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S‘I’.”:'._}I'*3}S IN Tim DIPHfl’EOQYTI'fTOEIE $311433

By

Will!“ J. Ddfl'Bit

A T313118

Submitted to the School of Grant. Studio. of mohignn
State College of Agriculture and Applied Sci-no.
in partial tulftllmmb of the "quiz-mont-
for the dogroo of

“AS? 3m 0?“ SCI ENC E

Mutant of Ch wintry

1952

 

“ "1 . R -"l'

ACKEOWE. my 5131'

The nuth-or with“ to” 02pm: hie eincere
eppreoietion to Dr. Harold Bart for hie timely
advice and encoungmm: during the amino of
this research and the preparation of thin man--
script. He also wishes to thank any tumor!
of the Chantry faculty for their help end
edvice of e personal neture mm; hie day «1
Michigan Stete Congo.

0......0‘.
.‘tltfiu
.“tO’
‘ttfi

l.
.

£28533 1.

TABLE OF CQFTEflTS

PAGE

IRTEOfiUCTIOH oeeeeeeeeeeeeeeeeeeeeeneeeeeeeeeeeeeoeeeeeeeeeeee
HISTORICKL eeeeeeee.eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeee

EX Jfilfiaflilb-eeeeeeeeeeeeeoeeeeeeeeeeeeeeneeeeeeeeeeeeeeeeeeee

009°.“

PYOOO&BPO. eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeae
TGbIC' eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeee :5
Figures Queer.eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeo. 52
DISCWSSIOH O? RSSUETS eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeee BU
Snfifilgr'eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeoe 65

BIBLIOGRAPHY eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeee 67

INTROMCT ION

IIITROWTCTIOH

The originel puerpeee of thin inreetigebien we to M the Diele-
Alder reaction of 4.0-diphminene with certain dimes. A may or
the litereture heel "reeled only ene preview eirbmpt eis this motion (24).
end 1121! In mueceeemie Beau" of the tether vigor-me eonditiene eun-
played. however. it II ten their further [study 01' the panel m len-
rented. The graduate which night eriee 2m each e rustion mid be of
eonsida'eble inherent ee polymeleer coupon!!!“

In the wane at the" ebudiee the method for me mum at
4.4‘diphmequinone m inreetimtea in nae CM)... line the Wed den
eeribod in the litexebnre did not tort in «If hen!“ A ennui-tenth
eneeeeerul method m develop“.

Swen e leek of need! with the melt-Alder reution he evident. are
turned ear attestation to the ebeerpbien epeotre of e water of eubetitutefl
diphenoqximue In «equation 11th thie ”It the martian of 3.3,h'8'e
tetanitMAhdihydmydiphmyl m undid. The dieeeoietien «mat
of thie eupound in Web! In determined mmme-ioeny.

.1.

IS

‘ 1,; :25

 

‘ \ .Ilurlllzl. I
Ill]

 

 

 

HISTORICAL

The parent compound of the diphenoquimne eoriee. 4.4'u-diphenequinooe.
no first prepared by Willetetter end Kalb. (l) in 1905. For ite prom“.
tion an ethereal eolution e! 4.4’adihydmxydiphewl m ehnken for twenty-
four houre with eilver amide or preferably lend dioxide. The filtered
reeidaae tee refluxed with benzene for fifteen to thirty minutes end the
lead dioxide lepereted by filtration of the hot eeltrtien. Dighemquinone
eee eepereted from the benzene eolutien. by cooling and mporetion. in
two form. firm. chrome ecid like. red eryetele em bright. eoft golden
needlee. The yielde enounted to forty-five to fifty percent. Snbeoqnent
vortex-e here ell need the prooerhre of Willetetter end Kelh. with elight
mdifieetiene. to prepere 4.4'odipheneqninone end frequently reported an.
tioulty in obtaining the poduet. Ono eruption m be Pie-er (71). the
mention the preperetion of diphenoquinone with leed tetneoetete but givee
no deteile. Velyeehko end Sheherbek (29) need the preoedure ei' Willete‘tter
end [elb end found the reeotion to go tell only after eel-wing out eertein
tedioue preliminezy preperetione euoh ee the preparetion of finely divided
4.0-dihydrouydiphewl by precipitetion "an e hot etiwl eeetete eolution
end the nee of drying egeute before the lend diaide aidetion etep.

Properties of 4.4'ndiphe1oqainone end ettmpte to eondme dipheno-
quinone with 1.8-dimthyI-l.8-bntediene et 90.100 degreee in e ealed tube
have been reported by Here Boon-Long (24). The potmtiel of the “phone--
outdone-diphenel meters wee «unlined by Pie-er (so) ueing e "dieoontimoue
titretion" method ehioh involved adding relying emnte of oxidising egent

to e eolotion of diphenol and mounting the potential of the eolutien et
regoler time intemle. By grouping the eerieue «estimate e eomeoeite
titretion our-re wee oonetmoted end the metal oxidation-reduction poten-
tiel eeleuleted tree it. Thie potential wee fund to be 0.954 volts end
is reportedly the higheet oxidation-reduction petmtiel or any organic
compound yet etudiedo The eelor. amnion-reduction potentiel end
etreeture of d.4‘-dipiameqeinene m enmrieed by mm, Berthier end
Pollmn (26). The head fiution in diphenoqzinone ee determined by the
mthod e! mleouler mitele fie reported by Cenleen (26). Other worker:
(2'!) here and the eexee towed to eeleelete the reeonenee mm of di-
pheeequinone. filing en empiric/e1 reletien that alete‘ between the
neenenee mergy end reaction! potentiel theee eorten here eleo predicted
the mum petmtiel e! the email. Beker end We. (as) here and
Fieeer'e (30) value of the oxidation peturtiel to eeleulete the relative
reeetiritv or 4.4'adiphenotminone ee mud eith e war of ketonee.
Derivetiree 31d ebeerptien epeetre o! diphenoquinone in eleohel end eodiun
ethylete eolutiooe here been reported (29).

The prevention of SJJ’J‘etetnehlore-duhdiphenoquinone eu reu.
ported by L‘egetti (a) prior to the firet preparetion of the parent compound.
Bie preparetion eoeeieted of ihe oxidetien of 3.5.3'5’ tetreehlero-hve
dih‘ydmxydiphmyl in eoetie eoid with nitrie eoid (381.50). The emai-
ing tetrebrom derieetive lee eiee prep-wed by fingetti in me eeee leaner.
Buyer (d) eleined to here prepared thie eubetenee by the uidetien of
tetabmghemlphthelein in eonontnted enlfurio eeid. However. 'ébir
(6.6.7) believed that sever W the m orientetien of eubetiteente

for tatrehrommouolphthelodn end this inoorreot orientation ie repeated
in Belle-hem. Hole chimed e prevention of 8.5.3!,5'dtotmbmmood.4'-
diphe’noqzinone Inporlor to ”not of hgetti. He confirmed metro!) on this
emu with etudiee on the street of vex-ions reaming egente. fioir eleo
propered new derivetivee of gei-dipheoomimne each ee dihmdimthyl-
diphonoquinone, etc. mm: by Emitter end Woollett (8.9) bee mbeteutieted
thgetti'e manor: end daemotarieetion or 8.8.3!,5' tetnhmm-d.d'-
diphmioone en! hoe ohm that the ooqotmd obtetned by Kettle end
Loenfimrt (11) by the eotion of sunlight on tetnbmoyolohmdiemne in
«than dinkide ie not the tetnbmm-diphommime ee claimed but 13on-
dihmghonylem oxide. Yheir work eleo refuted the etetenent of Keetle
end Wart thet the eotioo of trihronophenol bromide an ether triu-
hroaopheoohte in ohlorofm we Benediot'e— mem-dwhmoqzinom (10).
An inure-ting eontmverey he: eppeered 1n the litmtm-e eonoerning
the produot obtained hon iedine, phenol end dull. The 8.6.3:,5'4etm
10:10.4,4'ediphmom1nono dorivetive he been claimed es the mom or the
eotion of elk-e11 end iodine on phenol (12.15.14.18). It ie eleo chimed
thet the we product my be obtained by heating 8,4,6-Itflodophm1 with
code solution (16 ). by the eetion of iodine end am: on eeliovlie eoid
ed the one end not: hydroxybeneoie eeiee (18.16). by the “mum”
of dfihdiiododiphenie eoid vim line (1?), end by {he mien of iodine
end eode on 8,4.6dtriodophaol (11!). Hunter end Woollett (19) ehmed
that on preoeding Watson: New reunited in the fox-notion of
enerphoue comrade of high eoieouler weight. A form): correction he
been give: i’or Vortmn'e eonfimtion of Lmtemenn’e Red by Hunter end

Ehree (20) end by Woollott (251). An mthentie mole of 8.5.8.‘6'~tetre-
iodo-d.d‘-diphenoquinone one prepared by Einnter end Worse (20) but In
named incorrectly ee 8.6.8',d'dtetniodo-i.4'-diphenoquinone. beellett (21)
determined the oorreot mitioh or the iodine etom. The proper-etion me
through ozidetion of 8.5.3'.5'dtetmiodephenol with chronic oxide.

The ooteohld’odiphenoquinone bee been euggeotod by Shower (22) ee e
. bowie inpregnent for wood to reeiet urine organiem. 2.2'.3.3'.5.5',6.6'e
ochohlorodiphenoqninone nee node by aidieing 4,0-dihydrootyooteehlom
diphmyl or eimlteneooely uidieing end ohlorinetiog e polyhydroxy-poly-
chlorodiphemrl (23). I

A fairly large umber of other derivetivee of diphenoqninone here been
pronred. In general. these properetione have involved the oxidative
eonpling of eubetituted phenole. the oxidation of enbetituted diphonole or
enbetitution motion on eubetituente elreedy preemt on the “plum--
quinone moleue. The propntion of 8.8‘-dihydroo=y-d.e'-diphenoqainone
one reported by Hem-lob (31) en the entuidetion produot of moreiml
in alkaline eolution. Re reporte. however. low hydrogen unifies for the
compound (so-4.647: ioeteed of 8.73:). The problem or the aidetion er
mominol in eodiun ethylete eolutione bed been etudied exteneirely by
Velyeehko end Shoherbek (29) end they reported the prepntionof 2.2M-
dihydroxy-dfi'dighmwuinhydmne end the corresponding quinone. The
properetion of 8.3'ndibrono-2.6.8'.d'dtetnmethoxydiphmoquinone by
uidetion of 8-bronopyrogellel-2J-flnothyl ether no reported by bovine
(32) ee well ee the properetion of 3.3'odiohloro—I.6.2'.6'dtotremthouty-
diphenoqninone in e unm- mnu- (as). m propention of 3,8'cdimthyl-

5.5'-dirnetho:v-4.d'-diphcnoqzinane from 2ohyslmny-E-nsthonytoluone hoe
been described (34). The oxidation of 2.8adiacotyleninophoml we reported
to are totrnoetylnninodiphonoquinone by “Fran end Short (35).

{rho probable formation of totmzidodiphmoquinone froze totmbm‘mdin
phonoquinone with sodium oxide no reported by Fomeyrmki and ‘chlelmki
(36). The black-violet powder obtained docawooed with acids or elkeliee
and exploded at 80 degreee by friction or alight shock. Ito emplocibility
prevented mlyelee

The preparation of hmthyloa-othyl, z-neathyl-G-propyl. 8.6-diothyl
end Zdeothyl-a-eilyl phenole and their czidative equaling under the in»
fluence of chronic oxide in acetic ecid to the eorroeponding 3.5.3'J'o
tetrelkyl euhetituted diphmquinonoe bee boon described by Aurore and
Wittig (3'7). The procedure for the allyl comm is omitted. however.
as the yields were very «11 end emlyeie one not evocaagliebod.

‘Yhe preparation of 8.8.3'.Bi-itctrnmthyladfihdiphemquirone by oxide-
tire coupling of the respective phenol derivative he: been reported by
Moore end Vethorite (59-) using chronic oxide end by Weber! end Coegrwe
(39) using beneoyl pcmide in chloroform. Hort end Ceeeie (84) have
prep: red the 8.6.3'.6thctre-t-bntyl-d.4'-diphenoquinone by ozidetive
coupling of the corresponding gheiol using nitric ecid.

