"NMR. SPECTROSCOPY Fntreduction of me : ’ Nuclease magnetic stesonance [nme] %s . a vesy important technique for identification of organic © Compounds: In Miajovity of Cases, the entive Styuctuse Sof the compound Can be established by the data provided € ; by the NMR Spectya alone e Many nuclei may be Studied by NMR techniques, but hydrogen & Cashon axe Most Impostant + / NMP qives infosmation about the no: of ceach distinct type of nuclet- fos example it gives the Cinformation about the no- of each distinct types of hydrogen nuclei NMP Spectsoscopty 1s an absozption Spelteoscopic method - when molecule with magnetic nuclei ase placed oO1n @ powerful magnetic field, different enesqy states : oxe Cseoted cohich ose then detected by absosption of ight Of approximate enesqy: In the absence of the © magnetic field these different states have neoaly Same ener . Coo; OoNuclease Spin & Spin state Nucleus 4s the Endait spvely choxged pasiticle VE any nucleus that Contains efthes odd atomic numbes [odd no-of Protons) [o9 Odd nd- of neutsons (0x) odd atomts MASS [or) any too ose odd Can have a propesty called© ® oO .o °C ° c Spin = iconv | Spin quantum f mas Psoton Neutron, MAumbex (2) Examples Even Even ‘ven ° ve % aa E Odd Even Odd Yo, Bla -----] S Even Odd odd 1 “y Bae Odd z : af age ‘WW f Some atomic nuclei have magnetic propesttes « c fe thes associated Spin (1) make them behave like a ¢ bas magnet: c When these nuclei ase placed in a magnetic © Held Hy , these ase at+) allowed Sptn States (orientation ) exists ‘in the divection of the applted magnetic field . c Tn Case of hydvogen nucleus, the spin quantum Numbes I= '/a, So that tt has 2 allowed Spin States © [abla) +1= a] for tts nucleus: one fs +. % the othe is “Ya. [re a-Sptn State (+ th) @ P~ Spin state (1h) ¢ : C2000The two Spin states ane not of equivalent energy tT an ” appli fc field & these spite 1 Q enesqy level i applied magnetic fie pte Trt Q enesqy leve The Spin state t/a is of lowes enewqy Since Te aligned Cust the field, Lohile the sptn state -'p Ts the highes enesq, Lince it 1s opposed to the applied magnetic field. Thece Cenergy level vary divectly With applied magnetic field He - , “Yo 'h “ragnee field absent » 9000 Energy —> c reece ee ge applied magnetic Held 3 Fiq® ' Enesgy level echeme fos a nucleus Lotth T=1\/) 5 “te 2 C g ¢ g C G c e Hy c 5 C ° Magnetic freta Hp < : Fg® : The Vastatton Of energy with magnetic field C The difference tn energy blw these two levels is S Ac = Yh B[He a eee arKE & Bel Ho whese ¥ > qyromagnetic eta tio h > planks Constant Be applted magnetic field Relaxation (o») de excitation [© Satusation of nuclet hoe ee ee ee A nucleus Tm an Uppes Spin state wretusne to the lowe? spin State Ys called weloxation process Ng State srelaxation Nz state 2900000000000 tsangitfons Stmulte- ° Both upwasd % doronoond nucle au -neously takes place but te Uupwasd transitfons move @ obable then downtoond tsansitions due to excess nuclet ¢ pr takes place. © at o&-level, the oO net Closoxption of tadiation oo Th NMR phenomenon sometimes these is & >. Possibility of equal population of nuclet ak nucleas energy level, that Condition called Satusation ? AL satusati no net absosptfon of siadtatio: Signal will not Seen In the Spectsum These ose 2 types of srelaxation process: They axe » Spin -Spto sielaxation a) Spin - lattice welaxation eeo0n0n000o OO Spin -spin vrelaxatton : The wetusning of nucle! i¢ Gomes to Lower energy ¢ State, by weleasing enexgy to Loes enesgy State fic calle © Spin- spin Stelaxation c¢ © Spin lattice selaxation : @ of nuclet ig Comes to Lower energy State « The gretusning ¢ oly ereleasing enesgy +0 Componente of the lattice 7s © additonal, translational , wiotational %& Vibsational enesgt © 46 called gpin- lattice srelaxation . | fon : ¢ Boltzmann Equation : ‘ Accovding to this the mato of population of nuclei at PB % « levels depends o the energy Separation © blw nuclear energy Level [AE) & temperature CT): > Highey the AE nore population at d- level, move intensity € “in appeoarance of Signal: & Ne | -ae/ kr ¢ =e Ny i J (os) N. ~Ae[ kT se : Pires c e : Ne —> population of nuclei at B- level N,— > Population of nuctef at 4 - level ¢ Ae = E- Ey ¢ Cenerqy dtffeven ce] : k = Boltgmann's Constant = R No T = Tempesatuse in ke C0000 ODOPetineiple of NMR Nucleas. behavious Similax to Top] qyroscope’ Evesy sptaning posticle has the inbinsic psopesty [own Propesty). Any Sptning positicle which wiotates Obout a Olixection of external force the swotuttone Called psecesston The extesnal fosce may be gravitational, electsic ¢% magnetic etc: ©090000000 e Top & Jyroscope unde sqo precesston te these Ones Spinning objects Sjotates about the dlisection of gravita tions s . fosce + a. ‘ I! | 4 Sp e e € ¢ « ¢ c C ( inning Nucleus once placed tr extesnal magnetic field ¢ Undesqd wtotatton about dtsection of EMF with alignede ovientation- Rotations of Spinning nucleus about Ho ° Cc Aitsection Called nucleas. Precession (05) Laxmox precess tor [Nuclear precession obseswved by str- Joseph Loxmor No-of Stotations fn a given time by nucleus About directfor of Ho, Nuclear P¥ecessional frequency ( Lox mos frequency Wy) Sometimes stefesred ag Angular foequencies Of nucleus: wheneves precescing nucleus € ivsadiated with RF stadiatfon under stesonance condition, Cc oobooo“nucleus takes enesqy fsom sadiation undergo bsansttfo re © (fipping) then puecessione ose in Opposed Monney t — direction Opposite to divecton Of Hy - : The enesqy taken by the poecessing nucleus (ov) RE absorption tsansformed into NMR signal: Pres 2 = VHo|Be ; aT ¢ where 3 —> Eryx magnetic satto , : Fos hydsogen 1 = 269°53 vradiants | Tesla c “The purecessional feequency (7x) fe dtvectly Propostt- ie ~oral to the Stwengtn of the external field (Ho) ¢ ¢ « « COO0 MOD OO OOOShielding %& Deshielding [eo shielding. oa dia mayne Be 000 <— Para magne tie (os) deshtetding eeo0000000 Bo applied B induced (Opposes Bo) Tn the NMR Spectum ef an Osgante Gorn pound the es present estound the protone also play an important sole - € lhen @ Compound fg Kept in the Magnetic field, the aap Dsound the Protons by Cisculating Qenerate an induced magnet field. The ‘induced magnetic field may wieinforce (align) ler oppese the applted magnetic field « Sf fhe induced magnetic field Opposes the applied field, the effective magnettc field expestenced by the protons decseases: This % called ghielding & the protons axe Said © to be Shielded. Shielded porotons give Signal at lowes sé Values 7 TE the Induced magnetic field weinforce align) the © applied mognette field, the effectve magnete field exposiertec by the protons Increases. This ics Called deshielding & the ¢ pootone ase Said to be deshielded- Deshielded psiotons © 0° give Signal at highes 6&- values. 2°6 Chemical Shift @ ¢ if.caninantatanaas The absorxption forequenty of Sample pootons aunay cforom Standard protons : ©) the difference bj absolute porecessfonal feequency of Sample pootons & se ference [standasd) porotons (08) The absorption position of NMP signal in NMR Spechum cis Called as chemical Shift © S = Absorption frequency of Sample — Absosptton frequency of wefesence : Feequentty of the Insbument ( Yr (mtg) (o>) Shift in Hz ‘Trstsument frequency Tn MHe Units + "PPm’ | pasts per millions) c Chemical shift Pasiameters + . The oe kcale fos pmR Studies jg about 10 PPM ; ile fos “C the full wiange is oves 200 ppm a one oes signals In an Nm Specksum cale., Sielative to the wlesonance Positfor of 12 equivalent protons of tmeChemical shift measurement On &-scale : woo the powtons of Osqanic compounds sesonate at a down field then the protons