tabela do espectro infravermelho, Esquemas de Química Orgânica

Baixe tabela do espectro infravermelho e outras Esquemas em PDF para Química Orgânica, somente na Docsity! ESPECTROMETRIA NO INFRAVERMELHO UMA PARTE DO ESPECTRO ELETROMAGNÉTICO VIBRAÇÕES DE ABSORÇÃO DE UM ÁLCOOL FIGURA ESQUEMÁTICA DE UM ESPECTRÔMETRO DE INFRAVERMELHO O ESPECTRO DE INFRAVERMELHO VIBRAÇÕES FUNDAMENTAIS DE INFRAVERMELHO DO GRUPO CH, A A H x E MN gr Estiramento simétrico (-2853 em 7) Estiramento assimétrico (--2926 em ?) VIBRAÇÕES DE ESTIRAMENTO Scissoring Wagging (-1450 cmo) (=1200 em Ea A “mf / e 4 / L X Mm Rocking Twisting (-720em 1) (-1250 em NO PLANO FORA DO PLANO VIBRAÇÕES DE DOBRAMENTO VIBRAÇÕES FUNDAMENTAIS DE INFRAVERMELHO DO GRUPO CH, CH, / Deformação axial Deformação axia ormução engular simétrica simétrica (y, CH,) assimétrica (v,, CH)) no plano (à, CH.) 2853 em em e Deformação angular simétrica fora do plano (balanço) (mCIT,) 1350-2150 cm! assimétrica no plano (torcedura) (p CH,) 1350-11 CÁLCULO DAS VIBRAÇÕES DE ESTIRAMENTO Eq. DE Hogke . 20€ 1) My Met My D= qreç. vibraciama| c= Velc. de hz $ = comsl. de gorço de ligação (dias /Cara) My My E MASSAS dos átomos x aj (ums gramas mw = Sib F 5x4 dimos/cm —» ligação simíples * 40 o o —s» q ” sx 108 » “—s E 1 upla.s = 4 ” triplos Me = 19,8 n40 A = 464 x 4a a ] l--'-..L,..&....1..l-......_....1-.......t.lJ·w...!..!,,. l.l.l,,1.1,,1..u.1....L.!!....1.LL.11.L II.U.I..LlL.l..l..4.,l.l,l,ll.l.ll.l.Ul,l,l.llll,Wl,R,.J..:l. .WiW.il..i.lJlliW:ll.lll...iL!I.Ju.la.l.li..,. :: o.t11I1---,_,.-.--..-...._ II moo 200 Q:D I i Z5 3- 4 a J 8 aoo .----1,....,.....,.....,..,.._. .1..-1.....L.11......,u...J............._........,.. ...LJ...jLY,.......'--'alJLLL.Jb!--u. •W111oW11.11.1.1..._...,1,W..w.t.uu..........._.._.._..........,.........,,,_,J,1..,,t1-,..,.t ..,.,. ... fI1215llO30 +o t ILL! ;;ioog A. (-,' 111, 'It:/: {,t!t! l!q11re 8}. D, c-K Ii.ind (,1.u l""ifli.rt JIJ, 1"1!1!11,SO /J f,I 'flll·nlhir!d pmer ' l,a11J UU-119 en -•. CgwrJxm: the· ki:t,. 1111· .r,o,C'l;cln,r b fl'' {t f OlJ.l(JOfJ cm I J r tlJ r [l;r Pi.gtJr.6 • trr, (3. l 1 (7.2 . 11:ii C!l3, 2926 c;;C {1.4:J , QI CJ .a ,, -t. 1450 -1 (6.90 ) 6 J JI' VELE TH,,.. gl,.Mr 11.o C ill! Figr., J 6,) ra. ( , CH stretching frequencies TABLE 2 ALKENES (Non-diagnostic bands in italics) (e* in parentheses) 1) =CH, 3080, m (30) | vas CH, 2975 band overlaps with alkane absorption, 2975,m v. CH Bands higher than 3000 suggest presence E areia of unsaturated >CH- (alkencs, aromatics). 2) =CH- 3020,m rCH, Substitution type (c* in parentheses) ALCENOS (Continuação) duDstitution type (“an parentheses) ant c=0 BIC CH (outof:plane) Fi Ty » o & CH (out-of-plane igs. E (aut-of-plane) in-pláne) º 3) R/CH=CH, 1860-1800 | 1645, m (40) | 1420, 9905 (50), and 910 s(110); (term vinyi) | m (80) a “ea tº ame region 590 = asio Table 1, Cut me 14-16. o 910 H 1300, mw Dec a H *H 4 RA 1800-1750 | 1655, m (35) | 1415, 890 s (100--150) OC) >G=CH, 40 m (10-20) He R m (86) . Sant Same region Eta (term. methylenc) asin Table 1, 4 H 416. 