Conein (40,41) pregnred mamlcmithquuinono. and the dichloride of
thie eabetence by the notion of chlorine on ditmmol. He also prepared
dibromdithymminone by treatment with bromine in the m manor.

Sohlonb (42) moored 3.8'dimthyl-AA'wdiphoncqaimne-bio-ohlorimide
from e-toluidi no by oxidation with eodiun hypochlorite. Diphemquinom
none-chlorimide end bis-chlorimide were aloe prepared by Schlonk (42) by

the nation of ecdime hypeehlcrite on Mydmxy-d'aminodiphenyi end
beneidine respectively. fiilletatter end Felb (43) prepared (AH-dinnerw-
quincne-bie-mthylamonium chloride end the d,4'-diphmcquinoneobie~
dinethyimmoniun hydroxide we prepared from the pea-bromide (44.45) end
iron the pericdide (43,“). Schlenk (47) prepared i,£'-dipbequinone—
bieachlcrimide from 2.2'odieminodimerg1 with ecdime bypccblorite end else
prepared 2.0 diphcmqnincne ueing 8.4'udienincdiphenyl end ecdiun hypo-
eblerite. A diphemquincne tetrcphonyldinetbide nee mentioned by See! (48)
in work concerned with eelculetion of the reactivity energy requimmmt e!
quinenee. Alec included in time eeienlctim were the 9.13%- end 3.3%-
diphmcquincnceo

Lieberman end Berg (‘9) clei zed to have prepared 3,3.3‘.5'~tctre~
bydmy—G.4'-diphencquinone by treeting e eclnticn of 8.4.5.8545?-
bmbydmydiphwl with eleohclie iodine eelutien. Hoffman (50) prepared
3,8,3'.5'-tctremthozy-4.v-diphcncqnincne, «Mince celled eedriret. end
3.5.5!.ctueotnothmy-ew-dsphmoquamm from the wrcgellcl 1,8-dinethyl
end 1.3—diothyl other: viii: petueiuu dichmte. Kdzmnn, Rey end Run
(51) propel-ed the perchlcmtee of 4.4‘cdimacquincne-bie-dinethylemniun
mum. end diethylenmoniun hydroxide. The 3.5.3'J'dbetmbencemidc-
4.4'—dipbenoq‘1inene derivative eee premred by Hallow. Davie, Jonee end
Weill (52) by the oxidetive conplirg of dibmeenidephmcl Being eediun
nitrite.

The subject of the cherecterieetion of erietcl in the literetnre in
en intereeting one end eill be motioned briefly ee it is concerned with
the derivetivee of diphenoquincne. An encnyme lather (68) reported e
prepeution of erietel rm thyml in eodiun bydmide by treatment with

.7.

iodine. Since that time (1915) Woollott (56) reported erictol ee e nix-
tore of exbetencee containing e terry mteriel end e compound of high
mleouler weight. $5qu and ibupine (57) geve supporting evidence for
erietel not having I quinone or ketone etmotnre but identicel with
diododithynol. Bordeienu (53.64) reported the retention of 8.8'cdiodoo
3,2'.B,6'-tetnmbhyl~4.4'-diflienowincne end l.3',3.5‘dbetreicdo-8J'.6,8'-
tetmmethyl-d.0-diphminone in quantitative yield from the eorreepond-
in; diphenol omnde end mggoeted e tormle tor erietol ee the diner
o: diicdodithymldiphenoqnincne. In 1937 Pepin-am (so) prepered only
one compound by the treeteemt ot 8.4-diiedctiveol or 84deth
with elkeli. Thie mad he deeeribed ee eril'bol eni propoeod the tomle
o! diiedodithynoldiphmquimee for it. In the one paper. however. end
in future work (75) he rotere to erietol ee 2.3'odiodc-i-dithynol end
thyml iodide.

Willetetter end Kalb (69) end P100011 (68) here reportedly Phil!!!
“iv-dipbonoqninone diindde by fine midetion er bmidine. Sohmer (60)
hoe reported 4.4'udihydroxydiphem'l diqninone (3:) end

1:.

the prepntion of 5.5'dihydrorj-53'ndimcthyi-z .3'-1ip}wnoquimno has

been reported by ammo? (51)..

ESP; RI RENAL

in

if:

"J‘.

4.4:cdib5ydmx1diphayl (62)

Fifty gm of beneidine. 80 millilitore of hydrochloric eoid end
one liter of weter were fixed end diluted to five litm. Two humired
grease of mlfuric ecid wee edded. which formed e white precipitate of
beneidine eultete. Sodium nitrite (87 green) in tea :eillilitere of uter
wee edded gnduelly, leaving e clear, dork eeluticn. Steam no mood
through thie eolution for 80 wimtee. The crude 4.4'ndihydruydipherwl
hed eterted to leperete. ee the eelntion he cooled wimout filtering.
After cooling for eererel been the preoipitete .8 filtered end re-
exyebellieed from eoetio acid. giving 36 gren- (76 per cent) of e white
product which charred et :71 degreee end melted at 276-279 degreee
(uncorrected).

Activated Leedjiiozide (63;

Fifty gum or lead tetreeoeteto (73) wee etirred in 400 millilitere
of water in e one liter beaker until ell of the ecetete no comet-ted to
leed dioxide. Thie fixture wee centrifuged four time. weehin; with 400
nillilitm of weter eeoh time. The leed dioxide wee then euepended in
50 nillilitore or water. etirred. filtered end eeehed egein with 50 milli-
litere of ntu'. The mid: leed dioxide wee then washed with 85 milliliter

.9-

 

 

 

 

portion. of eeetone four time end eith 25 milliliter portions of other
four tine end dried in e um deeeieeter. The yield of light. eetree
hm lead diaide m 88.9 great (68.7 per cent). The eotivity of thie
product in memred by the ”tired of Gretta-nun end Wiehnd (70). Thue
.a-J gun. of lead dioxide me weighed eeeuretely end pieced in e use
milliliter Erlemer fleet into thieh tee game e! poteeeium iodide in
tire millilitere a! water In poured with linking. The mixture In cooled
in ice end ll nillilitere er Mutated hydreillerie eeid m edded.
After diluting to 80 millilitere the libereted iodine m titreted eith
mm mm thieeelfete. Anelyeie ei' eel: one mutien no eerried
at in thie laboratory giving an eetivity of 65 per eent. hm. eetivity
ee high ee 95 per eeut hee hen reported by Kuhn end Elmer hem thie
method of endyeie.

ag-dmmtmag

o:":=o

e) Hethod of Fieeer

Severe! ettmpte were nude to uidize 4.4i-dihydrexydiphewl with
lead tetreeeetete ee mentioned by Fieeer (71). Tu game of 4.4'edie
hydmydiphewl me dieeelved in 70 Mllilitere e!‘ ghoiel eeetie eeid
end treated via: fire 5mm of loud tetreeeetete. The eelntien hem
M red in color and e precipitete famed which we not emble in hot
bended» Further cooling of the filtrete gere no dipheneqninone.

~10-

 

—- I‘ve-7"“

 

One gren of 4.4’edihydrmrydiphmyl no dieeolved in 150 milliliter
of eeetie eoid end oeeled to elightly ebove the {reeling point. Lend
tetmcetete lee” edded ole-1y end there we obtained 0.65 gum or e block
eolid which did not melt bele- Sdo degred.

One gran of eA'dihydruydifiumrl m dimlved in 60 millilitere of
eeetie eoid. eooled to room tempereture and treated dropeiee with e
eetureted solution or lead tetmeetete in eoetie eoid. The eeler «lunged
pmgreeeively to cringe the: green. A brown precipitate mafilim Iced
dioxide formed.

Diphaneqsineno, wagered ee inducted below. ten dieeelred in eoetio
eeid deemed to e bleak eelid in tee to three bare et rem twenture.

b) The Method of Wilmetter end hell) (1)

The method of Willetutter end Kalb (1) one etteeyted eeverel tinee for
the preparetion or diWinone. In each one. e an hm preeipitete
oryetellieed from the hot beueeoe eelution ehieh in no I: mottled di-
phenoquimne ee deseribed by thoee euthore.

e) A léodifioetion of the Willethtter end Kalb Procedure.

Five green: of efi'dihydmydiphml no dieeolved in 720 mllilitere
of other. Treaty-tire grew 01 eotie‘eted lad dioxide In edded end the
mixture eheken on on eutmtie eheking nohino for forty-dive nimt ee.

The “lotion one filtered end {he l-d dioxide outta-noted by refluxing with
one liter of beneene end nbeequently via tee 500 milliliter portion: or
bemene eeoh being heated for fitted: dmtee et rdlnx tmperflmre. Cool-
ing or the mined extreote we 1.69 gm of red. eryetelline

.11...

diphmoquinone. Cwimtion of the mother liquor with e third extrmtion
of the leed dioxide elem end concentration or the totel eolution me
0.68 gm of edditionel diphenoquinone. After etanding for eoneidoreble
time. e11 riltmtee were tnoeted with ligroin precipitating .4 green of Led
eryetelline diphmimne (see next pemgreph). The total yield one 1.6?
grene (53.9 per cent).

Thin «pennant ee rel! ee othere varying the tine end concentration
of iced dioxide have euggeeted tut e retio est 4.4'dihydmydifizew1 to
“tinted leed dioxide 6‘ one to five end en ouridetion time of fifteen to
forty-five nimtee formed the optimal conditions for initiation. The
Wary from the nether liquor Vii-h ligrein imriehly yielded the gold
tone of diphenecinone with the one eruption deeoribed ebove. The red
tern of diphenoqzinone could be reexyetenieed to the gold torn from he!
benzene in so per cent yield. Baez ton- emu to e um. my;
melting eolid between 163 degreee end 168 degreee (met-rector!) verying
ended: for produote tron differut repetitiou-

Anelyeilc'
.9... J...
Rod 78.63. 78.57 ‘0“. 4.84
501d 78.39. 78o“ ‘059. ‘06:
Theory 73.25 4.33

§L535115H¢et greatly 14,0-dj‘phenoqgjmno _( 3:11

“-‘ ‘u

CH; (:12,
CF33 CR8

A“ AA A

’ All enelyeee mated eith en eeteriek were done by Clerk ’ficre-
enelytioel laboratoriee. Urbene. Illinoie.

an.

 

' ‘-i-$'V

A 500 milliliter round-bottomed flee}: equipped with e reflux eon-
demea- eee charged with 300 ailiiiitore of chloroform. 12.! grate of
2-hydrow-1.8-dinethyi heneme end 24.2 gram of homey! peroxide. This
mixture one enowed to reflux for four houre. The dark red eoiutien wee
then named with 100 niliiiitere of Iodine: bioerbomte (6 per cent) three
time end 60 mniiitcre once. The chloroform ieyer m dried over
euhydrm sodium eulfete and evaporation of the chloroform carried out in
e veouun et room temperature. The eoiid remaining after evaporation me
nabbed with 60 millilitere of other end filtered giving 5.40 green (45 per
cent) or 3,5,3',5'.tetmmethyi-d.4'diphonoquinone. Thie Wed, re-

ozyebenuod from eootio .014. melted at 205-210 (13ng (uncorrected).

lmlnie"
.2... .2.
Found 79.08. 79.24 6.31. 6e”

Thie enelyeie eho' probable imrity but the edded eeeurenee of the melt-
ing point nkee the identifioetion of the enhetenee emntively oertein.

