Bromo-2t-nltroblphenyL, obtalned by the mcthodl of Badlger

EO.UATION II

Z- Bromo-2t-nltroblphenyL, obtalned by the mcthodl of Badlger

and llaeaer14

"*e

^nedlucedt

^wtth lron

^andt

æetlc acldl,

^andt

the

p-tr'6luenesulphonyl

dlerfvatlve of the neeultant

^am!.ne

prepanedl.

The

blphenyl f

rom

the oyollsatlon reaetlon,

and a ut hcnt t

6 ¡-g-t

01 u en eaulphonyl- 2- êffi t no- 2 ^r

-

bnornoblphenyl

(tZOo)

_lvcre foundt

to be ldentloal

^.

Â.nalytleal data

ehoweÉl

the

remaln!.ng ^oompouadl

f;nom

the cyoll¡atlon raactlon to

have

a

moleoulan

formula of

OZOHtl+ NO

F.

^f

te lnfraredl

æeotrum ^elrowadl

a etrong

^band

at

16hB om.-1

,

^{pnoÞaÞly tlue}

to an

^arntdle

oanbonyl ^gpoup

¡ the

canpoundl was

thought to be

^a dtcnlvettve

of [-benzoylcarbazole (l _{ai¿s). [-Benzoyl-}

oanbaøole waa preparedt aoao¡rcltng

to

^{gtevene andt}

luckerrl06 b¡¡t the poaltlong of the

maxlma

ln ltg ultravlolct

npcetrum ahowed

no elmflarfty to those of tbe

unknown

oompound. At thlg stago,

^attempe

to ldentlfþ

the

unknown

naterlal

were dlleoontlnued .

.&n

altennattve

^appnoaoh

to

7-bnomophenanthrlcllne wae

thc

^Pechonn

eyolleatlon of the

dtlasonlum

ealt of

$-g-b ^{n omob enø} yl-S-mcth an e e ulphonyl -g-Þ ^{herqrl en edl I am I na} (f f

Za).

^f

t

wae eæpeotedt

that the formatlon of

phenanthrldllnc

dlenlvatlves

would

be

hlncleredl

by

thc

avallablllty of only

^one

vacant ortho posltton.

Howetter,

the clfmlnatlon of the alternatlve sltea fon eyolleatlon

89.

(tfre grtho poettlone of tho g-tolueneeulphonyl

_Broup)r whtoh wcre

present ln the

am!.nc

(tlZo),

Ëuggcsted

that

thc illhyrlrophenanthrldltne

(ttqa) ntght be

obtalnedl.

Whea

a ælutIon of the

dllasottgedl amtne

(f tZa),

prcparcdl

ualng

æiltum

nltrltc tn jfr

exceas

of that

thconetleaLLy

requlned,

wÊs cleeomposed

wlth

oopper

ar

oatalyst, â

neom¡loundr,

n.p.

97-98oC, waa

obtalned after

cl¡¡ronatographlo

aeparatlon of the neactlon

^procluete.

Thls

oompoundl was belleveel

to

Þc 7-bnom-!-mcthane- eulphonyl-5 _r6-dt 1Ïrydlnorphenanttrrlillne _¡ f t ^qd )

r

^{andl th!. s}

vlew

was strengthanedl when

lt gevc

7-þ¡rom@henanthrldllne

(lZq) _on

oxtdtatl.ve lgrdtrolyele

wlth glaalal aoettc

aoldl-

sulphurlo

aoldl andl potaeelum

permanganate.

Howeyer,

analytloal

^dt

ata

w6ra

lnooneletent wlth the formufa (llg4), but

appnoxtmatcdl

to Cr6H*¡fZgAObe.. That thf s

^rnatcnlal

wag

aotually a

m!.xtune

rather than

e purÐ compounil wa¡

ahown

by thtn layer

ehromatogaphy on

both ell1oa ^gcl

andl alumlna

platee.

