..

v ,nikov's rule~ Reglo,~Jective

9. hycfrogen halid e s . M a. rk.e-,>,- .- . ·- :,
f
9~S_l),. . (. ·: .· .
• : ,

-ecaldj~ :- i -

''
r ctioD
~~~-~q lp ,tjd.e, 'Jijdr~~e~q brbtnide, dt h)'cifoge:
_. ~ - alkell e ~s collV ertea ;by hr,,~,~
cle. ' , ·
q
i>On ding alk }'lha li
lochde 1 n to th e correS_

.(
 , ( f I •

CH2=CH2 + HI CH3CH2l ' "·

Ethylene Ethyl iodide

tib
1

~rovylene· CO~d yield eithe; of products, the n-propyl hali~~I or the iso-
propyl halide, depending upon the'orientatioh of addition, tliat is~\iependidg upon j'
which carbon ·atom! the hydroge~ and halogen become attached to. Actually, only· 'i
1
the isopropyl halide
.
is formed. .
•• (
., . . . I • ,.. . • , 1; ·: ~');/:i •
j
I ,. j

J •:
. trH3-CH CH2 · - * cH;~cH-CH2. . .• . . . ....tl..J!.J\.iS
~-;·v..l
\..,"': - • --·: • • · ... . • • 'I ·1 . )t# •,

. .. . . .
• ., ... . • \ .. " . a.
H 1··. ; .t ;.. ...'4 ... ,..\_..,•
-
-a
' : 1.
--f
.z !_,H
\
u •)'
. •\..' ·1 t'. .·-. A
l
........
,
•• I·• . ~" . "\ ••·•
,r •~•
•••t•.1·
>•
i~~l
rJ..f(
y~t~,·M
t .... ~i;.;.,# ""t.S

n-Propyl iodide , _. jf, ~<1 :{~:Ul ~'!NU

1
v.
CH3-CH=CH2 ---+ CH;-·CH-·CH 2•
• • • '."t . , , . l ., I - .. ,.
Actual product .
1 1 • .. •
1 I

,"': 1 • • " i l · ~1 ,....,.

' •
•• )
- ·. · •• 1-H · ' • • "I ,•• , • ' ' ., •'I - / . H , ·,.• • ... I
l
•' •
- :
•
• If:
•
~1 i
••· I
,.
• "I

lsopropyl iodide J
.. l
:
.
.I
..
',(.'-t!½ , •
. ,

~n the same way, isobµtylene could ·yield eithei of two products, isobutyl,halide or
• .. ·1 •. 1' ,.,\,.
•. : '>••;, •-'
- .: , J : .• • '1 : • - ,.•· •.' )' ""l
..),,• '~ • • ' •'-<.·
'1> ;r • ·(."'-<i, ,C, .>\;\,, f r',:~
" 1' •· ·, i ' ' .•
..
l
terr-butyl halide; here the orientatio·n of a~dit~on is S!J~h ~~at only the tert-butyl \
halide is formed.
;, • • J •• , CH,•• ••iH ••, (t Ir • • • --,--• • 1.•• • • '. •• l
··* ·
••I ,• ••, ./•,•.',

. / \ 3 ... .'.•i • .. ·.r • . • . . :. 3, • •. • • • . '. ,:- .. : •:, _.: -~• .·• ,, . l

• . . • CH 3-C CH 2 CH3- .:__CH . . . . . •· .~ • •.. _r ••'•.
'\c \ • , J 1i I ... • I I •2
•.•__, H-1 . ·: . · , •. H ': I . •
lsobutyl iodide ·
,l I
'·
3
7 1-·'t::H~:_r21i~1 .!~~·,,Cff';.'.:.1~ h"~~,:' . t <~:-i~~Ualpioa~~j'.: ~1~'-. c. \'
~' '.n-3.~::.: .i
1-H
, I ,, \ , , • ·I••• ' • • r, • \,I ( \ • • ;.~ • ' •
! · , ·• " ·• • - • ,. ' • ' • '· · • • · ' • J te,·I~-Butyl • ~., > •
, iod'"...i',
luC.....•.. \·'
'-
I • ., l •
•• •' ....·y •'·, · ) t.-·, a• ••"\ •,..,,.'" lr• ••·' •,." .
'l ••£j,i"'~-..J\ J "\•'\') \Jf:f'. ~1,.1
4

~,.1.,1 11 \.I.} ; ),~

. .;, ,t, .. ~w1 l I

/2hus, in the addition o~ a reagent YZ to an alke~e, orie~t~tion •~i'epends upon

which doubly ~n?~d ~ar~~n a~~epts ~·Jf.d Wh\ch accep1_S z. . .
/ On exaII11nat1~n of 13;1'SC\ ~~ber ofJ su~~ ,.~dditions.1 the Russian chcrnt~t
Vladimir Markovntkov (Un1vers1ty of K:azan)·observed tliat, where two isofuer1c
products are possible·, one,of $em usually preqominates. He pointed out-in 1869 '
