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Gas Chromatography of 3,4-Methylenedioxyphenyl

Derivatives
WALTER L. ZIELINSKI, JR., and LAWRENCE FISHBEIN
Bionetics Research laboratories, Inc., Falls Church, Vu.

A variety of 3,4-methylenedioxyphenyl derivatives, including the insecticide synergists, sulfoxide and


piperonyl butoxide, were chromatographed on columns of 3% Carbowax 20th and 4% ZF-1 fluorosilicone.
In addition to analysis of the free
derivatives, the acidic derivatives were
also analyzed as the methyl and trimethylsilyl esters, and the amine and
alcoholic derivatives as the trimethylsilyl ethers. In terms of Kovats indices
it was observed that the differences
in chromatographic retention between
the two liquid phases was in the range
of 3-5 carbon atoms for most of the
derivatives. Evaluation of the chromatographic data by means of the log of
the elution values for the respective
columns illustrated the relative influence
of aryl substituents upon chromatographic mobility.

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

aldehydes analyzed by gas chromatography by Prabucki and Lenz (32).


The present study reports the gas
chromatographic behavior of a variety
of 3,4-methylenedioxyphenyl derivatives and relates chromatographic mobility to the structure of these derivatives.
EXPERIMENTAL

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

The elution results of derivatives containing various functional attachments


to the MDO-phenyl base structure are
contrasted on the relatively high polar
and low polar partitioning liquids in
Table I. Chromatography of the free
acidic derivatives on Carbowax 20M
was accomplished with some difficulty.
Piperonylic acid gave a better peak
than 3,4-MDO-phenyl acetic acid; while
piperonyl acrylic acid was extremely
difficult to chromatograph as such.
Conversion of these acids to the methyl
esters by reaction with methanol in an
acidic solution of 2,2-dimethoxypropane
(27) facilitated their chromatography
and improved the peak symmetry. At
130' C. on QF-1 (100 ml. of nitrogen/
min.) the order of elution for the esters
was 4.6 :1.4 :1.0 for piperonyl acrylic :
3,4 - MDO -phenyl acetic:piperonylic,
respectively.
Alternately, preparation of the trimethylsilyl (TMS) esters
by reaction with trimethylchlorosilane

(TMCS) in pyridine followed by analysis


on QF-1 a t 175' C . for piperonyl
acrylic and 3,4-MDO-phenyl acetic,
and a t 140' C. for piperonylic gave an
elution ratio of 3.1 :1.0: 1.0 following
relation of the data to the elution of
piperonal a t these temperatures.
When silylation was attempted with
other 3,4-MDO-phenyl derivatives via
reaction with HMDS and TMCS in
pyridine ( 6 ) ,the following observations
were made : The preparation of piperonal
and piperonyl amine TMS derivatives
was not successful; the alcoholic derivatives reacted instantly; while 3,4MDO-phenyl isopropylamine was slow
to react owing to the steric influence of
the isopropyl methyl groups, and unreacted isopropylamine appeared as a
peak on the chromatogram even when
the reaction mixture was allowed to
stand overnight.
In evaluation of the chromatographic
data of the 3,4-MDO-phenyl derivatives
it was felt advantageous to obtain an
estimate of the relative polarity residing
in the functional moieties attached to
the aryl ring in position 1. This was
undertaken by subtracting the log of
the retention value for methylenedioxybenzene (MDB) from the log of the
retention values of the derivatives on
both liquid phases to obtain the chromatographic contribution of each position 1 moiety on each phase; followed
by subtraction of the adjusted QF-1
values from the respective adjusted
Carboaax 20M values.
aryl substituent influencec20M-QF1=
(log,

- 10gMDB)CZOM - (log, 10gMDB)QF1

Owing to the presence of a higher


dipole-dipole interaction on Carbowax
20M in contrast to the greater predominance of London forces on QF-1, the
moiety values obtained by this procedure serve to indicate the relative
polarity contributions of the aryl substituents to the chromatographic mobility of the derivatives. The relative
moiety polarities for the Carbowax
20M-QF-1 system are given in Table 11.
It must be kept in mind that these
values also include the influence of substituent interaction with the aryl ring,
which factor effects shifts in the overall
VOL. 38, NO. 1, JANUARY 1966

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

Table II. Influence of Aryl Substituents"

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

Carbowax 20M a t 160' C.; QF-1 a t 100' C.


