Feaotlón oennledl out wtth solutlon Bnepanedt

ÎAEE UT

B, Feaotlón oennledl out wtth solutlon Bnepanedt

Þy lnvenee

dtlazotlaatlon wlfÌa 9ß

^Greaas

^of

eodllum

nltrltc.

l+.5 ,

12.5

9

7

6.5 þ

It

17

than other leomer¡ subetltut€d tn the

þnzenoldt

rlngs.

the

appeananoc

of tha

Êovon-rn€lmbenod

rlng

compoundl

(1Æ)

_f

_e

_monc

dtlfflcult to ratlonallea.

^Thc

formatlon of thl s

^{conqpound dl}

urlng the

ayclf.

eatlon neaotlon

w111

be

tllseuseedl

ln ^gneater detail ln

Chapter

ffl.

Il[hen

a

JOS axeces

of

eodtum

nltrltG

wae ueeô

ln the drazotLaatton etep, the

^peohonn

oycrleatton of thc

amlne

(ø)

pnoclueedl,

ln adc[tlon to thc produota

alneadty mont lonacl

r E-benzyl-g-rto1u

^ene aulphonyl-g-bnomoanll l ^nc

(l¡O) ln

13fi

Vteldt.

^ITo

other

^exanrple

of

dtearnlnatlon hatl been obeerved

ln the eyclteatlon of the

amlnee

(Í!g), (tt Zc) or (ttZa). thc

yf e1d

of

4-bnorophenanthnldtlnc was nedluced under

theee eondlttlone, þut

consldenabLy more

of the thlazcpina (1eq)

_wae

obtalned

^(eee

Table Vf).

lwo notable

featur@a emenge fnom

the cyolleatlon

neaqtlona

of the

^amlne

(tz6). Flnetry, the

fonmatlon

of nelatfvcly hlgh ylelde of

4-bnomophenanthnld[nc evcn

though onLy one or.tho

posttfon ls avallable fon

tha

Fnonmaf.F

oyolteatlon;

andl aeoondtJ-y,

the

abeenoc

of

^an¡r

debnomlnatetl prodlucte dlesptte

the extenelve

removar

of the orthq

bnonlne atom dlur.lng

oyalleatlona of thc

^amlnee

(ü¿d

and

(fl29.).

101 . CTAPTER

IIT

r-I-It

UETH SJTPHONAMIDES pE4rVEp _FROU

&- ^{BEt{ 4flf.t} -9-P ffi }flßENEÐI AMI NE .

In

ar¡y aurvoy

of the llteretune of tho

Psohorr

reactlon, tt

1e

lmpoeslble t6

esoapc

the

oonoluslon

that,

dlcpendllng

on thc oondlltlonc, aycltaatlon

neaotlong

of

dllasonium

ealts

^{nlay pnooecil}

elthen lllg ^{homolytlo or}

^g!.9,

hetenolytta pathwaye.

Furthenmorc,

thene le a

^girowlng

bodly

of

^evlelenoe whf

eh tndlloatca that, th

favounabLc Gaaco,

þoth lonlo

^andl

nadloal

meohanlErnr may oo6ur slrnuLtaneously. ⁶⁶

t87 CertalnLy, no aingle

^{neahanl em}

oan

adequatcly

acoount

for thc

oosur¡rcnos

of thc oyollaatlon reaotlon

unclen

all posstblc oondttlons.

^A all

ecu¡slon of the cyclf

gatt,on neaotLon¡

desor.lbd ln the

preoeËllng

ohapters

musü

pnimarlly

be ooncernedl

wlth the nole of

oo¡lper

ln

theee

reactlon¡.

It

hac

fnequently

been anggeetctl

that the

^presencc

of

ooppcr,

whloh

la often eaEentlal for thc

Euoeees

of

^a

Peohonn

oyc1leatlon, favoun¡ e homolytlo nooo""",69

fn thla sontê:rt, an fntenestlng featune of the

copper- oatalysedl dleoonpoetttons

of the

dlagonlum

rplt¡

dlerlvedl

fron

_S-b enzyl -l{-be ^{nz ene aulp honyl}

-gp

^{henyl ened I amf n}

e

⁽

:¡f

⁾

and fnom

the g-tolueneeulphonyl

analogud

(1JÐ

_wa¡

_thc

fonrnatlon

of the srltan¡ (üÐ

andl

(üÐ ln

adtd!.tlon

to

the

dllhydrophenanthrfdtlneg

(l]!Ð

and

(f:Z). _{the formatlon} of the

fonmen

two

oompor¡ndle

lnvolvcs cyollsatlon lnts

benzcna

nlngg

whloh

arc

dleaotlvated

by the

^eulphonc

Eroup towardle

electnoptrtLto 'attaok.

