Ochem Reagents

Zipper Reaction

1. KNH₂/NH₃
2. H₂O

Allylic Halogenation

1. NBS/NCS, CCl₄, initiator, heat (∆)/light (hv)

Diels Alder

1. Heat (∆)

Free radical bromination (benzylic)

1. NBS, CCl₄, initiator, heat (∆)/light (hv)

Protection example

1. NaH/DMSO
2. Ph-CH₂-Br

Birch Reduction

1. Li or Na, liquid NH₃
2. Alcohol (i.e. ethanol)

Alkyne Reduction

1. Pd/C/BaSO₄

Sulfonation

1. SO₃/H₂SO₄

Nitration

1. Conc. H₂SO₄, conc. HNO₃

Bromination

1.Br₂/FeBr₃

Chlorination

1. Cl₂/AlCl₃

Friedel-Crafts Alkylation

1. R-Cl, AlCl₃, CS₂ (solvent)

Friedel-Crafts Acylation

1. R-COCl, AlCl₃ (>1 eq.), CS₂ or CH₂Cl₂/DCM (solvent)
2. H₂O

Clemmensen Reduction

1. Zn/Hg/HCl

Wolff-Kishner Reduction

1. H₂N-NH₂, KOH (base), Diglyme or ethylene glycol (solvent), 200°C

Reverse FC Alkylation

1. H₂O/H⁺, heat(∆)

NO2 Reduction

1. Fe/HCl OR Sn/HCl OR Pd/C/H₂

Diazotization

1. NaNO₂, HCl, 0-5°C

Sandmeyer Reaction

1. CuBr OR CuI OR CuCN, Diazonium Chloride

Benzene Regeneration (From Diazonium Chloride)

1. H₃PO₂

Oxidation

KMnO₄/H₂O/heat OR K₂Cr₂O₇/H₂SO₄/heat

Iodobenzene Formation

KI, Diazonium Chloride

Phenol Formation

H₂O, heat(∆), Diazonium Chloride

Reverse Sulfonation

H⁺/H₂O, heat (∆)

Benzene to cyclohexane (catalytic hydrogenation)

H₂/Pt, ethanol or acetic acid (polar solvent), pressure

Amide hydrolysis

NaOH, ∆

Amine to Nitro Conversion

O₃

CN Oxidation

H₂O/H₃O⁺, ∆

Elimination-Addition (Benzyne production)

300°C, strong base/nucleophile

Chichibabin Reaction

1.Pyridine, KNH₂, 1-4-dioxane, ∆

2. H₂O

Addition of CN

Base catalyzed (usually), i.e pyridine

Acetal/Ketal Formation

Excess alcohol/acid catalyst

Reverse acetal/ketal formation

H⁺, H₂O, ∆

Carbonyl compounds with amines

pH 4-5

Balyer-Villiger Oxidation

F₃C-CO₂-OH

Oxidation (past aldehyde)

CrO₃, H₂O, H⁺u

Oxidation (stop at aldehyde)

PCC (Pyridinium Chlorochromate) in CH₂Cl₂, rt OR Pyridine CrO₃ complex

Moffat-Swern Oxidation

1. Alcohol, DMSO, oxalyl chloride, CH₂Cl₂, -78°
   2.Et₃N, -20°

Protecting alcohols with acetals

Dihydropyran or Dihydrofuran, excess H⁺

CN to CH2NH2

1. LiAlH₄, ether, heat
2. Workup

Organometallic reactions (RMgBr, RLi, R2CuLi)

Ether

NaBH4

Alcohols, acids, or any solvent with a pKa <20

LiAlH4 solvent

Ether or THF (Non-protic solvent)

Oxidative Cleavage of Diols

HIO₄, H₂O

Disulfide formation

Br₂, NaHCO₃(base), RSH

Sulfoxide formation (and water)

RSR, H₂O₂

Sulfone formation

F₃C-CO₂-OH

Ozanolysis

1. O₃/MeOH
   2.Me₂S

Wittig Reaction (Phosphonium Ion Formation)

Ph₃P, CHCl₃, rt

Wittig Reaction (Carbanion/Alkene formation)

BuLi, THF

Dihydroxylation of alkenes (Formation of a diol)

1. OsO₄/Pyridine
   2.H₂S

Aldehyde to Carboxylic Acid (oxidation)

NaClO₂

Alkene Oxidation

1.O₃/CH₃OH/CH₂Cl₂
2.H₂O₂

Carboxylic Acid formation from organometallic reagents

1.CO₂
2.H₃O⁺/H₂O

Carboxylic Acid formation from nitriles

1.H₂O/OH⁻ Na⁺

2. H₃O⁺

Fisher Esterification (forward)

cat. H⁺

Fisher Esterification (reverse)

Excess H₂O, ∆

Acid Anhydride formation

Carboxylic acid/carboxylate, acid chloride

Ester synthesis

1. CsOH/KOH (strong base)
   2.DMSO, ∆, R-Br

Methyl Ester Synthesis

Diazomethane (does not react with alcohols and amines)

Acid chloride formation from acids

SOCl₂ or PCl₃ or PCl₅

Thioester formation from acid chlorides

M⁺ ⁻SR

Ester formation from acid chlorides

ROH, base

Amide formation from acid chlorides

RNH₂, base, rt

Carboxylic acid to amide (compatible with water)

DCC

Carbox. acid to ketone (organometallic)

R-Li, ether

Anhydride formation

2 carboxylic acids, (-H2O), heat, >200

Addition-Elimination

1. NaOH or NaOR, rt

2. H2O

Addition of Alkyl Lithium

1. R-Li, ether

2. H2O work up

Ester —> Aldehyde

DIBAL-H

Amides and LiAlH4

R-CH2-NH2

Nitrile —> aldehyde

DIBAL-H

Nitrile to ketone

1. R-MgBr or R-Li

2. H3O+

Ketene to amide

R-NH2

Baeyer-Villiger Oxidation of Ketone

mCPBA, H⁺, CH₂Cl₂ (3° R migrates best)

Beckmann Rearrangement

1) H₂N-OH (to oxime)
2)H₂SO₄ or H₃PO₄ (strong acid), heat

Arandt-Eistert/Chain elongation (First Step)

CH2N2

Arandt-Eistert/Chain elongation (Second Step, Wolff Rearrangement)

H2O

Curtius Rearrangement

acid chloride, NaN3, H2O

LDA, THF

Least substituted alpha hydrogen

Ketone —> aldol addition —> aldol condensation

1. NaOH, H2O

Michael Reaction

1,4 addition

Robinson Annulation

2 Michael additions ( intramolecular)

Malonic Ester Synthesis reagents

1. NaOEt

2. R-X

3. H3O+

4. Heat

Malonic Ester Synthesis

( malonic ester—> carboxylic acid)

Hoffman Rearrangement Reactants

1. NaOH, Br2

2. Heat

Hoffman Rearrangement

amide —> free amine and CO2

Mannich Reaction

RCOR, Formaldehyde, 2ndary amine —> RCOCH2CH2-NR2

Mannich Reaction conditions

HCl, EtOH, 60 C, 2h

Reductive Amination

Imine —> secondary amine

Reductive Amination

NaBH3CN, pH= 3-4

Hoffman Elimination

Least substituted Alkene

Removal of thioalkyl protecting group

Raney Ni, EtOH

Polyurethane

Polyester

polyurea

Polyether

Isotactic

Syndiotactic