ALDEHYDE AND KETONE NOMENCLATURE IUPAC SYSTEM

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ALDEHYDE AND KETONE NOMENCLATUREIUPAC SYSTEM

• LONGEST CONTINUOUS CHAIN WITH -CO IS
  PARENT
• DROP -e FROM PARENT NAME AND ADD -ONE FOR
  A KETONE, -AL FOR AN ALDEHYDE
• FOR KETONES, THE CO IS ASSIGNED THE
  SMALLEST NUMBER POSSIBLE
• CARBONYL CARBON OF ALDEHYDES IS UNDERSTOOD
  TO BE C1

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COMMON NAMES
FORMALDEHYDE ACETALDEHYDE
PROPIONALDEHYDE
BUTYRALDEHYDE
BENZALDEHYDE
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KETONE COMMON NAMES
ACETONE MEK
ACETOPHENONE
BENZOPHENONE
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PHYSICAL PROPERTIES

• BOILING POINTS HIGHER THAN HYDROCARBONS -
  LOWER THAN ALCOHOLS
• 4 - 5 CARBON ALDEHYDES AND KETONES HAVE
  FAIR WATER SOLUBILITY

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PREPARATION OF ALDEHYDES AND KETONES

• OXIDATION OF ALCOHOLS
• OZONOLYSIS
• REDUCTION OF ACID CHLORIDES
• REDUCTION OF ESTERS / NITRILES
• HYDRATION OF ALKYNES
• PINACOL REARRANGEMENT
• Friedel Crafts Acylation

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OXIDATION OF ALCOHOLS
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OZONOLYSIS
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REDUCTION OF ACID CHLORIDES
AN ALTERNATE IS THE ROSENMUND REDUCTION
Pd / C WITH QUINOLINE
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REDUCTION OF ESTERS / NITRILES
AN ALTERNATE REDUCTION WITH RANEY NICKEL
75 HCO2H WITH Ni . Al (H2)
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HYDROBORATION OF ALKYNES
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OXYMERCURATION DEMERCURATION OF ALKYNES
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PINACOL REARRANGEMENT
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FRIEDEL CRAFTS ACYLATIONS
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REACTIONS OF ALDEHYDES AND KETONES

• ADDITIONS OF ORGANOMETALLICS
• REDUCTIONS
• ADDITIONS OF CYANIDE
• HYDRATION
• ACETAL FORMATION
• ADDITIONS OF AMINES
• WITTIG REACTION
• OXIDATION OF ALDEHYDES

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Relative Reactivity

• Aldehydes gt ketones
• Acid Halides and Anhydrides gt aldehydes
• Esters and carboxylic acids gt amides and nitriles

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ORGANOMETALLIC REAGENTS

• COMPOUNDS WITH CARBON - METAL BONDS
• CARBON IS AT THE NEGATIVE END OF A DIPOLE
• THE MORE ELECTROPOSITIVE THE METAL, THE
  MORE IONIC THE CARBON - METAL BOND AND
  THE MORE REACTIVE THE REAGENT

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THIS IS A TEST!!
WHICH OF THE FOLLOWING ORGANOMETALLIC
REAGENTS IS THE MOST REACTIVE? LEAST?
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THIS IS A TEST!!
WHICH OF THE FOLLOWING ORGANOMETALLIC
REAGENTS IS THE MOST REACTIVE? LEAST?
Grignards most common organolithiums used when
a Grignard is no good enough cuprates etc when
Grignard too good.
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PREPARATION OF ORGANOMETALLICS

• GRIGNARD REAGENTS FROM ALKYL HALIDES WITH
  MAGNESIUM METAL
• ALKYL LITHIUMS FROM ALKYL HALIDES WITH
  LITHIUM
• SODIUM ALKYNIDES FROM ALKYNE WITH SODIUM
  AMIDE OR METAL HYDRIDE

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EXAMPLES OF ORGANOMETALLIC PREPS
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Conversion to Other Organometallics
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REACTIONS OF ORGANOMETALLICS

• REACT AS BASES WHEN EXPOSED TO REAGENTS
  CONTAINING PROTONS MORE ACIDIC THAN THOSE
  OF ALKANES.
• ADD TO ALDEHYDES AND KETONES
• REACT WITH EPOXIDES
• REACT WITH CARBOXYLIC ACIDS AND DERIVATIVES

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WARNING!!!

• Grignard reagents can not be prepared from alkyl
  halides which contain Hs attached to heteroatoms
• alkyl halide can not contain aldehyde, ketone,
  carboxylic acid or derivative, or epoxide
  functional groups.
• Compound that organometallic reacts with should
  not contain H-heteroatom.

