CA1242720A - 1-(2-oxyaminosulphonylphenylsulphonyl)-3-triazinyl- ureas - Google Patents
1-(2-oxyaminosulphonylphenylsulphonyl)-3-triazinyl- ureasInfo
- Publication number
- CA1242720A CA1242720A CA000515170A CA515170A CA1242720A CA 1242720 A CA1242720 A CA 1242720A CA 000515170 A CA000515170 A CA 000515170A CA 515170 A CA515170 A CA 515170A CA 1242720 A CA1242720 A CA 1242720A
- Authority
- CA
- Canada
- Prior art keywords
- fluorine
- chlorine
- alkyl
- substituted
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D521/00—Heterocyclic compounds containing unspecified hetero rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
ABSTRACT
Herbicidally active novel 1-(2-oxyaminosulphonylphenyl-sulphonyl)-3-triazinyl ureas of the formula
Herbicidally active novel 1-(2-oxyaminosulphonylphenyl-sulphonyl)-3-triazinyl ureas of the formula
Description
The invention relates to new 1~(2-oxyaminoxulphonyl-phenylsulphonyl)-3-triazinyl-ureas, processes for their prepara-tion and their use as herbicidesr It is known that certain l-arylsulphonyl-3-heteroaryl-ureas, such as for example, 1-(2-methoxy-phenyl-sulphonyl)-3-(4,6,-dimethyl-pyrimidin-2-yl)-urea, have a herbicidal action. However, the action of these compounds is not always completely satisfact-ory (compare U.S. Patent Specification 4,169,719).
New 1-(2-oxyaminosulphonylphenylsulphonyl)-3-triazinyl-ureas of the general formula (I) ~ S02-NH-OR R2 SO2-NH-C-NH ~
O ~, in which Rl represents an unsubstituted or substituted radical selected from the group consis-ting of Cl-C12 alkyl (l~nich may be substituted by fluorine, chlorine, cyano, Cl-C4- alkoxy,~Cl-C4-alkylthio, Cl-C4-alkyl-sulphinyl, Cl-C4-alkylsulphonyl, Cl-C4-alkylcarbonyl, Cl-C4-alkoxy-carbonyl, Cl-C4-alkyl-amino-carbonyl or di-(Cl-C4-alkyl)-amino-carbonyl), C3-C6-alkenyl (which may be substituted by fluorine, chlorine or bromine), C3-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-Cl-C2-alkYl, phenyl-C1-C2-alkyl (which may be substituted by fluorine, chlorine, ni ro, cyano, Cl-C4 alkyl, Cl-C4-alkoxy or Cl-C4-alkoxy-carbonyl) ~2~
and benzhydryl or phenyl (which each may be substituted by fluorine, chlorine, nitro, cyano, Cl-C4-alkyl, trifluoromethyl, Cl-C4-alkoxy, ; Cl-C2-fluoroalkoxy, Cl-C4-alkythio, trifluoromethylthio or Cl-C4-alkoxy-carbonyl).
R represents fluorine, chlorine, bromine, hydroxyl, cyclopropyl or Cl-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], or represents Cl-C4-alkoxy ~which is optionally substituted by fluorine and/or chlorine], or represents Cl-C4-alkylthio [which is optionally substituted by fluorine and/
or chlorine] or amino, or represents Cl-C4-alkyl- or di-(Cl-C4-alkyl)-amino [which are optionally substituted by fluorine] and R represents fluorine, chlorine, bromine, hydroxyl, cyclopropyl or C1-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], or represents Cl-C4-alkoxy ~which is optionally substituted by fluorine and/or chlorine], or represents Cl-C4-alkylthio [which is optionally substituted by fluorine and/
or chlorine] or amino, or represents Cl-C4-alkyl- or di-(Cl-C~-alkyl)-amino [which are optionally substituted by fluorine], o:r a salt thereof formed with a strong base have now been found.
. ~ - 2 -231~9-6319 The new compounds of the formula (Il are obtained by a process in which (a~ benzodisultams of the formula (II) ~ /~ ~ (II) in which R , R2 and R3 have the above-mentioned meanings, are reacted with water, lf appropriate in the presence of bases or acids and lf appropriate in the presence of diluents, or (b) benzene-1,2-disulphonic acid dichloride of the formula (III) O2-Cl (III) ~ S02-Cl is reacted with oxyguanidine derivatives of the formula (IV) R ~ R2 N--_~
~ -NH ~/ ~N (~V) N~Y R
in which R , R , R have the above-mentioned meaning, in the the presence of acid acceptors and if appropriate in the presence of diluents ~lst stage), and the compounds thereby obtained, of the formula (II), are reacted -without intermediate isolation - with water if appro-priate in the presence of bases or acids and if appropriate in the presence of diluents (2nd stage~.
.~
7~3 The new 1-~2-oxyaminos.ulphonylphenylsulphonyl)~3-triazinyl-ureas of the formula (I) are distinguished by a powerful herbicidal activity.
Surprisingly, the new compounds of the formula (I) show a considerably better herbicidal action than urea derivatives of the same type of action which are already known.
The invention preferably relates to compounds of the formula (I) in which R2 represents fluorine, chlorine, hydroxyl, cyclopropyl or methyl [which is optionally substi-tuted by fluorine and/or chl.orine], or represents Cl-C3-alkoxy [which is optionally sub-stituted by fluorine and/or chlorine], or represents Cl-C3-alkyl-thio [which is optionally substituted by fluorine and/or chlorine]
or amino or represents Cl-C3-alkyl- or di-(Cl-C3-alkyl)-amino [which are optional.ly substituted by Eluorine] and R represents fluorine, chlorine, hydroxyl~ cyclopropyl, methyl [which is optionally substituted by fluorine and/or chlorine], or represents Cl-C3-alkoxy [which is optionally sub-stituted by fluorine and/or chlorine].
-~ - 4 -~:~ J
t~ 23189-6319 -4a-or represents Cl-C3-alkylthio [which is optionally substituted by fluorine and/or chlorine] or amino, or represents Cl-C3-alkyl-or di-(Cl-C3-aklyl)-amino [which are op-tionally substituted by fluorine].
The invention particularly relates to compowlds of the formula (1 in which Rl represents Cl-Cg-alkyl ~which is optionally substi-tuted by fluorine or chlorine], C3-C4-alkenyl, Cl-C2-alkoxy-carbonylmethyl, phenyl, phenethyl or benzyl [which is optionally substituted by fluorine, chlorine, nitro, cyano, methyl, methoxy or methoxy-carbonyl], R represents chlorine, methyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, e-thylamino, dimethylamino or diethylamino and R3 represents chlorine, methyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, ethylamino, diemethyl-amino or diethylamino.
The chemical reaction which proceeds in the preparation process according to the invention described above under (a) can be outlined, for example, by the ~ . ~
f~
following equat;on:
CH;~CH~<3 ~52 N~ N~
NH~' 'iN 4H20 --~;02-N 3~
S02-N}~-0-~ ~2C~2--O
@~ CH
S2 ~ - C -~' S The reactions which proceed in the preparation process accord;ng to the invention described above under (b~ can be outlined, for example, by the following equation:
C5~1 1 ~iO;-~ H3 !;Oz ~ C 1 CH3 ~ r ~ 2 ~> N~i~N 1 S~2--- CM ~
H20 ~2 NH C5Hl 1 CH
S2 - NH- C-N}~
O ~
Formula ~II) provides a general definition of the Le A Z3 904 z~
benzodisultams to be used as starting substances in pro-cess (a) according to the invention.
In formula (II), R1, R2 and R3 preferably or particularly have the same meanings as have been mentioned above as preferred or as particularly preferred in the context of the substituent definition for formula (I).
Examples of the starting substances of the formula (II) are listed in the following Table 1 ORl R2 ~ SO2- ~ ~ tII) Table 1 Fxamples of start;ng substances of the formula (II) __ ~1 R2 R3 . . ~
-CH~CH-CH2 -OCH3 -OCH3 ~3 -OCH3 -OC2~5 -C~Hg-n -OCH3 -VC2H5 ~CH3 -OCH3 -N(C2H5)2 -C3H7-n -SCH~ -NH-C2H5 -C~H17 n -CH3 -OCH3 Le A_23 904 : ..
~2~
Table 1 - Continuat;on -E~2 R ~
. .
- CH2~ - c~3 - OCH3 - CH3 - VC~13 - SCH3 - CH3 - C~13 OC 2H5 - t~H2~3 - CH3 OC 2H5 -C~3 -SCH3 -NHC2115 -CH3 C~5 -OCH3 -C~3 -CH3 -C~3 -CH2-CH=C2~2 -C~3 -C~3 The compounds of the formula ~II) to be used in process (a) accord;ng to the invention have not previously been described ;n the literature. The compounJs of the 5 formula ~II) are obtained by a process ;n ~h;ch benzene-1~2~disulphonic acid dichloride of the formula (III) 5O2-~l (III) 502-~ 1 is reacted with oxyguan;d;ne derivatives of the formula (IV) Le A 23 90 ___ ~24~7;2~
RlD
~ -NH ~' ~ (IV) N~ N-~- R3 in which R1, R~ and R3 have the abovementioned meanings, in the presence of acid acceptors~ such as, for exampLe, pyridine or diazabicyclooctane (DABCO), and if appropriate in the presence of diluents, such as, for example, methyl-ene chloride, chloroform, tetrahydrofuran or dioxane, at temperatures between -30C and ~50C.
~orking up can be carried out by customary methods, 10 for example by concentrating the mixture, taking up the residue in methylene chloride, ~ashing the mixture with dilute hydrochloric acid and ~ater and separating off, dry-ing, filtering and c~oncentrating the organic phase, the products of the formula tII) remaining in the residue.
The benzene-1,2-disulphonic acid dichloride of the formula (III) to be used as the Starting substance is al-ready kno~n (compare J. Org. Chem. 31, (1966), 3289-3292).
Formula (IY~ provides a general definition of the oxyguanidine derivatives turthermore to be used as start-ing substances. In formula (IV), R1~ R2 and R3 prefer-ably or particularly hav the same meanings as have been given above as pre~erred or as particularly preferred in the context of the substituent def;nition for formula (I).
Examples ~h;ch may be mentioned of starting sub-stances of the formula (IV) are: N'-(4,6-dimethyl-s-tri-az;n-2-yl)-, N'-(4-methoxy-6-methyl-s-triazin-2-yl)-, N'-(4-ethoxy-6-~ethyl-s-triazin-2-yl)-, N'-(4,6-dimethoxy-s-triazin-2-yl)-, N'-(4,6-diethoxy-s-tr;azin-2-yl)-, N'-(4-ethoxy-6-methoxy-s-triazin-2-yl~-, N'-(4-methyl-6-methyl-thio-s-triazin-2-yl)-, N'-(4-ethylthio 6-methyl-s-triazin-
New 1-(2-oxyaminosulphonylphenylsulphonyl)-3-triazinyl-ureas of the general formula (I) ~ S02-NH-OR R2 SO2-NH-C-NH ~
O ~, in which Rl represents an unsubstituted or substituted radical selected from the group consis-ting of Cl-C12 alkyl (l~nich may be substituted by fluorine, chlorine, cyano, Cl-C4- alkoxy,~Cl-C4-alkylthio, Cl-C4-alkyl-sulphinyl, Cl-C4-alkylsulphonyl, Cl-C4-alkylcarbonyl, Cl-C4-alkoxy-carbonyl, Cl-C4-alkyl-amino-carbonyl or di-(Cl-C4-alkyl)-amino-carbonyl), C3-C6-alkenyl (which may be substituted by fluorine, chlorine or bromine), C3-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-Cl-C2-alkYl, phenyl-C1-C2-alkyl (which may be substituted by fluorine, chlorine, ni ro, cyano, Cl-C4 alkyl, Cl-C4-alkoxy or Cl-C4-alkoxy-carbonyl) ~2~
and benzhydryl or phenyl (which each may be substituted by fluorine, chlorine, nitro, cyano, Cl-C4-alkyl, trifluoromethyl, Cl-C4-alkoxy, ; Cl-C2-fluoroalkoxy, Cl-C4-alkythio, trifluoromethylthio or Cl-C4-alkoxy-carbonyl).
R represents fluorine, chlorine, bromine, hydroxyl, cyclopropyl or Cl-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], or represents Cl-C4-alkoxy ~which is optionally substituted by fluorine and/or chlorine], or represents Cl-C4-alkylthio [which is optionally substituted by fluorine and/
or chlorine] or amino, or represents Cl-C4-alkyl- or di-(Cl-C4-alkyl)-amino [which are optionally substituted by fluorine] and R represents fluorine, chlorine, bromine, hydroxyl, cyclopropyl or C1-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], or represents Cl-C4-alkoxy ~which is optionally substituted by fluorine and/or chlorine], or represents Cl-C4-alkylthio [which is optionally substituted by fluorine and/
or chlorine] or amino, or represents Cl-C4-alkyl- or di-(Cl-C~-alkyl)-amino [which are optionally substituted by fluorine], o:r a salt thereof formed with a strong base have now been found.
