chb-ch-chi - e-book.ram.edue-book.ram.edu/e-book/c/ch423/ch423-10.pdf · chb-ch-chi ar chb-ch=ch2 +...
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CHB-CH-CHI
Ar
CHB-CH=CH2 + HBr 2-bromopropane
C&-CHz-CH2-Br
l-broinopropane
CH 423 215
216 CH 423
VllTlJd 10.1 Apparent degree of dissociation (‘70) WI9 methyl-substituted “hexaphenylethanes”
0.1 M solution in benzene (To1 = CH3C6H4)
“(PhzTolC-):) ~ “(PhTolsC-):’ “(TolsC-):-
meta-To1 6.5 I 40
para-To1 5 5.5 1 6
(nuclear magnetic resonance (n.m.r.) spectrum)
Zn
PhsC-Cl -F PhsC* -+ Ph&-CPh,
X
(2) (3)
n"7lh hexaphenylethane WIU (1) ttzl”a I3lfl35l~U aromatic protons tViI&U
ILdtYl^ILh (2) ISlOZlTh aromatic protons 1111E olefinic protons n”afJ ~d~l~~a'llihJYnlY
~l¶JfI3dl-?n"ju' REiU dimerization ~~~6Fl'illflfll5~ triphenylmethyl redical W~J1hV!l
CH 423 217
Initiating reaction + F’
F. + CH4F2
+ HF+CH;- CH3F + F’
F1F’+CH,F + HF+CH,F’- CH2F2+F
F2F +CHzFz - HF+CHF;- CHF3 + F’
F’ + CHF, F2+ HF+CF; - CF,+ F’
218 CH 423
10.1 Stereochemistry
H ,,,,W”’ c -
/ b.,CHKH,
.I + OH- F HO-C L,-,’
\+ I-
r”,CfI,
CH 423 219
SO&H&HI
IPhCHz 0 K&OJC2H50H PhCH2 H
\c/ - lc/
/\ (b) /\CH3 H CHJ (3235
t-1
PhCHz OH
’ c’/ \
CHJ H
(+)
\_
K
(4)03
220 CH 423
(- )- CH,-CH-CO;
$lH
SJ inversion
(+ )-CHJ -
+T-( + )- CH,-CH-CO;
CHs HI
S,l retention
OH
(6)
CH 423 221
C& CH3\ /HAc=c\, + Br2
22? C!H 423
I + NH; -
CH-423 223
Benzyne
224 CH 423
‘bI
+ CzHs ‘%H
/ 1 Ha0 /,C2H5 -
c\
> W-b- c + C3HSO’H (14)
0
OH
CH 423 225
1. “lug fl.fl.1920 !~d@?flMld@s‘Ul ring closure v89 cyclopropane rings
x\c$c - x\ 7/\x c X
/c\c
R\C/CO-C03H OH
OH‘
R/\ =
COzH
CHrC02HCOIH
(1) (2)
2. I&Id1 2-bromo-Snitroacetophenone IJNdU¶J oxime ‘SE%@72 geometric isomers (A) LlW
tion
226 CH 423
H, NO,N ’
as:.. H,SO, 93 ‘5,: 0% 7 :/,
NH,
0I>
HNO,85X H,SO. 6% 34;/, 59%
CH 423 227
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