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TRANSCRIPT
Retrospective Theses and Dissertations Iowa State University Capstones, Theses andDissertations
1938
Amino and hydroxy derivatives of dibenzofuranLee Cannon CheneyIowa State College
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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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Preparation of Bl-(6-methoagr-.4«-dl'b@a»©ft»yl) from S-Metho3sy-4--dib9nK#.fa^lBa^ga«»it» iro*i4« . » » S8
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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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I. Dibenzofuran II. Phenanthrene
hv O r" vH
III. Morphine
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M l0iif ago as 1897, foiigericiitaa (if) dtrlflei tfc# nalair®
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®
r#«tdily ia &3t «i«©.li0l|,. csrystaliiaiag f-etm ttts -sel-r^t
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®
tmr th® m& « •'Wiws ®f fm the Ms#*
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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«.«. $&» ISSt (19S3),
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ftne® 0,tS g* ©f @o^>wa4 *»« fvm itm ftltmte, th»
•te'tal ms' l.«f0 f* m BS%,
MaJLm 6al©d» f©r % Si»t| I, 4m2f,* fmoAt
C, «i»l| H, €-t»*
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iib®o«?fii^l) is f©3«@i i« the a«tal«tl®n -smi ©adl&Moa ©f
'dlb^gofwwa* ' .
tB Reactiea -4«M'et.lw»ifttb«»8of« laaa. Qaealyl.
I«t@ a «©latloa sf 'f+tO g# {©.OS -awi#) ©f 4-«©tij©3iy^b«»»
fiiraa m& f.® f* mxo&ss) of -oalyl eW.ori.i» ia ?S •«!» -of
©©ataiaird' la a thre^^eekad HaaS: . qalp^i. irilA
gMwar aa€ ©©auteisep with a ealeiaB ehloilia t»b% ,»»s
p^toally atii«l I.4.7 g# (2 ®ace®s#J of s^aaiaw
'B&mmgh&Wtt a#ilttoa m .le® molmS. tk® f©fteti©a. aixturs,
i&teh ms tfe« to slo* mm t© i^a 't«p@mtaps« JW%»r
t%M. r@<l-fet©im: *i3Cttti*« wm iiit% 1«»
aad seid-,. the nitrobtatsu# w# maawi
and tbe boiled »itii »<Siw l |iteos4i» 9©lati«3ai •
wd fil.t»y«i*.-" Ifete «ei<lifie&tioa th.® JElltaat#
•C§*7 f*), ss' MiMlUmM.m -fmm ««®Me wjted' mt :S?i-»S1T®
ig «
mi wm t© mM toy-
•»l»i wa.tiaf .|®4a't«''
flm &!4®d waorphous, siteli-'ittsolwbi® soJULd m&» -^tmeiea
wltfc 3. ©f acatie acid, ftm iiis- eoli filtrate was obtaia«i
!•§ f. Ci^)- •®f tetone in th© fern-
#f e0j®rl«88 3a»»ilss,'®.p« 2S4®rf
Aa^# Cslci. for Cg^H^^^Ogi 0, ?««Sj % 4*29.
f©«adi G, fft.l| H, 4,S7.
acetic-acid insoliible residue, »Mch pvomd to b@ bl^-
(4-*a%lB»3cr*l«^beniiofuroyl). trm alt?ob«B8ea@ in
for» ©f pal« yellow ae@dl«% »# p# St®®# fim yield **# S*0 g* or:
S4.6$..,
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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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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