322bf07_final_key

322bf07_final_key - CHEMISTRY 322bL Please‘JiaL— FINAL...

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Unformatted text preview: CHEMISTRY 322bL Please‘JiaL— FINAL EXAM Print Last Name DECEMBER 17, 2007 First Name First four digits of USC ID _ _ _ _ -XXXX-XX TA's Name Grader (1) (15) __ (2) (15) __ _ (3) (15) __ —— (4) (15) __ __ (5) (20) __ __ (6) (15) _ __ (7) (15) __ __ (8) (10) __ __ (9) (15) __ _ (10) (10) _ (11) (15)__ _ (12) (15) __ _ (13) (15) __ Lab Day 8: Time (14) (10) __ (200) first letter of last name I will observe all the rules of Academic Integrity while taking this exam. Chemistry 322bL 3 [p -2- Name Final Exam “QC, (1) (15) Complete the reactions below by providing the missing products inside the boxes. Be careful to give all the important organic products, as requested. It is not necessary to give the byproducts or minor products of the reactions. "Workup" means treatment with water and bringing the reaction mixture to neutral pH. HZCOZCH3 (A) (i) excess LiAlH4/ ether (ii) workup (F0 CH3 (i) Mg / ether (ii) cyclohexanone (iii) workup (B) CH3CH2CH2CHzBr (i) (CH3CH2)2CuLi/ ether (C) 9:0 (ii) workup (i) excess CH3MgBr / ether (ii) workup H o. (i) CrO3/ aqueous acetone ‘ (E) CH3 (ii) workup H QH3 (D) C6H5C02Et 1 strong near 1700 cm" Chemistry 322bL -3- Final Exam 3 M C A (2) (15) Complete the reactions below by providing the missing products inside the boxes. Be careful to give all the important organic products, as requested. It is not necessary to give the byproducts or minor products of the reactions. "Workup" means treatment with water and bringing the reaction mixture to neutral pH. Name Na+ 'OAc (A) C6H5&H2CH3 + Cl' +H3NNHC6H5 H3 Fe (B) + Brz No2 C7H6N02BI' (i) 5.002 C.) (C) C6H5COOH Q H t CH (ii) (CH3)2CuLi/ether, —78°C 5 3 Cal-130 o 0 fl. (1) 1.0 e (I'BU) AlH, t l I _780C \ (D) C6H5CH2COZEt .. q 2 ° “e“ C Q HBCHZ 3 H a c t I , (u) workup L g gives ppt with 2,4-DNP ”LICGLLCW \ O OH .CrO 'Cl ' (E) CH3CH2CH2CHZOH + Q 3 CHZClz O + msg#25135 H H (PCC) flewf Z c}: “WEN Mum? Chemistry 322bL -4- Name Final Exam (3) (15) Complete the reactions below by providing the missing starting materials or products inside the boxes. Be careful to give all the important organic products, as requested. It is not necessary to give the byproducts or minor products of the reactions. “Workup" means treatment with water and bringing the reaction mixture to neutral pH. 0 KOH (A) 2 C G H 53 043 H20, THF C6H59=CH§C6H5 4 £130 1%. GU CH 3 ‘3' é’r‘d/v‘ Br' (i) 1.0 eq BuLi/ ether + (C) (C6H5)3PCH2C6H5 (ii) cyclopentanone / ether G‘d-K‘H - decolorizes l3r2/CCl4 a 0/. (i)1.0e NaOEt/EtOI—l - (D) CH3gCH2CH2COZEt q Q “'1 5 \ (ii) workup M u“ A c / Q c5116o2 H H2 136%“ “3 1% (E) + CH3CH2NH2 T \V , . C9H13N pk ‘63:” $6 I l Chemistry 322bL -5- Name Final Exam (4) (15) Complete the reactions below by providing the missing starting materials or products inside the boxes. Be careful to give all the important organic products, as requested. It is not necessary to give the byproducts or minor products of the reactions. "Workup" means treatment with water and bringing the reaction mixture to neutral pH. feHs Hnw- + CH I (QNHZ 3 (A) CH3 (excess) (100% ee) C. H2 (i) NaNOz, HCI, H20, 50C © " C CN, H O, (B) (11) u 2 warmup (H CH3 H HOCH2 (C) Elm/O BIZ H H O OH 2 HO H complete structure of D-family aldonic acid H———OCH3 [email protected] l- (D) CH3 