Professional Documents
Culture Documents
Derivatives
WALTER L. ZIELINSKI, JR., and LAWRENCE FISHBEIN
Bionetics Research laboratories, Inc., Falls Church, Vu.
in methylenedioxyphenyl
derivatives as synergists originated
with the work of Haller and coworkers
in 1942 (20, 21) who extracted sesamin
from sesame oil and demonstrated its
activity as a synergist for pyrethrins.
More recently, Beroza and coworkers
have prepared numerous methylenedioxyphenyl compounds with side-chains
containing diverse functional groups in
an effort to determine relationships
between chemical structure and the
activity of compounds as pyrethrin
synergists (3, 9, 12, 17, 19). Pyrethrin
synergists based on the methylenedioxyphenyl structure have been intensively
studied in regard to their roles in inhibiting biological oxidation (16,19, 31, 34XTERESTS
S6).
Analysis of 3,4-methylenedioxyphenyl
derivatives have been carried out colorimetrically with phosphoric acid (5, SO),
sulfuric and chromotropic acids (4, 7 ,
10, 16, 22, 25, 37), sulfuric and gallic
acids (14), 6-amino-1-naphthol-3-sulfonic acid and 6-anilino-1-naphthol-3sulfonic acid (33), ortho phosphoric
acid and ethyl acetate (23, 38) and with
4-dimethylaminobenzaldehyde and acetic anhydride (1, 2 ) ; and by paper (8)
and thin-layer (11, IS, 24) chromatography. Infrared absorption spectra
have been studied by several groups of
investigators (15, 18, 18). Piperonal
was included in a group of aromatic
The 3,4-methylenedioxy
(MDO)
bromobenzene, nitrobenzene, and acetanilide derivatives were obtained from
Frinton Labs. All other 3,4-MDOphenyl derivatives were obtained from
various commercial sources. Gas chromatographic analyses were carried out
on an F&M Model 1609 flame ionization instrument containing a modified
flow system which permitted on-column
injections into a glass column with the
effluent passing directly to the hydrogen
flame detector (Applied Science Labs.,
State College, Pa.). The columns employed were 0.25-inch X &foot glass
coils of 3% Carbowax 20M on hexamethyldisilizane (HMDS)-pretreated
Chromosorb W (60-80 mesh) and of
4%
QF-1
on HMDS-pretreated
Chromosorb G (80-100 mesh). The
analytical conditions of operations are
given in Table I. The hydrocarbon
standard mixture used to obtain Kovats
indices was obtained from Applied
Science Labs.
RESULTS AND DISCUSSION
41
Table
1.
Compound
Chemical name
MDO-benzene
3,4MDO-propylbenzene
3,4MDO-allylbenzene
3,4-MDO-bromobenzene
3,4-MDO-propenylbenzenee
Gas
Chromatography
Common name
Dihydrosafrole
Safrole
Isosafrbie
1-Methyl-2-( 3,4MDO-phenyl)
ethyl octyl sulfoxide
Sulfoxide
3,PMDO-benzaldehyde
Piperonal
3,PMDO-benzylamine
Piperonyl amine
3,PMDO-phenyl isopropylamine0
...
...
3,4MDO-acetophenone
3,PMDO-nitrobenzene
3,PMDO-benzyl alcohols
3,PMDO-phenolo
3,4MDO-benzoic acidosh
3,4MDO-phenylacetic acidssh
Piperonyl alcohol
Sesamol
Piperonylic acid
...
3,431DO-acetanilide
3,4-MDO-6-propylbenzyl( butyl)diethyleneglycol ether
3,4MDO-cinnamic acidO*h
...
Piperonyl butoxide
Piperonyl acrylic
acid
of
3,4-Methylenedioxyphenyl
Ring Position 1
-H
-CHzCH2CH3
--CHL!H=CHz
-Br
-CH=CHCHa
Derivatives
Carbowax 20Mo
Relative
RetentionC
Indexd
QF-lb
Relative
Retentionc Indexd
0.082
0.23
0.29
0.38
0.49
970
1240
1300
1370
1430
0.081
0.31
0.29
0.32
0.55
710
970
960
980
1080
0.501
1.oo
1440
1620
1640
1660
1.00
0.53,
0.66
1070
1200
1120
1210
1.4
2.0
2.5
3.9
9.7;
13.9j
1700
1800
1850
1970
ca. 2400
>2400
1.7
0.97
0.90
0.54
1.7i
2.6j
1440
1580
--N-C-CHa
-CHzCH&Hak
16.6'
1 7 . 2i
>2400
>2400
7.0i
14.31
1890
2110
-CH=CHCOOH
36'
>2400
5.69
1810
-CHzCH(CHa)
-CHO
-CHZNHZ
-C("z)(CHa)z
0
k CsHn
1.1
1.2
-&CHa
-NO2
-CHzOH
-OH
-COOH
-CHzCOOH
P O
I
I/
1.1
1300
1190
1180
1080
a 3% Carbowax 20M.
