Table Of Contentum m zm m & zm m m
Walter Behert Kmx
A dissertation submitted In partial fulfillment of the
requirements for the degree of Doctor of Philosophy
in the Department of Chemistry in %he Graduate
College of the State University of Iowa
August I950
ProQuest Number: 10666175
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' T v ^ o
W A r
0- 0 0 . &-
I wish t© express Ey appreciation i© Professor MLph I*.
Sbriner for Ms enthusiastic guidance throughout this
study. I als© wish to express ®y appreciation to the
faculty of the organic chemistry division of the State
University ©f Iowa* for ®a©y helpfnl suggestions*
r
os
X
U
ii
£m>
Charter %tx&
i wm m m m *?$. %
♦ * *
mmowmh m
i i j 3
H i mnmmtm vwssaam * * . . . . . . . . . . . . . 9
A, Btc&ies «a- 1,3~3iph6isyl~2~heE£opyryIi^ Salts. . . . 9
B. S tales© a 1,3* 4V£riph©isyl^2-ben2Gpyrylim Salts . . 14
j
C* Jgesevtega* Siraetnres of S^Bengopyrylim Salts. * , *2
15, Absorption Spectra of 2~Benz©pyryliPm Salts
and Helatsd Gomponnds. . . . . . . . . . . . . . . . 29
Mwmmmm
I? ..............................................................................4i
acid . . . . . i &I
H©©©phihaXie amfc^&rl&e . . . . . . . . . . . . . . . . 42
3-Phai^llsecomarla . . i * 42
1 # 3-Blphenyl-2~beasopyryl lam perchlorate. . . . . . . . 43
1# 3-Blph©Byl-2-Mns©pyrylitiEi chloride . . . . . . . . . 44
1 # 3~MpMnyl~2-ben2©pyrylinm bromide . . . . . . . . * 44
1* 3*Slph©nyl^2^'b©nzGpjr3rlinffi ferriehlorid©. . . . . ( . 45
1,3~£iphesyl~2~bensGpyryXinm ferri’broml&e . * . . . r'. .4 5
$
Ozonolysis of 1 3~d iphenyl-*2~'ben zopyry1 in®
perchlorate . . . . 4 6
Bensalphthallde . . . . . . 46
2,3^BiphenyIiEd©ne ........................ 4f
2Jfc3*Btphei^liad^©. . ..... 4 * * * . . . . . . . . . . 48
- (Q-Beiixoylphjenyl 5-ac©topfcenone and conversion to
1* 3^Iph®nyi~2~hen£opprylisaa perchlorate. . . . . . . 49
2* 3-'%Gsy-2#3-diphenylinda»on© * . . . 5©
3* 4^Biphes^liscconcJarlR . . . . . . . . . . . . . . . . 5©
3f ^Trlp3seajrl-2*-heiis:op7r^lli2Ei perchlorate . . . . . . 5©
OiKWJolysts of 1.3*4~triphenyl~2~)^n£opyrylinja
perchlorate . . . . . . . . . . . . . . . . . . . . .5 1
l~Phenyl~3* A-dti-t p* ~ni tr©phenyl )-*2-henKop^ry linan
perchlorate • • . • . • . . * • . . . . . • • . . • • 5 2
Osonolysis ©f l-phenyl~3. p* -ni trophenyl )~2~
beazopyrylicm perchlorate * . 4 . . . . . . . . . . . 53
Phenylphthalide . . ..................................... 54
ill
Chanter £a23.
o-aiieMoyi benzene. ....................5 ^
(p'-AiBlnobenzoyl )-e-benzojrl benzene. .............55
(p*-Hitrobenzoyl)*o*-benzeyl benzene. . . . . . . . . 56
Measurement of absorption speotra . . . . . . . . . 56
V SQNNAST .................... 62
n ttsuomtsm, . 63
m aiosa«?sr , .................................................................65
iv
X
Gh&pter I
Most organic! compounds are characterized By the fact that the
carbon atoms are covalently linked to other atoms* Relatively few types
of compounds possess physical md chemical properties indicating Ionic
structures in which the earhoa atom lo present as a positive earbenlum
ion or a negative Cartmnlon* £w© eltueturee possessing carbonim lone
are the trlarylmethyl derivatives (1) and hemsopyryllnai salts (II)*
fhese formulas represent only one of several contributing resonance alruc~
turee.
0
I
IE
A survey of the literature revealed that only two definite
examples of leobemaopyyyltum salts (III) have been prepared. Structure
(111) is isomeric with (II) and again the formula drawn is only one of
several resonance contributors. Because it represents an unusual and
Interesting type of carbonic® salt* It was of interest to devise methods
for the synthesis of isobenzopyry 1 ium salts and to study their properties.
Cl On.
3
Ofe&pter II
nm&itiCAi m wmmmwM*
In 1909 Etcher end I’elser (I) prepared th© dibonsopyxyllum sell
(?) ftm dibease~Oh pyroae (I?)*
Ft Uv
3 2 3 Z
Inspection of the structure of formula ? shows that it may be regarded
as a bemaepyyyliuja sail (rings A and B) or as an isobeasopyryl lum salt
(rings € and ®).
Only two examples of mfuestioaable isobensopyryllm salt struc
ture have been described. the parent tsobeazopyryUu® salt (VII) was
obtained V HttJttt and Eobinsoa (2) as the result of the action of lead
tetraacetate on tr^as-l T2-hydriadanedlol (VI)* ^he intermediates were
not Isolated hut the solution containing them yielded the ferrichloride
after addition of ferrio ohlorlde and hydrogen chloride.
CHO
\ f*
CH-CH
i
H
‘Eh© structure shown was based m the faet that mam.&a converted It to
ieoquinoliae.
Shriner and Johns tea (3) also prepared a salt of definite ise~
benzopyrjrllum nature hjr the action of phenylm&gne slum bromide on iso**
couei&ria*
ONfyoh
Ct H$flAg8>-
NH+O
-y m
5
$he addition compound was decomposed hy am ammonium chloride solution,
and the carhimol (II) yielded the perchlorate (X) upon treatment with
perchloric ad d.
It may he seen that these two preparations outline two distinc
tively different method© for the preparation of Isoheaisopyryliu® salts.
Both methods however* precede through the same type of heml^aeetal, or
homi-ketal, which may also he considered as a oarhl&ol.
Im the ease of j|& or $r| substituted phenyli aohenjsopyrylium
salts it would he espeeted that they might he prepared from either the
corresponding lactone* with phonyImagneslw hremi&e, or the diketone hgr
the simple addition of strong acid. with i*3^diphonyi*2^hens#p2rxylium
perchlorate (XII) these two procedures may he outlined as follows?
