CHE 204 Final Exam Reactions

Aldehyde + Grignard Reagent

Secondary Alcohol

Ketone + Grignard

Tertiary Alcohol

Ester + Grignard

Tertiary Alcohol

Acid Chloride + Grignard

Tertiary Alcohol

CO2 + Grignard Reagent

Carboxylic Acid

Epoxide + Grignard, Acid

Alcohol

Carboxylic Acid + Grignard Reagent (MgBr——R)

Carboxylate Ion + R

Amide + Grignard Reagent (MgBr——-R)

Deprotonated Amide + R

Nitrile + Grignard

Ketone

Aromatic Ring + R-Cl, AlCl3

Friedel-Crafts Alyklation (rearrangement possible)

Aromatic Ring + Acid Chloride, AlCl3

Friedel-Crafts Acylation (no rearrangement possible)

Aromatic Ring + Br2, FeBr3

Bromination

• Aromatic Ring with 1 Bromine

Aromatic Ring + Cl2, FeCl3

Chlorination

• Aromatic Ring with 1 chlorine

Aromatic Ring + HNO3, H2SO4

Nitration

• Aromatic ring with NO2 side chain

Aromatic Ring + SO3, H2SO$

Sulfonation:

• Aromatic ring with SO3H side chain

How do you restore sulfonation product to aromatic ring?

H2SO4, heat

Aromatic Ring + CO, HCl, AlCl3

Formylation:

• Aromatic ring with aldehyde side chain

Meta-Directing Substiuent + Friedels-Crafts Alkylation/Acylation

No Reaction

Alkyl Side Chain on Benzene + 1. KMnO4, -OH 2. H3O+, Heat

Carboxylic (Benzoic) Acid

Alkyl Side Chain on Benzene + Na2Cr2O7, H2SO4

Carboxylic (Benzoic) Acid

Benzene with C(CH3)3 Side Chain + 1. KMnO4, -OH 2. H3O+, Heat

No reaction (requires free hydrogen at benzylic position)

Benzene with C(CH3)3 side chain + Na2Cr2O7, H2SO4

No reaction (requires free hydrogen at benzylic position)

Ketone + H2NNH2, Base, Heat

Wolff-Kishner Reducation; Alkane

Aldehyde + H2NNH2, Base, Heat

Wolff-Kishner Reducation; Alkane

Ketone + Zn (Hg), HCl, Heat

Clemmensen Redcution; Alkane

Aldehyde + Zn (Hg), HCl, Heat

Clemmensen Reduction; Alkane

Ketone + H2/Pd, C

Clemmensen Reduction; Alkane

Aldehyde + H2/Pd, C

Clemmensen Reduction; Alkane

Nitro Group (NO2) + Zn(Hg), HCl, Heat

Clemmensen Reduction; Amine (NH2) Group

Nitro (NO2) group + H2/Pd, C

Clemmensen Reduction; Amine (NH2) Group

Nitro (NO2) Group + Sn/HCl

Clemmensen Reduction; Amine (NH2) Group

Aldehyde + NaBH4, H3O+

Primary Alcohol

Aldehyde + LAH, H3O+

Primary Alcohol

Ketone + NaBH4, H3O+

Secondary Alcohol

Ketone + LAH, H3O+

Secondary Alcohol

Carboxylic Acid + LAH, H3O+

Primary Alcohol

Ester + LAH, H3O+

Primary Alcohol + R-OH

Ester + DIBAL-H @-78, H2O

Aldehyde

Acid Chloride + LAH, H3O+

Primary Alcohol

Acid Chloride + NaBH4, EtOH, Acid

Primary Alcohol

Acid Chloride + LiAlH[OC(CH3)3]3

Aldehyde

Amide + LAH, Acid

Amine

Nitrile + LAH, H3O

Amine

Primary Alcohol + Na2Cr2O7 OR CrO3, H2SO4

Carboxylic Acid

Secondary Alcohol + Na2Cr2O7 OR CrO3, H2SO4

Ketone

Aldehyde + Na2Cr2O7 OR CrO3, H2SO4

Carboxylic Acid

Primary Alcohol + PCC or DMP

Aldehyde

Secondary Alcohol + PCC or DMP

Ketone

Aldehyde + Water

Hydrate (two -OH)

Ketone + Water

Hydrate (two -OH)

Aldehyde + Alcohol in Base

Hemiacetal (-OH, -OR groups)

Ketone + Alcohol (in base)

Hemiketal (-OH, -OR groups)

Aldehyde + Alcohol (in Acid)

Acetal (two -OR groups)

Ketone + Alcohol (in acid)

Ketal (two -OR) groups

Aldehyde + Ethylene Glycol (OH-CH2-CH2-OH)

Cyclic Acetal Protecting Group

Ketone + Ethylene Glycol (OH-CH2-CH2-OH)

Cyclic Ketal Protecting Group

Aldehyde + Primary Amine

Imine

Ketone + Primary Amine

Imine

Aldehyde + Secondary Amine

Examine

Ketone + Secondary Amine

Enamine

Ketone + Wittig Reagent

Alkene

Aldehyde + Wittig Reagent

Alkene

Nitrile + H3O, Heat

Carboxylic Acid

Alkyl Halide + Cyanide Ion

Nitrile

Aldehyde + Cyanide Ion

Cyanohydrin

Ketone + Cyanide Ion

Cyanohydrin

Diene + Alkene Dienophile

6 membered ring with one double bond

Diene + Alkyne Dienophile

6-membered ring with 2 double bonds

Diene + cis Dienophile

One product, 6-membered ring (at least one double bond)

Diene + trans Dienophile

Enantiomeric mixture of 6-membered ring (with at least one double bond)

EAS Ammonium Derivative (-N+R3)

Strong deactivator, meta director

EAS Haloalkyl (-CX3)

Strong deactivator, meta director

EAS Cyano (-CN)

Strong deactivator, meta director

EAS Nitro (NO2)

StrongEST deactivator, meta director

EAS Carbonyl

Moderate deactivator, meta director

EAS Sulfonyl (SO3R)

Moderate deactivator, meta director

EAS Halogen (X)

Weak deactivator, ortho-para director

EAS Alkyl (-R)

Weak activator, ortho-para director

EAS Amide

Moderate activator, ortho-para director

EAS Alkoxy (-OR)

Moderate activator, ortho-para director

EAS Hydroxy (-OH)

Moderate activator, ortho-para director

EAS Amine (-NR2)

Strong activator, ortho-para director

EAS Alkoxide

Strong activator, ortho-para director