Kimia Organik 2Semester Genap 2013

Enade P. Istyastono

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Aldehydes and KetonesAldehida dan Keton

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Aldehydes and Ketones

Page 276 - 304

Carbonyl Group: C=OGugus Karbonil: C=O

• The most important and widely occurring functional group in BOTH organic and biological chemistry.

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Carbonyl Group: C=OGugus Karbonil: C=O

• The most important and widely occurring functional group in BOTH organic and biological chemistry.

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Asam Etanoat - Asam AsetatEtanoic Acid - Acetic Acid

Carbonyl Group: C=OGugus Karbonil: C=O

• The most important and widely occurring functional group in BOTH organic and biological chemistry.

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Carbonyl Group: C=OGugus Karbonil: C=O

• The most important and widely occurring functional group in BOTH organic and biological chemistry.

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Carbonyl Group: C=OGugus Karbonil: C=O

• The most important and widely occurring functional group in BOTH organic and biological chemistry.

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Carbonyl Group: C=OGugus Karbonil: C=O

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Carbonyl Group: C=OGugus Karbonil: C=O

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Two Types of Carbonyl CompoundsDua Tipe Senyawa Karbonil

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Aldehida | Aldehyde

Keton | Ketone

Ester

Amida | Amide

Anhidrida asam | Acid anhydride

Asam karboksilat | Carboxylic acid

Klorida asam (!!!) | Acid chloride

Two Types of Carbonyl CompoundsDua Tipe Senyawa Karbonil

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Aldehida | Aldehyde

Keton | Ketone

Ester

Amida | Amide

Anhidrida asam | Acid anhydride

Asam karboksilat | Carboxylic acid

Klorida asam (!!!) | Acid chloride

Kenapa dibedakan?Clue => LG!!!

Two Types of Carbonyl CompoundsDua Tipe Senyawa Karbonil

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Aldehida | Aldehyde

Keton | Ketone

Ester

Amida | Amide

Anhidrida asam | Acid anhydride

Asam karboksilat | Carboxylic acid

Klorida asam (!!!) | Acid chlorideCANNOT!!!

Yes you CAN!!!

Naming Aldehydes and KetonesPenamaan Aldehida dan Keton

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Metanal | MethanalEtanal | EthanalPropanal…

Propanon | PropanoneButanon | Butanone3-Pentanon | 3-Pentanone2-Pentanon | 2-Pentanone2-Heksanon | 2-Hexanone3-Heksanon | 3-Hexanone…

Naming Aldehydes Attached to a RingPenamaan Aldehida Terikat Cincin

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Metanal | MethanalEtanal | EthanalPropanal…

Benzenakarbaldehida | Benzenecarbaldehyde

Sikloheksanakarbaldehida | Cyclohexanecarbaldehyde

2-Naftalenakarbaldehida | 2-Naphtalenecarbaldehyde

Common Names - Aldehydes and KetonesNama Trivial - Aldehida dan Keton

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

IUPAC Trivial | Common

Metanal | Methanal Formaldehida|Formaldehyde

Etanal | Ethanal Asetaldehida | Acetaldehyde

Propanal Propionaldehida|Propionaldehyde

Butanal Butiraldehida|Butyraldehyde

Pentanal Valeraldehida|Valeraldehyde

2-Propenal Acrolein

Benzenakarbaldehyde |Benzenecarbaldehyde

Benzaldehida | Benzaldehyde

Common Names - Aldehydes and KetonesNama Trivial - Aldehida dan Keton

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

IUPAC Trivial | Common

Metanal | Methanal Formaldehida|Formaldehyde

Etanal | Ethanal Asetaldehida | Acetaldehyde

Propanal Propionaldehida|Propionaldehyde

Butanal Butiraldehida|Butyraldehyde

Pentanal Valeraldehida|Valeraldehyde

2-Propenal Acrolein

Benzenakarbaldehyde |Benzenecarbaldehyde

Benzaldehida | Benzaldehyde

Aseton | Acetone

Asetofenon | Acetophenone

Benzofenon | Benzophenone

IUPAC Name ??? ======

Acyl - | Alkanoil -Asil - | Alkanoil -

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

R IUPAC TRIVIAL

H Metanoil | Methanoil Formil | Formyl

CH3 Etanoil | Ethanoil Asetil | Acetyl

… … …

C6H6 Benzoil | Benzoyl

If carbonyl considered as a “substituent” …Jika karbonil sebagai substituen …

• okso | oxo

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Metil 3-oksoheksanoat Methyl 3-oxohexanoate

