IV Elimination Reactions

8/3/2019 IV Elimination Reactions

1/42


2/42

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b-rd r > o-,..2 > U1 \ l.e. -8-,e [+iot\mav-n ) o v c x ku fe t>r V Y - ~ ed .,Gtc)Jc Q.c_e-\:o.-6o J ~ ~ ~ ~ v


4/42

Er- )be

5oo c

I

HI ,'1H - C_ _ _ _ _ C. - HI \I \ 'H 0

' I\ !'' - --:,..:::.-- c ......... R.6W> e ,..,k_.,.ed 'H .s:+a:h

0I} Wc:. = -+ R - c - 0

c " t.. ooc H.:2L ~ U 4 3 ~ . 3 . - Qt,_CH3CJ.1 / '3 o-coCH .3 ' , V'najOY) \ : J ~

Wo...4 Q 1 J u ~ d -t-ho. - t h ~ Yo1i- o"-t e . U ~ na..+io"' .ShoJd...i.ntevrvete.d Oh -the o{ t l e.. L h t ~ v m e d t c L t e

c.ovboc.Qtion ~ t a b i 1 { y . ~ c . . e t c d ~ lo.) ~ w U n Q ~ 3'7 tlme.b

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5/42

~ o - 0 - c . . . . _ C H . : ! c r ~ OCDcJ.f3

\ _ ~ ) l b)F\ Y " O ' " " ' ~ v ~ , - . f k i ~ bon r v o V J ~ tYlod-

lt\cyecued t t a b \ . 4 ~ o't e . ( . n c ' r ~ ~ - t d o u l J ~ bond.

- OF\ C.H h C ) ~ -~ c l k r ~ e c l be.th

so l e . h . O s . ~ U e

+(' .t_ / ,..,- 73 ""c- cI - ...._CHH 3

'/o)

), ......


6/42

" ' P ~ - r a \ . y ~ l s o - -t\-.e. eYjtl;wo 01v1d -thveo .kn e . ~ .

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( e - t ~ ~ Y O ) 0 ( . 0 ~ 3

'rh A44oc

"fh H

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rheltr.te.d .to U N ' I S b 1 e

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7/42

' P h - - - 1 ~ - o - - H

?h""C-==H /

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b u.A e ot de.u te.Y'ttvm l.a bEJs.The sy n e1Mlw.ntioV\ d e . m o ~ . d : . r c r l - e d by t1->')' te.V)tl 0\? crt de.Lf tY ' ) UJvn lh f"rocL..Ct Yl)YY) +h ( ! t Y ~ t h " f O Ye.o. c . ~ t ON'\d i ts ell wV_r,q-lion 1 n -t-he.~ v o d u c \ : ~ v c m th-veo Ye..o.c.. ~ t .

OPtC..

H - ~ 1 > ~ j c ~ H ..,_,____, . , ~ \ ' ' ' -4----P"' - ,,,"Y\-,'

)o ?h'\. I 1)c= - cI '-...\jvD.Ms)


8/42

t)OC.OCf-13

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9/42

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10/42


11/42

1 11 eGc - 0 - c -:- s 1\JQI

-c-=- c-\ I11 s1 I \1C- C - o - C +Na J :)H I

+ COS 1- c . . . Hme. YCQ r h u ~ )

So P ~ Y ~ s \ ~ Ot xOM-thcil-e eAte..Y ~ i e l d . A CM o . i ~ h e ; C : C . \ v b o n ~ t . S u t 1 t m e x O " - \ ) o ~

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12/42

mechOMAS W)

I sII AH - C - c. - o- c - sc..H\ \ 3-p h CH3$> l U-tH \ 3s) \:: c- l>h

( C13 s _ _Q j_H.. I/ '

So 1 1s1nal0 w cae..-t-H3 (_" C J ph\ -r ~ S H -r c.nsl-\3 ( I "H


13/42

i) t-JQ l-1' )

'ti c . s ~ '\'1i) CH3!

-+

1 ot umQ.yyamae.d hv.Wn,J cJh he .

-'1) NO.H.,...} c.s.,hi) Cfi3 I


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C H ~ cSJc - s ~ 6- '' -+-..) .s Ac . . H ~ H ~ s r n e ~ I CHuc-s 3-=-


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-

~ e ~ - l ~ ~ < - f i

~ c s ~ 1 ; ) ~ 1 : \ . _ U . . ) ~ C H )1.

A.

l _ C H ) ~ 4 1

LH r P ; ) c s ~

)@ r CHef' NO.

~ C H

ft It A.C-S ct13Ui - o - c:< /1.s


16/42

-

'1-\G.. )l) "'\ \ 1 I I

C13' '1>hc

H.3 c_ "-...c -==/'Ph

/ mec " " H

/ '-1c" C.H

.J

z.-cJkene.)


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syn s t ~ v ~ o s e l e . c . ~ . l t t : . / le.


