• TABLE OF CONTENTS
HIDE
 Front Cover
 Title Page
 Foreword
 Table of Contents
 Part I: Phenanthridine derivat...
 Part II: Catalytic alkylation of...
 Acknowledgement
 Biographical sketch
 Back Matter
 Back Cover














Title: Phenanthridine derivatives, part I, and the Catalytic alkylation of amines, part II ..
CITATION PDF VIEWER THUMBNAILS PAGE IMAGE ZOOMABLE
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Permanent Link: http://ufdc.ufl.edu/UF00098046/00001
 Material Information
Title: Phenanthridine derivatives, part I, and the Catalytic alkylation of amines, part II ..
Alternate Title: Phenanthridine derivatives
Catalytic alkylation of amines
Physical Description: 105 leaves : ; 28 cm.
Language: English
Creator: Shugar, Gershon Joseph, 1918-
Publication Date: 1943
Copyright Date: 1943
 Subjects
Subject: Phenanthrene   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
 Notes
Thesis: Thesis (Ph.D.) - University of Florida, 1943.
Bibliography: Bibliography: leaves 59 and 104.
Additional Physical Form: Also available on World Wide Web
General Note: Manuscript copy.
General Note: Vita.
 Record Information
Bibliographic ID: UF00098046
Volume ID: VID00001
Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
Resource Identifier: alephbibnum - 000554655
oclc - 13419767
notis - ACX9501

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Table of Contents
    Front Cover
        Front Cover 1
        Front Cover 2
    Title Page
        Title Page 1
        Title Page 2
    Foreword
        Page i
        Page i-a
    Table of Contents
        Page ii
        Page iii
        Page iv
        Page v
    Part I: Phenanthridine derivatives
        Page 1
        Page 2
        Page 3
        Page 4
        Page 5
        Page 6
        Page 7
        Page 8
        Page 9
        Page 10
        Page 11
        Page 12
        Page 13
        Page 14
        Page 15
        Page 16
        Page 17
        Page 18
        Page 19
        Page 20
        Page 21
        Page 22
        Page 23
        Page 24
        Page 25
        Page 26
        Page 27
        Page 28
        Page 29
        Page 30
        Page 31
        Page 32
        Page 33
        Page 34
        Page 35
        Page 36
        Page 37
        Page 38
        Page 39
        Page 40
        Page 41
        Page 42
        Page 43
        Page 44
        Page 45
        Page 46
        Page 47
        Page 48
        Page 49
        Page 50
        Page 51
        Page 52
        Page 53
        Page 54
        Page 55
        Page 56
        Page 57
        Page 58
        Page 59
    Part II: Catalytic alkylation of amines
        Page 60
        Page 61
        Page 62
        Page 63
        Page 64
        Page 65
        Page 66
        Page 67
        Page 68
        Page 69
        Page 70
        Page 71
        Page 72
        Page 73
        Page 74
        Page 75
        Page 76
        Page 77
        Page 78
        Page 79
        Page 80
        Page 81
        Page 82
        Page 83
        Page 84
        Page 85
        Page 86
        Page 87
        Page 88
        Page 89
        Page 90
        Page 91
        Page 92
        Page 93
        Page 94
        Page 95
        Page 96
        Page 97
        Page 98
        Page 99
        Page 100
        Page 101
        Page 102
        Page 103
        Page 104
    Acknowledgement
        Page 105
    Biographical sketch
        Page 106
        Page 107
        Page 108
    Back Matter
        Page 109
        Page 110
        Page 111
        Page 112
    Back Cover
        Page 113
        Page 114
Full Text












UNIVERSITY
OF FLORIDA
LIBRARY






NINE
PHEANHRDIE ERVAIVE
P-kl7,T1

AN....E
CAAYI AKLTOOFMINE






Ila,



IS




Imp

oil





I -j
low
oilmemo












4. Geneal Preetmr for lym~stl1 f i the

Ph.terlhridlae B

(a) phaaathritflMm

1. tabalatitn f datsa 3t

(') 9-etUse-phmen trtIAt* 33

( R. Ibktaia f dactai 1

(e) k-bwt w4-4n*tkexr,-pm---tnLse 39

3. talbulamae f dKa 37

(C) 7-kb~wlwine-mtw- uemLbmtwUlte 31
(*) 7-lhflnr-U-mmthear-hbmrlrtAUIm 39
(f) estblishmrt of the tlturoe of

a-U"-lht p-xir aqr-ts-pilM thridlae
(a) 7-erlarer-pfl tw>eman aetl l
1. albrlatie of data R

(h) e taUliLmst of tle strutare of

7-hrlnwar-p mafmanllsa t13

(1) 9-mth. rpyltwatlimasi
1. tabratla ar f ta 46

(J) 9-mt)at-shmatmhridtas '7
1. tabulatle of odat t

5. The Grtpaf leumtl e )9

(a) phmathrtiAM ka
(b) mbn l-2-aaslmewem

(C) beakl-a-3.bmleu3-sallMn I
to) ~r~111r ~-L~wI






40i



IL$NW"**"bom
*1jmpjwoo ww-Imm*
04L
40L
$0|











1. thaMtlaei et data g

(4) Sywethets l .f f -(ertbMhyfrayflsberl)-

e4tahu, 4amiAmt of

1. taualaties ef data 67

(e) pakthsi ef -1,' 1(ertwhndrqxy-

eyclohexyr) Oethylee tamine U

1. tabalatls of data

(f) Sr *tair of d1 nhy4yqulamaliMe

1. table of uerimtmal results

2. tabalatlea d data

(g) Sythkeis of qulmoallm 9

1. tablatie of data 97

(h) Sy3tbkeil of l-2-3-4-totral&re-

qlaeamlti ai

1. tabLlatiea of data 1e

I. S~m ryl Part II 10

9. Blbllegnphy Part II 10%

AGEbfM SDMM lo1

3W0IWAHIIO IT, S 104

cwMltn near 107




Ar la

fts *OA
400 MW mmAO*O ommp MAAt 000mm
A4 a bm"00wa
Ali lo,*o
4*s vf 0"g w f NOM1 o
vw0"W* o0 %o^wANOO












propurtims.

PhemaatMudk le h bem o wS thek i sel t a n mbaer of UAffi eat m a.

Itsa atrktare ha be e prlve repeatedly b diAffe1ret a thedLi f preq-

aat&ma. fT' irNtW7, thA momeelst ur e th.mr ghm t t h llea

Is met wetomt. The Irltitek aem M s ee uad the Ams eens, a@tlew.

In owATr tbe ellaste sflmteim, the latest sta oft flwmeriag the

ale, empllet y lMIJeN AuMl A ill b11 e useA thwe g this Aiesemt-
2
tim. -





7 (,

Phomathroiim

A review of the lites sre give the followvta isthotes of phm

thrlaoe .am Its ierivatiles.

1. Plate ame Anmkormit' (11) lseah0m synthLeel of phe ar&-

ALim irvelvetd pnuslsrA of thue tpnm f ~ sllliao smaimu tbomuk

a tet oube tit.ed witi palee hated to radmn.










kMUslitMme alint Piaem~P thritime m t mesw

2. Piltet a l Askermit (12) prlopsra orthm-phkal b-umae A,

atglitd ai them rodeos it. Ukt tlhr eobtarie by this MeOt W*


I













'Ol
|c
P-











4. Mtott Ma Bear (1 ) aNd *-slta bL&phl s tLeti te*,

rads the syl i~vatlvr, ad thu -sas-** the millMS o gve n
alkyl phomathriUe.



