Chp. 19: Aldehydes and Ketones

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20 Terms

1
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Oxidation of Alcohols

reagents: PCC, CH2Cl2

primary alc. → aldehyde

secondary alc. → ketone

2
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COOH → ketone

Grignard: 1. 2 eq. RMgX, 2. H3O+

Organolithium: 1. 2 eq. R—Li, 2. H3O+

1st eq. acts as a base, 2nd eq. acts as a nuc.

3
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nitriles (CN) → ketone

  1. Grignard/R—Li (1 eq.)

  2. H3O+

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acid chloride → ketone

R2—CuLi (1 eq.) (dialkyl lithium cuprate)

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esters + nitriles → aldehydes

  1. DIBAL-H

  2. H2O

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acid chloride → aldehyde

  1. LiAlH(tBuO)3 (bulky LiAlH)

  2. H2O

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aldehyde → primary alc., ketone → secondary alc.

NaBH4, H2O

8
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ALL carbonyls → alcohols

LiAlH4/LAH, H2O (“removes” carbonyl)

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COOH → ester

ROH , H+ (acid catalyst): Fischer esterification

10
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Hydration Rxns (H—O)

base conditions: OH-, H2O → nuc attack, proton transfer

acid conditions: H3O+, H2O → proton transfer, nuc attack

only formaldehyde is favored in equilibrium

11
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Acetal Formation (R—O)

base: R—O-, ROH

acid: R-OH2+, ROH

hemiacetal intermed: RO and OH group

12
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Cyclic Acetal Formation

diol (HO—CH2—CH2—OH), H3O+

useful protecting group (reactivity: acid chlorides (induction) > aldehydes > ketones > esters)

13
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Imine Formation (C=N—R)

R-NH2, H+

14
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Enamine Formation (C=C—N—R2)

R2—NH, H+

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Oxime Formation (C=N—OH)

HO—NH2, H+

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Hydrazone Formation (C=N—NH2) + Reduction

formation: HO—NH2, H+

reduction: NaOH/KOH, H2O, heat → reduces to alkane

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Cyanohydrin Formation (OH + CN)

HCN

OR 1. NaCN, 2. H2O/HCN

18
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Reducing Nitriles (CN)

CN → C—NH2: 1. LiAlH4, 2. H2O

CN → COOH: H3O+

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Wittig Rxn

preparing reagant: SN2, 1. PPh3, 2. BuLi (any strong base like NaH)

rxn: R=PPh3

alternative: HWE reagent → (RO)2(O=P)=C—COOR

favors (E) stereochem if Ph group is stabilized/conjugated (Z if not)

20
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Baeyer-Villiger Oxidation (ketone → ester, aldehyde → COOH)

RCO3H (MCPBA)

embedded O in ester adds to more sub. C

O for aldehyde adds to H