Chapter 22

What are amines?

derivatives of ammonia where one or more of the protons are replaced by alkyl/aryl groups; primary, secondary, or tertiary (one two or three R groups)

What are alkaloids?

naturally occuring amines isolated from plants

How are amines prepared from alkyl halides?

two step process; treat with NaCN to make nitrile then reduces with 1) xs LiAlH4 2) H2O to make amine

How are amines prepared from carboxylic acids?

carboxylic acid is treated with 1) SOCl2 2)xs NH3 to replace OH group with NH2 and then reduced to get rid of carbonyl group

How is aniline prepared from benzene?

NO2 is added to benzene group and then it is either reacted with H2, Pt to get NH2 group or with 1) Fe, Zn, Sn, or SnCl2, H3O+ 2) NaOH (second method will reduce only NO2)

How does ammonia readily go through alkylation?

treated with alkyl halide

What is the azide synthesis?

primary amines made by treating alkyl halide with NaN3 and reduction

What is the Gabriel Synthesis?

prepares primary amines without making secondary or tertiary amines; starts with potassium phthalimide and reacts with 1) KOH 2) halide that is exact same as product 3) H2NNH2

What is reductive amination?

ketone/aldehyde converted into an amine in acidic conditions and ammonia and then immediately reduced to get an amine

What is NaBH3CN?

reducing agent

How do you make a secondary amine from aldehyde/ketone?

R-NH2, NaBH3CN, [H+]

How do you make a tertiary amine from an aldehyde/ketone?

R-NH-R, [H+], NaBH3CN

What do amines react with to get amides?

acyl halides and pyridine

An amide made from acylation can use what as a protecting group?

CH3Cl, AlCl3; will add CH3 in para position

How is the protecting group removed and NH2 is made again?

NaOH, H2O or H3O+

What is Hofmann Elimination?

amino group is treated with excess methyl iodide and silver oxide to convert it to a leaving group, followed by strong base to give an alkene

What is nitrous acid?

HONO

How is nitrous acid made?

sodium nitrite (NaNO2) is treated with HCl

When a secondary amine is treated with NaNO2 and HCl, what is made?

N-nitrosamine (R2N-N=O)

When a primary amine is treated with sodium nitrite and HCl, reaction produces what?

diazonium salt (R-N triple bonded to N)

What is a aryl diazonium ion?

benzene with diazonium attached; made from aryl amine

What is a Sandmeyer Reaction?

aryl diazonium reacts with CuX to replace the diazonium group with X

What is the Schiemann reaction?

aryl diazonium reacts with HBF4 to replace diazonium with F

When an aryl diazonium is heated with water, what is produced?

diazo group is replaced with OH

What does H3PO2 do?

replaces diazo group in aryl diazonium to H

What is azo coupling?

electrophilic aromatic substitution reaction where aryldiazonium reacts with activated aromatic ring (benzene with activating group) to get azo group