Reaction Table - Chem 2211

Tables of Reactions - Up to Midterm #1

Here are all the reactions you are responsible for and their locations in the text. I have 2 tables here - the first is arranged by the functional group of the product; the second is arranged by the functional group of the reactant. Reaction may appear two or more times.

Synthesis of Functional Groups

Synthesis of Alkanes

From alkenes and alkynes (sections 4.11, 6.8)

R-CH-CH-R ---> RH₂C-CH₂R
R-CC-R ---> RH₂C-CH₂R

H₂, Pd/C
H₂, Pd/C (2 equivalents)

Synthesis of Alkyl Halides

Addition of X₂ to alkenes and alkynes (sections 4.7, 6.5, Experiment 5)
R₂C=CR₂ ---> XR₂C-CR₂X

X₂ in CH₂Cl₂ (X = Cl, Br)
(for alkynes, 2 equivalents add 4 halogen atoms)

Addition of HX to alkene and alkyne - Markovnikov (sections 4.1, 6.5)
HRC=CR₂ ---> H₂RC-CR₂X

HX (X = F, Cl, Br, I)
(note: can also be done in non-alcoholic solvent for Cl, Br)

Halohydrin reaction (section 4.7)
R₂C=CR₂ ---> (OR')R₂C-CR₂X
X₂ (X = Cl, Br) in water (R' = H) or an alcohol (R' = alkyl)

Synthesis of Alkenes

Dehydration of alcohol (section 12.5, Experiment 4)
R₂HC-CR₂OH ---> R₂C=CR₂
H⁺, (aq), heat (e.g., H₂SO₄, H₂O, THF, 50^oC)
H⁺, THF, 25^oC (3^o alcohols)
POCl₃, pyridine, 0^oC (2^o, 3^o alcohols)

From alkyl halide (section 11.2)
R₂HC-CR₂X ---> R₂C=CR₂
OH^- (aq)
KOH in ethanol
CH₃CH₂O^- in ethanol

From alkyne (section 6.8)
R-CC-R ---> RHC=CHR (cis)
R-CC-R ---> RHC=CHR (trans)
H₂, Lindlar catalyst
Li, NH₃ (l)

Synthesis of Alcohols

From alkenes (sections 4.5, 4.7-4.9, 20.6)
R₂C=CR₂ ---> (OH)R₂C-CR₂X
R₂C=CR₂ ---> (OH)R₂C-CR₂H
R₂C=CR₂ ---> (OH)R₂C-CR₂H
R₂C=CR₂ ---> (OH)R₂C-CR₂H
R₂C=CR₂ ---> (OH)R₂C-CR₂(OH)

.
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X₂ (X = Cl, Br) in water (halohydrin reaction)
1. BH₃, THF; 2. H₂O₂, OH^- (hydroboration) [anti-Mark.]
H+ (aq) [Markovnikov]
1. Hg(OAc)₂, H₂O, THF; 2. NaBH₄ [Markovnikov]
1. OsO₄; 2. NaHSO₃, H₂O

Synthesis of Ethers

Alkoxymercuration - Markovnikov (section 4.8)
RHC=CR2 ---> RH2C-CR2-O-R'
1. R'-OH, (CF₃CO₂)₂Hg; 2. NaBH₄

Halohydrin (section 4.5)
R₂C=CR₂ ---> (OR')R₂C-CR₂X
X₂ (X = Cl, Br) in alcohol (R'-OH)

Synthesis of Carbonyls

From alkene (section 20.8)
R₂C=CR'₂ ---> R₂C=O + O=CR'₂

1. O₃; 2. Zn / H₃O⁺

From 1,2-diol (section 20.7)
(OH)R₂C-CR₂(OH) ---> R₂C=O + O=CR'₂
HIO₄ in H₂O

From alkyne (through enol form) (sections 6.6, 6.7, 20.9)

R-CC-R ---> R-CH₂-C(=O)-R
R-CC-H ---> R-CH₂-C(=O)-H (aldehyde)
R-CC-H ---> R-C(=O)-CH₃ (ketone)
R-CC-R ---> R-C(=O)-C(=O)-R
1. BH₃, THF; 2. H₂O₂, OH^- (hydroboration) [no selectivity]
1. BR₃, THF; 2. H₂O₂, OH^- (hydroboration) [anti-Mark]
H₂SO₄ (H⁺), H₂O [Markovnokov]
KMnO₄, OH^-

Synthesis of Carboxyls

Acid from alkyne (section 20.9)
R₁-CC-R₂ ---> R₁-COOH + HOOC-R₂

1. O₃, -78^o; 2. H₂O

Reactions of Functional Groups

Reactions of Alkyl Halides

Formation of alkene (section 7.1)
R₂HC-CR₂X ---> R₂C=CR₂
OH^- (aq)
KOH in ethanol
CH₃CH₂O^- in ethanol

