Organic Chemistry Reagents
conc. H₂SO₄, heat
E1
Alcohol –> Alkene
regioselective – more substituted double bond
stereoselective – trans(E)>cis(Z)
Rearrangement around tertiary alcohol
Alcohol –> Alkene
regioselective – more substituted double bond
stereoselective – trans(E)>cis(Z)
Rearrangement around tertiary alcohol
HCl
Sn1
Alcohol –> Alkyl halide
regioselective – tertiary alcohol
Alcohol –> Alkyl halide
regioselective – tertiary alcohol
HBr (3)
Sn1/Sn2:
Alcohol –> Alkyl halide
Sn1- secondary and tertiary, Sn2 – primary
Free Radical:
Alkene –> alkyl bromide
markovnikov
HBr Addition:
Alkyne –> alkene
markovnikov, anti-addition
Alcohol –> Alkyl halide
Sn1- secondary and tertiary, Sn2 – primary
Free Radical:
Alkene –> alkyl bromide
markovnikov
HBr Addition:
Alkyne –> alkene
markovnikov, anti-addition
SOCl₂, base
Sn2
Alcohol –> Alkyl chloride
primary and secondary alcohols
Alcohol –> Alkyl chloride
primary and secondary alcohols
PBr₃
Sn2
Alcohol –> alkyl bromide
primary and secondary alcohol
Alcohol –> alkyl bromide
primary and secondary alcohol
Na₂Cr₂O₇ or CrO₃, H₂SO₄ **
oxidation
alcohol –> carbonyl
produces carboxylic acid in the presence of water when primary
alcohol –> carbonyl
produces carboxylic acid in the presence of water when primary
H₂CrO₄
oxidation
alcohol –> carbonyl
produces carboxylic acid in the presence of water when primary
alcohol –> carbonyl
produces carboxylic acid in the presence of water when primary
PCC or PDC, CH₂Cl₂
oxidation
alcohol –> carbonyl
alcohol –> carbonyl
HIO₄
oxidation
alcohol (2) –> carbonyl (2)
*alcohol must be in syn
alcohol (2) –> carbonyl (2)
*alcohol must be in syn
Br₂ w/ heat, light
free radical
alkane –> alkyl bromide
regioselective for tertiary hydrogen
alkane –> alkyl bromide
regioselective for tertiary hydrogen
Cl₂ w/ heat, light
free radical
alkane –> alkyl chloride
regioselective for equivalent hydrogens
alkane –> alkyl chloride
regioselective for equivalent hydrogens
O₂
combustion
alkane –> carbon dioxide + water
alkane –> carbon dioxide + water
2NaNH₂, NH₃
E2
vicinal or geminal dibrominde –> Alkyne
vicinal or geminal dibrominde –> Alkyne
3NaNH₂, NH₃ followed by acid workup
E2
vicuna or geminal dibromide — alkyne
*only when it’s a terminal alkyne
vicuna or geminal dibromide — alkyne
*only when it’s a terminal alkyne
1. BH₃, THF
2. H₂O₂, NaOH
2. H₂O₂, NaOH
Hydrobroration
alkene –> alcohol
anti-markovnikov, syn-addition
H: hydride shift, OH: water
alkene –> alcohol
anti-markovnikov, syn-addition
H: hydride shift, OH: water
dilute H₂SO₄
Acid-Catalyzed
alkene –> alcohol
markovnikov
alkene –> alcohol
markovnikov
OsO₄, catalyst
Hydroxylation
Alkene –> Alcohol (2)
syn-addition
Alkene –> Alcohol (2)
syn-addition
Br₂ or Cl₂, H₂O, CH₂Cl₂, cold/dark
Electrophilic addition
alkene –> alcohol/alkyl halide
Alcohol: Markovnikov
Halide: anti-Markovnikov
anti-addition
alkene –> alcohol/alkyl halide
Alcohol: Markovnikov
Halide: anti-Markovnikov
anti-addition
Br₂ or Cl₂, CH₂Cl₂, cold/dark
Electrophilic addition
alkene –> alkyl halide (2)
anti-addition
alkene –> alkyl halide (2)
anti-addition
H₂, metal catalyst (2)
Hydrogenation…
Alkene –> alkane
syn-addition
Hydrogenation…
carbonyl –> alcohol
Alkene –> alkane
syn-addition