Howevenr

the tm

spotg obsorvcdl wenc

too

^oLoee

togethen to

aLlow

eaparatlon by

arry phy¡loa1

mÊans

avallable.

The

rælt1ng polnt of

97-98oC ^oouLdl not be

ralsedl by repeeted enystallleatlon

Èom vanloug

solvents (ethanol,

methanolr oF benøenc/)il¡), by

ol¡-¡comatography on. alumlna

or by zone-meltlng

teehnlquea.

Ae

the materlal, rrepr

_97-g8oC ooulel

be

h¡rdnolyeedl

to

7-bnonophcnanthr'ldltne,

lt

^æemedl reasonable

to

^assumc

that

7-br" omo-5-methane euLphonyl-5, 6-a t ^{tÙra n ophe} nant ¡¡r I ^dl 1

rc

^wa s

one oompoaent

of thc mlxtu¡c¡

^An

attempt

^{was madle}

to

laolate the

ceeond oonpoundl fnom

lr¡nlrolyele

er¡penlmente.

Îtroweryen,

only a black, olLy naterlal

^remalnedl

after

eeparatlon

of the ^baelc 7-bromophenanthrLdllne.

^Repeated!

cxtnaetlon of thle

^neeldlue

wlth ether

and bcnzene

falled to yleldl

morc

than a

tnaoe

of

neutnaL

materlal.

^{The eeoondl}

oonrponent

of ^{thc mtxturc} le ^{probably e}

^{oompound whloh}

1c

oloseLy alLledt ln ^gtnucture to tha

etlhydlnophonanthrldlne

(ttoa)r _but

whloh

falletl to sunrlvc the

o¡rldlattve

hydrolyete.

^The

^wfdenoe at

^pnaeont

avaLlable

^{dloeg not}

permtt

any

ñIrther r¡leaulatlon

ae

to the

natune

of thle

eompoundl.

In adtdttlon to the

amlne

(ttZa)'

one ft¡rthen

oomÞoundl, whloh wae found

to

^have

the emplnlcal

^fonmula

Cf

ff

^f

^SSar

^was

tsolatedl from the neutral fnaetton.

Dtetlllatlon wlth ztnc

dluet ^gave oanbazole, whloh ^wag

ldentlfled ^by lt¡ ultnavtol.et

apeotrum,

ffid the

^melttng

polnt of lts plonate. ⁰ⁿ thle evldcnee, the

^oonpoundl

,l

SHlt

NSa

wag forrnul atcdt

a!

$-n6¡haneeulphonyloarbazolc

(IZZA).

Attenrpta

to

^pnovldle

^{deflnite pnoof} of lte

struotune hy an

lndlerpendlent

rynthertl ^trcre

unguccegefuL.

Ithe method

of

^{Stevens andt} Tuokenrlo6

whleh

uaÉt ueedl

euceegefully to

^prepare N-g-toluenesulphonyloanbazoLo

U¡¿g), ^falledt

^when methanesulphmyl

ottlorldle

wa6 uædlt

91 .

the carþagole belng

noeovcredl

unehanged.

Modllflcatlona

of thte

^{nethodl employlng}

longen Feaetlon tlmee

^wero

ogually unrc¡yantlng.

A

funther attcnpt, lnvolvlng

oondensatfon

of

methaneeulphonyl

ohlorlde wlth

tho

potaeslun æl.t of

^oanÞasole

ln llquld

^{anmronla, aLea} fatl-cdt.

Pncsumably

thc

methaneeulphonyl

oÌrlonlde

wae attaokedt mueh more

naadlly by

amlde

lonc present ln the

ryetem

than tf

^potaselum

oanbezn¡.c. ft le of lntereet to

notc

that

eondcncatton

of

canbazolc and g-tr6luencaulphony1

ohlortdle

^aLeo

falted

^unelcr

these condlttorsr

The oopper

catalysed

deoompogltlon

of lnvereely

dl I ez of I seil $-g- ^{brsr¡ob cnz yl} -1t[- net ha ^{n e} eulp honyl

-g-

phenylcnsdlarntna

(tlZA), _vhfoh

was prøpaned

ualng tOfi rmr€

æd!lum

nf.trlte than theonetleally requtred,

^affondlcdl

7-b nono- 5-üet ^{han e c uL p} honyl -5, ^{6- dt t hy dr op hena nt tu I d I ne}

(rtca)r _E.p.

