CA1077044A - Herbicidally active 2-dimethylcarbamoylimino-1,3,4-thiadiazolin-3-ide derivatives, process for their manufacture and their use - Google Patents
Herbicidally active 2-dimethylcarbamoylimino-1,3,4-thiadiazolin-3-ide derivatives, process for their manufacture and their useInfo
- Publication number
- CA1077044A CA1077044A CA271,481A CA271481A CA1077044A CA 1077044 A CA1077044 A CA 1077044A CA 271481 A CA271481 A CA 271481A CA 1077044 A CA1077044 A CA 1077044A
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- Canada
- Prior art keywords
- compound
- ide
- thiadiazolin
- dimethylcarbamoylimino
- living plant
- 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.)
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Classifications
-
- 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
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Herbicidally active 2-dimethylcarbamoylimino-1,3,4-thiadiazolin-3-ide derivatives of the general formula I
Herbicidally active 2-dimethylcarbamoylimino-1,3,4-thiadiazolin-3-ide derivatives of the general formula I
Description
iC377~)44 The present invention is concerned with new herbicidally active 2-dimethylcarbamoylimino-1,3,4-thiadiazolin-3-ide deri-vatives, with a process for the manufacture of these compounds and with their use.
1-(1,3,4-Thiadiazol-2-yl)-urea derivatives having a herbicidal action have already been known (German Offenlegung-sschriften Nos. 1,816,696 and 2,118,520). However, they have only a very limited spectrum of selectivity towards crop plants.
Accordingly, the problem upon which the present invention is based has been to make available a herbicidal agent, which, in addition to having an outstanding action against weeds, has a broad spectrum of selectivity towards crop plants.
This problem is solved in accordance with the present invention by the compounds of the general formula I, as defined below.
The present invention accordingly provides compounds of the general formula I
~i N N-B
¦¦ I / CH3 (I) R-s(O)n-C /C=N-CO-N e:
in which R represents an aliphatic hydrocarbon group, B
represents a monovalent metal equivalent and n represents 0, 1 ~.
or 2.
The compounds of the present invention are distinguished by a broad soil- and leaf-herbicidal action. They can be used for combating mono- or di-cotyledonous weeds (including certain un-desired plants not normally considered as weeds). h-With the compounds of the present invention there can be combated by the pre-emergence method and also the post-emergence r method agricultural weeds amongst which there ~ay be mentioned, for example, Sinapis ssp., Stellaria media, Sene\cio vulgaris, - 1 - ~.~ , .
. .
107704~
Matricaria chamomilla, Ipomoea purpurea, Chrysanthemum se~etum, Lam _m amplexicaule, Centaurea cyanus, Amaranthus retroflexus, E
Alopecurus myosuroides, Echinochloa crus galli, Setaria italica, Sorghum halepense and Lolium perenne.
For combating seed weeds there are generally used ~uantities within the range of from 1 kg of active substance per hectare to 5 kg of active substance per hectare. Thereby, the active compounds of the present invention have been found to be selective in commercial vegetable crops, for example bush-bean, ground-nut, potato, pea, rice, maize, sorghum and soya crops.
When two or more compounds of the general formula I are used the range of 1 kg to 5 kg refers of course to the total amount applied of these compounds.
At higher rates of application the compounds are also suitable as total nerbicides for the destruction or suspension E
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.
The present invention further provides a method of pro-tecting 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 selective herbicide.
The compounds of the present invention may be used either alone, or in admixture with one another or with other active substances. If desired, there may be added other defolia- 5 ting, plant protecting or pest combating agents depending on the purpose desired.
When it is intended to broaden the spectrum of action, other herbicides may also be added. For example, there are suit-able as herbicidally active components to be added active sub-stances of the group of triazines, aminotrizoles, anilides, dia-zines, uracils, aliphatic carboxylic acids and halogenocarboxylic acids, substituted benzoic acids and aryloxy-carboxylic acids, hydrazides, amides, nitriles, esters of such carboxylic acids, carbamic acid esters and thiocarbamic acid esters, ureas,
1-(1,3,4-Thiadiazol-2-yl)-urea derivatives having a herbicidal action have already been known (German Offenlegung-sschriften Nos. 1,816,696 and 2,118,520). However, they have only a very limited spectrum of selectivity towards crop plants.
Accordingly, the problem upon which the present invention is based has been to make available a herbicidal agent, which, in addition to having an outstanding action against weeds, has a broad spectrum of selectivity towards crop plants.
This problem is solved in accordance with the present invention by the compounds of the general formula I, as defined below.
The present invention accordingly provides compounds of the general formula I
~i N N-B
¦¦ I / CH3 (I) R-s(O)n-C /C=N-CO-N e:
in which R represents an aliphatic hydrocarbon group, B
represents a monovalent metal equivalent and n represents 0, 1 ~.
or 2.
The compounds of the present invention are distinguished by a broad soil- and leaf-herbicidal action. They can be used for combating mono- or di-cotyledonous weeds (including certain un-desired plants not normally considered as weeds). h-With the compounds of the present invention there can be combated by the pre-emergence method and also the post-emergence r method agricultural weeds amongst which there ~ay be mentioned, for example, Sinapis ssp., Stellaria media, Sene\cio vulgaris, - 1 - ~.~ , .
. .
107704~
Matricaria chamomilla, Ipomoea purpurea, Chrysanthemum se~etum, Lam _m amplexicaule, Centaurea cyanus, Amaranthus retroflexus, E
Alopecurus myosuroides, Echinochloa crus galli, Setaria italica, Sorghum halepense and Lolium perenne.