^Thl

e sltuat!.on

1e analogouc

to thc obeeryatlon of oyclleatlon lnto

^tho

pyrldlne

nueleu

sr whloh, although

eleactlvatedl towardla

attaok by catlonlo ncagentc, 1e susoeptlble to

fnec

radtoar

substt

tutlon.Tl tlo&11o

.{ocondltnßIvr thc oopper-oataLyeedl dleoompoeltlon

of

dlazontum

ealtB

^was

thought to tnvolve nadtlcal

lntennedlatee.71 ^t1o8

Ilowovcr, the reactlons

dlesorlbed honeLn wero

oarr.tcdl

out ln atnongly acldlto eolutlon¡ ln thc

^abaenoc

of water,

oondlltlona whlah

mlght be

^expeotedl

to

^favoun

hetenolytlo procê89cor Thenoforc, the poeelbfllty of

^an

lonlc neaetlon lnvolvtng thc

oanbonlum

lon ^(l¿Z)

^oe¡rnot

be dllemlseed,

partloulanly aa

an

lnternedllate of thic

natunc

chould

be hlgÌtl'y reaotlva anil

henee

relatlvely

flnon- ¡el

ectlv

" .76'78 ^{t1 1 1}

 oanbonlum

lon

meohanlrto'f

'74 sati efactorlly

eeoounte

for the

pnqpondcnancc

of thc

dllþdlrophersh-

thrtdlnce (ffÐ

andl

(:¡f)

obeervcdl

ln the oyollsatlons

whlch w6rrc oannied

out wlth eolutlong obtalned

^by

dtasstf eatlon wlth a 5fi

^cxeeee

of

ædllum

nttrltc.

Itroweven,

thl

e pathway oannot aocon¡nodate

the faot that

r"" L\.

I .,..: r_.

.i., ,

i n, ^i-l -

t-,'

I

^¡. -/ t\l ^{ftz' /-t} ./ ^'-¿

U5

c (- H

CS-, ¿

J\t I'

ti,:'

L

i,

!''

^. r ^t:')

II

jlli tii¡

t_î'ì ô C

'v i' i'

ll^

I

\ì l\l

¡\¡

i-i: C

rl

N

{-f

I

/tt \,H

J tt

lr! r!

a 'l \ì.r

!

I

U Zn

r"l

€01

the relatlve yleldt of

^{eultam ancl} dlLlryilnophenanthrltllne dterlvedl

fron thc

suÌphonamldlce

(Uf)

andt

(112)

depend

narkcdlly

on the

anpunt

of

^eodttum

nltnlte

^ueedl

!n

^the

dtazotleatl.on gtqp,

^w?rllc

the

^oomblncdl

^yleldl of

^prodluotg

le

approx!.mately

the

camo (eee

Table f ,

^page

68). It

was propoaedlll2

thtt thcee

^ohanges

!n the

oourse

of

the

oyollcattÒne åre rlelateil to tha

ooounnenoe

of a

^æoondlt

oonrpctlng

ayolleatlon ^neaetlon

^{whtch 1e favouredl}

^{by thc}

lnonease

fn the

ooncentFatton

of

ouprous

lone !n

thc

reaotlon mtxtoPo¡ ft

^was euggestedl

that thle

^neaotlon

lnvolvedl

a homolytlo

ÉP€oloe ^fonmedt Þy

the redluetlon of the

^oa¡bonlum

rsn (t?) _uv

_euproug

lsn¡ (or ^{by a}

^oompler

oontalnlng unlvalent

^oopper

).112

^{As waa} cnphasleedl

cartler ^(B.ge t8-t9), lt la ^llkeLy that thle

^honoLytlo

lntcrmcdltate exletg not aa a free radloal but

aa ^a æeeles whloh ^1B

og-ordlnated wlth

Gopp€Feo'f '9o

With thlg rcserdratlon, the

radlf

eal entlty

1e nopreeentetl

sa (1:E).

It folloçe

^fnom

thle rcpnesentatlon of thc

mechanlen

that tha ratto of

dlllrydrophenanthnldllne ^andl

¡ultan

^fonmcdt

fn theee o¡rolleatlone

^{ehould dlerpendl on}

the extcnt of redluotlon of the

eanbonlun

ton (ÉÐ to the radllaal (1¡g)

andt on

the relatlve neactlvltf et of the ^two

^benzene

^rf

nga towartle

eleotrophlllo

^andl

homolytlc attaek. th.at thc

obeervêd change

ln

thc

105

FiGU R

E II

'j /ì ^a-r

lii !

