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Retrospective Theses and Dissertations Iowa State University Capstones, Theses andDissertations
1938
Amino and hydroxy derivatives of dibenzofuranLee Cannon CheneyIowa State College
Follow this and additional works at: https://lib.dr.iastate.edu/rtd
Part of the Organic Chemistry Commons
This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State UniversityDigital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State UniversityDigital Repository. For more information, please contact [email protected].
Recommended CitationCheney, Lee Cannon, "Amino and hydroxy derivatives of dibenzofuran " (1938). Retrospective Theses and Dissertations. 13382.https://lib.dr.iastate.edu/rtd/13382
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DibroiHimtion of 4,S-.Mhjdro:^iifeg^io:jte*affl .« t&
DibTOsd.«ation of 4-Hydroxy~6-'m0th,oxyiateBa©fai"aa » » » St
Metbylation of 1,5-Dibrofflo-4-li3rdroxy-@~ aetbosydlbensofuraa St
Preparation of 4,6-J3iamiaodibenBofuraa • » •••*»*, fS
Preparation of the Picrat® ®f dibenz-ofuran » 84
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S»le« for fewmelatttT® i* | » Chea* S6e«* 47» .545, (19£5l7* • .
(5) ©Jaaa and fsa d®r fal, R»c. tym?» obi»«« §g. 26S CliiS). (4) Qilfflstt, «0rg3.nic Chmlgtiy*, John Wiley mi Sons Ine#^
i®w lork, 1958, p, 1Q76. {S| mm I* fhATm&ml,. 185
- s -
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I. Dibenzofuran II. Phenanthrene
hv O r" vH
III. Morphine
aetioo. It was liopsd tt*t ttsmigii pl^siolofi^eal
tests fe vart^ias iifcaoiofiama igriwtiw#, soa«
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( 7} l«y®8, Thesis, I©wa Stats 0»llage, ItM, C 8/ faa%B, !«*•, feotoml Ms»ertati«», lorn. 8%at« Odllegei, lSf6» ( 9) VaaSss, F#B*g &»eto3?al Mssartatioa, Iowa Stat® 0oll®f% ISM. (in) Kirkpatrlck, Doctoral Dissertation, Iowa -State College, X95S. {11) Saith, &»W,f Doctoral Bisse 'tatioii, Iowa Stats Goll®gQ, 19S6. (If) Di^cteral M»s«Ptatlon, l«*a State ISSf* (is) Parker, Soctoral Dissertation, Iowa State College, 19S7, (U) rnimm ^nd Ztymg, £, M* Si®*# M» ^415 Cl«84)* (If) Oilmo sai I&mg, IMA.. £, llfl (1« .
whieli f«^8.s #Mala»i fef aetlifia.'b-
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dlb«»so-ftt»a «•§••.}, 4, i~a4aetl»^ilb«a»cfttffaB#
\lg Sf •3/
IV. 4,5—Phenanthrylene V. 4,5-Phenanthridine Oxide Oxide
-tela© «ad hydroxy derivatives -svero cho=5®a l>ocaxs6» ef thair iaberent
ability to aetivate the aromatic TW#lj®s(a* ?h» 0©*fctmds were also
to In# a«bmitt©d for pharsiacologieai t#»t «at a ps^ew of «s«-
ftft fflsslgesics, coupled with the of ffSTisti#' p^fiological'
f»| ftes# pharia'dcological tBsts -sssr© carried otat In the labortt-ori^s of Parlce, Da '/is hpA Goi^panjr tbro^jgh the eourtesj of X/r. Dox and Dr. Bj^ater of that cospaM^,
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(17) This (18) Unpublished work by Mr, A, L. Jacoby, this laboratory. (19) SilwaRj, Bywate*, and F»rk©r, £» S» ClSSS). (20) Gilzaan, Brown, Bywater, and Kirkpatrick, J, M* 0!ms* So®*»
^ (1954), (gl) M^er and Krieger, Bjr», 1659 (ISgS). (tS) Boraclie &ad Sehaekn, Ber.. Sf. £498 ClS81)» (2S) lirkptttriek sad Fartor, £* Ohm, gge<.» 11^8 (ISSfi). (24) Unpublished work by Mr. Jack Swislowelqr, this laboratory.
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of tfe« inMffereat #»yg«a s 'ia' th# TO^pliia®-
M® r#searetoi®s »a aathylatorphaael (M} (St), » i^bataajea whiek t® •
ia ^9 iinal step of the att&yiati^a ®f wrpliia®
Coir eod«ia»|» Oxidation of acQtylmorphanol followed by hydrolysis
OCH3
VI, Methylmorphenol
im) foBgeriehtea, Bg£., ^ tm Cl»i7)| m$ (18iS)| m ' 5Sg (1900).
CSi) ®LlJBan, "Orgaois Clt@j»48t®y»|,. JFelw Sll . S®as' Inc.^, New lork, 195a, p. 3, ?.
VII. Morphenolquinone
St -
ia of the .©yaage-.^^. a&*ph^«slq«iwsii»
littofc is sls«st M 4,5-flie«fikiith3ryl®Be &xlA® de*lwtiw»
,S© far, these degradation pyoSttets imm all : synthetic
&p-pwmeh*, S»T®rih«les!S, fb« llkeiiho#d «,f Mttkisf t8»i«tlier tfe# 1-
mA •9»posiM.mm of ail>«»so'-fara» hy im&m «f « bridf®
f®r .sywlhiesis of 4*5-pli«iiatstferyl«B© mxi4m fin4s sttfp»rt
©f *a#,lofy ia literature,
fel^melsar hmm &«« pr@ptr«d tbmagli thm''
at«a ©f ih@ -vmrnM-lm i?«©tl©a i reia tfet eoafs-
ittwiwifta • til® lAatega ©f s tw^ew^boa eh&ia»
in 1911, ssearsi «««Qth»»»q:tii»©a@ .(OS) i«
»e^«t tmmMng mtM-mmo «ith ©xiayl -©lioyide ia
tb@ fTOSsaee ®f aJLtwimm eKlorfde* #«® .mttoansie m&M ms al»©
t&TmeA ia r#«,ctio»» lAter he prepaid %?-cte®t%'lpii©iian-'
tttr^aqBiaoas tfQ) fyoa ^s»i wEslyl
o=c—c-o COOH
M^erMaa and Zsuffa, Ber*. 44, ^04^ 856 (1911). (fO) Is;., ii* 1455 (mi) J 4^ 1186 (19lg)j
11,198(1913).
<» SB
m^v si*|:la.i' e©n4itl#ii#.# . ffee yt@ld «f ^--qaiaoo® «g
(ilf&eat© «eM feeiag fuaaai alBJittawesasly im tS»^l fmatity*
(cod). H,c
Z Ala.
^ tb®- hm^f iaataai M @3tp@et®d
Statt<liaf»r »4 ®0**©3pk«*® isi©l,«'fc®i th® mmmQ^irm
M»(l-««tli©3Ey-4Hia.|tothoyl)' i» 60 fimM wh.« i-»«®ttoi3Pi»i5litfett-
lea®, ©»lyi. elti#-S't#e mA siwiawi ofci4>rf.fe *»r© f?l,|
OCHj OCM3
l0t.a trae© ©f g-«-tjiBooe s»B|a be- i#©lst«d- -fim te® r@».©tiflB
i®&g«r »i ©irf- Iff) ©btained i-4 g* ®f g,7»»^K®tfe;03^»
ae«aaphth»®s«l»a« trm- .10 g« ©f f »7»iljBet!»3^mapl(ttele» %
(fl) §UtvM:^r, Schl©nk»,, m€ a^Vm Ofata--.: 4gt».. i,, $U (1921),
(7®) l^#s»r an<3 Gad, Ben* C3.ttf|».
ia tlie fri®d^-»®raftS' r«&e-tt®a*
m®xp@ct#51y, th« prejpoadei'aBt protoct ffovei t® hm 7HI«IIJ&3^*
0*«&pht^fwpaii»i.,:2-^©a%. regalttaf ttosmffe clesmga of oil® ©f
tli® *«tl»aiy3. -gwsap®*
l«l.ta«aT^ek*» syattesis ©f pym-ns ffS) is a •»»-.
©f iatiw&lsealar ooiMi«a»ftti©a tliTO«gh tti# frt@4el«8'raft»
paseM«a* Wms. "ttie se4€ etterlie ®f t,S»*'W.:fh®^l.«&«<ilae«ti#
s#ti »s tr«t«d aiwlnm at # tMfty »iaat«s
•Caltn&bTOtea® m ®©lirent|., sa %0> yi«M «f XKi-^"l^fl«^x5W3P®W8.
mm is©ia*to€« mm ©btaiaed ia a alml.lfti' ««aer
fiew mM if4) , fk& yiali «s ii©t *eatioa®€ la
tl® psteat*
HO
•OH
o=c c=o
(fS| <74)
Wstiseabeek, IfS (1915). rnmm ^patsat t ,SW /%il.. jfi, 199 (ISIO)
A mmmt- nynthm lB #f ' Interest mm m4wt@A
hj Sawaa moA (?i)» ^-Benzohyd-j^lglmtayie. acli ehlos'iiit
ms lati«»©lecial.ayl|f omAm&mi. wltlj alMi-aam sKlorli©
t,t-Mlete-i:,t,t,10,H,lf«hex«}iyar©»-S,4-beagpli«nma%hr©8e,
«a int03E»)Cti.at® -m a aw s^tli®tlc st>tite t© S^i-toaspheaantbrwae,.
Tha yi®M »a» Si*?! •»$ thesystleal*.
Bi# Inaction C?'®) has beea stteeessfidly tjssd f©r
t&@ sym%fa»ti# of slag where applics-feieas <jf'
few® falJM, Im §l»em9T-®&
that t>i8 -e^oawaaatiuB ;ppotoei ^-»]^«^3.frofi©sle «#t«r msi
oxalic »8t#r i» ©oairart®# mnmn' &%BA sulfuric mlA ial^ the
iliBStw ®f iadarHs-l,?-ii.fii&steoj^lle mi4^- Von Auwers and "
ZAlCls
(75) a»®& and Josh^i, •£#, ghcfe See.»« 4#S |lfSS| (76) l»af«alt, Coinpt. 2?«4>, ISt. nimMfZ
- 4t -
*^o COOR— •9
l^Her iff) Im lttS.|> t&« B-eagatjlt r»fteti.oa
to tk« Bert Mfli«r hmot^g »»mt9 %h» aal^ctei<i@ ©f S., 4
iilfiroaaphttesl«a#«l,f»aiaaitooxyli'e •aieid*. fm mra
ttes««- «ad a«r®»©rf ;C7t) Smom%mt&i ttot tM.® eyelimtisa
m§ ttp^lXmhlm to tke .asii,#' fer tfe«' ajnthmia of
IMjlfatielsfti* M|4F©e«i4K»is, e»§*, St.4-dil^4Kjpli«iayffithr0a«»l,,f»
dlearboxylie acid fhe®# yleMs ar@ alaost oa«atit»«*
tiv®» It i# reasoa&bl® t# ®xf»ct t?!# Be^aalt rmmtiou te fe«
eqmlly mppllemble I© th® ep-sll^tloia of m aryl»®«tie asid,,
proirid«i that » si»~a«be3?M riag e-ao im
l8lt#sobock C?5) tsmafos?*®d S,g*«^ali«l^ioMphe^l iat®
a ph«Mathir®«e a®riimtiv© %• »aat ®f th« %w®©i» ooadMaistloa*
Sabsaswaat dseldatieo prodrofti « SOJI .yieM ©f pk»Baathr©itwstalno«®»
d»finl.t«1.y ®gt8ljll»M.sf tlte fowatiea of the birfLif®,*,
CTTI w,a Iwmm ani MoHer,. £« lOf. 114 |fS| lles#r m& Herahberg, £*, gh«» ^2.«» i8Sl {1S55K
H—C-COOR ^C-COO«
—COOR
00«
- 4S -
KCN HOH CrO,
Aa mmpln ©f eyclizatlon bf direct water
©liffliafttion i® B»#o^e*s syntiiesis of t,8- .ihyiro:^elirf««iie
(ft) from .dtiifi»tflph.ar^lm-ucoaic acid,- fke coBi«n3»tioB
COOH
HOOC
CCHaCO)^ HzSO
eitMAicli®#, ^ mMimg ^ropwise S «1» of eowsf^atrat© salfttrie scli
iat© m lc»-e®l^ «l«tlon of th® mmmXt aeifi la ® '
of aeetle. -sBi^arlji©* • t ^i-BiaegtoxycliiTseo® 'm» rts-tslnea
pro«ptlf ia yi®M. k mooVn imlysls ftirai-shsd the
d@sir®sl t.,|Uiiiyii'03?ychr5''sen©»
Wmri&MB TOdlficatioBs of th» .Bl»eliE®r»S®pi«*»lstt r®aefcioa
(SO) Mav® t^mA eo»sii«»abl« spi^i-eatiott .i® th® syatb««is of
(79) Bmmern^f fe., 151 (1911). CtO) Bi«0lil@r and Hapl^^ekl-, .lgr*f S*' 5^0® (MfS)»
•» 44 •»
ts®^«laolin® aSksioid® {•#!.),• :pii®aaath?idia© a©riTatiir®g,., wMcb
ooutsi# aot «E^y m leo-tmiaolia# rl»i bat tb® fniaoMa®
mtol&mf tay«' imm pf sfimmi -If th@ «»a® r^aotloa* lergMi aai fall»
{$t} ^MTtea that sis© lilgli®i* la?»0«
lof« j, e^d %«• ia yi«Ms tvm ^t^lmAnQhlphmyltt
by pM>mphatm exyeitklsTLAB as tli« e©ad«a#laf a..f»»t« '
la it09,. fietst tui S»» »jatii@«i»«i pepft-rerise (SS), om
of tliB #|5i* alkal©ld#, apflicatloa ©f tit® Bia©hl»r»Ma^les»-.
