Органическая химия: Методические указания по специальности ''Химия''. Часть 1

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  • 011000 ( . .03)

    2003

  • 2

    , 4 24 2003 .

    : ., . .. . .

    .

    3 4 .

  • 3

    . , , .

    . ( ) , . , , . , . , , .

    . :

    ( )

    ( , SN1):

    ( , SN2). :

    , , .

    CH3 C

    CH3

    CH3X CH3 C

    CH3

    CH3+ + X

    -

    CH3 C

    CH3

    CH3+ + OR

    -CH3 C

    CH3

    CH3OR

    CR

    H

    H......

    ROX

    -

    C

    R

    X + OR

    H

    H_

    ROC

    R

    H + X

    H

    -

  • 4 , .

    . , ( ).

    -. .

    . .

    .

    :

    :

    (I)

    (II), (III). , (II).

    .

    (CH3)2C CH2 + (CH3)3CH (CH3)2CHCH2(CH3)3

    C

    CH3CH3 CH2 C

    CH3CH3 CH2

    C

    CH3CH3

    CH3

    CH3 CH

    CH3CH2

    C

    CH3CH3 + (CH3)3C

    CH3

    I

    +

    IIIIII

    (CH3)3CH

    +

    II

    H+C CH3CH3CH3

    +

  • 5

    - :

    . . (I) - (II), . . , - , :

    . :

    .

    C

    CH3CH3 CH2 C

    CH3CH3 CH2

    C

    CH3CH3

    CH3

    CH3 CH

    CH3CH2

    C

    CH3CH2

    I

    +

    III

    +

    H+C CH3CH3

    CH3

    +

    -H+C C

    HCH3

    CH3

    CH3

    C

    CH3CH3

    CH3CH2CH3t

    CH3CHCH3 + [H].

    .

    ..

    .CH3CH = CH2 + CH(CH3)2 CH3CHCH2CH(CH3)2

    CH3CHCH2CH(CH3)2 + CH3CH2CH3

    CH3CHCH3 + CH3CH2CH2CH(CH3)2 . .

    CH2 CH2 + CH2(CH3)2

    55%

    16%

    CH3CH2CH(CH3)2

    CH3CH2CH2CH2CH3

  • 6 -

    . , , , . : , , . - (SE2).

    :

    - , -. ( ), . - , .

    - . - , , , .

    . > . > . > . - , .

    R Cl + AlCl3 R ... Cl ... AlCl3 R + AlCl4

    + R ... Cl ... AlCl3 -AlCl4

    B

    -BH

    ; BH + AlCl4 B + HCl + AlCl3

    +

    +

    +

    -

    -

    -

    -

    + -

    R ... Cl ... AlCl3

    RHR

    +

  • 7 , . .

    :

    - . ,

    , . , - , :

    , -

    ( ) , . - - , .

    - .

    - -, . , 4- -1- - 1,2,3,4- ():

    -

    .

    R OH + H++

    +ROH2 R + H2O+ +

    CH3CHCH3RCH CH2 + H

    C3H7OH

    H+

    CH(CH3)2 + H2O

    H3PO4-H2O

    (CH2)3CH2OH

  • 8

    .

    , , , ( ):

    , (SN2) , . . .

    , .

    :

    , , , , - :

    NH3 + RX RNH3XNH3

    -NH4XRNH2

    RX

    R2NH2X

    R2NH R3NHX R3N R4NX+

    ++

    + -

    NH3-NH4X

    RX

    RX-NH4X

    NH3

    2 NH3 + (CH3O)2SO2 CH3NH2 +

    CH3O SO2NH4OArNH2 + (CH3O)2SO2 ArNHCH3 +

    CH3O SO2NH4O

    ArX + NH3 ArNH3XNH3

    -NH4XArNH2

    + -

  • 9

    - :

    -

    :

    ( ). . , , :

    :

    .

    .

    ArNHCOCH3CH3X

    -HX

    H2O

    -CH3COOHArNHCH3NCOCH3

    CH3Ar

    R C

    H

    O + NH3

    -H2O

    RCH NH

    H2 / Ni

    H2 / Ni

    -H2O

    R C

    H

    O + NH3 1

    RCH2NH2

    RCHNH2R

    C NH

    R

    R1

    -H2O1

    R CH

    NCH2R1

    R C

    H

    O + H2NCH2R1 H2

    NiRCH2NHCH2R

    C6H5NH2 HCl + ROH C6H5NHR HCl + H2OHCl + NH3 C6H5NHR + NH4Cl

    C6H5NR2 C6H5NR2 + NH4Cl

    .

    .

    ..