18/42

) 'LV\ some c.o.J.eA 1 up ""'rth CJ.jc:JJ.c. co mp oWV'Id..b 1 move.. s ~ b k o . l ~ t n "t>vY\"S p

v) r r h ~ Y ~ o .v t alto s ~ v ~ c . e..i)\;e.c.:ts . S o o m ~ ~ V V I ~ d i . . . , ~ c b o ~ o te \ L ~ V 1 0 U ~ " ' A.b d ~ i : ~ v ~ " ' ~ d b'J + \ - \ ~ " " ~ e . . d -to eS - t ~ V I C . . \ n ' \ : ~ y o . C - t - ; 0 ~ (r . ' I S OV to yeJ l e ,ve_ S"te.Y'IL h J t - ' l d ~ Y ~ l Vl +-\. aY o ~ d S -\: o::R,

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"( e. u.).. -\::~ ( ) . . M

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0\.1\C -CHI .3>H

f

IIc - o- c -sc..,3lf \

.....es-c -=- ~ . c . . ~ - -

L e , ~ ~ . : c. - c:- tv'e)Hc - c- Al \ > C - c - -+ N -t - ~ ~ o

CLCH, ,) " " 0- CH. A 0 i) Md::,1) Pt3--0 - - - - ; ., ,... ) - CJ..I_, ii}H / o u Ne:.. ' b , ~ .3

o.l q, e. \')

rl'l4 N tv)(


19/42

"t A.N M B .lc- 0 l--1 rh- = C J . i ~ E.)( ) s (9 - A....Ho R ~ r J - c.. c.- NR3 -C.=. . c' Jl-1


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cle v ~ ~ e . oi) '8 u_Q-te.V'\"'Q (' y I S c J t ~ t.Ot'th S t t O \ " l ~ l o ~ C d . M 0 IN t..vw't' C- phL\ \ \ R( .

I --....... C=c . . - + " ~ . : t - + l.J c.tH C l r t ~ fl..-cJ.\ I- - - > C-=. . c- -t - N ~ - ~ ~

' T o ~ e " ' e - p - . S l . J . . \ " 1 \ f l hy cl"Q 3 O heI- c - c

l l

IC-IH

N - N H Tt

ellN - NH -TS

\ . ,.....'c.O'\ c---ci II C:o

J.\

i} ;t R L,' ti}

'

_ ....1- C::::_ cIH

c. - c -'

c'-c . II0

c: c -t-1

lc = -0\


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. /MCw..MvYll ~ e c .! Cha } - : s f e ~ II )

400 CHAPTER l l Reacttoos ol Alkylllalldes Nucteophlltc Subslltul'ons and :hmtnatlons11.24 Or


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hercrses 40 l11 32 Propose ~ t r u c t u r e s for rorn(.XJtiiHis that fit the tollowmg d e ~ n p t r o m (a) \n illk}'l halide Ihilt ~ r v c s ;'I mrxlurc or three a l k ~ n e ~ on El. reactwn

(b) \n o r ( ~ n n h a ! i d e that 1vrll not undergo nudeophrhc sull\lltution(c) ,\n alkyl 11.11tdc that ~ r v e ~ til


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402 CHAPTER 11 Reactions of Al!(yl Hahdes: Nucleophthc Substitutions and EliminatiO!Is11.37 Order each of the following sets of compounds v.rtth n?spert to S!\2 reactivity:

(a) CH3 Cl1 IH5C-C - CI CH3CH1CHzCI CH3CH2CHCH3ICHa(b) CH3 Ct-ll CH:;I ' I .CH3CHCHCH3 CH 3CHCHzBr Ctl3CCH2B(I IBr CH3lei CH3CH2CH20CH3 CH3CH2CH20Tos CH3CH2CH2Br

11.38 Pred1ct the prodLct and give the stereochemlsti)' resulung fJom react10n ofeach of t.he following nucleophiles with (R)-2-bromooctane:(a) - eN (b) CH3COz- (c) CH3s-1 1.39 (.R)-2-8romooctane undergoes cacemization to give (:!.:)-2,bromooctane whenueated with NaBr in dimethyl sulfoxide. Lxplam.

11 .40 Reaction of th e fotloN\ng S t o s y l a t ~ w1th cyanide io11 y!elds a nitrile productthat also has.Sstereochemjstry. ~ p l a i nH OTos\ ! NaCN 7....c .....H3C Cl-t20CH3

IS stereochemstry)

11.41 Ethers can often be prepared hy SN2 reaction nf alkoxidt' 10ns Ro-, w1thalkyl halides. Suppose you wanted to prepare cydohexyl meuryl erhet Whlthof the two possjble routes shown below w o t ~ J d you choose? Explatn.cro- \+ CH3l !l crOCH,or _.,( r ' CH,o- J11.42 We saw In Section 7.8 that bwmohydrin:s are convened mto epoxid


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.