alfkt p«»oti.!©a* Bwtey and «o-w©i*#fs Ci4),, la ItlS, pabllslidA
inprm^A g«a»yal senditions fdr tk® frapaffttiea of isoq.ainolltt»s
bj tlAi reaction, ilac« that tla%, « mrl«ty ©f eoapl®* allea- .
loifls have b@®» freptpsd by the judieisa® «sl®otl©» «f
aai eoaiaaaii^ Sfaatg* fh# temperfttur® soi ti»» mi-iabjes als©
i»v® a |sr0f©a»4 «ff®et m tlie mmmes of tfee reactlea# la mm
fSil Bolllas, ^Synthesis of lit?©g©H liag 0®®po«nig», Srtt»gt B®n« liiffiited, London, 3.9?4, p, ?510,
t»t) ifergMi mA mi#, £• mm» B»c.. 1981^ f447} l&St |ti| Pietet and Gams, jSgr,, ^ 2945 (1909). |f4| Deek®r 'aaA co««o*k«rs, Jyro** WS» Sti (1.93.?) •
- 4S -
fliosptert^- «t mm fesa- •fsf*3*ed
mmmmtal wfe« pfeosflieKis j)«at#xiis m& phospi^rm «3^0lal#riae
hava fadlsi to' afford any l««ie la ISES, fer
MJU®a &M Iworfcla fSS) syailiasiiied i,S«4iii»tfe©:^aipoi^M»« .i»
yl«M fey « ®i4oi»f0» solutioa #f tli® c«rr«8potta-
lag talis Witt at mm teapsrmtar® ter
iweaty-fftttr tew#-*. Schlitli.,#?*# #<apgratli?®3.|r repeat
©f pukstelB® mthsw fSSj i» »• -elassiesi e3B»pl® «f •ft®
atyaatefe®®# «s# ©f plBsplieras 'featroMLoyli# «s a «©a4®asi-nf
agwt i» th© »a-etlea.
be ©f -ralBe la «stl»atliif
theyeiattTO mm ••!%& irtdeh a partiealar ^elisRtioa eaa to®
«!|j@e'ted i© ta-fc® fla.#©» An h«0 teaa -aai® te gl««a
pertiaaat ob«®if«tl©«» froa t&« lltemtwr®*
aad Brad»ber' •(§?) ii#o®v#refl t!»t %o
t&m m .slag «i il» im#
pr©*^^ by .a.r»r4tt aattexrl grwap ,sit«at«a a% tli« 4-p0#ltioB«
oa #f wfestitwted Ijefiieytbaaaulo
fteida to prodw}® corrsspoadlnf «athmq«lao«©i ^ M»» aad
mh-mvk«m {SM, SSt m} tfcat -saii
fSS) iSulland and Howarth, J. Gham, Sac., 19n8» 581, JIM# C«S) Selilittl©3r, M.Y, eka* Aete, J5, S«1 (10Sg), (8T| Fl®ser aa« SHL» |ta^» M» (ItM). (88; Graves and A4&m, iMd,, H439 (19R5). (89) iai?dft®ra®^ Adaas, ibid.. 45, S455 (19SS), (90) Ja®6b»©a «ad Mass, Ibid.. ^ISIS {lfS4).
m "
•passa-4i3p®e%inf attsehfti mtte te tfei® poei^a of
ootta«asfttloa hi»4®»i tl.« «lo.gat©, 0»s¥ers#ly, erfcho- ftad
diMettag gmvps ia tli©. »g-fe&o aai positions %o
%M% Et ifMch edai@tt»stioa. m$ to tak# #&e«
itSitad ti» cj«li8»tl#»*
la th@ #fattli0gis ef hy rf.ag
cl&sfflp®,. lorgia «4 CtB) a5t«4 tlmt tlie pmnmrn &f th#
aftfati-r© 'iiitso g»ap sspiously l^Mte tfe© Bisoliley-
iP#setio» piwi€«i- tfeat p^ap Wei's attaehei to th«
jd-ng- fttl>#titmt®i ia th» «^eMmtlea«- tfe^r stt»fts
te i^th»aize i«>tfe«l>*iae^ (fl), CaHew, IMlsaifl, %M Wmm-Tth
co^aelti^M that »•» «iostii« of tto« isoiitilao-liae i-iag is
i«P@Mdsat m the pf#B@a#e ©f « ©tttsagly ^-^treeti-rst gf^iap la tfe®
£»po.siti©tt •to tJat at wfeiefe aoa-ieasstioa is to take plae®*.» «
Tk<w also fewd tl»t a» g^g^lrecting fte^^ plms mM t@ th»
•sa^ii ®m<ft«ttefttloa ia to tmice flaee ©pewtly
ioMMted the Bi#elii®r-»«ple?slstl fsemstlom,
Satlewsj Ctt) has foiated oat tfeat th« ©a#® of • ®»b«ti.t'a-
ti©a ia m ftsottatie .aaelsttt by tti® frl«dsi~CTafts peaetios is
•ei^aaceii by th® i»t:w>iaeti©a of pe-fltive »tib®titw«Bt8,, m
tlie di»etligriawiao -aad aethoayl gs®up»»
(91) GalMwg Sulland, Rcmarth, £». ChSB* §2M»» i-92§m .(98) 8all®»sf, Ghm. Mm,.. IB-iT, m (WSS)*
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e6.««l®d oat -belew m iie^salt hmth mm utilimA during
aifiitloa, Md %o m&mm reactioa, effieieat stlrriiag mw
coatintied for five hmm »M,le the Mth gradttally «a«© to vmm
tmpm&imTei, ifhe aia»al* folatloa is eusteaariJ aidad to th®
stanaetts ©iiloriti® .aoititieai tbe mmm»m naa pm«tiQ®d ia tMs
m@m far tt@ sake of seaveaiene##.)
Tha wM-te i-liyd,ra2t-a#iib«i|©fttraa, i^irocKloilds tos fil.t0»d.
tff and ©ry»tallis«d imm. & X&rg& volmm ©f watsr. It irith
iTOompositioa at tke yieli wm W*$ g* er 87.5^,
toal mM* tor *» U,m, fomit W,
fto frs» S-ft^AmaiBoilbteo^fursa waat «bt»iBei by imm^simg
a tait -solatoii'sf tit® fcyifoefciffKii© Mtb sailaa «et«t®, fl» teas®
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ia %hm term mt msll pale yellow s®3ctt«», s, If4-4?S®|, iMeii
tuiMd to an osfaaf« e©l®i' ia 0©Bta„©t with th® ata©»fli»y««
teal* ealsi* fm ** ^4.14. frnmt », -Mm*
B0«i©ls® ?and Both® (3?) reperfe® a wslting point ®f tSi®
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ttB<50fi»iic« with tts pmem^mrm of Imjcmff (§4), #»« i^i« «f
papiesim bi^seli-ie' £» ISO ims 'isfB&ir® tJb@ '
yisM @f ©3El4»ti<m ^fs-^iuct (3). ?fc.e r®«tion *i3Et»r# ws e©©l«4
aero i«g;p®®« in an ice-salt t!ies»e®et#r •
wwd),, mod ©xyf©B tteo^afli mjlf^ic aei4 anii ^S8«i mmt
iRjia. 14»©l *»s BiFspt ov#i" til# auTtmrn ©f tfe# »®11 stiyj .
at swak m mte tha-t t&# teapemtar® i»# Miataiiwi liel©*' «4m mtil
a K0pitiip® tiist Its) «&0 obi*ii»8^».
llthiMs ^It w» hytoelyssi ia n fotts^lit#r beftk#? Ci0®»
teiaii jLe»-Mi4 aeii# Ifce p>rti©a' »«#• ;
awe® irllfc s»€ il#eayi«i.. 'Jl© -sih#? laywi-s wmm .
&mbt^iQd. ir. % 5&«rwll'|®j» fiaaa®!, ©«»lisd. iee i»i
&&ii @[email protected] alkali ms eoatiimsd mtil no torbiditif
Cm) tvmmttp ialX» »o> ohi»«> 47 dfl!6)» . (»S) Sila Sehaliie, £. S&e.. tOOt (lifS),
IS
to m iygiaified t© ths allt»-.-'
lia® eolutlea, an4 M-fs€>lf#€ «th»T ws» r^fwi % .fs-mtesl h«aM,»f
©a a h&t -i^ts. flie tet liquli ii&:S aetiifiM,
0®ol®a unde'r the ta,p ^th siaftki.ng, "Rw- «l»»t •M.te 4Nter€ge3Erit«>
#l!ft«ia«d|. seltiag at w«-» f©r
Mist p«rpos«#* •- 'tea- csystsllisattoB fmm |i«tf©l.ewi #tt«r
fb-,. f» 'Tf«41S| »©©&«© s«il.tiag at iOl-lSf.
fmu tfc« m%k& ifi^ep, afpreclAlifls ««omts »f • M*f
faftrll tow fe8«ii aai Its »t?«etttr« ls«» l®ea i«flalt^y
©stabllsfeei tfci«naili' Sfat&@»4t <ef# tli® e^5#i:l«^t|»
flia fltia of ^-butjrllithiwB trm ||«4Jtt4fl feroad . hm 'b^at
d©t®»in@i mpmtiMBmtallf (06) to. -mrj l>0tai@«i .§§--«§,8$, ispaad- .
iag m t&© jpaf^Mele sis%„ i» fwor &t tlie fiwly il-ri.a04'metal.
JL l»tg© emm&n ef iimAy mit lltfel«a l«eB tsswoA t© v#iy t«mr^
.ably imrmm %h& ytrnM of' astalaMoa Wie mpeactei.
®®t cm be sssTt .ia «tli«if &r4 b« ussi- i» ®it>s@o«eBt »etalatio»«»
fyoparattea. ©f Bi»>(4»»iifeQBaoftiCT|.| ti?m 4-ia.'baa8ef«jpyIaa.«8siiaB
Bpe^de
fttis aa aSaptattQB ef tli® eonpliag r®aetloa
^mmvermA by IriseiR a®# faia®r Ct?) »»d later «iee®#©f«lly
(Si:) ®.liaaa, Zoelliasi' ani Selby. km* Sh«.«. $&» ISSt (19S3),
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ftne® 0,tS g* ©f @o^>wa4 *»« fvm itm ftltmte, th»
•te'tal ms' l.«f0 f* m BS%,
MaJLm 6al©d» f©r % Si»t| I, 4m2f,* fmoAt
C, «i»l| H, €-t»*
* a£i0 . i^i»t a#tei«l3ai:tl-oo pTQw®& that M-C4-
iib®o«?fii^l) is f©3«@i i« the a«tal«tl®n -smi ©adl&Moa ©f
'dlb^gofwwa* ' .
tB Reactiea -4«M'et.lw»ifttb«»8of« laaa. Qaealyl.