+ rJz

UU

U'^7

i¡U

-t-

\. Ll

o

('al.-ìt ,

,i r

¿

-\ z- l.-

\,",

I

I I

I I

I

¡

Õi

,^i I

\rt I /

oourto of thc oyallsatlona

f e

a functton of

^lnonceeedl

oupnout

ton

ooncentnatLon

war

eupported

by a qualltatlvc

cxamtnatlon

of the effeot of aoatlo aolil- culphunlo

aeldl on

pneelpltate,il

eopper

ln thc

^prcaenco andl

ln thc

abeenoc

of

^æÉllum

nltnlto. ^Ilnder the oondltlon¡

malntalned ^dlunlng

thc oyolleatfona

about

50Í of ^thc

coppcr

ôlseolveô Ln thc

mlxod

aoida lnrcøpeatlvc of thc

preaenco

or

^abeenec

of nltrltcr

^Eowevsnr

only ln

^the

prêEonoc

of nltnitc ËrG poclttve teets for

ouprou¡

lone

obtalnedl wl

th

2¡2r _-Dllqul

nolyl

.

A

moohan!.Snr

elmllar to that

tuggcsted abovc, wea propocedl

by

Hulegcn ancl zar,le¡:87 !.n

an attonpt to

aEoount

for the cffeot of

^oopper on

tho

dcoompoeltton

of

dllasonlura

salts fn aotdlla mcdlla.

^Hulegen and Zahler ooneldlcn

that the lnltlal

oopporr-Gatalyscd dleoomposltlon

of the

dlaaon!.un

salt ^gfvee rf

es

to a

^radlf

oal,

whloh nay

elthen react

aB aueh,

orr altcnnatlvely,

tnanefc¡r an

eleotron to a

er¡prou¡

lon to giye a oatlon.

^AJ¡

lntnamoleeulan

clcotnophll!.o aubatttutlon

nay then

ooour. ff thl.s h¡potheele ta

appl!.crl

to ths ncaatlon¡

dcacnlbecl above,

the

meôhanlsm may bo ropreeentedl as shown

tn Flgurc ffl.

thc

eohemc

outllnadl ln Flgurc IIf cuggeetr that

an

lnonease

În thc onocntratlon of

ouprous

lons ln thc

107

FIGURE III

2

ñ¡t\l

Cir

t hi

rl

'f CU

^l

rj¡ l.l iri .-,

r

('¡ _-,

- "'l:

I ^¡ilt.){)

i'r;'-l

-+-

ì, ^! .: ,i\j

/\ I ;

'i rJ STJ

'l ^{¡-1 r?} ,l ¿-

I

I

,.,irl._.

lì:;,

^:]

C:ur'

-

^H+

-,\i

1_

r' I )

I rt

; ,ìf

''- i'ì'

ü r-',

JU'

1-1 ,-l , /i/.r./

resctlon

medltum would

favour the

fonmatlon

of thc

oarbonlum

lon

lntermedllate

(:¡Ð.

T{ow,

the avallabla

ortdlcnec Buggêets

that the

hlghen

yleldt sf sultan ln

aycl!.¡atlons ln

whloh

a _tAfi

cxcess

of

ædl!.urn

nltrltc

was employGd

!.n the dllazotlætlon rüæ

was

a dlreqt

reeuLt of the

fonmatlon

of

ouproue

lona. fhe

meohanf¡cn ehown

tn Flgura fff

learte

to the rathen

cunpr'lelng

oonolucton

that the lonlo lnternedllate

pnefenradl

to attaok a nlng

deaettvatedl towa¡cle

electnophlllo

subett

tutfon. 01eanly, thl e

gonorualon clleagrces çrith

oottunonLy acaqltedl ohemleal

pnlnolples

andl nendle!.s

thc

aoheme

outflned ln

^Flgune

rrr

untenable aa

an

explanatton

of the crpenfiuental neeultg.

îhc

onuo!.al

queetlon ln thla

^meohanf

etlc

dlf scugelon vouldl appean

to

be whether

thc

oorpperr-

oatalyged dleoompoettl.on

of thc

dfazon!.um

salt

itertved

ñom the

amlnc

(!!il _leada lntttalty to the

nacrloal

(ü9.)

on

to thc oatfon (!¡/).