. ~ - 2 -231~9-6319 The new compounds of the formula (Il are obtained by a process in which (a~ benzodisultams of the formula (II) ~ /~ ~ (II) in which R , R2 and R3 have the above-mentioned meanings, are reacted with water, lf appropriate in the presence of bases or acids and lf appropriate in the presence of diluents, or (b) benzene-1,2-disulphonic acid dichloride of the formula (III) O2-Cl (III) ~ S02-Cl is reacted with oxyguanidine derivatives of the formula (IV) R ~ R2 N--_~
~ -NH ~/ ~N (~V) N~Y R
in which R , R , R have the above-mentioned meaning, in the the presence of acid acceptors and if appropriate in the presence of diluents ~lst stage), and the compounds thereby obtained, of the formula (II), are reacted -without intermediate isolation - with water if appro-priate in the presence of bases or acids and if appropriate in the presence of diluents (2nd stage~.
.~
7~3 The new 1-~2-oxyaminos.ulphonylphenylsulphonyl)~3-triazinyl-ureas of the formula (I) are distinguished by a powerful herbicidal activity.
Surprisingly, the new compounds of the formula (I) show a considerably better herbicidal action than urea derivatives of the same type of action which are already known.
The invention preferably relates to compounds of the formula (I) in which R2 represents fluorine, chlorine, hydroxyl, cyclopropyl or methyl [which is optionally substi-tuted by fluorine and/or chl.orine], or represents Cl-C3-alkoxy [which is optionally sub-stituted by fluorine and/or chlorine], or represents Cl-C3-alkyl-thio [which is optionally substituted by fluorine and/or chlorine]
or amino or represents Cl-C3-alkyl- or di-(Cl-C3-alkyl)-amino [which are optional.ly substituted by Eluorine] and R represents fluorine, chlorine, hydroxyl~ cyclopropyl, methyl [which is optionally substituted by fluorine and/or chlorine], or represents Cl-C3-alkoxy [which is optionally sub-stituted by fluorine and/or chlorine].
-~ - 4 -~:~ J
t~ 23189-6319 -4a-or represents Cl-C3-alkylthio [which is optionally substituted by fluorine and/or chlorine] or amino, or represents Cl-C3-alkyl-or di-(Cl-C3-aklyl)-amino [which are op-tionally substituted by fluorine].
The invention particularly relates to compowlds of the formula (1 in which Rl represents Cl-Cg-alkyl ~which is optionally substi-tuted by fluorine or chlorine], C3-C4-alkenyl, Cl-C2-alkoxy-carbonylmethyl, phenyl, phenethyl or benzyl [which is optionally substituted by fluorine, chlorine, nitro, cyano, methyl, methoxy or methoxy-carbonyl], R represents chlorine, methyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, e-thylamino, dimethylamino or diethylamino and R3 represents chlorine, methyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, ethylamino, diemethyl-amino or diethylamino.
The chemical reaction which proceeds in the preparation process according to the invention described above under (a) can be outlined, for example, by the ~ . ~
f~
following equat;on:
CH;~CH~<3 ~52 N~ N~
NH~' 'iN 4H20 --~;02-N 3~
S02-N}~-0-~ ~2C~2--O
@~ CH
S2 ~ - C -~' S The reactions which proceed in the preparation process accord;ng to the invention described above under (b~ can be outlined, for example, by the following equation:
C5~1 1 ~iO;-~ H3 !;Oz ~ C 1 CH3 ~ r ~ 2 ~> N~i~N 1 S~2--- CM ~
H20 ~2 NH C5Hl 1 CH
S2 - NH- C-N}~
O ~
Formula ~II) provides a general definition of the Le A Z3 904 z~
benzodisultams to be used as starting substances in pro-cess (a) according to the invention.
In formula (II), R1, R2 and R3 preferably or particularly have the same meanings as have been mentioned above as preferred or as particularly preferred in the context of the substituent definition for formula (I).
Examples of the starting substances of the formula (II) are listed in the following Table 1 ORl R2 ~ SO2- ~ ~ tII) Table 1 Fxamples of start;ng substances of the formula (II) __ ~1 R2 R3 . . ~
-CH~CH-CH2 -OCH3 -OCH3 ~3 -OCH3 -OC2~5 -C~Hg-n -OCH3 -VC2H5 ~CH3 -OCH3 -N(C2H5)2 -C3H7-n -SCH~ -NH-C2H5 -C~H17 n -CH3 -OCH3 Le A_23 904 : ..
~2~
Table 1 - Continuat;on -E~2 R ~
. .
- CH2~ - c~3 - OCH3 - CH3 - VC~13 - SCH3 - CH3 - C~13 OC 2H5 - t~H2~3 - CH3 OC 2H5 -C~3 -SCH3 -NHC2115 -CH3 C~5 -OCH3 -C~3 -CH3 -C~3 -CH2-CH=C2~2 -C~3 -C~3 The compounds of the formula ~II) to be used in process (a) accord;ng to the invention have not previously been described ;n the literature. The compounJs of the 5 formula ~II) are obtained by a process ;n ~h;ch benzene-1~2~disulphonic acid dichloride of the formula (III) 5O2-~l (III) 502-~ 1 is reacted with oxyguan;d;ne derivatives of the formula (IV) Le A 23 90 ___ ~24~7;2~
RlD
~ -NH ~' ~ (IV) N~ N-~- R3 in which R1, R~ and R3 have the abovementioned meanings, in the presence of acid acceptors~ such as, for exampLe, pyridine or diazabicyclooctane (DABCO), and if appropriate in the presence of diluents, such as, for example, methyl-ene chloride, chloroform, tetrahydrofuran or dioxane, at temperatures between -30C and ~50C.
~orking up can be carried out by customary methods, 10 for example by concentrating the mixture, taking up the residue in methylene chloride, ~ashing the mixture with dilute hydrochloric acid and ~ater and separating off, dry-ing, filtering and c~oncentrating the organic phase, the products of the formula tII) remaining in the residue.
The benzene-1,2-disulphonic acid dichloride of the formula (III) to be used as the Starting substance is al-ready kno~n (compare J. Org. Chem. 31, (1966), 3289-3292).
Formula (IY~ provides a general definition of the oxyguanidine derivatives turthermore to be used as start-ing substances. In formula (IV), R1~ R2 and R3 prefer-ably or particularly hav the same meanings as have been given above as pre~erred or as particularly preferred in the context of the substituent def;nition for formula (I).
Examples ~h;ch may be mentioned of starting sub-stances of the formula (IV) are: N'-(4,6-dimethyl-s-tri-az;n-2-yl)-, N'-(4-methoxy-6-methyl-s-triazin-2-yl)-, N'-(4-ethoxy-6-~ethyl-s-triazin-2-yl)-, N'-(4,6-dimethoxy-s-triazin-2-yl)-, N'-(4,6-diethoxy-s-tr;azin-2-yl)-, N'-(4-ethoxy-6-methoxy-s-triazin-2-yl~-, N'-(4-methyl-6-methyl-thio-s-triazin-2-yl)-, N'-(4-ethylthio 6-methyl-s-triazin-
2-yl)-, N'(4-methoxy-6-methylthio-s-triazin-2-yl)-, N'-(4-ethoxy-6-methylthio-s-triazin-2-yl)-, N'-(4-ethylthio-6-Le A 23 904 ~Z~72~3 methoxy-s-triazin-2-yl)-, N'-(4-ethoxy-6-ethylthio-s-triazin-2-yl)-, N'-(4,6-bis-methylthio-s-tr;azin-2-yl)-, N'-4,6-(bis-ethylthio-s-triazin-2-yl)-, N'-(4-methyL-6-methylamino-s-triazin-2-yl)-, N'-(4-ethylamino-6-methyl-s-triazin-2-yl)-, N'-(4-dimethylamino-6-methyl-~-triazin-2-yl)-, N'-(4-diethylamino-6-methyl-s-triazin-2-yl)~, N'-(b-methoxy-6-methylamino-s-triazin-2-yl)-, N'-(4-ethyl-amino-~-methoxy-s-triazin-2-yl)-, N'-(4-d;methylamino-6-methoxy-s-triazin-2-yl)-~ N'-(4-diethylamino-6-methoxy-s-triazin-2-yl)-, N'-(4-ethoxy-6-methylamino-s-triazin-2-yl)-, N'-(4-ethoxy-6-ethylamino-s-triazin-2-yl)-, N'-(4-d;methylamino-6-ethoxy-s-triazin-2-yl)-, N'-(4-diethyl-amino-6-ethoxy-s-triazin-2-yl)-, N'-(4-methylamino-6-methylthio-s-triazin-2-yl)-~ N'-(4-ethylamino-6-methyl-thio-s-triazin-2-yl)-, N'-(4-dimethylamino-6-methylthio-s-triaz;n-2-yl)-, N'-(4-diethylamino-6-methylthio-s-tri-azin-2-yl) , N'-(4-ethylthio-6-methylamino-s-triazin-2-yl)-, N'-(4-dimethylamino-6-ethylthio-s-tria~in-'-yl)- and N'-(4-diethylamino-6-ethylthio-s-triazin-2-yl)-N"-methoxy-guanidine, -N"-ethoxy-guanidine, -N"-propoxy-guanid;ne, -N"-isopropoxy-guanidine, -N"-butoxy-guanidine, -N"-iso-butoxy-guanidine, -N"-sec.-butoxy-guanidin2, -N"-pentoxy-guanidine, -N"-isopentoxy-guanidine, -N"-hexyloxy-guani-dine, -N"-octyloxy-guanidine, -N"-allyloxy-guanidine, -N"-~2-chloro-ethoxy)-guanidine, -N"-~2-fluoro-ethoxy)-guani-dine, -~"-(2-chLoro-propoxy)-guanidine, -N"-(2-~lu~ro-propoxy)-guan;dine, -N"-(3-chloro-propoxy)-guanidine~ -N"-(4-chloro-hutoxy)-guanidine~ -N"-methoxycarbonylmethoxy-guanidine, -N"-ethoxycarbonylmethoxy-guanidine, -N"-~1-methoxy-carbonylethoxy)-guanid;ne, -N"-(1-ethoxycarbonyl-ethoxy)-guanidine, -N"-dimethylamino-carbonyl-methoxy-guanidine, -N"-(2-phenyl-ethoxy)-guanidine, -N"-phenoxy-guanidine, -N"-(4-me~hylbenzyloxy)-guanidine, -N"-(4-fluorobenzyloxy)-guanidine, -N"-(4-chloro-benzyloxy)-guanidine, -N"-(4-nitro-benzyloxy)-guan;dine, -N"-(2,6-dichloro-ben yloxy)-guanidine, -N"-(4-methoxycarbonyl-Le A 23 9~4 72~
benzyloxy)-guanidine and -N"-(4-ethoxycarbonyl-benzyloxy)-guanidine~
The starting substances of the formula (IY) are known ;n some cases (compare European Patent A-121,082).
The compounds of the formula (IV) are obta;ned by a process in wh;ch cyanoaminotr;az;ne der;vatives of the for~ula (V) ~2 N~-N ~ ~ ~ ~V) . R3 ;n wh;ch R2 and R3 have the abovement;oned mean;ngs, are reacted ~ith hydroxylamine derivatives of the formula (VI) H2N-OR1 (VI) ;n wh;ch R has the abovement;oned mean;ng, or hydrochlorides thereof, ;f appropriate ;n th~ presence of d;luents, such as, for example, ethanol, propanol or butanol, a~ temperatures between 20C and 150C, and, if appropriate, the react;on products are treated ~ith acid acceptors, such as, for example, ammoniaO potassium carbonate or sod;~m hydroxide.
The cyanoaminotriaz;ne derivatives of ~he formula (V) are known (compare DE-OS (German Publ;shed Spec;f;ca-t;on) 3,334,455).
The compounds of the formula ~Y) are essent;ally obtained by the following synthesis routes:
(a1) ~y reactions of alkali metal or alkaline earth metal salts of cyanamide - such as, for example, sodium cyanamide or calcium cyanamide - with chLorotr;azines of the formuLa (VII) Le A 23 904 ~l24L~7~0 Cl~'N~N (VII) in which R2 and R3 have the abovementioned meanings, if appropriate in the presence of acid acceptors and if appropriate in the presence of diluents, such as~ for example, ethanol, acetone, acetonitrile, dimethylform-amide, dimethylsulphoxide or water, at temperatures bet-ween -10C and 100C~ After the mixture has been con-centrated and the residue has been dissolved in water, the cyanoaminotr;azine derivatives of the formula IV) can be precipitated by acidification, for example with hydro-chloric acid, and isolated by filtration ~ith suction.
