4.The skessing 42 winimal when Chemica shift ditk bet? two coupled protone 4b mach Larger than thelr coupling constant. > Usually the gymmetrical natare of the theoretically Predicbed peak intensikea in a wwhtiplet 2 not observed. The triplet amd quortet are hot cymmetrical ond gve the apberance of Rearing amd shamting towards each other, The triplet 4 Shanted in downward direction while the quartet ia darted in the upward dlivection, These shapes actually offer an advartage. con there enable to pick our vehattd multiplets from & complex spectrum, TT TNoD D The magnitide of ditters for cis and trans bydvogens , AMthough He vomges of both sale overlap, for a poly Of isomeric ds Owl trams otkenes Sama 2d invariably gredley than Seip. The difterence beth Setsiand Tieame 22 on imp tool for Aistinguishing ds amd tyons alkenes, - > 9 mono~ cagapilid cubstituted ethylene CHy cH Yall Anvee bydroyenc are pon eqpivalent, they abt spit each they to yield complex multiplet. > Aromatic Coupling debenda on Whether the coupling protons ore ortho, meta or parade each other, ay ortho eae Gr» meta 2-3 Para 0-4. > For hydvogene to ave Yt order Sbectya, the cifgerence an H3 in theiy chemical Shifts (as) mutt be at eatt 4o tines Qreater than their coupding conctont be ~* Although the J does not deperd § value does, “the qrecter the the chemical chift ali AS Pb Tal, on field Strength bud tield strength, the qeediéy tH & tua gredley the possibility of Obtaining first order Spectva, r4) Nitroolkames — CA-No, 2) pmides ° » S g-€-Nn-® ° ~ @- em i ge — nc 3) Carborylic pci ° a-to® -Q-coon 4) Esters R- PHY, temp conch habure oY cdvent — became of A Bonding — Niet protons of Onmicles opbeay as § 5:0- 8-0 (eread) — ah tig pid exchange var oN da a ea singlet | —N-W proton never appears a4 trbtiplet, = Tr most aliphahtc amines RW, splithing (Coupling clueto ny) as not observed, et alt Se ith perhoh desde lend cbarackr yo 4 he eg “> i Mas y 98 Ko] ind ‘These are not (pme) myftivalent —> at 465c ody 0 ¢ ling Signa spr alt 6- cx, Ht, hydwogens. due to 4 vale - votation. Aa A | i ay ® R he oo. - = oe Ho b #0 n, Ho” FT H : goe oe Ma A Hy are diastewentobbe Mad Mave magnetially ancl chemically ditt 4) ales See f re tH, diasterentople*Enatiotopic protons may have dittt chemical chitts if the combd ca diwselved in am _obtically active compound.» Otherwise they Cont be — duskingul dn NMR, ¥ CHWY 4 the x atom or Grmpe in Cx WY wilt be diasereotopic if either W or Y ia Chive, * 4 protonc which cam not distinguiched in NMR are termed _isochronous, oe30 ‘mical and hh fre- # an Alphabetical Listing of Some Functional Groups and Cl ith Teale Absorption Hagens hea Frequency Ranges fom ‘and Groups or Class Intensities* Assignment and Remerks FA Acid halides Ba x Aliphatic 18101790 (s) stretch; fluorides 60 om‘ higher 965-820 (m) C—C streten 440-420 (3) CI~C=0 in-plane deformation ‘Aromatic 1785-1765 (s) =O stretch; also a weaker band (1750- 1735 em.) due to Fermi resonance 890-250 (5) C—C