-T""- w2i. _- 3



5. Miram MI Wval. (22) lMepuv ftLbet's metA f 6l ebiMwt
th & yl *-a M l as by rarMhLma the sailMe with DmI "taWl e
hMating 4Uth ss il hlrlds. This reletWU preseSr wemthly a d bpe le
ased iemetaLrL iU the pnpsn tle. of &WI, mh 1s phuI~ a"
altraepbylvat Ihoml tt"lIA aoi msrlass adiH miatb tms a~. *Inimfl
to qmtersr swAts bIr Vimmv m t, (7) WVSe hot a'i Te-lnom &Z*
selveit.






Fa ems f llc me pp i.







7. Petet ad Bmset (I) e tetlle isM li mlar MWa set as f e @
ferma aid eleltum t-parl boaseMte ab s prepaid t* --i M nnmtM.
forests mmm saitus cs-besl bemoans .t IregcSl s41p~ 10~.










"WON"** VWNMP MOO OW *000 061*44 *NOW








lW*"*ii6;o' OwAlip or t*mpswo WOW
AMP* 0 *Oka







'10
Ok*40 w stwww to *Now*
SNOW 406)



A),a
-HCO
IV -C




S


10. PiSt (15) by lmareli se.kes heated 1u0t Jwlt ee me&i t
taintedd phm-,t"ilme is a M y LA.



l^.^ -- I'L'



11. %a OFtLuw Aa* ar Of tl M &Ol aMmlt hl amatti s has bVs
*ltdait by Labloelu (9). hI rfat that whom ilph i e S ei io thyUkidt

ms tresSte atLi mt lm I of SlmasU amL, the asite-uPsdamd as 1s ot.
Wit me ws able mi mato Is aleemhl-etibr sltakm to gIv preo-



JL Fi tY





T. Hey I I ad blew (5) h-ated R-LAfs bipbh7 hbrtileiflrde Wih
methaml is me atuelave for 12 hmurs at 2as0-39C. aod obtained na1iL





Abntammsarltim
a-Msite bipheari bpyd tueriAd Atmeri
Ant ~np, phamatbltia
it basos

13. rbiPhamtkrlia has beas ftel ta be preo*t Is easl IS by
eo*LeU hi t aSmhO (19), ~hs lnlateA it at sh* he Its eemalta4
vith tiras rperd in the lltetIre. Sqh were fomei to be MIsAtlMt.

1k. Sup~1jC e it raeese s termaboU 6evin tr net 4 s a~





so"* g
l |i
Ii4
ow w sw wsatm* Mov |WA
Irw~ -OM #V*M OWOO*4|A
0-6
VOW IW0 W0 00000 *%O" A*

*"ANOII

W0#600 WmIt w mo*t










bat am belly, tUuy ehAbat rl iAma. In aste of fMfse.iL as they iod
pyedistet



NH A#-U

c c
a mls-alla rearroabwmest was involved ILtvirg atf s:





z -

Wh al &mmArill e ws mabjeeted to ea y slettllstlns, eat thn Nb t I
zItsated with alohol. A malysts g e tke ftrml to be G kjB keme-
puiitag to that if phwaptbhrdlame, ia e lt iltlllattim so the Oth~ r
heAt yielded aepldrltn, itain d of the p ouitd pmmauthr llio.
17. Krse ad Ul eo (I) obtatrit a Ok bas by the alss lm l 4*-
tillatima f ly erila, aa alkaloid. ims WI tallim .mpnpM Lt) l
at l1e.50O., and mamlymris 1wMu it to ib IphlmathrSAiL.


















. ...... : ::.. . . .: .:
m" ............ .... .iii.ii: ": i jE . ..i
..... .. a a...
= ..p t ..-.-...-.


Mi i: ...... ::::: :

4,
6Me u f
..... ..... .il ....
E F aimmbvnba a i Ase i
...S 0. b e........


ryy)












It eme that the reatLea hold s prees s wllr as iwethly to rI k

phimthkttdi as awitine. A sepioC toa mrv of the litoxturw ahlu

that in am eLe has phonthritin bees pepper by sthi mthl 4 ea

ever a refrsue I t a de t he ffset that thi rmetloti dees mt go

as predle6d, the workers alwys refr tr %si original artist the

wefk, as for a we have be e able to fine, hs mover been repeat.

SiLew theme aM mT r aaMlyr their pleeLt, vhish they hbeltre

to be akcr lo, we delit*e to repet their work. WUing anu pparatI

for working adTer rdteld pressure, we heated boasal o-lephl ol with

poaphlroeis patexide an otated a bas whteh melted at 140C. A mfl t

showed St to hen tIhe mlaSe femla Lf phw sth FMLn, mia as m

of prlftl-et by stwou iorlllatis vnsU distillatle, reeretalllas-

ties, or ooompesltlte of the hlydroeleride wald raise the meltii

poiat of tkhe eupeoad above 104*C. It, therefore, was asmeu that thl

tAhblrat.e *of this ail ha yiellot phaumtkrhrin. Various anm~

of pheephweem peatexlde wre saed rthk the -1 al a r uge of tewwe -

tons were siplefd. In all asse the fil smeepou d mlttl at lilS.

Wo motiag palt oLf aeridin In listed in the Ill te t as froim i07

to 112C., while the ntjertly of artiale give the mltlig polat of pAdal-

thrilie as 1040C.

As a result of this wevo we hTave os timt phenth trui am

be syntheaiAd from besal e-amiaephnml by ucing phophlrlas petl ite

as the Adeldating laget.

ring proved that euthesis by this l tht was feasible, a smitas

of deS&tlvr s were prepared tusin the r general pua wenr. hl s4l







ow 04 M w m a

i6





low












In this wase e of the pesiblitIee was 1eltmateo by sigtWeisLag

the other pmheomathitre uel earimg the pI yil l nstuan Vlth

these of the phemaethridiao ebt9a by saing smlli erlie s *e -s i l

s the starting aterlal.

The presence of an erthe-hydregjM at em em ring l at -n orth-

iytWar l greo em the othur ring Shul4 leas to the frestm m of tlh

sme phemathritine regrtless of whish ring the hydremyl *mp It

A&ttf t. A mbevr of ldfferet ail wr* pr epare whMi ever

ail made had eitherr em or mre hbytei po* in the erthe peitian

a the ring. All of these were treated mater vrying senmitiMs of

teber utare, proesar, mad omeaetratim with regrdt the tieytauti

soab, Lph pyhesri pataeid, in *rter to deIr iae whether or anet S

W ld yielA the oerrespeldi phima thtim e empaa l.

lvery mail oeemp d of e-maiphmel yieldat a pl mathrittAu Wee-

ever. tlhoese als in whih there was hdnqyl grew a the erthe

pealtiem of the amilie psrtian of the meloals failed to syellse. A

serlw of yails as prepared be ompylig 3-hbyodwy-)-mthe bomr kaNUra

=K rbstitlted amiliuos. The mill femNo vTry srily, Iby sAtit tlh

aUehyde ard mine together in aleh1l ad aming. hIMt reetsm y

be samflIifiet by the synthesis of keual eailime freom lbeaamla e eat

nllise :







ese Mallls Crystllalised t is rame wAeedes having the peepir SAtma



































Il~li Ilplaw:
Ow






WQI WLlir i ~i

...... .. .... .
...... ...


