CA2029349A1 - N-substituted-3-[(2,3-dimethylmaleimido)amino]-benzenesulfo namide derivatives, preparation process thereof and herbicidal compositions - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Disclosed herein are N-substituted-3-[(2,3-dimethyl-maleimido)amino]benzenesulfonamide derivatives of the for-mula (I):

Description

2 ~ 3 ~ 9 TITLE OF THE INVENTION:
N-SUBSTITUTED-3-~(2,3-DIMETHYLMALEIMIDO)AMINO]-BENZENESULFONAMIDE DERIVATIVES, PREPARATION
PROCESS THEREOF AND HERBICIDAL COMPOSITIONS
BACKGROUND OF THE INVENTION
1) Field of the Invention:
The present invention relates to N-substituted-3-[(2,3-dimethylmaleimido)amino]benzenesulfonamide deriva-tives, a preparation process thereof, and herbicidal com-positions containing the derivatives as active in-gredients.
2) Description of the Related Art:
Numerous compounds have heretofore been proposed as herbicides. Regarding N-substituted benzenesulfonamide derivatives, a variety of compounds has also been reported as herbicides.
For example, EP-A-116518 and Japanese Patent Ap-plication Laid-Open (KOKAI) No. 129276/lg87 disclose the use o~ N-(phenylsulfonyl)-N'-pyrimidyl- or triazinyl urea derivatives, which have one or more substituents on the phenyl nucleus, as herbicides. Illustrative of the sub-stituent on the 3-position of the phenyl nucleus include various groups such as NHCH3, OCH~CF3 and SCH2CF3.
There have conventionally been strong demands for , , , :

202~9 herbicides capable of exhibiting reliable herbicidal ac-tivity even at such low application dosages as bringing about the advantage of reducing the amount present in the environment, herbicides capable of exhibitin~ selectivity s between crops and weeds irrespective of variations in en-vironmental conditions, herbicides free from crop injury to the second crop in double cropping, etc. The present invention has been completed with a view toward meeting such demands.
The present inventors have found, as a result o~ an investigation, that a series of compounds still unreported in any publications known to the inventors and having a chemical structure different from the compounds disclosed in EP-A-116518 and Japanese Patent Application Laid-Open (KOKAI) ~o. 129276/1987 referred to above.

SUMMARY OF THE INVENTION
Therefore, an object of the invention is to provide novel compounds which show excellent herbicidal activity.
Another ob~ect of the invention is to provide a pro-cess ~or preparing novel compounds which show excellent herbicidal activity.
A further object of the invention is to provide in-termediates useful in the preparation of novel compounds which show excellent herbicidal activity.

202~3~9 A still further object of the invention is to pro-vide novel herbicidal compositions which show excellent herbicidal activity.
A still further object of the invention is to pro-S vide a method for controlling monocotyledonous or dicotyledonous weeds on an agricultural or non-agricultural land.
In one aspect of the invention~ there is thus pro-vided An N-substituted-3-t(2,3-dimethylmalsimido)amino]-benzenesulfonamide derivative of the formula (I):

N ~
, ~ NNH ~ SO 2 NHCONH~ O Z (I) H3 ~ R X2 wherein R is Cl, C1-C3 alkyl or Cl-C4 alkoxycarbonyl: Z is C~ or N; xl is Cl or C1-C3 alkoxyl; and x2 is Cl-C3 alkyl or Cl-c3 alkoxyl.
In another aspect of the invention, there is also provided a process for the preparation of an N-substituted-3-~(2,3-dimethylmaleimido)amino]benzene-sulfonamide derivative of claim 1, which comprise~ react-ing a 3-t(2,3-dimethylmaleimido)amino]benzenesulfonamide derivative of the formula (II):