stretch (Ar—C) or Cl stretch Aleohols Primary —CH.OH 3640-3630 (3) OH streteh, dil CCl, soln 1060-1030 (s) OF strotoh; lowered by unsaturation Secondary —cHROH 3630-3620 (s} OH stretch, dil CCl, soin 1120-1080 (a) (C—OH stretch; lower when Ris 9 branched chain or cyclic Tertiry —CR,OH 3620-3610 (s) OH stretch, dil CC, soln 1160-1120 is) S--OH stretch; lower when R is brenehed General OH 3360-3250 (s) OH stretch; broad band in pure solide or Hiquids 1440-1260 (m-e, br} C—O in-plane bend 700-600 {m-s, br) 6—OH out-of plane deformation Aldehydes 2000-2810) ni Histrotch with overtone _ {grec-a7a atc bend ed 1725-1695 (vs) C=O SITET slightly higher in CC, soln i 1440-1320 (3) H—C=0 bond in aliphatic aldehydes. ‘695-635 (e) S=C—CHO bend 1565-620 (8) C—C=0 bend Alkenes Monosubst_ —CH=cH, a See Vinyl Dieubst —cH=CH— = See Vinylone =cH— rea sno 200 oar 1890-1655 (vem) C stretch yee ‘850-790 (rn) CH out-of-plane bending Tetrasubst stretch, may be absent for aumme- 1690-18 79%w7y a ‘ical compounds Alkyl 2980-2850 (m) CH stretch, several bands 1420-1459 (rm) ° 1400-1360 (mn) “CHS deformation 740-720 bw} CH; rocking, 3390-2250 (rs) Fergie sy 100 (=) SEC, frequency raised by conjugation 680-580 (sf “Steoi bens saz tz ims Nh, stetch (di solne: bands shit to. 3400-3390 (m} 380-2940 and 3200-3180 in solid 1680-1660443) SO sun mise bend) 1650-1610 rn) ‘NH, deformation: sometimes appears as a ao ara Shoulder (Amide i bon 1420-1400 (r-s) CN stroten niga I bora) Secondary —CONHR 3440-3420 (m) NH stratetr (dil 8o[n); shifts to 3300-3280 in ure liquid or sola 1680-1640 (vs) 0 stretch (Amide bane) 1860-1530 (vs) 5, Ni nendiamid iibonch 1310-1260 (rn) CoN stretch wink 3 7 AssighMENt uncertain . Shee 8” sinani en = macau: w= weak: v= very: br > broad | Continved190 TABLE 8-2 Part ll / Vibrational Spectroscopy ‘An Alphabetical Listing of Some Functional Grows and Classes of Compounds An Alpha sorption Frequoncies inthe inrared—convd Frequency Ranges {em ') and Groups or Class Intensities™ ‘Assignment and Rat ‘Arrides—cont's TTeriany —CONR, 1670-1840 (vs) c=0 stretch Genera CONF, 630-870 (s) N-C=0 bend 615-538 (6) Ca out-of-plane bond 520-490 (ms) €—c=0 bend Amines Primary —NHs 3460-3280 (rm) INH stretch; broad band, may have some structure 12890-2810 {m) cH stretch ‘1650-1590 (s) pit deformation nT Secondary —NHR 335023300 [vw ret 1190-1130 (ml CoNetreton, "740-700 (rm) Nit deformation 1450-400 (wb) G—N—C bend Tertiry NR, 510-480 (s) C—N—C bend active tyarohalioae’ -ipgypisoee- = Iii stretch, several peas 30-1500 (mi nites mone or ee 2 ee i 'deformation (on NH, ‘Amino acids © —@—COOH 3200-3000 (8) tubonded NH, and OH streten:v broad band in solid state \or—cfil,c00" 1600-1590 is) ————> 60 andley stra 11550-1480 (m-s) “ey ENH,- deformation 42-1390 (w-m) ‘COO"sym stretch 560-500 (s) COO" rocking ‘Ammonium NH,” 3350-3060 (vs) i stretch; Brod band 11430-1390 (s) Ni, deformation; sharp peak anhydrides —CO ies-70 teh % 1770-1710 Sing=o etch 2 1220-1180 (vs) Seo Catrteh (higher in etc anhyarses) —do ‘aromatic compounds 3100-3000 (m) i steotch, severs! peaks 2000-1660 (w) GEeRone and combination bands 2000-1660 (viable) __-Aromatia.ingstretening 0 2). any ”_, 800-650 (8) Biot plane CH deform: tions (one or wo C Ps Spands depending OF substitution) es 190-820 (m-s) Ring deformations (two >2nds) Asides —N=N=N 2160-2080 (s) N=N=N stretch Bromo —C—Br 50-500 (m) c—Br stretch fort Buty! (CHy),o— 2390-2850 | Gi stretch; several bands ‘400-1370 (mm) i ani ee CH, deformations Carboiimides 2150-2100 (vs) N=CEN amtisym streteh a N=C=N— ' carbony! Yom 11870-1660 (vs, br) c= stretch Carboxylic acids 3850-9500 (s) on streteh (ona dissin) 3300-2400 (s, v br Sretijod OF stretch (solid and liquid states) 800-1740 (s) c= ‘moriorer (il soln 7710-1680 (vs) =e Stretch of dimer (slid and liquid states) 960-910 (s) ‘C—OH deformation 700-590 (s} | O—C=0 bend 350-465 (s) C—C=0 bend cnioro {850-850 (m) c—Clstrateh 580-490 (3) Ring deformation SM em‘TABLE 8-2 ‘An Alphabetical Listing of Some Functional Groups and Classes of Compounds ‘ii Their Absorption Frequencies in the Infrared cont'd Frequency Ranges ‘cm") and Groups or Class Intensites* Assignment and Remarks Diazonivm salts 12300-2240 (s) streteh ase f = Ethers. —C—O—C— Fluoroalky! CF, CH, etc. leooyanates —N=C=0 feothlocyanates —1 Ketones, - ‘cH, 2 Methyl —CH, Methylene —CH,— Naphthalenes Nitiles —C=N Nitro Oximes.-=NOH Phenols Ar—OH Phenyl C,H,— (645-575 (5) 31280-1220 (s)_ ———®C—O—C stretch in alkyl aryl ethers 1140-1110 (vs) 1276-1200 (vs) 1250-1170 (s) 1050-1000 (s) 1400-1000 (vs) 2280-2260 (vs) 2140-2040 (vs, be) 1725-1705 (vs) 1700-1850 (vs) 1705-1685 (s) ‘and 1650-1580 (rn) 11850-1830 (s) 1780-1770 (s) 1750-1730 (s) 2970-2850 (s} 2896-2815 (s) 2820-2780 (s) 1470-1440 (mm) 1390-1370 (m-s) )* 3080-3070 (mn) ‘and 3020-2980 (m) 1470-1450 (mm) ——5 645-615 (m-s) and 545-620 (s) 480-485 (variable) 2260-2240 (w} 2240-2220 (m) ‘580-530 Lm=s) 2 4870-1850 (vs) ‘480-1460 (vs 41360-1320 (vs) —~ B30 (m) {650-600 {s) {580-620 (rm) 530-470 (m-s) 2600-2590 (vs) 3260-3240 (vs) 1680-1620 (w) mani soa 200-300 (=m) 2000-1700 (w ‘—O=C antisym stretch 0-C—0 bend €—O~C stretch in dialkyl ethers C—O—C stretch in vinyl ethers C—O~C stretch in cyclic ethers (alkyl) C—O stretch in alkyl aryl ethers C—F stretch [=C=0 stretch =N=S antisym stretch -O stretch in saturated aliphatic ketones 0 stretch in aromatic ketones ‘,f-unsaturated ketones S=0 stretch in lactones ich in lactones. =O wretch in Elecones CH stretch in C—CH, compounds CCH stretch in methyl ethers (O—CH,) CCH stretch in N—CH, compounds CH, antisym deformation CH; sym. CH stretches in alkanes CH stretches in alke CH, deformation Insplane ring bending Out-of-plane ring bending =N streteh in aliphatic nite NN stretch in aromatic nitriles C=C—CN bend NO, stretches in aliphatic nitro compounds NO, stretches in a =H stretch NO, bend in aliphatic compounds NO; bend in aromatic compounds NO; rocking OH stretch (dil soln) OH stretch (solids) =N stretch; strong in Raman O=H ou-of-plane deformation OH deformation atic nitro compounds — CH stretch Four weak bands; overtones and combitiations~ ‘ContinuedTABLE 8-2 ‘An Alphabetical Listing of Some Functional Groups and Classes of Compounds ‘uth Their Absorption Frequencies in the Infrared—cont’d Y A Frequency Ranges C fem") and z Groups or Class Intensities’ Assignment and Remarks Phenyl—cont'd 1625-1430 (m-s) ‘Aromatic C=C stretches (four bands) 4 1250-1025 (n-s) CH in-plane bending (tive bends) 770-730 (vs) CH out-of-plane bending 710-680 (vs) Ring doformation 5 5560-420 (m-s) 19 deformation 4 Phosphates (RO),P=0 ‘ = alkyl Pee0 stretch q P—O-c stretch aryl 1315-1290 (vs) P=O stretch 7240-1190 (vs) P—0-C stretch Phosphines —PHy —PH 2410-2280 (mi) P—H stretch 1100-1040 (wom) P—H deformation 700-660 (ms) P—C stretch Pyridy CHAN 3060-3020 (CH stretch ° 1620-1580 (vs) ee eS ‘and 1590-1560 (vs) eet ones {840-720 (s) CH out-of-plane deformation (ong of two bonds, depending on substitution) 1635-605 (r-s) Invplane ring bending Silanes —SiM, 2160-2110 (mm) SI-H stretch Sit: '950-800 (s) Si—H deformation Silanes (ully substituted) 1280-1260 (m-s) $i—C strotch 1110-1080 (vs) Si—O—C stretch (aliphatic) 840-800 (rm) §\—O—C deformation sulfates R—-O—SO,-O-R 1140-1350 (6) 2 ; Gar ea $0 stretches in covalent sulfates R—0—S0,-M* 1260-1210 (vs) _S—O stretches in alkyl sulfate salts (M= Nar, R’, ete) and 810-770 (s} ‘OS strotch Sulfide, C—S— 730-570 (mm) —S stretch Suifones —S0,— 1360-1290 (vs) $0, antisym stroteh 4170-1120 (vs) 80, sym stretch {610-845 (ms) 80, scissor mode sulfonic ecids —S0,0H 1260-1150 (vs, be) $=0 stretch suttoxides ‘S: 11060-1030 (s, $=0 stretch Q / 610-845 (ms) 50, scissoring Thioeyanates. —S—C=N 2175-2160 (mm) CEN streten 1650-600 (w) S—CN stretch 205-400 (8) S—C=N bond thiols —S—H 22590-2560 (w) SH stretch; strong in Raman "700-850 (v) G=S stretch; strong in Raman Tristines C.N,Y, 1600-1500\vs) ‘Ring stretching 134.5-risubst 1380-1380 (vs) Ring stretching 820-800 (s} CH out-of plane deformation Vinyl CH=CH, 3098-3080 (m) CH, stretching and 3030-2980 (w-m) CH stratehing 51850-1800 (w-m) Gvertone of CH, out-of-plane wagging 11645-3615 (ms) C=C atratch 1000-350 (s} CH out-of-plane deformation 950-900 (vs) CH, out-of plane wagging t Vinyiene —CH=CH— 3040-3010 (mm) H, strtching 1665-1635 (w-m} stretch (cis isomer) 1675-1665 wr) G=C strotoh (rans isomen Bara plane deformation (cis isomer? 730-665 is) CH out-of plane deformation (trans isomer) Vinylidene zy ‘3096-075 (rm) H, stretching 7 1665-1620 (w-m) stretch 895-886 (9) Ch, out of plane wagging TT2285-2260 (s) N in isocyanates 2260-2200 (m-s). C=Niinnitrles 2260-2190 (wm) C=C in alkynes {disubstitution) 2180-2130 (m} in thioeyanates 2175-2115 (s) inisonitries 2160-2080 (m} in azides! 