For combating seed weeds there are generally used ~uantities within the range of from 1 kg of active substance per hectare to 5 kg of active substance per hectare. Thereby, the active compounds of the present invention have been found to be selective in commercial vegetable crops, for example bush-bean, ground-nut, potato, pea, rice, maize, sorghum and soya crops.
When two or more compounds of the general formula I are used the range of 1 kg to 5 kg refers of course to the total amount applied of these compounds.
At higher rates of application the compounds are also suitable as total nerbicides for the destruction or suspension E
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.
The present invention further provides a method of pro-tecting 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 selective herbicide.
The compounds of the present invention may be used either alone, or in admixture with one another or with other active substances. If desired, there may be added other defolia- 5 ting, plant protecting or pest combating agents depending on the purpose desired.
When it is intended to broaden the spectrum of action, other herbicides may also be added. For example, there are suit-able as herbicidally active components to be added active sub-stances of the group of triazines, aminotrizoles, anilides, dia-zines, uracils, aliphatic carboxylic acids and halogenocarboxylic acids, substituted benzoic acids and aryloxy-carboxylic acids, hydrazides, amides, nitriles, esters of such carboxylic acids, carbamic acid esters and thiocarbamic acid esters, ureas,
2,3,6-trichlorobenzyloxy-propanol and thiocyanate-containing agents. As other additives there are also to be understood, for example, non-phytotoxic additives, which cause a synergistic increase in action with herbicides, for example wetting agents, emulsifiers, solvents and oily additives.
The active compounds of the general formula I or mix- t~
tures thereof are advantageously used in the form of herbicidal preparations, for example powders, strewable preparations, gran-ules, solutions, emulsions or suspensions, with the addition cf liquid and/or solid vehicles or diluents, and, if desired, of surface-active agents, for example wetting, adherent, emulsifying and/or dispersing agents. ~;
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.
The active compounds of the general formula I or mix- t~
tures thereof are advantageously used in the form of herbicidal preparations, for example powders, strewable preparations, gran-ules, solutions, emulsions or suspensions, with the addition cf liquid and/or solid vehicles or diluents, and, if desired, of surface-active agents, for example wetting, adherent, emulsifying and/or dispersing agents. ~;
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.
3 -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.
As surface-active agents there may be mentioned, for example, calcium lignin sulphonate, polyoxyethylene alkylphenol ethers, naphthalene sulphonic acids and salts thereof, phenol sulphonic acids and salts thereof, formaldehyde condensates, fatty alcohol sulphates and also substituted benzene sulphonic aclds and salts thereof.
The total amount of the active compounds(s) of the general formula I 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), approx-imately 90 to 20% by weight of liquid or solid carrier and, if desired, also up to 20~ by weight of surface-active agent(s).
The active compounds may be applied in the usual manner, for example with water as carrier in quantities of spray liquor of about 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 it is also possible to apply them in the form of so-called microgranules.
Among the compounds of the general formula I there may be used in accordance with the present invention, more especially, those in which R represents an alkyl, alkenyl or alkynyl group containing up to 6 carbon atoms and B represents an alkall metal atom, preferably a lithium, sodium or potassium atom.
As alkyl, alkenyl and alkynyl groups there come into consideration for this purpose, for example, straight-chained and branched alkyl, alkenyl and alkynyl groups, for example methyl, ethyl, propyl, isopropyl, allyl, 2-propynyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, 2-butenyl, 1-methyl-2-propenyl, n-pentyl, isopentyl, neopentyl, tert.-pentyl, l-methyl-butyl, l-ethyl-propyl, n-hexyl and isohexyl groups.
The compounds of the present invention of the general formula I are salts, which exist ionically corresponding to the following polar formulae N Nl R-S()n ~ L N-CO-N B( ) >
N - - N
R-SIO) ~ - N-CO-N ~ c N N _ (_ R-S(O)n~ N-C-N / 3 B(+) , or formulated in general as N -N (-) O
R_5(o)n ~ S N ~
For the sake of simplicity these ionic forms 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 new compounds of the general formula I may be prepared, for example, by the process of the present invention r as defined below.
The present invention accordingly further provides a process for the manufacture of a compound of the general formula I, wherein (a) dimethylcarbamoyl chloride of the formula II
1~77044 N-CO-Cl (II) 8 is reacted in the presence of an acid-binding agent with a 1,3,4-thiadiazolylamine of the general formula III
N - - N
R-S(O)n-C /C NH2 (III) in which R and n have the meanings given above, to form a 2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-carboxylic acid dimethylamino derivative of the general formula IV
- N -- N CH
~1 1 3 , ; R-S(O)n-C C
S ~CO-N 3 (IV) , `CH3 in which R and n have the meanings given above, which is split with a metal compound of the general formula V
BY (V) , k 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-dimethylurea derivative of the general formula VI
N N
\ S \ (VI) in which R and n have the meanings given above, is reacted with a metal compound of the general formula V
sY (V) in which B and Y have the meanings given above.
- 6 - ~
10770~4 Each step of the process of the present invention may, if desired, be carried out in the presence of a solvent. E
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 invention the reactants are used in approximately equimolar amounts. As reaction media there are suitable polar organic ~ r solvents, alone or in admixture with water. Their choice depends, according to generally known view-points, on the metal compounds of the general formula BY used. As solvents or suspension media there may be mentioned amongst many, for example, acid amides, ~ -for example dimethylformamide, acid nitriles, for example aceton- r itrile, alcohols, for example methanol and ethanol, and ethers, for example tetrahydrofuran. h 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 ~' less polar organic solvents, for example with ketones, for example acetone, or ethers, for example diisopropyl ether.
Some specific compounds of the present invention are ~`
listed in the following Table:
-TABLE
Name of the compound Physical constant l ~
Potassium salt of 5-ethylthio-2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethyl-carbamoylimino)-5-methylsulphonyl-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethyl-carbamoylimino)-5-propylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-imino)-5-propylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
1C~7704~
Name of the compound Physical_constant Potassium salt of 2-(dimethylcarbamoyl-imino)-5-methylthio-1,3,4-thiadiazolin-3-ide . M.p. >250C
Potassium salt of 5-ethylsulphonyl-2-(dimethylcarbamoylimino)-1,3,4-thia-diazolin-3-ide M.p. >250C
Sodium salt of 5-ethylthio-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C J
Sodium salt of 2-(dimethylcarbamoylimino)-5-methylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 5-butylthio-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 5-butylthio-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C
Lithium salt of 5-butylthio-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 5-ethylsulphonyl-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoylimino) -5-methylsulphonyl-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoylimino)-5-methylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoylimino)-5-methylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 230C
(decomposition) Sodium salt of 2-(dimethylcarbamoylimino)-5-(2-propynylthio)-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-imino)-5-(2-propynylthio)-1,3,4-thiadiazolin ;
-3-ide M.p. ~250C
Lithium salt of 5-ethylthio-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C
Lithium salt of 2-(dimethylcarbamoylimino)-5-methylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoylimino)-5-isopropylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-imino)-5-isopropylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoylimino)-5-(2-methyl-2-propenylthio)-1,3,4-thia-diazolin-3-ide M.p. >250C
1(~77(~4~
Name of the com ound Physical ~onstant _ _ P _ _ ..
Potassium salt of 2-~dimethylcarbamoyl-imino)-5-(2-methyl-2-propenylthio)-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-imino)-5-hexylsulphonyl-1,3,4-thiadiazo-lin-3-ide M.p. 213C
(decomposition) R
Sodium salt of 2-(dimethylcarbamoylimino)-5-hexylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 236C
(decomposition) Potassium salt of 2-(dimethylcarbamoyl-imino)-5-hexylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 191C
(decomposition) Lithium salt of 2-(dimethylcarbamoylimino)-5-hexylsulphinyl~1,3,4-thiadiazolin-3-ide M.p. 178C
(decomposition) Lithium salt of 2-(dimethylcarbamoylimino)-5-isobutylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 193C
(decomposition) Lithium salt of 2-(dimethylcarbamoylimino)-5-pentylsulphonyl-1,3,4-thiadiazolin-3-ide M.p. 200C
(decomposition) Sodium salt of 2-(dimethylcarbamoylimino)-5-isobutylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 250C
Potassium salt of 2-(dimethylcarbamoylimino)-5-isobutylsulphinyl-1,3,4,-thiadiazolin-3-ide M.p. 250C
Lithium salt of 2-(dimethylcarbamoylimino)- ~.
5-hexylthio-1,3,4-thiadiazolin-3-ide M.p. 248C ~r Sodium salt of 2-(dimethylcarbamoylimino)-5-hexylthio-1,3,4-~d~ li... -3-ide M.p. 250C
~hl`~ c zo/;n p Potassium salt of 2-(dimethylcarbamoyl-imino)-5-hexylthio-1,3,4-thiadiazolin-3-ide M.p. 250C
Sodium salt of 2-(dimethylcarbamoylimino)-5-pentylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 226C
(decomposition) Potassium salt of 2-(dimethylcarbamoylimino)-5-pentylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 176C
(decomposition) L
Lithium salt of 2-(dimethylcarbamoylimino)-5-pentylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 174C
(decomposition) Sodium salt of 2-(dimethylcarbamoylimino)-5-hexylsulphonyl-1,3,4-thiadiazolin-3-ide M.p. 216C
(decomposition) 1~77044 Name of the compound Physical constant Lithium salt of 2-(dimethylcarbamoyl-imino)-5-isopropylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Lithium salt of 2-(dimethylcarbamoyl-imino)-5-(2-methyl-2-propenylthio)-1,3,4-thiadiazolin-3-ide M.p. 250C
(decomposition) c Sodium salt of 2-(dimethylcarbamoyl-imino)-5-isobutylthio-1,3,4-thiadia-zolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-imino)-5-isobutylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoyl-imino)-5-isopropylsulphonyl-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-imino)-5-isopropylsulphonyl-1,3,4-thia-diazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoyl-imino)-5-isopropylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 247C E
(decomposition) Potassium salt of 2-(dimethylcarbamoyl-imino)-5-isopropylsulphinyl-1,3,4-thia-diazolin-3-ide M.p. 240C h (decomposition) ~, Lithium salt of 2-(dimethylcarbamoyl-imino)-5-isopropylsulphinyl-1,3,4-thia- ~.
diazolin-3-ide M.p. 245C
(decomposition) ~
Lithium salt of 2-(dimethylcarbamoyl- ~' imino)-5-propylsulphonyl-1,3,4-thiadia-zolin-3-ide M.p. 250C
(decomposition) Lithium salt of 2-(dimethylcarbamoyl-imino)-5-isobutylsulphonyl-1,3,4-thia-diazolin-3-ide M.p. 175C ..
(decomposition) Lithium salt of 2-(dimethylcarbamoyl-imino)-5-pentylthio-1,3,4-thiadiazolin-3-ide M.p. 260C
(decomposition) Lithium salt of 2-(dimethylcarbamoyl-imino)-5-isobutylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
10770~
Name of the compound Physical constant Lithium salt of 2-(dimethylcarbamoyl-imino)-5-propylthio-1,3,4-thiadiazolin-3-ide M.p. 263C
(decomposition) Sodium salt of 2-(dimethylcarbamoyl-imino)-5-propylsulphonyl-1,3,4-thia-diazolin-3-ide M.p. >250C
Lithium salt of 2-(dimethylcarbamoyl-imino)-5-isopropylsulphonyl-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoyl-imino)-5-isobutylsulphonyl-1,3,4-thia-diazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-imino)-5-isobutylsulphonyl-1,3,4-thia-diazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-imino)-5-pentylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoyl-imino)-5-pentylthio-1,3,4-thiadiazolin-3-ide M.p. >250C t Potassium salt of 2-(dimethylcarbamoyl-imino)-5-propylsulphonyl-1,3,4-thiadia-zolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoyl-imino)-5-pentylsulphonyl-1,3,4-thia- - '~
diazolin-3-ide M.p. 240C r .
(decomposition) ~' Potassium salt of 2-(dimethylcarbamoyl- ;
imino)-5-pentylsulphonyl-1,3,4-thiadia-zolin-3-ide M.p. 230C
(decomposition) Sodium salt of 2-(dimethylcarbamoyl- t imino)-5-propylsulphinyl-1,3,4-thiadia-zolin-3-ide M.p. 256C
(decomposition) Lithium salt of 2-(dimethylcarbamoyl-imino)-5-propylsulphinyl-1,3,4-thiadia-zolin-3-ide M.p. 228C
(decomposition) Lithium salt of 2-(dimethylcarbamoyl-imino)-5-hexylsulphonyl-1,3,4-thiadia-zolin-3-ide M.p. 158C L
(decomposition) 1(~77044 The compounds of the present invention are colourless and odourless, crystalline bodies, which are excellently soluble in water, readily soluble in polar organic solvents, for example carboxylic-acid amides, for example dimethylformamide, sulphoxides, for example dimethyl sulphoxide, and lower alcohols, for example methanol and ethanol, are less soluble in carbonitriles, for example acetonitrile, and are insoluble in hydrocarbons, halogen- ~-ated hydrocarbons, ethers and ketones.
The following Examples illustrate the invention.
Examples 1 and 2 illustrate the manufacture of compounds of the general formula I and Examples 3 to 5 illustrate the mode of action of the compounds of the general formula I.
Example 1 Potassium salt of 5-ethylthio-2-~dimethylcarbamoylimino)-r 1,3,4-thiadiazolin-3-ide.
To a suspension of 30.3 grams of 5-ethylthio-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-carboxylic acid dimethylamide (M.p.: 91C) in 200 ml of methanol were added dropwise at room temperature, while stirring, 6.58 grams of potassium hydroxide of ~;
85% strength, dissolved in 100 ml of methanol.
The reaction mixture, after standing overnight, was brought to dryness in vacuo, and the residue remaining behind was digested twice with isopropanol and dried in vacuo.
Yield: 25.2 grams (93.4~ of the theoretical yield) M.p.: >250C
Analysis: Calculated: C 31.09~ H 4.10% N 20.72~ K 14.46 Found: C 30.89% H 4.31% N 20.43% K 14.72 Example 2 Sodium salt of 2-(dimethylcarbamoylimino)-5-methylsulphonyl-1,3,4-thiadiazolin-3-ide.
12.5 Grams of 1,1-dimethyl-3-(5-methylsulphonyl-1,3,4-thiadiazol-2-yl)-urea were suspended in 150 ml of methanol, and 1~77044 at room temperature a solution of 2 grams of sodium hydroxide in 100 ml of methanol was slowly added while stirring. æ
After standing for 2 hours, the solvent was distilled off ln vacuo, and the residue was first washed twice with 50 ml of isopropanol, then with diisopropyl ether and dried ln vacuo.
Yield: 12.6 grams (92.7% of the theoretical yield) M.p.: >250C @
Analysis: Calculated: C 26.47% H 3.33% N 20.58% Na 8.44%
Found: C 26.49% H 3.38% N 20.41% Na 8.49%
Each of the other compounds of the present invention listed in the Table above can be prepared in a manner analogous to that described in Example 1 or 2.
Example 3 In a series of tests carried out in a greenhouse the compounds of the present invention listed 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 mùstard and tomatoes as test plants by the pre- ~
and post-emergence methods. Three weeks after the treatment the ~!
results of the treatment were evaluated, the results being ~.
expressed by a numerical scale extending from 1 to 4, the value t 0 representing no action and the value 4 representing destruction of the plants. As can be seen from the Table destruction of the ~-test plants was generally achieved.
Compound of the present Pre-emergence Post-emergence invention Mustard Tomato Mustard Tomato Sodium salt of 2-(dimethyl-carbamoylimino)-5-propyl-thio-1,3,4-thiadiazolin-3-ide 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-propylthio-1,3,4-thiadiazolin-3-ide 4 4 4 4 ~77044 Compound of the present Pre-emergence Post-emer~ence c invention Mustard Tomato ~ustardTomato E
Potassium salt of 5-ethyl-thio-2-(dimethylcarbamoyl-imino)-1,3,4-thiadiazolin-3-ide 4 2 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-methylthio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Potassium salt of 5-ethyl-sulphonyl-2-(dimethylcarb-amoylimino)-1,3,4-thiadia-zolin-3-ide 4 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-methyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 4 Sodium salt of 5-ethylthio-2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-methylthio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 5-butylthio-2-(dimethylcarbamoylimino)- h 1,3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 5-ethyl- ~, sulphonyl-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide 4 4 4 4 Potassium salt of 2-(dimethyl- i;
carbamoylimino)-5-methyl- r sulphonyl-1,3,4-thiadiazolin-3-ide 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-methyl-sulphinyl-1,3,4-thiadiazolin-3-ide 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-methyl-sulphinyl-1,3,4-thiadiazolin-3-ide 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-(2-propynyl-thio)-1,3,4-thiadiazolin-3-ide 4 4 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-(2-propynyl-thio)-1,3,4-thiadiazolin-3-ide 4 4 4 4 1~77044 Compound of the present Pre-emergence Post-emergence invention Mustard Tomato Mustard Tomato Lithium salt of 5-ethyl-thio-2-(dimethylcarbazoyl-imino)-1,3,4-thiadiazolin-3-ide 4 4 4 4 Lithium salt of 2-(dimethyl-carbamoyllmino)-5-methylthio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-isopropyl-thio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-isoDropyl-thio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Potassium salt of 5-butylthio-2-(dimethylcarbamoylimino)~
3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-(2-methyl-2-propenylthio)-1,3,4-thia-diazolin-3-ide 4 4 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-(2-methyl-2-propenylthio)-1,3,4-thia-diazolin-3-ide 4 4 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5- hexylsul-phonyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 ~~
Sodium salt of 2-(dimethyl- ~.
carbamoylimino)-5-hexyl- t sulphinyl-1,3,4-thiadiazolin- j:
3-ide 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-hexylsulph-inly-1,3,4-thiadiazolin-3-ide 4 - 4 4 Lithium salt of 2-(dimethyl-carbamoylimino)-5-hexyl-sulphinyl-1,3,4-thiadiazolin-3-ide 4 3 4 3 Lithium salt of 2-(dimethyl-carbamoylimino)-5-isopropyl-thio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Lithium salt of 2-(dimethyl-carbamoylimino)-5-(2-methyl-2-propenylthio)-1,3,4-thia-diazolin-3-ide 4 4 4 4 1(~7704~
Compound of the present Pre-emergence Post-emergence invention Mustard Tomato Mustard Tomato -Sodium salt of 2-(dimethyl-carbamoylimino)-5-isobutyl-thio-1,3,4-thiadiazolin-3-ide 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-isobutvl- r thio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-isopropyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-isopropynyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-isopropyl-sulphinyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-isopropyl-sulphinyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 Lithium salt of 2-(dimethyl-carbamoylimino)-5-isopropyl-sulphinyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 .
Lithium salt of 2-(dimethyl- ~;
carbamoylimino)-5-propyl-sulphonyl-1,3,4-thiadiazolin- :;
3-ide 4 Lithium salt of 2-(dimethyl- ~:
carbamoylimino)-5-pentylthio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Lithium salt of 2-(dimethyl-carbamoylimino)-5-isobutyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 Lithium salt of 2-(dimethyl-carbamoylimino)-5-isobutyl-thio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Lithium salt of 2-(dimethyl- ~
carbamoylimino)-5-propylthio- -1,3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-propyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 ~771)4~
Compound of the present Pre-emergencePost-emergence invention Mustard TomatoMustard Tomato Lithium salt of 2-(dimethyl-carbamoylimino)-5-isopropyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-isobutyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-isobutyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 a 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-pentylthio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-pentyl-thio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-propyl-sulphonyl-1,3,4-thiadiazolin-3-ide a 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-pentyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 "
Potassium salt of 2-(dimethyl-carbamoylimino)-5-pentyl- ,.
sulphonyl-1,3,4-thiadiazolin- ~;
3-ide 4 4 4 4 Lithium salt of 2-(dimethyl-carbamoylimino)-S-isobutyl-sulphinyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 Lithium salt of 2-(dimethyl-carbamoylimino)-5-pentyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 ~ 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-isobutyl-sulphinyl-1,3,4-thiadiazolin-3-ide 4 L
Potassium salt of 2-(dimethyl- ,l carbamoylimino)5-isobutyl-sulphinyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 1(~770~
Compound of the present rre-emergence Post-emergence invention Mustard TomatoMustard Tomato ..
Lithium salt of 2-(dimethyl-carbamoylimino)-5-hexylthio-1,3,4-thiadiazolin-3-ide - - 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-hexylthio-1,3,4-thiadiazolin-3-ide - - 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-hexylthio-1,3,4-thiadiazolin-3-ide - - 4 4 sodium salt of 2-(dimethyl-carbamoylimino)-5-pentyl~
sulphinyl-1,3,4-thiadiaæolin-3-ide ~ ~ 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-pentyl-sulphinyl-1,3,4-thiadiazolin-3-ide ~ ~ 4 4 Lithium salt of 2-(dimethyl-carbamoylimino)-5-pentyl-sulphinyl-1,3,4-thiadiazolin-3-ide ~ ~ 4 4 Sodium salt of 2-(dimethyl- ~.
carbamoylimino)-5-hexyl-sulphonyl-1,3,4-thiadiazolin- S
3-ide ~ ~ 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-propyl-sulphinyl-1,3,4-thiadiazolin- i.