Exerc1ses 40J11 43 Show the ~ t c r e o c h e m l > t r v of the epoxtdc (see Problen. 11 42) you wouldobtain b}' k1rmatlon of a bromohydnn from l r m l . ~ - 2 - b u t e n e , followed by treatment wllh l>ase11.44 In ltght of your an)wer to Problem I I f2, what product might you cwe(tfrorn treatment of 4-b tC'lr'no .J-butanol with bnse7

Base 7

11 45 l hi? tollowmg tertiary alkyl brom1dc: does ny e H h ~ r 5111 1 or S ~ 2 . mechantsms Explato

11 46 In addiuon to not undcrg01ng subsbtullon r e < ~ c t i o n s . the alkyl bcom1de~ h o w n 111 Problem 11.-l 'l also fails to undergo an ellminalton react1on whentreated with bdsc. Explam

11 .47 I Chloro-1,2-dlp!Hmylcthant.' can undergo e2 ehmm,tllon to give' C'lthcrLi> ()r llaiiS-1 ,2-dtphenylethylene (stilbene). [)raw Newman PWJ\!CUons or rhere tCIIvt' contormaiKns lead1ng 10 both p o s ~ t b l e products, Jnd suggl?'>l i1 tLc1snn why t h ~ t r a n ~ . ~ l k e n e ~ ~ ~ h e maJOr product

1Chloro 1.2diphenyletha ne trans-1 2 Oiphenyte thv lene

11 4.8 rediCI the major alkene pl()duct of the fo1Jo1' 11111, El r e : - < ~ c l l o nHOAc:--eal 1

11 49 file tOS)'IJtc ol (2R.3S)- ~ - p h c n y l - 2 butanol undergoes F2. tlun1n.thon ontteatment v.rith socltum cthoxide to yH?Id (Z}-2-phenyl-2-butcne E.xplam,ustng Newman protections

, \ ! > s r g ~ a b l e ' " OWL Key Idea Problems


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4!14 CHAPTER 11 Reactions ot Alkyl Halldes Nueleophiltc Substttulions and Ehmtnat10ns11 .50 rn light of youz aruwer to Problem I tA9, wbich nlkt>ne, or Z, would youcxpect from a.n f.2. Eeaction on tile tosylmt- of (2R,3R)-3 phenyl-2-butanol)

Wbich alkene would resull .trom E2 lencuon on Lhe (2S,3R) and (2S,3S) tosylates? x.plain11 .51 How r ; ~ n you explain tbe fact that tmm- J-bromo2-methylcydohexrute!-'1 elds thenon-Z.1itsev elimination product 3roethylcyclohexene on lrenlment Wtth bc:tsel

CH3

H

KCH

trarrs-1-Btomo-2-methyleyclohexane 3-Meth yleycJoh exene11.5? f'rediCl th e p r o d u c t ( ~ ! of the following reoctJot\, indicalmg s\cn:ochem1str}'

where nece.ssarrEth;H>ol

11 .53 M e r a b o H ~ m of S-Adenosytbomocysteine rSectlon 11 6) involves the fol\owlngsequence. Ptopose a mechanism for the secon d s1ep...H NH3

s ~ c o);"'OH OH

5-Adenosylhomoeysteine

NAO+ NADH , W'- . _,..H NH3

HS ~ ) x ' ~ C02-11omocysteine

+

11 .54 Reaction of iodoethanc wHh eN- y t e f c t ~ a small amount of i ~ u l l i / . r l l t > , CHJCII2N ~ c . along with th e tlltnle C H : ~ C l - 1 \l ns the major productWrite clectrondot sttuflures for both products. ass1.gn for mal Cf1Jrges a. necessary. nnd ~ J r O p o s e mechanism:; ro account for then for natlcn11.55 '\ ll.:ynes can be made b)' dehydrohalogenllllOn of vinylic halides 111 a re,\c-tion lt)al. is essentially ;m E2 proce-ss. In st udy-ing the ~ L e r e o d ' l c n i i ~ t r y of thtSelimincJtioo, i t was found rbat (il2-chl


26/42

I:XSfC\SCS 40!11 .56 (5)-lButanol slnwlv rnc.emi7C.S on \l,11lding ;,, oilutl! )tJi tutlc ariel hplfllll

2Butanol

11 .57 ltcnc llon ot 1-1131 wtll 1 (R)-3-meLhyi-J-hexiHtol leMis t

HFumarate

11 .61 \I though ant p ~ o p l n n a r gcomell )" " f ) t c k w ~ d tor rz reawons, it 1 ~ 1 n b s o h l t ~ l \ 11e-


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406 CHAPTER I I Reactions of Alkyl Halides: N u c l ~ o p h i h c Sub stitutions and Eliminations11.62 In light of your answer to Problem 11.61, explain why one of the following

isomers undergoes E2 reaction approximately 100 lime:; as fast as the other.Which isomer is more reactive, and why?lal

Cl(b )

0

11.63 !'here are eighl diastercomers of l ,2.3.4 5,6-hexachlorocyf"lohexanc. l)rClweach ln its more stable chair conforma tion. One isomer loses HCl In anE2 reaction nearly 1000 times more slowly th an th e olhets. Whlcb isomerreacts so slowly and why?

11.64 Methyl esters (RC02Cll:1J undergo a cleavage reaction to yield carboxylateions plus iodomethane on heating wilh li l in dimethylformarnide:

li l"DMF CHaf

The following evidence has been ohtalncd: (I ) l he rt>action octurs muchfaster in DMF than in ethanol. (2) The correspondmg ethyl ester(RC02CH2CHJ) cleaves approximately I 0 limes more ~ l o w l y than the methyleste r. P r o p o ~ a mechanism for theTt'action. What other k i n ~ o i experimenta l evidence could you gather to support )'OUr h y p o t h e ~ l s ?