Conditions: column 160' C., injector 60 volt, detector 220' C., nitrogen carrier 99.5 ml./min., hydrogen 110
ml./min., air 450 ml./min.
4% QF-1 fluorosilicone. Conditions: column 100" C., injector 60 volt, detector 220" C., nitrogen carrier 106 ml./min., hydrogen
110 ml./min., air 450 ml./min.
c Relative to piperonal as 1.0. Piperonal elution: 4.25 and 1.35 minutes a t 160" C. and 200" C., respectively, on Carbowax 20x1;
4.25 and 0.65 minutes a t 100' C. and 160" C., respectively,
- , on QF-1.
d Calculated from CS-C~ohydrocarbon mixture. e Presence of impurity a t 0.36 relative retention and 18.3% chromatogram peak area on QF-1 a t 100" C.
f Sulfoxide decomposition product.
Additional peaks revealed a t 0.096, 0.28, and 0.35 relative retention and 14.8, 25.8, and 12.5y0
chromatogram peak area, respectively, on QF-1 a t 100' C.
0 Relative retention to piperonal of TATS derivatives: 0.27, 0.45, and 0.45 for sesamol, .piperonyl alcohol and 3,4hlDO-phenyl isopropylamine, respectively, on Carbowax 20M a t 160' C. ; 2.7, 3.9, and 9.9 for piperonylic acid, 3,4MDO-phenylacetic acid and piperonyl
acrylic acid, respectively, on Carbowax 20M a t 200' C.
Relative retention to piperonal of methyl ester derivatives: 1.2, 1.7, and 5.5 for piperonylic acid, 3,4MDO-phenylacetic acid and
piperonyl acrylic acid, respectively, on QF-1 at 130" C.
i Chromatographed a t 200' C.
Nitrogen carrier 89 ml./min.
j Chromatographed a t 160' C.
Nitrogen carrier 86 ml./min.
k Also present a t ring position 6: -CHZOCZH~OCZH~OC~H~.
I
Aryl substituenth
-CH&H&Ha
0
II
-CCHa
-CH=CHCHa
-CHzCH=CHz
-CHO
-H
-C(NHz)(CHs)3
-Br
-CHzNHz
--NO2
-CHzOH
-OH
Substitution Contribution
Carbowax 20M
QF-1
0.45
0.58
1.23
0.78
0.55
1.09
0.00
1.17
0.67
1.13
1.39
1.48
1.68
1.32
0.83
0.55
1.09
0.00
1.13
0.60
0.91
1.08
1.05
0.83
Polarity
Contributionc
-0.13
-0.09
-0.05
0.00
0.00
0.00
f0.04
+0.07
+o. 22
+ O , 31
4-0.43
+ O . 85
42
rn
ANALYTICAL CHEMISTRY
"
(1954).
(8) Ibid., 28, 1550 (1956).
(9) Beroza, M.,J . Agr. Food Chem. 4,
49 (1956).
(10) Ibid., p. 53.
(11) Ibid., 11, 51 (1963).
(12) Beroza, M., Barthel, W., Ibid., 5,
855 (1957).
(13) Beroza, M., Jones, W. A., Anal.
Chem. 34, 1029 (1952).
(14) Blum, M. S.,J . Agr. Food Chem.
3, 122 (1955).
(15) Briggs, L. H., Colebrook, L. D.,
Fales, H. RZ., Wildman, W. C., ANAL.
CHEM.29,904 (1957).
(16) Eegriwe, E., 2. Anal. Chem. 110, 22
(1937).
(17) Fales, H. &I., Bodenstein, 0. F.,
Beroza, M., J . Econ. Entomol. 49, 419
(1956).
43