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Spectroscopier

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Abhishek Thakur
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118 views68 pages

Spectroscopier

Useful for upsc

Uploaded by

Abhishek Thakur
Copyright
© © All Rights Reserved
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ere page Howhback kage 630 53) vil) Hy CH04 4, CH Cy NH CH [born back FRM, Ty NHy — mol 3 Ha NE mye 62) UN) othe ef —= iran beck © 536 ) = (ans J oO or | a | xi | ) Yost icontl oT Hh xii) PRgos and LAN HW xiv) & } See ate ay eo Cp aly ot Ca xvi) Hac = CHOU, Cd Hy Hy CHO 1 O 4 xvii) caer =n cH, ord cy, E ey ot =e xvii} HOS Cony omd — CHy Cgc EN XIX) arcocty arch G4, = cr cH, Oh RR) CH, Og woH and OH CH, Fig © x) a bubpe, 1)3—bubadine amd a-bubyhe xxii) Hype amd cH, OH yoelad Me muavry xe) cyclohexene and t-hexene 12-2 (b) Ne murrry oe XXIV) CHy chy COOH cm HD CHCHyCHo 1262 | Mcmurey i) OncH oy Cen, | Ceo sty 1700. cw! ° ound on AHS a oy e Fermi vesonance 220-2 mop c=0 ctr 2740 on! ° Coty oh, ° it) ie lon amd, a See. 9735cn! cao cy, 1715 aq) ° : An) acne sid-ocn, amd a, waco Lo, 4 CoO Me 17)/Scn Co tr 1730 cot oh Ste mig O-H str 2600~B200/ very bond) C—D Str 1200¢7 C=C sty l6S0 em! (Character fel ¢ rea) CHC Gy §ezocm . wv) Chg My CH = CHy CH, Hs Ca cH =C-H Boboan! =c-H Boca! O.cee 16S cm! CEC 2150-2400 ews! : , —H ”) ar Z ao) 2830-2700 ci! aap Aoyblet which 44 vot present an kere (ocetophenare ) t bia, 2 vy A. F _onlA) am aig These ave pot Rr SS ois cei aes cui? tw canpd (A) Soom 275 5 2 ér0~1080 cant WW ancl Ch OH, NA CH, CH, has two bends in the 340-350 vii) Ong Cy Og Hh NM» Ant: The primary amine az region @lere ad the seconday y awine has ody one, =. amd > The termina? alkyle (at the right) will have a cher} nt due te BCHH Group, Both wih yi ii) = bara at 3300 cm have fegks in the 2150-2400 cmt region clue to eee grour dude the bemol fron the terminal ° Odkme wil be more Antence because it ia lesa gynmetrical. Twpra ved Spectroscoby ~ S) Comment on the indicated o- amd c=o Styetdling vibrations Tey the Stereo isomeric pairs: 1,36h4 @ 11,3689 Ond Ssso om ty T , 3548 omd 1703 cmt anh IE, S635 ond 1793cmH4, congo” aoe come cog Me AG) w Uap °* ay OE Wt cis stevenisomevic fairs of combound I ond tr and TE ond Ww only One member trom each baiy permits hy drogen bonding Jeading to Jowering in the o-y amd cao Stretchings, whe ores ’Scome O=come : EE Ore a w on “s " 2 Ie 8) ecters of o-chlorobengcic acid show two cao stretching freqtencies. Explain. Gs Tn O-chlo wbengoic acid esters the field expert the cao prequency dn the rotational Asomer (sae ) ancl not jn the ASomer (IE), Novimbly both isomers are Present, so thar two c= stretching absorptionc are observed, CH. fie s oF ot a mek +2) les) here in isomer (2), «a near the C=o ground and its negative field repels the ron-bonehing dlectrone of the carbony 0 ongacn. Thus, the Yorce cnstant of c=0 bond 4s Increased resulting in shitting of the C=o0 ctr to @ higher +requeneay, Cuch chiftdtes not ocuy An the isomer (EL). so cso Sty in T) & les tom DO. Q) How com TR ond UV Shectroscopy be used to determine when ‘the pollmcing veaction Ws completed! o i as Zz 1 A, Wye~ C= CH= CoH nyc- oro | i > ge — CECH CH = ony C— CSCH Eh — es Ay Sdlitont— the Uv Spectrum of the starting material ui shoo Amax ck 237 amd Sto nm due te conjugated C=C ond C=o grubs vespectely, There amds wilh dlissappear on O Completion of the veaction. Similarly the T-R absorption bomd in the segion 2665- 2685 crt due to conjugated C=0 group (present dn the Starting materioh wth dissabeay on completion of, the reoction, Tr addition, A pew TR absorption bomd wi appear around 3330 cm due to hydrogen bonded 6-h Qyoup. S) Dh the cubstitated phencls the o-h Stretching ua ak 3608 crt in (2), ok 3605 amd 3643 om inlae) amd of o E43 cm in (Ir). Explain. on UH ® wD (uy | PE ah pet-butylphenst (2) oly a single hyclroafl frepency 4s sem ok 3608 cm*che to arrocated oO group [intermale calas), Tn the 0- isomer (TE), bands are seen od both 36S and 36US cmt Showing thot in some mitecules there <4 ovmociation Whereas in others the OW da not hydwgen bonded due to crowding by 4-butyh-groap. Tr 276 di-tertiory butyl phenct only a single hydroxyl freqpency ta seen af 3643 cm! Since two ditjerert molecules are not able tp Approach close enough to jorm om interindeclar hydregen bond. B) 2-lyclrory- 3—eee vikro Gcetophenone showas two carbonyh cbr. frequencies at 1632 amd 465e cml, Exphain, Bos a on tare due to Competing hydrogen boncl Noa formation amc therefore as q veubtop — cH the equilibium chown below. | ae RAN «a Ommn, : eee | we Mee nae I So ae C=0 Stretch. However,on association with the on group the The structure with free CarbonyX shows the hormah conjugated | C=0 Stretch 4a further shifted to Lower frequen (heassvcid) 8} o-Nitvophenct hoa am o-K bamd at gac0 cal iin kKBy pellet ag WAY ad in Ctl, Sdution, Dheveat in the para isomey the | © volues ove ditierent in tuo media (pellet 2380; cucls stati, 3520 crs), Gyplatn by writing gkractures amd their effect | on their vodablity. ©. | ions SO - a or” | ot \ govt phenat) he a Ph Ne | more volatile because of of ~ En ZR, : —nityobhernck Nony-the feny — le bree ntl 2 not cides by medium ies bonding ) a in pellet but har See aaa ection H-bonding dlimishes in ches «olution ee net) due fees dilution wedng dn bat aka oe @) Predict the frequency Skit of the carbonyl absorption in tee aldehydes 4-3. O=c-Hs, n-C=o Bwcco " gy. ww B Ww Ant: Cyoloherome aorboxaldehyde 1) pdeing saturated uh absorb cround 4730 cw, Tn bengaldehyde (2),the alocorption will be Shifted de to lower trequency (4700 cmt )due to conjugation, Tn sobioabdehyde (3) the internal chelated hydvog en bonding comes a further Ravge frequence Shift 0 axom 1666 om, An acyl group is veadihy detected from the TR: Spectroscopy Sinee the Cao sty frequency varied with the junctional group 5 Le with G. From the following trends tin the strong carbonyl Sty absorption peak in the 1700 cm * region, identrty & porticular acid devivelive in each cue. (nr! AG) ‘\ syoo-4eas cm (s65-5-54p) ° i) Aye0—4ng0 cmt amd 2800-4850 cm* (two bands) Wi) aya0- 4750 cmt iV) 1630-4690 aa © Pes i) Acid chlorides Redo . © i) Esters R-L-or ° ° ii) ombydyides_R- E—o— Cag ° WV) pmides R- C—WHy &) Certain acyl compounds, eg carboxylic acida, aldehydes amd amides hove turthey distinctive features other than explained An the question above. Explain. dn the ior Boo cmt which ds absent in esters, Furthermore, carboxylic addy showw a c~o Sty Frequency ait ~4A5O Ct, Where ad CHo Stretching in esters rormabhy Occurs ay two relat ay shong oo din the region 4050 +o 4300 oat > Bidshisledamd etre shoo no Gheabtion dn thi broad region Hus they ave readily Cistinguishalde ram Carboxylic gc <3 ¢ ics and ertey Amides diplay ny Stretching in the oso +o 3640 ont Fegion and chow amother Strong aborption band in the 460040 4645 cyt region due to N-H bending. | | { Q) Using ER spectroscoby , how coil You distinguish the following Asomevic compounds ) be] IgG, C= CHS amd Chace CU fms Hse C= cH vodl show Strong absorphon boancly ek *~ 3300 cmt, 2400 amd 625 cm* due to =c=4 Stretching, cac stretching amd = coy bendling vibrations Bier 6UL, these Lands toilh. be absent in the IR Spectrum of SMC HCH, TE chould be noted that reac Goma wilh dio be absent din the DR shectrum of ACS cen, because the Symmetrical cubctituton males the crc shy ze inactive. b) y= Ch-0 cH, andl CH, CH, CHo SRS CHg—CHe co willl chow a Strong Yop band hear 1720cm% amd amothey weak band (aPheaving aa a chowblet dio to | Feri vetonamce ) th the region ATo0~agcecim* due to aldehyale De-ye cap scAEeSoupmeallpmchow am strongebond in _sbretehinge™ | (©) Axiakwouelmequiterisk"o=HmgrouP-= pue to 2-3 diaxial o4 the oxic o-| wy group ta hindered amd Hus its absorptem frequenty ta wised. dy ie oO 7 Oh caer. oma Pate ° Ww casos DoW (ar) Tn compound 2) interaction, the Stretching vibration ef SSLEB | the non-binding elechors on Oxygen increases the (4 M) carjugation , terding to dower the c=0 freqpeney, Heve rm) ds dowinant ees However, tin phenyh esters Ay The por bordking electrons ave. gartly daineteeeteie ing, omd theiy conjugation with C=O ie consequently, himivished When His hajpens ~I effect of oxygen o becomes ctometnont and C=o moves to higher frequency ° 6 Aceto Phentne (ese-Ph) omd & Bengolldehyde (hoes > Both show cao sty areund Avoocm* but the Bengoldehyde wil alco Show He charatteristic aldehyde “Hh sty absorptions (near 2200 err 1), eahich ave absent from the acettphenone spectrum, B\ Explain Why C=o Sty Frequency tor m-chlavobenszcic acid ia higher than thos for p-chlovobengoic acid 9 Ans. ae ee a Q zy du Wa) m-chlovo benzoic acid p-chlovo benzoic. acid Only inductive efgect of Q ia considered when the As meta cubstituted g since cl has tcr) effect so i+ (2) hos higher ao cty trequency than), OQ Pio due to(+m) ettect of chlorine 4s clominant thom RSE) eect MES" “Antone, postion force canstamt of cao bond so Cx ctr frequency decreciies th sacbe para basition, ) Giving reasons arramge the plowing compounds in order of tncrearing wavelength of carbonyl absorption in their DR sperba iy SS - oe ° Oo 0 > Ub) leo Ors bere, o> a> PO) Since dohte lord Gs in conjugation bith c=o Broup so it wild decvease the C=o ct. Yrequency, Th rest (ay and (b) (oa (eo) hice) Ans = 6 > ab * Q) Hoo Gal Could infrared Shectrscopy be used to Lutinguich the | Wembers of the xollowing pairs and how reliable could | these dintinctions be } A) Naturah Rubber (chs— pulyicoprere) amo! butyd rubber puly—Lsepers) ome Notural rubber stil contoins an alkene gros butyo vubler does not, the presence of @ Wed] mediwm lana ter cac Sty will identity the former with reasonable Certainty, a) usingty-wme er, H) 2 ct 441204) Hornbacb Page = ° vi ° © 4418 (C) Hornbeck Prog my Sol and oa sae J Hw iC iv) . f 14.48 (A) ovr ee omd ake vy Ae fh ‘ 1s sa, Gy nd QO C EAs 2005, tom) 4 a 8 : Fyn ae 4 4 L CNTR 3! enc eee = Ss Cts anos, 20m) te 3 Vil) capo Sth cmd Heo cts cry. cy vii) Og CH=CH CHE cmc A ) ora’ aed or a how these a Cam be clistinguished 14 Horne ch Page sare Fae ix as i a 3 C= clenyc CH, and CH, HH = cH ba oO ° ‘ v x) cay 0 Ch, SH, omd Par Gea | ge S41 £43 ‘ele el 214) | Explain hod OMMGRRERISBEY could be used to clistinguish betaeen these Comboundl imgeets, oe $5, toenbeey ho a Or + ot iti ee a >. j = oo ) Explain how mecdwmspectrometyy Cowl be used to clurbinguish between these compounds Pyle S36 (S17, Wornlack 8} Ce | Om. oS it) i i PRISE amal . i. AAW oe sag iv) @)How coud you dhutinguich Girma ek the ioairg Compounds eo ay theiy tntrared ss 4) Ss 4 wi od 2 56 ° Q\P compound forms cis— Ay2— imme thy Icychipropane hen it iy re duced with Hy and Fd, the 4h NMR Spectrum Of the <0m bound shows oadey two Sgn Singlets , aha 2a the Structure of the combound, K CA ) How cold yu We TH—-NMR spechospy Yo distinguish among the tpllowing exters } ; . ° 6 tH, \ anes exh, weedy cn, y CH, COC, CH nde St ae Tae Oe ae ee Spectroscopy +> 0 GMitw0 dinsterenmeric compound A omd B, posser the. general formula indicated below, Compound A gives a sing fet in its SH wR spectrum tor the ving “He group, while B gives a milliplet. Draio tbree-dimencional Structured formulas toy the two deveoisomers ak g basis tor explaining these Spectro dak . o BN (Reb simsPine eg chensshy) ow eeg ns BNa)riccum how 44 NMR Spectra could be used tp diatinguich | the folowing dsomevs ip ee Ssh Pine) ey Be Gee GN3}Propose a structure for each of the ellowing compounds bated Upon spectyoh Chavacteristics . (Reb: StPine) a) 8 fichy- Smelling Liquid with elemental amaly sis of C=68-aafo A= 15-04 Yo andl N= 16-08%/>. The dnfraved spectwm hos q chovactevictic” Jouble Peak ak 3200 cm? (3.0Km) and the tH- NMR shows wedonemce feaks at og ($9) ,2-4[s,2), amd 2-3 "(s, 2) pom by B hydyocarbon GHig with Anne at a4 (m2), 2-0 (ma) Sie S-€( broad, 4) “and Seo nime Peaks ak 22,25 emd 127 pbm, S) A shid with meecubar ion at 206 Ghose TR. cpectrum haa g broad absorption strom 3300 48 2.900 cnt) [3:04 3pm) a ual @4 characteristic bone, at 47.30 eat! (5978 pm ond 4740 oF! (S-8 pm). the 4h wink hoa Peaks of 4:0(ch3), 24 (m3), Bel sa), 7-3/( SS)ayh 14-2 ( 5,2) Hin Maula cong ring with chavacteictc. aie absorptions at 22t0%) (4S pm) ancl 19 30 cm! [58 Km) and 2n—wme beaks af 2S 4) omd 3-8( 8/3) bbm Explain the tack thot te wm peak ak a7 ppm, which accounts fpr jour protony 44 a singlet, &) A hydrocavbe showing a meeculay ion ot mjz.