3'533' lfi'jotygghioro-dd'dihfirexydim

Cl ‘ (31
(31 Cl

4.4'a-dihydroxydiphonyi {three gram) wee axepamied in 400 milliliter!
of eoetie eoid in e three-hooked fleet equipped with e etirrer end reflux
condenser. Thie eeiution the euhj noted to e etreem of chlorine gee with

flirting for one to two home. The 4.4'c-dihydroxydiphenyl dissolved end

~43-

the tetrachlorodiphonol command eognretod. After three houm of etirring
the oolid command me filtered end rooxyetellized from en ethyl alcohol-

enter nixture. The yield of 8.5.8'.S'ototrochlorooi.4'adihydmxydiphowl

was 8.12 grams (98 par met} before reomotellieetion. WP. 236.239

degreoe { unocrroct ed ).

gms' Ig'ytetnohlorg-dfi'qdiphgnoggimne

Cl Cl
Cl Cl

A sample of 8.5,3'.5“etetreohloro-d."-dihydroxydiphwl (4.4 gm)
wee dieeolred in eootio eoid (loo millilitere) in e 500 milliliter three.
necked fleet: equipped vith e etirror, reflux oonieneer and dropping
funnel. The tomoretnre wee mind to 98 dogreee end the etirred eolu-
tion treeted with 10 milliliters of nitric eoid ( D 1.80). After ten
nimtee an reection mixture wee cooled end filtered. The yield of
8.5.3'.5'utotreoh1ore—4Ahdiphmminone. deep red eryetele with e purple
glint. meet.“ gram (46.4 percent). The eompeond did not melt, oher or
deoonpoee below 340 degree... It me reoryetellieed in poor yield from

ehloroi'one.
Amlyeie. 'C 21 Cl
Found 4.4.31. 44.61 {.23. 1.58 41.23. 41.47
Theory «.3 1.24 44.1

enelyeie in thie- leboretory for chlorinw oeing the PM? Bout method
a“. 45.81. ‘5e‘7e

.14..

f3

 

LEJQ'Lfi'gtotigongm-fiv-dihydmxydioheryl Leg)

We 1‘10a

Bonnidine (18.4 5mm) no dieeolved in 300 nillilitore of acetic
acid. Rented with so zrdnilitore of nitric eoid (a 1.39) end dieeotieed
dish 14 gram or eodion nitrite in 7D Mllilitere of water by adding the
letter eolution to the bemidine «lotion elouly with etirring. Kittie
eoid (30 millilitore) (D 1.50) m eddod to the eolution end the mixture
me heated oeroi‘ully on e Ito-an hath. Following the tepid evolution of
geese e oryetelline product leper-tied end after hating for one hour the
deletion no cooled end filtered. The eolid wee reezyetellieed from
eceeie eoid, yield 26.6 gram (70 percent ). Hating point. 813-317 do-

greee (uncorrected).

Amnu‘ c a x
me 4001‘. ”02? 1091' 19 7‘ 14.77. 1‘099
Theory 89.! 1.85 15.3

finely-1e in thie laboretoxy for nitrogen ueing flu time method
gave 18.76 and 15.73.

8.5.835'gbebmgbfimtylgjv-diphomqg‘inpqe

c4“: “439
0- <:>=-
c‘fl, c439

.16-

S

E

 

 

A omde eupply of thie compound we obtained directly from
Dr. 2mm Herb end Fun): A. Cueie Jr. The compound Ine mnmullieed
from ethyl elcohol. The melting point me 241-846 degreee (uncorrected).
At 335 degreee the compound reel-recs“ from dark red. etout needles to
etriking red end yellow. long needle-like cryetnle.
Attenuated Diele Alder ligation of Dighenotminone
' with Fyologoggnd—fcn; *
e) In ethyl eleohol
The procedure of Albrecht (66) we first need for the attempted con-
donation of diphenoquinone with oyolepentediene. (All oyolopenbediene
need in the following «perineum In obtained by deetmctive di ehilletion
of dioyelopentediene rm iron eire through en effieiene eelnm at GO
degreee) (67). One gm of i.d'odiphenoquincne Ill euepended in 150
nillilitere of ethyl eloohol. The eolutien we cooled to lO-lfi degreee
end five milliliter-e of cyclopmtedione nee edded. Ho immature the
‘8 ables-red. The reaction mixture no etirred at £0 degreee for three
houre during which it became very clerk. After eoolixg. block. eoft
needlee (0.83 gm) were filtered which changed to been ob 800-12") de-
groee but did not melt: below 340 degreee.

b) In became

One gun at diphenoquinone nee amended in 150 milliliter! of
beneene which bed been dried over eodiue end distilled. Thie eelutiu
he pieced in e. 500 milliliter two-necked fleet end etirred e1: reel!

«manure while four gnu of eyelepenbediene one edded. The nixture

~18-

Kaila! .‘5

 

 

one the: heated to reflux end etirrod for two houre. Ho visible reeotion
hed teten pleee end in order to dieeelve ell of the diyhenewinone. 300
millilitere of benzene tee edded. Addition! oyolopontedieoe nee edded
heneeth the eorfece of the refluxing eelution et opprexintely thirty
simte intemle. five millilitere Wee times. two 10 milliliter portion
md e finel five lilliliter portion. The eolution eee etirred et reflux
for e totel of eighteen houre. The brown reeotien fixture eonteining I
he": ten precipitate no flltu'ed et 70 dogroee end one gm of e ten
eelid eee ebteined which did not melt or (me teloe 840 degree‘e. The
pole yellow filtrate no eeoled end treeted with ligroin giving e light
ten eelid (.05 gun) iaioh beeeme pliehle et 80 degreee thengim to yellee.
At 160 dogreoe it bubbled. expended. end boom «ricer to £80 degreee were
it hardened end formed e bleak brittle eolid to 840 degreee. Anelyeie of
the first ieoleted ten preoipitete gave a .. 76.43. 76.42 K .. 6.85.

8.28. 6.33.

An ettwted motion in benzene et 40 degreee for three been re-
enlted in recovery of diphenewinene end e lull mount of e dert bro-n
eolid which did not melt below 840 degree).

Eleni: reeotione of oyelopentediene end eloohel It 40 degreee for
three hmre end oyolopentediene in tongue et reflux for eighteen houle
geve e dork red eubetenee in the one of the eloohol ehioh ohenged to
lawn et 250-340 dgreee mob like the period: eolid ebteined from
eloehol. The benzene eolution gave e red eolid which dxanged to light
ten et zoo-340 degreoe such like the viola Alder motion predaot in

bone one.

eel 7.

c) 13o eel-root

Uiphmocpinone (.6 gm) nee pleood in e 500 milliliter three.-
nooked fleck with 0.6 gren of ouproue chloride end 100 millilitere of
oycloomtediene. The mixture me etirred at me tmpemttxre for three
hour-e. A ample of the eolid enepeudod «mound et thie point did not
melt below 340 degreee but changed from deri: to light hm. Dipheno-u
whom no prmmbly mixed with it end deoompoeed et 170 degreee to e
grey-flute eelid. The eolution tee heeted to reflux tworeture which
elourly increaeed. After nineteen hcnre there one ieoleted .32 gm of
e dad: ten eubotenoe in fine needlee ehioh did not eolt or decouepoee
below 340 degreoe.

d) In ohloreforn

Six-tenth of e gren of diphmoquinone end 88 lillilitore of freeth
dried end dietilled chloroform were oherged in e 300 milliliter tee-t
necked fleek. Another 100 nillilitore of dalomforu wee edded end 20
nillilitere of cyclopentediene. The eelution one etirrei for one hour
in the cold end then heeted to 60 degreee. The mixture ohengod color
efter five been of reflux from very clerk to e green-yellow. After
eerenteen houre of reflux m. homogeneouo eolution eee cooled end e grey-
green precipitate (.08 gm) filtered ehioh did not eelt. oher or de-
compoee below 340 degreee. Upon further cooling of the filtrete, there
one ieeleted .03 gm of e pale yellow eolid. the neJority of which
changed to treneperent eryetele from 180-330 degreee end theee emtele
melted end deconpoeed tron 265-265 dogreee. Concentration of the filtrete
end further cooling geve edded yielde of the yellow-orenge eubetonoe.

.18-

 

m

 

 

A blenk reeotioo or diweooquinone in ohlorofon no mo in the
em moor with twenty-oi: hour: of refluxing tine end gave 0.46 green
of e dark brow eolid on first cooling. lhie mteriel changed to ten
et 240 degree: end did not oher. melt or decompoee below 340 degreoe.
Concentretion end cooling of the filtrate we 0.14 gem of en orengo-
ten eolid. the crenge pert seemingly melted et 130-160 degree- end the
ten portion cheoged to twenties-eat cryatele daioh melted from £20 to
860 dogre. to e greet liquid which mined oleer to 840 dogma. The
cxyetele were loot distinct et‘ eporexintely 230 degree“ ‘Phie nteriel
see not further ineeetigeted.

Attmtsd mole Alder Reaction of! 58:,5'otetremethflo
4,4'edighonoqg5inono via: Cyc opontedimo

 

Ono grem of recrystallised 3,5,8'J‘dtetremethyl-dgd'odlphuo-
mime in 150 nillilitere of chloroform m chergod in e 300 milliliter
two-meted fleck en! lo milliliterl of cyclopentedime m eddcd to the
stirred deep red eclution. Bo tomereture chenge m cheat-red end the
mixture nee elloeed to stir et teen tmeutoro overnight. After eight
honre the eolution we etill e deep red. The tonpnmro m roiled to
40 degrees for one hour end is millilitore of cyclepentediene edded
during this time. The eolution we brought to reflux end 10 sillilitere
of cyclopmtedime wee edded. After ten hour. of reflux axe eolotion
wee pieced under vecmm end the chlorofom mpcnted. leaving e yellow
liquid containing; e red precipitate. Thie solution wee filtered end
the yello-r filtrete cooled. The ecluticn cryotellieed to loft plieble
pletelete Ihich melted elightly ebovre row: temperature. The red eolid.
ccoteseimted with the yellow liquid, weighed 1.69 gun. to m rubbed

~19-

with 10 millilitere of other end filtered 517113 0.97 groan (9'7 per cent)
of 8.5.359 totmmthyl-d,d'-digfionoqzinone, ’11. P. 202-213 degrees.
the starting oompmmd.

Attempted Oxidatioq of 3,5,3jjfiidtctrenitgoo
* {til-dih'idgyxydiphgfi

 

e) Fuming nitric eoid

3.6,3'.5‘etetrenitm-4.4'-dihydrcxydi12:02:11 (3.57 grass, .01 E’olc)
no dissolved in 1:35 nillilitcre of ecetio acid in e 500 milliliter three-
necked flask equipped with e etirror, reflux condenser end e dropping
funnel. The eolution one treated at 90 degrees with 30 Idllilitore of
nitric acid (I) 1.50) (0.71 liole) tripled dropwioe. lie also of oxidation
no evident.

h) Load dimide

One gram of 3.5.3'.6'4tetrenitro-4.4’—dihydrc:qrdiphml m pertielly
dieeolved end the minder mcpmded in 250 millilitere of other in e
one liter glen stoppored bottle. Five gm of ectiveted lad dioxide
((33) one added end the mixture elmkon for one hour on e mohino. The
residue wee filtered end the solid wee refluxed for fiftem dmrbee in
125 milliliters of bonem old: one 3mm of ectireted lead dioxide edded.
The benzene eee recovered eleer. The lead dioxide recidne wee attracted
with 75 Idliilitere of acetone giving e yellow elightly cloudy eolution.
fro eign of oxidation no evident.

The oxidation procedure outlined by Kuhn (£53) no oerried out. To
e boiling amnion of eotiveted leed dioxide in 100 nillilitere of
bmme no added two green of 8.5.3' .5'atetnnitm-i.“edihydmydiphmlo

~20-

’Iho minim m shaken vigor-moi)! for two minutes. filtered and approxi-
mtely 50 Mllilitofl of hunter» mpomtoi under vemum. Thom was
recovered 0.8 gram of bright yellow 3.5.3’,5'-tatmnitro~4.4*-dihydm>:y-

diphaxyl. 2-50 other prochot we isolated.

a) Bmoyl peroxide
Oxidation: wore attempted using bouncy! peroxide in acid and basic
solutions. Seaingly no oxidation taken place.

(1) Chronic acid

An oxidation mo ottom‘g'stod using sodium diehmmto in o sulfuric
acid-notor- oolutiuo. The mixture olmngezi from yellow to deop red after
fiz‘tm minutee. Cooling, extracting with other and evaporation of the '
oth er gave e dark gum oolizi that could not be purified. Further ox-
tnobiom with bonemo. arbor! tetrachloride. nitrobenzene end ligroin
pmod fruition.