The chlorotriazines of the formula (VII) to be used as starting substances for the preparation process described above under (a1) for the cyanoaminotriazine der;vatives of ~he formula (V) are known and/or can be prepared by processes which are known per se (compare U.S.
Patent Specification 3,154,5~7 and U.S. Patent Specifica-tion 4,160,037).
In another process, cyanoaminotriazine derivat;ves of the formula (V) are obtained by a procedure in which (a2) dichlorotriazines of the formula (VIIa) N--~ (VIIa) Cl ~' ~N
~ ~3 in which R3 has the abovementioned meaning, are reacted with aLkali metaL salts or aLkaLine earth metaL saLts of cyanamide, such as, for example, with di-sodium cyanamide, in the presence of a diLuent, such as, Le A 23 904 ~2~
for example, water, at temperatures between -10C and +50C, ancl the metal salt thereby obtained of the mono-chloro-cyanoaminotriazine of the formula ~Va) ~1 NC-N~ ~ ~N (Va) ;n ~hich R3 has the abovementioned meaning~
i5 converted into the free monochloro-cyanoaminotriazine of the formula (Va~ with an acid, such as~ for exa~pler hydrochloric acid.
The corresponding cyanoaminotriazines of the formula (V) in which R2 represents alkoxy, alkylthio, alkylamino or dialkylamino can be prepared from the mono-chloro-cyanoaminotriazines of the formula ~Va) by reaction with alcohols or alkanethiols or ~ith alkali ~etal salts of these compounds or with monoalkyl- or dialkyl-amines.
The hydroxylamine derivatives of the formula (VI) furthermore to be used as starting substances are likewise known and can be prepared by processes which are known per se (compare Chem. Pharm~ 8ull. 15 (1967), 345~ ~ulln Soc. Chim. France 1958, 664; Synthesis 1976, 682; J. Chem.
Soc. 1930, 228 and HeLv. Chim~ Acta 45 ~1~62)~ 1387).
The benzene-1,2 disulphonic acid chloride of the formula (III) ~o be used as the starting substance in process (b) according to the invention is already known (compare J. Org. Chem. 31, (1966), 3289 - 3292).
Formula (IV) provides a general detinition of the oxyguanid;ne derivatives to be used as starting substances in process (b) according to the invention. In formula (IV)~ R1, R2 and R3 preferably or particularly have the same mean;ngs as have been g;ven above as preferred or as partiçularly preferred in the context of the subst;tuent definition for formula (I).
Le A 23 90~
~2~
- ~3 -Examples of compounds of the formula (IV) have already been given above in connection with the descrip-t;on of the starting substances for process (a). The preparation of the starting substances of the formula (IV) has already been described above in connection with the description of the starting substances for process ~a).
Process (a) according to the ;nvention for the preparation of the new compounds of the formula (I~ is preferably carried out in ~ater as the solvent. Other possible diluents are all the inert organic solvents, but preferably aprot;c polar solvents. These include, for example, ketones, such as, for example, acetone and methyl ethyl ketone, nitriles, such as, for example, aceton;~r;le and prop;on;trile, d;methylsulphox;de, sulpholane~ 1,2-d;methoxyethane and dioxane.
Process (a) is preferably carried out in the pre-sence of bases or acids. Preferred possible bases are alkali metal or alkaline earth metal hydroxides~ such as, for example, sodium hydroxide, po~ass;um hydrox;de and calcium hydroxide, tert;ary am;nes, such as~ for example7 triethylam;ne, N,N-dimethylan;line and ~,N-d;methyl-benzylam;ne, and n;trogen-heterocyclic compounds, such as, for example, pyridine or diazab;cyclooctane (DABCO~.
Su;table acids are, ;n particular~ mineral ac;ds, such as, for example, hydrochlor;c acid, hydrobromic acid or sul-phur;c ac;d.
The react;on temperatures can be var;ed ~ith;n a substantial range in process (a) according to the inven-t;on. The react;on is in general carried out between 0C and +100C, preferably between 10C and ~80C.
Process (a) according to the invention is in general carried out under normal pressure.
For carrying out process (a), in general between 1 and 100 moles~ preferably between 5 and 50 moles~ of water ancl, ;f appropr;ate, between 1 and 3 moles, prefer-ably between 1 and 2 moles, of a base or acid are employed Le _ 904 ~2'7~
per mole of benzodisultam of the formula (Il).
The reaction components are usually brought to-gether at room temperature and the reaction mixture is stirred until the reaction has ended.
Working up can be carried out in the customary manner; for example by acidifying the reaction m;xture -for example with hydrochloric acid - and concentrating it to about half the volume and isolating ~he product of the formula (1~ obtained as crystals by filtration ~ith suction.
Process (b) according to the invention for the preparation of the ne~ compounds of the ~ormula (I) is preferably carried out using diluents. Possible diluents are virtually all the inert organic, preferably aprotic polar solvents. These include optionally substituted hydrocarbons, such as, for example, methylene chloride, chloroform, 1,2-dichloroethane, toluene, xylene and chlorobenzene, nitriles, such as, for example, aceto-nitrile and propion;trile, ethers, such as~ for example~
1,2-dimethoxyethane, tetrahydrofuran and dioxane, and dimethylformamide~ dimethylacetamide, dimethylsulphoxide, sulpholane, pyridine and 2-methyl-5-ethyl-pyridine.
Virtually all the acid-binding agents ~h;ch can usually be employed can be used as acid acceptors in ~he first stage of process (b~. These incLude, in particular, alkali metal and alkaline earth ~etal hydroxides, alkali metal and alkaline earth metal hydrides~ organometallic compounds, such as butyl-l;thium, and furthermore ali-phatic~ aromatic or heterocyclic amines, such as trimethyl-amine, triethylaminer N,N-dimethylaniline, N,N-dimethyl-benzylamine, diazabicyclooctane tDABCo), diazabicyclo-nonene ~DBN), diazabicycloundecene (DBU), pyridine, 2-methyl-5-ethyl-pyridine and 4-dimethylaminopyridine. The corresponding statements made above fQr process (a) apply to the bases or acids to be used, if appropr;ate, in the second stage of process ~b).
Le A 23 904 " 7 ~
~: ~ ~
The reaction temperatures can be varied within a substantial range in process (b). The reaction is in general carried out between -80C and ~100C, preferably between -30C and +50C. Process tb) according to the invention is in general carried out under normal pressure.
For carrying out process (b), in genPral between 1 and 2 moles, preferably between 1nO and 1.2 moles~ of benzene-1,2-disulphonic acid dichloride of the formula (III) and 2 to 5 moles, preferably 2 to 3 moles, of an acid acceptor and, subsequently, between 1 and 100 moles, preferably between 5 and 50 ~oles, of ~a~er and, if appropriate, between 1 and 3 moles, preferably between 1 and 2 moles, of a base or acid are employed per mole of oxyguanidine derivative of the formula (IV) in the first stage.
The reaction components are usually brought to-gether at room temperature or with external cooling and the reaction mixture is stirred until the reaction has ended.
Working up can be carried out in the customary manner, for example by concentrating the reaction mixture, if appropriate, and/or diluting i~ ~ith an organic solvent which is v;rtually immiscible ~ith w~ter~ such as, for example~ methylene chloride, washing it with dilu~e hydro-chloric acid and with ~ater and drying, f;ltering and concentrating ito The produc~ of the formula (I) ~hich remains in ehe residue is made to crystallize by tritura-tion with a suitable organic solvent, such as, for example, ethanol, and isolated by filtration with suction.
The active compounds according to the invention can be used as defoliants, desiccants, agents for destroy-ing broad-leaved plants and, especially, as weedkillers.
8y weeds, in the broadest sense, there are to be under-stood all plants which grow in locations where they are undesired~ ~hether the substances according to the inven~
tion act as total or selective herbicides depends essen-Le A 23 904 tialLy on the amount used.
The act;ve compounds according to the invention can be used, for example, in connection with the ~ollowing plants:
Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinssga~ Cheno-podiumr Urtica~ Senecio, AmaranthusO Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesban;a, Ambrosia, Cir-sium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Linder-nia, Lamium, Veronica, Abutilon, Emex, Datura, Viola,Galeopsis, Papaver and Centaurea.
Dicotyledon cultures of ~h~ genera: Gossypiu~, Glycine, Beta, Daucus, Phaseolus~ Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycop~rsicon, Arachis, ~rassica, Lac-tuca~ Cucumis and Cucurbita.Monocotyledon weeds of the genera- Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, 8rachiaria, Lolium, ~romus, Avena, Cyperus~ Sorghum, Agro-pyron, Cynodon, Monochoria, Fimbr;stylis, Sagittaria, Eleocharis~ Scirpus, Paspalum, Ischaemum, Sphenoclea, DactyLocten;um~ Agr~stis, Alopecurus and Apera~
Monocotyledon cultures of the genera: Oryza, Zea~ Triti-cum, Hord~um, Avena, Secale, Sorghum, Panicum~ Saccharum, Ananas~ Asparagus and Allium.
However, the use of the active compounds accord;ng to the invention is ;n no way restricted to these genera, but also extends in ~he same manner to other plants.
The compounds are suitable~ depending on the con-centration, for the total combating of ~eeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the com-pounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plan~ings, orchards, vineyards~ citrus groves, nut orch-ards, banana plantations~ coffee plantations, tea plantations, rubber plantations, oil paim plantations, cocoa Le A 23 904 ,~
~2~26~
plantations, soft fruit plantings and hopfields, and for the selective combating of weeds in annual cultures.
The active compounds according to the invention are suitable for combating mono- and dicotyledon weeds in monocotyledon crops by the pre-emergence and post-emer-gence method.
The active compounds can be converted to the cus-tomary formuLations~ such as solutions, emulsions, wett-able powders, suspensions, powders, dusting agents, pastes~ soluble powders~ granules, suspension-emulsion concentrates, natural and synthetic materials impr2gnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in known mannerS
for e~ample by mix;ncg the active compounds with ex~enders, that is liquid solvents and/or solid carriers, optionally ~ith the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or foam-forming agents.
In the case of the use of water as an extender, organic solvents can, for example, also be used as auxi-l;ary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics and chlor;nated ali-phatic hydrocarbons, such as chlorobenzenes, rhloroethyl enes or methylene chlorider aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum frac-tions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones~ such as acetone, methyl ethyl ketone, me~hyl iso-butyl ketone or cyclohexanone, strongly polar solvents,such as dimethylformamide and dimethylsulphoxide, as ~ell as water.
As solid carriers there are suitable: for example ammonium salts and ground natural minerals, such as kao lins, clays, talc, chalk, quartz, attapulgite, montmoril-lonite or diatomaceous earth, and ground synthetic miner-Le A 23 904 ~z~
als, such as highly disperse silicic acid, alumina and silicates, as solid carriers for granules there are suit-able: for e~ample crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tc,bacco stalks; as emul-sify;ng and/or foam-forming agents there are suitable:
for example non-ionic and an;onic emulsifiers, such as polyoxyethylene-fatty acicl esters, polyoxyethylene-fatty alrohol ethers, for example ~lkyLaryl polyglycol ethers~
alkylsulphonates, alkylsulphates, arylsulphonates as well as albumin hydrolysation products; as dispersing agents there are suitable: ~or example lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and naturaL and syntheti~ polymers in the form of powders, granules or latices, such as gum arabic~ polyvinyl alcohol and polyvinyl acetate, as well as naturally occurring 20 phospholipids, such as cephalins and lecithins, and syn-thetic phospholip;ds, can be used in the formuLations.
Further addit;ves can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prus-sian blueO ~nd organ;c dyestuffs, such as alizarin dye-stuffs, azo dyestuffs and metal phthaLocyanin~ dyestuf~s~
and trace nutrients such as salts of iron~ manganese, boron~ copper, cobaltr molybdenum and zinc.
The formulations in general con~ain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
The active compounds accord;ng to the ;nvention, as such or in the torm ot their formul~eions, ean also be used~ for combating ueeds, as mi~tur~s ~ieh known herb;-cidesO f;n;shed ~ormuL~tions or tank mixtufes be;ng pos-s ibleO
Le A 23 904 Possible components for the mixtures are knownherbicides, such as, for example, N-(2 benzothiazolyl)-N,N'-dimethyl-urea, 3-(3-chloro-4-methylphenyl)-1,1-di-methylurea~ 3-(4-isopropylphenyl)-1,1-dimethylurea, 4-amino-6-(1,1-dimethylethyl)-3-methylthio-t,2,4-triazin-5(4H)-one, 4-amino-6-t1,1-dimethyl-ethyl)-3-ethylthio-1,2,4-triazin-5(4H~-one, 1-amino-6-ethylthio-3-(292-dimethylpropyl)-1,3,5-triazine-2,4-(1H,3H)-dione, 4-amino-
benzyloxy)-guanidine and -N"-(4-ethoxycarbonyl-benzyloxy)-guanidine~
The starting substances of the formula (IY) are known ;n some cases (compare European Patent A-121,082).
