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Problem 27b
Predict the carbenoid addition products of the following reactions.
(b)
Problem 27c
Predict the carbenoid addition products of the following reactions.
(c)
Problem 28(a)
What are the products of the following reactions, assuming that one equivalent of each reagent is used in each reaction?
a.
Problem 28a
Show how you would accomplish each of the following synthetic conversions.
a. trans-but-2-ene → trans-1,2-dimethylcyclopropane
Problem 28b
Show how you would accomplish each of the following synthetic conversions.
(b)
Problem 28c
Show how you would accomplish each of the following synthetic conversions.
(c)
Problem 29a,b
Predict the products, including stereochemistry where appropriate, for the m-chloroperoxybenzoic acid epoxidations of the following alkenes.
a. cis-hex-2-ene
b. trans-hex-2-ene
Problem 29c,d
Predict the products, including stereochemistry where appropriate, for the m-chloroperoxybenzoic acid epoxidations of the following alkenes.
c. cis-cyclodecene
d. trans-cyclodecene
Problem 30
a. Propose a mechanism for the conversion of cis-hex-3-ene to the epoxide (3,4-epoxyhexane) and the ring-opening reaction to give the glycol, hexane-3,4-diol. In your mechanism, pay particular attention to the stereochemistry of the intermediates and products.
b. Repeat part (a) for trans-hex-3-ene. Compare the products obtained from cis- and trans-hex-3-ene. Is this reaction sequence stereospecific?
Problem 31
Magnesium monoperoxyphthalate (MMPP) epoxidizes alkenes much like mCPBA. MMPP is more stable, however, and it may be safer to use for large-scale and industrial reactions. Propose a mechanism for the reaction of trans-2-methylhept-3-ene with MMPP, and predict the structure of the product(s).
Problem 32a
Predict the major products of the following reactions.
a. cis-hex-2-ene + mCPBA in chloroform
Problem 32b,c
Predict the major products of the following reactions.
b. trans-hex-3-ene + peroxyacetic acid (CH3CO3H) in water
c. 1-methylcyclohexene + MMPP in ethanol
Problem 32d,e
Predict the major products of the following reactions.
d. trans-cyclodecene + peroxyacetic acid in acidic water
e. cis-cyclodecene + mCPBA in CH2Cl2, then dilute aqueous acid
Problem 33
When 1,2-epoxycyclohexane (cyclohexene oxide) is treated with anhydrous HCl in methanol, the principal product is trans-2-methoxycyclohexanol. Propose a mechanism to account for the formation of this product.
Problem 34a,b
Predict the major products of the following reactions, including stereochemistry.
a. cyclohexene + KMnO4/H2O (cold, dilute)
b. cyclohexene + peroxyacetic acid in water
Problem 34c,d
Predict the major products of the following reactions, including stereochemistry.
c. cis-pent-2-ene + OsO4/H2O2
d. cis-pent-2-ene + peroxyacetic acid in water
Problem 34e
Predict the major products of the following reactions, including stereochemistry.
e. trans-pent-2-ene + OsO4/H2O2
Problem 34f
Predict the major products of the following reactions, including stereochemistry.
f. trans-pent-2-ene + peroxyacetic acid in water
Problem 35a
Show how you would accomplish the following conversions.
a. cis-hex-3-ene to meso-hexane-3,4-diol
Problem 35b
Show how you would accomplish the following conversions.
b. cis-hex-3-ene to (d,l)-hexane-3,4-diol
Problem 35c
Show how you would accomplish the following conversions.
c. trans-hex-3-ene to meso-hexane-3,4-diol
Problem 35d
Show how you would accomplish the following conversions.
d. trans-hex-3-ene to (d,l)-hexane-3,4-diol
Problem 36a
Give structures of the alkenes that would give the following products upon ozonolysis–reduction.
(a)
Problem 36b
Give structures of the alkenes that would give the following products upon ozonolysis–reduction.
(b)
Problem 36c
Give structures of the alkenes that would give the following products upon ozonolysis–reduction.
(c)
Problem 37a
Predict the major products of the following reactions.
(a) (E)-3-methyloct-3-ene + ozone, then (CH3)2S
Problem 37b
Predict the major products of the following reactions.
(b) (Z)-3-methyloct-3-ene + warm, concentrated KMnO4
Problem 37c,d
Predict the major products of the following reactions.
(c)
(d) 1-ethylcycloheptene + ozone, then (CH3)2S
Problem 37e
Predict the major products of the following reactions.
(e) 1-ethylcycloheptene + warm, concentrated KMnO4
Problem 37f
Predict the major products of the following reactions.
f. 1-ethylcycloheptene + cold, dilute KMnO4
