CHEM 238B Winter 2010 Quiz Keys

CHEM 238B, Winter 2010
QUIZ KEYS
Name _________________ Section ________________ CHEM 238B Quiz 1 Version A
1. Give an IUPAC name for each of the following structures
a.
Br
b.
c.
Br
(1Z, 3E, 5Z)-1,6dibromohexa-1,3,5-triene
o-fluorophenol
4-methyl-1-phenyl cylcohexan-1-ol
2. Draw an arrow-pushing mechanism for the following problem and show the major product that will result from the reaction.
QUIZ KEYS
3. Classify the following heterocyclic molecules as aromatic, anti-aromatic, or not aromatic, according to Huckels rule. a. b.
HN HB
O
H B NH BH N H
antiaromatic (not aromatic okay) 4. Give the major product for each reaction shown here:
1,2-addition @ cold temperature is kinetic control 1,4-addition observed w/ heat is thermodynamic control
H 1 2 3 4
aromatic
Cl Br Br Br Br
1 mol. HCl -80oC
Cl
2 mol. Br2 25oC 1 mol. HCl 50oC
1 mol. Br2 -80oC 1 mol. Br2 50oC

Br Br Br Br
5. Write the major product of this reaction.

OH
Br2 H2O
Br
hydration of bromonium intermediate occurs at benzylic position, not tertiary

Name _________________ Section ________________ CHEM 238B Quiz 1 Version B 1. Give an IUPAC name for each of the following structures
QUIZ KEYS
a.
Br
b.
OH
c.
Br
NO2
(1Z, 3Z)-1,4-dibromohexa1,3,5-triene
p-nitrophenol
4-ethyl-1-phenyl cylcohexan-1-ol
OH
Br2 H2O
Br
hydration of bromonium intermediate occurs at benzylic position, not tertiary 3. Classify the following heterocyclic molecules as aromatic, anti-aromatic, or not aromatic, according to Huckels rule.
a.
NH
b.
HN HB
H B NH BH N H
Aromatic
Aromatic
QUIZ KEYS
5. Give the major product for each reaction shown here:

H 1 2 3 4
Cl Br Br Br Br
1 mol. HCl -80oC
Cl

Br Br Br Br
QUIZ KEYS
Name _________________ Section ________________ CHEM 238B Quiz 1 Version C
1. Give an IUPAC name for each of the following structures
a.
Br Br
b.
c.
(1Z, 3Z)-1,3-dibromohexa1,3,5-triene
m-nitrotoluene
4-t-butyl-1-phenylcylcohexan-1-ol
2. Give the major product for each reaction shown here:

H 1 2 3 4
Cl Br Br Br Br
1 mol. HCl -80oC
Cl

Br Br Br Br
QUIZ KEYS
5. Classify the following heterocyclic molecules as aromatic, anti-aromatic, or not aromatic, according to Huckels rule. a.
O
b.
HN HB
O
H B NH BH N H
antiaromatic (credit for not aromatic, can be if Os are sp3)
aromatic
QUIZ KEYS
Name _____________________ Section ____________________
CHEM 238 B Quiz 2 Version A 1) Draw the missing intermediate and product in the reaction below; where E+ is an electrophile.
2) Circle the choice which best describes the relative rates of intermediate and product formation in the reaction above. a) Same b) Slow, Fast c) Fast, Slow 3) For the pair of compounds given below choose which one will react faster with the indicated reagent and write a chemical equation for the faster reaction. Fluorobenzene or (trifluoromethyl)benzene with benzyl chloride and aluminum chloride

