Final Key - CHEMISTRY 322aL Please 0— FINAL EXAM Print...

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Unformatted text preview: CHEMISTRY 322aL Please \ 0— FINAL EXAM Print Last N me JUNE 29, 2009 First Name First 4 digits of USC ID —XXXX-XX TA's Name Grader (1) (15) __ (2) (15) __ __ (3) (15) (4) (15) __ __ (5) (25) (6) (20) (7) (30) __ ___. (8) (15) ___. __ (9) (15) __ __ (10)(10)___ __ (11>(25) __ __ (200) first letter of last name I will observe all the rules of Academic Integrity while taking this exam. Chemistry 322aL Final Exam -2- Name 3 flack m (1)(15) Complete the chemical reactions below by providing the organic product or products, as requested, within each box. You do not need to show byproducts of the reactions or any mechanisms. Show or describe stereochemical details in the products wherever they are important, such as a racemic form of a chiral product. Pay attention to the prompts below the boxes. (i) NaNHz/Liq NH3 " H (A) CH3CH2CH2C=C (ii) C6H5CHZBr en, en 19M 5-2-5. Q42} A Y 9H5 (B) Hf? VCHZCHzBr + NaCN , . CH3 / acetonitrile (100% ee) CH3SOZC1 amine base (C) CH3CH(OH)CH2CH3 (100% ee) (S) CbHs (D) H '(FVBr CHzCH3 H20 / acetone (100%ee) as 0.. cu.- Me 4;,— heat \ major product only C9H120 CH 1 Ml (E) Br + NaOEt heat 0 3 / H3 ethanol H _ gal-3 mayor product only decolorizes Brz / CCl4 Chemistry 322aL —3- Name Final Exam 3,415.. (2)05) Complete the chemical reactions below by providing the organic product or products, as requested, within each box. You do not need to show byproducts of the reactions or any mechanisms. Show or describe stereochemical detai s in the products wherever they are important, such as a racemic form of a chiral product. (i) hot aq. KMnO4, KOH (ii) 1—130+ (A) (i) 0304 / pyridine (ii) aqueous NaH503 H3 . (C) (1) BH3THF/THF CH3 (ii) H202,KOH/H20,TH1= (i) Hg(OAC)2/THF, H20 (ii) NaBI—I4, KOH/H20, THF h (E) /V|\ + HBr eat peroxides Chemistry 322aL L 4- Name Final Exam 3 #6 fl (3X15) Complete the chemical reactions below by providing the organic product or products, as requested, within each box. You do not need to show byproducts of the reactions or any mechanisms. Show or describe stereochemical details in the products wherever they are important, such as a racemic form of a chiral product. (A) 00H + PBra T 031-- product is insol in cold, conc H2504 v 2 5‘»- OH (i) NaH/THF h I s (3) CH (ii) CH3I M 41‘4“" H (C) + Mg“ CH3 :2 (D) C6H5CH2C ECCHZCI-IZOSi(CH3)3 CH3CH2,’ , NaOEt (E) CH3CH2> CK“;in O EtOH Chemistry 322aL -5- Name Final Exam A 3 Ac (4)(15) Complete the chemical reactions below by providing the organic product or products, as requested, within each box. You do not need to show byproducts of the reactions or any mechanisms. Show or describe stereochemical details in the products wherever they are important, such as a racemic form of a chiral product. oH (A) CH3§CH2CH2CH2COZEt (i) NaBH4, HZO/THF (ii) workup as q Vt‘um“ ‘er C8H1603 (i) excess LiAlH4 / ether . B C H CH COOH ( ) 6 5 2 (ii) workup (.ka CHILHLD H product is insol in aq HO.- pH (C) CH3CH2CH2CHCH3 + 003 H20 / acetone (1) Mg / ether (D) 3 (ii) CH3CH2CH2 H (iii) workup (i) Mg/ ether (as a racemic form) (iii) workup (E) CH3CH2CH2CH2Br Chemistry 322aL -6- Name Final Exam (5) (25) Answer the questions below. (A) (10) All the valence-level electrons are shown or implied by condensed structural formulas in the chemical species below, but formal charges are missing in some cases. Indicate on the line below each species whether it is a cation, anion or neutral, and add all missing formal charges to the structures. Place the charges immediately next to the atoms on which they reside. (B) (10) Indicate on