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22 CH203 Fall 2014 Lecture 22 October 24.pdf

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  • 8/10/2019 22 CH203 Fall 2014 Lecture 22 October 24.pdf

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    !"#$% '()*+,( ##-)*./(, #01 #$20

    344546) 784.9(:8;.:

    6=8;.:

  • 8/10/2019 22 CH203 Fall 2014 Lecture 22 October 24.pdf

    3/23

    !"

    #$%&

    (#)*+," *,,$-.")/#

    0

    1

    2

    !, 34,$ 0 56 17

    "80562

    "8

    2561

    "89 #"#$%& ,4 )*+:)+,"

    ;/#? ,"

    / //#? @.+," >/)/#

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    @7( 84454 ,8=6)84

    0

    *+,( .A *7( *H. D.BB6/4( D,.=+)*B .A /,.E6:8;.: 8* *7( (:= )8,/.:BI

    J. D,.=+)* A,.E /,.E6:8;.: 8* *7( E6==4( )8,/.: 6B ./B(,F(=I K75L

    H2C

    HC13CH3

    [1-13C]Propene

    CH2

    HC13CH2 H2C

    HC

    13CH2

    Br Br+

    Br2

    H3CC

    13CH2

    Br

    M$NM$

  • 8/10/2019 22 CH203 Fall 2014 Lecture 22 October 24.pdf

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    @7( 84454 ,8=6)84 O ,(B.:8:)( E.=(4

    M

    3 ,(B.:8:)( E.=(4 .A *7( 84454 ,8=6)84 B7.HB *78* *7,(( (4()*,.:B )8: /( E.F(= *.

    9(:(,8*( *H. (G+6F84(:* ,(B.:8:)( ).:*,6/+*.,BI P8)7 78B 8: +:D86,(= (4()*,.: .: 8:

    (:= )8,/.:I 3Q8)R .A *76B (4()*,.: 6: (6*7(, B*,+)*+,( .: =68*.E6) /,.E6:( H644 96F( *7(

    ./B(,F(= D,.=+)*I

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    S

    3 E.4()+48, .,/6*84 E.=(4 .A *7( 84454 ,8=6)84 B7.HB *78* *7( ).E/6:8;.: .A *7,(( #!

    .,/6*84B 96F(B *7,(( "E.4()+48, .,/6*84BI @7( ,8=6)84 (4()*,.: .))+D6(B 8 :.:/.:=6:9 T-

    6: H76)7 *7(,( 6B :. (4()*,.: =(:B6*5 .: *7( )(:*(, )8,/.:1 H76)7 46(B 6: *7( :.=( .A *7(

    T-I @7(,( 6B :. (4()*,.: =(:B6*5 8F8648/4( *. ,(8)* H6*7 /,.E6:( 8* *76B D.B6;.:I

    @7( 84454 ,8=6)84 O E.4()+48, .,/6*84 E.=(4

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    @7( 84454 ,8=6)84 O E.4()+48, .,/6*84 E.=(4

    U

    3 ).ED+*(= (4()*,.: =(:B6*5 E8D .A *7( :.:/.:=6:9 T- )4(8,45 B7.HB *7( 48)R .A

    (4()*,.: =(:B6*5 .: *7( )(:*(, )8,/.:I

  • 8/10/2019 22 CH203 Fall 2014 Lecture 22 October 24.pdf

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    344546) /,.E6:8;.: .A 8 48,9(, B5B*(E

    V

  • 8/10/2019 22 CH203 Fall 2014 Lecture 22 October 24.pdf

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    344546) /,.E6:8;.: .A 8 48,9(, B5B*(E

    X

    @7( E6:., D,.=+)*1 %C/,.E.C2C.)*(:(1 ).E(B A,.E /,.E6:8;.: .A *7( 6:*(,E(=68*(

    ,8=6)84 H6*7 8 E.,( B+/B;*+*(= ,8=6)84 )8,/.: /+* 8 4(BB B+/B;*+*(= =.+/4( /.:=I

    @7( E6:., D,.=+)*1 2C/,.E.C#C.)*(:(1 ).E(B A,.E /,.E6:8;.: .A *7( 6:*(,E(=68*(

    ,8=6)84 H6*7 8 4(BB B+/B;*+*(= ,8=6)84 )8,/.: /+* 8 E.,( B+/B;*+*(= =.+/4( /.:=I

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    344546) /,.E6:8;.: .A 8 48,9(, B5B*(E

