CA2029348A1 - N-substituted-3-(nitrogen-containing 5 membered ring)-benzenesulfonamide derivatives, preparation process thereof and herbicidal compositions - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Disclosed herein are N-substituted-3-(nitrogen-containing 5-membered ring)benzenesulfonamide derivatives of the formula (I):

(I) wherein is , , , or ;

R1 is H, C1, C`-C3 alkyl or C`-C4 alkoxycarbonyl; Z is CH
or N; x1 is C1-C3 alkyl, C1-C3 alkoxyl or C1; and X2 is C1-C3 alkyl or C1-C3 alkoxyl, a process for the prepara-tion thereof, and herbicidal compositions containing the N-substituted-3-(nitrogen-containing 5-membered ring)-benzenesulfonamide derivatives as active ingredients.

Description

TITLE OF THE INVENTION:
N-SUBSTITUTED-3-(NITROGEN-CONTAINING 5-MEMBERED
RING)-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-(nitrogen-containing S-membered ring)benzenesulfonamide derivatives, a preparation process thereof, and herbicidal compositions 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. N-substituted benzenesulfonamides contain-ing a 5-membered ring bonded to the benzene ring and a pyrimidine ring or 1,3,5-triazine ring bonded to the nitrogen atom include, for example, the compounds of the following formula disclosed in GB 2 112 784 A and GB 2 112 783 A:
R ~ W
SO2NHC-N-A (I) 2~293~

wherein Q is a s-membered ring, R3 is H, F, Cl, Br, CH3, X

CF3 or OCH3, R4 is H or CH3, W is 0 or S, and A i8 N--~

in which X is CH3, OCH3 or Cl, Y is CH3, C2H5, CH2OCH3, OCH3, 0C2H5 or the like, and Z is CH or N.
There have conventionally been strong demands for 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 exhibiting selectivity between crops and weeds irrespective of variations in en-vironmental conditions, herbicides free from crop injurv to the second crop in double cropping, etc. The present invention has been completed with a view toward ~eeting such demands.
The present inventors have found that a series of compounds having a 5-membered ring on the 3-position of benzenesulfonamide as opposed to the inclusion of a 5-membered ring on the 2-position of benzenesulfonamide in the compounds disclosed in GB 2 112 784 A and GB 2 112 78 A referred to above has excellent herbicidal activity, leading to the completion of the present invention.

SYMM~Y Q~_TH~NVENTION

.
, , ..

2~2~8 Therefore, an object of the invention is to provide novel compounds which show excellent herbicidal activity.
Another object of the invention is to provide a pro-cess rOr preparing novel compounds which show excellent herbicidal activity.
A further ob;ect of the invention is to provide in-termediates useful in the preparation of novel compounds which show excellent herbicidal activity.
A still further object of the invention is to pro-vide novel herbicidal compositions which show excellent herbicidal activity.
A still Surther object oS the invention is to pro-vide a method for controlling monocotyledonous vr dicotyledonous weeds on an agrlcultural or non-agricultural land.
In one aspect oS the invention, there is thus pro-vided an N-substituted-3-(nitrogen-containing 5-membered ring)benzenesulfonamide derivative of the Sormula (I):

X' CN~ s o 2 NHCONH~ ~

Rl x2 wherein CN_ is ~ N-- , ~ N ~ N--,or ,~N<~N

R1 iSH~ Cl, C1-C3 alkyl or C1-C4 allcoxycarbonyl; Z is CH

20293~

or N; xl is C1-C3 alkyl, Cl-C3 alkoxyl or Cl: and x2 is C1-C3 alky~ or C1-C3 alkoxyl.
In another aspect of the invention, ther~ is also provided a process for the preparation of the above N-substi'cuted-3-(nitrogen-containing 5-membered ring)-benzenesulfonamide derivative, which comprises reacting a 3-(nitrogen-containing 5-membered ring) benzenesulfonamide .:
derivative of the formula (II): , CN~ S O 2 NH 2 (~) Rl wherein CN - and R1 have the same meanings as defined above, with a phenylcarbamate derivative of the following formula (III):
O X
~ OC N H

wherein Z, X1 and x2 have the same meanings as defined above.
In a further aspect of the invention, there is also provided a 3-(pyrrol-1-yl)benzenesulfonamide derivative useful as an intermediate in the preparation of the above N-substituted-3-(nitrogen-containing 5-membered ring)-benzenesulfonamide, which is represented by the following rormula (II-A):

.:

2~2~348 ~RZ ~ R~ A) wherein R1 has the same meaning as defined above and R2 is H or CH3.
In a still further aspect of the invention, there is also provided a 3-(2,3-dimethylmaleimido)benzene-sulfonamide derivative useful as an intermediate in the preparation of the above N-substituted-3-(nitrogen-containing 5-membered ring)benzenesulfonamide, which is represented by the following formula (II-B):

~ B) H3 C 0 R' wherein Rl ha~ the ~ame meaning as de~ined above.
In a still further aspect o~ the invention, there is also provided a 3-(3,5-dimethylpyrazol-1-yl)benzene-sulfonamide derivative useful as an intermediate in the preparation o~ the above N-sub~tituted-3-(nitrogen-containing 5-membered ring)benzenesul~onamide, which is represented by the following formula (~-C') N \~ S 0 2 N H 2 H3C ~ R~ C' ) wherein Rl is Cl-C4 alkoxycarbonyl.
In a still further aspect Or the invention, there is 2~2~3~8 also provided a herbicidal composition comprising a her-bicidally effective amount of an N-substituted-3-~nitrogen-containing 5-membered ring)benzenesulfonamide derivative of the formula (I) and an agronomically-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-(nitrogen-containing 5-membered ring)benzenesulfonamide derivative of the formula (I) or a herbicidal composition comprising said derivative.

ao . :

.