Reactions of Alkenes

Addition of X₂ (section 4.7, Experiment 5)
R₂C=CR₂ ---> XR₂C-CR₂X
X₂ in CH₂Cl₂ (X = Cl, Br)

Addition of HX - Markovnikov (sections 4.1)
HRC=CR₂ ---> H₂RC-CR₂X

HX (X = F, Cl, Br, I)

Synthesis of alcohols or ethers (sections 4.5, 4.7-4.9, 20.6)
R₂C=CR₂ ---> (OR')R₂C-CR₂X
R₂C=CR₂ ---> (OH)R₂C-CR₂H
R₂C=CR₂ ---> (OH)R₂C-CR₂(OH)
RHC=CR₂ ---> RH₂C-CR₂-O-R'
RHC=CR₂ ---> RH₂C-CR₂-O-R'

X₂ (X = Cl, Br) in water (R' = H) or an alcohol (R' = alkyl)
1. BH₃, THF; 2. H₂O₂, OH^- (hydroboration) [anti-Mark]
1. OsO₄; 2. NaHSO₃, H₂O
1. R'-OH, Hg(CF₃CO₂)₂; 2. NaBH₄ [Markovnikov]
H⁺, R'-OH

Synthesis of carbonyl (section 20.8)
R₂C=CR'₂ ---> R₂C=O + O=CR'₂

1. O₃; 2. Zn / H₃O⁺

Reactions of Alkynes

Addition of X₂ (section 6.5)
RCCR ---> RXC=CXR ---> RX₂C-CX₂R
X₂ in CH₂Cl₂ (X = Cl, Br)

Addition of HX - Markovnikov (section 6.5)
RCCR ---> RHC=CXR ---> RH₂C-CX₂R
HX (X = F, Cl, Br, I)

Hydrogenation (8.6)
RCCR ---> RH₂C-CH₂R
R-CC-R ---> RHC=CHR (cis)
R-CC-R ---> RHC=CHR (trans)
H₂, Pd / C
H₂, Lindlar catalyst
Li, NH₃

Synthesis of carbonyl (sections 6.6, 6.7, 20.9)

R-CC-R ---> R-CH₂-C(=O)-R
R-CC-H ---> R-CH₂-C(=O)-H (aldehyde)
R-CC-H ---> R-C(=O)-CH₃ (ketone)
R-CC-R ---> R-C(=O)-C(=O)-R
1. BH₃, THF; 2. H₂O₂, OH^- (hydroboration) [no selectivity]
1. BR₃, THF; 2. H₂O₂, OH^- (hydroboration) [anti-Mark]
H₂SO₄ (H⁺), H₂O [Markovnokov]
KMnO₄, OH^-

Synthesis of carboxylic acids (section 20.9)

R₁-CC-R₂ ---> R₁-COOH + HOOC-R₂
1. O₃, -78^o; 2. H₂O

Reactions of Alcohols

Dehydration (section 12.5, Experiment 4)
R₂HC-CR₂OH ---> R₂C=CR₂
H⁺, (aq), heat (e.g., H₂SO₄, H₂O, THF, 50^oC)
H⁺, THF, 25^oC (3^o alcohols)
POCl₃, pyridine, 0^oC (2^o, 3^o alcohols)

Diol to carbonyl (section 20.7)
(OH)R₂C-CR₂(OH) ---> R₂C=O + O=CR'₂
HIO₄ in H₂O

Last updated, August 26, 2005
Page maintained by Craig MacKinnon

Addition of X₂ to alkenes and alkynes (sections 4.7, 6.5, Experiment 5) R₂C=CR₂ ---> XR₂C-CR₂X	X₂ in CH₂Cl₂ (X = Cl, Br) (for alkynes, 2 equivalents add 4 halogen atoms)
Addition of HX to alkene and alkyne - Markovnikov (sections 4.1, 6.5) HRC=CR₂ ---> H₂RC-CR₂X	HX (X = F, Cl, Br, I) (note: can also be done in non-alcoholic solvent for Cl, Br)
Halohydrin reaction (section 4.7) R₂C=CR₂ ---> (OR')R₂C-CR₂X	X₂ (X = Cl, Br) in water (R' = H) or an alcohol (R' = alkyl)

Dehydration of alcohol (section 12.5, Experiment 4) R₂HC-CR₂OH ---> R₂C=CR₂	H⁺, (aq), heat (e.g., H₂SO₄, H₂O, THF, 50^oC) H⁺, THF, 25^oC (3^o alcohols) POCl₃, pyridine, 0^oC (2^o, 3^o alcohols)
From alkyl halide (section 11.2) R₂HC-CR₂X ---> R₂C=CR₂	OH^- (aq) KOH in ethanol CH₃CH₂O^- in ethanol
From alkyne (section 6.8) R-CC-R ---> RHC=CHR (cis) R-CC-R ---> RHC=CHR (trans)	H₂, Lindlar catalyst Li, NH₃ (l)

