PS_7-Key - Problem Set#7 Swager 5.12(Due Friday November 4...

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Unformatted text preview: Problem Set #7 Swager 5.12 (Due Friday, November 4, 2011 at 4PM) 1. Consider the following reaction that occurs by a free radical chain mechanism. A2 + CD -———> AD + AC The bond dissociation energies (kcalr‘mol) are: A-A 40 A-C 70 A-D 65 C-D 80 a. Write the initiation and propagation steps for this reaction. 1:). Calculate the reaction’s free energy. 0. Which is the rate limiting step? Explain. 1:! o 'en fle‘[email protected] A'T‘EUE -—'> Ac + 0' ___§ waters-“r 5mg 24' +40 +30 - 7O 4/0 +40 ~95” 2. Give the dominate mono-bromination product(s) from these radical reactions. Explain your answers. [trey-£4 “ /“ <5- A's /\ / m Cf \ z, x 9 —- a, ’15.- fir "B.- NBS AWE” \ RO-OR, heat :6" fir m 8' 0'? this “'5 > 0 3/ I :‘ncfeusir? \ (—1"- l 5*:th 0 é' 6:- 1 """~ '---.. In 1;» r :3 R0-OR,heat 31‘. 5‘ fir 2 am: ' l H: '53. _ M-v o6 WW , \/- . ‘- + \¢ 1 a / / NBS /)ér\ ,8 "' RO-OR,heat ' "Wt stable {8- . \ 3. Rank order the reactivity of the indicated hydrogens for an abstraction reaction by a free radical halogenation. Explain your reasoning. 1 MM 3 Magi—:15 R 3 W A |-I2(3:(3|-|2 B A C T l T raw '9 . “V “NE/{D /\. /\/ MM_ 4. Radical chlorination reactions with CCL1 and peroxides begin with the two initiation steps shown below. Which of the compounds A-D is the product when the hydrocarbon shown reacts with CCl4 in the presence of peroxides? Provide a curved arrow mechanism. A .. Ro—{jR —u- 2R9- ' Initiation steps Rad/34233.3 —.- Ref—c]: + -CCI3 Rooaicclg1 F EEK; cu CI3C 0'30 A (:1 0' B colEl CCI3 D c: C5530 ‘7 fl; -——-7 C/// > -——-7 u ccl3 M w'flifi- M W Cl C C! c 4r > 3 —'CC[ 5. Which reaction will proceed at the highest rate? Explain your answer and why the other reactions have lower relative rates. r 6/ MAL M *6 N ON A c” L QM "‘3'? .6.;°a;:' DMF ban m __ C- 21? 6. Rank the following series of compounds on their ability as nuoleophiles (l=best, 4=worst). Series 1 H20 NH3 PH3 GPHQ 4 3 a" ’ mg 916.: {Zak}! ' a E” 0"“ F «f Polarfifiu Ho. Series 2 ext %CH(CH3)2 %CH(CF3)CH3 655305, / a? 3 7L Pagoch geelaflu’flggtl M W. ‘2 «a a: (flacciwolel K g m {piecing-w gi§k€lrwmd ‘ a: gleam“ \93 wt meufwg (indgc-anch flaw—I" 7". Rank the following compounds as leaving groups (1=best, 4=wors ‘IT ‘IT eNH2 %H C“b—s-——oH3 eb—T—CF3 | | ,L o o \ #3 go bowl ‘f’ke‘fi q“: {104' i cc} LC: 8. Rank order (1 = fastest) the relative rates of the following compounds for 8N2 reaction with NaCN in dimethylsulfoxide (DMSO) solvent. Would you expect larger or smaller relative rate differences for 3N2 reaction with N aOCH3? (Hint- consider the relative sterics of each Nu") ‘5 Br Br 5 ‘5 Br Br Br 6”: e E m A B C D E o 3 a 20 / 9/ stew: Ia u/g‘ltm‘c loam! 6'_ 5+3“; Mats-99”» f {A ¢_F:!U-k- f“ Lurk! p; I 6+cfl‘t. {he on or W: X C {he fl C Shfltjflgk 5"“; 4'3 $0 fit “mv‘ltfl c'F‘Fec-‘LS ($1. 5 “fit/"W ’0’ Er- éroM-f’f m-H Herve, [4036" 5-0 Airécr rel. Gear-abet e “(335 m-l'e d .--C'Peren c #5 ...
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PS_7-Key - Problem Set#7 Swager 5.12(Due Friday November 4...

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