H H30+ ‘ CH3 H o CHsoCHz H 2 lasa- L complete open-chain structure DC (E) C6H5CH2NH2 + C6H5COOH C O c m 8 ~ ether Col-lg ”2. H C ” DCC =C6H11N=C=NC6H11 C14H13NO Chemistry 322bL -6- Name Final Exam 2% (5) (20) Circle the correct answer for each question or statement below. (A) In the structure below, the oxidation states of the indicated carbons are (circle answer below) CH3§CH2$ H3 A +2, B +2, C+1 A +2, B +3, C +1 A B c “M 3+2, c-1 (B) The resonance stru 7"" a w1 contribute more to the hybrid in each pair below is + CH3-CH=CH(:H2 CH3-CI-I-CH=CH2 CH2=CH-O-CH3 CHz-CH=O-CH3 1 II ' ' I II A B (circle answer) A I, B I A I, B II A II, B II (C) According to the Hiickel rule and experimental observations, which of the following structures are "aromatic" and show unusual stability? + (circle answer below) D O 9 O IandII only 11 II and 111 I II III IV (D) Z-Methylcyclopentanone reacts with LDA (lithium diisopropylamide) in an ether solvent to produce the kinetic enolate that reacts with trimethylsilyl chloride to give as the major product (CH3)3SiCl H3 LDA kinetic enolate major product ether Si(CH3)3 Si<CH:)3 H3 (CH3)3Si i(CH3)3 (circle answer) (E) The faster reacting arene in each pair below in the nitration reaction is H3 CH3 CH3 1 (circle answer below) A I, B I A I, B II AII,BI AII,BII # I II A B Chemistry 322bL Name_____ Final Exam L 37/ «64¢ (5) Contd. (F) Bromination (Brz/ Fe) will provide mostly ortho/para products with which of the arenes below? E (circle answer below) H3 CH NH CH3 N02 I, II and III only I II and IV I II (C) A compound CSHwO gives a yellow precipitate with 12 / KOH solution, but does not give a precipitate with 2,4—DNP, nor a silver mirror with A g(NH3)+ reagent. The structure below consistent with these results is a H (circle answer) CH3CHZCH23CH3 CH3CH2CH2CH2§H . (H) The I{order of acid Hstrength (strongest to weakest) of the compounds below is (circle answer below) I>II>III III>II>I III>I>II ICIII13 (I) aInd (J) Which I01f the following four properties will be displayed by compounds I and II? CHZOH (314on HO H H0 H3 H 1 H (A) Will rotate plane—polarized light. (B) FormsI an osazone. (C) Is a reducing sugar. (D) Undergoes mutarotation. (i)Compound I (j)C Compound 11 (circle answer below) wer below) . all four ( all four ) only A AandB AandC AandB AandC Chemistry 322bL -8- Name Final Exam (6) (15) Answer the questions below. (A) (5) Circle the stronger base in each pair of structures below. ( CH3CH;CH;NH:) CH3CH2 H2 in a IAbliels- er reaction ' ‘ ' ' ' ' reaction with CH3CH20H -NHCH3 *O—f-NHCH—A hydrolysis Wlth H30+/ H20 polypeptide A """"""""" labeled Gly ._qr1292cy2€pti44§€-__- Ala is C-terminal amino acid partial hydrolysis {GlyAla Phe.Gly Ser.Va1 Provide the sequence of the K polypeptide in the box. Chemistry 322bL -9- Name Final Exam (7) (15) Answer the questions below about the aldoses I - VIII. Ho Ho Ho Ho H0 H0 HO HO OH H H H OH H OHH H H H H H OH H OH H H H H H H H OH H OH H H H H H OH OH H CHZOH HZOH H20H HZOH HZOH HZOH CHZOH CHZOH 11 III I I IV V V VII VIII HO (A) (2) Complete a Fischer structure (to the \‘l’ O H right) of the aldose (not shown above) that is epimeric with I at C-2. H OH CHZOH ’—. (B) (2) Which of the above aldopentoses give the same osazone? 131: 3 33— (C) (2) Which aldose or aldoses give aldose III by the Ruff degradation? 