CA2029347C - N-substituted-3-(substituted hydrazino)-benzenesulfonamide derivatives, preparation process thereof and herbicidal compositions - Google Patents
N-substituted-3-(substituted hydrazino)-benzenesulfonamide derivatives, preparation process thereof and herbicidal compositionsInfo
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Abstract
Disclosed herein are N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives of the formula (I):
(see fig. I) wherein R1 is CF3, COOH or CC1=CC1COOH, R2 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, a process for the preparation thereof, and herbicidal compositions containing the N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives as active ingredients.
(see fig. I) wherein R1 is CF3, COOH or CC1=CC1COOH, R2 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, a process for the preparation thereof, and herbicidal compositions containing the N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives as active ingredients.
Description
TITLE OF THE INVENTION:
N-SUB~ u~ -3-(SUB~ u~ HYDRAZINO)-BENZENESULFONAMIDE DERIVATIVES, PREPARATION
PROCESS THEREOF AND HERBICIDAL COMPOSITIONS
BACKGROUND OF THE INV~N'l'lON
1) Field of the Invention:
The present invention relates to N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives, a preparation process thereof, and herbicidal compositions containing the derivatives as active ingredients.
N-SUB~ u~ -3-(SUB~ u~ HYDRAZINO)-BENZENESULFONAMIDE DERIVATIVES, PREPARATION
PROCESS THEREOF AND HERBICIDAL COMPOSITIONS
BACKGROUND OF THE INV~N'l'lON
1) Field of the Invention:
The present invention relates to N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives, a preparation process thereof, and herbicidal compositions containing the derivatives as active ingredients.
2) Description of the Related Art:
Numerous compounds have heretofore been proposed as herbicides. For example, U.S.Pat.No.4,632,695, U.S.Pat.No.4,664,695 and Japanese Patent Application Laid-Open (KOKAI) No. 129276/1987 disclose a wide variety of compounds, including N-substituted-3-substituted ben-zenesulfonamide derivatives containing N~C(CH3)=CHCOCH3, NHC(CH3)=CHCOOCH3, NHCH3, OCH2CF3 or SCH2CF3 on the 3-position and a pyrimidine xing or a 1,3,5-triazine ring on the nitrogen atom.
There have conventionally been strong demands for herbicides capable of exhibiting reliable nerbicidal 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 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 that compounds still unreported to date and having a substituted hydra~ino group on the 3-position of benzenesulfonamide as opposed to the inclusion of NHCtCH3)=CHCOCH3, NHC(CH3)=CH-COOCH3, NHCH3, OCH2CF3 or SCH2CF3 on the 3-position of benzenesulfonamide in the compounds disclosed in EP-A-116518 publis~led August 22, 1984 and Japanese Patent Application Laid Open (KOKAI) No. 129276/1987 published June 11, 1987 have excellent herbicidal activity, leading to the completion of the present invention.
SUMMARY OF THE INVENTION
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 for 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.
2 ~
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-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-(substituted hydrazino)benzene-sulfonamide derivative of the formula (I):
Rl CH ~NNH S02NHCONH ~
~Rl N~X2 wherein R1 is CF3, COOH or CCl=CClCOOH, R2 is H, Cl, C1-C3 alkyl or C1-C4 alkoxycarbonyl; Z is CH or N; Xl is Cl-C3 alkyl, Cl-C3 alkoxyl or Cl; 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 the above-described N-substituted-3-(substituted hydrazino)benzene-sulfonamide derivative, which comprises reacting a 3-(substituted hydrazino)benzenesulfonamide derivative of the formula (II):
Rl CH NNH S02NH2 R' wherein R1 and R2 have the same -~n; n~s as defined above, with a phenylcarbamate derivative of the following formula ~III):
O X' ll N
~ OCNH
x2 wherein Z, X1 and x2 have the same ~~nings as defined above.
In a further aspect of the invention, there is also provided a 3-(substituted hydrazino)benzenesulfonamide derivative useful as an int~ - ai ~te in the preparation of the above N-substituted-3-(substituted hydrazino)benzene-sulfonamide, which is represented by the following formula (II) R' CH~NNH 50 2 NH 2 ~ (II) R' wherein Rl and R2 have the same meanings as defined above.
In a still further aspect of the invention, there is also provided a 3-hydrazinobenzenesulfonamide derivative useful as an inte ~~iate in the preparation of the above 3-(substituted hydrazino)benzenesulfonamide of the formula (II), which is represented by the following formula (V'):
2OÇ?J9~7 ~ (V ) wherein R2 is H, C1-C3 alkyl or Cl-C4 alkoxycarbonyl.
In a still further aspect of the invention, there is also provided a herbicidal composition comprising as an active ingredient the N-substituted-3-(substituted hydrazino)benzenesulfonamide derivative of the formula (I).
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-(substituted hydrazino)benzenesulfonamide derivative of the formula (I) or a herbicidal composition comprising said derivative.
f~ ~ 3 ~ ~
The N-substituted-3-(substituted hydrazino~-benzenesulfonamide derivatives of the present invention, which are represented by the formula (I), have not been disclosed in any publications known to the inventors of the present application, exhibit reliable herbicidal ac-tivity at low application dosages and show selectivity be-tween crops and weeds. The herbicidal compositions of the invention, which contain the above derivatives as effec-tive ingredients, are suitable particularly fcr controll-ing 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-(substituted hydrazino)benzenesulfonamide derivative represented by the formula (I) in the invention include those shown in Table 1.
3 ~ 7 Ta b I e N_~
R' CH--NNII 502NIICONH~OZ
'~( N ~' R' Compound R' R2 X' X2 Z
No .
1-1 CF3 11 OCI13 OCI13 Cll I-2 COOII ' 11 OCI13 OCI13 Cll I-3 CF3 Cl OCI13 OCI13 Cll I-4 COOII Cl OCIJ3 OCI13 CH
I-5 CF3 Cl~3OCI13 OCH3 Cll I-6 COOII Cl13OC113 OC113 Cll I-7 CF3 COOCI13 OCI13 OCI13 Cll I-8 COOII COOCH3 OCH3 OCH3 Cll I-9 CF3 COOC211, OCI13 OCI13 Cll I-10 COOII COOC211, OC113 OCI13 Cll I-ll CF3 COOCH3 Cl OC113 Cll I-12 COOII COOCI13 Cl OCI13 Cll I-13 CF3 COOCH3 Cl13 Cl13 Cll I-14 COOII COOCH3 Cll3 cll3 Cll I-15 CF3 COOCI13 ~C113 Cll3 Cll I-16 CF3 COOCI13 OCI13 Cl13 N
I -18CC I -CC I COOII C I OCI13 OCII 3 Cll I-l9 CCI-CCICOOII COOCH3 OCI13 OCil3 Cll 3 ~ 7 The N-substituted-3-(substituted hydrazino)ben~ene-sulfonamide derivatives represented by the formula (I) can each be synthesized by reacti:ng a 3-(substituted hydrazino)benzenesulfonamide derivative of the formula tII) 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 reaction formula:
R' CH=NNH SO2NH2~ N__~
~ 2~ OCNH ~ O ~
R(m) X2 X
N__~
Rl CH-NNH SO2NHCONH ~ O Z
(I) wherein R1, R2, Z, Xl and x2 have the same ~~An;ngs 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, dia~abicyclononene, diazabicycloundecene or the like can be used as a base.
The reaction is conducted at a temperature in a range of from -20~C to 100~C, preferably from 0~C to 50~C
for a reaction period in a ranqe of from 0.5 hour to 24 hours.
2 0 ~9 ~L~7 _ 9 After 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 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-(substituted hydrazino)benzenesulfonamide derivative represented by the formula (I) can be obtained with high purity.
The 3-(substituted hydrazino)benzenesulfonamide derivative represented by the formula (II), which is a preparation intermediate and is employed as the starting material in the above reaction, can be synthesized in ac-cordance with the following reaction formula, using as a starting material a 3-aminobenzenesulfonamide derivative represented by the following formula (IV):
H2N So2NH2 H2NNH SO2NH2 \[~ 1 ) Diazotiz?tion \~
R2 2) Reductlon R2 (~) (V) R' CH=NNH SO2NH2 R' CHO ~
(~) wherein Rl and R2 have the same re~n;ngs as defined above.
25Synthesis of the compound represented by the formula ~2~3~7 ~ 10 --(II) in accordance with the above-described reaction can be practiced in the following manner. The 3-hydrazino-benzenesulfonamide 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 - is stirred to-gether with trifluoroacetaldehyde ethylhemiacetal, glyoxylic acid monohydrata or mucochloric acid at 30-120~C, preferably 70-90~C for 0.5-8 hours in acetic acid or propionic acid or at room temperature for 5-7 hours in 6 N sulfuric acid. After completion of the reaction, the reaction product is collected from the reaction mixture by filtration or the reaction mixture is evaporated to dry-ness under reduced pressure and if necessary, is purified by washing, whereby the compound represented by the for-mula (II) can be obtained with good purity.
The compound represented ~y 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-nitro-aniline derivatives, for example, by the process described in Chem. Ber., 90, 841 (1957) or J. Macromol. Sci. Chem., 1969, 941, namely, by synthesizing 3-nitrobenzenesulfon-amide derivatives and then reducing the nitro groups with SnCl2 in methanol or ethano:L conta.ining 35~ hydrochloric acid.
Further, the compound represented by the formula (IIT) can be obtained from phenyl chloroformate and the corresponding 2-amino-4,6 di-substituted pyrimidine (or 1,3,~-tria~ine), for example, by the proc~ss described in European Patent Specification No. 238,070 published September 23, 1987.
