syntheses of certain furan and difuryl derivatives
TRANSCRIPT
Retrospective Theses and Dissertations Iowa State University Capstones, Theses andDissertations
1936
Syntheses of certain furan and difuryl derivativesEllis Vincent BrownIowa State College
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Recommended CitationBrown, Ellis Vincent, "Syntheses of certain furan and difuryl derivatives " (1936). Retrospective Theses and Dissertations. 13351.https://lib.dr.iastate.edu/rtd/13351
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Aaal* aaled* S^^0^3?gi Br» S9.?0
f©i©df »r:» sm.io# St,W.
&3itii^ttea Qf »«Ti->Stbro8iQfi^yl • l#^¥l
Wim gTam» ©f t&e me ir@fl«®@d ia ©tfesr wltb
S #©- of pyriilij®. Ss salt s@pamt©<l om #oeliag so tfe#
s^liitloa m@ ©Etiaete'd with WBteT- ami t'a© wmtm ®3:tra©t t»at-
e4 witM BoMwm kfAroxid# at 0. flie s©lMtioii was aeldiflei.
" - 18 •
mad wttb stbef t© give 0»S g. of furoic mid a»p»
12f-»30® 0« f&ls w&B of tie- t&#oyeti0al aaoimt. fli© acid
was tdteBtifled mim4. aelttag point witti am autbentt© sample
and siiowd a© h&logen t@«t m fusion with aoditia,
fiir© graas (0,02 b©!#) of tli® ketoa© and 10 g» of
oaleiOT iifdrojdide »iir® s«sp©s#®d in lase-mtter and tisated with
2,S g. Qt in soltitloa. tm aixtaye was
beated, a©li.tfl«d aad @t*asi'-«xti'aet#d to glw 1,4 g. of aold»
this waa @f the theoretlsal saemt of fumits add seltlsg
point fixe fui-olo- aold wm Ideiitified by «ix8d «®ltiag
poifflt wltb m mut&entio saffiplt as4 ®howid m halogen teat m
fmi^n wltft s©dltja.
Mil tli® otbef fmetl'©a« froa a ditejoalaatloa «»
iie-^e stt%»ltt®d to oxl&ttoa la tbe mhow® wmmT ljut so tae®
of a ooai^.«ad ©ootaliiing mmlwm imlogm. was fouad.^
jgomlnatloa of, S^STQaofwyyl leAyl. letone,*
lth.yl 5-bf0aof«arQats (10) was ooawrted to st&yl
i»l3rowiftirofl a©®tate by tfe®' 01.;®t«ea ooafensatlon ia S#
yield, fb© e-^yl S-broasfiJcrofl a®etate wa» hydrolfased hf
dllttte ttilfiisio aoid la yield to gif® g-broaofuryl aetliyl
km torn, fo 20 g, (0.1© mol®} of S«l>roaoftirfl aethyl tetoa«
ia 100 CO. of oarlJo-B disiiifli# mB added 24 g. (0^,15 aol#) of
bromiae at w&m tesperattir© *ltli sttrj^iag. fbe rmotlm mix-
ttire was alltwed to stir liwtil the bydrog®ii toromlde ©'roXmtios
aad thm p0tire4 lat© mtm. Tim ©ayfeoa
was ms^&0€- wltii soilm lalearboaat® solatioB, 4:ried, aiQd tke
aolv@nt mmm€, fht AlstHltt m-i®r rsdmsH pms^
mm&* Tm f2ra©-ti©B feeiiisg ISO^iS®' 0, at It «i, pi^s-sai® m,m
It in til® aad ttoea wm& a^^fstal-
Itsed t€s the 'OQHstaat »@ltiag potot &f 0» fhe yislt
m« 21 g* &f V, $^Mhx<mofwefl ketoia®. TM» ms ®f
tit® tbeQTetleal ^momt*
•teal, QmlM* tm S^^glrgs Ir, 59, fO
F&m^t BTf 6t.©l,. §t,S&,
Qxifetioa. of'».« §«>Q-lM0«#fia»y3>..lemyl letoae,
f0 1 g* C0..004 iiols) ©f tb© keto-SMS md 2 g* ©f #iJL-
eiia kftoxld© 8«»pead®<l la «a« 8t€d@d 0,6 g, <if pQts#-
siiMi peSMyogaust® i» solution, fb© r@ao-tloB alxtOT® mm hmt&d,
»©ldifl#4, suai ethBT'^xWmted to fl¥# O.Si g. of
aelA» fbis me 3# ©f th« tMeratls&l mmmt. fh& mtd ©a r©-
©i^ystalXlmtlus a#lt©d at 18# 0. and a mixed TOltlag p^imt with
m spe©iM«a s&owed m MpMmmim*
fo- 1 g. C.O-'OO'^ aol@) ©f %hQ kntme mm addted 3. co* #f
pyridine in etJaeaf. mixttare was xeflooted &m 'bovpr m&
fbe reatda# wgts dts#-ol*@d la water, tieatei wltli s«fdi'iai
Jiyitoxlt# at €5®, mud mthm ®xttae%«<S to yl@M 0,& g.
©f mold. &ls iis«,fO^ ©f tfete tb@oretl©al mmemt sf S-l>r©ffi<s->fi3tro|e
go «.
add. fMs weld wa» li«atifle€ Isy its aeltlng poiat s»d a
ffli3E®4 ®3.tiaf point wltto «a smtfeeatlo sp00ia®a-#
iifetaftgyl Ketaae^
methft festos© was prepaid i bf th© a@tfe#-d
@f Hakes (34)* fht« 0©mp©«Bi, ms sli@« to b® g-altro-S-neetyl
fwaij by the fellcurtui mmtlm* ia etkey m®
pmpai,T&A hf Mat tag g. C0»^ *>!«) of potasslwi toydteoMd® Im
200 ©»• Qf ®©.tbfl aleotel wlt!i g. (0»2 aole) of attimso-
fflg'tftfl ^ io 300 0e» ©f etbfi iaiA distilling tlie
mlxtttre dime0a«tMa»« m-4 etter. To this seiiitioa ms
14.1 g, {Q'ml »©!©) 'Of 5«nItrofi»fi»al <3i), A rapid aTOlutloo
@f aitr^E %mk plae® Mtdt -aftgjr tbe of tli# tea©-
tiosj tb@ #tli«r ms %md tli« prodaet ©rf«tallig@t-.
i«ltlag point ©f 5-alty«»-2*'ike8tflfTta'a.n f8-?8,5® S* Ilasd with
tile altroft»yl ®®thfl ketoa# of liaket t8«f8.S^ 0.
Btt'gofgrvl Methyl g®t<»l«i-,
ittg t© til® ssasittTity -ef tl@ fwraa. altTO gSQVip t©
slkall^., tkis sxi*t was pxepatei l» aoit g&l«tioa. fo S f.
C0.*02» mola) ©f S-altrofiitfl »ettiyl k«t®»e and 4 g* (Q*06
aiol©) of fcty^oxylaalu® ^ydrootiloride ia alcohol soluttoa mM
added Qm half es. ©f ooftGeatmt#^ liydrootoloriQ aeid. fbe
mixtme was hmt&d. t© 100® f©f 2 io m oldssd Tesssl.
field of S-»Bit» fwyl ketexta®, »ltlag paint
16f-8® mB 6.1 g. fUis was 9^ of th© tli#©yetl®al momi.
