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. New reactions since Midterm #2 are designated with coloured text.

Synthesis of Functional Groups

Synthesis of Alkanes

From alkenes and alkynes (sections 7.7, 8.6) R-CC-R ---> RH₂C-CH₂R	H₂, Pd/C
From carbonyls (section 19.10) R-C(=O)-R' ---> C-CH₂-R' (both aldehydes and ketones)	H₂NNH₂, KOH

Synthesis of Alkyl Halides

From alkanes (Sections 5.3, 10.3)
C_nH_2n+2 ---> C_nH_(2n+2)-yX_y
X₂, hn (X = Cl, Br)

Addition of X₂ to alkenes and alkynes (sections 7.2, 8.4, Experiment 2)
R₂C=CR₂ ---> XR₂C-CR₂X

X₂ in CH₂Cl₂ (X = Cl, Br)

Addition of HX to alkene and alkyne - Markovnikov (sections 6.8, 6.9, 8.4)
HRC=CR₂ ---> H₂RC-CR₂X
HX in ether (X = Cl, Br)
KI in H₃PO₄ (X = I)

Halohydrin reaction (section 7.3)
R₂C=CR₂ ---> (OR')R₂C-CR₂X
X₂ (X = Cl, Br) in water (R' = H) or an alcohol (R' = alkyl)

Allylic bromination (sections 10.5, 10.6)
R₂C=CR-CH₂-R ---> R₂C=CR-CHBr-R
NBS in CCl₄

Conversion from alcohol (section 10.7, Experiments 3 and 4)
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 (18.5)
R-O-R' ---> R-OH + R'-X
H-X in H₂O (X = Br, I)

Synthesis of Alkenes

Dehydration of alcohol (section 17.7, Experiment 1)
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 7.1)
R₂HC-CR₂X ---> R₂C=CR₂
OH^- (aq)
KOH in ethanol
CH₃CH₂O^- in ethanol

From alkyne (section 8.6)
R-CC-R ---> RHC=CHR (cis)
R-CC-R ---> RHC=CHR (trans)
H₂, Lindlar catalyst
Li, NH₃

From carbonyl (Wittig Reaction) (section 19.12)
R₂C=O ---> R₂C=CHR'
Ph₃P=CHR', THF

Synthesis of Alcohols

From alkenes (sections 7.3, 7.5, 7.8)
R₂C=CR₂ ---> (OH)R₂C-CR₂X
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.
1. OsO₄; 2. NaHSO₃, H₂O

From carbonyls: aldehydes and ketones (17.5, 17.6, 19.7)
R₂C=O --->   R₂HC-OH

R₂C=O --->   R₂R'C-OH
R₂C=O ---> R₂C(OH)₂
.
.
1. NaBH₄, ethanol; 2. H₃O⁺
1. LiAlH₄, ether; 2. H₃O⁺
1. R'MgBr, ether; 2. H₃O⁺
H⁺, H₂O
OH^-, H₂O

From carboxyl: esters and acids (sections 17.5, 17.6)
RC(=O)-O-R" --->   R₂HC-OH + HO-R"
RC(=O)-O-R" --->   R'₂RC-OH + HO-R"
RC(=O)-O-R" --->   RHC=O + HO-R"
1. LiAlH₄, ether; 2. H₃O⁺
1. R'MgBr, ether; 2. H₃O⁺      (esters only)
1. DIBAH, toluene; 2. H₃O⁺      (esters only)

Cleavage of ethers (18.5)
R-O-R' ---> R-OH + R'-X
H-X in H₂O (X = Br, I)

Synthesis of Ethers

Alcohol plus halide (Williamson synthesis) (section 18.3)
R-O^- + R'-X ---> R-O-R' + X^-
(X = Cl, Br, I; R'-X should be 1^o)

Alkoxymercuration - Markovnikov (section 18.4)
RHC=CR2 ---> RH2C-CR2-O-R'
1. R'-OH, (CF₃CO₂)₂Hg; 2. NaBH₄

