Oxidations and reductions

Alcohol oxidation: menthol (a secondary alcohol) with Na2Cr2O7; aq. H2SO4 gives p-menthan-3-one (the six-membered cyclic ketone).

Nitro reduction: ethyl 4-nitrobenzoate (a nitro compound) with H2 (3 atm), PtO2; CH3CH2OH gives benzocaine (the aniline).

Aldehyde oxidation: piperonal (an aromatic aldehyde) with KMnO4; H2O, 75 °C gives 1,3-benzodioxole-5-carboxylic acid.

Benzylic oxidation: 2-methylpyridine with KMnO4; H2O, Δ gives picolinic acid (the arenecarboxylic acid).

Birch reduction: benzoic acid (an acyl-deactivated arene) with 1) Na, NH3, CH3CH2OH; 2) aq. HCl gives 2,5-cyclohexadiene-1-carboxylic acid (the 1,4-cyclohexadiene).

Clemmensen: 1-(2-hydroxyphenyl)hexan-1-one (an aryl ketone) with mossy Zn(Hg); aq. HCl, CH3CH2OH, Δ gives 2-hexylphenol (the deoxygenated product).

Ester / amide reduction: N-methyldodecanamide with LiAlH4, ether; Δ gives N-methyl-1-dodecanamine (the reduced product).

Wolff–Kishner reduction: 6-oxo-undecanedioic acid (a dialkyl ketone) with H2NNH2, KOH; ethylene glycol, Δ gives undecanedioic acid (the deoxygenated product).

Aromatization: 4-methyl-3,5-dioxocyclohexane-1-carboxylic acid (a 1,3-diketone) with excess; Br2; AcOH gives 3,5-dihydroxy-4-methylbenzoic acid (the phenol). 95% yield.

Dakin oxidation: o-vanillin (an aromatic aldehyde) with H2O2; NaOH, H2O; 40 - 50 °C gives 3-methoxycatechol (the phenol).

Disulfide formation: a thiolate and potassium cation with I2 (0.5 equiv per thiolate) gives benzoyl disulfide.

Imine reduction: spiro[1,3-dihydroindene-2,3'-indole] (an imine) with LiAlH4 gives 1,3-dihydrospiro[indene-2,3'-indoline] (the aniline).

Birch reduction: o-xylene (an alkylbenzene) with Na, NH3; CH3CH2OH, ether gives 1,2-dimethyl-1,4-cyclohexadiene.

Benzylic oxidation: chloro-(4-methylphenyl)mercury (an alkylbenzene) with 1) KMnO4; aq. NaOH, Δ; 2) HCl gives p-(chloromercuri)benzoic acid (the arenecarboxylic acid).

Birch reduction: 2-ethoxynaphthalene with Na; CH3CH2OH, Δ gives 3-ethoxy-1,2-dihydronaphthalene (the 1,4-cyclohexadiene).

Clemmensen: 3-benzoylpropionic acid (an aryl ketone) with Zn(Hg); HCl, H2O; toluene, Δ gives 4-phenylbutyric acid (the deoxygenated product).

Alcohol oxidation: a primary alcohol with DCC, DMSO, pyridine·TFA; benzene (Pfitzner–Moffatt) gives the aliphatic aldehyde.

Nitro reduction: 2-nitroaniline (a nitro compound) with Zn, CH3CH2OH; aq. NaOH, Δ gives o-phenylenediamine (the aniline).

Alcohol oxidation: cyclooctanol (a secondary alcohol) with CrO3, H2SO4; H2O, acetone gives cyclooctanone (the eight-membered cyclic ketone).

Alcohol oxidation: 4-cyclopentene-1,3-diol (an allylic alcohol) with CrO3, H2SO4; aq. CH2Cl2, 0 °C gives 2-cyclopentene-1,4-dione (the α,β-unsaturated ketone).

Nitrile reduction: phenylacetonitrile with H2, Ra(Ni) (2000 psi); NH3, 130 °C gives phenethylamine (the primary amine).

Nitro reduction: 3-nitrobenzaldehyde dimethyl acetal (a nitro compound) with H2 (1000 psi); Ra(Ni); CH3OH gives 3-(dimethoxymethyl)aniline.

Nitro reduction: 2-nitrobenzaldehyde (a nitro compound) with FeSO4, HCl; NH4OH, H2O; 90 °C gives 2-aminobenzaldehyde (the aniline).

Nitro reduction: 1-methyl-2-nitro-4-propan-2-ylbenzene (a nitro compound) with H2 (1000 psi); Ra(Ni); CH3OH; 100 - 120 °C gives 2-amino-p-cymene (the aniline).

Alcohol oxidation: a secondary alcohol with Na2Cr2O7; H2SO4, AcOH; H2O, benzene gives the six-membered cyclic ketone.

Birch reduction: anisole with Li, (CH3)3OH; liq. NH3, THF gives 1-methoxycyclohexa-1,4-diene (the 1,4-cyclohexadiene).

Benzylic oxidation: 2-chlorotoluene (an alkylbenzene) with 1) KMnO4, H2O; 2) HCl gives 2-chlorobenzoic acid (the arenecarboxylic acid).

Aldehyde oxidation: vanillin (an aromatic aldehyde) with Ag2O, NaOH, H2O, 55 °C; then HCl gives vanillic acid (the carboxylic acid).

Nitro reduction: 2-nitrobiphenyl (a nitro compound) with H2 (25-50 psi), 5% Pd/C; CH3CH2OH gives 2-aminobiphenyl (the aniline).

Aldehyde oxidation: 3-thiophenecarboxaldehyde (an aromatic aldehyde) with Ag2O; NaOH, H2O gives thiophene-3-carboxylic acid.

Ester / amide reduction: 3,5-dinitrobenzoyl chloride (an acid chloride) with LiAlH(O-t-Bu)3; diglyme, −78 °C gives 3,5-dinitrobenzaldehyde (the reduced product).

Wolff–Kishner reduction: 3-methyl-1,2,4-cyclopentanetrione (a 1,3-diketone) with NaOAc, H2O; 2) KOH, ethylene glycol; 180 °C; 3) HCl gives 2-methyl-1,3-cyclopentanedione (the deoxygenated product).

Ester / amide reduction: a cyclic anhydride with LiAlH4; THF, Δ gives the reduced product.

Alcohol oxidation: a secondary alcohol with (tBuO)3Al; acetone, benzene, Δ gives the α,β-unsaturated ketone.

Aldehyde oxidation: heptanal (an aliphatic aldehyde) with KMnO4; H2SO4, H2O gives heptanoic acid (the carboxylic acid).

Alcohol oxidation: 1-butanol (a primary alcohol) with Na2Cr2O7; (2 equiv.); 3; H2SO4; (6 equiv.); (8 equiv.); H2O gives butyl butyrate (the ester).

Ester / amide reduction: N,N-dimethylcyclohexanecarboxamide with LiAlH4; ether, Δ gives N,N-dimethylcyclohexanemethanamine (the reduced product).

Benzylic oxidation: 4-nitrotoluene (an alkylbenzene) with Na2Cr2O7; aq. H2SO4, Δ gives 4-nitrobenzoic acid (the arenecarboxylic acid).

Clemmensen: a six-membered cyclic ketone with Zn, HCl; ether, −20-0 ¬∫C gives the deoxygenated product.

Clemmensen: 3-hydroxy-2-methoxybenzaldehyde (an aromatic aldehyde) with Zn(Hg); HCl, Δ gives 2-methoxy-3-methylphenol (the deoxygenated product).