CA1090350A - Herbicidally active 2-dimethylcarbamoylimino-1,3,4- thiadiazolin-3-ide salts - Google Patents
Herbicidally active 2-dimethylcarbamoylimino-1,3,4- thiadiazolin-3-ide saltsInfo
- Publication number
- CA1090350A CA1090350A CA278,903A CA278903A CA1090350A CA 1090350 A CA1090350 A CA 1090350A CA 278903 A CA278903 A CA 278903A CA 1090350 A CA1090350 A CA 1090350A
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- Canada
- Prior art keywords
- substituted
- compound
- general formula
- compounds
- thiadiazolin
- Prior art date
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
- C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
- C07D285/135—Nitrogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention provides herbicidally active 2-dimethylcarbamoylimino-1,3,4-thiadiazolin-3-ide salts of the general formula I
The present invention provides herbicidally active 2-dimethylcarbamoylimino-1,3,4-thiadiazolin-3-ide salts of the general formula I
Description
1~90350 The present invention is concerned with new herbicidally active 2-dimethylcarbamoylimino-1,3,4-thiadiazolin-3-ide salts, with a process for the manufacture of these compounds and also with their use.
` 1-(1,3,4-Thiadiazol-2-yl)-urea derivatives having a her-bicidal action have already been known (German Offenlegungsschrif-ten Nos. 1,816,696, 1,901,672 and 2,118,520). However, they have insufficient action against undesired plant growth in crop planta-tions.
The present invention provides a herbicidal agent which has an excellent action against weeds and also a wide spectrum of selectivity towards crop plants.
The present invention accordingly provides compounds of the general formula I
N - -N-B
11 1 / CH3 (I) R-C C=N-CO-N
in which R represents a tertiary butyl group and B represents a ~20 lithium sodium or potassium atom.
The compounds of the present invention are distinguished ~` by their broad soil-herbicidal and leaf-herbicidal action. They can be used for combating mono- and di-cotyledonous weeds.
~.
, .' . i .
;30 ~ -- 2 -- ~A;
, With the compounds of the present invention there are combated by pre-emergence and also by post-emergence methods agricultural weeds, for example Sinapis ssp., Stellaria media, Senecio vulgaris, Matricaria chamomilla, Ipomoea purpurea, Chrysanthemum segetum, Lamium amplexicaule, Centaurea cyanus, Amaranthus retroflexus, Alopecurus myosuroides, Echinochloa crus galli, Setaria italica, Sorghum halepense, Lolium perenne and Galium aparine.
For combating seed weeds there are generally used rates of application of 0.5 kg of active substance per hectare to 5 kg of active substance per hectare. When two or more compounds of the general formula I are used the range of 0.5 to 5 kg refers of course to the total amount applied of these compounds. There-; by, the active compounds of the general formula I have proved to be selective in crops of useful plants, for example bush bean, ground-nut, potato, pea, maize, rice, sorghum and soya crops.
At higher rates of application the active compounds are also suitable as total herbicides for the destruction or suppression of waste land flora during a period of vegetation.
The present invention accordingly also provides a herbicidal preparation which comprises a compound of the general formula I, in admixture or conjunction with a suitable carrier.
The preparation may of course contain one or more compounds of the general formula I.
The present invention further provides a method of protecting a living plant against weeds, wherein the area in the vicinity of a living plant is treated with a compound of the general formula I.
' lt~90350 The present invention further provides a method of protecting a crop area against weeds, wherein a crop area is treated with a compound of the general formula I.
The present invention further provides a method of protecting a waste land against weeds, wherein a waste land is -~ treated with one or more compounds of the general formula I, the compound(s) being used in a total amount of more than 5 kg per hectare. -The present invention further provides a pack which comprises a compound of the general formula I together with instructions for its use as a herbicide.
The compounds of the present invention may be used ,.
`~ either alone, orin admixture with one another or with other active substances.
Depending on the purpose desired, there may be mentioned -~ in this connection, for example, the following herbicidally - active substances which may, if desired, be added to the '.~ compounds of the invention only immediately before use:
i substituted anilines, -, 20 substituted aryloxycarboxylic acids and also salts, esters and amides thereof, substituted ethers, substituted arsonic acids and also salts, esters and amides thereof, substituted benzimidazoles, substituted benzisothiazoles, ~ substituted benzthiadiazinone dioxides, ;.
substituted benzoxazines, substituted benzoxazinones, substituted benzthiazoles, ., ~"
10~)350 : substituted benzthiadiazoles, ~ substituted biurets, `. substituted quinolines, : substituted carbamates, substituted aliphatic carboxylic acids and also salts, esters and amides thereof, substituted aromatic carboxylic acids and also salts, esters and amides thereof, - substituted carbamoylalkyl-thio- or dithio-phosphates, substituted quinazolines, : substituted cycloalkylamido-carbonthiolic acids and also ; salts, esters and amides thereof, . substituted cycloalkylcarbonamido-thiazoles, substituted dicarboxylic acids and also salts, esters and amides thereof, substituted dihydrobenzofuranyl sulphonates, substituted disulphides, ~:
substituted dipyridylium salts, ~ . .
' substituted dithiocarbamates, ~: 20 substituted'dithiophosphoric acids and also salts, esters and . - amides thereof, substituted ureas, ~ substituted hexahydro-lH-carbothioates, -: substituted hydantoins, substituted hydrazides, :~
- substituted hydrazonium salts, .: .
.-` substituted isoxazole-pyrimidones, substituted imidazoles, substituted isothiazole-pyrimidones, :
' ~t~90350 substituted ketones, substituted naphthoquinones, substituted aliphatic nitriles, substituted aromatic nitriles, substituted oxadiazoles, substituted oxadiazinones, substituted oxadiazolidinediones, - substituted oxadiazinediones, substituted phenols and also salts and esters thereof, substituted phosphonic acids and also salts, esters and amides ;,` thereof, substituted phosphonium chlorides, .
;~, substituted phosphonalkyl-glycines, i. substituted phosphites, substituted phosphoric acids and also salts, esters and amides thereof, substituted piperidines, substituted pyrazoles, . substituted pyrazolalkyl-carboxylic acids and also salts, r 20 esters and amides thereof, substituted pyrazolium salts, substituted pyrazolium alkyl sulphates, substituted pyridazines, substituted pyrimidines, substituted pyrrolidones, ` substituted pyridazones, ; substituted pyridine carboxylic acids and also salts, esters and amides thereof, ''.
1(~90350 substituted pyridines, substituted pyridine carboxylates, substituted pyridinones, substituted pyrimidones, substituted pyrrolidine carboxylic acids and also salts, : esters and amides thereof, substituted pyrrolidines, substituted aryl sulphonic acids and also salts, esters and amides thereof, substituted styrenes, -substituted tetrahydro-oxadiazine-diones, substituted tetrahydromethanoindenes, :.