~ NH ~ 502NH2 (~) '. ~ . ~;,,, , 20293~9 wherein R is Cl, Cl-C3 alkyl or Cl-C3 alkoxycarbonyl, with a phenylcarbamate derivatiYe of the following formula (III):
O X' ~ 1I N ~ tm) wherein Z is CH or N, xl is Cl or C1-C3 alkoxyl, and x2 is Cl-C3 alkyl or Cl-C3 alkoxyl.
In a further aspect of the invention, there is also provided a 3-~(2,3-dimethylmaleimido)amino]benzene-sulfonamide derivative useful as an intermediate in the preparation of the above N-substituted-3-[(2,3-dimethyl-maleimido)amino~benzenesulfonamide, which is represented by the following formula (II). -In a still further aspect of the invention, there is also provided a herbicidal composition comprising a her-bicldally effective amount of an N-substituted-3-~(2,3-dimethylmaleimido)amino]benzene3ulfonamide derivative of the formula ~I) and an agronomi¢ally-acceptable vehicle or diluent.
In a still further aspect of the invention, there is also provided a method for the control of monocotyledonous or dicotyledonous weeds on an agricultural or non-agricultural land, which comprises applying to the agri-cultural or non-agricultural land the N-substituted-3-t(2,3-dimethylmaleimido)amino]benzenesulfonamide deriva-tive of the formula (I) or a herbicidal composition com-prising said derivative.

, ~ .
~:

~0293~9 The N-substitut~d-3-[(2,3-dimethylmaleimido)amino]-benzenesulfonamide derivatives of the present invention, which are represented by the formula (I), exhibit reliable herbicidal activity at low application dosages and show selectivity between crops and weeds. The herbicidal com-positions of the invention, which contain the above derivatives as effective ingredients, are suitable partic-ularly for controlling before or after germination dicotyledonous and/or monocotyledonous weeds in important crops, for example, such as wheat, rice, corn, soybean, cotton, beet, potato, tomato or the like. They are also usable for the control of weeds not only on agricultural lands such as upland fields, paddy fields and orchards but also on non-agricultural lands such as athletic fields and factory sites.

DETAILED_DESCRIPTION OF PREFERRED EMBODIMENTS
Specific examples of the N-substituted-3-t(2,3-dimethylmaleimido)amino]benzenesulfonamide derivative represented by the formula (I) in the invention include those shown in Table 1.

2029~9 Ta b I e 1.

)[~NNII~gO2NllCONll~ O z Compound ¦ R ¦ Xl l X2 ¦ Z

I -1C I OCII 3OC113 Cll CU~ ~ ' OC113 OCI13 Cll I -3COOC113 OC113 OC113 Cll I -4C O OC ,11, OCI13 OCI13 Cll .. _ . I -6 C O O C 2 D ~ OCI13 CH 3 N

I -8C O OC 2 H 5 C I OCII 3 Cll The N-substituted-3-[(2,3-dimethylmaleimido)amino]-benzenesulfonamide derivatives represented by the formula (I) can each be synthesized by reacting a 3-~(2,3-di~ethylmaleimido)amino]benzenesulfonamide derivative of the formula (II) and a phenylcarbamate derivative of the following formula (III) in the presence of a base and in an organic solvent in accordance with the following reac--- tion formula:

: ~ NNH ~ 502NH2 + ~ OCNH~ O Z

to (m) H3C 0 X' r--Z N
H3~ ~NNH S02NHCONH~ O Z

:: R
(1) :
, ~
" ;" ' '' ', . ~ ` ~.' ' .

. ~ . . . - .
.
.. . . . . .

2~2~

wherein R, z, xl and x2 have the same meanings as defined above.
In the above reaction, dimethylacetamide, N-methyl-pyrrolidone, acetonitrile or the like can be used as an organic solvent. On the other hand, diazabicyclooctane, diazabicyclononene, diazabicycloundecene or the like can be used as a base.
The reaction is conducted at a temperature in a range of from -20C to 100C, preferably from 0C to 50C
for a reaction period in a range of from 0.5 hour to 24 hours.
A~ter completion of the reaction, the reaction mix-ture is added to an aqueous solution of dilute hydro-chloric acid and the precipitate thus formed is collected by filtration. The preclpitate is dried in air and then purified by a purification technique such as reprecipita-tion or column chromatography or by a washing technique, whereby the intended N-substituted-3-[(2,3-dimethyl-maleimido)amino]benzenesulfonamide derivative represented by the formula tI) can be obtained with high purity.
The 3-t~2,3-dimethylmaleimido)amino]benzene-sul~onamide derivative represented by the ~ormula (II~, which is a preparation intermediate and is employed as the starting material in the above reaction, can be synthesiz-ed in accordance with the following reaction formula, .