= 102, reonance peaks jn the th- nmr ot 7-4 (85) amd 34 (S)4) POY amd characteristic TR absorptions of ado ont (US Rm) omc 3349 few! ( 3-0 pm). #) B hydrocarbon, bp 44°¢, with a characteristic TR absorption ek 1640 c* (62pm) amd H-NMR peaks ot 4-0 (5,9), 4:3(m3) omd 5-7 (m, 4) Phe. @)4) when 4:5 —hexone —3-0% 4A bested , an sormeic compound A A hod characteristic TR absorptions rat 4+ cam be recovered. | oc A700 owt (3-7 pm) 2736 cml (5:76 Hm) amd 4650c) * [606 Am) omd a wank U-v. absorption at 290 nm. Suggest a Sstructave for Ay Q)S\ MLA reaction of ACertoin heterrcydle with ethyl chloro formate produces a Compound (Ce hios) whose ty—nmk spectral chovacteristics ave S phm 4.9 (3, t, 3=7 43) 224138); 38 (91a, D=7H3), Ctl dit, TASH), omcl 74 (Aids J=Shy), Suggest a structural formula for this material. @ G6} qreatment of 4-tert butyl cyclohexomone with the oblong seqpence of reagents ferme a mixture of products in which A predominales. iyhen iA (CHD | | Wasuins D pe + others, U/) cg scam er [cube THE vi 4308 A has a small mass spectral molecular ion ab mje = 208, bose peak ot =43 ,amd amother Sighiticmt peale ot Ms 57. Its LR Spectrum chows characteristic absorpbons eo ok A745 cml (5:85 Km) ond aggo ct | 610 Am). the Lie we Spectvum exhibits +200 broad mulbplets’ one centered ab 54 Ppp, (Bone centved ot 47 Phm (42) which dncluder on Pha rent Shove sighal ot 2.0 bbin, and singlet at 0-9 ppm(9). Tdentity A amd oukhine the reactors by which itt. formed, )T) Steam distitlaton OF Seaves trom a Samtohina plamt gbeciet produced am oi which could be Purified by gas chromoto- Qrakhy to give a pure Lqpid , bb 180- 222'c, Clement amalysis showed the presence OF only c Hand 0, andl | Combustion gave a Composition of C= 78-90 "bh and H= lo-64o, Mar spectrol analysis showed the molecular jon at n/p = 153 Omd the Uv Spectrum showed Amax = 238 nm( e=2xI04 J, Chororctevictic TR. absorption were observed at 1670 cml (593 pm) amd 2630 com! (64. pm). The An nme Shecky um Showed peaks ot 1.8 bbm ( $/6), LB pbm (S13), 2-4 phn USi3) and 4-9-9 Phin (m4) .2dentity the compound. $)2a) ral 9) There ace fpr esters with metecdlar formule G Hy. How cout they be Gistinguished by 4 wang, (onutery | 8) How could the Sgrels in the 6S 24. fhm region of their ty nag Spectra, istinguish among the potlawing Combroumcla } ( Brice’) Chg octy oct, o 6 Noy z Q) Sketch the Yplloaing spectra that Would be obtaines py O 2 Chomethansd: (Brule) the 4n- ume Spectwm pra dry Sample of the allcohd BS The 4a nme Spectrum or a, semble of the alcoht that combing | % trace amount OF acid No. BP HOR call FH Me be aml ty Prove that the adalition of HOr to Pr pene follow the rule that says thet the dectrophile Adc to the Sh® arbor bonded to the greater no oF hidvegens, (Bruise) = 9\ a hoa many ae Spbew in the Anning Spechum of Fess compound! > @.Mo. A430, Page 607 tombech —_| of (See soth y } ns Spectrascopy probleme trom Chaper — a4 of Orgamic Chemishry by He ttmann S88 STRUCTURE DeTemaon oF oncawe coMPoLNoS By working with mass spectral fragmentation Patterns, itis possible to develop Nery Keen insight into the ways that molecules disintegrate under high-energy saatons. This permits identfaiion ofthe smucture ieee the pieces and insight i ow they were produced. In conjunction with an, structural tools, MS Provides invaluable insight into molecular formula ang connectivity issues in a ‘molecule andl is thus an important tot in structure clucidation (eemtifying drugs and drug tating since it guns nly minute quantities rae etim). It has been sent onthe Mars probe flock ne amino acids as an ts fanart lite forms on Mars. One goal of eumeat reson wis to use MS pater, Mace etueeng pepies and oligonucleotides by en fragmentation Whe cree PNOMENY is thas an important analytec) ert tural tool ora lution continues at rapid pace i remaine important component of siruetural investigation BIBLIOGRAPHY Far an alternate discussion of instrumental fecimiques see J. W. Coo Techniques for Organic Chemists, Wiley ltersetnee, tog York, 1980, A complete discussion of modern instrumental techniques for structu Sth ed., Wiley Interscience, New York. For a more advanced discussion see A. B:Derome. Modern NMR Techniques for Chem ‘istry Research, Pergamon, Oxtord, 1987, The elastic text on "SC NMR is G. C. Levy, RL Lichter, and G. L. Nelson, Carbon: Yer ear Magnetic Resonance Specimscopy’ Die, Wiley: tnterscie 0. we, New PROBLEMS MLL. For the following compounds, label the spin systems present, label the Symmelry Properties of protons where possible (homotopic, enantiotopic, Prowems — 389 diastereotopic), and predict the splitting pattern for the protons) indicated by an arow. @ 9 He ) o. SL cH, <— Hy ~CHy cH, " © cKO MH on, Hy—o fh OS i if GiecHy we © a «a ~*~ nec—{(C))-cit- cl clic a ak ‘Tell how you could use 'H NMR to distinguish the following pairs of ‘compounds, Be specific as to what data you would look for and how you ‘would interpret it. There might be more than one feature in the 'H NMR that could be used so give a complete answer. (a) 9 cH 113. No, @ @ H (ky © and eae on Tall how you could use °C NMR 10 distin sraupounds. Be specific as to what data you pre iguish the following pairs of would look for and how you Hat combi i There might be more tan one fore "C NMR that could be used so give-a complete answer meietes) 4, Prowes — 994 wy © @ ° cH, 0 9 i, AK at otal : o th © OCHCH, OcH:CHy ee a Oe wocrncts © ae ©p-on,, ae Hy and Q . or Orava = Ho OE ovan CK ren ° "yw chy ‘Tell how you could use IR spectroscopy to distinguish the following pairs ‘of compounds. Be specific as to what data you would look for and how you would interpret it. There might be more than one way to distinguish them by IR so give a complete answer. fa) oO oO @ Prosiems = 993 11.8. Tell how you could use mass spectrometry (MS) to distinguish the fol- lowing paits of compounds, Be specific as to what data you would look for and how you would interpret it. There might be more than one way te) ie 0 «@ ™ cl “Om Om, 11.6. Rationalize the major fragmentation pathways observed for ethyl pheny- Jacetate A and diethyl phenylialonate B. hy! phenylacetate ” CyHGCHSCOSCHSCHy nw 168 Invensity 9 100 150 394 Intensity ‘STRUCTURE DETERANATION OF ORGANIC COMPOUNDS Diethyl phenyimalonate 118 CoHSCHICOSCH,CH), mw 