Organic II Exam II Reagents/Reactions

KMnO

KMnO4 on Benzylic Carbon

Oxidation of Alkyl Benzenes, Benzylic Carbon oxidated to Carboxylic Acid

Zn(Hg) + HCL + Heat (Clemmenson’s) on Benzylic aryl Ketone

Reduction of Aryl Ketones, reduces Ketone to Carbon

NH2NH2 + OH- + Heat (Wolf-Kischner) on Benzylic aryl Ketone

Reduction of Aryl Ketones, reduces Ketone to Carbon

H2 + Pd-C on Nitro Group

Reduction of a Nitro Group, reduces nitro to Amine

Fe + HCL on Nitro Group

Reduction of a Nitro Group, replaces Nitro with Amine

Sn + HCL on Nitro Group

Reduction of Nitro Group, replaces Nitro with Amine

Br2 + FeBr3 on Benzene

Polyhallogenation of Benzene

Br2 (1 equiv) + FeBr3 on Benzene

Single Hallogenation of Benzene

What groups will Friedal-Craft reagents not react with?

Amines and EWG groups.

What causes re-arrangement within a Friedal-Crafts EAS?

If the carbon chain is longer than two carbons, it will re-arrange.

HNO3 + H2SO4 on Benzene

Nitration, substitution of H with NO2

SO3 + H2SO4 on Benzene

Sulfonation, substitution of H with SO3H

ROCL + AlCl3 on Benzene

Friedal-Craft Acylation, substitution of H with a Ketone

DBN on Halogens

Reduction, replaces with Pi Bond

What type of atom increases Dienophile Reactivity by pulling electrons away from the Pi-Bond?

Electronegative/EWG’s

H-Br on Butadiene, (-78*)

Kinetic Product, 1,2 Halogenation

H-Br on Butadiene, (40*)

Thermodynamic Product, 1,4 Halogenation

H2 + Pd-C on Alkene

Syn Hydrogenation of Alkene to Alkane

H2 + Lindlar’s Cat on Alkyne

Syn Hydrogenation of Alkyne to Alkene

H2 + Pd-C (2 equiv) on Alkyne

Double syn-hydrogenation of Alkyne to Alkane

Na + NH3 on Alkyne

Anti Hydrogenation of Alkyne to Alkene

LAH + H2O on Alkyl Halide

Reduction of Alkyl Halide, X replaced with H

RCO3H + H2O + (H+ or OH-) on Alkene

Anti-Dihydroxylation of Alkene to Alkane via OH

OsO4 + NMO + NaSHO3 + H2O on Alkene

Syn-Dihydroxylation of Alkene to Alkane via OH

O3 + Zn + H2O on Alkene

Oxidative Cleavage

O3 + H2O on Internal Alkyne

Oxidative Cleavage into two Carboxylic Acids

O3 + H2O on Terminal Alkyne

Oxidative Cleavage into Caboxylic Acid and CO2

PCC on 2* Alcohol

Ketone

mCPBA on Alkene

Epoxidation

NaBH4, CH3OH on Aldehyde or Ketone

Reduction of Aldehydes and Ketones, 1* or 2* Alcohol

1) LAH 2) H2O on Aldehyde or Ketone

Reduction of Aldehydes and Ketones, 1* or 2* Alcohol

H2, Pd-C on Aldehyde or Ketone

Reduction of Aldehydes and Ketones, 1* or 2* Alcohol

NaBH4, CH3OH on a-b Unsaturated Aldehyde or Ketone

Reduction of C=O ONLY, Alkene remains the same.

H2 (1 equiv), Pd-C on a-b Unsaturated Aldehyde or Ketone

Reduction of C=C ONLY, Ketone/Aldehyde remains the same.

H2 (excess), Pd-C on a-b Unsaturated Aldehyde or Ketone

Reduction of both C=O and C=C.

1) S-CBS, 2) H2O on Ketone off of Benzene

Enantioselective Ketone Reduction, OH on Wedge.

1) R-CBS, 2) H2O on Ketone off of Benzene

Enantioselective Ketone Reduction, OH on Dash.

1) LAH, 2) H2O on Acid Chloride

Full Reduction of Acid Chloride to 1* Alcohol

1) LiAlH[OC(CH3)3]3, 2) H2O on Acid Chloride

Single Reduction of Acid Chloride to Aldehyde

1) LAH, 2) H2O on Ester

Full Reduction of Esters to a 1* Alcohol

1) DIBAL-H, 2) H2O on Ester

Single Reduction of Esters to an Aldehyde

1) LAH, 2) H2O on Carboxylic Acid

Reduction of Carboxylic Acids to 1* Alcohols

1) LAH, 2) H2O on Amide

Full Reduction of Amide to Amine

CrO3, H2SO4 on Aldehyde

Oxidation of Aldehyde to Carboxylic Acid

Na2Cr2O7 on Aldehyde

Oxidation of Aldehydes to Carboxylic Acid

KMnO4 on Aldehyde

Oxidation of Aldehydes to Carboxylic Acids

Ag2O, NH4OH on Aldehyde

Oxidation of Aldehydes to Carboxylic Acids

Ag2O, NH4OH on 1* or 2* Alcohol

No Reaction.

