Kinetics of the Chemical Hydrolysis and 3D-QSAR Study of 5-Substituted Benzenesulfonylurea Compounds†

doi:10.7503/cjcu20160257

Abstract

Abstract:

The hydrolysis of 9 new 5-substituted benzenesulfonylurea compounds with good herbicidal activity under acidic, neutral and alkaline pH conditions was investigated in laboratory studies. HPLC-MS was used to identify degradates and to study the pathway of hydrolysis. Comparative molecular field analysis(CoMFA) method was applied to the study of the three-dimensional quantitative structure activity relationship(3D-QSAR) on the relationship between the structure of the 5-substituted benzenesulfonylurea compounds and the half-life of hydrolysis. The results showed that the hydrolytic degradation of 5-substituted benzenesulfonylurea followed first-order kinetics. It was easier to be hydrolyzed in acid buffer solutions. Acid-catalyzed cleavage of the sulfonylurea bridge was the first step of degradation, and thus produces 5-substituted benzene sulfonamide and amino-heterocyclic. Amide group further hydrolyzed producing the compound c(6-amino saccharin) and d(saccharin). The 5-substituted benzenesulfonylurea compounds hydrolyzed significantly faster than the parent compounds, Monosulfuron-methyl and Metsulfuron-methyl, under the same conditions. The hydrolysis rate decreased with the increase of the number of alkyl carbon atoms on the amide group and the increase of the volume of the alkyl group. The CoMFA model was able to predict the hydrolysis half-life of this series of compounds.

Key words: 5-Substituted benzenesulfonylurea compound, Hydrolysis, Half-life, Comparative molecular field analysis(CoMFA) model, Three-dimensional quantitative structure activity relationship(3D-QSAR)

CLC Number:

O625

TrendMD:

WANG Meiyi, MA Yi, WANG Haiying, CAO Gang, LI Zhengming. Kinetics of the Chemical Hydrolysis and 3D-QSAR Study of 5-Substituted Benzenesulfonylurea Compounds^†[J]. Chem. J. Chinese Universities, 2016, 37(9): 1636.

Figures/Tables 7

Fig.1 Chemical structures of monosulfuron-methyl, metsulfuron-methyl and compounds A—I

Fig.2 General structure of the compound

Table 1 Kinetic parameters of 11 compounds hydrolysis in the buffer solutions with different pH values

Compd.	pH	Hydrolysis kinetic equation	Correlation coefficient, r²	t_1/2/d
A	5	c_t=27.584 $e - 0 . 1238 t$	0.9797	5.59
	7	c_t =28.33 $e - 0 . 0658 t$	0.9633	10.53
	9	c_t =40.645 $e - 0 . 0341 t$	0.9846	20.33
B	5	c_t =32.742 $e - 0 . 0751 t$	0.9850	9.23
	7	c_t =35.078 $e - 0 . 0418 t$	0.9560	16.58
	9	c_t =26.865 $e - 0 . 0418 t$	0.9682	27.40
C	5	c_t =41.195 $e - 0 . 1625 t$	0.9491	4.26
	7	c_t =37.482 $e - 0 . 0923 t$	0.9677	7.51
	9	c_t =40.132 $e - 0 . 0379 t$	0.9834	18.29
D	5	c_t =25.889 $e - 0 . 1475 t$	0.9799	4.70
	7	c_t =28.745 $e - 0 . 1086 t$	0.9866	6.38
	9	c_t =27.331 $e - 0 . 0398 t$	0.9650	17.42
E	5	c_t =25.087 $e - 0 . 0735 t$	0.9772	9.43
	7	c_t =30.564 $e - 0 . 027 t$	0.9559	25.67
	9	c_t =23.949 $e - 0 . 0127 t$	0.9670	54.58
F	5	c_t =31.059 $e - 0 . 0835 t$	0.9205	8.30
	7	c_t =26.675 $e - 0 . 0259 t$	0.9585	26.76
	9	c_t =24.018 $e - 0 . 0166 t$	0.9765	41.76
G	5	c_t =25.407 $e - 0 . 0964 t$	0.9608	7.19
	7	c_t =22.595 $e - 0 . 0188 t$	0.9646	36.87
	9	c_t =24.338 $e - 0 . 014 t$	0.9747	49.51
H	5	c_t =23.536 $e - 0 . 0653 t$	0.9716	10.61
I	5	c_t =20.351 $e - 0 . 075 t$	0.9843	9.24
Monosulfuron-methyl	5	c_t =27.629 $e - 0 . 0506 t$	0.9861	13.70
Metsulfuron-methyl	5	c_t =24.098 $e - 0 . 0299 t$	0.9861	23.18