Halohydrin (section 7.3)
R₂C=CR₂ ---> (OR')R₂C-CR₂X
X₂ (X = Cl, Br) in alcohol (R'-OH)

Synthesis of acetal (section 19.11)
R₂C=O ---> R₂C(OR')₂

2 R'-OH, acid catalyst
(NOTE: know what happens if you use a diol!)

Synthesis of Carbonyls

From alkene (section 7.8)
R₂C=CR'₂ ---> R₂C=O + O=CR'₂

1. O₃; 2. Zn / H₃O⁺
KMnO₄, H₃O⁺ (continues to acid if aldehyde initially made)

From 1,2-diol (section 7.8)
(OH)R₂C-CR₂(OH) ---> R₂C=O + O=CR'₂
HIO₄ in H₂O

Oxidation of alcohol with PCC (section 17.8)
RR'HC-OH ---> RR'C=O

(primary alcohol gives aldehyde, secondary gives ketone)
PCC in CH₂Cl₂

secondary alcohol oxidation with Cr⁶⁺(section 17.8)
R₂HC-OH ---> R₂C=O
CrO₃ in acidic (H⁺) acetone

primary alcohol oxidation with Cr⁶⁺ (section 17.8)
RH₂C-OH ---> RCOOH
CrO₃ in acidic (H⁺) acetone

from ester (aldehyde created) (section 17.6)
RC(=O)-O-R" ---> RHC=O + HO-R"
1. DIBAH, toluene; 2. H₃O⁺ (esters only)

Synthesis of Carboxyls

From alkene (section 7.8)
R₂C=CHR' ---> R₂C=O + R'COOH
KMnO₄, H₃O⁺

Acid from aldehyde (section 19.3)
R-C(=O)-H ---> R-COOH

CrO₃, H⁺
Ag⁺, NH₄OH (= Ag⁺, NH₃, ethanol) (Tollen's reagent)

Reactions of Functional Groups

Reactions of Alkanes

Formation of alkyl halides (sections 5.3, 10.3)

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

X₂, hv (X = Cl, Br)

Reactions of Alkyl Halides

Reaction with deprotonated alkyne (section 8.9) - see also, Grignard reactions
R-X + R'CC:^- Na⁺ ---> R'CC-R

(X = Br usually)

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 7.2, Experiment 2)
R₂C=CR₂ ---> XR₂C-CR₂X
X₂ in CH₂Cl₂ (X = Cl, Br)

Addition of HX - Markovnikov (sections 6.8, 6.9)
HRC=CR₂ ---> H₂RC-CR₂X

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

Allylic bromination (sections 10.5, 10.6)
R₂C=CR-CH₂-R ---> R₂C=CR-CHBr-R
NBS in CCl₄

Synthesis of alcohols (or ethers) (sections 7.3, 7.5, 7.8, 18.4)
R₂C=CR₂ ---> (OR')R₂C-CR₂X
R₂C=CR₂ ---> (OH)R₂C-CR₂H
R₂C=CR₂ ---> (OH)R₂C-CR₂(OH)
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

Synthesis of carbonyl (section 7.8)
R₂C=CR'₂ ---> R₂C=O + O=CR'₂

1. O₃; 2. Zn / H₃O⁺
KMnO₄, H₃O⁺ (continues to acid if aldehyde initially made)

Reactions of Alkynes

Addition of X₂ (section 8.4)
RCCR ---> RX₂C-CX₂R
X₂ in CH₂Cl₂ (X = Cl, Br)

Addition of HX - Markovnikov (section 8.4)
RCCR ---> RH₂C-CX₂R
HX in ether (X = Cl, Br)

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

Deprotonation and reactions with alkyl halide (section 8.9)
R-CC-H ---> R-CC-R'
1. NaNH₂; 2. R'-X

Reactions of Alcohols

Dehydration (section 17.7, Experiment 1)
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 (section 10.7, Experiments 3 & 4)
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)