R-X + 2Li

R-Li + LiX, Prep of Organolithium Reagent

R-X + Mg, using (CH3CH2)2O

R-Mg-X, Prep of Gringard Reagent

2 R-Li + CuI

R2Cu- , Li+ , LiI, Prep of Organocuperate Reagent

1) RMgX or RLi, 2) H2O on Aldehyde or Ketone

Forms 1*, 2*, or 3* Alcohol

1) RMgX or RLi (2 equiv), 2) H2O on Ester

Forms 3* Alcohol

1) RMgX or RLi (2 equiv), 2) H2O on Acid Chloride

Forms 3* Alcohol

1) R2CuLi, 2) H2O on Acid Chloride

Forms Keytone

1) Co2, 2) H3O+ on R-MgX

Carboxylation, creates Carboxylic Acid

1) RLi, RMgX, or R2CuLi, 2) H2O on Epoxide

Reduction to Alcohol

1) RLi or RMgX, 2) H2O on a-b Unsaturated Aldehyde or Ketone

Reduction to allylic alcohol (3*), 1,2 Addition

1) R2CuLi, 2) H2O on a-b Unsaturated Aldehyde or Ketone

Only C=C Reduction, 1,4 Addition

TBS-Cl , Immidazole on Alcohol

Protecting Group, replaces -OH with -OTBS

TBAF on Protecting Group OTBS

Removal of OTBS, replaces with -OH

NaBH4, CH3OH

or

1) LAH, 2) H2O

on Aldehyde or Ketone

Addition of Hydride, 1* or 2* OH

NaCN, HCl on Aldehyde or Ketone

Addition of Cyanide, alongside OH.

Ylide on Aldehyde or Ketone

Wittig Reaction, Merges to form Alkene

RNH2, Mild Acid on Aldehyde or Ketone

Addition of 1* Amines, Imine Formation

R2NH, Mild Acid on Ketone or Aldehyde

Addition of 2* Amines, Enamine Formation

H2O, OH- or H+ on Aldehyde or Ketone

Hydration, Creates gem-diol

ROH (2 equiv), H+ on Aldehyde or Ketone

Addition of Alcohols, Creates Acetal + H2O

OH- on Cyanohydrin (CN + OH)

Conversion to Aldehyde or Ketone.

H2O, H+ or OH-, heat on Nitrile

Hydrolysis to a-hydroxy carboxylic acid

H2O, H+ on Imine or Enamine

Hydrolysis to Aldehyde or Ketone

H2O, H+ on Acetal

Hydrolysis to Aldehyde or Ketone

Base on Carboxylic Acid

Acid-Base Rxn, Carboxylate Ion

H2O, H+ on Nitrile

Hydrolysis, Carboxylic Acid

H2oO, -OH on Nitrile

Hydrolysis, Carboxylate Ion

1) LAH, 2) H2O on Nitrile

Full Reduction, 1* Amine

1) DIBAL-H, 2) H2O on Nitrile

Single Reduction, Aldehyde

R’MgX or R’Li on Nitrile

Organometallic Reagents, Ketone

1) NaCN, 2) H2O, H+ on Halide

Replaces Halide with Carboxylic Acid

SOCL2 on Carboxylic Acid

Synthesis of Acid Chlorides, Acid Chloride

Acid Chloride + Carboxylate Ion

Synthesis of Anhydrides, Anhydride

Heat on Dicarboxylic Acid

Intramolecular Cyclic Anhydride

H2O + Pyridine on Acid Chloride

Carboxylic Acid

H2O on Anhydride

Two Carboxylic Acids

H2O, H+ on Ester

Carboxylic Acid

H2O, OH- on Ester

Carboxylate Ion

H2O, H+ on Amide

Carboxylic Acid and R2NH2

H2O, OH- on Amide

Carboxylate Ion and R2NH

R’OH + Pyridine on Acid Chloride

Ester

R’OH on Anhydride

Ester + Carboxylic Acid

R’OH + H2SO4 on Carboxylic Acid

Ester and H2O

NH3 (2 equiv.) on Acid Chloride

Amide

NH3 (2 equiv.) on Anhydride

Amide

NH3 + Heat on Carboxylic Acid

Amide

R’NH2 + DCC on Carboxylic Acid

Secondary Amide

NH3 on Ester

Amide

1) Gabriel’s Reagent, 2) KOH on Alkyl Halide

1* Amine + Di-carbondioxidebenzene

H2, Pd-C -or- Fe, HCL -or- Sn, HCL on Nitro Group

Reduction, 1* Amine

1) LAH, 2) H2O on Nitrile

Full Reduction to 1* Amine

1) LAH, 2) H2O on Amide

1*, 2*, and 3* Amines