Carbonyl

Aldehydes and ketones.
Addition reactions Chapter 16
Outline 1. Structure and physical properties of carbonyl compounds 2. Nomenclature of aldehydes and ketones 3. Preparation of aldehydes and ketones 4. Nucleophilic addition to the carbonyl group 5. Reduction of aldehydes and ketones 6. Reactions of aldehydes and ketones with Grignard reagents 7. Acetals and their use in synthesis 8. Reaction of aldehydes and ketones with ammonia and its derivatives 9. Wittig reaction 10. Oxidation of aldehydes and ketones 11. Aldehydes and ketones as electrophiles
CH2 1.34 A H3 C H H 3C
O 1.21 A H
The carbonyl group (C=O bond) is shorter, stronger, and more polar, than the C=C bond CH2 H 3C CH3 H3 C O O CH3 R CH2 H Aldehydes (R is H) or ketones (R is not H) Reacts with bases Reacts with nucleophiles Reacts with acids
b.p. = -6.9 oC Q = 0.5D Unsoluble in water
b.p. = 56.5 oC Q = 2.7D Soluble in water
O CHO CHO
3-methylbutanal pentan-2-one 2-methylcyclohexanecarbaldehyde
Priority for citation as the principal group: aldehyde > ketone > -OH > -SH O OHC
4-oxopentanal
Alternative naming: O dimethyl ketone (acetone)
CH3C(O)- acetyl group
HC(O)- formyl group
PhC(O)- benzoyl group
3. Preparation of aldehydes and ketones

a. Oxidation of alcohols b. Friedel-Crafts acylation c. Hydration of alkynes d. Ozonolysis of alkynes e. Cleavage of glycols
OH H5IO6 O OH H H O
+
H CH3
4. Nucleophilic addition to the carbonyl group

O Nu R R1 O H R R1
-
OH Nu H
+
Nu R R1 NuO C
+
R
+
R1 O H
R1
R1
Activation of the carbonyl group
Aldehydes are more reactive, than ketones due to the steric reasons and a larger positive charge on the carbonyl carbon in aldehydes. Addition to C=O bonds is faster, than addition to C=C bonds due to the higher polarity of the C=O bond, but less favorable thermodynamically due to the stronger C=O bond vs. the C=C bond. Example: Cyanohydrin synthesis
5. Reduction of aldehydes and ketones

O NaBH4 R CH3OH R1 CH3 H O H R R1 H B H H
-
OH H R R1
O OH H R R1 CH3
O H B H
-
H This anion can reduce three more carbonyl groups
The carbonyl group can be reduced by catalytic hydrogenation, but it is less reactive, than the C=C bond
OH H2, Ni Heat, pressure H O H2, Pd/C H O
Clemmenson Reduction
O R1 R R1
Cannizzaro Reaction
Zn/Hg, HCl
Crossed Cannizzaro Reaction

O H O OH-, H2O H OH O
6. Reaction of aldehydes and ketones with the Gringard Reagent

O H H+ R2 Mg R1 Br O Mg Br R2 R R1 H +, H 2 O
+
OH R2 R R1
Depending on R, R1, and R2, the reaction can produce primary, secondary or tertiary alcohols. R-Li is often used instead of R-MgBr. Example:
O 1. CH3(CH2)3Li H3 C CH3 2. H+, H2O H3C 80% OH (CH2)3CH3 CH3
7. Acetals and their use in synthesis

O R2OH, H or OH R R1
+ -
OH OR2 R R2OH, H+
OR2 OR2
R1 R R acetal 1 hemiacetal Stable at neutral conditions Stable at neutral and alkaline conditions
OH
HO
R2
OH O
H
+
R O H
+
R1
R1
R2 OH
H R R1 O
-
OR2 O R2 R R1 hemiacetal
O R2 R
OR2 R1
H O
+
H OR2 OR2 OR2 R acetal R1 OR2 H O OR2 C R

+ +
OH OR2 R R1 hemiacetal
R1
R2
H O R2
R1
R1
Examples:
O CH3 CH3OH, H+
OCH3 OCH3 CH3 Methyl phenyl ketone dimethylacetal
O HOCH2CH2OH, H
+
Cyclohexanone ethyleneacetal
Acetals and hemiacetals can be formed intramolecularly