the line below each structure whether the structure is chiral or achiral. Identify all stereocenters in the structures with asterisks (*). A stereocenter is defined according to the definition used in lecture and in our text. I‘M HZCHZEHBrCH=CH2 ceral (C)(5) Indicate whether the following pairs of structures represent the same compound (SC), enantiomers (E), diastereomers (D), or constitutional isomers (CI). Chemistry 322aL -7- Name Final Exam (6) (20) Answer the questions below. (A)(5) Circle the more stable isomer in each pair below. (B) (15) Answer the questions below. (i) (3) Provide a complete lUPAC name for the \ the structure to the right on the line below. (i - -n:..+\\ —- - 2;“ (ii) (3) Provide a complete IUPAC name for the o 0 the structure to the right on the line below (PQ- im’~‘¥‘\ Kl g I. a '0 u. r‘ «H- r «n - H 9 <1 (iii) (3) Provide a complete IUPAC name for the the structure to the right on the line below. -- 3‘bromo -'j—- net—N; l-l*E°~“"*Km K (iv) (3) Provide a complete IUPAC name for the the structure to the right on the line below. S-Sk!‘ PO -' fibflfil‘r mL+\3\"l-gflj~( Pg (CgCflYQCHZ BED (EH3 HCECCHZCIZCHZCI CH3 L (v) (3) In the box to the right, complete the Newman projection formula of the meso diastereomer of 2,3—dichlorobutane. 46 mt” 1 % (flu. JCMW. Chemistry 322aL -8- Name Final Exam 1 A/ «dac (7) (30) Circle the correct answer for each question or statement below. (A) The correct molecular formula and U-number (degrees of unsaturation) of the structure below are (circle answer below) NCOOH (29111002 4U l C H o 4U C9H1202 5U / 9 12 2 (B) The numbers of valence electrons in the two chemical species below are (circle answer below) 16,11 4 17,115 methyl radical methylene (CH2) I 11 17,114 (C) Intermolecular hydrogen bonding is important in the condensed states of (circle answer below CH3CHzg-I C6H5CH=CH§OH (CH3)2CHCH2NH2 1,11,111 I II III I, II only II (D) The order of acid strength (strongest to weakest) among the labeled H in the structure below is I I ,3 :1) (circle answer below) H-CECCHZCEHCHzo-H I>II>III I>III>II H p III>II>I / III>I>II ) (E) The order of base strength (strongest to weakest) among the following carboxylate amons IS _ _ - (circle answer below) c113cho2 CH3CHC02 CH3CHC02 1>11>111 CH3 F C1 I II III II>I>III II>III>I (F) When the following alkyl bromides are reacted with N aOEt/EtOH, the ratio of (substitution product lelimination product) will be largest with (Circle answer below) C CH3CH2CH2CHZBr) (CH3)3CBr CH3CHCH2Br CH3CH2CHBr ‘ CH3 CH3 Chemistry 322aL -9- Name Final Exam 1 “ch (7) Contd. A (G) Which of the following observations are consistent with the SN] mechanism for nucleophilic substitution? I The reaction rate does not depend on the concentration (circle answer below) or choice of nucleophile. II A change from a polar protic to a polar aprotic solvent I,II,III I,III,IV leads to a dramatic rate increase, often many powers of 10. II,IV III The products may show rearrangements occurred. IV When the reaction is at a stereocenter, inversion is observed. (H) What are the expected alkene products in the reaction below? 