4) Write a structural formula for the compound: (Z)-2-Phenyl-2-butene
QUIZ KEYS
5) Provide the reagents required at each step of the provided reaction.
1) AlCl3 2) NBS 3) strong base, NaOEt KOtBu etc 4) Zn0 (Hg) and aqueous acid
6) Propose a synthesis of 4-acetyl-2-nitrotoluene starting with toluene.
QUIZ KEYS
Name _____________________ Section ____________________
CHEM 238 B Quiz 2 Version B
7) Propose a synthesis of 2-bromo-4-tert-Butyltoluene starting with toluene. If an ortho, para mixture is formed in any step of the reaction, assume that you can separate the two isomers.
8) Provide the reagents required at each step of the following reaction.
1) AlCl3 2) NBS 3) strong base, NaOEt KOtBu etc 4) Zn0 (Hg) and aqueous acid
QUIZ KEYS
9) Draw the missing intermediate and product in the reaction below; where E+ is an electrophile.
10) Circle the choice which best describes the relative rates of intermediate and product formation in the reaction above. d) Same e) Slow, Fast f) Fast, Slow
11) For the pair of compounds given choose which one will react faster with the indicated reagent and write a chemical equation for the faster reaction. Methyl benzoate or phenyl acetate with bromine/FeBr3 in an inert solvent.
12) Draw the structure of allylbenzene:
QUIZ KEYS
Name _____________________ Section ____________________
CHEM 238 B Quiz 2 Version C 1) For the pair of compounds given choose which one will react faster with the indicated reagent and write a chemical equation for the faster reaction. Toluene or chlorobenzene with a mixture of nitric acid and sulfuric acid
2) Draw the missing intermediate and product in the reaction below.
3) Circle the choice which best describes the relative rates of intermediate and product formation in the reaction above. g) Same h) Slow, Fast i) Fast, Slow
QUIZ KEYS
Propose a synthesis of pure 2-bromotoluene starting with toluene. If an ortho, para mixture is formed in any step of the reaction, this would not be a pure product as required.
4) The following structure may be represented by at least one alternative resonance structure in which all six-membered rings correspond to Kekul forms of benzene. Write such a resonance structure for:
5) Provide the reagents required at each step of the following reaction.

Cl
1
O
Br
1) 2) 3) 4)
AlCl3 NBS strong base, NaOEt KOtBu etc Zn0 (Hg) and aqueous acid
QUIZ KEYS
QUIZ #3.1 (Ch. 13-14) Name__________________________ Sec_______ (03) I. Provide unambiguous systematic names for the following organometallic compounds:
(07) II. For the compound shown below, predict the 1H and 13C NMR spectra, including peak multiplicities.
(03) III. J-coupling by alcohol protons (the OH) is observed when the 1H NMR spectrum is obtained using a polar aprotic solvent (e.g., DMSO-d6) because intermolecular proton exchange is hindered by hydrogen bonding with the solvent. Please explain: (a) How to distinguish primary and secondary alcohols from one another using this concept. (b) The effect of treatment with excess D2O upon the alcohol proton resonances.
(02) IV. Circle the compound that contains a more polar metal carbon bond, and briefly explain why:
QUIZ KEYS
(12) V. Consider the following reaction used in the total synthesis of the natural product Asteltoxin. Intermediate (B) illustrates an example of what is known as a [2,3] sigmatropic rearrangement, which you have not seen yet, though as a budding intellectual you find utterly fascinating(!). Note reactions (1) and (2) are two distinct additions that are performed in the same reaction flask (also recall that Ph = phenyl):
(a) Propose a synthesis of the starting material (A) from a vinyl halide and electrophile of your choice.
(b) Draw the principal organic products formed between (A) and n-butyl lithium in step (1) of the reaction.
(c) How many 13C resonances would be observed in (A)? How about (C)?
A:____ _____
C:____ ______
(Compound (A) is symmetrical, (C) has symmetry only in the phenyl substituent) (2 pts each; 1 pt if 6 or 7 assigned to (C)) (d) Ignoring the phenylsulfoxide unit, how does the UV max change from (A) (C)? ___________________________ Acceptable responses: redshift; increases from conjugation; goes above 231 nm; suggests longer max (2 pts) Also: C appears at lower energy (longer max ) due to greater conjugation OR <200 becomes 220 -235 nm (03) VI. Perform a retrosynthetic analysis on the following target molecule (TGT), working back to the ketone shown; you do not need to provide reagents, just the synthetic intermediates and a brief descriptor of the transform (i.e. bromination, formation of Grignard reagent, dehydrobromination, protonation of anionic product, etc.):
QUIZ KEYS
QUIZ #3.2 (Ch. 13-14) Name__________________________ Sec_______ (03) I. Provide unambiguous systematic names for the following organometallic compounds:
1
H NMR
13
C NMR
O
(a) (c)
(b)
methyl propionate
(a) 4.0 ppm (3H, singlet) (b) 2.2 ppm (2H, quartet) (c) 1.0 ppm (3H, triplet) (1 pt each; -1 for switching signals; -1 for wrong mult.)
200-220 ppm (C=O) 60-90 ppm (OCH3) 20-50 ppm (CH3C=O) 0-40 ppm (CH2CH3) (1 pt each; -1 if any multiplicities)
(03) III. J-coupling by alcohol protons (the OH) is observed when the 1H NMR spectrum is obtained using a polar aprotic solvent (e.g., DMSO-d6) because intermolecular proton exchange is hindered by hydrogen bonding with the solvent. Please explain: (a) How to distinguish primary and secondary alcohols from one another using this concept. (b) The effect of treatment with excess D2O upon the alcohol proton resonances.
(SEE ABOVE)
(02) IV. Circle the compound that contains a more polar metal carbon bond, and briefly explain why:
QUIZ KEYS
(12) V. Consider the following reaction used in the total synthesis of the natural product Asteltoxin. Intermediate (B) illustrates an example of what is known as a [2,3] sigmatropic rearrangement, which you have not seen yet, though as a budding intellectual you find utterly fascinating(!). Note reactions (1) and (2) are two distinct additions that are performed in the same reaction flask (recall that Ph = phenyl):
(SEE ABOVE)
(SEE ABOVE)
(c) How many 13C resonances would be observed in (A)? How about (C)? (d) Ignoring the phenylsulfoxide unit, how does the UV max change from (A)
A:_________ (C)?
C:__________
___________________________
(03) VI. Perform a retrosynthetic analysis on the following target molecule (TGT), working back to the ketone shown; you do not need to provide reagents, just the synthetic intermediates and a brief descriptor of the transform (i.e. bromination, formation of Grignard reagent, dehydrobromination, protonation of anionic product, etc):
(SEE ABOVE)

