Final Exam - Summer 10

Final Exam - Summer 10 - Chemistry 322bL Basic Organic...

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Unformatted text preview: Chemistry 322bL Basic Organic Chemistry August 9, 2010 FINAL EXAMINATION K Q Answer the following questions in the space provided. Please to make your answer as legible as possible. If we cannot read your a ' empt given Please remember that C-C-C-C without hydrogens and “stick” struc given N0 credit (except for rings only). entations will be You may use the backs of pages for scratch paper. I. (18) II. (10) III. (30) IV. (50) v. (30) v1. ( 10) VII. (16) VII]. (10) IX. ( 12) x. (14) TOTAL (200) Chemistry 322“. Final Examination page 2 August 9, 2010 LAST NAME I. (18 pts) Provide names for the following structures, or structures for the following names, as appropriate. Either IUPAC or common names are acceptable. (c) Hobs/CH3 (a . CH3\‘=.._ /C—CHZCH2CH2-C-NHCH2CH A) ‘6 ' I ‘ * . - I ~ NH L" L." 5“ N“ u" 4’11.‘ - t 0/ M I n ’ g ’ ’ ‘ ‘ goal” :1 11/4 4] A (d) acetic anhydride (e) THF (0 DMF C3 0 <1) cu38~o~&c:43 <3) \N—-c// M configuration, etc. <5) 75*b’ L 1"“. HO OH . 8Q QC— 0 H O OCHZCHg W OH Chemistry 322bL Final Examination page .3 August 9, 20") LAST NAME ll. (10 pts) (:1) Draw all additional reasonable resonance contributors to complete a good representation for the anion below. Partial structures are provided for your convenience. You may or may not need all of them. (30 pts) Fill in the blanks or circle the best answer for each of the following. III. (3) Give the pKa of the following acids (:tl units). OH O (b) Which one of the following molecules has the longest wavelength Km“ for its UV—Visible Chemistry 322bL August 9, 2010 Final Examination page 4 LASTNAME_fi_~_wnw_fifl__wnmw_‘m_fi_m_ (c) Which of the following reacts fastest with Nal in acetone? (e) Which of these molecules is the most acidic? (Fill in TWO blanks.) 42> F/Q/COQHHZN/QKCOgHCHaQ/ Least (t) Nucleophilic addition to the ac following? (Fill in TWO blanks.) O H <0 Easiest For simplicity, assume that al /C\ /C\ o) CH30H2 H CHg‘CHg O Slggngsi (g) Label each of the followin Which is the least acidic? OQ/COQHOZNOCOQH mad yl carbon occurs fastest and slowest for which of the COZH CH3 W O H 0 ll /C\ CH3'CH2 OCH3 g molecules as aromatic, anti—aromatic or non—aromatic. l of these molecules are glanar as written for your assignment. Chemistry 322bL August 9, 2010 Final Examination page 5 LAST NAME (h) In one short sentence. state what is meant by thermodynamic control of a reaction. Pom , new ‘ when E; flit szt‘efirmmt. rain} if; a“ fit (We (revemlbh pro §~orMQhM1 (i) In one short sentence, state what is meant by kinetic control of a reaction. pmM/frocw (3335’ M Wu , i ;°Vm(lfl ~ v rs.’ gaming gmfiionéhb 0" FE e .W ( j) Circle all of the structures below that do OT r resent valid 711 molecular orbitals (bonding, nonbonding, or antibonding) for l,3,5«hexatriene. (Ignore the relative size of the contributing atomic orbitals. Light and dark lobes represent the “+” and “-—” algebraic Sign (not charge) of the atomic wave functions contributing to each MO.) Mflflm/d’ g g I g V alt H *' e. H2 alt @{gflt/ofi/E ,A é@é%09 9 9'9 alt Megan/ea @(eWHZ/eW/éz 0" e o e e e e (k) Which one of the following most readily undergoes Friedel—Crafts alkylation with CH3C1 and AlCl3? Chemistry 322bL Final Examination page 6 August 9, 2010 LAST NAME IV. (50 pts) Give the main organic product(s) for the following reactions, or provide reagents and conditions to carry out the indicated transformations. as requested. More than one step may be required for a given compound. Be sure to note product stereochemistry and/or regiochemistry wherever relevant. You do not need to balance the equation, show byproducts, or show any mechanism. “Workup” means treatment with water. dilute aqueous acid, or dilute base as appropriate to generate the product shown, followed by isolation of the product by appropriate means. (Note that “No Reaction" is always a possible answer.) (a) (EH3 AlCl 4\- .. Q + CHg-C‘I-CHrCl ————-3—-> gr,” Cr (Mi-CH3 / large CH3 0 H3 \mt X (b) OH 0 H2004 ’ ll HO*CH2 CH ._..