_{AD eLectron}

_tnanefer

_{Þy tho}

ooppcn

to the

rtlazonlum

lon

thereby pnornottng

honolytlo

flsston of the

C-l{ bonða seemt

thc

moet

llkcly

altennatlvc.

Tlr.Ls

explanatlon of the role of

^ooppcr

ln thc

dleoonposltlon

of

dlaøontum

eaLte te

^genenally

aeewtedl

ln the Ilteratur.e.65 169t91 îhc

fonmatlon

of

a oatlonlo

lntermedllate

by a elml.lar prooets

(eec

{ 09.

Flgure Ir) ts allfftcr¡Lt to vlsualf ee.

^Howevenr

lt tc not lnoonoelvablc that, ln

^¡uoh

a etrongly

^aot.dlle

nedlum,

a oatlonlo lntermellate

^{may be formcdl}

^on

^thc

netal

^sunfaoe

^{rather than by en cloct¡on tnanafer}

neohanl sm.

It

!.o poea!.ble

to

auggcøt

a

th!.ndl ncehanl@

for the

ooppof-6atelyaadl dteoompoaltLon

of thc ^dllasotlad

üntncs (fÐ

andl

(IIÐ

whloh provldles

a

more

attnaetlvc

cx¡planatlon

of the ex¡lerlmental faot s.

^The

lnlttal

pr¡ooclg

!s

oonetderedl

to be

^el

eotron transfer by thc

ooppa¡r

to the

dtazonlBË.

lon

theneby

promotlng

fonmatlon

of thc nactloal (üg). It wlLl

^be reme¡abered

that a gualltattve

examlnatfon

of the effeat of acetfo soldl-

Eulphuric

^{aoldt on}

Preolpltatcdl

^ooppcr

[n tho

^preÊencc

and

ln thc

^abecnoc

of

^ædl!.um

nttnlte

^revealedl

^that

11fi

of the

^{ooppen dtl eeolvedl}

¹ⁿ the

^{mlxedl aotdl}

s ln

^eaoh

o88G¡ cuprlo tonc rculdl

therefornc ^be

prceent ln

^eaoh

ayclleatton lrrerpeotlvc of ^the

^pr6s6noe

or

absenee

of

GtEoeaB

nltrltc.

^Ílheae

^{suprlo long could oxldtee}

^thc

radl.oal (üg) to the oatlon (:!lÐ wlth

^conounrent

fonnatlon of

^cupnous

lon¡. ^llhe posstbl}lty of

^{Euoh an}

o:rldletloa-nedluctlon

reaotlon

^1e

wcl1

s¡Pportedt

by

^thc

work

of

^Koohl

,11,

^who

¡uooesefully

^ueeü

thle

^ooncept

^to

ÊIpleln thc ^reactfons of nadloal

^reagente

ln ^thc

presonec

of oupnlo ¡alta. In the

rystem undlcr dllscuealon

It Ls llkely that a radlloal-cuprlo oonplcr axtste

!.n equ!.1!.bntun

wlth a catlon-orÐrour corplsx.

Fu¡rthenmoro,

ln thc

^presênce

of a langc

ooneentnatlon

sf

^cupnlo

tona the equlllbntun

wouldl

bc

expectedl

to favour

tha

oetlonlc lntennerlLate. fn ryclleatlon¡

sanr!.crl out

uelrg a ,fi

^cxoase

of

ædllum

nftrtte to dttasotlse

tho am!.nc,

the

oarbonlun

lon

meohanlørn ahouldl ¡lrcdomlnata

wlth a lesscr oontrfbutlon frorn the radtleal

^proc€88¡

Tl¡1t ls ln

^agrcament

wlth

cæperlmental oÞeervatloa.

I Pß

^cxceae

of

soatlun

nitrtte In thc dlagotleatlon

stsp oausea an

lnoreaac tn the

oonoent¡ratloa

of

ourpoue

lon¡

ln the ryeten.

Thc balanco

of the cqulllbrlum

1¡

thereby

nevenacô and

the radloal-ouprto

complex beoome¡

the

pneilomlnant

reaotlng apeoles. the

lnoreaecdt yleld!

of thc aultan (!¡Ð

andl

the

oonnespontllng dtecneaee

in th¡ yleld of the

dllhydrophcnanthrldlne

(J-!Ð

obtalnodt uadcr theee

oondlltlons provldler

_aupport

fon thL¡

lryBotheals.

Thc noohantgm

of the cJ¡oll.satlon rcastlon

nay be neprceonted

as

shown 1n

Flgure _fV.