, .
.
.
.. ~ -- 2~2~8 The N-substituted-3-(nitrogen-containing 5-membered ring)benzenesulfonamide derivatives of the present inven-tion, which are represented by the formula ~I~, exhibit rQliable herbicidal activity at low application dosages and show selectivity between crops and weeds. The her-blcidal compositions o~ the invention, which contain the above derivatives as effective ingredients, are suitable particularly 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 agricultur~l lands such as upland fields, paddy fields and orchards but also on non-agricultural lands such as athleti¢ ~ields and ~actory site~.

Speci~ic examples o~ the N-substituted-3-(nitrogen-containing 5-membered ring)benzenesulronamide derivative represented by the formula (I) in the invention include those shown in Table 1.

, , ., :

.
' ' ':

21~29~48 Tab I e -- X' ' CN ~ S O 2 N H C O N H~

Co~pound .
NO. CN - X 2 I 1 Gc .1 3 . OCI13 OCII, Cll 10 I-2 C~'l" _ ~. OCII, C
I-3 ~N- Cl OCI13 OCI13 I -4 C H 3 Cl OCII3 Cll3 Cli .__ . ~ . .. _ . ._. ._ ___ .__ I -5 ~N-- Cll. OCN, OCIl, Cll _ I l ~~ ~. OCl, OCN. CH

I -7 C N 3 COOCH3 OCII3 OCII3 Cll 20 I l ~ ~ . OCII, Cll ~ ~ ~ I_9 ~N-- COOC211~ OC113 OCI13 Cll I -I D ~ ~ O ~C ~ ~ . OCI ~ OCII. Cll .

........... , .... -..... ,.~ . .
... .. . . .. .. . .. . ..
, .... ~ . .. .

.
. ~ . . . . .. . ~ ; .
. . . . ~ - . . ..

- 2~293~8 T a b I e 1 (1:: o n t' d) Co~pound CN- -- X X Z

5 I-ll ~N- COOCI13 Cl OCI13 Cll I-12 ~N-COOCI13 Cl13 C113 Cll _ -13 ~N-- Cl OCI13 Cl13 U

I -14 ~N -COOCI13 OCI13Cl13 N
1-15 ~ H OCI13OCI13 1-16 CC)~N-- Cl OCII3 OCII3 Cll ~ K ~ ~~I ~ ~ OCII~ Cl~

I-18 ~13C)C~O COOCI13 OCI13 OCI13 20 ~ l9 ,~' ~I CCII, C
I-20 . C ~1. 0~1.CCII~ CH

- 2~293~8 The N-substituted-3-(nitrogen-containing 5-membered)benzenesulfonamide derivatives represented by the formula (I) can each be synthesized by reacting a 3-(nitrogen-containing 5-membered ring)benzenesulfonamide derivative of the formula (II) and a phenylcarbamate derivative o~ the following formula (III) in the presence of a base and in an organic solvent in accordance with the following xeaction formula:

O Xl CN , S O 2 N H 2 _ 11 N~
10 ~ R1 +~ O C N H
(~) (m) x2 xl ~ CN ~ S O 2 N H C O N H~
( I) wherein CN_, R1~ Z X1 and x2 have the same meanings as defined above.
In the above reaction, N,N-dimethylacetamide, N-methylpyrrolidone, acetonitrile or the like can be used as an organic solvent. On the other hand, diazabicyclooc tane, diazabicyclononene, diazabicyc~oundecene or the like can be used as a base.
The reaction is conducted at a temperature in a range of from -20C to lOO'C, preferably from O-C to 50C
for a reaction period in a range o~ from 0.5 hour to 24 - . . ~ : , .
', :' : , .

~2~34~

hours.
After completion of the reaction, the reaction mix-ture iq added to an aqueous solution of dilute hydro-chloric acid and the precipitate thus ~ormed is collected by ~iltration. The precipitate 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-(nitrogen-containing 5-membered ring)benzenesulfonamide derivative represented by the formula (I) can be obtained with high purity.
The 3-(nitrogen-containing 5-membered ring)benzene-sulfonamide derivative represented by the formula (II), which is a preparation ~ntermediate and i8 employed as the starting material in the above reaction, ¢an be synthesiz-ed in accordance wlth any Or the following reaction ~or-mulae (A), (B) and (C), using as a starting material a ~nown 3-aminobenzenesulfonamide derivative represented by the following formula (IV~:

~ CH3 C OC H 2 ,. ,. I

(A) ~ + >
Rl , nt) R' . ~R2 ~ S 02 NH2 (~ - A) ; ' ,, ' .
.

2~293~8 H2N SO2NH2 ~
~B) ~ + H3C. o Rl - >

~N ~ SO2NH2 (~-B) (C) ~ 1) Diazotizat~on R' 2) R~duction R~
~lV) (V) CH3CO\

CH3CO/ . ~
? J =N~ ~ SO2N~2 H3C R' (~--C) wherein Rl and R2 have the same meanings as defined above.
Synthesis of the compound represented by the ~ormula (II-A) in accord~nce with the re w tion formula (A) can be practiced in the following manner. A compound represented by the ~ormula (IV) and a 2,5-dialkoxytetrahydrofuran or 2~2~8 acetonylacetone are stirred at S0-120~c for 0.5-10 hours in acetic acid or propionic acid or in dioxane which con-tains 35% hydrochloric acid or 95~ sulfuric acid in a catalytic amount. After complétion o~ the reaction, the solvent is distilled off thoroughly, and the residue is washed with water and is then collected by filtration.
The residue is then purified by column chromatography, whereby the compound represented by the formula (II-A) can be obtained with good purity.
Synthesis of the compound represented by the formula (II-B) in accordance with the reaction formula (B) can be practiced in the following manner. A compound represented by the formula (IV) and 2,3-dimethylmaleic anhydride are stirred at 50-120-C for 5-60 hour~ in pyridine, a¢etic acid or propionic acid. The solvent is then distilled O~r, rollowed by the addition of ice water to the residue.
Subsequent to acidification when pyridine was used, the resultant mixture is thoroughly stixred, and the resulting solid matter is collected by filtration and then dried in air, so that the compound represented by the formula tII-B) can be obtained with good purity.J
Synthesis of the compound represented by the formula (II-C) in accordance with the reaction formula (C) can be practiced in the following manner. The compound represented by the formula (V), which has been obtained by ---` 21~293~8 diazotizing the amino group of the compound represented by the ~ormula ~IV) and reducing the thus-diazotized deriva-tive, and acetylacetone are stirred at 40-120C ~or 3-20 hours in acetic acid or propionic acid or in an alcohol, such as methanol or ethanol, containing 35~ hydrochloric acid o~ 95% sulfuric acid. After completion of the reac-tion, ice water is added to the reaction mixture and the pH of the mixture thus obtained is adjusted to pH 6. The precipitate thus formed is collected by filtration, dried in air and if necessary, purified by column chromato-graphy, whereby the compound represented by the general ~ormula (II-C) can be obtained with good purity.
The compounds represented by the ~ormula (IV), which were used in the above reaction ~ormulae (A)-(C), can be obtained rrom the corresponding nitrobenzene derivatives, ~or example, by using the process described in Bull. Chem.
Soc. Jpn., 55, 3824 (1982): or ~rom the corresponding 3-nitroaniline derivatives, ~or example, by the process de-scribed in Chem. ~er., 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.
Further, the compound representsd by the ~ormula (III) can be obtained ~rom phenyl chloroformate and the 2~2g~8 corresponding 2-amino-4,6-di-substituted pyrimidine (or 1,3,5-triazine), for example, by the process described in European Patent Spscification No. 238,070.
Speci~ic examples o~ the compounds represented by the formulae (II-A), (II-B) and (II-C) and useful as prep-aration intermediates are summarized in Table 2 to Table 4, respecti~ely.
In addition, specific examples of the compound represented by the formula (V) are shown in Table 5.
Table 2 R~

~2 ~ R I
.
Coupound Rl R' No. . . _ ~- A -1 H _ H
~- A - 2 H CH3 ~-A - 3 C I H
~- A -4 C I CH3 ~- A - 5 CH3 ~- A - 7 C O O CH3 H
~ -A - 8 C O OCH3 CH3 ~- A - 9 C O OC2H5 H
~- A -l0 CO O C2H5 CH3 .~, ..
`' - : ' -`- 2~2~3~8 Tab l e 3 H 3 C~ 0 . . __ Compound No . R

Ir--B- 2 C I
~ - B - 3 C H 3 Il--B--4 C O O C H 3 '-:
Tab I e 4 /e~C H 3 Co~pound No. I R' l n-- --2 ~C 0 0 C H ---:

: :
:

~ ' ' , ' ,1 . ~ ' ` ~ .
.
' ' :
- ~ .
' - "

- 2~2~3~

T ab le 5 NH 2 N H ~ 502 N H2 ¦

I Col~ound No._ R`
-V- 2 _ V - 3 _C0 0 C H3 ¦
V- 5 C 0 0 C2 Hs The N-substituted-3-(nitrogen-containing 5-membered ring)benzenesulfonamide derivatives exhibit reliable her-bicidal activity at low application dosages and show se-l~ctivity between crops and weeds. The herbicidal com-po~ltion~ o~ the invention, which contain the above com-pounds as e~ective ingredients, are there~ore suitable ~or controlling either be~ore or a~ter emergence monocotyledonous weeds and/or dicotyledonous weeds in im-portant crops such as wheat, rice, corn, soybean, cotton, beet, potato and tomato.
Exemplary dicotyledonous weeds which can be control-led by the above N-substituted-3-(nitrogen-containing 5-mem ered ring)benzenesulfonamide derivatives of the inven-tion include Amaranthus, Bldens, Stellarla, Solanum, Abutllon, Con-valvulus, ~atrlcarla, Gallum, Llndernla, etc.
Illustrative monocotyledonous weeds include .

.
.
' :'. ' ' .

202~8 ~ 18 -Echinochloa, S~taria, Digitaria, Avena, Cyperus, Alisma, Monochoria, etc.
The herbicidal compositions of the invention may take any preparation forms such as wettable powder, emul-sion, powder, granule and the li~e. Known agronomically-acceptable vehicles (diluents) and aids can be used.
The applicable places of the N-substituted-3-(nitrogen-containing 5-membered ring)benzenesulfonamide derivatives and herbicidal compositions 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 factory sites.
Examples:
The prQsent invention will hereina~ter be described by the following examples.
Synthesis Example 1:
Synthesis of methvl 2-r (4.6-dimethoxypyrimidin-2-yll-a~laQ~bonyl-a~ æsul~o~yll-4-~lH-pyr yl)benzoate (Compound ~o. I-7) At room temperature, 141.5 mg ~0.5 mmol) of methyl 2-(aminosulfonyl)-4-(lH-pyrrol-l-yl)benzoate and 137.5 mg (O.5 mmol) of phenyl (4,6-dimethoxypyrimidin-2-yl)-carbamate were dissolved in 1.5 m~ of N,N-d~methyl-acetamide. Then, 82.1 mg of 1,8-diazabicyclo~5.4.0]undec-7-ene were added, followed by stirring for 5 minutes. The 20293~