., , substituted tetrahydro-diazole-thiones, -~
` substituted tetrahydro-thiadiazine-thiones, ~-substituted tetrahydro-thiadiazolediones, : substituted thiadiazoles, substituted aromatic thiocarboxylic acid amides, substituted thiocarboxylic acids and also salts, esters and amides thereof, substituted thiolcarbamates, -substituted thiophosphoric acids and also salts, esters and amides thereof, substituted triazines, substituted triazoles, substituted tetrahydro-oxadiazole-diones, substituted thioureas, substituted uracils and ~-substituted uretidine-diones.
:
~;
.
1(!~()350 Furthermore, there may also be used other additives, for example non-phytotoxic additives which produce with herbicides - a synergistic increase in action, for example wetting agents, emulsifiers, solvents and oily additives.
Advantageously, the active compounds of the general formula I or mixtures containina them are used in the form of herbicidal preparations, for example powders, strewable preparations, granules, solutions, emulsions or suspensions, ~' with the addition of liquid and/or solid vehicles or diluents, ` 10 and, if desired, of surface-active agents, for example wetting, adherent, emulsifying and/or dispersing assistants.
Suitable liquid carriers are, for example, water, aliphatic hydrocarbons, aromatic hydrocarbons, for example benzene, toluene and xylene, cyclohexanone, isophorone, dimethyl sulphoxide and dimethylformamide, and also mineral oil fractions.
.` As solid carriers there are suitable, for example, .... .
mineral earths, for example tonsil, silica gel, talcum, kaolin, attaclay, limestone and silicic acid, and vegetable products, for example meals.
. 20 As surface-active agents there may be mentioned, for example, calcium lignin sulphonate, polyoxyethylene alkylphenyl ethers, naphthalene sulphonic acids and salts thereof, phenol sulphonic acids and salts thereof, formaldehyde condensates, fatty alcohol sulphates and also substituted benzene sulphonic - acids and salts thereof.
The total amount of the active substance or substances -~
in the various herbicidal preparations may vary within wide ! limits. For example, the preparations may contain approximately 10 to 80% by weight of active compound(s), approximately 90 to ~, .
: `' l(~9~J350 20% by weight of liquid or solid carrier and also, if desired, up to 20% by weight of surface-active agent(s).
The application of the active compounds may be carried out in the usual manner, for example, with water as carrier in quantities of spray liquors from approximately 100 to 1000 litres per hectare. It is also possible to apply the active compounds by the so-called "low volume" and "ultra-low volume" methods, and also to apply them in the form of so-called microgranules.
The compounds of the present invention are salts which ; 10 exist ionically corresponding to the following polar limiting formulae : 30 A~ g .
1(~9()350 . ~, .
N N I(--) R ~ / N CO N f ( ) ~ >
\5 ., < B (+) < >
N
R ~ ~ ~(~) CH
S ~ ' or formulated in general as -- N~
I `I /CH3 R ~ ~ CH
1(~90350 For the sake of simplicity these limiting formulae are not shown by the general formula I, but it is to be understood herein that each compound of the general formula I includes any one of the aforesaid ionic forms.
The hitherto unknown compounds of the general formula I may be prepared, for example, by the process of the present invention, as defined below.
The present invention accordingly further provides a process for the manufact~re of a compound of the general formula I, wherein (a) dimethylcarbamoyl chloride of the formula II ~.
3 \
N-CO-Cl II :~
is reacted in the presence of an acid-binding agent with a 1,3,4-thiadiazol-2-amine of the general formula III
: R-~ C-NH2 III, .
\ S /
., .
. in which R has the meaning given above, to form a 2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-carboxylic acid dimethyl-amide derivative of the general formula IV
. ~ - - . - . .
: .
, .
- ' , . :-. . ~
.
~ 0350 po-~
. ~
in which R has the meaning given above, which is split with a metal compound of the general formula V
' 10 B( )Y( ) (V), in which B has the meaning given above and Y represents a hydrogen atom or a hydroxyl, lower alkoxy or amino group, or (b) a 1-(1,3,4-thiadiazol-2-yl)-3,3-dimethyl-urea derivative of the general'formula VI
R-~ ~ ~C-~H-C0-~ < ~VI) , . .
20 in which R has the meaning given above, is reacted with a metal - compound of the general formula V
, B( )Y( ) (V~
in which B and Y have the meanings given above.
~, Each step of the process of the present invention may, if desired, be carried out in the presence of a solvent.
. . .
The reaction of the components is carried out at between 0 and 100C, but generally at room temperature.
. .
~ For the synthesis of the compounds of the present - 30 invention the reactants are used in approximately equimolar ~1 quantities.
:
--~ lQ90350 .~
As reaction media there are suitable polar organic solvents, alone or in admixture with water. Their choice depends on generally known considerations regarding the use of the metal - compounds of the general formula B( )Y( ). As solvents or suspension media there may be mentioned amongst many, for : example, acid amides, for example dimethylformamide, acid nitriles, for example acetonitrile, alcohols, for example methanol or ethanol, and ethers, for example tetrahydrofuran.
For synthesizing the compounds of the general formula IV there may be used as the acid-binding agents all the usual acid-binding agents, for example organic bases, advantageously tertiary amines, for example triethylamine or N,N-dimethylaniline, pyridine derivatives, or inorganic bases, for example oxides, hydroxides, carbonates and alkanoic acid salts of alkali metals or alkaline earth metals; liquid acid-binding agents may serve simultaneously as solvents.
The isolation of the compounds of the present invention formed is carried out finally by distilling off the solvent used under atmospheric or a reduced pressure or by precipitation with weakly polar organic solvents, for example with ketones, for example acetone, or ethers, for example diisopropyl ether.
The compounds of the present invention are colourless and odourless crystalline solids, which are excellently soluble ~` in water, readily soluble in polar organic solvents, for example carboxylic acid amides, for example dimethylformamide, sulphox-ides, for example dimethyl sulphoxide, and lower alcohols, for example methanol and ethanol, sparingly soluble in carbonitriles, for example acetonitrile, and insoluble in hydrocarbons, halo-genated hydrocarbons, ethers and ketones.
', ~ .
`- 109()350 :`
The foilowing Examples illustrate the invention. Examples `;; 3 to 5 illustrate the mode of action of the compounds of the gen-` eral formula I.
Example 1 ; 27.1 Grams of 5-ethyl-2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-carboxylic acid dimethylamide melting at 100C
were suspended in 150 ml of methanol. There was added dropwise, while stirring, a solution of 4 grams of sodium hydroxide in 100 ml of methanol at room temperature. After 3 hours there was obtained a clear solution, from which the methanol was then dis-tilled off in vacuo. The residue that remained was digested with acetonitrile, filtered with suction to remove the washing agent ~-and dried ln vacuo at 80C.
Yield: 15.5 grams (69.8% of the theoretical yield~ of the sodium salt of 5-ethyl-2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-ide having a melting point of >250C.
C7HllN4NaOS M.W.: 222.26 Analysis Calculated: C 37.83% H 4.99% N 25.21% Na 10.34~
Found: C 37.70% H 5.05% N 24.95% Na 10.76%
Example 2 , .
