Lahey, Francis Norman

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PAPERS 
DEPARTMENT OF CHEMISTRY
Volume I 1942 Numbers 20, 21, and 22 
20. The· Constitution of Evodionol
BY 
F. N. LAHEY, D.Sc., A.A.C.I. 
21 . A Spectrographic Study of Evodionol and its
Derivatives 
BY 
F. N. LAHEY, D.Sc., A.A.C.I. , 
22. The Ultra-Violet Absorption Spectra of T agetone
and Related Ketones 
BY 
T. G. H. JONES, D.Sc., A.A.C.I. and F. N. LAHEY, D.Sc., A.A.C.I. 
Price : Three Shilling! 
PUBLISHED AS ORIGINAL PAPERS BY THE UNIVERSITY OF QUEENSLAND 
DATE OF PUBLICATION: 
16th NOVEMBER, 1942 
VOLUME 1. 
DEPAR'l'.MEN'l' 0]' CHB�HS'l'RY. 
1942. NUMBER 21. 
A SPECTROGRAPHIC STUDY 0]1 EVODIONOL 
AND ITS DERIVATIVES. 
By 
F. N. I;AH.EY, D.Sc., A.A.C.L 
Department of Chemistry, University of Queensland. 
DATE OF PUBLICATION: 
J 6'rH NOVEMBER, 1942. 
18 
A SPECTROGRAPHIC STUDY OF EVODIONOL AND 
ITS DERIVATIVES. 
By F. N. LAHEY, D.Sc., A.A.C.I.
With the establishment of the constitution of evodionol as recorded in the 
adjoining paper of this publication, it was considered desirable to subject evodionol 
and a number of its derivatives to spectrographic analysis. The results have been 
found to have an important relationship to the work of Morton and Sawiresl on the 
spectrographic study of rottlerin. The whole series of substances studied while 
closely related to many examined by Morton and Sawires, differs in general in the 
position of the carbonyl group. 
Confirmation of som,e of the conclusions and generalisations made by these 
authors has been obtained particularly with regard to the effect of the benzopyran 
nucleus which in the case of evodionol and its derivatives is not complicated by the 
effect of m,any chromophoric groups as in the rottlerin series. At the sam,e time, the 
interpretation of the absorption curves of evodionol and its derivatives in terms of 
known chromophoric arrangements confirms the constitutional formulae adopted. 
All spectra were obtained using alcohol as a solvent while in some cases the 
results were repeated in hexane solution. A high voltage spark discharge between 
tungsten steel electrodes in conjunction with a Hilger Spekker photometer and 
Hilger medium quartz spectrograph were used to obtain the spectra. 
The substances examined spectrographically are given in the following list :-
0 
""" ,CH3 
c .... 
I 
CH3
HO 
/Cfi.? 
CH2 OH 
1. 5 : 7-dihydroxy-6-acetyl-2 2-dimethyl-chroman. 
2. Evodionol (R = CH,, R' =H). 
3. Methyl evodionol (R., R' =CIT,). 
I 
RO 
Ph-CH=£H-CO 
OR 
7. Benzylidene-evodionol (R = CH,, R' =H). 
8. Benzylidene-methyl-evodionol (R, R' = CH,).
CH.jCO 
OR 
4. Dihydro-evodionol (R = CH,, R1 =H). 
5. Dihydro-methyl-evodionol (R, R' = CH,). 
G. :"l -hydroxy -7 -nwthoxy-6-acetyl-2 : 2-dimethyl-
r hroman (R = H, R1 = CH,). 
I CXO" ,CH3 
RO C 
l'CH3 
Ph-CH=CH-CO CH 
/ '2 OR CH2 
9. Benzylidene-<lihydro-evodionol (R = CJI,, 
R'=H). 
10. Benzylidene-dihydro-methyl-evodionol (R, 
R' = CH,). 
.I 8PJ<:I'T/1Uf!h'.lf'l-l/1' ::;'/'/Ill' u1: AI'Of)f();VUL .1.\'/i ITS /IERJJ'A1'lT'FS. 10 
0 0 
/ ""' /CH3 
Ph-CH c 
I 
I "cH3 
CH,? CH 
"' 
/ co 
OCH3 CH 
11. :3-methoxy-8 8-dimethyl-1 : �-I\rrano-[3, 2, 
go] -flavanone. 
/ 0 
""" /CH3 Ph-CH c, 
I I CH3 
Cfi,? 
/CH2 " 
co 0CH3 CH2
12. 5-methoxy-8 : 8-dimethyl-6 : 7 -dihydro-
1 : 2-pyra.no-[3, 2, g)-flavanone. 