The compounds of the formula (IV) are obta;ned by a process in wh;ch cyanoaminotr;az;ne der;vatives of the for~ula (V) ~2 N~-N ~ ~ ~ ~V) . R3 ;n wh;ch R2 and R3 have the abovement;oned mean;ngs, are reacted ~ith hydroxylamine derivatives of the formula (VI) H2N-OR1 (VI) ;n wh;ch R has the abovement;oned mean;ng, or hydrochlorides thereof, ;f appropriate ;n th~ presence of d;luents, such as, for example, ethanol, propanol or butanol, a~ temperatures between 20C and 150C, and, if appropriate, the react;on products are treated ~ith acid acceptors, such as, for example, ammoniaO potassium carbonate or sod;~m hydroxide.
The cyanoaminotriaz;ne derivatives of ~he formula (V) are known (compare DE-OS (German Publ;shed Spec;f;ca-t;on) 3,334,455).
The compounds of the formula ~Y) are essent;ally obtained by the following synthesis routes:
(a1) ~y reactions of alkali metal or alkaline earth metal salts of cyanamide - such as, for example, sodium cyanamide or calcium cyanamide - with chLorotr;azines of the formuLa (VII) Le A 23 904 ~l24L~7~0 Cl~'N~N (VII) in which R2 and R3 have the abovementioned meanings, if appropriate in the presence of acid acceptors and if appropriate in the presence of diluents, such as~ for example, ethanol, acetone, acetonitrile, dimethylform-amide, dimethylsulphoxide or water, at temperatures bet-ween -10C and 100C~ After the mixture has been con-centrated and the residue has been dissolved in water, the cyanoaminotr;azine derivatives of the formula IV) can be precipitated by acidification, for example with hydro-chloric acid, and isolated by filtration ~ith suction.
The chlorotriazines of the formula (VII) to be used as starting substances for the preparation process described above under (a1) for the cyanoaminotriazine der;vatives of ~he formula (V) are known and/or can be prepared by processes which are known per se (compare U.S.
Patent Specification 3,154,5~7 and U.S. Patent Specifica-tion 4,160,037).
In another process, cyanoaminotriazine derivat;ves of the formula (V) are obtained by a procedure in which (a2) dichlorotriazines of the formula (VIIa) N--~ (VIIa) Cl ~' ~N
~ ~3 in which R3 has the abovementioned meaning, are reacted with aLkali metaL salts or aLkaLine earth metaL saLts of cyanamide, such as, for example, with di-sodium cyanamide, in the presence of a diLuent, such as, Le A 23 904 ~2~
for example, water, at temperatures between -10C and +50C, ancl the metal salt thereby obtained of the mono-chloro-cyanoaminotriazine of the formula ~Va) ~1 NC-N~ ~ ~N (Va) ;n ~hich R3 has the abovementioned meaning~
i5 converted into the free monochloro-cyanoaminotriazine of the formula (Va~ with an acid, such as~ for exa~pler hydrochloric acid.
The corresponding cyanoaminotriazines of the formula (V) in which R2 represents alkoxy, alkylthio, alkylamino or dialkylamino can be prepared from the mono-chloro-cyanoaminotriazines of the formula ~Va) by reaction with alcohols or alkanethiols or ~ith alkali ~etal salts of these compounds or with monoalkyl- or dialkyl-amines.
The hydroxylamine derivatives of the formula (VI) furthermore to be used as starting substances are likewise known and can be prepared by processes which are known per se (compare Chem. Pharm~ 8ull. 15 (1967), 345~ ~ulln Soc. Chim. France 1958, 664; Synthesis 1976, 682; J. Chem.
Soc. 1930, 228 and HeLv. Chim~ Acta 45 ~1~62)~ 1387).
The benzene-1,2 disulphonic acid chloride of the formula (III) ~o be used as the starting substance in process (b) according to the invention is already known (compare J. Org. Chem. 31, (1966), 3289 - 3292).
Formula (IV) provides a general detinition of the oxyguanid;ne derivatives to be used as starting substances in process (b) according to the invention. In formula (IV)~ R1, R2 and R3 preferably or particularly have the same mean;ngs as have been g;ven above as preferred or as partiçularly preferred in the context of the subst;tuent definition for formula (I).
Le A 23 90~
~2~
- ~3 -Examples of compounds of the formula (IV) have already been given above in connection with the descrip-t;on of the starting substances for process (a). The preparation of the starting substances of the formula (IV) has already been described above in connection with the description of the starting substances for process ~a).
Process (a) according to the ;nvention for the preparation of the new compounds of the formula (I~ is preferably carried out in ~ater as the solvent. Other possible diluents are all the inert organic solvents, but preferably aprot;c polar solvents. These include, for example, ketones, such as, for example, acetone and methyl ethyl ketone, nitriles, such as, for example, aceton;~r;le and prop;on;trile, d;methylsulphox;de, sulpholane~ 1,2-d;methoxyethane and dioxane.
Process (a) is preferably carried out in the pre-sence of bases or acids. Preferred possible bases are alkali metal or alkaline earth metal hydroxides~ such as, for example, sodium hydroxide, po~ass;um hydrox;de and calcium hydroxide, tert;ary am;nes, such as~ for example7 triethylam;ne, N,N-dimethylan;line and ~,N-d;methyl-benzylam;ne, and n;trogen-heterocyclic compounds, such as, for example, pyridine or diazab;cyclooctane (DABCO~.
Su;table acids are, ;n particular~ mineral ac;ds, such as, for example, hydrochlor;c acid, hydrobromic acid or sul-phur;c ac;d.
The react;on temperatures can be var;ed ~ith;n a substantial range in process (a) according to the inven-t;on. The react;on is in general carried out between 0C and +100C, preferably between 10C and ~80C.
Process (a) according to the invention is in general carried out under normal pressure.
For carrying out process (a), in general between 1 and 100 moles~ preferably between 5 and 50 moles~ of water ancl, ;f appropr;ate, between 1 and 3 moles, prefer-ably between 1 and 2 moles, of a base or acid are employed Le _ 904 ~2'7~
per mole of benzodisultam of the formula (Il).
The reaction components are usually brought to-gether at room temperature and the reaction mixture is stirred until the reaction has ended.
Working up can be carried out in the customary manner; for example by acidifying the reaction m;xture -for example with hydrochloric acid - and concentrating it to about half the volume and isolating ~he product of the formula (1~ obtained as crystals by filtration ~ith suction.
Process (b) according to the invention for the preparation of the ne~ compounds of the ~ormula (I) is preferably carried out using diluents. Possible diluents are virtually all the inert organic, preferably aprotic polar solvents. These include optionally substituted hydrocarbons, such as, for example, methylene chloride, chloroform, 1,2-dichloroethane, toluene, xylene and chlorobenzene, nitriles, such as, for example, aceto-nitrile and propion;trile, ethers, such as~ for example~
1,2-dimethoxyethane, tetrahydrofuran and dioxane, and dimethylformamide~ dimethylacetamide, dimethylsulphoxide, sulpholane, pyridine and 2-methyl-5-ethyl-pyridine.
Virtually all the acid-binding agents ~h;ch can usually be employed can be used as acid acceptors in ~he first stage of process (b~. These incLude, in particular, alkali metal and alkaline earth ~etal hydroxides, alkali metal and alkaline earth metal hydrides~ organometallic compounds, such as butyl-l;thium, and furthermore ali-phatic~ aromatic or heterocyclic amines, such as trimethyl-amine, triethylaminer N,N-dimethylaniline, N,N-dimethyl-benzylamine, diazabicyclooctane tDABCo), diazabicyclo-nonene ~DBN), diazabicycloundecene (DBU), pyridine, 2-methyl-5-ethyl-pyridine and 4-dimethylaminopyridine. The corresponding statements made above fQr process (a) apply to the bases or acids to be used, if appropr;ate, in the second stage of process ~b).
Le A 23 904 " 7 ~
~: ~ ~
The reaction temperatures can be varied within a substantial range in process (b). The reaction is in general carried out between -80C and ~100C, preferably between -30C and +50C. Process tb) according to the invention is in general carried out under normal pressure.
For carrying out process (b), in genPral between 1 and 2 moles, preferably between 1nO and 1.2 moles~ of benzene-1,2-disulphonic acid dichloride of the formula (III) and 2 to 5 moles, preferably 2 to 3 moles, of an acid acceptor and, subsequently, between 1 and 100 moles, preferably between 5 and 50 ~oles, of ~a~er and, if appropriate, between 1 and 3 moles, preferably between 1 and 2 moles, of a base or acid are employed per mole of oxyguanidine derivative of the formula (IV) in the first stage.
The reaction components are usually brought to-gether at room temperature or with external cooling and the reaction mixture is stirred until the reaction has ended.
Working up can be carried out in the customary manner, for example by concentrating the reaction mixture, if appropriate, and/or diluting i~ ~ith an organic solvent which is v;rtually immiscible ~ith w~ter~ such as, for example~ methylene chloride, washing it with dilu~e hydro-chloric acid and with ~ater and drying, f;ltering and concentrating ito The produc~ of the formula (I) ~hich remains in ehe residue is made to crystallize by tritura-tion with a suitable organic solvent, such as, for example, ethanol, and isolated by filtration with suction.
The active compounds according to the invention can be used as defoliants, desiccants, agents for destroy-ing broad-leaved plants and, especially, as weedkillers.
8y weeds, in the broadest sense, there are to be under-stood all plants which grow in locations where they are undesired~ ~hether the substances according to the inven~
tion act as total or selective herbicides depends essen-Le A 23 904 tialLy on the amount used.
The act;ve compounds according to the invention can be used, for example, in connection with the ~ollowing plants:
Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinssga~ Cheno-podiumr Urtica~ Senecio, AmaranthusO Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesban;a, Ambrosia, Cir-sium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Linder-nia, Lamium, Veronica, Abutilon, Emex, Datura, Viola,Galeopsis, Papaver and Centaurea.
Dicotyledon cultures of ~h~ genera: Gossypiu~, Glycine, Beta, Daucus, Phaseolus~ Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycop~rsicon, Arachis, ~rassica, Lac-tuca~ Cucumis and Cucurbita.Monocotyledon weeds of the genera- Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, 8rachiaria, Lolium, ~romus, Avena, Cyperus~ Sorghum, Agro-pyron, Cynodon, Monochoria, Fimbr;stylis, Sagittaria, Eleocharis~ Scirpus, Paspalum, Ischaemum, Sphenoclea, DactyLocten;um~ Agr~stis, Alopecurus and Apera~
Monocotyledon cultures of the genera: Oryza, Zea~ Triti-cum, Hord~um, Avena, Secale, Sorghum, Panicum~ Saccharum, Ananas~ Asparagus and Allium.
However, the use of the active compounds accord;ng to the invention is ;n no way restricted to these genera, but also extends in ~he same manner to other plants.
The compounds are suitable~ depending on the con-centration, for the total combating of ~eeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the com-pounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plan~ings, orchards, vineyards~ citrus groves, nut orch-ards, banana plantations~ coffee plantations, tea plantations, rubber plantations, oil paim plantations, cocoa Le A 23 904 ,~
~2~26~
plantations, soft fruit plantings and hopfields, and for the selective combating of weeds in annual cultures.
The active compounds according to the invention are suitable for combating mono- and dicotyledon weeds in monocotyledon crops by the pre-emergence and post-emer-gence method.
The active compounds can be converted to the cus-tomary formuLations~ such as solutions, emulsions, wett-able powders, suspensions, powders, dusting agents, pastes~ soluble powders~ granules, suspension-emulsion concentrates, natural and synthetic materials impr2gnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in known mannerS
for e~ample by mix;ncg the active compounds with ex~enders, that is liquid solvents and/or solid carriers, optionally ~ith the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or foam-forming agents.
In the case of the use of water as an extender, organic solvents can, for example, also be used as auxi-l;ary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics and chlor;nated ali-phatic hydrocarbons, such as chlorobenzenes, rhloroethyl enes or methylene chlorider aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum frac-tions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones~ such as acetone, methyl ethyl ketone, me~hyl iso-butyl ketone or cyclohexanone, strongly polar solvents,such as dimethylformamide and dimethylsulphoxide, as ~ell as water.