of Ths: dk Tms =0, then the Scale i¢ 6 - Scale. On T-Scale Tk TMs signal staxted fsom lo ppm then the Scale ‘1s T- scale Deshielding chreldi shielding down fietd “up Field” TMS . high frequency Low fiequerty te 9 € ag S54 3a P S Lepm) S4T =10 = T= l0-& [o) &= lO-7 © € i 7 i ; i ‘ c € c € ¢C € e e € « c € Cc C Refesence used tr nine 3 : ere C The Standasd giefesence Compound vohich is € Universally accepted & Used fox most PMR & cme Specht: ic TMs [tetsa metny! silane) Stouctuse of Tras is CHa Pipe Sore 1 He - a5 chy CH Tt is Choosen as a wieference because , ) Ibis a Volatile Liquid ep = aq% COCOO0CZ0000) TMs having one Set of protons shows only 1 Signal tn @ othe NMR Spechum Lohich ts set into “oO” ppm. ©2) Further mose, Silicon fc electso positive eelative b0 Caxbon : & tends to donate electson density tO [he methyl groups these ¢ by Yncseasing theis Shielding ow TMs 4s nighhg Soluble fn almost all Osganic Solvents vohich ore used fos Te-wme ‘ a) Because of ‘its Loto boiling point it Can be easily removed Sfeor-. Sample folutfon aftes siecosding ta - nme 09 Tt is Kghly inert Compound. € Disadvantages OF TMS € Some of the Sample CHa-cl > CHy-By > CHy~ 6-WR $-34 6-26 o- 2 The no-of EN atoms ‘increases, deshieldtng also tncreace Hence increases the $-Vvalues- el a i Hilt Ca < Helter Sel ae} B08 Sass spay § = Gt — Hen, —cl S$oq GER S32 CHg - ¢ < CHa-N < CHO esr ees eee reese ee Ancreasing $- values ecoo3enoaneo eof OOoS Greater ‘the no of hydsoqen atoms on Casbon increases (A — o@ the magnetic shielding \ ‘ -¢-H > -e-H > : j ‘ H ms > ‘§, 2 8, ©) Arisotvopic Effect * ¢ The chemical shifts Of protons of an aAvomatic asym alkenes, Aleynes, & aldehydes [Cannot be explainec oy the effect ‘Of EN hydrogen bonding ete: The psotons of these systems] Show abnosmal ehamter) Shifts: due to © anisotropic effect € | Tsotscpte effect ¢ Unifosm distibution of Property () ertect Anisotropic effect + Non- Uni form dishibution of Propesty [0 eftece ‘ When Systems Containing Ml - electsons oe Kept fin the € € cmagne tic field -thic magnetfe field is not Uniform around external magnetic field , the 1s of the System ase also cixculated - Cixculation of these elections generate a 2° induce ‘the molecule» As a siesult, non- Homogeneous magnetic pield ic generated (io the vicinity of fhe molecule | “Thc called aMmSotsopic effect Due to anisotsopic effect, the protens of the - bonding cntatning systems Show abnormal chemical shifts: : lineation Of proton depends” on Ovientation of molecule 7m 3D Space In external magnetic field. Amsotvopic effect of Ethylene : when Ethylene molecule once placed 1m the applied enagnetic field - Ethylene is Dviented Pexpendiculay to theapplied magnetic field The 2° magnetic ffeld ts generated © by the Checutations of wes of the c=c bond & ali the tie protons of ethylene molecule tlocated fn the deshielded ¢ wregion - Hence psotons of the altenes qive signal at highé& Arnisobsopic effect tn Acetylene Acetylene is @ Lineas molecule When acetylene fe Kept pavallel to the applied magnetic Field » the 2° ymagneti« field genesated by the civculation of 1e%s Shielded the : acetylene pototons - Hence acetylinic protons Stesonate at lowes field &-value. The chemical shift Value of ethylenic Proton's @ Bass. . e H + 4 € ae ¢ Et c) &) C4 4 NX ° H H € c « € ¢ finisobsopic effect in Benrene + Bentene is Oxtented ees to the externa magnetic eld 5 delocalisation of Tes cyltnolafeally over the asomatic sting, generates a Bu magnetic froxce - The © Moagnette field opposes the applied field at the centre of CcKoting je weinforce -[align) at outside the oring As a See the asomatic protons present astound the pertphesal oto the weting expestences highes magnetic freld than the Capplied magnelte held» Hence Signal ts erecosded at highes value oO) oO © Aniisotsopte effect In