Omitting the MDB correction a t 200" C. for Carbowax 20M and 160' C. for QF-1,
the substituent polarity differences for piperonyl butoxide, 3,4MDO-acetanilide; 3 , 4
MDO-phenylacetic acid, piperonylic acid, and piperonyl acrylic acid were +0.40, +0.69,
+1.04, +LO8 and f1.13, respectively.
c For the Carbowax 2OM-QF-1 system under the experimental conditions employed.
b

42

rn

ANALYTICAL CHEMISTRY

"

polarity of the substituent. Understandably, a truer polarity estimate


could be obtained, should the system
contain a column possessing less polarity
than QF-1. The values serve to illustrate, however, the relative degree
of polarity residing with the respective
polar substituents at ring position 1.
A similar approach using a Carbowax
20M-SE30 system has been employed
in evaluating chromatographic elution
data for simple and N-substituted carbamates (39).
ACKNOWLEDGMENT

The authors acknowledge the technical assistance of Lee Martin.


LITERATURE CITED

(1) Acheson, R. M., Bearnley, D. P., Can.


J . Biochem. Phyaiol. 38, 503 (1960).
(2) Acheson, R. M., Booth, D. A.,
Brettle, R., Harris, A. M.,J . Chem.
SOC.1960, p. 3457.

(3) Alexander, B. H., Barthel, W., J.


Org. Chem. 21,1102 (1956).
(4) Allen, P. T., J . Aar. Food Chem. 10,
' 249 (1962).
'
(5) Alien,
Allen, P'
P.. T.,
7 Beckman, H. F., Fudge,
J. F., Ibid., p. 248.
(6) Bentley, R., Sweeley, C. C., Makita,

M., Wells, W. W., Biochem. Biophys.


Res. Commun. 11.
11, 14 (1963).
(1QfiR)
(7)
ANAL. CHEW.26. 1970
. , Beroza. M.. ANAL.
I

(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).

(18) Gender, W. J., Samour, C. M.,


J . Org. Chem. 18,9 (1953).
(19) Gersdorff, W. A., Piquett, P. G.,
Beroza, M.; J . Agr. Food Chem. 4 ,
858 (1956).
(20) Haller, H. L., LaForge, F. B.,
Sullivan, W. N., J . Econ. Entomol. 35,
247 (1942).
(21) Haller, H. L., LaForge, F. B.,
Sullivan, W. N., J . Org. Chem. 7, 185
(1942).
(22) Hansen. 0. R.. Acta Chem. Scand.
7; 1125 (1953).
'
(23) Jones, H. A., Ackerman, H. J.,
Webster, M. E., J . Assoc. Ojic. Agr.
Chemists 32,684 (1949).
(24) Klouwen, M. H., Terheide, R.,
Kok, J. G. T., Fette, Seifen, Anstricmittel 65, 414 (1963).
(25) Langejan, M., Pharm. Weekblad.
92,693 (1957).
(26) Lichtenstein, E. P., Schultz, K. R.,
Cowley, G. T., J. Econ. Entomol. 56,
485 (1963).
(27) Lorette, N. B., Brown, J. H., Jr.,
J . Oro. Chem. 24.261 (1959).
(28) Mhson, L. H., Puschett, E. R.,
Wildman, W. C., J . Am. Chem. SOC.
77, 1253 (1955).
(29) Moore, B. P., Hewlett, P. S., J . Sci.
Food Agr. 9, 666 (1958).
~

(30) Pavolini, T., Malatesta, A,, Ann.


Chim. Applicata 37, 495 (1947).
(31) Philleo, W. W., Schonbrod, R. D..
Terriere, L. C., J . Agr. Food Chem. 13;
113 (1965).
(32) Prabuiki, A. L., Lenz, F., Helv.
Chim. Acta 45,2012 (1962).
(33) Sawicki, E., Hauser, T. R., McPherson, S., ANAL. CHEM.34. 1461
(1962). '
(34) Schmidt, C. H., Dahm, P. A., J.
Econ. Entomol. 49.729 (1956 ).
(35) Sun, Y. P., Johnson, E.-R., J . Agr.
Food Chem. 8,261 (1960).
(36) Terriere, L. C., Boose, R. B., Roubal,
W. T., Biochem. J . 79, 620 (1961).
(37) West, P. W., Sen, B., 2.Anal. Chem.
153,477 (1956).
(38) Williams, H. L., Dale, W. E.,
'

Sweeney, J. P., J . Assoc. Ofic. Agr.