2140-2100 (wem) C=C in alkynes (monosubs 2000-1650 iw) Substituted benzene rings 11980-1950 (s) C=C=C in allenes 1870-1650 (vs) ‘€=0 in carbony! compounds 1870-1820 (s) ‘C=O in Bactones 1870-1780 (vs) C=0 in anhydrides 1820-1800 (s) C=O in acid halides 11780-1760 (s), in plactones 1765-1725 (vs) = ini anhydrides ‘1760-1740 (vs) in o-koto estors 1780-1730 (s) in Sactones 11750-1740 (vs) in estors 1749-1720 (s) in aldehydes 1720-1700 (s) in ketones 1710-1680 (s) C=0 in carboxylic acids 1690-1640 (s) C=Nin oximes 1680-1620 s) ‘and NH, in primary amides 1680-1635 (s) C=O in ureas 1680-1630 (m-s) nes, etc 11680-1630 (vs) C=O in secondary amides 1670-1640 (s-vs)_ C=O in benzophenones 1670-1650 (vs) C=0 in primary amides 1670-1630 (vs) 0 in tertiary amides pter 8 / Grou» Frequencies: Infrared and Raman 193 ‘TABLE 8-3 ‘ANumerical Listing of Wavenumber Ranges in Which Some Functional Groups and Atsses of Compounds Absorb in the Infrared ‘Range (om-') and intensity Group and Class Assignment and Remarks 13700-3600 (s) —OH in alcohols and phenols OH stretch (dil soln) '3520-2320 (m-s}__ —NH, in aromatic amines, primary amines __NH stretch (dil soln) and amides 3420-3250 (3) ~OH in alcohols and phenols OH stretch (solids and liquids) 3360-3340 (m) NH, in primary amides NH, aatisymm stretch (solids) 3320-2260 (m) =OHin oximes O=H stretch .» 3300-3280 (m-s) CCH in acetylenes CH stretch 3300-8280 (s) NH in secondary amides INH stretch (solids; also in polypeptides and proteins. 3200-3180 (s) —NH, in primary amides NH, sym stretch (solids) 43200-3000 (vb). NH" in amino acids INHG" antisym stretch 3100-2400 (v be) OH in carboxylic acide H-bonded OH stretch 3100-3000 (m) -CH in aromatic and unsaturated C—H stretch hydrocarbons 2980-2850 (m-s) —CH, and—CH,— in aliphatic CCH antisym and sym stretching ‘compounds 2860-2700 (m) CH, attached to 0 oF N CH stretching modes 2650 w-m) _—CHD in aldehydes —_ —Qvertone of CH bending (Fermi resonsnce) FeOsO SN ih ae aaTaRE NH stretching moaes 2720-2560 (m) —Oh'in phosphorus oxyacide ‘Associated OH stretching 2600-2540 (w) SH in alkyl morcaptans 'S—H stretch; strong in Raman 2410-2280 (m) —PH in phosphines P—H stretch; sharp peak 2300-2230 (m) N==N in diazonium salts N stretch, aq soin "=O antisym stretch stretch CSC stretch; stong in Raman, CEN stretch NEC stretch N=N antisym stretch C=C stretch ‘Several bands from overtones and combinations C=C=C antisym stretch C=O stretch ‘antisym stretch; part of doublet C=0 stretch; lower for aromatic acid part of doublat | C=0 stretch; enol form C=O stretch stretch; 20 cm" lower if unsaturated C=O stretch; 30 em-* lower if unsaturated stretch; 20 cm lower if unsaturated stretch; fairly broad ©: stretch ang NH, stretch; broad band stretch stretch (Amide | band) stretch stretch (Amide | band) stretch “Ker = strong. m = medium, w = waak, v= very, br = bros Continued194 TABLE 8-3 ‘A Numerical Listing of Wave! Classus of Compounds Absorb in the Infrared—cont’d Hange (em ") and intensity® 1655-1635 (vs) 11650-1820 (wm) Group and Class ‘C=O in B-kotone esters N—H in primary amides number Ranges in Which Some Funetional Groups and art ll / Vibrational Spectroscopy chet Assignmet