K E YI. CH310N Spring Anslyn. May 12,2010. Final Exam. Please PRINT the first three letters ofyour last name in the boxes below.

Transcription

1 CH310N Spring 2010 Anslyn May 12,2010 Final Exam Please PRNT the first three letters fyur last name in the bxes belw. K E Y PRNT Full Name UT-ED _ 1) (9pts) 2) ( 6 pts) 3) ( 12 pts ) 4) ( 6 pts ) 5) (35pts) 6) ( 8 pts) 7) ( 10 pts ) 8) ( 10 pts ) 9) ( 10 pts ) 10) ( 12 pts ) 11) ( 10 pts ) 12) (10pts) 13) ( 12 pts ) Bnus) ( 3 pts ) Ttal Scre ---- (150 pts)

2 1. a) Give either the cmmn names r the UPAC names fr the fllwing mlecules. (Frm ntes, 2 pints) OH ~OH L L i 1 _ b) Give the UPAC name fr the fllwing mlecule. (2 pint) C c) Draw the chemical structures fr the fllwing mlecules. (Frm ntes and HW, 2 pints) ""~~J/(!.l_) H N-methy1-(2E)-pentenamide N, N-Dimethy laniline

3 d) Draw the fllwing prjectins f D-ribse. Fr each Hawrth prjectin, circle the anmeric carbn. (3 pints) Fischer prjectin f Hawrth prjectin f t)-ribse Hawrth prjectin f a- D-furanribse 13-0-furanribse \-l---ot'\ H OH r{--t--ok 0\' 0\-1 /1-) V2 0'1 Ot} r, 2. Belw are the structure and the H-NMR f the amin acid, phenylalanine. Circle the prtns that crrespnd t the peaks at 3.17 ppm and 3.42 ppm, and explain the.splitting pattern bserved fr these peaks. (6 pints) Explanatin: H H -rhe's2.. V(0 t (1 <; 0 c e d; a') tej<_t ~ l c. AY'" \(, (\ 0') hclve Clr (c. \ C<. t \9_C lv\e"'-f\ \1"\J l~ c, t 5H H, triplet H H ppm

4 3. a) Prvided are the H-NMR spectra and chemical frmula fthree aldehydes (Hint: A and B react t give C, shwn in 3b). Please give the structures fr all three cmpunds (12 pints) Cmpund A, CSHOO: 2H, t 6H, d ~M 1H,m llili. lh, s H 2H 1H lh, s

5 6H, d ~ 0 ~H H, s 5H,--A---, H, s / H,m b) Given that A and B are the starting materials f a reactin which makes prduct C, prvide the name f the reactin. NaOEt, EtOH Cmpund A + Cmpund B Cmpund C Reactin Name:

6 4. During the last class day, Dr. Sessler intrduced us t the chemical methd knwn as the Edman degradatin. Please briefly explain hw this prcess wrks. What is the name fthe reagent used fr this prcess? Where in the mlecule des this reagent wrk? What infrmatin is gained frm perfrming this analysis? (6 pints) fei'!;x er,jt,. \ Te- \ r \Xl,' i ex'?- rec,d~j! ' ~ W\\~ r; "?r U \ 1 $(Jfh/(t':nl.-:t~. ( (0 t: (l ))(,.1, b ) r J J) } ~{\~ '{ t ) ~\lv"t(!.c. d Or, t~r.v- N-h.i n '.,. \ flus ) ('~/~,)""" T lr, j <, eru->5 \ ~ (r; p(~l"\ +e.r\ C(VV,./'u et(,js d,.",..j t~ ly~(e,," h tl,. tt a. J JT f. l' 5. Fill in the bx with the apprpriate reactant, reagent, r prduct. Sme bxes require mre than ne step. (35 pints) a) Frm hmewrk, prblem 19.53d + NaOEt EtOH b) Frm hmewrk, prblem <: 1. Heat

7 c) Frm class ntes 2. A C 0 U~ - d) ~H ~ ~CN OH Heat ~011 OH e) Frm hmewrk, prblem 16.24a <±) Ph3P~ e f) ~C 1. c> -

8 g) 1) Ntx.N 1 2) L: A\if ) 2) L.; A(r1 ~ \4."'\0 ' 3) H'O'O er-. N H 2...f ~"::: C ~NH ~ MeO.0 MeO.0 MeO.0 2 h), , HO~ ---"~r AC 3 i) Frm hmewrk, prblem 20.14b Kinetic prduct Thermdynamic prduct c + j) r: 1. NaOEt, EtOH 0 ~O~ V0

9 k) 1) Frm class ntes 1. NaN0 2, Hel ~ ~ m) Frm hmewrk, 15.12d n) Frm class ntes C +

10 0) ~N/ ~ ~ LiAH.. 4 ~~ 2.Hp a 1. ~MgBr 2. Vel 1. LOA Df6H... -;f ~H -) 0 r ~. (,