,,l
.
""~
 /
•sic: 9.5 ADDITION OF HYDROGEN HALIDES
365
/ ~ t h e orientation.of addition follo
ws a pattern•\vhil)h we can summarize as! /,I
the addition of an. acid to the ca,:bf,n-:-earbon doub
le
the acid attaches _itselfto the carbon that already bo~ of an a/k~ne, the hydrogen of
holds the greater nuvu,er ofhyd,:oge"!;
this statement 1s generally kno wn as Mar
kovnlk.ov'~rule ]'~u s; "Un to everyone
that hath shall be given,., or u The m as has, gits O •
~hu s,i in the ~dd itio n to pr:opylene we • ,
~ee that the hydrogen goes io the carbon
b~ w o hydrogen atom s rath er th~
tp \he carbon,bearing one. In t~e additio1;1
to isobutylene, the hyd rog en goes to the
carb on beariqg,two hydrogens rathe~ than
to the carbon bea ring non e.
Using Mar kov niko v's rule,, we can corr . .
ectly pre.diet the principal produ~tlJf
many reactions. For ex am pl~
.
~C l;l1 CH -.C H2 + HI ~ 1
CH3CH1~}i1CH3
I-Butene . ,sec-Butyl iodid~
(2-lodobutanc)

/ CH
I 3
CH 3C=C H-C H 3 + HI
2-Mcthyl-2-butene
...
tert-Pcntyl iodide
(2-lodo-2-mcthyl butane)

CH 3CH= CHC H3 + HI GH~CHICH2CH3

2-Butene sec-Butyl iodide'
(2-lodobutane) • '

CH2=C H0 + HI CH 3CH1Cl
Vinyl chloride t-Chtoro-1-iodocthane •
(Chlo roeth cne)
CH CH2CHICH2CH3 + CH3CH1CH1CHI
~ CH3
3C~2CH= CHC H3 + HI \.Jod open tane 2-Jodopentane
~Pentene . •
/in 1-pentene each of the doubly bonde.dhcarbprod
ons holds one hydrogen, so th~t
uct to predomi
~r di ng to the rule we should expect nate. Here again
ne1tbler equal• quantities of the two isomers
the.prediction is ess en~ ·Y correct, roug
actually being obtained.
y . .
. .
.r=rhe examples ha nvolved the addtdtton of b drogen iodide; exactly similar
. c~oride and, except ro·r special
results are obtained in the 'add1·fon 1 . of- hy rogen 'd
conditions indicated in the·following secti~: of hydrogen brom1 e. •
, rientation, give exclusively or ,nearly
Reactions that from the standpoint o, od
-exclusively one of seve
the Latin regjo, direction, and pronoun d "reejio "~
i e
ce
ts
' raI poss 'bl isomeric pro uc are called regl osel ecdv e. (From
.
:J
• • , ., .
• r f
,.. ' r--'
<
' \·
Ao

••
·--tµ lflf-" "l'~,;-·-'U- ..
-~~ ~tf J :::~ .'~~·~'~.-dil;rdituiJolij1fot{OriCJl •• tion'( Sec s.29),
... ~~l epi :-- S,,i .~~
ta~~nof;~!l~ ;- -~9v1ilk~v!•qf-
th'e ~P~-~~ins-fpm.c~,. b~t,.~~ a· widi lt&
~qns._ not pf !~1 .p:q ~p~ .n a·•toms
· rf h dr ' on o~~ c subs ~t~,1 •8· ~~C f I ... ~- r , , ,'for. ,t)u~'\r .
~U¥l~rs o y Q.S~ ~ c:t carb 9n • •., • • .
~-fl~ ~2\y" g"-"m 7PA.. J.tle • ': • -' 1tl . . 'll'i'l "1 ._.,,. • ';i
t. t
f ,. i·,..., , • '"
t ;(,i:'S:
, . "'!<'.'•H· • .,.t;~ '•£;" t~ l\• 1:' • ,, :_..,._
, •
r,\q- • '
l,1lla. l a., ......nTw ir ,- ~. • .. :. ' '<i~\
1(4 "'f• • • ""' 1 It',. ;11... •
, •;• ..,
•4 •;~lf, kJ~- ~~ .. '
~ i~1.:;.....~-~ "
$!·.,i\R .l,r.
..,. ••7
;,, .,. • ••
- ·.,Pi ~_.. ., ... ~.- "'A" • 4·• • :i
s 1:-'SL~ xtl rut:f'""m ~---