3-ide 4 4 4 4 ' Lithium salt of 2-(dimethyl-carbamoylimino)-5-propyl-sulphinyl-1,3,4-thiadiazolin-3-ide . 4 4 4 4 n . . .
Example 4 Q
In a series of tests carried out in a greenhouse the plants listed in the following Table were treated before their emergence with the listed agents being tested at the rates of application given. For this purpose the agents were in each case applied uniformly to the soil in the form of an aqueous r solution using 1 kg of active substance per hectare with 500 litres of water per hectare. The results show that the compounds of the 107704~
present invention, in contradistinction to the known compounds used for comparison, have a good selectivity. The results are expressed by a numerical scale extending from O to 10, the value O representing destruction of the plant and the value 10 representing no damage.
F
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As surface-active agents there may be mentioned, for example, calcium lignin sulphonate, polyoxyethylene alkylphenol ethers, naphthalene sulphonic acids and salts thereof, phenol sulphonic acids and salts thereof, formaldehyde condensates, fatty alcohol sulphates and also substituted benzene sulphonic aclds and salts thereof.
The total amount of the active compounds(s) of the general formula I 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), approx-imately 90 to 20% by weight of liquid or solid carrier and, if desired, also up to 20~ by weight of surface-active agent(s).
The active compounds may be applied in the usual manner, for example with water as carrier in quantities of spray liquor of about 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 it is also possible to apply them in the form of so-called microgranules.
Among the compounds of the general formula I there may be used in accordance with the present invention, more especially, those in which R represents an alkyl, alkenyl or alkynyl group containing up to 6 carbon atoms and B represents an alkall metal atom, preferably a lithium, sodium or potassium atom.
As alkyl, alkenyl and alkynyl groups there come into consideration for this purpose, for example, straight-chained and branched alkyl, alkenyl and alkynyl groups, for example methyl, ethyl, propyl, isopropyl, allyl, 2-propynyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, 2-butenyl, 1-methyl-2-propenyl, n-pentyl, isopentyl, neopentyl, tert.-pentyl, l-methyl-butyl, l-ethyl-propyl, n-hexyl and isohexyl groups.
The compounds of the present invention of the general formula I are salts, which exist ionically corresponding to the following polar formulae N Nl R-S()n ~ L N-CO-N B( ) >
N - - N
R-SIO) ~ - N-CO-N ~ c N N _ (_ R-S(O)n~ N-C-N / 3 B(+) , or formulated in general as N -N (-) O
R_5(o)n ~ S N ~
For the sake of simplicity these ionic forms 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 new compounds of the general formula I may be prepared, for example, by the process of the present invention r as defined below.
The present invention accordingly further provides a process for the manufacture of a compound of the general formula I, wherein (a) dimethylcarbamoyl chloride of the formula II
1~77044 N-CO-Cl (II) 8 is reacted in the presence of an acid-binding agent with a 1,3,4-thiadiazolylamine of the general formula III
N - - N
R-S(O)n-C /C NH2 (III) in which R and n have the meanings given above, to form a 2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-carboxylic acid dimethylamino derivative of the general formula IV
- N -- N CH
~1 1 3 , ; R-S(O)n-C C
S ~CO-N 3 (IV) , `CH3 in which R and n have the meanings given above, which is split with a metal compound of the general formula V
BY (V) , k 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-dimethylurea derivative of the general formula VI
N N
\ S \ (VI) in which R and n have the meanings given above, is reacted with a metal compound of the general formula V
sY (V) in which B and Y have the meanings given above.
- 6 - ~
10770~4 Each step of the process of the present invention may, if desired, be carried out in the presence of a solvent. E
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 invention the reactants are used in approximately equimolar amounts. As reaction media there are suitable polar organic ~ r solvents, alone or in admixture with water. Their choice depends, according to generally known view-points, on the metal compounds of the general formula BY used. As solvents or suspension media there may be mentioned amongst many, for example, acid amides, ~ -for example dimethylformamide, acid nitriles, for example aceton- r itrile, alcohols, for example methanol and ethanol, and ethers, for example tetrahydrofuran. h 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 ~' less polar organic solvents, for example with ketones, for example acetone, or ethers, for example diisopropyl ether.
Some specific compounds of the present invention are ~`
listed in the following Table:
-TABLE
Name of the compound Physical constant l ~
Potassium salt of 5-ethylthio-2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethyl-carbamoylimino)-5-methylsulphonyl-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethyl-carbamoylimino)-5-propylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-imino)-5-propylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
1C~7704~
Name of the compound Physical_constant Potassium salt of 2-(dimethylcarbamoyl-imino)-5-methylthio-1,3,4-thiadiazolin-3-ide . M.p. >250C
Potassium salt of 5-ethylsulphonyl-2-(dimethylcarbamoylimino)-1,3,4-thia-diazolin-3-ide M.p. >250C
Sodium salt of 5-ethylthio-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C J
Sodium salt of 2-(dimethylcarbamoylimino)-5-methylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 5-butylthio-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 5-butylthio-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C
Lithium salt of 5-butylthio-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 5-ethylsulphonyl-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoylimino) -5-methylsulphonyl-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoylimino)-5-methylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoylimino)-5-methylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 230C
(decomposition) Sodium salt of 2-(dimethylcarbamoylimino)-5-(2-propynylthio)-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-imino)-5-(2-propynylthio)-1,3,4-thiadiazolin ;
-3-ide M.p. ~250C
Lithium salt of 5-ethylthio-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C
Lithium salt of 2-(dimethylcarbamoylimino)-5-methylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoylimino)-5-isopropylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-imino)-5-isopropylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoylimino)-5-(2-methyl-2-propenylthio)-1,3,4-thia-diazolin-3-ide M.p. >250C
1(~77(~4~
Name of the com ound Physical ~onstant _ _ P _ _ ..
