SUBSTRATE REAGENT REACTION MECHANISM MAJOR PRODUCT BYPRODUCT NOTE

catalyst

ALKANES

CH4 Cl2 or Br2 Radical Halogenation SR CH3Cl HCl

ALKENES

CH2=CH2 H2 Catalytic Hydrogenation Cis AE CH3-CH3

(Pt, Ni, Pd) (Reduction)

CH2=CH2 HX Hydrohalogenation Trans or anti AE CH3CH2X X on more substituted

Organic monohalide C; H on less
substituted C

CH2=CH2 X2 Halogenation Trans or anti AE CH2XCH2X

Vicinal dihalide

CH2=CH2 HOH Hydration Trans or anti AE CH3CH2OH

H2SO4 Alcohols

CH2=CH2 Neutral or basic Hydroxylation REDOX (Oxidation) Diols

KMnO4 (aq.)

CH2=CH2 Acidic KMnO4 Oxidative Multiple Bond REDOX (Oxidation) If terminal = CO2 + H2O
Cleavage If internal = RCOOH

CH2=CH2 Peroxyacid Epoxidation REDOX (Oxidation) Epoxide RCOOH

CH2=CH2 X2 , H 2 O Halohydration Trans AE Halohydrins HX

HO-C-C-X

ALKYNES

HCCH H2 Catalytic Hydrogenation Cis AE CH2=CH2

(Lindlar’s Catalyst) (Reduction)
 HCCH HOH Hydration Trans or anti AE Enol Markovnikov’s rule
H2SO4, HgSO4 H2=CHOH
Ketone Keto-enol
R2CO Tautomerism

HCCH HX Hydrohalogenation Trans or anti AE CH2=CHX

HCCH X2 Halogenation Trans or anti AE CH2X=CH2X

HCCH Neutral or basic Hydroxylation REDOX (Oxidation) Diols

KMnO4 (aq.)

HCCH Acidic KMnO4 (aq.) Oxidative Multiple Bond REDOX (Oxidation) If terminal = CO2 + H2O
Cleavage If internal = RCOOH

HCCH NaNH2 Acetylide Formation Acid-base reaction (or SN) Acetylide NH3

AROMATIC COMPOUNDS

Benzene X2 Halogenation SE Halobenzene HX

FeX3 or AlX3

Note activators and

Benzene Conc. HNO3 and Nitration SE Nitrobenzene HOH deactivators
Conc. H2SO4

Benzene Fuming H2SO4 Sulfonation SE Benzenesulfonic Acid HOH

(conc. H2SO4 + SO3)

Benzene RCOX (Acid halide) Friedel-Crafts Acylation SE Aromatic ketone HX

AlX3 Cannot undergo
friedel-craft if the ring
contains a deactivator
Benzene RX (Alkyl halide) Friedel-Crafts Alkylation SE Arenes HX
AlX3

Benzene Zn(Hg), conc. HCl Clemmenson Reduction SE Acyl to Alkyl

heat

Ethyl Benzene KMnO4, H2O REDOX (Oxidation) SE If terminal = CO2 + H2O

If internal = RCOOH
 (Benzoic Acid)

ALKYL HALIDES

R-X Mgo Synthesis of Grignard AN R-Mg-X Condensation

Reagent Grignard reagent Reaction (ANE)

R-Mg-X H2 O Hydrolysis E R-H Mg(OH)X

Basic magnesium
halide

R-X Strong or weak nucleophile; dependent on SN1 Racemization 3o>2o>1o

substrate; polar protic solvent (enantiomeric
products)

R-X Strong nucleophile; dependent on both substrate SN2 Inversion prod. 1o>2o>3o
and nucleophile; polar aprotic or nonpolar solvent

R-C-X Nu- elimination E1 R=C X-

heat

R-C-X Nu- (basic) elimination E2 R=C X- Major product in more

heat substituted C atom

ALCOHOLS AND PHENOLS

R-OH H-X Hydrohalogenation SN1 R-X H2 O Most reactive with 3o

Hydrogen halide alcohols
ether

R-OH p-TosCl SN1 or SN2 ROTos Pyridine HCl

Toluenesulfonyl
chloride
pyridine

CH3CH2-OH H3O+, THF dehydration E1 CH2=CH2 Less substituted Follows Zaitsev’s rule
More substituted alkene product
alkene product

R-OH KMnO4/CrO3/ REDOX oxidation Aldehydes →

(1o) Na2Cr2O7 Carboxylic acids

(2o) Ketones

R-OH Dess-martin REDOX oxidation RCHO

(1o) periodinane
CH2Cl2
 Ar-OH Na2Cr2O7 REDOX Oxidation Benzoquinone
phenol H2 O

Quinone SnCl2 REDOX Reduction Hydroquinone

H2

ETHERS

ROR’ HBr or HI Acidic Cleavage SN2: If 1O or 2O R’Br or R’Cl + ROH Br or I will bond with
SN1: If 3O the less sterically
hindered R between 1o
and 2o
If there is a tertiary R,
Br and I will
automatically bond
with it

EPOXIDES (AKA OXIRANES)

ROH NaO metal or NaH Williamson Ether RONa+ H2 In short:

Synthesis (Alkoxide Ion) ROH+NaH→H2+RON
a
RONa R-X SN2: If 1O or 2O ROR’ NaX RONa+RX→NaX+R
SN1: If 3O OR