The following table summarises the spectrographic data obtained. Unless 
otherwise stated all spectra were obtained using alcohol as a solvent:-
TABLE 1 
MAXIMUM AND MINIMUM VALUES OF ,\ (mp,) AND €· 
---
---
Evodionol (2) .. 
(in hexane) 
-
--
Dihydro-evodionol (4) 
-
-
-
-
. -
. . 
5-hydroxy-7 -methoxy-6-acetyl-2 
methyl chroman (6) 
-
--
-
. . 
. 
. 
: 2-di-
.. 
.. 
.'5 : 7 -dihydroxy-6-acetyl-2 : 2-dimethyl 
chroman (1) 
----
Methyl-evodionol (3) . . 
--�· 
Dihydro-methyl-evodionol (5) 
-----
Benzylidene-evodionol (7) 
(in hexane) 
-----
. 
. 
Benzylidene-dihydro-evodionol (9) 
-
-
--
Benzylidene-methyl-evodionol (8) 
-
--
. . 
. . 
. . 
. 
. 
. 
-
. . 
. 
-
--
Benzylidene-dihydro-rnethyl-evodionol ( 1 0) 
-- ---
----
-
-----
-
---
5-methoxy-8 : 8-dirnethyl-1 : 2-pyrano- [3, 
2, g)-flavanone (11) 
----· 
5-rnethoxy-8 : 8-dirnethyl-6 : 7-dihydro 
pyrano-[3, ,, 
.. , g)-flavanone (12) 
,\max. €max. ,\min. 
350 4000 320 
- 294 9000 
262 44000 
350 5000 318 
- 292 8500 
262 42500 
- 333 3750 
288 15600 
- 332 3400 
292 18400 
- 345 3250 248 
293 21000 
- 306 5100 
256 17400 
273 6700 250 
389 10900 374 
321 25800 2940 
281 24200 2550 
395 9500 362 
308 26000 255 
280 25200 
- 386 8750 2550 
333 21300 
362 4000 252 
290 27000 
292 10700 330 
-
-
--
-
---
-
---
-
345 4000 317 
(weak)290 11500 
261 37000 
341 3000 251 
288 18500 
€min. Fig. 
2400 2 
1800 2 
1 
1 
1500 1 
3 
4800 3 
10500 4 
22500 
11500 
9500 4 
12000 
3500 4 
5500 5 
2700 3 
----- -
-
---
22000 6 
I 3500 6 
:20 A SPECTROGRAPHIC STUDY OF EVODIONOL _1N1J ITS Dl!JRIVATJVES. 
(\ 
i \ 
hi ,/ ,. n " 
•I I• /' 
I 
>-..m,u. 
.D'gJ., 
Dthydro- t!vodionol (4). 
5-hydroxy- 7-mefhoxy-6-ocefyl- 2:2-dimethyl- chrornon (6). 
5; 7-dlhydroxy-6-aafyl-z :z-dimt!lhyl­
chroman (1). 
220 240 260 
/ 
CBO 300 
A.m,t.�. 
_fig d., 
Melhyl-evodlonol ( J). 
'Oihydro -rn�fhyl- evod/onoJ '(.s ). 
320 340 
8tmz!lli d�ne -·dihydro -m<"lhyl-evodl'onol ( 10). 
i'JO 260 290 .JZO 350 
A.m,.u . 
f!'g:.£:_ 
Evodionol in alcohol ( Z). 
Evodionol i'n hexone (2). 
"· 
I 
I I 
I 
I 
I 
I 
I 
' 
' 
' 
I 
i 
I 
I 
I 
I iJ I 
I 
I 
I 
I 
I 
I 
I 
I 
I 
I 
I 
I 
I 
I 
I 
380 
C 30 C60 290 .320 .JSO JBO 4to· 
>..m,u. 
£19� 
Benzy!tdene- evodionol in alcohol {7). 
B�nZ!Jiidene -evodionol in hexane (7). 
Benzyltdene- dihydro- evodt'onol (3). 
A SPECTROGRAPHIC STUDY OH EVODIONOL AND ITS DERIVATIVES. 21 
I 
r 
---, 
1 
I ' ' ' I ' i'500r0 I � I I ·I I I I us,oo : \ 
I I I I 
I I 
200r 
1 
\ 175r 1 
\ ,:
r \\ t' ' \ 
'-_ 
5000 \ • 
'.. j 
i'SO 275 300 J25 350 37S 400 ���5 
>-.m)L.. 
fig d., 
8-cinnomoyl-5: 7-dih!Jdroxy-;: 2-dimelh.!JI-chro"'on. 
Benzylidene -mdhyl-evodionol (8). 
.300 JSO 400 
)..,m,u . 