An oxidation attmpt Ming chronic oxido in ooetio tell! on 8.5.3' .8“-
totnnitro—ifi’ndihydmxydiohmfl gave only recovery of tho etu'tim
com.

o) Pom-3mm pemngonnto

Tm grom- ot 3.6,8',5‘utotmnitro-d.4'-dihydroxydighmyl m placed
1%: a 850 milliliter mafia-bottmd flask with six gm of poteooima
pemngomte and 100 milliliters of at". Ten per cont sodium hydroxide
(two milliliters) was added. I. M1111 ooodeooor attached and the mixture

refluxed for one hour. The magma” dioxide no filtered and the solu-
tion cooled. Thor-e ”pointed e rod precipitate which one filtered and

 

3

E

 

ne’hed with When Thie oompmmd. e etrikiog red color. me reoryotel-
lieed from enter and did not melt. char or decompose below 840 dogs-eon
but burned rapidly in the three of e humor. The compound in eoid
Isolation rogoomted the dihydroxy compound and eftor emlyeie it one
decided that it woe probably the dieodium edit or 8,8,3‘,6'dtotrenitro-

4,4'odihydmwdiohowl.
Amlylie"
Carbon .. 34.16 Mb 4.64 Alkaline
33.96 Aeh 1.98 Alkaline
Eydrogen 1.57. 1.36
Witt-05m 13.13. 12e33

Another oxidetion ettmpt with poteeeium pemngeoete in poteeeium
hydmide eolution me carried out et room taupemture. Ho heat one

generated end there no no epooreot reaction.

t) Lead totmoetete

One gm of 3.5.3',o'dtotnnitm-efilodihydroxydiphenyl m dieeolved
in ion milliliter: of acetic eoid et 80 degree“ Too gm of load totte-
eeotote nu added with stirring. The eolution booene red. than cloudy.
After ten uimtee e bro-m precipitate one filtered. The rather liquor,
on cremation. geve e 0.58 gm yield of e met-colored solid which did
not nelt. char or dwompoee below 340 degreee but mined with exploeive
repidiw in the {lane of e homer. Other oxidation etteupte of the one
order. varying the tampereture end time of the motion. imorporetim
eeetie eohydrido in eons ooeee, gave yielde of on orange-met eolid ehioh

did not melt ohm- or decomee helm 840 degrees but borne! exploeively
in the flute of e humor.

«42-

011. gm ef 5,6.3'.5‘otetrenitro-d.d'-dihydroxydipliemyl in so Hilli-
liter of dried benzene me placed in e 300 milliliter tee-neoked their
end 1.! game of leed tetreeoetete edded ed; 80 degrees. The Isolation
timed bleak npidly end nee refluxed for e ehorb time. After cooling e
den-k eelid nee ieeleted end efter netting with other there ruined en
onnge eeapennd which are not: weighed. It did not melt. oher or decompoee
below 840 degreee but burned exploeively in the flea of e burner. Another
oxidation “taupe in beneene e1: roan tenneretnre with repid stirring gore
e yield at e derk eolid nhieh believed ee previenel: deeoribed. Further
menu; or the nether 11w genre I 5.14 colored eelid which den-toned
between 800 end 340 degreee but did not melt or repidly decompose below
840 degreee. The gold colored eelid nee serenely entire in the flame of
e burner.

One gm of 5.6.3“.5'-tetrenitm—i.4'-dihydrexy~diphenyl en die-
eolved in 80 nillilitere of nitrobeneene in e 800 milliliter tee-necked
fleet. Leed tetreeeetete (1.8 grease) nee edded. the ”lotion beeeme
dark red end View. The eelnoion nee heeted for e eheri: tine end e
red. jelly-like owned filtered which burned vigorously. The jelly-
like enbetenee nee nebed with ether end eflser repeated rubbing with
ether, there ruined e dexk red eelid which did not eelt, m:- er deem-
poee below 840 degreee but exploded in the flene at e burner. It ne
imlnble in chloroform and eleohel. PM the eeeled Ruth. liquor,
there ene ieeleted e gold-eolered eelid which burned upleeively mob
like the geld-colored eolid from the benzene aidetidn. It dnonpoeed,
chem-ed end "bounced boio. 340 degree! primrily et :00 degreee.

43-

All of the uploeive emme obtained by land tetraecetete
oxidation ettenpte loot there expluive ohereoter when heated elderly to
340 degreee on e neltim block.

43399331911 figeotre

Chlornfom nee purified ee described by Fieeer (l2) end ethyl alcohol
purified by dietilletion from eeloime oxide. Abeorption epeotre in the
ultreviolet end vieihle reqione were detox-mm no follow: Diphenoqninone
in ethyl eleehol. Thie amount! m emeitive to light end underwent de-
emeitien when in chloroform eehxtiene. Decenpoeition me elee evident
in eloohol eelutiene but the time element nee tevoreble if the epeotrnn
we determined repidly. 8.8.3'.B'e0etrenethyl-i.e'-diphenomimne end
8.6.3' ,B'dtebre-t-bntyl-dfi'v-diphenoqninene were determined in elcohel
end ohlomfern. 3.5,3',Bidetreohlorod."-diphenogxinone eee determined
in chloroform. Thie command ended-um deemition in eleehol lulu-
tiene. 8.6.8'J'awnnitm-AJ'odmdrmdiphmyl nee determined. in
ebeolute methyl eleehol. et verim mmntiem of hydrogen chloride
end eodinn nethylete in WI eleohel. From the epeetrel dete of ihie
mud en ionization eonetent nee almleted.

All ebeerption epeetre were taken on Beekmn Mel DU Querte Spectro-
photometer-e undated for work in the vieible end dune-violet regiene
reepeetively. Querte ebeerptien eelle (one centimeter) were need through.
eut the inveetigetione

.24-

m

U}

 

 

can» you one. new one» no» coma“ on. .eoaneeoeegdees.e..soeo~go.u.eaa.m..n.n.n
own. new new. no“ new. ”no cocoa ea. onoceeeog.snue-...enae»=nzoseaoop1.a..».n.n
I... 2.... I... at. I... I... code. no. eaaegaeeu...1~§§£§e!n.3.6.»
53802.“. 1. e53. Eefinowpm 11
one. "on amen con came m.ema ocean an. once“neosandeos...e.Hduensea.ncan:.u..n.m.»
asaa us. sac cu- .i: .3: combo ea. eaoaeeoaeogneo:.e.e.~egpeeaspoov.n..u.o.n
1...... .i. one» «3 83 «.8» 8on 8» aaegonefia
u 134 u “#34 u «an: m “an“?

 

E

11]

note“. Egan in die. noufiwmmfi

H 35h

 

 

 

 

 

 

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fine «3 one. a» donned eh" u 3 a
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fig granule. ”on .3 £an do .88
7.x... 8123

:88. mono...» ,8 $3958 demoed. BEE:
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HH mamdh

 

‘ .—

TABIJI I II

VIfiIB'LZF: A3339 mJ’EEAVIOL';71‘ 1.330%??? ICE RPECWV‘J OF DI PEEICQTYITTCHE
Ifi'ETHYL AnconcL .
(1.97 x 10-4 a. 1.97 x 1.0-5 n)

”*7 _ , - A A- A.—

W fi‘v‘v w.“

 

X279 5 “’5 ‘—
590 107 2.029
580 117 $.088
570 123 1.080
560 137 3.127
050 147 3.167
040 183 3.363
530 203 3.300
830 333 3.348
510 37‘ 3.438
500 325 2.513
490 ‘21 1.634
480 498 0.693
‘70 599 0 .177
‘60 736 0.867
‘50 1030 3.013
440 1830 3.360
‘30 #310 3.620
‘30 9540 8.980
‘10 25100 0.400
‘00 47800 4.679
897 55900 4.007
396 58000 0.763
393 62600 4.797
39‘ 53700 0.754
303 81300 4.783
39' 57400 0.759
390 57100 4.756
388 55000 0.707
880 50800 0.706
370 55000 4.653
370 39300 0.093
865 . 32600 4.513
360 23300 0.413
855 30700 4.316
350 16800 0.310
345 12500 0.090
340 9240 3.966
335 6850 3.836
830 0930 3.893
820 8730 3.570

.37-

Continued next page

 

m

04

 

TABLE 111 o Contiwuod

 

1‘69“) 5 1°“ ‘—
320 3700 3.431
313 2040 3.310
310 1510 3.179
305 1160 3.085
300 , 930 2.991
395 91‘ 3.961
394 903 3.958
393 019 3.963
390 949 3.977
385 1060 3.025
390 1180 3.073
378 1310 3.117
.70 1490 3.173
365 8150 3.333
363 3820 3.050
363 3990 3.478
361 3990 3.078
260 2840 3.453
359 3680 3.420
358 3580 3.013
337 2670 3.410
356 3640 3.433
355 2800 3.447
334 3010 3.479
353 3130 3.493
353 3130 3.496
351 3030 3.481
350 3880 3.459
349 2780 3.044
348 2700 3.431
347 3720 3.‘35
345 3770 3.443
345 2840 3.453
8“ 3930 3.087
343 2960 3.471
303 2990 3.076
341 9990 3.076
300 3990 3.478
339 3010 3.479
338 3000 3.486
336 3200 3.505
334 3370 3.538

428-

Contimod nut pug.

 

‘I'ABLE III - Concluded

 

 

 

m * A “f ‘1 * “ in =
X Govt-v) 5 34°: 2
’38 3090 3.543
'30 3630 3.550
223 3800 3.580
:23 3950 3.597

‘ Reading. from 590 to 430 M

m 323 to 228 my.

inclusiv. var. falcon nuns tho 1.97 x 10" M.
solution, the minder using th. 1.97 x 10"5 H

«nation.

~29-

EJSI

 

 

 

 

TABLE IV

 

VISIBH-i 13:0 mmnoLm 1030927101: sprr 01'” 3.5.31 .51.
'rzmmmmpauv-oxmrmmrwmw m mm. 11.00001.

 

 

 

(1.04 3 10°43! 1.34 x 10-514)‘
097*) E 1‘5 5
685 11 1.041
580 21 1.342
515 1s 1.204
570 1'! 1.431
665 11 1.431
860 as 1.580
555 as 1.580
550 .1 1.013
845 49 1.690
840 as 1.011
535 02 1.064
530 11. 1.051
826 125 1.001
820 152 1.181
516 190 3.379
no 220 1.350
005 as: 1.463
500 348 1.542
495 .40 1.644
490 565 1.76:
485 145 1.871
.30 007 1.005
075 1330 8.124
.70 1880 3.100
463 1610 1.417
‘60 8800 .0580
.50 5600 8.761
.50 9300 1.934
«a 12600 4.100
«.0 19000 1.179
435 17000 1.440
430 39100 0.591
426 63100 4.717
.3: 58800 4.760
.20 02700 4.707
413 68300 1.310
417 06400 4.52:
.10 00900 4.828
415 01100 4.821

‘A‘

Continued but page

 

TABLE I? o (3011131111106

 

 

v

v—-'-*—

 

A @709 £ 6
41‘ 67600 ‘0530
413 67100 4.827
413 66900 4.825
‘10 85500 ‘0815
‘05 59600 ‘0775
‘00 53200 4.726
390 €1700 44620
380 28200 ‘4450
370 18290 40360
360 11000 60941
$50 6800 3.798
345 ‘640 30667
3‘0 3440 34537
335 _ 2480 3.395
330 1820 3.250
325 1320 3.120
320 935 20971
315 663 20323
310 473 2.673
305 343 2.543
300 273 3.435
297 I 230 20393
295 23‘ 8.369
393 231 2.56‘
102 220 2.350
291 238 2.358
290 334 2.369
288 :55 20389
386 331 2.417
23‘ 388 3.459
38' 337 3.528
280 408 3.611
278 533 ’4???
873 743 3.872
37‘ 1100 84041
27! 1570 3.193
370 2030 3.508
333 2340 84359
286 3450 3.391
26‘ 2650 3.423
253 2950 3.470
380 3280 3.513
258 3440 3.537

~51-

Contimod next pugs

TABLE IV «- Concluded

 

 

 

W __ 1 — wuww:
«069789 a Les €-
258 8840 3.842
284 8810 3.858
282 8820 8.582
280 4080 3.804
246 4880 8.631
840 4880 8.881
88 4080 8.808
280 4700 8.87:
228 8850 8.688
228 8040 8.884
224 8240 8.719
22: 8920 8.778
220 8410 8.807

" Hauling. run :20 to 845m,» and 480 to 888 .5... 1881041"
an an: on the 1.84 x 10'4

Men on tho 1.04 x 1

N Iolut 1011.

31!. 00111131 011.

All other: taro

Mam: v

VISIBLE m mrmnomr fiiBf‘DRI’I’ICII SI’LLCTRTITJ 0: 8.8.8'.5'
'1‘SEPAdanL-‘J"-DIP€£F3?OQT'I?TCP?:£ 18 mm. ALCOHOL
(1.80 x 104.8. 1.88 a 10.538).