As solid carriers there are suitable: for example ammonium salts and ground natural minerals, such as kao lins, clays, talc, chalk, quartz, attapulgite, montmoril-lonite or diatomaceous earth, and ground synthetic miner-Le A 23 904 ~z~
als, such as highly disperse silicic acid, alumina and silicates, as solid carriers for granules there are suit-able: for e~ample crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tc,bacco stalks; as emul-sify;ng and/or foam-forming agents there are suitable:
for example non-ionic and an;onic emulsifiers, such as polyoxyethylene-fatty acicl esters, polyoxyethylene-fatty alrohol ethers, for example ~lkyLaryl polyglycol ethers~
alkylsulphonates, alkylsulphates, arylsulphonates as well as albumin hydrolysation products; as dispersing agents there are suitable: ~or example lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and naturaL and syntheti~ polymers in the form of powders, granules or latices, such as gum arabic~ polyvinyl alcohol and polyvinyl acetate, as well as naturally occurring 20 phospholipids, such as cephalins and lecithins, and syn-thetic phospholip;ds, can be used in the formuLations.
Further addit;ves can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prus-sian blueO ~nd organ;c dyestuffs, such as alizarin dye-stuffs, azo dyestuffs and metal phthaLocyanin~ dyestuf~s~
and trace nutrients such as salts of iron~ manganese, boron~ copper, cobaltr molybdenum and zinc.
The formulations in general con~ain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
The active compounds accord;ng to the ;nvention, as such or in the torm ot their formul~eions, ean also be used~ for combating ueeds, as mi~tur~s ~ieh known herb;-cidesO f;n;shed ~ormuL~tions or tank mixtufes be;ng pos-s ibleO
Le A 23 904 Possible components for the mixtures are knownherbicides, such as, for example, N-(2 benzothiazolyl)-N,N'-dimethyl-urea, 3-(3-chloro-4-methylphenyl)-1,1-di-methylurea~ 3-(4-isopropylphenyl)-1,1-dimethylurea, 4-amino-6-(1,1-dimethylethyl)-3-methylthio-t,2,4-triazin-5(4H)-one, 4-amino-6-t1,1-dimethyl-ethyl)-3-ethylthio-1,2,4-triazin-5(4H~-one, 1-amino-6-ethylthio-3-(292-dimethylpropyl)-1,3,5-triazine-2,4-(1H,3H)-dione, 4-amino-
3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one, 2-chloro-4-ethylamino-6-isopropyl-amino-1,3,5-triazine, the R-enantio-mer of ~trimethylsilyl)-methyl 2-~4-(3,5-dichloro-pyridine-2-o~y)-phenoxy]-propionate, the R-enantiomer of (2-benzyl-oxy)-ethyl 2-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionate, 2,4-dichlorophenoxyacetic acid, 2-(?,4-di-chloropheno~y)-prop;onic acid, 4-chLoro-2-methyl-phenoxy-açetic acid, ?-(2-methyl-4-chloro-phenoxy~-propionic acid, 3,5-diiodo-4-hydroxy-benzonitrile, 3,5-di~romo-4-hydroxy-benzonitrile and diphenyl ethers and phenylpyr;dazines, such as, for example, pyridates. Surprisingly, some mix-tures also exhibit a synergistic action.
Mixtures with other kno~n act;ve compounds, such as fungicides~ insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents wh;ch i0prove soil structure, are aLso possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution~ such as ready-to-use solu-tions, suspensions~ emulsions, powders, pastes and gran-ules~ They are used in the customary man~er, for example by ~atering, spraying, atomizing or scattering.
The ac~ive compounds according to the invention can be applied either before or after emergence of the plants. They can also be ;ncorporated in~o the soil before sowing.
Le A 23 904 124?~7;~0 The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.01 and 10 kg of active compound per hectare of soil surface, pre-ferably between 0.05 and 5 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the following examples .
Le A 23 9G4 ~2~
Preparation ExampLes Example 1 SO2-NH-O-CH~ oc~3 S02-NH- C--N~ ~N
o OCH3 (Process ta)) 5 mL of concentrated hydro~hlor;c acid are added to a mixture of 4.3 9 tD~01 mole) of the compound of the foLLowing structuraL formula OCH3 O~H3 ~'SO2 $02-N ~
and 40 ml of water, with vigorous stirring. Stirring is continued at 20 to 30C for 2 hours and the precipitate formed is then filtered off hith suction.
After drying, 3.9 9 (87~ of theory) of 1-(2-methoxyaminosulphonylphenylsulphonyL)~3-(4,6-dimethoxy-1~3,5-tria~in-2-yl) urea of melting point 162C (decom-position) are obtained.
Example 2 ~ S02-N~-O-C~3 oc~3 il ~
~O~3 (Process (b)~
7.1 g (0.025 mole) of benzene-1,2-disulphonic acid chloride are added in portions to a mixture of 5.Sg (0.025 mole) of N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-N''-metho~y-guanidine and 50 ml of pyridine at -10C. The mixture is stirred at -10C for 3 hours and then at 20 - 25C for 12 Le A 23 904 hours. The solvent is then stripped off and the residue is taken up in 200 ml of ~ater. The mixture is filtered~
The fiLtra~e is acidified with concentrated hydrochloric acid. After about 1 hour, the presipitate formed is 5 filtered off with suc~ion, ~ashed with methanoL and then dried.
6.1 9 (54% of theory) of 1-(2-methoxyaminosulphon-ylphenyLsuLphonyl)-3-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea of melting point 160C are obtained.
The compownds of the formula (I) listed in the fol-lo~ing Table 2 can also be prepared by the processes des-cribed by way of example in the preceding Examples 1 and 2:
S02-N~ 2 SO2-NH~
O R~
Table 2 3 -~2~5 -~H3 3C 3
Mixtures with other kno~n act;ve compounds, such as fungicides~ insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents wh;ch i0prove soil structure, are aLso possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution~ such as ready-to-use solu-tions, suspensions~ emulsions, powders, pastes and gran-ules~ They are used in the customary man~er, for example by ~atering, spraying, atomizing or scattering.
The ac~ive compounds according to the invention can be applied either before or after emergence of the plants. They can also be ;ncorporated in~o the soil before sowing.
Le A 23 904 124?~7;~0 The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.01 and 10 kg of active compound per hectare of soil surface, pre-ferably between 0.05 and 5 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the following examples .
Le A 23 9G4 ~2~
Preparation ExampLes Example 1 SO2-NH-O-CH~ oc~3 S02-NH- C--N~ ~N
o OCH3 (Process ta)) 5 mL of concentrated hydro~hlor;c acid are added to a mixture of 4.3 9 tD~01 mole) of the compound of the foLLowing structuraL formula OCH3 O~H3 ~'SO2 $02-N ~
and 40 ml of water, with vigorous stirring. Stirring is continued at 20 to 30C for 2 hours and the precipitate formed is then filtered off hith suction.
After drying, 3.9 9 (87~ of theory) of 1-(2-methoxyaminosulphonylphenylsulphonyL)~3-(4,6-dimethoxy-1~3,5-tria~in-2-yl) urea of melting point 162C (decom-position) are obtained.
Example 2 ~ S02-N~-O-C~3 oc~3 il ~
~O~3 (Process (b)~
7.1 g (0.025 mole) of benzene-1,2-disulphonic acid chloride are added in portions to a mixture of 5.Sg (0.025 mole) of N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-N''-metho~y-guanidine and 50 ml of pyridine at -10C. The mixture is stirred at -10C for 3 hours and then at 20 - 25C for 12 Le A 23 904 hours. The solvent is then stripped off and the residue is taken up in 200 ml of ~ater. The mixture is filtered~
The fiLtra~e is acidified with concentrated hydrochloric acid. After about 1 hour, the presipitate formed is 5 filtered off with suc~ion, ~ashed with methanoL and then dried.
6.1 9 (54% of theory) of 1-(2-methoxyaminosulphon-ylphenyLsuLphonyl)-3-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea of melting point 160C are obtained.
The compownds of the formula (I) listed in the fol-lo~ing Table 2 can also be prepared by the processes des-cribed by way of example in the preceding Examples 1 and 2:
S02-N~ 2 SO2-NH~
O R~
Table 2 3 -~2~5 -~H3 3C 3
4 -CH~-~H~C~2 -OCH3 -OCH3 ~ -~3 -~C~
-C4~9 -OC~3 -OC~5 7 -C~3 -~H3 ~3~7~~ -SC~ N~2H5 9 -CH3 ~~3 O~H3 174 Le A 23 904 ~2~7;~
Tab l e 2 - Cont i nuat i on E x amp l P Rl R2 R~ Me l t i n g ~ l7 n -~H3 ~ CH3 11 ~CH2{~9 -CH3 -OCH3 177 12 -~H3 -OCH3 -SCH3 1~ -CH3 -~H3 ~C2~5 201 14 -CH2~ -CH3 ~2~5 212 -~H3 -SCH3 N~C~5 16 - t~ C 2H5 ~ OCH3 17 -CH3 -C~3 -CH3 ~ 240 1~ -CH2-~H-~ ~2 3 19 -CH2-CH~CH3)~ -c}~3 -C2H5 156 -CH2-CH ~ C~l~ ) 2 ~ 3 -OCH3 ~ 76 21 -CEI~CH3)2 -CH~ 0~2H5 183 22 -C:H ( CH3 ) ;2 C2HS -NHCH~ ~08 23 -CH~ -OCH~ -NHCH ~ 197 24 -CH2~3 -C)C2H5 -)IHCH~ 197 La~3 904 _ 24 -Table 2 - Continuation Example Meltin~
No. R1 ~2 R3 point ( C) -CH(CH3)2 -CH3 -OCH~ 192 27 -CH2 ~ -OCH3 -OCH3 155 ~5 28 -CH3 -CH~ -N(CH3)2 182 Cl 29 -CH2 ~ -CH3 -C~3 154 Cl 31 -CH2CH(CH3~2 -CH3 -N(CH3)2 170 ~5 33 -CH(CH3)2 -CH3 -NHCH3 2S7 34 -CH2CH(CH3)2 -CH3 -NHCH3 -CH3 -C~3 -NHC2H$
36 -CH(CH3)2 -CH3 -NHC2HS
37 -CH2CH(CH3)2 -CH3 -NHC2H5 Le A 23 904 Preparation of the starting compounds of the formula (II~
Example tlI 1) ~OCH3 OCH3 2 ~<N
7.1 y (0.025 mole) of ben~ene-1,2-disulphonic acid
-C4~9 -OC~3 -OC~5 7 -C~3 -~H3 ~3~7~~ -SC~ N~2H5 9 -CH3 ~~3 O~H3 174 Le A 23 904 ~2~7;~
Tab l e 2 - Cont i nuat i on E x amp l P Rl R2 R~ Me l t i n g ~ l7 n -~H3 ~ CH3 11 ~CH2{~9 -CH3 -OCH3 177 12 -~H3 -OCH3 -SCH3 1~ -CH3 -~H3 ~C2~5 201 14 -CH2~ -CH3 ~2~5 212 -~H3 -SCH3 N~C~5 16 - t~ C 2H5 ~ OCH3 17 -CH3 -C~3 -CH3 ~ 240 1~ -CH2-~H-~ ~2 3 19 -CH2-CH~CH3)~ -c}~3 -C2H5 156 -CH2-CH ~ C~l~ ) 2 ~ 3 -OCH3 ~ 76 21 -CEI~CH3)2 -CH~ 0~2H5 183 22 -C:H ( CH3 ) ;2 C2HS -NHCH~ ~08 23 -CH~ -OCH~ -NHCH ~ 197 24 -CH2~3 -C)C2H5 -)IHCH~ 197 La~3 904 _ 24 -Table 2 - Continuation Example Meltin~
No. R1 ~2 R3 point ( C) -CH(CH3)2 -CH3 -OCH~ 192 27 -CH2 ~ -OCH3 -OCH3 155 ~5 28 -CH3 -CH~ -N(CH3)2 182 Cl 29 -CH2 ~ -CH3 -C~3 154 Cl 31 -CH2CH(CH3~2 -CH3 -N(CH3)2 170 ~5 33 -CH(CH3)2 -CH3 -NHCH3 2S7 34 -CH2CH(CH3)2 -CH3 -NHCH3 -CH3 -C~3 -NHC2H$
36 -CH(CH3)2 -CH3 -NHC2HS
37 -CH2CH(CH3)2 -CH3 -NHC2H5 Le A 23 904 Preparation of the starting compounds of the formula (II~
Example tlI 1) ~OCH3 OCH3 2 ~<N
7.1 y (0.025 mole) of ben~ene-1,2-disulphonic acid
5 chloride are added ;n portions to a mixture of 5.6 9 tO.325 mole) of N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-N''-methoxy-guanidine, 6 9 (0.025 mole) of DA~C0 and 60 ml of methylene chloride at -10C. The mixture is subsequently st;rred at 0 to -5C for 15 hours~ The reaction mixture 1Q is ~hen washed ~ith ice-cold dilute hydrochloric acid and ice-water. The methylene chloride solution is dried and concentrated.
