91Ó°ÊÓ

Draw two different ways to prepare each ketone from an acid chloride and an organocuprate reagent: (a) \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{COCH}_{3}\); (b) (CH \(_{3}\) ) \(\mathrm{CHCOC}\left(\mathrm{CH}_{3}\right)_{3}\).

Synthesize each compound from cyclohexanol, ethanol, and any other needed reagents.

Draw the product formed when pentanal \(\left(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CHO}\right)\) is treated with each reagent. With some reagents, no reaction occurs. a. \(\mathrm{NaBH}_{4}, \mathrm{CH}_{3} \mathrm{OH}\) g. [1] \(\mathrm{CH}_{3} \mathrm{MgBr} ;[2] \mathrm{H}_{2} \mathrm{O}\) b. \([1] \mathrm{Li} \mathrm{A}\left[\mathrm{H}_{4} ;[2] \mathrm{H}_{2} \mathrm{O}\right.\) h. [1] \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{Li} ;[2] \mathrm{H}_{2} \mathrm{O}\) c. \(\mathrm{H}_{2}, \mathrm{Pd}-\mathrm{C}\) i. \([1]\left(\mathrm{CH}_{3}\right)_{2} \mathrm{CuLi} ;[2] \mathrm{H}_{2} \mathrm{O}\) d. \(\mathrm{PCC}\) j. \([1] \mathrm{HC} \equiv \mathrm{CNa} ;[2] \mathrm{H}_{2} \mathrm{O}\) e. \(\mathrm{Na}_{2} \mathrm{Cr}_{2} \mathrm{O}_{7}, \mathrm{H}_{2} \mathrm{SO}_{4}, \mathrm{H}_{2} \mathrm{O}\) k. [1] \(\mathrm{CH}_{3} \mathrm{C} \equiv \mathrm{CLi} ;[2] \mathrm{H}_{2} \mathrm{O}\) f. \(\mathrm{Ag}_{2} \mathrm{O}, \mathrm{NH}_{4} \mathrm{OH}\) I. The product in (a), then TBDMS-CL, imidazole

Draw the product formed when 1 -bromobutane is treated with each reagent. a. Li (2 equiv) d. The answer in (a), then \(\mathrm{H}_{2} \mathrm{O}\) b. \(\mathrm{Mg}\) in \(\left(\mathrm{CH}_{3} \mathrm{CH}_{2}\right)_{2} \mathrm{O}\) solvent e. The answer in (b), then \(\mathrm{D}_{2} \mathrm{O}\) c. Li (2 equiv), then Cul (0.5 equiv) f. The answer in (a), then \(\mathrm{CH}_{3} \mathrm{C} \equiv \mathrm{CH}\)

What reagent is needed to convert \(\left(\mathrm{CH}_{3}\right)_{2} \mathrm{CHCH}_{2} \mathrm{CH}_{2} \mathrm{COCl}\) to each compound? a. \(\left(\mathrm{CH}_{3}\right)_{2} \mathrm{CHCH}_{2} \mathrm{CH}_{2} \mathrm{CHO}\) c. \(\left(\mathrm{CH}_{3}\right)_{2} \mathrm{CHCH}_{2} \mathrm{CH}_{2} \mathrm{C}(\mathrm{OH})\left(\mathrm{C}_{6} \mathrm{H}_{5}\right)_{2}\) b. \(\left(\mathrm{CH}_{3}\right)_{2} \mathrm{CHCH}_{2} \mathrm{CH}_{2} \mathrm{COCH}=\mathrm{CH}_{2}\) d. \(\left(\mathrm{CH}_{3}\right)_{2} \mathrm{CHCH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{OH}\)

What reagent is needed to convert \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{COOCH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{3}\) to each compound? a. \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{OH}\) b. \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{C}(\mathrm{OH})\left(\mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{3}\right)_{2}\) c. \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CHO}\)

As discussed in Sections \(12.12\) and \(20.8\), some oxidizing agents selectively oxidize a particular functional group, whereas others oxidize many different functional groups. Draw the product formed when \(\mathrm{HOCH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CHO}\) is treated with each reagent (a) \(\mathrm{CrO}_{3}, \mathrm{H}_{2} \mathrm{SO}_{4}, \mathrm{H}_{2} \mathrm{O} ;\) (b) \(\mathrm{PCC} ;\) (c) \(\mathrm{Ag}_{2} \mathrm{O}, \mathrm{NH}_{4} \mathrm{OH} ;\) (d) \(\mathrm{Na}_{2} \mathrm{Cr}_{2} \mathrm{O}_{7}, \mathrm{H}_{2} \mathrm{SO}_{4}, \mathrm{H}_{2} \mathrm{O}\).

Propose at least three methods to convert \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{Br}\) to \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{CH}_{2} \mathrm{CH}_{3}\).

Devise a synthesis of each alcohol from organic alcohols having one or two carbons and any required reagents: (a) \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}(\mathrm{OH}) \mathrm{CH}_{3}\); (b) \(\left(\mathrm{CH}_{3}\right)_{3} \mathrm{COH} ;\) (c) \(\left(\mathrm{CH}_{3}\right)_{2} \mathrm{CHCH}_{2} \mathrm{OH} ;\) (d) \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{OH}\).

Propose two different methods to synthesize 1 -octen-3-ol \(\left[\mathrm{CH}_{3}\left(\mathrm{CH}_{2}\right)_{4} \mathrm{CH}(\mathrm{OH}) \mathrm{CH}=\mathrm{CH}_{2}\right]\) using a Grignard reagent and a carbonyl compound. 1-Octen-3-ol is commonly called matsutake alcohol because it was first isolated from the Japanese matsutake mushroom.