 

 

A W) e ’08 £
890 88 1.680
580 ‘3 1.63‘
670 59 1.7T3
580 70 1.8‘6
580 91 1.969
840 118 3.058
850 189 3.111
530 150 I.l78
510 188 1.37‘
500 320 3.3‘!
‘95 238 8.378
‘90 880 30“?
‘88 333 3.531
‘80 393 3.593
‘75 527 8.722
‘70 769 3.888
‘65 12‘0 3.098
‘60 2050 8.81!
‘55 3730 5.57.
‘50 6‘50 3.810
“5 11500 ‘.061
“0 19700 ‘.295
‘85 32‘00 ‘.511
‘50 ‘8‘00 ‘.685
‘38 55500 ‘.7“
‘36 62000 ‘.792
‘2‘ 87000 ‘.826
‘33 88300 ‘.83‘
‘33 69600 ‘0348
‘31 70700 ‘o8‘9
‘30 70800 ‘.850
‘19 70600 ‘.8‘9
‘18 69900 ‘08‘5
‘17 69100 ‘.8‘0
‘15 67800 ‘08”
‘1‘ 64500 ‘oBIO
‘1‘ 61‘00 ‘.788
‘10 58700 ‘.769
‘00 51300 4.710

‘_. 4

Continua nut page

.58-

TABLE‘V’arConttunad

“:4“; M ‘

 

a: A _

 

A 07%) 5 Log 8
390 36100 ‘.581
360 3‘600 ‘.391
370 16500 ‘.316
360 9760 3.990
350 6810 3.764
3‘3 ‘390 3.643
3‘0 3200 3.517
333 0460 3.389
330 1830 3.260
336 1340 3.127
320 96 9 3 .990
316 753 3.677
310 6a 2 . 780
306 646 3.739
30‘ 336 3.731
303 343 2.736
303 346 3.730
301 646 3.739
300 350 3.7‘7
696 661 0.76‘
396 613 3.766
10‘ 666 3.617
393 70‘ 0.676
390 763 0.663
386 690 3.950
382 1030 3.033
'76 1‘70 3.167
376 1970 3.396
370 3360 3.373
67‘ 0860 3.656
373 3510 3.545
372 ‘120 3.616
371 ‘660 3.666
370.3 4830 3.66‘
370.0 ‘910 3.691
269.3 ‘920 3.692
069.0 ‘8‘0 3.663
366.3 ‘710 3.676
366.0 ‘610 3.664
267.0 ‘370 3.641
266.3 ‘360 3.629
366.0 ‘310 3.62‘
365.0 ‘330 3.636

Continua nut pag.

 

 

 

’—

Ir

 

TABLE V .. Concluded

 

 

 

 

=========r x—‘:~—A~*-- T“ ‘0 —— -‘ A“ :35‘5"'1==
IXQp§;.) £ L03 4E
363.0 4250 3.628
264.3 4330 3.637
284.0 4440 3.647
862.0 5130 3.710
261 5430 3.735
860 3480 3.739
859 5380 3.723
388 5060 3.704
836 4600 3.663
255 4510 3.854
284 4820 3.653
253 4600 3.663
252 4700 3.672
261 4740 3.676
250 4720 3.874
249 4650 3.668
248 4590 3.663
247 4530 3.656
246 4500 3.653
143 4500 3.633
244 4510 3.654
242 4620 3.668
240 4730 3.673
238 4830 3.684
236 4910 3.891
234 4960 3.693
338 4990 '3.898
230 3060 3.704
328 3120 3.709
826 3170 3.714
824 6280 3.723
822 6490 3.740
220 3960 3.773

 

" wine. for 220 to 350 A,» and 45:: to 690 11:01:25“.
were taken on the 1.86 x 10" M. solution. All othm
mo taken on the 1.86 x 10-533.

-85:

TABLE} VI

'5131553 AFD'WLTRAVIOLST Afieonpwrnu 99355555'05 5.5.3'.5'-
TSTRAWEEHYL.4.4t.01?nuwaenrvcva In 5550505055
(1.6? x 10-45 . 1.57 x 10'5",”

 

A 90/“) 2 L05 6
500 50 1.475
550 15 1.255
550 15 1.255
570 15 1.255
500 36 1.555
550 66 1.819
340 84 1.933
530 126 5.100
520 155 2.525
510 225 1.555
500 535 2.525
490 491 1.591
485 617 1.790
450 502 1.904
473 1110 3.045
470 1550 3.190
465 1350 5.571
450 3700 3.559
455 7250 3.860
450 11300 4.063
445 15000 4.255
440 27400 4.455
435 41500 4. 615
430 56600 4.153
425 55100 4.540
422 72700 4.565
421 13200 4.5 55
420 73200 4.865
415 72600 4.5 51
415 71100 4.555
415 59900 4.545
414 86800 4.525
415 55700 4.504
410 61000 4.785
400 50600 4.704
300 37200 4.571
380 24400 4.387
370 16200 4.210
360 9760 3.933

 

-36-

Continued 54x5 pugs

Hi

 

 

TABLE VI «- Concluded
W

 

A G7“) a “3 6
350 BOZO 3.701
345 3780 3.573
340 2750 3.439
335 2090 3.320
330 1500 3.178
320 767 3.885
310 871 2.569
800 168 .0835
'95 125 3.100
I90 102 3.009
388 132 3.121
280 363 1.568
373 1360 3.130
.70 3230 3.343
'65 2560 3.408
360 3100 3.491
855 3220 3.508
.50 3870 3.585
'45 3830 3.583

m «Iran on the 1.67 :

V1111” for 245 to 350 my.

and for 460 to 6004/...
‘0 3011131011.
var. man an the 1.67 x 1041!. 00100100.

.37-

_.__..___ M WM

inch-1‘"
A11 othu- ulna

TABLE VII

710101;; 11:0 01.701710an 10000377100 09.007001: 0}? 3.5.1555“-
7;070147-0mnp4.4'.01 01021700010000 :0 00003000001

(1.05 x 1047:. . 1.00 x 1

0‘50. )"

 

A 67—) 0 Log 8
890 07 1.000
000 04 1.000
070 00 1.771
000 70 1.070
000 100 2.000
440 124 1.000
630 100 1.190
580 100 1.200
510 881 2.044
000 209 1.410
490 200 1.400
490 030 2.020
400 094 2.090
480 ‘98 1.002
473 724 1.000
470 1100 0.041
400 1900 0.400
400 0400 0.544
400 0400 0.012
400 11900 4.070
440 10900 4.020
440 00000 4.044
490 01000 4.711
430 00000 4.004
429 00100 4.014
420 00000 4.010
427 cm 4.020
420 00900 4.010
420 00000 4.010
414 04400 4.009
422 02100 4.790
‘20 00900 4.709
410 49400 4.094
‘00 42200 4.020
090 17900 4.440
000 19100 4.101
870 11000 4.071
300 7400 1.071
300 0740 3.709

-38-

0000111106 next p050

 

ll

TABLE VI!— Continuod

_ WA

A __ w

A95») £ 1.05 £

 

 

350 4380 3.642
305 3300 3.519
'00 2500 3.398
355 1880 3.270
330 1390 3.143
325 1020 3.009
320 ’45 3.87:
315 551 3.741
310 ‘10 3.613
305 335 3.525
300 303 3.489
299 308 3.489
293 508 3.489
296 313 8.490
294 340 8.533
293 562 8.559
290 389 3.590
28 ‘31 8.620
280 ‘51 8.683
'3‘ 033 0.730
:82 692 1.840
380 900 3.973
278 1370 3.137
276 3170 3.837
’74 3390 0.517
'72 0140 3.817
'71 4340 3.627
370 4160 8.819
:69 3970 3.599
'33 3810 8.581
337 8730 8.578
880 3900 3.591
234 0390 3.648
263 0560 3.663
262 0800 3.681
:01 0780 3.019
360 4650 3.868
258 0230 3.829
357 4150 3.619
386 0130 3.818
255 4170 3.820
35‘ 4330 3.626
'53 4330 8.6.0

 

-69-

Continued nut pug.

TABLE VII - Concluded

W

 

 

252 4510 3.635
351 ‘310 3.835
350 4300 3.63‘
248 ‘260 3.829
347 4250 3.628
243 4260 3.629
245 4290 2.553

 

" van.- for 245 to see” incluotv. .nd 46:) to 890 Jay.
incluslv. war. mm on the 1.85 x 10"4 H. .olution.
All othor. war. taken on the 1.85 x 10“ at «1131510114.

 

 

.400

TABLE-3'. VIII

vzcxzzs 350‘snfnxvzcnam aascnrwzcx*syscrxsu'oy 3,5.3'.5v.
1-:-:rzs_a.cn1.o.4.4'«.nmmmqnmmrs n: mummy-om
(1.03 x 10-4 a; 1.83 x 10'50)‘

 

X («t/u) E. Log 6

 

000 11 1.041
670 22 1.342
680 a? 1.431
850 44' 1.644
640 98 1.991
530 131 8.111
620 806 8.486
510 508 8.754
600 1080 3.033
496 1820 8.188
400 2100 3.340
485 0110 3.493
400 4320 3.656
475 6340 3.808
470 8180 3.963
465 10000 4.134
400 10800 4.197
455 00100 4.464
450 41500 4.018
445 55300 4.748
440 66800 4.828
438 10200 4.840
436 71400 4.854
455 71000 4.050
434 71400 ‘ 4.884
432 69700 4.843
430 66900 4.020
488 05200 4.801
427 61000 4.785
426 50300 4.778
424 55700 4.746
48! 62700 4.722
420 49000 4.008
415 48000 4.080
410 41500 4.618
408 38300 4.548
400 87900 4.446
890 17900 4.288
380 11300 4.058

Continua! and: page

 

TABLE VIII atCOntinnoé

m

 

A Q9»)

 

£. Log El
370 8610 3.820
360 3740 5.573
358 2730 3.436
850 2000 3.301
548 1460 3.164
340 1070 3.029
355 776 2.890
330 558 3.742
325 393 3.594
320 290 3.463
315 213 2.328
510 155 3.199
308 188 3.168
300 203 3.305
298 257 2.410
296 371 3.609
294 563 8.751
292 918 2.983
290 1500 3.176
228 2310 3.364
286 8090 3.490
284 3‘60 3.538
283 3470 3.540
282 3410 3.533
281 3340 8.524
280 3820 3.521
279 3870 3.538
278 3510 3.548
876 4030 3.605
274 4430 3.646
273 4520 3.858
3?! 4610 3.653
871 4440 8.647
270 4380 3.642
269 4370 3.641
368 4450 3.648
266 4830 3.684
264 5220 8.718
262 6360 3.731
861 5590 3.738
260 5550 3.728
259 5340 3.728
258 5350 3.728

.42.

Continued next pug.

TABLS'VIII - Concluded

 

 

values var. taken on the 1.83 x 10.5 H. ”1211:1011.

~43-

‘KCryna 2. Log El
257 5380 5.731
253 5460 3.737
255 5570 5.745
25‘ 5630 3.751
253 5740 3.759
253 5790 3.703
251 5050 3.767
250 5850 3.767
249 5900 3.771
248 8850 3.767
347 5740 3.759
346 5350 3.767
245 5740 3.759

’ Values for 245 to 8601-70» and 480 to 1580»: inclusive
taro turn on the 1.83 x 10.4 SI ”1.21:1... 111 other

m;

TABLtE IX

vxsmL-a 11:0 mmmmm'r 19909911109 8.0:me 0:9 8.6.3'.6'-
r:.:rzwrrrno-1.4'-mmm}:mxmmm 12.: 1001111. 1100001.
(1.76 x 10" 11.. 1.75 x 10"5 11.)"

A..—

 

 

Abpx 4 AWL E
940 0 140 5130
120 07 135 1730
510 119 130 «00
000 233 329 4320
490 190 120 4200
.91 500 325 4100
100 591 114 1250
475 710 123 4200
170 029 112 1170
401 900 111 0110
460 1090 120 4350
451 1200 115 4770
450 1310 110 5530
«a 1400 105 11000
140 1490 100 15100
430 1570 199 16400
430 1950 190 17000
115 1140 194 19100
420 1940 190 19100
411 1900 190 19000
.10 1090 109 19700
000 1290 195 19700
400 1520 10. I9600
195 1950 190 88600
190 3240 175 17400
880 4140 170 10300
170 4910 165 15000
170 1220 160 14900
360 9030 255 15000
160 5860 100 13000
159 9990 245 12900
100 0910 140 12200
355 5920 155 11000
154 0900 250 12400
862 1900 926 11900
150 0790 223 13100
140 5030

#M

‘ V1100: for 540 to 810m,» Inclusive. were tutu on the

1.76 x 10'" 11 101001011. 111 othm war. taken on the
1.70 :1 10451:. «1001.0.