...... ... ... ..... ...m..











to Kefl'3 IDiS


ThM prepuMtiUs of the atll or Sehiff's Ds er VIh wvew at

as iaterrnMiao in the spathesis of th phiMusthriitU 4wLnwtins,

are IderslbeA in the follevi g pas. Sev na osils wsve prspawt,

uat slz proviLemly report* alls were resystheiet.
















too" Atme a pbog o lkaie



mas 36 b* 40 amm
pop"" 4







-W ?












(c apom )







Uqulasr qatitieL (0.1 mol) fa 4-ethqr be.smlbgde anL 5ar -

pheml wer tdisasol is boil nga l ee i heat est vrwnr l SLats.
A witMW eimaw e. tA4&t a 2 the iStlaS filtea VWqt uWO SI1td

tb Mho ht flltmta until tmAbLity beg Mae the mea allowed be
aml. Crystals wsre filtered ff ma reMVyalllsed fIr P# afI am-

mat.


Imartlal formal

Ilouomlar v ightt


015 t15 l
Si. ~-tb

lItSr sea


tALar

Analysis
a~tti ge r


Vwr sat uLe L& kIt al hL

.5-83*8.
U. "3n.


5.0 U JurM
,,Z.Y ;eagettaL


T"ll


IX


















ho *#W#Mkaoo "Wow

36010ok





pomp*
*MWA 0*0
Amp" 40
*40"w 5,11,
AW












NO



O--0

tiiallar qmatities (0.2 ale) of t3-alt-beMMalht*e sad ae *Ie-*

phmel wre "Uted together in belllag aleekl. ar sellg iSseMth

nao.l aseparaWt oat. It ws rearstallietd frem 9% etemml.


i4rplrta1 lrs3
NMlef lar Vtight
Celr

Peru




swtv




Titelo
Tig"


C13 % 03
2mk


Imtoles in almelter


salable i htt *otael
sleelable nL star

133 roeeire in litbeamm (21)
fiund mllMat
11.4% 11. w

73 tbarwttim




OFF"

IO*0*IP40A 0O" m" WW
*plo
I 0*

__p* o"O rao
I ~p iiiiiiiiiiiiiiiii











2-3 3nemnNIXALg.MnUM

(Mew G'up )


Iimslau quatitiLe (0.2 mle) of 2-3 I.tle-trbseanl6Fhl amd

-miasphemwrl ann Ulnlved Isa bllin lelali. On elaC saystall

aml atedi at. Saerystallliatlom fuse 9o thamel adt ietilated Ie-

eal yelsla te p~e base.


hAtrial Trmla

Halsletar WeLght

oeler

S*lbtility

thmel

wtar

Maltiag Point

lalystis

nitrogen


15 '15 3
EST










fel e sa M gttr

5.2% 5."

SO| lM emnlc


TeldL







Rado



*A*

la











p-NwamwrnuA&~.hwIMn


OH





qLinmlar qlttlie (0. male) of malilelle eal h 4e mt artdf

were ekat together to beilla. Wbem the yel.tla meled, alneel wme

MiAe a d a precipitate formed. It us rneerytallltL froma 9 9 hMmA

aa activatA shareeal.


hnLriesl FrewU

MUeInlar wight

Oeler

Frm

SeWttillty


13 1 1 0
197

6llow

.rytlllie


rlsehel

NLtert





Aalysi o

ttrgen


snAeal la het Sat-

ime0a3ble

"-" -90.9 6"rhNAEMl

W-*1'. amfm%- (14)

femun INISMAOSt

6.e 7..oa
Sa I~l


n161








W-al 7-O O
4*#00 oAW 0*Mxwma Otxv.4 p

44 0INu N jw owo *"owo*OL4


|6 $Iw"w"ow 0*o











.-KaImAENL.e..-Aunm


rlaimular qm aittes (0.2 mol) of k-metl zyr alml- lflr aM

2-auasphaml Fere Usslved in bellag6 alewhel. Whom the metiM

eZled, crystals l ppa ad rat. Teeo vere resrystallilrL fi 9f

hemal and astivated csareel.


atlrisal Yomals,

Nlee-lar Weight

Celer

Sluability


enter






altvoym
m teIIea
YloItr


el0 13 N 2
it7

lih t-buff


bhlatbe in het eotal
iseetmbte

90-91'e. experluen

e C. eqprtedl in liteMrMn (k)

IOWA g41sulated

5.^9 6.1$5

74% teeretlrte


A









ow anM WV I Mjwf
!Iwoo o 000* 0o"f wMOP


















Q ; C HCC-H




het 4-aeatbeetwse aseU we e Almsiveit is b1eLiN e aeAal. @O sa nms

mitsal spimbek4 eat. These w"ve rwrpretllised fm 905 eOteal aa

nmtivutd haef4u .


Liwien1 brmla

NUfealar Weight

aleer


Semtli tF








sitrege

Tliel


h95 3 1 o
271


flswalwst


8mLsrt in hot oubael

imselwble

?3a-B33I*
feMe" Oe~lat ted

5.0% 5.t%

79% t1wettel













tii4t
400Wm w





















itwuliLr qpmtit*Io (0.2 mel.) oft b-eerebemON tesr e em

2-midnmhlamerl uwe d issll La be<ag aseeel. @am twltmg, WY ait-

t l use attate atd athe MTes oef the bemur mSth t La~de Il -

lis ti. Ihe aml preewlpAb e m~ e reeeystallised fhWiM f t t.


pirAal Feewmi

Hlemalar Vetht

Coler

Inm

Setlbillty

etbamel.

%nter
wt r

M.iutal Pintm



Ahalysi

2l tru es


13 i' 8 l
231.5

yellow






ia"tAble
94lC. lperimetal

rVC. rqeheA ma l te Uwm a (m)

iad Vtnt aS ed



yi tbesMeetlnI


Tiat'










A












404mamom mew *am ow"Mm* to*** *M ON* 40
~AV* 00 4000 *0 Omo %dWW,*O wSmi- Ve *4

1* 4040 a *0 04 OWOMM" tv owwwom wo **M VAP
40 qftfta sow *A*** 40 40 .40 a* ow M*w

a* "immmo veow owmwll **memo owwwww
Alm* a* ftak ~ 4ho Im Avow 46powb



VOW


Amm




Alm"




............




............
............




*0






GUIm L PM56 a 78M lIM W M UfhSUUm UI


A muectin veTMel fited with a sWM esiem JleWS aM attaldMk

by mams s a sami td tpemset sMftheA to a diatilatItm fl .k

vLk served as a o wheeler. Siommld to the side ai of twe euemLM

we a wn pim fitted wtlh a vapr t rA a -a memetir. e onW

aiefo4a vealt ml e heated by maes of mi Al bath is tflt a theeuAtmet

as Imenargld.

The au. se mixed iaMtotwly vit equal veam at pholapems

pmot&nxae oa tlhe psmue reb n e to 5-2I m. Ihe rosItL vesel m

mth leveM" nlt the all bath an. a Leafmlib tempeartu w se esltaImi

for a eertari tim lteralm. After tk req nrd tim laster l te ro-

actlm veT *I1 m .lsomentedl free the aoset- sa allow be to s1.