resultant mixture was allowed to stand for 15 hours.
Thereafter, 0.2 n~ of 35% hydrochloric acid was added to 20 ml O~ iCQ water, ~ollowed by the addition o~ the reac-tion mixture in 0. 2 n~ portions under stirring. After the reaction mixture was stirred for 20 minutes/ the resulting precipitate was collected by ~iltration and dried in air. Using dichloromethane and petroleum ether, the crude product was purified by reprecipitation into a white solid. Yield: 196 mg (85%). Its physicochemical properties are shown in Table 6.
Synthesis Example 2:
Synthesis of mçthyl 2-r(4-metho~-6-methyl-1~3 5-triazin-2-yl~aminoc~r~ony nYrrol~
At room temperature, lO0 mg (0.36 mmol) o~ methyl 2-(aminosul~onyl)-4-tlH-pyrrol-l-yl)benzoate and 85.7 mg (0.33 mmol) of phenyl (4-methoxy-6-methyl-1,3,5-triazin-2-yl)carbamate were dissolved in 1.5 mC of N,N-dimethyl-acetamide. Then, 65.7 mg (0.43 mmol) of 1,8-diazabicyclo-t5.4.0]undec-7-ene were added, followed by stirring for 5 minutes. The resultant mixture was allowed to stand for 4 hours. Thereafter, 0.2 mC of 35~ hydrochloric acid was added to 20 mC of ice water, followed by the addition of the reaction mixture in 0.2 mC portions under stirring.
After the reaction mixture was stirred for 20 minutes, the . . . , ~ , . ~
. . : .
:

2029~8 resulting precipitate was collected by filtration and dried in air. Using dichloromethane and hexane, the crude product was purified by reprecipitation into a pale yellow solid. Yield: 79.5 mg (54~). Its physicochemical properties are shown in Table 6.
The other N-substituted-3-(nitrogen-containing 5-membered ring)benzenesulfonamide derivatives shown in Table 1 were also synthesized in a similar manner to Synthesis Example 1. Namely, after obtaining crude pro-ducts by a similar procedure to Synthesis Example 1, they were separately purified by chromatography on a silica gel column, reprecipitation or washing. Physicochemical properties of each o~ the N-sub~tituted-3-(nitrogen-containing 5-membered ring)benzenesul~onamide derivatives are shown in Table 6. Incidentally, in Table 6 and Table 10 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-(nitrogen-containing 5-membered ring)-benzenesulfonamide derivatives, the solvents employed and the yields attained were as follows:
Compounds purified by column chromatography:

-- 2~293~8 Compound No. Solvent employed Yield I-4 CH2Cl2 . 68 Compounds puri~ied by reprecipitation:
Compound No.Solvent employed Yield I-9CH2C12 + petroleum ether 74 I-12 CH2C12 + hexane 81 I-13 CH2C12 + hexane 56 I-14 CH2C12 + hexane 54 I-15 CH2C12 + petroleum ether 61 I-20 CH2C12 + petroleum ether 68 Compounds puri~ied by washing:
compound N-9olvent employed . Yield I-lCH2C12 + petroleum ether 61 I-3CH2C12 + petroleum ether 68 I-5 petroleum ether 57 I-7 petroleum ether 85 I-8 CH2C12 + petroleum ether 53 I-10 CH2C12 + petroleum ether 76 ll CH2C12 ~ hexane 78 I-16CH2Cl2 + petroleum ether 64 I-17CH2C12 + pQtroleum ether 72 I-l9 CH2C12 + petroleum ether 73 2~29~

-w 1~ ww-3 w^w w=-W. w 3 - w~- 3 ~ =^ 3~ô-- ~-3 3- 3=~-wo-3w~=w ~w 3 ~ 3 4 w ~ 3~ 3 ~=~ 3 3 ~ w 33 w 33 3 ~ ~ ~ ~^ ~ ~- ~ ~ ~ ~ s ¦ ~ ., ~ O O ¦ 00 ~ O O O O O m E l ~ ._~ OO I O ~_ c~> ¦ O t~ ~_ ~100o _ -- ~ ~ = --,w~ ~
~:: . _ . _ _ .~_ ~ 0~, ~ O ~ 8 _ u~ ~, ~ , ~ o I _ .~ uu~ ~ _ ~ u~ ~o _ _ _ _ ~b, ~o CD ~ ~0 O~
.
~o l l l l l l l l ~ _ _ ~z _ _ _ _ _ ~ _ ~ _ _ *

2~2~3~

T ~ b -- CD I ~ O --_ ~ _. -- _ _ ~ -- C~ U7 N ~ r_ _ . _ ~ _- ~0~ ~V ~ g~ ~. ~ __=

_ _ = C~ e~ ~ _ _ _ CO --CO C.~ C.~-- ~.~ =
_ l 01:~1 O~ 00~ ~ D0 0~ o~D CO~_eO, Oc~ _~,_ 0~

'4 I ~ ~ 3~ ~ ~1" ~ ~ ~ ~ ~
O _~ . .._ . _ _ _ D ~ ¦ ~ ~ ~r ~ CD o l o o . o o o o I o o u~ u~ _ o o E 1 ~ x o o I o u~ _ o o o o r- ~ co o o ~
~ I oo oo o~OI ~o~ oo ~h oo aoo oo~ ooo ~Y I ~ ~c~ ~o~l Ou~ oo oo oo ooo t-~o ooo m I _ m _ ol m ~ o m o m o o o¦ ~ o o o o . .
~ S~ a~ _ _ ~ ~ o m m _ ~ _ _ m _ o m m c,~ _ _ O~ _ e~ ~ ~ c _ =~ _ _ ~ _ o 1 ~ ~r I ~ cl~ ~ll ~ r CD ~- 1 _ __ _ ~ ~ m u~ ~ ~ ~ ~ u~ u~ ~ u~
3 _ _ __ _ _ ~ ;; _ o o ~ o o ~ c~ ~ _ o~
~ .~. C.~ C" ~ ~ ~_ o~ CO ~ ~ C~
~_ w _ ~ w lo ~1 1~ lo ' , Synthesis Example 3:
~ynthesis of preparation intermediate, methYl 2-(aminosulfonyll-4-(lH-yrrol-l-yl)benzoate ~Com~ound No. II-A-7) In 3 me of acetic acid, 300 mg (1.3 mmol) of methyl 4-amino~2-(aminosulfonyl)benzoate and 0.23 me of 2,5-dimethoxytetrahydrofuran were dissolved, followed by stir-ring at 110C for 1.5 hours. Acetic acid was then dis-tilled off, followed by the addition of 30 me of ice water. After the mixture thus obtained was stirred for 20 minutes, the resulting precipitate was collected by fil-tration and dried in air. The brown solid thus obtained was puri~ied by column chromatography, using silica gel ~"Wako Gel C-300", trade mark; product of Wako Pure Chemi-cal Industries, Ltd.) and dichloromethane, thereby obtain-ing the title compound as a white solid. Yield: 175.7 mg (48~). Its physicochemical properties are shown in Table 7.
The other compounds shown in Table 7 were also synthesized in a similar manner to Synthesis Example 3.
The yield and physicochemical properties of each of the compounds are also shown in Table 7.