- 31
StMHf
%* tt baa Mm sbom that is Ijyomlmtloa' ©f
B-ftiryl mthfl ket©»e tti® ftmt l^ireals® eatexs tim sid®
Qhrnln* It MM been fwdrthei' sliow^ tbat tb® a®©oa4 br«la©
will mlso,#at®r tHe sld®
!• la the Ixeoaimtton ©f §-br«®-o»2 farrl mthfl
Mtms t&© larcaaima eutet® tM elialo.
3# fli® nltm-fwtfl atttofl teetoae p»par©4 %f
llak'ts l»8 •be®a showa tts. stthfl ketoiae..
cs.^ BtwrnsmB » tsi BiFoim siiiif
tmmnmnon
It is ieajit a large amiibsjr of
o.ospow48 CS«5 aM aaa? pMmflMteA heterdoylio mm»
pouads lav«- ^«a ps®payr©^. vexf littl® *©rfe leas putollslisd
mm&mlsg %h% aitrnjl mitleM of eoa^wais. fhe @f
tla# dlftfffl® Blgit ^ said t# started •*!%& lat^ais C2f)»
wito Isslate-fi the fim% S, 5»-itiiiit3?fj-2-,3<-dif«!rf3., m«
a ^y-jiiroduet ta tto altmtioft &f tmm im 1^5-» fb©
Qt taii QOspo-iaa4 wm n&t @l-i©t«lalfee€ at this time. Idw?e3r»
It Wat deftJBltelf ffoirM ft© ^ ^•^-5*--tlBltro-'2»3*-dif^yl try
mmrn (28) tB 1931,
fM ti.m% mtk %&mM€ tfe® ^^®pamtl-es ©f a
Siftttyi t-fp® of @o*p®iat ms ttiat «f I#a'dte aad Stisisikt '{M)
use-d tke BmmsJtf a©-tliod of i^laf elo«t»e-. ffea
mymth&wtB,: wtiieli iwolvts t&a ©f Bnterm
irith. »aettv@ balogeao altpfcatle ©ttoers, ald#layi!l©s or teton®®
im tlie pre'Saae® of a l>a8«, fleiis 3-a^|'J.--3-fw©i® aottte. Ttoe
most logi#^ i»a6tioa aisdliaalsn wntoli my tea fmm ttm
litemtme- aited is sh&m m f©ll0Wi-i
* 33 *
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H H 01'«»0<^0M3ll^g .+ lOH -
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-0' 03 «401
"fiii®, m@®baolSM appeass plat»i¥l@ fot tm reasons.
first,etlier •»aets la tli® pr®®eii-ce of
water la tB.©. followiag aafts^r C33.)?
01 Ql IS — m^m
03. OB a-^--o-o0^g +
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fit© s«©atm kjAmxiM mm-tf mw®B as a
t© remo*® tfe® iiyi3t0g«a ahlorlA® ff^pa ffoluttoa. If th© r@-
aetlsn is tiie UBmi-^mmim.1 mmMly hmsMB iam
to the mtmmpmdlog alde&fdte. S«©<in€, Pl&a@@x and
AJlMBi i^2) as w®Il as W<&rm (S3) shomi tteat ekl^r-
a©®taltoMyit ©md «tbfl r®it©t in t&e pri#eso@
0f mmamia, 1» etise;r tolatim to form '
fwoate.
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fiseyl I ling t ©f
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tim. ioSld® iGeliege-, IfBS. I- | .
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tfmreate i 3 p2* •t S.#f tfafl- s 0iO.iip-' $ p -di0arBo®tb©xf*4, i Mag 4*-'4ifmi!#£''aBd aai€ t .Om
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41tb®iig&- ®i>ti®®l st«dl@a oa tkis ©oupoimd are a®t Q«spl®te4»
t&e »«g-al:f#;sii©\alA WBWf imtemBti&g m tbm
ttxoetmfs 'of: tlie finrg® s4ag.*
iipieiiiim
StMf af, tgyi .Ketone It® Oamoliag
S#fo?€ «aef-taktijg tii@ pfefaa-atiQa' ©f
k0tmB- ftm t-Wea^fw^ it was a^^issMs
stwAf t&0 dpMam m&Mtimm fox %M& pr®^m%i©m -of fwsyl.
ii@t&fl ketos® ftea timg s adilf amilalil® fwtm-m
S'mfeh#§ig .of, g'-figyl Matiiyl. .Ketes# fi>.eai fmm.^
S-fatyl. iisttoyl le^tea# im& Tm^n pmp&m^ W Btieltstdlia
|3s) f5<» fiaa» mmtyl @fel#'r44e ts tag mtor4ifq«® ae«is«t
tlil©ael(i®t .stsBBls sMorl^t f»rtS© ehlsyltot ©r ilas
»i eatalftts. la oxfer t# aif©id thm hf^X'^^n <3lil©rlt# to
whilst tmm it tt »©«»€ te#st t® tis@ aestl®
iyaliytelii. i W ) im8t@md of asstf'l
Wm 1* A s.0itttii@a ©f' ® f. (0*4 »1@) ©f aliMlmaa
i» 40 e©.. of ©afbea ms stiary@€ aad eoolei
t# 0® 0, k miMmB #f 10 g« •(©•IS of fii«ia.,, 30 §•
astls) ©f a©stl© asMfdivide* aa-fi S) ©#*- ©ar^s. tjlsolfilte
Wii.s s44e4 drupwlse. fa# ir©-a.atl« wms mllQmA to mm t© ro#a
t^ispei-stwe aa4 stiifsfd 0®e horn* fhm fssaysti©® aiiet-aifit m#
te#» .ie«o®|j©sed poflsfis® 0mte ©5a0tea i©s# astttml.i»4 wit&
•so^dlw .b,rijrmli©, ana stesa atstiilet. fl^e ms
til® toled# ast %&e ©tfeear r#ffi0¥»4'.
fhmm jf@aat»t 2»4 f« ©f feayl
11^® 0* a»:d-%©-lll»g at iS^i# §» mi®f ^ mm* fs^essitre* this
was of the tummtimt m&mtm TM fi#M t39)
©lil©rlto ms-
l»^i« la this mmetlm 24 g. (0.18 »ols) of
by^-oas ehloriafi la XOO m» of iry ©tlier treat^^
a qf 10 g'* c0.»1.§ aole) ef fmfaii., 30 f.. {0*3 »!#) ©f
a©#tle iiAfaside,, aad ^ e@» lif im sam® a«m«r
as Im tlS0 fi3p:it. r«. ftie ftslA of U^fwtft m&%hj% kstoae ms
S.f3 g* 03? 3^ tfae %hmT®t%^w3. aao^t* "fb# yl®li (SS) us-
tog «4a© ©iilorit© »d ac©tfl- QhlQXim mm 3^- of the tbeoxet-
i©al»
Sm I. Aastbts? Tvm «as la s stailar waa^r.ex-
tMat IS g» (0*1 mte) of f©»l© sWa.rl^^. 1» SO se* of
o«tfb©a dlsuafl^ ms wi-^ m mtJEtiar# @f to g, |0*3S
mlM) ©:f 36 g» (0.1 sq1«) aoeti<J a^rdrl€e and SO
©s, of S-aiftJOB fli# fliisl bf tfels wm 3^-
of t&s"
tet. -..4,« A alxtw# of 10 g« (0«li -aolt) ©f ftaras
witU ©«., #f ^mmm. aa<l aj g.. (©•S «ol«) sf a©®t:i$ aafe._yarldi®
was ©aisled and t#®ale€ m%th & @sl.mtioa ©f 40 §,• (0-,M s©l®)
®f staami© ©to^iflsl©" ts m «#. «f lieasta®. 4f%®y
mmMmg up in tM @ttst©aa?f »isb@x yi&ld
- m •
tetoae i g-. fliis 'Wm SO^- ##
field mitig ae-etfl efel^rii®' (Si) and stemio ©felorl!i@"ms 1^*
gj sagatiga a-fttroyl QhlQTiM,
fm kmB^T^d mmd gmm (2 aol@s)
Bioal it©t<i wm aified %'Q g-» .(S »!«») of t@@feat©ai
tjatoafl alil.0sli# 'lui-d tli# at:et'«© m® f^T -©igii-i
At %&« ©a-i ©f tbis tlas @xe©#$ e&lerl.i® r@-
ao-mt- fef <t|»$lllmtl0m- at a^QSf^rt® pr®»aiB3re aa-d tM.
