25 CH203 Fall 2014 Lecture 25 October 31

  • Upload
    buch203

  • View
    218

  • Download
    0

Embed Size (px)

Citation preview

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    1/43

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    2/43

    !"#$% '()*+,( #-

    .)*/0(, %12 #$13

    #

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    3/43

    4,(( ,567)58 958/:(;5

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    4/43

    =567)58 )957; >()95;7?>

    3

    @(*95;( 5;6 )98/,7;( ,(5)* 7; 5 ?(,7(? /A ?*(B?C

    1D !957; 7;7

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    5/43

    =567)58 )957; >()95;7?>

    -

    @(*95;( 5;6 )98/,7;( ,(5)* 7; 5 ?(,7(? /A ?*(B?C

    1D !957; 7;7

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    6/43

    =567)58 )957; >()95;7?>

    H

    @(*95;( 5;6 )98/,7;( ,(5)* 7; 5 ?(,7(? /A ?*(B?C

    1D !957; 7;7

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    7/43

    =567)58 )957; >()95;7?>

    J

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    8/43

    4,(( ,567)58 )957; ,(5)

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    9/43

    =567)58 )957; >()95;7?> E ,(:7/?(8()

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    10/43

    =567)58 958/:(;57?*,I

    1$

    CH3

    CH3

    CH3

    Br2, heat

    YB()7AI ?*(,(/)9(>7?*,I 7; *9( B,/6+)*Z?[D

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    11/43

    =567)58 958/:(;57?*,I

    11

    R9( 7;*(,>(675*( ,567)58 7? \5*D PA *9( ,567)58 A/,>? 5* 5 )97,58 )5,0/;2 5;I

    ?*(,(/)9(>7?*,I 7? 8/?* 7; *9( B,/6+)*?D

    CH3

    CH3

    CH3

    Br2, heat

    CH3

    CH3

    CH3Br

    CH3

    CH3

    CH3Br

    +

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    12/43

    =567)58 958/:(;57?*,I

    1#

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    13/43

    =567)58 )957; ,(5)>/;6]? Q/?*+85*(C R9( *,5;?7/,( ?7>785, 7; ?*,+)*+,( */ *9( ?B()7(? */

    G97)9 7* 7? >/,( ?7>785, 7; (;(,:ID

    ^_/*9(,>7) ,(5)

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    14/43

    13

    R9( ?>588(, !!ab 7?2 *9( 8(?? ?(8()

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    15/43

    K88I87) 0,/>7;5

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    16/43

    5."1#6

    !"/()%. (%%17$./8"

    9

    :

    ;

    !% ? :@

    "A9>?;

    "A

    ;>?:

    "AB "."1#6 %= /()*/)%.

    3C" 1/8">7"8"14$.$.# &8"2 %.

    8C" D/6 =1%4 9 8% : $& 8C"

    &8"2 DC$(C C/& 8C" '/1#"&8 "A

    !/8" 7"8"14$.$.# 81/.&$)%. &8/8"

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    17/43

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    18/43

    R9( 588I8 ,567)58 E ,(?/;5;)( >/6(8

    1d

    K ,(?/;5;)( >/6(8 /A *9( 588I8 ,567)58 ?9/G? *95* *9,(( (8()*,/;? )5; 0( >/F(6 */

    :(;(,5*( *G/ (e+7F58(;* ,(?/;5;)( )/;*,70+*/,?D ^5)9 95? 5; +;B57,(6 (8()*,/; /; 5;

    (;6 )5,0/;D Kf5)` /A *97? (8()*,/; 7; (7*9(, ?*,+)*+,( /; 675*/>7) 0,/>7;( G788 :7F( *9(

    /0?(,F(6 B,/6+)*D

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    19/43

    1S

    K >/8()+85, /,07*58 >/6(8 /A *9( 588I8 ,567)58 ?9/G? *95* *9( )/>07;5/8()+85, /,07*58?D R9( ,567)58 (8()*,/; /))+B7(? 5 ;/;0/;67;: @.

    7; G97)9 *9(,( 7? ;/ (8()*,/; 6(;?7*I /; *9( )(;*(, )5,0/;2 G97)9 87(? 7; *9( ;/6( /A *9(

    @.D R9(,( 7? ;/ (8()*,/; 6(;?7*I 5F578508( */ ,(5)* G7*9 0,/>7;( 5* *97? B/?7/8()+85, /,07*58 >/6(8

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    20/43

    K88I87) 0,/>7;5

    #$

    =567)58 0,/>7;5/+;*? /A *9( *G/

    B/??708( B,/6+)*?D

    W,/>7;5(675*( 95BB(;? 5*

    +;(e+58 ,5*(?D

    P* 7? :(;(,588I /0?(,F(6 *95* *9( >5g/, B,/6+)* 7; ?7>785, ,(5)/,( ?+0?