' fþ

abova meohanlem

doas not

_Bneoludle

thc

poælbll!.ty of

eaoh

cpeolct glvlng rlse to Þoth thc

dllhydlrophenanthnldllnc

(:-:Ð

and

the ¡uttam (ü9,).

Howevcr,

the yleldls of

proetuote undan

glvcn oondlitlonl

ouggcat

that the

oanbonlu¡u

lon lntermedlate pnefans to

111

FI GURE iV

l¡

t\^,

N li

L

I rr

l:l-i. _¡

¡.; .

'l-_..'

,'--i\\

C,¡

I

SO²

t, tii- ++

LLI

-.Ni.-- LJCt t'2 ^.J

L

.,-N-

/\!l -i

|.í-l !t ì

1L

ettaats

the phenyl rlng

attachedl

to the

metfurlenc ^group

whlle the radtcal

lntermedltate

prefenc to attaok thc phenyl nlng

^ad _Jaocnt

ts the

eulphonc

g¡roup. Íhat

attaok by the

sarbonlum

lon at the 9g@, poeltlon of

^tha

phenyl

nf.ng attaohedt

to the

eulphone

group le

^pnobable

wa3 etrown

by ^the

^wsrk

of

Lew!"r111 whø

lnvestlgated

^the

ratc of neaotlon sf the ^phenyl oatlon

dlenlved from bcnøonodllazonlum

galta. _Although thla

wonk provldlea cvldlenoc

for the

^verTr

^hlgh ¡rcaotlvlty of the

^phenyl

catlon, the

^neaeon

for ^the

^unuaual

lnetablltty of ^thta

qpeolee when oomparodl

wlth other eleotnophllear

^hac

neoelvedt soant

attentfon. f"ftllk

Buggeetedl

that

tha

trensltton etate lnvolved ln the thermal

êecorposLtlon

of

phenyldlazonlum

lons

^poeeeBses

a hlgh

^degnee

of radtoal aatlon charactcr.

The tntenmedllate phsnyl

oatlon ls

^negandled as

belng ln a

süate

tn whleh

^a

r-elçotron of the

^benzenc

nlng

^hae

faLLon, wlth

sonoertoel

unooupllng, tnto the

^opcn

c l¡rbrllt

⁽ tpz)

onbltal of the oatlon (t.e.n _the onbl.tal

^ocoupledl

by thc

C-H algma bondt

ln ^the

phenyldllazontun

Lon). Îhle

oonoept

of

uncoupllng

to ^{glve a} tnlplet

^phertyL

^oatlon

çae ^usedl

to

account

ftr. the snal1

^dlegnee

of gêlecttvlty

¡hown

by tha oatlon !.n tte neactlons wlth nucleophtlos.

thc rcle of biredlcat

^oarbonlum

^long ln

the

11 lt

'|'15.

ôeoorrpogttlon

of

dllazonlum

salts

^seema

worthy of funther ooneldlcnatlon,

Hulegan andl zâtù"o88 suggeatedl

that

the

reaotlvlty of the

oarbonlum

lon

^formedl

ln

dllasonlum

eal,t

neaotlonc

ln

^{aolctLo medlla may}

be

^dlue

to a dllfferenoe

ln

^geometrÌf

of the oatlon rhcn

eon4ranedt

to the

^Énonmaln

oa^nbonlum

lon whlch

^drowg

_æ2 hfUnldtlsatloa.

^Âlthough

no dlnsct

^evt-denoe

le avallablc to

auppont

thlg vlert lt 1g of lnterest to note that a theoretloaL

estimatc Þy

Klrnbrttl15

suggeate

that a tetrahcdtnal

oarbonlum

lon (Ð')

^1e

leea stablo than thc ærra4ondtlng ^planar forn

⁽

"p2) by

2h

Koal. For the

^punpoges

of thle

dttecueelon, howevar,

lt 1g sufftalent to

^neoognlse

that the hlghly noaetlve nature of thc catlon (gÐ

ouggesta

that oycLleatlon fnto the phenyl nlng dJaoent to

the

¡ulphone ^grouB !.e

poeeible.

The aultams

(!f4)

andl

(llfl 1ælated

fnom

neacttone ln

whleh oanbonlum fon

lntermedlates are

^expeoted

to pretloninate

may

be

aaoounted

fon ln thl s

way.

The

fonrmtlon of the biphenyrs(thZa)

and (tirZU) dtuntng

the

deoompoaltlon

of the

tllazonlum

ealt sf

^the

aulphonamldlc

(t

^ql

) ^{tnvolves thc} eLlrnlnatlon of thc

aulphone group !.n

the

fonmatton

of ftj]d or of ^thc

benzyllo

mettrylcne

group ln the turmatlon of (l!Iþ)

ae

well as the migratlsn of the

^{attaohadl þenzene}

^nlng.