    2$

    @7( E6:., D,.=+)*1 %C/,.E.C2C.)*(:(1 ).E(B A,.E /,.E6:8;.: .A *7( 6:*(,E(=68*(

    ,8=6)84 3 H6*7 8 E.,( B+/B;*+*(= ,8=6)84 )8,/.: /+* 8 4(BB B+/B;*+*(= =.+/4( /.:=I

    @7( E6:., D,.=+)*1 2C/,.E.C#C.)*(:(1 ).E(B A,.E /,.E6:8;.: .A *7( 6:*(,E(=68*(

    ,8=6)84 W H6*7 8 4(BB B+/B;*+*(= ,8=6)84 )8,/.: /+* 8 E.,( B+/B;*+*(= =.+/4( /.:=I

    ".H =. H( (B;E8*( *7( ,(48;F( (:(,96(B .A *7( 6:*(,E(=68*(BL Y: *76B )8B(1 H( =.:Z*78F( *. (B;E8*( O H( )8: (>8E6:( *7( ,(B+4*B .A 8: 8)*+84 ,(8);.: 8:= B(( H76)7

    D,.=+)* D,(=.E6:8*(=I @7( E8[., D,.=+)* E.B* D,./8/45 )8E( F68 *7( 6:*(,E(=68*( .A

    4.H(, (:(,951 7(,( W1 =(*(,E6:(= *. /( B. (>D(,6E(:*8445I

    Y* 6B 9(:(,8445 ./B(,F(= *78* *7( E8[., D,.=+)* 6: B6E648, ,(8);.:B H644 /( *7( .:( H6*7

    *7( E.,( B+/B;*+*(= =.+/4( /.:=I

    vs.

    3N 4(8=B *. E6:., D,.=+)* WN 4(8=B *. E8[., D,.=+)*

  • 8/10/2019 22 CH203 Fall 2014 Lecture 22 October 24.pdf

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    K.74O\6(94(, /,.E6:8;.:

    22

    OOH3C

    H3C

    OOH3C

    H3C

    Br

    N

    O

    O

    Br

    O

    OO

    O

    CCl4, reflux

    Y: 8 K.74O\6(94(, /,.E6:8;.: *7( 84R(:( 6B =6BB.4F(= 6: )8,/.: *(*,8)74.,6=( 8:=

    .:( (G+6F84(:* .A JW] 8:= 8 BE844 8E.+:* .A /(:^.54 D(,.>6=( 8,( 8==(=I @7(

    ,(8);.: 6B /,.+97* *. ,(_+> *. 6:6;8*( *7( ,(8);.: /5 )4(8F6:9 *7( D(,.>6=(/.:=I

    @7( D,.9,(BB .A *7( ,(8);.: 6B A.44.H(= /5 H8*)76:9 8B *7( JW]1 H76)7 6B

    6:B.4+/4( 8:= B6*B 8* *7( /.Q.E .A *7( B.4+;.:1 6B ).:F(,*(= *. B+))6:6E6=(1

    H76)7 _.8*B *. *7( *.D .A *7( B.4+;.:I

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    3YWJ 8B 8 ,8=6)84 6:6;8*.,

    2#

    3^./6B6B./+*5,.:6*,64( `3YWJa 6B 8:.*7(, ).EE.: 48/.,8*.,5 ,(89(:* +B(= *.6:6;8*( ,8=6)84 ,(8);.:BI 3YWJ (46E6:8*(B J#H7(: H8,E(= *. 96F( *H. #C

    )58:.D,.DC#C54 ,8=6)84BI

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    W,.E6:8;.: #*. 8 )8,/.:54

    2%

    3 75=,.9(: #*. 8 )8,/.:54 6B (8B645 8/B*,8)*(= *. 4(8F( 8 ,8=6)84 H76)7 6B

    B*8/646^(= /5 =(4.)846^8;.: 6: E+)7 *7( B8E( E8::(, 8B 6B *7( 84454 ,8=6)84I

    Cl

    O Cl

    O

    Cl

    O

    Cl

    O

    NBS

    HBr

    CCl4

    85 oC

    H Br

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    @7( /(:^54 ,8=6)84

    20

    3 /(:^546) 75=,.9(: 6B 8/B*,8)*(= *. 4(8F( 8 ,(B.:8:)(CB*8/646^(= /(:^546) ,8=6)84I

    H H

    BDE 372 kJ/mol BDE 376 kJ/mol

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    @7( /(:^54 ,8=6)84 O /(:^546) 784.9(:8;.:

    2M

    W,.E6:8;.: .A (*754/(:^(:( +:=(, ,8=6)84 ).:=6;.:B 96F(B 8B *7( .:45 D,.=+)*

    ,8)(E6) 2CD7(:54C2C/,.E.(*78:(

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    @7( /(:^54 ,8=6)84 O /(:^546) 784.9(:8;.:

    2S

    @7( 48,9( =6b(,(:)( 6: 7.E.45;) W.:= c6BB.)68;.: P:(,96(B /(*H((: 8 /(:^546) !C"/.:= 8:= 8: 8,54 !C" /.:= (>D486:B H75 :. 8,54 /,.E6=(B 8,( A.,E(= 6: *7( ,8=6)84

    /,.E6:8;.: .A 8 B5B*(E H76)7 78B 8 /(:^54 !C" 8F8648/4( A., ,(8);.:I

    H

    BDE 376 kJ/mol

    H

    BDE 473 kJ/mol

  • 8/10/2019 22 CH203 Fall 2014 Lecture 22 October 24.pdf

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    @7( /(:^54 ,8=6)84 O /(:^546) 784.9(:8;.:

    2U

    OH

    O

    H3C

    4-Methylbenzoic acid(p-Toluic acid)

    OH

    O

    H2C

    OH

    O

    H2C

    Br

    4-(Bromomethyl)benzoic acid

    NBSbenzoyl peroxidechlorobenzenereflux1 hour

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    6=8;.:

    2V

    6=8;.: .A

    A8*B 6:*. B7.,*C)786: 84=(75=(B 8:= R(*.:(B H76)7 8,( ./[();.:8/4( 6: *8B*( 8:= .=.,Ie

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    6=8;.:

    2X

    '6:.4(6) 8)6=1 H76)7 6B A.+:= 6: E8:5 .64B 8:= 6: /+Q(,1 ).:*86:B 8 210C=6(:( A+:);.:84

    9,.+DI @7( !"# 75=,.9(:B B7.H: 6: ,(= 8,( 844546) 6: /.*7 =6,();.:B 8:= B. 8,( E.,(

    ,(8);F( *78: 8 :.,E84 844546) 75=,.9(:I

    `X"12#"aCX12#C-)*8=()8=6(:.6) 8)6=f '6:.4(6) 8)6=

    R

    11 22

    33

    44

    R

    H H

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    6=8;.:

    #$

    3 ,8=6)84 BD()6(B g 8/B*,8)*B .:( .A *7( =.+/45C844546) 75=,.9(:B *. 4(8F( 8 ,(B.:8:)(C

    B*8/646^(= )8,/.: ,8=6)84I

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    6=8;.:

    #2

    @7( ,8=6)84 8Q8)RB -#*. 9(:(,8*( 8 D(,.>6=( ,8=6)84 H76)7 *7(: 8/B*,8)*B 8:.*7(,

    75=,.9(:I @7( (:= D,.=+)*B .A *76B )786: 8,( ).ED4(> E6>*+,(B .A B7.,*1 F.48;4(1 8:=B;:R5 E.4()+4(B H76)7 8,6B( A,.E *7( B(F(,84 H85B *78* .,98:6) D(,.>6=(B )8: =(9,8=(I

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    6=8;.:

    ##

    ]7.H: 8/.F( 6B .:( .A *7( H85B *78* .,98:6) D(,.>6=(B =(9,8=( 8 )786:I "(,( 8 D(,.>6=(

    ,(8,,8:9(B H6*7 (46E6:8;.: .A

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    6=8;.:

    #%

    c68*.E6) .>59(: 6B F(,5 ,(8);F( *.H8,=B ,8=6)84B /()8+B( 6* 6B 6*B(4A 8

    =6,8=6)841 H6*7 *H. +:D86,(= (4()*,.:B 6: 6*B 7697(B* .))+D6(= E.4()+48,

    .,/6*84I


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