After seella, the reatllm sirLtme rs treated by Ifffeas t aenmes

Ia irder to lowlkst the reallttig pbemthrUlfe.

A Ilrti, quart tWbs, altm)d t.*-ml lap was eed te dretmsa

whether resetlwa tad taken plaw. The faile do met fLmsomus under the

ifltLumes of the ultya-vitet light. WThe hmathlflliaa flmtees with

minor ma~tq fom brLLgt blame to beltUit agmer m' pVlelm, 6e -

lag oe the mbaktMflat nep is the mlame. Mhe yiM Ia mal mW

we low, evmer mm n lifgll S$ at the mtheem4wml.



















71
*-Moto womw)w **ON" 40000wo *f wo
mo~ aw saw4now 4a **m" Ammow
I* ow ow uw# 04b jw sow**,


0404tow i0ow"ta" i* op*. Oki*
ow mom
1** *0*0* wo *Ow4wma ft ow "Wo 4wo VIAOwsoookk
pllfil VO $00046 ?A AWOMMW 0 *0004
W* 00*4*











hAhLinll lm~ I


IMrleal foranl

MaLsaelar Weight

Ow sali.. Form
ftler





t1or
water

dilute hyA~milerle mid

IMeliag etit


Amlyswi

attragm


013 aq I

179

Semoeums flabo.

ukita








1040 rl (ela in sIalf

14' ArlaprisfLI
sdttul

tos eiefflLatilao

10"Mfl1kLtkL


7.7%


slts te






--




lowl





















iSertal amla

Meleautr Weight

Mitting Netat

ObystalX1 m form














So trf*
ether

Mc1 (dllute. 131)



attromen


"-5 '3 N e


aM3
l39




ib


.aai. Ieste a
vwy sb Lte I he t

sewble La olA
melble ia sold

fee" InLMLMatl

6.1% 6.9 %


qg-a Nga FMimlIlmI





,MOW

iiiiiiiiiiiiiiiiiiii
000"61*6 ~go mA wt* O
" Q 0 "Wd '1V F W MOWW"o wO
iiiiiiiii*inoiiimwii0ii0*0 0 0"ot00
4" 4 Omw 0aw o iNiiiiAO01o
Owom amalI# *0 atmwiw *t4go"OA












ila 5.9. The reactioeairelvTd reSo .ha as u follow:













Thim sew sail, 2-bkMmsylexy-3-mlshexgybf l-aai-Uphemel "a6 the t..i.

for the ynathesis Of 7-iaxlrlexy-l U-mt&y-phlaeathlMi wiskh Li

dils mses in the following paJM.












I 0
64OU W mat
*wo&*
oum a e**sa











7-3BEW1 OTLX --I-TaMM XT PIMUWDIW IBRM












CC.CCGcMHr
The 2-Maseylar-- -thre.qxy-beu l--a ephaml as heated uelar

reduce pressure for tw hears at 340OC. he resetions m was A s1m-

posed with aleehel, oAl wter added. The resulting solutim was .

traeted several ties with other, folleved by ovperatle of the om-

bia*d other extracts. The residUe as reerystallield osevra ties

with aloebml which yielded white orystals med a g. The erystaLs aid

gi were vaamm distilled, and the distillate sa recrystalliatim frem

alcohol malted 99.5-100.50C. The distillate bhd the =mll of rittaf

abbage. The compoud flaereseas yelleo wrder the sltin-vrelt light.

The caleulate pereatage of aitrgem wa 6.11), that feed 6.0%.


















Iiglitl~ ul UAialig. aMs. ai n.il ns. t.. a. ..
rt; itB a Homfim maM to a41gi an Ga



A*i asW. a so por -in .L4M
um*|,fj^^_ m^^ j^ -St~.j- Wf
a -HBraI'a^W^^ ^ W.i:l'f^P"~B w~^


nn
Mee

as


-S"

qiim .


5I%~t
Eu'lr
-a ---r


am



I.M


pIMI












WUZ LISIKSMW OF TsB STRUCTrTI OF a-KNYITOT-10- )M DXT PHnL IDTHNRIM


VTr an emaI ties of the previews five pages it Is evident tMt

2-byarezy-10--umtho phoamathridiu ws fewmmtd by tihe dfldatlem ofa the

2-ha lrea-3--Uthq-beaa3o l-a2-aimephei l by the fOllowuLa resmetlte


/---/


cu



far, the synthesis of the 7-hydraxy-8-aetho phemathrldine married at

is WMabipgums. One hyTrexl graop was hIseked, the reaction carried mt,

and then the hyd l group resitred.







sA^ -^A
eC- r Cl c( lcc,
If the two esmponad are id atial, they should tae the me mM -

ting poiat ad shMuld mot give a depHressi whVe a sixtare melting petl

iI twe *m. A mixture melting paint of the two compenal prepared abeve

seftea at 1200C. ad faindly mlts at 137C Oa thi basis It wa son-

cliued that the two coipwidi were et lidtlal.













I 1 t
*woAmm-f 4w] 4w*0.*w

d"" 4b* ~0 wom il "a: supw im


U61$1 111111110111" tf .,kt M %4 ft











7-BT OXT PMUInTRIDIfl


Irterll Fenrla

Mlealar VWeight

Ieltding Petit
Mall"r Point

Ogler

Crystalline Form

Selubility



aleekel

ether

Analysis

al trea


0l3 1 0

195

1ee-lojC.

vItel le

uitgeue flatem





seluble in het aleeel

soelble is seld ether

fema eu lewlmed

7.0% 7.18%






!o


#* .Os*o vodvwa mmo 0*0aw
i ii



*40 0 Am owgit ... .. ...........
%MOW agaMW
44 oft
#mo/w/-




10iiiiiiii .... A* *Avi *aoo w m wtmw j.jf













pnrw ed by tUF follleiag e qutiea


CfC0 H1,
041


h.wretre the phimthrid.o rather ised frm 2-hydrQbeui-el-2-mai.

has the felleviag equatler:


J
c-~c
Ct. HI-




ljjm [W[M
MO1R Wo"
i40 &A
I
"W*A 1*4 ~ 101oms -*VW 10:Awtw
I 44 "*0*W.6 w""k oA"" 0
*00 AV|O(W&0 PWO AM f O "tMVNW












9-fl pmaom "nr


mprlval arDslS

ftlre.mr "w6u

ktali itri








alehgh
otk111erm
Gor
AaItaluit







Amyt*l

malram


an

,bate,
edlmqlo IJ nmNl,


dWble la





6.6qI


~4 naJ

add Saw

had










la -


Ho




H



,allm. :0 um go e moma b"11 -a f-man seeA~ an momgea
Oa ifV lll amlM .f. f,,%la sa. SO -Mauf 90mM W
nSmmn avIoi ,Vi am4. usr naY~aPe., L loMe mo
InF dMu SMAmaI i/ m6uSe. *0 GaMfW A bUMM em
olaw do 4Aow0t4 ,ao. no mmanag at sto "ab"""t
oma 0s a. T300 ON plbmmif" #am 1" 7.2%.