Specific examples of the compound represented by the formulae (II) and useful as the above preparation intermediate are summarized in Table 2.
In addition, specific examples of the compound represented by the formula (V) are shown in Table 3.
Tab le 2 R' CH= NN H S 0 2 NH 2 --~\ R 2 Compound No. Rl R2 ~-lC F 3 H
~-2C 00 H H
~-3 CF 3 C I
~-4C 00 H Cl ~-5 CF 3 CH3 ~-6CO OH CH3 ~_7C F3 COOC H3 ~-8CO OH COOC H3 ~-9 C F3 CO OC 2 H 5 ~-lOC 00 H COOC 2 H 5 ~-ll HO O C CCI- CCI - C I
~-12 HO O CCC l= CCI - COOC H 3 . V
2~ ~J J~ 9 3 5r. 7 ~ ~.2 ~
Tab le 3 H 2 NN H ~ SO 2 N H 2 RZ
5Compo~nd No. R2 V-l H
V-2 Cl The N-substituted-3-(substituted hydrazino)benzene-sulfonamide derivatives exhibit reliable herbicidal ac-tivity at low application dosages and show selectivity be-tween crops and weeds. The herbicidal compositions of the invention, which contain the above compounds as effective ingredients, are therefore suitable for controlling either before or after emergence monocotyledonous weeds and/or dicotyledonous weeds in important crops such as whea~, rice, corn, soybean, cotton, beet, potato and tomato.
Exemplary dicotyledonous weeds which can.be control-led by the herbicides of the invention include Amaranthus, Bidens, Stellaria, Solanum, Abutilon, Convolvulus, ~atricaria, Galium, Lindernla, etc.
Illustrative monocotyledono~ls weeds include 2 ~ 2 ~ 3 L~ 7 Echirlochlo~, Setari~, Digit~ria, Aven~, Cyperus, Alism~, Monochoria, etc.
The herbicidal compositions of the invention may take any preparation forms such as wettable powder, emul-sion, 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 factory sites.
Examples:
The present invention will hereinafter be described by the following examples.
Synthesis Example 1:
Synthesis of methYl 2-~14 6-dimethoxy~vrimidin-2-yl)aminocarbonylaminosulfonyl~-4-r~2.2.2-trifluQro-ethYlidene)hYdrazino1benzoate (Compound No. I-7) At room temperature, 166 mg (0.5 mmol) of methyl 2-(aminosulfonyl)-4-[(2,2,2-trifluoroethlidene)hydrazino]-~o benzoate and 137.5 mg (0.5 mmol) of phenyl (4,6-dimethoxy-pyrimidin-2-yl)carbamate were dissolved in 1.5 m~ of N,N-dimethylacetamide. Then, 86.1 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 15 hours. Thereafter, 0.2 ~ of 35% hydrochloric acid was added to 20 m~ of ice water, followed by the addition of the reaction mixture in 0.2 me portions under stir-ring. After the reaction mixture was stirred for 20 minutes, the resulting precipitate was collected by fil-tration and dried in air. Using dichloromethane as an eluent, the crude product was purified by chromatography on a column of silica gel ("WAKO GEL C-300", trade mark;
product of Wako Pure Chemical Industries, Ltd.). The title compound was obtained as a white solid. Yield:
162 mg (64~). Melting point: 201-202~C. Its physico-chemical properties are shown in Table 4.
Synthesis Example 2:
Synthesis of methyl 2-[(4 6-dimethoxy-1 3 5-triazin-2-yl)aminocarbonylaminosulfonyll-4- r ( 2 2 2-trifluoroethylidene)hydrazinolbenzoate (Compound No.
I-20) At room temperature, 166 mg (0.5 mmol) of methyl 2-(aminosulfonyl)-4-[(2,2,2-trifluoroethlidene)hydrazino]-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, 86.1 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% hydrochloric acid was added to 30 me of ice water, followed by the addition of A
-- lCi --the reaction mixture in 0.2 m~ portions under stirring.
~fter the reaction mixture was stirred for 20 minutes, the resulting precipitate was collected by filtration and dried in air. Using as an eluent a 1:9 mixed solvent of methyl acetate and benzene, the crude product was purified by chromatography on a column of silica gel ("WAKO GEL C-300", trade mark; product of Wako Pure Chemical In-dustries, Ltd.). The title compound was obtained as a white solid. Yield: 103 mg (41%). Melting point: 117-119~C (foamed). Its physicochemical properties are shown in Table 4.
The other N-substituted-3-(substituted hydrazino)-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 proce-dure to Synthesis Example 1, they were separately purified by chromatography on a silica gel column or washing.
Physicochemical properties of each of the N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives are shown in Table 4. Incidentally, in Table 4 and in Tables 5 and ~ which will be given subsequently, the abbrevia-tions in the columns for NMR data have the following mean-ngS:
~: (ppm), s: singlet, d: doublet, t: triplet, q: quartet, m: multiplet, dd: double doublet, .
2~2~4~
br: broad.
Further, with respect to the individual N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives, the solvents employed upon purification thereof and the yields attained were as follows:
~2~
Compounds purified by column chromatography:
Compound No.Solvent em~loYed Yield I-l CH2C12 49 I~9 CH2C12 59 I-13Methyl acetate + benzene 67 I-14Methyl acetate + benzene 55 I-15Methyl acetate + benzene 24 I-20Methyl acetate + benzene 41 Compounds purified by washing:
Com~ound No. Solvent emploYed Yield I-3 petroleum ether 93 I-4 CH2C12 + petroleum ether 79 I-5 petroleum ether 81 I-6 petroleum ether 62 I-8CH2C12 + petroleum ether 70 I-12 CH2C12 + hexane 80 I-14 CH2C12 + hexane 70 I-17 CH2C12 + petroleum ether 57 Tab I e 4 mpound MS(I /e) Melting No. O ~) Pointor IR (KBr, cm~) NMR (~) (A) (B) Decomposltion Point (~C) 29 55132-135 3300-2700,1710.1610.1570.149Q. CDCI3 3.947(611.s) 5.783(1H.s) 7.068(111.q.4 27Hz) 7.443-7.138(5il.m) I-l 3 1 Decompositior 1450.1370.1250.1160.1120.580 8.536(1H.s) 12.701(1H.s) 168-170 3350-2500.1710.1600.1570.1490, d6-DMS0 3.908(611.s) 5.990(111.s) 7.l79(111,s) 7.374(111,dd,6.7111z.1.8311z) I-2 - 155Deco~positlon 1450.1360.1310.1220.1200.1160. 7.482-7.533(211.m) 7.707(111.s) 10.548(1H.s) 11,468(1H.s) 580 12.594br (211. s) 3420-2800.1710.1600.1570.1490. d6-DMS0 3.898(611.s) 5.990(1H.s) 7.29(111.d.7.3Hz) l.430(1H.q.4.2Hz) 1-3 327 155 204-206 1440.1370.1350.1280.1250.1220 7.59(1H.dd.7.311z~1.411z) 7.797(1H.d.1.411z) 10.65br(111.s) 11.525(1H.s) 13.019(1H.s) 146-147 3300-2600.1700.1610.1570.1490. d6-DMS0 3.915(6H.s) 6.020(1H,s) 7.196(1H,s) 7.372(1H,dd,8.5511z,2.44Hz) 1-4 -- 155Decomposition 1450.1360.i290.1220.1200.1160. 7.580(111.d.8.55Hz) 7.878(111,d,2.44Hz) 10.665br(111,s) 1030.820.630.580 11.559 (lH . s) 12.994br (111. s) 13. Ollbr (lH, s) 187-189 3300-2600.3280.2930.1710.1600. CDCI3 2.585(3H.s) 3.954(6H.s) 5.805(111,s) 6.980(1H.q.4.3Hz) I-5 307 155 Decomposition 1570.149Q.1450.1360.1240.1160. 7.221(1H.d.8.511z) 7.3Q6(111.s) 7.394(1H.dd.8.5Hz,1.51~z) 1120.760.700.590 7.719(1H.d.1.51iz) 8.414(111,s) 12.735(1H,s) 149-152 3250.3150-2600.1710.1610.1570. d6-DMS0 2.504(311.s) 3.911(6H.s) 6.020(111,s) 7.155(111,s) 7.289-7.370(2H,m) I-6 -- 155Decomposition 1490.1450.1370.1360.1220.119Q. 7.782(11i.s) 10.587(111.s~ 11.417(1H.s) 12.508br(111,s) 1170.590 12.728br (111. s) I ~,3 3400-2800.3260.3100.2950.1720. d6 -DMS0 3.762 (3H, s) 3.947 (6H, s) 6.010 (lH, s) 7.366 (111, d,8Hz) ~ ,~