1', m (D) (2) Which aldose or aldoses are formed from IV by the Killiani-Fischer synthesis? E] m (E) (2) Which of the above aldoses give meso aldaric acids + { 4 f / when reacted with HNO3? flu 1m 1 M A N 7% “.06 4 O 1141, (F) (2) Which aldose above OH (G) (2) Is IX an on or Banomer? is in equilibrium with the H o( cyclic herniacetal IX? H H 1 (H) (1) Is IX a furanose or H OH pyranose? HOCHZ H extramose IX Chemistry 322bL -10- Name Final Exam (8) (10)You are asked to separate a mixture of benzoic acid, cyclohexanol and phenol using simple extraction technology. You design the scheme outlined below. Provide the missing chemical structures inside the boxes. 1 (i) dissolve in diethyl ether '; and add to separatory funnel E (ii) extract ether solution with aqueous NaHCO3 E solution and separate ether and water phases ,. ............... .L .................. --- C23 aqueous phase 5 (3 C01 Na (0, : extract ether phase (i) add HCl solution with aqueous NaOH 5 until pH ~1-2 SOIUtiOH and separate 5 (ii) extract aqueous phase ether and aqueous phases 5 with diethyl ether and ,- ------------- i ----------- .- a separate phases Eether ®E aqueous :’ """" ‘ E - h : ether : @ 'phase 1 p ase : phase 6) ; § (i) add HCl solution . until pH ~1-2 #V" A V ‘1’ (D (ii) extract aqueous phase ether : with diethyl ether and hase Ese arate hases J)- --------- . ___P ------ P ------------- * aqueous phase Chemistry 322bL -11- Name Final Exam (9) (15) Answer the following questions. (A) (7) For each structure below, add the missing nonbonding electron pairs and draw the important resonance structures that contribute to the hybrid. You do not need to draw the hybrid. (B) (8) Reaction of 2,4,6-trinitroanisole with sodium methoxide in methanol produces an unusually stable and isolable sodium salt called the Meisenheimer complex. ' 3 Draw a structure for this stable salt in the box below. CH3 02 N02 No2 Meisenheimer Complex '——' (ii) (3) Explain the unusual stability of this particular Meisenheimer complex in general terms. Tb; Hem 'N‘two 5"”?5 $002sz +\¢_ Ob‘ktoefi 55$ ember“? QW‘fimSkVL— dl—\oca\(zo~5fi°~\ QS‘ JVKL ’N-jL-Rug 1\'\0‘\S(, Ago Aka. Qogcr-Fvl 1L\t L‘HWM- ‘1)L+\’\A t—aLJ\ OL‘O‘KHT o‘f' +—\J\ OF‘HMD ’V\t‘+l~o fiflulbz £114,wa +Ln._ oxm‘tow. (iii) (2) If 2,4,6-trimethylanisole is added to a solution of sodium methoxide in methanol, will it form a similarly stable Meisenheimer complex? Why? QC“; No. T\M_ ML-i'leu fir-019$ ”K CH3 0 “43,9 W «Ni «mu Lshiathzk +—\«o\ CH5 mxt‘oflm \mhtmtdtkt‘K. Chemistry 322bL -12— Name Final Exam (10) (10) Answer the following questions about valine. Valine is an a-amino acid widely found COOI-I in protein structures (about 6.6% of the ' residues). Its general structure is shown in the box. Titrimetric experiments reveal acid dissociation constants of pK1 = 2.29 and pK2 = 9.74. HZME‘H CH(CI-I3)2 (A) (3) In Boxes 1, II and III provide the dominant structural form of valine at each indicated pH value. an Cat-13) 2.. 111 near pH 10 (B) (2) Provide the chemical equation for the equilibrium associated with pKI. e: H g; (CH3\§u~cchooH + HLO :_.. KCH3)2CH-C|HC01 + 2(o Nl @NHL Q *3 (C) (2) Provide the chemical equation for the equilibrium associated with pKz. _ e @ CCH332EH~QHCOCJ *- \-\.LO :— (CH3)§H~$HC0L+ H30 @Hs ‘_NH'L (D) (3) Define isoelectric point Ehenomenologically. Calculate the isoelectric point for valine and circle your answer. ”Flag \‘SO¢\¢¢+r~iC (Don/(‘5‘ 1; 4—K p’v‘t u.) cm Ck Solk'lrfvv'w. D‘F— W OLMt-KD «Lid Slabs-)3 Mimima~\ @m‘oilgfi -\—o Canduc‘t‘k QMVH—AT. __.