Term
| the most important mechanism in the rxns of aromatic compounds |
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Definition
| electrophilic aromatic substitution |
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Term
| mechanism of electrophilic aromatic substitution |
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Definition
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Term
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Definition
the resonance-stabilized carbocation that results from an electrophile attacking an aromatic ring
[image]
[image] |
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Term
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Definition
sigma complex
[image]
[image] |
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Definition
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Term
| mechanism for the bromination of benzene |
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Definition
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Term
| the strong electrophile formed in the bromination of benzene |
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Definition
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Term
| energy diagram of the bromination of benzene |
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Definition
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Definition
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Definition
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Term
| the catalyst often used in chlorination of benzene |
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Definition
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Definition
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Term
| reagent often used in iodinization of benzene |
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Definition
| nitric acid (HNO3)
this is an oxidant, not a catalyst |
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Term
| how the iodine cation (I+) is made |
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Definition
| H+ + HNO3 + 1/2 I2 --> I+ + NO2 + H2O |
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Definition
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Definition
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| mechanism for nitration of benzene |
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Definition
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Definition
| [image] and [image], respectively |
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Definition
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Term
| mechanism of the sulfonation of benzene |
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Definition
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Definition
| [image] and [image], respectively |
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Definition
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Term
| mechanism for protonation of the aromatic ring |
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Definition
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Term
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Definition
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Term
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Definition
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Term
| the rate-limiting step for electrophilic aromatic substitution |
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Definition
| the 1st step (formation of the sigma complex) |
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Term
| rxn coordinate diagram for aromatics substituted at different locations |
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Definition
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Term
| the type of substituent an alkyl group is on a benzene |
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Definition
| an activating substituent, ortho- and para-directing |
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Term
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Definition
| an alkyl group donating electrons to a benzene ring it's attached to to stabilize a positive charge |
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Term
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Definition
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Term
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Definition
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Term
| mechanism for ortho attack on an aromatic with an alkoxy group |
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Definition
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Term
| mechanism for meta attack on an aromatic with an alkoxy group |
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Definition
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Term
| mechanism for para attack on an aromatic with an alkoxy group |
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Definition
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Term
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Definition
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Term
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Definition
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Term
| mechanism for ortho attack on an alanine |
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Definition
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Term
| mechanism for para attack on an alanine |
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Definition
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Term
| functional groups in order of activating an aromatic ring (DRAW THIS!!!!) |
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Definition
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Term
| compounds in order of activating an aromatic ring (DRAW THIS!!!!) |
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Definition
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Term
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Definition
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Term
| what an electron donating group does for the positions of the benzene ring |
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Definition
activates primarily the ortho and para positions
[image] |
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Term
| what an electron withdrawing group does for the positions of the benzene ring |
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Definition
deactivates primarily the ortho and para positions
[image] |
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Term
| mechanism for ortho attack on a nitrobenzene |
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Definition
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Term
| mechanism for meta attack on a nitrobenzene |
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Definition
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Term
| mechanism for para attack on a nitrobenzene |
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Definition
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Term
| rxn coordinate diagram of nitrobenzenes compared to benzene |
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Definition
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Definition
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Definition
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Definition
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Definition
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Definition
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Definition
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Term
| the type of substituents halogens are on benzenes |
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Definition
| deactivating, but ortho and para-directing |
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Term
| why halogens are deactivating, but ortho and para-directing |
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Definition
1: they are strongly electronegative
2: they have nonbonding electrons that can participate in the pi system |
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Term
| mechanism for a benzene with a halogen substituent doing ortho attack |
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Definition
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Term
| mechanism for a benzene with a halogen substituent doing meta attack |
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Definition
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Term
| mechanism for a benzene with a halogen substituent doing para attack |
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Definition
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Term
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Definition
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Term
| rxn coordinate diagram of clhorobenzene vs. benzene |
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Definition
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Term
| table of directing effects of substituents (DRAW THIS!!!!) |
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Definition
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Term
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Definition
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Term
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Definition
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Term
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Definition
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Term
| which group on a benzene ring is a stronger director? an activating group or a deactivating group? |
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Definition
| usually an activating group |
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Term
| 3 classes of substituents on benzenes |
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Definition
1: powerful ortho and para-directors that stabilizete sigma complexes through resonance (these are the strongest)
2: moderate ortho and para-directors, such as alkyl groups and halogens
3: all meta directors (weakest) |
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Term
| substituents on benzene in order of strongest to weakest |
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Definition
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Term
| powerful ortho and para-directors on benzene rings |
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Definition
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Term
| moderate ortho and para-directors on benzene rings |
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Definition
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Term
| the meta-directors on benzene rings |
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Definition
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Term
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Definition
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Term
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Definition
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Term
| Friedel-Crafts alkylation |
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Definition
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Term
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Definition
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Term
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Definition
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Term
| mechanism of a Friedel-Crafts alkylation |
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Definition
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Term
| another example of the mechanism of a Friedel-Crafts alkylation |
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Definition
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Term
| 2 common methods for generating the carbocations needed in Friedel-Crafts alkylations |
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Definition
| -protonation of alkenes
-treatment of alcohols with BF3 |
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Term
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Definition
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Term
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Definition
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Term
| how BF3 converts an alcohol into a carbocation |
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Definition
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Term
| how electrophilic substitution on benzene occurs |
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Definition
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Term
| Friedel-Crafts rxns work only with... |
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Definition
-benzene
-activated benzene derivatives
-halobenzenes
They don't work with strongly deactivated systems. |
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Term
| limitations of Friedel-Crafts alkylation |
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Definition
1: they work only with benzene, activated benzene derivatives, and halobenzenes
2: susceptible to carbocation rearrangements
3: the products are more reactive than the starting material, since alkyl groups are activating substituents |
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Definition
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Definition
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Definition
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Definition
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Definition
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Term
| (acid chloride) acyl chloride |
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Definition
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Term
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Definition
| (acid chloride) acyl chloride |
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Definition
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Definition
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Definition
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Definition
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Definition
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Definition
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Definition
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Definition
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Definition
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Definition
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Term
| mechanism for Friedel-Crafts acylation |
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Definition
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Term
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Definition
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Term
| why acylation stops after 1 substitution |
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Definition
| because the acyl group on the product deactivates it towards further substitutions |
