Chapter 21 and 22 Reagents

Provide the function for the Reagent: H₃O⁺

Used to acid-catalyzed keto-enol tautomerization

Provide the function for the Reagent: NaOH or NaOR

• Used to form a reversible enolate (carbonyl and enolate are at equilibrium)

-Nearly complete enolate formed when protons are alpha to two carbonyl groups

Provide the function for the Reagent: LDA or NaH

• Forms irreversible enolate

Provide the function for the Reagent: [H₃O^₊], X₂

• Alpha halogenation in acidic conditions

• Adds to more substituted alpha position of ketone or aldehyde

Provide the function for the Reagent:

NaOH, Br₂

• Alpha halogenation in basic conditions

• Multiple halogenations occur

Provide the function for the Reagent:

1. [H₃O⁺], X₂

2. Pyridine

• Used to convert ketone or aldehyde to a ⍺,β-unsaturated ketone or aldehyde

Provide the function for the Reagent:

1. xs NaOH, xs X₂

2. H₃O^₊

• Multiple halogenations occur

• Used to convert a methyl ketone into a carboxylic acid

Provide the function for the Reagent:

1. Br₂, PBr₃

2. H₂O

• Hell-Volhard-Zelinsky reaction occurs

• Adds a bromine atom at alpha position of a carboxylic acid

Provide the function for the Reagent: NaOH, H₂O

Adol addition occurs:

• Two of either the same ketone or aldehyde react together

or

• Two different aldehydes and/or ketones are crossed

Provide the function for the Reagent: NaOH, H₂O, Heat

• Adol condensation reaction occurs

Provide the function for the Reagent:

1. NaOR

2. H₃O⁺

• Used in Claisen Condensation

Provide the function for the Reagent:

1. LDA

2. Aldehyde or Ketone

3. H₃O⁺

• Used for directed adol reaction between two different aldehydes and/or ketones

Provide the function for the Reagent:

1. LDA

2. Ester

3. H₃O⁺ (workup)

• Used for directed adol reaction between two different esters

Provide the function for the Reagent:

1. LDA, -78ºC

2. RX

• Alkylation of the alpha position

• Used to add an alkyl group (R) to the alpha position of an aldehyde or ketone

With an unsymmetrical ketone:

• R group adds to less substituted side

Provide the function for the Reagent:

1. NaH, 25ºC

2. RX

• Alkylation of the alpha position of an aldehyde or ketone

With unsymmetrical ketone:

• Add R group to the more substituted side

What are the structures for Ethyl acetoacetate and diethyl malonate?

Provide the function for the Reagent:

1. NaOEt

2. RX

3. H₃O⁺,Heat

Acetosynthetic ester synthesis

• Ethyl Acetoacetate can be converted into a monosubstituted derivative of acetone

Malonic ester synthesis

• Diethyl malonate can be converted into a monosubsituted derivative of acetone

Provide the function for the Reagent:

1. NaOEt

2. RX

3. NaOEt

4. R’X

5. H₃O⁺, heat

Acetosynthetic ester synthesis

• Ethyl Acetoacetate can be converted into a di substituted derivative of acetone

Malonic ester synthesis

• Diethyl malonate can be converted into a di subsituted derivative of acetone

Provide the function for the Reagent: (Gilman Reagents)

1. R₂CuLi

2. H₃O⁺

Micheal reaction

• Add one R group to the beta position and a hydrogen to the alpha position

• 1,4 addition product

Provide the function for the Reagent: (Grignard Reagents)

1. RMgBr

2. H₃O⁺

• Makes a 1,2 addition product

Provide the function for the Reagent:

1. R₂CuLi

2. R’X

3. H₃O⁺

Micheal reaction

• Add one R group to the beta position and the R’ group from step 2 to the alpha position

Provide the function for the Reagent:

1. R₂CuLi

2. R’X

or

2. H₃O⁺

• R group is added to the beta position

With RX as the second step:

• Add second R group to alpha position

With H₃O⁺ as the second step:

• Add a hydrogen to the alpha position

Provide the function for the Reagent:

1. NaCN (or KCN)

2. xs LiAlH₄

3. H₂O

• Used to convert an alkyl halide into an amine

• Adds one more carbon to starting material

Provide the function for the Reagent:

1. SOCl₂

2. NH₃

3. xs LiAlH₄

4. H₂O

• Used to convert carboxlyic acid into an amine

Provide the function for the Reagent:

• Creation of nitration of aromatic ring using HNO₃, H²SO₄, and then

1. Fe or Zn, H₃O⁺

2. NaOH

• Reduces aryl nitro group (NO₂) to an amino group (NH₂)

-NaOH is required to get neutral amino group

Provide the function for the Reagent:

1. SnCl₂, H₃O⁺

2. NaOH

• Selectively reduces an aryl nitro group (NO₂) to an amino group (NH₂)

-NaOH is required to get a neutral amino group

Provide the function for the Reagent:

1. NaN₃

2. LiAlH₄

3. H₂O

• Converts alkyl halide into an amine

-Adds one more carbon to starting material

Provide the function for the Reagent:

H₂, Pt

• Reduces NO₂ group into an NH₂ group

• Reduces (Azide) N₃ into an NH₂ group

Provide the function for the Reagent:

1. KOH

2. RX

3. NH₂NH₂

Gabriel synthesis

• Reaction starts with pthalimide

  

• Makes primary amines

Provide the function for the Reagent:

H⁺, NaBH₃CN

• Used to recieve a reductive amination

• Reaction occurs between a ketone/aldehyde and an amine/ammonia

To get the product:

• Remove the carbonyl carbon oxygen atom with a double bond and connect the N atom in the amine/ammonia to the former carbonyl compound by a single bond

Provide the function for the Reagent:

xs CH₃I

• Used to convert amine/ammonia to a quaternary ammonium salt

Provide the function for the Reagent:

1. Excess CH₃I

2. Ag₂O, H₂O, heat

Hoffman elimination

• Elimination of beta H and NH₂ (or NHR’, NR’R’’) to make an alkene

• A less substituted product is the major product

Provide the function for the Reagent:

ROCl

• An amine will undergo acetylation, giving an amide

Provide the function for the Reagent:

NaNO₂, HCl

• Converts primary amine into a diazonium salt

• Converts a secondary amine into an N-nitrosamine

Provide the function for the Reagent:

CuCl

• The diazonium group is replaced with a chlorine atom

Provide the function for the Reagent:

CuBr

• The diazonium group is replaced with a bromine atom

Provide the function for the Reagent:

CuI

• The diazonium group is replaced with a Iodine atom

Provide the function for the Reagent:

CuCN

• The diazonium group is replaced with a Cyano group

Provide the function for the Reagent:

HBF₄

• The diazonium group is replaced with a fluorine atom

Provide the function for the Reagent:

H₃PO₂

• The diazonium group is replaced with a hydrogen atom

Provide the function for the Reagent:

H₂O, heat

• The diazonium group is replaced with a OH group

Provide the function for the Reagent:

ROH, heat

• The diazonium group is replaced with a OR group

Provide the function for the Reagent:

Br₂, 0ºC

• Add a bromine atome to the C2 position on a pyrrole ring by replacing an H atom

Provide the function for the Reagent:

Br₂, 300ºC

• Add a bromine atome to the C3 position on a pyridine ring by replacing an H atom

How can you identify amines from Spectroscopy?

Ir spectroscopy:

• Primary amine has two sharp peaks around 3300 - 3500

• Secondary amine has 1 sharp peak around 3300 - 3500

  

• Tertiary = N/A

Mass spectrometry: