zimm-exam2-Fall05 - Organic Chemistry 345 Name(Pleasé...

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Unformatted text preview: Organic Chemistry 345 Name (Pleasé Write Clearly) Fall 2005 Exam 2 Student ID means) 'Seat Number Question Points Grader's Initials 1 L 2 § 3 3 4 2/0 10 n L _ 13 9 NOTE: 2 Pts for each Equation; 5 Pts for each Explanation. Organic Chemistry 345 Fall 2005 Exam 2 - a 95/5 1 1) Give the products of synthesis as isolated after workup. a) p-Methoxybenzaldehyde + Diethyl Malonate FMQQ@-CH:Q(C°OEAL {5 EtzNH EtOH ‘l 2 ti b) PhCHZCHz-NMe/Z ——>Excess M64 I M PA cuycHLAC/DMJ .. 1) 2 KNH2, Liq NH3 .c) Ph-C-CH -C-CH -CH .,' - - ('5 2 H “2 3 2 B IB 'd PFC/wig (I: “5' o I ) enzy_ row 9 [(1> D CH3)“; N d) “ U 1' {bk/“1.90 Cl /COOMe )N 0 EB 7 9 2"on e) 1 a Me, t r k - - “A .. ‘ Ph-CH . CH tooH - - \COOM 2) Di! NaOH A P 2' 0 -. New; e o 3)A110 o f) ' 1) N OEt ' CW». a . CH3-C-CH2—COOEt C c—CH«00°E’(’ g 2) Benzyl Bromide g g) Ph2/C-C\Ph2 H+ - Where”); HO OH 0 “III6 ' Q” h) Ph'fi'CH'CQOEt 1”“ (f; ' o . Ph COOH G 4:00;} 1) Ph COOH 110°C pt" o Phthalirnide _—_.. _ 9.. cegflfihflé j) 1) KOH,EtOH o / 2) n-Butyl Bromide e 2) How do you explain beta-dicarbonyl compounds having a pKa of about 10 (i.e. Ka = 10'”) While ordinary ketones have a pKa about 20(Ka = 1020) ? Use Acetone and Cyclohexane—1,3-dione as your two comparison examples. Your answer requireélrawing some resonance structures. Draw all wlnch are posmble and relevant. Q - - .i O: ‘5 ' 16 m 3. ' = I n D (21127? “473% “a” if“). L/ 11 J (g: M 3’ 4:60.434“. s (imam; Organic Chemistry 345 v o Yuma; m alt/QMU mmfixfiéi/flq SKI u.de I C. Fall 2005 Exam 2 Name (Please Write Clearly) 3) Number the following in order of Increasing basicity (1 Least basic, 3 Most basic) CH3CH2CH2:' _3_, LDA 2.,Ethoxide I . 4) Give the products of synthesis as isolated after workup. o /’\ a) an“ ’?>j‘° Ethylene Glycol, TsOH A K o I quc. god“ i b) Dimethyl Adipate ———> ' NaOMe c) OMe I I 0H. _, a +— We HI A - I ‘ 2.. d) O-CH2-CH=CH-Me 0H [M ' CH u ' w ’ \ A e) + _ N=Q=D Phjfi-rthN benzene A o --— OH 0 f) Fremy‘s Salt @ - > _ (K803)2N=o r . Na. 0 - I I g) p-t-Bu-Ph-ONH2 . Clo-1L8“— (911”PHL> 4‘4. f (5:! H NaOCl +6 0 ' K. (H (W h) s s 1)BuLi 5 S‘ Y 2) Benzyl Bromide Effie Et . - b H 1) Ph - PM N /\C(COOEt)2 It}. )0” Et . Urea, NaOEt Bf )S—fi o ' u . . - _' -Q-‘IJHMQ - J) Ph-N=C—O MeNH2 ,014..NH 5) Write out the mechanism of theCurtius Rearrangement. As usual, put in all arrows, charges, unshared electrons. Organic Chemistry 345 K Fall 2005 Exam2 Name (Please Write Clearly) 6) Give the products of synthesis as isolated after workup. 0 a) 1.Benzy| Iodide 0 HUPL) N (5 2. H20 workup b) Ph-C—NH-Et “A'H4’ Etzo Pk ~ C H:- VH E”! MeO d) MeZC-OOH G diIHZSO4 A “s . «6 e) * KNH2 ‘0 +_ I: Q Liq.NH3 Q I)“:— NH; Cl * is a isotopic carbon; just use the * to designate it in the product. 1) Ph-CHz-CHz-clsH-CH3 )0 Lr-c Harcch FETCH» NMe3 OH' '® (+3 . - g) e o\ HMEZ _ A [ . I m . h) N@ ET I Br H3P02 @1‘ Me 3* i) p-Bromoaniline @ r 1) HNo2 2) CuBr 4" C Li? . I _ Ethyl Propionate ——> c (43c (4L0; Circa ° C‘f/ NaOEt 1'7 Organic Chemistry 345 K C __2‘_ Spring 2005 Exam2 Name (Please Write Clearly) 7) In the equilibrium between hydroquinone and quinone, which way is the equilibrium shifted by introduction of a cyano—group at carbon 2? Explain stabiliza‘ztgn with one important resonance structure. :O’H «341/th fix (it: "Q hVM‘tm 9M Wot Qua/s 461:1: N: —————/— 8) Which is more acidic, p-cresol or p-nitrophenol? e-IJOM’LEMI , (ans). Now, Draw the resonancestructure responsible for the enhanced acidity. [tum gag/nerd“ .. «mew/v hm): K ' ' @ a r Meiji) fi fi 9) in the Hauser method of selectively alkylating a 1,3-dione as Ph-C-CHz-C-CH3, ‘ draw the dianion structure and indicate which is the more basic site which thus is %_ alkylated With (e.g.) methyl iocll‘ide. g: Q 8km“ . rim»! 31c ,- __'"4_Q.—éz{ hasrc a m“ Wig .Pk,§;.é.z+s,:CHz. M‘C I414”??? at g: 3’ riff 3 “WM o' :0‘- " 10) Explain the difference in basicity of p-cyanoaniline compared with aniline. Which is more basic? l in . Nowgaw the resonance structure responsible‘for th difference in basicity. [{— IN 3(0)sz ill-wr- tr less 50:: mam Wino Wf. I "i ' as 3\ c [744:5 Rem/twice}: Ari” IZ— 'fi‘k WM» “In/0% ill/:9 IS MMJ‘V’ Amine is treated with Benzenesulfonyl Chloride and Sodium Hydroxide solution and the solid amine dissolves to give a clear solution. You can conclude that it is a EYImWZ (Primary, Secondary, Tertiary) Amine. - ‘ 1@ few 12) You wish to synthesize m r m, enzene and have p— cetanilide as the starting maten'al. Give a reasonable synthesis. (HINT? Brominate first). W“ W” firm. :I RV" firm/8w I 8 q; Fe Big ; l / @ 1W ' > 1/ CH} Gib air I 05 914390; How) Kc»; 13) What base could be used to prepare LDA from Diisopropylamine? 1314 L: (Butyllithiurri, Lithium Ethoxide, Lithium Hydroxide) BLANK SCRATCH PAGE FOR YOUR USE — BUT N O ANSWERS ON THIS PAGE WILL BE GRADED . W Exec/0+ @y /3 - ...
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This note was uploaded on 03/27/2008 for the course CHEM 345 taught by Professor Zimmerman during the Fall '07 term at University of Wisconsin.

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zimm-exam2-Fall05 - Organic Chemistry 345 Name(Pleasé...

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