Reagents for Reactions

Electrophilic Aromatic Substitution

strong electrophile & acid catalyst (mostly)

Bromonation to Benzene

Br₂, FeBr₃ (Catalyst)

Nitration (NO₂)

H₂SO₄, HNO₃

Sulfonation (SO₃H)

SO₃, H₂SO₄

Chlorination

Cl₂, AlCl₃

Iodination

I₂, HNO₃

Synthesis of Aniline (NH₂)

HNO₃, H₂SO₄; Metal (Zn, Sn, Fe), HCl

Friedel-Crafts Alkylation (alkyl group w/ rearrangment)

R-Cl, AlCl₃ where R = carbon chain

Generating cation with H-F

H-F & acid

Generating cation with BF₃

BF₃

Friedel-Crafts Acylation (add alkyl group w/o rearrangment)

R-C=O-Cl, AlCl₃

Clemmensen Reduction reagents (Ketone Acylation)

Zn(Hg), HCl

Wolf-Kishner Reduction reagents (ketone Acylation)

NH₂NH₂, KOH

Formylation reagents (aldehyde acylation)

CO, HCl, AlCl₃, CuCl

Nitration of isopropyl benzene

HNO₃, H₂SO₄

Nitration of Anisole

HNO₃, H₂SO₄

Nitration of Nitrobenzene

HNO₃, H₂SO₄

Nitration of Halobenzene

HNO₃, H₂SO₄

Removing SO₃H from benzene

dilute H₂SO₄

Removing COR from N

dilute H₂SO₄

Birch Reaction (hydrogenation)

Na, NH_3(l), EtOH

Halogenation (add halogen)

Br₂, light

Permanganate oxidation (carboxylic group)

1) KMnO₄, NaOH, 100C 2) H₃O⁺

Diazotization reagents (get diazonium salt from aniline)

NaNO₂, HCl, H₂O

get OH on benzene with diazonium reagents

H₂O

get F on benzene with diazonium

HBF₄

get H on benzene with diazonium

H₃PO₄

get I on benzene with diazonium

KI

Sandmeyer reaction get X on diazonium

CuX (X = Br, Cl, CN)

Substitution by Elimination/Addition

strong nucleophile in excess, its conjugate acid; heat

Substitution by Addition/Elimination

strong nucleophile, heat; need LG & e^- w/drawing group on ring

Nucleophilic Substitution of Alkohalide 1

weak nucleophile

Nucleophilic Substitution of Alkohalide 2

strong nucleophile

Hydration of Alkenes for markovnikov

H₂SO₄, H₂O or 1) Hg(OAc)₂, H₂O 2) NaBH,4

Hydration of Alkenes for anti-markovnikov

1) BH₃, THF 2) H₂O₂, NaOH

Alkyne Nucelophile addition to carbonyls

1) R-CC^-NA⁺ 2) H₃O⁺

Grignard Addition to carbonyls

1) R’-MgBr 2) H₃O⁺

Hydride Addition to Carbonyls

1) LiAlH₄ 2) H₃O⁺ or NaBH₄, H₃O⁺

Chromium Oxidation (OH → =O)

Na₂Cr₂O₇ or CrO₃, H₂SO₄ → gets H₂CrO₄ that reacts

Oxidized primary alcohol to aldehyde (OH → =O)

PCC or Swern

Oxidize with using transition metals (OH → =O)

Swern

Make ROH strong nucleophile

NaH or NaNH₂

Acidic Activation (R₃COH → carbocation)

H⁺ (acid)

Tosylation (OH on carbon to halide)

1) TsCl, pyridine 2) NaBr

Reactions to get X instead of OH on carbon (multi-step)

HX

halide instead of OH on C in one step

PX₃; Br w/ PBr₃, Cl w/ PCl₃, I w/ P + I₂

Thionyl chloride (get Cl instead of OH on carbon)

SOCl₂

Reduction to Alkanes from alcohol

1) TsCl, pyridine 2) LiAlH₄

Elimination of Alcohols to Alkenes

POCl₃, pyridine

Synthesize 1,2-diols

OsO₄, H₂O₂; syn addition

Pinacol Rearrangement (1,2-diol → =O)

H₂SO₄

Periodic Cleavage (1,2-diol → 2 ketones/aldehydes)

HIO₄

Williamson Ether Synthesis

Na^+-OR

S_N1 for ethers

HOR

Oxidative Fragmentation

1) O₃ 2) (CH₃)₂S or HIO₄

Hydrolysis of Alkynes (get =O)

1) HgSO₄, H₂SO₄, H₂O or 1) (Sia)₂BH 2) H₂O₂, NaOH + tautomerization

Ketone from Carboxylic Acid

1) CH₃Li (2 eq.) 2) H₃O⁺

nitrile (CN) on alkyl

alkyl-X, NaCN

Nitriles (CN) to Aldehyde

1) DIBALH 2) H₃O⁺

Nitriles (CN) to Ketones

1) CH₃MgBr 2) H₃O⁺

Cyanohydrin Synthesis

HCN, NaOH (catylase)

Acidic Hydrate Formation

H₃O⁺

Basic Hydrate Formation

NaOH, H₂O

Hemiacetal/Hemiketal formation

NaOCH₃, CH₃OH

Acetal/Ketal Formation

CH₃OH (2 equivalents), H₂SO₄

Cyclic Acetals

HO(CH₂)₂OH, H⁺

Imine Formation

R-NH₂, CH₃CO₂H

Enamine Formation

NHR₂, CH₃CO₂H

Addition of Thiols

2CH₃SH, ZnCl₂

Thiols to Ketones

H₃O⁺, HgCl₂

Desulfurization

Raney Ni;

Make ketone/aldehyde from thiol with two H groups

1) Li(CH₂)₃CH₃ 2) Br-R 3) H₃O⁺, HgCl₂

Wolff-Kishner Reduction (any C=O)

NH₂NH₂, NaOH, H₂O

Clemmensen Reduction (only in aromatic rings)

ZnHg, HCl

Baeyer-Villiger Reaction (ketone/aldehyde → ester)

mCPBA, NaOH

Wittig Reaction (ketone/aldehyde → alkene)

RPPh₃, ketone/aldehyde

Ylide synthesis

1) PPh₃ 2) Li(CH₂)₃CH₃