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Term
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Definition
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Term
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Definition
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Term
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Definition
| [image] and [image], respectively |
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Term
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Definition
| [image] and [image], respectively |
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Term
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Definition
| [image] and [image], [image], and -OH, respectively |
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Definition
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Term
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Definition
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Term
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Definition
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Term
| when nucleophiles can displace halide ions from aryl halides |
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Definition
when there's strong electron-withdrawing groups ortho and para to the halide
example:
[image] |
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Term
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Definition
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Term
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Definition
| [image] and H+, respectively |
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Term
| mechanism for nucleophilic aromatic substitution (addition-elimination) |
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Definition
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Term
| sanger reagent (2,4-dinitrofluorobenzene) |
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Definition
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Term
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Definition
| sanger reagent (2,4-dinitrofluorobenzene) |
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Term
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Definition
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Term
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Definition
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Term
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Definition
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Definition
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Term
| the benzyne mechanism: elimination-addition |
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Definition
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Definition
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Term
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Definition
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Term
| mechanism for nucleophilic aromatic substitution (benzyne mechanism) |
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Definition
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Term
| how the organolithium reagent is made |
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Definition
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Term
| how the lithium organocuprate is made |
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Definition
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Term
| how coupling of the organocuprate with an alkyl, vinyl, or aryl halide is done |
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Definition
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Term
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Definition
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Term
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Definition
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Term
| some palladium catalysts that can be used in the Heck rxn |
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Definition
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Term
| Suzuki rxn (Suzuki coupling) |
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Definition
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Term
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Definition
[image]
preserves stereochemistry |
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Term
| how alkylboronate esters are made |
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Definition
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Term
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Definition
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Term
| mechanism of the Suzuki rxn |
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Definition
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Term
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Definition
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Term
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Definition
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Term
| catalytic hydrogenation of aromatic rings |
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Definition
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Definition
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Term
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Definition
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Term
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Definition
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Definition
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Term
| mechanism for the Birch reduction |
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Definition
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Term
| the type of substituted benzene C that gets reduced in a Birch reduction |
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Definition
the one that bears an electron-withdrawing group
example:
[image] |
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Term
| the type of substituted benzene C that does not get substituted during a Birch reduction |
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Definition
the one that bears an electron-releasing group
example:
[image] |
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Term
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Definition
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Term
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Definition
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Term
| some functional groups that usually survive permangenate oxidation |
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Definition
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Term
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Definition
| [image] and H+, respectively |
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Term
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Definition
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Term
| mechanism for halogenation of a benzene's side chain |
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Definition
[image]
however, significant amounts of isomers are produced |
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Term
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Definition
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Term
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Definition
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Term
| what first-order nucleophilic substitution requires to give a carbocation |
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Definition
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Term
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Definition
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Term
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Definition
| [image] and [image], respectively |
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Term
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Definition
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Term
| transition state for SN2 displacement of a benzylic halide |
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Definition
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Term
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Definition
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Term
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Definition
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Term
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Definition
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Definition
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Term
| mechanism for the tribromination of a phenol molecule |
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Definition
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Term
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Definition
| [image], [image], and [image], respectively |
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Term
| mechanism for electroophilic substitution of phenoxide anion to form salicylic acid |
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Definition
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Term
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Definition
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Term
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Definition
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Term
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Definition
| [image] and [image], respectively |
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Term
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Definition
| [image] and [image], respectively |
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Term
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Definition
| [image] and [image], respectively |
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Term
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Definition
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Term
| some strong deactivating groups |
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Definition
| -NO2
-SO3H
-CN
-CF3
-[image] |
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Term
| why benzenes with NH2 and NR2 substituents don't work well with AlCl3 catalysts |
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Definition
| because the N atom complexes with the AlCl3 catalyst |
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Term
| how to protect the NH2 group on a benzene from the AlCl3 catalyst |
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Definition
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Term
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Definition
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Term
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Definition
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Term
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Definition
| [image], [image], and [image], respectively |
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Term
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Definition
| [image] and [image], respectively |
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Term
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Definition
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Term
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Definition
| [image] and [image], respectively |
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Term
| sulfonation, forwards and backwards |
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Definition
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Term
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Definition
| forward: [image]
reverse: H2O, heat |
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Term
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Definition
| [image], [image], and [image], respectively |
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Term
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Definition
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Term
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Definition
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Term
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Definition
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Term
| Friedel-Crafts alkylation |
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Definition
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Term
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Definition
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Term
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Definition
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Term
| activating, ortho, para-directing substituents |
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Definition
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Term
| deactivating, ortho, para-directing substituents |
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Definition
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Term
| deactivating, meta-allowing substituents |
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Definition
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Term
| nucleophilic aromatic substitution |
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Definition
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Term
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Definition
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Term
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Definition
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Term
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Definition
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Term
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Definition
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Definition
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Definition
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Term
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Definition
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Term
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Definition
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Term
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Definition
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Term
| nucleophilic substitution at the benzylic position |
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Definition
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Term
| oxidation of phenols to quinones |
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Definition
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Term
| summary of electrophilic aromatic substitution of benzenes (DRAW THIS!!!!) |
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Definition
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Term
| summary of substitutions of aryl halides (DRAW THIS!!!!) |
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Definition
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|