Table 1 Kinetic parameters of 11 compounds hydrolysis in the buffer solutions with different pH values

Compd.	pH	Hydrolysis kinetic equation	Correlation coefficient, r²	t_1/2/d
A	5	c_t=27.584 $e - 0 . 1238 t$	0.9797	5.59
	7	c_t =28.33 $e - 0 . 0658 t$	0.9633	10.53
	9	c_t =40.645 $e - 0 . 0341 t$	0.9846	20.33
B	5	c_t =32.742 $e - 0 . 0751 t$	0.9850	9.23
	7	c_t =35.078 $e - 0 . 0418 t$	0.9560	16.58
	9	c_t =26.865 $e - 0 . 0418 t$	0.9682	27.40
C	5	c_t =41.195 $e - 0 . 1625 t$	0.9491	4.26
	7	c_t =37.482 $e - 0 . 0923 t$	0.9677	7.51
	9	c_t =40.132 $e - 0 . 0379 t$	0.9834	18.29
D	5	c_t =25.889 $e - 0 . 1475 t$	0.9799	4.70
	7	c_t =28.745 $e - 0 . 1086 t$	0.9866	6.38
	9	c_t =27.331 $e - 0 . 0398 t$	0.9650	17.42
E	5	c_t =25.087 $e - 0 . 0735 t$	0.9772	9.43
	7	c_t =30.564 $e - 0 . 027 t$	0.9559	25.67
	9	c_t =23.949 $e - 0 . 0127 t$	0.9670	54.58
F	5	c_t =31.059 $e - 0 . 0835 t$	0.9205	8.30
	7	c_t =26.675 $e - 0 . 0259 t$	0.9585	26.76
	9	c_t =24.018 $e - 0 . 0166 t$	0.9765	41.76
G	5	c_t =25.407 $e - 0 . 0964 t$	0.9608	7.19
	7	c_t =22.595 $e - 0 . 0188 t$	0.9646	36.87
	9	c_t =24.338 $e - 0 . 014 t$	0.9747	49.51
H	5	c_t =23.536 $e - 0 . 0653 t$	0.9716	10.61
I	5	c_t =20.351 $e - 0 . 075 t$	0.9843	9.24
Monosulfuron-methyl	5	c_t =27.629 $e - 0 . 0506 t$	0.9861	13.70
Metsulfuron-methyl	5	c_t =24.098 $e - 0 . 0299 t$	0.9861	23.18

Table 2 Degradates of hydrolysis of compound A detected by HPLC-MS

Component	t_R/min	ESI-MS, m/z
A	9.50	420(M-H)⁺
a	5.62	285(M-H)⁺, 344(M+CH₃CO₂)⁺
b	4.10	110(M+H)⁺
c	4.60	197(M-H)⁺
d	3.94	182(M-H)⁺

Scheme 1 Potential hydrolysis pathways for compound A

Fig.3 Steric field of CoMFA model

Table 3 Measured and predicted hydrolysis half-life of 11 compounds

Compd.	R₁	R₂	R₃	Z	t_1/2/d
Compd.	R₁	R₂	R₃	Z	Measured	Predicted
A	C₂H₅CONH	CH₃	H	C	5.59	5.88
B	t-C₄H₉CONH	CH₃	H	C	9.23	9.26
C	CH₃CONH	CH₃	H	C	4.26	5.48
D	CF₃CONH	CH₃	H	C	4.70	5.62
E	C₆H₅	CH₃	H	C	9.43	8.91
F	o-NO₂PhCONH	CH₃	H	C	8.30	9.07
G	o-OCH₃PhCONH	CH₃	H	C	7.19	9.13
H	CH₃CONH	CH₃	OCH₃	N	10.61	10.70
I	CF₃CONH	CH₃	OCH₃	N	9.24	9.84
Metsulfuron-methyl	H	CH₃	OCH₃	N	23.18	22.82
Monosulfuron-methyl	H	CH₃	H	C	13.70	14.27

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