236 163 200 Give (0 instrumental methods that would permit you to distinguish the following, Explain what data you would use and hee would allow you to make the distinction, @ pe ° ae ae and ‘och, Br Br ) Hoo cy © | Sdution to Chapter af of Prgante Chemictry by Hofmann craeren 1 463 (CHAPTER 11 ILL (a) cSoublet of quarets — (b) 10, enantiotopic W CH, <— triplet pene %, Pn CHeCH, tomotopie sextet or mulipler % AXy faa? Fux *%, "e, x ~ Be ek fo aes © acai fhe i ea ae eames the 3 hed ales he ely sia eo ‘This svutd nave attic etme 18 ppm as one etn vi spa iF eee, Beanie Ze eS Saficcdtachis pm, come NNN atl SRN “The iterate aes ofthe “The intent te othe a" Zane et OCH; bE and = O=S=0 Ko; a NOs ‘Te aromatic prs we be ‘The aromatic signs wad t a & sree AAD uaresnpe Bevery ame 8 oS Soci, and Oo Nit L nc, ti ye’ mwepaceit, — ptpapmapeet eee eee foe eae (ky M3. (a) OO) «© @ © CHAPTER TY 465 i ; ; | ee { ett recesses ana Loe Seles ° of _ eA cnt, 3 ou i ee en miscorinc hems Sut spety ) Magee sea mis Somes bar —rectemny CO=CP ime rs - on Oro FO Stereo cri tenn br er A a ee ae eH aay HG Sh cn, 8 Teme ore ceet Te tren poset ParacenSem cima pve pen cae Scacesage gman een one [an CH; O 8 cH, nae chs ots o ou, OCH.CH; OCH.CH; he ee of Axes Sontea eect Sect, ‘aroma dcop ep fre abe in sana 468 SOLUTIONS 10 cHAPTEN PROBLEMS “hee pts not ecu ch, Ht 7 tc C)-cn, npn geen ci, » 4 Ay and CHACH, ‘oct.eit, 1 ‘a (hy Aya chy 2s si 14. fa) 0 © Shc and sone, itso! ania ty on bat bP ora ia et ©) o oO Open 2 Opa how aye’ tw’ weit condita? WW) H=C=C=CHLCHLEN and ye =C=C—CHLCN Aeramins! CH = 3400 emt “ni termina acetyiene: fe) hale) ¢ ee oncojutet eos (T1Dem! Unseen 1650 ca! cy 9 oScu, , NOAA ry ts Sent Pate oo a and on NO ae Hycky lent ear! 2 meO))-cit ant nye L7H ©) (h) oO oO Sch Sak a OH EB ried ctu atiae be Scone, Soot o ) ° i Ss ane Soke ae col sheets! ® HC )- al ° we-cne{O)-0, 0 awn ° Oral « Orouel, ‘Would haves M~ 31 peak 1s. ‘Would hive big M ~ 15 pat COnAPTER 11 467 408 SoLUNOWS 10 CHAPTER PROBLEMS O%.« O sa mae rae ae wo eo ade, * Wohnen ya 1S Se eae ® ct N oOo, = B a 1c “CH, eaiconights et “would be very sppaet in the parent fon, “Om, on “NI CHy salad ianinnrs 16. A a e, e OM gency —* CLS OCH CHs 119 yo ‘mie =9) 8 C oe ‘OCH;CHs + BO Oo Soct.ces © Socticity ale= 91 = oO 2 ‘OCH;CHy © ae ies 163 ‘HO. oo lens 08 nei WI. @) Br oO oO ee Br ao ot a he Stn oy ee IR hese vate elo aren ) HOO H n? Hye“S ie WH H t tae et ce ers Norma Soom tet 18 sped aise 2 ea sinters alee Me ansaid NR vga (©) LTH ont Sent nes CRM os "NMR is 201 Mom: oratmetyine mannan resonances de tn steric deahedig, 470 SOLUTIONS To CHAPTER pROwENS ” Ohana $-Gp-oucy coher! ma ap ewig itr HN a ENA C0 ebm 0 ppm PENNA: C0 es Be ot eda ° i Rieti a e ut cH, “ae Se He b nae nm ei Ct -30 Songs nee ‘Somes acm Aster eee eto c r Spectroscopy problems trom Ovgame Chemistry ‘one chlorine atom; if the Mand M ++ 2 peaks are about the ‘same height, the compound contains one bromine atom, Characteristic fragmentation patterns are associated with specific functional groups. Electron bombardment is most likely 10 dislodge a lone-pair electron. A bond between cat= ‘bon and a more electronegative atom breaks hererolyticaly, with the electrons going to the more electronegative atom. A bbond between carbon and an atom of similar electronegativi- ty breaks homolytically; a cleavage occurs because the species that is formed isa resonance-stabilized cation. Spectroscopy is the study of the interaction of matter and ‘electromagnetic radiation. continuum of different types of electromagnetic radiation constitutes the electromagnetic spectrum, High-energy radiation is associated wit high fre- quencies, ange wavenuenbers, and short wavelengths Infrared spectroscopy identifies the kinds of functional groups in a compound. Bonds vibrate with stretching and bending motions. Each stretching and bending. vibration ‘cccurs with a characteristic frequency. It takes more energy to stretch a bond than to bend it. When a compound is bom- by PLY Brute Problems | 517 bared with radiation ofa frequency that exactly matches the frequency of one of its vibrations the molecule absorbs ener- gy and exhibits an absorption band. The functional group Tegion of an IR spectrum (4000-1400 em") is where most of the functional groups show absorption bands; the fingerprint region (1400-600 cm’) is characteristic of the compound as a whole. “The position, intensity, and shape of an absorption band help identify functional groups. The amount of energy re- quized to stretch a bond depenls on the strength ofthe bond: Stronger bonds show absortion bands at larger wavenum- bers. Therefore, the frequency ofthe absorption depends on bond order, hybridization, electronic, and resonance effects, The frequency is inversely related to the mass ofthe atoms, so heavier atoms vibrate at lower frequencies, The intensity ‘of an absorption band depends on the sizeof the change in ipole moment associated with the vibration and on the tnumber of bonds responsible forthe absorption. In order for a vibration to absorb IR radiation, the dipole moment of the ‘molecule must change when the vibration occurs. F key Terms atbsorption hand (p. $00) ‘base peak (p. 486) bending vibration (p. 499) fa clezage (p. 490) lectromagnistic radiation (p. 497) tpn region (p. S01) fragment fon peak (p. 485) frequency (p. 497) Hooke’s law ¢p. 503) functional group region (p. S01) inrazod radiation (p. $00) infrared spectroscopy (p. 483) spe infraced spectrum (p. 500) mass spectrometry (p. 483) mass spectrum (p. 485) ‘MoLatfery rearangement (p. 494) rotecular ion (p. 484) rnominal molecular mass (p. 485) ‘dial cation (p. 484) roscopy (p. 497) stretching Inequency {p. 502) stretching vibration (p. 499) wavelength (p. 497) wavenumber (p. 498) I Problems 30, Which peak would be more intense in the mass spectrum ofthe following compounds-—the peak at n/t = 57 or the peak at mjz= 702 a. 3-methylpentane b, Qmethytpentane ‘31, List thee factors tha influence the intensity of an IR absorption band, ieee ‘af the fotlowing pairs of compounds, identify one IR absorption band that could be used to distinguish between them: 3 3 » CO) a crenenencrcnen cH, I = CH,CH,CH=CH, and CH,CH,CH=CCHy a -CH,CHOM and -CHCH, Praenon and C oe i & CHsCOCH;CHs and CHsCCH,OCH, CHCH; and CRSCHSC 1CHy Beuice ( chepler 13) | 518 CHAPTER 13. Mass Spectrometry and infrated Spectroscopy 0 cncn.tn and crycrtcn, j. CHCH{CH;OH and CH;CH,0CH; apt ° g 9 Co and tr k. CILCHLENH, and chicH.eoct, ivd-butene and rraas-2-butene L Ons and Ol 33. a How could you determine by IR — had occured? a, of o 1 After purifying the produet, how could you determine that all the NH3NHL had been removed? ‘4. What identifying characttisties would be present in the mass spectrum of a compotind containing two brofne atoms? 