There are 19 problems on 22 pages. Please make sure that you have them all.

Transcription

1 EMISTRY 222, Spring 2001 Review Problems Page 1 There are 19 problems on 22 pages. Please make sure that you have them all. 1) Give an unambiguous name for the following compounds. e sure to use cis/trans, E/Z or R/S where appropriate. a) cis-3-chlorocyclohexanol l b) 4-bromo-2-propyl-1-hexanol c) 2-bromo-5-nitrophenol N 2 d) 1-penten-3-one e) 1,(4E)-heptadien-6-yne f) 3-(1-methylpropyl)-1-heptyne

2 EMISTRY 222, Spring 2001 Review_Problems Page 2 1) ontd. 2 g) 2-bromo-4-chlorobenzoic acid l h) N N-propyl-4-methyl-3-octanamine 2 i) trans-1,3-cyclohexanedicarboxylic acid 2 j) E-2,5-dimethyl-5-octenoic acid k) 2-bromopropanal l) 3 2 l 3 2-bromo-2-methylbutanoyl chloride m) N methyl-5-cyanopentanoate

3 EMISTRY 222, Spring 2001 Review Problems Page 3 2) Rank the following in order of: a) Increasing acidity 3 N 3 D < < D < b) Increasing rate of reaction in a Diels-lder reaction < < c) Increasing rate of reaction with an electrophile N 3 N 2 D < < < D

4 EMISTRY 222, Spring 2001 Review_Problems Page 4 Question 2, contd. g) Increasing acidity 3 D < < < D f) Increasing rate of hydrolysis N 3 l 2 3 < < 3) Give the number of enolizable hydrogens for each compound

5 EMISTRY 222, Spring 2001 Review_Problems Page 5 4) Rank the following in order of increasing energy D < E < < F < D < E F 5) Draw the M's (π orbitals) for the following systems: 6) When in a flat configuration, which of the following compounds are: a) romatic? F N b) Non-aromatic? D c) ntiaromatic? E N N D E F

6 EMISTRY 222, Spring 2001 Review Problems Page 6 7) Give the alkyl bromides you would use to make the following ketones using the dithiane synthesis shown. R 1 - = Ph 1. uli 2. R 1 -X 3. uli R 2 - = S S 4. R 2 X 5. 3 Ph 8) Propose a Wittig synthesis of 3-hexene, using 1-propene as your only source of carbon 1. 3.TF RR 2., 2 2 P Ph 3 P 1. PPh 3 2. uli 9) Give a synthesis of acetonitrile from ethanol 3 N Na 2 r 2 7 / 2 S 4 Pl Sl 2 3 l N 3 3 N 2

7 EMISTRY 222, Spring 2001 Review Problems Page 7 10) Keto-enol tautomerism can be catalyzed by base. The mechanism is shown below for the case of acetone a) The pka of acetone is ca. 19, the pka of water is ca. 16. Is deprotonation of acetone by hydroxide exothermic or endothermic? endothermic b) f and, which will be the major resonance contributor to the structure of the enolate anion? c) Draw a detailed (arrow pushing) mechanism for the acid catalyzed conversion of acetone to its enol d) Draw a detailed (arrow pushing) mechanism for the reverse reaction

8 EMISTRY 222, Spring 2001 Review Problems Page 8 11) ere is an important acid catalyzed reaction which illustrates many of the features of many acid catalyzed reactions. Give a complete arrow pushing mechanism for the reaction ) Give a complete arrow pushing mechanism for the following reaction. e careful indicate if any of the steps are reversible. 3 Na 3 3 heat 3 3

9 EMISTRY 222, Spring 2001 Review Problems Page 9 13) Give the major organic product for the following reactions. Show stereochemistry where appropriate. a) 1. P 3 2. Mg.TF b) 2 c) Me KMn 4, boil 2 t-u t-u d) heat e) NaEt heat f) P

10 EMISTRY 222, Spring 2001 Review Problems Page 10 13) ontd. g) 1. Sia 2 /TF 2., h) N N 3 2. Lil 4 1. Sl 2 i) 2 2. ll 3 j) heat/kmn k) N 1., 2, heat 2. 3 (neutralize) N 2 1. Mg, TF D l) 2. D 2

11 EMISTRY 222, Spring 2001 Review Problems Page 11 13) ontd. m) Et 1. NaEt/Et/heat Et 2. 3 /heat o) NaN N p) N heat N N N q) heat Na, heat r) Et s) N 2 l 3 t) 2

12 EMISTRY 222, Spring 2001 Review Problems Page 12 13) ontd. u) N 1. 3 Mg 2. 3 N v) ( 3 ) 2 N 3 N ( 3 )N 2 w) 3 x) 1., RR 2. NaN N 14) Give the reagents/conditions to perform the following transformations. Some will require more than 1 reagent, in which case use the and notation. a) Sl 2 l b) 1. 2 /P Na, N 3 (l) c) Et d) 1. g(c) 2, Et Na e) 3 Mg

13 EMISTRY 222, Spring 2001 Review Problems Page 13 14) ontd. f) Ph 1. Sia 2.TF Ph 2 2., 2 2 g) MP Lil 4 h) PhMg Ph i) 2. 3 j) 3 t-u 2, hν 2 t-u k) N 1. Lil N 2 l) gs 4 2 S 4 m) 3 N 3 heat N

14 EMISTRY 222, Spring 2001 Review Problems Page 14 15) Show how you would make compounds from compounds. Show intermediates, reagents, but do not give arrow pushing mechanisms. a) 2 N N 2 1. KMn 4 / /heat Lil N N 2 Sl 2 l l N 3 b) Na 2 r S 4 3 Na c) 2, hν 1. PhMg 2. 3 K t-u K t-u Na 2 r S 4

15 EMISTRY 222, Spring 2001 Review Problems Page 15 15) ontd. 2 d) Sl 2 3 Mg l 2 3 Mg 2 e) 2 3 Li Li Li 3 N f) heat N P N 1. 3.TF N 2., 2 2

16 EMISTRY 222, Spring 2001 Review Problems Page 16 15) ontd. g) K P TF 2., 2 2 h) N 3 ll 3 Sl 2 l i) Et Et 2 1. Na , heat Et Et Na Et Et

17 EMISTRY 222, Spring 2001 Review Problems Page 17 15) ontd. F j) N 3 / 2 S 4 F 4 N 2 N 2 l N 2 N 2 2 /Fe 3 2, Pt NaN 2 /l 2 k) l ll 3 1. Mg.TF separate isomers 2, hν

18 EMISTRY 222, Spring 2001 Review Problems Page 18 15) ontd. l) you must make the ortho-isomer exclusively with no contamination from the para-isomer N 3 2 S 4 3 P 2 separate isomers here 2 Pt N 2 N 2 2 Fe 3 N 2 N N 2 m) Ph (hint, ethyl acetoacetic ester synthesis) Ph P 3 Ph heat Et NaEt 3 Ph Et heat Ph

19 EMISTRY 222, Spring 2001 Review Problems Page 19 16) Determine the structure of the compound which has the IR, 13 and proton NMR spectra given below. The molecular formula is (This is an easy one!!) sa

20 EMISTRY 222, Spring 2001 Review Problems Page 20 Determine the structure of the compound which has the IR, 13 and proton NMR spectra given below. The molecular formula is (This is easy too!!) sa32 3 triplet 3 multiplet 2 multiplet 2 quartet

21 EMISTRY 222, Spring 2001 Review Problems Page 21 18) Draw the structure of the compound which has the IR, 13 and proton nmr spectra given below. The molecular formula is If you can not determine the complete structure, write as many molecular fragments as you can. sa This one is just a little bit harder!! 3 3 2

22 EMISTRY 222, Spring 2--1 Review Problems Page 22 sa53 19) Determine the structure of the compound which has the IR, 13 and proton NMR spectra given below. The molecular formula is X this one is harder! doublet triplet triplet triplet triplet