EPOXICONAZOLE 609

EPOXICONAZOLE
609

N
O
N
N

Cl

ISO common name Epoxiconazole

Chemical name (2RS, 3SR)-1-[3-(2-chlorophenyl)-2,3-epoxy-2-(4-
fluorophenyl)propyl]-1H-1,2,4-triazole (IUPAC);
rel-1-[[(2R, 3S)-3-(2-chlorophenyl)-2-(4-fluoro-
phenyl)-oxiranyl]methyl-1H-1,2,4-triazole (CA;
135319-73-2)
Empirical formula C17H13ClFN3O
RMM 329.8
m.p. 135 °C
v.p: Less than 1 × 10–5 Pa at 20 °C
Solubility In water: 0.007 g/l (deionised), heptane: less than 1 g/l;
acetone: 44 g/l; dichloromethane: 291 g/l, all at 20 °C
Description Crystalline solid
Stability Stable at normal temperatures, and in light and air and
at pH 3 - 7
Formulations Suspension concentrates and emulsifiable concentrates

38
 EPOXICONAZOLE 609

EPOXICONAZOLE TECHNICAL
*
609/TC/M/-

1 Sampling. Take at least 100 g.

2 Identity tests
2.2 GLC. Use the GLC method below. The relative retention time obtained
from the sample should not deviate by more than 1 % from that of the authentic
reference standard obtained under the same conditions.
2.2 Infrared. Prepare potassium bromide discs from the sample and from pure
epoxiconazole using 1.3 to 1.5 mg material and 300 mg potassium bromide.
Scan the discs from 4000 to 400 cm-1. The spectrum obtained from the sample
should not differ significantly from that of the standard.

3 Epoxiconazole

OUTLINE OF METHOD
Epoxiconazole is determined by capillary gas chromatography using flame
ionisation detection and tetraphenylethene as internal standard.

REAGENTS
Tetrahydrofuran GC grade
Epoxiconazole standard of known purity, better than 990 g/kg
Tetraphenylethene purity at least 97 %
Internal standard solution. Weigh into a volumetric flask (200 ml)
tetraphenylethene (1.6 g) and dissolve in tetrahydrofuran.
Calibration solution. Weigh in duplicate (to the nearest 0.1 mg) 50 mg (s mg)
epoxicanazole standard into separate volumetric flasks (50 ml). Add by pipette
to each flask internal standard solution (5.0 ml). Dilute to the mark with
tetrahydrofuran and mix well (Solutions C1 and C2). The solution is known to
be stable for at least one day.

APPARATUS

Gas chromatograph equipped with a flame ionisation detector, split/splitless

injection and an automatic sampler
Column. fused silica, 30 m × 0.32 mm (i. d.) and 0.25 µm film thickness, coated
with crosslinked 100 % dimethylpolysiloxane (DB-1 or equivalent)
Integrator or electronic data system

*
CIPAC method 2001. Prepared by the German Committee (DAPA). Chairman W Dobrat. Based. on a method
supplied by BASF AG, Germany.

39
 EPOXICONAZOLE 609

PROCEDURE

(a) Operating conditions (typical)

Column Fused silica, 30 m × 0.32 mm (i. d.) and 0.25 µm
film thickness, coated with crosslinked 100 %
dimethyl-polysiloxane (DB-1 or equivalent).
Detector Flame ionisation
Temperatures
Column oven 230 °C
Injection port 280 °C
Detector 280 °C
Gas flow rates
Carrier gas (helium) 80 kPa; adjust the carrier gas pressure to obtain a
retention time of about 5 to 6 minutes for epoxi-
conazole
Hydrogen and air As recommended for the particular instrument
Split ratio 1 : 50
Injection volume 1 µl
Retention times epoxiconazole: 5 - 6 min
tetraphenylethene: 6 - 7 min
Note If it is necessary to clean the GLC column, apply a short temperature
program up to 270 °C, at a rate of 30 °C/min and hold for 4 min.