Synthesis of Aldehydes and KetonesSintesis Aldehida dan Keton

• The best: the oxidation of alcohol!– Primary alcohols => Aldehydes

– Secondary alcohols => Ketones

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Note: PCC = pyridinium chlorochromate

Synthesis of Aldehydes and KetonesSintesis Aldehida dan Keton

• The best: the oxidation of alcohol!– Primary alcohols => Aldehydes

– Secondary alcohols => Ketones

– Tertiary alcohols => ?Competence – Conscience – Compassion

Konteks – Pengalaman – Refleksi – Aksi – Evaluasi

Oxydation of AldehydesOksidasi Aldehida

Asam karboksilat | Carboxylic acid Simplest method = menggunakan Tollens’ reagent (Ag+ in

dilute aqueous ammonia (NH4OH))

Kenapa keton tidak bisa? No removable “H” Oksidasi formadehida? -> asam metanoat -> CO2 +H2O Mekanisme reaksi? KO1? …

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Oxydation of AldehydesOksidasi Aldehida

Asam karboksilat | Carboxylic acid Simplest method = menggunakan Tollens’ reagent (Ag+ in

dilute aqueous ammonia (NH4OH))

Kenapa keton tidak bisa? No removable “H” Oksidasi formadehida? -> asam metanoat -> CO2 +H2O Mekanisme reaksi? KO1? …

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Nucleophilic Addition ReactionsReaksi Adisi Nukleofilik

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Nucleophilic Addition ReactionsReaksi Adisi Nukleofilik

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Nucleophilic Addition ReactionsReaksi Adisi Nukleofilik

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Some negatively charged :Nu =>• HO- (ion hidroksida | hydroxide ion) • H:- (ion hidrida | hydride ion)• R3C:- (karbanion | carbanion)• RO- (ion alkoksida | alkoxide ion)• N≡C:- (ion sianida | cyanide ion)

Some neutral :Nu =>• H2O (air | water)• R-OH (alkohol | alcohol)• H3N: (amonia | ammonia)• R-NH (amina | amine)

Nucleophilic Addition Reactions - ReductionReaksi Adisi Nukleofilik - Reduksi

• Example: Propanone =>

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Propanon | Propanone Ion 2-propoksida2-propoxide ion

2-Propanol

Nucleophilic Addition of Water - HydrationAdisi Nukleofilik Air - Hidrasi

• Example: Propanone =>

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Propanon | PropanoneHidrat propanon

Propanone hidrate

Nucleophilic Addition of Water - HydrationAdisi Nukleofilik Air - Hidrasi

• Dg katalis basa | Base-catalyzed:

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Nucleophilic Addition of Water - HydrationAdisi Nukleofilik Air - Hidrasi

• Dg katalis asam | Acid-catalyzed:

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Nucleophilic Addition of Water - HydrationAdisi Nukleofilik Air - Hidrasi

• Note:– Equilibrium reaction ~ depends on the structure.

Ex: acetone in water = 99.9% ketone 0.1% gem diol, but vice versa formaldehyde in water.

– Slow in pure water, catalyzes by acid/base. No change in equilibrium position.

– Differences in acid/base catalyzation:• Base: Hydroxide ion much better :Nu than water.• Acid: Protonate the carbonyl, makes it much better

electrophile.