~44-

TAB L": X

015151.53 5‘10 01115710021 1150551105 95151125 0? 5.5.51.5“
T.::TRAT?I’{‘50-4,4'~311i'1'2):-1‘;:;'1”:3Iszigié'IL '15 A 1.47 x 10'65
scvrrm 0? 5001011 Fit-311571513 IT: ’11::5‘11‘. ALCOHOL

 

 

 

 

 

(1.55 x 10-4 5 1.55 x 10--5 up
A he) a Aéggl E
550 155 551 1100
550 500 550 1100
550 1510 559 1700
510 2750 555 1710
510 5550 551 1700
500 4950 555 1710
590 5510 555 1750
550 7550 550 1510
570 9290 555 1950
550 10500 550 5100
555 10700 555 5550
555 11000 550 5510
555 11000 515 5550
555 11000 510 9550
551 11000 510 15500
551 11000 500 17500
550 11000 191 51500
550 10500 190 51500
550 9250 159 51500
510 7590 155 51500
510 5500 151 51500
500 5510 155 51500
550 5550 155 51500
555 5510 155 51100
510 5050 150 50100
515 2550 170 17500
570 1750 150 15500
555 1710 150 15100
555 1700 150 15900
555 1590 150 11500
551 1590 125 11700

“ V5105: for 630 to 490 and 400 to 325 Ann/u. 10101115105
1501-5 taken on tho 1.66 x 10‘"?! solution. A11 other ulna
were taken on the 1.66 x 10-551 "1111:1005

1135111 concentration: 501011355 than this. 111-0010115050 tho
rod indium 55.11: mntloned 111 the 55555105 to 0151:1110 tabu-
nitrodlphmoi with alkaline permngnmto.

TABLE XI

1713mm mu mmame-rr mmnwm swam a? 8.5,3'.5'-
TESTRAHITRO-‘lfl'unld‘i'.).-.(.u.‘1‘1$22-$n.u;€1'a'. 11; A 1.3 x 13%;:
5mm 10w OF 3093:! 25-11: imu'm m mum. @610?an
(3.09 x 1042, 2.0-9 2 10"531)*

“A —A

 

_ A 64;) A £ A Qty-1 E
‘90 6930 361 3740
480 7300 360 3730
470 9190 359 3730
460 10500 358 3720
450 _ 11200 :57 3720
“9 115-30 856 3720
“6 11300 355 3720
.07 11300 350 3760
“6 11300 340 4060
445 11300 330 5120
«4 11200 380 11200
443 11100 310 20200
‘43 11100 800 29100
“I 11100 :90 “em
“0 11100 289 33300
‘30 9780 388 33800
420 8000 387 33800
410 6610 888 33700
400 5220 285 33500
390 («820 280 32500
380 4150 370 30100
370 3830 260 39200
865 8770 :50 27700
86‘ 3750 240 36300
863 8750 330 38200
362 3740 .22 29300

. Van” for 400 to 330 Alt/K inclusive we" {man on the
3.09 x 10" H notatiom All othm were than on the
1.09 a: 10-5 Haolution.

TABL31XII

VISIWLE A“?! TWATBAi'IOL.-}T A‘YI‘GVEF’Z'IWQ SPLICEEZA {3? 3,5,3. '5‘.

“M r-- a :9 "rd-'1“. .6. . v
73‘ «uku; '..'_'.-'-4"1'-.

w-“r- w-
‘ ‘ ) "1.)le ‘¢J J. . 1

in.

up. !_ffl ~53 fi- r wars”

.1”; u I? A 1.00 X 10 “at.

fi-flvf

301mm: or mum! ”WA": 1"! ‘IL‘TEIYL Ammo;
(3.01 x 19"4‘3, 2.91 x 19-511}.

 

 

 

Ang-v) _ g M M u__ __.. e

480 8200 345 4190
470 2980 3&0 4290
‘60 3820 535 #450
450 4450 332 4740
440 {970 331 4550
430 5340 330 4950
‘25 5280 335 5730
424 '290 520 10700
£22 0200 310 19800
‘20 5280 500 28400
410 5090 390 32000
400 4770 389 32700
390 4390 230 52300
380 4190 287 32700
375 4120 886 32700
370 ‘110 980 31300
365 $130 270 20800
360 4130 £50 25000
355 €140 330 33300
350 $140 223 23400

' Value. for $50 to 385 A,“

2001 I 104

‘47-

).4._‘ ___

inclusive were taken an the
:5 ulntion. All othm warn tutu on the
2.01 x 10-5 a: solution.

RA}!

 

 

TAWLB XIII

'VISIBLS ATD‘ULTfifiVIGLE? hnrcwanoa SPECTRA G? 3.6.3'.5'-
TarruAYITm-h4unmmm‘mxm{=~;?m. I}: A 7.8 x 10"5 M.
SOUTH-2C! C“? 8031*“! 'efmwma m WWW ALCOKOL
(1.91 x 104:: 1.91 x 10-52)‘

___.__‘ u. A A A

 

Mat) e A655; 6
460 1770 350 4640
470 8410 845 4590
460 8100 344 4690
450 8670 343 4570
440 4owo 842 46?0
430 4300 341 4570
438 4320 340 4550
426 4560 339 4650
424 4360 338 4540
432 4370 33? 4570
420 4670 336 4660
410 4300 336 4580
400 4190 330 1 4780
899 4140 825 8260
891 4180 820 8160
890 4130 310 18800
369 4130 300 86800
380 4190 290 81000
876 4420 889 31100
865 4640 286 81200
860 4610 287 51200
359 4630 286 81000
358 4640 260 89700
86? 4640 £10 26600
364 4660 250 23200
853 4640 830 81000
851 4640 323 80600

" Value: for 460 to 820m} incluatvo wort taken on tho
1.91 x 10'" I caution. All other values were «km on
th. 1.91 x 10-5 m «nation.

VISIBLE} ETD ULTRAVIOL’IT AESCRF’PIGEI EPE‘CTRA OF 3,5.3'.5‘-

01010 IN

Ta-‘mmxmmwmnwmoxmzmnm. In A 3.9 x 10-5 11
30130100 0? 0001011 110010100 13.1 10mm. 11.00001.

(1.90 x 10-4 11 . 1.90 x 10-5 0):-

 

) Qty») 8 A (~19) 6
400 1100 845 5000
470 1040 040 4030
400 1940 035 4040
450 1310 531 4050
445 1440 :30 4540
«0 2570 :29 4550
430 2070 320 4050
430 1770 021 4500
430 3000 025 4640
420 0000 320 0030
415 2990 010 10000
410 3070 300 27500
405 0150 290 32200
4m 3270 :09 32200
390 3430 200 32300
390 3000 :87 52300
300 4100 200 32200
310 4700 100 30900
860 5240 :70 37700
357 5200 100 25400
300 0310 100 133.00
355 0320 :40 22300
354 5300 130 11100
301 6260 22: 11700
050 5230

W

" V4100. for 480 to 820 my»

1.00 x 10-4

fl 301131310114

the 1.90 x 10"5 M solution.

~49-

111011101100 Ioro‘takm on tho

All other ulna van taken on

 

 

 

7.131;. -: .7

Vlfrnnd Ava 01001710L:0 1000007100 0?10721 0? 3,5,31,57-
TJ’RAVIT30-4.4'~010Y0002701000070 10 A 1.05 x 10-40.
SOUTH“! m“ mix-20052;}! CE-EYABR103 117 1.7103211. 1.7.002;ch

(1.87 I 10.4 $5 , 1.87 x 1.3.5 1;)!

A.- A _ u._ A.

0929““ #51: 3 J69» e ‘_

440 118 812 2770
420 465 010 2810
400 1040 800 8080
090 2770 000 3910
380 4140 295 4920
870 5490 290 7270
880 6410 283 0300
:50 6400 2'86 :95
856 6530 39.4 11400
855 8850 880 15400
554 61560 270 20000
853 8510 360 34900
30:: 6510 200 85700
351 6030 256 36100
350 6560 254 38100
340 0460 252 35000
530 4190 250 35200
520 5110 248 84200
316 2050 240 20300
314 2790‘ £30 20100
223 1?300

* ValLos for 000 to Bhfihgyb inclusive
were taken on the 1.37 x 10' 1. solution.
All'ot10rs ucre taken on the 1.97 % lO”5 P-
solution.

.51.

 

 

 

——-9-
A 6"") T? i 30 1‘8 1

”71‘ _ *1 , _ 0 ___1. ,. ‘.r' '3‘} "-0 ;, - _‘ -: ~. ‘n'? ‘4. g
-? T214 m.mol~;0 and 3101-013 1105010301011 “meow; -.n
0 01

 

 

 

 

0‘ ’ '- w... v‘\.\'. r -.' A 4 ." h. —u- \
O; H’ , ‘i ' '114_v‘;u7Y;OUIl1.301.“; \. ~. 111'»; tJ 1 9
. . r

I
,.
\. -‘ 1"." 'J ,'

..: 11 ,,‘| A. ' g 1 1.. .,.
1 ~ .f ‘1‘ - '1 .

'\
r

.Wa‘,‘

1-.
O
:5
1.
o r“

x 0

 

5.0

40

3.0

2.0

47010—5

 

u

A

 

 

I
-\'\
111
1’."

00‘ V

I ' [T '_‘ 1
OJ. ‘4‘ , (J , 'J ’

.N \ r'
-7 I "I 1 y 1’!

I I

-11C‘Jlo t ' i 1"." '3
1n0911"033 (

O \

‘4 l

7n1'1:

.; z- .0 ,.
'v'_a L. I M '

, .' .. . J
7-!
901 0.;
r* \
v." . o

I: ’P

“ 'fi "Q-U'! ’.
11.):101 [071

...' ‘ v
::\l'-] J.

1 A
-'I
.1.
0‘ .
, A at... '
o
, L. , k)

(a

-but‘1

'-

4-, 1—
0 "Jul

:Jueotra

C
1 zqvu~r
4" "‘ .

- .
a
t

1"" ’ ,‘

0“
k

1 A '«_-

a.

 

4,31,: CI’O-

 

 

I I 0’ I v I
...+
. In".
' 0
0
4.0 '-

0. .0

‘4 l 4

‘0 .0 l \

o .s l 0
‘. .' 1
0
0
4

z ,3
.0. k. a
0......I ..
O
1
E

2.0 '-

0.,0——-

 

.Aégr9'____’

 

.! 1 ”juice 3

The Ultraviolet and Visible Absorption

gjpectra in_ r L,L'-diflflu3hOPUifiJLe.
r3 '0 t e :1": i r; (-3 d i n t h i :5 1;. :31" i: t o TY .

flotprflncd hv JQEVA .5:

911d

 

 

I
I.

 

"O

00

 

70

iv

,'_V

 

A
U

i an“

7

_ v Y ’.
o . . A. Q
fl
A", ) i‘irrnre 4.
O ' g “ J" "I r: ' r'
Lbsorhfion nctrra ( 7KL-“flan ; Oi 0,“,0 ,1
o v L 4 .1 u 01 , a--1 I, ‘. v’\ ‘ -.-: 1r. :' ‘1' - 6 ~
111*:1‘c-" ',' '-1.;.“ .1 0st, «'1lU;.v:';_ _ 1. ..m o.“ i... .11 a. .
- . . , v ,
° ~ f -+-‘v~« Vu‘r’1'i*1-'r ail-491:». 1
In 20111-‘1‘ iol‘ O 1.xi1lklnltl‘LLJL 0.1. 'u A f.) \.'L I.-. v,

on f0110‘1'.’5_?1:, 1

J ' .

 

 

.
1 i‘CLu

--13 . _1

 

K‘IY TO TIL":.":.'E 4

Curve 1 .- Tetmnitmdiphenol
.OlutiOflo

Curr. 8 .- Tetmitmdiphanol
oolutlon.

