orgo chapter 19 rxns

won't be cooked this time

benzene +Br2 + FeBr3

bromobenzene + HBr

benzene + Cl2 + FeCl3

chlorobenzene + HCl

Nitration
benzene + HNO3 + H2SO4

Benzene-NO2 + H2O

sulfonation
benzene + H2SO4 + heat

benzene-SO3H

fridel crafts acylation
benzene + acyl chloride + AlCl3/H2O

benzene- in ketone

does not happen under meta directors

fridel crafts alkylation

benzene + RCl + AlCl3

benzene w alkyl chain
does not occur for meta directors

gatterman koch
CO + HCl + Benzene + high pressure + AlCl3/CuCl

benzaldehyde

benzene-carbonyl + H2/PdC

benzene-CHR (methylene)

benzene-carbonyl + H2NNH2, HO-, heat (wolff-kishner)

benzene-CHR (methylene)

bromobenzene + R-B-(OR)2 + PdL2 + HO- (suzuki coupling)

benzene-R

bromobenzene + gilman

benzene-R

methylbenzene + Br2/hv

bromomethylbenzene

bromomethylbenzene + Z-

zmethylbenzene (replaces bromine with nucelophile)

methylbenzene + H2CrO4

benzene-COOH

benzene-NO2 + H2/PdC

benzene-NH2

benzene-NH2

will not undergo fridel crafts, must be protected by acetylation to be nitrated

benzene-NH2 + NaNO2 + HCl @ 0 deg

azide
benzene-N⁺≡N

azide + CuBr

bromobenzene + N2(g)

azide + CuCl

chlorobenzene + N2(g)

azide + CuC≡N

benzene-nitrile + N2(g)

azide + HBF4 + Heat

fluorobenzene + N2(g) + BF3 +HCl

azide + KI

iodobenzene + N2(g) + KCl

azide + H3O + heat

phenol + N2(g) + KCl

azide + Cu2O + Cu(NO3)2 + H2O

phenol + N2(g)

azide + H3PO4

benzene (elimination of azide) + N2(g)

benzyne rxn

NaOH, H2O, 340deg, 170 atm
-Cl is leaving group, replaced by OH
OH attacks halogen

—NH2, —OH, —OR

strong activating, ortho para

—amide, —ester (must be attached to noncarbon)

moderately activating, ortho para

—benzene, —R, —CH=CHR

weakly activating, ortho para

—halogen

weaking deactivating, ortho para

—aldehyde, ester, ketone, carb acid

moderately deactivating, meta

—NO2, —CN, —SO3H, —N⁺R3

strongly deactivating, meta

bromobenzene or chlorobenzene + -OH + 130 deg
nucleophilic aromatic substiution (NAS)

phenol