--` 2 ~ 8 Ta b I e 7 Com pound Y I e I d ~S (m/e) Me l t l og No. M Pol nt or I R ( K B r, c m ~ ' ) (X) Deco~ Pos I t I on _ Pol nt ( C ) 3330.3240,3090.1600.1490.1320.
~-A-l 42 222 1S8-160 1310.1150.;100.1070.940.890.
800.730.680.610 3350.3250.3050.2910.1600.1480.
-~-2 74 250 104-107 1430.1390.1310.1300.1150.920.
. 800.150. Gso . sso .530 3340.3250.3I30.1600.1490.1460.
~ -A-3 B9 258 154-160 1350.1170.1070.1030.940.890 840.800.740.120.700.S90.510 3330.3230.3090.2910.1550.1470.
-A-4 62 284 185-188 1400,1340. lllO. lOS0.1035.910.
Docomposed 850.110 . 590.510 3370.3270.1810.1500.1330.1290.
~-A-S 48 238 118-121 llB0.1140.1070.940.120.620.
~00.590 3350.3250.30l0.29aO.1550.1490.
-A-B 78 264 174-177 1450.1400.1330.1170.1070.920.
910.850.770,120.600.530 _ 3320.3230.2950.1710.1600. i500.
~ -~-l 48 280 lB2-165 1440.1340.1320.1300.1280.1170.
1150.1050.940.870.770.730.690 3380.3270.2920.1710.1800.1440.
~-A-8 63 308 168-llo 1410.1350.1320.1300.1170.1130.
780.600 3300.3230.3130.29ao.l700.1600.
-A-9 Ba 294 158-160 1500.1350.1210.1170.1120.10l0.
1050.800.180.140 3310.3260.2980.2920.1l00. IB00.
-A-l 60 322 l9S-19l 1400.1350.1320.1300. L160.1150.
780.600 ,. ,.. ~ .. ,. . ~ .
. ~
.
;- .
- s - 202g3~8 Synthesis Example 4:
Synthe~is o~ pre~axation intermediate. ~-chloro-5-(2.5-dihydro-3,4-dimethyl-2,S-dioxo-lH-pyrrol-l-Yl)benzenesul~onamide (Com~ound No. II-B-2) In 3 ml of pyridine, l mmol of 5-amino-2-chloro-benzenesulfonamide and l.O5 mmol of 2,3-dimethylmaleic an-hydride were stirred at 9O-100C for 9 hours. Pyridine was then distilled ofS from the reaction mixture, followed by the addition of 20 m~ of ice water and O.l m~ of 35%
hydrochloric acid to the solid residue. A~ter the mixture thus ~ormed was stirred ~or 20 minutes, the resulting precipitate was collected by ~iltration and then dried in air. Yield: 93~. It~ physicochemlcal properties are shown in TablQ 8.
The othér compounds (Compound No. II-B-l to Compound No. II-B-3) shown in Table 8 were also synthesized in a manner similar to Synthesis Example 4. The yield and physicochemical properties of each o~ the compounds are also shown in Table 8.
Tab 1e 8 Co~pound Yleld MS(~/e) Meltlng No. M Polntor I R (K B r, cm~') (X) Deconpos1tion __ ~ Polnt (~) 3340,3250.1780.1700.1480.1440.
~-3-1 94 280 209-211 1400.1340.11B0.1100.790.730.
870.590.5~0 ... .

.
. . -- ~

2~293~8 __ ~350,3250.1780.1700.1470.1gO0 ~-B-2 93 314 ' 199-202 1390.1340.,1170.1080.1040.910.
830.730 710.600.530.5~0 ~ . . _.
3350.3250.1760.1710.1690.1530.
~-B-3 91 294 190-1~2 1490.1390.1330.1170.1150.1080.
900.830.730.720.610.590 3400-2900.1710.1680.1600.1490.
~-B-4 43 338 159-162 1440.1410.1390.1350.1310.1290.
1170.1150.1130.1090.~060.860.
780.730.670.600.530 Synthesis Example 5:
Svnthesis o~ prepara,tion i~çl~s~ L-~thyl 2-~amino~ul~Qnyl)-4-(2,5-dihy~xo-3,~ L~hYi~2 5-~iQ~o-l~Dvrrol-l-yl)~enz,o~a~ 9~9~ e-In 3 m~ of acetic acid, l mmol o~ methyl 4-amino-2-(aminosulfonyl)benzoate and 1.05 mmol of 2,3-dimethylmaleic anhydride were stirred at 80-C for 40 hours. Acetic acid was then distilled off from the reac-tion mixture, followed by the addition of 20 m~ of ice water to the oily residue. After the mixture thus formed was stirred for 2 hours, the resulting precipitate was collected by filtration and then dried in air. Yield:
43%. Its physicochemical propertles are shown in Table 8.
Synthesis Example 6:
Svnthesis of prepar,ation i~tç~diate, methyl_2-. . .
. , ~ .
.
,:

2~293~

~aminosulfonvl)-4-(3 5-dimethyl-lH-pyrazol-1-Yl~benzoa-t-e (Compound No. II-C-2) ~1) Svnthesis o~ ~e~hyl 2-~minosulfonyl)-4-hydrazino-benzoate (C~Qund No. V-4):
To a mixture of 6 m~ of 35% hydrochloric acid and 6 m~ of water, 3 g of methyl 4-amino-2-(aminosulfonyl)-benzoate were added, followed by stirring at room tempera-ture for 5 minutes. ~rhe reaction mixture was then cooled with ice water, followed by the addition of 3 mL of an aqueous solution of 0.95 g of sodium nitrite under stir-ring over 2 minutes to conduct diazotization.
In 6.52 m~ of 35% hydrochloric acid, 6.78 g of stannous chloride were dissolved. The resulting solution was cooled with ice water and stirred, ~ollowed by the ad-dition of the diazotized compound prepared above.
After the resultant mixture was stirred for 20 minutes, it was left over for 15 hours in a refrigerator.
The reaction mixture was then transferred into a 3-~
beaker, to which 38 g of sodium bicarbonate were then added under stirring to adjust the pH to 6. The mixture thus prepared was then extracted twice with 300 m~ of methyl acetate. The extract was dried over sodium sul-fate, and methyl acetate was distilled off to obtain a pale yellow solid. Yield: 2.76 g t86%). Melting point:
168-170C. Its physicochemical properties are shown in ~- 2~2~

Table 10.
~2) SYnthesis of methyl 2-(aminosul~onyl)-4-(3 5-dimethyl-lH-p~ Ql~ y~)benzoate (Com~Qund No. II-C-2):
A mixture o~ 3 m~ o~ methanol, 0.36 m~ o~ 95~ sul-~u~ic acid and 1.~ mmol o~ the compound (Compound No. V-4) synthesized in the above procedure (1) was cooled with ice water and then stirred, to which a solution of 1.2 mmol of acetylacetone in 0.36 m~ o~ acetic acid was added over 2 minutes. The resulting mixture was stirred for 20 minutes, and then at 80C ~or 8 hours. Then, the reaction mixture was cooled to room temperature, added with 2.5 g o~ sodium bicarbonate powder and 5 m~ of water, and then stirred. After the pH of the resultant mixture was ad-~ust~d to pH 6 with aceti¢ acid, 15 m~ o~ water were added. The precipitate thus rormed was collected by ~il-tration and then dried in air. Yield: 71S. Its physico-chemical properties are shown in Table 9. In addition, physicochemical properties o~ the compound (Compound No.
II-C-1) synthesized in a similar manner are also shown in Table 9.
Further, physicochemical properties o~ other prepa-ration intermediates synthesized in a similar manner to the above procedure (1) are also shown in Table 10.

,., ' ' ~ ' ~
.~ .
, .
. ' '' ' ,',''',, " ~ ' , ','- " '' ' ' :
, ;... . . ..

2 ~ $

Ta b I e 9 Compound MS(~/~) Mel tlng No. M Polnt or I R (K B r, c m~l) Deco~Posltlo Polnt ('C) ;' 3280.3160.2960.1590.15-50.1470.
-C-l 285 212-215 1390.1370.1330.1170.1050.820.
, 800.590 __ 3400-2800.3350.3070.2950.1725.
-C-2 309 112-175 1600.1550.1440.1350.1310.1290.
1170.1130.1060.900.780.150.710, , 590.530 Ta b I e 1 O
Coe Pound MS (s /o) Me l t I ng ~' No. M Point or I R (K B r, c m~1) NMR ( ~) Docosposi t lo polnt (lC) 33~0.3350.3300.3220.1600.
V-l 187 L13-116 1470. 1340.1330.1290.1140.
1090.780. 680.580.510 8370.8880.81 - 80.a970.1590.
V-2 221 155-158 1560. 1460.1330.1270. .
DecosPositlo 1160.9,70.830.74,0.690.590.
550.510 , 3300.3250.3010.1610.1490. d6 -DMSO:2.409(3H.s) V-3 201 161-184 1300.1160.1140.920.820. 4.025br(21J.s) 6.840 690. B00.520. (lH .dd .8.511z.1.811z) 6.901 (lH. s) 7.048 (lH
d 8.5Hz) 7.148 (2H s) 7.349 (111. d .1.8Hz) 3350.3310.325-0.1680.1630.
V-4 245 168-170 1590.1440.1350.1330.1300.
1270.1170.1160.780.700.600 3320.3210.2980.1700.1590.
V-5 259 la2-124 1370.1320.1300.1270.1250.
Doconpositlo~ 1150.1120.770.740.700 ' , ~ ' , -- 202~3~8 Compounds obtained in a similar manner to Synthesis Example 2 are shown in Table 11.

T ab le 11 Xl ~ CN ~( s o 2 N H C O N H~

Co~pound .
NO. CN - R 1 X ' X 2 Z
I -21 ~N - H OCH3 OCU3 N

I -aa ~N - CH3 OCH3 CH3 N

I -28 ~N - ~H~ ~H, OCH~ N

I -~4 ~N - Cl OCH3 OCU3 N

I -as ~N - COOCI;3 OCII3 OCH3 N

1 25 ~N-- ~ ~ l. CN3 N

I 27 I~N COOC2HS OCH3 OC53 N

', , ~ . .

2~293~

T a b I e 1 1 tC o n t ' d) Com pound NO. CN R I X 1 X 2 Z

5 ~

I -29 ~N - COOCH3 OCH3 CH3 N

1-3~ ~ ~ ~ ~ acll, .
.
. .
.- .