Diol to carbonyl (section 7.8)
(OH)R₂C-CR₂(OH) ---> R₂C=O + O=CR'₂
HIO₄ in H₂O

Conversion to ether (Williamson synthesis) (section 18.3)
R-OH ---> R-O-R'
1. NaH, THF; 2. R'-X

Oxidation of alcohol with PCC (section 17.8)
R₂HC-OH ---> R₂C=O

(primary alcohol gives aldehyde, secondary gives ketone)
PCC in CH₂Cl₂

secondary alcohol oxidation with Cr⁶⁺ (section 17.8)
R₂HC-OH ---> R₂C=O

CrO₃ in acidic (H⁺) acetone

primary alcohol oxidation with Cr⁶⁺ (section 17.8)
RH₂C-OH ---> RCOOH

CrO₃ in acidic (H⁺) acetone

Reactions of Carbonyls

Reduction to alcohols (sections s 17.5, 17.6)
R₂C=O --->   R₂HC-OH

R₂C=O --->   R₂R'C-OH
.
.
1. NaBH₄, ethanol; 2. H₃O⁺
1. LiAlH₄, ether; 2. H₃O⁺
1. R'MgBr, ether; 2. H₃O⁺

Acid from aldehyde (section 19.3)
R-C(=O)-H ---> R-COOH

CrO₃, H⁺
Ag⁺, NH₄OH (= Ag⁺, NH₃, ethanol)   (Tollen's reagent)

From carbonyls (section 19.10)
R-C(=O)-R' ---> C-CH₂-R'
(both aldehydes and ketones)
H₂NNH₂, KOH

Addition of H₂O or HCN (sections 19.6, 19.7)
R₂C=O ---> R₂C(OH)₂

R₂C=O ---> R₂HC-CN
H⁺, H₂O
OH^-, H₂O
HCN

Synthesis of acetal (section 19.11)
R₂C=O ---> R₂C(OR')₂

2 R'-OH, acid catalyst
(NOTE: know what happens if you use a diol!)

Conversion to alkene (Wittig Reaction) (section 19.12)
R₂C=O ---> R₂C=CHR'
Ph₃P=CHR', THF

Reactions of Carboxyls

Reduction to alcohols (sections 17.5, 17.6)
RC(=O)-O-R" --->   R₂HC-OH + HO-R"
RC(=O)-O-R" --->   R'₂RC-OH + HO-R"
RC(=O)-O-R" --->   RHC=O + HO-R"
1. LiAlH₄, ether; 2. H₃O⁺
1. R'MgBr, ether; 2. H₃O⁺      (esters only)
1. DIBAH, toluene; 2. H₃O⁺      (esters only)

Reactions of Ethers

Cleavage of ethers (section 18.5)
R-O-R' ---> R-OH + R'-X
H-X in H₂O (X = Br, I)

Last updated, November 26, 2003
Page maintained by Craig MacKinnon

From alkanes (Sections 5.3, 10.3) C_nH_2n+2 ---> C_nH_(2n+2)-yX_y	X₂, hn (X = Cl, Br)
Addition of X₂ to alkenes and alkynes (sections 7.2, 8.4, Experiment 2) R₂C=CR₂ ---> XR₂C-CR₂X	X₂ in CH₂Cl₂ (X = Cl, Br)
Addition of HX to alkene and alkyne - Markovnikov (sections 6.8, 6.9, 8.4) HRC=CR₂ ---> H₂RC-CR₂X	HX in ether (X = Cl, Br) KI in H₃PO₄ (X = I)
Halohydrin reaction (section 7.3) R₂C=CR₂ ---> (OR')R₂C-CR₂X	X₂ (X = Cl, Br) in water (R' = H) or an alcohol (R' = alkyl)
Allylic bromination (sections 10.5, 10.6) R₂C=CR-CH₂-R ---> R₂C=CR-CHBr-R	NBS in CCl₄
Conversion from alcohol (section 10.7, Experiments 3 and 4) 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 (18.5) R-O-R' ---> R-OH + R'-X	H-X in H₂O (X = Br, I)

