Sintesis Senyawa Organik

Aldehida dan Keton

Nama Kelompok :

1. Berta Yuda Sisilia P. (131810301051)2. Viki Amalia (131810301053)3. Laiqotul Lutfiyah (131810301041)

Reaksi dan Sintesis

Aldehida

Keton

Reaksi Adisi Nukleofilik

1. Addition of hydride ( )

C

O

R H(R')C

OH

H

H(R')RNaBH4, CH3OH

or[1] LiAlH4; [2] H2O

H-

C

O

H3CH2C H

[1] LiAlH4; [2] H2OC

OH

H

HH3CH2C + Li+OH

-

Contoh:

2. Addition of Grignard Reagents ( )R-

C

OH

R''

H(R')RR'' mGx or R'' Li

or[2] H2O

C

O

R H(R')

C

O

H3CH2C HC

OH

HH3CH2C + Li+OH

-Li[1]

[2] H2O

Contoh :

3. Addition of cyanide ( )CN-

C

O

R H(R')

NaCN

HClC

OH

CN

H(R')R

C

O

CH3 H

NaCN

HClC

OH

CN

HCH3

Contoh:

4. Wittig ReactionC O

R

H(R')

+ CPh3P

R

(R')H

Contoh:

5. Addition of 1° amines

Contoh:

C O

R

H(R')

N

R

(R')H R''

R''NH2

mild acid

6. Addition of 2° amines

C O

R

H(R')

R2NH

mild acid

NR2

(R')H

C O

CH3

CH3mild acid

NH

CCH3 CH2

N + H2O

Contoh:

7. Addition of H2O – hidration

C

O

R H(R')

H2OH

+ or OH

-

C

OH

OH

H(R')R

C

O

CH3 CH3

H2OC

OH

OH

HH

Contoh:

8. Addition of alcohols

C

O

R H(R')

+ R''OH(2 equiv)

H+

C

OR''

H(R')R + OH2

OR''

C

O

H3CH2C H

CH3OH(2 equiv)

TsOH + OH2C

OCH3

HH3CH2C+

OCH3

Contoh:

9. Kondensasi Aldol

C

O

CH3 H

base

2C

OH

H

CH2CH3 C

O

H

chromic acid, permanganate, Ag+, etcH

O

R OH

O

R

CHO

+ Na2Cr2O7 / H2SO4

COOH

10. Oksidasi Aldehid

Contoh:

1. Oksidasi alkohol sekunder (2⁰) dengan reagen Cr

6+

C

OH

H

CH3CH3C

O

CH3 R'

base

2

CH3 C

H

OH

CH3

K2Cr2O7 C O

CH3

CH3

PCC

COOH

Sintesis Keton

Contoh:

2. Reaksi klorida asam dengan organometalik

C

O

CH3 HC

O

R R'

base

2

C

O

H3CH2C Cl

[1]CH3CuLi

[2] H2OC

O

H3CH2C CH3

Contoh:

3. Asilasi Friedel-Crafts

+ C

O

R Cl

acid chloride

AlCl3C

R

O

+ C

O

CH3 Cl

AlCl3C

CH3

O

Contoh:

4. Hidrasi Alkuna

R C C H

alkyne

H2O

H2SO4

HgSO4

C

O

R CH3

CH3 C C HH2O

H2SO4

HgSO4

C

O

CH3 CH3

Contoh:

C C

R'

R''

R

H

(1) O3

(2) (CH3)2SC O

R

H

+ CO

R''

R'

5. Ozonolisis Alkena

SS

H R

(1) BuLi

(2) 10 R'-X SS

R' R

H+, HgCl2

H2OC

O

R R'

thioacetal thioketalketone

6. Sintesis Keton dengan 1,3-Dithianes

R C OH

O LiOHR C O

-

O

Li+ R'-Li

R C O-

R'

O-

Li+

H3O+

R C OH

OH

R'

-H2OR C R'

O

asam karboksilat karboksilat litium dianion hidrat keton

7. Sintesis keton dari Asam Karboksilat

Sintesis

Aldehida CrO3

piridinaRCHO

Alkohol Primer Aldehida

1. Oksidasi Alkohol

1-heptanol Heptanal (84%)

Contoh :

CH3(CH2)5CH2OH + CrO3 . 2 N CH3(CH2)5CHO

RCH2OH

Alkohol PrimerRCHOAldehida

RCH2OH

CH2 OH

Cyclohexylmethanol

N+

H

CrO3Cl-

(PCC)

CH

O

Cyclohexanecarbaldehyde90%

C5H5NH+CrO3Cl

- (PCC)

2. Reduksi Klorida Asam

(1) LiAlH[OC(CH3)3]3

Contoh :

Klorida Asam

NO2

O2NCl

O

(2) H2O. H+

(1) LiAlH[OC(CH3)3]3 , -780

NO2

O2NH

O

C

O

R H(or Pd, BaSO4, S)

Aldehida

(2) H2O. H+

3. Gatterman-Koch Formylation

HCl + CO +

GAlCl3 , CuCl

G C

O

H

G = Hydrogen, an Activating group or halogen

benzaldehyde derivates

O2N

CCl

OContoh :

+AlCl3 , CuCl

CO, HCl

CH3

CHO

toluenep-methylbenzaldehyde (major)

(50%)

4. Hidrasi AlkunaHydroboration-Oxidation (anti Markovnikov Orientation)

R C C R(1) Sia2BH

(2) H2O2, NaOH

R

H

H

OH

CH2 C

O

HR

Enol (not isolated)Aldehyde

CC

H

Contoh :

ethynylcyclohexane

(1) Sia2BH

(2) H2O2, NaOH

CH2 C

O

H

cyclohexylethanal(65%)

5. Ozonilysis of Alkenes

C C

R

H

R'

R"

(1) O3

(2) (CH3)2SC O

R

H

++ O C

R'

R"

S(H3C)2 O

Contoh :

CH3(1) O3

(2) (CH3)2S

O

O

CH3

HI -methylcyclohcxene

6-oxoheptanal(65%)

6. 1,3 Dithianes

SS

HH

(1) BuLi

R-X(2) 10 SS

HRalkylation

1,3-dithiane thioacetal

H3O+, HgCl2

C

O

R H

Aldehida