mm mewa-iistlllsd* f&sir© »a^- gis g# ©f B«'ftir©i'l
sblorlt®- feoiliag fs® at is ira. f»##.8ti»# ftkm wm 8f
Qf %M t&eo3?et;i@al aas'^t.
Oft §^WTQm--*B'*'fm'&le AQM^
cs»e hma^®4 isi t lta emm,© ©tatiastsrs mlts)
of (stf fet-mlb© {40) w6« %%B- 0&mm 0f m hQmt
ittto ISl g. CI «©1«5 of fw#fl eiiloifltfe ta s !.•«
liter rO'XiBft-%©tt«»©4 f3a«k pre^iieA' wttla. a gxtsm^glass
flm fM tmm tli# €3;'©fpl«f fiBioel pas»@4
pt&t^lf tlia aat t®a«he€ t;@ wttliia 10 «* &f
tM swfitse -of the It m« f®mil a€va»%ag«®iia!
to- %dd tl# %»©ii4»© m% mm t-e'«pe-ra%«te m "l&e
te#fi» •mm. €m%ng t-lie e©«se df wd tls#
rsfl.«s:@.d til® aiM-lti©a»
all M %1ie "tsur&nl^e &»€ li«-®a a^ed tfes flsak m-®
- Z2 -
tm as oli Mtb mA lusated at ISO * 11§® for 4
apij exlmtely m* of watei? mm aided ajid tto stat-
tii3» p0iarm, into m mnrnmB ©f -sodiw #a*bomt« jom-featod
is a S-f.3,4t«.$ flask* ft mis tolled a mftm @0a-<fea®e*
mtll tfee oily l.a.y«f •dlsmppeai-ed. fhmm th@ s©l»-
tl©a m,& tMated with Ireiled m sfetoft tia@» asid
fb© mjm wQtutlm ms piDsped lut© a &f o-mmm*
&ydiroolil©tl© aeid aad l0s», aad t&e frtatpitated aeids
filtered 'l?:r »wstim* there wm ©tetatotd 360 g. of «ix®d a©ids.
ffe® mixture ©f S-»teoao-i-fwap©l@ aad 4,6«-Hdlt>s'o«s*2-
farcjio mMd wm -s@pipeat..@d tlie metli#d af Hill aad tsRger (41),
«liiali iep«ids oa tht dlffe^#ii©s ta 8#lwMliti#s of tbe 'bmrtmi
talta la dilmte m€m^m mmmi&m §m» hw^dm4 gmm of tfe©
mixed aetd dts«olTed ta a llt#» «f mtsr iO-60
#«. &f mmmtmt&d awsaia* As ®»es» of a 10^- a®-
lwtl#a of i)a.3riQ® ©fel^rid© wm added, wMcU mm«A
%im Qi tb0 Mieltm salt of the 4,S'*di'bxoiio»»g»ftapail'<3 aeid.
fliiS' wm B-B:p$jemted 1>y filtmti©® and th« aeid y@g@nemted W
pQ-mimg- tU& fearlim talt.,, is fera ©f s tllek paste-i^ ist©
m teolliag s-'OlntloB @f^ 2S «f aifiifd:ro«# sedi?» srtsdLfate in
500 0Q^ of. A few gmas ef lorit ma added, th-© s#lii-.
tloa filtered ti©t.» «od p©w©d with stlrriitg iato a aixtnf©
®f ie« and 0mmmtmte4 liyir^®®fel©yi<i aold* fkm 4,&»di%»®©^
3-fw»io &eid «®f«&t®d in light fefowB- erystala »lt«d
f om is& ieo <> • g,
^ m ^
fli# mm ol>tatB#d' toy bsilt'Bg:
t%» filttat# frea t-h® fearii* e&iojrtie ip2?@©ipttmttoB t#-w»:0"rt
©xe@#8 dmmm%&p addiaf a».€ pen^rlag into o©ld
.@&ae®otifat#4 hydyo^hlort©- a©lA» the ©reil# rnQiA »©it@4 180-
18b^ Q,
Wmn 1.1 aol#s <^f feieosta© mm m®^ witJi I mX& of
faroyl the ylsli of S^-ts^osQ-g-ftiroio acid m» 75^
m€ 110 meld was Isolated, •fliea O.S a©l@
•©f lisoalne to 1 atolt «sf tamfX elileyia® wmn uased, tks yteM
of S-^%i;©ao«3-f*HPoio asid w&s ZBf* fUm mimg the dtwetions
0t ioimmm 2.2 a©les of hm&tm with I mole of ft»©yl
•e&loyii©^ the ratio ©f 4,S*ti%^©M«f'yi^®t© to §-b:«3ffl©ftt»i-0 was
Wf t& M0* ^ehmmm mp&rteA 10^ yield Msh
pTO^Isl© aa€ Mas aet d^lissted, -owe rmMiw^g
twees ft aa4 tslag 2*f »l#s ®f %® 1 »#le ©f
foroyl » thm mtio of 4,6-^lto»«f«i?©i@ to
iweoi& mM mm tsif mxi.A thB total ylsl^ wm fnmd to
to© fl^* fmrntm^t It ms' ad^mMe to tiff 3#S 'm©l©@
of hit^mm..with X »ole of fmroyl diloride aad tlie mt4@ 4,i-
diM©aof»i»oi@ to 5-t>rom©ftaf0l§ sotd ia tils s-m mm l§&f to
0^ iusd tM tofel flel4 wm • Although t&ts a©e®^lis&#d
t&« pwi-pose of gittlmg all 4,S-Ai'bTO«o«'fwoi© aa4 a© S-fefOJ®©-
twtQlo &©i<i» tfees-e ims too large an ©mo@ss of %ji^«la® tis®-d
aM tMs out ti# fiold down to Sff'«
~ 34 -
frm th& it 0m ^ mma t&at tit#
ooT-i«©t asawt ©f 'baroaias fst tte waetlom* mtf
a-furoio aeid ms mm 1»1 »@1@« t© 1 ml» ©f
A &mp&mlm ®f Xi#l g. |CI,l a0l«) -af
aeti ia. a molmtlsm of' 2f g, {0.1 m%&) ®f ffl«.yG«rt#
©liloiriis la m0 0®. of mm boiled ta at ^isttlltag flssfc
ptsTided with a aa4. tbe ©II irtiiefe «t«aa distilled
me se»pa^e^, -dritd, aa4 gt?# i,6 g» ®f a-fe^oa®-
fmm C'to)- "feotlisg at 103® 0« at i.tw5s^®fl@ pte^sar®.