Chemists 39,872 (1956).
(39) Zielinski, W. L., Jr., Fishbein, L.,
J . Gas Chromatog.3,260 (1965).
RECEIVEDfor review July 19, 1965.
Accepted November 8, 1965. Study
supported by Research Contract PH
43-64-57, National Cancer Institute, National Institutes of Health, Public Health
Service.

Rapid Gas Chromatographic Determination of C, to C,,


Hydrocarbons in Automotive Exhaust Gas
EMMETT S. JACOBS
Research and Development Division, Organic Chemicals Department, Jackson laboratory,
E. 1. du font de Nemours and Co., Wilmington, Del.

b A gas chromatographic procedure


is described for the rapid determination of C1 to Clo hydrocarbons in
automotive exhaust gas. The method
features the application of a programmed temperature run from -55"
C. to $140" C. with a single open
tubular column and flame ionization
detector. As many as 85 C1 to Cl0
paraffins, olefins, and aromatic hydrocarbons may be determined within
13 minutes. Automatic integration of
the flame detector signal is used to
provide
instantaneous quantitative
analysis for as little as 1 p.p.m. (v./v.)
of each hydrocarbon. The equipment
and operating conditions of the chromatographic method are discussed
and an analysis of exhaust gas is
illustrated.

automotive exhaust gas is needed to


ascertain its relation to air pollution
problems. Altshuller ( I ) has stated in
a review that the largest effort in the
application of gas chromatography to
air pollution has been directed toward
investigations of auto exhaust gas composition. However, there is still a need
for refinement of the analytical methods
to provide a more rapid determination
OXPREHENSIVE ANALYSIS Of

of the composition of autc -haust,


namely, hydrocarbons, oxidized fragments, nitrogen oxides, etc. Most of
the gas chromatographic procedures
applied to auto exhaust gas have employed a number of different packed
columns connected in series to provide a
full range hydrocarbon analysis. Such
procedures may require as long as two
hours to obtain a complete analysis of a
single exhaust gas sample.
Recent advances in gas chromatographic instrumentation and technique
such as flame and electron capture
detection, temperature programming,
and open tubular columns should afford
a means for a more complete exhaust
gas analysis in a shorter time. McEwen
(6, 6) used one packed and one open
tubular column to effect a two-stage
separation of hydrocarbon gas mixture.
The gas sample was injected into the
cold (dry ice, -78" C.) packed column
which was warmed with water to elute
the C1 to Ca hydrocarbons. The higher
(C, to C,) hydrocarbons were then
backflushed off the packed column onto
the open tubular column which was
temperature programmed to 80' C. to
provide rapid elution of these higher
boiling hydrocarbons.
The method proposed in this paper
uses only a single open tubular column

with an initial subambient temperature


of -55" C. followed by a temperature
program to a final temperature of
140' C. This procedure yields a fast and
efficient separation of the full range
(C1 to GO)of hydrocarbons found in
auto exhaust. The use of a large sample
and a large split ratio provides a hydrocarbon sensitivity of 1 p.p.m.
EXPERIMENTAL

Apparatus. A Perkin-Elmer Model


800 gas chromatograph with an
adapter for open tubular columns was
used for this study. All coated open
tubular columns were used as purchased from Perkin-Elmer. The detector heaters were rewired by connecting directly to 110 volt power line
to maintain the detector a t or near
100' C. during subambient temperature periods. This was necessary to
prevent water from flame combustion
from condensing and corroding electrical points in the base of the detector.
A Leeds & Northrup Type G Speedomax recorder with a 2-mv. range,
second full scale pen response was used
to record all chromatograms. The recorder was also equipped with an Insco
multispeed chart drive which provided
variable speeds from 1 to
of the
basic chart speed of 12 inches/minute.
An Infotronics Model CRS-11HS
extended range digital integrator with
VOL. 38, NO. 1, JANUARY 1966

43

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