2Q2g3~9 using as a starting material a 3-aminobenzenesulfonamide derivative represented by the following formula (IV):

N2H S02NH2 ~2NNH S02NH2 ~( 1 ) Diza~tization ~
R 2) RedUCtion R
(IV) (V) ~ r-~ H3C 0 H3C ~ H

(~) wherein R has the same meaning as defined above.
Synthesis of the 3-t(2,3-dimethylmaleimido)amino~-benzenesulfonamide derivative represented by the formula (II) can be practiced in the following manner. A 3-hydrazinobenzenesulfonamide derivative represented by the formula (V), which has been obtained by diazotizing the amino group of the compound represented by the formula (IV) and reducing the thus-diazotized derivative, and 2,3-dimethylmaleic anhydride are stirred at 30-120-C, pre~erably 70-90C for 0.5-4 hours in acetic acid or propionic acid. After completion of the reaction, the reaction mixture is evaporated to dr,vness under reduced pressure and the resulting crude product i5 purified by column chromatography, whereby the 3-~(2,3-dimethyl-- , - , ~

2~293~

maleimido)amino]benzenesulfonamide derivative represented by the general ~ormula (II) can be obtained with good purity.
The compound represented by the formula ~IV), which was used in the above reaction formula, can be obtained from the corresponding nitrobenzene derivative, for exam-ple, by using the process described in Bull. Chem. Soc.
Jpn., 55, 3824 (1982); or from the corresponding 3-nitroaniline derivatives, for example, by the process de-scribed in Chem. Ber., 90, 841 (1957) or J. Macromol. Sci.
Chem., 1969, 941, namely, by synthesizing 3-nitrobenzene-sulfonamide derivatives and then reducing the nitro groups into amino groups with SnC12 in methanol or ethanol con-taining 35% hydrochloric acid.
Speci~ic examples o~ the 3-~(2,3-dimethyl-maleimido)amino]benzenesulfonamide derivative represented by the formula (II) and useful as a preparation intermedi-ate are summarized in Table 2~
In addition, specific examples of the compound represented by the formula (V) are shown in Table 3.

~293~.~9 Tab le 2.

H3 C O _ R
Compound No.

. ~- 2 C H 3 ~ - 3 C O.OCH 3 ~--4 C O O C 2 H 5 T ab I e 3.
N2 N NH ~ S O2 NH2 Compound No.

V --2 C I .
V - 3 C~3 Furthar, the compound represented by the formula (III) can be obtained from phenyl chloroformate and the corresponding 2-amino-4,6-(di-substituted) pyrimidine (or 1,3,5-triazine), for example, by the process described in European Patsnt Specirication No. 238,070.
The N-substituted-3-~(2,3-dimethylmaleimido)amino~-~ benzenesul~onamide derivatives exhibit reliable herbicidal : ~ activity at low application dosages and show selectivity ~ between crops and weeds. The herbicidal compositions of : : :
~ 25 the invention, which contain the above compounds as effec-.
' .
- , - . .