I 1 'l':'i-

I / ,! ,j

0 t,.

C i-! L.

'l '- ll

-r l-r ^-,-l í-i j-,-

il-i '

'l'*l À

\l

-\?\¡ .

i\l

I :) l-i 'ff c

tl

¡,1 ¡"!

L

"t

\_

î.r!

I I

I

H]

v

t, îi

./ç )-l

,+-'-_-_- -¡--__

_-___.

rts--*- --.--

ll

7

i:.,'i n

\

c

7 L,

ill+

H;-

iij ^{, c, .}

-jiJ

<_.__

(

tJ t-l

r,ld

/lr 4nl ^I

ñti

7 tl 4"¡l

i'iri

+ N

6t

L

L

-r L-l ^{¡ i-/}

t\l \*'

:v

rt!þ---4

|.r

.!"

'7 (.

0 ^{qd' O Ucl} 0

ì.J ⁺ UJ-

Z

115.

lha

ooeur'enee

of

auoh rearrangementa drurlng Peoho¡rn

cyolt eatlon

has

not

becn neeognf eed prervlouely.

Ifowcven,

theec reenrangments

may be

related to

two sldlc

reaotlone

whlch havc been obeerveü dlunlng tha

oyoll gatton of dlasott

ecdt

E-aubgtltutcd

g-emtnobeng-

anllldlc¡. rn

one oase

the nlgratlon of ^{a pherlyl}

_$ror¡p

(lP, to 1[Ð le ^lnvolvad

^andt

fn the otherr ollmlnatton

of a

næthyl group

llnkeci to the

arnfcte nf tnogen

($1 _to

lJ¡¿).58

Hcy andl Moynehao62

h"r"

ahown

that the

nlgratlon of ^phenyl

groupe

lnvolvee the

for¡natf

on of a

flve-membencd qpfno

lnternedlate

andt occur.a

only ln the

preeenoe

of oopper.

From

a

etudty

of the

^pnodusts

f

eolated

f¡rom

reaotlong wlth

uney:nrnetrleally

eubetltuted

s-g-amlnobenzoyldrphenylamlnaa,

theee

authons havc

oonoluðod

t}ìat c homolytlc

meohsnlsr

le

openatlr¡e.

Howevor,

the

appanent

flon-¡eleetlvlty of the attacklng 4eof ee ln reacttone

Tytth

the

unsymmetnieally eubetttuted¡

oompoundle doee

not

neoeaeanlly

lnply a

homoLytlo prooêBg¡

As alneatly dlsoueeedl,

a

oanbonlum

lon

formed

ln s¡ch

^a ryetem wouldl be

htghly

neaetLve and thenefone

relatlvery nonFgeleotlve.

Penhapr

the beet

argument

ln

favoun

of a bonolytle

mechanlenn Ln

thts tnstanec la

the

obeorvatlon by

Hey ancl iloynehan

of tho fallune of

the

¡pearrangemant

reaotfon tn the

abEence

of eopper. rt

t¡ of latclcct to notc, hortvæ, thrt thc rcarrangamnt

rc¡otlon

oÞærvcll

üy Sttla¡ aat Llbbqrlt6 rm

l¡olatd tÉbca¡oÈroponc

^(1ÀÉ)

bt' alcco@o¡ltton of ttrc

ûla¡oaler ælpbt; dlrrilwô froa

9:g.aelnophcnJrl-p-

fleorcsol (üÐ,

_{Daosæted Ëy}

_rarntng

en aguroer

eol6Íe ælutloa rltheut a catalyrt.

HO ^..+

NH₂

w ¹⁴⁶

Docpftc tha euggaltfoa ùy Eulgao anû

^zahlcp8?

thet thc fo¡çatlon of a ?tv¡-mborcü

?tEg

l¡tcrnot!.atc

lr ^lhrour.i!

^ÈU

tonto attacl, !.t

f

a posstbtc

_thûù

rcür"an3æot r of tho ty?c ucuttoaet

eÈovs

ny

^procccû

Èrt æ¡ro

thrn on;

^ËGshratæ

âçadlng

oa

tlra tcactloa

oond!,tlons

rad çattal

rcqut,rcraoat¡

rtthln ür; uolaculc.