__________,, H \ g \CHa H2304, H20- 6) CH3 acetone, 50 °C (C) fi 0 o l 1% H3O peroxides +_ N \ on + N—Br ccuu / 8f 0 (d) cm <3 C 1 excess LiAlH \NHCHg ) Etzo 4 CH30\ a 2) H20 0 OCH3 workup Chemistry 322bL Final Examination page 7 August 9, 2010 LAST NAME (6) O 0 catalytic O Q ‘ CH3 (LL NaOEt J'3 CH3 + CHg—‘zCH/ CH3 HOEt j 0 CH3 C p/ \ ~50 \ 3 2% MM?) W7 *0 Owiyv 91:51] flak" CHVC’ 0‘0 A ((3 CH \ CHg-C\/ \lcwcm3 +CH3020-CEC-COZCH3 ....__.. l ’- 3 H H 1% (“CM ‘ Vole”; C? 4%" M‘w CH3 con/VJ W t H Grieg/Roma + 2CHaCH2M£fi3r 1) Etzo Qus \ H /E“CHJCH} CH3 2) workup 2 \ \ ” CHlCH» 1 %\ (“4’”) WC) L41“. cr‘ ~34; 3 I O (h) OH $1 v" acne HO O rvregsm4 Cu 0/ HO H (excess) Ox NaOH, H20 3 OH 3 CH5 (g) OCH3 (0 AC 0 / GAL“. HO C “22 OH ACZO O ri ine . H&/OH py 0d C /O A C C OH 00 Chemistry 322M. Final Examination page 8 August 9, 2010 LAST NAME (+) U) ( ) fi NH3—CH-CO—NH-CH-CO-—NH—CH2—CO§- éHa 06% ¢\ N/\NH 1) Ph~N-.:C:S, pH ~ 9 \ Q 2) anhydrous HCI, CH3N02 //———.< 3>Ha°“'"A o 043 + Q“ (-5 ms @440 NH CH1 (0,, (k) éuags H-«-« OH HO H PhNHNHz New“ ¢ 2;». A HO H m... (E: N N H ¢ H0 H \4 o H W H O ‘ 4 H CHZOH HM (1) H-— OH 1) KCN, HOAc C” HO H 2) Ba(OH)2, H2011 I OH H ' H HO H 3) H30“) H 0 '4 H H H OH 4) Na/Hg, H20, pH ~4 U (3 H ( h wb th 0d 1‘) , H S O 0 pr UCS ‘ ¥ CHQOH I /n M, H a” H ON CA CH \ 3 % 6JfA ’40” Lb” <+> , Ph’ ‘CH + CH2=CH—PPthr() W 2 Chemistry 322M. Final Examination page 9 August 9, 2010 LAST NAME (n) m w cu -—--m M49: C019 F NHg—CH*CO-NH*CH~COQ’«) N02 61“ /\ \ (EH3 0&2 + g W \‘é/fi CH3 5504:: N02 buffer ‘ MD) 0553043 (0) Pb (mgocH2 O /\O “’0” CH3 OMe H30 C! O 0‘3 ‘4 CHao CH3‘O H :4 0043 l %“ W’ :1— 0 /§:/ (P) 0130 HO“ H CH30H . HO H solvent H catalytic H O n 0“ Hgso4 . OH H 0” CW0 u on (q) o H H H CH20~C——NH -CH—CO-NH—CH-CO ' c'H3 Wm g m H + H Cil..(0-~N)JCH~CO}“> i4 ‘ - @ ‘2» cw Chemistry JZZhL Final Examination page 10 August 9, 2.010 LAST NAME V. (30 pts) Provide reasonable syntheses (i.e., minimum number of steps, good yields, good stereoselectivity, good regiochemistry, etc.) for the molecules shown below starting with the indicated starting materials and using other needed organic or inorganic reagents of any kind except as specified. For all of the syntheses below, show the molecular structure of any group or reagent at least once. Thereafter you may use an abbreviation if you wish. Be as specific as you can regarding reagents and conditions. Show the product formed from each important step of your syntheses. Be sure to indicate if a step results in formation of an ortho-para isomer mixture, but assume that such mixtures are readily separated. Do not show mechanisms. (M53 LINE CH3 its CH3 ~ 1: 4......— lggl 140 ML NpAC H NHZ @NGOH . 3 Q” Mam-l 3 Winn: @G. 'é/‘LBY‘ ___H....___> Nahaz o x . _ Has (not: A, w‘ 8r the“ i . ..‘..... u a o») u 5040 (b) Show how you would use the Strecker synthesis to prepare leucine from 3-methylbutanoic acid and any other needed reagents. (Recall, the Strecker step uses NH4C1 and KCN.) CH3 (+) 002—) CH3 < CH3é3HCH2002H ————— «a» NHa-éwCHgéHCHa flu“ “0 (in C) i ’5 ~ . CU“ ( LPN” (9 Li ulxxéogm o uuqct ll 1 .. 0430441504 MN (3 u o t A 1 £143 Chemistry 322bL Final Examination page ll August 9, 2010 LAST NAME (c) In the following if you get stuck getting to any intermediate, then just jump to it and continue. a ,3 0 ' 3@ <10? l a) 5M 0 .e0 Q CH3 3 Arm M ix) <5 3 Zn (H tomcat} N Cont N00” no“? A’Qu‘fi /t\’l\ “m mmfi CH} ’73) M/ /\ Li L n 3 c) \‘C’ /<: E 9 fl“ L‘ 814 (H CH5 '5 I ‘ ‘\ V"); ‘ 2) <~J Chemistry 322bL Flnal Examination page l2 August 9, 2010 LAST NAME W (C!) The artificial sweetener Aspartame", shown below, is the monomethyl ester of the dipeptide NAspPhec. Given the side—chain monobenzyl ester of aspartic acid (Asp(OBn), shown below) for one of your starting materials, show a synthesis of Aspartame. o o < Aspartame == NAsp-PheC-OCH3 == Neg-owgwrl-oH—aocm (EH2 OH; (+) H 002“) © C01 Cling Asp(OBn) : NHg-oH-Cog Cl” CHQ‘COQCHQPh Q ‘L t l l Phe = fishy-{403" W +0—CL-HH “CU ~(‘OJ H , CHg-Ph wi‘B’KO’l— ® CllaOll HAL)qu en nub 04403043, ® My W $010343 M“ “ ‘ _‘ __ 6 c141 (ms (19 +@ > MD.