List of Reactions for Exam 2 (CH232, summer 2007) * = mechanism cover ed
chapter 17 - alcohols - material relevant to carbonyl chemistry
* aldehyde reduction with NaBH4 or LiAlH4 to 1˚ alcohol
* ketone reduction with NaBH4 or LiAlH4 to 2˚ alcohol
* ester reduction with LiAlH4 (2 equiv) to 1˚ alcohol
Grignard reagent formation from RX + Mg in ether solvent
* Grignard reagent addition to formaldehyde to form 1˚ a lcohols (homologation rxn)
* Grignard reagent addition to aldehydes to form 2˚ alcohols
* Grignard reagent addition to ketones to form 3˚ alcohols
* Grignard reagent addition to esters (twice) to form 3˚ alcohols
* Grignard reagent addition to CO2 to form carboxylic acids (homologation rxn)
* phenol preparation by cumene oxidation/hydrolysis
* 1˚ alcohol oxidation with Jones reagent (H2CrO4) to make carboxylic acids
* 1˚ alcohol oxidation with PCC (pyridinium chlorochromate) to make aldehydes
* 2˚ alcohol oxidation with Jones reagent (or PCC) to make ketones
* alcohol conversion to silyl ether with TMS chloride/pyridine (reversible protection/deprotection)
chapter 18 - ethers, epoxides, sulfides
* Williamson ether synthesis NaOR + 1˚R´X = ROR´ (SN2)
ether formation by alkoxymercuration/demercuration of alkenes
* epoxidation of alkenes with peracids (RCO3H, specifically mCPBA)
* epoxide formation by halohydrin formation/deprotonation
* ether cleavage by strong acids (HBr or HI)
* Claisen rearrangement of allyl vinyl ethers or allyl aryl ethers
* epoxide ring opening - acidic conditions
* epoxide ring opening - basic conditions (SN2)
* thiol formation via thiourea alkylation with RCH2Br / hydrolysis
* sulfide formation via thiolate alkylation (SN2)
* disulfide formation via thiol oxidation with I2 or Br2
disulfide cleavage to thiols via Zn,H+
* sulfide oxidation with H2O2 or RCO3H to sulfoxides
* sulfoxide oxidation with RCO3H to sulfones
chapter 19 - aldehydes and ketones
* aldehyde formation via 1˚ alcohol oxidation with PCC,CH2Cl2 (ch 17)
aldehyde formation via DIBAH reduction of esters
* aldehyde or ketone formation via alkene ozonolysis (ch 7)
* ketone formation via 2˚ alcohol oxidation with PCC,CH2Cl2 or Jones reagent (ch 17)
* aryl ketone formation via Friedel-Crafts acylation (ch 16)
methyl ketone formation via HgII catalyzed hydration of terminal alkynes (ch 8)
ketone formation via cuprate reaction with acid chlorides
* aldehyde oxidation to carboxylic acids via Jones oxidation (aq H2CrO4)
* reversible hydration of aldehydes and ketones (acid or base catalyzed)
* cyanohydrin formation from aldehydes or ketones via addition of HCN
* alcohol formation from aldehydes or ketones via hydride (NaBH4 or Li AlH4) or Grignard reagent additions
* imines from aldehydes or ketones via reaction (condensation) with 1˚ amines
* enamines from aldehydes or ketones via rea ction (condensation) with 2˚ amines
* Wolff-Kishner reduction of aldehydes or ketones with hydrazine, NaOH, ∆
Clemmenson reduction of aldehydes or ketones with Zn, H+
* acetal formation (reversible) of aldehydes or ketones by rxn (condensation) with alcohols (C=O protection)
* Wittig reaction of aldehydes or ketones with phosphonium ylides to form alkenes
* Wittig reagent (phosphonium yilde) formation from (1) RX, Ph3P / (2) nBuLi
* conjugate addition of 1˚ and 2˚ amines to α,β-unsaturated ketones or aldehydes
conjugate addition of organocuprates to α,β-unsaturated ketones or aldehydes