(b Preparation of sample solution. Weigh (to the nearest 0.1 mg) into a volumetric
flask (50 ml) sufficient sample to contain about 250 mg (w mg) epoxiconazole.
Dissolve in and fill to the mark with tetrahydrofuran, and mix thoroughly. Transfer
by pipette (10.0 ml) of this solution to a volumetric flask (50 ml) and add by
pipette internal standard solution (5.0 ml) using the same pipette as for the
preparation of calibration solution. Fill to the mark with tetrahydrofuran and mix
well (Solution S).

(c) System equilibration. Set proper flow rates, and allow the column to equilibrate
at 230 °C. Inject 1 µl of the calibration solution to confirm the predicted retention
times and check if a stable baseline is obtained. Adjust the carrier gas flow rate to
obtain the required retention times and resolution. Then inject in five fold 1 µl
portions of the same calibration solution and determine the response factor (fi) and
retention times. Repeat the injections until the response factors obtained do not
differ by more than ± 1.0 % from the mean. If consistent and unacceptable
differences between calibration solutions are obtained, prepare new solutions.

(d) Determination. Inject in duplicate 1 µl portions of each sample solution and

bracket a series of sample solution injections by injections of the calibration
solutions as follows:

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 EPOXICONAZOLE 609

calibration solution C1, sample solution S1 (double injection), calibration solution

C2, sample solution S2 (double injection), calibration solution C1, and so on for
further sample solutions.
Measure the relevant peak areas and calculate the response factor (fi).
Calculate the mean of each pair of response factors bracketing the injections of
two sample injections and use this value for calculating the epoxiconazole content
of the bracketed sample runs. The response factors and retention times for
successive injections should agree within 1 %.

(e) Calculation

Ir × s
fi =
Hs

Hw × f × P×5
Content of epoxiconazole =
Iq × w

where:
fi = single response factor
f = average response factor
Hs = area of the epoxiconazole peak in the calibration solution
Hw = area of the epoxiconazole peak in the sample solution
Ir = area of the internal standard peak in the calibration solution
Iq = area of the internal standard peak in sample solution
s = mass of epoxiconazole in the calibration solution (mg)
w = mass of sample taken (mg)
P = purity of epoxiconazole standard (g/kg)

Repeatability r = 15 g/kg at 972 g/kg active ingredient content

Reproducibility R = 22 g/kg at 972 g/kg active ingredient content
Based on a study with 25 participants and 50 values.

41
 EPOXICONAZOLE 609

EPOXICONAZOLE SUSPENSION CONCENTRATES

*
609/SC/M/-

1 Sampling. Take at least 1 l.

2 Identity tests
2.1 GLC. As for epoxiconazole technical 609/TC/M/ 2.1.
2.2 Infrared. Dry approximately 10 ml sample and proceed as for
epoxiconazole technical 609/TC/M/2.2.

3.Epoxiconazole. As for epoxiconazole technical 609/TC/M/3, except:

(b) Preparation of sample solution. Weigh (to the nearest 0.1 mg) sufficient
sample to contain about 250 mg (w mg) epoxiconazole into a volumetric flask
(50 ml). Add tetrahydrofuran (about 40 ml), swirl and place the flask in an
ultrasonic bath for about 5 minutes. Allow to cool to room temperature, fill to
the mark with tetrahydrofuran and mix well. Allow any insoluble material to
settle (within 15 min) and transfer by pipette 10.0 ml of the supernatant liquid to
a volumetric flask (50 ml). Add by pipette internal standard solution (5 ml)
using the same pipette as for the preparation of calibration solution. Fill to the
mark with tetrahydrofuran and mix thoroughly.

Repeatability r = 2.4 g/kg at 123 g/kg active ingredient content

3.3 g/kg at 115 g/kg active ingredient content
Reproducibility R = 7.0 g/kg at 123 g/kg active ingredient content
10 g/kg at 115 g/kg active ingredient content
Based on a study with 25 participants and 50 values.

4 Suspensibility (draft method)

REAGENTS AND APPARATUS As for 609/TC/M/3 and MT 15.