2~293~

- 12 ~

tive ingredients, are therefore suitable for controlling either before or after emergence monocotyledonous weeds and/or dicotyledonous weeds in important crops such as wheat, rice, corn, soybean, cotton, beet, potato and tomato.
Exemplary dicotyledono~s weeds which can be control-led by the herbicides of the invention include Amaranthus, Bidens, Stellarla, Sol~num, Abutilon, Convolvulus, Matricsr~a, Galiu~, L~ndernia, etc.
Illustrative monocotyledonous weeds include Echinochloa, Setaria, Digitaria, Avena, Cyp~rus, Alisma, Nonochoria, etc.
The herbicides of the invention may take any prepa-ration forms such as wettable powder, emulsion, powder, granule and the like. Known agronomically-acceptable -- - vehicles (diluents) and aids can be used.
The applicable places of the herbicides according to the invention range from agricultural lands such as upland - : fields, paddy fields and orchard to non-agricultural lands such as athletic fields and ~actory sites.
Examples:
The present invention will hereinafter be described by the following examples.
Synthesis Example 1:
SYnthesis of ethvl 4-r ~2.5-dihydro-3 4-dimethyl-2.5-dioxo-lH-~yrrol-l-vl)amino~-2- r ( 4.6-dimethoxy-PYrimidin-2-yl)aminocarbonylaminosulfonyl]benzoate (Compound No. I-4) At room temperature, 158 mg (0.43 mmol) of ethyl 2-(aminosulfonyl)-4-t(2,5-dihydro-3,4-dimethyl-2,5-dioxo-lH-pyrrol-1-yl)amino]benzoate and 118 mg (0.43 mmol) of phenyl (4,6-dimethoxypyrimidin-2-yl)carbamate were dis-solved in 1.5 me of N,N-dimethylacetamide. Then, 73 mg of 1,8-diazabicyclo~5.4.0]undec-7-ene were added, followed by stirring for 5 minutes. The resultant mixture was al-lowed to stand for 15 hours. Thereafter, 0.2 me of 35%
hydrochloric acid was added to 20 me of ice water, fol-lowed by the addition of the reaction mixture in 0.2 m~
portions under stirring. After the reaction mixture was stirred for 20 minutes, the resulting precipitate was col-lected by filtration and dried in air. Using dichloro-methane as an eluent, the crude product was purified by chromatography on a column of silica gel ("WAX0 GEL C-300", trade mark; product of Wako Pure Chemical In-dustries, Ltd.). Vield: 162 mg (58%). Mel~ing point:
121-123C ~decomposed). Its physicochemical properties are shown in Table 4.
Synthesis Example 2:
Synthesis of methyl 4-r(2 5-dihydro-3.4-dimethvl-2.5-dioxo-lH-~Yrrol-l-Yl)aminol-2-rf4.6-dimethoxy-.

r~
~A

1.3 5-triazin-2-yl)aminocarbonyllbenzoate (Compound No. I-7) At room temperature, 172 mg (0.5 mmol) of methyl 2-(aminosulfonyl)-4-t(2,5-dih~dro-3,4-dimethyl-2,5-dioxo-lH-pyrrol-l-yl)amino]benzoate and 138 mg (0.5 mmol) of phenyl (4,6-dimethoxy-1,3,5-triazin-2-yl)carbamate were dissolved in 1.5 me of N,N-dimethylacetamide. Then, 76 mg of 1,8-diazabicyclo[5.4.0]undec-7-ene were added, followed by stirring for 5 minutes. The resultant mixture was allowed to stand for 6 hours. Thereafter, 0.2 me of 35~ hydro-chloric acid was added to 20 me of ice water, followed by the addition of the reaction mixture in 0.2 me portions under stirring. After the reaction mixture was stirred for 20 minutes, the resulting pracipitate was collected by filtration and dried in air. Using a 1:2 mixed solvent of methyl acetate and benzene as an eluent, the crude product was purified by chromatography on a column of silica gel (IlWAKO GEL C-300", trade mark; product of Wako Pure Chemi-cal Industries, Ltd.). Yield: 59 mg (22%). Melting point: 123-127C. Its physicochemical properties are shown in Table 4.
The other N-substituted-3-~(2,3-dimethylmaleimido)-amino]benzenesulfonamide derivatives shown in Table 1 were also synthesized in a similar manner to Synthesis Example 1. Namely, after obtaining crude products by a similar 2~2~3~

pro~edure to Synthesis Example l, they were separately purified by chromatography on a silica gel column, re-precipitation or washing. Physicochemical properties of each of the N-substituted-3-[(2,3-dimethylmaleimido)-amino]benzenesulfonamide derivatives are shown in Table 4.
Incidentally, in Table 4 and Table 6 which will be given subsequently, the abbreviations in the columns for NMR
data have the following meanings:
~: (ppm), s: singlet, d: doublet, t: triplet, q: quartet, m: multiplet, dd: double doublet, br: broad.
Further, with respect to the individual N-substituted-3-~(2,3-dimethylmaleimido)amino]benzene-sulfonamide derivatives, the solvents employed upon purification thereof and the yields attained were as fol-. ........ lows:

2~2~3~9 Compounds purified by reprecipitation:
Com~ound No. Solvent employed Yield (%) I-l CH2C12 + petroleum ether 38 I-2 CH2C12 + petroleum ether 75 5Compounds purified by washing:
Com~ound No. Solvent employed Yield (%) I-3 petroleum ether 40 Compounds purified by column chromatography:
Compound No. Solvent em~loyed Yield (~) I-5methyl acetate + benzene 22 I-6ethyl acetate + benzene 21 I-7methyl acetate + benzene 22 . I-8ethyl acetate + benzene 64 _ ~ . _ 1~ = ~ = _ 2 ~ _ el- = ~ ~ = C`~
_ _ _ _ ~ ~ G _ ~ ~ --U~_ _ ~ ~ Co U~ ~ --C~ U~ ~ CO ~J
'O= V~_ ~2 =_ CO_ C~ ~= co_ ~ ~CO eor- 2~- _~ =CO _c~ =CO
0~ ~q~= c~CO ~l_ CO~ O= CO~ CO_ _ e~ _ a~ _ _ co c~ c Co O Ul eo ~_ P'= ~ t_CO _= O- =0~ CO~ =0~
_ Ul CO Ul ~ Ul U~ O ~ Ul t- CO ~ Ul ~ _ ~
0 ~ _~ co= co _ ~c co~ c~ eoc~ ~rc Z ~3 u~ ~ 0 ~ O ~ Ul = = ~o 2 û~ ~ o = ûl =
u~ ~ c~ ~ û~ = u~ û~ ~O e~ ~ ,0 Ul ~- O ~ ~
O = ~ = ,=~ U~ C~ _ _ CO _ _ - ~ CO _ C~ = _ +
_ ~~ coo - eC.`~ ~ = c.~, ~ co e~r = C~O C,~ ~ ;~ = CU~
0 c~ e~ = ca = e~ coO ~ co co cr~ eO _ eO ,co co co X X
UIUI =o=_ =O__ =o=5 co_,~ =o=L =o= eo=5 . \~0 ~ cO ~O ~OP cO e~ c~ CO C--O r- UO c ~r ~--0 ~o c~ co c0O ~ r D e~ t-- c.~i eo C ~ co e~ _ ~o r_ C~ ~ C~--co t--c~ --- co t--CC ~ Z

~ O _ O _ _ O O O eo _ O O O O _ CO ~
00 eoOO ~0~- eo O 00 t-~oo0 000 .
o o o _ O ~r c.~ cO o o o ~ co r- co 0 0 0 t~ _ +
m ~ O ._ 0~ 0 O O O O O C~ ~p _ a U~ cJO~ O O 0~ 0~ 0 ~ / O
. P: 00 C~oo OOOOU~ 000 ~C~ O~CO '0~_ eO~ U
- C~ ~O~ ~o~O o~c e~coc~ OO Io~~ oo0 l o ~ ~ ~ O O ~0 ~ ~ ~ v, ~:
~ ~ ~ 0 ~P~ 0~ ~ O ~ c ~ c~ ~ c~ _ e~ ~O eo ~ z ~ #~3 u, ~ u, u, ~ er ~ ~ o ~o _ _ u~ ~ ~ - O~ 0 0 ~ 0 ~ c~
_ _, _ _ _ _ _ _ P:
~i l cl cl l l el l el *

20293~9 Synthesis Example 3:
Synthesis of preparation intermediate ethyl 2-(aminosulfonvl)-4-~(2.5-dihydro-3.4-dimethyl-2 5-dioxo-lH-pyrazol-1-yl)aminolbenzoate (Compound No.
II-4) (1) Svnthesis of ethyl 2-(aminosulfonyl)-4-hydrazino-benzoate (~om~ound No. V-5~:
Ethyl 4-amino-2-(aminosulfonyl)benzoate t2.44 g;
10 mmol) was finely ground and then added to a mixture of 5 m~ of 35% hydrochloric acid and 5 m~ of water. The mixture thus prepared was stirred for 5 minutes at room temperature. It was thereafter cooled with ice water and under stirring, a solution of 0.72 g (10.5 mmol) of sodium nitrite in 3 m~ of water was added over 3 minutes to con-duct diazotization.
In 5 ml of 35% hydrochloric acid, 5.2 g ~27.4 mmol) of stannous chloride were dissolved. The resulting solu-tion was cooled with ice water and stirred, followed by the addition of the diazotized compound prepared above.
After the resultant mixture was ~tirred for 20 minutes, it was left over Sor 15 hours in a reSrlgerator.
The reaction mixture was then transferred into a 2-~
beaker, to which 2~ g of sodium bicarbonate powder were then added under stirring to adjust the pH to 6. The mix-ture thus prepared was then extracted twice with 700 m~