2V NaOEt M N )K/ EtOH r I II III I is major, II is minor II is major, I is minor II is major, I and III are minor II is major, III is minor (circle answer) (1) Which of the following addition reactions to 1,2-dimethylcylopentene are stereospecific syn-additions? HI epoxidation catalytic 31.2 /CC14 (Cifde answer below} with a peroxy acid hydrogenation II, III, IV I II 1 III IV only III I,II, III (I) The number and types of separable monochlorination products produced in the photochlorination reaction of 2-methylbutane are (circle answer below) four products: 3 achiral one chiral our uoro ucts: 2 achiral, 2 chir I five pro- ucts: 1ra , one chiral five products: 2 achiral, 3 chiral CH3¢HCH2CH3 + C12 CH3 heat CSHIICI (K) Photochlorination is carried out on butane. If the relative reactivities in this reaction are secondary-H/primary-H = 3.0/1.0, the observed product ratio (I/ II) will be hv heat (circle answer) I/II= 2/1 3/2 2/3 @I -~' -—- 1 (1 g 7/0/19 my) CH3CH2CH2CH3 + c12 CH3CH2CH2CH2C1 + CH3CII-I2CHCICH3 "g: Chemistry 322aL -10— Name Final Exam (7) Contd. l «Ck (L) A comparison of the photobromination and photochlorination reactions of 2- methylbutane will reveal CH3QHCH2CH3 + X2 CH3 heat (circle answer below) Canx -P a o - nomination is faster and much more site selective. -Photobrormnation is s ower and much more Site selective. -Photo '1 cum on IS aster an- much more site se ective. —Photochlorination is slower and much more site seledtive. (M) Which of the following procedures will convert propene into propyl alcohol? oxymercuration then demercuration direct H+/H20 I II hydroboration then oxidation HBr (peroxides) then KOH/ H20 111 ' IV (circle answer) 1,111 1,111,1v only 111 (N) In the reduction of A to B below, the change in the formal oxidation state of the bolded carbon is (circle answer below) I—I CH3CH23H "U"- CHgCHZCHon +2” -2 +2 -~> 0 A B +1 -+-3 (0) Which of the substituent groups (G) may not be present during a Grignard reaction as shown below? (circle answer below) + RMgX ........ , only I I and II 1, II, III, IV C G = (3112011 -CH3 -CH2NH2 -C SCH 1 11 111 IV Chemistry 322aL -11- Name Final Exam (8) (15) Answer the questions below. (A) (10) Provide detailed structural formulas for A,B and C within the boxes below based on the provided information. Answer the questions in the shadow box below. Compound A decolorizes a solution of Brz/CC14. 1H NMR single resonance 13C NMR two resonances A (:Q‘Ht5 V H /Pt Li poisoned catalyst liq. NH3, 63°C Provide complete IUPAC names for B and C on the lines below the boxes. What is the stereochemical relationship between B and C? @ D§¢K%+lfio mt T‘S .. MW af ”(17‘ mm .2:er (B) (5) Provide detailed structural formulas for D and E within the boxes ase on the provided information. 7’ O H H+ H Pt (3 .. ® 2/ ea 13C NMR shows only a single resonance D C6H120 E CGHIO ir: strong bands 3200-3400 cm‘1 (i) 03, (31.1202, -78°C (11) ZR, H2O HgCHZCHzCHZCHzg-l Chemistry 322aL —12- Name Final Exam (9) (15) The photoinduced free radical chain bromination of propane at 125° C produces a mixture of 1-bromopropane and 2-bromopropane, as shown below. fir CH3CH2CH3 + Br2 M. CH3CH2CHzBr + 0&3;ch3 (3% ) (97%) (A) (4) Calculate the relative reactivity of a secondary-H to a primary-H in propane at 1250 based on this result. Show all your work and place your answer in the box. R1914 gfi-h ._. 31 (Putt lie-+1 I) “Z 1 fl ‘— X «ch T“ ~ 3 ’H Q17 (‘14 U l '7 X’Vl‘l‘k R , .31 Rt“- 11 1. fi— —- ,_\fl7 R110“; k<%> .— 3 ~R..H- 3 )(l J l l R(2°-H)/R(1°-H) (B) (6) Use the homolytic BDE values in the table in Appendix A to calculate the standard enthalpy change (AHO) for the rate-determining step of the competing free- radical chain reactions that yield 1-bromopropane and 2-bromopropane. Note that you will not need to use all the values given in the table. Show your calculations and place your answers in the boxes below. (i) 1—bromopropane c 0“ CH + 3 . ___9Q\-\3QHCH +~ HBr ‘ H3 1 3 .- " 2' 1° 5;? °- _. — .. g +C(82+l0 (ii) 2-bromopropane ' t CH3¢’+&H3 +~ Br" ___, cHschHJ +~ HBF +1 1%, ZC—H (C) (5) The BDE of HCl is 103 kcal/mol. Briefly explain how this value explains the much faster rate of the photochlorination of propane at the same temperature. For fi-k‘ mfisut TOD EDS “~31?