I«t@ a «©latloa sf 'f+tO g# {©.OS -awi#) ©f 4-«©tij©3iy^b«»»
fiiraa m& f.® f* mxo&ss) of -oalyl eW.ori.i» ia ?S •«!» -of
©©ataiaird' la a thre^^eekad HaaS: . qalp^i. irilA
gMwar aa€ ©©auteisep with a ealeiaB ehloilia t»b% ,»»s
p^toally atii«l I.4.7 g# (2 ®ace®s#J of s^aaiaw
'B&mmgh&Wtt a#ilttoa m .le® molmS. tk® f©fteti©a. aixturs,
i&teh ms tfe« to slo* mm t© i^a 't«p@mtaps« JW%»r
t%M. r@<l-fet©im: *i3Cttti*« wm iiit% 1«»
aad seid-,. the nitrobtatsu# w# maawi
and tbe boiled »itii »<Siw l |iteos4i» 9©lati«3ai •
wd fil.t»y«i*.-" Ifete «ei<lifie&tioa th.® JElltaat#
•C§*7 f*), ss' MiMlUmM.m -fmm ««®Me wjted' mt :S?i-»S1T®
ig «
mi wm t© mM toy-
•»l»i wa.tiaf .|®4a't«''
flm &!4®d waorphous, siteli-'ittsolwbi® soJULd m&» -^tmeiea
wltfc 3. ©f acatie acid, ftm iiis- eoli filtrate was obtaia«i
!•§ f. Ci^)- •®f tetone in th© fern-
#f e0j®rl«88 3a»»ilss,'®.p« 2S4®rf
Aa^# Cslci. for Cg^H^^^Ogi 0, ?««Sj % 4*29.
f©«adi G, fft.l| H, 4,S7.
acetic-acid insoliible residue, »Mch pvomd to b@ bl^-
(4-*a%lB»3cr*l«^beniiofuroyl). trm alt?ob«B8ea@ in
for» ©f pal« yellow ae@dl«% »# p# St®®# fim yield **# S*0 g* or:
S4.6$..,
toal-*' felea# for CggHggO^t: 1,, 4#-St# Po^iiti'
0, 7t.S| 1, 4.68,
Sot a. traee of the hoped-for g^ftriLftoa® eotild b© foiiwl.
frled«l»G'imft8 Resjot^oa 4*M«tlao«'dib«azof«rma m& giblogoae»trl
Chloride
lato « #©l«ttoa of ttmB gm C®*Q6S »o3.«) of 4-®etbo:^^b«iO»«
fmrna mA. t,® g* wale) ©f ©lilor»«o«tyl ehlorii® ia 66 of
ie»-.«old Jiitrobenaan® -oostalawd ia m fla. eqjjipped with
a«el»aaieal stirrer aad coni«i,s«r, mm iatit^iaeed S,:S g» C0«06|!«f .'ipls)
of anl^am^s eijloriiQ, •&« addi.tio» ©xtsnAiag o-r«r a thl.rty-
»ii«ite interval, l^e batb ms allowed to -slowly cos# vmm
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^<lw«Wl©yle a@ld» Sa r«s«ltinf hrmmf #tiely solid was filtes
from %hm oooled solT»tio% dried;, and twice eTystelliaflri fuom
alcotiol to ff©Aie© eoloi!t®»s a&eMm of l-®tlj02alyl"-4-»etho:^il-
fei«ajKsft*»a a^M.ag stMrply at 11S®» ji@ld -©f pare eo»fe«!di-
TOs 6*4 g,. (4M) *
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a, m,&$ M, 43t.
Ryteolysig of l«l%hoaaBlylHN»«tk»xyilt>«a»fqgita
fta© grm. (0,0057 sole) ®f l<^tiM»3ialyl«4-«9tb©3jyii.l>«aofiifaa
in 45 ml, of 15 sodim i^ifwactia s®l«tioa Mt4
r©fl«x@<S ia Bm&.imth'f&r wmm Jmursm -Th& emtmts m«ire
rim®d imto a fesakei* irtltb «t®r to aak# th® total twlai
al.f "tt® r®s«ltiaf sol'stlon wa® heatad to bolHag.
filtered* -Os ^&w ^Kslii «. sAItosj' salt eTystalli.a«d e«t* •
1tti« eMlled selwtloa «»b 'M» salt m-9 mahM iritii
lee imter, smd * tot' -saliitioa Qt -sislt *«#• »eiaifl'0a. with
hyi»cWl©jde aetd t® yield 450 mg* of par®, pale y«lle* 4*m@isSmw
l-' hmmtw^l*oG»0mm&ii.e acli, »• p». ^#11' -f^Bs
alB©^l «AiM'ted m <Amgm ia- p®-iat# Gteaoaatrntsi-
stdL^ri-e a«i€ ml&rM th© keto &ciA de©p r^d» iim
t© r^tee«- ttie keto' groijp hj tti# ca.«BE8a8«a--.
mt Martin (99) mmm «g«s»wfml, the k®t© Qmygma. «mT0^n§
•CS»> lartta, ..£• mim* fee,,. Um (mm}
i f
toai-. Galed, for S, 6S.64| H, 5.?S.
Fomdi C, 66*^1. «, S,fS.
Ia ©i^er to wteM-islh coaelwstTsly tljat the etiioaralyl.
gmw liad mtmTsd th« l-|xsMtio% a soiatioB #f 0»S g» of the
fce-te *el4 S ai* ®f soiitm %(ir®xia® «d f5 of latsr
»8S te a toeii* Ten iiiilllit»r® •©£ S8 p©t»gsii» p«r« .
«ffii^saat« »©ltttioa was then sifei in sasll i»rtloag ©ver a
|)0:p1©4 ®f »iaiit»®«. -K-lut# gijlf^ie acid wm
&ic«d mtil m iistirict acid reacti-oa to was ob»erv»i.«
Aftar tolling "tee solutioa for flTs »latat#% tt »a® saA®
alkalia# wltb soil® l^itoexxde, fcilt® wms added, *»»
eoati.BW«d fw waetlier fl-r« »la«tes, sad,, finally, tlte toltttdLoo
waa filtessd aod acidified# fha eo©led »el«1dLon yl«ld«d
mgrn ©f wMt© asid, «• f» .877-17®®* A aixod «asltiag peiat
detewiiBatioa »ith .a«ttoati.e' 4HWtl» '<4-dib©azofa?ast0arbo2Qfli«'
add •stsfeiis^d ib® idtetity of tli« two acid«»
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Oae-Half g«a of 'tli® isto meld «»s di««!i9«d ia S aa,« #f
^mhol fcta^r «s .add»d trntil th© solatt.oa faiatly tuaebldt
%ha tttifeidily rmrnvmi. wttli a fm dreps of alc®lK»l». Siam-
®»S gm &i w»s nided al©»g with 0#f5.
f# ©f aodiwB aixtttr® *rss Ti^»«sly stoakea., •flac»d
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(18.,if) aaltlag «t 108-109®, «:^atsilii«tloa f»ss* th«
ta*® g®ly«t «ised tbe melting pcniat ®f tile eolorl®s» naaS#®
to lll-Mf®, i-^alatt «@a#tant ©a furtli«r t««fystalli«»
tioa» An alcstajMo solution of tfcs phewl «»s eeleyad gmm
th® aiiltl^B «f fsieasl© eMtorlde s^laM^a. A Bi»a selting palat
with aaa s«th«aMe apmimm (ISl .slM«r«i m dapressioa,
Igolatl.#n «f th® ipaawei® S^lerai^g'-4««>^orr<tlbgagefagaai
m» ae©@»pliali®i by th» f®ll®«lag .fa^ecsdares
fh® .«q«0OttB layef ©f tti® fllty&ts »s sepaimtsd fro® tJi«-
mthsT l^er, iMeh w»s «tr'aet»d M,tlt t-S|l alkali «atil
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lorf-t# 8b€ tmmS ©f ®th«jr fesfei?® flltrati-oa and «el«tlHdSitios».
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tmm W$ al<»te3., la tiie.foxa ®.f jlll aeedles, at. p* lOi-liW®*.
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late & "boiling .geltttioa ef 0,t.®S g«. C0*0®t4 «©!.«) #f pl«yi.e
aetd ill S »1* #f al.«>hol, was pwar-ad a b#43,j.i^ sal-atlos «f 0»W
g, (0,0012 mlm) of 4,i~iiaatt»^at%»B.Mf»raa Im f jA* ©f aleotol*
k ©rs-gtalliss precipitat® f©»#i l»iedlately. Boilinf
ms ©©attaasi fm m« alsat ,. after r' j.ch the Hmk w« all©*»(i
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soXutlom t© msmwe any aoiis# leidifieatloo of th®
filtrat.® farol9h»d 0»S? g« «f as aeld wlileli »as la,t®r poelti-rajy
litntifiei &b 4,8«»iiB9thog-*l.»dl1a#ttaQftti*saeiijeteexrlle aeli, »# p*
SSf-.S»S ,
the »oliS was taAr&eted CSexiile.t apparetiig
*ith ai« of aestlft acid to yl®M 0«S g. (1,0«4^) ©f
ke'tonej, a« p. SS4-8S#»
^&3.» Ofli.ed« f©?' ®# T2#1.7;| Hy. 4i»6S.<> Fo®Kslt
•c, sad m,«4| 1, 4«»I ami 4,eS,
f» &tt«»ptg to fs?sp».y0 tha «xl»® w»?© wiacesssf .
Tit§ palm yellow, mtr-mmly insoluble r®site» fr«« tlie
ae«tic*a0j,d wstraetlsn «?y0talli.s®d fyo» aiirobssaea® is the torm
©f wBTf s«ll m»®€ia.s, e« f» sbsf© S00^<, Iialysis 8li©»®<i th« '••f
c©»|io»4 % fe® M««C 4 • S«»di«ettio3g«-l.->ittjeas#fttyayl| • Th© y±.#M iras
1,1 g, of t!i© the^rotieal).
Csicd-in f®»? _70'»SS:f Bj. 4#„SS« Powidf
G, ?««®4 «ai W*mi a, 4, mmA 4»6§ ,
pgegafsMea ef
gma» C*5»l ffm at€m#| of fiaely mt MtMao
mm »asp®B<l«i in TSO «f s©fiw»-43rlei etii©r, «ai m sslutidii
of S0S i» Cl«5 »les) of n-batyl te©aii© ia tSO- idl. #f ether was
aid®d -bo th@ apMly ®tl»ei. stt»pen«i#a» Stlyrlag mm
^atiaaed for em boiir after aiditiua »s c©»pl®t«»
MMmt & altfegea the a-btttfilltliimt w»m stmimi.
thwBffc g3.s«s *O0l Into a 0.ask eeatelsiiig ISS g» (0,f75 of
4-««tl» 'ii'b«aaofar«j ilfsolvpi 4b S?X) ©f ^ther# the geatly
»tiw-ie4 #©ltttioa, wMek.secfa tamed ta eel#?, ms all«w®i
Iw rm&M memigkt &% mfim •
iftsr tew# l»i «iftp90ii, tte »@tslatio-tt
•wa« c©©l«i t© '-l# i» as feftHialt Isattij, aad bTOsine mpot ms
awept tat© tfc® <sol4 eolufeiea by a^aat ©f oitwjgsa 'bttbbllBf
thr&mgh bJ»o»ia»,, i» a gulfuflc mM msh battle, *M'©&
we wftifaei Ijy a mlem bmmar* Bapiag-the tise- &f ia.troAietl«%
ttie mm mt ollmsi to yl#e lft®y serefal
hmia a a#^t4*e col.«. •!#»%• '(M) wm$ ©fet&laei fTOm tte rei-
|ry©wi &e«®s m.a toy th© eaatlo^a
SkMltlm 0f a #at««ted s«liiti©ii toilw- MsAfite to tit#
mfiily stirr®!, ies-eold aixtwre* The etb«r tas' @xt«ct#d
witlj mMim W«alflte;»oltttloa, wasfead with-l #oiii» esirbottate
s©lwtioB| th.#« t*l@© witli wat«, fiftftilj i»i®4 ©-rer
mH-m ©i^fate,
the eilisi!' »«,» f®31«iaf. filtyfttloo,, «id tfc© dark
r#i-fe»wi oil wa» aisMllM st pj^sTOre. fb® trmtim
0t b# p» |4 0i.i g*, s©3.idlfied» It
met s mngs ©f 75-03;®.# Foils' erf§1mXHm&tt&m from p®tiro«-
l®iai {b« p» r»itefi tte© »©ltlag point to 1JL#»
te®.th.«r re«ipyst#lli»ati®a fpem tMs selTftat and algo from zlmhoX
p*
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ggei&yatioB of
la iatiaat© ai*tttr« of S g. (O.OIB racle) of 4-b»ii©*S-
»«tliD.i^«li!jsaiofiir,a» tai ® ,g« of f»ihly eeppoiae feKsBli®'
mm pl&md. la & iarg® ie®t •to'b.e, eowf^fi i^th, 150 m1» &t e&men-
trat#i i»e.oi« liyd?exid«j> aad elsctrisallf lsat«d. ia i.