9-MEmL FruANTHlRIDInE


mptriel TForm l

eleenalar Weight

eltina Point

Oystallie Ferm

Selabllilt

water

aloeoel

other

Aaalsis

altregon


ill 'll B
193

111-3.10C.

almster of handles



IolAbls is a eUld after

soluble in hut alcohol

salable in col ether

feoat nalesla te

7.1% 7.32%








qo *


ot*m
+A Wt 0 6 1//*Am"
qt*04os4O amet*
pw "omop og ow *** oo# o"











&ime dissolvedi I absolute e er was pt ate the eap tery fumau l bte

aTded drewise wtil addition was eeplete. After refl n ing ftr 2 hmIs

the reflex mcemner was replnaed by a LL ebilMg ee eer sa all of the

other distilled ff. Then the residue a earned with 200 eo. of aiter

acidified vith O9 ee. of concentrated mafurie acid for ens hour. The

revmttig slati n wase aede basic, and aztaeted several times with etbur.

The ae Amed other extracts wvre eyapeated to drymess aad the residl e

kELma up in aleekel. Recrystalliatioa from dilute aleeel yield.e white

Stesmeea crystals melting at 104C. A *xItre melting point with phba-

mathridiue sh*d me depression. ree these results we aeeeludat that

m reacties had taken place.

The next method to be tried involvAd the oddities of the GrigLe

resgeat to the aeyelised anil. After aMditie the ring oueld be ided

by the previTws methode sed for the symptkels of pheaMthrifdme, It

has beem raperted in the litemralr t th the Brigea rn k will rest

with bemsl-allime In the fellewng mner:


C

Thferefre ia a a flege

with bIeml-e-aulinpheal t

- te giving a bottltateod p


/ ev-

6 6
maser, the Grimar reegnm should rent

o giv a seeoadary adAe whlch ouald be wele-o

hemmathridina











iiiiiiiiiiii,,,.. ... .. ....... ........
O w 11 10e: .. ......

Aww 0 MtAmwto* om 004 oe
VO JW 0 0"O A i NWNNO400











plat with beGM-e--minehroml was tal.em. The rOesties which Aid see

as probably am sUALtLts whiek Lseeapsed ea ac ltifotias SMu&St the

original ewGMlMi.

Aaether attemt to hbe the Grigard resunt reset with the a&L

we trial, but this tie t the beast of the ail w nu sed instesi of th

free sail. Theuarettelly. the lmaetle skhald presetd in the fellow.a









6g1 V






ape rimetnl ta -l

Kethkl macLtil litulwa mi prqtli asserting the the Iaeepr preo-

eede. The heiail-2-bemiaslezr aniline mpeaLIe in Ly either mR wau~

ireivi L to t I Gi wrli resgut with siirrlg. A iolent reattlies li

place ca mlzixg, eailag the ether to rOlufl very raptily. Aft" all ot

the lail hId beU aiLM d, the rietils mixture as relaxed for e bear.

Them 0S0 e. f water eoatainiag o0 gcme of aemeartntlei lfurl stAL

ms aUioi and the ether evaprateA. A brai- prielpitate relasin is

the flask.

Cemeamateld cdilus hydreoii loluttea was *L to the fla*c auil

the reNetse Mixre wa base. to litom theM I masell we aida.










:O laH daR IMit sunB Sa OM e IM M aua a MNaAfMb lHU

ON"4 aOD oft A Ww-agema- Mea mpats nI
S a,. m me n tr ite.



*s -laf ein*olmim I, aF** a tol$. w=t as dwsn
ail n s we n a. esen a s assr |e e


t."_.'









h-'>


I 'li a r I... I o l
ha lia: ai l n u l a .e







oIi



L "-- irl 11* Iii~it I~ IrI----~*II















L-b sw-l-2-a lphml fir the s kk roea wma sxed intlately

with phfephbrea paemtaL&e in the reastime vessel at boat ppgler ftw

ee hear, the stoe beina u er 5 m. of merwar. A white e~MeI ll2me

sompeeu was ditilled late the receltr, adl wken reensftalliteL gen a

mltang point of 10I-30. JAlymlsis shed that the oew uad wa met

phuathridme, which molts at 293 C. (El), but I-phevl-besameale (X).

Mhe resetie inrmlvd my be mIhew by the fellwing mother:







C,


rl Ulel l oi fth Mer letlna used In the attempted formation f phlia

tk rlme, only the 2-pheaol-beMe sele was formeA.




mw

so momI*$*
oil mr"ov W Alo&

* V ot m
mN

ft wmkw&
1 Mf 4osrwad m v, *mo




- .


STYII S or T. PiiWn-DIEnMuo-ArTISes


When beasalAebhyd* ws heated in albeme of the slvet wilt lkbea-

saphthol, a pranetlelly quantitative yiel4 of 9-plhe l-1-E, 7-5 Ilbe-

smansthem uws frmeA.





ON




The crystalline eompenad was ina.std a4 fomd to ekek with easteata

lited Is Bellsbeia. It had previaLly been proWped r r bl-A tI beLt-

mnhthl with beasel ahlori e by I heat n beta-mpkthel with besie-

hyt In acetie acid selntien In the presoase f osem temtlted hypt uerie

meAd.

pewrimetal

As omeme of besaltehldye me sded to breta-maphVtI, A the real-

bAng solAtles was belled for te mLastee. After smelig aleshel was

added to the *eliSdfled assa nd errstalb s l e to fem. S'e impemd

ws very iseoluble even in boillm 9 aleohel, n lesbing wittl bt al-

elii1 remoTed the areacted phemal and al&de The 9-phelll-l-, 7-1

dibeans-amabhas m extremely sll'bl Ia Mold chlerefem, and Its ml-

tlag point mr 119-19 C,.









FOR
to4woo 40*wm" *vmw mf

AV*"*
4* mo *owat0












S UEmT Mit I


1. The nMw syntheis of phemathridize h beena reported.

2. The following aew phkemthridias have been eyuflkeesed.

a. 9-etheyphlimakhritte

b. 4-hydf* -le-metezphemaut&ri dln

e. T-hydNl~-s- -meiab yphemathrditne

d. 7-hbdro pLhmaathridise

s. 9-metherphemathridine

f. 9-m thliphenamthrliiae

g. 7-bmseylezy-x -stheM yphe athridtim

3. The following new Schiff'e Uaes have bees synthesiled.

a. 4-etheryboeasl-2-amiaspkeel

b. 2-hflhozy-3 me tLhexybm l saili

e. 2-h4tneqx-3-utbyqbmi l-g-amlawphnel

A. 2-ditmetherobem-nl-2-aimpbeolM

a. 2-hyfroxy-3-me thybeaml-4-athlequapL line

f. 2-Iydrez-3-me the zP tami hemel

g. 4-hytmeanxw Ml--omiaephkel

4. 2e failUtw of s -aulae--mphbel-t4-mle acitd so ce r ki-e wt

with beaMRlAeske mlner Skt aelititm triel ii t4&t.

5. The unresotivity of the bKmal-2-aaiopheel beama the M l rt

retgent kh be investigated.