“ CL.) . c ' QL§¢HLQH3+ <\ —9 CH- H‘LCHL +— H-C.\ 5H0 : 395933," BDE _ z-gsfiszfl AHO .3 bHD 7- —103 4— (as; -—S Kat/Mal . ’9 cu duck» + %\ cuscuz'cuji—ct O J 5 Q \gui/VNW ow :—\°3 +—C\S =- ” 50+k caMPL—HMS K03 qu Q£e+k¢rmts \o. 3‘ (a U0 r- Q’KC F57 bal‘fi.‘l"-3 QE¢ ephgflflq‘ki €1,311:— mfg - Chemistry 322aL -13— Name Final Exam ' (12) (10) Define or explain the bolded terms below as they apply to the reactions described. (i) (2) Markovnikov' 3 rule applies in the ionic addition of HBr to propene. cuscuau,‘ + 143,. ———> Q\‘¥3<HBrQA The rum swag +1“? ix Hag “4—4-\'\'\°~\ rt ‘7” “‘3**~*3 "V‘o umSjHM¢ *h‘t¢L\ QU‘e—Nzfi’ 'Hng H adds +0 "rkK C0,? ‘DOvm ‘QL+\'\ T-kfi art-«1‘1!- "\Kthq— O‘F‘ H . (ii) (2) The Zaitsev product dominates 1n the dehydrobromination of 2—bromo-2- methyébutane with sodium ethoxide in ethanol. QH3 “gunmen; +~ Naosa- —“" “acumen; 4— <44 3% 25'— CH2. C H 3 MG 3 a h M ‘15“:1 E'CLPl'Slqs {‘qu 1*‘313 +\"‘:* "N 41'“ SK d‘\fidr°k“l°3&-K.HO'K F‘L‘LcHOms +4“ mayor °-\k¢«g Fwd u._+ Ros fkc. firm-CHE mun—Eoc- 0“" O—\\g\(\ 31"" P5 QNK'KA. fi'kk (lu‘hh‘ k“""~d. (iii) (2) There IS a stereoelectronic requirement in the removal of a B-proton 1n the tertia utyl carbocation to form isobute ”Q: ne. cu @565 U W4 (3.5% ng ‘C 6‘3 T'lM. Q: \MMN‘LGA Mo mu 1* lug o.\\1:._¢L ‘0\‘\’\A. ”Fluv— O'g- +4.; Cuvb°e-+§ork+¢'€ae.ilr+£f< ‘Gf-hAa-f-owa a“? +k'x \0°~\11‘W3El/T‘-HO PK +ko O-\\&- x3. . (iv) (2) )poxidation of (Z)- -2-butene with a peroxyacid' IS a stereospecific reaction. l Pa ‘V‘L‘l‘ 9, :6 H Eu .1 3c“ -—‘—‘> CH»; O‘Q‘Hl XCfl({ZYH3 a...» CI} 7Q‘C93 4’2“!» R—Q"°Io\/,¢ " ogck H c': i’o A sYM-«iii-Hom occurs. TL.‘ Mcskofi'zk clogs 15+ «HOLD +L"\ . . . . 0 'HM '1" d: 013in N:- (V) (2) The hydroboration of 1sobutene is a hi hly regioselective reaction. ha \I' (c Cb ‘m Po.“ (CH3) 4: QHL + BH- THF aLCH-L ;\}§§;E +° ”g“ 9C¢H9§rzq1l+z H"B—I+ T7“ Cbmph.‘ \F-f FUuC-u-Ku r- TS «Ada +6 *kk l¢¢~§ SKESR‘L-aj‘; Cat-Ben. Ar. bafk S+lr¢¢ a-g‘w‘d— Q\‘ QW’I-J'C F‘ku3m3 A Chemistry 322aL -14- Name Final Exam (11) (25) A Table of Reagents is provided in Appendix B for your use in designing the syntheses requested below. Other reagents may be used as needed but the syntheses must utilize the indicated starting materials. Each step in a synthesis must be a separate chemical equation showing reagents and products. Mechanisms are not required but stereochemical details in your structures must be shown, wherever they are important. 1-methyl-trans-1,2-cyclohexanediol (as racemic form) E! .4 a at; C0 \ +— 3 1—} ‘3? L/ @ CO? ”8' 1*“ r L/ Kb“ M 2 H DfH-t T- MP? C- 0H .r H OH H3 H 3&0 C610; cums: Mtg) (C) (5) ““““““““ ‘> C‘t't '3 2-methylcyclohexanone ‘ C 1 3 B H 'TH F (as a racemic form) G 3 [THIS CHS’HOH C 0 CH5 \. fl _ (“\HtothOt-‘IHLO 2 H ~LLfl~> / 3‘11 {truce—oil) O Chemistry 322aL -15- Name Final Exam (11) Contd. (D) (10) Design two syntheses of 1-phenyl-1—propanol using organic starting sources selected from among the following compounds and any other needed reagents. All the carbon atoms in the final product must come from the allowed starting organic compounds. QH C6H5CHCH2CH3 1-phenyl-1-propanol S" “(A allowed organic starting materials CH3CH20H CH3CH2CHZOH C6H5CH20H CH3CHzBr C6HSBI' CH3C Hzc H231“ Not all of the above compounds will be needed in the syntheses. Synthesisl O C A C 0H + CVO “Cl C b S‘ “1 @:r J m1$\q__> “H32“ \'QQL.'~ Br‘ M ca Q“ m: : Cal-l ‘2... 0 g 3 2-3? Q+kll~ QHSQHLM'fign fl CeHséCHiff-Il OH H C \{éucu cu ~_§ ‘ L 3 < H3o® Synthesisz ‘? csscucww {o «rot-Hex M3 caches or "Pee" 0 a Mo, Cd Cu 2+: 0““S ” fl 3 H ...
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