Organic Chemistry 2: Need to Know

Benzene

Toluene

benzene + CH₃

Xylene

benzene + 2CH₃

Benzoic acid

benzene + C=O OH

Acetylphenone

benzene + C=O CH₃

Anisole

benzene + O—CH₃

Aniline

benzene + NH₂

Anilide

benzene + C=O NH₂

Phenol

benzene + OH

Markovnikov

The bigger compound goes on the more substituted carbon

Hydrohalogenation reagents

HX (X: halogen)

Hydrohalogenation mechanism

• markovnikov addition

Acid-Catalyzed Hydration reagents

H₃O⁺ Or H₂O/H₂SO₄

Acid-Catalyzed Hydration mechanism

• markovnikov addition

• sometimes a hydride shift will be necessary

Acid-Catalyzed addition of an alcohol reagents

CH₃OH/H⁺

Acid-Catalyzed addition of an alcohol mechanism

• markovnikov

Halogenation reagents

X₂/CCl₄ (X: halogens)

Halogenation mechanism

• anti addition (one wedged other dashed)

Halogenation in H₂O reagents

X₂/H₂O (X: halogens)

Halogenation in H₂O mechanism

• markovnikov

• anti addition

Halogenation in alcohol reagents

X₂/CH₃OH (X: halogens)

Halogenation in alcohol mechanism

• markovnikov

• anti addition

Oxymercuration-Demurcuration reagents

Hg(OAc)₂, H₂O / NaBH₄

Oxymercuration-Demurcuration mechanism

• markovnikov

• anti addition

Alkoxymercuration-Demurcuration reagents

Hg(OAc)₂, CH₃OH / NaBH₄

Alkoxymercuration-Demurcuration mechanism

• markovnikov

• anti addition

Hydroboration-Oxidation reagents

BH₃ THF / H₂O₂ , NaOH

Hydroboration-Oxidation mechanism

• anti-markovnikov

• syn addition

Catalytic Hydrogenation reagents

H₂ / Pd/c

Catalytic Hydrogenation mechanism

• syn addition

• meso

Hydrobromination with peroxide reagents

HBr / ROOR

Hydrobromination with peroxide mechanisms

• anti-Markovnikov

Epoxidation reagents

RCO₃H or MCPBA

Epoxidation mechanism

• syn addition

Anti-Hydroxylation reagents

RCO₃H / H₃O⁺

Anti-Hydroxylation mechanism

• anti addition

Syn-Hydroxylation (1) reagents

OsO₄ / H₂O₂

Syn-Hydroxylation (1) mechanism

• syn addition

• meso

Syn-Hydroxylation (2) reagents

KMnO₄ (cold, dilute) / OH^-

Syn-Hydroxylation (2) mechanism

• syn addition

• meso

Ozonolysis under reducing conditions reagents

O₃ / Zn/H₂o

Ozonolysis under reducing conditions mechanism

Ozonolysis under oxidizing conditions reagents

O₃ / H₂O₂

OR

KMnO₄ (hot,conc.) / H₃O⁺

Ozonolysis under oxidizing conditions mechanism

THE FOLLOWING MECHANISMS FOR ALKYNES (triple bonds)

THE FOLLOWING MECHANISMS FOR ALKYNES (triple bonds)

Dehydrohalogenation of vicinal dihalides reagents

KOH, ethanol

OR

NaNH₂, NH₃

Dehydrohalogenation of vicinal dihalides mechanism

Alkylation of acetylide anions reagents

1) NaNH₂ then 2) RCH₂Br

Alkylation of acetylide anions mechanism

• if it starts off as terminal triple bond then product becomes internal and vice versa

Addition of HX to alkyne reagents

HX / ether (X: halogen)

Addition of HX to alkyne mechanism

Addition of X₂ to alkyne reagents

X₂ / CH₂Cl₂

Addition of X₂ to alkyne mechanism

• do it twice to go from triple bond to single bond

Mercuric sulfate catalyzed hydration reagents

H₂SO₄, H₂O / HgSO₄

Mercuric sulfate catalyzed hydration mechanism

Hydroboration-oxidation of alkyne: hydration (reagents)

BH₃ / H₂O₂

Hydroboration-oxidation of alkyne: hydration (mechanism)

Catalytic hydrogenation (1) : reduction (reagents)

2 H₂ / Pd/c

Catalytic hydrogenation (1) : reduction (mechanism)

Catalytic hydrogenation (2) aka Lindlar : reduction (reagents)

H₂ / Lindlar catalyst

Catalytic hydrogenation (2) aka Lindlar : reduction (mechanism)

• cis product

Lithium in liquid ammonia: reduction (reagents)

Li / NH₃

Lithium in liquid ammonia: reduction (mechanism)

• trans product

Conversion into acetylide anions reagents

NaNH₂ / NH₃

Conversion into acetylide anions mechanism

Alkene to Alkyl halides using allylic bromination reagents

NBS / light,CCl₄

Alkene to Alkyl halides using allylic bromination mechanism

Alcohols to Alkyl halides using HX reagents

HX / ether (X: halogens)

Alcohols to Alkyl halides using HX mechanism

• reactivity order 3^o > 2^o > 1^o

1^o and 2^o Alcohols to Alkyl halides using SOCl₂ reagents

SOCl₂ / Pyridine

1^o and 2^o Alcohols to Alkyl halides using SOCl₂ mechanism

1^o and 2^o Alcohols to Alkyl halides using PBr₃ reagents

PBr₃ / ether

1^o and 2^o Alcohols to Alkyl halides using PBr₃ mechanism

1^o and 2^o Alcohols to Alkyl halides using HF reagents

HF / Pyridine

1^o and 2^o Alcohols to Alkyl halides using HF mechanism

Palladium-catalyzed Suzuki-Miyaura reagents

Pd(PPh₃)₄ / CaCO₃ THF

Palladium-catalyzed Suzuki-Miyaura mechanism

Grignard reagents

R-Mg-X , ether / H₂O or H₃O⁺

Grignard mechanism

• adds the R to reactant

• makes the O into OH

IR range 3200-3500

O-H

IR range 3000-3050

C_sp² - H

IR range 2900-3000

C_sp³ - H

IR range 1650-1750

C=O

IR range 1600-1650

C=C

IR range 1050-1250

C-O

IR range 1650-1680

amides

IR range 1685-1715

aldehyde/ketone

IR range 1680-1710

Carboxylic acids

IR range 1735-1760

esters/lactones

IR range 1760 and 1820

Anhydrides

IR range 1800

acyl halides

NMR range 0.8-2.0

hydrogen is on an alkyl chain

NMR range 2.0-2.5

hydrogen is attached to an allylic carbon

NMR range 3.0-4.5

electronegative atom is attached to the same carbon as the hydrogen

NMR range 5.0-6.0

hydrogen is attached to an alkene carbon

NMR range 7.0-8.0

hydrogen is attached to an aromatic carbon

NMR range 9.7-10.0

aldehyde

NMR range 11.0-12.0

carboxylic acid

IR range 690-710 and 730-770

monosubstituted benzene ring

IR range 735-770

o-disubstituted benzene ring