. ' . . ' ' of ethyl acetate. The extract was dried over sodium sul-fate, and ethyl acetate was distilled off to obtain a pale brown solid. Yield: 2.66 g (98%). Melting point: 122-124C (decomposed). Its physicochemical properties are shown in Table 6.
(2) SYnthesis of ethyl 2-Laminosulfonyl)-4-rt2 5-dihvdro-3 4-dimethYl-2~5-dioxo-lH-~rrol-l-~l)aminobenzoate (Com-pound No. II-4):
The compound synthesized in the above procedure (1) [Compound No. V-5; 259 mg (1 mmol)] and 132.6 mg (1 mmol) of 2,3-dimethylmaleic anhydride were dissolved at room temperature in 4 me of acetic acid, followed by stirring at 80-90C for 3 hours. The reaction mixture was then evaporated to dryness under reduced pressure. Using dichloromethane as an eluent, the crude reaction product thus obtained was purified by chromatography on a column of silica gel ("WAK0 GEL C-300", trade mark; product of Wako Pure Chemical Industries, Ltd.). Yield: 203.8 m~
(55%). Melting point: 184-186C. Its physicochemical properties are shown in Table 5.
In addition, physicochemical properties of the other compounds of the formula (II) synthesized in a similar manner to the above-described procedure are also shown in Table 5.
Further, physicochemical properties of other prepa-r .

-` 2~2~3~

ration intermediates synthesized in a similar manner to the above procedu~e (1) are also shown in ~able 6.

T ab le 5.

Compuund Yleld US(~/e) Mflltlng Polnt .
No. orDeco~posltlon IR (KB r, cm~') (%) M~ Polnt (~) ~-1 87 329216-221 3370.3320.3270.1180.1730.1600.
1550.1410.1340.1175.1165.590.
109-111 3379.3320.3260.1170.1710.1600.
~-2 62 309Deco~posed 1480.1320.1310.1150.1130.1080.
_ 1050.920.680.590.510 3320br.2950.1780.1720.1600.1430.
~-3 47 353120-125 1340.1310.1280.1250.1170.1120.
_ 1090.1050.930.7l0.l10.700.590.
3380.3250.2980.1780.1720.1700.
~-4 55 367184-186 1600.1420.1320.1290.1270.1240.
_ 1160.1130.1090.1050.780.700.600.

. ~:
' 2~2934~
~ 0~ ~ Or CD a cr~ co o ~ o CD o~ o a~ ~n _ _ _ a ~ _ ~ _ _ o _ _~ o o o a o o o o o o o ; C~ ~ V C~ U~ eD e~ eo e~ t- ~ o m O ~ O O a~ O O O O O O
O _ ~ ~0 _ O ~ ~ _ ~ ~ t_ O O . O O t_ O O ~ O O O O O O
P~ c-~ ~ oo c~ r o ~ _ o cl~ a a e~ a _ _ o o o O O eo o o '~ o o o o o o o~ ~ o ~_ CO o o o o o U~ ~7 ~ ~ ~ U~
o~ _ _ c ~ _ cn ~~ _ ~ o~ _ _ o~ _ _ ~O O .
~1 _ _ _ oo O ~ ~a ~ ~ ~) l ~1 o CD ~el~ o D ~ _ u~ _ o~ ~ o ... ~ _ ~ ~ _ ~ _ _ _ ~
E-~ ~c~c c~ ~

' : ~ _ _ C~ _ e~ C`~ . ~ e~
.
_.
cn ~ ~ ~o oo ~ _ oo oo oo oo a-o l l ~' _ 2g~9~9 Compounds obtained in a similar manner to Synthesis Examples l and 2 are shown in Table 7.
Tab I e 7.

