Chem 22 Summer 2000 Exam 1 Review Sheet
Reactions covered in
Chapter 11
1.
Reaction of alcohols with HX ---------> _________________
Reaction
Conditions:
_________________________
Can
be SN1 or SN2
reaction, depending on the degree of substitution of the alcohol
As
always, first order reactions are subject to rearrangement
If
SN2 mechanism, only HI and HBr work well.
If
SN1, HI, HBr, or HCl can be used.
2.
Reaction of ethers with HX ---------> _________________
Reaction
Conditions: _________________________
Can
be SN1 or SN2
reaction, depending on the degree of substitution of the ether
As
always, first order reactions are subject to rearrangement
If
SN2 mechanism, only HI and HBr work well.
If
SN1, HI, HBr, or HCl can be used.
aromatic
ethers do NOT lose oxygen
3.
Reaction of alcohols with PBr3--------->
_________________
Reaction
Conditions:
_________________________
two
step mechanism
results
in inversion of the original alcohol
4. Reaction of alcohols with SOCl2 ---------> _________________
Reaction
Conditions:
_________________________
three
step mechanism
results
in inversion of the original alcohol
5.
Formation of sulfonate esters from alcohols --------->
_________________
Reaction
Conditions:
_________________________ (several choices of reagents)
reaction
converts hydroxyl group into a good leaving group
two
step mechanism results in a net loss of HCl
6.
Dehydration of alcohols
---------> _________________
Reaction
Conditions: (two possible) _________________________
_________________________
E1-like
mechanism
carbocation
rearrangement possible
the
more unstable carbocation formed, the more heat is required
What
are the special conditions for 1° alcohol reactions?
7. Epoxide
openings
Nucleophilic
opening goes by ________ mechanism
characteristics: ____________________________
Acid-catalyzed
opening goes by ________ mechanism
characteristics: ____________________________
8.
Synthesis of sulfides
Net
reaction:
______________
---------> ______________
Comparison
to corresponding ether synthesis
9. Synthesis and reaction of sulfonium ions
10. Synthesis of organometallic compounds
Alkyl
Halide to organolithium: Reagents
/ solvent:____________________
Alkyl
Halide to Grignard: Reagents
/ solvent:____________________
organolithium
to organocuprate: Reagents /
solvent:_________________
11. Reactions of organometallics:
Grignards
+ epoxides makes ______________________________
organocuprate
+ alkyl halide makes ________________________
acid
/ base reactions
12. Hofmann Elimination
Reactant
is quaternary amine hydroxide
Synthesized
by an amine reacting with _________ followed by _________
How
is this reaction different than a typical E2 reaction? Why?
13. Cope Elimination
Reactant
is amineN-oxide
Synthesized
by a _____ amine reacting with _________
How
is this reaction similar to the Hofmann elimination? How is it different?
Concepts covered in
Chapter 11 (including Ch. 26 material)
1. How are
typical SN and E reactions changed when
the leaving group is not a halogen?
Leaving
Groups: OH, OR, NR3, OTs, OTf, OMs
2. Lucas
test for degree of substitution of an alcohol.
3.
Stereochemical aspects of alcohol substitution reactions: halogenation, sulfonate esters.
4.
Nomenclature and structure of heterocyclic ethers, and other non
aromatic heterocycles. (Sec 26.1)
5.
Phase-transfer catalysis:
crown ethers and quaternary amonnium salts.
6. Arene
oxides and aromatic carcinogens.
7. What is
the nature of organometallic compounds?
How does the identity of the metal affect the reactivity of a
organometallic compound?
8.
Stereochemistry of the E2 and related elimination reactions.
Reactions covered in
Chapter 14 (including Ch. 26 material)
1.
Electrophilic Aromatic Substitution: know reagents for
Bromination _________________ Chlorination _________________
Iodination _________________ Nitration _________________
Nitrosation _________________ Azo-coupling _________________
Sulfonation/desulfonation _________________ Friedel-Crafts Acylation _________________
Friedel-Crafts Alkylation _________________
2.
Aromatic side-chain reactions:
know reagents and starting materials for
Benzylic Oxidation: _________________ Benzylic bromination _________________
Carbonyl reduction (2) _________________ _________________
Nitro reduction _________________ Aryl Diazonium Formation _________________
N-Nitrosamine Formation _________________
3.
Reactions of Aryl Diazonium ions:
know reagents for
Bromination/Chlorination _________________ Nitrile Formation _________________
Iodination _________________ Fluorination _________________
Phenol Formation _________________ Replacement with H _________________
4.
Nucleophilic Aromatic Substitution: know reagents and starting materials
for
SNAr reaction: _________________ Benzyne reaction _________________
5.
Naphthalene and Aromatic Heterocycle reactivity
Electrophilic
Substitution:
What
is the regioselectivity? How are
the reagents different?
How
do they differ in reactivity?
Nucleophilic
Substitution of pyridines: The
Chichibabin reaction.
Reagents: _________________
Why
does this work?
Concepts covered in
Chapter 14 (including Ch. 26 material)
1.
Nomenclature of simple, substituted benzenes (ortho, meta, para) and
some polycylic benenoids
2.
Nomenclature of some simple aromatic heterocycles
3.
Activation/Deactivation towards EAS by substituents
4.
ortho-,para-, or meta-director substituents
5.
Synthetic considerations for EAS reactions:
acylation/reduction
avoids rearrangement of alkyl cations
activated
rings may not require catalysts/may yield poly-substitution
aniline
is too active for many EAS reactions--can be protected with an amide
Friedel-Crafts
reactions fail on rings less active than chlorobenzene
When
two or more substituents can direct EAS, which substituent determines
reactivity?
6.
Substituent effects on acidity of phenols, benzoic acids, or anilinium
ions:
inductive
and resonance effects.
7. Orbital
picture of benzyne