and Remarks ‘C=O stretch; enc! form NH deformation (Amide i! banc) termi Malar ar secre seis, BC ses MT m fecimee Exes Se ta ora ear eee ame iginwomaiccmominde ——ngurrtraggt veetmoim act re cr etee) raat operon te seroseeoya) ——_oorhenton ed st Ce ae ssn-ssoim ‘Maps ai 1, Reman An 0 seprmim) Mana canven je eee 1565-1475 (vs) NHin secondary amides NH deforination (Amide |! band) 1560-1510 (s) Triazine compounds Ring stretch; sharo band 11550-1490 (s) NO, in aromatic nitro compounds NO, antisym stretch oto HN ee Ha aa Sere, RENEE Scrempnae so anh SSieoimel REN Cin aanoe ‘earache ‘eit RR Secu een ene Ga haces Vaio) Sic vac iiny rt me ee Sama faes ‘aso 00> gi neronyts ed te Emacs vom-tons) ‘Slane nie es sagan a ene Reems Beit, Galea Sheet an Bei RRMA ESP compos copenes weet, pape SB ren Betas Ra econ eats Baiesia, Menor Saepors Ree reat 1236-1295 (vs) SO, in sulfones: PE Tasta, EASES emma 1300-1200 (vs) N—Oin pyridine Nroxides rami) Ono nt oes vmeceroias Peg aa coment eto eee Bice = ume Soa Soresjpter 8 / Group Frequencies: Infrared and Raman TABLE 8-3, 195, ‘Numerical Listing 0’ Wavenumber Ranges in Which Some Functional Groups and Gissses of Compounc's Absorb in the Infrared—contd ange (cm) ; gad itonsity* Group and Ciass ‘Assignment and Remarks TiRO-1100 fH) CoB in tlocarbonyt compounde HS stretch; song in Raman fise-toroWvs) —— G—O—Cin aliphatic etmors. C=O" Canty strech 4120-1080 (3) CaoHin soconcary or araary €=0 stretch alcohols 1120-1030) CNH in primary aliphatic amines C=N stretch Hoo-1000|vs) «SiO Stim sloenes SiS! ati strtch {090-1040 (3) SO,H in sutton ecide 50 aym atch {oss-1018() CA Ob in oye slo eo stetch {60-1028 vs) Hl, Olin primary alcohols = stretch {00-1046 vs} SO malyr sutovides Sao stretch {oss-815 vs) P—0-~¢ in organophosphorus POC antieym stretch compounds, 1020-950 (w) Carbon rng in eylc compounds Ring breathing mode; strong in Reman 400-850) Gimli, nyt compounds 2G cutotplane deformation 920-860 (vs) CH=CH in rane doubstuted stones H outotplane deformation 360-900 =) Gi=ch, inv compounds Gh eutotplene wag 200-965 (vs) ch ~. invinvdenes cH, out. phplane wag 290-805 v0) 1.2.craubatiuted benzenes CH out-of plane deformation (two bands) be0-Ye0 ve, br) RN primary amines, NH wog 280-720 vs) SiC in organest¢on compounds SC ereteh 850-220 (vs) 4 3.rieubatitoted bensenes CH out plane deformation 850-1008)" SCH inal Ch recing 850-790 (mi cmd in riubsttutedalken CH out-of plane deormation £50-550 (m) Cin chloro compounds CCl streten 0-31 isubetuted Serzones GH our plane deformation +“ ws) Parte menses GH out-of pane deformation 870-200) Tirines GH out-of plane deformation s15-810 (8) CH=CH n vinyl others CH our plane wog 810-790 ve) S2adteranubstuted benzenes CHloutot lane deformation va david bersoes GH outofplans deformation (two bends) 728-680 (a futod bonzenés Cr ut-o-plane-deformnation ftwo-bendel— 778-850 tm) CS in aulfon| chordes oS eretehr strong in Ramon o-ss0 Monosubatuted branes Gitoutorplane deformation (wo