ADDITION REACTION OF CARBONYL

Elgaliza Karina Devi (4301409046) Yohanna Indah S. (4301409062) Ryandono Adhi K. (4301409069)

Reaksi-reaksi Aldehid dan Keton

Reaksi Adisi
+ Karbonil bersifat polar sehingga dapat diserang oleh Nukleofilik (Nu:-) atau elektrofilik (E+)
O O C R R

Nu
R

E
C R

Reaksi Umum

Faktor-faktor yang mempengaruhi reaktivitas aldehid / keton :

Muatan (+) pada karbon karbonil Faktor stearik Naiknya Reaktivitas

Nucleophilic Addition Reactions In general, aldehydes are more reactive towards nucleophilic addition reactions than ketones inductive effect steric effect

Nucleophilic Addition Reactions

1. The inductive effect Alkyl groups are electron-releasing groups

The carbonyl carbon atom is less electron-deficient in ketones less susceptible to nucleophilic attack

Nucleophilic Addition Reactions

2. The steric effect

In aldehydes, one group being attached to the carbonyl carbon atom is a small hydrogen atom the carbonyl carbon atom of aldehydes is less crowded more susceptible to the attack of nucleophiles

2. The steric effect

In ketones,

the two alkyl or aryl substituents at the

carbonyl carbon atom cause a greater steric hindrance to the nucleophiles from approaching the carbonyl carbon atom

e.g. in pentan-3-one,

Nucleophilic Addition Reactions

The general order of decreasing reactivity of carbonyl compounds towards nucleophilic addition reactions is:

where R and R represent alkyl groups, and Ar and Ar represent aryl groups

Adisi dengan Air

ex :

Adisi Alkohol

Mekanism formation of acetal from hemiacetal

Adisi Nukleofolik HCN: Sianohidrin

The addition of HCN itself to the carbonyl group of aldehydes and ketones takes place very slowly

HCN is a poor nucleophile

Cyanide ion is able to attack the carbonyl carbon atom more rapidly than HCN itself

Cyanide ion is a stronger nucleophile

Produk Sianohidrin
Sintesis asam-asam amino

Contoh Mendelonitril (kelabang)

Mekanisme Adisi Nukleofolik HCN: Sianohidrin

O HCN R R' OH R CN R' suatu sianohidrin

Dengan HCN murni reaksi sangat lambat Dengan penambahan sedikit basa atau ion sianida reaksi cepat

O C H N

CN HCN H

HO

CN H C N

Benzaldehida

Mandelonitril (88%) (suatu sianohidrin)

15

Adisi Nukleofilik Pereaksi Grignard: Pembentukan Alkohol

Pereaksi Grignard adalah nukleofil karena ikatan karbon-magnesium sangat terpolarkan dengan kerapatan elektron yang tinggi pada karbon

MgX

O R

MgX

H3O+

OH HOMgX R Alkohol

Karbonil

Intermediat tetrahedral

#3 synthesis of alcohols. Used to build larger molecules from smaller organic compounds.

RMgX +

H H formaldehyde O C

O C

RCH2OMgX

H+

RCH2OH 1o alcohol + 1 C

RMgX +

R'CHOMgX R

H+

R'CHOH

R' H other aldehydes

R 2o alcohol + X C's

O R-MgX + C R' R" ketone

R' R-COMgX R"

H+

R' R-COH R" 3o alcohol + X C's H+

O RMgX + H2C CH2 ethylene oxide

RCH2CH2OMgX

RCH2CH2OH 1o alcohol + 2 C's

Planning a Grignard synthesis of an alcohol:

a) b) The alcohol carbon comes from the carbonyl compound. The new carbon-carbon bond is to the alcohol carbon.

O C

+ RMgX

OH C R

New carbon-carbon bond