Et 11 f«-i* ten i»Wf,» flie t«pe&t»p@ mn thm rti«©i to
as® »ai leX-i «@a»taat for Iid«rs:«
&e eool©fl «§• «f!«s©i, th« »lli. t»» la *
S0ft«s, m& th« ©oateate vme «xt»et©i -faiie# «itli a total wl-
»» e.t Wi »1# of ether, fte «th«r .sala-biea tried- ©f«if
g©iim salfat#, filtei»ei, «ai t© «. eaweat of
gmmom if^ogaa. eSloriie*. fh& pyeclpltatei pais ptA aaiii®
a. p* f84»f.S5 wtigtoi l*tS g», mpmmmtlmg s
jieU JS.Sf* fhe salt mm AmotmA in. feot mt#?, sb4,
feileiAiif Mworits,. ehi®fl4# «as lotyo»
#ae®i ist© tb© fiitrat#- to fora festr-^liks, .BS«iie.S3i
a.» p, tfS^fS# »3i,glit iitetloimtiom*
.?»« 4«««la©«.4-««th0^iite^aif©foma, »« f.» lOS®- mtw ob- .
in tii® f©r» mf «ao»-#iIt# mm&M-m hy aj&M.ng
hyAm^is to a kot ©f the lifa»ehl@rl«Se«
Cftlsi, for .1, f.S?« FowmSi I-, 6,5S»
• ?0
.1. «f i»SS g* (0,0094 mole) ©f 4~amliQO~S«aeth0^»
Mbmmturmi, fS ml. of ®!ir>t.---:at-bolling hy^b3?esie aeii Isf,
gr. &ad gf 'A. ©f seetie mM wm- refltaM ia a s«al
l«tli tm aiao ©a slo« e©-0liag|, 1,4 f«. (31^) of 4««*ia©-
lsytoofc»«iie, »* .p.», SSS® with iseeapogitiea,
sttt» f&« l^drobraidda wi® ii«g©l-v0i., la, 60 «!• of
hot wtsffj iigegted with Iorit«, filtered, and mw
til® iiyi»c:hS.«ri€ft ^ tSs introAaotioii of gaseow s¥l©rid«»
fii« sssll wfetts plates wi 4««lfl©-»S^layclr©ag'{iil«i2©fttr&a
eSl#rli«..iislt«i at fiS-tS#® wit!i d»e«Bf©0iti©a« fhs jleM mm
1.SS f. or fS*?^.
•®i# fr«« |ja«* im» ol..bi-d.n#4 %y Mmahrlng -salt in fcoi
mtm ismmrsl .imps &{ liy^ifoelileirt®' aeit w«r® added to prw^t
preclpit&tinf th.e with, gaterated
pota^aitw se»ltttl©a, iigsolirittf the preetpit&te by the
•sdiitiiSB of MfflioftiaB ^iroxld®, aad, fimlly, preeipitsting tte
fr«» t«s» hf c«titioiisl:y mMing SOf ae«tie acid sslatioa aatll
aH tac® of tfe e&r «f Maoaia l*i ¥aai»!i«?i. fh« alkali-
solable, ®@3l«rl«#s tte©ile« #f 4-««^w>-4-hyir®^iil«t«oftty®,» tkas
©btsiaei aeltsd at Itl.S-lSf fh« eonpsaad *»6 mt di:gk»
mlLmmS. hy aMoephmrie Qi^gam,
Ab«1.. -felea., f©r %#gOgi8 I, ?.0S. f«wadt 7.1S.
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la yefTlf@rator two fid® sol«tio» was th«a
ai€®d impmiBe to s boiling- soltttion of 75 gm of eoppey
sttlfs-le ia E,» *3.* #f water la & iistHliag fla»k
fittau «itii a «oaisa#«r* the »telte aelld *Meh st«a« dis-
tiH®€ was iis»©lved, ia 6f 3Q&tm l^*l»xld© golctl&ttj treated
with Isfit©,. flXt@p®i, aai a©iilfl®i, fh® wMte • aaeil«s mt
a«th«ttc l~toroa©-S~liydroxy-4-*#t1ioxj-ii.b«80fttaa ttes
»• p# 161-18S®, *®tglied 0*f gm (glf ylaid)# So depresaion ia
aelting fotut ms obeervad •whm tMis ooapo^iad «as aixei *itli
tl3« fewsim-tioa proiiaet 9t S<-liyiro3^*-4--ffietli»^ydib«Kaof'ai'aa*-
Pyepftysttea of l»#:roao-4«6««ii»et}»gdil3>«ggefcr
f« « fifereasly sti^ai selutioa of 2S.«i gm. {0«1 mla)
of 4,6-dl»»tho*yii'baaaoftt?a,a lo SOO of s«#tl« ae3.i was
@M»A 100 si, « mlmx solatisa ©f breaia# la aeetie
«eM« aiAl whits cir/etalit ^iip^nrsd jast fcsfoy© additioa w#
coBpl®%«» fh» rmctlnn mixtfrnm w&a tb«a stirrstl tm two kwrs
at -mm tmpmrmtnT&f wtorawpoa it w«# poia»@d iato -mm lit«r of
m&tmrg «i tto ®®iii flltarea eff# The l«bWfai©-4,,6-
s. 14T-14®,S®, was ©^tsia®d ia tS#
,yi0:M» Cry«?ialligation f-rom #ne aai oa#-»half- litem of ale©hol
prodaeti ff*4 a '7 yieli, ®f psarly plst-esi ssdltlaf
sharply at 152®. ConeentrMtioa of tli« a®tli8t» liqtior 1#€ to th#
» m »
vmmrmtj &i 5»7 g# #f proiaet s»ltiiig at 144-14?^*
Aasl,*. Gslei# By, f8»01» Br,
te.ts,
gibfoaiaa'y.aa of'
fo a aolatioa ©f S#0 g, (Q^QIM a©l.»|
4,6-4i*#tl®^iib®assfiffflp#tt ia ISO »!.• ef aeetls mi& »as
aiii4 ft#? A* mt & CS*S ,»jlar solatioB of broalas ia ae«tic
aeii# Sttwiiig «a# e©atia»d for thir saa«t@ «ft©r ad^J.iloa
was ee«plat@« Mmxt mming it ms ofeserred t'ttat whit# asadles
d^pO'Sit®!." Tha y«ll0W solttMoa '*at hmMS, ©a tti« water
batli. f©r ©at «d ®a«<-half fcois'.s fta4 «ol#A. By filteatioa,
t.,SS f, ©.f silky a««ai®8 of l,f«*iibr©Bio-*4,fW4l»®tho3^dil5«iiio»
fttrsa, »« p, 167-iSi®, mm obtaiasl#, l».s3oys^y of 0»9f g. of
fttfw fyos ths aeeti^e aeilt soimtioa gav# & total yi©14
of S,?f g, or f#,:
la»X« Calei, tm C^j^HnQOjtlrgs^ B?, 41.4S# Poiiaii
Br,
llteoaliiaM.Qa. of 4«6-Pihyilro3^iibegsofn»a
T© ft. toltttloa ®f. a#0 g* CO.Ol »le} of 4,S-dil^as*oxy~
iibwiso.ftiE'aii ill fO of asstic add was slewly atf&i |«itb
eoastsst slia xn ) 40' A, ©f a O.S awlar sol-ati©!! ©f bnjaiaa in
acstie aeli« Beeolorimtion ws inetaRtaaeotts, A preeipitat#
slmtf staaiiag mwfm^% the Beaetioa ai*-
tmm mm i»ar«d Int® fSO li, ©f waterj, aa€ erad®
«• pi tSf^SS# mith isce^titioa,,
ms f41t«p«i &tt ia fwntltatlve yi#li, tli« pirs <«sfotMid,
p» g3S-»t€1J® -^tli ie»m|«6iiiio», »a» 8.®©«^M by c^stalllia-
tioa tvm a^l«a##
A»Io foT- C^r^gO^^gt Bi-, 44»St«
By, 44.»7?.
IW.i©ae« fer %h& as«3 stra#iar» *»# obtRlB€^i hj t!»
f«3.1o«l»f Wfthylatidai
lato s golttti'i&B ©f 1»§ g* C0*06ti mla} »f
6-41ky5»^dibea»£«pa i» 16 .»!• of aeefea® eott"t»li»i la a
tbr«&^ii»sk®a .flMk, with stlirey, eorf»a#»r, m€
fww#!,' wm %*ff g* CO»QS?f of
A selaMoa &t 6#SS g* f0-*llS ml@} ©f p©ta##iM
ia $ A* #f water- ws -ttiea ftdied i»ff®d»e t© th&
r«flt«iag, selmttea. Stlrrilaf m». ©oatiaiiai tm
^rty sion:t«Sj, »ai th© rsaetion .rtxtar® wms tli«a illatsd «£tli
wttr *ni tiMrnTeAm fh« yl®M) ms
p«ri.Jl,=®€ l3y ciY»taHl®ati©a trtm ae#tle aeltf. fit® l«ag silley
ttoift firMa.l»»4|, a« p» wer® lieatioal C*iass4
•eltiag pelat d«teSB£afttl«»| wltli tim&m se.cure bj the air«et
ai.b»»laatt©a of 4t6-M»#ti«3^iil5miofttratt.
—• 82
of 4<4Ii'ii?oay-«'6««e"tli0iytfibeggofai'«a
toi « s«l«ti©s at S«M g, weile) of
wtlioayiilj^a^ofaaraa ia 8© ifl.# »f «0tte mlS. wm slowly &M&&
A* eif s ®*f aulas' solatldn of teoalas ia asette a:8i<i#
Wm&%9TlzmM.m. mms aot eon»M#ml>ls »«
qtaiTOi ts Mspei the l>»aia« rnArntm deloriess ae«tile# slowly
Mt&r atmM.ag ov^rttl^t at mtm impsm.t-mB.p th»
3?eitetloa mtxtars wm «©!«# mA to wbtftla a,l? f# «f
as. par® compoi^nd,, p».' tfwhlsh Is ir®iy prebsbly
l,S-4ibi«»« l ii?o: - -adtiioi lll»sii8efi»rsa tst* fo31m%ng
sxperimmii).*
Mai. f©r %iigO#%t- B?, Wov&At
MV-0 • 45«i0«
tethylattoB mt l*'8**dllt»ao'~4t*teiigejKr»-»6««»thiQxy^baBawf»yaa
T& m golntlea «f 0«S g, (0»{»1BS sole) #f •
l,,S-iife2m»*4-%dr0sy»-#*w#iliesyiilj«a«ift3*a» asi 4,77 g»
fO»CIS7S la'10 ai» ©f fte«toa« wm
aia«4 i3?op»l#e tsitfe' fftis-yisg a i©lTiti« &t S»55 gm (0»Uf *©1®)
©f in S «1# «f flwtef• lefliwdog m# ©®a«
tiawi for tMr%- »ia«i»s after aiMitioa wag ©®a^#t®# fb®
reg^tiea slsrfcw® ms iiltited wittt «0O of water mM
to ©fetsia « qoastitstivs fl-sii «f aethyl" e l pmimtm Mrngj
fflolorl^ss a##dle# ©f
-»#s «-
a, p» iiystallizei tr&n m&M-c aeid# i ispressiea
ia »eliisg ptiat wma ©bservei when this coapoaai ms IntimAtmXj
*txsi witk l,S-. b»»-i,6-4is!efhoxydi1»eB*ofaym«
ia<a.*- Cialcd* fmf Sr,- Boanit BTj,
41.SS,
yg8i»ya%lea 4<g*jM.aadBodi1?en^fagatt.
fl» method #f Bwe^fcorer (lOS), lAieli 1ms ^®b effsetiwlj
«tlliso4 ia »e®ai fmm l»y' fl«s«r asi «o-work«ps (lOS) fw-.