- 2~2~3~8 Formulation examples and tests will hereinafter be dQscribed. It should be borne in mind that the vehicles (diluents) and acids, their mixing ratios and effective components can vary in wide ranges, respectively.
Formulation Example 1: Wettable Powder Compound (Compound No. I-7) 50 parts A salt o~ ligninsulfonic acid5 parts A salt of alkylsulfonic acid 3 parts Diatomaceous earth 42 parts The above ingredients are mixed and ground into a wettable powder. For application, it is diluted with water.
Formulation Example 2; ~m~L8iQn Compound (Compound No. I-9) 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 Examle 3: Granule Compound (Compound No. I-14) 8 parts ~entonite io parts Clay 45 parts A salt o~ ligninsulfonic acid7 parts The above ingredients are mixed intimately and after the addition o~ water, were kneaded and then ~ormed into ' - ., ., - . , .

20~93~
.

granules by an extruding granulator. They were then dried to provide a granular ~ormulation, namely, a granule.
Test 1: Tç~t on Herbicidal Activity by Fo~ aEplication Herbicidal solutions of each test compound, which had been prepared by dissolving at predetermined con-centrations such a wettable powder of the test compound as that described in the above formulation example, and sprayed at dosages of lO g/ha and 100 g/ha over foliar parts of Am~r~nthus retroflexus (Redroot pigweed), Bidens pilos~ (Common blac3cjack), SlDapis ~rvensls (Wild mustard), stell~riB medla (Common chickweed), Cassia obtusifoli~ (Sick-lepod), SolAnum nlgrum (Black nightshade), Abut~lon theophr~stl ~Velvetlea~), Convolvulus arvensls tField bindweed), ~strlc~rls chsmomllls (Wild chamomile), Setsrl~ vlrldl~ ~Green ~oxtail), Echlnochlos frumcntsc~ arnyard grass), Aven~ f~tu~Wild oat), and Dlglt~rl~ ~dsc~nd~ns (Henry crabgrass) which had been allowed to grow individually to 2-4 leaf stage in pots. Fourteen days later after spraying o~ the test com-pound, its herbicidal activity was evaluated in accordance with the below-described system. The results are sum-marized in Table 12.

Ranking system:
Herb~ çtivity 0: No e~ects 1: le~s than 31% o~ total kill 2: 31-50% o~ total kill 3: 51-70% o~ total kill 4: 71-90% o~ total kill 5: 91-100% o~ total kill .

, ..... ~ ', . ~

-- 20293~8 _ U~u~ ~ ~u~ ~ a ~ ~ Ou~ Oo OC ~u: =O =~: ~' 5 -c o~n u~ u~4~ u~u~ u~ ~a u~ ~u~ ~P~ ~ u~ o~ U~Y~ , oo ou~ ~ u~u~ ~u~ u~u~ ~ c~ u~ Oer U~C ~ ~U~ u~m ~, ~ u~ ~ ~ ~-n ~o~ ~ u~n ~ o.~n u~ ~: G~ ~U~
~ ~ u~ u~ ~ ~ ~ ~ u~ ~u~ ~ ~u: ~a ou~ u~

~ I ou~ u~ ~u~ c~a e~ ~ o~ o~ u~u~ o~u~ u~u~ ~ c~ u~~

c: o~ ~u~ u~u~ ~ u~u~ u~ c~l~ u~~ ~ u~u~ u~: ~ c~~ e.~
~ o cr~ ~ c~ ~ In ~ ~ a ~ n ~ n ~ ~ m ~ n ~ d~ v~ ~ a m ~ ~ n ~ m _ ~ ~ ~ ~ ~n ~ ~ ~ ~ ~ ~n m ~n u~ ~ ~ ~ ~ ~ o m u~ ~a ~ u~
~ ~ ¦ ~ ~ m ~ ~ ~ ~ a ~ ~ ,,n In u~ ~ u~ u~ ~ ~ ~ ~ u~ u- u~ ~ _ o _ ~ ~ In .n ~ ~ ~ ~a ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ In ~ n ~ ~ n u~ n I~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ In ~ ~ ~ ~ ~ In ~ ~ n m u~ u~

20 o~ ~. ~ =~ ~n~ ~n ~u~ ~ u~u~ _~n u~In n~ n~ u~

l l l l l l l l l 1o _ c~l I ~1 , 25 C~2 _ _ _ _ _ _ _ _ ~ _ _~ _ _ _ ~ ' .' ~ ., ' ,, ' ~- 2029348 .~ _ _ c~ l 1 1~ o 1 ~ _ __ ~ .
~ u~l O~ O lu~ ~0 O 1 ~ ~ o~
~ _ C
~ O O O d' 1~ ~ o o ~ 6~
oo ~ oc X~l o~ C~t - 'V .
_ _ _ _ as 0 e~
o ~ ~ C o ~ o ~ o CC U~ U~ s ~
oo ~r oc ~~ oe~ ~u~ ~ ' ~ C~ _ _ ~ ~ o ~ ~ U~ ~ ~ ~ U~ o C~ ~ U~ _ ~
o o _ __ 6 C~ o ~ o ~r o~ o: u~u~ o c ~ u~ g~
N O o o O G O C O C~l O C ---a C ~ '~
~--o~o~ ~u~ ~ u~u~ ~ u~u~

~ . U~ U~ U~ U~ U~ U~ U~ U~ ~ ~ ~ U~ . . .
~ c~ cn ~
~ _~ : ~
3 o e~ ~ u~ c~ ~t ~ ~ o c~ ~ ~a _ ~ u~ ~ ~ ~ ~ ~ u~ o ~r ~ ~ 2 - O C L. ~ 0 lo o o o o o o o o o o o c c~
3 o _ O _ O _ O _ O _ O _ O C ~ ~
q ~ : ~ _ ~ a~
u~ e~ t- OD ~ ~ ~ CC~ O
O. l l l l l l ~,C _ _ _ _ l_ _ ~Ll O

