Reactions of Amides and Enols/Enolates

How do you make an amine with an alkyl halide (a carbon chain with a Br, I, Cl, I)?

• Use NaCN/Sn2 (This makes C-N bond) —>

• Use 1. xs LAH/ 2. H2O (This makes RNH2) —>

How do you make an amine from a carboxicilic acid (COOH)?

• Use 1. SoCl2/ 2. xs NH3 (This makes an acid chloride) —>

• Use 1. xs LAH/ 2, H2O (This makes RNH2)—>

How do you make an amine from benzene (6 membered ring with double bonds)?

• Use HNO3/H2SO4 (this creates NO2 substitiuent)

• Use H2/Pt OR 1. Fe, Zn, Sn, SnCl2/ 2. NaOH (This makes RNH2)

How do you make an amine using an azide (N=N=N)?

• Use Na3N (This attaches N3 to end of chain)

• Use H2/Pt OR 1. LAH/ 2. H2O (This makes RNH2)

How do you make an amine using Gabriel synthesis (pthalimide)?

• First make Potassium Pthalimide by using KOH (gets rid of Hydrogen on pthalimide)

• Potassium Pthalimide is alkylated with RX/Sn2 (This adds an R group to the N on the Pthalimide)

• Liberate the amine with H3O+ or 2NH2 (This creates RNH2)

How do you make a primary amine with reductive amination (starting from a ketone)?

• Use NH3/H+, NaBH3CN

How do you make a secondary amine with reductive amination (starting from a ketone)?

• Use RNH2/H+, NaBH3CN

How do you make a tertiary amine with reductive amination (starting from a ketone)?

• Use R2NH/H+, NaBH3CN

What three ways can you make a primary amine?

• Use Gabriel Synthesis (Potassium Pthalimide Group—> 1. RX/NH2NH2)

• Use Azide Synthesis (N=N=N —> 1. RX/ 2. H2, Pt

• Use Reductive Amination (NH3 —> ketone + NaBH3CN)

How do you add an alkyl group to an amine?

• Use an acyl chloride (ketone with a chlorine)

What should you do if you want to brominate or do a friedal crafts on an amide ring?

• Use an acyl chloride to protect (This turns NH2 into a NH)

• Then use Br2 (This adds Br on correct position)

• Use NaOH to return NH2 to normal

• Friedal Crafts is same thing except CH3Cl

What is the sandmeyer reaction?

• A diazonum salt (R-NN) is replaced with (Br, CN, I, or Cl) with the reagent Cu(Br, Cl, I, CN)

How can you use a sandmeyer reaction to install a carbox. acid (COOH)?

• First use HNO3/H2SO4 (This makes NO2)

• Next use Fe, H3O+ and NaOH (This inevitably makes NH2)

• Then use NaNO2, HCl (This makes the diazonium salt)

• This where the intimediary is

• Finally, use 1. CuCn/ 2. H3O+, heat to add COOH

How do you add a F starting with a diazonium salt (NN)?

• Use HBF4 (This replaces NN with F)

How do you add an OH starting with a diazonium salt?

• Use H2O/heat (this replaces NN with OH)

How do you add H starting with a diazonium salt?

• Use H3PO2 (This replaces NN with H)

How does azo coupling work/ what does it look like?

• It adds an R group to one of the N’s, and the N triple bond becomes an N double bond

How do you make a mixture of ketone and enolate from a ketone (reversible)?

• Use NaOH

How do you make an enolate from a ketone (irreversible)?

• Use LDA or NAH

What reagents do you use to halogenate a ketone?

• Use H3O+/Br2

Will the enolate form under acidic or basic conditions?

Basic (-OH)

What do you use for an aldol condensation reaction/what does it look like?

• Use H or OH/heat

• The E isomer will be favored

• THIS ONE GETS DRAWN WEIRD REFER TO NOTES

How do intramolecular aldol reactions work?

• Use NaOH, H2O/heat

• COUNT FROM ONE C=O TO END OF CHAIN

• CREATE A RING AND INSTALL DOUBLE BOND

• IF GOING IN REVERSE YOU CUT THE DOUBLE BOND

What do you use for claisen condensation and what does it look like?

• Use NaOEt/H3O

• SAME THING AS CONDENSATION PRODUCT YOU PUT THE TWO MOLECULES TOGETHER JOINED BY DOUBLE BOND

What do you use for a dieckmann reaction and what does it look like?

• Use NaOEt/H3O

• SAME THING AS INTRAMOLECULAR

• YOU CREATE A RING

What do you use for alkylation of the alpha position?

• Use LDA/RX

How do you get the thermodynamic product from alkylation (less substitued)?

• Use LDA at low temp (-78)

How do you get the kinetic product from alkylation (more substituted)?

• Use NaH at 25