I -7 351 155 201-202 1600.1580.1490.1450.1370.1350. 7.494 (lH. q .4.911z) 7.765 (111. d .811z) 7.855 (lH . s) 10.631 (lH
. s) 1300.1270.1240.1190.1170,1110. 11.771(1H.s) 12.579(1H.s) ' e~
890.820.630.580 148-149 3400-2700.1710.1600.1570.1440. d6-DMS0 3.795(311.s) 3.950(611.s) 6.010(111.s) 7.257(1H,s) I-8 - 155DecomPositlonl37o~l35o~l27o~l23o~l2lo~ll9o~ 7.440(111.dd.8.5511z.1.8311z) 7.777(1H.d.8.5511z) 7.903(1H,d,1.8311z) 1160.1110.580 10.638(1H.s) 11.783(1H.s) 12.574(1H,s) 12,750br(1H,s) 125-128 3320-2700.3280.1710.1590.1570. Cl)C13 1.347(311.t.7.33Hz) 4.010(611.s) 4.296(2H.q.7.33Hz) 5.790(1H.s) I-9 365 155 Decompositlon 1490.1440.1350.1290.1260.1230. 7.107(111.q.4.2711z) 7.457(1H.s) 7.491(1H.dd.8.54Hz.2.44Hz) 1190.1160.1110.630.580 7.780(111.d.8.54Hz) 7.865(1H.d.2.44Hz) 9.024(1H.s) 12.662(1H.s) 3300-2600.1710.1600.1510.1490. d6 -DMS0 1.237 (3H . t .7.3311z) 3.945 (6H . s) 4.222 (2H . q .7.33Hz) 6.003 (lH . s) I -10 - 155138-140 1450.1360.1270.1240.1220.1200. 7.250 (lH . s) 7.431 (111. dd .8.5511z .1.83Hz) 7.770 (111. d .8.55Hz) Decomposltion 1170.580 7.900(1H.d.1.83Hz) 10.634(1H.s) 11.759(1H.s) 12.555(1H.s) 12.750br(lH. s) *) (~), ~ + * *) (B) R I CH=NNH~ S 0 2 N=C=O - _~X ' ~ +
R 2 H 2 N ~ O Z
N--~ X 2 , Tab I e a~ (Con t ~ompound ~!S(m/e) ~lel tlng No. ~ ) Point or I R (KB r, cm~ ) NMR (~) (A) (B)Decompositlon Point (~C) 144-146 3340,1740.1610.1580.1410.1375, CDC13 3.881(3H.s) 4.147(311.s) 6.495(111.s) 1.169(111,q.3.661lz) 1-11 351 159 DecomrJosed 1310.1290.1190.1130.590 7.528(111,dd.8.5511z.2.4411z) 1.805(111,d,8.5511z) 7.8l2(1H.d.2.4411z ) 1.894(111,s) 8.966(111.s) 12.198(111.s) 140-143 3400-2800.1730,1590.1580,1450. d6-D~lSO 3.788(3il.s) 4.045(311.s) 6.819(111.s) 7.250(1il.s)1-12 -- 159 De- r ~ed 1360.1295.1275.1125.590 7.442(111.dd.8.5511z.2.44~1z) 7.792(1H.d,8.55ilz) 7.897(111.d,2.4411 z) 10.902(111.s) 11.771(111.s) 11.951br(111.s) 12.750br (lil,s) 154-158 3300-2700.il30.1720.1620.1480. CDC13 2.514(611.s) 3.878(311.s) 6.159(111.s) 7.190(1H.q.3.06Hz) 1-13 351 123 D~co_,~sed 1410.1450,1360,1310.1290.1260. 7.521(1H.dd.8.54Hz.2.44Hz) 7.765(111.d.8.5411z) 7.889(111.d.2.4411z) 1130,600 8.275(111.s) 9.269(1~.s) 13.370(1~1,s) 145-150 3400-2600.1750br.1635.1590. d6-D~lS0 2.435~611.s) 3.757(311.s) 7.016(111.s) 1.245(111.s) 1-14 -- 123 DPcnn~rosA.l 1490.1480.1460.1370,1300.1270, 7.430(1H.dd.7.94Hz.1.8311z) 7.764(1H.d.7.9411z) 7.886(1H.d.1.8311z) 1190.1150.610 10.602(111.s) 11.761(111.s) 12.l50br(1H.s) 13.3D4(1H.s) 152-154 3300-2800.1150.1620.1590.1470. CDC13 2.492(311.s) 3.866(311.s) 3.986(3H.s) 6.295(11i.s) 7.158(111.q.
1-15 351 139 Decomrosed 1450,1370,1310,1280,1260.1130. 3.0511z) 7.509(111.dd.8.5411z.2.44Hz) 7.775~111.d.8.5411z) 7.792(111.
s) 600 7 . 884 (11i . d . 2 . 441iz) 9 . 227 (lH . s) 13 . 275 (111, s) 101-105 3300-2800.1730.1610.1570.1450. CDCI3 2.633(311.s) 3.898(311.s) 4.086(311.s) 7.194(1H.q.3.6611z) ~, 1-16 351 140 D -- r -ed 1360.1300.1270.1240.1170.1110. 7.526(111.dd.8.5511z.2.4411z) 7.804(111.d.8.5511z) 7.842(111.d.2.4 41lz) 820.590 8.235(111.s) 9.154(111.s) 12,615(1H.s) - 144-146 3350-2700 .1760 .1630 .1600 .1480 . d6 -DMS0 2 . 500 (311. s) 3 . 803 (311. s) 3 . 996 (311. s) 7 . 250 (111. s) 1-17 - 140 DecomrJosed 1390.1310.1280.1200.1180.1150. 7.453(1H.dd.8.5411z.2.4411z) 7.799(111.d.8.5411z) 7.891(111.d.2.44Hz ) ;~.
850.620 11.085(111.s) 11.776(1H.s) 12.$13(111.s) 12.75(1H.s) 142-144 3300-2700.1120.1600.1580.1540 d6-D~lS0 3.915(611.s) 6.025(111.s) 7.321(1H.dd.8.541iz.2.4411z) 1-18 -- 155 DecomFosed 1500.1450.1360.1260.1220.1170. 7.563(111.d.8.5411z) 7.831(111.d.2.44Hz) 8.795(1il.s) 10.697(111.s) 1020.810.160.690.590 11.666(111.s) 13.02br(111.s) 11 of COOli vas not observed.
148-149 3300-2800.1730.1610.1580.1450. d6 -D~IS0 3.152(311.s) 3.947(611.s) 6.012(1tl.s) 7.370(1H,d.8.5511z) 1-19 -- 155 Decomposed: 1380.1290.1270.1250,1220.1110, 7.l64(111,d.8.5511z) 7.875(1H.s) 8.830(1H.s) 10.634(1H.s) 1110.1020.590 11.898(1H.s) 12.577(11i.s) 11 of COOII Yas not observed.
117-119 3300.3200-2800.1730.1600.1570. CDC13 3.898(31i.s) 4.110(611.s) 7.167(111.q.3.6611z) I-20 351 156 Decomposed 1500,1460.1380.1360.1300.1210. 1.527(111.dd.8.5511z.1.3311z) 7.799(111.d.8.5511z) 7.845(11 1.d.1.8311z) ~ 1245.1170.1120.815.590 8.111(11~.s) 8.959(11~.s) 12.261(11~.s) .
r~J ~ 3 ~ ~
Synthesis Example 3:
Synthesis of Preparation intermadiate methyl 2-taminosulfonyl)-4-r(2,2 2-trifluoroethYlidene~-hydrazinolbenzoate tCompound No. II-7) 5 (1) Synthesis of methYl 2-~aminosulfonyl)-4-hydrazino-benzoate ~Compound No. V-4~:
To a mixture of 6 me 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. The reaction mixture was then cooled with ice water, followed by the addition of 3 me 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, followed 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 ~2~
pale yellow solid. Yield: 2.76 g (86%). Melting point:
168-170~C. Its physicochemiccll properties are shown in Table 6.
(2) Svnthesis of me~hyl 2-~aminosulfonYl)-4-r~2 2 2-trifluoroethylidene)hydrazinolbenzoate (Compound No.
II-7):
In 4 ml of acetic acid, 367.5 mg (1.5 mmol) of the compound synthesized in the above procedure (1) (Compound No. V-4) and 0.21 m~ of trifluoroacetaldehyde ethyl-hemiacetal were dissolved, followed by stirring at 80~C
for 3 hours. Acetic acid was then distilled off from the reaction mixture and 30 m~ of ice water were added to the pale yellow residue. The insoluble matter was collected by filtration and then dried in air. The title compound was obtained as a pale yellow solid. Yield: 421 mg (86%).
Its physicochemical properties are shown in Table 5.
The other compounds shown in Table 2 were also synthesized in accordance with the above reaction formula.
Either the following reaction conditions (a) or (b) were employed.
(a) After reaction for 3-5 hours at 80-90~C in acetic acid in a flask, acetic acid was distilled off, and the reaction product was scraped out from the flask. As an alternative, the reaction product was washed out with a poor solvent from the flask, collected by filtration and then dried in air.
(b) After reaction for 5-7 hours at room temperature in 6 N sulfuric acid, the insoluble matter was collected by filtration, washed with water and then dried in air [see Chem. Ber., 115, 3706-18 (1982)].
The following yields were achieved under the respec-tive reaction conditions:
ComPound No. Reaction conditions Yield (%) II-1 (a) (scraped out)98 II-2 (b) 93 II-3 (b) 76 II-4 (b) 96 II-5 (b) 40 II-6 (b) 85 II-7 (a) water 86 II-8 (a) H2O/methanol (1/1) 46 II-9 (a) H2O/ethanol (1/1) 58 II-10(a) H2O/acetonitrile (1/1) 27 II-ll (b) 75 II-12(a) H2O,CH2C12 32 The physicochemical properties of these compounds are shown in Table 5.
In addition, ths physicochemical properties of the other compounds shown as preparation intermediates in Table 3 are given in Table 6.
~J~3~
.