Aldehyde : c wohen aldehydic group 16 oxiented Pexpendiculay “tothe applied magnetic field. the 2° magnette field genesated by the cisculation of és of “c=o0" qroup, deshetided the Caldehydic protons: Hence, Aldlehidic protons siesonance at Highes © $-value- the chemical Shift value of alde hyd The hi : ic proton is Alc ‘ gh 6- value Of aldehydic Pporotons fs due to Combined © effect of high electronegattui ty of Oxygen & Anisotsopte © effect Produced by the Te®s of the Casbony! group ] O00000000Anisobsopte effect in (18) Annulene : Due bo Anisotropic effect, In [1] Anoulene the : Cuter psotons oe dechielded & the innex protons ene Shieloled- Hence outes perotons give Signal at $9:28 & Annes powotons qive Signal at §- 2:9 eee 6 Sees au Tnnex hydrogens -af Outer hydaegens ~ Fagg Ring ree (18 1 e®s) ('sJ Annulene 9 Hydeogen bonding + Hydaogen bonded protons absorbs at down bield 00000000 than the non-hydsegen bonded psotons- Due to high EN or the atom to which the pswton is attached [ hyolsogen bondi] The elechon denctky ound ts decreased as Compared to © that tre non hydsogen bonded protons: fs a result , the c hydsogen bonded Protons ane Slightly deshielded % absorb ¢ at down peld than the ron- hydsogen bonded psotons: Th& Shronges the hydrogen bonding, (The lowes will be the fad at Lohich the proton Aosorbs | the higher will be the © $ value © R—-O—H free state (in dilution ) © :eee R-o~ : i s . CHa —CHe fu, = CH ¢ & =o0gS 6-528 ¢ € C C C € ¢ Cc C C Cc Cc Cc C C C ©Spin - Spin Coupling : i The splitting of NMR Signal due to the muttal anfluence of Sptn Osientations of neighbouring powtons © tundes magnetic field fs called as Spin -Spin Coupling this Spin- Spin Guplings occuss through bonds. © These Couplings provides an information about natuse Sf « Cc no-of Heighboushood psotone In o Sample - : Explanation ‘ 7 In this phenomenon, ‘the Spining nucleus of O protone Udill be Influenced ky tne Spins of Neigh bousing protons in © e 2 ways Hp Hog 4p Ha Hoy, 7 e = Carer et —_ e ‘A ee, ie e x- type Nee e : lene In agwen Solution there axe approximately eqpa no: tions of X &% Y type molecules at any given time So 2 absosp' ‘intenstty ose obstesyeat for poten A (ire THO Nearly equal Tn the Same tea , prothh Sresonance of A Te Spite by peroton B) A also splits pxoton B Since proton A Can have & Spin states Thic genesal phenomenon fs called ac Spin - Spin Splitting C C The hydsogen on Carbon B has tue spin ¢ oxtentations: Tn x-type, te has +2, in Y-type it has nooc T n Tf n= 2 (arb) = ath)” = (0? + 2ab+ bY) = Peter = ats coo 000KTE n=3, @rby” = Arby = ab + 3ahbb+ 20h + b+ i = PY suru rscocre 3 ye 1344 @000 pin - Lpin Coupling 78 Common in 2 bond Separation neighbores (vicinal) e-€ Coupling toansmits Via {nter weaving Covalen™ bonds © thets e°'s but not through Space: igh Sp G@mmon featuves t ) Chemically ecytivatlent protons do not Couple ‘i 4 &e CHa el Magnitude of Coupling Constant mainly dependent 6n no: &f- intesvening bonds & Shuchwal wielationship blw protone tohich bore ‘Involving in Coupling ‘ > With increase in distance biw Pootons , coupling vatue © usill ke decreased . Types of Couplings : Couplings ore of 3 types ) \icinal Couplings 2 Geminal Couplings 5 Long stange couplings @ Allylic Couplings ) Homo allelic Coupling © Axomatic Couplings ) Vicinal couplings Protone altached to the adjacent Casbon atoms dee Called AS Vicinal psiotons: The Coupl?ng intesacHons bho these protons ase Called Vicina! Coupling - These ane Seperated br 3 bonds: \ - c c EE pS OOOO KDODDO000000000:0 in otTU is also called as 3 bond Gupling % have a Coupling ( pang ong — Goastant abbreviated Sy &) Ty ¢ e ¢ « ¢ ¢ DMOOOODDD0D0D0D0DD DA DDDADO Factors : Nicinal Coupling constant Jy. (09 3p is dependent on t- Athedal angle a EN of an atom 3: Bond length 4. Valence angle oDihedsal angle (8) : Angle of Sepesatfon blo adjacent Vicinal protons is CoMled aS dihedval angle oa c 1 "toed i ° | fe 8 =60 S cH Se h 4 SO of &. eclipsed Gouche 6 =4e nH \ ie, Ss Hoe Zorigd — when @= 0 or 8E—> Te lange i 8 <9 —> J. ts Small H Ana Relation blu Tc & © is given by kaxplus eqpation % kazplus Cusve Jie = A +E GSO + CQCE Hese A, B& c ane Constants.