85. Assuming that the force constant is approximately the same for C—C, their stretching vibrations —N_ and C—O bonds, predict the relative positions of Bio, A nase spectrum shows significant peaks a = 87,115,140, and 143. Which ofthe following compounds is response for ‘at muss spective: 4,7imethyl-Loetano, (dimethyl-4-detanol, oF 2,2.4-trimethyl-+-heptanol? 37. How could IR speetioscopy distinguish between 1 5-hexadiene and 2, Aiexadiene? 38, Acompound gives « mass spectrum with peaks at m/e = 77 (408), 112 (1008), 114 (234%), and essentially no other peaks. ‘Meaty the eompound. 5), What hydrocarbons will have # molecule on peak at m/z = 112? e 4D, inthe Following boxes, fist he types of bonds and the approximate wavenumber at which each type of bond is expected to show an 1 asouption 3600 3000 1800 "oo 1 41, For euch ofthe IR spectrin Figures 13.35, 13.36, and_ 12.37, four compounds are shown, In each ease, indicate which ofthe our ‘ennpounds is responsible for the spectrum. a. CH.CHCH.C=CCH, — CHACH,CH;CHLOM CHYCH.CHCH.C=CH jesse di Oo Gwe! ee akan cals ccike A Figure 13.36 TheiiR spectrum for Problem 4b, Cc 3 OM a A Figure 13.37 The if spectrum for Problem 41. 520 CHAPTER 13. Mass Spectrometry and Infrared Spectroscopy 412, What peas in their mass spectra would be used to distinguish etwoen 4-methyl-2-pentanone and 2-nethy-3-pertanone? 414. A compound is known t be one oF those shown here. What absorption band in he compound's IR spectrum would allow you 1 iehiTy a ee. 7 5 i -* crt a A 0 t How could spectroscopy distinguish stony T-hexyn, 2-hexyne and hex? For sach of the IR spe ih Figures 13.38, 13.39, abd 1340, indicate which ofthe five given compounds is responsible for the specttuin 4. CHCHCH=CH, CHYCHSCHCHOH — CHy=CHCHCH-ON CH:CH,CHOCHy eee 13.38 “The IR spectrum for Problem 45a, h. Co cr" oe on co lt i 13.39 « The IR spectrum for Problem ab. A Figure 13.40 ‘The IR spectrum for Problem 45c. 46, Each ofthe IR spectre sown in Figo 1341s the spesteum of ne of he following compounds, ent compo that _sesponsible for each spectrum. 3 i i i 4 By cy cbs sigh ad 522 CHAPTER 13 Mass Spectrometry and infrared Spectroscopy Figure 13.41 (continued) Predict the major characteristic IR absorption bands that would be given by each of the following compounds: ‘4 _CHCH.ON : o eecuen.en 4 Go ° Cocicts ; = & Co « & meee hs. |b or i sith 18, Girt that the fence constants ace similar for CH and C—C bonds, explain thy he stretching vibration of a C—H bod ‘occurs at a greater waventmber. 49 ‘The IR spectra of a compound with motseutar formula CsH,0 was obtained in CCl, and is shown in Figure 13.42, Mentity the '50, he IR spectrum shown in Figure 13.43 ithe spectrum of one ofthe following compounds deity the compound. fro co geo oO oe Ken pons A Figure 13.44 ‘The IR spectrum for Prablem 51, 524 CHAPTER 13 Mass Spectrometry and infrared Spectroscopy the moteciar formula of a saturated aeyelic hydrocarbon With aM peak atmy/z = 100 with a relative intensity of 27.52%. and an M+ 1 peak with a relative intensity of 2.107%. BP Cierlate the approximate wavenumber at which a C=C stetch will occur, wiven thatthe force constant forthe C=C bond is Wy Was 4, ‘Thee 1 and mass spectra for three diferent eompourils Felstive abundance: Figure 13.46 ‘The IR and mass spectra for Problem S4b, A Figure 13.47 ‘The I and mass spectra for Problem Sd. 4 ; 14) | Beuice (copter — 576 cHapTeR 14 NMR Spectroscopy and U8 mente ial oneguimlem protons ita contpund ithe step oie imegraton curves measure 405,27, tcc et fom eft to righ across the spectrum. Give he tener ‘Pompound whose 'H NMR spectrum would show these integrals in the observed order BRB ow coud 1 NMR csnguisn beeen the compound neath of te folowing pairs? & CHCHACHOCH, and CH,CHLOCH CH, f O af O SACHS mt meKeHEINO, ——¢ Cae us cucae ie Ee oa «ot dae, at cit is Ios oS gts z os 47. Anwwer the following questions: Barrer ie lationship between chemical shit n ppm and operating fequeney? > What isthe relationship between chemical shift in bers and operating frequency? a ats lationship berween coupling constant and operating frequency? © How does the operating frequency in NMR spectroscopy ‘Somars with he operating frequen in I and UV/Vis spectcscopy? ‘48 The HNMR speciza ofthe isomers with molecula fomala CiHlgBr are shown here, Which isomer produces which spectrum? <—— tregency solution fpr 1k F svn Hern bach absorption at 1683 cm’ is due to a carbonyl group. The absence of bands for other carbonyl containing functional indicates that the tamper ketone or a eater, Itis often difficult to determine with certainty whether a is a ketone or an ester based solely on its IR spectrum. In this case there is a strong band near 1250 cm’, but it is broad as the C-O band of an ester normall ote that the group of a co gated Ketone should appear 26 1875 om" whereas that of a conjugated ester should appear at 7 conjugated ketone. Vare due sp’. hybridized a cm” are due to em region atid the oe band near 700 om a agests the presence of an aromatic ring. The strong absorption at 1715 group. The strong C-O band near 1200 cm” indica is an ester. Thd observed shif of the carbonyl bant\ to a lower \e (at the right) will have a sharp be up. Both will have peaks in the 2150 but the band from the terminal al less symmetrical. b) The conjugated aldehyde (at the left) will have the abgorption for its C=O group at lower wavenumbers (1710-1690 cm’) thah the non- conjugated aldehyde\(1730 cm’). c) The amine will have bands will be of weakeh intensity and less broad than the 0 alcohol, which will appear in the 3550-3200 om’ region. d) The ester will show for its C=O group near 1740 cm”, whereas that for the ketone will appear near 