CHEMISTRY 241 FALL 2009 PROBLEM SET #10 1.

Outline the synthesis of the following : a) butanoic acid from 1-butanol b) acetaldehyde from 2-butanol c) acetone from propene d) acetic acid from ethylene e) 1-iodobutane from butanoic acid 2. From among the isomeric compounds of molecular formula C4H9Cl, choose the one having the 1H NMR spectrum that: a) Contains only a single peak b) Has several peaks including a doublet at = 3.4 ppm c) Has several peaks including a triplet at = 3.5 ppm 3. . The NMR spectra for some isomers having the formula C4H10O are summarized as follows. Deduce the structure of each compound. a. 0.95 (t, 3H); 1.52 (sextet, 2H); 3.30 (s, 3H); 3.40 (t, 2H) b. 1.15 (s, 1H); 1.28 (s, 9H) c. 1.20 (t, 3H); 3.45 (quartet, 2H) d. 0.90 (d, 6H); 1.78 (m, 1H); 2.45 (t, 1H); 3.30 (t, 2H) e. 1.13 (d, 6H); 3.30 (s, 3H); 3.65 (septet, 1H) f. 0.95 (t, 3H); 1.50 (m, 4H); 2.20 (t, 1H); 3.70 (dt, 2H) g. 0.92 (t, 3H); 1.18 (d, 3H); 1.45 (m, 2H); 1.80 (d, 1H); 3.75 (m, 1H) 4. There are nine possible structural isomers of C4H8Br2. Two of them have the following NMR spectra. Deduce the structures of each and indicate the logic used in your assignment a. 1.7 (d, 6H); 4.4 (quart, 2H) b. 1.7 (d, 3H); 2.3 (quart, 2H); 3.5 (t, 2H); 4.2 (m 1H)

5. For each of the questions below, provide the most reasonable answer. a) Draw a compound that would show two singlets in the NMR spectrum. b) A compound that would show a triplet at 3.5 in the 1H NMR
O O H 3C C H3

O C H3 O C H3

c) A compound that would show a triplet at 2.1 in the 1H NMR

O O

O O

O O

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O NaBH4

COOMe 1. CrO3, H2S O4, H2O 2. LiAlD4, (CH3C H2)2O 3. H3O +

OH

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6. Compound I (C5H10O) reacts with one equivalent of HI to give a single product II (C5H11IO). Further reaction of II with HI (or reaction of I with an excess of HI leads to the formation of III (C5H10I2). Reaction of III with NaOH in H2O gives IV (C5H12O2) which on reaction with CrO3/pyridine gives V (C5H8O2), a compound that can also be prepared by reaction of cyclopentene with O3 [followed by workup of the ozonide with (CH3)2S]. Show structures for I-V. 7. Show a reasonable pathway for the synthesis of J, starting from cyclopentene and any other one carbon starting materials (methane, methanol, methylbromide, etc.) that you desire. Remember to include all necessary reagents for each of the steps that you propose. Indicate how many stereoisomers, if any, of J are possible .
O H H

8. Propose a synthesis of n-butyl ethyl ether (CH3CH2CH2CH2OCH2CH3) starting from ethylene (CH2=CH2) as the only source of carbon. 9. Propose a synthesis of Elixir 217, the structure of which is shown below, starting from bromobenzene, cyclopentene, and any other compounds containing three carbons or less. Show all necessary reagents for each of the steps that you show in your synthetic scheme.
H H Elixir 217 cyclopentene bromobenzene C H3 Br

10. Devise a synthesis of the compound shown below, using cyclohexanone as the only source of carbon in the product. You may use any other reagents that you desire. Clearly show your proposed reaction pathway, including all reagents that would be required for each of the steps that you propose.
OH H H OH

11. Devise a synthesis of the ester shown below starting from bromobenzene and alcohols of three carbons or less as the only source of carbon. Show any other necessary reagents for each of the steps that you propose.
O O n-Bu H

12. Show a reasonable pathway for the synthesis of the compound shown below starting from alcohols of 3 carbons or less. Remember to include all necessary reagents for each of the steps that you propose. Indicate how many stereoisomers, if any, of the product ketone are possible.
H O H

13. Develop a synthetic procedure for making the following molecule starting with compounds containing four carbons or less. Show all necessary reagents for each of the steps that you propose.
C H3 C H3C H2C H C H2C H2 H 3C

H C C H2Br

C C H2C H C H3 C H3 C H2C H3

14. Propose a mechanism to account for this rearrangement, showing double headed arrows to indicate the movement of all electron pairs. Is the acid catalytic or stoichiometric in this reaction? (Hint: This reaction can be performed under anhydrous conditions, i.e., in the absence of water).

H+
O

15. The accompanying NMR spectrum is that of an oil containing nitrogen and showing a molecular weight of 131 in the mass spectrum. IR: 1730 cm-1. Propose a structure that is consistent with these data.