Dehydration of alcohol (section 17.7, Experiment 1) 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 7.1) R₂HC-CR₂X ---> R₂C=CR₂	OH^- (aq) KOH in ethanol CH₃CH₂O^- in ethanol
From alkyne (section 8.6) R-CC-R ---> RHC=CHR (cis) R-CC-R ---> RHC=CHR (trans)	H₂, Lindlar catalyst Li, NH₃
From carbonyl (Wittig Reaction) (section 19.12) R₂C=O ---> R₂C=CHR'	Ph₃P=CHR', THF

From alkenes (sections 7.3, 7.5, 7.8) R₂C=CR₂ ---> (OH)R₂C-CR₂X 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. 1. OsO₄; 2. NaHSO₃, H₂O
From carbonyls: aldehydes and ketones (17.5, 17.6, 19.7) R₂C=O ---> R₂HC-OH R₂C=O ---> R₂R'C-OH R₂C=O ---> R₂C(OH)₂	. . 1. NaBH₄, ethanol; 2. H₃O⁺ 1. LiAlH₄, ether; 2. H₃O⁺ 1. R'MgBr, ether; 2. H₃O⁺ H⁺, H₂O OH^-, H₂O
From carboxyl: esters and acids (sections 17.5, 17.6) RC(=O)-O-R" ---> R₂HC-OH + HO-R" RC(=O)-O-R" ---> R'₂RC-OH + HO-R" RC(=O)-O-R" ---> RHC=O + HO-R"	1. LiAlH₄, ether; 2. H₃O⁺ 1. R'MgBr, ether; 2. H₃O⁺ (esters only) 1. DIBAH, toluene; 2. H₃O⁺ (esters only)
Cleavage of ethers (18.5) R-O-R' ---> R-OH + R'-X	H-X in H₂O (X = Br, I)

Alcohol plus halide (Williamson synthesis) (section 18.3) R-O^- + R'-X ---> R-O-R' + X^-	(X = Cl, Br, I; R'-X should be 1^o)
Alkoxymercuration - Markovnikov (section 18.4) RHC=CR2 ---> RH2C-CR2-O-R'	1. R'-OH, (CF₃CO₂)₂Hg; 2. NaBH₄
Halohydrin (section 7.3) R₂C=CR₂ ---> (OR')R₂C-CR₂X	X₂ (X = Cl, Br) in alcohol (R'-OH)
Synthesis of acetal (section 19.11) R₂C=O ---> R₂C(OR')₂	2 R'-OH, acid catalyst (NOTE: know what happens if you use a diol!)

From alkene (section 7.8) R₂C=CR'₂ ---> R₂C=O + O=CR'₂	1. O₃; 2. Zn / H₃O⁺ KMnO₄, H₃O⁺ (continues to acid if aldehyde initially made)
From 1,2-diol (section 7.8) (OH)R₂C-CR₂(OH) ---> R₂C=O + O=CR'₂	HIO₄ in H₂O
Oxidation of alcohol with PCC (section 17.8) RR'HC-OH ---> RR'C=O (primary alcohol gives aldehyde, secondary gives ketone)	PCC in CH₂Cl₂
secondary alcohol oxidation with Cr⁶⁺(section 17.8) R₂HC-OH ---> R₂C=O	CrO₃ in acidic (H⁺) acetone
primary alcohol oxidation with Cr⁶⁺ (section 17.8) RH₂C-OH ---> RCOOH	CrO₃ in acidic (H⁺) acetone
from ester (aldehyde created) (section 17.6) RC(=O)-O-R" ---> RHC=O + HO-R"	1. DIBAH, toluene; 2. H₃O⁺ (esters only)

From alkene (section 7.8) R₂C=CHR' ---> R₂C=O + R'COOH	KMnO₄, H₃O⁺
Acid from aldehyde (section 19.3) R-C(=O)-H ---> R-COOH	CrO₃, H⁺ Ag⁺, NH₄OH (= Ag⁺, NH₃, ethanol) (Tollen's reagent)

