FinalKey_Wi05 - NU Chem 210-2, Winter 2005 Final exam 2 l....

Info iconThis preview shows pages 1–6. Sign up to view the full content.

View Full Document Right Arrow Icon
Background image of page 1

Info iconThis preview has intentionally blurred sections. Sign up to view the full version.

View Full DocumentRight Arrow Icon
Background image of page 2
Background image of page 3

Info iconThis preview has intentionally blurred sections. Sign up to view the full version.

View Full DocumentRight Arrow Icon
Background image of page 4
Background image of page 5

Info iconThis preview has intentionally blurred sections. Sign up to view the full version.

View Full DocumentRight Arrow Icon
Background image of page 6
This is the end of the preview. Sign up to access the rest of the document.

Unformatted text preview: NU Chem 210-2, Winter 2005 Final exam 2 l. (30 pts) Complete the following reactions, be careful to give all the major carbon-containing products, starting materials, or reagents. Clearly indicate the stereochemistry when relevant. If there is no reaction, say so. Assume that Friedel-Crafts alkylation can be stSpped at single alkylation.B Iced-M1, 4, ‘ B G N 984“? a; __ a) rise/c133 7») #51; mob 6’“ Q ” — 3) 7 ‘3') A a) a) C w” u A 6) “30" a = a, 4) 345°" [0) swr‘m/s w 9mm; amt "on hammer-affix L (PM O = ) M 0* Z) 3) W3 Ref l 9W b) 4) Zia ) A/Ztl O W C" My“, u/ 9.4pr I‘m/’63 CF3 Q Ca?» )Fowfi CF3 1) Hum} J “1504 a a ma 0 a C) / y' J N/u\< all No; 4) “'003) “150* 5) HMO; O H 9T$0HW) V0”, .5 911; o d) A Z) up” emu. E01 0 “5,03 7 Mot OH 97.1: 2) Q’Va) Fog-W3 0 6) Q 3) K095 A NJ\/ 4.) Zn (i ) We 4) 51:6 2) "93 WW g) (541 / 3) Zkotfiw) A NU Chem 210-2, Winter 2005 Final exam 3 2. (30 pts) For a-c, gives the IUPAC name of the structures shown. For d-e, complete the given reactions, be careful to give all the major carbon-containing products, starting materials, or reagents. Clearly indicate the stereochemistry when relevant. If there is no reaction, say so. a) (5 pts) Using Hfickel’s rule only, classify the following as-drawn planar molecules as being aromatic, antiaromatic, or neither. Write your answers below the molecule. If you cannot tell, say so. H H | H H 5'3 3 [it . \ W m /_\ w 0 [.159 @09 M W W Mm i“? m. g b) (4 pts) Match the following compounds with the following pKa values: 4.3, 4.19, 3.98, and 3.41. Write the appropriate pKa values below the correct molecule. - 1P1“ 4-nitrobenzoic acid benzoic acid 4-chlorobenzoic acid 4-methylbenzoic acid 3.4! 4.1? 1.?! 4.3 c) (4 pts) Match the following compounds with the following pKa values: 18.0, 9.95, 7.1, and 7.8. Write the appropriate pKa values below the correct molecule. thiophenol ~phenol cyclohexanol 4-nitrophenol ‘9‘“ 1.? Q4? {to . 7n! d) (4 pts) Match the following compounds with the following pKa values: 10.64, 9.74, 5.25, and 10.72. Write the appropriate ‘pKa values below the correct molecule. MeNH3Cl MeZNHZCl MegNHCl pyridinium chloride 10.64 torn 4.14 » 92? e) (4pts) Arrange the following dienophiles in order of better reactivity toward cis-1,4-butadiene: l'xu ethylene, ethyne, bengyne, 1,2-dibromoethme. (369i > 7 >Wm$€ wt“. gm)?» 555*A‘MM 2% f) (5pts) Arrange the following compounds in order of increasing chemical reactivity toward nucleophilic acyl substitutions: acetic acid, acetamide, acetyl chloride, acetic anhydride, ethyl acetate. LEAST WW < C MT (26mm ' é {(xu mmh"wz,am gamma madame Wm g) (4pts) Arrange the following compounds in order of increasing N—H proton acidity. Place 1 under the most acidic structure and so on. 4 would be the least acidic. O p O . O ' 0 NH NH /U\ "— 2 . 