After incipiënt distillation, 4.6 g (43X of theory) of the compound of the abovementioned structural 15 formula are obtained in the form of an amorphous mass.
The substance is charac~erized by the H1-NMR
spectrum.
The compounds of the formula (II) listed in the following Table 1 can be prepared by the process descr;bed by way of e~ample in the prereding example:
~_R1 ~2 SO2_ ~ ~ , ~ (II) ~2-~ R3 Le A 23 904 _ 26 --TabLe 3 Examp l e 3R1 R2 E~3 poi nt ~ ~ J
I I - 2 C2~5 - OCH3 - OCH3 I I -3 -CH2-CH-t H2 -OC}13 OCH ~
1 I-5 -C,IH9~ OCH3 C2H5 I I - 6 - CH3 - QCH3-N ~ C2Hs ~ 2 1 I-7 -C3H7-n -SCH3 -NHC~H5 I I-8 C~3 ~3 -OCH3 amorphous I I -9 C8H17 n -CH3 -OC~ 3 I I - 10 - CH~ CH3 - t)CH3 I I -11 ~~ ~3 -S~CH3 -~CH3 I I -12 -~ H3 0~2H5 II-13 2~9 3 C~C2H5 amorphous I I-14 -c~3 -SCH3 -NHC2H5 I~ 15 -c~3 C2~5 ~3 I I-16 -CH~ -C~3 -C~;3 amorphous II-17 -CH2-C~ 2 -CH3 -CH
Le A 23 904 .. . ..
~ 2,gL2i7;2~
Table 3 - Continuation -Ex amp le _ ~2 point (C) 10II-13 2 ~ 3 -C2H5 amorp~us II-15 -CH3 C2H5 -OCH~
II-16 -CH3 -~H3 -CH3 amorp~us 15II-17 -CH2-CH=CH2 -CH3 -CH3 II-18 -CHz ~ COOC2Hs ~~3 -CH3 195 20II-l9 -CH(CH3~2 -CH3 -OCH3 amorphous II-20 -CH(CH3)~ -CH3 C2H5 amorphous lI-21 -(CH2~7~c~3 -OCH3 -OCH3 110 ~5II-22 -CH2- ~ -OCH3 -OCH3 185 II-23 -CH2 ~ -CH3 -CH3 150 Le A 23 904 Prepara~ion of starting compounds of the formula (IV) Example (IV-1) C ~<
N~C2~5)2 H~ ~CH3 A mixture of 66.5 9 tO.3 moLe) of 2-cyanamino-4-5 diethylamino-6-methoxy-s-triazine, 50 9 (0.8 mole) of 0-methyl-hydroxylamine hydrochloride and 300 ml of ethanol is heated at the boiling poin~ under reflux for 15 hours.
It is then filtered, the fiLtrate is concentrated, the residue is taken up in about 200 ml of water, the mixture 10 is rendered alkaline with sodium hydroxide solution and the product thereby abtained as crystals is isolated by filtration ~ith suction.
35.0 9 (43% o~ theory) of N'-(4-diethylamino-6-me~hoxy-s-triazin-2-yl)-N"-methoxy-guanidine of melting 15 point 112C are obtained.
The compounds of the formula ~IV) listed in the follo~ing Table 4 can be prepared analogously:
o R2 ( IV) }}N~, N~
~fC-N ~ ~N
NH' ~
Le A 23 904 Tab l e 4 E
IV-2 -CH ~ -SCH3 NHC2H5 11?
IV-3 -CH3 -SC:H3 -N}~CH3 IV-4 CH3 -Cl -N~C2~5 ~2 IV-5 -C2~5 -OCH3 -N~C2}~5)2 IV-6 -C3H7-n -SCH3 NHC2H5 I V- 7 rH ( CH3 ) 2OCH ~ -NHCH3 IY-B -cH2-cEl=cH;2-OCH3 -N(CH3)2 IV-9 -C4H9-~ -OCH3 -N(CH3);~
IV-10 -CH2~ )Cil3 -N(CH~2 IV-ll -C1~2COOC21~15-OCH3 -N(GIH3)2 1 V- 12 - CH2~t::H3~ t ~3 -N ( CH3 ) 2 IY- 13 -CH3 -~H3 -OCH3 126 IV- 14 -C:H2~ 3 -OC:H3 1 12 IV-1~ -~ 8~17 3 Le A 23 904 ~2~7~3 ~ 30 -Table 4 - C~ntinuation Example Melting No. Rl R2 R~ poin~ (C) IV- 16 -CH2{~ -S~H3 ~HC2H5 122 IV- 17 -C:H3 -CH3 -''~2H5 I~-18 ~~ H2~9 CH3 0::2H5 n21 - 1 .5~2-a I V- 1 9 - CH3 - CH3 - ~H3 11 2 IV-20 -CH2~ -CH3 -CH3 IV-21 -CH2-C~=CH2 -~H3 -CH ~
IV-22 -~H3 -OC113 -OCH3 107 IV-2~ -CH2~ ~~3 -OCH3 127 IV-24 - :H2-C ~ CH3 ~ 3 -~H3 -CH3 IV-25 -CH2C~2-OCH3 -OCH 3 -( ~3 IV-26 -CH2cH2-c2H5 -C3~3 -C~13 IY- 27 -CH2CH2-S~H3 -CH3 C2 IV-2B -CH~CH2-S~ 2}~5 -CH3 -C:H~
IV-29 -CH2-CONH~ -OCH3 OCH3 Le A Z3 904 - . .
2~
Tab l e 4 - Cont i nuat i on ExamP~e Rl E~2 R3 po7nt ( C) IV-:~O -C~12-CH-CHCl ~CH3 -C}~3 IV-31 -CH[~9J 2 -CH3 -CH3 I V - 3 2 - C [~J - CH ~ H3 I V ~ 3 3 - CH3 C 2H5 ~ OCH3 IV-34 -c~3 -SCH ~ -OCH3 ~t }~3-OC2H6 OCH~
IV- 6 -~H3 -NH-C~H5 -OCH3 IV-37 -~H3 -N~CH3)z -OCH3 IV-38 ~~ H3 -SCH3 IV 39 ~~ ~3 -NH-C~3 ~~ ~3 IV-~O -CH ~N ~ CH 3 ) ;~-C~3 Le A 23 904 ~iL2~7~
- ~2 -Preparation of starting substances of the formula (V) __ _ _ .
Example (V-1) ~NH- CN
(Process (a1)) A soLution of 18.0 g (0.21 mole) of the d;sod;um salt of cyanamide in 100 ml of water is added dropw;se to a suspens;on of 28~7 9 (Q.2 mole~ of 2-chloro-4,6-d;methyl-1,3,S-tr;az;ne ;n 100 ml of ;ce-water at a temperature of 0C to 5C in the course of 4 hours, with v;gorous s~;r-r;ng. The m;xture ;s then subsequently st;rred at 20C
and left to stand for 15 to 16 hours. After ac;d;ficat;on to pH = 2 w;th concentrated hydrochlor;c ac;d, the prec;p;-tate ;s filtered off with suction, ~ashed four times w;th 20 ml o~ ;ce-water and dr;ed.
19.7 g (66~ of theory) of 2-cyanam;no-4,6-dimethyl-1~3,5-tr;a~ine of meltin~ point 241C (decomposition) are obtained.
Example (V-2) H3CO~
~NH- CN
~3~o (Process (a2~) A solution of 1.6 9 (0.069 mole) of sod;um in 20 ml of methansl is added dropwise to a suspension of 6 9 (0.032 mole) of 4-chloro-2-cyanoamino-b-methoxy-1,3,5-tria~ine in 50 ml of methanol at 20C to 30C. The mixture is then subsequently stirred at 20C for 15 hours. The solvent is distilled off, the residue is dissolved in 30 ml of ~ater and the solution is acidified with hydrochloric acid~ The Le A 23 904 crystals formed are filtered off ~;th suct;on and dried.
509 9 t92% of theory) of 2-cyanoamino-4,6-di-methoxy-1~3,5-triazine are obtained. The product is characterized by its H-NMR spectra.
S The compounds of the formula (V) l;ste~ in the follo~ing Table S can be prepared analogously to Example (V-1) and (V-2):
~2 ~3C-N ~ ~ (V) Table 5 Example ~elting ~o, R2 R~ po;nt (~C) Y-~ OC~3 N(t 2H5~2 ~14 V- 4 - SCH3 - t~lC 2H5 Y~ 6 - C l -N ~ C2H5 ) 2 1 S ~
~-7 -OCH3 -CH3 184 V- 8 - OC}I ~ H3 ) ~ - c~3 V- 9 S~H3 ~ ~H3 V- 10 -5C2H~i -CH;3 ;cH ( cH ~ ) 2 - C~3 Le A 23 90~
~2~ 2~
- 3~ _ Table 5 - Continuation ~eltin~
ExamPle R2 R~ point ~aC) i~' o . _ _ ~
V-13-NHCH(; ~3)2 ~eH~
V-14 -N~CH3)2 -~ H3 V- 15 -C2H5 -~13 195 (decomposition) ' -16 C2H5 -OC}I
V- 17 -~CH3 -~}~3 V- 1~3 OC2H5 -OCH3 V- 19 -Ot:H3 -!NHCH ~
V-20 O~H3 -N~CH3~2 Preparat;on of starting substances of the formula tVa) Example tVa-1) H3~0 N ~ NH-CN
~1 A solution of 9 9 tO.043 mole) of the sodium salt of 4-chloro-2-cyanoamino-6-methoxy-1,3,5-tria~ine in 90 ml of water is acid;fied with hydrochloric ac;d and the crystals formed are then filtered off ~ith suction.
Le A 23 90b .
After incipiënt distillation, 4.6 g (43X of theory) of the compound of the abovementioned structural 15 formula are obtained in the form of an amorphous mass.
The substance is charac~erized by the H1-NMR
spectrum.
The compounds of the formula (II) listed in the following Table 1 can be prepared by the process descr;bed by way of e~ample in the prereding example:
~_R1 ~2 SO2_ ~ ~ , ~ (II) ~2-~ R3 Le A 23 904 _ 26 --TabLe 3 Examp l e 3R1 R2 E~3 poi nt ~ ~ J
I I - 2 C2~5 - OCH3 - OCH3 I I -3 -CH2-CH-t H2 -OC}13 OCH ~
1 I-5 -C,IH9~ OCH3 C2H5 I I - 6 - CH3 - QCH3-N ~ C2Hs ~ 2 1 I-7 -C3H7-n -SCH3 -NHC~H5 I I-8 C~3 ~3 -OCH3 amorphous I I -9 C8H17 n -CH3 -OC~ 3 I I - 10 - CH~ CH3 - t)CH3 I I -11 ~~ ~3 -S~CH3 -~CH3 I I -12 -~ H3 0~2H5 II-13 2~9 3 C~C2H5 amorphous I I-14 -c~3 -SCH3 -NHC2H5 I~ 15 -c~3 C2~5 ~3 I I-16 -CH~ -C~3 -C~;3 amorphous II-17 -CH2-C~ 2 -CH3 -CH
Le A 23 904 .. . ..
~ 2,gL2i7;2~
Table 3 - Continuation -Ex amp le _ ~2 point (C) 10II-13 2 ~ 3 -C2H5 amorp~us II-15 -CH3 C2H5 -OCH~
II-16 -CH3 -~H3 -CH3 amorp~us 15II-17 -CH2-CH=CH2 -CH3 -CH3 II-18 -CHz ~ COOC2Hs ~~3 -CH3 195 20II-l9 -CH(CH3~2 -CH3 -OCH3 amorphous II-20 -CH(CH3)~ -CH3 C2H5 amorphous lI-21 -(CH2~7~c~3 -OCH3 -OCH3 110 ~5II-22 -CH2- ~ -OCH3 -OCH3 185 II-23 -CH2 ~ -CH3 -CH3 150 Le A 23 904 Prepara~ion of starting compounds of the formula (IV) Example (IV-1) C ~<
N~C2~5)2 H~ ~CH3 A mixture of 66.5 9 tO.3 moLe) of 2-cyanamino-4-5 diethylamino-6-methoxy-s-triazine, 50 9 (0.8 mole) of 0-methyl-hydroxylamine hydrochloride and 300 ml of ethanol is heated at the boiling poin~ under reflux for 15 hours.
It is then filtered, the fiLtrate is concentrated, the residue is taken up in about 200 ml of water, the mixture 10 is rendered alkaline with sodium hydroxide solution and the product thereby abtained as crystals is isolated by filtration ~ith suction.
