Reaction Table - Chem 2211

Tables of Reactions

I have 2 tables here - the first is arranged by product (reactions arranged by functional group of the product); the second is arranged by the functional group of the reactant. Each reaction we've covered may appear two or more times.

Synthesis of Functional Groups

Synthesis of Alkanes

From alkenes and alkynes (sections 4.11, 6.8)

R-CC-R ---> RH₂C-CH₂R

H₂, Pd/C

Synthesis of Alkyl Halides

From alkanes (Section 9.2)
C_nH_2n+2 ---> C_nH_(2n+2)-yX_y
X₂, hf (X = Cl, Br) [NOTE: hf = light]

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

X₂ in CH₂Cl₂ (X = Cl, Br)

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

HX in ether (X = Cl, Br)
KI in H₃PO₄ (X = I)

Addition of HX to alkene, anti-Markovnikov (section 4.10)

HRC=CR₂ ---> HXRC-CR₂H

HBr with peroxide

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

Allylic bromination (section 9.5)
R₂C=CR-CH₂-R ---> R₂C=CR-CHBr-R
NBS with peroxide

Conversion from alcohol (sections 12.1, 12.3, Experiment 6)
R₃C-OH ---> R₃C-X

HX in ether (X = Cl, Br, I, usually 3^o alcohols)
SOCl₂ in pyridine (X = Cl, 1^o or 2^o alcohols)
PBr₃ in ether (X = Br, 1^o or 2^o alcohols)

Cleavage of ethers (12.6)
R-O-R' ---> R-OH + R'-X
H-X in H₂O (X = Br, I)

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

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)

.
.
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

Cleavage of ethers (12.6)
R-O-R' ---> R-OH + R'-X
H-X in H₂O (X = Br, I)

Reduction of carbonyl (18.4, 20.1)

R-C(=O)-R' ---> R-CH(OH)-R'

R-C(=O)-R' ---> R"RC(OH)-R'
.
.
1. NaBH₄, ethanol; 2. H₃O⁺ (aldehyde or ketone)
H₂, Raney Ni (aldehyde or ketone)

R"-MgBr, H₃O⁺ (Grignard reaction)

From carboxyl (20.1)

R-C(=O)-O-R' ---> RCH₂OH + HO-R'
R-C(=O)-O-R' ---> R"₂RC-OH + HO-R'

1. LiAlH₄; 2. H₃O⁺ (carboxylic acid or ester)
R"-MgBr, H₃O⁺ (Grignard reaction, happens twice)

Synthesis of Ethers

Deprotonated alcohol plus halide (Williamson synthesis) (section 11.9)
R-OH ---> R-O-R'
1. NaH, THF; 2. R'-X

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 (ketone)
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 Alkanes

Formation of alkyl halides (section 9.2)

C_nH_2n+2 ---> C_nH_(2n+2)-yX_y

X₂, hv (light) (X = Cl, Br)

Reactions of Alkyl Halides

Reaction with deprotonated alkyne (sections 6.9-6.10)

R-CC-H ---> R-CC:^-
R-CC:^- + R'-X ---> R-CC-R'

NaNH₂ (or another strong base)
substitution step (X = Br usually)

Formation of alkene (section 11.2)
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 in ether (X = Cl, Br)
KI in H₃PO₄ (X = I)

Allylic bromination (section 9.5)
R₂C=CR-CH₂-R ---> R₂C=CR-CHBr-R
NBS with peroxide

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, (CF₃CO₂)₂Hg; 2. NaBH₄ [Markovnikov]
H+ (aq) [Markovnikov]

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 ---> RX₂C-CX₂R
X₂ in CH₂Cl₂ (X = Cl, Br)

Addition of HX - Markovnikov (section 6.5)
RCCR ---> RH₂C-CX₂R
HX in ether (X = Cl, Br)

Hydrogenation (section 6.8)
RCCR ---> RH₂C-CH₂R
R-CC-R ---> RHC=CHR (cis)
R-CC-R ---> RHC=CHR (trans)
H₂, Pd / C
H₂, Lindlar catalyst
Li, NH₃

Deprotonation and reaction with alkyl halide (sections 6.9-6.10)
R-CC-H ---> R-CC-R'
1. NaNH₂; 2. R'-X

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)

Conversion to alkyl halide (sections 12.1, 12.3, Experiment 6)
R₃C-OH ---> R₃C-X

HX in ether (X = Cl, Br, I, usually 3^o alcohols)
SOCl₂ in pyridine (X = Cl, 1^o or 2^o alcohols)
PBr₃ or PCl₃ in pyridine (X = Br, 1^o or 2^o alcohols)

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

Conversion to ether (Williamson synthesis) (section 11.9)
R-OH ---> R-O-R'

1. NaH, THF (deprotonation of alcohol to give R-O^-)
2. R'-X (substitution of X^- with R-O^-)

Reactions of Carbonyls

Reduction of carbonyl (18.4, 20.1)

R-C(=O)-R' ---> R-CH(OH)-R'

R-C(=O)-R' ---> R"RC(OH)-R'
1. NaBH₄, ethanol; 2. H₃O⁺ (aldehyde or ketone)
H₂, Raney Ni (aldehyde or ketone)

R"-MgBr, H₃O⁺ (Grignard reaction)