was 6i»^. of tlfce©retieal mmmt*
pgepa^a»i0» ©f' §-l3?^o*a*ftsgyl.x.eitoi
A alxtwre of t® g, (0#.es a©l«) of 2-termii©fw® witli
100 Q0.» of- irf t»aE®a@ an4 'iS g» i0»^S5 «®1@) ©f m&%i^ aUK
lij rlle saa- t»i,ted wttfe a s#lmti0ii of if© g*
(©•SS m&%^) ©f 'sniiFdsouie stasis ©florid® ia 200 ©©,• ©f
at mm fb« mmtim aixtwa wa#
m^me4 hf |»W1B§ isle lesh-soM mter#. a#atralt2:0d wttfe
:a®4l*im st®a« was- #1»talii©€
SO' g-, S»-tec»t-2-f«|-l attiifl ket#a© 3«lMQg palst 5.
fills t® S1^ af thm %h^mmtiQ&kt mmm%»
Itoeteea gra-aa C^.l sole.) ©f 5-fejr©«!h-a'«fiaaffl »%hfl
)mtm% was tested *ltti XG g. #f ©csfpa* p©.wd«T and &®:a,t«d to-
20# (leslde tsisp@mte@) mt w&t0li folat mtemal »-
flim»d 2spidl.f» fh.® t8«p#?attir# ms fe#m at 30s® o. for ose-
lialf Hi® g>©at«ftts 0f tb© flasK mrnm itl,l0W«d .to s©-©!. Mid
mm t&-oyo«[glil.f #xt»@i%04 wltb tttit-r sad tliss wiilt
After ?sa©V3l of ttie s®l¥®at« tber® mm ©felaiJBed ©alf
©rlglaai f© dif»yl ©oi^d l»
fomd* ,
Itngtess g,mag CO»i «©!©.) ©f tli-@ k#toa@ m® placed
la a %uh® wltli 10 g* @f aad 1 eo. ®f gla#l«l
®0e-tl0 aeid*, s«a.l«d|. mA &@-ated te ^0 0. fo-T ©n#»l®,lf -h^m*
fbie ©oa^letelf «l®«o«spos#d tli® «i,t®rial aad ao
|3nr©d«i©t ms isolated*
A 't&i^d 19 §, .(0,1 mole) -of %k® let«@ wmm lieat©d to
0. aad tfealed wltfei smll portions of aettmted coppe-i;
(43).. Afte,3? t-teattag thi« ram©-tl0a as to the first
fim tto aaibe.tial ethMT tfeg® tlis *j®«fcai»g:$d i&etmm m« Iso'latsd.
-of Itfayl S*$gQ»0'>g*'f-a^-6a'fc®»
One miwtf gmm (1 »1«) ©f f«ofl
•©&l'Sridt «as '^ftsmlsatsd witli 1^1 s©!®-® ^SNsatia® sis -prt-
fiomaly t#p-Grted» HQwtwf* Ittslesi ©f 'j^-®©i^0iiig with
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of Bifigirl»'S*.5*-'dlQai"l>0iiylio AQ14#-
In a saall flM.lc cdatslalag tO o©* ©f giataslla# (40)
warn pl»«©4 0»56 g. t0».0§3 aelel «f
a.©id aii€ 2 g.. ©f mp^t pewdeif. ffe® flask ma fe®at«4
to SOO® CJ. aat a large mmmt &f earlicini diexi-^ m® mwelwrnd*
Aftej reas'Ttag tb# ©•oppsi' and tliea. tl® Qiits^llB© with
a@td,: tMm ms ©M«,laed a ttme ©f ©om-po-tm# wlileh was i®-
atatsl© to- aiaejml mtM* fills *a« S-tt^-^ifupefl bat
thm m iAfe-ntlfinati-oa.
[email protected]. :qf etfayl mfoat# (44)
. fQwr fow-teutiis grams {0»03 mlm) ©f tlie pre-
wioxmXf dessxl^d ethyl 5-%?oais-'t"»fiiirmt® C^) i^# teale€ is
a Oayitis taM with S.4 g-, (S.Og nole) of aexoaric eliloi^ide
aai 10 -0.e» iG«.I4 m#l#) #-f umtfl slil©ri«Se* f&e tmb® m& its
©©iit@iits mm feeatei f© 110 -*• ISS® G- toT § hf^urs* At tli«
@a4 of t-lilB llffl#, ibe tmm mm m&lBd. m4 tli« oonteats @3:-
txsattd with Tfe® efh®^ m-B rmomA and tfe.® yesldij®
@[email protected] distilleii to B*i g, of -etttfe et^yl g-^hl&f-o-B-fweat®.
fbi9 ms fQf -of tUe th9'omtl0a.l &mmi* Sie ©mci® »ro4««st
«a@ piirlfie€ hf ss,p©»tfl@a.%l-o» to t&s aeid ms 2^
©jffstailiged# fli« ffisltlag ©f s-®lil»t<}-a« f»oi« a i-a
ma lfi-^18# 0, file a©id «at thm ooawj-tt-i to tli@ est©3?
by ttoattb-g wifh. p<is.ta©3ils>tli;ei di«««lvtag sji
mW^ms &thft tistllllag*
liim -•«**
'Mmlim. mi I fit ft
Bmmmtmm gma» (0»1 »!#) ©tbfl. &*@fcl0,ro-3»-
fwoate ms t»sted ultfe W g* ©f ©©ppef- p&n^er mnd U-emtM
to 13# f* at poiat tH© fctei-lal rsfliaxet mpidlr* Aft®y
toeing at tlii® te^fatiiar© fm 1 hmm the mtmrtml mB
ti»0t@d ia tM- mm^ wmmm, lo t»## of a, 4.%fwtf% mn f©mi»
te0l^i' If g» ©f %lt@ #std^ m» plft©©# la
a 6aritts tm"be' wltii %Q g, #©pp@^ pm&mw sad 1 m» glaelmi
a#«tl© a#tt# @eale-4, mA hmMmt %G 3i# ^0. for li©ar.
Aft#IP ®xtmslt»g 'aad ^ tm t&® asml mo il-
ftitfl 1 . ©ma.la®€,
-'qf l-tliyl
tijtg ester ^wm pmpmm4. hf ferosisatloa of 2. i^le
®f fafoyi Qhl^tide m pmvt&mlj @m@pt thmt 2*f
mol&8 &i hmmiB0 »#» mei. i*l aoles ays l@fert:.
file lj3P©aisat«d fn.mw% m« aMe4 to aleoli©!-#.
©fat might' md tt®tilled, tMm «as ©fetalned IfS f, of ethyl
4»S-»difet©»?^g-fia©at8» Bits me tli« tbeor#tlc»l S3«n»t
m®lte€ sf-ss®' c.
twenty gsaM C0»Of a#l#) #f th# m%m itad W
of -wtare ta 310^ CI# Aft«r t&® «»imi t»at*at
- 40 -
only a tmee of a possible difuryl was isolated. Tempera
tures as high as 360® in a sealed tube with 1 oo» of glacial
acetio aoid failed to give more than a trace of a o«»apo\md
which it was hoped would be diethyl 4,4*-dibroiao-5,5»-difuryl-
2,2*-dicarboxylate.