)~NNII~SO2NHCONH~ O Z

-- R X X Z

I _9 COOCH3 OCH3 OCH3 N
I-10 CI OCH3 Cl13 N
I -11 Cl OC113 OCR3 N
I I-12 CH3 OCHg CH3 N

~1 -14 C I OCH3 CH3 CH
I -15 Cl Cl13 CH3 CH
I -16 COOCH3 OCH3 Cl13 CH
I I-17 COOCH3 Cl13 CH3 CH
I -18 CH3 Cl13 CH3 CH

Formulation examples and tests will hereinafter be described. It should be borne in mind that the vehicles (diluents) and aids, their mixing ratios and effective components can vary in wide ranges, respectively.
EQxmulation ~xam~ Wettable Powder Compound (Compound No. I-4) 50 parts A salt of ligninsulfonic acid 5 parts A salt of alkylsulfonic acid 3 parts Diatomaceous earth 42 parts The above ingredients are mixed and ground into a 2~293~9 wettable powder. For application, it is diluted with water.
Formulation_Example 2: Emulsion Compound (Compound No. I-5) 25 parts Xylene 65 parts Polyoxyethylene alkylaryl ether10 parts The above ingredients are mixed intimately into an emulsion. For application, it is diluted with water.
Formulation Exam~le 3: Granule Compound (Compound No. I-7) 8 parts Bentonite 40 parts Clay 45 parts A salt of ligninsulfonic acid 7 parts The above ingredients are mixed intimately and after the addition of water, were kneaded and then formed into granules by an extruding granulator. They were then dried to provide a granular formulation, namely, a granule.
Test l: Test on Harbicidal ~ctivitv by Foliar Application Herbicidal solutions of each test compound, which had been prepared by dissolving at predetermined con-centrations such a wettable powder of the test ¢ompound as that described in the above ~ormulation example, and sprayed at dosages o~ 10 g/ha and 100 g/ha over foliar parts of Amaranthus retroflexus (Redroot pigweed), 3idens pilosa (Common blackjack), Sinapis arvensls (Wild mustard), 2~293~

Stellaria media (Common chickweed), Cassia obtusifolia (Sick-lepod), Solanum nigrum (Black nightshade), Abutilon eheophrasti (Velvetleaf), Convolvulus a~vensis (Field bindweed), Matricaria chamomills (Wild chamomile), Seearia viridis (Green foxtail), Echinochloa frumentaceum (Barnyard grass), Avena faeua(Wild oat), and Digiearia adscendens (Henry crabgrass) which had been allowed to grow individually to 2-4 leaf stage in pots. Fourteen day~ later after spraying of the test com-pound, its herbicidal activity was evaluated in accordance with the below-described system. The results are sum-marized in Table 8.

... . ....

.

.. ..

2~12~3~9 Ranking system:
Herbicidal activity 0: No effects 1: less than 30% of total kill 2: 30% (inclusive) - 50% (exclusive) of total kill 3: 50% (inclusive) - 70% (exclusive) of total kill 4: 70~ (inclusive) - 90~ (exclusive) of total kill 5: 90% (inclusive) -100% (inclusive) of total kill 2~2~

~ noa~ L~ ~

~ e ¦ = ~ ~ ~ L -- c ~ m = ¦ ~ ` -- ~-. c~ ~ _ a~ _ u~ ~ u~ c~ ~ a~ ~ a~ ~ C~- ~ _ ¢ _ o ~ ~ e ~ U~ ~ _ U~ ~ U~ ~ ~C~ U~ ~ U~ ~ ~ U~ ~ ~
~ _= c~ == ~7= --r .,= ~= ~= _~

e = = = = -7 = = = = = = = = = = = ~ O c~ ~0 c ~ = ~ ~ = = ~o = _ ~c = = = = = e _ o --O O .Q Co C~
C~ a~ u~ ~ u~ _ ~ u~ ~ _ u~ c~ ~ e~ u~ ~ ~ C ~ ~S O
~d 1~ ~ ~
,...... E- c~_ u~ ~ u:~o u~ ~u~ ~u~ :~ ~
U~ = ~ ~ ~ ~ ~ U~ U~ U~ ~ ~ ~ ~ ~ ~o . CL _ _ ~ cd Q~ ~ u~ ~ ~ ~ u~ ~ u~ u~ u~ ~ _ ~ =
_ _ _ 6~ ~
e ~ U'~ ~ U~ U~ U~ U~ U~ ~ ~ ~ U~ ~ ~ ~ U~ _ U ~

o~ _c oo ooO _o ooO ooO _o _o aa~ v _ _ _ I _ _ _ _ _ e l ~~ ~~ ~~ =~ =~ l ol~ ~

- ~ .~. , :

2~293~
.