5) R R 1660, m (10) | 1415, 780-675 m (40), ambigu- pega m (10-20) | ousand variable. OM) H H . Srecé (eis) egg? 5 Ra? 1675, w (2) 965 s (100) o O) no pe SH De=07 (trans) ºm 7R Rº 1670, wm 840-800 s (40). Vibration ) s 04 of single H;not as useful OM Rr ho as others. (Eri-subs.) BRA 1670, w No outofplane bending qi O gm Intensificd Alabgent], Et if honded JC=C-cH,- may be de- fietracanha.) fitectigso tected by 5 CH, bending sec (Table 1, 15). ALCENOS (Continuação) Conjugated double bonds Group “ C=C & CH (out-oE-plane) Figs. 9) Diene 1650 and 1600 Position not affected much by conjugation. “The trans 965 band is sometimes shifted to 990. The cis band is usually found at 720, occasionally as a group of bands. 10) Triene 1650 and 1600; sometimes only one band; sometimes addi- tional shoulder on 1650 band, trans-cis-trans and cis-trans-trens systems have bands at 990 s, 960 m, and 720, o) 11) Polyene 12) Enones Broad band at 1650-1580. sec Table 8 [p. 16). 990970 if trans-double band present. PADRÃO DE SUBSTITUIÇÃO BENZENOS SUBSTITUÍDOS Folisiotnira te as [o e us om [o e 6 PARA FERHAR REE! ) Í É z ] ij = = 3 sos ps ii E. à [ E 7 À h bet inombiu "DES TIE] k : T mea WA [7 CChR BEI, v Tr si - h TT ER ERREER! s ves] ums EN, Pa Rd | f E “ / + f + e a] ve ma 1:35 Ermsleaid : 1: K PADRÃO DE SUBSTITUIÇÃO BENZENOS SUBSTITUÍDOS Amteugaruted HR Squeetrum AA TA E | a) LM | tattedara | bi táiga ' 4 fé Espectral de benzenos substituídos mma monossubatituido Em E CHa És di! num Ea. estiramento | R CUT TH? estiramento. » CH monossubstiúído o torardo piano | estiramento nto ÓcG a G aromático ado como o uu ao cg TT go ui mo 106 são E “oo 1500, END Cu Espectro infravermelho do tolueno (líquido puro, placas de KBn). qa pç a SEXO ortossubstituido «” Ea CHeCHa . | E > CHzCHa É º 7: estramento o E) 2 - - mm - - A sp estiramento ortossubstituído os estimistito C=G aromáticô. "77 forardo plana Vir CH . Cad a to Camo am Camo tm Eccm tom as ET a NUMERO U= NDA fot Espectro infravermelho do orto-clietilbenzeno (líquido puro, placas de KBt. am2s 5 e 5 5 metassubstituído £ CHECHa É a "estiramento | o CH? CHsCHa EVA : estiramento — iramento ] b e + is C=€ aromático metassubstituído fora do plano Cao aeo seo Caos amo so amo ts Cimo ico Jos ao emo “ão vação ne ontiaicu= Espectro infravermelho do meta-dietilbenzeno (líquido puro, placas de KBr). maêb Sa com e gua 9 a a : ” | : ms CHeCHa pareisubetiuido " : o a CHaChHs parassubstituído e Betsp' w. estiramento “Testamento Torardo plano “ C-Hspê 777 /C=€ aromático TUTO Soo ame ato “amo ato ze amdo remo ráco taco Uagoo! "é em! se NÚMLHO DE NDA estar! Especiro infravermelho do pora-dietilbenzeno (líquido puro, placas de KBn. 1'"-ihc I M i.i:111 ·II: !Jl'IU.lld. -• -"'"-- · . .. p. . <Ft- .. I .,,. .. • .. SRi.iw Y!!:f:>l' 11 L011-· O'} <1l ;2-iLQ!O..;. Dl'iiel,b1 ill, ,In :p. yliici.l t i Ii. J I.I 6} h.