11 .65 The reaction of l< hlorooctane \vith CH3C02- to giveoctyl acetate is greatlyaccelerated by adding a smaU quantity of 10l1ide ion. b:plain.11.66 Compound X is optica lly inactive anti has th e formula C1611 16Br2. On treatment with strong t)ase. X gins h y d r o c t ~ r b o n YC1611 11. Compound Yabsorbs

2 equivalents of hydrogen when reduced over a palladium catalyst and reactswith ozone to give two fragments. On e r agment, Z. Is au aldeh)'de with formulaC7H60. The other fragment is glyoxal, (CH0)2. Write the reactions involwd.and suggest structures for X. Y, and Z... What is the stereochemlstr} of X?11 .67 When a primary alcohol is treated wilh p-tolut?nesullonyl chloride ;1t room

temperature In th e presence of an organic base such as pyrrdioe, a lOsylate isformed. When the same r ~ a c t i o n is carried ou t at higher temperature an alkylchloride Is often (armed. Explain.

Pyridine, 60 c

Assgpabte to OWL & Key toea Problems


28/42

Exercisus 4t11.68 SN2 reac tions take place with inversion of conligUJatlon anti S : - ~ 1 reaclior.tal-.e place wllh racllmization. Th e following sul>stJtulion rcadion. howlveoccurs with Ctlmplete retc'lllicm of configurat ion. Propose a mechanl\m.

11 .69 Propose illllCChanism for the following r ~ u c l i o n J ll lmpnrtant step in till labomtory synthesis uf proteins:

+

11 .70 The amino acrd methionine Is formed by a melll}'lnlioll renctlon tJf homocysteine \vith ,\'-mcthyltetrahydrofolate. nte stereochemistry of the reactiorhas been probed by carrying ou t the translormation using a dor1or with J chiral 1nethyl gwup" that contains protiunt (H). deuterium !D) .md tritium (T 'isotopes o f hydrogen. Does the mcthylalion re11ctlon occur with inversion oJrelentltln of configuration?

Meth!Ortlno uvn thase

111-Methyttetrahydrofo la te

Methionine

H+ I) ( N ~

Tetrohydrofolate

11 .71 Arnines are converted into a l k e n e ~ by a two $tep p r o c e ~ s called the Ho/1111111'elimi!lalioll. Sl"2 reaction of tlw amine wllh an excess ot CI-J3t in fl r) l 'leJrlelds an intermediate that Ltndergoes E2 reaction when treated with !>liveoxide as lwsc. Pentylami11e, tor cx


29/42

'olulion< to Prchlt'lllS

I J .1 lra lt'l:) : As cles;nbcd tn \\ orkdl E u . _ ~ I I deJ:tify the Ia p o ; : ; ~ ar.d tilec ty u:tter l>:uw !lc product J!:lor d:e!aon. - : v ~ tbc COl! tgut on at tl!c

11 ..

I I .5

ra y ce:: And rep ace d-.e C2\ ng ~ - ? v.;h lr.c nxlcapln ae n::a::m:"olulloo:

ttS

Ib)

('' ,.. 8r" J-R' " ~ ~ ' 4 3

H CH 3 Br' ,,c c-H ~ ' ' R , . , s ' c ~HH

C H ~ ~ KOH

d

0OK3

Br

JJ5Jl .6 ! > t r ~ ~ U c y ~ ! : l t : p cm,"--caTeC'Cm(Q e ! e c u - t b e c : ' e a o f t h e u ~ ~

l h c e ; . ~ n: 1.1e kll\ :;gg1ocp. Ten ary W I ~ are less ract ve : ~ a n $ : s"ost.'A!t:S < W b t ~ t : e.t re \-c ha n pnm I' bslnl:eS

11.1

ll .

Solullon:Li rftfm>Y ------- \lonmxfrW'

< ~ T o s c::y ""'dl\f< .:;;n 9CCI ron ather Altkl '' ' Ilk' pi "" IK l;,ru o:arbo..;at.onr.:er.:'.edi;:en:s.Jt.'lg "3 mrituc:cl J611 the R und .S en;ull omc:t c acclatc:' I h.: : 0 of t l r ~ n ! r u r r : c - r s pml> > ' ' ~ c n10


30/42

1 I 9 it n:x:tien h:ul P f ~ w;t:J comp!ctc in\-us:on s : r . ~ r e r ! " ! ~ wiL" w:.te to 11.-m a n u ~ t u : e CifRandSalc:oholt. The nuo c.fe n a n t J C . . ~ b c me o 50.50

11 11 := ) l't'latcd tc car-;:ocatJor. Jt1billt). Thus. 51l!:>Stratt.!' t!la fon:; :hemo;;: ~ ; ; , l l k : : < l r l > . X : l l . ! l ! ! ' ~ l\re the m o ~ ~ t i , e :r s.,1 rea:: ,.,-- -------- - -Mostpnmil.l)

11 12-8< - - - BI-

C h : ; . O ' ! : : - t = C H 2 C.'i;)CtiC:-=C>i2 0 ! ; , : < " ; : : ! : 0 1 = C . . , C ~ - J1h e wo o r o m o b t l e ~ c : > :oon ~ s a m e t ' l) he: tllrbocatlon in the ratdum'H:g step