© ——= Dihedval angle fos vicinal protons uohen B=0 & [80 Tie 8 tela He PPA) Gurling 6 =90 T,..= Ot DHE min 5 Coupling vie Bt 5 He B= 60 Jyte = Kawplus ~ Cusve The Coupling ‘Intevactons blo cis protons are Called Jor, % Coupling ‘IntexacHons bli tsans protons Call Jasans Couplings Soa eae 5 oo oo aes sc ae oe ee ue UM a y c= Cc cc 7 Ne 7 N u cis trans (6-15 Hz) (u-18 He) In Grenevsal, tsans Couplings asie Stongex than cis Couplings e Conformatfonallty witgid cyclo hexane dexivatives axe bes’ examples for this porinciple- c ceet ae Es j Bond length Valence angle = B= 187 Taya = 84013 Ha ¢ He : eis : ©=60 He I. jee ¢ Te 7 SS He Ha ai < € ay a | ¢ vic ¢ ¢ The factors 4nclude the bond benglh Ree, the Valence ( 9 , Angles & & 9, & EN of any Substituents attached to the Casbon atoms will also fnfluence the Ty. value- ¢ u im ¢ s 7 4B, aH H 4 : nn wi 7 Los F Ly oS coe g val x ce lalence 2 ¢ elecho neaative sth les ¢ Bond teng a SaBetruente 3) Germinal Coup ling « Dh the protons axe attached to Same casbon Aton © ose called Geniinal pswtons, these ase Sepesated bye C Loads) Coupling fntesactons blio these protons ane called C © Gerinal Goupltng- : The Coupling Constant Jeger (2) Fy fs usually cheqative & With increase %! the angle b/w the Coupling © Protons Tgemn Nalue decreases moves to +ve direction. « C C c Mn, Me ee 4 4ene taen, loo” =3s H2 ios” = [2 He las? Ohe more than +ve se. Cyclo propane p> = -Yto -4 He Cyelo butane "J = -4 to -lU He Cyclo pentane TF nto ty He Cyclo hexane % = (eR to WY He Factors » The value of geminal Gupling constant depends on the hybridisation of Casbon beaxtng Protons As the S-oxbita) chavactex of the Ovbital *ncreases the Coupling Constant become positive \SEN al Cc CH= Cc 7 NY y ley tag OH CODD0D0C0D0AAOHOD0DOO0000000000 3) Long viange Couplings (°7) Coupling ble protons Seperated bay more than 3 ¢ bonds occuss Th olefins , acetylenes, osiomatics , hetevo ¢ avomatics & Strained sting Systems - These Couplings one Called long wrange Coupling @ Allylic Couplings Us) The Coupling ‘interactions bho allylic & oleftn Protons The allylte Coupling Constant bw O-3HE- an oO mD OOOO% / Cac i / Nu € Ty = 0-3 He b) Aromatic Coupling * ' TE involves Coupling blo meta Psotons, Coupltng bs Ll powa protons % Coupling bv oxtho Protons: Ortho © Coupling fs not o beng etange Coupling because the Ostho : protons ose Seperated by a 3 bonds: Ho : I y A ¢ i i ¢ = G-10 ene Fenn nH ¢ “o) Homo allelic Couplings The Coupling intexactons bio 2 allylic protons C ©Called Homo allylic Coe ltngs TE occtess very srarely & © the Cc & vewy Small & in bfwo 0-2 He- f ‘ —e-c= cc ) ¢ c c lr : Coup ng c “H : omo nuclear 5 wilt Heteso nucleax Strfilax nuclet Couplin " e different nucle? Couplen: : ‘interaction ) ( il tnteractten) eH ee bh Me c » SN « ae at oer ‘ Ree Re SipCoupling Strong Coupling 1) Three & lese than 3 bond Seperation Gk: Gieminal, vicinal , Ostho, cis | Teans a) T is loxge J Shovt gange Coupling 5 H-NME ! I* oxdes ) Bae 7 a) It follows (nt) rule 3) Tk follovas pascale teiangle &) Move Separatfon of Signals (widely Ai fferent Chemical shift values) 5 Stmpltey spectsum Weak Coupling 1) Mose than 2 bond Sepasa! Gupltng 2 Allylic, Homo allylic , meta} paxo. 5) = 4c lene 3) Long stange Coupling 5eov000 Non- first osdes (0%) 2"4 oxdey ) 6 Ates » . : a) tt doesn't Follow (9 #1), 2) Ft doesnlé follow pascdis wile COD9DFDO0A2HOO000 &) Mesging of Signals 3) Complex Spectoum Eallall oiiallaltallallollellellelt alts)¢ Poe Se NMR @ ¢ co The study of Casbon nuclei ‘through nucleas magnetic Gwreconance (NMR) Spectroscopy 6 An Important technique « _ fox determining the Sfeuctuse of Oxganic, molecules - ¢ FT-NMR Instumentations makes it possible to obtain © gwutine Carbon Spectra easily: « : ohon-equivalent Casbons & to identify the types CF Carbon Carbon Spectsa Can be used to determine the now of Kakoms [metny!, methylene, axomatic , Casbony! ete) that ¢ ; cmay be psresent in Q Compound + Thus, Coxsbon Nmap provides edizect information about the Casbon Sfeleton of A © molecule - Some vf pstinciples of Pswoton NMR apply to the co Study ef Casbon Nee & Structural detesmination is © genevalig easier with Carbon-13 NMR cpecka than With pewoton NMR Both techniques exe Used together to co Getesmine the Stucke of An Linknousn Compound - : The Carbon -13 nucleus c Casbon ~ Ir (%) fe the Most Abundant Totope Q © Ceaton, & WEIS NMR inactive Since it has Q Spin Of tev. © Combon-13 to "has Odd mass lo) odd no: of Netitsons ¥ does have nucleas Spin with T= We C But the wesonances of 0 Huclet ase move aifficul me observe than those of psoton ('H) “They axe about 6000 «Bienes weaker than powton sesonances for 2 major teasonsFirst, the natural abiindance of Caxbon -13 Tn; © vl = @ Ves tow (ve ri) Ina Sample, Tf the total no: GF’ 4 l P Cf ¢ casbone 1s low, there is A possibility to have very less © 2 nuctet (ow) No "& Huclei at all- En molecules centering 1% dookope - TE fs not possible to find to "S nuclet on. € C Second, Since the Giysomagnetic siatio ofee nucleus #6 A. Smallers, than that oF huydlzogen Hence aw adjacent ¢-atoms ast high abundance - "S nucle? alvocnys have wiesonance at a lower a Ehan hydrogens (pswtons) fe astound fy. ® 0 ¢ 7OOFOCOADD2DA00OA20000000; Peroton Coupled Specka - Sptn - Spin splitting of aw ob, OT The probability of finding two % atoms in the Same’ “emotecule ag low & the probabilthy of finding two 2% qtome adjacent +o each othes in the Same molecule 4s even lowes © Therefore, we wiasely observe homo nucleaz (Carbon - Cashen) Spin - spin Splitting pattesne wheve the ‘Interaction occurs bw ' tooo ™% atoms - ! ‘ But, if the protons attached to '& akoms, the Spfns cof protons disectly “intevact ustth the Spin of Cazbon % Cause © the Casbon Signal to be split according to the (n+1 tule _ (Splitting Signal can predict by nt! siule)- this is heteronuctea {carbon hydsogen) Coupling where the IntesacHons O¢c urs bfuo © Q different types of atoms: This ts Also called as one —bone ; Coupling because Gupling occurs by Separation of one bond © Splitting of Ne ustth the altached protons Seance 3 < atom with a attached The stesonance of & atoms, is Sptit into a quartet nit = ofl = OPpossible spin combinalons Tntexacts With Carbon to give O 4). Here the © Ai tfesent pear of the Multiplet - i tthe stesonance of a '@ atom with 9 attached casrotons, is Split into a triplet t& with 1 attached porotons , 4s spltt into a doublet g% with no paotons , No Splre ts possible - 4 4 al wl Ly i — y 1 \ H % protons Q protons | proton © profon¢ to € Cc ¢ © —c-H —c—h € C éTl Sal net = at) nteleitl N+ =OFl | te = = 2 =| C: n= no-of psxotons on the Same <-ator] i Methyl Casbon Methylene Methine Qua tesnary Caxbon Caxbon Casbon 090080083 C No: of Signals appears in the Spectsum depends ae one signal (Singlet) noro¢, Chemically non - equivalent Caxbons - € v ‘ i = . ji 2 ivalent —© te Nov of Signals = Noro chemically now ieee al cx: +) ¢ Cha —CH,-OH q = PED De ey ¢ “ a” ob e 2 SKE OF Non -eqrtivalent c-atome ay Ss 7 So, it gives 2 signals : c fox a8 3) cH ¢-chy ¢ b—ot au bow : os ° @ q ~ éh, +8 -oncl a 5 c i) CHa Cha e -0-CHy -s) cy Fete eH 7 a a a ~ Vv a v ys te © ¢c € eee ¢ ee Cc one Set of casbon © c Cc Nore + chemically non- equivalent Cavbons checking ig Same os proton. sa0ceceo®. ©) Pewton