«y,11n1, ·.... ........ . ;1I •. OOAON!I.1' -- .t. 'P estiramen/l'O c-H - I esttrarrumto C=Cii ofHz-N-c q _ aromatiOO-J" L II mo oos-.ibstlfu.Td'o fora, _p_!ano I I . IJ 00 :!BOO2400 . 1 600IA(IO121,1!1100D I -· iro e;J(I, e.. . '·. lB@ ... (H.' FIO Ci! ' • Espectro infravermelho de i5ocianato de benzila{lfquido puro, pla·c.:i,s de KBr). 1TAB1.E A : Jt;; .M GROIJP.S ® liABlE .ii, 2: GltQUPS TABLE 5 · AL<;OHOLS AND PHENOLS Tobie·Sa O-H Stretch. ing vibration St•te of OK cm·• •• Shape Rcmuka Figs. Free (monomctric) 364-0~36l0 so-100 sharp Dai mc:anarc-d in so-Qfled non- polar (CCI,. CHCI,, etc.•) dilu« solutions. . Water ab.sorptionat 3710cm·• whc-n solution is da.mp. 6 )rs---Olf r-OH • phenolic OH 3640 . 3630 . S62.0 3610 70 60~50 45 2) -0-0-H. bydso- P._c:roxidc 3560~SSSO[I . . latumol II-bond. S) dimcrk S600~S50'0 . . r.ithc:r sh.up Usually hidden in polytn(ric bwd (oidt> infra) unless·,po1ymer for- mation is hindcTCd by stcric hin- dt:11\(C• Abso_rptions .irising frcm H•bond. with poW' sol\•cnu s:uc.h u ethers, kctoncs. a.11d amines also appur inthis c,:gio•n. e ) polymeric S400~3200 . . . strong .. broad .. • With solids and•liquiJs, this broad ab50rption is the only one ob- .scrvtd; in dilute iolution.s. aC• companied b>·monomer band. free md usoc. ., NH of amines and amides alsooppcor >t 3500~8200 cm·1 • First overtone of' IIC=O (ca. 1720 cm·•t•lso appcanat 3500~ MOO cm-J. but can be diffcnnti· atcd bccuusc of low. intensity, ,a< 10. ..Water of crystaDizatK>n: &.bo ., S600~SIOO cm·1, but not ,. strong and .sorncwh t nan'Owcr; wo wc.,k band at 1 0-1615 cm·• (H-0-H bendingvibr>tion). @, 22 @ TAB E 6. ETHERS AND RELATED GROUPS e• o( vC-0 bands are usually greater than 200. · -· - .. -·· Croup BaDd (cm-1) Rcma,k, Fip. 1) EU>ttJ. scntta .l alt.and ri°Qf -C(l) 1150-1070 C-0-C anlu:ym.1ltttd1ing:.Commo-r\ withothtr C-0bands. £!1«1of o-bru,chii,g unolur. Qv uom. aDd vinyl •C-0-C 1275-1200 Antisym. rtrctchlng. Common with orhcr •C- 0. So-allcd "1250 cm-• band." .0-C or vinyl ethcn intcnsUicd,. Sym. flrcldling. Weaker llun 1250cm-• nd. . 1075-1020 . Mcchoxyl sroup basfollowi113 b>Jld, in :addition. alq,h. 28 < 3 •· 0- 2815. CH, ,ym. mc1chiftg. Yells in -OC,H,. The asym,.1rc1ching is., m0-2970 (pr<,cnt In -OC,111) but position is no1>-chan<1<ri11ic.-OCH,IZJ 50) arom. -OCH,1'1 2M0 CH, ,y111. nrctch1ni. Fonowing b1ndi 11,o pracnt,butposition oon-charxtcristk: SOOO, 2950. 2915 (thc3a atastriplc1S), 1<160and •1340,(ICH). l250 -C-0-Canti,ym.stretch• "'8), 1180 and 1125 .(methyl rockin.g•Del arorn.7);1040~1.020 (-C-0- Csvm.sttctch•••I. @ .. - -- 4) Spltok<tal or stcioidal , Apoat.nins(l,61 IS50- 650 bny cllanctcnstic sh"'l' band,. 