_ _ _ ~ ~ _ C" ~ ~ _ ~_ . ~ ~ ~ C D~ o C
_ _ _ C"_ ~ _ _ ~
VJ ~ V~ ~J O U~ ~ T - _ _. 4,) 0 c~ -- o oo C~n ~-- o--~r co~ o- ~o ~0 ~ C~ ~0 v ~ v ~ ~
o o u~ o o o o ' o oo o o o o o o o o t - o ~ o o o o o o ~ o o _ _ ~~ _ _ ~1~ _ _ e~ _ _ _ . _ _ _ _ 0~ 0 _ O _ _ _ _ _ _ _ _ _ C~ ~ ~ ~ o r_ o o~ ~O ~ ~ ~~ t_ ~ o O ' ~ ~ ~~ ~ ~ ~ ~ ~ ~
, t - ~ o u~ o O~ U~ CO _ C.~ ~ C ~ ~ ~ ~ ~ ~
~,, -- _ ~ _ O _ _ O er~ l C~ _ O C~ _l _ O _ ~ _I _ _ _ C~ _ C'l _ _ '~P ~ ~ r-- . O t-- . CO eCI eC~ O O C~l O U~ O ~ O O~ ~
O O c_ O O O O ~ O ~ ~ ~~ U~~ ~ ~ C~o ~~~ ~_ o o CC~ ~4 00 0 ~ o O
_, O~ _ t_ Cr~ _ CJ~ C~ _ ~I C~ _ _ t_ C~l _ _ C.~ _ _ C~ _ _ ~ C~ _ _ C~ _ 00 ~ _ CO 0~ _ C.~ _ _ O
o o o co c~ - o - ~ ~ ~ o - - c~ cn u~ ~ o c~ o o c~ ~r ~ o o o co o o -- oo - e-- u~
~ O t~ C~> O O _ O CO
_ C C~ C ~ C ~ ; C I ~ ~ C~
2~3~7 T a b I e 6 Compounli Mel tlng No. ~lS(mJe) Polnt or I R (ICB r, cm~l) N~IR (ô) Deconposi tlon Polnt (~C) 3360 . 3350 . 3300. 3220, 1500.
V-l 187 113-116 1~170. 1340.1330.1290.1140.
1090.780. 680.580.510 1 55-1 58 337 0 . 3330 . 3130 . 2910 . 1590 .
V-2 221 Deco~Poscd 1560. 1460.1330.1270.
1160 . 910. 830. 140 . 690 . 590.
S50 . 510 3300.3250.3010.1610.1490. d 6 -DMSO:2.409(311.s) V-3 201 161-164 1300.1160.1140.920.820. 4.025br(211.s) 6.840 . 6gO . 600 . 520 (111. dd . 8 . 511z .1. 81iz) 6 . 901 (lll . s) I . 048 (111 .
d . 8 . 511z) 7 .148 (211. s) I . 349(111 .d .1. 811z) 33S0.3310.3250.1680.1630.
V-4 245 168-1l0 1590.1440.1350.1330.1~00.
1210. 11 10 . 11 60. 780 . lO0 . 600 1 22-1 29 3320 . 3270 . 2980 . 1l00 . 1 5gO .
V-5 259 Decomposed 1370.13Z0. 13ûO. 1270 .1250.
1150.1120.110,140.700 ~$2~3~7 Compounds available in a similar manner to Synthesis Example 2 are summarized in Table 7.
Table 7 X ' N __<' R I C H = N N H \r''''Y/ S 0 2 N H C O N H ~ O Z
~ N
CompoundR l R 2 X I X 2 z No .
I -21 CF3 H Cl13 OC~3 N
I -23 CF3 Cl CH3 OCI13 N
I-24 CF3 Cl OCH3 OCI13 N
1 -26 CF3 Cl13 OCH3 OCI13 N
I-21 CF3 COOC2Hs Cl13 OCH3 N
I-28 CF3 CoOC2Hs OCH3 OCI13 N
I -30 COOH Cl OCH3 OCI13 N
I -33 COOII CoOC2H5 CH3 OCI13 N
I -34 COOH COoC2Hs OCI13 OCI13 N
I -36CCI-CCICOOII Cl CH3 OCI13 N
I-40CCI~CCICOOH CoOC2Hs OCH3 OCH3 N
~2~'7 Formulation examples and tests will hereinafter be described. It should be borne in mind that the vehicles (diluents) and aids, their mixing ratios and e~fective components can vary in wide ranges, respectively.
Formulation ExamPle 1: Wettable Powder Compound (Compound No. I-7)50 parts A salt of ligninsulfonic acid 5 parts A salt of alkylsulfonic acid3 parts Diatomaceous earth 4~ parts The above ingredients are mixed and ground into a wettable powder. For application, it is diluted with water.
Formulation Example 2: Emulsion Compound (Compound No. I-ll)25 parts Xylene 65 parts Polyoxyethylene alkylaryl ether 10 parts The above ingredients are mixed intimately into an emulsion. For application, it is diluted with water.
Formulation Example 3: Granule Compound (Compound No. I-17)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 formula1ion, namely, a granule.
Test 1: TQst on Herbicidal Ac1:ivitY bv Foliar A~plication 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 10 g/ha and 100 g/ha over foliar parts of Arnsranthus retroflexus (Redroot pigweed), Bidens pilosa (Common blackjack), Sinapis arvensis (Wild mustard), Stellaria media (Common chickweed), Cassia obtusifolia (Sick~
lepod), Solanum nignlm (Black nightshade), Abutilon theophrasti (Velvetleaf), Convolvulus arvensis (Field bindweed), M~tricaria ~-hJ -il7~ (Wild chamomile), Setaria viridis (Green foxtail) Echinochloa frulDentaceum (Barnyard grass), Avena faeua(Wild oat), and Digitari~ adscendens (Henry crabgxass) which had been allowed to grow individually to 2-4 leaf stage in pots. Fourteen days 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.
Ranking system:
Herbicidal activit~
0: No effects z5 1: less than 3196 o~ total kill 2: 31-50% of total kill.
3: 51-70% of total kill 4: 71-90~ of total kill 5: 91-100~ of total kill 2~293d7 ~ O --~ O O c~ c~ O c~ O c~ o u~ o u~ O ~r o c~ o c~ o c.~ o ~ u~ u~
e_ o u~ o o o c~ c~ o o c~ ~ er In ~Y ~ O ~ O ~ ID U~ U~ U~
'~:
o _ ~ ~ o ~.r o Is~ o ~ ~ u~ u~ u~ L~
C~
C~
s C~
C~
o --c~
o.
L~
-c 2, - ~
~ o c~ ~
~ z T a b l e 8 ( C o n -' d ) CNO~POUnd AOsplgeat(g/ohna) A.r. B.P. S.a. S.m. C.o. S.n. A.t C.a. M.c. S.v. E.f. A.f. D.a.
1 -17105555555555 ~ 20 1005555555554440 ,c~
I -l9105555445553110 o~
1005555555554441 ~3 Note) h.r.:Amaranthus retroflexus S.n.:SolanuE nlgrum S.v.:Setaria vlridis B.p.:Bldens pilosa h.t.:Abutilon theophras~i E.f.:Echinochloa frumentaceum S.a.:Sinapis arvensis C.a.:Convolvulus arvensis A.f.:AYena fatua S.m.:Stellaria media ~.c.:Matricaria chamomilla D.a.:Digitaria adscendens C.o.:Cassia obtuslfolla ~$12~
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. ~ater suspensions of each test compound (con-centrations of the active ingredient: 1 ppm and 50 ppm) were. separately poured in an amount of 5 m~ per dish into the Petri dishes. Seeds of Am~ranthus ret~oflexus (Redroot pigweed), Bidens piloss~ (Common blac:kjack), ~atricaria chamom.illa (Wild rh~ ~~; le), S~lanum nigr~m (Black nightshade), Echinochloa oryzicola (Barnyard grass), Cyperus iria (Rice flatsedge) and Setaria viridis (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 28~C. 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.
Growth inhibition rate 0: No inhibition 1: less than 31%
2: ~1-50%
3: ~1-70%
4: 71-90%
2~2~
5: 91-100%
2.~2~3l~
Ta b I e 9 ComPoUn~ Concen-No. tratlon ~.r. B.p. M.c. S.n. E.o. C.l. S.v.
(ppm) 5~ 4444345 I-l 13343455 5~ 5454555 5032452 ~ 3 3 l~ ~
-- 3~ --T a b I e 9 (C o n t' d) Compound Conccn-No. traLlon A.r. B.p. M.c. S.n. E.o. C.l. S.v.
(ppm) 1 -16 1 1 O 3 2 ~ 2 3 3 4 4 ~ 4 5 SO 4 3 ~ 3 5 4 5 Note) A.r.:Amaranthus retroflexus E.o.:Echlnochloa oryzfcola B.P.:~ldens pilosa C.l.:Cyperus lrla M.c.:Matrlcarla chamomllla S.v.:Setarla vlrldls S.n.:Solanum nlgrum
Numerous compounds have heretofore been proposed as herbicides. For example, U.S.Pat.No.4,632,695, U.S.Pat.No.4,664,695 and Japanese Patent Application Laid-Open (KOKAI) No. 129276/1987 disclose a wide variety of compounds, including N-substituted-3-substituted ben-zenesulfonamide derivatives containing N~C(CH3)=CHCOCH3, NHC(CH3)=CHCOOCH3, NHCH3, OCH2CF3 or SCH2CF3 on the 3-position and a pyrimidine xing or a 1,3,5-triazine ring on the nitrogen atom.
There have conventionally been strong demands for herbicides capable of exhibiting reliable nerbicidal 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 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 that compounds still unreported to date and having a substituted hydra~ino group on the 3-position of benzenesulfonamide as opposed to the inclusion of NHCtCH3)=CHCOCH3, NHC(CH3)=CH-COOCH3, NHCH3, OCH2CF3 or SCH2CF3 on the 3-position of benzenesulfonamide in the compounds disclosed in EP-A-116518 publis~led August 22, 1984 and Japanese Patent Application Laid Open (KOKAI) No. 129276/1987 published June 11, 1987 have excellent herbicidal activity, leading to the completion of the present invention.
