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Organic Chemistry 328 SI
Ochem Tutoring Position is still available!
Quiz 4 (Probably over chapter 24-25)
Final Exam Review:
Wednesday 4/26 from 5-7pm
Ag Engineering 100
Monday 5/1 from 4-6pm
About Final Test
Similar to last semester
About 75% cumulative (15-23) and 25% new (24-27?)
How should you prepare for this exam?
Old Material (8 Questions)
Reactions of Amines
Formation of Diazonium Salts
Reactions of Diazonium Salts
Name this compound.
How many degrees of unsaturation does benzene have?
Order the following in order of increasing reactivity for an addition-elimination reaction?
IV = III < I < II
IV < III < I < II
III < IV < II < I
III < IV < I < II
Why won’t this reaction occur?
The lone pair on nitrogen will act as a Lewis base, which will prevent the formation of the expected Lewis acid-base electrophile
Like all of the meta directors, NO2 is a strong deactivator and will prevent the reaction from occurring
The electrons on the negatively charged oxygen will react violently with the aluminum to produce aluminum oxide instead of the desired product
This is a trick question, the reaction will occur under normal conditions.
Limitations of Friedel-Crafts Electrophilic aromatic substitutions
Reaction cannot occur when…
NO2 is on the ring
NH2, NHR, or NR2 are on the ring
N lone pair acts as a Lewis base
Polyalkylation occurs with R groups
R groups are electron-donators (activators)
To minimize this, excess amounts of benzene are used.
Does not occur with Friedel-Crafts acylation
What is the product?
None of these.
Br2 / FeBr3
I and II
A mixture of 1-hexanol and hexanoic acid in diethylether is shaken with an aqueous sodium bicarbonate solution. Which line below correctly describes the major organic species in the two resulting immiscible solutions?
Uses solubility differences to separate and purify compounds.
Water or aqueous solutions (10% NaHCO3 or 10% NaOH)
One compound must dissolve in the aqueous layer, and the other in the organic layer
Carboxylic acids will separate from organic compounds when deprotonated
Amines will separate from organic compounds when protonated
Quaternary Ammonium Cations
Amines (pg. 794)
 LiAlH4 /ether
Which alkyl halide was used?
 –OH / H2O
Reductive Amination of Aldehydes and Ketones
SM: Ketone or Aldehyde
NH3, Primary Amine, or Secondary Amine with H2/Ni or NaBH3
Primary, secondary, or tertiary Amine, respectively
*Details: Dehydration of carbinolamine to form an imine, and then reduction to form the amine.
*Should recognize this from chapter 19!
Hofmann and Curtis Rearrangements
Preparation of Amines
Reaction and Starting Material
Direct Nucleophilic Substitution – SN2 Alkylation of Alkyl Halide
NH3, Primary, or Secondary Amines
• Best for production of Primary Amines an quaternary ammonium salts
• SN2 Mechanism
• Best for CH3X or RCH2X
• Over alkylation typically occurs
Nitro Compounds (-NO2)
or Fe, H3O+
or SnCl2, H3O+
Primary, Secondary, or Tertiary Amines
Alkyl Azides -
 NaN3 / EtOH
 LiAlH4 / H2O
Azide replaces halogen and then is reduced into an amine
• Azide ion (N3-)
• Explosive reagent
Gabriel Synthesis –
Preparation of Amines Continued
Reductive Animation – (Ketone/Aldehyde with amine)
NH3, Primary Amine or Secondary Amine /
H2/Ni or NaBH3
• Adds one alkyl group from a ketone or aldehyde to a nitrogen nucleophile
NaOH, Br2 / H2O
By Product: CO2
• Forms Bromoamide which is deprotonated and rearranges to form Carbamic Acid
• Spontaneous decarboxylation forms the amine
• NOTE: LOSS of a carbon
SM: Acid Halide (Typically Acid Chloride) or Acyl Azide (start at reagent 2…)
1. NaNO2 / H2SO4
(Forms Acyl Azide)
2. H2O / Heat
By Product: CO2 and N2
• Acyl Azide loses N2 and rearranges into Isocyanate
• Decarboxylation forms the amine
Alkylation and Acylation (Chapter 21)
What is the major product?
 CH3I (ex)
Reactions with nitrous acid (HNO2) (Formation of Diazonium Salts)
What forms from this reaction?
An aryl diazonium salt
An alkyl diazonium salt
A nitrosonium ion
Reactions of 1˙ Amines with nitrous acid
 CH3I (excess)
• LESS substituted (Minor product)
Reactions with nitrous acid
-Formation of Diazonium Salts
NaNO2 / H2SO4
Alkyl diazonium salt
• Product used in Substitution or Coupling reactions
Reactions of Aryl Diazonium Salts
None of these
A diazonium salt, No reaction will occur with NaI.
Draw the products.
Phenol (replaces with –OH)
HCl / CuCl
Aryl chloride (replaces with –Cl)
HBr / CuBr
Aryl bromide (replaces with –Br)
Aryl floride (replaces with –F)
NaI or KI
Aryl iodide (replaces with –I)
CuCN or KCN
Benzonitrile (replaces with –CN)
Benzene (replaces with –H)
Coupling to form Azo Compounds
(Y = NH2, NHR, NR2, OH)
• Best for production of Primary Amines an quaternary ammonium