5) Epolty (1,7,9,IZJ < sooo (.a40) 3040<•·20) ·S050<••30) .Epoxy mcchinc group or chain compound, aDd ·11ninlu1 rinp. Epoxy mcll>inc g,oupofslnlin<:d rinp. Mcthyl<nc group or tcrmin.t epoxy nni:$. ·@ 1250 So "8 µ band..; •ym. m,tdling or rin ,I' 960~ 810 So <d "II µband": uym:,intching or “e TRANSMITÁNCIA, SETRANSAITANCIA Espectro IV de ÉTERES nús so - : so | CHe(CHp), —-O-(CHo),CHs | : “ dibramentids º dobramentos TH, CHa emma aaa a - | CHsp?- : - " w 4 estiramento estiramento C-O “emo eco seo ido amo esco HO ago aço O ti06 eo soá sem “ao <aço DE ONDA K Espectro infravermelho de éter dibutílico (líquido puro, placas de KBr). so estiramento - o CHsp2 a . CoHspê Jo 7 o estiramento CO" ss E=C aromático 2 monossubstituição fora: do, plano “estiramento ” 11 PAL palha aa 1400 1200 Cs 200 soa E o . “oo Cêso ao 2a ati 2000 iso Uriêgo NÚMERO DE NDA icta=) Espectro infravermelho de aniso! (liquido puro, placas de KBr). TABLE 8 CARBONYL GROUPS (Bold figures denote vC=O) Croup Band (cm-1 ) Remarks Fig$. 1 Ketone -CO- .. . . . . .. . . ........' .. I a) o., P•un53td. I b) Ar-CO- 1 c) «, 8..,.,6•uruatd. 1 d} er, D•o.',8'-unsatd. 1 c) Ar-CO-Ar 1 f) l>-(;0-R 1 g) 7 mcmb. and larger I h) 6-membcred I ;) 5-membered I j) +-membered J k) $-membered I I) a-halo• c;:-r XO (X:halogen) Im) --CX1-CO- and -CX-CO-CX (X, halogen) 1715 1100i•Hph.HI~ ?•? • •\• ! v ;-! 1, 16n 1690 1665 1695 1705 1715 1745 1780 1850 shift of 0~+25 shift of o~+4S a 300...,.600. Values of CHCL, solutions and solids, lower by 10~20 c : m- 1 • V..alucs of gases., +20 cm·1 , OccasionaJl)' over• tone at ca. 3400 cm"1 • e3 50~150. C.'\used by C-C-C bending ...a.n.d.c.-.c..,m..:t.c.h.i,.ig..o.f .-.C.-.(C..O..)-.C.-....... i-C=C shows c-lear-ly 3t 1650~1600 cm-1 ; in i-cit {OM'O$, may be shifted below 1600 ct.0-1 andintensity becomes com- parable to that of vC=O. Affoctcd by I, M, and stcric effects of substitucnts. Conj. with c:yclopropane lowers by ca. 20 cm-'. Same as standard value. Shift caU$ed by conj. with un$.,td. groups it same wilh aliph. kttones. Shift caus-ed by conj. with unsatd. groups is same with aliph. ketooes. Shift to higher freq. is larger the smaUcr the angle between C=O and C-X. No shift when angle exceeds 90°. Following \'alucs .tpply to td . .a.liph. .tnd cyclic kcton<.:s: -CJ, 0....+25;-Br, 0 +20; ..1, O....,+lO cm-1 Effccl of single halogen subuitution air pears addith·ely. Shift of +46 cm-J results when Cl on both sides of C=O a.re in sameJlane with C:1:O. C xistencc of sevc.r conformers ive rise to each corresp. band, the rcJat1vc intensities of which arc dependent upon state of mca.<iurement. .e..,. @...\ e.