Hankyong National .Sodium acetylide Cyclohexanone Sodium-1-ethynyl cyclohexyloxide 1-Ethynyl cyclohexanol

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  • Hankyong National University 16-1

  • Hankyong National University 16-2

    : C=O(Carbonyl )

    Aldehyde : RCH=O

    Ketone : R(C=O)R

    C=O

    C O sp2 1

    2p 1

    O 2 : sp2

    Carbonyl (C=O)

  • Hankyong National University 16-3

    A. IUPAC

  • Hankyong National University 16-4

    A. IUPAC

    Alkane e al

    Aldehyde C=C CC : en yn

    CHO : carbaldehyde

    Aldehyde IUPAC

    CHO C6H5 CHO

    3-Methylbutanal 2-Propenal

    (Acrolein)

    (2E)-3,7-Dimethyl-2,6-octadienal

    (Gerabial)

    Cyclopentane-

    carbaldehyde

    trans-4-Hydrocycyclo-

    hexanecarbaldehyde Benzaldehyde trans-3-Phenyl-2-propenal

    (Cinnamaldehyde)

    1 2

    3

  • Hankyong National University 16-5

    A. IUPAC

    : C=O Alkane

    Alkane e one

    Ketone IUPAC

    O

    O O O

    Propanone

    (Acetone)

    Acetophenone Bezophenone 1-Phenyl-1-pentanone

  • Hankyong National University 16-6

    Aldehyde : acid ic oic aldehyde

    Ketone : carbonyl 2 Alkyl Aryl ketone

    (Acid )

    C.

    O HCH

    O HCOH

    O CH3CH

    O CH3COH

    Formic acid Formaldehyde Acetic acid Acetaldehyde

    O O O

    Ethyl isopropyl ketone

    Diethyle ketone

    Dicyclohexyl ketone

  • Hankyong National University 16-7

    C=O :

    bp : Alcohol, Acid > Aldehyde, Ketone >

    (+) ()

    16.2 bp

    bp()

    Dimethyl ether CH3CH2OCH2CH3 74 34

    Pentane CH3CH2CH2CH2CH3 72 36

    Butanal CH3CH2CH2CH2CHO 72 76

    2-Butanone CH3CH2COCH3 72 80

    1-Butanol CH3CH2CH2CH2OH 74 117

    Propanoic acid CH3CH2COOH 71 141

  • Hankyong National University 16-8

    Carbonyl(C=O)

    (Nu:)

    C=O ( )

    (Lewis )

  • Hankyong National University 16-9

    Carbonyl(C=O) Chiral Racemic

  • Hankyong National University 16-10

    A. RMgX(Grignard )

    : RMgX RLi RCC: :CN:

    Grignard Organolithium Alkyne Cyanide

    (Nu:)

    CMg : [C()Mg(+)]

    C=O Carbonyl

    Aldehyde Ketone + Grignard Chiral

    Alkoxide(O[MgBr]+) :

    Alkoxide(O[MgBr]+) () 1 Alcohol

    Formaldehyde 1 Alcohol

    A.

  • Hankyong National University 16-11

    Alkoxide(O[MgBr]+) () 2 Alcohol

    Chiral , Rcemic

    Aldehyde(Formaldehyde ) 2 Alcohol

    Ketone 3 Alcohol

    A. RMgX(Grignard )

  • Hankyong National University 16-12

    B. RLi(Organo Lithium)

    Carbonyl RMgX ( )

    N2

    B. RLi(Organo Lithium)

  • Hankyong National University 16-13

    Alkyne Alcohol OH CC

    C. RCC:( Alkyne)

    -Hydroxy cyclohexyl

    methyl ketone

    -Hydroxy cyclohexyl

    acetaldehyde

    Sodium acetylide Cyclohexanone Sodium-1-ethynyl

    cyclohexyloxide 1-Ethynyl cyclohexanol

    H2O

    H2SO4, HgSO4

    1.(sia)2BH

    2. H2O2, NaOH

    1-Ethynyl

    cyclohexanol

    C. RCC:( Alkyne)

  • Hankyong National University 16-14

    1 ( Carbonyl ) 2 (Cyanohydrin Cyanide Anion )

    HCN(Hydrogen Cyanide) : (pK=9.31) pH=10

    HCN + Aldehyde/Ketone Cyanohydrin( Carbonyl )

    O OH

    CH3CH + HCN CH3CCN 2-Hydroxy propane nitrile(Racemic) (Acetaldehyde cyanohydrin) H

    D. :CN:(Cyanide )

    D. :CN:(Cyanide )

  • Hankyong National University 16-15

    Oxaphosphetane triphenylphosphine oxide+ Alkene

    Betaine( ) Oxaphosphetane

    Phosphonium Ylide Aldehyde / Ketone Alkene

    Witting : .(C=O Ketone .

    1 (Oxaphosphetane )

    2 (Oxaphosphetane )

    Phosphoniumylide Betaine Oxaphosphetane

    Oxaphosphetane Triphenylphosphine oxide

    Alkene

    Cyclohexanone Phosphonium ylide Methylenecyclohexane Triphenylphosphine oxide

    Ylide()

  • Hankyong National University 16-16

    Aldehyde / Ketone + Ylide

    Ylide E

    Ylide Z

  • Hankyong National University 16-17

    C=O gemdiol(geminal diol, )

    : C=O (, Acetone : 99% )

    A. : Carbonyl

    /

    /

  • Hankyong National University 16-18

    Hemiacetal(halfacetal) : OH OR

    Hemiacetal : 5 6

    Hemiacetal Chiral .