J I I 3 S t m h : ~ . Both ; : b ~ t r ~ t c s have .Ul}'lic ~ o u s .:nd m ght react e u ! t ~ r b) .:n s,.. I E!1 S'l:?route. T"e :cnwn1 mc-.chantsm IS c!etermmcd by the leaving group, :he ~ h c : n : . o: the:nucleopmkSoiUJion:c.a T-'-i x ~ l l c n p ~ c b a b l ) ocam b) a n S ~ I :;JCCllar.&m. HCI ct111e:-cr the roor OH,caY:!lg group 11110 nn C(CC) U!l -OiiJ e.t1ng g;-ot;p, :me the po li i s.ol\'enl ~ J ! C t . . z e > - . ~ e ~ a - . > n l t l l : r m e d : < ~ : t " . (b)Th.s reJttucn 1 \:e-; p liCe "itn l n e g a t i v e ~ ~ c . l u . . ~ . : i n u c : e o p . ~ t k en 1 p o ~ . 4!=nc!olvcnl 1: 1$ llkcl} thnr the m>Cuon llCC'un by an S!l;2 me>:hm:'m

Chaptu II

riOFPAflet ~ < ( J C l a l i O l l PP;. t!lc c:alior. cycl) ;mxk ol trte doub!t' bora - C : u u o c ~ RmlCMI Ollm -H ytelo l.r..onelll!Smany wayr. o;S po5stb>1:.The m.t)OI elunumtio'l prociu.c: 1:1 each ClUe has tiM:

~ u b s t u u t c c ! oo...b;e bondSo lulioo:(a) S I C ~ C'-':;I I - fiase IC H , C k z C t - - ~ - . ! -- C>-i3::..,p=CC>i3

r , : ~ o:( t n u D > L ! . . . I ~ d ! ; ! n u b ~ bar;!)

Crl.3ICH;P-i= ":c;.!CJ-Jmmor(duubiu:u;ed Joctrl" ! c )


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(b) CH., OH, '(-!:!I I &s n

(C)

C H p o < ~ - C H C " i 3 - C r i ; C H C < ' ~ = C C H 3

()

< > ~ , rna;or( : e : r ~ , g ; ~ .:!.ouble bond) ( l r . S I I b s ~ ~ l c bond)

fH.! CM3 CH3CHCH:f.CHCHJ

mmor(c;n:biut ne d d a u b ! ~ bor.d)

I!~ H C H C > = C H C ~ Q-cH=Ctt2majOr mmor

. J9

(:n\l lbstlMldouhle bond) t m o n p s u h $ l l l ~ c l dlluhle hund)II .1 t Mnttcv: for ma\lmum ytctd, the alii}I hahoe rr.lcl;,nt Ah11uld nne g1vc ll mnllure ofp ,,J .c;, c c: :r tUO.,

"iulutlon:

l ~ r II

( I R , . ! R ) I , l l ) i b r o m u J , 1 d l p h ~ n \ l ~ t h a n f :

( ' ~ CI!S d n n ~ iJ:toa e\lope,,p!ar.Jr ~ m e u y or - H nnd

H

The ketlr' -csu!r.ng rrom I 2 ('fofl1.n1Uon b (1.) l b:o:no-1.2 d1phenylerhy ene.Solullon:

Plr-t:T-Brfi-Q-Pl'l

I I S ~ n t i ' ( J : As tn lh t pr t \ ous probk'.m dnl"' 1he ::rocnsre convcn it to a l'\ewn:3!:projecu.:v.: anj ro c lt.e gro .rs so lh11lhe If nr. Br to be clururuu.ed h a ~ C ' Z!IIJlllprnpbmr reb:ior.

Solution:H,C, 1CHzt;l 3p-c, tZ)J \ltlhyf-!-peotenl'

H Cli.!


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11.1'1

11.!11

The more ..:ab!ecor.f.r.-...;u o:-..I 0: ac;; o! he l\1.'0 sornt:s p c ~ abcn>e, the I ~ lt"NOO%\ group S a}\1.;1)' ~ i l l :llr :!Of"C.., ;C1CO!Ifnm:xuon. 'Jb: CIIIU!t t 11:{ ~ u l l l l e : El ronditi!Xl ~ " C E . ~ - H ra " 'JC ant pcnph:urarnangcmellt t ravnrs E! clt.or.nZloc.