@ e e @ e Espectros IV de ALDEIDOS nicrons e sw vos up 1? = 7º — harmônicade |. banda de Em c-0 Ria o cadeia lônga º É aldeído CHalCHa)CHaÇ-H ao CH Õ zo . estiramento | no . c=o o CHspê estiramento Os » 1 vi na aco 2800 boo Como aum 2000 caso 1800 tdoo rico one amo E “ee NÚMERO CE QNOR ot) Espectro infravermelho de nonanal (líquido puro, placas de KBr). sosons a 4 : : To Ss Gm RAE 2 £ É . É o estiramento Ma k Emo CHsp dai H C-H Ê C-H ô Es aldeído conjugação” & a estiramento e C=0 a CHsp conjugação do t 1º : Nes estiramento CON pans tora dóplano o in na 1 aa so aso amo Bgob O Rio ER E amo “09 NUMERO DE ONDA (= Espectro infravermelho de crotonaldeído (líquido puro, placas de KBr). nicrons am2s 3 4 5 e Todos po msg gas " & - estiramento — C-Hsp? aldeido CH SL TRANSMITÂNCIA - -conjugação do Cc mo - estiramento 0) aromiático...... mienpssubstituição 10 - fora dá plano o 1 voa e a e amo amo êooo amo zum do iso 4 ao 1a06 são co do to qa + NUMERG DE ONDA (CM) Espectro infravermelho de benzaldeído (líquido puro, placas de KBr). ÁCIDOS CARBOXÍLICOS 3000-2500 1760 (monomer) 1710 (dimer) 1420 1300-1200 920 3 a) C=C-COOH and 1720 (monomer) a Data are mostly for dimers because H- bonding power is unusually strong, and they exist also in gas state. Very characteristic. Group of small bands. Band at highest freg. is due to vO0H, and others are combinations. 3550 cm”! in monomers. Considerably stronger than ketonic »C=O, up to 1500. Two bands may be ob- served with gases or solutions. Both due to coupling betwcen in-plane O-Hbending and C-O stretching of dimer. o--H—O Cs na à Broad, medium intensity. O-H out-of-plane bending of dimer. 2 Ar-COOH 1690 (dimer) 3 b) c-halo Shift of Values for «Br anda-CL Larger foro-F, +10-20 cm"! ca, +50 em t, - 4 Carboxylate 1610-1550 and C-O antisym. and sym. stretching, resp., (55),(G0) -COO- 1400 o of CG E So When an acid is converted into its inor- ganic salt, the five characteristic freg. are replaced by these two. Instead of being converted t6 inorganic salts, they can be changed to ammonium salts by adding few drops of Et,N to CHCI, solution; carboxylate jons are not formed in CC while addition of NH, or p-amincs gives confusing NºH, and N*H, bands that overlap with =COO” band. • ... • - f-llEOIJEtrtC'f" ICM'"') ......• ' e .....I: WAYflENGTH ,- ' ' 0. • " " .. ,. .... ..,. . , .. . ...... .. Q\Cff,fCl'l, ei-. - O':I • u • "" ,.., "" ,.., • • •.... .... ,... ,... .., ""' ... ... • LACTONAS [ Group Band (em!) Remarks Figs. mo 51) »=0 1770 — o 5m) 1840 o 5 n) [e 0 1750 when a-H is present: |In nonpolar solvents (CCI,, €S,), the 4 O: Si) = 5 >=0 o 5) =0 1785 and 1755 (doublet) 1770 1790 1735 1720 1760 Table 10-4 higher band is stronger, while in polar solvents (CHCL,, CH,CN, CH,OH) or liquids and solids, the lower band is stronger[2]. vC=C is weak. Around 1780 in nonpolar solvents, and ca. 1760 in polar solvents; affected by polarity of solvents. Influenced by M and other effects of substituents on arom. ring. The band is not split, contrary to a, &- unsatd-y-lactones. vC=C at 1660 cm” (s). Same