Bisfesd is 0xe®ll®at jieM*
la eaeit ef four Cariue tia'b®©, a jBlarfcarB ©f X«0 f» C0*005
©f 4,S-41fcytro5£yd.iben3ofuraii, ?.,S f. of Msttlflt®
iiss0lT®<i 1B is «1. of ^ater, azii IS ©f eottceatr«t«i: mm»
aiw i^TOseiie was 8«al©€, tb» t«b«f *er8 tfcea si Itl-
Its® is w, «|.«etric furnaco tor Msity fim eoolai
wmr& -mA thrf.ee with. m. total -rel-.
'mm ©f iW of ffe@ ©tier golatloa mm washM thftf--
®a^ly *iih iO l)f^o*lid s»lmtiofi aai th« *itii m%#f,
fha 4| ®-di8«ia©iS,t)«aofuran hyiiro-eKtorli®^ a^, p* *ifli
d@e»ipaei'&©% was frecipit'?.t«d fyea the drl®a ,sol«tio»
by list ef Sry $mmmi» hjiftfgsa elil©rlds» fh®
|1«M «a« 4»4 g. or 81^ of th® tli«or«tl€al» fim
CiOt) Bucherer, £_» prakt, Chea.. (iOll fimBT mA iao-«»rk«rs, £• SS« SSS.*# M* (Itse)!
li, 478 (19S7).
wm MwBAwmi. in fS- tot *ts-r wi
S0i4t% flltsrei p»0ip4.tat«i wltl ^®«a» hytogea
ehX«rf.<i®». Sao»-*M.t© t&mmA lAA&k s®lt©d «t tfS® wifli
feeos^sitloa*
teal. Cttlci, for G._gH3^^0S^Glg» 1, I0«i3, f»tiatft»
», M.St.
the fr»e %i-As»l»ilfewa«fa^« wa.g llberaterd bj tte
ttiiitJou ef ssB&niw to a solntida of tli® hyfe©-
eWL#rii®* tlt« e©Hpo«i crystaj-llit#! fBW ia tt»
itsm ©f colorless psi.»% ai, p# 15f®,
py0'Bi.yat4#a of the fieyate of 4-»8*M>MlttDai'b«,80fmm
late & boiling solution ©f 0,4S f.» (0«^Sff ttol®} ©f
%i«4iaai,»ito#ag©fti»i la f aleol»l mm foared a botl-
i»g s©lttti®a ef §*SS g« (0,00£4 »1«) ©f picrle aeid In t al«
of aleshel* tli« jierat# ery«t«lli!iei iasoiistely in
tfe® fom of #Maj plat##* tore alcoMl (6 al..} ws tte
^Itttioa 9m boilsd &m laisute, e®©l©i a»a filtered: to s«0«r# a
ppodaet aelttag at ^IK' with; iscosspeslttos* l#c:^®tallis«tl0a
trm.- slsshel "prcduced eM-ny r«4-b»«ii pistes, ». p* fAi® wltli
pTOSsom^ei. €#ce»poa4tlea,
=IAO"!-=6»5°7®S' ».«•«•
TomnSl U, 16.?8.
• fh@ author is .fFfsteTul to ly, f.. B. -Qmk tor thi# ttic^o-. Ijeldalil «alf»l»»
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fyaaagaMott ef S«4«^ag$to3eyitli«»f»r»
fs a «ma ®f 1,15 g, tO.OOffi a©l®| ®f S,€-ii-
^tott^iiljsatofar*® S® 10 »1» -©f si^stie aa%'-3rl«i«i mms •mM'ai. #»®
Amp «f e0»C'sat«t0d SEfl.f«Tic ®el4, Mter th® mmm ae®tl®
«alg^4r£i© hai !»•»» fey bodllug th® i»eaetloa alxtaw
«ltb XCXJ «l#. ws'fc#*', iiaisstia^ ecwprtai, ta tli» f&m. et
«a ©il, »s ^th ®ther» Imp^ratida ©f -tt.® isisi
»tli«r solmtiea t«§S §• ei a«iie-
ib®aa©ffia'«a,, a* p* lOO-lOg®. 0^«teHi«Moa trm
fllevft-fesi tto a#lting point to 104-105®*
ealct* for %e%gOg: 6, S7*S| 1, 4^f8.. Mmm
% «f..8f 1,
^Aestrlettiott ef 4«6*>M««tl«>^iiteaagQfa^m
I»te a flAsk ^th stiriw «ai e^aimwr t©ff»d
with, a Gfcl0?ii« tabs wst iat3?o4ae&i » s@ltiti«a ©f
lf*SS f, (0*0781 'S©!#! #f 4,6«-il-a«tlio^^ib«»»©famn s»i S»i^
g» ,aBl«| #f a©® '! fttilorli# ia ef ^
wlt»b®o»«Be, Aftsr ®ti»«4 fsaetioa sixt-ar# fcad fee«B
ls«®r#@ ia aa ie» tor 10#lf §• CO,,OfSi
»ls) of powered ai^irais al,®rf.a» eKl»rid« 9mw iatrottased
-
iBE fstttcas mmt' n -of mm Iteiir. M%»t ttiditloa
ms th« ©oatoits «f tlt» flatk- wars alloirai to siswly
e©at® ^ mm. tMfer«twr©.,, «oi silrri-iig was msMm^A for tMsttty
%irolysis witfe ie« aai kyiyoehftefic aeii ptsmimA vmar^
li #f tfce nitrote»ai«t #*•»» to to M.smlvm a3J.
®f %%& mmltdrng, r«€ solid in #«« iitsr #f Itl t>toii®a«-etli«r
i^t wdl.te fmilttre# fflierefore, tfc® fidte solii was
*asli®€ ihoiwifliay witii lOf ^mhomAs soi^tioa foSlft*®d
% and ftaally dried, 8«7sb.'Allizatl©a'fm* alc©l«5i
yleMsi S»ii g«. «f very pale piait psisw, m« p» *S^*
I#G^#talli«M.oa from alcohol &t iiliata aefttos© pfoiaeai «
e©lorl«iS« .m^am&p. tet ^0 seltiag feiat rmmiBmi eoa»taa%»
fii« raft mlutim mm wmhmi with lQf
mrbem^%@ selattea, digested *Ath *oslt®|, flltsr®4# aai the
#0l?riait ilitilled#. tl® »#^tlag light .r©i soIM m@
witii a liter «f alc&hol sail filtered to r»m©-re m saall
fURfltlty ©I* ^mrpkms i*«i »M.eh mlt^i ebovm S0O®« to
eotllof "tti« solution, mlsmd erystsls Bsp&TBtei whl0k mltB&
».t .Recjystalllnation frm hmsm& iurMahmA 4»5 g,
of fiafc ffi«8 '©f l-«.o»t.yl-4,:S«-ii«sthoa^4lfe«aofw» »^tiag ft*
total yitlt ©f •fiwJmct,, tter^fore, *a# lt,S5
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•isoilwE «xira6t# fmm ••ttii* solntloa, aftar
lorlt# timt®ent, filtrafioa m& aeiilfieatioa, »a» ©totsiasi
2mf9 f» #f iiy ael-ilc wfeiefe fro* alcohol
ia tte@ fsfa «f small colo3fl@ss nesdlss, a» p* fOl-fO#* fkls
p§.Ttimlly mr ^®aol mm aot fttptfe®!'
lB*estigst«i*
fl» Imymr *«s ws#ii«i *ltli mtsr,, .s©M.a»
»a tfes fli© r^iMmg im •
i(©lii Cll*t §•) «elte# st fro» alcohol
g, (5B*S% yi«li| of eoloylee-e of
l,»a®#tfl-S^f-iteiithoKjdibensofti;r«, a« p« f0®«. lecryitalli^w
ti»a ®lc©tol, a£%»r tves.tmmt with iorite, yisliei co1#t»
l«ia a«®€tes, »• p*
teal, Sftlei,. £@r %g%404t 0, fiaOf «# S-tt.
Frnrnm 0, fl*a aai 70.54t ••»» S-43- aai
It m® assertaiaei that tii# t.c.#tyl gmnp mmplmd. the 1-
f©siM»a %r jsr-sfaring m »mlm^S-f4f-4imtk&^Mhmmimm tkmu^
kyimly«l:8 mi the acetamino (l«rf,TatiTO by ®«eksK«
Tmvmmgmmn af tfce oxime. & -siai aeltiag pjiat A«t9i*inatl©a
*fltli tM« mS.m aai
*ii».tion of til® kasiia
fw«% m deprassicis.
•* 00 *
f»e@<lurs described lims li «»iatttially tfest wifelsl
fai?k«r fXSl ^fisyeA te -tti® ©f l-«eatyl-4-
f© a a©l«ti@a,#f e-«?.t §• C0-««t4S »le| of
iiastfeo^iilaiizofuratt ia ICX) #f ,aleol»l »» t»4 g»,
<0.0545 »l») of hydroxjlairdne %tooeiilotid.© i#f5 f*
(§•111, »1»| ®f pitaesiiisi iiwol-rei ia li a4» ©f
wsier, mixtttps was- l»t plat©
f«.r fits ^«»d irte SQO al« ©f **-^8% Mia acli *itto
aestie s©ii «ai filtsrsd.. fhe |i,«l# (f*! g«| #f
wMt« 0o21i t.l»s ofeteiaed aslt©i at iS?-41i#|E®#
tlon from alcohol (sloi! oooliag| 6«tf $m (9f
of larf0 ipal® pisfc platas of l-*e-®%l.»4,,6-«iia0ti»^ilb©ag©ft»raa,
. a» f • Stttees|tt«t. reerfStaHimtloa 'from -felie
&m9 mlrm% ei«wt«a th# poiot to ®i-g04®-# .
O&le#,. f©? S» 4.«» W&mi% %, »,a«*
gyie«ra.M>0a ef tb®. cf
F®lli(*iag tfee procedure of ^arkiKr a Kixtmr® ©f S«0
(0.01S§ role) of l-aestyl-S,4-tt»®^^ii%easofttr«a, l»f f*
f§.»iS?i »1©| ly-aroxyli^a# hy^wefel®rlfi», T5- «i* of aleob®!.,
«ai 5»i f* (0,089 mole) ©f potftwlaa hyiroxii# ia li ©f
wat©!? was refluxffii « tit® Itoi fl*t« f»3f fi^» toows* the mmctim
m -
mm ia'te fW ©f sai aeiiifi«4
seetio aeii. femished a awatitettv# yi«M of
opttd® ©j^»^ «» p* 151*164®# IscrjatsHis-tttlctii tmm alsotel
gmm eol«rl#»» wm&m «f
tmm ©xi»,, »• f•«. lS€--iff«f for® mm
4#4f f« #r
tosi* Calei..-f0.r.6j^^l|gf^lt i, 4»m» fwa^i 1, S*ll.
ttf l«*4g«tyi>'4.«g-cttji«tt9acratb8it%ofuratt
- -
'fe s Siitipnaie'a of i»f g#, <9»QUS et
4,-6-4ia«tto^€l:lmtfofwaa ^xtw® !» » A* ©f •^afeydroa# %«as«a«
*88 stdwl,. ia -mm :fos'ti0% S-».S f» (©.lilBS aei#} ©f ftilv®s4»«i
f^sphQwm f»»tachlori(l®» Ih.® reaetiem »lxt«a»t ms slak«tt tm
mimtm:f ii»£og »M©& tt*# -^is^epas balii® ils»©tT»i,.
i«i the ©Iftay #6l«tioa fal® fi-fteo la IM# «n»
«i?aag»sftt m« »et4e»ttly ©xo-feeart®,.
