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Reducing Reagents Reagent Sodium Borohydride NaBH4 Preferred Solvents Functions Reduced Reaction Workup 1) simple neutralization 2) extraction

of product 1) careful addition of water 2) dissolve aluminum salts 3) extraction of product 1) careful addition of water 2) dissolve aluminum salts 3) extraction of product

ethanol; aqueous ethanol aldehydes to 1-alcohols 15% NaOH; diglyme ketones to 2-alcohols avoid strong acids 1,2-reduction of enones is favored by CeCl3 inert to most other functions Lithium ether; THF aldehydes to 1-alcohols Aluminum avoid alcohols and ketones to 2-alcohols Hydride (LAH) amines carboxylic acids to 1-alcohols LiAlH4 avoid halogenated esters to alcohols compounds epoxides to alcohols avoid strong acids nitriles & amides to amines halides & tosylates to alkanes most functions react Lithium tri tether; THF fast: Butoxyaluminoh avoid alcohols and acid chlorides to aldehydes ydride amines (at -78 C) LiAlH(Otavoid halogenated 3-amides to aldehydes (at -78 C4H9)3 compounds C) avoid strong acids nitriles to aldehydes (at -78 C) slower: aldehydes to 1-alcohols ketones to 2-alcohols Diisobutylalumin THF; toluene fast: um Hydride avoid alcohols and acid chlorides to aldehydes AlH[CH2CH( amines (at -78 C) CH3)2]2 avoid halogenated 3-amides to aldehydes (at -78 compounds C) avoid strong acids nitriles to aldehydes (at -78 C) slower: aldehydes to 1-alcohols ketones to 2-alcohols Diborane ether; THF carboxylic acids to 1-alcohols B2H6 = 2 BH3 sulfide complex in aldehydes to 1-alcohols CH2Cl2 ketones to 2-alcohols complexes with amines nitriles to amines avoid alkenes & alkynes esters & epoxides slowly reduced Hydrogen & alcohols, ethers, alkenes & alkynes to alkanes Catalyst hydrocarbons (fast) H2 & Pt, or or carboxylic acids nitro groups to amines (fast)

1) careful addition of water 2) dissolve aluminum salts 3) extraction of product

1) dilute acid or H2O2 2) extraction of product filter to remove catalyst

Pd, or Ru, or Ni

Modified (poisoned) Catalyst Reactive Metals Na, or Li, or K liq. ammonia & ether co-solvents or alcohols or amines

imines to amines (fast) aldehydes & ketones to alcohols (slow) nitriles to amines (slow) may remove benzylic groups alkynes to alkenes acyl chlorides to aldehydes ketones to 2-alcohols alkynes to alkenes conjugated -systems (e.g. aromatic rings, dienes & enones) cleaves C-X and benzylic groups cleaves activated substituents nitro groups to amines C=O (aldehyde/ketone) to CH2

1) quench with NH4Cl 2) extract product extract product from salts

Mg or Al or Zn or Fe

water, alcohols, acetic acid or aqueous mineral acid

Many related hydride reagents, having different reductive power and selectivity, incorporate a variety of organic ligands on the hydride carrier atom. Among these are: lithium triethylborohydride (super hydride), potassium tri-sec-butylborohydride (KSelectride), sodium bis(2-methoxyethoxy)aluminumhydride (Red-Al), sodium cyanoborohydride, sodium triacetoxyborohydride. various organosilanes and in situ generated aluminum hydride and dichlorohydride. Organoborane derivatives having modified reactivity relative to borane itself include: bis(1,2-dimethylpropyl)borane (disiamylborane), 9-borabicyclo[3.3.1]nonane (9-BBN) & catecholborane (BHcat)

Oxidation Reagents Reagent Jones Reagent H2CrO4 Preferred Solvents aqueous sulfuric acid & acetone (avoid acid sensitive systems) Functions Oxidized Reaction Work-up 1) destroy excess reagent 2) extract product

Collins Reagent CrO3 2 C5H5N

1-alcohols to carboxylic acids aldehydes to carboxylic acids 2-alcohols to ketones avoid amines and sufides methylene chloride 1-alcohols to aldehydes (CH2Cl2) 2-alcohols to ketones

1) filter inorganic salts 2) wash with aqueous acid 3) remove CH2Cl2 solvent

Pyridinium Chlorochroma te ClCrO3 C5H5NH Dimethyl Sulfoxide (CH3)2S=O & DCC or Ac2O or (CF3CO)2O or SO3 or (COCl)2 Potassium Permanganate KMnO4

methylene chloride 1-alcohols to aldehydes (CH2Cl2) 2-alcohols to ketones

CH2Cl2 or ethers or DMSO

A Mild Procedure 1-alcohols to aldehydes 2-alcohols to ketones

1) filter inorganic salts 2) wash with aqueous acid 3) remove CH2Cl2 solvent 1) neutralize reactants 2) remove solvents

water and aqueous solvent mixtures

Osmium Tetroxide OsO4 Periodic Acid HIO4 Lead Tetraacetate Pb(OCOCH )4 3 Peracids CH3CO3H C6H5CO3H, etc. Ozone O3

pyridine often used catalytically water or aqueous mixtures benzene or acetic acid CH2Cl2 or ethers

aldehydes to carboxylic 1) destroy excess acids reagent 2-alcohols to ketones 2) extract product alkenes to vicinal-diols (vic.glycols) alkynes to carboxylic acids avoid amines and sufides alkenes to vicinal-diols (vic.glycols) vic.-glycols to carbonyl 1) destroy excess compounds reagent 2) extract product vic.-glycols to carbonyl compounds alkenes to epoxides ketones to esters avoid amines and sufides cleaves alkenes & alkynes avoid benzene derivatives amines and sufides 1) destroy excess reagent 2) extract product 1) destroy excess reagent & ozonides 2) extract product

CH2Cl2 or CHCl3 (sometimes alcohol)

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