.f.ig.:.L 
Roffluin in alcohol. 
230 
-� ___j_ __  l_ i \ \J 
260 290 3ZO 
).. m,u. 
JSO 380 
S· methoxy-8·8- d!methy!-J:z-pyrano-
[3, z,g] -flavanone (11}_ 
s-methoxy-8:8-dimethyl· 6,7- dihydro­
t:t-pyrano- @ ,.2. � -flavanone (li) 
500 
I 
I 
22 A SPECTROGRAPHIC S'l'VDY OF EVODIONOL AND ITS D'ElflVATlVES. 
The parent substance of those examined can be taken as 5: 7 dihydroxy-2 
2-dimethyl-chroman which gives the following absorption maximum (M:orton 
and Sawires, loc. cit.) :-
272mJ.t Emax. 624 
All the substances related to evodionol have a carbonyl group in position 6. 
The introduction of a carbonyl group in position 6 into 5: 7-dihydroxy-2: 2-
dimethyl-chroman (see table 1), (fig. 1) has much the sam,e effect as introducing it in 
position 8. Both the very intense band at 294mJ.t and the band at 345mJ.t have been 
shown. by M:orton and Sawires1 and by M:orton and Stubbs2 to be benzenoid in 
character. 
The effect of mono-etherification of the 6-acetyl compound is seen by comparing 
the curve of the dihydroxy compound above (fig. 1) with that of dihydro-evodionol
(fig. 1) and the synthetic 5-hydroxy-7 -methoxy-6-acetyl-2 : 2-dimethyl-chroman. 
A decrease in intensity is observed (e.g. from 21000 to 15600 for the principal maximum 
of dihydro-evodionol), accompanied by a slight displacement towards shorter wave 
lengths (293mJ.t to 288mJ.t). Morton and Sawires (loc. cit.) point out that mono­
etherification of 5: 7-dihydroxy-8-,8-phenyl-propionyl-2: 2-dimethyl-chroman in 
the ortho hydroxyl has a marked effect on intensity causing it to fall from 22500 to 
5570. This effect is not observed in the 6-carbonyl compounds as the remaining 
hydroxyl is also ortho to the carbonyl group. From fig. 1 it is also observed that 
mono-etherification in position 7 has a less marked effect on the position and intensity 
of the band than in position 5. 
Complete etherification has a marked effect on the intensity of the absorption. 
This can be seen by comparing the E values of the principal bands in evodionol and 
methyl-evodionol (44000 to 17000), dihydro evodionol and dihydro methyl evodionol 
(15600 to 7600). 
A study of the spectrographic data in table 1 or of the curves of those substances 
containing the 1 : 2 benzo-pyran nucleus compared with those of the corresponding 
saturated chromans clearly shows the striking effect this double bond has on 
absorption. A completely new band appears near 262mJ.t (unless displaced by other 
effects) of great intensity in the absorption curve of all substances containing the 
benzopyran ring. For example, the data for evodionol and dihydro-evodionol are 
again here quoted to illustrate this point:-
,\max. 330 
288 
Emax. 
Emax. 
3750 
15600 
dihydro-evodiorwl. 
,\max. 350 
294 
262 
evodiorwl. 
Emax. 
Emax. 
Emax. 
4600 
9000 
44000 
The introduction of the new band at 262mJ.t is accompanied by a slight displace­
ment of the other bands towards longer wave lengths (345 to 350mj.t), while the 288mJ.t 
band now located at 294mJ.t is almost lost by the partial super position of the intense 
262mJ.t band. This introduction of a new strong band can be seen in the several pairs 
of substances examined which have benzopyran and chroman nuclei. These results 
are in good agreement with the findings of Morton and Sawires (loc. cit.) who obtained 
a new and intense band at 273mJ.t in the curve for iso-rottlerin due to the benzopyran 
nucleus. The difference in location of this band is due principally to the hydroxyl 
group in position 5 in evodionol being methylated. Furthermore in iso-rottlerin a 
dihydro-y-pyrone nucleus also blocks the other hydroxyl group although this has been 
shown to have a little or no effect on the position of the bands. To demonstrate this 
A Sl'ECTl!(H{lUNliC ST!'Dr OF !WOJJIONOT, .I.YTI ITS JJEL'IVATIVES. 2:-l 
the benzylidene compounds of evodionol and dihydro-evodimlOl were prepared and 
converted into the corresponding dihydro-y-pyrone compounds (ll) and (12). These
substances have absorption curves very little different from those of the original 
evodionol and dihydro-evodionol. 
It is interesting to compare the spectrum of (ll) with that obtained for the
substance (13) by Morton and Sawires (loc. m:t.). The data calculated by these authors
for this substance is here repeated together with the data for (11). 