^m. I»t, . IrnMoa was fo«ffed ©a. ie«, iBssi« «Xkall»e
•itk W$ »ifi» eai%o»1» m%vM.m aai tli«a Jast seid wlt%
awtie «0i4# .ffe.® !•»»&•©€ lAtli staM, aai * qtiaatt*'
tatlw ji®li ®f «ltlt» oPtti® fsoiact, a.» p» wa®
eff* Crystallxzitioa f»t» raised «»ltiag
mr
foiat ©f the to 144®*
fits yl^a w,® g,»i? g.* .®r ?i«4f# leci^stalllmtioa ftm
'hmrnmm *Mte *loi»c?fsta3U.ee aasilea, p» f44«g4S®.
teal. Csl«€« tm %g%^4*5 *# S, 4.tS»
fid# «ploy@i by Fuj sj' (IS) for tte® rmrrmgrn^-
asai ©f l«««.se%'l-4-«®thoxydibeK»fi»aa «xl»©, i» .aw^ewlmt ®isi«
lar to •tot by Bachaaaa t»i Boata®r (1©4) t® pla©a&«i-
chssilstiy*
iB^aama 8®a.g3f«aeeaeat of l-Aeetyl.«>»i;,t4»dia«t^^atte«a.8ofiir«tt
to a g^lmtioii #f S..S g, CO,®t$ »el©) of l-sc«tyl«S,4-
Hmotho'X^SL'bms&imm -©xtwe ia id.* «f
mu la sffisll portion#^ S*5 g. i®l®) «f palvei**
liei pli©gffc&?«!3 pentschlorii#, A rl^Tom rsactlca toek
p.-ae«, After #t»aiisg. f#r fi*« Kiaatas, %h» rad-broia sol«»
ti©a was ps^red: oa i«%. *ft4® aitelia# wltli .»©ttw earteaat#
solatia, mi tli« atetie seii wm iat»aiie®a -antil *i3E-
tar# w» ieflaJtelj acid t© lltens. Sabaiaf'ttwt to tfe«
rsaoml #f tfe® hmmm. toy itesfta il»till*tioa, S#S f».
•ttto' erma® «. f-« 1S1--
192° wm efetg4a«i# ?h» iiieoierM ms
(104) l*®lsffiann aad Boata«r, £* .Soe»» M. tf7, S097 (1956).
f m ©
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miwyg ©ImagM to tlie fria*tl0 ferm ss tfc#
b©ai«a# gmdnaily ceolti#
irnCLm OaX«i* for C^QH^gOgM^s 1, 8*44# f woAt *>. 8,S1,»
,p»oeiar© used by lrt» faal## (8) t® ?®^ee 1?-
l>«»aB«ai>>4*li|r'iy03Qrdib-3Bso^fora& "WES -ftlteftsi#
gra® (0.003 mole) of l-»beas»i^2io-^^8-»d4s»tliexy»
dttodftss^ttfan was dissolved ia 40 i^# #f seetie acid*
ttls tot S0l«ti« .*as sitfei giwdmUy a «ittM.oa #f 0*0 g«
©•f #taiE»w iif54r«t« ia IS »i eoaosntmt .
ellerle a©i4«. fh® eolo'? of tfee reactisa slxtire q«leWly
Cteafgi from orang® t© mA fwrtfcsr »©oa
4i#p»31'Sd ^ti. m%©Tm 'brndng tfes Mgfet, a wblta' e«|>l®x tin
#&l.t #f th,® m^m e^stallized ©at* tit®»£o3F«, la orter
a*lti@,j -ttie soluti&» wmm ecwlM is « ie® t>atb
«iii mMwi i^troxide was mMmi. mtil tli® preei^tstei tJ,a
-imJ rediisolTOd* ffe« solatloa ma tli« mm&e> acii
iKltit %«fcpoettt&xd® «0M# mA.f flaaily,. •sligh'ttt.y ba®l® 'Mtto
isjiwxii## the Itberatesi sM.m ms ©xtriietsS *l-tfe
tk« «"ttier golutlott »# iri®i ©wr sodtta sal£st«.,, mxA
«iae 'hydrochlorii® s«s pr»eipitmtai *l.tt hyirso-*-
f#a to solmtloa of the Ig^TOtsMloylide, attb-
#eqw»t lo^lt® tfm'tosBt tei ww iiseos^sM
•itl waiia This
iibsawfaeaa ivm *«iha3aoi ia th® torn ©f »6lJ.
fsXa puppls «««&«, », p. fh« yi«li wm» 0.«t4 g#,
#r ©J" Wm •a»or«tlea3.,*:
Csisi* f»r Cj_4H^g05Wi I, §.??• WemA*. 1, S.SS*
i]rtgoly84.«. ef
ffMi (0*007 mole) «f
4ilM6a2ofuraii Mflux©a for 9l0% kotti-s i«. * telotloa eoa-
sistiag ®f ^ A* @f ^a«entrsted «ei.a a,tti lOl*
of «a.c0lioi» Snail -mtf pal© pin n©Bil«» ©f
wer»
few. «»« sooled aolutd#a., a# |d«M ma 1*S8 g. ®r
0f a &$ t&® hfi»elil»yii.» was dl8»l*
ia kot wfeTji «8i tt^e fm& a# i^.«S-48t®, ms librnt^ , • -
at»i ly til# itddltioa ©? mm&al-m lyferf-is, laerfstalllmtiwtt
f»» e#th«i0l' with tls# poiat
•to •
fids a^jm .»ai matfe«alie l-«4as-4;,6«-ii»©ttea^ail)8nz©fwi'ant
'reittetlsn ©f 3.»b«saasit,8p-4,p,-S-iiaet!^ayiibeB®ofQriaa,
*®y® f»wei i#«8tie«-t ¥y saans of & ^stssl Mltiag pslat
- m ".
mi l^ttpeao^S^i'-iisetheaarii^an.Kiftiaias
iatiwte mixtore of 7.5 g. (0.0244 aolel #f l-bs^a©-
I,4»-4l«»ttojyai1isni£ofuraa, li*0 g. of p&*ier«A eti^»WB
fer©«id% «a4 liO «!• ©f aoncentatei mmsim> was
li«at«i ia, m i^®etric#Uy bsated 1»o»b tor mA mm-
hmm «4 s ©f tfSwf^#
ths c«st®ttts of tti© tettlj *«r®- axtraatai tivm
t4a«s •I'lli E tetRt irolie«' sf iOO aa.., «f fhls
solttttott ©f -aa® alia® m# iilsd ofemtght ©if®r aulfat®*
Q«#«oat Igteegwi chlorf-i® freeipitetei «^ne- hyire
eaorlfe ,£»* tfcw- filt@r«4 att«f tslttttos. The oroft®
eyUsrld# was 44»0©lv«4 ia hoi watsR, and fto B©lati©ft *ae
ilg«st«t «ltk forf.t» mni Ultwet# Jwso-!ri.affl
p^elpitetei §•# gm.f: a 19»1# jioM, ©f pals pirple l,-«sl»o*
S,4«-ii»the*[email protected], ja, f«. Sseilss *bieh
ciyst»il4.»«l f«s« diluta saetkaaol |»s0«as©4 «» umlterei
pi'lal.
Iti. C«lcd, for Gi4HX505Nj I, S.fS, F&anis I, S-.i4*
jyigolrsis 0f l-»Aeet&}aino«^«4->Maetli6B^lfe»BS0fm'«
I »mMaati©« of 1,6 g. (0»00s8 of iHaeetasim-
5,,4»ii»eitea;yttb«»fw«»,. »1* ®f alcohol, aai 5*0 g* of
p©ta##iii» ^<tooxli« *ss j?®fl«*84 ia « sAai batli for t» !io«rg«
Mlatiom €30 A* «f «a1i»r precipitated sM platss
m »
iM.®h were filtered off «i. esyptsaiiaei,,, f©ile*ii^ hwimt
Isidte dilate s0iliaw^l» tie tateow wMt»
of 1.--«*ia©-S,4-iiJi®tlio^iil>©a»f«ra% m» f»
tiated pwfl® ia ib® at»j.Spl»«P®<i Tte yi«li
»« #»®S §» .or 47, 0f tl© %hmmt3.&Am^
A ai*»i a»ltiaf p>liit i«t®»laati«a Mth satteaMe I-
g,4-#i«i!th»^itb8«taoftir8» #et«blisl»i th® sf tte twa
A aolution of 6,0 g. {0,03 .wil®) #f
ftimn ia 45 ®f ISf f©ta.»»t«a ^-irexiifie m» illtjted wife
^ al. »f water «ad plac«i. la #. 500 al# fl.a«k «etil.f!Ss@i with
io.»*"l»^3»twe thew«*«tefJ aat im§rAmg fmael# at®
^Itttioa was tlisa «oolM to t® hj immmi.iim. ia m iiE»»»alt bath,
fhm ii*sisaim salt s^in-y.da ms pr^arsi as folios®? T®
« ic«-wli •s©lMtloB @f 7*f5 f* TOla) of aailin© hydro-
^3«j4A# ia tS A* of wt«r was 4f g» «f eracksi
los aai W*3, al* «f concent.rat«d fcyirdehlcrie aei4» fh@a .a
•soltatiea ©f .p?©fai?sa" tmm 4*ff g# (Q-*QBW
«jf #«It ia tS A* wa,t0r, »a« foursi ao*a tto.® ei^. of th®
•b#AS:@r mttl. * well atirrsi., i®@-coM BotnUon
Jjwsii&tsiy » digtiset "bl^e spot ©a eaiaiia iodid®*-
itarcli fsfdf.
af -1.« S .S-fMma.
Ilk »»
fiii» #alt s©latl0% e©ol®d to 0°. was trt-ettsd
ioi® t%» :si#0 »f fltrtE «0»talai,iif tfes ©©M* 8ti.tT«i alks-
lia« ©f Wi» at nvmh & »t® tl»t tli®
tti» iid mt exc#ei 'S®» .B«teaiea3. #tliTi'ng *«© esatlBaei' f©?