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REACTION OF GRIGNARD WITH FORMALDEHYDE
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REACTION OF GRIGNARD WITH OTHER ALDEHYDES
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REACTION OF GRIGNARD WITH KETONES
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SYNTHESIS WITH GRIGNARD REAGENTS

• CIRCLE THE CARBON WITH THE HYDROXYL GROUP.
• REMOVE AN ALKYL GROUP FROM THAT CARBON ...
  THIS WILL BE THE GRIGNARD REAGENT
• THE REMAINING GROUPS ARE PART OF THE
  CARBONYL COMPOUND

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EXAMPLES OF GRIGNARD SYNTHESES
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PREPARATION OF ALKYL HALIDES

• ADDITION OF HYDROGEN HALIDES TO ALKENES
• MARKOVNIKOV ADDITION (UNLESS PEROXIDES WITH
  HBr)
• HYDROBORATION FOLLOWED BY BROMINE WITH
  SODIUM METHOXIDE - ANTI-MARKOVNIKOV
• HALOGENATION OF ALKANES
• hv or high temps ... Br prefers 3ogt2ogt1o

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GRIGNARD REACTIONS WITH ETHYLENE OXIDE
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SYNTHESIS WITH GRIGNARDS REVISITED
STARTING WITH ALKENES WITH 6 CARBONS OR
LESS
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Formation of epoxides

• Peroxyacid with alkene
• Halohydrin with base

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Reactions with esters and acid chlorides
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Reactions with esters and acid chlorides
NOTE PRODUCT HAS TWO IDENTICAL R GROUPS
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ORGANOMETALLICS WITH ACID CHLORIDES PART DEUX
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ORGANOMETALLICS WITH ACID CHLORIDES PART DEUX
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ORGANOMETALLICS WITH NITRILES
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ORGANOMETALLICS WITH CARBOXYLIC ACIDS
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ORGANOMETALLICS WITH CARBOXYLIC ACIDS
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ORGANOMETALLICS WITH CARBOXYLIC ACIDS
SOLUTION
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PROBLEMS
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PREPARE EACH OF THE FOLLOWING USING A GRIGNARD
SYNTHESIS
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A NASTY ONE!

• STARTING WITH 2-METHYL-1-BUTENE AS THE ONLY
  ORGANIC STARTING MATERIAL, PROPOSE A SYNTHESIS
  OF 3,6-DIMETHYL-3-OCTANOL

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REDUCTIONS
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ADDITIONS OF CYANIDE
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PRACTICE PROBLEM
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PRACTICE PROBLEM
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PRACTICE PROBLEM
HYDROLYSIS OF NITRILE
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PRACTICE PROBLEM
HYDROLYSIS OF NITRILE
DEHYDRATION
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HYDRATION
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HEMIACETAL FORMATION
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ACETAL FORMATION
NOTES - IN THE ABSENCE OF ACID, A
HEMIACETAL FORMS - ACETALS ARE STABLE IN
BASE - USEFUL PROTECTING GROUPS - IF A DIOL
IS USED, A CYCLIC ACETAL RESULTS
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CARBOHYDRATES

• POLYHYDROXY ALDEHYDES AND KETONES - MOST
  FIT THE FORMULA Cm(H20)n
• CLASSIFIED AS ALDOSES OR KETOSES
• CLASSIFICATION BASED ON CARBONS - HEXOSE,
  PENTOSE

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ALDOHEXOSES
ENANTIOMERS OF GLUCOSE
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D or L DESIGNATION
ENANTIOMERS OF GLYCERALDEHYDE
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CYCLIC FORMS OF GLUCOSE
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GLYCOSIDE FORMATION
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ADRIAMYCIN (DOXORUBICIN)
ANTIBIOTIC - ANTITUMOR DRUG
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HYDROLYSIS OF DISACCHARIDES
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ACETALS AS PROTECTING GROUPS
PREPARE FROM
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RECALL
PROBLEM
CAN NOT BE PREPARED
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SOLUTION
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application
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ADDITIONS OF 1o AMINES
2,4-DINITROPHENYLHYDRAZINE A
2,4-DINITROPHENYLHYDRAZONE
PRODUCTS ARE USEFUL IN STRUCTURE
DETERMINATION
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OTHER USEFUL 1o AMINES
HYDROXYL AMINE HYDRAZINE PHENYL
HYDRAZINE SEMICARBAZIDE
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Wolff-Kishner Reduction
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ADDITIONS OF 2o AMINES
PRODUCT IS AN ENAMINE
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Reductive amination
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WITTIG REACTION
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OXIDATION OF ALDEHYDES
TOLLENS TEST FOR ALDEHYDES
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a,b-unsaturated carbonyl compounds
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Polarization of the CC

• CO has more single bond character
• Two sites for nucleophilic attack
• carbonyl carbon
• beta carbon
• direct attack add to CO kinetic product (1,2
  addition)
• conjugate addition (Michael Addition) appears to
  add to CC thermodynamic product (1,4
  addition)
• if reversible conjugate addition

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Direct addition

• Hydrides (LiAlH4 , NaBH4)
• Organolithium reagents
• Grignards competition between additions

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PROBLEM