?bc cllçls¡tloa of _fl-strÞVl ^groupt rlrf

oh

h¡r

Ècra oÈ¡a¡rçcû

rcpcataaÌft ûurlng

Paohsrr

raasttoar rl.th g.eatno-þlctþlÈcramttlðcr (l!l) t¡r tn

cvÇry t,natanoc,

aooopaatuil by tl¡a

r*oplaocncnt

of thc dta¡oatrü

^gFoup

117.

by

_þdtrogen (ndteamlnatlonn

),60161

^Theee

^reactlons

^nay

oeoun

ln the

^abecnce

of

oopp"o58r95r96 urr6

tt

has bcen ruggcetedl

that thcy

^pnooced

by the transfcn of

^lydrogÇn

slther

ag

atorf9 o"

ea

anloo5g'95'96 to glve (lllÐ _or (üС l¡ea¡reotlvcly.

These lntermedllate

e aro

poatulatedl

to

^undlcngo

hytlrolyslc ts glve thc

^prodtuct

(f¡Ð

anct an

aldcttyilcr tndl, ln faot,

alelcl:ydlce have been rleteotedÌ

ln

aevener lnstanoe s.59 ^r95

lhe biphenyl¡ (t¡Z)

_obtatncdt

tn thc

^pnesenÈ

wonk fnom

the

dtlasotlcêat anr!.na

(üÐ

_and

thc

oorr€,rIrondHng oonpound¡

from the

dtlazotlaect amlne

(f¡g)

_couldl

alnllarly

have bøen

darivcdl elthen fnon the

^oanbonlunr

fon (!lZ) or

fnom

the nadllsat (üÐ. ff tt le

^aeeuneat

that both

^ø¡lcof es oan undlengo

tntnanoleculan oyolleatlon

to form not only

elx-nambescdl

rlnga (ae ln llj

^and

1Ð but

^aLao

tht flvÞmenbered lntenmcdlatee (t¡a),

_{from the}

1on

(t ¡7),

o¡r

(14Ð,

_fnom

_{the radtloal} (lIgJ, _thcn

_the

blphenylc (tLZ)

aroaâ fnom

the eptrane et¡ruotuller (![g.)

oF

(ü9J

_by

phenyl mlgnrtton

andt hydtnolyal¡.

The hypotheEle

thpt

elplranee

ere lntermedlatec

ln thc phenyl

ml,gnatlons obeorrrcd

ln the present

çork,

lc

uupponted

by tho tttentLfloatlon of the Eplro-

katone (llÐ

_ag

_{the naln pnduot} of the

dtecompoeftton

of the

dllasonÍ,um

lon ^(tçO),

L\IL

-zos-

=

f,

-zu¡-

x :=

':}-.

¡ 'I

i"o

' I z":ri

ç

t! ñ

¿tl'1 ',

(q (e

i

.j l

ì'r' íì ^{\-.: i a \-}

t; í\,

-J

-:Hl-

={

^'=f,

^-¿os-

.rli -

tt*l t-' I I

+

7 ^t,rì

f _t I lt

L

7 ç) tr

o/\

I

ilr r.zl\

I I

I I

Ñ rr-

,Ã.

I

ô I

IiII

I

0/, i

I

ñ

(^.,-

|

\)Í1,

ZF-r, öLL ^r\l

i(:t

L¡'".¿

l¿

119.

CH3

+ N2

---+

N

2^{Htr C}2^H5

0

15

ft lr lntera¡t to notc that thc

ooppon_

Oat

alyactl _eyell

_¡at 1 on

of

_{$-Þ eüEy]}

_-E-6thanc

_aulÞ

bnyl-g-

phcnyl.cncdLarufac

fatledl to

^prodluoo

a blphcnyt

oo¡!¡rcæonü!.ag

to (r¡zi)

though

the btpheryl nesulttng Fou ctlnlaatton of thc metþlcnc

_ßror¡p (oonrseponding

ts 1!&)

^w"e

obtainc¿l _wban

a

_3Ð$

*oea¡ of

aodltun

nlt¡ritc rac

^uscd

la tho

dtasot!.gat!.oa

rüap. tfhle¡ _togcthen wtth

thc abccaoc

of a aultan,

rn:ggaat¡

that aolthcr the

oa¡rbonlum

loa latermeillatc nor thc

radt!.cel

lrtermadlatc

arsc

¡ufflolo-ntly rcastlvc to aohfcvc cr¡bgtftution at

^e

¡etunatcd

GarÞôÞ

lton. Ecaatlon of tht¡

arnlnc undlcr

dltff,oncnt

eondl!.ttona

of

eodttun

nltpfta

oonesntnatlon

prorfdlcs

_no dtl.

gtlngtlon _bctracn isnlo

and

radlloal

ProGügËo!.