'ola!'J - C ' i , ) C : " f ; ~ ~ su!wilut on proi!a:1M: rt'U'UO:I ()(.CUTS b) I!Jl $..,2 ~ . r u n beclnue L':C I U \ K t r o ~ : C IJ pnnull' ). the nlll:leoph lc1i nO!IbasJC ! l ( l l . ~ j':odto.! IS a S C ' l i l J I ~ I O r . product(b )

O i ~ 2 C H C H ; C H 3 KO.., - CHp1Pi-CHOH3~ d l l . ' ) stn::r.g !l!s e el:r:unau 4lld vuclcophllcs ere bn e.T"oel mmauon p : O O ~ arc:c ~ ~ r d : !hemajt.l p:od 1o."1 has the :rum .suhsll:U'cd dooblc !nmd,1n : ~ c c o r t b n : : e ... ,:,,z.t:s.e, s rule(c)

1) ::;:::::j __ . S C - i l - ':aD

1- ) (!o,;:s:z::(hry SOJ;!s T&IC= " , /IC goods r u t : . l ~ C r pnxbc: I 1), ~ . . 0 1 1 a pootct nu;;~ : W O : l a : l d e :runo::on odxl fmncd

0

...c,1 t:.o>...} 1:-.uu: r--= ~ ' l e ; ! ) ~ efd

1 un-o. !Cf base bo!h

..'c ... ! ....o, .-Vi:!f Q ff.. c-3 o'le \cald) t-ItS ..r. . e .x e o , ~ : : u ; e oca:rs to) &'1

!' 1J pro;j.C'e tt e R Ke .. e


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11.2

I I .:Z4

12

Rurt of Alk7l Halhl..,., ' i u c l > p h l l ~ ~ l l h t h u t l o M au 1 lnatlcD'

cH " ' ' c ' ' ~ ~ s , -" iC'"" ' 'H

. NaCN-fi"2c cHJ"... c"' 'Cti,OHr R , ,

NCH

24 \

The 1-..;as a a IY,e cnlondc graup and a pnllllt)' by my SJ'O'IP s,. Zrt.X.'Jl :1 at .br. secon ) urton10 g;YC !he R cy.IIIO pnxlu;t beaiiK: b)drmlc!c Ipoor lca.v: :& &l p

R!>t ~ ~ ~ th eft uJeuf he mulccu:e .so l . ~ l l l i : J e 1t>Ups to be tlmr.ncted h1\C: 11n an Ipenpl11nbr fl'la undup lle dOU"Ie bord H lh r p!od!ICl has the F conflgt nttlmt

O l ~ " m 1 : 1 - ~ C t i p i ~ 1ha' on lhc CCIIlCC.\11&11011of bath ahtylhaiJtk nd

l.ldoat11 gt c rntr ofallc) I!d c ~ a r u n c l o

::.u11.27

11 . 28

11.19

ch.,,..,. 11

O l ~ J Ilet'.::t:y ha :de

This In n Ss l t:.t;;UOO. ~ h o s e rntc d c ~ ' l d ! y oo the c:onccntra on of 2 cO>:!methyt!Ntme. Rate .. .t : ~ , IRXI Tnpfing L'le COTlCaltratlor. or kv 112 de .. ,, c.s t h e ~ 0: racuon.(b)fbMr: the COIICUltmlon o clhi: by Q on "WI ~ r . ' l y l d h u ~ s lbe pola.'lf)clllle solvent tnd I c c ~ the rael l

(tJ)

(0

CH3C-CH(CH.3}2 ',IS11.1"1 " & b A ~ e CH3C-C- ! - m n g s : 1 , ~ 1 n ~ d ~ = O I C H J

~ ~ ~ - B t o-C(Cti3J3 - ~ < i ~ - o - c u : ~ l l 3 NaBr''

0 1 ~ l l C IU NH3

{CH3!JC-O-CH3 HO { C H J ) ~ C = C H : ! (mu or) Crru:101l

IJ m he l ~ a UJ E' wp. LnCe "'01ouu betuI '2 dispLlcc:ue u odidc: oo C H _ ~ . . Q l o t

f'Oph I,.J S ll"...c C'oo- IS m o ~ e reawvtc:mem n 2 tromoprop m: byC.'\


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11 . 11 Because , , n u r . t : ! l r o p a n ~ 15 ;mn lr.V ' l 2 . ! o a : ~ if ' tr.e rcacl:nu :mxtec.l '-y etiits 1Sd -.:E2 nu,c;hanmrl, ckpending on lhe b a l t C l l ~ O'ld tht: . t m o ; ~ n t oi ~ c : " 1 i c h . n d r ~ m e 111 then u c ! ~ m t e . (n)

C : - 1 C t < ~ N a r - . . " " ~ - ll:a&Pol:>pe;:r (c!.irr. - . < ~ l i o ; ; y.oduct) s tlso fO;"t!W.d bc::aa}e :-:a."lH; IJ a !>lf..mg

!I.>}

(c)

(c)

C H ~ t ! ~ ~ ;{. o c { C H 3 , ~ - C>I:;CH=CH 2 - OOC(CI-!J)3 K6 CHa:'"',P;PC\CHs)a

.C 1> n:rong. Pulq base tnlll hrmr a;,oot e o ~ r r u r . ~ : an ..s ,.ell as,a:,T.c: -.ubs:it ..tJol .Ch3CM2Cr.7E! Nal --- c ~ ~ C H _ , I N.at!rC H ~ ' - i C H : 1 B 1 Na. c::CH - CH3C.'iaC!+.!C.=CH

1 1 31 To ptedrct rr.:clroph:IJcu;;, n=:.'!r.'x:r g w d c l : ~ (1) n c o m p a n n ~ ; nudr.oprJlcs tb ! lca\C lh N.,lo;ICQptul.ct:y t n c r e o " ' - ~ Ir< g:rngdown a coJutnJJ 01 lhe penodl..: tane.(3}A fll:gli!Jvel\ Chllfged rucleopt .le i l l U J > ~ I i l i l ) m;:,rc reACuve thanrrncr.ural nudeop.ht.eMort! N ~ J r l t < r J p i : l f l c ut s Nllci,vphlhC Rea5on