6. Two ne pberl-dibela e-artb-u have beea prer"od.









IIM
Ji. *
oalS.ft.*.*o
vn'Int* 4'oot
AOLa1t










VMS II


hbalytLI A*hlabkUe of AMme


Primay am .semaur aleSeble will tDtS with p5&twy a seeMIaiW

aImee umer the lafIeme of esItlyste to JelU ~weery ad tetbrwy

aiNes reepettlely. eM resetlm my be eaieeset by WMhe falle iW

equatlemes I


gfles / I'g -- MR'g / R

lwwee, seles it hM been *sea (12) thAt tetiary alao eles t sOw

thi type of reetio, the meekitmi f khe reartle mry be sewe to

be the 4ebragimwttes of the slelbel first to give bth a4dybte or Imto .

vwich wuld tkhe roent with a am ne to ie pIratet whie Is really

Wytpgea-td to give an ane (20).

cagena -- 0 / t


2ceflW / n -k io2om / ma


Itblhe (13) f 51.1 thae term esOie ew ueor fimrA eMt* at a" a&

effieleMSt etalyst at I0-5iE i0 Oa tSre e phe seaem Stess sar .

Lee ad methaeol et glve hh yJi of ~w h allis lL I sale Ptri

Stait alaini smde Iave so ete epn k ver1a of u 2pl ta

setelry Ma tertiary aMleS with mt &IL at WtE, y eAm s taf (3I).

T. B. Jeahes (11) ad A. J. 1.1 (5) wei tMhe ws-rlee dl

the Maiee with Sthe AleeMl is mantelvels at a toeatwe f l* 7*4. Wth







fi o "W0wto tomb 6
4"4fv|*,n *oo 040" wAW 0
41111" W JN 'o N t o fwo o #4A
*JI* 44 A 0 W
010000f"*0s 0om boam L
404 4" *0004 0 .*0












oer nemaple:

-C-Co s,- N

S -- -Cu cu c
I \ /
f -N--C -cru C-- tc8



The formatie of secodary &maies from primary amise daring Wre-

gimtioe of cysaide over alakel may rewlt from the felb ring mempbeal :

1. The mime my remet with the aleehol ased as a melvat to gitv

the alkyl&atel ine ad u~er.

2. Two me-lele of the primary am e Wy reast with tihemelve to

give a see tary aide with the eliisatiom ef a m -losle of

ameals.

3. The alkylidere Imise sm wpoads may react with themselves.

Kindler (12) showed that ever palldiu primary mines mdervet the type

#2 eation give abeve to yield Seondary aiecs. h tertiary mieme

were ftomed a Is observed i the alckyatie of mi e. with a al shl.

laeely copper chrilte aoslyst has eme into extensiv use as

oatalyt. Generally there is a trace of peMlshue fluoride, or baria

chrealte or other promoters mixed with the eatalyrt. fiaM and AdhisU

(1i) obtained good yields in their wyntheell of prlidees, pipertiise,

ad hesu-hytreasepiaes by carrying out their resetivs at E90-w26t. femla

a00-i40o atmephwree of hdrol uand 700-10 ec. of diSaXe per mole of

dismiss. ad glycol ver apper chremit. Is gameral iAm (17) fean t624

glycols reacted with amines whAe the hyrogenatin was enrled t li









wwwo"'O" VOW ""W ll,*Wwmmw 0 4*00W
opoo"t pof k *%w* top Aftoo


OWN" *40mot so "Ot *To *00 ^" bh*o to*
vow"" **O*loo* 4,J).




Il






asmu ry of the Prblem


The reactions of peoxy s~epeudis are almost always of the additlei

type. They usually react with compoands containing a labile hkd"ew

stoa, such as aleholes, phoelel, mines, et. As Illstrated by the

folloving equation, the ethylen exide rig speas up in euch a way that

the labile hydrogen atm attaches itself to the oxide lilpe to faer a

hydroxyl group, while the rest of the radical migrates the rosmintai

portion of the oxide:

C--H QuU- eW c -
-0 2 Or R' AFi I




With this generali'ation in mind we decided to attempt to synthtotse

2,3-baazopyraziae by the catalytic alkylatiom of mines. That is, we wnmU

prepare in the tnterediate amino alcohol and then cyclise to the pyrasik e

denrtative. Cyclehexesn oxide reacts with ethylene diaine to yield

I(orthe-hydrory-celclkehxyl )-ethylenedamite:


rC C 4






This reaction in compleiatdA by the fast that the -tkhlen iLmine oks t



S' di(orthe-hydrozv clehe 1) t iem .Has mu .


)-C- C-- &j
LI L


-c4 CII C w


N. / Cwe't. IC.
C<-a *N / *
^Cu C







No Oftmwi 14 0 1loo"I
t Aiiiiiiiiiiiiiiiiiiiiii
rA

V 00Vf




aI


/C
r " -


BOwever, two Mi*e of the oxide my rest with
di(boetsldrdxyethyl)-e-phyla dlieame:


tNtI Cfl cjLJY 1O

OS


the ditaim to give N-i'-


nI r ci 2SJ --
^of" 4 C'9 ,,, CH,) 4 1 "4 7 pH X C 04 H,


M Um the N-(betabydroxyeth7l)-o-phkeaflme lain I s hired, a larger
molar excess of the diamuie is used, so that the peuribility of the -I'
di-(behohydro q thyl)-o-pheyrlenediamime bet g formed will tbe diminiwed.
It s understood that there will be some of the by product former In a
reactisa.
The N-(betah.drexyothyl)e-phaWylmedi tae ea be internally eatl -
tically alkylated as follows to yield 1-2-3-41 tetrahydrpopyrlal :


SaN
4 C1
C.'t


14

i.,










to1 Imo *W 1)







0 i
!CH
C %A
*AlkiM






















3. Hydrolysis of the l-A4-ibeasoerulforly, 1-2-3-4 tetmraw r-

beaspyraine (7):
c.4 C- =V

C.







It is soluble la other, aleehol, calel fore beatso and hot ster. An

aqueom solution gives a blue sta i vith silver nitrate. It eLdts

2-3-beasepyraline ao exitdtio with poteassiu ferreya"d.t (10). Ferrie

chloride solution gives a violet or blue eolor on beiag mized vith a

auleeus solution which on a&dtilet of 01 turns greas or lihLt yellow

and which further changes to brown or rd an beating.

The 2-3 bmeaoprazine or quineolime and its doPlvtivies e be

prepared by the following methods:

1. Reaction of o-phosyleaMSainle am alr ol or its sedtl eEl-

fito addition predsdt is an aq Ma*s soluti (6, 7):




MEMO poll








































C, "C r4l






14



C










5. Bleelion of e-pheylmls alw ai & sa alplh-ket-aseld:


-0
N14 c-C



6. bactles of a aBptkqulee



' "


0:n


---


7. Oxidation of 1-2-3-4 tetrahydrobeasepyrsitia


N
a\
CH
Itt
94


0"4


r :

2NI


to qineallina:


-# 2 1.