PROCEDURE

(a) Preparation of suspension and determination of sedimentation. MT 161.

(b) Determination of epoxiconazole in the bottom 25 ml of suspension. After
removal of the top 225 ml of suspension, transfer the remaining 25 ml
quantitatively into a volumetric flask (100 ml) with tetrahydrofuran, fill to just
below the mark with tetrahydrofuran and place the flask in an ultrasonic bath for
5 minutes. Allow to cool to room temperature, and fill to the mark with
*
CIPAC method 2001. Prepared by the German Committee (DAPA). Chairman W Dobrat. Based on a method
supplied by BASF AG, Germany.

42
 EPOXICONAZOLE 609

tetrahydrofuran. Transfer by pipette 20 ml of this solution into separate volumetric

flasks (50 ml), add by pipette internal standard solution (5 ml). Fill to the mark
with tetrahydrofuran and mix thoroughly.
Determine the mass of epoxiconazole (Q g) by 609/TC/M/3.

(c) Calculation

111× (c - Q)
Suspensibility = %
c

where:
c = mass of epoxiconazole in the sample taken for the preparation of the
suspension
Q = mass of epoxiconazole in the bottom 25 ml of suspension (g)

EPOXICONAZOLE SUSPO-EMULSIONS
*
609/SE/M/-

1 Sampling. Take at least 1 l.

2 Identity tests
2.1 GLC. As for epoxiconazole technical 609/TC/M/ 2.1.
2.2 Infrared. Dry approximately 10 ml sample and proceed as for
epoxiconazole technical 609/TC/M/2.2.

3.Epoxiconazole. As for epoxiconazole technical 609/TC/M/3.

Repeatability r = 2.1 g/kg at 86.3 g/kg active ingredient content

Reproducibility R = 4.2 g/kg at 86.3 g/kg active ingredient content
Based on a study with 26 participants and 52 values.

*
CIPAC method 2001. Prepared by the German Committee (DAPA). Chairman W Dobrat. Based on a method
supplied by BASF AG, Germany.

43
 EPOXICONAZOLE 609

EPOXICONAZOLE EMULSIFIABLE CONCENTRATES

*609/EC/M/-

1 Sampling. Take at least 500 ml.

2 Identity tests
2.1 GLC. As for epoxiconazole technical 609/TC/M/ 2.1.
2.2 Infrared. Evaporate to dryness 1 ml sample in a stream of clean, dry air and
proceed as for epoxiconazole technical 609/TC/M/2.2.

3.Epoxiconazole. As for epoxiconazole suspension concentrates 609/SC/M/3,

except omit the ultrasonic treatment.

Repeatability r = 4.8 g/kg at 78.9 g/kg active ingredient content

Reproducibility R = 4.8 g/kg at 78.9 g/kg active ingredient content
Based on a study with 24 participants and 48 values.
0.06

Tetraphenylethylene
Epoxiconazole
0.04
Volts
0.02
0.00

0 2 4 6 8 10 12 14
Time (min)

Fig 12 GC chromatogram of epoxiconazole technical

with internal standard tetraphenylethylene

44
 EPOXICONAZOLE 609

0.08

Diastereomere of epoxiconazole
0.06
Volts
0.04 0.02
0.00

0 2 4 6 8 10 12 14
Time (min)

Fig. 13 GC chromatogram of diastereomer of epoxiconazole

0.
06
Tetraphenylethylene

0.
Epoxiconazole

04

Vo
lts

0.
02

0.
00

0 2 4 6 8 10 12 14
Time (min)

Fig. 14 GC chromatogram of epoxiconazole SC

45
 EPOXICONAZOLE 609

80

75

70
2992,8

65

60

55
1607,6
%T
50
1436,1
45
1137,5
3100,7
40 1029,6
1231,9

35

30 1274,3

25 765,6

20 1515,1

4000 3500 3000 2500 2000 1500 1000 500

Wavenumbers (cm-1)

Fig 15 IR spectrum of epoxiconazole

46