51.- Compound a is an alkyne with the molecular formula C5H8.

When treated with aqueous sulfuric

acid and mercuric sulfate, two different products with the molecular formula C5H10O are obtained in
equal amounts. Draw the structure of compound a, and draw the two products obtained.
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52.-Propose an efficient synthesis for each of the following transformations:

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53.- Draw the structure of each possible dichloride that can be used to prepare the
following alkyne via elimination:

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54.- Draw the structures of compounds A to D:

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55.- Draw and name four terminal alkynes with the molecular formula C6H10.
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56.- Preparation of 2,2-dimethyl-3-octyne cannot be achieved via alkylation of
acetylene. Explain.
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57.- Identify the reagents necessary to achieve each transformation below. In each case, you will need
to use at least one reaction from this chapter and at least one reaction from the previous chapter. The
essence of each problem is to choose reagents that will achieve the desired stereochemical outcome:
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58.- Identify reagents that you would use to achieve the following transformation:

.
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59.- In the upcoming chapters, we will learn a two-step method for achieving
the following transformation. In the meantime, we have already learned reactions that can be used to
accomplish this transformation, although more than two steps are required. Identify reagents that you
could use to achieve this transformation:

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60.- A terminal alkyne was treated with NaNH2 followed by propyl iodide. The resulting
internal alkyne was treated with ozone followed by water, giving only one type of carboxylic
acid. Provide a systematic, IUPAC name for the internal alkyne.
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61.- The following reaction does not produce the desired product but does produce a product that is a
constitutional isomer of the desired product. Draw the product that is obtained and
propose a mechanism for its formation:

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62.- Propose a plausible mechanism for the following transformation:
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63.- Propose a plausible mechanism for the following tautomerization process:

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64.- Using acetylene and methyl bromide as your only sources of carbon atoms, propose a synthesis
for each of the following compounds:

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65.- Propose a plausible mechanism for the following transformation:

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66.- Propose a plausible mechanism for the following transformation:

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67.- A small class of natural products, called α,α-disubstituted α-amino acids (Chapter 25), have
been the targets of several synthetic techniques, because these compounds are structurally
complex (representing a challenge for synthetic organic chemists), and they exhibit notable effects on
biological activity. The following transformation was part of one such synthetic technique:
(a) Identify reagents that can be used to achieve the following transformation
(b) Assign the configuration of the chiral center in the starting material and in the final product.
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68.- Treatment of one mole of dimethyl sulfate (CH3OSO3CH3) with two moles of sodium acetylide
results in the formation of two moles of propyne as the major product:

(a)Draw the inorganic, ionic species that is generated as a by-product of this reaction
and show a mechanism for its formation.
(b)2-Butyne is observed as a minor product of this reaction. Draw a mechanism
accounting for the formation of this minor product and explain how your proposed mechanism is
consistent with the observation that acetylene is present among the reaction products.
(c)Predict the major and minor products that are expected if diethyl sulfate is used
in place of dimethyl sulfate.
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69.- Salvinorin A, isolated from the Mexican plant Salvia divinorum, is known to bind
with opioid receptors, thereby generating a powerful hallucinogenic effect.It has been suggested that
salvinorin A may be useful in the treatment of drug addiction. Terminal alkyne 2,shown below,was
used in a total synthesis of salvinorin A. Propose a plausible mechanism for
the formation of 2 from alkyne 1. (Hint: refer to Problem 9.8.)

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70.- Halogenation of alkynes with Cl2 or Br2 can generally be achieved with high yields, while
halogenation of alkynes with I2 typically gives low yields. However, the following reaction is
successfully completed with I2 in high yields (94%) to afford a potentially useful
functionalized and conformationally constrained diiododiene synthetic intermediate.
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71.- The following compounds exhibit tautomerism, with a particularly high enol concentration.
Compound 1 exhibits an enol concentration of 9.1%, as compared with the enol
concentration of 0.014% for (CH3)2CHCHO. Compound 2 exhibits an enol concentration
of 95%:

(a) In compound 1, determine the hybridization state of the carbon atom adjacent to both rings, as well
as the expected bond angles associated with that hybridization state.
(b)Draw the enol of compound 1, and once again, determine the hybridization state and
expected bond angles of the carbon atom adjacent to both rings.
(c)Determine whether the bond angles increase or decrease when compound 1 is
converted into its enol form, and explain why steric effects favor a relatively large enol concentration
in this case.
(d)Explain why the enol of 2 is even more favored than the enol of 1.
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72.- Upon treatment with aqueous acid, compound 1 is converted into compound 2.