Reaction with deprotonated alkyne (section 8.9) - see also, Grignard reactions R-X + R'CC:^- Na⁺ ---> R'CC-R	(X = Br usually)
Formation of alkene (section 7.1) R₂HC-CR₂X ---> R₂C=CR₂	OH^- (aq) KOH in ethanol CH₃CH₂O^- in ethanol

Addition of X₂ (section 7.2, Experiment 2) R₂C=CR₂ ---> XR₂C-CR₂X	X₂ in CH₂Cl₂ (X = Cl, Br)
Addition of HX - Markovnikov (sections 6.8, 6.9) HRC=CR₂ ---> H₂RC-CR₂X	HX in ether (X = Cl, Br) KI in H₃PO₄ (X = I)
Allylic bromination (sections 10.5, 10.6) R₂C=CR-CH₂-R ---> R₂C=CR-CHBr-R	NBS in CCl₄
Synthesis of alcohols (or ethers) (sections 7.3, 7.5, 7.8, 18.4) R₂C=CR₂ ---> (OR')R₂C-CR₂X R₂C=CR₂ ---> (OH)R₂C-CR₂H R₂C=CR₂ ---> (OH)R₂C-CR₂(OH) 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
Synthesis of carbonyl (section 7.8) R₂C=CR'₂ ---> R₂C=O + O=CR'₂	1. O₃; 2. Zn / H₃O⁺ KMnO₄, H₃O⁺ (continues to acid if aldehyde initially made)

Addition of X₂ (section 8.4) RCCR ---> RX₂C-CX₂R	X₂ in CH₂Cl₂ (X = Cl, Br)
Addition of HX - Markovnikov (section 8.4) RCCR ---> RH₂C-CX₂R	HX in ether (X = Cl, Br)
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
Deprotonation and reactions with alkyl halide (section 8.9) R-CC-H ---> R-CC-R'	1. NaNH₂; 2. R'-X

Dehydration (section 17.7, Experiment 1) 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 (section 10.7, Experiments 3 & 4) 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)
Diol to carbonyl (section 7.8) (OH)R₂C-CR₂(OH) ---> R₂C=O + O=CR'₂	HIO₄ in H₂O
Conversion to ether (Williamson synthesis) (section 18.3) R-OH ---> R-O-R'	1. NaH, THF; 2. R'-X
Oxidation of alcohol with PCC (section 17.8) R₂HC-OH ---> R₂C=O (primary alcohol gives aldehyde, secondary gives ketone)	PCC in CH₂Cl₂
secondary alcohol oxidation with Cr⁶⁺ (section 17.8) R₂HC-OH ---> R₂C=O	CrO₃ in acidic (H⁺) acetone
primary alcohol oxidation with Cr⁶⁺ (section 17.8) RH₂C-OH ---> RCOOH	CrO₃ in acidic (H⁺) acetone

Reduction to alcohols (sections s 17.5, 17.6) R₂C=O ---> R₂HC-OH R₂C=O ---> R₂R'C-OH	. . 1. NaBH₄, ethanol; 2. H₃O⁺ 1. LiAlH₄, ether; 2. H₃O⁺ 1. R'MgBr, ether; 2. H₃O⁺
Acid from aldehyde (section 19.3) R-C(=O)-H ---> R-COOH	CrO₃, H⁺ Ag⁺, NH₄OH (= Ag⁺, NH₃, ethanol) (Tollen's reagent)
From carbonyls (section 19.10) R-C(=O)-R' ---> C-CH₂-R' (both aldehydes and ketones)	H₂NNH₂, KOH
Addition of H₂O or HCN (sections 19.6, 19.7) R₂C=O ---> R₂C(OH)₂ R₂C=O ---> R₂HC-CN	H⁺, H₂O OH^-, H₂O HCN
Synthesis of acetal (section 19.11) R₂C=O ---> R₂C(OR')₂	2 R'-OH, acid catalyst (NOTE: know what happens if you use a diol!)
Conversion to alkene (Wittig Reaction) (section 19.12) R₂C=O ---> R₂C=CHR'	Ph₃P=CHR', THF