Amines Flashcards
Amines can be thought to be derivatives of….
Ammonia (Instead of three hydrogen it’s three R groups)
What are the four types of Amines? 
- primary (One R group)
- secondary
- Tertiary
- Quaternary (ammonium salts, 4 R groups) 
The N in amines is _____ hybridized. 
sp3
Simple amines are CHIRAL But chirality can be ignored as the two enantiomers inner convert rapidly at room temperature through a ____________. 
Pyramidal inversion (think of an umbrella) 
Tetrahedral ammonium salts with four different are groups are _______. 
Chiral. Chirality cannot be ignored! 
Primary amines are named as…..
Alkanamine
The parent chain is the longest carbon chain that contains the amine group 
What is the -NH2 group called when naming primary amines with more than one functional group?
Amino
Common name of primary amines?
Alkylamines
Common name for naming Symmetricalsecondary and tertiary amines?
Prefixes such as di, tri, tetra,… are used. 
How are unsymmetrical secondary and tertiary amines named? 
N- common names of Primary amines.
N-methylethylamine (common name)
N-methylethanamine (IUPAC name) 
How are aromatic amines named? 
As derivatives of aniline
Exceptions see page 470
amines have a higher priority than
Alkenes, Alkynes, ethers, and halides
What kind of amines can hydrogen bond? 
Primary and secondary
 because primary and secondary amines can H bond, they have….
Higher melting point and boiling point than comparable substances but lower than alcohols and carboxylic acids
___________ amines have lower boiling point and nothing point and then primary amines. 
Tertiary
Low molecular weight amines have _______ odors
Fishlike
Diamines smell like…
Cadavers
Amines with odd number of nitrogens have ____ molecular weights.
Odd
Amines have N-H bands at 3300-3500cm-1
How many of these bands do primary, secondary, tertiary amines have? 
Primary amines have two
Secondary amines have one
Tertiary have none
The N-H proton is desheilded at ____ -_____ ppm.
2.2-3.0 ppm
Does not split signals of adjacent hydrogen
The C of C-N is desheilded at ____-____pppm
30-50
Complex basic amines derived from plants
Alkaloids
These interfere with the normal functioning of the brain. Some are pain killers.
2-Phenylethylamine and derivatives
What are the three ways to prepare amines?
- nucleophilic (SN2) Substitution with nitrogen Nucleophiles
- Reduction of nitrogen containing functional groups
- Reductive amination of Aldehydes and ketones
For nucleophilic substitution to get primary amines use…
2ŃH3 and R-X
For secondary and tertiary amines, use…
And quaternary?
R’NH2 (secondary)
R’2NH (Tertiary) 
Access alkyl halide and R’3Ń (amine with three groups) 
What is used in the Gabriel synthesis of primary amines? 
-Alkyl halide + phthalimide
OH-
———->
H20
-Primary Amine + dicarboxylate and X-
What is used for the reduction of nitro compounds?
What kind of amine is produced? 
H2/Pd
Fe/HCL
Sn/HCL
Primary amine R-ŃH2
What is used to reduce nitriles? 
- LiAlH4
- H2O
Produces a primary amine
What is the catalyst for reductive amination of Aldehydes and ketones? 
NaBH3CN
Amines Usually lone pair of electrons in nitrogen to react as __________ or _________.
Bases, Nucleophiles
For a reaction to take place the PKA of the reactants Has to be ________ Than the PKA of the product. 
Less
Be higher the PKA of the conjugate acid, the __________ the amine as a weak base And vice versa
Stronger
Alkyl amines are more _____ than NH3 since the alkyl groups are Electron donating groups (EDG) 
Basic
Alkyl amines are more _______ than aniline because the long pair of electrons on the end is de localize in Aniline through resonance. 
Basic
EDG (-NH2, -OH, -OR, -NHCOR, -R) make arylamines more ______ than aniline.
Basic
EWG (-X, -CHO, -COR, -COOR, -COOH, -CN, -SO3, -NO2, NR3+) make arylamines _______ basic than aniline.
Less
See page 489
Alkylamines are ________ than amides
More basic
See page 489
Arylamines are _____ than NH3
Less basic
Electron pairs that are de-localized in part of the aromatic system are more or less basic than lone pairs that are localized? 
Less basic
Localized electron pairs are more basic
Pg. 490
Does a higher or lower sp3 character make it more basic?
Lower
Amines react with carbonyl groups to give ___________ or ___________ compounds.
Substitution, addition
Reaction converts first an amine to a quaternary Ammonium salt, the salt is in converted to an alkene
What kind of reaction is this?
Hoffman elimination reaction
What is the major product in Hoffman elimination reaction?
Non-Zaisev (Least substituted) 
Phenyl hydrazine and 2,4-DNP (primary amines) react with aldehydes and ketones to give….
Crystalline phenylhydrazones (imines) with distinctive MP
____________ (a primary amine) reacts with aldehydes and ketones to give crystalline semicarbazones (imines) 
Semicarbazide
What can be used to identify aldehydes and ketones? 
Semicarbazone (primary Amine) 
What type of projections are used to show the sugars in DNA and RNA?
Haworth projections