35.0 9 (43% o~ theory) of N'-(4-diethylamino-6-me~hoxy-s-triazin-2-yl)-N"-methoxy-guanidine of melting 15 point 112C are obtained.
The compounds of the formula ~IV) listed in the follo~ing Table 4 can be prepared analogously:
o R2 ( IV) }}N~, N~
~fC-N ~ ~N
NH' ~
Le A 23 904 Tab l e 4 E
IV-2 -CH ~ -SCH3 NHC2H5 11?
IV-3 -CH3 -SC:H3 -N}~CH3 IV-4 CH3 -Cl -N~C2~5 ~2 IV-5 -C2~5 -OCH3 -N~C2}~5)2 IV-6 -C3H7-n -SCH3 NHC2H5 I V- 7 rH ( CH3 ) 2OCH ~ -NHCH3 IY-B -cH2-cEl=cH;2-OCH3 -N(CH3)2 IV-9 -C4H9-~ -OCH3 -N(CH3);~
IV-10 -CH2~ )Cil3 -N(CH~2 IV-ll -C1~2COOC21~15-OCH3 -N(GIH3)2 1 V- 12 - CH2~t::H3~ t ~3 -N ( CH3 ) 2 IY- 13 -CH3 -~H3 -OCH3 126 IV- 14 -C:H2~ 3 -OC:H3 1 12 IV-1~ -~ 8~17 3 Le A 23 904 ~2~7~3 ~ 30 -Table 4 - C~ntinuation Example Melting No. Rl R2 R~ poin~ (C) IV- 16 -CH2{~ -S~H3 ~HC2H5 122 IV- 17 -C:H3 -CH3 -''~2H5 I~-18 ~~ H2~9 CH3 0::2H5 n21 - 1 .5~2-a I V- 1 9 - CH3 - CH3 - ~H3 11 2 IV-20 -CH2~ -CH3 -CH3 IV-21 -CH2-C~=CH2 -~H3 -CH ~
IV-22 -~H3 -OC113 -OCH3 107 IV-2~ -CH2~ ~~3 -OCH3 127 IV-24 - :H2-C ~ CH3 ~ 3 -~H3 -CH3 IV-25 -CH2C~2-OCH3 -OCH 3 -( ~3 IV-26 -CH2cH2-c2H5 -C3~3 -C~13 IY- 27 -CH2CH2-S~H3 -CH3 C2 IV-2B -CH~CH2-S~ 2}~5 -CH3 -C:H~
IV-29 -CH2-CONH~ -OCH3 OCH3 Le A Z3 904 - . .
2~
Tab l e 4 - Cont i nuat i on ExamP~e Rl E~2 R3 po7nt ( C) IV-:~O -C~12-CH-CHCl ~CH3 -C}~3 IV-31 -CH[~9J 2 -CH3 -CH3 I V - 3 2 - C [~J - CH ~ H3 I V ~ 3 3 - CH3 C 2H5 ~ OCH3 IV-34 -c~3 -SCH ~ -OCH3 ~t }~3-OC2H6 OCH~
IV- 6 -~H3 -NH-C~H5 -OCH3 IV-37 -~H3 -N~CH3)z -OCH3 IV-38 ~~ H3 -SCH3 IV 39 ~~ ~3 -NH-C~3 ~~ ~3 IV-~O -CH ~N ~ CH 3 ) ;~-C~3 Le A 23 904 ~iL2~7~
- ~2 -Preparation of starting substances of the formula (V) __ _ _ .
Example (V-1) ~NH- CN
(Process (a1)) A soLution of 18.0 g (0.21 mole) of the d;sod;um salt of cyanamide in 100 ml of water is added dropw;se to a suspens;on of 28~7 9 (Q.2 mole~ of 2-chloro-4,6-d;methyl-1,3,S-tr;az;ne ;n 100 ml of ;ce-water at a temperature of 0C to 5C in the course of 4 hours, with v;gorous s~;r-r;ng. The m;xture ;s then subsequently st;rred at 20C
and left to stand for 15 to 16 hours. After ac;d;ficat;on to pH = 2 w;th concentrated hydrochlor;c ac;d, the prec;p;-tate ;s filtered off with suction, ~ashed four times w;th 20 ml o~ ;ce-water and dr;ed.
19.7 g (66~ of theory) of 2-cyanam;no-4,6-dimethyl-1~3,5-tr;a~ine of meltin~ point 241C (decomposition) are obtained.
Example (V-2) H3CO~
~NH- CN
~3~o (Process (a2~) A solution of 1.6 9 (0.069 mole) of sod;um in 20 ml of methansl is added dropwise to a suspension of 6 9 (0.032 mole) of 4-chloro-2-cyanoamino-b-methoxy-1,3,5-tria~ine in 50 ml of methanol at 20C to 30C. The mixture is then subsequently stirred at 20C for 15 hours. The solvent is distilled off, the residue is dissolved in 30 ml of ~ater and the solution is acidified with hydrochloric acid~ The Le A 23 904 crystals formed are filtered off ~;th suct;on and dried.
509 9 t92% of theory) of 2-cyanoamino-4,6-di-methoxy-1~3,5-triazine are obtained. The product is characterized by its H-NMR spectra.
S The compounds of the formula (V) l;ste~ in the follo~ing Table S can be prepared analogously to Example (V-1) and (V-2):
~2 ~3C-N ~ ~ (V) Table 5 Example ~elting ~o, R2 R~ po;nt (~C) Y-~ OC~3 N(t 2H5~2 ~14 V- 4 - SCH3 - t~lC 2H5 Y~ 6 - C l -N ~ C2H5 ) 2 1 S ~
~-7 -OCH3 -CH3 184 V- 8 - OC}I ~ H3 ) ~ - c~3 V- 9 S~H3 ~ ~H3 V- 10 -5C2H~i -CH;3 ;cH ( cH ~ ) 2 - C~3 Le A 23 90~
~2~ 2~
- 3~ _ Table 5 - Continuation ~eltin~
ExamPle R2 R~ point ~aC) i~' o . _ _ ~
V-13-NHCH(; ~3)2 ~eH~
V-14 -N~CH3)2 -~ H3 V- 15 -C2H5 -~13 195 (decomposition) ' -16 C2H5 -OC}I
V- 17 -~CH3 -~}~3 V- 1~3 OC2H5 -OCH3 V- 19 -Ot:H3 -!NHCH ~
V-20 O~H3 -N~CH3~2 Preparat;on of starting substances of the formula tVa) Example tVa-1) H3~0 N ~ NH-CN
~1 A solution of 9 9 tO.043 mole) of the sodium salt of 4-chloro-2-cyanoamino-6-methoxy-1,3,5-tria~ine in 90 ml of water is acid;fied with hydrochloric ac;d and the crystals formed are then filtered off ~ith suction.
Le A 23 90b .
6.7 9 (84% of theory) of 4-chloro-2-cyanoamino-6-methoxy-1,3,5-triazine of melting point > Z60C are obtained.
The product is characterized by 1H-NMR spectrau The following compounds, for example, are obtained 5 analogously:
Example (Va-2) CH
NH- CN
>~
~1 Melt;ng point 105C (decomposition) Example (Va-33 ~ ~ -CN
>~
Cl : Melting point > 250C
Le A 23 904
The product is characterized by 1H-NMR spectrau The following compounds, for example, are obtained 5 analogously:
Example (Va-2) CH
NH- CN
>~
~1 Melt;ng point 105C (decomposition) Example (Va-33 ~ ~ -CN
>~
Cl : Melting point > 250C
Le A 23 904
7~0 Example A
Pre-emergence test/greenhouse Solvent: 5 parts by weight of acetone Fmulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a su;table preparation of active com-pound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsi-fier is added and the concentrate ;s d;luted w;th water to the des;red concentration.
Seeds of the test plants are sown ;n normal so;l and, after 24 hours, watered w;th the preparation of act;ve compound. It ;s exped;ent to keep constant the amount of water per un;t area. The concentration of act;ve compound in the preparat;on is of no importance, only the amount of active compound appl;ed per un;t area be;ng decis;ve. After three ~eeks, the degree of damage to the plants is rated in X damage in comparison to the development of th~ untreated control. The figures denote:
OX = no action (like untreated control) 100X = total destruction In this test~ for example, the compound of prepar-at;on example (9) shows a better action than compar;son compound (A~ C= 1-(2-methoxy-phenylsulphonyl)-3-~4,6-dimethyl-pyr;mid;n-2-yl)-urea~.
Le A 34 904 :~z'~
Example_8 Pos~-emergence test/greenhouse Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of aLkylaryl polyglycol ether To produce a suitable preparation of active com-pound~ 1 part by weight of active compound is mixed ~ith the stated amount of solvent, the stated amount of emulsi-fier is added and the concentrate is diluted with water to the desired concentration.
Test plants which have a height of 5 - 15 cm are sprayed with the preparation of active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is so chosen ~hat the particular amounts of active compound desired are applied in 2,000 l of ~ater/ha. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. The figures denote:
0~ = no action (like untreated control) 100% - total destruction In this test, for example, the compound of preparation example t9) shows a better action against ~eeds in, for ex-ample, wheat than comparison compound (A).
Le A ?3 904 .
Pre-emergence test/greenhouse Solvent: 5 parts by weight of acetone Fmulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a su;table preparation of active com-pound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsi-fier is added and the concentrate ;s d;luted w;th water to the des;red concentration.
Seeds of the test plants are sown ;n normal so;l and, after 24 hours, watered w;th the preparation of act;ve compound. It ;s exped;ent to keep constant the amount of water per un;t area. The concentration of act;ve compound in the preparat;on is of no importance, only the amount of active compound appl;ed per un;t area be;ng decis;ve. After three ~eeks, the degree of damage to the plants is rated in X damage in comparison to the development of th~ untreated control. The figures denote:
OX = no action (like untreated control) 100X = total destruction In this test~ for example, the compound of prepar-at;on example (9) shows a better action than compar;son compound (A~ C= 1-(2-methoxy-phenylsulphonyl)-3-~4,6-dimethyl-pyr;mid;n-2-yl)-urea~.
Le A 34 904 :~z'~
Example_8 Pos~-emergence test/greenhouse Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of aLkylaryl polyglycol ether To produce a suitable preparation of active com-pound~ 1 part by weight of active compound is mixed ~ith the stated amount of solvent, the stated amount of emulsi-fier is added and the concentrate is diluted with water to the desired concentration.
Test plants which have a height of 5 - 15 cm are sprayed with the preparation of active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is so chosen ~hat the particular amounts of active compound desired are applied in 2,000 l of ~ater/ha. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. The figures denote:
0~ = no action (like untreated control) 100% - total destruction In this test, for example, the compound of preparation example t9) shows a better action against ~eeds in, for ex-ample, wheat than comparison compound (A).
Le A ?3 904 .
Claims (24)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A 1-(2-oxyaminosulphonylphenylsulphonyl)-3-triazinyl-urea of the formula in which R1 represents an unsubstituted or substituted radical selected from the group consisting of C1-C12 alkyl, (which may be substituted by fluorine, chlorine, cyano, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkyl-sulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl, C1-C4-alkyl-amino-carbonyl or di-(C1-C4-alkyl)-amino-carbonyl), C3-C6-alkenyl (which may be sub-stituted by fluorine, chlorine, or bromine), C3-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C2-alkyl, phenyl-C1-C2-alkyl (which may be substituted by fluorine, chlorine, nitro, cyano, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkoxy-carbonyl), and benzhydryl or phenyl (which each may be substituted by fluorine, chlorine, nitro, cyano, C1-C4-alkyl, trifluoromethyl, C1-C4-alkoxy, C1-C2-fluoroalkoxy, C1-C4-alkylthio, trifluoro methylthio or C1-C4-alkoxy-carbonyl).
R2 represents fluorine, chlorine, bromine, hydroxyl, cyclopropyl or C1-C4-alkyl (which may be substituted by fluorine or chlorine), or represents C1-C4-alkoxy (which may be substituted by fluorine or chlorine), or represents C1-C4-alkyl-thio (which may be substituted by fluorine or chlorine) or amino, or represents C1-C4-alkyl- or di-(C1-C4-alkyl)-amino (each of which may be substituted by fluorine) and R3 represents fluorine, chlorine, bromine, hydroxyl, cyclopropyl or C1-C4-alkyl (which may be substituted by fluorine or chlorine), or represents C1-C4-alkoxy (which may be substituted by fluorine or chlorine), or represents C1-C4-alkyl-thio (which may be substituted by fluorine or chlorine) or amino, or represents C1-C4-alkyl- or di-(C1-C4-alkyl)-amino (each of which may be sub-stituted by fluorine), or a salt thereof formed with a strong base.