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    21/43

    R9( 0(;hI8 ,567)58

    #1

    K 0(;hI87) 9I6,/:(; 7? 50?*,5)*(6 */ 8(5F( 5 ,(?/;5;)(X?*50787h(6 0(;hI87) ,567)58D

    H H

    BDE 372 kJ/mol BDE 376 kJ/mol

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    22/43

    R9( 0(;hI8 ,567)58 E 0(;hI87) 958/:(;57;5/(*95;(

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    23/43

    R9( 0(;hI8 ,567)58 E 0(;hI87) 958/:(;5

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    24/43

    K667

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    25/43

    =567)58 5667

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    26/43

    =567)58 56677?*? *9(,(A/,( B,/B/?(6 5 ,567)58 )957; >()95;7?>D

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    27/43

    =567)58 5667

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    28/43

    =567)58 5667/,( ?*508( %/)5,0/; )5

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    29/43

    k95* 7;A/,>5l

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    30/43

    k95* 7;A/,>5l

    1D

    R9( 8/)5

    Z)9(>7)58 ?97m[D R(88? +? *9( 8/)58 (8()*,/;7)

    (;F7,/;>(;* /A *9( 9I6,/:(;D

    #D R9( ;+>0(, /A 67V(,(;* 9I6,/:(; ,(?/;5;)(?D R(88?

    +? 9/G >5;I ?(*? /A ;/;(e+7F58(;* 9I6,/:(;? 5,(B,(?(;*D

    %D R9( ;+>0(, /A 9I6,/:(;? 7; (5)9 ;/;(e+7F58(;* ?(*

    0I 7;*(:,50(, /A ;(7:90/,7;: 9I6,/:(;?D

    -D

    R9( /,7(;*5

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    31/43

    !9(>7)58 ?97m

    %1

    R9( )9(>7)58 ?97m /A 5 B,/*/; 7? 7;\+(;)(6 0I

    *9( (8()*,/; 6(;?7*I 7; 7*? 7>>(675*(

    (;F7,/;>(;*D

    ^8()*,/;(:5? G7*96,5G (8()*,/;

    6(;?7*I2 6(?97(867;: *9( B,/*/;2 5;6 ?97m7;:

    7*? ?7:;58 */ 97:9(, BB>D

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    32/43

    !9(>7)58 ?97m

    %#

    R9( )9(>7)58 ?97m /A 5 B,/*/; 7? 7;\+(;)(6 0I ?>588

    >5:;(>(675*( (;F7,/;>(;*D

    W/7;6+)(? (8()*,/;X,7)9 B7X0/;6(6 A+;)5:;(

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    33/43

    !9(>7)58 ?97m

    %%

    R9( )9(>7)58 ?97m /A 5 B,/*/; 7? 7;\+(;)(6 *9(

    9I0,767h5/,( ? )95,5)*(, 7; *9( )5,0/; 0/;67;: /,07*582 *9(

    )8/?(, *9( 0/;67;: (8()*/;? 5,( */ *9( )5,0/; ;+)8(+?D

    R9( 5f5)9(6 B,/*/; 7? 6(?97(86(6D

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    34/43

    YB7;X?B7; )/+B87;:

    %3

    Z"M 1[,+8(CPA 5 9I6,/:(; 95?

    "9I6,/:(;? ;/;(e+7F58(;**/ 7* 0+* (e+7F58(;* 5>/;:

    *9(>?(8F(? /; *9( ?5>( /,

    56g5)(;* 5*/>Z?[2 7*? 1"Xc@=

    ?7:;58 7? ?B87* 7;*/ Z"M 1[

    B(5`?D

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    35/43

    YB7;X?B7; )/+B87;:

    PA "5?B87*? "0G7*9 5 )/+B87;: )/;?*5;*#2 *9(; "0?B87*? "5G7*9 *9( ?5>(

    )/+B87;: )/;?*5;*D

    PA I/+ ?(( *9( ?5>(#F58+( ,(B/,*(6 A/, *G/ ?(*? /A >+8

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    36/43

    YB7;X?B7; )/+B87;: G9(;# F58+(? 5,( ?7>785,

    #505;6#0) 5,( )8/?( */ *9( ?5>( >5:;7*+6(0()5+?( *9(I 5,( 7; 5 \(_708( )957;D =/*5( F58+(D

    P; :(;(,582 G9(,( I/+ G/+86 (_B()* */ ?((

    Z; M1[ _ Z> M1[ B(5`?2 5 \(_708( ?I?*(> 87`( *97?G788 :7F( Z; M > M1[ B(5`?D

    Z; M1[ _ Z> M1[ o S B(5`? (_B()*(6

    Z; M > M1[ o - B(5`? /0?(,F(6

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    37/43

    YB7;X?B7; )/+B87;:

    C C

    HH

    C C

    H H

    C C

    H

    H

    C C

    H

    H

    H

    H

    C C

    H

    C H

    H

    H

    H

    H

    H

    H

    %#2 F7)7;58HXd "h

    %#2 F7;I87) &'(

    -X1$ "h

    %#2 F7;I87) )*+"(

    11X1d "h

    ,#2 F7;I87) -./'"+0

    $X- "h

    ,#2 -./'"+0

    $X- "h

    1#2 588I87)

    $X1 "h

    ,#2 2*)32

    JXS "h

    %#2 >(*5

    #X% "h

    1#2!+*+

    $X1 "h

    R9( >5:;7*+6( /A *9(

    )/+B87;: )/;?*5;*

    *(88? +? ?/>(*97;:

    50/+* *9( ?B5(*,7)

    ,(85

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    38/43

    R9( )/+B87;: )/;?*5;*2 p2 5;6 *9( q5,B8+? )+,F(

    R9( q5,B8+? )+,F( B,(67)*? *95* F7)7;58 "X" )/+B87;:? G788 0( :,(5*(?* 0(*G((; B,/*/;? G7*9

    1d$T 5;6 $T 679(6,58 5;:8(? 5;6 *95* )/+B87;: G788 0( 8(5?* A/, B,/*/;? *95* 5,( S$T A,/>

    (5)9 /*9(,D

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    39/43

    c+>0(, /A 9I6,/:(;? 0I 7;*(:,5(88? 87`( 08+(0(,,7(?[ 95? *G/ ?(*? /A (e+7F58(;* 9I6,/:(;? 5;6 5

    >/8()+85, A/,>+85 /A !H"1#.#D R9( */*58 ;+>0(, /A 9I6,/:(;? 7? 1#D R9( */*58 7;*(:,58

    7; *9( c@= 7? #% M HJ o S$ +;7*?D

    S$ +;7*?r1# " o JD- +;7*?r"D

    R9( B(5` 5* # BB> ,(B,(?(;*? #%rJD- o % "D

    R9( B(5` 5* 1D- BB> ,(B,(?(;*? HJrJD- o dDS " o S "D

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    40/43

    k9(; 9I6,/:(;? 67?5BB(5,

    R9( !"% 9I6,/:(;? 7; >(*95;/8

    7; *9(?( *9,(( 67V(,(;* c@= ,+;?

    5BB(5, 5* 50/+* %D3 BB>D R9(

    ,(?/;5;)( /A *9( ." 9I6,/:(;

    F5,7(? A,/> %DHH */ 3D1S BB>D

    R97? 7? *IB7)58 0(95F7/, A/,9I6,/:(;?2 *IB7)588I ." 5;6 c"2

    G97)9 )5; 9I6,/:(; 0/;6 */ *9(

    ?/8F(;* 5;6 */ /*9(, >/8()+8(?D

    !/;)(;*,5B+,77)58 ?97m /A

    *9( (_)95;:(508( 9I6,/:(;D

    !"%."

    !"%."

    !"%."

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    41/43

    k9(; 9I6,/:(;? 67?5BB(5,

    K667;: 5; (_)(?? /A s#. */ *9(

    c@= ?/8F(;* (_)95;:(? 588 *9(

    9I6,/:(;? /; *9( >(*95;/8 ."D

    !"%." 0()/>(? !"%.sD R9( s6/(? ;/* 5BB(5, 7; *9( c@=

    ?B()*,+>D R9( !"% 9I6,/:(;?

    ,(>57; 5* %D3 BB>D

    !"%.s

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    42/43

    k9(; 9I6,/:(;? 67?5BB(5,

    "I6,/:(; 5*/>? 0/;6(6 */ /_I:(; /, ;7*,/:(; 5*/>? )5; (_)95;:( G7*9 (5)9 /*9(, A5?*(,

    *95; *9( ( 7* *5`(? */ 5)e+7,( 5 1" c@= ?B()*,+>D R97? B,/)(?? 7? :,(5*8I A5)787*5*(6 0I

    *,5)(? /A 5)76 /, 05?( 7; *9( ?/8+B/,*5;* A+;)7;(?2 5;6 5>76(?D Y7:;58? A/, (_)95;:7;: " 5*/>? 5,( :(;(,588I

    0,/56 ?7;:8(*? *95* 6/ ;/* *5`( B5,* 7; ?B87t;: G7*9 /*9(, ?7:;58?D

    A. Pentanoic acid (valeric acid)

    Figure 16100 MHz 1H-NMR spectrum of pentanoic acid.

  • 8/10/2019 25 CH203 Fall 2014 Lecture 25 October 31

    43/43

    k9(; 9I6,/:(;? 67?5BB(5,B.

    Trans-2-hexenoic acid

    Figure 17 100 MHz 1H-NMR trans-2-hexenoic acid.

    Figure 18100 MHz 1H-NMR spectrum of cyclobutanecarboxylic acid.