6;? El «M w" o OW> I z, 4 § N (V (V V Nah; N’s/fl} N NU Chem 210-2, Winter 2005 Final exam 4 3. (30 pts) Propose a curved arrow mechanism for the following reaction. Show all the proton transfer steps. Please make sure to show the mechanism in which the oxidizing species NO+ is generated. a O NaNOz, HCI (aq) \ o - 5°C at; Ho L 5 O O + N2 " L2- ‘5‘ 0 it ( max“ “*3 w a“ «09¢ {w $0 "‘7‘9’“ /N L / “to Mr \N: . / : kto/ I/ é—-——' 37((9 "‘ \N=0»(t- —-—a N N K0,“ NU Chem 210-2, Winter 2005 Final exam 5 4. (30 pts) The Ritter reaction, as shown in the first step of the two-step reaction sequence below, is especially valuable for the synthesis of amine containing tertiary alkyl substituents. In the second step, the Ritter product is hydrolyzed to the amine. a) Propose a curved arrow mechanism for the reaction sequence below. Show all the proton transfer steps. Hint: Think carefully about the nucleophilic and electrophilic components of each reaction. ’ H20 « H .~ HCN & ——> >'OH H2804 O KOH “HZ (I Ritter prOdUCt @ lee) or g? fill 69 1” at? .> __..3 —— NQQ—ur @ are “2° ll 6’9 §¢N -: L \ ,— F7)?” 2 L" ASOt @Q? 304. (6) 0 A4 1+ @ p~c H504 / e" H- ’7: y, [:7 "7 54%) M ii OH -‘ [*0‘1“ 7 O “9,,” QaAL _(_ kale b) What is the product of the itter reaction using CH3CN instead of HCN followed by reduction of the Ritter product with LAH and work up with mild acid? Draw its formula. e 7/»)N/ QM? NU Chem 210-2, Winter 2005 Final exam 6 5. (30 pts) From benzene, tert—butylamine, acetone, and any carbon-containing starting materials with a 2 carbon or less, propose a synthesis of albuterol (Proventil), currently one of the most Widely used inhalation bronchodilators. You may also use TsOH, PPh3, the Swern reagent (dimethyl sulfoxide and oxalyl chloride), NBS, tosyl chloride, pyridine, PCC, mCPBA, peroxide, and any inorganic reagents. Your synthesis must contain compound A as a key intermediate. NH 0 \ —-—> O” 0 HO A .r Albuterol (2,, @9 or u + 0H «0* OH’ /.,JM (at (J 9L» @d — ‘ 29032. A MafiquA on _..—--—> \ M M A (0‘ ‘ )LOU/ou\ & ou @ j—ifie so“ flutfiw fl W’K‘w V”) we?“ /0 , “0 a“ 2,)le {To LHi% ‘6 U, W“ “ ° 0 & Who? 0 0 A f it no N“ (ix 4 fl, ‘ - ‘ 1C '0 l/ l *2. no’rfiPw , \ ForUlMlUfi V / o no)?! W419 0; ( ban; 1.}; posertOVl .mgmzmare W” U/ m “D H , A or P . r 0 5) Ci . mmwr erIKlHS D Q £99 ‘0‘” (8(1va 00+ ed ones ' M r0 86': pathkg 2V1 CO V 1’ Ho NU Chem 210-2, Winter 2005 Final exam 7 6. (30 pts) From benzene, pyridine-2-carboxaldehyde, and any non-nitrogen carbon-containing starting materials with 2 carbon or less, propose a synthesis of the following molecule. You may also use TsOH, tosyl chloride, PPh3, the Swem reagent (dimethyl sulfoxide and oxalyl chloride), NBS, pyridine, PCC, mCPBA, peroxide, and any inorganic reagents. / C‘)‘ U 9x 011 , ° /tSt"fiL I I [A [0, I” a Lt ...
View Full Document

This note was uploaded on 06/12/2008 for the course CHEM 210-2 taught by Professor Coddens during the Winter '08 term at Northwestern.

Page1 / 6

FinalKey_Wi05 - NU Chem 210-2, Winter 2005 Final exam 2 l....

This preview shows document pages 1 - 6. Sign up to view the full document.

View Full Document Right Arrow Icon
Ask a homework question - tutors are online