1715 cm". In addition, the ester will have a intense band for the\C-O group in the 1300-1000 cm” region. ) The alcohol will show a b absorption for its OH group in the region ‘of 3550-3200 cm”. The absofption for the OH group of the fic acid will be broader than that for the alcohol and will be centered near 3000 ‘em’. In addition, the carboxylic acid will have an absorption for its C=O. group near 4740 cm", f) The ether will have an intense band in the 1300-1000 em” region due to the C-O bond, due to the =C. bband of the 208 2 The dependence of and hredral ag refered to. the Korps eationshy fer Martin Karplus Harvard Specbroseopy problems trom Care. Or gate, Chemistry by ay ‘CHAPTER THIRTEEN Spectroscopy Sh Annalee exhibits « 'H NMR spectrum that is anosoal in thi in ation to a peak at «5 PP. it contains second peak having a chemical shift 8 of ~1.9 ppm. A negative vase fag if, temical shift indicates thatthe protons are more shielded than those of teaeliploing is Peak is 1.9 ppm wofcd from the TMS peak. The high-field peak has half the aren of he Tow. Field peak. Suggest an explanation for these observations. US}-Annalene 1236 Fis the only isetope of aie tht asus atu, an has a male spin of {@) Toto how many peaks will the proton signal i the "HNMR spect of methyl fluoride be spit? 4 fo How many peaks will the Horie signal inthe "F NMR spectrum of methyl fluoride be split? (6) The chemical shift of the protons in methyl fori is 8 4.3 ppm. Given that the Seminal 'H-"F coupling constant is 45 He, specify the B values at which posh are observed in the proton spectrum of this compound at 200 MH». ‘FRA gore the vicinal counting constant between two prions vais withthe angle between sands ofthe H—C—C—H unit. The coupling constant is greatest when the prone Descent, litedral angle = O° oF 180%) and smallest when the angle is approximately a BaarTts, with the al of molecular models, how you could distinguish betwenr cia hears, chleroeyclopropane and is trans streosorner on the bess oftheir 1H NMR spectra Uniessop wie oferedtne SARBB The rn tanstion in the UV spectrum of sransstibene (trans-C,H,CH=CHC,H.) reset accepted theoret Seon 2 i epprociractr ne comeac wih 83 nm forthe cis sereoisomer. The extinction ene Pree aly tice as great for trast as For ci-slbene. Both facts sre normale ie Pemeteaa rms of moe effective conjugation of the electron system in irans-alfoene Coane compogat Mosel ofeach sereoisomer, and identify the rason forthe decreased effcvente ot ‘conjugation in is-stilbene. 12,32 "Ps the only phosphors isctpepresat at natura aban and has a melear spin of f, The 1H NMR spectrum of timethyl phospite, (CHOP exits ndhenie ee ‘methyl Protons with a spliuing of 12 Hz. {@) Into how many peaks is the 'P signal spit? (© tat is the diferce in chemical shift i here) between the lowes and highest field peaks ofthe P multiplet? PRRREY seve in section 13.13 satan NMI speceum isan average scrum ofthe conforma creacattlted by » molecule. From the folowing deta, eximate She percenaees of cas ‘statoral bromine present in bromocyeloherene 3.48299 3381 omy 8395 pm By uo ) eel TF eae pm Ce Problems (GRAD totcared spectroscopy is an inherently “faster” method than NMR, and an TR spectrum is Superposition of the spectra of the various conformation, rater than an average of them. When |.2.dichloroethane is cooled below its freezing point, the crystalline material gives an IR spectrum consistent with a single species that has a center of symmetry. At room temperature, the IR spec- nuit of Liquid 1,2-dichloroethane retains the peaks present in the solid, but includes new peaks as ‘well, Explain these observations, PBI .ve spectroscopy is used to probe transitions between rotational energy levels in mol cells, (a) A typical wavelength for microwaves is 10°? m, compared with 10° m for infrared ‘radiation, Is the energy separation between rotational energy levels in a molecule greater o less than the separation between vibrational energy levels? (b) Microwave ovens cook food by heating the water in the food. Absorption of iniewowave radiation by the water excites i to w higher rotational energy state, and it ives off this excess energy’ as heat when it relaes t ils ground state. Why ave ‘brational and electronic nergy states not involved in this process? 1143 ‘The peak in the UV-VIS spectrin OF acetone [(CH):C=0] corres tothe n> teansition appears at 279 nm whe hexane isthe solvent, but shifis to 262 mim in water. Which is ‘none polar, the ground electronic state or the excited state? 43.44 A purticular vibration will give an absorption peak in the infrared spectrum only i the dipole ‘ounent ofthe molecule changes during the vibration. Which vibration of carbon dioxide, the sym- “april stretch or the antsymmetrcal stretch, is “infrared active"? wed Gace Spinel teh Anime sete fe protons im the methyl group shown in ialies in the following structure are highly sede uo ge ign 038 ppm pied fam TMS. The te ey ow on te sie a fhm has @ more normal chemical shift of 0.86 ppm downfield trom hy is the indicated methyl group so highly shielded? (Building a moleetilat model eat help.) CHs 13.33 1334 13.35 Cavey opth ‘The peak at highest m/z in the mass spectrum of the compound is m/z = 134; this i likely to cor- respond to the molecular ion. Among the possible molecular formulas, C,H, correlates best with the information from the 'H NMR spectrum. What is evident is that there sa signal due to aromatic Protons, as well asa triplet-quartet pattem of an ethyl group. A molecular formula of C,H, sug- ‘ess a benzene rng that bears two ethyl groups. Because the signal forthe aryl protons is so sharp, they are probably equivalent. The compound is p-diethylbenzene. cH ‘CH,CH, $72p9m——H 5.27pm 5.13 ppm (Singles) (Quacet) ipl) > Dietylbeneene ‘There is a prominent peak in the infrared spectrum of the compouind at 1725 em~!, characteristic of C= stretching vibrations. ‘The 'H NMR spectrum shows only two sets of signals, 9 twplet at 61.1 ppm and a quartet at 8 2.4 ppm. The compound contains a CH.CH, group as its only protons. Its "C NMR spectrum has three peaks, one of which is at very low field. The signal at 8 211 ppm isin the region characteristic of carbons of C=O groups fone assumes tha the compound