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H2C
HC13CH3
[1-13C]Propene
CH2
HC13CH2 H2C
HC
13CH2
Br Br+
Br2
H3CC
13CH2
Br
M$NM$
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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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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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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
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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
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
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
8/10/2019 22 CH203 Fall 2014 Lecture 22 October 24.pdf
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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
8/10/2019 22 CH203 Fall 2014 Lecture 22 October 24.pdf
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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
8/10/2019 22 CH203 Fall 2014 Lecture 22 October 24.pdf
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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
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;.:
2M
W,.E6:8;.: .A (*754/(:^(:( +:=(, ,8=6)84 ).:=6;.:B 96F(B 8B *7( .:45 D,.=+)*
,8)(E6) 2CD7(:54C2C/,.E.(*78:(
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;.:
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
8/10/2019 22 CH203 Fall 2014 Lecture 22 October 24.pdf
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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
8/10/2019 22 CH203 Fall 2014 Lecture 22 October 24.pdf
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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
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R
11 22
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R
H H
8/10/2019 22 CH203 Fall 2014 Lecture 22 October 24.pdf
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6=8;.:
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B*8/646^(= )8,/.: ,8=6)84I
8/10/2019 22 CH203 Fall 2014 Lecture 22 October 24.pdf
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6=8;.:
#2
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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
8/10/2019 22 CH203 Fall 2014 Lecture 22 October 24.pdf
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6=8;.:
##
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,(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