*iaat@% sft«f li!,® »s«tt<@a «ixt«r« mm
«i tl4@ vmy #«rl m%M tiltami •&££-* tmm
•a<s»tie aeii S»1 • g* «f -mwf iask te@«a mier#cjyst3liia®.
wte-flal, »• ft# lesfjytelltsaM.'OB
th« »«e «(lv#at, attesiei «s9agMe»M@ loss fie® to
reiiiiifleAtlGB.|, raised tJi@ Bslttag ^ist to fti® wltb dee©#^*!-
tioa. ft»iyg«# rwe«l«4 tliat tld# ®«bstaa:««,», wMeii
At«olv«i in «e«t0» «lth th«> f«ia«.tioa ©f a. l>fllM«at rm ©©!©%
mB-.f aeiwtHy, « «i#rt"yativ% i.» #», 1,
laasMcIt •« tk« aitWfWB.
irtlws v0m amrly t$ 1©% it mm »g»ia®4 Wm% tfm i»pari% •»©
iai« ii1immm.m.m 'iwimtiir-®!*
i^aftefi staMlity to thm aai m
psm &m^mA »s laolatai by tii« falloslof p»®o.«dttr®t f® a
r«£lttxiBg, sttwei seimtion ©f g« (Qm9H% mlm) @f l^mre
3..,Jg®»%24.1(«8«i«a©-4#S»dlhydrex5'4il»a»itofta, #.»S g»: -Cl5»0?S
toI®) &t iiaei^'l gulfa-fee, tO ml» ef &o«io» -was 8low%'
aMei m S6l»ti»a #.f lS#f f# »ol«) #f p©t&»slwa
ia 1§ li.« #f lafluxinf ftai stirrf af; »«r« eootiiwM f®r
tw®a%-fiife iri.-iiiit«s after the alkali Mi b®ea ittt3?oiiac»i«
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C, SS.4S} H, 4*4&# femAt
% Si.Sl I, 4m*
gftgtemtloa mi 4*:fl-*g.»eftojavl' teeimofBiyla»:!eft«gi'i» Bgs»l.i»
Ife'to a. SOS ^:* JSatk «5i»ipp®*S »«0.liaiile«l »tiiT®*
«i 2@^la»® '©eiitsiar »t p-lft««4 % s«lmti©» of tt,S f» .C0»0fS
H»l©| ef i*fefwa«4','S«4i»»tite: iib'«B#fOm» ia 'SW5 ®f
su^^reae- (Isl fey i#t«r f*#' g*. '(O.OSt
ml.9} ftf *iM>©n lifti. feem' «d a aiismgm
iftestpJiB?® p?©vi4ei,, tk0 i»eM.oa. ms iaitiatei. fey th« sAiittoa
#f tfc# »»cM#a pi daet ootaiaii f»ott a ejyst&l @t i#aiis#
;«itb • ft f»w «fia#siaB fiMag»« Hi® r#aetl®» aixtwe. was flf@3psms3y
refluxed ®tiyr®i fas* « .#ii6-fcoiay tatarral* Csrboaattos wm
mmw 'SSa^md. % filtsriag ifc# QriptaM loMtloa mier ss a'teo#*
pl»M nitrog.':n lato a large ^x&mB &t solid c»Aob
After stiiiidlsf ©veraight, tli@ p«>itt0t **» iiyirolym## witti
Is# s»i l^a»'ehl-o<eic aeli aifl: the »©lii wa-s flltereS fries
eoiatiom* fh« l»®a««n@-eth®r Isy-mt *»# twice «dtii 10^
»oiiwi hydroxide solat4«a» ft® slkalin# axtraet was ftidsi to tfc»
eoMdj contained in « hsAmp aai sedlaa ^iroaid®
wfts iall»@Aie«)S -aatil tti© fe#sk#r. w&s 'fttll-* Hie soltttisa
mm kmt&A to Isoiliaif «atf seiiiflM litli
ftcli* fkB wM-te amorphous acid obtftliiei by filtratioa ery»ts.lli.s®l
fw» «e»Mc seid Im tte fmvm- of ir«y eitail nae^les, »» p.» ttf-ESS®*
c^. o r4
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- 105 -
ygjemgattioa- #1' •M&a&aetta'l. .4«i*at8gt^g«4»»ii^%tnioftga3. l»-lcii»
'f*rker, s»applyiag the dlscoretx of ktm&t «Bi Sgisrt (107)
to Ahmmfwem ^hrnxBtTy, syntheaised 4-^l5e»aofttfyl«.s®%iwi4®
.f»m 4«»M'h«»fa»a0arbo:xylici seii fey mmrmgmmt &lmm»
4-«ito»«ofaifl k®tene«. *&# gm«siiaf three prepmmMmrn^^
^ieb eolleatiTelf eons titrate a .ffsttetie wwt® to- 4,§-il»©tli03^«»
1-Ategnzofurylaeetie -te mm %a#«i o-» fr©e#iof«« issei'l'bea ^
f»k«r (1?).
1&S r«i;aired «eid chloride wa# py«pa»<l by reHming H«S
f* (0,042 msie) of 4^fi~di!Kethoxy-l*«ii%«a55o 'ure»e«rl»syli0 aci-i"
*lih 80,0 g, (0,67S moX®) of thionj^i ^l©Eii« ter %m aai ««»
balf iN&«aPs, iaring ^hich tine the ®o3Jli seii slo»lf t©
s sJ««' rei solution. The mxmm elii©3?ti« "ms
iiaiillei mft «t diwiuisli^S; presmm •* m tmpmmtmrm -©f
(water beth), lie criide pini; acid cfele?ti«, aft#r oiyst&lliaAw-
%!#». trmt .neltei -©*©1? « lAi®, iaisfinJt® faage ^lek
indleated incosplets conversion, furifleation w&e »£f»ct©i
boiliag ifed 8ttb»tanee »ittt pe.t»l«» mWtm (li# .p» Tf-lli®)* :1&®
aoli ii*0olv«i, mi^ S«f f» ©f Mp&Bp •oa-ee.arerted'ft®!#
wa-e y^ved by fi3.tration* The edlesl®®® «hi.c!i Cfparat«i
f»a cooled solutloa mslt®# %% tii« ,yi«M •mm
f, j&r SO*5^ 0f the th#or«ticsl* .^»«plj©3ras p«at«-
(10f> toit «d listert, Ber,, CltSf).
104 *
eMloride maia fwntisto mxpsrlm |4elis)* 'Rls aoi# cKlorf,i« wa#
m% ftjrtii©? parlfi^i er m^ym§, feat w®« ilrsetty la tIte fellow*-
Inf pirowittm#
Iftis iis«®stSaa« prepared f«» W sl», mt «th,yl
»etl9-lc«J%««te % the nethod «f feehBsaa (IQB},. €L9mlm€. i,»
®C»-.tt5 #.f aafeydrotts itm plm^ im »
w«fc»t fXask i«K»rg®d In m le» bath aai «itfc « *®elaaaical
f© «ffi.«Aently sti»©i »«« iatrMacai, la •
f&T%iem.p. €*t g* (0.0S15 welsl of 4,6-^Jiettho^-.l»^l«a.s»»
,fttmae»ffe0»yli« mM ett©rii»» M%»f tlvm alaa,t#s &f Mtirrtrng^
too Am mt acl^iroas M&xmm wms aiiei to «ffeet #ol.Htioii.* fk«
ic© imAM me -aafi ei«»r yell©* »«ctl®a olxtwe ir«8
•te utmi overrdght* .
fhs aexfc f»r9t J^Ho* crystals of iiaasesstlgl
#,6-ilia@tli0ay«l-iib«t»furyl ksto»% a» f, lit® ^
»»» tmm ftie fi©M »« 1*M g* -m 13...^ ®f
tbs
ialcd. for feuaii »I, f*S3.*
ly yffiwvliig %U® mlirmt at il*ijd.^«i .tr®«®wre, 4»?S g,». #f
i«bat«ae®> tto« crudo iiAssmeti^l k«to»e., m# ol)t«l.a@i*
«a to s®eB3F® aatserial tmm pstre-
l,®w ®-tb«r I p% 77«115°| ws sw«ti»B# 8Wi&#' «eis«
* ffci® author is grate,fttl to Mr., !*• B, ifp«ra®B for tttis Dumas analysis*
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Wmmm'nM.Qm ®f 4«6->131tt9thoay~-I~ditensefiagyl.aQ«'y.e MM
, A alxtiire of 0*S g, {§*00176 *©!#) of 4,8-iiM0tlw^-4.*^
diljettgeffliylaeetaalio, fS ®1» of IS^ s«ilm hyfii^oxid© tijlatiea
aad S 84* of ^c&kol was Ttflaxwi f©r tMrte^a hs«rB b«f©rs &
^Imr g^lutioa w&b ®eal.is«d», fhs raftctloa .alxtttps *ms
wi'lh ^ «!• 0f tater,. geutly bollei witii a .fiacfe, of ieritej «si
.feiiifioatiofi «f tie solaticfa pre©Jfitstei tbs
acid ia -mmly qaantitafclw a* p. •S04*^S®» fwo efystal-
Haattona' tmm ^coliol cclt-ylegs. «f 4,.6-^-
!«©tlioxy~l-!Mb«3KofttrylaeetiG acli, »* f» ffc# jtmtM
wm Q,MB g.» OS* 71 »7^ of the thooretle^*
Ms^*. Caled. for <3i6iIi405X 6, «, 4:,i5« f«w4t
C,. «f*t| E, 4.99.
Qycllsatiott of l<-Ao0taBdBO'«4«g-<iiBethO!XrclIbeg.g^ofnr«R
fey the Blsghler-M8gigg«a.sfei Rg-feetlon
A,. .ISnplopng ©geenti&lly tlis fTOtseiaJ*# isT«l«p»i hf
mS. l»Ilg for thu preparation of f-tafcstltatsi pi^Ra-ftkei^il^
Jeri-Tatiwa iBt)f 1.45 g* f 0«0©S ml®) of
asthoxytllleosofttx'n.a »a.s g^tly r^fltixei 0».O g« ®f £»»iily
iigt411«i. mmie a ®f an li9«r* ift«
tit® prodaet is tS idl». #f water, tlie iti^roXysi®
smMmlj h&nm« so violeat tlmt io# wae water «as
«ia9i to • tk® totsl 100 ^iA9»apoii M&tMtim
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«i I© atairttng ms eb lmsA tmm tSw usiil-
fi«i Si.» hmm vmsMm iras ^«tr.6.ct®i *ltli- m Mvgm
vmlwrn t ®th#r» fb9 mth9.w i»a iridi »ttli m&m
«afl l0®jval of tlie aolvaat left an ©il
wbiefc cftili »t h& eiystalllaed.. lo «fg»aic material
c#«l<l be igftlstM f»a the eth0y-i»»li&l® re#iAi«»
- 110 -
» I. f c 11 i 1 0 I
Bgjtfgg .tlig. l-*- »iii. f«>yoaitio-»® 4».'Pib®atGfta'«ys
C»ilTO-'IAir»8<.- S«v«»tl attsapts 'to prepays m phmmfktylmm ©xl€©
teimtif# fey latfaisolecsiAai' s3%laM,®® &t l"«<sKl9»«c»iyl-4-.
ia fitmmm ©f alwAa*
tlie 4B!©rfe»«sg of tiie '©hlosiB# «toa wafer tite aoaiitida#
©f .tbs 'r«eii©a» Vmti&tion ia solvsat «ni
wa^tloaf, m% a tmc* -of fti« i»siy®i. 0T <&f
««a- %1» .possible latinwftl.emilwr m&e^m pmMc^ wm tomoA* la
merj caw ftitlitv. tfei! starting aateriml was r»ew®if»i or liop«l®s#
<i«eoapegltl©ft 'feok flae®* It l» of lat«r»st to »t«' that tJi«
^Iel0g®a •'fec» la dtleeo-fteatiits feelmvss io a siMlar ,
^^lo»ay {108} m# iaaM« t© al%l6t» mmthjl f«.fa«3at® with «t^3.
ehl©»&»wtste ia the ©f al^d-aa* elilojli®.»
ffcii- laolattsa ©f fi^s ths
Friedel-Craftg rsacttoa of <i^#tho3?jiil>«aofto«tt with #mlyl
ohlorida suggested that in order to realiz© tfee feimtloa of fhe,
i®8ir«4 J iuinona with oxalyl chl©ri.ie., botii tlw'l- sai
®f the :Mbenaofuran auelaw »l»mia b® sotivstM. hy tte iatroi«etiott
of suitabl© g^atituent® ia th© 4-. s»i-
4,6-dimethoxyii'b@ns5ofva'an was pr«sps»i «»4. to tit®
ClOB) Calloway, Boctoral Disserta'ttott, Stat« Coll»f% 1955, p. 87.