:

' 2~293~8 Test 2: Germi~ation Test of Seeds Two sheets of filter paper were placed in a super-posed relation in each o~ Petri dishe~ having a diameter o~ 9 cm. Water suspensions o~ each test compound (con-centrations o~ the active ingredient: l ppm and 50 ppm) were separately poured in an amount of 5 m~ per dish into the Petri dishes. Seeds of Amar~nthus retroflexus (Redroot pigweed), Bidens pilosA (Common blackjack), ~atric~rla chamomilla (Wild chamomile), Solanum nigrum (Black nightshade), Echinochloa oryzicola (Barnyard grass), Cyperus irla (Rice flatsedge) and Setarl~ virldls (Green foxtail) were placed at a rate of 10 seeds per dish in the Petri dishes. They were thereafter allowed to germinate in a constant-temperature chamber at 28-C. Fourteen days later a~ter placement in the Petrl dishes, the degrees o~
germination and growth inhibition were observed vicually.
The observation results were ranked in accordance with the below-described 6-stage system. The results are sum-marized in Table 13.

, G~owth inhibition rate 0: No inhibition 1: lesB than 31%
2: 31-50%
3: 51-7 0%
4: 71-90%
5: 91-100%

.::

:

- 2029~

T a b 1 e 13 Conpound Concen- _ _ _ _ No. t ratlo A . r . B. P . ~1. c . S . n . E. o . C . I . S . v .
S (PP~) 1-1 O O O O 'O O O
4 3 5 4 4 g S
_ 4 4 5 3 4. 5 S

I _5 1 4 3 4 3 4 4 4 -~ 1 1 3 0 0 3 3 3 _ 1 -7 l 4 4 5 4 5 5 5 . 1-8 l 5 4 5 4 5 5 5 I-lO 5 2 5 5- 3 -0 2 I -1 l 2 2 2 2 0 2 3 . 50 4 3 5 5 5 4 5 I -la 1 0 0 0 0 0 0 0 ~ _50 2 2 4 3 3 4 4 , 1_14 1 0 0 4 2 0 2 -0 .

:: -2~29348 T a b l e 13 (C o n t' d) Co~pound Conc~n- _ _ No tratlon A r B p M c S n E o C I S v I-15 l 4 0 0 4 0 4 0 4 5 5 _ : . _ I-l9 l 3 0 0 0 0 0 0 I-~0 l 4 4 4 4 5 5 5 Not~) A r Auarsnthus r0trotl0xus 8 o Echlnochloa orYzlcols B p Bld0ns Pllosa C l CYP~rus Irla ~ c~ Matrlcarla cha-o-llla S v Setarla vlrldls S n Solanuv nlgrun ~- :

, :. , .

Claims (16)

1. An N-substituted-3-(nitrogen-containing 5-membered ring)benzenesulfonamide derivative of the formula (I):
(I) wherein -is -, , , or ;

R1 is H, C1, C1-C3 alkyl or C1-C4 alkoxycarbonyl; Z is CH
or N; X1 is C1-C3 alkyl, C1-C3 alkoxyl or C1; and X2 is C1-C3 alkyl or C1-C3 alkoxyl.

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

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

4. A derivative of claim 1, wherein is , R1 is H, C1, CH3, COOCH3 or COOC2H5, Z is CH, X1 is OCH3, and X2 is OCH3.

5. A derivative of claim 1, wherein is , R1 is H, C1, CH3, COOCH3 or COOC2H5, Z is CH, X1 is OCH3, and X2 is OCH3.

6. A derivative of claim 1, wherein is , R1 is COOCH3, Z is CH, X1 is C1, and X2 is OCH3.

7. A derivative of claim 1, wherein is , R1 is COOCH3, Z is CH, X1 is CH3, and X2 is CH3.

8. A derivative of claim 1, wherein is , R1 is H, C1, CH3 or COOCH3, Z is CH, X1 is OCH3, and X2 is OCH3.

9. A derivative of claim 1, wherein is , R1 is C1 or COOCH3, Z is CH, X1 is OCH3, and X2 is OC3.

10. A derivative of claim 1, wherein is , R1 is C1 or COOCH3, Z is N, X1 is OCH3, and X2 is CH3.

11. A process for the preparation of an N-substituted-3-(nitrogen-containing 5-membered ring)-benzenesulfonamide derivative of claim 1, which comprises reacting a 3-(nitrogen-containing 5-membered ring) ben-zeneoulronamide derivative of the formula (II):

(II) wherein and R1 have the same meanings as defined in claim 1, with a phenylcarbamate derivative of the follow-ing formula (III):

(III) wherein Z, X1 and X2 have the same meanings as derined in claim 1.

12. A 3-(pyrrol-1-yl)benzensulfonamide derivative of the following formula (II-A):

(II-A) wherein R1 has the same meaning as defined in claim 1 and R2 is H or CH3.

13. A 3-(2,3-dimethylmaleimido)benzenesulfonamide derivative of the following formula (II-B):

(II-B) wherein R1 has the same meaning as defined in claim 1.

14. A 3-(3,5-dimethylpyrazol-1-yl)benzene-sulfonamide derivative of the following formula (II-C'):

(II-C') wherein R1 is C1-C4 alkoxycarbonyl.

15. A herbicidal composition comprising a her-bicidally effective amount of an N-substituted-3-(nitxogen-containing 5-membered ring)benzenesulfonamide derivative of claim 1 and an agronomically-acceptable vehicle or diluent.

16. 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-(nitrogen-containing 5-membered ring)benzenesulfonamide derivative of claim 1 or a herbicidal composition compris-ing said derivative.