as with aliph. esters. Same as with aliph. esters. Same as with aliph, esters. vC=C at 1685 emo! (5). a-Pyrones. See Table 10-a for py rones. ANIDRIDOS Acid anhydride 1820 and 1760 Relative intensity of two bands variable. aj Band separation usually ca. 60 cm”, ABA but this may differ from 35 to 90 em-i according to type [8]; lower band absorbs near v»C=0 of corresp. ester or lactone. Higher and lower band, resp., is stronger in acyclic and eyclic anhydrides[4]. 1300-1050 1-2 strong bands arising from C-0-C portion. acrylic- or benzoi 1785 and 1725 6-membered 1800 and 1750 | AG=0, 50-70 cm'[9). a, Bansatd. 1780 and 1735 | AC=O, 45 em”! when double bond is endo | (67) 6-membered (75 cm"! when exo) 3). 5-membered 1865 and 1785 | AC=0, 80 cm-![3]. maleie 1850 and 1790 | AC=0, 60 cm. 1790 em”! band is split and behaves similarly to 5 m[3]. phihalic 1850and 1770 | 1770 cm"! band is split and behaves simi- larly to 5 m[2). Val o o w E SE CHyC- 0-0 -€ Cho LD k E j b Epis pisa ij trt TI pi ipi edisri do JA Adil 200 ato 3000 E E] toy nao 1200 1000. dom eso «00 FREQUENCY pet Group AMIDAS Band (em?) Remarks Figs. 10 Amide =CO-N primary -CONH, secondary =CO-NHR- tertiary Free Assoc. two at: several: 3500,5400 3350-3200 1690 1650 1600 1640 3440 3300 3070 1680 1655 1530 1550 1260 1300 1650 1650 Complicated but extensively studied.[1] Influenccd by state of measurement as with -COOH. Data for both free and assoc, states are given. vNH vC-0, “Amide 1 band.” Mainly 5NH, “Amide 1 band.” Shifted higher upon association. Solid specira of -CONH, show two strong bands at 1650-1640, but “I band” is stronger. In concentrated solutions, all four bands arising from free and assoc. states may appear. vNH, 3300 cm”? band considered to be due to trans assoc. form (structure [ in figure shown). Band at 3070 is due to first overtone oÉ N-H in plane bend. In cyclic lactams, 3440 when free, and 8175 (dimeric, structure 11) and 8070 em”! when assoc. (3800 lacking). “Amide 1 band” Mainly 6NH, mixed with vC-N, “Amide 1 band." Present only in trans amides; in cis amides (e.g., small ring lactams) it is weak and shifted to 1440 cm! Mainly vC-N, mixed with SNH, “Amide HI band.” Shift in positions of free and assoc. vNH and “Amide I-III bands” is consistent with assigament. Thus contribution of limi structure Ib is enhanced upon association. R H R a oh C-N ec C=N 2 < Roo > a (la) (1b) Vo “ pi N-H O dimeric lactam (11) Solid IR of amides are, however, especially sensitive to crystal orientation. Effect of substituents may thus not be exerted correctly, and a slight complication in structure may prevent the shift of “1” and “II” bands to lower frequencies in the solid state. In concentratéd solutions the assoc. and free absorptions both appear. Since H-bonding with NH is absent, posi- ion is only slightly higher in the free i =O groups).