contains only carbon, hydrogen, and one oxygen atom and that the peak at highest m/z in is mass spectrum (m/z 86) corresponds to the molecular ion, then the ‘compound tas the molecular formula C.H,0. All he information points to the conclusion thatthe compound has the structure shown, I CH,CH,CCH,CH, Pemanone [18]-Annulene has nwo different kinds of protons; the 12 protons on the outside periphery ofthe ring are different from the 6 on the inside. ‘These different environments explain why the HNMR spectrum contains twopeaksin a2: | ratio, The Jess intense signal, that forthe interior protons, is more shielded than the signal forthe ouside protons. ‘This results fromthe magnetic field induced by the citculating electrons ofthis aromatic ring, which Feinforces the applied field inthe region ofthe outside protons but opposes it in the interior of the ring. “srectnoscoY 337 Protons inside the ring ae shielded by the induced field to significant extent—so much so that their signal appears at 8 =1.9 ppm, (a) The nuclear spin of F is +5, that is, the same as that of a proton, The splitting rules for "°F'H couplings ae the save a hose for =! Thus, the single rine atom of CHE | splits the signal for the protons of the methyl group into a doublet. (0) The setoF tee equivalent protons of CHF splits the signal for fuori into a quartet. (6) The proton signal in CH,F is a doublet centered at 5 4.3 ppm. The beteen the two halves ofthis doublets 45 Hz, which s equivalent to 0.225 ppm at 200 MEtz (200 “Thus, one line of the doublet appears at (4.3 + 0.225) ppm and the other at (4,3 — 0. 5-42 poo Fas 84525 ppm 64.075 ppm 1837-188 Suns tec ating xs ee a vie hi Sat Gade and Staton Ma tal. You should use Learning By Modeling for these exercises, 1839 Hecause "'P fas a spin of iis capable of sping the 'H NMR signal of protons in the same ‘molecule. The problers stipulates tht the methyl protons are coupled through tree bonds to phos- phorus in trimethyl phosphite. = , (a) The reeiptocity of splitting requires thatthe protons split the “'P signal of phiosphorts. There tare 9 equivalent protons, and so the “'P signal is split into ten peaks. (©) Bach peak in the "P multiplet is separated from the next by a value eal to the 'H-"'P cou- pling constant of 12 Hz. There are nine such intervals in a ten-fine multiplet and so the sepa- ‘ation is 108 Hz berween the highest wad lowest eld peaks ia the milple, 1340 The trans and cis isomers of {-bromo-4-rer-butyleyclohexane can be taken as models to estimate the chemical shift of the proton of the CHBr group when it is axial and equatorial, respectively, in the two chair conformations of bromoeyelohexane. An axial proton is more shielded (63.81 ppm for trans |-bromno-4-tet-butyleyclohexane) than at equatorial one (6 4.62 ppm for cis ie butyleyclottexane), 5.4.62 ppm 53.81 ppm 53.95 pp ; Lt pit i (CIL.C Hy. jr mga meet meme Tess shielded ‘more shielded ‘The difference in chemical shift between these stereoisomers is O81 ppm. The corresponding pro- ton in bromocyelohexane is 0.67 ppm more shielded than in the equatorial proton in eis-1-bromo-4- ‘ert-hutyleyelohexane. The proportion of bromocyclohexane that hasan axial hydrogen is therefore 0,67 0.81, oF 83%. For bromocyclotexane, 83% of the molecules have an equatorial bromine, and 179 have an axial bromine JAA ‘The two staggered conformations of 1,2-diehloroethane are the anti and the gauche: HL se H H. i cl toes, eer ee HOW H a ia re TI TT 238 13.42 13.43, 1344 1345 ‘SELF-TEST secrnoscopy {ne species present at low temperature (erysaline|,2dichloroethane) has a center of symmetry and is therefore the anti conformation. Liquid 1,2-dichloroethane is a mixture of the anti and the ‘gauche conformations, (@) nergy is proportional to frequency and inversely proportional to wavelength. The longer We seveleneth, the lower the enerey. Microwave photons have a wavelength inthe range of 1o-* tm, which is longer than that of infared photons (on the order of 10"! m), Thus, mic Crowave radiation is lower in energy than infrared radiation, and the separation between pot. {ional energy levels (measured by microwave) is fess than the separation between vibrational energy levels (measured by infrared). (©) Absorption of & photon occurs only whem is energy matches the energy difference between {0 adjacent energy levels in « molecule. Microwave photons have energies that meich the differences between the rotational energy levels of water They are not sulficientl high in en, rBy to-excite a water molecule toa higher vibrational of electronic energy state 2A shit in the UV-Vis spectrum of acetone from 279 nm in hexane 10262 nm in water isa shift ro shorter wavelength on going from a less polar solvent toa more polar one, This means that he ee, fone, lowering its energy. Because the energy gap between the ground state and the excited state me caine itmust mean thatthe ground state is more solvated than the excited state and therefore more Polar than the excited state. a Ground state F-™" ]s@ more solvated |. 6 inwater ‘Acetone in hexane Accione i water {ne dipole moment of eazbon dioxide is zero and doesnot change during the symmeitie stretching rence The symmetric stretch isnot “infared-active,” The atisymimetic sich genermes ge Pole moment in carbon dioxide and is infrared-active. Syma serch nochangein —_Antisymmetic sth dipole moment reset Aipole moment ‘84 esl of unequal C=O bond dsuncer, Soletions to molecular modeling exercises are not proved in this Study Guide and Solutions Man. ‘wal. You should use Learning By Modeling for these exercises, PART A A-1- Complete the following table relating to 'H NMR spectra by supplying the missing data for cetries | through 4. Spucninaaey Chemical shift frequency Ppm on @ 60 MHz - 366 o 300 Mie 435 - © oes 3.50. 