Organic Chemistry Functional Group Chemistry: Alcohols, Ethers, and Carbonyls Syllabus

Functional Group Chemistry: Alcohols, Ethers, and Carbonyls syllabus — full chapter and topic list

Expand any chapter to see its topics and sub-topics. This is the whole examinable outline for Functional Group Chemistry: Alcohols, Ethers, and Carbonyls in Organic Chemistry, not a summary of it.

1. 1

   Alcohols, Diols, and Thiols

   4 topics

   • Synthesis of Alcohols
   • Reactions with Hydrogen Halides and SOCl2/PBr3
   • Oxidation of Alcohols
   • Tosylation and Protecting Groups
2. 2

   Ethers, Epoxides, and Sulfides

   3 topics

   • Williamson Ether Synthesis
   • Cleavage of Ethers
   • Ring-Opening of Epoxides
3. 3

   Aldehydes and Ketones

   5 topics

   • Nomenclature and Structure
   • Nucleophilic Addition
   • Wittig Reaction
   • Reduction and Grignard Addition
   • Oxidation of Aldehydes
4. 4

   Carboxylic Acids and Derivatives

   5 topics

   • Acidity and Structure of Carboxylic Acids
   • Nucleophilic Acyl Substitution
   • Acid Chlorides, Anhydrides, Esters, Amides
   • Fischer Esterification and Hydrolysis
   • Nitriles
5. 5

   Enols, Enolates, and Carbonyl Condensations

   5 topics

   • Keto-Enol Tautomerism
   • Alpha Halogenation and Alkylation
   • Aldol Condensation
   • Claisen Condensation
   • Michael Addition and Conjugate Addition

Functional Group Chemistry: Alcohols, Ethers, and Carbonyls flashcards for Organic Chemistry

21 of 50 cards from the Functional Group Chemistry: Alcohols, Ethers, and Carbonyls deck — real questions with worked answers.

1. What reagent reduces both aldehydes and ketones to alcohols, and what selectivity does it have toward esters and carboxylic acids?

   $\ce{NaBH4}$ (sodium borohydride) reduces aldehydes to $1^\circ$ alcohols and ketones to $2^\circ$ alcohols. It is a mild hydride source and generally does NOT reduce esters or carboxylic acids.

2. Which hydride reagent is strong enough to reduce esters, carboxylic acids, and amides, and why must it be used in dry, aprotic solvent?

   $\ce{LiAlH4}$ (lithium aluminum hydride). It reacts violently with water/protic solvents (liberating $\ce{H2}$), so it is used in anhydrous ether or THF, then worked up with acid.

3. How are alcohols synthesized from alkenes by acid-catalyzed hydration, and what regiochemistry results?

   $\ce{H2O}$ with catalytic $\ce{H2SO4}$ adds across the double bond with Markovnikov regiochemistry ($\ce{OH}$ on the more substituted carbon), via a carbocation intermediate.

4. What reagent combination gives anti-Markovnikov, syn hydration of an alkene without rearrangement?

   Hydroboration-oxidation: $\ce{BH3}$ (or $\ce{9-BBN}$) followed by $\ce{H2O2}$/$\ce{NaOH}$. The $\ce{OH}$ adds to the less substituted carbon with syn stereochemistry.

5. What are the products and regiochemistry of oxymercuration-demercuration of an alkene?

   $\ce{Hg(OAc)2}$, $\ce{H2O}$, then $\ce{NaBH4}$ gives Markovnikov alcohol with no carbocation rearrangement (proceeds through a mercurinium ion).

6. When a $1^\circ$ alcohol reacts with $\ce{HBr}$, what mechanism operates and why?

   $S_N2$: the protonated alcohol ($\ce{-OH2+}$, a good leaving group) is displaced by $\ce{Br-}$ in one step. $1^\circ$ substrates disfavor carbocations, so backside attack dominates.

7. When a $3^\circ$ alcohol reacts with $\ce{HCl}$, what mechanism operates?

   $S_N1$: the alcohol is protonated, water leaves to form a stable $3^\circ$ carbocation, then $\ce{Cl-}$ attacks. Rearrangements are possible.

8. What does $\ce{SOCl2}$ do to a $1^\circ$ or $2^\circ$ alcohol, and what are the byproducts?

   It converts $\ce{R-OH}$ into $\ce{R-Cl}$ (alkyl chloride). Byproducts are $\ce{SO2}$ and $\ce{HCl}$ gas, which drive the reaction forward.