QltaLanlie is a ejrtalllas ome eod melting at 27'C., boIls at iO-2S23C.
7690 marar awd )ao a qIlaelLte-like *er In thbs 91A met a gApNsUtaa-

lI" *etr a hating. It is nlmble in all pruerptme it mater, alael,
othrr, sas beasme. It can obe xLAted with pelasLemw por at to
ppvrime di rbeaw lle acli (19). It frme alts with neral aeL, **-
alle eldt, and platijm chloride. A tmtber of dtrivatiLves ha been pro-
pared (8-9-16). A seltle of the free base an water gies white pre-




ic i


II n













Orplate frthees

Cellectlve elume. 1932

c HU

~II C1) 1c 4

-'. cI L -., /




1H1 a solution of 25 grse o metric shler a is 500 sm. InuM e

a 5 liter Flrit s80 gras of aracked iee wao a4L&. A ol i ea4Sets

of 190 lgree ef RL 1i 500 ee. of Mater was added ad a spit eamin

of hklerne was p4ac4 Late the mirtxre whieh was me *t bela Ow 9h

addities of eMerine wms msntmed a il Uthe yllow p lgittaPite of 0

disappeared. Them o00 of geld ithes &U (1.5 i) ws addA with

stirring. The ome trat lol of 51 w" stoeiamed bl y a4dilg L men a

Inmee to a- eases of KEl sbaitL, ae4Alfie with Uil, tAl Mtamtt

with sodium thiewilfate. lJ We l the conembrtntin m M bt)wea 3.-"

4%. th ammset meessar to rset with 123 gnam (1.5 mawl) of esele-

hroie was ealcula ted.

In a I liter ShMa better flack with a good mldhamtl etlre M

plasce 123 pame of scyelhszam saL to It was aded4 I tihe OeSNla

matnt of MBl slutlon. Ish mixture e kept )rJOV 15l m*t was si-

red vrigtrely untll 1 e. test partietl ve m y~elw eLter Ihm tr1ste0

vith lI solution atnd dtlate E. When the first portie *if II1 be

reset4 a seead pertiea Is a4& ant Ithe pEWe rN. rs M mlI




V- 1 M W
4wwo0 o*Oot pO "
%tuot *W wo*o Ott pw o o
4MWO 000% iWO*a O 4t4M"4
AW4wwW t mmt











Oylebseeme Sxide

*rpmla Byntheses

0eoletive Tlume, 1932


IS a I liter I. flak fitted vithb a meehaiGl sirtl r wia

pla el a stelatioe of 70 grame of setia hpbaroxl li 00 ae. water.

To this sIlati L was auded 230 gram of -Uhlero-eyelohoaMel. The

mixur r ws bst rodigareasly for 1 heru. The stLrring uns surpe

oau the upper Layer ysparatred l a separs fmo yt It wa distilled

tkreugh ant effieloat eslum, sa. the folleving fesmtiL cslleetet,

100-129; 129-13h, 134-175. The first fraction Is geloboume ozxde

Mla vter which ir e sarated with a seopratery f aml before the use* a

Aiotillation. After the fraitieo boiling 100-129 wse elleeted, th

oeat6orsr wa rumored and Iried teore gily before selleetiag the mesad

freastlo. All of the fraction were refractloatut and the portiat bitlt

19-1p* ais enlleotet."

Whom this work ws repeated 6% of the theorttel l yield wa oh-


talnse.








so 4"i" m
Aw im *04* n a oomo** p
ot4wk4 om*^ elo O w040.4
"1~oo pw owooova"t*4osw&t
im kMW:4M W fS00 l'i
fomolo*No




I:..~d


sTMBIs f I-Cu-(BarFMroDIrM sL)-.*-inifTLLE DIUMNIM





e F4Z Nr P C P
,. ",, -^




According to Babel and MatICCrish (13 eMtylel e xde resets

with -phieale dilmi in a sealeA Wto is the present s of Wake

to yielXd U-(fbtahtremznthrl)phMoe t dia n 1am. I wrm, wolk ra-

rted -m at thim Institatiea tilising this type reacti'k of pOfW

Meemupom indiesses that the use of the solew tinb kf Imemssay.

Oesequently, ve preceded te rry at this ren tia in cold smthml,

sitae ethyloee erde and the e-phewlem ddesMd are sluebl la that



Mketly 106 game of e phetml Al se were diselvt wIun

methemel (e. "*.) Ia a 2-liter beaker, fitted with a meehtel

stirror as a g islet tbe. Tha smeottia was them reMed msor to

rem toeratur. Thirty wae (2/3 mue) of etbhrle e.zid me

pored into a Mt0 e*. eusties flask nmected t the Cms telet aMe

by mea of a pl e of rbber tabilo. t~h flask me them soat lth

a rubber stepper. 9he etirer mu put Lute Ostiw, and the ethtiN

otide llowe1 te distill Ilewly into the ethemel sDMtiSa. ( IM

ethylene oxide is poiteaes, 1t t I e be haled early If kept it

a e lluder w ide premmre.) After the othyleoe zxrie hat distilled

into the mthasel solution, uhidh had MOt d dk ioet tih nr mSM





.............. I M 4c M,


19milip I" squ am 1000004pow


7-
400 4000yamp looms it 100110000 wwwomma 400060 40C Ift
jMqpww *0000 0400oft 4ANWO
w"06" 0%000
*4 ***No **4060 wt loop*
400 owwwwo 40010how ee vamow"aw
"N"IM00101100 WNW**
A Abompis idNIO
Now *00 aw *0010
low
40*0*^ woo *444w* %4 A00404*0 0"Now imo 440
loop 40044ok 6600 joli aw w 40mew

At am 00000 *mwo aw OOM -
41400*00wo, 4OW04 Ivow wo a oat 1A



oil
loop

INS001106 Ov VOW a "wo -I-. I "a- OWS4 *0 ADS*

40ft *mow
4" mow mow 46 owmmmsl.
00WOONFIS Amu


TRW sum











Other rua we' mae s witch LO gm f tthe -~lLe lM eu L

were Liemlvei In the wm ntheael Seluatlon ad gems of t iL.O

exile (1 mole) were dAetill1 eleowly lat the UMdia. w3atLa. Va

e thanel was ilitillld off at atmhoepheria pIreom e adi t reltm

fratiatedoa thregh a keort lar at atmosphlrie pnrenir. fwe

foattims were obtained:

lIt fraetieo 256 / 760 -. -morar

efd fractie bp 338/ 760 -. wrmri

In this ease 60 ame of the uarnetd -pheileme dismiss wre rsen

as the first fratile. It diltillle easily and selldtA t eelAlUg.

The secod fraction of 60 Cuw (R6.5% theory) was wmyetallise ftn

be s.m ad gave m mixture melting piealt Aresmian whme takes wlh

pure N-(bet1ldreuethyl)*-pheaglw ldantae. A few gem t a high

beillag red *il vwre obtained, whi e was r how to be "M' it(beStllie-

xqMethl)--kWph1lease amaLe by its bi iag point.

The largest male Patt of tl se ezxLe to e -phevlaee Itliate

Mea wa 1 1/3 o 1. der the sme seaitLeme as se prer4m mJr ,

60 game (1 1/3 ale) of othylene exie wa elewly "sltllet t4l ML

gram (1 male) ef e-phebale diamie ln 1390 -. memlum1 a a@Ser

first distilling off the es hawl, thk r-silae distilled at altmeltig

preensre thrscgh a b1ort mele. Tw fisetin se m bttas t

lit fra*etm ip ~W6C./76o -. am, y

2ad fraetir n bp 9e ./76e m. meMr*

Fifrt Fam of the waorsted e-pkhmlese hiaAe (fseeSi ftl)
were recrvered. A tetal of i gream at the $-(Vbrsgesfhir w qt )















,-(betehoyrn yethyl )-.-paexvlae diamte




SnJH Cl c, MOT0

'IVH


impriel fermla

Noseelar Weight

Melting Paint

Geler

Solubilitl

tbel me




ethmael

dilate Cl

Aalysis

nitrogen


CI 612 02

15

6 1e6.4-107.5 .





fairly soluble la btt, slightly ai
seel


very solble

very solble

very soluble



s. 1


ael0alated
u.Uiaf






cI f42

Uf*M W 1 MOM1 60000 m OMM

fto W-dW*OLAW 00
Oki 40010* MOMEo00*W W*
*Aob lo ""s pw"%*nt&* 60A A
mm 4sombo
*6AtmoN%.w* Nw
*A**6 OIfk So
404*!h *Iy -4*
*a*0 m # wiso4 *:**0*sf




A ,.


diaute MWhd at 7T,- It me as p O IW btI tr e tWIu e tgt

rise uet by tse iJelidah methios. A bollUg petat riem of S0.JW.

was obtained vws 2.3k" gam of the sampeld were diswelvT i 9

mms of ettime (X1 eersiame previetslr t be 1.05). this a a

ormieuJar vwght of 193. The salcalate saleesaJ r wveltt wa 16.