11 6. Fr each f the fllwing cases, circle the side f the equilibrium which will be favred and prvide a brief explanatin. (8 pints) //'...~' ' ~_~'7""'_'.""""".";." ' """ + + H / / 17'f1Jtvr:~,in,.. f ayl!l(\t '!c<lt<, "lw/, 'f'~ rj~;.'l t, 7 f ' r';l7;'i' 10"'" r " C " t be. co"jv)"'kj "ii~ ~J rt.r., 1 '''j' 71, Spt'(,c(.. s s~}.. hp'h' d,l.t.d J ljj rl, t ~( \ [),,~ ;)t " {:, r, ()fbi {t; l (<,.3 Cii,>t',J fi {"{~"'\< (v('."/y:.l,,). 'V.r7 ( J,{ etc (\ nu 1, '" \,,' "i " (," J" t:» "" "r, a v' j ",: r,;, (, (Ji ~"," fw ';":: ;, if", 'k," (, '.~.i. 1 -, s, ',. ",' a-...~ t- ~ 1, ), " \, U-, '\ \ c {.,J,r c,;l,,'y.""f.' \! " ;" "'''\, J,t. (~, "" r- J "":.:",~.;" ( \ ( N r 0\ c,

12 0 7. Please draw the mechanism fr the frmatin f an enamine frm the ketne and 2 amine, as shwn belw. This mechanism is neither acid nr base catalyzed, and prceeds with nly the reagents shwn. Yur mechanism shuld include all participating lne pairs, applicable frmal charges, and required arrw pushing t indicate flw f electrns. (10 pints),.-r \ :, / L-) 6.. ~ ~~-._~ Q 6 XD~jJ? (0" 6 /C) X L/ (_. \, ~.. _,....,..,T'"'!} ' '' >J [J '.' (17 N.,," \ \ / '----1 i c--...., u --_.'~ / i t) r ~,>.,-:,

13 8. Using nly benzene as a surce f carbn, shw hw yu wuld synthesize the fllwing cmpund. Yu may use any reagent, as lng as it cntributes n carbn atms t the final prduct. Nte: yu d nt need t prvide a mechanism fr the transfrmatins. (10 pints) (,., c.j. -.. Hw 3 ---~ > ).A e! i, '.3 Fee ). N;~J) J. Hu ' '-'--"'~ -~~ rlt s....! n,) \l. YC j i'

14 9. Please draw the mechanism fr the hydrlysis f an amide in basic cnditins, as shwn belw. Yur mechanism shuld include all participating lne pairs, applicable frmal charges, and required arrw pushing t indicate flw f electrns. (10 pints) (~),'c::.- G 0' O-f1~:O\{ V "J -----) /""JJH") -( ( \ /

15 10. (Frm hmewrk, prblem 23.57) Shw hw yu wuld synthesize the prduct, an antihistimine Histapyrrdine, using nly the given starting materials as surces f carbn. Yu may use any reagent, as lng as it cntributes n carbn atms t the final prduct. Nte: yu d nt need t prvide a mechanism fr the transfrmatins. (12 pints) CNH+ [:: ,H 6 1b O~N:O Histapyrrdine,~ r ';',.._--~,'" '"; (\ J,.. /'/ )L'A",,, if...j \O~B{ \ ",i /""\ U~ L tj -----~_,

16 11. When frmaldehyde is left in acidic water, it frms the dimerized prduct that is shwn belw. Please draw the mechanism fr this transfrmatin. Yur mechanism shuld include all participating lne pairs, applicable frmal charges, and required arrw pushing t indicate flw f electrns. (10 pints). ~H-() -\ ') ', a U... - H-'\.f1 ~ {~,.),/ ''-../.. - i U H(} 0: -~\ \ <: \ ----~ ' \ t \ ' \\., /?f / --~-,-~-

17 12. Shw the steps needed t cnvert ethanl int the fllwing prduct. Yu must nly use ethanl as yur surces f carbn atms. Yu may use any ther reagent needed as lng as it cntributes n carbn atms t the final prduct. Nte: yu d nt need t prvide a mechanism fr the transfrmatins. (10 pints)./"oh 0 A(O~ ~O' \( c (j \ 1 ~~OH ) ~Oll > ) ( f t j.j" n )

18 13. The Henry reactin, shwn belw, is ne that we have did nt explicitly cver in class, Hwever, the mechanistic steps are similar t the nes we have seen previusly fr carbnyl additin. Given this infrmatin, please draw the mechanism fr this reactin. Yur mechanism shuld include all participating lne pairs, applicable frmal charges, and required arrw pushing t indicate flw f electrns. (12 pints) NaOEt EtOH C! fu):. 6-~ ~ BONUS: While gardening this last weekend, Dr. Anslyn was bitten by ants. What is the chemical cmpund that causes ant bites t hurt?