reagents Flashcards
PCC (C5H5N, ClCrO3) / CH2Cl2
oxidize alcohols to aldehydes (primary) and ketones (secondary)
H2CrO4 / H2O
oxidize aldehydes and primary alcohols to carboxylic acids, secondary alcohols to ketones
- primary alcohols require 2 eq
CO2 after grignard
adds carboxylate (H+ wu forms carboxylic acid)
+1 to C chain
*use protecting groups for ketones/aldehydes (acetals)
KMnO4
oxidize alkyl group to carboxylic acid
- won’t work for t-bu
SOCl2 / pyridine
turn carboxylic acids into acyl chlorides and amides into nitriles
2 eq grignard + acyl chloride
3° alcohol
- carbonyl –> OH
- 2 additions of grignard alkyl group
NaSR + acyl chloride
form thioester (replace Cl with SR)
NaBH4
reduces acyl chlorides and aldehydes to primary alcohols, ketones to secondary alcohols
LiAlH4
reduce everything
ester formation
- acyl chloride + ROH / Et3N (remove HCl)
- carboxylic acid + ROH w/ acid cat. (remove H2O)
- SN2 of R-carboxylate + 1°/2° alkyl halide
- carboxylic acid + CH2N2 (adds CH3 to O)
amide formation
- acyl chloride + xs amine / Et2O
- ester + amine / cat. H+, heat
- anhydride + amine (carboxylate as LG)
carboxylic acid formation
- grignard + CO2
- alkyl + KMnO4
- ester/amide/nitrile/acyl chloride/anhydride + cat. H+/H2O (basic = carboxylate)
- aldehyde/1° alcohol + H2CrO4
lactone formation
1 molecule w/ carboxylic acid and OH, cat H+
ester + alcohol
transesterification
ester + 2 eq grignard
3° alcohol
- carbonyl –> OH
- 2 additions of grignard alkyl group
- kick out ester
amide + grignard
form ketone (protonated amine LG)
*only works with 3° amides
amide + dibal-H
reduction to aldehyde
how do carboxylic acids react w/ grignard
acid base - form carboxylate, no addition
anhydride formation
- carboxylate + acyl chloride
nitrile + grignard (then H+, H2O, heat)
- replace triple bond to N w/ carbonyl
- 1 addition of grignard alkyl group
AcOH (acetic acid) + Br2
Br addition to a-carbon of ketones and aldehydes
- product can undergo SN2
NaOH + Br2
2 Br additions to a-carbon
*exception: acetic acid type ketone (can be attached to benzene) forms carboxylate + CHBr3
Na/KOH, heat
form a,b-unsaturated ketone (attach the molecule to itself at the a-carbon in place of the O)
*creates dienophiles
1 eq LDA + ketone
form b-hydroxy ketone (attach ketone to a-carbon as a tetrahedral)
- new C-C btwn alpha and beta carbons
1 eq LDA, alkyl halide + ketone
add alkyl group to alpha carbon of ketone (SN2)
- 1° and methyl alkyl halides only
ester (ROR’) + NaOR’ / R’OH
form b-keto ester (add ester to itself at a-carbon in place of OR)
*R group of ester and base must be the same
*requires 2 alpha C-H protons
aldehyde/ketone + 2° amine
form enamine (C=C-N)
*reversible with H2SO4, PHI, H2O
aldehyde/ketone + 1° amine
form imine (C=N)
NBS, CCl4, hv, heat
allylic bromination (add Br to C next to double bond)
terminal alkyne + BR2H / NaOH, H2O2
replace triple bond w/ aldehyde
O3 / Zn, S(CH3)2
cut alkene and add carbonyls –> form ketone + aldehyde or break ring
HNO3 / H2SO4
add NO2
NaNO2 / cat. HCl + RNH2
replace NH2 with N2 (form RN2+)
benzene + RCl / FeCl3
add R where the halogen was
Zn(Hg) / HCl
reduce carbonyls to alkanes
(NH2)2 / NaOH
reduce carbonyls to alkanes
benzene + CO, HCl / FeCl3
benzene –> benzaldehyde
grignard + formaldehyde (H2-C=O)
form primary alcohol with extra carbon (add C-OH)
H3PO4, heat + alcohol
more substituted alkene
- works with similar acids (H2SO4, TsOH)