- HI
rtactittii li-tli ©»lyl elildrlig. late*-
eostfaasftttoa .pr®ott#isi *itii tfe© of
• ia .eaioeileat yield. both
mfbaa iiattlfli# i^tmhmzmum •^•mm -^lojsS m solvit#ji aot
«. trais:® ®f t&e &r^vAmmB could i,8©l«,tei*
Mkmlm., fsiltt» ©ffepta to ^atM@sia» a
isriwtiw. fr#® l»ae@taaiw-4,S-«ii»
»tiio^iil>eB2ofB3?M, %• apfllemtloa ©£ tlis 14B«il#r«Mspl«3palski
spaaotlea .(80)# la »t»#p«et it •£» thowfht that p»l>*l5ly tlwi
JjSf&«ei ooailtioas mrm tm Ammtle*- ia- llgW Sclilittler* s
sy»th©»i# of fi&atsin® (86), phosphorus paatm®tt«i'Me in Ml.4
ohl0»fo».©ff«g' possibilities.
fhe receat syatliasis of
aeisj h&s gappliei & coa| i»J wliich bolis aapf^etdaatsi pronisa
of yisldtaf & 4,S-p!i#aaiithsyl#ao oxida i«rl:*atlTO. Qn# •owiiG-
c«»afiil pr»liisiin&rj attegpt te seM»v« ring closnr# 1»..i b#®
^.escribed. Again, it Is prcl>abla that tli« eonditions w«r#
too harsh. fMo^l cKlori^e, «pl0yed, f#? In th®.
thsgis of Di.el*H njdrocarbcn (109), isight yisld A pws? acid
chloride, an.d thirty mimjtes at 0® raaeti®#,,
the optiBMffi conditions for WeitsenbSck^s 8jatfc»ii« (7"^) of 1,6-
dil-sydrojiypyrexie, troulo poseiblj affoi*<? rsfteMea tis«» 1113
(109) Hillefflsn, B@r., 69, mm
- 3M -
*«ts 'by feteteawa mi 12.©®t»l (110) fcfT th0
ooai«M*-|loa of fliSBfeatltj^lpjmpisttte aeids,.
CwKfi-atlT® :«d.i@ao®, »spporfes tfce lA@a tiis% th« 4,.S-
fh«Bsaihryl0Be o3d& a-acXettS i» 8tt%|«et.9i to eo»g,ii®?sM@
Mmma sp@@t»sl Clli} laiieste tl«t taie h&asme rimgrn ia
th& Mhmmfvmm ^aoleoula Ar» ilstortttt. ilttoagli s g&oMy'
mmhmr ©f idbyimttog &g ntfc mm iwmstig&t»&, Seiaidt «ai
liteff (us) *«!*©- aaaM,® t» gyatlia#ia« a 4pi-pii®»a«thiyl«© osEiis
fidsoas 'ftm 4,,6~dil^iro:^la«mtii»a«alw»» ?iog ©legare.
WImrmm » of 400® ts p@q-^fei to |}rspa» g;-Mpls«©l
from aS-teasefttMaj/feBgerichten a»i 5Itt®«r |3,1S) ha*® d©wa8t»tei
th© ©^gen' bridge ia wrpheaol &m !>•© clsa.*®^ fey fwida id tit
fotssslw at ?!S0®,
Setalatioa. The ssleeti-v© &i i-®t^l0*Aasiole
Cm) classically i«»astmt®s that tits partlewlay laelsar
f«tt rej-lac^A 4ep9s4s oa tfc@ mtare of t&© astaJ. wMeh is iatr©»
ittoad* Wrm «xt«af4"fe astsliitioa atndt®# ia this, labemfeff (M,.
ISjp, 5% 3.M,,. lis. If I, tlte. .fsHeiiiiif, gmmmHimtlm- hm® hm&
(110) Bachmann e.nd Kloatael, £, ig,« Ch®m« Poc,, to# ft©7 (19^)« (111) Donzelot aad Chaix, Compt« rend*, SO?,. S51 XlS8i)» (112) Schmidt ,and K&fsf, Bgr., S§, 57€S IHOS). (lis) Vongerichten aad Dittiaer, Ber,, 59, ITlfc" (1906), (114| Gll^sn and Kirby-f £, Org« Cheis.« Ij 146 (1956), (llsl Jacoby, Doctoral Dissei'tatiori, St^te Oollega, lif8«
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^•^4 ef 068 proitect, t,'*-diB#tl»ay-i-«3ib«as5fwrylIltMaK, e©ml4
if 4,6-41*«-t.bo^€lit«as©fttrsis *«ya acted to fefe.#
lafi-ttsac® ©f th« S'«a *«talatiiig agaat. foi"th@r»i*a, p»¥i*ij.iif
that two «isimlanta ©f ^-tetyllltliiw wsre «ploy@d, it KigM %e
f©ggilile to iiai-stslste tl»«'fetero-TOb@tit-«iM 4,6-disetla3^4ife«a^0»'
fays© ti© fmMn% 8,f-dl31ttoi©~4,j>0*^ii»#tl»s^ailj«a»f«i»am, for K,?*-
aisatto^MfhMfi Ms %m& diastalatei i» SQ<. jivM fill') 'Wadm
them iB m sati»fs«toi9' «xfl«atioa for the
fo*0rf«l orfcte-oyj eating- inflTa«t©@ exei»t®i by mthmr mS. tertiary
mim gmi^B ta 0rgBmalMM *#talsti©tts# It has beea «tige®st«t
that »et«Iati»a Is & function ef tfe® miMty ©f tbe h^^rogm
mplmmi (US) {119)« Tto that th® 0a«® hjiPofM «f m
a»*stie c^cle im aot mlrny^ ly amy setal iS: as
®pfs»a,t eeatr oa tion to tMs !€«»• fe, l«i»y PAo®*lt® #f tMs
lafeomtorj l»s asi« tfc« l»t#i*#8tiag obesrw-atioa tlist ft vi^lefcus
sy#t« 1»
fha Ckmpllng of Q,rga»aIh.eU.
is^lattom ©f M«^6-TOttK}3cy--4-iife«ttaQf«,tjl.) ioilming .sst^ntioa
of ^th sabaafa«®t oxliatioB sf tli@ adtala-
M-oa fs»®iuct justified an for mmhrndsm of tbi»
(117) Unpnblishsfl: work by author. (lis) Comat an5 fh®laad, £« M, Cbsm. Soc*, 5^ Iflt |lI9) Sils&n and Brewer, ibid,. 58.
- ms -
©statoiifiwa reaeMeii,. Rjrtbsrror^-, sAssfwat
to tM# m iwrettlgatioii ef tte s©liiti©a rmsimiag
im» th® ®«taliktl.oa of iibeazofia'aa f©Il»w«d hj- o^iatioa »£ tb»
pmdmet Mmlosmi. tlie presses# of M»{4-iifees»fattyl) in consii®3P»
afel« qwyatitlei# fhsrsfore^. %M.s coa^lmg reaetioa appeared t® ¥©
fsseral.
It is vmmmmyi:e te ©eaei^e that thi@ ©©apli'Hg p»e©»if
itirlag tlis oaiiatloa of tfe® ©ygiaolitliim 0#Bpo«wl, litMiiB
p«s^xi4« fcad^ tli.« other termd:, for »»reli of the 3.it«r-
sttar® rwrnli^d tliat fooster (ISO) has m ftaal©fewi ip@ae-
ii©a «f « eTgRBettsiiaB eo»f#wii4» fh«ii iry miv was pss«@i tferoagh
a lifui#. awsats tolatioa, ef ai.pli«Bfl*«t^ls®diws, tetyaphsnjl-
fittaia# sai »»&« w«f« tte proAiats ohtsAmmA* toostey
has eoael«i#i tliat fs»mtioa ©f «» orgaalc f«»oxl4© as m
0iEiiatto» pmittet la %pical «aly ©f thee# oygaaoalksli eoapjuart#
*M«k AW isfiTstiTOB «f ffrm «iicals»*
Sine® mmimlng evidence las hmm for th«
®f ©fganic peroxii«t ioriag tli« e*ii»tlon of
mvyl frngmts iltl) (94)# the ®aff©gtsi »0eh#,iiii» for
til® eem^lag yeaett^a ef thes© orgaaolitM.w cmpwm&B is ail tii®
mom plawiMs, tli® ps-ssiMlit? ttot mm^ing "pmcmAM prior t©
oxl^datien b« yeaiily i»»gtif&t«a by ©ftAomtioa of the
(120) l9©st«% CiSSt)-*-ClSl) fort#y mA £. M* Sg£.» II* 28S0 (IfSJ)*
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Mmo-t aai fc^*l»ati0a mt
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»®tm«ae» of »»e%ictts-- |17)j , A, #a^Le #f
IdadJy fe, ?.» f., fms-Msr, tfse
raiaesi according to his dirs-etions (15) to %1m mifv@^ndln.g
mi.mm This i-brojso-S-amiao-^-Eiethoxydibeasefijwft tranii-
thfeugh th^ dla.3oali» s^t,. to m&mUJS l-l5«ais©-«S»
li^ir«::^«4-aetaoxydibenKofu-*' a. fk# <s«*fotiai. mm
by tb« iiyegt l>»c«l,ii«ttoa of S«%ftPG3^-i--««tlwi3^M%®iiiso«.
fap®»» Methylatioa of
pip©ime«i tte® mm ttet 0te-taia«i ia «xe^l,«iit yl«li
^ .d^reet ij»aiiisttion of AmtjlAttm
#f, S^4*#a«t^^iSI»a2ofuraa was, ^#©. shown tb®
l-posittoa .toy th« followiiig »eri«s -of ?®a#ti#asi fb® mTTmp»nA->
m^m« was converted to thn iieeta«i.a»' isrivati'w % *««» ©f
rf««ws8®a»eat» g»&0«Q'a«at l^fea^sis »©©«»«#
m «8i» MeaMcsi i^tfc aatltsiitl.©
fijwaa §TmfmmA. ly firect aiaatiom ©f l«b»BO»S,4».Sl»et!t03gfiii-.
hmminm&rn
Bi-Ci-mbsnaofuryl) »ae spithssis#® toy eoupling
If* means #f. aohyiroiis .eaprlc cijl©rli»«.
• 120' *
wimm m
T ' l,3{?)-DibKj«io-i-hydrox^r-S-iiiethoxy-
1, S(t)-Eibr«)mo-4,6-di®ethosy—
1<*8TOS!®-«
1-^Qaxtoo^-
6-1-^thosy- — 4-Fv-lithi\M
6-^etho3jy-4-bromo«
8—Metho3sy-
Bromide
1,5,9-fftlsaatiaftta®-4,6-dlBethoxy-
\ Esteae .
I 4, 6-Dim«tlK>xy-l-4ib«itsofisa^l.-acotsmlde
I 4^ 6~Dia8 thojcjr-l^lhenzoSviryh*' acetic Acid
t Att€Bpt«€ Gireligatiea Ills) Si^l'' I'l
Bi- ( 4-<lil}en2!ofxsyl'
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gM..ps ef th« he-f-eranaei^sj? iii«a»far«iiis la tbl#
tatesi## His foIl4»wlisf is
to ttte base#, tm assigati stifmetwrei;,
M yteid'Sf
&hmmtmm ms tli«
4-4i^iro»^-S-aethoxydlbenao,furan (IS) iltti
etti®rf.a9* , By analogy irith all kno-m mttrn- ©f, m^iSmg pitoel#
aaa txnder similar coadltio» it «s» ag8«tt«4 tli«
l5«6t8afl®«> entBTod the l-positioa, tm *&« tit®
fositiea i» or wh«a. t&« mmM.m mniim i» .sti^agly b»#ie
^®8 coupliag t«&e |£lac# appreciaW# «xt«at« ffcs
-Qiat tte p©si tion Dam te thm- ^®ii©3.1c #tlier gmup
Cff-positloti) *«# lavolv##. ia eo^lBg »a#ti©a eaa b# d®fi-
sltoly tm ^«aelio, like iiffoM
fwducts only TOd«s* Ke^ti-onal cerfitioas or witfe
aegatlwly snbstitijit^d diazo-com^aiit,.: flieiijf to©, wten cofipliof
do®# tftfc# It 1# wjtabl# tfe&t tJ» allfl f«®«p ef the pbenoMc
•tiles' 1# peftiallj or •00aj|>|..et«ly |f«®ir©«J; Is the prociass (ItS) •
ClMl ^.unders, *Th.e Arosatie Dia2o-C0^poti»t8*ai$d fh«ir Technical ApplicJ^-tions", Sisterd & Co## London, 1956, pp. 104 8«g,«
fits)- iawers and !ticha©lig, Ser., 47,
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