8.1 Grams of 1-(5-tert.-butyl-1,3,4-thiadiazol-2-yl)-3,3-dimethyl-urea melting at 121C were dissolved together with 0.853 gram of lithium hydroxide in 70 ml of methanol. The solu-tion was then concentrated in vacuo, and the residue . . .
was triturated with a mixture of diisopropyl ether and isopropanol, filtered off with suction and washed with diethyl ether. By drying in vacuo at 120C there were obtained 7.8 grams (93.8%
of the theoretical yield) of the lithium salt of 5-tert.-butyl-
` 1-(1,3,4-Thiadiazol-2-yl)-urea derivatives having a her-bicidal action have already been known (German Offenlegungsschrif-ten Nos. 1,816,696, 1,901,672 and 2,118,520). However, they have insufficient action against undesired plant growth in crop planta-tions.
The present invention provides a herbicidal agent which has an excellent action against weeds and also a wide spectrum of selectivity towards crop plants.
The present invention accordingly provides compounds of the general formula I
N - -N-B
11 1 / CH3 (I) R-C C=N-CO-N
in which R represents a tertiary butyl group and B represents a ~20 lithium sodium or potassium atom.
The compounds of the present invention are distinguished ~` by their broad soil-herbicidal and leaf-herbicidal action. They can be used for combating mono- and di-cotyledonous weeds.
~.
, .' . i .
;30 ~ -- 2 -- ~A;
, With the compounds of the present invention there are combated by pre-emergence and also by post-emergence methods agricultural weeds, for example Sinapis ssp., Stellaria media, Senecio vulgaris, Matricaria chamomilla, Ipomoea purpurea, Chrysanthemum segetum, Lamium amplexicaule, Centaurea cyanus, Amaranthus retroflexus, Alopecurus myosuroides, Echinochloa crus galli, Setaria italica, Sorghum halepense, Lolium perenne and Galium aparine.
For combating seed weeds there are generally used rates of application of 0.5 kg of active substance per hectare to 5 kg of active substance per hectare. When two or more compounds of the general formula I are used the range of 0.5 to 5 kg refers of course to the total amount applied of these compounds. There-; by, the active compounds of the general formula I have proved to be selective in crops of useful plants, for example bush bean, ground-nut, potato, pea, maize, rice, sorghum and soya crops.
At higher rates of application the active compounds are also suitable as total herbicides for the destruction or suppression of waste land flora during a period of vegetation.
The present invention accordingly also provides a herbicidal preparation which comprises a compound of the general formula I, in admixture or conjunction with a suitable carrier.
The preparation may of course contain one or more compounds of the general formula I.
The present invention further provides a method of protecting a living plant against weeds, wherein the area in the vicinity of a living plant is treated with a compound of the general formula I.
' lt~90350 The present invention further provides a method of protecting a crop area against weeds, wherein a crop area is treated with a compound of the general formula I.
The present invention further provides a method of protecting a waste land against weeds, wherein a waste land is -~ treated with one or more compounds of the general formula I, the compound(s) being used in a total amount of more than 5 kg per hectare. -The present invention further provides a pack which comprises a compound of the general formula I together with instructions for its use as a herbicide.
The compounds of the present invention may be used ,.
`~ either alone, orin admixture with one another or with other active substances.
Depending on the purpose desired, there may be mentioned -~ in this connection, for example, the following herbicidally - active substances which may, if desired, be added to the '.~ compounds of the invention only immediately before use:
i substituted anilines, -, 20 substituted aryloxycarboxylic acids and also salts, esters and amides thereof, substituted ethers, substituted arsonic acids and also salts, esters and amides thereof, substituted benzimidazoles, substituted benzisothiazoles, ~ substituted benzthiadiazinone dioxides, ;.
substituted benzoxazines, substituted benzoxazinones, substituted benzthiazoles, ., ~"
10~)350 : substituted benzthiadiazoles, ~ substituted biurets, `. substituted quinolines, : substituted carbamates, substituted aliphatic carboxylic acids and also salts, esters and amides thereof, substituted aromatic carboxylic acids and also salts, esters and amides thereof, - substituted carbamoylalkyl-thio- or dithio-phosphates, substituted quinazolines, : substituted cycloalkylamido-carbonthiolic acids and also ; salts, esters and amides thereof, . substituted cycloalkylcarbonamido-thiazoles, substituted dicarboxylic acids and also salts, esters and amides thereof, substituted dihydrobenzofuranyl sulphonates, substituted disulphides, ~:
substituted dipyridylium salts, ~ . .
' substituted dithiocarbamates, ~: 20 substituted'dithiophosphoric acids and also salts, esters and . - amides thereof, substituted ureas, ~ substituted hexahydro-lH-carbothioates, -: substituted hydantoins, substituted hydrazides, :~
- substituted hydrazonium salts, .: .
.-` substituted isoxazole-pyrimidones, substituted imidazoles, substituted isothiazole-pyrimidones, :
' ~t~90350 substituted ketones, substituted naphthoquinones, substituted aliphatic nitriles, substituted aromatic nitriles, substituted oxadiazoles, substituted oxadiazinones, substituted oxadiazolidinediones, - substituted oxadiazinediones, substituted phenols and also salts and esters thereof, substituted phosphonic acids and also salts, esters and amides ;,` thereof, substituted phosphonium chlorides, .
;~, substituted phosphonalkyl-glycines, i. substituted phosphites, substituted phosphoric acids and also salts, esters and amides thereof, substituted piperidines, substituted pyrazoles, . substituted pyrazolalkyl-carboxylic acids and also salts, r 20 esters and amides thereof, substituted pyrazolium salts, substituted pyrazolium alkyl sulphates, substituted pyridazines, substituted pyrimidines, substituted pyrrolidones, ` substituted pyridazones, ; substituted pyridine carboxylic acids and also salts, esters and amides thereof, ''.
1(~90350 substituted pyridines, substituted pyridine carboxylates, substituted pyridinones, substituted pyrimidones, substituted pyrrolidine carboxylic acids and also salts, : esters and amides thereof, substituted pyrrolidines, substituted aryl sulphonic acids and also salts, esters and amides thereof, substituted styrenes, -substituted tetrahydro-oxadiazine-diones, substituted tetrahydromethanoindenes, :.
., , substituted tetrahydro-diazole-thiones, -~
` substituted tetrahydro-thiadiazine-thiones, ~-substituted tetrahydro-thiadiazolediones, : substituted thiadiazoles, substituted aromatic thiocarboxylic acid amides, substituted thiocarboxylic acids and also salts, esters and amides thereof, substituted thiolcarbamates, -substituted thiophosphoric acids and also salts, esters and amides thereof, substituted triazines, substituted triazoles, substituted tetrahydro-oxadiazole-diones, substituted thioureas, substituted uracils and ~-substituted uretidine-diones.
:
~;
.
1(!~()350 Furthermore, there may also be used other additives, for example non-phytotoxic additives which produce with herbicides - a synergistic increase in action, for example wetting agents, emulsifiers, solvents and oily additives.
Advantageously, the active compounds of the general formula I or mixtures containina them are used in the form of herbicidal preparations, for example powders, strewable preparations, granules, solutions, emulsions or suspensions, ~' with the addition of liquid and/or solid vehicles or diluents, ` 10 and, if desired, of surface-active agents, for example wetting, adherent, emulsifying and/or dispersing assistants.