Curve 3 .. 1'stflnitmdidmnol
lolution.

Curve 4 1... Tatmnitmligmenol
solution.

Cu". 6 an Tetmnitrodiphenol
solution.»

Curve 6 .- Tatnnitrodiphenol

Curve '7 1.... Tetmnitrodiphenol
00111131011.

1:: 1.47 x 10-2 11; aodium mahhylnto
in 1.5 x 10"4 H sodium mathylato
in 1.04 x 104 11 sodium mthylato
in 7.8 x 10""5 H sodium methylato
in 3.9 a: 19-5 3.! nodium mathylate

in neutral methanol.

in 1.85 x 10.3 as hydrogen chlarmo

0-4

j.

 

60

SOP

45.

401-

6H0"

 

 

 

 

39’0 a2 3; k 55 to llz I..4 #— '

llot of the eytinctinn confficiont 3f
3,5,3',5'-trtranitrm-L,L'-dihy4raxvdivhenyl
F." 35 vs the C“SC"Igll‘fitiun (“11' 151411.111

\ J

1‘”. I

l"
T 1'71”, Sflfite 5‘. ;‘,_'-,:'"T“. .L. 7357111JT1-ljp" :7 .

w- r.-

 

DTfiCVF‘Q ‘
011,101.? C? HERMES

 

 

 

DIQC 7-7313 I (‘3‘! 0}" Rev-133711? S

The preparation of 4.4’odiphoqu‘incne as described by fiilletéltter
and Kalb (1) involved the oxidation of 4.4'a-dihydroxydiphony1 with lead

dioxicie to them in equation (4:). The pmoodure involved choking on

HO-H-OH 1. Foot—+o:"=o + PbC o- 130 (e)

other eolution cf 4.4'-dihydrcarydiphenyl with e euepmion of lead
dioxide at: room temmture for twenty-four hours. The ratio of lead
dioxide to diphenol nee ton to once In our bowie. several attempts to
repeat this prepnntion resulted only in the {creation of e brown.
finely divided, lead dioxide-like precipitate which hue been national
by other vex-tore (so). time of the 4,4'-diphenoqoinone one obtained.
Menu worker: (29) also reports contain difficult!” in obtaining
it. A procedure has been devices, the detail. of which are in the ex-
perimental part. for the preparation of 4.4'c-diphonoquinone in good
yield. Au ectiveted 1am ammo m prom-ca according to the pro-
cedure of Kuhn end Hemmr (63). With this oxidising agent it In.
possible to shorten the oxidation the to betmn fifteen end forty-
five nimtce end reduce the ntio of lead dioxide to diphencl to five
to one for optima ouidetion conditions. The yield for oxidation in
this Hammer in fifty to fifty-five percent, which is comparable to that
reported by Willmtter and Kalb although. 0.: stated above. we could
not reproduce their "mite. Using the procedure herein deecribed.
ciphencquimne m obtained ccneietmhly.

‘5!!-

 

It In:
women:
mummy be

mammals of

Physrtiee.

though I pr:
Met in t
wan-1.3.1
"some. 1
“Hon lith
“‘1 pan

It was thought desirable to investigate the Dick-Alder reaction of
4.0-diphcnoquinone with cyciopcntediene. The compound that mold thee-
reticelly be formed in en equimolor reaction ie ohm in Figure (9.) end
componmde of thie genoml etmcture might possibly have carcinogenic

0
ll

0(0

'5

Figure (a)
properties. The reaction ie well known (69) using bmcquinone and 9.1-.
though e. prurient worker (24) hed lewdngly toilet! to obtein the deeired
product in this type of reaction «in; he'odiphenoquinone and 1.341-
eethy1-1.8-butediene it we thought that the condition were pccibly toe
vigoroue. A deteiled deeoriptien of the ettnpte be eerry out the re-
action nth diphenoquinene em! eyoiopeotediene ie ecuteined in the experi—
mtel pert and eoneieted of adding cyclepeotediene to e eelution er
euepeneien of diphenoquinone et verieue teepemturee end in uric-1e ecl-
vente. In one case no eolvent we need em! cyclopentedieoe tee preeent
in come at the eterh of the reaction. In the Monty of experimte
~there m belated only emtelline eubeteneee ehich owed to be high
molecule: fight decompoeition or polymeriaet‘icn producte of dimmquinone
end et no time no there iecleted my eubetanoe which would eeen to re-
eeuble the addition product. Under the conditions herein described. there-
fore. 4.4'diphmoquinone. preluany became of flu imbility, in no

.59-

 

 

 

 

we; .— I'E 'g _; ’-' fl #4.

 

 

. - ‘f
_ ’ '4 J ‘1'" ,

my movable: e typical quincne ouch ea 1,6-benzoquinone with reageot to
the Ciel; Alder reaction.

Because there he been very little experimmml emit done in studying
the eboorption epectre of the diphenoquimne eat-ice. en investigation we
earl-ted out to dotoraine the epoctre of four M11336“ of thie eeriee in
the ultmiclot end rieible region» “foo eclrenrte were nooeoeery for e
comrative grouping became of doomeition of one of the eoriee in each
eelrmt ee described in deteil in the expel-imam pert. i‘he absorption
neuron in the“ tee eeivmte eon reedily be atomized by reforence to
Fight-en 1 out! 3. Thin etudy of the oheerptioo epectre of four diphmo-
ouinooos hoe chem :1 mm in the mums: absorptim also to longer we

 

longtime as the Iciee prcoeode fro»: diphonequinone to tctremthyladiphono-
qninone to tetmdt-imtyldiphonoqoimm to tetmohlomdiphenoquimno. It
is observed from Tobie I of the «perineum pert end rm Fight-0e 1 end

 

i that thie ehitt in only e mm one end thfi the inteneity of eboorption
famine emoroxiutoly cement. It it grobeble that the min ebeorptien L

peak in the visible region ie due to rooomooe er the type shade in "
Wine (b) with diphmoqcinone. ‘

lM~e=©=©=e~6~~t

The eubetituozte apparently om rclativoly little effect on than princi-
pl resonance form. It in pcoeible. timer. thet inductive. hypemnjun
getive em! resonance effect: c! the groups my be of some imcxtenoe in
«planning the minor ehii‘te to longer wave length- ee duodbed.

'The absorption epeotrme or dip‘xmoquioone in ethyl eloohol (figure 1)

egreee favorably with that reported by E’eiyeehho and Shoherbek (29) with

 

some minor discrepancies. The two epectm my be compared readily by
reference to Figure 3. while the above mentioned nonzero reported an ab-
eorpticn bond with a maximum at MOM/4... , the present work ohm this
mimm to be at 395 my. , with on extinction of 62800 comer-oi to 44700
previously reverted. Ynlwehko end Shcherbek also report one absorption
bend in the vicinity of 255 pvt/u. with mime extinction of 367’) while
the preemrt ever! repel-to tun cheerytien min in thin vicinity. one at
261.2622 M/n- with extinction 3990 end one et 252 "y. with extinction
8130. The euperier receiving power of the present day inntmmente my
coconut for the discrepancies.

It was thought particularly desirable to obtain 3.6,8'.5'~tctrenitro-
4.4‘-diphcnoqxinone became it we felt that this eubetitnont might have
e mzor effect on the expectant of the diphenoqninone nation. This ooze-
peund had not been provieuely described. We prepared 3.5.3'.5'dtetrenitm-
4,4'dihydmydiphenyl by the method of Honcho and Scholten (65). This
procedure in daeoribed in deteil in the experimental port end consisted
in diuotiention end nitration of banning with subsequent hydrolyeie.
Attempts were mde to oxidiee thin whetenoe to the desired tetrenitrodi-
phenoquinone and these are deteribod in detail in the experimental pert.
Ana; the oxidising agent: used more nitric acid (1391.50), activated 1nd
dioxide. beneoyl peroxide, chronic acid. pomeiun pemngemte end lend _
tetracetnte. The alkaline pemngnmte oxidation ettewt resulted in
ieoletion or! the dieodimn colt (3) of the tetmnitmdiphmol which me e.
bright red eryetelline substance. The wet pro-ailing oxidation ettempte
were with lead tctneoetete from which were isolated e meter of oiniler

-61.

 

 

 

 

cnnge-red eryetalline eclide which did not melt: or decomcee rapidly
below 840 degreee but decomposed ezplceively in the flame at a burner.
None of theee. homer. leaned to be pure 3,5,8’.5'-tebranitm~4.4'a
diphenoquinone but my have contained tbie eubatanee. It in felt that
further cert ehculd be carried cut in an attempt to isolate and character-b
he the tetnnitredipbcquinom.

airing the experience with 8.6,3‘e5'dbetranitre-dfl'odihydmyfl-
pheuyl it wee chewed that in alkaline solution the color changed from
yellow to red. Therefore. it we decided to may the abeerptien apectra
or thie eubetance in alcoholic mention: of varying acidity. The remit.
of this etndy are tabulated in Table II of the «perinatal part and my,
be readily examined by reference to Figure 4. It it noted that m ab-
acrption min are formed between 320 and 490 nut/u. in the varim concen-
trations of acidity. The incentifar of either aim ae mural by the
inflection coefficient is directly propel-kiwi co the concentration at
alkali or acid at a particular wave length and this ie illustrated by the
plot in Figure 5. That the phenolic unwound icniaee in antral alcohol
eciuticn ie chem by the inereaae in abeerptdcn mine at Buny- all the
eelutiene uncured go free alkaline to neutral fie acid. Thie lenieatiea
more probably fallen the court!!! or reaction illuetreted in equation (c)
where POE repreeente the tetranibrediphencl and PO“ represente its: amnion.

POE .- Gaze}! = H)" .- CHSOH; (0)
Curve 7 of Figure 4! represents a hydrcgen chloride ccnemtmticn in
tethancl of 1.35 x 10" a. A aimilar curve with only one—tenth of thin
concentration of acid abated a claim alncet identical eith that of

~52.-

 

 

(hirve 7 (See Tables K? and m. Experimental Port). It ie therefore
likely that this curve represents the mists convex-e101: of the tetra-
nitrodiphenol to its undisecciated form

In curve 1 of Figure 4. the minimm in the region of 858 A7“ is
considerably below that of the other our-res (2-7), and is shifted slightly
toned longer wavelengths. It is also noted that this curve no longer
passes through the isobeetic points. Curve 2 represents the highest
alkali concentmtion for ahich the curve still passes through the isobeetic
points. We believe that our" 1, therefore, represents a partial ionisat-
tion of the second proton from the tetranitrodiphenol. It is therefore
likely fleet curve 2 represents the complete comer-sine of the tetranitmo
diphenol to its mun-anion.

On the besis of these asmmticns. at a certain ears length, the
curve for the strongest aoid solution (curve 7, Figure 4) indicates the
total conversion to P01! and the strongeet alkaline solution of the same
seriee (curve 2, figure 4) indicates complete conversion to PG“. The
relative percent of PO“ and P03 preeent in the neutral solution (curve 6.
Figure 4) can then be oeleuleted from the intensities of. absorption
expressed so extinction coefficients at the particular are lmgth. With
these values an icnieotion content. I. in alcohol (which does not take
into consideration the smell ionisttion of methyl alcohol itself) can be

calculated using equation (d).

X !

     

61‘0" 3 00:01‘ (5)
' P03

A typical calculation would involve using the values of intensity
(extinction coefficients) at 5587:. ahid: are 6600, 5929 and 3720

«:63-

 

 

for curves 7. 6 end 2 respectively. These valuoe give the relative por-
centoge concentrations as W“? O .763 and W . .237. Substitution of
these values in equation (d) and using C 8 original concentration of FOR
in melee oer liter we would have

I 3 e337 0 3 e237 6
e763 0

3 e337 5
.563

3 .0738 B

 

The value of c for curve 6, Table II of the «perinatal port is equal to
1.76 x 1’)" 11%. Therefore

r, e 1.50 a: m"
in average value of I, calculated from raluee at three wave lengths between

350 and see zen/1. gm. 1.27 I .19 x 10'5.

 

 

 

Sm? ’ARY

1.

4::

SW!“ 5A.???

An efficient procedure for the preparation of 4,4'u-diphmoquinone bee
bed: developed. It involvee oxidation of 4.4'cdihydmydipheno1 with
en motivated 1nd dioxide in other mepeneion at roan taper-attire for
fifteen to forty-five minutee. The yield is 50—66 percent of the
theoretical.