Test 2: Germination Test of Seeds Two sheets of filter paper were placed in a super-posed relation in each of Petri dishes having a diameter of 9 cm. Water suspensions of each test compound (con-centrations of the active ingredient: l ppm and 50 ppm) were separately poured in an amount of 5 me per dish into the Petri dishes. Seeds of Amaranthus retroflexus (Redroot pigweed), ~Idens pilosa (Common blackjack), ~atrlcar~a chamomllla (Wild chamomile), Solanum nlgrum (Black nightshade), Echlnochloa oryzicola (Barnyard grass), Cyperus iria (Rice flatsedge) and Setaria virldis (Green foxtail) were placed at a rate of lO seeds per dish in the Petri dishes. They were thereafter allowed to germinate in a constant-temperature chamber at 28C. Fourteen days later after placement in the Petri dishes, the degrees of germination and growth inhibition were observed visually.
The observation results were ranked in accordance with the below-described 6-stage system. The results are sum-marized in Table 9.

2~2~34~

Growth inhibition rate 0: No inhibition 1: less than 30%
2: 30% (inclusive) - 50% ~exclusive) 3: 50% (inclusive) - 70% (exclusive) 4: 70% (inclusive) - 90% (sxclusive) 5: 90% (inclusive) - 100% (inclusive) ~.

:; `
:

.

.
, - , . ~
- . , -.

2i~293~

T a b I e 9 Co~pound Concen _ _ No tratio A.r. B.p. M.c. S.n. E.o. C.i. S.v.

_ I -2 1 4 4 5 3 4 4 5 . _ _ . . . _ _ .

so---- 4 3 5 4 2 4 3 50 4 4 _5 3 4 3- 5 Noto) A.r.:Auaranthus rotroflexus E.o.:Echlnochloa oryzicola B.p.:Bidons Pilosa C.l.:Crperus iria M.c.:Matricaria chanoailla S.v.:Sotaria viridis S.n.:Solanuu nlgru--

Claims (9)

1. An N-substituted-3-[(2,3-dimethylmaleimido)-amino]benzenesulfonamide derivative of the formula (I):

(I) wherein R is C1, C1-C3 alkyl or C1-C4 alkoxycarbonyl; Z is CH or N; X1 is C1 or C1-C3 alkoxyl; and X2 is C1-C3 alkyl or C1-C3 alkoxyl.

2. A derivative of claim 1, wherein Z is CH.

3. A derivative of claim 1, wherein Z is N.

4. A derivative of claim 1, wherein Z is CH, R is C1, CH3, COOCH3 or COOC2H5, X1 is C1 or OCH3, and X2 is OCH3.

5. A derivative of claim 1, wherein Z is CH, R is COOCH3 or COOC2H5, X1 is OCH3, and X2 is CH3 or OCH3.

6. A process for the preparation of an N-substituted-3-[(2,3-dimethylmaleimido)amino]benzene-sulfonamide derivative of claim 1, which comprises react-ing a 3-[(2,3-dimethylmaleimido)amino]benzenesulfonamide derivative of the formula (II):

(II) , wherein R is C1, Cl-C3 alkyl or C1-c4 alkoxycarbonyl, with a phenylcarbamate derivative of the following formula (III):

(III) wherein Z is CH or N, X1 is C1 or C1-C3 alkoxyl, and X2 is C1-C3 alkyl or C1-C3 alkoxyl,

7. A 3-[(2l3-dimethylmaleimido)amino]benzene-sulfonamide derivative of the following formula (II):

(II) wherein R is C1, C1-C3 alkyl or C1-C4 alkoxycarbonyl.

8. A herbicidal composition comprising a her-bicidally effective amount of an N-substituted-3-[(2,3-dimethylmaleimido)amino]benzenesulfonamide derivative of claim 1 and an agronomically-acceptable vehicle or diluent.

9. A method for the control of monocotyledonous or dicotyledonous weeds on an agricultural or non-agricultural land, which comprises applying to the agri-cultural or non-agricultural land an N-substituted-3-[(2,3-dimethylmaleimido)amino]benzenesulfonamide deriva-tive of claim 1 or a herbicidal composition comprising 7 said derivative.