orgo midterm 3 reactions

general mechanism for acid chloride reactions

acid chloride + HOH

carboxylic acids

acid chloride + HOR

esters

acid chloride + NH₃

primary amide

acid chloride + NH₂R

secondary amide

acid chloride + NHR₂

tertiary amide

acid chloride + N₃^-

acyl azides

acid chloride + CN

acyl nitriles

acid chloride to anhydride

R'COOH/R'COO^-

can acid chlorides do friedel crafts

yes only with aromatic compounds

acid chloride + metal hydride

primary alcohol with intermediate aldehyde

acid chloride to aldehyde

rosenmund reaction OR 1. LiAl[OC(CH₃)₃]₃ 2. H₂O

acid chloride + organometallic reagents

tertiary alcohol (kinda)

acid chloride to ketone

R₂CuLi

general reaction of anhydrides + acid

ester hydrolysis in base

ester hydrolysis in acid

transesterification in acid

transesterification in base

esters + organometallic reagents

tertiary alcohol (kinda), same as acid chloride + organometallic reagentse

esters + metal hydrid

primary alcohol

ester + DIBAL-H

aldehyde

why does DIBAL-H make an intermediate aldehyde but metal hydrides make alcohol

DIBAL-H is more sterically hindered

amide hydrolysis in base

to protonate, add acid

amide hydrolysis in acid

amide + metal hydride

nitrile hydrolysis in acid

nitrile hydrolysis in base

which is better: nitrile hydrolysis in base or acid

acid, base creates side effects

nitrile + organometallic reagents

ketone

nitrile + metal hydride

primary amide

nitrile + catalytic hydrogenation

primary amide

Baeyer-Villiger reaction (aldehyde/ketone + peroxy acid)

aldehyde → carboxylic acid

ketone → ester

beckmann rearrangement (ketone + NH₂OH and H₃O⁺)

amide

Beckmann rearrangement for cyclic compounds

For nitriles, how can you predict stereochem of product

the R group anti to the OH is the group that migrates

wolff rearrangement (acid chloride + CH₃N₂)

diazo ketone

Arndt-Eistert reaction (ketone + CH₂N₂ + heat)

adds extra CH₂ on R group of starting carboxylic acid

curtius rearrangement (acid chloride + NaN₃)

hoffmann rearrangement (amide + Br₂, KOH, H₂O)

amine, CO₂, H₂O

why is removal of an ⍺ hydrogen favored over further hydrogens

1. resonance stabilized

   1. stabilization from C=O dipole (electrostatically stabilized)

what are the two nucleophiles for carbonyl chemistry at ⍺ position

enol or enolate

keto-enol tautomerization in acid

keto-enol tautomerization in base

first create an enolate

why are products of carbonyl chem at ⍺ position racemic

enols and enolates are planar, they can be attacked from both sides

halogenation in ⍺ position for ketones and aldehydes

why doesn’t halogenation in acidic conditions continue like deuterium and replace all the ⍺ hydrogens

because adding a halogen would withdraw electrons at ⍺ position, disfavoring formation of enol

halogenation in ⍺ position for ketones/aldehydes in base

enolate is produced thus all ⍺ hydrogens are replaced

haloform reaction (methyl ketone + base)

product of halogenation at ⍺ position in base is further reacted with base

halogenation of carboxylic acids at ⍺ position

⍺-bromo acid bromide

halogenation of carboxylic acids at ⍺ position (catalytic PBr₃)

adding strong acid reacts with the ⍺-bromo acid bromide

what is ⍺-bromo acid bromide similar to

acid chloride (bromide can be replaced to make amide, carboxylic acid, ester)

halogenation of esters in ⍺ position

alkylation at ⍺ position for ketones and aldehydes

alkylation for carboxylic acids

requires 2 eq of strong base to remove both carboxyl hydrogen and ⍺ hydrogen

alkylation of ß-dicarbonyl compounds

hydrolysis and decarboxylation of ß-dicarbonyl compounds

ß-keto ester synthesis

direct alkylation of esters

alkylation of amines

secondary amines only

adol condensation of aldehydes/ketones in acid

aldol condensation of aldehydes/ketones in base

aldol condensation to unsaturated aldehyde/ketone (in acid)

aldol condensation to unsaturated aldehyde/ketone (in base)

knoevenagel condensation (ketone/aldehyde + base)

⍺, ß-unsaturation diester (anion stabilizing groups can be carboxylic acids, carbonyls, etc)

michael reaction (⍺, ß-unsaturated carbonyl compounds)

intramolecular aldol condensation

crossed aldol condensation

two different carbonyl compounds (4 possible products)

claisen condensation with ketones

claisen condensation with 2 esters

results in claisen product and transesterification product

dieckmann condensation (intramolecular claisen condensation)

crossed claisen condensation

robinson annulation (michael addition + aldol condensation)

makes six membered ring

mannich reaction

beckmann rearrangement (ketone → amide)

beckmann rearrangement (cyclic)

wolff rearrangement (acid chloride → diaz ketone)

diazo ketone exposed to light

carbene

arndt-eistert reaction (extra CH₂)

curtius rearrangement

hoffmann rearrangement (amide→amine)