SUMMARY OF THE INVENTION
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 for 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.
2 ~
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-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-(substituted hydrazino)benzene-sulfonamide derivative of the formula (I):
Rl CH ~NNH S02NHCONH ~
~Rl N~X2 wherein R1 is CF3, COOH or CCl=CClCOOH, R2 is H, Cl, C1-C3 alkyl or C1-C4 alkoxycarbonyl; Z is CH or N; Xl is Cl-C3 alkyl, Cl-C3 alkoxyl or Cl; 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 the above-described N-substituted-3-(substituted hydrazino)benzene-sulfonamide derivative, which comprises reacting a 3-(substituted hydrazino)benzenesulfonamide derivative of the formula (II):
Rl CH NNH S02NH2 R' wherein R1 and R2 have the same -~n; n~s as defined above, with a phenylcarbamate derivative of the following formula ~III):
O X' ll N
~ OCNH
x2 wherein Z, X1 and x2 have the same ~~nings as defined above.
In a further aspect of the invention, there is also provided a 3-(substituted hydrazino)benzenesulfonamide derivative useful as an int~ - ai ~te in the preparation of the above N-substituted-3-(substituted hydrazino)benzene-sulfonamide, which is represented by the following formula (II) R' CH~NNH 50 2 NH 2 ~ (II) R' wherein Rl and R2 have the same meanings as defined above.
In a still further aspect of the invention, there is also provided a 3-hydrazinobenzenesulfonamide derivative useful as an inte ~~iate in the preparation of the above 3-(substituted hydrazino)benzenesulfonamide of the formula (II), which is represented by the following formula (V'):
2OÇ?J9~7 ~ (V ) wherein R2 is H, C1-C3 alkyl or Cl-C4 alkoxycarbonyl.
In a still further aspect of the invention, there is also provided a herbicidal composition comprising as an active ingredient the N-substituted-3-(substituted hydrazino)benzenesulfonamide derivative of the formula (I).
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-(substituted hydrazino)benzenesulfonamide derivative of the formula (I) or a herbicidal composition comprising said derivative.
f~ ~ 3 ~ ~
The N-substituted-3-(substituted hydrazino~-benzenesulfonamide derivatives of the present invention, which are represented by the formula (I), have not been disclosed in any publications known to the inventors of the present application, exhibit reliable herbicidal ac-tivity at low application dosages and show selectivity be-tween crops and weeds. The herbicidal compositions of the invention, which contain the above derivatives as effec-tive ingredients, are suitable particularly fcr controll-ing 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-(substituted hydrazino)benzenesulfonamide derivative represented by the formula (I) in the invention include those shown in Table 1.
3 ~ 7 Ta b I e N_~
R' CH--NNII 502NIICONH~OZ
'~( N ~' R' Compound R' R2 X' X2 Z
No .
1-1 CF3 11 OCI13 OCI13 Cll I-2 COOII ' 11 OCI13 OCI13 Cll I-3 CF3 Cl OCI13 OCI13 Cll I-4 COOII Cl OCIJ3 OCI13 CH
I-5 CF3 Cl~3OCI13 OCH3 Cll I-6 COOII Cl13OC113 OC113 Cll I-7 CF3 COOCI13 OCI13 OCI13 Cll I-8 COOII COOCH3 OCH3 OCH3 Cll I-9 CF3 COOC211, OCI13 OCI13 Cll I-10 COOII COOC211, OC113 OCI13 Cll I-ll CF3 COOCH3 Cl OC113 Cll I-12 COOII COOCI13 Cl OCI13 Cll I-13 CF3 COOCH3 Cl13 Cl13 Cll I-14 COOII COOCH3 Cll3 cll3 Cll I-15 CF3 COOCI13 ~C113 Cll3 Cll I-16 CF3 COOCI13 OCI13 Cl13 N
I -18CC I -CC I COOII C I OCI13 OCII 3 Cll I-l9 CCI-CCICOOII COOCH3 OCI13 OCil3 Cll 3 ~ 7 The N-substituted-3-(substituted hydrazino)ben~ene-sulfonamide derivatives represented by the formula (I) can each be synthesized by reacti:ng a 3-(substituted hydrazino)benzenesulfonamide derivative of the formula tII) 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 reaction formula:
R' CH=NNH SO2NH2~ N__~
~ 2~ OCNH ~ O ~
R(m) X2 X
N__~
Rl CH-NNH SO2NHCONH ~ O Z
(I) wherein R1, R2, Z, Xl and x2 have the same ~~An;ngs 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, dia~abicyclononene, diazabicycloundecene or the like can be used as a base.
The reaction is conducted at a temperature in a range of from -20~C to 100~C, preferably from 0~C to 50~C
for a reaction period in a ranqe of from 0.5 hour to 24 hours.
2 0 ~9 ~L~7 _ 9 After 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 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-(substituted hydrazino)benzenesulfonamide derivative represented by the formula (I) can be obtained with high purity.
The 3-(substituted hydrazino)benzenesulfonamide derivative represented by the formula (II), which is a preparation intermediate and is employed as the starting material in the above reaction, can be synthesized in ac-cordance with the following reaction formula, using as a starting material a 3-aminobenzenesulfonamide derivative represented by the following formula (IV):
H2N So2NH2 H2NNH SO2NH2 \[~ 1 ) Diazotiz?tion \~
R2 2) Reductlon R2 (~) (V) R' CH=NNH SO2NH2 R' CHO ~
(~) wherein Rl and R2 have the same re~n;ngs as defined above.
25Synthesis of the compound represented by the formula ~2~3~7 ~ 10 --(II) in accordance with the above-described reaction can be practiced in the following manner. The 3-hydrazino-benzenesulfonamide 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 - is stirred to-gether with trifluoroacetaldehyde ethylhemiacetal, glyoxylic acid monohydrata or mucochloric acid at 30-120~C, preferably 70-90~C for 0.5-8 hours in acetic acid or propionic acid or at room temperature for 5-7 hours in 6 N sulfuric acid. After completion of the reaction, the reaction product is collected from the reaction mixture by filtration or the reaction mixture is evaporated to dry-ness under reduced pressure and if necessary, is purified by washing, whereby the compound represented by the for-mula (II) can be obtained with good purity.
The compound represented ~y 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-nitro-aniline derivatives, for example, by the process described in Chem. Ber., 90, 841 (1957) or J. Macromol. Sci. Chem., 1969, 941, namely, by synthesizing 3-nitrobenzenesulfon-amide derivatives and then reducing the nitro groups with SnCl2 in methanol or ethano:L conta.ining 35~ hydrochloric acid.
Further, the compound represented by the formula (IIT) can be obtained from phenyl chloroformate and the corresponding 2-amino-4,6 di-substituted pyrimidine (or 1,3,~-tria~ine), for example, by the proc~ss described in European Patent Specification No. 238,070 published September 23, 1987.
Specific examples of the compound represented by the formulae (II) and useful as the above preparation intermediate are summarized in Table 2.
In addition, specific examples of the compound represented by the formula (V) are shown in Table 3.
Tab le 2 R' CH= NN H S 0 2 NH 2 --~\ R 2 Compound No. Rl R2 ~-lC F 3 H
~-2C 00 H H
~-3 CF 3 C I
~-4C 00 H Cl ~-5 CF 3 CH3 ~-6CO OH CH3 ~_7C F3 COOC H3 ~-8CO OH COOC H3 ~-9 C F3 CO OC 2 H 5 ~-lOC 00 H COOC 2 H 5 ~-ll HO O C CCI- CCI - C I
~-12 HO O CCC l= CCI - COOC H 3 . V
2~ ~J J~ 9 3 5r. 7 ~ ~.2 ~
Tab le 3 H 2 NN H ~ SO 2 N H 2 RZ
5Compo~nd No. R2 V-l H
V-2 Cl The N-substituted-3-(substituted hydrazino)benzene-sulfonamide derivatives exhibit reliable herbicidal ac-tivity at low application dosages and show selectivity be-tween crops and weeds. The herbicidal compositions of the invention, which contain the above compounds as effective ingredients, are therefore suitable for controlling either before or after emergence monocotyledonous weeds and/or dicotyledonous weeds in important crops such as whea~, rice, corn, soybean, cotton, beet, potato and tomato.
Exemplary dicotyledonous weeds which can.be control-led by the herbicides of the invention include Amaranthus, Bidens, Stellaria, Solanum, Abutilon, Convolvulus, ~atricaria, Galium, Lindernla, etc.
Illustrative monocotyledono~ls weeds include 2 ~ 2 ~ 3 L~ 7 Echirlochlo~, Setari~, Digit~ria, Aven~, Cyperus, Alism~, Monochoria, etc.
The herbicidal compositions of the invention may take any preparation forms such as wettable powder, emul-sion, 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 factory sites.
Examples:
The present invention will hereinafter be described by the following examples.
Synthesis Example 1:
Synthesis of methYl 2-~14 6-dimethoxy~vrimidin-2-yl)aminocarbonylaminosulfonyl~-4-r~2.2.2-trifluQro-ethYlidene)hYdrazino1benzoate (Compound No. I-7) At room temperature, 166 mg (0.5 mmol) of methyl 2-(aminosulfonyl)-4-[(2,2,2-trifluoroethlidene)hydrazino]-~o benzoate and 137.5 mg (0.5 mmol) of phenyl (4,6-dimethoxy-pyrimidin-2-yl)carbamate were dissolved in 1.5 m~ of N,N-dimethylacetamide. Then, 86.1 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 15 hours. Thereafter, 0.2 ~ of 35% hydrochloric acid was added to 20 m~ of ice water, followed by the addition of the reaction mixture in 0.2 me portions under stir-ring. After the reaction mixture was stirred for 20 minutes, the resulting precipitate was collected by fil-tration and dried in air. Using dichloromethane as an eluent, the crude product was purified by chromatography on a column of silica gel ("WAKO GEL C-300", trade mark;
product of Wako Pure Chemical Industries, Ltd.). The title compound was obtained as a white solid. Yield:
162 mg (64~). Melting point: 201-202~C. Its physico-chemical properties are shown in Table 4.
Synthesis Example 2:
Synthesis of methyl 2-[(4 6-dimethoxy-1 3 5-triazin-2-yl)aminocarbonylaminosulfonyll-4- r ( 2 2 2-trifluoroethylidene)hydrazinolbenzoate (Compound No.
I-20) At room temperature, 166 mg (0.5 mmol) of methyl 2-(aminosulfonyl)-4-[(2,2,2-trifluoroethlidene)hydrazino]-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, 86.1 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% hydrochloric acid was added to 30 me of ice water, followed by the addition of A
-- lCi --the reaction mixture in 0.2 m~ portions under stirring.
~fter the reaction mixture was stirred for 20 minutes, the resulting precipitate was collected by filtration and dried in air. Using as an eluent a 1:9 mixed solvent of methyl acetate and benzene, the crude product was purified by chromatography on a column of silica gel ("WAKO GEL C-300", trade mark; product of Wako Pure Chemical In-dustries, Ltd.). The title compound was obtained as a white solid. Yield: 103 mg (41%). Melting point: 117-119~C (foamed). Its physicochemical properties are shown in Table 4.
The other N-substituted-3-(substituted hydrazino)-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 proce-dure to Synthesis Example 1, they were separately purified by chromatography on a silica gel column or washing.
Physicochemical properties of each of the N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives are shown in Table 4. Incidentally, in Table 4 and in Tables 5 and ~ which will be given subsequently, the abbrevia-tions in the columns for NMR data have the following mean-ngS:
~: (ppm), s: singlet, d: doublet, t: triplet, q: quartet, m: multiplet, dd: double doublet, .
2~2~4~
br: broad.
Further, with respect to the individual N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives, the solvents employed upon purification thereof and the yields attained were as follows:
~2~
Compounds purified by column chromatography:
Compound No.Solvent em~loYed Yield I-l CH2C12 49 I~9 CH2C12 59 I-13Methyl acetate + benzene 67 I-14Methyl acetate + benzene 55 I-15Methyl acetate + benzene 24 I-20Methyl acetate + benzene 41 Compounds purified by washing:
Com~ound No. Solvent emploYed Yield I-3 petroleum ether 93 I-4 CH2C12 + petroleum ether 79 I-5 petroleum ether 81 I-6 petroleum ether 62 I-8CH2C12 + petroleum ether 70 I-12 CH2C12 + hexane 80 I-14 CH2C12 + hexane 70 I-17 CH2C12 + petroleum ether 57 Tab I e 4 mpound MS(I /e) Melting No. O ~) Pointor IR (KBr, cm~) NMR (~) (A) (B) Decomposltion Point (~C) 29 55132-135 3300-2700,1710.1610.1570.149Q. CDCI3 3.947(611.s) 5.783(1H.s) 7.068(111.q.4 27Hz) 7.443-7.138(5il.m) I-l 3 1 Decompositior 1450.1370.1250.1160.1120.580 8.536(1H.s) 12.701(1H.s) 168-170 3350-2500.1710.1600.1570.1490, d6-DMS0 3.908(611.s) 5.990(111.s) 7.l79(111,s) 7.374(111,dd,6.7111z.1.8311z) I-2 - 155Deco~positlon 1450.1360.1310.1220.1200.1160. 7.482-7.533(211.m) 7.707(111.s) 10.548(1H.s) 11,468(1H.s) 580 12.594br (211. s) 3420-2800.1710.1600.1570.1490. d6-DMS0 3.898(611.s) 5.990(1H.s) 7.29(111.d.7.3Hz) l.430(1H.q.4.2Hz) 1-3 327 155 204-206 1440.1370.1350.1280.1250.1220 7.59(1H.dd.7.311z~1.411z) 7.797(1H.d.1.411z) 10.65br(111.s) 11.525(1H.s) 13.019(1H.s) 146-147 3300-2600.1700.1610.1570.1490. d6-DMS0 3.915(6H.s) 6.020(1H,s) 7.196(1H,s) 7.372(1H,dd,8.5511z,2.44Hz) 1-4 -- 155Decomposition 1450.1360.i290.1220.1200.1160. 7.580(111.d.8.55Hz) 7.878(111,d,2.44Hz) 10.665br(111,s) 1030.820.630.580 11.559 (lH . s) 12.994br (111. s) 13. Ollbr (lH, s) 187-189 3300-2600.3280.2930.1710.1600. CDCI3 2.585(3H.s) 3.954(6H.s) 5.805(111,s) 6.980(1H.q.4.3Hz) I-5 307 155 Decomposition 1570.149Q.1450.1360.1240.1160. 7.221(1H.d.8.511z) 7.3Q6(111.s) 7.394(1H.dd.8.5Hz,1.51~z) 1120.760.700.590 7.719(1H.d.1.51iz) 8.414(111,s) 12.735(1H,s) 149-152 3250.3150-2600.1710.1610.1570. d6-DMS0 2.504(311.s) 3.911(6H.s) 6.020(111,s) 7.155(111,s) 7.289-7.370(2H,m) I-6 -- 155Decomposition 1490.1450.1370.1360.1220.119Q. 7.782(11i.s) 10.587(111.s~ 11.417(1H.s) 12.508br(111,s) 1170.590 12.728br (111. s) I ~,3 3400-2800.3260.3100.2950.1720. d6 -DMS0 3.762 (3H, s) 3.947 (6H, s) 6.010 (lH, s) 7.366 (111, d,8Hz) ~ ,~
I -7 351 155 201-202 1600.1580.1490.1450.1370.1350. 7.494 (lH. q .4.911z) 7.765 (111. d .811z) 7.855 (lH . s) 10.631 (lH
. s) 1300.1270.1240.1190.1170,1110. 11.771(1H.s) 12.579(1H.s) ' e~
890.820.630.580 148-149 3400-2700.1710.1600.1570.1440. d6-DMS0 3.795(311.s) 3.950(611.s) 6.010(111.s) 7.257(1H,s) I-8 - 155DecomPositlonl37o~l35o~l27o~l23o~l2lo~ll9o~ 7.440(111.dd.8.5511z.1.8311z) 7.777(1H.d.8.5511z) 7.903(1H,d,1.8311z) 1160.1110.580 10.638(1H.s) 11.783(1H.s) 12.574(1H,s) 12,750br(1H,s) 125-128 3320-2700.3280.1710.1590.1570. Cl)C13 1.347(311.t.7.33Hz) 4.010(611.s) 4.296(2H.q.7.33Hz) 5.790(1H.s) I-9 365 155 Decompositlon 1490.1440.1350.1290.1260.1230. 7.107(111.q.4.2711z) 7.457(1H.s) 7.491(1H.dd.8.54Hz.2.44Hz) 1190.1160.1110.630.580 7.780(111.d.8.54Hz) 7.865(1H.d.2.44Hz) 9.024(1H.s) 12.662(1H.s) 3300-2600.1710.1600.1510.1490. d6 -DMS0 1.237 (3H . t .7.3311z) 3.945 (6H . s) 4.222 (2H . q .7.33Hz) 6.003 (lH . s) I -10 - 155138-140 1450.1360.1270.1240.1220.1200. 7.250 (lH . s) 7.431 (111. dd .8.5511z .1.83Hz) 7.770 (111. d .8.55Hz) Decomposltion 1170.580 7.900(1H.d.1.83Hz) 10.634(1H.s) 11.759(1H.s) 12.555(1H.s) 12.750br(lH. s) *) (~), ~ + * *) (B) R I CH=NNH~ S 0 2 N=C=O - _~X ' ~ +
R 2 H 2 N ~ O Z
N--~ X 2 , Tab I e a~ (Con t ~ompound ~!S(m/e) ~lel tlng No. ~ ) Point or I R (KB r, cm~ ) NMR (~) (A) (B)Decompositlon Point (~C) 144-146 3340,1740.1610.1580.1410.1375, CDC13 3.881(3H.s) 4.147(311.s) 6.495(111.s) 1.169(111,q.3.661lz) 1-11 351 159 DecomrJosed 1310.1290.1190.1130.590 7.528(111,dd.8.5511z.2.4411z) 1.805(111,d,8.5511z) 7.8l2(1H.d.2.4411z ) 1.894(111,s) 8.966(111.s) 12.198(111.s) 140-143 3400-2800.1730,1590.1580,1450. d6-D~lSO 3.788(3il.s) 4.045(311.s) 6.819(111.s) 7.250(1il.s)1-12 -- 159 De- r ~ed 1360.1295.1275.1125.590 7.442(111.dd.8.5511z.2.44~1z) 7.792(1H.d,8.55ilz) 7.897(111.d,2.4411 z) 10.902(111.s) 11.771(111.s) 11.951br(111.s) 12.750br (lil,s) 154-158 3300-2700.il30.1720.1620.1480. CDC13 2.514(611.s) 3.878(311.s) 6.159(111.s) 7.190(1H.q.3.06Hz) 1-13 351 123 D~co_,~sed 1410.1450,1360,1310.1290.1260. 7.521(1H.dd.8.54Hz.2.44Hz) 7.765(111.d.8.5411z) 7.889(111.d.2.4411z) 1130,600 8.275(111.s) 9.269(1~.s) 13.370(1~1,s) 145-150 3400-2600.1750br.1635.1590. d6-D~lS0 2.435~611.s) 3.757(311.s) 7.016(111.s) 1.245(111.s) 1-14 -- 123 DPcnn~rosA.l 1490.1480.1460.1370,1300.1270, 7.430(1H.dd.7.94Hz.1.8311z) 7.764(1H.d.7.9411z) 7.886(1H.d.1.8311z) 1190.1150.610 10.602(111.s) 11.761(111.s) 12.l50br(1H.s) 13.3D4(1H.s) 152-154 3300-2800.1150.1620.1590.1470. CDC13 2.492(311.s) 3.866(311.s) 3.986(3H.s) 6.295(11i.s) 7.158(111.q.