decoupled "e -spectsa ; Now a days the majority oF ee NmeR Specha ase evblained ac proton - decoupled spectsa - The decoupling techrigu Celieninates all Interactions blo protons & % nuclet- Hence , only Ginglets ase observed fn a decoupled NipeR Spechum © (tie this technique simplifies the Spectsum %& avoide ovet~ “Lapping multiplets ) Tt has the disadvantage that the é information of attached protons ts last - psroton clecoupling ts accomplished by Stmulta- porotons {rn the molecule usith = neously Twradiating all of the a broad Spectuums of feequencies in the Proper range - , Due to fryadiation (double); the proton undergo staptd Suproord & dounteard tsansitions, Among all theis Spin states : These saptd transitions decouple any Spin -Sptn Tntesackor blw the hydeogens & the & nuctet- © [ve by rapid changes, all Spin enterachons ose averagec on ero & the Caxbon nucleus experfences only this average ; Spin Gate for the attached hydrogens etather than > (ov) More distince spin States - © Proton Coupled % Pooton decoupled Spectsum of the Q- butanol ; 7 2 z 4 CHa — CH— CH CHa oH eono0od sana®) peroten ~Coupled 7 v T T T T sat 220 200 RO 60 Ho «120 «loo Bo GO Sc LPpm fsom TMs) ’) Psioton - decoupled TAA c i ee AO anaanernaannd7 : Chemical shift + & a: 13 Albsosption position of Signal in C-NMP Ts Called Cas chemical shift e "& chemical shifts expressed in parts pes milltons clPpm) from tetsa methyl silane (TMS) - The Carbone of fhe “methyl groups of TMs (not the hydrogens ) ose Used for the Pa “The chemical Shifts oppeas over a Stange of © © tO 220PPm ¢ Evesy non-equivalent Casbon atom in an Ovgante olecule gives sise to a pear with different Chemical Shi(t a This Chemical shige values ase divided into Y Sectors First Section Contains, satuvated c-atoms fsom 8 to 60 ppm: the Next SecHon contains saturatecl c -atom. With electronegative atome fron Yo to 80 ppm - the 34 section CAncludes alkenes; azsomatic % alkyne casbon atoms -fsvom ¢ foo to 35 ppm- Finally, the fourth section Contains Caxsbony Cosbons which appears at lotoest field walues fom C\SS to 220 ppm Approximate 'e chemical shite Ranges (PPM) : (For Selected type of Carbon ) Range (Ppm) ¢ pe of Caxbon C 7 R-cHs © R-ch, Cc Ra-cH i 3 c eat e Set ¢ Cc -N &-30 \e- BS Q0- 60 0 -4o 25-65 20 - 6535-80 Uo- 80 65-940 100 - ISo wo -t4o Wo - 195 1S5 - 185 ISs- 18S (es - 220 ©000000000000000 Electsoneqativity , hy bofidisation & anisotropy aul t affect 136 c.g value Tn nearly the Same fashion as H&s © 7OCOOO0O0O0O000000000o Nuclear magnetic otesonance Spectrometer + Continuous - wave (CAI) Enstyument RE (60-MHz) Oscitlatoy The basic elements of @ classical 60 MHz NMR CSpectsometes oie RE ( 60 MHz) Oscillatoy , Magnets, 7 Sample cell, RF detectos, Recosdes- ; In thie technique, the sample is dissolved Ia a _ Solvent (Usuatly ¢Dclg) % @ Small amount of TMS is © Added to Serve as an Internal sieference The Sample cell fs “a small cylindstcal glass tube that is placed fn the gap ble «the faces of the pole pieces of the magnet: The sample © tube fe always Spinning astound tts axis, £0 the test Cmoterial expertences uniform magnetic field. Also fn the «Magnet gap, & Coil fs attached to GO MHz RF qeneratef cThfs Coil Supplies the electromagnetic enerqy used to change ¢the Spin ovientations of the protons: in Ancthes coil is also Attached toa RF detector ¢ which pevxpendiculas to the RF Oscillatox Coil & it Steceives the Resonance freqsency ( enerqy) When no absorption © of enerqy is taking Place, the detectos Coil does Not — receiver any of the enerqy given by the RF Oscillator ¢ coil When Sample absosbe enesqy y the Mieovientation a the nucteas Spins fnducee a RE Signal fr the plane of the detector Coil: The cw NMR Spectrometes Uses @ Constant © frequency Re stadtation % Vastec the magnetic field © Stsength. AS the