    ..C6H5NHR

    HCl + ROHC6H5NHRHCl + NH3

    C6H5NR2 HCl + H2O

  • 10 ,

    - SN2 :

    - -

    - . .

    - :

    :

    ,

    . - , - , , , . - .

    RO + R SO4R- 1 1 1 1 -ROR + R OSO3

    ArO + R OSO3R- 1 1 1 1 -ArOR + R OSO3

    O H:O-

    O

    O

    O

    -

    -

    -

    ArO + RX-ArO ... R ... X- ArOR + X

    -

    R X + R OH

    R X + R ONa

    11

    ROR + HX

    ROR + NaX11

  • 11 ,

    :

    . ,

    :

    1,2- 1,3-

    :

    . .

    , :

    ,

    .

    C O + R OHRH

    R CH OH

    OR

    C

    OH2

    ORH

    RCH OH

    ORR

    CH OR

    ORR

    11

    1

    1 11

    1

    1

    H+

    H+

    +

    +

    ++

    RCHOR + H2O

    RCHOR + R OH

    CH2CH2

    OH

    OH

    CH2CH2

    OH

    OH+

    -2H2O

    CH2CH2 O

    CH2

    CH2O

    RO + HX

    R

    ROH

    R11

    +X-

    CH2OH

    CH2OHO C R

    H

    +

    +CH2CH2

    O

    OCHR + H2O

    CH2CH2OH

    CH2OHO C R

    H

    CH2

    OCHR + H2OCH2

    O

    CH2

  • 12

    ,

    . , . , , .

    , . , ( , , , . .).

    , . (, , .). , , , , , , , , , , . ( , , ).

    ,

    .

    C H

    CH3

    CH3R

    hv C

    CH3

    CH3R . .+ [H ]

    I II

    C

    CH3

    CH3R . O2 C O

    CH3

    CH3R O

    I-II

    C O

    CH3

    CH3R OH C O

    CH3

    CH3R + [OH]

    .

    VIVIII

    II + V C R

    CH3

    CH3OC

    CH3

    CH3R I + V OHC

    CH3

    CH3R + II

  • 13 . .

    , , .

    . . - , , ; - , (IV) :

    , , . , , , , .

    . , .

    ( . .):

    , (-) ,

    . -

    , :

    - ++ 32[OH] + Co OH + Co.[H ] + Co H + Co

    . 3 2+ ++

    C CO

    CC + RCOOHR COOOH+

  • 14

    :

    ,

    .

    :

    . , .

    . .

    1,2- :

    ( 90 %) . -,

    C CH

    CH3 CH3

    H

    OCC

    HH

    CH3CH3

    CH3COOOH

    -CH3COOH

    C CR

    R R

    R

    11

    OOH

    C RO

    .. .. ..C C

    O

    R RR R

    1 1 + RCOOH

    C CR R

    R R1 1

    OCC

    RR

    RR1 1

    O2Ag

    C CR H

    R R1

    2

    + O3O O

    CO

    CR RR H1

    2 H2O

    -H2O2C O

    R

    R1

    + COR

    H

    2

    C CKMnO4

    OH- C C

    OH OH

    + 2KMnO4 + 4H2O + 2MnO2 + 2KOHC CR

    H H

    R3 C C

    H H

    RR3

  • 15 :

    , .

    , , :

    . ,

    - :

    , .

    :

    RCH CH2 RCO

    OH

    C CR

    R R

    R1

    1

    RCO

    OHRC

    O

    OH1

    +

    C OR

    RC O

    R

    R+

    1

    1

    C OR

    RR C

    OH

    O+

    1

    R CH CHR

    C CR

    R H

    R

    [O]+ CO2 + H2O

    [O]

    [O]

    [O]

    1

    1

    R CC

    HR H

    KMnO4 R CC

    OHR OH

    H

    H

    IO4-

    CI

    CRR

    H

    H

    OH

    OHO

    ORC

    O

    H2 + IO3 + H2O

    -

    C C CH2R C C C ROOH

    H

    C C CHR

    OH

    C C C RO

  • 16 ,

    .

    . . , . , - :

    . .

    - . , , 4- 4--:

    - ,

    , .

    () :

    OH

    OH

    O

    O

    NH2

    CH3

    OH

    OHCH3

    O

    O

    O2V2O5 C C

    OCC

    H

    H

    O

    O

  • 17 -

    , :

    .

    , . - , ( - , , 400-500) :

    9,10- :

    . , (, - - ), . , . - ( ), , . . , , (

    O3 O

    O

    O

    O

    O

    O O

    O

    O

    3H2O

    -3H2O23

    C

    C

    OH

    HO

    O

    O

    COOH

    COOH CO

    CO

    O

    O

    O

  • 18 ) ( ) :

    :

    , -, , .. - :

    .