1-15 351 139 Decomrosed 1450,1370,1310,1280,1260.1130. 3.0511z) 7.509(111.dd.8.5411z.2.44Hz) 7.775~111.d.8.5411z) 7.792(111.
s) 600 7 . 884 (11i . d . 2 . 441iz) 9 . 227 (lH . s) 13 . 275 (111, s) 101-105 3300-2800.1730.1610.1570.1450. CDCI3 2.633(311.s) 3.898(311.s) 4.086(311.s) 7.194(1H.q.3.6611z) ~, 1-16 351 140 D -- r -ed 1360.1300.1270.1240.1170.1110. 7.526(111.dd.8.5511z.2.4411z) 7.804(111.d.8.5511z) 7.842(111.d.2.4 41lz) 820.590 8.235(111.s) 9.154(111.s) 12,615(1H.s) - 144-146 3350-2700 .1760 .1630 .1600 .1480 . d6 -DMS0 2 . 500 (311. s) 3 . 803 (311. s) 3 . 996 (311. s) 7 . 250 (111. s) 1-17 - 140 DecomrJosed 1390.1310.1280.1200.1180.1150. 7.453(1H.dd.8.5411z.2.4411z) 7.799(111.d.8.5411z) 7.891(111.d.2.44Hz ) ;~.
850.620 11.085(111.s) 11.776(1H.s) 12.$13(111.s) 12.75(1H.s) 142-144 3300-2700.1120.1600.1580.1540 d6-D~lS0 3.915(611.s) 6.025(111.s) 7.321(1H.dd.8.541iz.2.4411z) 1-18 -- 155 DecomFosed 1500.1450.1360.1260.1220.1170. 7.563(111.d.8.5411z) 7.831(111.d.2.44Hz) 8.795(1il.s) 10.697(111.s) 1020.810.160.690.590 11.666(111.s) 13.02br(111.s) 11 of COOli vas not observed.
148-149 3300-2800.1730.1610.1580.1450. d6 -D~IS0 3.152(311.s) 3.947(611.s) 6.012(1tl.s) 7.370(1H,d.8.5511z) 1-19 -- 155 Decomposed: 1380.1290.1270.1250,1220.1110, 7.l64(111,d.8.5511z) 7.875(1H.s) 8.830(1H.s) 10.634(1H.s) 1110.1020.590 11.898(1H.s) 12.577(11i.s) 11 of COOII Yas not observed.
117-119 3300.3200-2800.1730.1600.1570. CDC13 3.898(31i.s) 4.110(611.s) 7.167(111.q.3.6611z) I-20 351 156 Decomposed 1500,1460.1380.1360.1300.1210. 1.527(111.dd.8.5511z.1.3311z) 7.799(111.d.8.5511z) 7.845(11 1.d.1.8311z) ~ 1245.1170.1120.815.590 8.111(11~.s) 8.959(11~.s) 12.261(11~.s) .
r~J ~ 3 ~ ~
Synthesis Example 3:
Synthesis of Preparation intermadiate methyl 2-taminosulfonyl)-4-r(2,2 2-trifluoroethYlidene~-hydrazinolbenzoate tCompound No. II-7) 5 (1) Synthesis of methYl 2-~aminosulfonyl)-4-hydrazino-benzoate ~Compound No. V-4~:
To a mixture of 6 me 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. The reaction mixture was then cooled with ice water, followed by the addition of 3 me 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, followed 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 ~2~
pale yellow solid. Yield: 2.76 g (86%). Melting point:
168-170~C. Its physicochemiccll properties are shown in Table 6.
(2) Svnthesis of me~hyl 2-~aminosulfonYl)-4-r~2 2 2-trifluoroethylidene)hydrazinolbenzoate (Compound No.
II-7):
In 4 ml of acetic acid, 367.5 mg (1.5 mmol) of the compound synthesized in the above procedure (1) (Compound No. V-4) and 0.21 m~ of trifluoroacetaldehyde ethyl-hemiacetal were dissolved, followed by stirring at 80~C
for 3 hours. Acetic acid was then distilled off from the reaction mixture and 30 m~ of ice water were added to the pale yellow residue. The insoluble matter was collected by filtration and then dried in air. The title compound was obtained as a pale yellow solid. Yield: 421 mg (86%).
Its physicochemical properties are shown in Table 5.
The other compounds shown in Table 2 were also synthesized in accordance with the above reaction formula.
Either the following reaction conditions (a) or (b) were employed.
(a) After reaction for 3-5 hours at 80-90~C in acetic acid in a flask, acetic acid was distilled off, and the reaction product was scraped out from the flask. As an alternative, the reaction product was washed out with a poor solvent from the flask, collected by filtration and then dried in air.
(b) After reaction for 5-7 hours at room temperature in 6 N sulfuric acid, the insoluble matter was collected by filtration, washed with water and then dried in air [see Chem. Ber., 115, 3706-18 (1982)].
The following yields were achieved under the respec-tive reaction conditions:
ComPound No. Reaction conditions Yield (%) II-1 (a) (scraped out)98 II-2 (b) 93 II-3 (b) 76 II-4 (b) 96 II-5 (b) 40 II-6 (b) 85 II-7 (a) water 86 II-8 (a) H2O/methanol (1/1) 46 II-9 (a) H2O/ethanol (1/1) 58 II-10(a) H2O/acetonitrile (1/1) 27 II-ll (b) 75 II-12(a) H2O,CH2C12 32 The physicochemical properties of these compounds are shown in Table 5.
In addition, ths physicochemical properties of the other compounds shown as preparation intermediates in Table 3 are given in Table 6.
~J~3~
.
_ _ _ ~ ~ _ C" ~ ~ _ ~_ . ~ ~ ~ C D~ o C
_ _ _ C"_ ~ _ _ ~
VJ ~ V~ ~J O U~ ~ T - _ _. 4,) 0 c~ -- o oo C~n ~-- o--~r co~ o- ~o ~0 ~ C~ ~0 v ~ v ~ ~
o o u~ o o o o ' o oo o o o o o o o o t - o ~ o o o o o o ~ o o _ _ ~~ _ _ ~1~ _ _ e~ _ _ _ . _ _ _ _ 0~ 0 _ O _ _ _ _ _ _ _ _ _ C~ ~ ~ ~ o r_ o o~ ~O ~ ~ ~~ t_ ~ o O ' ~ ~ ~~ ~ ~ ~ ~ ~ ~
, t - ~ o u~ o O~ U~ CO _ C.~ ~ C ~ ~ ~ ~ ~ ~
~,, -- _ ~ _ O _ _ O er~ l C~ _ O C~ _l _ O _ ~ _I _ _ _ C~ _ C'l _ _ '~P ~ ~ r-- . O t-- . CO eCI eC~ O O C~l O U~ O ~ O O~ ~
O O c_ O O O O ~ O ~ ~ ~~ U~~ ~ ~ C~o ~~~ ~_ o o CC~ ~4 00 0 ~ o O
_, O~ _ t_ Cr~ _ CJ~ C~ _ ~I C~ _ _ t_ C~l _ _ C.~ _ _ C~ _ _ ~ C~ _ _ C~ _ 00 ~ _ CO 0~ _ C.~ _ _ O
o o o co c~ - o - ~ ~ ~ o - - c~ cn u~ ~ o c~ o o c~ ~r ~ o o o co o o -- oo - e-- u~
~ O t~ C~> O O _ O CO
_ C C~ C ~ C ~ ; C I ~ ~ C~
2~3~7 T a b I e 6 Compounli Mel tlng No. ~lS(mJe) Polnt or I R (ICB r, cm~l) N~IR (ô) Deconposi tlon Polnt (~C) 3360 . 3350 . 3300. 3220, 1500.
V-l 187 113-116 1~170. 1340.1330.1290.1140.
1090.780. 680.580.510 1 55-1 58 337 0 . 3330 . 3130 . 2910 . 1590 .
V-2 221 Deco~Poscd 1560. 1460.1330.1270.
1160 . 910. 830. 140 . 690 . 590.
S50 . 510 3300.3250.3010.1610.1490. d 6 -DMSO:2.409(311.s) V-3 201 161-164 1300.1160.1140.920.820. 4.025br(211.s) 6.840 . 6gO . 600 . 520 (111. dd . 8 . 511z .1. 81iz) 6 . 901 (lll . s) I . 048 (111 .
d . 8 . 511z) 7 .148 (211. s) I . 349(111 .d .1. 811z) 33S0.3310.3250.1680.1630.
V-4 245 168-1l0 1590.1440.1350.1330.1~00.
1210. 11 10 . 11 60. 780 . lO0 . 600 1 22-1 29 3320 . 3270 . 2980 . 1l00 . 1 5gO .
V-5 259 Decomposed 1370.13Z0. 13ûO. 1270 .1250.