QUIZ #3.3 (Ch. 13-14)
QUIZ KEYS
Name__________________________ Sec_______
(03) I. Provide unambiguous systematic names for the following organometallic compounds:
(03) III. J-coupling by alcohol protons (the OH) is observed when the 1H NMR spectrum is obtained using a polar aprotic solvent (e.g., DMSO-d6) because intermolecular proton exchange is hindered by hydrogen bonding with the solvent. Please explain: (a) How to distinguish primary and secondary alcohols from one another using this concept. (b) The effect of treatment with excess D2O upon the CH2O resonance of alcohol (CH3)2CHCH2OH.
(A) SEE ABOVE (B) The observed doublet of doublets would become a doublet, since the O-H proton exchanges with 2D (NMR silent!) (02) IV. Circle the compound that contains a more polar metal carbon bond, and briefly explain why:
QUIZ KEYS
(12) V. Consider the following reaction used in the total synthesis of the natural product Asteltoxin. Intermediate (B) illustrates an example of what is known as a [2,3] sigmatropic rearrangement, which you have not seen yet, though as a budding intellectual you find utterly fascinating(!). Note reactions (1) and (2) are two distinct additions that are performed in the same reaction flask (recall that Ph = phenyl):
(SEE ABOVE)
(SEE ABOVE)
(c) How many 13C resonances would be observed in (A)? How about (C)? (d) Ignoring the phenylsulfoxide unit, how does the UV max change from (A)
A:_________ (C)?
C:__________
___________________________
(03) VI. Perform a retrosynthetic analysis on the following target molecule (TGT), working back to the ketone shown; you do not need to provide reagents, just the synthetic intermediates and a brief descriptor of the transform (i.e. bromination, formation of Grignard reagent, dehydrobromination, protonation of anionic product, etc):
(SEE ABOVE)

QUIZ #4.1 (Ch. 15-16)
QUIZ KEYS
Name_________________________ Sect_______
(05) I. Suggest appropriate starting materials for the series of reactions below, all of which lead to the alcohol shown.
(05) II. Predict the major organic product, including stereochemistry as needed, in the following reactions. Also provide an unambiguous systematic name for the products.
(06) III. Outline a practical synthesis of isobutylbenzene (PhCH2CH(CH3)2) starting from benzene, isobutyl alcohol (HOCH2CH(CH3)2) and any necessary organic and inorganic reagents.
QUIZ KEYS
(04) IV. Draw the principal organic product and an arrow-pushing mechanism for the reaction below.
(06) V. The following epoxidation strategy has been reported in the chemical literature. (a) Propose a reasonable arrow-pushing mechanism. Note the numbered carbons in the substrate and product. (b) Briefly comment on why this reaction was chosen to prepare this particular epoxide instead of using the epoxidation reactions you have learned so far (e.g., mCPBA, or Br2/H2O then intramolecular SN2).
(04) VI. In the presence of thiophenol (PhSH) under strongly basic conditions, the 2,3-epoxy-1-ol below is converted in high yield and regioselectivity to the 2,3-dihydroxy thioether product depicted. The mechanism of this hydroxyl transfer reaction is known as the Payne Rearrangement. Show an arrow-pushing mechanism for this reaction (HINT: Start off by deprotonating the alcohol in the starting material. ALSO: Use the product stereochemistry as a guide!!!!!!).

QUIZ #4.2 (Ch. 15-16)
QUIZ KEYS
Name_________________________ Sect_______
(06) I. The following epoxidation strategy has been reported in the chemical literature. (a) Propose a reasonable arrow-pushing mechanism. Note the numbered carbons in the substrate and product. (b) Briefly comment on why this reaction was chosen to prepare this particular epoxide instead of using the epoxidation reactions you have learned so far (e.g., mCPBA, or Br2/H2O then intramolecular SN2).
(SEE ABOVE)
(05) II. Suggest appropriate starting materials for the series of reactions below, all of which lead to the alcohol shown.
(05) III. Predict the major organic product, including stereochemistry as needed, in the following reactions. Also provide an unambiguous systematic name for the products.
QUIZ KEYS
(06) IV. Outline a practical synthesis of isobutylbenzene (PhCH2CH(CH3)2) starting from benzene, isobutyl alcohol (HOCH2CH(CH3)2) and any necessary organic and inorganic reagents.
(04) V. Draw the principal organic product and an arrow-pushing mechanism for the reaction below. Note the reactant is a single enantiomer, so stereochemistry should be included in the product.
(SEE ABOVE)

QUIZ #4.3 (Ch. 15-16)
QUIZ KEYS
Name_________________________ Sect_______
(05) I. Suggest appropriate starting materials for the series of reactions below, all of which lead to the alcohol shown.
(05) II. Predict the major organic product, including stereochemistry as needed, in the following reactions. Also provide an unambiguous systematic name for the products.
(06) III. The following epoxidation strategy has been reported in the chemical literature. (a) Propose a reasonable arrow-pushing mechanism. Note the numbered carbons in the substrate and product. (b) Briefly comment on why this reaction was chosen to prepare this particular epoxide instead of using the epoxidation reactions you have learned so far (e.g., mCPBA, or Br2/H2O then intramolecular SN2).
(SEE ABOVE)
QUIZ KEYS
(06) IV. Outline a practical synthesis of isobutylbenzene (PhCH2CH(CH3)2) starting from benzene, isobutyl alcohol (HOCH2CH(CH3)2) and any necessary organic and inorganic reagents.
(04) V. Draw the principal organic product and an arrow-pushing mechanism for the reaction below.
(SEE ABOVE)

CHEM 238B Winter 2010 Quiz Keys

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CHEM 238B Winter 2010 Quiz Keys

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CHEM 238B, Winter 2010

1. Give an IUPAC name for each of the following structures

(1Z, 3E, 5Z)-1,6dibromohexa-1,3,5-triene