Potassium salt of 2-~dimethylcarbamoyl-imino)-5-(2-methyl-2-propenylthio)-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-imino)-5-hexylsulphonyl-1,3,4-thiadiazo-lin-3-ide M.p. 213C
(decomposition) R
Sodium salt of 2-(dimethylcarbamoylimino)-5-hexylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 236C
(decomposition) Potassium salt of 2-(dimethylcarbamoyl-imino)-5-hexylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 191C
(decomposition) Lithium salt of 2-(dimethylcarbamoylimino)-5-hexylsulphinyl~1,3,4-thiadiazolin-3-ide M.p. 178C
(decomposition) Lithium salt of 2-(dimethylcarbamoylimino)-5-isobutylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 193C
(decomposition) Lithium salt of 2-(dimethylcarbamoylimino)-5-pentylsulphonyl-1,3,4-thiadiazolin-3-ide M.p. 200C
(decomposition) Sodium salt of 2-(dimethylcarbamoylimino)-5-isobutylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 250C
Potassium salt of 2-(dimethylcarbamoylimino)-5-isobutylsulphinyl-1,3,4,-thiadiazolin-3-ide M.p. 250C
Lithium salt of 2-(dimethylcarbamoylimino)- ~.
5-hexylthio-1,3,4-thiadiazolin-3-ide M.p. 248C ~r Sodium salt of 2-(dimethylcarbamoylimino)-5-hexylthio-1,3,4-~d~ li... -3-ide M.p. 250C
~hl`~ c zo/;n p Potassium salt of 2-(dimethylcarbamoyl-imino)-5-hexylthio-1,3,4-thiadiazolin-3-ide M.p. 250C
Sodium salt of 2-(dimethylcarbamoylimino)-5-pentylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 226C
(decomposition) Potassium salt of 2-(dimethylcarbamoylimino)-5-pentylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 176C
(decomposition) L
Lithium salt of 2-(dimethylcarbamoylimino)-5-pentylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 174C
(decomposition) Sodium salt of 2-(dimethylcarbamoylimino)-5-hexylsulphonyl-1,3,4-thiadiazolin-3-ide M.p. 216C
(decomposition) 1~77044 Name of the compound Physical constant Lithium salt of 2-(dimethylcarbamoyl-imino)-5-isopropylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Lithium salt of 2-(dimethylcarbamoyl-imino)-5-(2-methyl-2-propenylthio)-1,3,4-thiadiazolin-3-ide M.p. 250C
(decomposition) c Sodium salt of 2-(dimethylcarbamoyl-imino)-5-isobutylthio-1,3,4-thiadia-zolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-imino)-5-isobutylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoyl-imino)-5-isopropylsulphonyl-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-imino)-5-isopropylsulphonyl-1,3,4-thia-diazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoyl-imino)-5-isopropylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 247C E
(decomposition) Potassium salt of 2-(dimethylcarbamoyl-imino)-5-isopropylsulphinyl-1,3,4-thia-diazolin-3-ide M.p. 240C h (decomposition) ~, Lithium salt of 2-(dimethylcarbamoyl-imino)-5-isopropylsulphinyl-1,3,4-thia- ~.
diazolin-3-ide M.p. 245C
(decomposition) ~
Lithium salt of 2-(dimethylcarbamoyl- ~' imino)-5-propylsulphonyl-1,3,4-thiadia-zolin-3-ide M.p. 250C
(decomposition) Lithium salt of 2-(dimethylcarbamoyl-imino)-5-isobutylsulphonyl-1,3,4-thia-diazolin-3-ide M.p. 175C ..
(decomposition) Lithium salt of 2-(dimethylcarbamoyl-imino)-5-pentylthio-1,3,4-thiadiazolin-3-ide M.p. 260C
(decomposition) Lithium salt of 2-(dimethylcarbamoyl-imino)-5-isobutylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
10770~
Name of the compound Physical constant Lithium salt of 2-(dimethylcarbamoyl-imino)-5-propylthio-1,3,4-thiadiazolin-3-ide M.p. 263C
(decomposition) Sodium salt of 2-(dimethylcarbamoyl-imino)-5-propylsulphonyl-1,3,4-thia-diazolin-3-ide M.p. >250C
Lithium salt of 2-(dimethylcarbamoyl-imino)-5-isopropylsulphonyl-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoyl-imino)-5-isobutylsulphonyl-1,3,4-thia-diazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-imino)-5-isobutylsulphonyl-1,3,4-thia-diazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-imino)-5-pentylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoyl-imino)-5-pentylthio-1,3,4-thiadiazolin-3-ide M.p. >250C t Potassium salt of 2-(dimethylcarbamoyl-imino)-5-propylsulphonyl-1,3,4-thiadia-zolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoyl-imino)-5-pentylsulphonyl-1,3,4-thia- - '~
diazolin-3-ide M.p. 240C r .