bends) z renores 740-720 wm) (CH. In hydrocarbons {i rocking In methylene chains; inonsty “Zopends on shin length 730-665 8) CH=CH incisdsubstiuted alkenes Hout plane deformation 720-8001, b«)__‘Ar—OH in phenols GH cuter plane deformation Ho-sr0 mt sin suindes, Oo 8 cretehsatrong in Rartan 400-890 (6) G—e—0 in eatboxyic acids O—C=0 bending 95-405 i) Ox e— EHO in ehdohydes == CHO bending 20-620 (s) On in aconols C—0—H bending 20-560 (s) Cece itin ayn C—H bending 20-200 (w) S=CEN in thseyenaies SC eettyatrong in Raman 20-000 (e) NO, in aliphatic tro cermpounds No, detormetion 50-800 (=) Jar €Fy in aromatic flvororethy| deformation two or three bands) combounde 50-500 =) “Brin bromo compounds c—ratreten Gis-sisim-s) —_-Naphthalonee irflane ting taforation 15-275 0) OnE neaee One O bene 620-690 (8) in vity! compounds 1, ttn 635-605 (m-s) Prt Incplane ring deformation 30-570 0) in amides Continued196 Part ll / Vibrational Spectroscopy TAL che TABLE 8-3 ‘A Numerical Listing of Wavenumber Ranges in Which Some Functional Groups and Classes of Compounds Absorb in the Infrared—cont'd and Intensity* Group and Cis Assignment and Remarks a 690-568 (s) —CO—C in ketones —CO—C bend 615-5: 0 in amides C=0 out-of-plane bend 610-565 (vs) 50, in sulfony! chiorides. $0, deformation 819-645 (m-s) 50; in sulfones C1 in iodo compounds C-—C—CN in nitriles C—C—CN bend NO, in aromatic nitro compounds NO, deformation J Ring in cyclostkanes Ring deformation Ring in benzone derivatives In-plane and outof-plane ring ‘deformations (two bands) 0 vs ‘50, ia sulfony! chloride: $0, roe O- « © 0 in aldehy 0 tae =. vin alkyl groups: ‘Chain deformation modes (two bands) 0-610 4) C=0 in totones c—C=0 bend p ° 00 8 —€- in amino acids —¢- rocking . ‘0 508-545 6) GH. in vinyl compounds twisting 350-468 (a) E—C=O in carboxylic acids c—c a 346-520 (6) Naphtnalenes Invplane ring deformation 520-470 (rns) NO, in nitro compounds NG, roeking 320-490 m8} Co~cin ethers C—0-—~C bend 510-400 (s} C—N—Cin amines C—N—C end 430-488 variable) Naphthalene Gur-ot-plane ring >ending 440-420 3) ChE Cm=0 in acid chlorides Gi=C=0 invplan deformation i 405-400 3) S—CEN bend ; A TABLE 8-4 , Characteristic Frequencies of Functional Groups in the Raman Spectra of Complex Molecules Frequency Ranges tom"') and Groups or Class © Intensities* ‘Assignment and Remarks Acetvienes _ =CH 3240-3270 (8) CH tratch (oynes) R—C=C—R 2300-2190 (5) EMC stretch in diaubstitured seetylen sometimes two bi nds (Fermi doublet) R-cmcH 2140-2100 (6) G=C stretch in monoalkyl acetylenes 650-800 (m) E= CECH deformation 9 Acid chlorides AC 1900-1790 is C=O atetch ct , iconols ROH 4400-3300 vw) ft stretch; broad band 1450-1350 (m) OH insane bend 1150-1050 (rm-s) C—O antisym stretch 970-806 (s) C=C“ sym stretch p : Aldehydes Laas 1730-1700 (rm) C=O stretch iH »»-Alkanes (general) 2900-2600 (vs) CH stretch ~ Yars-1480 (5) hi, antisym dotormation 1360-1300 (m-s) CH, bend 340-230 (5) =-€—C—C— bend Tare erongi = media = weakiy~ weniBr = Ba