R2 represents fluorine, chlorine, bromine, hydroxyl, cyclopropyl or C1-C4-alkyl (which may be substituted by fluorine or chlorine), or represents C1-C4-alkoxy (which may be substituted by fluorine or chlorine), or represents C1-C4-alkyl-thio (which may be substituted by fluorine or chlorine) or amino, or represents C1-C4-alkyl- or di-(C1-C4-alkyl)-amino (each of which may be substituted by fluorine) and R3 represents fluorine, chlorine, bromine, hydroxyl, cyclopropyl or C1-C4-alkyl (which may be substituted by fluorine or chlorine), or represents C1-C4-alkoxy (which may be substituted by fluorine or chlorine), or represents C1-C4-alkyl-thio (which may be substituted by fluorine or chlorine) or amino, or represents C1-C4-alkyl- or di-(C1-C4-alkyl)-amino (each of which may be sub-stituted by fluorine), or a salt thereof formed with a strong base.
2. A compound according to claim 1, in which R2 represents fluorine, chlorine, hydroxyl, cyclopropyl.
or methyl (which may be substituted by fluorine or chlorine), or represents C1-C3-alkoxy (which may be substituted by fluorine or chlorine) or represents C1-C3-alkylthio (which may be substituted by fluorine or chlorine) or amino, or represents C1-C3-alkyl- or di-(C1-C3-alkyl)-amino (which may be substituted by fluorine) and R3 represents fluorine, chlorine, hydroxyl, cyclo-propyl, methyl (which may be substituted by fluorine or chlorine), or represents C1-C3-alkoxy (which may be substituted by fluorine or chlorinel, or represents C1-C3-alkylthio (which may be substituted by fluorine or chlorine), or amino, or represents C1-C3-alkyl- or di-(C1-C3-alkyl)-amino (which may be substituted by fluorine).
or methyl (which may be substituted by fluorine or chlorine), or represents C1-C3-alkoxy (which may be substituted by fluorine or chlorine) or represents C1-C3-alkylthio (which may be substituted by fluorine or chlorine) or amino, or represents C1-C3-alkyl- or di-(C1-C3-alkyl)-amino (which may be substituted by fluorine) and R3 represents fluorine, chlorine, hydroxyl, cyclo-propyl, methyl (which may be substituted by fluorine or chlorine), or represents C1-C3-alkoxy (which may be substituted by fluorine or chlorinel, or represents C1-C3-alkylthio (which may be substituted by fluorine or chlorine), or amino, or represents C1-C3-alkyl- or di-(C1-C3-alkyl)-amino (which may be substituted by fluorine).
3. A compound according to claim 1, in which R1 represents C1-C8-alkyl (which may be substituted by fluorine or chlorine)C3-C4-alkenyl, C1-C2-alkoxy-carbonyl-methyl, phenyl, phenethyl or benzyl (which may be substituted by fluorine, chlorine, nitro, cyano, methyl, methoxy or methoxy-carbonyl), R2 represents chlorine, methyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, ethylamino, dimethylamino, or diethylamino and R3 represents chlorine, methyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, ethylamino, dimethylamino or diethylamino.
4. A compound according to Claim 1 wherein R1 is methyl, ethyl, n-propyl, isopropyl, 2-propenyl, n-octyl, benzyl, 2-methylpropyl, 3-methylbutyl or 2,6-dichlorobenzyl, R2 is methoxy, methylthio, methyl, ethyl or ethoxy, and, R3 is methoxy, ethoxy, diethylamino, ethylamino, methylthio, methyl, methylamino or dimethylamino.
5. 1-(2-Methoxyaminosulphonylphenylsulphonyl)-3-(4,6-di-methoxy-1 3,5-triazin-2-yl)-urea of the formula .
6. 1-(2-Methoxyaminosulphonylphenylsulphonyl)-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea of the formula .
7. A method of combating weeds which comprises applying to the weeds or to their habitat a herbicidally effective amount of a compound according to Claim 1.
8. A method according to Claim 7 wherein the compound is applied in the form of a composition containing said compound as active ingredient in admixture with a suitable carrier or diluent.
9. A method according to Claim 8 wherein the active ingredient concentration in said composition is between 0.1 and 95% by weight.
10. A method according to Claim 8 wherein the active ingre-dient concentration in said composition is between 0.5 and 90%
by weight.
by weight.
11. A method according to Claim 7, 8, or 10 wherein the compound is applied as a pre-emergence herbicide.
12. A method according to Claim 7, 8 or 10 wherein the compound is applied as a post-emergence herbicide.
13. A method according to Claim 7, 8 or 10 wherein the compound is applied to an area of cultivation at a rate of between 0.01 and 10 kg/ha.
14. A method according to Claim 7,8 or 10 wherein the compound is applied to an area of cultivation at a rate of between 0.05 and 5 kg/ha.
15. A method according to Claim 7, 8 or 10 wherein such compound is 1-(2-methoxyaminosulphonylphenylsulphonyl)-3-4,6-di-methoxy-1,3,5- triazin-2-yl)-urea.
16. A method according to Claim 7,8 or 10 wherein such compound is 1-(2-methoxyaminosulphonylphenylsulphonyl)-3-(4-methoxy-6-methyl-1,3,5-triazdn-2-yl)-urea.
17. A process for preparing a 1-(2-oxyaminosulphonylphenyl-sulphonyl)-3-triazinyl-urea of the general formula (I) as defined in Claim 1, which comprises (a) reacting a benzodisultam of the formula (II) (II) in which R1, R2, and R3 have the meanings given in Claim 1, with water, or (b) reacting a benzene-1,2-disulphonic acid dichloride of the formula (III) (III) with an oxyguanidine derivative of the formula (IV) (IV) in which R1, R2 and R3 have the meanings given in Claim 1, in the presence of an acid acceptor, and further reacting the compound so obtained, of the formula (II), with water.
18. A herbicidal composition comprising a herbicidally effective amount of a compound according to Claim 1 as active ingredient in admixture with a diluent or carrier.
19. A herbicidal composition comprising a herbicidally effective amount of a compound according to Claim 1 as active ingredient in admixture with a solid diluent or carrier, or in admixture with a liquid diluent or carrier containing a surface active agent.
20. A composition according to Claim 17 or 18 wherein such compound is according to Claim 2.
21. A composition according to Claim 17 or 18 wherein such compound is according to claim 3.
22. A composition according to Claim 17 or 18 wherein such compound is according to Claim 4.
23. A composition according to Claim 17 or 18 wherein such compound is 1-(2-methoxyaminosulphonylphenylsulphonyl),-3-(4,6-di-methoxy-1,3,5-triazin-2-yl)-urea.
24. A composition according to Claim 17 or 18 wherein such compound is 1-(2-methoxyaminosulphonylphenylsulphonyl)-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19853528100 DE3528100A1 (en) | 1985-08-06 | 1985-08-06 | 1- (2-OXYAMINOSULFONYLPHENYLSULFONYL) -3-TRIAZINYL UREA |
| DEP3528100.6 | 1985-08-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1242720A true CA1242720A (en) | 1988-10-04 |
Family
ID=6277766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000515170A Expired CA1242720A (en) | 1985-08-06 | 1986-08-01 | 1-(2-oxyaminosulphonylphenylsulphonyl)-3-triazinyl- ureas |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0213378A1 (en) |
| JP (1) | JPS6233163A (en) |
| KR (1) | KR870002103A (en) |
| AU (1) | AU6093586A (en) |
| BR (1) | BR8603715A (en) |
| CA (1) | CA1242720A (en) |
| DD (1) | DD248727A5 (en) |
| DE (1) | DE3528100A1 (en) |
| DK (1) | DK372486A (en) |
| ES (1) | ES2000130A6 (en) |
| HU (1) | HUT44136A (en) |
| IL (1) | IL79604A0 (en) |
| ZA (1) | ZA865860B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK536582A (en) * | 1981-12-07 | 1983-06-08 | Du Pont | HERBICIDE SULPHONAMIDES |
| BR8401507A (en) * | 1983-04-04 | 1984-11-13 | Du Pont | STABILIZED WATER COMPOSITION |
| US4548638A (en) * | 1983-08-22 | 1985-10-22 | E. I. Du Pont De Nemours And Company | Herbicidal sulfonylureas |
-
1985
- 1985-08-06 DE DE19853528100 patent/DE3528100A1/en not_active Withdrawn
-
1986
- 1986-07-25 EP EP86110264A patent/EP0213378A1/en not_active Withdrawn
- 1986-08-01 CA CA000515170A patent/CA1242720A/en not_active Expired
- 1986-08-04 DD DD86293406A patent/DD248727A5/en unknown
- 1986-08-04 IL IL79604A patent/IL79604A0/en unknown
- 1986-08-05 JP JP61182879A patent/JPS6233163A/en active Pending
- 1986-08-05 BR BR8603715A patent/BR8603715A/en unknown
- 1986-08-05 KR KR1019860006458A patent/KR870002103A/en not_active Application Discontinuation
- 1986-08-05 ZA ZA865860A patent/ZA865860B/en unknown
- 1986-08-05 DK DK372486A patent/DK372486A/en not_active Application Discontinuation
- 1986-08-06 HU HU863428A patent/HUT44136A/en unknown
- 1986-08-06 ES ES8600905A patent/ES2000130A6/en not_active Expired
- 1986-08-06 AU AU60935/86A patent/AU6093586A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| DK372486A (en) | 1987-02-07 |
| ZA865860B (en) | 1987-04-29 |
| DK372486D0 (en) | 1986-08-05 |
| DE3528100A1 (en) | 1987-02-19 |
| DD248727A5 (en) | 1987-08-19 |
| HUT44136A (en) | 1988-02-29 |
| EP0213378A1 (en) | 1987-03-11 |
| ES2000130A6 (en) | 1987-12-16 |
| JPS6233163A (en) | 1987-02-13 |
| IL79604A0 (en) | 1986-11-30 |
| KR870002103A (en) | 1987-03-30 |
| AU6093586A (en) | 1987-02-12 |
| BR8603715A (en) | 1987-03-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1341034C (en) | Heterocyclic 2-alkoxyphenoxysulfonylureas and the use thereof as herbicides or plant growth regulators | |
| JPH0267262A (en) | (hetero)aryloxynaphthalene having substituent bonded through fulfur | |
| CA1225407C (en) | Substituted phenylsulfonylurea derivatives, a process for their preparation and their use as herbicides, and new intermediate products for their preparation | |
| AU596238B2 (en) | Triazolo-pyrimidine-2-sulphonamides | |
| US4586951A (en) | Herbicidally active substituted phenylsulfonylurea derivatives | |
| US4459151A (en) | Herbicidally active fluorine-containing 4,6-diamino-s-triazines | |
| US4732711A (en) | Herbicidal novel 1-(2-trifluoromethoxy-phenylsulphonyl)-3-heteroaryl-(thio)ureas | |
| US4470842A (en) | Herbicidally active novel 3-alken(in)yl-mercapto(amino)-4-amino-6-tert-butyl-1,2,4-triazin-5-ones | |
| CA1166250A (en) | Substituted tetrahydropyrimidinone derivatives, process for their preparation and their use as herbicides | |
| CA1244015A (en) | Benzodisultams | |
| US4386953A (en) | Herbicidally active substituted 6-halogeno-tert.-butyl-1,2,4-triazin-5-ones | |
| US4725304A (en) | Fluoroalkoxyphenylsulphonylguanidines | |
| CA1242720A (en) | 1-(2-oxyaminosulphonylphenylsulphonyl)-3-triazinyl- ureas | |
| KR920007555B1 (en) | Method of preparing for 1-(2-oxyaminosulfonylphenylsul-fonyl)-3-heteroaryl-urea | |
| CA1292230C (en) | 3-substituted 1-(2-halogenoalkoxy-benzenesulphonyl)-3- heteroaryl-(thio)ureas | |
| JPS62120384A (en) | Thienylsulfonylguanidine derivative | |
| CA1278570C (en) | Benzodisultams | |
| CA1218366A (en) | Herbicidally active n.sup.1,n.sup.2- disubstituted-n-azolecarboxamidines | |
| US4426523A (en) | Preparation of 1-amino-1,3,5-triazine-2,4(1H, 3H)-diones | |
| DD237784A5 (en) | HERBICIDE MEDIUM | |
| US4846881A (en) | 3,4,6-trisubstituted 1,2,4-triazin-5(4H)-one herbicides | |
| EP0173321A1 (en) | Sulfonyl-guanidinopyrimidine derivatives | |
| CA1230118A (en) | Sulphonyl-iso-thioureido-triazine derivatives and process therefor | |
| JPH06199848A (en) | Substituted thienylsulfonylurea | |
| EP0611759A1 (en) | Pyrimidinyloxy/triazinyloxy alkanol derivatives and their use as herbicides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |