Embed Size (px)
Citation preview
1
Some Practice Problems for the Carbonyls Test 3 Draw the Products and Mechanisms for the following Reactions
1.
2.
3.
4.
5.
6.
O 1. PhMgBr
2. H3O+
H
O 1.
2. H3O+
MgBr
Ph PhAldehyde"enol"
OH OOH, H2O
Ph Ph
OH O
Ketone"enol"
H+, H2O
OH
OHO+ H2O
Hydrate
H+
OMe
OHO
Hemiacetal
+ MeOHH+
1. Protonate2. Add3. Deprotonate
1. Protonate2. Add3. Deprotonate
2
7.
8.
9.
10.
11.
12.
NHMe
OHO+ MeNH2
H+
Aminol
OH
NHMeNMe+ H2O H+
AminolImine
H
O
OH
OH
H
H2O, H
H
O
OMe
OH
H
MeOH, HOMe
OMe
H
MeOH, H
H
O MeOH, H
O
HO OH
H
1. Protonate2. Add3. Deprotonate
1. Protonate2. Add3. Deprotonate
Hydrate to carbonyl, water elimination, acid conditions: 1. Protonate 2. Lose water 3. Deprotonate
Acetal/ketal formation:Hemicetal/hemiketal formation: 1. Protonate 2. Add Alcohol 3. DeprotonateHemicetal to acetal subsitution: 1. Protonate 2. Eliminate water 3. Add alcohol 4. Deprotonate
Hemicetal formation: 1. Protonate 2. Add Alcohol 3. Deprotonate
Hemicetal to acetal subsitution: 1. Protonate 2. Eliminate water 3. Add alcohol 4. Deprotonate
3
13.
14.
15.
16.
17.
18.
H
OOH
H+
O
OH
H+
O
OHMeOH O
OMe
OMe
OH
H
HOH, HOMe
OMe
H
HOH, HH
O
H+
O
OMeH2O O
OH
H
OOH
H+
O
OH
H2O, HMeO PhOMe
Acetal/ketal to carbonyl, acetal/ketal hydrolysisAcetal/ketal to hemicetal/hemiketal substitution: 1. Protonate 2. Eliminate Alcohol 3. Add water 4. DeprotonateHemicetal/hemiketal to carbonyl elimination: 1. Protonate 2. Eliminate alcohol 3. Deprotonate
Hemiacetal/hemiketal to carbonyl, second phase of acetal/ketal hydrolysisHemicetal/hemiketal to carbonyl elimination: 1. Protonate 2. Eliminate alcohol 3. Deprotonate
Carbonyl to hemicetal/hemiketal addition, first stage in acetal/ketal formation: 1. Protonate 2. Add alcohol 3. Deprotonate
Hemicetal/hemiketal to acetal/ketal substituion, second stage in acetal/ketal formation: 1. Protonate 2. Lose water,3. Add alcohol 4. Deprotonate
Hemicetal to carbonyl 1. Protonate 2. Lose alcohol 3. Deprotonate
Acetal to Hemiacetal, substitution1. Protonate 2. Lose alcohol 3. Add water 4. Deprotonate
Acetal to Hemiacetal, substitution, phase 1 in acetal hydrolysis1. Protonate 2. Lose alcohol 3. Add water 4. Deprotonate
4
19.
20.
21.
22.
23.
24.
H2O, HOO
Ph H
O
aminolPhase 1:Aminol Formation(an addition reaction)
Phase 2:Aminol to Imine(an elimination reaction)
H2NMe, HPh NHMe
OH
H
- H2O, H
Ph H
NMe
Ph H
O+ H2NNH2
H
H
ONH2
H+
HN
OH
H+
HN
OH
N
Ph H
NMe
aminolPhase 1:Aminol Formation(an addition reaction)
Phase 2:Aminol to Imine(an elimination reaction)
H2O, HPh OH
NHMe
H
- MeNH2, H
Ph H
O
Imine to carbonyl, imine hydrolysisImine to aminol: 1. Protonate 2. Add water 3. DeprotonateAminol to carbonyl: 1. Protonate 2. Eliminate nitrogen 3. Deprotonate
Aminol to Imine, last stage in imine formation1. Protonate2. Lose water3. Deprotonate
Carbonyl to Aminol, first stage in imine formation1. Protonate2. Add nitrogen3. Deprotonate
Carbonyl to imine formationCarbonyl to aminol: 1. Protonate 2. Add amine 3. DeprotonateAminol to imine: 1. Protonate 2. Eliminate water 3. Deprotonate
Acetal/ketal to carbonyl, acetal/ketal hydrolysisAcetal/ketal to hemicetal/hemiketal substitution: 1. Protonate 2. Eliminate Alcohol 3. Add water 4. DeprotonateHemicetal/hemiketal to carbonyl elimination: 1. Protonate 2. Eliminate alcohol 3. Deprotonate
5
25.