0

0

150

1

fhe

ecohantna pnopotcd

(Ffgurc IV) for thc

ooppor-cataLysedl deoompoeltlon

of ^the

dlazonf.um

ælta sf the

^am!.Êea

(!fÐ

ancl

(f:d

1g ateenctent

on thc nolc

of

oupnou¡

lone ln

theeo

¡reactlona. In the

^hopo

of oÞtalntng funthen lnfonnatlon 1n

eupport

of thls

nc o henl en

[-b

^{e n zyl -Irû.b en r e ne sulp ho nyl-g-p h enyl encdl 1 amf n c}

rg¡ alfasottecd uelng FÉ

^nonc

^ædlun nltrlte

than

thcoretloally

ragutnedl (aulphamtc

aold

was usodt

to

tlcstnoy

exe€as

nltroua aoldt)

^andl

the dlazonlun

eol'utlon

ras

dleooíþoeed

ualng

ouproua ohLonldle ae

oatalyet,

Pnevlouel5rr oupnoue

ohlor.tde

^(anrl

oupnle _eulphate)

fraA

been

Bucoeeefully

ueecl eB

a catalyat

1n Pechorn

neaotlone

by ^De

lfan

andl

hlr

oolleaguee

but the functlon

of thc oatalyat ln

pnomot!.ng

lntramoleoular aubetltutlon ras not

dleouseod

.74r78 .Atttnugh

eìr¡¡roue

ohlonlde ra¡

apparently

ausooeeful

ln oatalyefng the oyclleatlon

ln the ^present rork, thc rcaotlon

^pnodluet wae oontanrlnatedl

with

oolourerl matarl¡J

s.

clrronratograpl\y

of the ncutral

¡rroituet

ylel.ctcit

thc blphenyl (lUZ^,

and

the

dttrydtro- phenanth¡:ldltnc

(t}Ð

_1n

yleldls

comparablc

to

thoac obtaf.nadl

ln the

oorreeponding ooppeF-catalyædl

oyollsatton ^(ee"

TablÇ

I).

Howæer,

only rcd oll

was

obtalnedl

ln later fnaotlons of the

oh-r'omatognaphlo

acpanatlon ancl

all attarBts to lsoletc pure

oorpoundle

falledl. Certaln of thceo oÎIy ñaotlons

had lnfnarad

rpeatna very ¡tmllar to

thoee

of thc

eultam

(lg)r

whlch

721.

l@ltee that thta

^{ompound waa fonmed} La

the

noaotlon cven though

lte lsolatlon ln the pune state

^couldl not

be affectodl.

It

was

uafontunate that thc

nøaetlon ^pnoduct oouldl

not bc

ana\racdl

oorÌpletely ae the

yf eldtg

of tho blphcnyl (t¡Ze)

anrt

the

dtlhydnophenanttr:ptdlnc

(I1r)

¡oe¡ncdl

to lndloate that

ouproue

olrl-orlils

was

aa efflalent

aB ooppcn

fn

^pnomotfng

oyellaatfon.

Fneeunably thc

flnat st€p ln

dleoompogltlon

of the

Cllaaonlum

æ.lt

^vas

cleotron

furansfer

ñom thc

suproua

lon to the

dtlasonlum group t,heneby pnornotlng

honolytf

o

f 1aelon.

Ocldatlon

of the

radl!.aal

þ

^{oupnl,c !.one oouLcl}

^then

^ooour

^at

outllnedl ln the

^meahanlsn ahown

ln

^Flgune

IV. ft

waÊ

expeoteil

that the lapgo

exoe¡e

of

ouprûue

lone

^preeent

ln the

medl!.un wouldl

be

^¡mne

effectlve ln ^promotlng

^a

nadloal

^proocee

than

^scomedl

ts bo the

oaee

fnon

a

oonetdanatt.on

of the llmlted product

dtata

avallable.

the neactlon

wac

not,

^howeven, homgeneous, andl

lt 1¡

poealbla that the

ouproua/auprfe

ton ratlo

was not

rlgnlfloantly

^hLghen

ln thlE reactlon than ln

^thoea

oatalyeedl

Þy

oepporr

thc nceulte

obtalnedl

fron the

experlment

fn

whloh

zulphamlc acldl

vae

^adlrlcdl

to a aolutlon of thc

dlaøotleedl am!.n6

(ïÐ to

dleetroy Groese

nltrous

aetdl