(a)In the first step of the accepted mechanism, one of the triple bonds is protonated to give a vinyl
carbocation. Generally, vinyl carbocations are too unstable to form,but this case represents an
exception.Using resonance structures,explain why a vinyl carbocation can be formed in this case.
(b)In the second step of the accepted mechanism, the vinyl carbocation is attacked by the nearby triple
bond in an intramolecular fashion,resulting in another vinyl carbocation, which is then captured by
water (H2O). Draw a complete mechanism showing the conversion of 1 to 2.
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73.- Which of the following compounds is converted into carbon dioxide and acetic acid (CH3CO2H)
upon ozonolysis?

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74.- All of the following methods can be used to prepare 2-butanone (CH3COCH2CH3)
EXCEPT:

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75.- Which reagents will achieve the following transformation?

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76.- Roquefortine C belongs to a class of natural products, called roquefortines, first isolated from
cultures of the fungus Penicillium roqueforti. Roquefortine C, which is also present in blue
cheese,exhibits bacteriostatic activity (it prevents bacteria from reproducing),and it is known to exist as
a mixture of two tautomers, as shown here:
(a) Draw a base-catalyzed mechanism for the tautomerization of roquefortine C.
(b) Draw an acid-catalyzed mechanism for the tautomerization of roquefortine C.
(c) Predict which tautomer is more stable and explain your rationale.
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77.- Natural products that contain the N-1,1-dimethyl-2-propenyl group (called an N-
reverse prenyl group) often exhibit antitumor or antifungal activity.The synthesis of a
particular N-reverse prenylated indole antifungal compound begins with the two steps shown below:

(a) Draw the structure of compound 2 and show a reasonable mechanism for its formation.
Note that i-Pr2NEt is a base, and CuCl is usedas a catalyst. The latter can be ignored
for our purposes.
(b) Identify the reagents necessary for the conversion of 2 to 3.
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78.- The two lowest energy conformations of pentane are the antianti and the anti-gauche forms, in
terms of arrangements around the two central C−C bonds. A recent study analyzed the conformations
of 3- heptyne as an “elongated” analogue of pentane, where a carbon- carbon
triple bond is “inserted” between C2 and C3 of pentane.Interestingly, the
researchers found that in each of the two most stable conformations of 3- heptyne, C1 and
C6 are nearly eclipsed (looking down the alkyne group). In one of these
conformations, C4 and C7 are anti to each other (looking down the C5−C6 bond); and in the
other conformation, C4 and C7 experience a gauche interaction. Draw the following:
(a) A wedge-and-dash structure for each of the two lowest energy conformations of
pentane.
(b)A wedge-and-dash structure of the conformer of 3-heptyne that is analogous to
anti-anti pentane.
(c) A Newman projection that illustrates the eclipsed nature of the lowenergy
conformations of 3-heptyne.
(d) Newman projections that illustrate the difference between the two
lowest energy conformations of 3-heptyne.
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79.- A variety of phenyl-substituted acetylenes (1a–d) were treated with HCl to give a
mixture of E and Z isomers, as shown below:

(a) As we saw in Problem 9.72, vinyl carbocations can form if they are stabilized
by resonance. Draw the vinyl carbocation that is formed when phenyl-substituted
acetylenes are protonated by HCl and explain the regioselectivity observed in these reactions.
(b)By comparing transition state stabilities for the step in which the vinyl carbocation
is captured by a chloride ion, provide an explanation for the stereoselectivity (the E:Z ratio) observed
in the reactions of 1a–d.
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