In the hope of getting this difuryl 2 g. (0.007
mole) of 5,5*-dlfuryl-3,2*-dicarboxylate was treated with S g.
(0.014 mole) of bromine in carbon disulfide solution. How--
ever, careful fractionation of the resiiLting material result
ed in the recovery of the original ester and no evidence of a
dibrofflo comi^und.
This run was repeated using bromine in boiling carbon
tetrachloride solution but no dibromo product could be iden
tified.
grep&imtiOB of 3-Broao-5-aitrofuran (28).
fwenty-eignt grams of nitric aoid of specific grav
ity 1.61 was dropped with stirring into 60 g. of acetic an
hydride at a temperature from -10 to -5® o. A mixture of
9.5 g. of 5-broao-2-furoic, prepared as previously described,
with 50 g. of acetic anhydride was prepared by warming to
dissolve the acid and then allowing the solution to cool.
This left part of the aoid precipitated but in a very finely
divided state. Hie second mixture was a^ed to the first in
* "ifi, *•
^irtleas., tlie t©ap#ra.tii» being kept as fee-fore, fh©
aatsrial was aliewed lo stii- ob© ham after tlia fiaal a-dfti*
tlcm aad decompot-ed wltli a of ie@ amd mt@r» fhis
so-lmtioa was ©xtraettd witb tte#e p.ortle«s of ether and ihen
tfe.« -st-lier mmoT&€ to Issf® a wai steam tts-
tillet. M oil was ©Maloed ^iQh rapidly orfstil.llgtd t©
gl"?® 3.S g.,- of dry 2*teQ»-i'<^itr®f«a'aB* Bil-s was -of tlto
t^oretioal aaomt#. 'Ri# prottjst nelte# at 0, aad ite
liollisg point ms IIS^ 0« at IS m. pr@s«w@«
P-r®parati-<m. of g<-*-liaityo-*-,§,« 3-»^*-diflaryl»
Mettod A* ti$M gwmm (O;.©# ml®) of B-teoso-S-^itroftsaJi
wm Mats-ii oae-^lislf iio« «ltli 10 f. of -oop|«r powtier, fh#
s«a©tion ti&e was giarrowa^fed a iKtal 'Imtli wlilofe ma ti«ld
•ftt SOO 0* f!i« e.o»teats of tli-e tab# w®re waa&ed with etiier.,
dlssolTed 4a aad fllt®r@#» After rgiw^al of th-@
«®ae., tliere re»aia.©d 0.4 .g* of .SifS^-dli-iiitro^ajg^^difurfl.
fiiis mm 9^ of the the-orettsal maoimt, 4ft#r seireral er^-
•feslli^aJ^loBe fxom tli# pr-otnot m^lttd 313-31# 0,
letii-oii ,E. Qm hmd-TBd. grams of fttraii (27) mi aitrsted Is
thi® «®ml mamer, Aftsr deooi^oiEiHg tii« mltrmtim al3ctt»«
witfe mter^ ti,©r® 1,»S of a prodaot whloU «a» is-
solii'ble is etber. -Sew ml orystallimtioas from lioa^ene
t>rottg!it a@lttsg polat of t^is produot to gl3»31# G* By
t-lie metliod of alited a-elttsg poiiJts it was stowa to Ijo
- 42 -
m%u the piP'Otot pr©paJ@4 Isf tn© first Mtli^d* as
jieli i^s #f tie wmmt^
Ptmmtm%lm d- m B ithsg..
gas was pasted luto liOO ©©• of sBsliF<S3feiai
©titsy for so boasTit,. wa® dittillet m a w&t@T
fcatfe tQ i.00® G» aad tlie 4isfell,lat€ mm fxmthm 0M#risat«d*
fh,& mmMm>S. »3?e fmdtl»sa.ts€. Ssillag ra»g@
C- at ^ am* pmmmtm* A B €0gf#e fmeti^ m# tmkm m the
sm@m4 fmetlenatioa, f'm jieM wm SO© gm* ofeL^jS^di^hXmo'^
©thfl etli©y»
ftggmmtlQa of Acli«.
Oa# ©ttble eeatlaetefs ©f mt^er ms plmmA Ir
a 3»ae©]te#d flaal:-. Oae aad thirty S^BMB {X
mile} of mBto&mtie ester and 142 g. (1 »le) of o/. ,^3-
€Solil03»®tiifl etiier C^) C'^^) fXit©©d la m@ trapping ft»*
asi 143 g* {l*B -©f pfrldlae (M) mm plm©@4 1» t^e
Qth&t* Tim tm mlntlmm were allewttt^ drop into tfee flasi:
with stirrlag m &# t# finisli slmiiltaB#©wlF ia 1| tour®, fli®
aistur# mS' t© stir for 16 howm at 0.# ex-
t»0t®d wltli ©tbe*., wltfe 3§0 @©» #f 20^ .li|€r©©b3L€sri0
ii@ldL# dried m&T soMw aulf^.te, amd <ii»tilltd« T&# fmetios
teiliag 70*1.00^ 0* at ^ «»• pretstjtr® mm mpomlfled to glir®
4S f» ©f a-ffi@tbfl»S-f«roio asii. It aaf ^ ©rystaiilss^d
- 4S ^
twm m- ©©awrted dlJ-gctlf -t© tli# sster fey dissolviag ia
&thfl al@©liol aaat gmtamtiaf mlmtton With toydro-
gem $hil.0tl,-i® gas,
gyoatm lgas of 2"e®tto3. 1*£iirqte- aem>
Iia a S0§ m* flgtsk witu a (lr#p--
plag a»d wm pla©@d W g. 10.2^
»0l@) of (4§) is 2..S© ©©• of glaelal
a©«tlo seiA.. A s«1.1 mkf^t4m was aM#«l to-
Isjfee glacial aeld %m tstaar# aiAydf^w ooatitlQUs., fo
tStis was siied at # 0, §6 g* C0'«35 sole) |18 a©.)
'Qf Iromitt® is 50 m*. of flaolsi aoetl© mlA, W^m ail ©f tti®
liad Mm a^«4, %M mlMtmm m# stirimA fm tw0
^-d allewed t# stand at wmm
fh@ mXx'^m® mm p&wteA Int.© l©©-mt®r., filt®r@€, aad ^ted to
giva 3C.g g.. of- i-^l>roato«3-'ais'lbfl-Ma-rGio soi4 siting IIS-
IIS® 0» Tki-n is tO^ of %%& tb©os»©tloal mastiiit,
later if jgatiom .of. AmlA*
, Sixty-one grams CQ*3 mmlBm) ©f
-fwr©t0 mid m& r@fl«xed f©r S i;0-«re with 35Q g. (3.3" sole®)
of tkimfl. elilorld®* fli©- mmmm tfeloafl ofel-oriia was r@-
SQWi at ats^splieric ftrassnrgi, fbe r®sld»e ms aidfet slowly
with stirring to 300 s©, ®f a^©lmte #tliyl ^and
fiaxe# 4 .tears. fher@ ms ©tetaiBed m dlstillatloa 58 g. ©f
et&yl teiliog 132^134® &% 38 mm*
presaare, fbi& mB 8^ of %%& ttieosatioal aaomt,
Sapctaifieatlea ©qimlTalents Ca,lo*<i for 33g,0
A. t^remgat-i om. of, S >S*-*gt»etliFl*';3* 3* »di©ar^oet^oigy-g, 3* -
jrefltixed, fo:r eae Mws' with. 20 g.. of 0#pp#r powd®!* kaepiag th©
teth t«p©sa,tti» at 3i0® 8. The r^aetios mlJttnm wm .allowed
t© ©oolp extmetet wlt& i&t'h&tf »<l fhiftf-fiv®
giMis of tHe mehaiiged e-st^r wm m<t3mem4» fhem temimd a
tarry sttfestaun®© wbl0li *s sapo»tfl@4 with alc^liollc pQtmwim
hydstoxl^* Wpm aei-difyiag this ©.olotlos so dlftxryl aolA waa
©malaed.
lereigatieit. &f ^«5**5i«tte.lfa3?aa •( 36).