Hydrogenation…
carbonyl –> alcohol
Peroxyacetic Acid (RC(=O)OOH)
Epoxidation
Alkene –> Epoxide
Same side of DB = same side of ring
Alkene –> Epoxide
Same side of DB = same side of ring
1. O₃
2. H₂O, Zn or S(CH₃)₂
2. H₂O, Zn or S(CH₃)₂
Oxidative Cleavage
Alkene –> Ketone or Aldehyde
Alkene –> Ketone or Aldehyde
1. O₃
2. H₂O
2. H₂O
Ozonolysis
Alkene –> Ketone or Carboxylic Acid
Oxonolysis
Alkyne –> Carboxylic Acids
Alkene –> Ketone or Carboxylic Acid
Oxonolysis
Alkyne –> Carboxylic Acids
H₂O
Hydrolysis
Alkyl halide –> alcohol
Alkyl halide –> alcohol
Strong Base, Heat
E2
Alkyl halide –> alkene
more substituted double bond
trans (E)>cis(Z)
Beta hydrogen and halide MUST be anti
Alkyl halide –> alkene
more substituted double bond
trans (E)>cis(Z)
Beta hydrogen and halide MUST be anti
Williamson Ether Synthesis
Sn2
alkoxide ion + alkyl halide –> Ether
regioselective: primary alkyl halides
alkoxide ion + alkyl halide –> Ether
regioselective: primary alkyl halides
NaOH
Sn2
vicinal halohydrin–> epoxide
Backside attack
Halide and oxygen must be anti
inversion of configuration
vicinal halohydrin–> epoxide
Backside attack
Halide and oxygen must be anti
inversion of configuration
H₂SO₄, HOCH₂CH₃
ring-opening
Epoxide –> alcohol
markovnikov
Epoxide –> alcohol
markovnikov
1. NaOCH₂CH₃, HOCH₂CH₃
2. Aqueous Acid
2. Aqueous Acid
ring-opening
Epoxide –> alcohol
anit-markovnikov
Epoxide –> alcohol
anit-markovnikov
1. Organometallic (Grignard)
2. Acid Workup
2. Acid Workup
Grignard
Carbonyl –> Alcohol
anion attacks C; hydrogen on oxygen results from acid workup
Carbonyl –> Alcohol
anion attacks C; hydrogen on oxygen results from acid workup
1. LiAlH₄
2. Acid Workup
2. Acid Workup
LiAH
Carbonyl –> alcohol
hydrogen attacks C; hydrogen on oxygen results from acid workup
Carbonyl –> alcohol
hydrogen attacks C; hydrogen on oxygen results from acid workup
NaI, acetone
Sn2
bromide –> iodide
inversion of configuration
bromide –> iodide
inversion of configuration
NaNH₂, NH₃
Alkyne –> Alkyne (-)
Excess of H₂, Pd
Hydrogenation
Alkyne –> alkane
Alkyne –> alkane
H₂, Lindlar Pd
Semi-Hydrogenation
Alkyne –> Alkene
Cis
Alkyne –> Alkene
Cis
Na, NH₃
Semi-Hydrogenation
alkyne –> alkene
trans
alkyne –> alkene
trans
2HBr or 2HCl
HBr Addition
Alkyne –> Geminal Dihalide
markovnikov
Alkyne –> Geminal Dihalide
markovnikov
Br₂ or Cl₂
X₂ Addition
alkyne –> alkene
anti-addition
alkyne –> alkene
anti-addition
2Br₂ or 2Cl₂
X₂ Addition
alkyne –> tetrahaloalkane
anti-addition
alkyne –> tetrahaloalkane
anti-addition
H₂SO₄, H₂O, HgSO₄
Acid Catalyzed Hydration
Alkyne –> Enol/Tautomer
markovnikov
tautomerization occurs to more DB to create a carboxyl group
Alkyne –> Enol/Tautomer
markovnikov
tautomerization occurs to more DB to create a carboxyl group
HBr Peroxides
Free Radical:
Alkene –> alkyl bromide
anti-markovnikov
HBr Addition:
alkyne –> alkene
anti-markovnikov
Alkene –> alkyl bromide
anti-markovnikov
HBr Addition:
alkyne –> alkene
anti-markovnikov
1. BH₃-THF
2. NaOH, H₂O₂
2. NaOH, H₂O₂
alkene –> alcohol
anti-markovnikov
syn-addition
anti-markovnikov
syn-addition
H₂SO₄, heat
ether synthesis
2 alcohols –> ether
only works with symmetrical, primary alcohols
2 alcohols –> ether
only works with symmetrical, primary alcohols