Suitable liquid carriers are, for example, water, aliphatic hydrocarbons, aromatic hydrocarbons, for example benzene, toluene and xylene, cyclohexanone, isophorone, dimethyl sulphoxide and dimethylformamide, and also mineral oil fractions.
.` As solid carriers there are suitable, for example, .... .
mineral earths, for example tonsil, silica gel, talcum, kaolin, attaclay, limestone and silicic acid, and vegetable products, for example meals.
. 20 As surface-active agents there may be mentioned, for example, calcium lignin sulphonate, polyoxyethylene alkylphenyl ethers, naphthalene sulphonic acids and salts thereof, phenol sulphonic acids and salts thereof, formaldehyde condensates, fatty alcohol sulphates and also substituted benzene sulphonic - acids and salts thereof.
The total amount of the active substance or substances -~
in the various herbicidal preparations may vary within wide ! limits. For example, the preparations may contain approximately 10 to 80% by weight of active compound(s), approximately 90 to ~, .
: `' l(~9~J350 20% by weight of liquid or solid carrier and also, if desired, up to 20% by weight of surface-active agent(s).
The application of the active compounds may be carried out in the usual manner, for example, with water as carrier in quantities of spray liquors from approximately 100 to 1000 litres per hectare. It is also possible to apply the active compounds by the so-called "low volume" and "ultra-low volume" methods, and also to apply them in the form of so-called microgranules.
The compounds of the present invention are salts which ; 10 exist ionically corresponding to the following polar limiting formulae : 30 A~ g .
1(~9()350 . ~, .
N N I(--) R ~ / N CO N f ( ) ~ >
\5 ., < B (+) < >
N
R ~ ~ ~(~) CH
S ~ ' or formulated in general as -- N~
I `I /CH3 R ~ ~ CH
1(~90350 For the sake of simplicity these limiting formulae are not shown by the general formula I, but it is to be understood herein that each compound of the general formula I includes any one of the aforesaid ionic forms.
The hitherto unknown compounds of the general formula I may be prepared, for example, by the process of the present invention, as defined below.
The present invention accordingly further provides a process for the manufact~re of a compound of the general formula I, wherein (a) dimethylcarbamoyl chloride of the formula II ~.
3 \
N-CO-Cl II :~
is reacted in the presence of an acid-binding agent with a 1,3,4-thiadiazol-2-amine of the general formula III
: R-~ C-NH2 III, .
\ S /
., .
. in which R has the meaning given above, to form a 2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-carboxylic acid dimethyl-amide derivative of the general formula IV
. ~ - - . - . .
: .
, .
- ' , . :-. . ~
.
~ 0350 po-~
. ~
in which R has the meaning given above, which is split with a metal compound of the general formula V
' 10 B( )Y( ) (V), in which B has the meaning given above and Y represents a hydrogen atom or a hydroxyl, lower alkoxy or amino group, or (b) a 1-(1,3,4-thiadiazol-2-yl)-3,3-dimethyl-urea derivative of the general'formula VI
R-~ ~ ~C-~H-C0-~ < ~VI) , . .
20 in which R has the meaning given above, is reacted with a metal - compound of the general formula V
, B( )Y( ) (V~
in which B and Y have the meanings given above.
~, Each step of the process of the present invention may, if desired, be carried out in the presence of a solvent.
. . .
The reaction of the components is carried out at between 0 and 100C, but generally at room temperature.
. .
~ For the synthesis of the compounds of the present - 30 invention the reactants are used in approximately equimolar ~1 quantities.
:
--~ lQ90350 .~
As reaction media there are suitable polar organic solvents, alone or in admixture with water. Their choice depends on generally known considerations regarding the use of the metal - compounds of the general formula B( )Y( ). As solvents or suspension media there may be mentioned amongst many, for : example, acid amides, for example dimethylformamide, acid nitriles, for example acetonitrile, alcohols, for example methanol or ethanol, and ethers, for example tetrahydrofuran.
For synthesizing the compounds of the general formula IV there may be used as the acid-binding agents all the usual acid-binding agents, for example organic bases, advantageously tertiary amines, for example triethylamine or N,N-dimethylaniline, pyridine derivatives, or inorganic bases, for example oxides, hydroxides, carbonates and alkanoic acid salts of alkali metals or alkaline earth metals; liquid acid-binding agents may serve simultaneously as solvents.
The isolation of the compounds of the present invention formed is carried out finally by distilling off the solvent used under atmospheric or a reduced pressure or by precipitation with weakly polar organic solvents, for example with ketones, for example acetone, or ethers, for example diisopropyl ether.
The compounds of the present invention are colourless and odourless crystalline solids, which are excellently soluble ~` in water, readily soluble in polar organic solvents, for example carboxylic acid amides, for example dimethylformamide, sulphox-ides, for example dimethyl sulphoxide, and lower alcohols, for example methanol and ethanol, sparingly soluble in carbonitriles, for example acetonitrile, and insoluble in hydrocarbons, halo-genated hydrocarbons, ethers and ketones.
', ~ .
`- 109()350 :`
The foilowing Examples illustrate the invention. Examples `;; 3 to 5 illustrate the mode of action of the compounds of the gen-` eral formula I.
Example 1 ; 27.1 Grams of 5-ethyl-2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-carboxylic acid dimethylamide melting at 100C
were suspended in 150 ml of methanol. There was added dropwise, while stirring, a solution of 4 grams of sodium hydroxide in 100 ml of methanol at room temperature. After 3 hours there was obtained a clear solution, from which the methanol was then dis-tilled off in vacuo. The residue that remained was digested with acetonitrile, filtered with suction to remove the washing agent ~-and dried ln vacuo at 80C.
Yield: 15.5 grams (69.8% of the theoretical yield~ of the sodium salt of 5-ethyl-2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-ide having a melting point of >250C.
C7HllN4NaOS M.W.: 222.26 Analysis Calculated: C 37.83% H 4.99% N 25.21% Na 10.34~
Found: C 37.70% H 5.05% N 24.95% Na 10.76%
Example 2 , .
8.1 Grams of 1-(5-tert.-butyl-1,3,4-thiadiazol-2-yl)-3,3-dimethyl-urea melting at 121C were dissolved together with 0.853 gram of lithium hydroxide in 70 ml of methanol. The solu-tion was then concentrated in vacuo, and the residue . . .
was triturated with a mixture of diisopropyl ether and isopropanol, filtered off with suction and washed with diethyl ether. By drying in vacuo at 120C there were obtained 7.8 grams (93.8%
of the theoretical yield) of the lithium salt of 5-tert.-butyl-
2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-ide having a ` melting point of >250C.
CgH15LiN4OS M.W.: 234.26 Analysis Calculated: C 46.15% H 6.45% N 23.92% Li 2.96%
Found: C 46.04% H 6.33% N 23.73% Li 2.68%
Each of the other compounds of the present invention listed in the following Table may be prepared in a manner analogous to that described in Example 1 or 2.