26.
27.
28.
29.
30.
H+
N H2O HN
OH
H
ONH2
H+
HN
OH
Ph
O 2 Br2, 2NaOH
H2O
O 3 Cl2, 2NaOH
H2O
O1. LDA
2. Br
1. LDA
2.OEt
O
Br
R-X electrophile produces alpha-alkyl product1. Deprotonate2. Alkylate
R-X electrophile produces alpha-alkyl product1. Deprotonate2. Alkylate
X-X electrophile produces alpha-halo products, often with multiple halogens1. Deprotonate2. Halogenate3. Repeat until all alpha-H's are replaced.
Imine to Aminol, first step in imine hydrolysis1. Protonate2. Add water3. Deprotonate
IAminol to carbonyl, final step in imine hydrolysis1. Protonate2. Eliminate nitrogen 3. Deprotonate
6
31.
32.
33.
34.
35.
36.
1. NaOEt
2.EtO OEt
O O
Br
1. NaOEt2.
3. NaOEt4. BrCH2CH=CH2
EtO OEt
O O Br
O OH+
NaOMe OO
H
H
O NaOH, H2O
cold H
OOH NaOH, H2O
warmup H
OPh
Ph Ph
PhPh
H
O NaOH, H2O
cold
NaOH, H2O
heatPh
H
O+
NaOEt
EtOH0ºC
O NaOEt
EtOHheat
Ph
Aldehyde electrophile produces beta-hydroxy carbonyl1. Deprotonate2. Add to aldehyde carbonyl3. Protonate
Aldehyde electrophile produces beta-hydroxy carbonyl1. Deprotonate2. Add to aldehyde carbonyl3. ProtonateAldol to enone:1. Deprotonate2. Eliminate hydroxy anion
R-X electrophile produces alpha-alkyl product1. Deprotonate2. Alkylate
To polyalkylate, deprotonate-alkylate again
7
37.
38.
39.
40.
41.
42.
NaOH
H2Ocold
H
O
O NaOH
H2Ohot
H
O O NaOCH3
HOCH3cold
NaOCH3
HOCH3hot
Ph OMe
O NaOCH3
HOCH3
OEt
O NaOEt
HOEt
MeO CH3 Ph
O
MeO
ONaOMe+
MeO
O
Ph
O
CH3
MeO
O
OMe
O 1. NaOCH3, HOCH3
2. H+, H2O, heat
2.
Ester electrophile produces beta-keto carbonyl1. Deprotonate2. Add to ester carbonyl3. Eliminate alkoxy anion
Ester electrophile produces beta-keto carbonyl1. Deprotonate2. Add to ester carbonyl3. Eliminate alkoxy anion
Ester electrophile produces beta-keto carbonyl1. Deprotonate2. Add to ester carbonyl3. Eliminate alkoxy anion
Aldehyde electrophile produces beta-hydroxy carbonyl1. Deprotonate2. Add to aldehyde carbonyl3. ProtonateAldol to enone:1. Deprotonate2. Eliminate hydroxy anion
8
43.
44.
NaOMe
MeOHOMe
O
Ph OMe
O+
NaOMe
MeOHOMe
OO+
Ester electrophile produces beta-keto carbonyl1. Deprotonate2. Add to ester carbonyl3. Eliminate alkoxy anion
Ester electrophile produces beta-keto carbonyl1. Deprotonate2. Add to ester carbonyl3. Eliminate alkoxy anion