700 @ 100 Miz 2 of TMs Pe i A calledtion of Shecbocupy Btfime from difteremt ohebters of Momy MeMurry Problems: (7th edition 0) i, 20.56 m Propose a structure fora compound CglH;202 that dissolves in dilute NaOH and shows the following 1H NMR spectrum: 1.08 5 (9 H, singlet), 2.2.6 (2H, singiet), and 11.26 (1 H, singlet) 20.86 What spectroscopic method could you use to distinguish among the follow: ng three isomeric acids? Tell what characteristic Features you would expect for each acid. CHyCHy)gCOZH (CH) gCHCHyCO2H iCHg)gCOH Pentanoic acid 3-Methylbutanoic acid 2.2-Dimethylpropanoie acid 20,57 How would you use NMR (either $C or #H) to distinguish between the fol- Jowing paits of isomers? Ze (a) COoH OH oo OO CoH mee OH Wo) HOZCCHZCH;COpH and CHgCHICOzHIz fe) CHyCH,CH,CO,H and HOCH, CH;CH2CHO aes {dl (CHy),C=CHCH{COH and beds CO2H Problem 19.25 | How might you use mass specromelsy to distinguish between the following pairs of ssomers? (a) “-Methy!-2-hexznone and 4-métinyl-2-hexanone (b) i Heptanone and +-heptanone (©) 2Methylpentanal and J-methyipentanat 18.62 Acic-catalyzed dehydration of 3-hydroxy-3-phenyleyctohexanone leads to a0) unsaturated ketone. What possible structures are there for the product? At sehat position in the IR spectrum would you expect each to absorb? If the actual product has an absorption at 1670 cm™!, what as its strucrune? 19.63 @ Compound A, MW ~ 86, shows an IR absorption at 1730 cin™" and a ¥ simple 'H NMR spectrum with peaks at 9.75 (1H, singlet) and 1.2.6.9 N, singtet), Propose a structure for A 19.64 m Compound B is isomeric with A (Problem 19.63) and shows an 1R peak at 1715 m=! The IH NMR spectrum of B has pews at 24 T= 7 M2), 2.1.8 (8 H, singlet), and 1.2.8 (6 H, doub’ structure of B? 1H, septet, hat is the 18.46 Disparhure, CyyHyyO, 48. sex attractant released by Abe female gypsy moth, Lvonemetraa dispar. the TH NMR spectrin of disparture: shows a large absorption’ iv the atkane region, 1 to 2.6, and a triplet at 2.8 6 ‘Treatment of disparlire, first with aqueous aie) and then with KMnOg, yields two sree acids: identified as undecanaic acid and Gmethylheptanoic acid. (khinO, cleaves L.2diols to yield carboxylic acids. Neglecting stereochemistry, propose a Sructute for dispute, The actual compound isa chiral molecule with 78S stereochemistry, Draw disparture, showing the correct stereochemistry. 1854 m The red fox (Verlpes vulpes) uses a chemica} comniunication systern based on ccelit marks iit urine. Recent work has shown one componeitt of fox urine 10 be a sulfide. Mass spectral analysis of the pure scent-mark component shows M+ = 116.18 spectroscopy shows an interse band at 490 em=!, and 1H NMR spectioscopy reveals the following peaks: 17183 H, single, 2.11 6H, singietys 227 62-1, triplet, J = 42 Hey; 257 82H, tiple, = 4.2 Hay 4.73 8 (2H, Broad Propose a structute consistent with these data. (Note: (CHa) absorbs at 2.181 48.55 @ Anethole, CygH,s0, a major constituent of the oil of anise, has the 'HNMR spectrum shown, On oxidation with ‘NajCrz0s, anethole yields [agai benzoic acid. What is the structure of anethote? Assign all peaks in the spectrum, and account for the observed splitting patterns 47.61 # Compound A, CoH pO. is one of the basic building blocks of nature. AIL steroids and many other naturally occurring ¢ are built from pound A. Spectroscopic analysis of A yields the information: 1k 3400 m="; 16aGem=! HNME: 1.63 6(3 H, stnglet); 1.70.6 (3H, singlet); 3.83 8 (1 H, broad singlet); 415612 H, doublet, | ~ 7 Hz); 5.706 (1 H, triplet, |= 7 Ha) (a) Mow many double bonds and/or rings cloes A have? {b) From the IR spectrum, what is the identity ‘of the oxyger-containing func tional group! {e) What kinds of protons ace responsible for the NMI absorptions listed? (a) Propose a structure for A 4759 w Propose a steucture consistent with the following speettal data for 4 compoutid Cet Ox: TR 3350 m=" | TH NMR: 1.246 (12 1, singlet); 1.868 4 H, singlet), 1.95.6 12H, singlet) Qussor- ES 15.43 1-Phenyl-2-buterie has an ultraviolet absorption at Agia, * 208 nm fe = $000), On treatment with a small amount of strong acid, isomerization occurs and a ‘ep SUBSIANCE WET Apage = 250m (e ~ 15,800) ts formed. Propose o strug- ture for this isomer, and suggest a mechanism for its formation. 15.46 m What is the structure of a hydrocarbon that has M* = 120 in. ‘trum and has the following "H NMR spectruin? 7.285 (5 H, broad singlet); 2.90 6 (1H, septer, J = 7 Hz); 1.22.6 (6 H, doubler, T= 7Ma 16.45 & Propose stiictures for compounds that fit the following descriptions @ Collis HNMR: 7.18.4 (4 H, broad singlet; 2.705 (4 H, quartet, J = 7 Hz), 1.205 (GH, triplet, f = 7 Hz) mass spec- 1745 cm"? ©) Cio HNMR: 7.0644 4, broad singlet), 2.85.6 (1H, septet, f= 8 Hz); 2.284 (BH, singlet; 1.20 3 (6H. doubles, /= 8 He) IR 825 em=! 15.41 Compound A. CsH,o, yields three substitution products, CyHoBs, on reaction with Brg, Propose two possible structures for A. The 'H SMR spectrum of A shows a comp'es four-proton multiplet at 7.0 8 and a six-proton singlet at 2.30 6, What is the structure of A? 1.29 @ 3.Chloracyclopropene. on treatment with AgBF,, gives a precipitate of AgCl and a stable solution of # product that shows a single 'H NMR absorp- ion at 11.04 5. What is a tikely stracture for the product, and what i its rela- thon to Hickel’s nile? 2-Chloroeyelopropane 21.67 How would you disting y pairs? Tell what differences you would expect to see. (a) N-Methylpropanamide and N,N-dimethylacetamide (b) 5-Hydroxypentanenitrile and cyclobutanecarboxamide (©) 4-Chloroburancic acid and 3-methoxypropanoy! chloride (@) Ethyl propanoate and propyl acetate (sh om) 21:52 n some of hp IR spectroscopy lon cn difereait etwcen the ioe, For others, either or a combination of 'H NMR and IR data is necessary. @) oxordiven oud Methylpropanamide —_N,N-Dimethylacetamide WR 1680 em! 1650 cmt (Nesubstituied amide) (N.N-isubstituted amide) }HNMR: — o9e methy! group three methyl groups ‘one ethyl group inguish spectroscopically between the following isomer . € ©) yongctyoHsoHsO=N On s Hydroxypentaneniteite Cyctabutanecarhoxamide ie 3300-3400.err"t ae Caen (amide) ik 2a 1810 em th ; i inoen" (carboxylic acid) o } one dosiers er . Ethyl propanoate 2 ¥ 1H NMR: (wo rriptets bb ‘wo quartets = ‘one quartet ‘one multiplet a Mise Question’ ice cen meena B (Call) Th “HNMR spectra of compound Akan ‘orcas ofthe signals ars indicated in parentheses) Tho snd aaquattet (2), Identify compounds A and f, jafbon with an M peak at m/z'= 100 witha rave intensity of TTAB, sad mM + | peak witha miatwe messy Teepe mee tnvomantes which» C=C shiek wil cco, svd the fume comma. forthe C=C bond is 10 105 ge?

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