TIP - These purple boxes Too small? Eye strain?
Expanded version at 4x
are clickable and go Reactions of Alkanes resolution (60 pages instead of 15) available
Index Some keywords to the Reaction Guide upon request. Write an email with “Reaction
page for each reaction Maps Expanded Version” in the header to
Page 1 - Alkanes (and Index) alkane halogenation (chlorination and bromination) support@[Link]
(contains mechanism
+ more examples)
Page 2 - Reactions of Alkenes addition of HX, bromination, hydroboration, ozonolysis,
Alkane Alkane Cl CH3 H CH2Cl
dihydroxylation (OsO4 ) epoxidation (m-CPBA)….
bromination H CH3 chlorination
Page 3 - Reactions of Alkynes Lindlar, Na/NH3, acetylide addition, synthesis of alkynes via Br CH3
elimination, hν hν
2 1
Page 4 - Reactions of Alkyl Halides SN1, SN2, E1, E2, plus rearrangements (hydride and alkyl shifts) Br2 Cl2
H CH3 H CH3 H CH3
Page 5 - Reactions of Primary and Secondary alcohols Alkyl halide Alkane Cl
oxidation to give aldehydes and ketones, alkyl halide formation
(SOCl2, PBr3), Williamson ether synthesis, elimination…. (bromide)
Cl
Page 6 - Reactions of Tertiary Alcohols, and Ethers Alkyl halides from alcohols, elimination, ether formation, ether Selective for tertiary Alkyl halides
cleavage… TIP - these numbers Cl
alkyl halides (chlorides)
correspond to the
Page 7 - Reactions of Epoxides and Grignard Reagents opening epoxides with Grignards and other nucleophiles, multiple products
“Specific Examples” list
opening epoxides under acidic conditions…. (not selective)
shown below
Page 8 - Reactions of Organometallics formation of organolithium and Grignard reagents, reactions with
aldehydes, ketones, esters, acids, CO2 ….
Page 9 - Reactions of Aromatic Compounds electrophilic aromatic substitution, side chain
modification, nucleophilic aromatic substitution…. H H
Page 10 - Aldehydes and Ketones Addition reactions to aldehydes and ketones, Wittig reaction, C hν CH3 hν
Br Br
reduction of aldehydes and ketones 4 CH3 3 C
Br2 Br2 H H
Page 11 - Carboxylic Acids and Esters synthesis of carboxylic acids, Fischer esterification, ester hydrolysis,
addition of Grignards, reduction with LiAlH4, partial reduction… or NBS or NBS
Alkyl groups adjacent
Page 12 - Acid Halides and Anhydrides acid halides from acids with SOCl2, hydrolysis, Friedel-Crafts Benzyl halide to pi bonds Allylic Allyl halide
Benzylic
acylation, reduction, Grignard addition… bromination
bromination
Page 13 - Enols and Enolates keto-enol tautomerism, decarboxylation, aldol reaction, enamines, Br
Reminder: an example of a benzyl halide is C6H5CH2Br Reminder: an example of an allyl halide is C
enolate formation, michael reaction, Robinson annlation…. H H
Page 14 - NItriles and Amines synthesis of nitriles, reduction of nitriles, reductive amination, C6H5Br is a phenyl halide Br is a vinyl halide
imine formation, synthesis of amines…
Page 15 - Dienes and Miscellaneous Reactions Rearrangements: Cope, Claisen, pinacol, Curtius, Wolff,
Strecker synthesis, Canniarro, diazonium salts…
Some Abbreviations Specific examples
CH3
C
i-Pr isopropyl C H Bn Benzyl
Me Methyl, –CH3 1 Chlorination of alkanes
CH3
Et Ethyl, –CH2CH3 Cl2 (1 equiv)
CH3 CH4 CH3Cl
Pr Propyl, –CH2CH2CH3 t-Bu tert-butyl C CH3 Ph Phenyl hν
CH3
Bu Butyl, –CH2CH2CH2CH3 Cl
Cl2 (1 equiv)
hν light (UV or visible radiation) O 1° primary (carbon, alcohol, amine, alkyl halide) hν
Ac acetyl C
CH3
Δ heat 2° secondary (carbon, alcohol, amine, alkyl halide)
3° Cl2 (1 equiv) CH2Cl Cl
O tertiary (carbon, alcohol, amine, alkyl halide)
Ts Tosyl Cl
p-toluenesulfonyl H 3C S hν Cl
4°
→
O quaternary (carbon, ammonium salt)
→
Cl
note: these are the same!
O 2 Bromination of alkanes
Ms Mesyl methanesulfonyl H 3C S
LDA Lithium di-isopropyl amide N
O strong, bulky base Li Br2 (1 equiv) Br
O
hν
Cl OH
m-CPBA meta-chloroperoxybenzoic acid O
DCC N,N’-Dicyclohexyl carbodiimide
makes epoxides from alkenes,
useful for making amides N C N
also esters from ketones O
3 Allylic bromination
NBS N-bromosuccinimide N Br O
DIBAL Di-isobutyl aluminum hydride Al allylic bromination, NBS (1 equiv) Br
bulky reducing agent H bromination of alkenes O CH3 C
hν NBS = N Br
O H H
DMP Dess-Martin Periodinane AcO OAc
I OAc PCC Pyridinium chlorochromate Cl Cr O
N
oxidizes alcohols oxidizes alcohols 4 O
O O
H Benzylic bromination
H H N-Bromosuccinimide
O CH3 NBS (1 equiv) C
TBAF Tetrabutylammonium fluoride Bu4N F Br
LiAlH(OtBu)3 Lithium tri(t-butoxy) aluminum hydride fluoride source for removing hν
reduces acid halides to aldehydes silicon protecting groups
Page 1 - Alkanes (and Index) Page 1 - Alkanes (and Index)