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Nucleophilic Addition of AlcoholsReaksi Adisi Alkohol

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Some negatively charged :Nu =>• HO- (ion hidroksida | hydroxide ion) • H:- (ion hidrida | hydride ion)• R3C:- (karbanion | carbanion)• RO- (ion alkoksida | alkoxide ion)• N≡C:- (ion sianida | cyanide ion)

Some neutral :Nu =>• H2O (air | water)• R-OH (alkohol | alcohol)• H3N: (amonia | ammonia)• R-NH (amina | amine)

Nucleophilic Addition of AlcoholsReaksi Adisi Alkohol

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

R = H, aldehydesR = alkyl, ketones

Asetal | Acetal

Nucleophilic Addition of AlcoholsReaksi Adisi Alkohol

• Note: Useful for the following condition, which is NOT unusual …

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

?

Nucleophilic Addition of AlcoholsReaksi Adisi Alkohol

• LiAlH4 ?

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

?

LiAlH4

Nucleophilic Addition of AlcoholsReaksi Adisi Alkohol

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

• So … use acetal as a protecting group

Nucleophilic Addition of AminesReaksi Adisi Amina

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Some negatively charged :Nu =>• HO- (ion hidroksida | hydroxide ion) • H:- (ion hidrida | hydride ion)• R3C:- (karbanion | carbanion)• RO- (ion alkoksida | alkoxide ion)• N≡C:- (ion sianida | cyanide ion)

Some neutral :Nu =>• H2O (air | water)• R-OH (alkohol | alcohol)• H3N: (amonia | ammonia)• R-NH (amina | amine)

Nucleophilic Addition of Amines: Imine FormationsReaksi Adisi Amina: Pembentukan Imina

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

R = H, aldehydesR = alkyl, ketones

Imina | Imine

Nucleophilic Addition of Grignard ReagentsReaksi Adisi Reagen Grignard

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Some negatively charged :Nu =>• HO- (ion hidroksida | hydroxide ion) • H:- (ion hidrida | hydride ion)• R3C:- (karbanion | carbanion)• RO- (ion alkoksida | alkoxide ion)• N≡C:- (ion sianida | cyanide ion)

Some neutral :Nu =>• H2O (air | water)• R-OH (alkohol | alcohol)• H3N: (amonia | ammonia)• R-NH (amina | amine)

Grignard ReagentsReagen Grignard

• Apa itu reagen Grignard? KO1!

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Grignard ReagentsReagen Grignard

• Apa itu reagen Grignard? KO1!

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Grignard ReagentsReagen Grignard

• Apa spesialnya reagen Grignard?

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Nucleophilic Addition of Grignard Reagents – Alcohols FormationsReaksi Adisi Reagen Grignard – Pembentukkan Alkohol

• Apa spesialnya reagen Grignard? Karbanion!

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

R = H, aldehydesR = alkyl, ketones Alkohol| Alcohol

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Nucleophilic Addition of Grignard Reagents (GR) – Alcohols FormationsReaksi Adisi Reagen Grignard – Pembentukkan Alkohol

• Note:– GR + Formaldehyde -> 10 alcohols– GR + Other Aldehydes -> 20 alcohols– GR + Keton -> 10 alcohols

• Weakness: – Can’t be prepared from organic halides that has

other reactive functional groups: Br-Molecule-FG• FG: -OH, -NH, -SH, -COOH } The GR can be protonated• FG: aldehyde, ketone, amide, nitrile, nitro, sulphon }

The GR adds to these groups.

Conjugate Nucleophilic Addition ReactionsReaksi Adisi Nukleofilik Konjugasi

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Direct (1,2) addition:

Conj. (1,4) addition:

α,β-UnsaturatedR = H, aldehydesR = alkyl, ketones

Ion enolat | Enolate ion

Aldehida/Keton jenuhSaturated aldehyde/ketones

Some Biological Nucleophilic AdditionReaksi Adisi Nukleofilik Biologis

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Some Biological Nucleophilic AdditionReaksi Adisi Nukleofilik Biologis

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Serahkan pada biokimia (sem 4?) …

Competence – Conscience – CompassionKonteks – Pengalaman – Refleksi – Aksi – Evaluasi

Next … Carboxylic Acids and Derivatives

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