/0 
Ph-CH 
I
CH2 
"-co 
� \nax. 370mfL. 
E"max. 4000, 
\ Amax. 345mfL. 
( Emax. 4000, 
OH 
13 
305mfL. 
10200 
290mfL. 
11500, 
270mfL. 
34000 
261mfL 
37000 
(Morton and Sawires) 
(13) 
(ll). 
The methylation of the hydroxyl in position (5) in the substance (13) above, 
which apart from the C-methyl group in the para position to it is the only difference 
between the two substances, would account for the displacement towards shorter 
wave lengths. The two results show good agreement except in the E" values of the 
principal band where for substance (11) a lower E value would be expected than for 
substance (13). 
Because of the close relationship of the benzylidene derivatives of evodionol 
and dihydro-evodionol to rottlerin and other substances examined by Morton and 
Sawires these substances were examined spectrographically. The character of the 
absorption curves is completely altered by this change. More ill tense absorption
is observed and all the bands appear displaced a con.siderable distance towards the red 
end of the spectrum. Such a drastic change is to be expected with the introduction 
of a new benzene nucleus conjugated through a double bond with the carbonyl group. 
The band at 350mfL in evodionol now appears at 389mfL with its intensity increased 
from 4600 to 10900. In the case of benzylidene-dihydro-evodionol the 333mfL band 
is moved to 386mfL, and the 288mfL to 333mfL. Allowing for the displacing effect of 
the 0-methyl group present, it would be anticipated that the corresponding dihydroxy 
body 5: 7-dihydroxy-6-cinnamoyl- 2 : 2 dimethyl chroman would exhibit maxima 
still further towards the red in the region of 390-400mfL for one band and 340-345mfL 
for the other. A similar curve would be expected for the isomeric 5 : 7-dihydroxy-8-
cinnamoyl-2 : 2-dimethyl-chroman although Morton and Sawires do not record any 
band in the 400mfL region for this substance. On repeating the absorption curve of this
substance, excellent agreement with the results recorded by Morton and Sawires was 
obtained but in addition an inflexion m the region of 410m,tt with € value 7000, was
also obtained. Their statement of greatly enhanced absorption at 345mfL due to 
the cinnamoyl group leads one to think that the cinnamoyl group causes an increase 
in E value of the band originally located at 345mfL. It seems more probable that the 
effect of the cinnam,oyl group is one of displacement towards the red end of the 
2+ .1 SPECTROOEAPHTC STUDr nF ET"()DJONOL AND ITS DERIVATIVES. 
spectrum, i.e., a bathochromic rather than a hyperchromic effect, causing the principal 
band originally at 293mfL, E 21000 to be moved to 345mfL, while the 345mf.t band is 
displaced to 410mfL where it appears as an inflexion due to the superposition of the 
intense band adjacent to it. The rest of the absorption curve for this substance agreed 
with that found by Morton and Sawires. 
By analogy the spectrum of rottlerin would be expected to show a band in the 
same vicinity viz. in the region of 400mfL. The curve recorded by Morton and Sa wires 
was repeated using hexane as a solvent but the low solubility of rottlerin in this solvent 
prevented the obtaining of any lower E values than those recorded by the Liverpool 
workers. Although these workers state that most of their spectra were obtained 
using 96% alcohol it seems likely that hexane was used for rottlerin for their results 
were readily repeated in hexane. When the absorption was carried out in alcohol 
the whole nature of the absorption curve was altered. The maximum, sought in the 
region of 400mft was readily located at 415rnf.t Emax. 17600, but the two intense maxima 
at 294mf.t Emax. 34800 and 350mfL Emax. 27100 were replaced by a single maximum at 
· 300mft €max. 38400. (fig. 7).
Because of this marked difference in the spectrum of rottlerin due to solvent 
effects, it was thought worth while to repeat the spectra of evodionol and benzylidene­
evodionol in hexane. The positions of the maxima of evodionol were practically 
unaltered and only slight differences in E values were recorded. In the case of 
benzylidene-evodionol the maxima were not so well defined (see fig. 4), but the character 
of the curve was not altered as in the case of rottlerin. 
The author wishes to express his thanks to Dr. J. E. Mills, University of Sydney,
for introducing him to the technique of absorption spectrophotometry and for repeating 
four of the absorption curves. 
REFERENCES. 
1 MORTON AND SA WIRES, J.C.S., 1940, 1052. 
2 MoRTON AND STUBBS, J.C.S., 1940, 1347. 


A spectrographic study of evodional and its derivatives

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A spectrographic study of evodional and its derivatives

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