9. What does $\ce{PBr3}$ convert an alcohol into, and why is it preferred over $\ce{HBr}$?

   $\ce{PBr3}$ converts $1^\circ$/$2^\circ$ alcohols to alkyl bromides ($\ce{R-Br}$) via $S_N2$, avoiding carbocation rearrangements that can occur with $\ce{HBr}$.

10. What is the product of oxidizing a primary alcohol with $\ce{PCC}$ versus with $\ce{KMnO4}$/$\ce{Na2Cr2O7}$?

    $\ce{PCC}$ (pyridinium chlorochromate, anhydrous) stops at the aldehyde. Strong aqueous oxidants like $\ce{KMnO4}$ or $\ce{Na2Cr2O7}$/$\ce{H2CrO4}$ oxidize a $1^\circ$ alcohol all the way to a carboxylic acid.

11. What product forms when a secondary alcohol is oxidized, and can a tertiary alcohol be oxidized?

    A $2^\circ$ alcohol oxidizes to a ketone. A $3^\circ$ alcohol cannot be oxidized (no C–H on the carbinol carbon) without breaking C–C bonds.

12. What is the Swern oxidation and what is its key advantage?

    Oxidation using $\ce{(COCl)2}$ (oxalyl chloride), DMSO, and $\ce{Et3N}$. It converts $1^\circ$ alcohols to aldehydes and $2^\circ$ to ketones under mild, non-metallic conditions without over-oxidation.

13. What is tosylation and why is a tosylate useful in synthesis?

    Reaction of an alcohol with $p$-toluenesulfonyl chloride ($\ce{TsCl}$) and base gives an alkyl tosylate ($\ce{R-OTs}$). $\ce{OTs}$ is an excellent leaving group, converting a poor leaving group (OH) into one that undergoes $S_N2$/$S_N1$/E2 without changing configuration at that step.

14. Name a common protecting group for alcohols using silicon, and how is it removed.

    A silyl ether, e.g. TBS (tert-butyldimethylsilyl) formed with $\ce{TBSCl}$/imidazole. It is removed with fluoride source such as TBAF ($\ce{Bu4NF}$).

15. State the Williamson ether synthesis reaction and its mechanism.

    An alkoxide ($\ce{R-O^-}$) reacts with an alkyl halide ($\ce{R'-X}$) via $S_N2$ to give an ether $\ce{R-O-R'}$. Best with methyl or $1^\circ$ halides to avoid E2 elimination.

16. In the Williamson ether synthesis of a mixed ether, which fragment should be the alkoxide and which the halide when one is tertiary?

    The alkoxide should come from the more hindered ($3^\circ$) piece and the halide should be the less hindered ($1^\circ$/methyl) piece, since $3^\circ$ halides give elimination instead of substitution.

17. How are ethers cleaved by strong acids like $\ce{HI}$ or $\ce{HBr}$, and what determines which C–O bond breaks?

    Excess $\ce{HX}$ protonates the ether oxygen; halide attacks the less hindered carbon by $S_N2$ (or the more substituted carbon by $S_N1$ if it gives a stable carbocation). Products are an alkyl halide and an alcohol (which can react again to give a second alkyl halide).

18. When phenyl methyl ether (anisole) is cleaved with $\ce{HI}$, what two products form and why?

    Phenol + $\ce{CH3I}$. Halide cannot attack the $sp^2$ aromatic carbon, so cleavage occurs at the methyl–O bond, giving phenol (not aryl iodide) and methyl iodide.

19. Under acidic conditions, at which carbon does an epoxide (oxirane) ring open, and with what stereochemistry?

    Under acid, the nucleophile attacks the more substituted carbon (more carbocation-like) with anti (trans) stereochemistry via backside attack.

20. Under basic/nucleophilic conditions, where does epoxide ring-opening occur?

    Under basic conditions the nucleophile attacks the less hindered (less substituted) carbon by $S_N2$, with inversion and anti addition.

21. What drives the ring-opening reactivity of epoxides compared to ordinary ethers?

    The strained three-membered ring ($\approx 60^\circ$ bond angles) has significant ring strain, which is relieved on opening, making epoxides far more reactive than acyclic ethers.

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