1150.1120.110,140.700 ~$2~3~7 Compounds available in a similar manner to Synthesis Example 2 are summarized in Table 7.
Table 7 X ' N __<' R I C H = N N H \r''''Y/ S 0 2 N H C O N H ~ O Z
~ N
CompoundR l R 2 X I X 2 z No .
I -21 CF3 H Cl13 OC~3 N
I -23 CF3 Cl CH3 OCI13 N
I-24 CF3 Cl OCH3 OCI13 N
1 -26 CF3 Cl13 OCH3 OCI13 N
I-21 CF3 COOC2Hs Cl13 OCH3 N
I-28 CF3 CoOC2Hs OCH3 OCI13 N
I -30 COOH Cl OCH3 OCI13 N
I -33 COOII CoOC2H5 CH3 OCI13 N
I -34 COOH COoC2Hs OCI13 OCI13 N
I -36CCI-CCICOOII Cl CH3 OCI13 N
I-40CCI~CCICOOH CoOC2Hs OCH3 OCH3 N
~2~'7 Formulation examples and tests will hereinafter be described. It should be borne in mind that the vehicles (diluents) and aids, their mixing ratios and e~fective components can vary in wide ranges, respectively.
Formulation ExamPle 1: Wettable Powder Compound (Compound No. I-7)50 parts A salt of ligninsulfonic acid 5 parts A salt of alkylsulfonic acid3 parts Diatomaceous earth 4~ parts The above ingredients are mixed and ground into a wettable powder. For application, it is diluted with water.
Formulation Example 2: Emulsion Compound (Compound No. I-ll)25 parts Xylene 65 parts Polyoxyethylene alkylaryl ether 10 parts The above ingredients are mixed intimately into an emulsion. For application, it is diluted with water.
Formulation Example 3: Granule Compound (Compound No. I-17)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 formula1ion, namely, a granule.
Test 1: TQst on Herbicidal Ac1:ivitY bv Foliar A~plication 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 10 g/ha and 100 g/ha over foliar parts of Arnsranthus retroflexus (Redroot pigweed), Bidens pilosa (Common blackjack), Sinapis arvensis (Wild mustard), Stellaria media (Common chickweed), Cassia obtusifolia (Sick~
lepod), Solanum nignlm (Black nightshade), Abutilon theophrasti (Velvetleaf), Convolvulus arvensis (Field bindweed), M~tricaria ~-hJ -il7~ (Wild chamomile), Setaria viridis (Green foxtail) Echinochloa frulDentaceum (Barnyard grass), Avena faeua(Wild oat), and Digitari~ adscendens (Henry crabgxass) which had been allowed to grow individually to 2-4 leaf stage in pots. Fourteen days 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.
Ranking system:
Herbicidal activit~
0: No effects z5 1: less than 3196 o~ total kill 2: 31-50% of total kill.
3: 51-70% of total kill 4: 71-90~ of total kill 5: 91-100~ of total kill 2~293d7 ~ O --~ O O c~ c~ O c~ O c~ o u~ o u~ O ~r o c~ o c~ o c.~ o ~ u~ u~
e_ o u~ o o o c~ c~ o o c~ ~ er In ~Y ~ O ~ O ~ ID U~ U~ U~
'~:
o _ ~ ~ o ~.r o Is~ o ~ ~ u~ u~ u~ L~
C~
C~
s C~
C~
o --c~
o.
L~
-c 2, - ~
~ o c~ ~
~ z T a b l e 8 ( C o n -' d ) CNO~POUnd AOsplgeat(g/ohna) A.r. B.P. S.a. S.m. C.o. S.n. A.t C.a. M.c. S.v. E.f. A.f. D.a.
1 -17105555555555 ~ 20 1005555555554440 ,c~
I -l9105555445553110 o~
1005555555554441 ~3 Note) h.r.:Amaranthus retroflexus S.n.:SolanuE nlgrum S.v.:Setaria vlridis B.p.:Bldens pilosa h.t.:Abutilon theophras~i E.f.:Echinochloa frumentaceum S.a.:Sinapis arvensis C.a.:Convolvulus arvensis A.f.:AYena fatua S.m.:Stellaria media ~.c.:Matricaria chamomilla D.a.:Digitaria adscendens C.o.:Cassia obtuslfolla ~$12~
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. ~ater suspensions of each test compound (con-centrations of the active ingredient: 1 ppm and 50 ppm) were. separately poured in an amount of 5 m~ per dish into the Petri dishes. Seeds of Am~ranthus ret~oflexus (Redroot pigweed), Bidens piloss~ (Common blac:kjack), ~atricaria chamom.illa (Wild rh~ ~~; le), S~lanum nigr~m (Black nightshade), Echinochloa oryzicola (Barnyard grass), Cyperus iria (Rice flatsedge) and Setaria viridis (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 28~C. 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.
Growth inhibition rate 0: No inhibition 1: less than 31%
2: ~1-50%
3: ~1-70%
4: 71-90%
2~2~
5: 91-100%
2.~2~3l~
Ta b I e 9 ComPoUn~ Concen-No. tratlon ~.r. B.p. M.c. S.n. E.o. C.l. S.v.
(ppm) 5~ 4444345 I-l 13343455 5~ 5454555 5032452 ~ 3 3 l~ ~
-- 3~ --T a b I e 9 (C o n t' d) Compound Conccn-No. traLlon A.r. B.p. M.c. S.n. E.o. C.l. S.v.
(ppm) 1 -16 1 1 O 3 2 ~ 2 3 3 4 4 ~ 4 5 SO 4 3 ~ 3 5 4 5 Note) A.r.:Amaranthus retroflexus E.o.:Echlnochloa oryzfcola B.P.:~ldens pilosa C.l.:Cyperus lrla M.c.:Matrlcarla chamomllla S.v.:Setarla vlrldls S.n.:Solanum nlgrum
Claims (13)
1. An N substituted-3-(substituted hydrazino)-benzenesulfonalnide derivative of the formula (I):
(I) wherein R1 is CF3, COOH or CC1=CC1COOH, R2 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.
(I) wherein R1 is CF3, COOH or CC1=CC1COOH, R2 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 derivative of claim 1, wherein Z is CH.
3. A derivative of claim 1, wherein Z is N.
4. A derivative of claim 1, whexein R1 is CF3, COOH
or CC1=CC1COOH, R2 is H, C1, CH3, COOCH3 or COOC2H5, Z is CH, X1 is OCH3, and X2 is OCH3.
or CC1=CC1COOH, R2 is H, C1, CH3, COOCH3 or COOC2H5, Z is CH, X1 is OCH3, and X2 is OCH3.
5. A derivative of claim 1, wherein R1 is CF3 or COOH, R2 is COOCH3, Z is CX, X1 is C1, and X2 is OCH3.
6. A derivative of claim 1, wherein R1 is CF3 or COOH, R2 is COOCH3, Z is CH, X1 is CH3 or OCH3, and X2 is CH3.
7. A derivative of claim 1, wherein R2 is C1 or COOCH3, Z is CH, X1 is OCH3, and X2 is OCH3.
8. A derivative of claim 1, wherein R1 is CF3 or COOH, R2 is COOCH3, Z is N, X1 is OCH3, and X2 is CH3 or OCH3.
9. A process for the preparation of an N-substituted-3-(substituted hydrazino)benzenesulfonamide derivative of claim 1, which comprises reacting a 3-(substituted hydrazino)benzenesulfonamide derivative of the formula (II):
(II) wherein R1 and R2 have the same meanings as defined in claim 1, with a phenylcarbamate derivative of the following formula (III):
(III) wherein Z, X1 and X2 have the same meanings as defined in claim 1.
(II) wherein R1 and R2 have the same meanings as defined in claim 1, with a phenylcarbamate derivative of the following formula (III):
(III) wherein Z, X1 and X2 have the same meanings as defined in claim 1.
10. A 3-(substituted hydrazino)benzenesulfonamide derivative of the following formula (II):
(II) wherein R1 and R2 have the same meanings as defined in claim 1.
(II) wherein R1 and R2 have the same meanings as defined in claim 1.
11. A 3-hydrazinobenzenesulfonamide derivative of the following formula (V'):
(V') wherein R2' is H, C1-C3 alkyl or C1-C4 alkoxycarbonyl.
(V') wherein R2' is H, C1-C3 alkyl or C1-C4 alkoxycarbonyl.
12. A herbicidal composition comprising a herbicidally effective amount of an N-substituted-3-(substituted hydrazino)benzenesulfonamide derivative of claim 1 and an agronomically-acceptable vehicle or diluent.
13. A method for the control of monocotyledonous or dicotyledonous weeds on an agricultural or non-agricultural land, which comprises applying to the agricultural or non-agricultural land an N-substituted-3-(substituted hydrazino)benzenesulfonamide derivative of claim 1 or a herbicidal composition comprising said derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2029347 CA2029347C (en) | 1990-11-06 | 1990-11-06 | N-substituted-3-(substituted hydrazino)-benzenesulfonamide derivatives, preparation process thereof and herbicidal compositions |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2029347 CA2029347C (en) | 1990-11-06 | 1990-11-06 | N-substituted-3-(substituted hydrazino)-benzenesulfonamide derivatives, preparation process thereof and herbicidal compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2029347A1 CA2029347A1 (en) | 1992-05-07 |
| CA2029347C true CA2029347C (en) | 1997-12-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2029347 Expired - Fee Related CA2029347C (en) | 1990-11-06 | 1990-11-06 | N-substituted-3-(substituted hydrazino)-benzenesulfonamide derivatives, preparation process thereof and herbicidal compositions |
Country Status (1)
| Country | Link |
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| CA (1) | CA2029347C (en) |
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1990
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