~; ." ' .," ~
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:
.,' ~t~$'03SO
Name of the compound Physical constant Sodium salt of 2-(dimethylcarbamoylimino)- M.p.: 288C
5-isopropyl-1,3,4-thiadiazolin-3-ide (with decomposition) Sodium salt of 5-tert.-butyl-2-(dimethyl- M.p.: 306C -carbamoylimino)-1,3,4-thiadiazolin-3-ide (with decomposition) Potassium salt of 5-ethyl-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p.: ~250 DC
.;: Lithium salt of 5-ethyl-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p.: >250C
:~ Sodium salt of 2-(dimethylcarbamoylimino)-: 5-propyl-1,3,4-thiadiazolin-3-ide M.p.: >250~C
Sodium salt of 5-isobutyl-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p.: ~250C
Lithium salt of 2-(dimethylcarbamoylimino)-5-isopropyl-1,3,4-thiadiazolin-3~ide M.p.: >250C
Sodium salt of 2-~dimethylcarbamoylimino)-5-methyl-1,3,4-thiadiazolin-3-ide M.p.: >250C
; Lithium salt of 5-(1,1-dimethylbutyl)-2-. (dimethylcarbamoylimino)-1,3,4-thiadiazolin-
CgH15LiN4OS M.W.: 234.26 Analysis Calculated: C 46.15% H 6.45% N 23.92% Li 2.96%
Found: C 46.04% H 6.33% N 23.73% Li 2.68%
Each of the other compounds of the present invention listed in the following Table may be prepared in a manner analogous to that described in Example 1 or 2.
~; ." ' .," ~
,,~ : . -.
'?
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:
.,' ~t~$'03SO
Name of the compound Physical constant Sodium salt of 2-(dimethylcarbamoylimino)- M.p.: 288C
5-isopropyl-1,3,4-thiadiazolin-3-ide (with decomposition) Sodium salt of 5-tert.-butyl-2-(dimethyl- M.p.: 306C -carbamoylimino)-1,3,4-thiadiazolin-3-ide (with decomposition) Potassium salt of 5-ethyl-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p.: ~250 DC
.;: Lithium salt of 5-ethyl-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p.: >250C
:~ Sodium salt of 2-(dimethylcarbamoylimino)-: 5-propyl-1,3,4-thiadiazolin-3-ide M.p.: >250~C
Sodium salt of 5-isobutyl-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p.: ~250C
Lithium salt of 2-(dimethylcarbamoylimino)-5-isopropyl-1,3,4-thiadiazolin-3~ide M.p.: >250C
Sodium salt of 2-~dimethylcarbamoylimino)-5-methyl-1,3,4-thiadiazolin-3-ide M.p.: >250C
; Lithium salt of 5-(1,1-dimethylbutyl)-2-. (dimethylcarbamoylimino)-1,3,4-thiadiazolin-
3-ide M.p.: >250C
Sodium salt of 5-butyl-2-(dimethylcarbam-.'r oylimino)-1,3,4-thiadiazolin-3-ide M.p.: ~250~C
~ Lithium salt of 5-butyl-2-(dimethylcarba-. 20 moylimino)-1,3,4-thiadiazolin-3-ide M.p.: >250C
: Example 3 ,.
In a series of tests carried out in a greenhouse the compounds of the present invention mentioned in the Table below were each sprayed at a rate of application of 5 kg of active substance per hectare, dissolved in 500 litres of water per hectare, on to Sinapis sp. and Solanum sp. as test plants by the pre- and post-emergence methods. Three weeks after the :
1(~903SO
treatment the results thereof were evaluated, the results being - expressed by a numerical scale extending from 0 to 4, the value 0 representing no action and the value 4 representing destruction of the plant. As Will be seen from the Table destruction of the ; test plants was generally achieved.
.
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Sodium salt of 5-butyl-2-(dimethylcarbam-.'r oylimino)-1,3,4-thiadiazolin-3-ide M.p.: ~250~C
~ Lithium salt of 5-butyl-2-(dimethylcarba-. 20 moylimino)-1,3,4-thiadiazolin-3-ide M.p.: >250C
: Example 3 ,.
In a series of tests carried out in a greenhouse the compounds of the present invention mentioned in the Table below were each sprayed at a rate of application of 5 kg of active substance per hectare, dissolved in 500 litres of water per hectare, on to Sinapis sp. and Solanum sp. as test plants by the pre- and post-emergence methods. Three weeks after the :
1(~903SO
treatment the results thereof were evaluated, the results being - expressed by a numerical scale extending from 0 to 4, the value 0 representing no action and the value 4 representing destruction of the plant. As Will be seen from the Table destruction of the ; test plants was generally achieved.
.
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1~)90350 Example 4 In a series of tests carried out in a greenhouse the plants mentioned in the following Table were treated before their emergence with the listed agents being tested at a rate of application of 1 kg of active substance per hectare. For this purpose the agents were in each case applied uniformly to the soil in the form of an aqueous solution using 500 litres of water per hectare. The results show that the compounds of the present invention have a better action than the known compound used for comparison. The results are expressed by a numerical scale extending from 0 to 10, the value 0 representing destruction of the plant and the value 10 representing no damage.
' ` 20 .~
lO9V350 . ' F eFI~aS o o ~ I I o d ~aulOdI o o o o o o o o ,~ s umula~l~ues~u;~ o o o o o o o o e UmF11~9 ~1 o I I r~
snu,~u~leur~ o o o o o o o o .
ealne~ua;) o o t~ N I O ~ ~
. . _ ~ e umFulel o o o o o o o ~
- _ _ O O
' 11:) ~FI~:'Fl~ o o o o o o .. a) -.
'A OF~)auaS O O O O o O o o tJ~
~11 Ul ~F~a~s o o o o o o ~ In ~
S I I 1 o I o ~ o ~ -~ ~ ~, a~ F~ I ~ I ~ I o o azF~ oo I ~ o 1~ 0 0 0 o .
,- ~aa I I co ~ oo c~ o ~
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~ ~ ~ ~ ~ ~ ~ .
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a;)u~sqns aAF~ F ~ 1 ~ ~ ~ ~ ~ ~ ,1 ~ P~ ~
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O N~ ~ S IO ~ (I~ ~rl a) O E~ 1 S I ~ ~ ~ ~k rl ~ ~1~ ~D~1 1 I O ~ ~ '~ O ~
,~~ N ~D r ~ N ~ ~~ ~) ~
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~:O ~ ~ NO ~ q~ N O N ~
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O ~ ~ O
Q~ a) .~
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1~)90350 Example 4 In a series of tests carried out in a greenhouse the plants mentioned in the following Table were treated before their emergence with the listed agents being tested at a rate of application of 1 kg of active substance per hectare. For this purpose the agents were in each case applied uniformly to the soil in the form of an aqueous solution using 500 litres of water per hectare. The results show that the compounds of the present invention have a better action than the known compound used for comparison. The results are expressed by a numerical scale extending from 0 to 10, the value 0 representing destruction of the plant and the value 10 representing no damage.