“ < 40.3-uu~él.l«m~uu.—ol "ho/MP ('0 CH: ED / CD; + maggocomueummcu; on 041325 C(ltuafls Chemistry 322bL Final Examination page 13 August 9, 2010 LAST NAME VI. (10 pts) When the carbon~6 CH20H group of an aldohexose assumes a pyanose form of the sugar, it can eliminate 21 mol ecule of water in forming an internal glycosidic linkage with its own anomeric center. This is the “anhydro” form of the sugar, as shown at the far Pk(:40, HEY/O fight. H OH HO H CH2‘—“O In water near 100 C, idose exists about 80% in the anhydro form. Under the same conditions only HO H H OH M about 0.1% of glucose exists in this form. H OH HO H oUsing chair (or whatever) structural diagrams for H OH H OH an Singdro these molecules, explain the difference in CHQOH CHZOH g propensity of the two molecules to exhibit this , behavior. D-glucose D-idose l C,\uCos@ ((le QHJBH U )4 OH <87 “SSE/JAM s2...— %‘§>fi 0’29 2?in Chemistry 322bL F inal Examination page [4 August 9, 2010 LAST NAME WWW VII. (16 pts) What is the 1° structure of a protein? / 2 7 m A A St @W \ each What is the 2° structure of a protein? LDCEQ situailu -—}.e,. d-heiiyj \\ ll VaMam ) bead/s What is the 3° structure of a protein? Comflfli’B-D QH‘UMIKM - fiiohuidr or In sequencing a polypeptide, what information does use of the Sanger reagent provide? ‘ , ‘ ‘ \ touth N~ 'éerm \waQ ammo 40C” What information does use of carboxypeptidase yield? C‘fflrmiwao AA What information does the Edman degradation give? N “fer/mind? Why does the Edman procedure give so much more information than use of carboxypeptidase? Edwin removes oni 4% M AA mien dead mi so can WIMfi (93mm; ifs-253% gun/K3 §€%WMQ3%\O. ‘3 M Calhoxfjpe‘o‘hdme «93621936 C‘EGUiijlj firvmlh’to A. l . _ W3 av mix” Aafieet‘fe C @avi a. Chemistry 322bL Final Examination page 15 August 9, 2010 LAST NAME WWW VIII. (10 pts) ’I‘rehalose is a disaccharide that can be obtained from yeasts, fungi, sea urchins, algae and insects. Deduce the structure of trehalose from the following data. Be careful to explain what each Qiece of information tells you about the structure, and then draw the actual structure. 1) Trehalose gives no reaction with Tollins‘ reagent or Fehling’s solution. fl— It does not form a phenyl osazone when treated with phenyl hydrazine. It does not mutarotate. M 2) Acid hydrolysis of trehalose yields only D~glucose. 3) Trehalose is hydrolyzed to glucose by a-glucosidase but not by fl-glucosidase enzymes. 4) Exhaustive methylation of trehalose followed b 2,3,4,6-tetra-O—methyl~D-glucose. 5) The structure of trehalose is mum W Mm Mum mm D glaqulbii‘c (acelJT We“ (MW in? We 2) Tim Melanie M Q D»8lucose cirth y acid hydrolysis yields only Chemistry 322M. Final Examination page 16 August 9, 2010 LAST NAME IX. (12 pts) (a) Write a detailed mechanism for the following reaction. Only the fig; structures (in order from 1 to 5 if more than 5 are written) will be graded. A couple of points are given for the quality of the “arrow formalism” that you use. intermediate Note: Even if you cannot establish the configurations, be given for partial are sufficient to demonstrate that you know what the chemical transformations are. Chemistry 322bL August 9, 2010 Final Examination LAST NAME itcéo H O H )J (4 ll H H OH CHZOH D—preposterose, A l HNO3 B, optically active attial credit wil structures if they l ...
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This note was uploaded on 01/22/2012 for the course CHEM 322B taught by Professor Jung during the Spring '08 term at USC.

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Final Exam - Summer 10 - Chemistry 322bL Basic Organic...

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