EPOXIDE HX, Ether Ring Opening SN2 like: If 1O or 2O Halohydrin X or the halogen will
SN1 like: If 3O is present bond with the 1O
SN2 (accdg to Torres) (between 1O and 2O)
X will bond with 3O if it
is present

EPOXIDE H+, HOH Ring Opening SN2 1,2 diol (glycol)

ALDEHYDES

RCHO KMnO4/CrO3/ REDOX Oxidation RCOOH

Na2Cr2O7

RCHO H2 O Hydration AN Hydrate

(basic OH-) or (acidic (gem diol)
H+)
 RCHO HCN Cyanohydrin formation AN nitriles

RCHO NaBH4;ethanol REDOX reduction Primary alcohols

RCHO R-Mg-X Addition of grignard AN Secondary alcohols

reagent

RCHO RNH2 Imine formation ANE RCH-Imine

RCHO R2NH Enamine formation ANE Enamine

RCHO H2NNH2 Wolff-Kishner AN RCH3 N2 + H 2 O

KOH

RCHO ROH Acetal formation ANE Hemiacetal → acetal H2 O

Acid catalyst

KETONES

R2CO H2 O Hydration AN Hydrate

(basic OH-) or (acidic (gem diol)
H+)

R2CO HCN Cyanohydrin formation AN Nitriles

R2CO NaBH4;ethanol REDOX reduction Secondary alcohols

R2CO R-Mg-X Addition of grignard AN Tertiary alcohols

reagent

R2CO RNH2 Imine formation ANE R2C-Imine H2 O

 R2CO R2NH2 Enamine formation ANE Enamine H2 O

R2CO H2NNH2 Wolff-Kishner AN R2CH2 N2 + H 2 O

KOH

R2CO ROH Ketal formation ANE Hemiketal → ketal H2 O

Acid catalyst

CARBOXYLIC ACIDS

RCOOH SOCl2 SNAcyl RCOCl

RCOOH PBr3, SNAcyl RCOBr

Ether

RCOOH heating Acetic anhydride H2 O Only acetic anhydride

(2 moles acetic is prepared this way
acid)

RCOOH ROH Fischer Esterification SNAcyl Ester H2 O

Acid catalyst (RCOOR’)

RCOOH NH3(alc.) ammonolysis SNAcyl Amide H2 O

DCC (RCONH2)

RCOOH RNH2(alc.) aminolysis SNAcyl Amide H2 O

DCC (RCONHR’)

RCOOH 1. LiAlH4, ether REDOX Reduction Primary alcohol

2. H3O+ (RCH2OH)

ACID HALIDES (CARBOXYLIC ACID DERIVATIVE)

RCOX H2O Hydrolysis SNAcyl RCOOH HX

RCOX Carboxylate anion SNAcyl Acid Anhydride

(symmetrical or
unsymmetrical)

RCOX ROH Alcoholysis SNAcyl Ester HX

(RCOOR’)

RCOX R’-NH2 (alc) Aminolysis SNAcyl Amides HX Trisubstituted amines

(RCONHR’) can’t be used

RCOX NH3 (alc) Ammonolysis SNAcyl RCONH2 HX

 RCOX 1. LiAlH4, ether REDOX (reduction) SNAcyl Primary alcohol HX
2. H3O+ (RCH2OH)

RCOX 2 R-Mg-X Grignard SNAcyl Tertiary alcohols

(Grignard reagent)

RCOX R2CuLi Diorganocopper SNAcyl Ketone R’Cu

Lithium (RCOR’)
diorganocopper
(Gilman) reagent

ACID ANHYDRIDES (CARBOXYLIC ACID DERIVATIVE)

(RC(O))2O H2O Hydrolysis SNAcyl RCOOH RCOOH

(RC(O))2O ROH Alcoholysis SNAcyl Ester RCOOH

(RCOOR’)

(RC(O))2O R’-NH2 (alc) Aminolysis SNAcyl Amide RCOOH

(RCONHR’)

(RC(O))2O 1. LiAlH4, ether REDOX reduction 2 Primary alcohol

2. H3O+ 2 (RCH2OH)

ESTERS (CARBOXYLIC ACID DERIVATIVE)

RCOOR’ H2O, NaOH Hydrolysis SNAcyl RCOOH R’OH

H3 O + saponification

RCOOR’ NH3 Aminolysis SNAcyl RCO-NH2 R’OH

ether

RCOOR’ 1. ROH Trans esterification SNAcyl Ester R’OH Double bond O will
2. H3O+ or base (RCOOR’) Primary alcohol become ester
Ester must not have
the same

RCOOR’ 1. LiAlH4, ether REDOX reduction RCOH R’OH

2. H3O+ Primary alcohol Primary alcohol

RCOOR’ R-Mg-X Grignard SNAcyl Tertiary alcohol

(Grignard reagent)

AMIDES (CARBOXYLIC ACID DERIVATIVE)

RCONH2 H2O, NaOH Hydrolysis SNAcyl RCOOH NH3

H3 O +

RCONH2 1. LiAlH4, ether REDOX reduction RCH2NH2 H2O

 2. H3O+

NITRILES

RC≡N H2 O Hydration AN amide

RCONH2

RC≡N H2O, NaOH Hydrolysis RCOOH NH3

H3 O +

RC≡N LiAlH4, ether REDOX reduction RNH2

Primary amine

RC≡N R-Mg-X (Grignard R2CO NH3

reagent), H2O