A eatotioa of SO g- a<>l®| of 4twtliyl.f«rsa
(§0) in 250 0©, ©f #t&fl alesliel m& addet to the mTemB.timg
solu1;io« pi^pai'td itom 135 g. (0»S »le) of serea^ls elil©rld©-,
82 (1 aoXe) of mhy^mm BoMm a.@»tate*. and SOO m* ©#
wstsr, Pi^elpltatleii ^gaa wltblm oo© aiBrnt# and,
found.
oths't -©gastasts &wmi
I 1^ 1.49431 I l,49f0| . 0® 1.388
WR^ 0al@*4 4t.4?.» Otes- 48.as.
Fifty gmme ©f ©tliyi -5»^i'0m©-3--ffletliyl-3*'fmr<3ata wa«
stlnelag im 2 days, %im mrnutim ms ©cutlet®. f&© eymd®
p-rod»t;, a oc^npleE of tbe typs d®setl"bsd lif §iljma
aBi frlglit (42)* was filtered aad r«fXa3t®4 wltb a llt®r of
etbfl al®oli©l for s houm* fte ©doled fllt^pate yi©lfe.dL SO g«
of a Xlgkt ^ ©TfitalXiae g-©Xid »ltisg at XSS-X^K)^-, fliie
mmm 4©^ of %im tbeoretl0al
Fgemyrafeioa &f Z*&-^Mmm'liUwl*^3-'±m4x3fwem»
tightf grams 0.*Si§ aoXe) ©f t&e mei'o^rlaX was
s«siJ©«sl®€ ia 50© ©f stirred r&pldly dasrtog tlie
slow mddltlQB. of a s©Xall©a of Sg g. (0*15 »ole) of i.odine
and 83 g# CO-S aole) of potaaaiiy® loil^lg" ta SOO oo, of water.
After tke last aidltloa* tlie mi^taa?© "mm stirred for one botir,
til® «mo@ss of iodla© wm r©'iltt0#t rttn aottia tfalostiaXfate, aiid
the mlxt'iir© steam Al stilled- $%em diitlllat® was «1lier
e-jEtrao'ted. fiie «th©r extraot m&m dried ovar anlifdrotts so^diia®
swlfat® aad t&e ©tlisr removed* Fraotiomtto© of the TOSldwe
ta an atttosplier® of iiltr<%#a SB g, of 2,S dls@tlifl-
3--iodofaraii Cas) feoiltag at 64-^® &t 10 as. iMfessmre, Biis
m« 40^ of tfee t&eoretioal ataowt*
ooyaoliaa of a.«.s^--dl»ethyl~g->lodof ^«
fweijtf»t«o grws'(0,,1 »ol#) of tie lod© oompoimd aBd
10 g, of eopper powder ii©r@ sealed to a tab© aad bsatod to
1^® 0* for l/jg hottr. C«pl#te dsooapositloa took plaes aad
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l&wpiiig- if it l»ft Is t&e flie distillate oob-
•fealaiag tlie-Mtifeyl fwttmsl m& tbea adi^d al#iig with a s©li4-
tl©n ©oapised of 15 g. of S0€l» Itfcteoxi^ and ea®iigh mfei'
t© male© 1 'to 1 J./2 liter# of s©I»tiQa, fts eoist#ii%s of thm
flasfc, wa.« Seated %Q Mlllsg and tetled for ^ minute:® witfe a
refliax 0-©ai1teiis#y, Tfes s©di» salt mm tb«a- filtered and tli©
mlutlm 0«i#@nt»Rtsd to ©©> @o»©@Btrated solution
mm lsoll8d wltlfe lorl* & fsw ate»tes» filt@T®d, aad tli# acid
fo-r»ed bf peering Into aa i!X€i@g» of dll^t« hydro^lil®?!© acid.
Om ftltrati« M g« of 5-«tfefl-'S-'ftii'©lo «lltag at 10--i«-
108^ 0^ «as Isolated, *bl0fa is siiffietiitttlr •ptaf'® fot mast
purposes* fhm field was 11^ of t&e tM:omt-imt wmmt tesed
m tfee leiraXos# ^e®ld.t» of tn® gm©r©s0.
Istgyifi'gatiiB Qf §'^et^i'l«a*figeie A®id>
Sixtf-tiif-ea gsaas |0*§ mis} ©f S-ae't&yl*'2--f«3?oie
^Id was di#s©l¥«d la ^0 ©©•. #f aafefd^oiw m&thfl ,a,lmiiot and
tli@ solatia, ms sat^JO'sted wltli ^ydso-gem gas, After
standiaf me:^ night tke alsotel wm mmm^ «id©r dt®iai«!ied
pmm&wm aad the ar#»idml mtes wms f:m0ti#Bat@d %m wmmmp
f!i#re wm oMaiaed m g, of metliyl i-jaetfefl-S-fuBoat© boillmg
mt EOl-^ S, at atttsspfesi'le prnrnn^^m l&ls la 86^ of t!i®
tli«0Mti^«il aeotmt.
— 48 -
grmm {0*12 sol#) of ©etbyl §-"a#tfe|rl-2-
f^-oatt was -sfeak@a 34 Moats, is s solutioa ©©ataialag SO #©•
of ©t&yl alOQb©!, €5 g.. (0,1S' aele) of s@re«rie aestate, aa<l
800 se, 0f distilled mter. At tbe ©ad of ttiis tiae tli# soln*
tlon was filter^ aad ms&ed witfe seires'al qasuatitl©#. of al
cohol.