' ` 20 .~
lO9V350 . ' F eFI~aS o o ~ I I o d ~aulOdI o o o o o o o o ,~ s umula~l~ues~u;~ o o o o o o o o e UmF11~9 ~1 o I I r~
snu,~u~leur~ o o o o o o o o .
ealne~ua;) o o t~ N I O ~ ~
. . _ ~ e umFulel o o o o o o o ~
- _ _ O O
' 11:) ~FI~:'Fl~ o o o o o o .. a) -.
'A OF~)auaS O O O O o O o o tJ~
~11 Ul ~F~a~s o o o o o o ~ In ~
S I I 1 o I o ~ o ~ -~ ~ ~, a~ F~ I ~ I ~ I o o azF~ oo I ~ o 1~ 0 0 0 o .
,- ~aa I I co ~ oo c~ o ~
o~oa O l O O O O O O
~ ~ ~ ~ ~ ~ ~ .
:.~nu-puno~g o oo o o o o o o - -. ~ ~ ~ . ~ ~ ~ ~
;ueaq ~sn~ I I I I 1~ , ~ ~ .
a;)u~sqns aAF~ F ~ 1 ~ ~ ~ ~ ~ ~ ,1 ~ P~ ~
.'. I I ~` a~ O . , Is ,~ o .: ,1 ~ ~ I v a) s,~ ~ ~ s I ~ ^ ~ v ~ ''I ~''I ~) ~ ~~''1 ~1 ~~) ~~I N
O N~ ~ S IO ~ (I~ ~rl a) O E~ 1 S I ~ ~ ~ ~k rl ~ ~1~ ~D~1 1 I O ~ ~ '~ O ~
,~~ N ~D r ~ N ~ ~~ ~) ~
S~ rlh ~ --~~ o N
t~ S ~ I ~--O V., . . ~ ~ ~~ ~-- o ~ la I N~1 ~1 1 ~1 ~ I1~ I N~1 r lCN la ~ 0~1 rl~-1 N
5~ ~ R ~ ~ ~ ~SI -rl S N~S ~ 111 IO Z ~) ~ a ~ ~ v u~ r~1 ` S ~l I ` ~ S~1 d O `V ~ ~1 a) ~ IO ~ ~ s In r~ s h 'I~ ` ~ ~ ` I I--S
~,'. ~ ~ r o ~ n I~ S
'' a) .o~ v ~ IH ~ ~ O ~ ~ ~ OO ~ ~ `~ O a '.' aJ ~ O P~ O ~ O ` ~ ~` O ~O ~~ U~
~ O~ a ~ I h a) o ~-,~
.. ~ ~ o ~ ~ ~n o~ ~ ~ ~o ~~, I ~
,, S.~ ~ ~ a) s ~ o I O ~ 1 0 ~Ql O~1 r-l~) ~ ~
- ~ O ~ ~: ~3 S
~1 rl ~ QS ~ -1 Ql~ QQ ~1 Ir) a) 11 a) k ~ ~ ~ ~
:; ~ O O E~ I O ~ O O O ~,1 o o u~o ~o o ~ rl P~ O ca ~ V cn E~ ~ v~ V
:.
, ,, .
` 1090350 Example 5 . .
In a series of tests carried out in a greenhouse the plants mentioned in the following Table were treated after their emergence with the listed agents being tested at a rate of application of 1 kg of active substance per hectare. For this purpose the agents were in each case sprayed uniformly over the plants in the for~ of an aqueous solution using 500 litres of water per hectare. Also in this case, three weeks after the treatment, the compounds of the present invention exhibited a high selectivity coupled with an excellent action against the weeds. The agent used for comparison did not exhibit a good action. Again, the results are expressed by a numerical scale extending from 0 to 10, the value 0 representing destruction of the plant and the value 10 representing no damage.
.. .
~ 20 . .
;.
~, ~~ -22-:`
so ~ - - -` F elle~aS o o ~ ~ r~ ,1 ~ o o o :` _I
d eau~odI o o o ~ ~ o o o o u~
~ s umula~ues~l~la o o o o o o o o o ~
- e umFIe3 o o o o ~ ~ ~ o o o I Sn~ueleU}~ o o o o o o o o o ~
-:~ ealne~ua~
. .
e umlu~e~ o o ~I ~ o o o o o ~ -u,:) eF~e~FI~e~ o o ~ ~ o o ~r o o co 'A OF )auaS o o o o o o o o o ~r - u~ ellella~
lOS ~ I I O Q) .,a;~l~r ~ :
.. . I I o 1~ o o 1~ 1 1 o ~1 aZFe~ I ~ o CD o a~ c~ I I o O
-~ ~
, eaa I I o c,~ ~ ~ I` I I o 11 o~e~a I r 1` 1 1- 1 , , , O ~' ~nU-pUnOlg 1~ ~ O O O c~ I o ~`ueaq ~sn~ 1 r 1 1 1 1 1 1 1 co aoue~sqns aAF~e ~o e~
l l l l l l ~c r Q I _ Q~ O
~ d 0 Q
; ~ ~ I h ~ ~ Ei ,1 rl n~ I ~ ~ O
., O '~ ~ ~ ~ ~ o~ _ I , . 8 6 Ar) --~ ~ IE. ~ ~ I E, ~ 6 ~ (ET~
r~ n~ I ~ o r~ ~ Q I~I o : i ~ Q ~ ~ N ~ 6 I Q I~ I ~ ~ I N O
U O ~ ~ ~1 ~ o --~1~ I o ~ ~ t~a~ ~I t"
~I N ~ 11~ -- I N I O r-l ~rl I O ~ N ~ o ~1) ri ~ ~d ~5 ~1 I N ~1 111 ~1 N ~ ~1 ~I N ~ (11 Q ~1 ,1 ~I N
,1 Q ~ t~ d S o ~ ~ ~-rl I
~:: ~ a Ei (~ ~ I ~
.; ~ E~ E'. rl Q ~ r o z ~d ,A, ~s ~1 1 ~ ~,~ ~1 ~ o ,~ u ,~
,- . ~ ~~ro ` e~ N ~ Lr) ~ ` I ~ ~1 .~ ~ ~ ~ ~ ~ o ~ ~ ~ ~ o ~ ~ ~r ~ ~ o ~ o o: a) ~
'; O ~ O ~1 0 ~ O ` ~ ~ ` O ` O ` ~ ~ ~ t~^ ` ~ U) ~' ~ ~ ~ ~1 ~ E. ~ I t,. ^ ~~ ~ E. r,. ~1 aJ
O ~ ~ ~1-- O
nJ p~ t~ ~ td OEi F:l ~^. o ~ I ~a o ~ 4 r,^. ~1 o . . ~ ~ ~.^. O L ~ t,^. ~ O ~ 1~^ ~ ~ ~1 ~ o ~ 8 ~ Ei r~ E. ~ o ~ Ei ~ Q~ E~ 3 ~ ~ ~ ~
o ., ~ ~ ~ rl Q ~ S ~1 -1 h rl ~1 .~ Q Q, ~,) U~
ô o o, o a o o o Ei rl o O I o o ,1 ~ o ~ ~ E. I
u) cn ~ tn Ei ~ ta ~ Ei u~ U) u~ E. ~ L~ O
` --23--. .
.
~,'. ~ ~ r o ~ n I~ S
'' a) .o~ v ~ IH ~ ~ O ~ ~ ~ OO ~ ~ `~ O a '.' aJ ~ O P~ O ~ O ` ~ ~` O ~O ~~ U~
~ O~ a ~ I h a) o ~-,~
.. ~ ~ o ~ ~ ~n o~ ~ ~ ~o ~~, I ~
,, S.~ ~ ~ a) s ~ o I O ~ 1 0 ~Ql O~1 r-l~) ~ ~
- ~ O ~ ~: ~3 S
~1 rl ~ QS ~ -1 Ql~ QQ ~1 Ir) a) 11 a) k ~ ~ ~ ~
:; ~ O O E~ I O ~ O O O ~,1 o o u~o ~o o ~ rl P~ O ca ~ V cn E~ ~ v~ V
:.
, ,, .
` 1090350 Example 5 . .
In a series of tests carried out in a greenhouse the plants mentioned in the following Table were treated after their emergence with the listed agents being tested at a rate of application of 1 kg of active substance per hectare. For this purpose the agents were in each case sprayed uniformly over the plants in the for~ of an aqueous solution using 500 litres of water per hectare. Also in this case, three weeks after the treatment, the compounds of the present invention exhibited a high selectivity coupled with an excellent action against the weeds. The agent used for comparison did not exhibit a good action. Again, the results are expressed by a numerical scale extending from 0 to 10, the value 0 representing destruction of the plant and the value 10 representing no damage.
.. .
~ 20 . .
;.
~, ~~ -22-:`
so ~ - - -` F elle~aS o o ~ ~ r~ ,1 ~ o o o :` _I
d eau~odI o o o ~ ~ o o o o u~
~ s umula~ues~l~la o o o o o o o o o ~
- e umFIe3 o o o o ~ ~ ~ o o o I Sn~ueleU}~ o o o o o o o o o ~
-:~ ealne~ua~
. .
e umlu~e~ o o ~I ~ o o o o o ~ -u,:) eF~e~FI~e~ o o ~ ~ o o ~r o o co 'A OF )auaS o o o o o o o o o ~r - u~ ellella~
lOS ~ I I O Q) .,a;~l~r ~ :
.. . I I o 1~ o o 1~ 1 1 o ~1 aZFe~ I ~ o CD o a~ c~ I I o O
-~ ~
, eaa I I o c,~ ~ ~ I` I I o 11 o~e~a I r 1` 1 1- 1 , , , O ~' ~nU-pUnOlg 1~ ~ O O O c~ I o ~`ueaq ~sn~ 1 r 1 1 1 1 1 1 1 co aoue~sqns aAF~e ~o e~
l l l l l l ~c r Q I _ Q~ O
~ d 0 Q
; ~ ~ I h ~ ~ Ei ,1 rl n~ I ~ ~ O
., O '~ ~ ~ ~ ~ o~ _ I , . 8 6 Ar) --~ ~ IE. ~ ~ I E, ~ 6 ~ (ET~
r~ n~ I ~ o r~ ~ Q I~I o : i ~ Q ~ ~ N ~ 6 I Q I~ I ~ ~ I N O
U O ~ ~ ~1 ~ o --~1~ I o ~ ~ t~a~ ~I t"
~I N ~ 11~ -- I N I O r-l ~rl I O ~ N ~ o ~1) ri ~ ~d ~5 ~1 I N ~1 111 ~1 N ~ ~1 ~I N ~ (11 Q ~1 ,1 ~I N
,1 Q ~ t~ d S o ~ ~ ~-rl I
~:: ~ a Ei (~ ~ I ~
.; ~ E~ E'. rl Q ~ r o z ~d ,A, ~s ~1 1 ~ ~,~ ~1 ~ o ,~ u ,~
,- . ~ ~~ro ` e~ N ~ Lr) ~ ` I ~ ~1 .~ ~ ~ ~ ~ ~ o ~ ~ ~ ~ o ~ ~ ~r ~ ~ o ~ o o: a) ~
'; O ~ O ~1 0 ~ O ` ~ ~ ` O ` O ` ~ ~ ~ t~^ ` ~ U) ~' ~ ~ ~ ~1 ~ E. ~ I t,. ^ ~~ ~ E. r,. ~1 aJ
O ~ ~ ~1-- O
nJ p~ t~ ~ td OEi F:l ~^. o ~ I ~a o ~ 4 r,^. ~1 o . . ~ ~ ~.^. O L ~ t,^. ~ O ~ 1~^ ~ ~ ~1 ~ o ~ 8 ~ Ei r~ E. ~ o ~ Ei ~ Q~ E~ 3 ~ ~ ~ ~
o ., ~ ~ ~ rl Q ~ S ~1 -1 h rl ~1 .~ Q Q, ~,) U~
ô o o, o a o o o Ei rl o O I o o ,1 ~ o ~ ~ E. I
u) cn ~ tn Ei ~ ta ~ Ei u~ U) u~ E. ~ L~ O
` --23--. .
.
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A 2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-ide salt of the general formula I
(I) in which R represents a tertiary butyl group and s represents a sodium, potassium, or lithium atom.
(I) in which R represents a tertiary butyl group and s represents a sodium, potassium, or lithium atom.
2. A compound as claimed in claim 1, which is the lithium salt of 5-tert.-butyl-2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-ide.
3. A compound as claimed in claim 1 which is the sodium salt of5-tert.-butyl-2-(dimethylcarbamoylimino)-1,3,4-thiiadiazo-lin-3-ide.
4. A method of protecting a living plant against weeds, wherein the area in the vicinity of a living plant is treated with a compound as claimed in claim 1.
5. A method as claimed in claim 4, wherein the area is treated with a compound as claimed in claim 2 or 3.
6. A method as claimed in claim 4 wherein a single compound of the general formula I is used for the treatment in an amount within the range of from 0.5 to 5 kg per hectare.
7. A method as claimed in claim 4, wherein two or more compounds of the general formula I are used for the treatment in a total amount within the range of from 0.5 to 5 kg per hectare.
8. A method of protecting a crop area against weeds, wherein a crop area is treated with a compound as claimed in claim 1.
9. A method as claimed in claim 8 wherein the crop area is treated with a compound as claimed in claim 2 or 3.
10. A method as claimed in claim 8 wherein a single compound of the general formula I is used for the treatment in an amount within the range of from 0.5 to 5 kg per hectare.
11. A method as claimed in claim 8 wherein two or more compounds of the general formula I are used for the treatment in a total amount within the range of from 0.5 to 5 kg per hectare.
12. A method as claimed in claim 8 wherein the crop is a bush bean, ground-nut, potato, pea, maize, rice, sorghum or soya crop.
13. A method of protecting a waste land against weeds, wherein a waste land is treated with one or more compounds as claimed in claim 1, 2 or 3 the compound(s) being used in a total amount of more than 5 kg per hectare.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2623657.7 | 1976-05-24 | ||
| DE19762623657 DE2623657A1 (en) | 1976-05-24 | 1976-05-24 | 2-DIMETHYLCARBAMOYLIMINO-1,3,4-THIADIAZOLIN-3-ID-SALTS, PROCESS FOR THE PREPARATION OF THESE COMPOUNDS AND HERBICIDAL AGENTS THESE CONTAINED |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1090350A true CA1090350A (en) | 1980-11-25 |
Family
ID=5979098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA278,903A Expired CA1090350A (en) | 1976-05-24 | 1977-05-20 | Herbicidally active 2-dimethylcarbamoylimino-1,3,4- thiadiazolin-3-ide salts |
Country Status (36)
| Country | Link |
|---|---|
| JP (1) | JPS52144671A (en) |
| AT (1) | AT355368B (en) |
| AU (1) | AU512025B2 (en) |
| BE (1) | BE854971A (en) |
| BG (1) | BG27900A3 (en) |
| BR (1) | BR7702545A (en) |
| CA (1) | CA1090350A (en) |
| CH (1) | CH630234A5 (en) |
| CS (1) | CS195333B2 (en) |
| DD (1) | DD129853A5 (en) |
| DE (1) | DE2623657A1 (en) |
| DK (1) | DK143228C (en) |
| EG (1) | EG12841A (en) |
| ES (1) | ES458100A1 (en) |
| FI (1) | FI64362C (en) |
| FR (1) | FR2352809A1 (en) |
| GB (1) | GB1582571A (en) |
| GR (1) | GR72091B (en) |
| HU (1) | HU180092B (en) |
| IE (1) | IE45196B1 (en) |
| IL (1) | IL52034A (en) |
| IN (1) | IN155913B (en) |
| IT (1) | IT1080397B (en) |
| LU (1) | LU77391A1 (en) |
| MX (1) | MX4627E (en) |
| NL (1) | NL7704219A (en) |
| NZ (1) | NZ184056A (en) |
| PH (1) | PH14097A (en) |
| PL (1) | PL102738B1 (en) |
| PT (1) | PT66587B (en) |
| RO (1) | RO72225A (en) |
| SE (1) | SE422792B (en) |
| SU (1) | SU701538A3 (en) |
| TR (1) | TR20262A (en) |
| YU (1) | YU39588B (en) |
| ZA (1) | ZA773127B (en) |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1195672A (en) * | 1968-02-01 | 1970-06-17 | Mobil Oil Corp | Novel Urea Derivatives and Herbicides containing the same |
| US3565901A (en) * | 1969-01-29 | 1971-02-23 | Air Prod & Chem | Certain salts of 1,3,4-thiadiazol-2-ylureas |
| CH554886A (en) * | 1970-01-15 | 1974-10-15 | Air Prod & Chem | Herbicidal and fungicidal 1-(1,3,4-thiadiazol-2-yl)-3-substd. ureas - prepd. from 2-amino-5-substd.-1,3,4-thiadiazoles and N,N'-carbonyldiimidazole |
| CH570391A5 (en) * | 1970-01-15 | 1975-12-15 | Air Prod & Chem | 1,3,4-Thiadiazole herbicides and fungicides - prepd. by reaction of carbamoyl chlorides with alkali metal derivs. of 2-amino-1,3,4-thiadiazoles |
| CH556862A (en) * | 1970-01-15 | 1974-12-13 | Air Prod & Chem | 1-(1,3,4-Thiadiazol-2-yl)-urea derivs as herbicides - and fungicides, prepd. from 2-amino-1,3,4-thiadiazoles |
| US3803164A (en) * | 1972-05-22 | 1974-04-09 | Lilly Co Eli | Simplified one vessel preparation of 1-(5-alkyl-1,3,4-thiadiazol-2-yl)-1,3-dialkyl-ureas with azeotropic drying |
| JPS5235672B2 (en) * | 1972-05-22 | 1977-09-10 | ||
| JPS4929189A (en) * | 1972-07-07 | 1974-03-15 | ||
| FR2237894A1 (en) * | 1973-06-29 | 1975-02-14 | Velsicol Chemical Corp | Thidiazolyl ureidoacetaldehyde acetals - as herbicies |
| JPS5220533A (en) * | 1975-08-05 | 1977-02-16 | Nippon Soken Inc | Collision detection apparatus |
-
1976
- 1976-05-24 DE DE19762623657 patent/DE2623657A1/en not_active Withdrawn
-
1977
- 1977-03-29 DK DK137577A patent/DK143228C/en not_active IP Right Cessation
- 1977-03-30 YU YU839/77A patent/YU39588B/en unknown
- 1977-04-08 SU SU772468119A patent/SU701538A3/en active
- 1977-04-18 NL NL7704219A patent/NL7704219A/en not_active Application Discontinuation
- 1977-04-22 BR BR7702545A patent/BR7702545A/en unknown
- 1977-04-22 ES ES458100A patent/ES458100A1/en not_active Expired
- 1977-04-26 FI FI771323A patent/FI64362C/en not_active IP Right Cessation
- 1977-04-26 BG BG036126A patent/BG27900A3/en unknown
- 1977-04-27 IN IN609/CAL/77A patent/IN155913B/en unknown
- 1977-05-04 MX MX775713U patent/MX4627E/en unknown
- 1977-05-05 IL IL52034A patent/IL52034A/en unknown
- 1977-05-09 GB GB19295/77A patent/GB1582571A/en not_active Expired
- 1977-05-10 NZ NZ184056A patent/NZ184056A/en unknown
- 1977-05-13 IE IE989/77A patent/IE45196B1/en unknown
- 1977-05-17 TR TR20262A patent/TR20262A/en unknown
- 1977-05-19 PH PH19788A patent/PH14097A/en unknown
- 1977-05-19 CS CS773305A patent/CS195333B2/en unknown
- 1977-05-20 DD DD7700199045A patent/DD129853A5/en unknown
- 1977-05-20 RO RO7790421A patent/RO72225A/en unknown
- 1977-05-20 CA CA278,903A patent/CA1090350A/en not_active Expired
- 1977-05-20 CH CH627377A patent/CH630234A5/en not_active IP Right Cessation
- 1977-05-21 PL PL1977198291A patent/PL102738B1/en unknown
- 1977-05-23 GR GR53537A patent/GR72091B/el unknown
- 1977-05-23 SE SE7705982A patent/SE422792B/en unknown
- 1977-05-23 HU HU77SCHE607A patent/HU180092B/en unknown
- 1977-05-23 PT PT66587A patent/PT66587B/en unknown
- 1977-05-23 AU AU25418/77A patent/AU512025B2/en not_active Expired
- 1977-05-23 EG EG311/77A patent/EG12841A/en active
- 1977-05-23 FR FR7715683A patent/FR2352809A1/en active Granted
- 1977-05-23 LU LU77391A patent/LU77391A1/xx unknown
- 1977-05-23 IT IT23863/77A patent/IT1080397B/en active
- 1977-05-24 BE BE177847A patent/BE854971A/en not_active IP Right Cessation
- 1977-05-24 AT AT370077A patent/AT355368B/en not_active IP Right Cessation
- 1977-05-24 ZA ZA00773127A patent/ZA773127B/en unknown
- 1977-05-24 JP JP6038277A patent/JPS52144671A/en active Pending
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