    Anomeric Carbon : Hemiacetal Chiral C

    Anomer : 2 Hemiacetal()

    Anomer : OH CH2OH ( Anomer)

    B. Alcohol : Acetal

    Hemiacetal(halfacetal)

  • Hankyong National University 16-19

    H+ ROH

    H+ Alcohol O Hemiacetal

    1 ( Alkoxide )

    RO Carbonyl C

    2 (Carbonyl )

    3 (Hemiacetal )

    B. Alcohol : Acetal

    Alcohol Alkoxide ()

    Alkoxide

    () Hemiacetal

  • Hankyong National University 16-20

    Hemiacetal Alcohol Acetal

    Acetal :

    OH

    Acetal : 2 OR

    Hemiacetal Diethyl acetal

    Acetal

    Acetal

  • Hankyong National University 16-21

  • Hankyong National University 16-22

    NH3 / 1 Amine + Aldehyde / Ketone RC=NR

    RC=NR : Imine or Schiff

    Imine : , ( C=N Conjugation )

    A. NH3

    O CH3CH + H2N CH3CH=N + H2O

    H+

    O + NH3

    H+

    NH + H3O

    Acetaldehyde Aniline An Imine

    Cyclohexanone Ammonia An imine

  • Hankyong National University 16-23

    Aldehyde / Ketone Alcohol Hemiacetal

    1 ( Carbonyl )

    2 (OH N H+ Imine )

    A. NH3

    Imine

  • Hankyong National University 16-24

    A. NH3

  • Hankyong National University 16-25

    H2NNH2 : Hydrazine

    O + H2NNH2 NNH2 + H2O

    Hydrazine Hydrazone

    B. Hydrazine

    Cyclopentanone

  • Hankyong National University 16-26

    : C=O C

    : H

    : C H CH : C = H =

    H : CH, CH2=CH, C=H < C=O < OH

    Enolate Anion :

    Enolate Anion : C=O H+

    A.

    A.

    Enolate Anion

  • Hankyong National University 16-27

    H+ HA( ) Carbonyl Oxonium Cation

    1 (Oxonium Cation )

    H+ A Enol +

    2 (Enol )

    A.

  • Hankyong National University 16-28

    B. Ketoenol Tautomerism

    1 H Aldehyde / Ketone : enol

    Aldehyde/ Ketone : Keto ( Keto )

    C=O > C=C but CH OH

    enol C=C C=O Conjugation .

    2,4-Pentanedion( Di-ketone) enol

    : H

    B. Ketoenol Tautomerism

  • Hankyong National University 16-29

    Aldehyde

    O2 / H2O2 (Aldehyde Carboxylic acid) : Radical

    A. Aldehyde

    A. Aldehyde

  • Hankyong National University 16-30

    Ketone (Aldehyde )

    Ketone Chromic acid, Potassium permanganate .

    Ketone + (K2Cr2O7, KMnO4) + / enol

    Cycloketone

    B. Ketone

    B. Ketone

    Nylon-66

  • Hankyong National University 16-31

    Aldehyde 1 Alcohol , Ketone 2 Alcohol

    Aldehyde Ketone C=O Methylene(CH2)

    H:(Hydrid Anion, )

    H: : NaBH4(Sodium Borohydride), LiAlH4(Lithium Aluminium Hydride, LAH)

    NaBH4 :

    LAH : ((C2H5)2O, THF)

    (, ) : H2, , Alkoxide

    A.

    A.

  • Hankyong National University 16-32

    (Pt, Ni) H2 OH

    : 25 100

    : 1 5

    C=C, CC

    B.

    B.

  • Hankyong National University 16-33

    (LiAlH4, NaBH4) ( (C=C) )

    C=C

    C.

    C. D.

    : Imine C=N Ni CN

    D.

  • Hankyong National University 16-34

    E. Carbonyl Methylene

    Clemmensen : Aldehyde / Ketone + Zn(Hg) + HCl Methylene(CH2)

    Conc. HCl Clemmensen

    3 Alcohol :

    Acetal : Carbonyl .

    Wolff-Kishner

    E. Carbonyl Methylene

  • Hankyong National University 16-35

    C=O Hydrazine

    Hydrazone

    1 (Hydrazone )

    - TautomerismN=N

    2 (Tautomerism N=N )

    R

  • Hankyong National University 16-36

    H+ Hydroxide Anion

    N

    H+ Hydroxide Anion

    3 ( Hydroxide Anion )

  • Hankyong National University 16-37

  • Hankyong National University 16-38

    Keto-enol Tautomerism enol

    1 (enol )

    enol X2(Halogen ) Haloketone

    2 (Haloketone )

    H+ Acetic acid( ) Haloketone

    3 (Haloketone )

    C. Halogenation

  • Hankyong National University 16-39

    H+ Enolate Anion

    1 ( Enolate Anion )

    Enolate Anion Halogen Bromoketone

    2 (Bromoketone )

    C. Halogenation

  • Hankyong National University 16-40

    C. Halogenation

    Halogenation .

    Halogenation

    Halogen Carbonyl

    Halogenation Halogenation

    Halogenation

    Halogen

    Halogenation Halogenation

    Halogenation