Alkoxymercuration - Markovnikov (section 4.8) RHC=CR2 ---> RH2C-CR2-O-R'	1. R'-OH, (CF₃CO₂)₂Hg; 2. NaBH₄
Halohydrin (section 4.5) R₂C=CR₂ ---> (OR')R₂C-CR₂X	X₂ (X = Cl, Br) in alcohol (R'-OH)

From alkene (section 20.8) R₂C=CR'₂ ---> R₂C=O + O=CR'₂	1. O₃; 2. Zn / H₃O⁺
From 1,2-diol (section 20.7) (OH)R₂C-CR₂(OH) ---> R₂C=O + O=CR'₂	HIO₄ in H₂O
From alkyne (through enol form) (sections 6.6, 6.7, 20.9) R-CC-R ---> R-CH₂-C(=O)-R R-CC-H ---> R-CH₂-C(=O)-H (aldehyde) R-CC-H ---> R-C(=O)-CH₃ (ketone) R-CC-R ---> R-C(=O)-C(=O)-R	1. BH₃, THF; 2. H₂O₂, OH^- (hydroboration) [no selectivity] 1. BR₃, THF; 2. H₂O₂, OH^- (hydroboration) [anti-Mark] H₂SO₄ (H⁺), H₂O [Markovnokov] KMnO₄, OH^-

Addition of X₂ (section 4.7, Experiment 5) R₂C=CR₂ ---> XR₂C-CR₂X	X₂ in CH₂Cl₂ (X = Cl, Br)
Addition of HX - Markovnikov (sections 4.1) HRC=CR₂ ---> H₂RC-CR₂X	HX (X = F, Cl, Br, I)
Synthesis of alcohols or ethers (sections 4.5, 4.7-4.9, 20.6) R₂C=CR₂ ---> (OR')R₂C-CR₂X R₂C=CR₂ ---> (OH)R₂C-CR₂H R₂C=CR₂ ---> (OH)R₂C-CR₂(OH) RHC=CR₂ ---> RH₂C-CR₂-O-R' RHC=CR₂ ---> RH₂C-CR₂-O-R'	X₂ (X = Cl, Br) in water (R' = H) or an alcohol (R' = alkyl) 1. BH₃, THF; 2. H₂O₂, OH^- (hydroboration) [anti-Mark] 1. OsO₄; 2. NaHSO₃, H₂O 1. R'-OH, Hg(CF₃CO₂)₂; 2. NaBH₄ [Markovnikov] H⁺, R'-OH
Synthesis of carbonyl (section 20.8) R₂C=CR'₂ ---> R₂C=O + O=CR'₂	1. O₃; 2. Zn / H₃O⁺

Addition of X₂ (section 6.5) RCCR ---> RXC=CXR ---> RX₂C-CX₂R	X₂ in CH₂Cl₂ (X = Cl, Br)
Addition of HX - Markovnikov (section 6.5) RCCR ---> RHC=CXR ---> RH₂C-CX₂R	HX (X = F, Cl, Br, I)
Hydrogenation (8.6) RCCR ---> RH₂C-CH₂R R-CC-R ---> RHC=CHR (cis) R-CC-R ---> RHC=CHR (trans)	H₂, Pd / C H₂, Lindlar catalyst Li, NH₃
Synthesis of carbonyl (sections 6.6, 6.7, 20.9) R-CC-R ---> R-CH₂-C(=O)-R R-CC-H ---> R-CH₂-C(=O)-H (aldehyde) R-CC-H ---> R-C(=O)-CH₃ (ketone) R-CC-R ---> R-C(=O)-C(=O)-R	1. BH₃, THF; 2. H₂O₂, OH^- (hydroboration) [no selectivity] 1. BR₃, THF; 2. H₂O₂, OH^- (hydroboration) [anti-Mark] H₂SO₄ (H⁺), H₂O [Markovnokov] KMnO₄, OH^-
Synthesis of carboxylic acids (section 20.9) R₁-CC-R₂ ---> R₁-COOH + HOOC-R₂	1. O₃, -78^o; 2. H₂O

Dehydration (section 12.5, Experiment 4) R₂HC-CR₂OH ---> R₂C=CR₂	H⁺, (aq), heat (e.g., H₂SO₄, H₂O, THF, 50^oC) H⁺, THF, 25^oC (3^o alcohols) POCl₃, pyridine, 0^oC (2^o, 3^o alcohols)
Diol to carbonyl (section 20.7) (OH)R₂C-CR₂(OH) ---> R₂C=O + O=CR'₂	HIO₄ in H₂O