file exttd# a®f©sorial thus ©l3taift#i i®,« sti8*p@-aded ta
iOO 0Q, 0f eoM v&teis m& ioiiii©-f>©tssgl«iB Iodide solutic® m.m
ad<ls4 until no »©r® todia© m.m .aft#f se»ml minutes*
fk® exQm& iodise *aa *lth «o«iiti« tbiostilfat® m& t^®
mixtmr# etkes* Aftei* m»ming tli® ether, tliare *a,«t
•©•fetaia@4 30 §* ©f «et&fl .i-»ffie'thfl*4-'ldao-a-fuso:ste» fliis was:
80^ of tlie theosstical tfter^ two arfstalUmtlosi'®
ixm astlifl aloo^ol tbe »ltiag point ms ©onstajat at -SS® 0*
ami. . as io*d fm i i , m.m,
f^mdi i, 38.,.®.,. 38»/sg.*
pyaeafatleB. of. Simethfl. :i^&>.*M»ttol«>A^,4«.»'dtftt?yl*am..g».-'
di#ar^3eylatq>
Seveifal t^ial-a mBm iiade to ©aiipl# a^thyl S-metfefl-
4-i©do-3«-fiiaroa.te with oopi®.!- p©»i«r at at»iph«iris
a»d a t@spe-iatiiJ?® ®f aljout 300® Q» fTae@s tto.at w®t@ mlxmst
imposBihM to isolat# tlit ©aly msult of this -method*
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so -a©@toacetate,. lOB g. (1 aole) of ae^ti© a^irfiydrlfie., aad li7 g,
(1 aole-) .©f potass!tta ati©el»t.t« ia a 1-11.tey rom-d-lstittoasd
flatk fitted lAtk s r®fl» @0a4eBs©r was heated two Itijurs in
a *at®rfls® aixtars mm -slloired to mot aad ms'dis-
s#lire<i iB mt#r. fb© wster #«l:ttttoii ms etlier-extraet## aad
thea tlie etber solutiss mm treated wltlt sodiM ©ax'boiiat# so-
Imtioa. fill® mtutim ms a-eitifled iritb #oM dilate atil-
ftmiQ mid mi. et&e3r-*#EtTm@tei«. fli« «th®r selmtios was 4ri©4
mm soiita. sulfate m4. distilled mtll the tbex-
momt€s 3Kgtst#f#d 100® at 30 !»• pressufe, fMe jfeildtM im
ths flasfe was thmm with M g. of oopper p©Mef and
lieat@4 to Bm * 3®® S, im QW^s to tf.eearfeox:ylat® t!i@ soM.
Aft#! dsea^feoxylatioa tlie ^emtmiag »t#ylal was distilled
aadsr- dlnialsbed ptm&me* ?fe§ &s©ti©a tjelling at 83-SS® 0.
at 6 TO. pireatur®, or at 14 aa# was eittifl
^tbfl-^faarost®* f&@ fieM was If g, *«.« 10^ of tb@
t&«0J@ ttQal »©mtw
Met&od.3t fmm%7 gtay»® of s«diM was r@aot«d with ©tHyl
•a©®t©a9®tate. (62) la the ^j«tal mmnm to fo-rm the sodit»
salt, fals sodtcm amlt was tli#B @©i^l®d toy mmms of iodise
ai»a tms® wm obtaiatd iO g, of cymd© dlttlifl dia©©to»»-
oimt#. liie ©TOd$ di@tlifl dta^©tosa0®liiat@ f?oa tli®
j*im ms dissolved Im lOO' ©©*• ©f coaaentmted tmlftirl© aeid*
©ooled, and allowed to stand ofey migHt. ffie next day
- SI -
aixttir© was pourad witfc stirring iato B «f iee-wat#^.
fh% mfcsr solution was ©tjb©^ ©xtrsotud ant tfee
was •tymit Qmloltm Ifter areaoyal t^t efeer,
%h& pra4aot mm distilled «ciex dlalBl#&e4 p?e«««rs,. and %hm
fm&tlm boiliiig 0, at SO aa., was e©lle©t@d, fh#.r®
«sii ©Mai»e4 3S g. ©f dt^tkyl 2|».i-it»thifl-3t4-tt©mrte03iylitte*
fMs' @ste:r tbea tJeemtea *lta M g, #f p©tas»tm ifaroxldte
ia 3S§ m* af etfeer sa€ te^wght to tbe Ijolllug -poiat*
Aftsr fsa^Tlug tb,« fey it.sttllatlao, tite ««lt <lis-
solved tB water and a©i(iifl©4 witk hf^o^ltlarto acid to gl^e
gs g-, 0f 2,5-aiaet&yl-3,4 didsf'feoxflis fb® field ma
pm«ti0allf Qmstltatlve. ftiis aol€ plasei. Is m spigela.l
fls®k laving m ©alasg^d si,4© 10 g, @f ©sppty f©w<lex ww
aa,d tb.® flaak b@at«€ tm s aetal featli natil daearfeoxy-
latios was eoaplete, fbe a©44,. wbteli «»bll®ed Into
•st4e aria of the flasfc# wmB MBmXmd In sod^w Uf4s-midB md
r@p?re0ipitate€ hf asMlfylag. ftiew -mm ©fetaiaed 13.§ g. of
3,S-diast&fl-3*fwol0 aold mltiag 113*134® 0- fhU was 71f
of tie t&eo-j©tl0al mmmt* Tb# aold fxos %m of thm ^b&m
«iss mn dlssolwd in 3^00 ©o* of «ali7^o«s ©tfeyl aloobol amd
mtuyated wtth Ufdm§®m. o&lori(l© ga®, AftmT staadiag o¥'®y Blg&t» tfe@ aMofeol mm a&d the prodTOt Alstillet
mier 4i:iai,slslie€ pTmmm* flitfe mm obtalssA 38 g. of ©tbyl
B,-i^dlmethfl--3-f®roat@ "feolllag 8S»8SP Q* at 6 m», pr@ssiar®»
?bis mm of tSis eieoi^-tlo-al aaotait.
:-af t%tmt 3*,§'*0"l.»-feh.'rl*»4-»io<lo*.3'-'furoat#»
^ •S«'r©mt©®m gmm CO*!, sol#) of ©ttiyl S«i
fiitoats ms witli SO g. (O^li »®le) of a@'ir@i3api#
•etsta i» i^©©b©l-^mt#s aelatioa^. Oyystali app#,axed in !§•
slaiites Init tie mmotim wm allowed t© simte 12 bo-urs^, fh©ra
w» ofetaiaed 4S g. -of t^li® sfmde ^renftal. This pieotust km
smspeaiet 4a a lites of mt©f m<& treat® d witli a s©2.«ti€ai of
Zf g» mole) o.f i©4lae SO g. (0-. 3 ml%) of potas-
st« ioAidt im ISO oo* of The mmtlm uixtm^ m.M
wllfe sotl« thi©gslfaft©f ©tftsf #xtm0ts€» asd the
et&er re-»¥#d. f!i.e @o3lia o"b'talfi®4 *a» ©obtaaiaat®#
with inorgMio mmmy f.k®i>@foy©, th&.
oiigaaie ms dtsiolwi !» petTOletia Afteit
removal of tlii# «ol¥@at» %h& ttiifl g,t-«dlTOtlifl-'4-l©d0-^
fiiroate mm arystalli.seA fmm sstMyl alo^oStol. fh&Tm m& o^>-
tslned 31 g» BKlttng 4S-43® S-. fhin was fl$> of %M ttoofet-
toal aaomt.,
0al©*«i for I» 4S.a^
fomd|, 1, 43«flt 4s*s0»
4.4* "-^dtf igyl*
glefi©» gsaas (0,Q3f ®ol.e| of ethyl 3,S-dla©tlifl-*4-
lodo-s-fia^oat© ms &@at#d to 310®' c. (omtsl^le trnmpmntrnte)
Si -
with IQ ©f mprn^ powdfer tm t/'Z Tb® iuslfe
tare tm& to aa liigfe ms 300® 0, fha mmQttm mm _
©0Ole4^ a^ii^©t®€ witli efltgy,, mi. ftlt©i?@d. flm #•!&©?• •was
:r$M.ye€ aad thm prosaist s.2f»taii.l®e4 fi-®* aleeltoi.. ftmm
Was. ©Malaei 3.S g. of i,»g«,Sj5» %et3raiwt%l-3,3*-dliiaxfe©«-
tfaoxy-^4,4*'-4if uryl »ltisg Si-Sg*S®, f&ls ms §S^ ©f tlie
aftef tw© f«3?t!i©i' i'sdjpf'stahlmtlma
from sfeyl .alo©li©l» S&lMm'4. 1»f a smtoiiiatlQat mt€-:rial
aelted 81,S-8a..S^ 0.
