8/2/2019 Sintesis Obat - 01 Karbonil
1/12
Reaksi-Reaksi Substitusi
Alfa Karbonil
8/2/2019 Sintesis Obat - 01 Karbonil
2/12
8/2/2019 Sintesis Obat - 01 Karbonil
3/12
Karbonil
Aldehide Ketone Amide
Asam Kaboksilat Enone
Karbonil
8/2/2019 Sintesis Obat - 01 Karbonil
4/12
Reaktivitas
Oxygen is more electronegativethan carbon, and thus morereactive with nucleophiles
The alpha hydrogensis 1000
times more acidic than atypical C-H bond.
Amides are the most stable of thecarbonyl couplings due totheir high resonance
stabilization between thenitrogen-carbon and carbon-oxygen bonds.
Carbonyls would be alkylatedby nucleophilic attack byorganometallic reagentssuch asorganolithiumreagents andGrignard
reagents.
Carbonyls also may bealkylated by enolates as inaldol reactions
http://media/wiki/Nucleophilehttp://media/wiki/Alpha_hydrogenhttp://media/wiki/Alkylationhttp://media/wiki/Nucleophilic_attackhttp://media/wiki/Organometallichttp://media/wiki/Organolithiumhttp://media/wiki/Grignard_reagenthttp://media/wiki/Grignard_reagenthttp://media/wiki/Grignard_reagenthttp://media/wiki/Grignard_reagenthttp://media/wiki/Organolithiumhttp://media/wiki/Organometallichttp://media/wiki/Nucleophilic_attackhttp://media/wiki/Alkylationhttp://media/wiki/Alpha_hydrogenhttp://media/wiki/Nucleophilehttp://media/wiki/Nucleophile8/2/2019 Sintesis Obat - 01 Karbonil
5/12
Reaksi-ReaksiPenting
Wittig Reaction, to create analkene
Wolff-Kishner reduction
Clemmensen reduction
Conversion into thioacetals
Hydrationhemiacetalsandhemiketals to acetals andketals
Reaction with ammonia andamines to form imines
Reaction with hydroxylamines toform oximes
Reaction with cyanide aniontofom cyanohydrins
Oxidation with oxaziridinestoacyloins
Reaction with Tebbe's reagentand phosphonium ylidestoalkenes
Perkin reaction and aldolreaction
Aldol condensation
Cannizzaro reaction
Tishchenko reaction
http://media/wiki/Wittig_Reactionhttp://media/wiki/Wolff-Kishner_reductionhttp://media/wiki/Clemmensen_reductionhttp://media/wiki/Thioacetalhttp://media/wiki/Hydration_reactionhttp://media/wiki/Hemiacetalhttp://media/wiki/Hemiketalhttp://media/wiki/Acetalhttp://media/wiki/Ketalhttp://media/wiki/Ammoniahttp://media/wiki/Aminehttp://media/wiki/Iminehttp://media/wiki/Hydroxylaminehttp://media/wiki/Oximehttp://media/wiki/Cyanidehttp://media/wiki/Cyanohydrinhttp://media/wiki/Oxaziridinehttp://media/wiki/Acyloin%23Enolate_oxidation_by_sulfonyloxazirineshttp://media/wiki/Tebbe%2527s_reagenthttp://media/wiki/Phosphonium_ylidehttp://media/wiki/Alkenehttp://media/wiki/Perkin_reactionhttp://media/wiki/Aldol_reactionhttp://media/wiki/Aldol_reactionhttp://media/wiki/Aldol_condensationhttp://media/wiki/Cannizzaro_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Cannizzaro_reactionhttp://media/wiki/Cannizzaro_reactionhttp://media/wiki/Aldol_condensationhttp://media/wiki/Aldol_condensationhttp://media/wiki/Aldol_reactionhttp://media/wiki/Aldol_reactionhttp://media/wiki/Aldol_reactionhttp://media/wiki/Perkin_reactionhttp://media/wiki/Alkenehttp://media/wiki/Alkenehttp://media/wiki/Phosphonium_ylidehttp://media/wiki/Tebbe%2527s_reagenthttp://media/wiki/Acyloin%23Enolate_oxidation_by_sulfonyloxazirineshttp://media/wiki/Acyloin%23Enolate_oxidation_by_sulfonyloxazirineshttp://media/wiki/Oxaziridinehttp://media/wiki/Cyanohydrinhttp://media/wiki/Cyanohydrinhttp://media/wiki/Cyanidehttp://media/wiki/Oximehttp://media/wiki/Oximehttp://media/wiki/Hydroxylaminehttp://media/wiki/Iminehttp://media/wiki/Iminehttp://media/wiki/Aminehttp://media/wiki/Ammoniahttp://media/wiki/Ketalhttp://media/wiki/Ketalhttp://media/wiki/Acetalhttp://media/wiki/Hemiketalhttp://media/wiki/Hemiacetalhttp://media/wiki/Hydration_reactionhttp://media/wiki/Thioacetalhttp://media/wiki/Thioacetalhttp://media/wiki/Clemmensen_reductionhttp://media/wiki/Clemmensen_reductionhttp://media/wiki/Wolff-Kishner_reductionhttp://media/wiki/Wolff-Kishner_reductionhttp://media/wiki/Wolff-Kishner_reductionhttp://media/wiki/Wittig_Reaction8/2/2019 Sintesis Obat - 01 Karbonil
