Orgo Exam 3

Oxidative cleavage of alkynes (alkyne to 2 COOH)

1. O3, 2. H2O

Oxidation of primary alcohols OR alkylbenzenes

Na2Cr2O7, H2SO4, H2O

Carboxylation of Grignard reactions (R-MgBr → RCOOH)

1. CO2, 2. H3O+

Carboxylic acid reduction to alcohol (RCOOH → RCH2OH)

1. LiAlH4, 2. H3O+ or BH3*THF

Acid chloride/anhydride to carboxylic acid (COCl → COOH)

H2O

Carboxylic acid to acid chloride (COOH → COCl)

SOCl2

Acid chloride/anhydride to ketone (COCl → COR)

R2CuLi

Acid chloride to ester (COCl → COOR)

ROH, Pyridine

Acid chloride to amide (COCl → CONH2)

xs NH3

Acid chloride/anhydride to alcohol (COCl → CR2OH)

1. xs RMgBr, 2. H3O+

Acid chloride/anhydride to aldehyde (COCl → COH)

1. LiAl(OR)3H

2. H3O+

Acid chloride/anhydride/ester/carboxylic acid to alcohol (COCl → CH2OH)

1. xs LiAlH4

2. H3O+

Acid chloride/anhydride to amide (COCl → CONR2)

xs R2NH

Acid anhydride

RCOOCOR

Carboxylic acid to symmetric acid anhydride

Heat

Acid anhydride to carboxylic acid

H2O

Acid anhydride to ester

ROH

Ester to carboxylic acid (COOR → COOH)

1. NaOH, 2. H3O+ OR [H+], H2O

Ester to amide (COOR → CONH2)

NH3

Alkyl halide to nitrile (RX → RCN)

NaCN

Amide to nitrile (CONH2 → CN)

SOCl2

Nitrile hydrolysis (CN → CONH2 → COOH)

H3O+, heat

Nitrile to ketone (CN → COR)

1. RMgBr, 2. H3O+

Carboxylic acid to asymmetric acidic anhydride (RCOOH → RCOOCOR)

Acid chloride, pyridine

Carboxylic acid to ester (COOH → COOR)

[H+], ROH

Nitrile to amine (CONH2 / CN → CH2NH2)

1. xs LiAlH4, 2. H2O

Ester to aldehyde (COOR → COH)

1. DIBAH, 2. H3O+

Alpha halogenation of ketones (alpha hydrogen → halogen)

[H3O+], Br2

Alpha halogenation of carboxylic acids (hell-volhard-zelinsky) (alpha hydrogen → halogen)

1. Br2, PBr3, 2. H2O

Haloform reaction (ketone alpha carbon → OH)

NaOH, Br2

Methyl ketone to carboxylic acid

1. NaOH, Br2

2. H3O+

Aldol addition (combines two aldols into a ketone/aldehyde and an alcohol)

NaOH, H2O

Added aldols → unsaturated aldehyde (OH → double bond)

Heat

All claisen condensations

1. NaOR, 2. H3O+

Alkylation via Enolate Ions

1. LDA, -78 C, 2. RX (kinetic) OR 1. NaH, 25 C, 2. RX (thermodynamic)

Malonic and Acetoacetic Ester Synthesis

1. NaOEt, 2. RBr, 3. H3O+, heat

Michael Addition (adds to beta position of condensed aldol)

1. R2CuLi, 2. H3O+ OR 1. KOH, 2. CH3CH2CH2COH, 3. H3O+

Michael Addition (Stork Enamine) (ketone to enamine, adds at alpha position)

1. R2NH, [H+], (-H2O), 2. stabilized condensed aldol, 3. H3O+

Robinson annulation = Michael addition + intramolecular aldol condensation

NaOH, Heat

Alkyl Halide to Amine (RBr → RCH2NH2)

1. NaCN, 2. xs LiAlH4, 3. H2O

Carboxylic acid to amide (COOH → CONH2)

1. SOCl2, 2. xs NH3

Nitration of benzene

HNO3, H2SO4

Benzene NO2 → NH2

H2, Pt, OR, 1. Fe/Zn/Sn/SnCl2, H3O+, 2. NaOH

Azide synthesis (RX → RN3)

NaN3

Azide to Amine (RN3 → RNH2)

H2, Pt, OR 1. LiAlH4, 2. H2O

Gabriel Synthesis (Makes RNH2)

Phthalimide + 1. KOH, 2. R-X, 3. H3O+H2NNH2

Ketone to Amine (C=O → CNH2)

NH3, [H+], NaBH3CN

Ketone to Amine (C=O → CNHR)

RNH2, [H+], NaBH3CN

Ketone to Amine (C=O → CNR2)

R2NH, [H+], NaBH3CN

Acylation (RNH2 → RNHCOR)

Acid chloride (ClCOR)

Hoffman Elimination (less sub)

1. Excess CH3I, 2. Ag2O, H2O, Heat

RNH2 → RNN (only useful if R is benzene)

or R2NH → R2NNO

NaNO2, HCl

Sandmeyer Reaction (Ph-NN → PhX)

CuX (X = Br, Cl, I, CN)

Schiemann reaction / Fluorination (Ph-NN → PhF)

HBF4

Ph-NN → PhOH

H2O, Heat

Ph-NN → Ph

H3PO2

Ph-NN → R-Ph-N=N-Ph

R-Ph, (R = activator)

Pyrrole → 2-Bromopyrrole (Pentane but NH, adds Br adjacent)

Br2, 0 C

Pyridine → 3-Bromopyridine (cyclohexane but N, adds Br meta)

Br2, 300 C