    ( ) , :

    CH3CH3

    COOH

    COOH

    CH3

    CH3

    COOH

    COOH

    COOH

    COOH

    CH3

    CH3

    CH3 NH2(CH3CO)2O

    -CH3COOHCH3 NHCOCH3

    KMnO4

    NHCOCH3HOOC -CH3COOH

    H2ONH2HOOC

    C

    H

    [O]C.

    ( C+

    )

  • 19

    .

    :

    , :

    :

    . :

    CCH3

    CH3H

    hv

    I II

    -IIIO2

    + CH3COCH3t o

    -[H ]..C

    CH3

    CH3C

    CH3

    CH3O O

    CCH3

    CH3O OH OH

    RCH2OH RCOOHArCH2OH ArCOOH

    K2Cr2O7H2SO4

    R CO

    HRCH2OH

    C OR

    RCHOH

    R

    R1

  • 20

    :

    .

    , :

    , .

    , , , , > = < . .

    . - , , . . , :

    CH3CO

    OH+ CrO3 CH3COOCrOH

    O

    O+ H

    +CH3COOCrO

    O

    O

    -

    N + CrO3+N Cr

    O

    O

    O

    CH3COOCrO

    O

    O

    -R2CHOH + + H+ R2CHOCrO3H + CH3COOH

    R2C O + HCrO3 + H- +R2C

    H

    OCrO3H

  • 21

    , ,

    .

    . , . , , .

    :

    , , , .

    1,2- () - :

    . , :

    .

    C OH

    CH2

    CH3

    CH3 H-H2O

    [O]C CH2

    CH3

    CH3

    H+C O + CO2 + H2O

    CH3

    CH3

    CH3OHCu, 600oC

    CH2O + H2

    Ag, 350oCCHCH2CH3OH

    CH3 CCH2CH3 + H2O

    CH3

    HIO4C C H

    OH

    ROH

    R R1

    CR

    RO

    1

    + RCH

    O

    C CO

    H H

    OHOCH2C

    H

    OCH2 CH2OH OH

  • 22

    , . : , , , , .

    :

    . ( ):

    -

    , , :

    , . , .

    :

    R CH

    O+ H2CrO4 CHOCrO3H

    OH

    R

    CH3 C

    H

    OCrO3H

    OH

    RCOOH + HCrO3 + H- +RCOOH + R CH2COOH

    1

    CCH2R

    O

    RCH21

    RCH2COOH + R COOH1

    CH CO

    CH2RR

    R1

    2C

    RR

    O + R CH2COOH12

    CHCOOH + R COOHRR

    12

    -H2O[O]

    [O]

    OH-

    COH

    O

    R +RCH2CCH2R1

    O

    1COH

    O

    R

    RCH2COOH + R COOH1

    11-RCH C R

    O

    RCH C R

    O

    11-RCH2CCHR

    O

    RCH2C CHR

    O

  • 23 :

    , , , , .

    , .

    ( , ), . , , , , :

    80%.

    - - - . - . , :

    RCH2COOH + R COOH1

    [O]

    [O]HF

    +H

    CCH2R

    O

    RCH21

    + 11RCH2C CHR

    OH

    H

    RCH2C CHR

    OH

    COH + R CH2COOH

    O

    R 11+ 1CCH2R

    OH

    C

    H

    R

    HCCH2R

    OH

    RCH

    O HNO3

    150-160oC

    HNO3O

    (CH2)3

    COOH

    COOH

    (CH2)4

    COOH

    COOH

    SeO2

    SeO2

    SeO2

    RCCH2R

    O

    1 1RC CR

    O O

    O O

    O

    RCH2CO

    HRCC

    H

    O

  • 24 .

    - . , :

    ,

    . ()

    , - . . RO2. , , . :

    :

    , ,

    , , - - . , - , . - - , - - , .

    RCOOR + R COOH

    1

    C

    O

    OH

    RR

    O CR

    O

    1RCR + R COOOH

    O

    1

    OH OH + RO2..

    OH O + ROOH

    RO2 + HO O ROOH + O O

    .

  • 25

    1. . . . : - . 1998. 360 . 2. . . . .: , 1990. 751 . 3. . . .: . 1981. . 1. 678 .

    . 2. 651 .

    1. . ., . ., . . . .: . 1973. 623 .

    2. . ., . . . .: . 1970. . 1. 623 . . 2. 744 .

    3. .., . . . .: . 1979. 519 .

  • 26 , . . , . .

  • 27

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