An inveetigetion of the Dido-Alder reaction of 4,4'cdiphenoquinone
end 8.6,3',8'utetmmthy14.4'-dimmquinene with eyelopantediene hue
been carried out. Diphengcpinone deemed under the oomiitione of
the motion. The tote-methyl derivetive wee recovered endlenged. In

no can m e definite addition compound ieoleted and identified.

The eheorption in the ultraviolet end vieible regions of Mir-dimme-
quinone. 8.5.3',6'~tatmmethy1od.4' diphemquimne end 8.6.3'.5' tetre-
t-hutyl-dfi'dipheminene in ethyl eloohol end 5.5.3'.5' tetremthyle
4.4'ediphenoqainone. 3.6.3'.fi‘ctetredtoMtyI-ne.4'~diphenogzinone end
8.5.3‘.6'-tetreohlom-4.4'adiphanoquinene in chloroform he. been re-
ported.

Th. .1:th oxidation or 3.5.5'.5'4flflfitmge'dlhydmydiphml
to 3.5,3'.E'dtotmnitmod.4’;diphenoquinone he. been inveetigeted. The
deeired product we not obteined but experimental vi“ lead totmoetete

u the oxidising agent were promising.

6. The ionization eonetent of 3.5.3'.5'-tetrenitro—4.4'dimdroxydiphewl
in methenol bee hem determined epeotmphotemotrioelly and found to

be 1.27 z .13 x 10".

 

 

456-

B I ELI OGRAF’HY

l.
2.
8.
4.
5.
e.
7.
B .
9.
10.
11.
12.
13.

14.

15.
16.
1?.

18.

19.

80.
81.

B I ELI OGPAPZIY

filletitter end Kalb, Ber. 33. 1232 (19-05).

liegetti. Ber. 39.. 226 (1880).

Birth! and Butler. J. Am. Chem. Soc. £31 1366 (1939).

Buyer. Ann. 223.. 133 (1880).

‘51:, s. Ari-ice. J. 501. g. 322 (1913). C.A. 1,3955 (1913).
3101?. s. M's-tee. J. Sci. 3. 253 (1913). C.A. 1, 2380 (1913).
Hair. Free. Chem. Soc. 53. 308 (1908)- C.A. g, 1007 (1908).
Hunter end ‘fioollett. J. Am. Chem. 806. g. 149 (1921).
meter end Woollett. J. Am. Chan. 300. g. 181 (1921).
Benedikt. Ann. 323, 128 (1379).

Keetle end Lowenhert. Am. Chem. J. a. 21 (1902).

Iemerer end Bmtngor. Ber. ‘13, 861' (1878).

tieeeingor end Vortmrm, Ber. 23.. 8314 (1889).

Beyer and 60.. D. R. P. 62828; Full. 8 80?. Boilebeim ”Handbuoh der

Orgmieehen Chane.“ Julius Spa-1.3g». Berlin. 1925. Bend VII.
742e

CCWI. Chm. F". fig 87. 99. 131 (19-93).
leutemnn, Ann. 339., 809 (1861).
sehulte. BOP. 32... 317 (1678)e

Bmgenlt Comet. rend. 148, 140‘. Beileteine “mndbueh der Organieehen
Chemie," Juliue smug”, Berlin, 1&5. Bend VII, 74!.

“Mliflbt end Hunter. Jo Al‘e Ch”. 300. 3.3.. 153. 553 (1921). Jo AIM
Ch“. 300. 22.. 2‘75 (nu).

Tfiuutertnd nor... J. Am. Chem. Soc. 39. e704 (1933).

woollott. J. Am. Chem. See. 3.53. 861 (1937).

.67-

 

23.
2‘.

.5.
I6.
I7.

28.

29.

80.
31.
32.
33.
I4.
35.
86.
37.
88.
89.
d0.
41.
£2.
43.

Shoemker, Tint. military Betebliehmmt (U. 8.). Sympoeiun on Wood.
Wedxington. June. 1949. Office of novel Research; C. A. 34;.
8656 (1950).

FNM’B no math to 33°11‘11“ Chem. 17. Se Patent 2.449.08B. 538th
14, 1943, c. A. g, 313 (1949).

Rare Boon-tong. J. Phem. Aeeoc. Sims 1, d, 5. 18 (1938). C. A. g.
5017 (1949).

mun... Berthier, Pullnn. Bull. loo. chin. Fume. lg, 450 (1948 ).
aeolian, Trans. Fendey See. 38;. 108 (1946).

Within and Syn-kin, Ante Phyeieoohie. W. R. 8. S. a. 921 (1946).
C- Ae a. 7179 (1947)e

Beker end mice, J. Am. Chem. See. 62 3305 (1940).

Vlly‘lhkfl and ShOhOI'blk. J. Gen. Ch”. U. Se Se Re 8, 1597 (1933 ).
Ce do 33. 4569 (1939)e

Fieeer, J. Am. Chem. Soc. .53, 4915 (1930).

Henrioh. Sitzber phyeik. nod. Seeietet Erlengen. 71. 199 (1939).

0.11. E, 3997 (1941).
Levine. J. Am. Chan. See. 33' ‘79? (1926).
Levine, J. In. Chen. See. 33' 2719 (1926).
Fijian and ram... 9.2-. £3. 1907 (1920).
From end Ebert. J. welds. ehem. 329.0 76 (1924). 0.11. _1_8_, 5180 (1924).
Koroeyneki and Hewlelmki. Bull. toe. shite. France 332. 1186 (1924).
We end Wittig. fies“. 233. 1870 (1924).
Anson and animate. Ber. 59. see (1905).
Wetere end Coegmve, J. Chen. Soc. 5&1. 38!!
60min, Bull. eoe. chin. France (4) g 682 (1908).
Cousin end Herieeey. Bull. eee. chin. France (4) a 586 (190?— ).
Sehlenk. Ann. egg :1? (1908).
mums:- end we. a... g. 3751 (1004).

 

‘4.

46.
47.
48.
49.
50.
81.
51.
83.
64.

56.
66.

57.

88 .
89.
60.
61.
62 .
63.
64.
65.
66.

67.

Prion, Bar. Sol. 3342‘ (1904).

Fries. Arm. gig. 128 (1906).

Mllofittar and Picoard. Ber. 31 3251 (1908).

9.91.19. A... 33927: (1999).

Soul. Naturdumotnrtm 39., so (1949). C-A- fl, 4005 (1943).
Lieberman and Borg, Bar. 2 1887 (1876).

Hermann. Ber. 11 335. 801 (1878). '

Kdn'mnn. Ron and Ema. 9.1.. Chin. Am 3. 163 (1922).

Wool1ott, Davin. Jone. and Neill. J. Am. Chem. Son. fig. 861 (193?).
c. v. Box-601m. Arch. mam. £3. a (1934). 0.9. 99, 23:59 (1934).

C- V. BOMOlIm, Ann. ”is univ. 38.”. Pt. I 3.3.. '40 (1937). C. A.
353. 5902 (1939).

Poplar-‘16., Arch. chem. Fin. 9 2341 (1937). C. A. E. 4553 (1956).
WoolIatt. J. Am. Chem. Soc. 32. 638 (1921).

11019. And arguing. Amulet. m. cm. 1'13. gain. 11. 89 (1919).
c. A. 33, 3188 (1919). .

P1003111. an. :2 1855 (1915).

9111.939... and Kalb. Ber. i2. 84'“ (1906).
schfilor, Arch. mum. £1.59 2'71 (190?).

Brannon “amt-h. 33. 174 (1889).

Hirsch, Ber. 33. 335 (1889).

Kuhn and Bamr, Ber. E. 413 (1950).

Earl: and Gas-1.. J. Am. Chen. Soc. 33. 3179 (1951).
Bench. and 993110th, Ber. g3. 608 (1917).
Albrecht. Am. a: 348 (1906).

Fntnlmgh and Hintholvood. J. Churn. Soc. .1333 186.

~69-

69.

69.

7’3.

71.

73.

74 .

0

Anon, Mmzmmoski Janma1 1913 153.C°“‘° .93.. 3397 (1915)-

”0rganio Reactions," John $1193! «:25 Son. Inc... firm York, flaw York,
1949, Vol. V. p. 136.

Cafitemnn and Wialand. ”laboratory Wished. of Organic Chmis‘c. ,"
3&cm11m um! 60.. Limited. London. 1941. p. 325.

Mouser. ”aporimntl in Organic Chantry} D. C. Heath and Comm.
flew York, 21w York, Second edition. 1941, p. 9.39.

Fieacr. ”Expat-imam: in Organic Chemistry." D. C. Haath and Compaq,
How York, 1?” Tent, Second edition. 1941. p. 865.

"Inorganic Whack," Mm! 21111 Beak Company, 1219., 1399: York and
Landon, V01. 1. 1939, p. 41?.

”Inorganic Synthesis.“ Macaw Hill Book Conway, Inc... New York and
London, Vol. II. 1946, p. 1.

Poplawk‘l. anipl Chem. 1. 173 (1948). C. A. 33. 7958 (1948).

~70-

 

 

 

 

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9.999139 1.9 92:99 9199.99:o<9v1m9:5 991.3

3!

AT! AB EYI‘RAC'I'

Submitted to the School of Gndmtc Studio: at 9161x150:
Stunt. 9.11.5. a! Agriculture an Applied Selim.
in putt“ fulfillnmt of the "quire-Into
for the degree of

$8.8? ER OF SCIJ‘IICE
Departmmt d Chantry

Your 1952

Apprwod

 

no primary purpose of this investigation was to study the Dido-Alder
motion of h.h'-diph~enoqninone with certain dimes.) Only one previous
attempt .s such . reaction had been ad. by Hare Boon-Long (2n) .1». ..::pr
tho condensation of 2,3—dinethyi-IJ-bntodiene lwith MM-dipheuoquinm st s
high temperature and obtained inconclusive results. It was believed that

reaction conditions which were too vigorous had been need and that further

investigation was warranted. The polynnolear products which night be format

by this reaction nay have interesting properties so carcinogens.
Dish—Alder reactions were attempted using cyclozsentodiene and law-

diphenoqoinone in urious solvents. at Various temperatures and with uriens

concentration ratios of rosotants. At no tine was there isolated as. oonpoond

which could he considered an s condensation product. b,h'-Diphenoqoinone

seemed to be too unstable in the reaction even at low temperatures. possibly
decomposing to polymers.

In meetion with the above work the prepnretion of hw-oiphonoquinone

was investigated in some detni 1. Only one ssoaingly applicable preparation

(1) had been reported and this entailed considerable difficulty for certain
worker. (29). The preparation was unsuccessful in our hands. A consistently
successful synthesis of b.h'-diphenoquinone using a modifiestion of this
reported prooednrs was devised. -

The ultraviolet end visible absorption spectre of b,h'-diphonoqninone in
”MI deohol, 3,5,3’,5'-tetmmetlv1—h,h'-di}menoquinone and 3.5.3' .5'-tstrs-
tubutylulnhII ..diphonoquinone in ethyl alcohol and chloroform and 3.5.385"-
tetrschloro-h.b'-diphenoqninone in chloroform were determined. L comparison
01' results for h,h'.diphenoqninone determined in this laboratory' and those
9.th by 9mm and W (29) 9.. been drawn.

 

 

In ooonectior
mauve-5.555
ztmptsd using O
muted as such I:
15¢. leading to co
obstemes poseibl;
ifi'diyhomquinom

The dissociati
Manure-Mann};

cucund to be 1.?1

In connection with the work on spectre, the oxidation of 3,5,355'-
tetmitro-Mb'dihyfloxydiphwvl to the corresponding diphenoquinone wee
sttsmpted using s Variety of oxidising agents. hone of the ominous was
isolated as such but oxidation with lead tetrnncetote seemed moot promise
tug, lending to compounds with explosive ohnrooteristies. These letter
«substances possibly contained amounts of the desired 3.5.3'J‘utetrsnitro-
&,h'-diphonoquinone.

The dissooistien constant for the mono dissociation of 3.5.355”-
tetronitM.M-dihydroxydiphenyl ens deternined speetrophotonettioelly
and found to be 1.27 3.15 n 10.. in methyl elcohol.

 

 

 

l STATE UNIVERSITY LIBRARIES

1293 030710697

 

MICH GAN
3