___________________________ PRINT NAME

Typical 1H and 13C Chemical Shift in Organic Molecules Chemical Shift

0.8 1.0 1.2 1.4 1.4 1.7 1.6 1.9 2.2 2.5 2.1 2.6 1.7 3.1 3.4 3.6 3.6 3.8 3.3 4.0 0.5 5.0 4.6 5.0 5.6 5.2 5.7 6.5 6.0 9.5 9.5 9.9

Type of Hydrogen
Primary alkyl, RCH3 Secondary alkyl, RCH2R Tertiary alkyl, R3CH Allylic, R2C=CRCH3 Benzylic, ArCH2R Next to carbonyl, R(C=O)CH2R Alkyne, RC CH RCH2Br RCH2Cl RCH2OH, RCH2OR OH, SH, NH2 Terminal alkene, RHC=CH2 Terminal alkene near electronegative atoms Internal alkene RHC=CH2 Internal alkene near electronegative atoms Benzene and aromatics, ArH Aldehyde, R(C=O)H

Chemical Shift
5 20 20 30 30 50 30 45 20 40 20 40 25 50 50 90
307 EXAM III DRAFT FALL 2011

Type of Carbon
Primary alkyl, RCH3 Secondary alkyl, RCH2R Tertiary alkyl, R3CH Quaternary alkyl, R4C Allylic, R2C=CRCH3 RCH2Br RCH2Cl RCH2OH, RCH2OR

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65 95 100 160 170-175

___________________________ PRINT NAME Alkyne, RC CH

Alkene, Aromatic Ester, R(C=O)OR Aldehyde or Ketone, R(C=O)H , R(C=O)R

190 210

307 EXAM III DRAFT FALL 2011

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___________________________ PRINT NAME

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307 EXAM III DRAFT FALL 2011

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___________________________ PRINT NAME 1. Rank the following alkenes in the order of increasing heats of hydrogenation (lowest heat of hydrogenation first, greatest heat of hydrogenation last) 1 2 3

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A. B. C. D. E.

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2.

1 1 1 2 2

< < < < <

2 5 4 3 3

< < < < <

3 4 5 5 4

< < < < <

4 3 3 4 5

< < < < <

5 2 2 1 1

Rank the following compounds in the order of increasing degrees of unsaturation (least unsaturated first).

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C3H3Cl3O 1 C6H6O 4 2 5 2 2 5 < < < < < 1 4 1 1 4 < < < < < 3 3 4 5 3 < < < < < 4 1 3 3 2 < < < < <

C5H9Cl4N 2 C10H6Cl2 5 5 2 5 4 1

C5H6O2 3

A. B. C. D. E.

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307 EXAM III DRAFT FALL 2011

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___________________________ PRINT NAME 3. Which of the following reactions will stereospecifically produce meso compounds?

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!
All 3 and 4 1, 2, 3 2 and 3 2 and 5

A. B. C. D. E.

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4.

Apply your general knowledge of IR spectroscopy to unscramble the following. You have four IR spectra, and five possible structures, as shown below. Assign the correct structure to each spectrum.

Spectrum a) 3350 cm1 (broad); spectrum c) 1630;

spectrum b) 1630, 1750, 3030 cm1;

spectrum d) 1738 cm1.

A. B. C. D. E.

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1c, 2a, 4d, 5b 1c, 2b, 3d, 5a 1b, 3c, 4d, 5a 2a, 3d, 4c, 5b 1b, 2a, 4d, 5c

307 EXAM III DRAFT FALL 2011

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___________________________ PRINT NAME 5. What color is your exam?

A. B. C. D.

White Pink Blue Yellow

307 EXAM III DRAFT FALL 2011

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___________________________ PRINT NAME IX. (12 points) Write out the complete mechanism of the reaction indicated below. Include all electric charges, participating lone pairs and indicate all electron movement with appropriate curved arrows. You may not need as many steps as given.

! ! ! ! ! !
IY.

! !
On the axes provided, sketch the reaction coordinate diagram for the above reaction.

B.

(12 points) Write out the complete mechanism of the reaction indicated below. Include all electric charges, participating lone pairs and indicate all electron movement with appropriate curved arrows. You may not need as many steps as given.

! ! ! ! ! !

! ! !
On the axes provided, sketch the reaction coordinate diagram for the above reaction.

B.

307 EXAM III DRAFT FALL 2011

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___________________________ PRINT NAME 2X. (12 points) Devise a synthetic scheme for the transformation shown. The sequence should consist of a set of distinct chemical reactions leading to the target molecule. Include all reagents, essential solvents and intermediate products. Once you write the structure of a compound you can designate it with a Roman numeral and use that in the rest of the scheme.