.M:al« Oalo*d for s S, S4.€?j S, S.^*
Fom4t 0» 64»^| H, S»i6«
S&BQBif of .2*2*
fb& pmvl&mlf feseri^t mt&T wms sapoalfle^ witfe.
strsBg alQefeoli^ p®%ass4» tte mmm4,
th& msidm t3r#at@4 «lt;& mtsr# iffl4 f#mr©d tato » ieaF-^yto©-
®lil0rls aeii aixtMoc©, Itoe regultiitg a®14 was- eryatalltsefi
several %lmm fmm aJtesbol and aeit®-4 ^0--281^ 0. flie f-l®ld
wm pmQtlQAl giaaatltati¥®»
M^mt3csXi'smttm. eqmlmX-en.t, for XW*0
WQm&g 1 ,»2
ao&si-* gs-ls'-i 0 * fe0'*40i bf
F<jm4i G# SS..80; H, S»34.
- S4 -
atwisf
1* A aWbey of mv ©#ap@mis la tli® Mtmf% s@3ri#s
lair® mte f#p©3?t®i,
3. jmeiatatal to tli.6 i'e&stiob !©• f#3m tte
tlte'flsj a ©f til® »aetlvt*fef ©f ff0» .telog@a« attsshed
to til# furs® irtog teas !»©» sa4@« fM mml s@iPl®a B:r^ 0,1
teis be#m to applr« Iegati¥@ iaerssJ© tfct®
aattvity of tli# irnXo^m In o®€@r o# dfe#»sgti^ ©ffaet are? •
-ClOOQ^g^ OOOHg* Oae of gfotaps In at posttica
a4Ja.0sat- to -m h&togmn gxmtlf taefeasea its . fh^m
g3?©ap0 fteii- la a fmm a S-lml^gsa la©reas-g Its
aetl'Tltf m^sre thaa ife®ii in a 4-p©stttofi*
S. J® aH: attempt to find a difuryl whisH mjiild
mh&m tis diffceiifl type of Isose'^lsa,, 3,i«t§,5*'(--t®'fcmMtiiFl'-'
a0i# feas Im^n prepajred.
Optleal o» ills mwp&mA will %# of imtmmt %M
elaeslilatisg tl© of %hB fmm ring*
** ss ***
mmmsmn
.iqg,# 6^4 { M f Z ) . ,
a. Mill aS'i Mnnin^t M* Agm€>-^ 188 (1891),
S» liXl »d lartsliora. Sex*-* lt»: 448 43.SSS),
4. mter^ig:, gliem* .ssg,**' -clsai),
§• B-oe-9®&#a aad ooworlcera, #• @i#a* S©©*# |f) Mt ?4f (1899); Em* SBS- Im-* lit,3.® (lS9i).
8 miirnt i- ja- im&- M*
t« s©ete-t3tger>. iritigfe gat.» '
s» s®s#l©a$,. j. 1 . 0fa^a» s8s.»* iwmq)*
9. S^., 43 a»BS), jm*
10* s©©s®te« am Wetm^ MM-' * m« 3-^33 (itsl),
11. (%) !• ites. 8i0 (ism)| aaa,, a6l»' 37® 113®5| '<
Cto) iil^B aat Ijig&t, te#.. » §Q.> 833 C3.SS2.)*
12,» m0w?©|i|'&fmis«e, am iiott#, c^gi>» y®a4,.. 18.0> t93
13, I. FisiieT, £. Qhm* a €)a ftS ClSSQ)*
14. tow* 'g. "gbeei-. i#a», M« tliOe).
1§, loumu, dufmlsse, aad tea* £* 1:4 •( 192? i.
16. Fri«M., It, mS (IS8S|...
17. rnimm aM frigM, mm» §m.'* M* C19S1).
«• 56 1"
i?m.' HlXl'asd M* SISS- I** (ISiS).
IS, ailaan a»6 fool#f» impaMitled*
3.9. Ca) l.A- loies, j,, §, gf (108S).
.(fej iixBm- i-# l.A« C188S),,
(e) gM§* J., J,l?:e (1806),
, (t) jg, gg cli8?5.
(#) ^ss. . , ,§is* y..1.0<473 fl8'8'8) -»
I f ) . . . < l 8 S t ) ,
20» qllmis and irlght., j, jg,* .bss* -ss»» mt 3s4§ 13.930)»
21. ailnaii foimg, s22.*# m* c1ss4).
St, lonareii^ Dttfrals®#, aii4 <JeIsM©a, 4aia.. eMs««7» S Cli2?)»
2S, 0.. F, f«fcrd, £, gsg.,* 181« 22Qf US2S>.
24. Sidles-* geg* $m»* SIE*# li#
as. otiimM i»d lyifbt, j, Sss* l2l*» M* m. Amm a»4 fm&f QMm.^ IB^ mi. (1953),
a?, lar^ais, Mti* oMa, 4* iS3 Cl»5).
Bi, ft4»k®s.,., lee* tgmy> Q&im-., > Ci9Sl|.
29.- loads gad Sitaakl., gMya* # |M. i&M* i44^ iOl cisaf)!
S>* Wmmsff.. B0S. » 490 Cltll)..
sx* fttts . «d sclliota.efe® '., | .#. hgf. |3.si4)»
sg, plao.s|| aad all3iiil:» lli, ssbs .. M» t,. m
33-- i*, t, «l cld3-#.,
m. selefcstats* g#iy» ema« j4» ..aes
r- m -
m» a. m'-QUml Thesis, Iowa Slat® College, 1933,
36. %* 1. Smi'taert B©@tsml f!ieii:l®,"'lewt State 0oli«g©i» 1633.
3f , staals. f an.d adaat , Qimu* SMS."* '{WW)*
m> I©Iv> qhim. MSa» M* (1930).
39. A^mmm -m€ Soil#?* £, Jg. ilSS* iSS.*»- .Jt# 3.889
40. slieptat lla«l©*, aad MMmm-t £» M* slss* ji£** m» SOBS (19®).- ^ •
41. Sill •aa:i S«ag®s» 4a* Mat*« 2|.* 13-5 (1S85)*
42» StlsaA ana, frlgHt, 1. (ISSS).
4i. H«ly. sMs.. M§M*.S^- (18S2),
44. Hill MQkmmt 3Sa C iSiT).
E. J, fasdteir^al,. BQStoml f&«si4s# lam Stat® 0oll©ge, ism,
46. ismrr* iss. , M* *493 cmi|.
4f. ailoau, BmtmTt. and lIS* SMl»* §1* .aas2|.
Prlmte- fros J, Jotoson t© D?* a. ?• iflgbt,
49. §il a».t Slid Siiit&, B@s« ISSI.- SMfl-• S# C1S32). '
50, eetefesteto. miw* m%m» s- {19^}*
Sl^ 800tt aat Joiiiiscsa, £, Cfeea. i.®e>« Mm 3SS3 (1922).
Sa, fiiorr» II, S86i C18S4).