1?A-1254C,

Ln

21fi

vteldt. Analytloal

ctata and

oxtdletlve

hydl¡rolys1

a to

7-bnomop henanthrldtlnc

(l¿Z)

oonflrmedl

the stnueturc of thl¡

^oompeuncl.

The

hfghor coneentratlon of

ædlum

nltnlte

ueed

ln the dlazotleetlon etcp agaln altcrcd the

oourao

of the oyelleatloa. In adilttlon to the

^puro

dt I hydl rop henent hn f d

lne

⁽

!t9Ð r

E-Bre t hane aulp honyl- Z-aml no- 2f-bnomobtpher¡yl (tZOa-) wae obtalnedt

ln

2llß

vteldl.

Furtharmore, the

^y

leld of

$-methaneeulphonyloanbazofe (l¿gg.)

ras dlrastlcaLly

^{nedlucedt unden}

theec condltlons

^(see

llable V). The etnuetura of thc btBhenyl (tzoa¡

waa

oetabllehed

Þy

hydnolyele of the

methaneaulphonyl group andl eubacquent oonversloa

of the

^amlne

to

the

¿-tolucneaulphonyl dlerlvatlvc.

^{Thc oompound pnoved}

to þc ldentloal wlth the

$-g-tolueneeuLphonyl-2-amlno-2r- bromoblphenyl (1209.) obtalnedl fnom

the oyclleatlon of

^thc

amlne

(ttZo¡

_on

_by

dtlneot e¡rnthesle.

Fron lablo V, lt ls

obvlous

that thc

oouræ

andl

extent of the

etdlc

mactlons tn the eryolleatton of the

^a¡n!.nc

(ttZa) are pnofoundly

lnfluenoedt

by tho

^amount

of

^eodllum

nltrlte ^present dlurlng dlazotlsatlon. It

^waÊ

of lntenest' to oarry out

one

eyolleatlon wtth

dllazotlscdl E-g-b ^{¡romob e nz} yl -$- ^{me t ha ne a ulp ho ttyl} - g-p hcny 1 sn edl I an I no

after

sulphamle

aold

hadt been ^adtdl edl

to the eolutlon reeultlng

fnom

the

fnvense

dllazotleatlon wlth a

SO|E

srßcese

of

^eorllum

nltr.lte.

^lfhe arnlne was oorq)lctely

consumedl

ln thl¡

e4pentment,

but the yleld of

^thc

dllÌrydrophenanthrldllne

(ltqa)

ücorcasad

slt ghtly ae

^dtl¿l

the ^yteldl of the btphenyl (IæjÐ. 0n the othsr þd,

more

of the

^oanbaøol

e (j329)

_{wae obtatnedl}

_than ln

^any

pnevloue

oyolfeatlon of thls

snlncr

7-Bromophenantlrrldltnc

(¡Zz¡

_wae

preeent ln

^the

baslo naterlal fron

caoh

of thc oyelleatlone of the

amlne

95.

TAETE V

P SCHORR REACTI ONs 1¡lI TH E-q- BROMOBEN4íL-N-METIIANE SULPHOIV:(L-

E-PHEIÍLEI{EDIAIÍINE ⁽

tt

ZA) PERCENIAC'E YTET.Dg

-

17

25.5

15.5

1

t _{A, Raaotlon}

_eanniedt

_out wlth eolutfon

^prepanedt

þy

tnveneo

dttazotteatlon wtth !$

^exoeeÈ

of

sodtum

nltrlte,

B, reactlon carnled out wlth solutlon

^pnepanccl