___.__——— @ “3P; p\<\ +o\<2_ 2-. 2-1C\+Q-7L1 7. 2.. Chemistry 322bL -13- Name Final Exam (11) (15) Complete the synthetic sequences below by providing the missing structures inside the boxes. L (A) (9) @ H3 C; CH; CH3§ CH3 0 H C CH NH 1.. ‘ (i) Fe, HCl, HOAc 0 (ii) HO‘, H20 / NO 2 soluble in aq HCl C9HllNO (i) C12, Fe (ii) HO‘, H20, heat H 7 (i) NaNOz, HCl, H20, 5°C \\C? 3 (ii) H3P02, H20, 25°C N Ht C7H8NC1 C7H7Cl soluble in aq HCl l (i) 1.0 eq NaOEt 02% 4 (i) NaOH, H20, heat (ii) H30+ (iii) vigorous heat (-C02) Chemistry 322bL -14- Name Final Exam (12) (15) Answer the questions below. (A) (7) Vigorous heating of N,N-dimethy1—3-methylpiperidinium hydroxide (1) yields II as the major product. Sketch a mechanism (using the curved arrow formalism) that explains this result. In the shadow box indicate the factor driving the regioselectivity of this reaction \ S (O~\+N\(L Tim. rL§105¢\k<-*t“’+\( ‘l “.96 mmuuurs'b +‘AL NFL. (or MONA QC? Ac‘g ‘3‘“ _ (B) (8) Reaction of m-chlorotoluene with sodium amide in liquid ammonia yields all three possible toluidines, as shown below. Provide a mechanistic scheme that explains this result and circle and name key intermediates. Use the curved arrow formalism. Chemistry 322bL ~15- Name Final Exam (13) (15) Provide plausible and efficient syntheses of the three compounds below, as requested. (i) C6H58CH2C02Et """""" ’ C6H53CH2CH2CH3 with any needed RX compound and reagents L17\~°“°tN¢-°E*~ (ileH my 0 o ("HSECHZCOLE—r ______——> (#6 :2 cu COLE 1~ —\___z_‘f (FA Q“ swag" cit-4:943 “A H49 v O 445$: MARE?“ was! <2 -ccaz) Q Mica; céquHco; +N_H racermc orm (111) C6H5CH20H 0r C6H5COOH ------- -> C6H53—I --------- -> with any needed reagents with any needed reagents PQC E (.J-lfQHLOH (“29\1_ SOC—\L augcooH -—-> C Chemistry 322bL —16- Name Final Exam (14) (10) To achieve the directed coupling of two amino acids (such as Phe and Gly) to produce the dipeptide Phe.Gly, protecting and activating groups are used. Design a non- Meerifield synthesis of Phe.Gly using the reagents in the box below, and any other needed materials. DCC (see below) isnot necessarily required in the synthesis. Remember to remove the blocking and activating groups. + + (L) H3N(IZHC02' H3NCH2C02' (cH3)3<:o§o§oc(cn3)3 c1803 CH2C6H5 Gly di-t-butylcarbonate ethyl chlorocarbonate Phe (TBOC) c H N=C=NC H c H CH Br and any other C6H5CH203C1 6 11 6 11 : 6 5 2 , needed reagents b l chloroformate DCC : benzyl bromide enz n y 1 Note: You will not need to use all of the reagents + . u H HgNHCH CO - m thls box. There are several WEHZC 6H5 2 2 ways to prepare the dipeptide. ‘9 G3 o o e D Glues o 0 ‘5 H$N<\HC—OL + Rb” E03“ Ho 7+0»- MHfiHud—t (37:32—61? +02 mac‘s-M04505 “5&5“? QfliCsH (- is) T (.1!sz onhcfgd and °~K*t‘\la.h Pkg 0 o C) Q 9 a? 0 C? +OENHQ\4£OEQE+ + HsNQHaCUZ —-——-’>~\—o& NHC‘HL NH CA-tZQeoH éHcsnr «29“: HQ\ or CFSCDDS Q3 0 0 Q) Q - Q H3N§H2COL 'l' +ofloh‘0’r L JVOE N 0115006 k———————1') Ho ('IleHS'CI/Agp C) c) 0 £9 HM +ol£~HcH tow (eHS Ho 2. L H2}! «£00339;— <—- 4 Or more and my QFscool'l ,_. Dec 0 0‘ l: = flaewzwcazmwfl O —-\—o‘é N¥5$H<°°H +~ HzNQttZEoci-QJSQQ .Q\‘5£¢V\ r .- , (MIX (OmJVA @ D¢?r0+¢c.b O O +°XMH$43NHC £5;ng HS- 0 thwsws— a o “Q “3“?” E nu <91 0:. Hog3 0 (9 (605 “*> HZNC—HBMHCH: Ho 4412 {Hafoflr o r ...
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