18) " NH2 NH.3 Ru;e I ru J(b} C H ~ C 0 1-lzO R ~ ~ ! ar3(c) F"- 6" 3 ~ ~ ~ o : 3:1u.: eophtlc( d ~ (CH3 . 3? {C-1.1\:!:-. Rde:2(c) ,- o- RUle 2\1) -c=N -oc-.! R.:attVJ!y d1arh

S c c : ! II

11 ..n

11.3 3

C b o p ~ ll

i"JC, ,- i HJc, ,cf-13C=-CI \ C=CI \H CH3 H H

(!!), . . . ~ ~ s ~ !J h ot.'ic;r "inylieorganoMJMlu, d o e ~ 1 : . ~ r r . : c ~ o p t d t : s : i b ~ n t u : t o n ' < .

Thrn .k}-lllhlule gtves the leu subst.tutedcy:Jo:;!lcc::-e ( n c ; ; 7 . . 4 l t ~ p : " Q C ! ! ! . ~ ) F . l i : r u r u ! ! : : ~ r : to f= hr Zait.se product dae.. nGl Ol:"ur bccJ!i' C H C H

l R NlmOI1l.ltani' 1 Brnmo-2 2-Rrnmnhularu!me1hylpropane

BIO i ~ J I2-Rron1n 2-meth .vlp rllpBilt


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1 1 . ~ 4 An lkohol ~ e : ~ \ ' t : ! t e d s o a : H ~ l ~ h): t "t)ltiffemu route$ m lllluaies rn.::t l 1lle,,. " ctl1cn h.avc adrntJall S:I"X"Ilml: fo:mul:s 1:x1tdiffer !lc $ p: of speorou:10n. 11-.el"clan:. a: $0mc ~ i l or ucps mlhc:se rcaaon 6CQuen::el tner on ofC O ! d l ~ a1 the dn:ll l carbon= 1 - ~ e ocxurrcd. l.ct ud) cx h tep of hc: Ptll!ld Kcr. tenCS lO :llS ,.hv.e 1:- usiofi IS OCCJ.Jnr.g.OTO!0 . . 3 ~ _ r - \ f a J o l l ~

In ltep I. l h ~ a o: !!OI n - a c t ~ wrth J ) O ! l l ' i ~ u m me\31 ro pnx1uee a potasstum a km!.tdc S ncrthe bo::d bet"ecn arbon ar.d o ~ ~ sc:: hu "10< bern tr.ol:en, lk { ~ B a o n oceua 1n thul !Cp.Thepo:&Wil a Oli!Ce act as a IW('!eophl!e an the S..;2 d $ p ~ m e n t on C'Hl< HJUr tnstep 2 hut!wC-Br bo:ldcl .. e"CT.IIOl the C.Obondot l h e a ~ o ! d : , that is o k e < ~ So 1


36/42

11.;\l> {.R>-2 B : ~ ; : J < ' D C ! . " l ! l t ' I S ~ IC'CCnt!.l)' ::rrtl."' ;;:::Jc.. Wt1 ..n l . l ' l . : I C q : U e ~ s - . ~ f U ~ S : J ! U ! J Q : ' j S n ~ . : -SN2 r e - . . t e ~ H : > H $ pnu:ee(]" lh ; ; n e r ~ : r n o:.; .:'"u.rra::wr- tne crml:gur.>:,on at the eIa Bt-N ~ ; ' C-Br ~ J - C I \Cs"J Cst-13IR J-2-Urom\loclan!"t : i f f l p h , J ~ rrodra!a) H

-c .: C ~ - : . ~ ' - " C - r -s C,HlJ

Cbl ...,o.;:P>-2- Ct-aC02 - .,.CK3\s Cr-'"'3

(cl H CHCH3S- C"i3S-C ... -s \c.,-;;a11.39 Aite:r t;Q% of t ' t e J ~ t a r t ; n g mateml hB5 rciid(J, the rc..c;1ion nux:ure wr.$t:>LS of 5 0 ~ lr)'1hromuocta:Je ~ n d r S } - 2 - b r o m o o t t ~ : : At th1s perm, the R starung mnte naltsmmr!elt'l) rnceml.ted

11 . -I 0 Ao:..:-ord:ng 1 C . s h 1 1 - l ~ g o ! d i'relog :ulcs t( e:her p!t"p:tniiOl't ~ : ; : u < > e 'MoJmeJJ-,nne \-ery :eact>-c tTl5:-:! d:spl:in=:11:s

ikn:::.IJI; lll!>i:,O!lchtryht!.!ua.kane Will'. II b a . ~ i : : : nJcll.:>p.'ute y:eld\ h.,h s t ~ h t rJHon ..:tael:":l ":l:to:1 p r c ~ b : : : u . Thts il a k! 5 SO\illi!le'.o:y mellCC o ' ~ t ~ e r ;rtpa-'1111!111