MLtrem by Ieldal: sll nSted 14.-i, fOI 14f .. fe eempa

Larks"m an steatali. A total of 5 ass were adr.

The felleawlag evti e e uwne to seow tait the ftwele of ti

Iil' Ai(butmrhlsemthrl)-e-.pblamLe 4nmioe Ms

M C H CC HCo 1.1

Ct P L(C &M C.M


iintead of t e pessblle forual

/ CH C3c-
C ;, C /,( c g-

A-

One teeth ale of the eimpsna (19.6 gome) w tiselwled I 300 ec.

of water aMd 30 of meem- tem t htJwoehlerlc stad e ad Lt. LU.

aSted mtll tihe slaU teqpoerstrs m belav 5*0., at tha J gO.

of useeMatstA kltrwetLerc aelt paseit Si. The 19 ltSv am6tet

selti, me as et it ta il eta tes rdot t eae he. keft. a

em-best gram et 4im.thrl mimine we w &od and the esoluttes sial.

Thos, vessth emda seoatts as am4oL amtil the seltAsm me betAs. a

filtering the reatiate* mxturs, sely a guess wm -w abtatied, hlk

It to the bIleef that soly a aIt e oeqp ea might hov beem f t.









01,10"PiOw wo NOW "POW *dwmw












5-II DI-(ABIIAIE ixnTUfL)-0- WI IDUwNL


'1 C i(p Cr i H

NV Cei r cn


D&rtual PrmSIa

MAeenlar WVgkt

Nelrtag Pelat

bitLLi Pehat

Color

Stablity





--E--
alerhol


Abemomme
diumbe 31

Anmlyis

S tges.

mleealr eight


010 16 "2 2
196

97-9901.

t 5-2"O*C./1 m. MrfcWry

pldkish violet

darkae an tasting



ery Soluble In eold

izeelable La -*l4

selable

esalla ed flad

14.# 9.

19< 1




















7*4#W WiOWim 4b Of irMri< *h b .m 4



wS.ii ms :s. hw ijp iia luill 1ii w






Ii::....... .. . .... .... Wa t j .
qgiifCi *P-M '. me v o ilr **m lE NX
.... . .... .. a, e





*1 age piii::i i m ain Meir Bn s mia tii, in




.... -. .iiiiiiii miiii
es a ~so a q14 i











lit ifUmtte mLew Te./B5 I. mery

IS f Mtea i .le'C./35 m. mw~ y

he first fra lm Ms maSed .tb Lse MIt e, lme 14 tel At at

12i. aer aI IphAS pmeanw tl SeMAl Sme*atB, via Ml

%l*h a pOelkwr dw es eralllalt to Ivw a r lleak ISt mes.

to mthUg ptlat of the mpoma wa daettrmet L a trned stM

peat Wppantas. The petat of clear seLtcti was 4101. The oepm
mue a mub-l.l *l&d at mm tbempMrbar, mind It mtalem4 thWt

jpaty re llm es f te member of timu tht it tas rViesfmttlao .

A 79 yeld o tof r eolrp m w ebaista. st empSms vw*ly

eluble IL etohme, rmotheamr thb, twrt1ey lbateLe, ms *eld rtew.

It ma MllyrtA by rmas f a KJe Mald. aemrantlmi. fitLages amLgo

late 17.9K, fie 17.70. A total t fwr nRs we mAhe.











*amu asw
4041
meses Ima a
I ssa
gat
age me as












STWianIS O -P' BI-(iTBn sia3lriTnmI)-WMnL manuIS


C I.

C I t- I
1l-


?H? CL r \w,



'P" 1 1C,"


h white eryrstal whiek smepeatea t from the reetlem abtlwE

daring tire sBYtMeil of the N-(Ortthbrarveerfehm etq)-ettariL e i mhe

vwe shu t bh e Ui I-NI tl(ertbetIraWs1l hia(l)-.ethleMe rAgue.

They m It at 05-0U &ad wert Laneale Is bells atheMel. ft-

Wtr*oo ealaML tei 11.1, f em 11.0O. te sntretare wa prewdA tW

synthetis.

Nigh grosm (0.0 m-t) tf N-orthadral reruelhml-a*hlrem

tda were dissolve Is amthmel mit 5 SJ m ef qaI relehimme eOld

(a."5 mle) were aded. The selattai wm hietea e a stem btth a"t

the methaml riv* a ff. tlMe W *mle wvre o btahmd ea cn e lg.

Thes mtteod at Wi9g-.. Mat pm -m depressiem wvim a states a-

tig po-Lwt am trka with te erystmle etura L aeA tlh sputlbes of

the X-erthmladLMqreleeMtL-ethylem diamie. The remati s my be

expreimed as fellows:






L~ /
"C rI %4 C.' 1

ru kmC 'r w
L-"^ CII, t Cli ^C ^,





















cx?V#4- CH












STEUr1iS Or B IUrXmCpinunI"ln




C It, (II Cf e
C U




Thirty gr ef ll-(orthQlorenuio9 ql )-etklume Aist b

*e. of purified dlonae, and 6 gr i of wpper oraite catalyst were

place in the bob of an Amerian Intrument Oompa *Rubm Shair".

The bomb Mws ele*d and the presr. ea the mesttioe mature raised

to 100 poend per square Ich with hyrLge n. Them th prmsare w

farther lacresed to 800 pounded per square anch with attragml Sih

benmb w agitafte for i hears at &I 0C. After ceoling, the r m tea

mixture ws peered at of the b.t ana the estalyut, which had mot

turnd a bright copper oelor was filtered off. The di ase was hs-

tilled off through a ishrt eelau, and the the eenlue was tilitlltA

at atmospheric pressure. 0e fraction wal obtain, afn it ballet

at 23-7*. There had beet M reaetita.

Sims we heI that temperature plays an mporteat part in the

atalytie alkflatiea of amines, w &Aeeled to raLee the tmeratuar

to sea if we eald obtain n latea l al&ylaties. fhrefore, 30

gracm of -(orthl hdre yorelohexl)-etly1eme diasMu 40 ee. of

purified dioanm, ua 7 Cgme of eopper-hrmi t catalyst were plan

in the benb. Pressure oa the reuettem Atrae as raised to 10l p elS

per (r- itSk with hydr gef, and the further inameaset- 4 lO piwA

pt square tneh vith altMege. The b ass w tated for heaL s at




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