H H HO H H O OH H OH OH OH Open form of glucose OH OH H H OH H HO OH H OH E-glucose
Due to the stability of acetals toward bases and nucleophiles, they are often used as protecting groups
COCH3 ? COCH3
Br HOCH2CH2OH, H+ H3C O O Br Mg Br Mg O H3 C HO O 1. CH2O 2. H+, H2O
Aldehydes may undergo condensation in the presence of acids

O CH3 H+ H 3C O O O CH3
H3 C H
H+
CH2 HO O
H H
8. Reactions of aldehydes and ketones with ammonia and its derivatives

. . H C . R3 H if R1 = H . . H C N R3 . . if R2 = H . -H2O H C . carbinolamine OH R2 N R3 . enamine -H2O . . C R2 N R3 . O R1 . . C O
-
R2
R1 N
+
R2 R3
imine, if R3 starts from H or C oxime, if R3 = OH hydrazone, if R3 = NH2
Examples:
O H NH2 Heat H N
-H2O NH2 HN
H 3C Heat -H2O H3C N O2N NH NO2
NO2
+
H3C CH3 NO2
H 3C
H3C NH CH3
+
H 3C H
H+ -H2O
H3C
H3C O KOH H2N NH2 H2N N Heat -N2
82%82%
O P
Ph Ph Ph CH2
O Ph
Ph
H 2C
Ph Ph
P Ph
Ph
NaH Ph H3C P Br
+
Ph Br Ph SN2 CH3 P Ph Ph
Ph
This reaction is a common method for conversion of carbonyl compounds to alkenes
O R H
KMnO4, H2O, H+ or K2Cr2O7, H2O, H+ R
OH
O Ag2O, H2O, NH3 R H R
+
O
-
Ag
R R O R1 Heat R1
+
KMnO4, H2O, H
+
R1 OH
OH
+
OH
R OH
Bayer-Villiger oxidation
HO O H+ H
HO
HO CH2O, H+ OH
OH H HO H resin OH OH
+ +
OH
H3 C H3 C
CH3 O
+
H OH KOH, heat H
H3C
CH3 CH3
H3C
CH CH3 3 H3C CH3 CH3
H3C H3C H3C OH OH OH HO
OH
HO HO HO
CH3 H3C H3C CH3 H H3C 3C CH3 H3C H3C CH3 H3C CH3
O NH
+
R H , heat
+
NH
HN

Carbonyl

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Aldehydes and ketones.

Addition reactions Chapter 16

b.p. = -6.9 oC Q = 0.5D Unsoluble in water

b.p. = 56.5 oC Q = 2.7D Soluble in water

Alternative naming: O dimethyl ketone (acetone)

CH3C(O)- acetyl group

HC(O)- formyl group

PhC(O)- benzoyl group

3. Preparation of aldehydes and ketones

4. Nucleophilic addition to the carbonyl group

Activation of the carbonyl group

5. Reduction of aldehydes and ketones

H This anion can reduce three more carbonyl groups

Crossed Cannizzaro Reaction

6. Reaction of aldehydes and ketones with the Gringard Reagent

7. Acetals and their use in synthesis

H OR2 OR2 OR2 R acetal R1 OR2 H O OR2 C R

OCH3 OCH3 CH3 Methyl phenyl ketone dimethylacetal

Acetals and hemiacetals can be formed intramolecularly

Br HOCH2CH2OH, H+ H3C O O Br Mg Br Mg O H3 C HO O 1. CH2O 2. H+, H2O

Aldehydes may undergo condensation in the presence of acids

8. Reactions of aldehydes and ketones with ammonia and its derivatives

imine, if R3 starts from H or C oxime, if R3 = OH hydrazone, if R3 = NH2

H 3C Heat -H2O H3C N O2N NH NO2

H3C O KOH H2N NH2 H2N N Heat -N2

This reaction is a common method for conversion of carbonyl compounds to alkenes

KMnO4, H2O, H+ or K2Cr2O7, H2O, H+ R

O Ag2O, H2O, NH3 R H R

CH CH3 3 H3C CH3 CH3

H3C H3C H3C OH OH OH HO

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