~ C H ~ .... C-Cn \BrRo:.ate wnurilthe C-t'bom! 10 th,:t -()H nd-B: me l ~ i f 11patt

: q : i C t - 1 ~ . . , .-C-Cn .1 _1

L 1"13C t . . -n:nro\llil.lf?t0t..");;

.. l - 1 ~ 0 SN::! rnbplncemen1 Br-

r - f ~ Crl..c ...,.. 'l'iJC f.lr

-Br l> j

0\t1 : - - - - a ~ ' t

> j ~ !3r-


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I I .HRra 1 of All;yl Hali1101 tlf't!pltiUt 'abtlhut lon 1ntt lUI nll

ktho-..u1c remou a pro!oo rom thebydr yl gl()l;j) of 4oreo.l bu

S ~ 2 d pa c - . n ~ t r > f S r - o \ 0 -vre'li' the yc c ether IC"Ir.ohycrofuran

I' HOCHl

1 1. 4 < 1 l ~ e rm sttpm n '\ I d 1 s p b c : e ~ Is ~ a t ron or the t:.obWll;c to fOilll a pllln4r spud w h o c ~ l l o o 111d a l e a ~ m g ~ 'The c:IUbocaton th:t w01:'d torm fromClu ton f th1' alky h:ll de can't betOtr.epl:mar1:1ccauscor rhc ngJd strurtUre 01 thr.I'J tke Bc:ou;; - 'IIJOI ;:ouiblr to form the nee WirY arba oo an NI


38/42

11.49II

o T o ) RPh ;:..c _ C'"'3

H

lSJ

Dra.,. ~ c w m a n proJe:::Uonof tnt t t l ~ ) late: ol llR.JS}-3-phenyl-2-bllrannl and ~ t c the"'JC4:!i Ut..tlllhe ..OTo. and lhe -H Y. L'le adj(hr.lng carbo!) vom a.re anh pmp1ll:1cd m the: r . r e ~ t o u ~ prl!hlem. vou crm shov. tnat t.lun:fll!tltl'lL"ll!n the t o s ~ ~ u : of r . R . J R ~ J - p h c n y 2-bi:'..Jirl()l g;ve . the -alkene

MH3C ..._ (: ...,OTcs

R'RH3C .,... c-.,.,..

'"lC-.. ..-"c-IIc1 1 ~ " ..... , ,1El- l Pbc:n) 1-1-hu tene

II Sl

l l .H

E2 tt.att. . ~ . , . . w."C lha! tbc two l ' l t O m ~ '" ' le el:m!na;c:d :'ll!VC a !'Cnol..r.&r rt!:!uons.'l pSinct- ~ ~ ~ m : ; : > O ~ S J 'l1t !m brr>mlne and the b ~ r t r a g e n Ill C2 1>1 penp1a"ar e h m i r u ~ t ! r m IICCUTS tn II t t:O:'lht.llii!V drrc


39/42

11 . 54

~ : ~ A1e" ne., -.... i

r n-u OttC : ~ \ \dC'no


40/42

11.57 11lr c h . r ~ l l t T " > 1 1 1 ! ) ;tlrohnl !R)3-mcl.hyl-.3-l;c:\ru-.o n:IIC!li w:th HBtl')' nn S..,l pnrt,wayIIBr j t ' O ! O l - . ' " ! : Z ~ the h)'OroAyl g n : r ~ > p ,.'tu;>lt)OMSUite st IS thusf - ~ - m e d In gr;;;tcr abunv.mce

Br ' c ..., t>n EZ-;; . ,. ...., Eflr-1rur.'Of"01 3CH:_> -; Ct-13

...,

I ZR.3\12- f l romo 3-nn lhvl-:Z-phen) lpt>nh1ne

Tne .S. ~ R ) IMJmer n i ~ u v 1 e l d ~ E pr.-xlurt

( f ' I J - ~ 1 e t h ) l 2 -p h c n ~ I 2-pen t ~ n e

11.611

11.61

11.6!

UPtt 11

A & J : - - ~ e 1 e ~ o : o ~ . . a u - d lea. m\\ ~ : o u p depa.ru,fn.-:ur.1;W!!u..'ll:::-

A r ~ m i n t

- u , c ~ c c , H

fumarateOc.c ol l'lC i!Ulr ret]_ollrCll\CnL> '-' E:!;: marw!:ion IS !he need fnr _;!C'1plao M . , ' C O ! r o e ~ - - y w h ~ : : l : op!lm:7cS orMal c' er:up 1n the tr.uu.t.on s t a t c ~ l e n d i n t ! to o1l!rene l ' f ~ Y - l u ~ Two t y p e ~ ofr(:u:- ; u ; ~ amr.ge.'";)l:nts ol ;;ub$:in:er-.:5 :uepossible- syn and .. u._

o\ of L'\c dcwer:l!ed bromo :ompoun ~ ~ C l ' . J l t : S.: :c r.e:he t)n nor anu j!CI1pl.m.ar el.muu.:tar. u powtt:c for Rc!untlld'IOf occur by a ~ ; , .,er. El ""lie


41/42

11.6 .1 d:Jii, H (l H 0H t--

"'I 11 t


42/42

t

IV Elimination Reactions

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