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! ! ! ! ! !

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307 EXAM III DRAFT FALL 2011

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___________________________ PRINT NAME 2Y. ( 12 points) Devise a synthetic scheme for the transformation shown. The sequence should consist of a set of distinct chemical reactions leading to the target molecule. Include all reagents, essential solvents and intermediate products. Once you write the structure of a compound you can designate it with a Roman numeral and use that in the rest of the scheme.

! ! ! !

! ! ! ! !
3X.

! ! ! ! ! !

(12 points) Fill in the missing item-reactant, reagent or product in each of the following reactions. Answers must be written in the boxes provided. Indicate stereochemistry for products when necessary.

! !

! ! ! ! ! ! ! ! ! ! ! !

307 EXAM III DRAFT FALL 2011

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___________________________ PRINT NAME 3Y. (12 points) Fill in the missing item-reactant, reagent or product in each of the following reactions. Answers must be written in the boxes provided. Indicate stereochemistry for products when necessary.

! !

! ! ! ! ! ! ! ! ! ! ! !

307 EXAM III DRAFT FALL 2011

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___________________________ PRINT NAME 4X. (10 points) A. Write out the complete mechanism for the reaction shown. Include all electric charges, participating lone pairs and indicate all electron movement with appropriate curved arrows. You may not need as many steps as given.

start here

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! ! ! ! B. Can electrophilic bromine addition to alkenes involve rearrangements? ________ ! ! C. Explain why in ten words or less. ! ! ! ! ! ! ! ! ! ! !

307 EXAM III DRAFT FALL 2011

1 ! 1

___________________________ PRINT NAME 4Y. (10 points) A. Write out the complete mechanism for the reaction shown. Include all electric charges, participating lone pairs and indicate all electron movement with appropriate curved arrows. You may not need as many steps as given.

! !

start here

! ! !

! ! ! ! B. Can electrophilic bromine addition to alkenes involve rearrangements? ________ ! ! C. Explain why in ten words or less. ! ! ! ! ! ! ! ! ! ! !

307 EXAM III DRAFT FALL 2011

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___________________________ PRINT NAME 5X. (12 points) A. The compound shown below will be transformed into an alkene when treated with sodium ethoxide. Using the template provided, fill in the Newman projection of the compound as shown then fill in the Newman projection leading to the elimination reaction.

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B. Using the template provided fill in the structure of the resulting alkene and write in the space provided, give the correct IUPAC name of the compound including any necessary stereochemical designations.

307 EXAM III DRAFT FALL 2011

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___________________________ PRINT NAME 5Y. (12 points) A. The compound shown below will be transformed into an alkene when treated with sodium ethoxide. Using the template provided, fill in the Newman projection of the compound as shown then fill in the Newman projection leading to the elimination reaction.

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B. Using the template provided fill in the structure of the resulting alkene and write in the space provided, give the correct IUPAC name of the compound including any necessary stereochemical designations.

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307 EXAM III DRAFT FALL 2011

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___________________________ PRINT NAME 6X. (14 points) For the following reactions, fill in the missing substances in the appropriate boxes.

! ! ! ! A. ! ! ! B. ! ! !
C.

! ! ! ! ! ! D. ! ! ! ! E. ! ! ! !

307 EXAM III DRAFT FALL 2011

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___________________________ PRINT NAME 6Y. (14 points) For the following reactions, fill in the missing reagents or products in the appropriate boxes.

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A. B.

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C.

! D. !
E. F.

! !

307 EXAM III DRAFT FALL 2011

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___________________________ PRINT NAME 7X. (12 points) The 1H spectrum shown below belongs to a compound of composition C6H12O. The IR spectrum has a characteristic signal at 1630 cm1 but no signals at either 1700-1730 or 3300-3400 cm1.!

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Using the 1H chemical shift table provided and the multiplicities of the signals, derive the structure of the compound and draw it in the box.!

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307 EXAM III DRAFT FALL 2011

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___________________________ PRINT NAME 7Y. (12 points) The 1H spectrum shown below belongs to a compound of composition C6H12O. The IR spectrum has a characteristic signal at 1630 cm1 but no signals at either 1700-1730 or 3300-3400 cm1.! Using the 1H chemical shift table provided and the multiplicities of the signals, derive the structure of the compound and draw it in the box.!

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! !

307 EXAM III DRAFT FALL 2011

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