6/12
,-Unsaturated carbonylcompounds
,-Unsaturated carbonylcompounds are an importantclass of carbonyl compoundswith the general structureC
=C
(C=O)
Examples of unsaturatedcarbonyls are acrolein(Propenal)mesityloxideacrylic acid andmaleicacid. Unsaturated carbonyls
can be prepared in an aldolreaction and Perkin reaction
As a general rule withunsymmetric electrophiles,hydrogen attaches itself atthe -position in anelectrophilic addition
Since ,-unsaturatedcompounds areelectrophiles, many ,-unsaturated carbonylcompounds are toxic,
mutagenic andcarcinogenic. DNA Canattack the carbon andthus alkylated. However,the endogenous scavengercompound glutathione
naturally protects fromtoxic electro hiles in the
http://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Tishchenko_reactionhttp://media/wiki/Acroleinhttp://media/wiki/Mesityl_oxidehttp://media/wiki/Mesityl_oxidehttp://media/wiki/Acrylic_acidhttp://media/wiki/Maleic_acidhttp://media/wiki/Maleic_acidhttp://media/wiki/Aldol_reactionhttp://media/wiki/Aldol_reactionhttp://media/wiki/Perkin_reactionhttp://media/wiki/Electrophilic_additionhttp://media/wiki/DNAhttp://media/wiki/DNAhttp://media/wiki/Electrophilic_additionhttp://media/wiki/Electrophilic_additionhttp://media/wiki/Perkin_reactionhttp://media/wiki/Perkin_reactionhttp://media/wiki/Aldol_reactionhttp://media/wiki/Aldol_reactionhttp://media/wiki/Maleic_acidhttp://media/wiki/Maleic_acidhttp://media/wiki/Acrylic_acidhttp://media/wiki/Mesityl_oxidehttp://media/wiki/Mesityl_oxidehttp://media/wiki/Acrolein8/2/2019 Sintesis Obat - 01 Karbonil
7/12
KarakteristikSpektra
Spectroscopy Infrared
the C=O double bond absorbsinfrared light at wavenumbersbetween 1600-1900 cm-1. The exactlocation of the absorption iswell understood with respectto the geometry of themolecule. This absorption isknown as the "carbonylstretch" when displayed on an
infrared absorption spectrum
NMR (Nuclear MagneticResonance)
the C=O double-bond exhibitsdifferent resonancesdepending on surroundingatoms, generally adownfield shift. The 13CNMR of a carbonyl carbonis in the range of 160-220ppm.
http://media/wiki/Infraredhttp://media/wiki/Wavenumberhttp://media/wiki/Wavenumberhttp://media/wiki/Infrared8/2/2019 Sintesis Obat - 01 Karbonil
8/12
Kondensasi Aldol
An aldol condensation is anorganic reaction in which anenol or an enolate reacts witha carbonyl compound to forma -hydroxyaldehide or -hydroxyketone, followed by a
dehydration to give aconjungated enone
Aldol condensations areimportant in organicsynthesis providing a goodway to form carboncarbonbonds
http://media/wiki/Organic_reactionhttp://media/wiki/Organic_synthesishttp://media/wiki/Organic_synthesishttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Organic_synthesishttp://media/wiki/Organic_synthesishttp://media/wiki/Organic_reaction8/2/2019 Sintesis Obat - 01 Karbonil
9/12
Reaksi SederhanaAldol
M k i
http://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bond8/2/2019 Sintesis Obat - 01 Karbonil
10/12
Mekanisme-Mekanisme dalam
Reaksi AldolThe first part of this reaction is analdol reaction, the second part adehydrationan elimination reaction. Dehydration may beaccompanied by decarboxylation when an activated carboxyl group
is present. The aldol addition product can be dehydrated via twomechanisms; a strong base like potassium t-butoxide , potassium
hydroxide or sodium hydride in an enolate mechanism, or in an acid-
catalyzed enol mechanism.
http://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bond8/2/2019 Sintesis Obat - 01 Karbonil
11/12
Mekanisme ReaksiEnol-Aldol
http://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bond8/2/2019 Sintesis Obat - 01 Karbonil
12/12
Mekanisme ReaksiEnolat-Aldol
http://media/wiki/Carbon%25E2%2580%2593carbon_bondhttp://media/wiki/Carbon%25E2%2580%2593carbon_bond