Reactions of Carboxyls

Reduction to alcohols (section 20.1)
R-C(=O)-O-R' ---> RCH₂OH + HO-R'
R-C(=O)-O-R' ---> R"₂RC-OH + HO-R'

1. LiAlH₄; 2. H₃O⁺ (carboxylic acid or ester)
R"-MgBr, H₃O⁺ (Grignard reaction, happens twice)

Reactions of Ethers

Cleavage of ethers (section 12.6)
R-O-R' ---> R-OH + R'-X
H-X in H₂O (X = Br, I)

Last updated, October 24, 2005
Page maintained by Craig MacKinnon

From alkanes (Section 9.2) C_nH_2n+2 ---> C_nH_(2n+2)-yX_y	X₂, hf (X = Cl, Br) [NOTE: hf = light]
Addition of X₂ to alkenes and alkynes (sections 4.7, 6.5, Experiment 5) R₂C=CR₂ ---> XR₂C-CR₂X	X₂ in CH₂Cl₂ (X = Cl, Br)
Addition of HX to alkene and alkyne, Markovnikov (sections 4.1, 6.5) HRC=CR₂ ---> H₂RC-CR₂X	HX in ether (X = Cl, Br) KI in H₃PO₄ (X = I)
Addition of HX to alkene, anti-Markovnikov (section 4.10) HRC=CR₂ ---> HXRC-CR₂H	HBr with peroxide
Halohydrin reaction (section 4.7) R₂C=CR₂ ---> (OR')R₂C-CR₂X	X₂ (X = Cl, Br) in water (R' = H) or an alcohol (R' = alkyl)
Allylic bromination (section 9.5) R₂C=CR-CH₂-R ---> R₂C=CR-CHBr-R	NBS with peroxide
Conversion from alcohol (sections 12.1, 12.3, Experiment 6) R₃C-OH ---> R₃C-X	HX in ether (X = Cl, Br, I, usually 3^o alcohols) SOCl₂ in pyridine (X = Cl, 1^o or 2^o alcohols) PBr₃ in ether (X = Br, 1^o or 2^o alcohols)
Cleavage of ethers (12.6) R-O-R' ---> R-OH + R'-X	H-X in H₂O (X = Br, I)

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

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)	. . 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
Cleavage of ethers (12.6) R-O-R' ---> R-OH + R'-X	H-X in H₂O (X = Br, I)
Reduction of carbonyl (18.4, 20.1) R-C(=O)-R' ---> R-CH(OH)-R' R-C(=O)-R' ---> R"RC(OH)-R'	. . 1. NaBH₄, ethanol; 2. H₃O⁺ (aldehyde or ketone) H₂, Raney Ni (aldehyde or ketone) R"-MgBr, H₃O⁺ (Grignard reaction)
From carboxyl (20.1) R-C(=O)-O-R' ---> RCH₂OH + HO-R' R-C(=O)-O-R' ---> R"₂RC-OH + HO-R'	1. LiAlH₄; 2. H₃O⁺ (carboxylic acid or ester) R"-MgBr, H₃O⁺ (Grignard reaction, happens twice)

Deprotonated alcohol plus halide (Williamson synthesis) (section 11.9) R-OH ---> R-O-R'	1. NaH, THF; 2. R'-X
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 (ketone) 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^-

Reaction with deprotonated alkyne (sections 6.9-6.10) R-CC-H ---> R-CC:^- R-CC:^- + R'-X ---> R-CC-R'	NaNH₂ (or another strong base) substitution step (X = Br usually)
Formation of alkene (section 11.2) R₂HC-CR₂X ---> R₂C=CR₂	OH^- (aq) KOH in ethanol CH₃CH₂O^- in ethanol

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 in ether (X = Cl, Br) KI in H₃PO₄ (X = I)
Allylic bromination (section 9.5) R₂C=CR-CH₂-R ---> R₂C=CR-CHBr-R	NBS with peroxide
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, (CF₃CO₂)₂Hg; 2. NaBH₄ [Markovnikov] H+ (aq) [Markovnikov]
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 ---> RX₂C-CX₂R	X₂ in CH₂Cl₂ (X = Cl, Br)
Addition of HX - Markovnikov (section 6.5) RCCR ---> RH₂C-CX₂R	HX in ether (X = Cl, Br)
Hydrogenation (section 6.8) RCCR ---> RH₂C-CH₂R R-CC-R ---> RHC=CHR (cis) R-CC-R ---> RHC=CHR (trans)	H₂, Pd / C H₂, Lindlar catalyst Li, NH₃
Deprotonation and reaction with alkyl halide (sections 6.9-6.10) R-CC-H ---> R-CC-R'	1. NaNH₂; 2. R'-X

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)
Conversion to alkyl halide (sections 12.1, 12.3, Experiment 6) R₃C-OH ---> R₃C-X	HX in ether (X = Cl, Br, I, usually 3^o alcohols) SOCl₂ in pyridine (X = Cl, 1^o or 2^o alcohols) PBr₃ or PCl₃ in pyridine (X = Br, 1^o or 2^o alcohols)
Diol to carbonyl (section 20.7) (OH)R₂C-CR₂(OH) ---> R₂C=O + O=CR'₂	HIO₄ in H₂O
Conversion to ether (Williamson synthesis) (section 11.9) R-OH ---> R-O-R'	1. NaH, THF (deprotonation of alcohol to give R-O^-) 2. R'-X (substitution of X^- with R-O^-)