magnetic field Strength is Aneseased , HE Pulecessional frequencies of all the proton fncvease- tchep the Precessional foegpreney of A given type of Psoton smeaches G0 MHz, tre Te has stesonance . Changing ie field Systematically boiings all of the different types of - protons4n the, Sample Tnto stesonance & the Instrument mesponds by metording this as a otesonance Signal (oy € Peak. « Because the chemical shift of the peaks in Tite Spectum ose Calculated foom frequency di fferencest from TMS - So this type of Spectsum is Said to be a’ frequency domain Spectrum - »O0 0000000‘7 - 13 ' Comparisons between’ C % H NMR sop PMR che | Gionilarities ic) Te has a Spin 3) Spr c bes 45 2 pin quantum numbex T Yr 9 Te gives the information Coloout the no: of Chemi cally I non- equivalent nuclet Ic ) Tt gives the in formatton (> About the nucle? t (hybridisation , attached atoms) Differences 4) Tt is the study of Spin change -of peroton nuclet - &) Teis homo nucleas Coupling 3) Spin- Spin Splitting ic Very Common in 3 bond Separation oUre blo Vicinal pyotons) ) Splitting Signals poovides the infosmation aloout the Neighbouring poiotons- i) No: of Signal fn a Spectoum tells us how many different » types of protons. ) Tt has a Spin Spin glontlum number te I= Yo i) Tt gives the In formation Oboutk the No: oF chemically non-equivalent nuclei - y Te gives the information about the envisonment of the nuclei. ) Tris the Study of Spin changes of Caxbon nuclet 2) Tris hetevo nuclear Coupling Is) Spin -Spin Splitting is very Common in 1 bond Sepesation 4) Splitting Signals provides how many hydrogens osie ottached to each Carbon atom 5) No- of Signal tn a spechum tells us how many different types of Casbons§ Totegration tells us the No.of Porotons. +) Te gives the iindtyect informa: -tion of the Caybon Skeleton. 8) Gienesal chemical shit Tange 1-20 ppm 4) Grenesat Coupling Constant Values upto 20 Hz Wo) TL siequives Go mur frequen 1) Continuous ave & ET NMR methods axe Used. ¢ 9 Integrals are not used #ne cmMR- © a Tt Gives the ditect *Ofowret -on of the Caxbon Skeleton. €)General chemical shitt vange 0-200 ppm. 4) General Coupling Constan® slange 100 -Q50 Hz It) Pt wreguives IS MH2 - Frequency. iD) FT NMR method fe Used. -ODOCOCOCOOOCOCO000000000 Fo0000GROUP CH, CH, Ar—O-H R-NHp 9 I I R-C-NHy SHIFTS: 1 PPM —t=t— 1H - NMR VALUES BASIC VALUE 0.9-1.15 13-156 15-176 10-146 9-116 05-456 4-865 05-56 5-865 1.5 PPM | NH, i —S-R GROUP VALUE R-S-H 1-26 Ar—S-H 3-46 R-CSCH 1.5 -2.56 R-C==C-H_ 45-656 Cp 65-86 2PPM. 2.5 PPM 3 PPM —OH —F 1 —0-C-R‘Type of Vibration Frequency Intensity Page (nr) Reference cu Alkames (stretch) 2000-28560 8 a CU (bendy 1430 and 1375 m CH thend) 1465 m Aikenes (stretch) 2100.20, m Be loutof pune bend) 1000-080 s {stretch) 3150-3050 s a (out-of-plane bend) 900-090 5 Alkyne (stretch) ea, 3300 . 35 Aldehyde 0-280 w 56 2800-2700 w cc Alkane Not interpretatively useful cc Alkone 1680-1600 ma 33 Aromatic 1600 and 1475 mw a3 cc Alkyne 2250-2100 mw 35 co Aldehyde 1740-1720 s 56 Ketone 1725-1705 58 Carboxylic seid 1725-1700 5 62 Ester 1750-1730 s 6 Amide 1700-1640 5 7 Anhydride 1810 and 1760 s B Acid chloride 1800 n co Alcohols. ethers, esters, carboxylic acids, anhydrides 1300-1000 47, 50, 62,64, and 73 Ont Alcohols, phenols Free 3650-3600 a "7 Hebonded 3400-3200 m 47 Carboxylic acids 3400-2400 m a Nei Prinary and secondary amines and amides (streteh 3500-3100 m ” (bend) 1640-1550 ms ” Amines 1350-1000 mies, 4 Imines und 0 1690-1640 wes 1 cen Nites 2260-2240 m n X=C=¥— Allenes, ketenes, isocyanates, isotbiocytiates 2270-1940 ms 7 N-o Nito (R-NON) 1550 and 1350 s ” san Mercaptans 2550 w 8 S-O Sulfoxides 1050 s 8 Sulfones, sulfonyl chlorides, sullates, sulfonamides 1375-1300 and s 82 1350-1140 OX Flucnide 1400-1000 s 85 pride 788-540 s 85 < 067 5 85 Scanned with CamScanner