(decomposition) ~' Potassium salt of 2-(dimethylcarbamoyl- ;
imino)-5-pentylsulphonyl-1,3,4-thiadia-zolin-3-ide M.p. 230C
(decomposition) Sodium salt of 2-(dimethylcarbamoyl- t imino)-5-propylsulphinyl-1,3,4-thiadia-zolin-3-ide M.p. 256C
(decomposition) Lithium salt of 2-(dimethylcarbamoyl-imino)-5-propylsulphinyl-1,3,4-thiadia-zolin-3-ide M.p. 228C
(decomposition) Lithium salt of 2-(dimethylcarbamoyl-imino)-5-hexylsulphonyl-1,3,4-thiadia-zolin-3-ide M.p. 158C L
(decomposition) 1(~77044 The compounds of the present invention are colourless and odourless, crystalline bodies, which are excellently soluble in water, readily soluble in polar organic solvents, for example carboxylic-acid amides, for example dimethylformamide, sulphoxides, for example dimethyl sulphoxide, and lower alcohols, for example methanol and ethanol, are less soluble in carbonitriles, for example acetonitrile, and are insoluble in hydrocarbons, halogen- ~-ated hydrocarbons, ethers and ketones.
The following Examples illustrate the invention.
Examples 1 and 2 illustrate the manufacture of compounds of the general formula I and Examples 3 to 5 illustrate the mode of action of the compounds of the general formula I.
Example 1 Potassium salt of 5-ethylthio-2-~dimethylcarbamoylimino)-r 1,3,4-thiadiazolin-3-ide.
To a suspension of 30.3 grams of 5-ethylthio-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-carboxylic acid dimethylamide (M.p.: 91C) in 200 ml of methanol were added dropwise at room temperature, while stirring, 6.58 grams of potassium hydroxide of ~;
85% strength, dissolved in 100 ml of methanol.
The reaction mixture, after standing overnight, was brought to dryness in vacuo, and the residue remaining behind was digested twice with isopropanol and dried in vacuo.
Yield: 25.2 grams (93.4~ of the theoretical yield) M.p.: >250C
Analysis: Calculated: C 31.09~ H 4.10% N 20.72~ K 14.46 Found: C 30.89% H 4.31% N 20.43% K 14.72 Example 2 Sodium salt of 2-(dimethylcarbamoylimino)-5-methylsulphonyl-1,3,4-thiadiazolin-3-ide.
12.5 Grams of 1,1-dimethyl-3-(5-methylsulphonyl-1,3,4-thiadiazol-2-yl)-urea were suspended in 150 ml of methanol, and 1~77044 at room temperature a solution of 2 grams of sodium hydroxide in 100 ml of methanol was slowly added while stirring. æ
After standing for 2 hours, the solvent was distilled off ln vacuo, and the residue was first washed twice with 50 ml of isopropanol, then with diisopropyl ether and dried ln vacuo.
Yield: 12.6 grams (92.7% of the theoretical yield) M.p.: >250C @
Analysis: Calculated: C 26.47% H 3.33% N 20.58% Na 8.44%
Found: C 26.49% H 3.38% N 20.41% Na 8.49%
Each of the other compounds of the present invention listed in the Table above can be prepared in a manner analogous to that described in Example 1 or 2.
Example 3 In a series of tests carried out in a greenhouse the compounds of the present invention listed 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 mùstard and tomatoes as test plants by the pre- ~
and post-emergence methods. Three weeks after the treatment the ~!
results of the treatment were evaluated, the results being ~.
expressed by a numerical scale extending from 1 to 4, the value t 0 representing no action and the value 4 representing destruction of the plants. As can be seen from the Table destruction of the ~-test plants was generally achieved.
Compound of the present Pre-emergence Post-emergence invention Mustard Tomato Mustard Tomato Sodium salt of 2-(dimethyl-carbamoylimino)-5-propyl-thio-1,3,4-thiadiazolin-3-ide 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-propylthio-1,3,4-thiadiazolin-3-ide 4 4 4 4 ~77044 Compound of the present Pre-emergence Post-emer~ence c invention Mustard Tomato ~ustardTomato E
Potassium salt of 5-ethyl-thio-2-(dimethylcarbamoyl-imino)-1,3,4-thiadiazolin-3-ide 4 2 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-methylthio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Potassium salt of 5-ethyl-sulphonyl-2-(dimethylcarb-amoylimino)-1,3,4-thiadia-zolin-3-ide 4 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-methyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 4 Sodium salt of 5-ethylthio-2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-methylthio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 5-butylthio-2-(dimethylcarbamoylimino)- h 1,3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 5-ethyl- ~, sulphonyl-2-(dimethyl-carbamoylimino)-1,3,4-thiadiazolin-3-ide 4 4 4 4 Potassium salt of 2-(dimethyl- i;
carbamoylimino)-5-methyl- r sulphonyl-1,3,4-thiadiazolin-3-ide 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-methyl-sulphinyl-1,3,4-thiadiazolin-3-ide 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-methyl-sulphinyl-1,3,4-thiadiazolin-3-ide 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-(2-propynyl-thio)-1,3,4-thiadiazolin-3-ide 4 4 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-(2-propynyl-thio)-1,3,4-thiadiazolin-3-ide 4 4 4 4 1~77044 Compound of the present Pre-emergence Post-emergence invention Mustard Tomato Mustard Tomato Lithium salt of 5-ethyl-thio-2-(dimethylcarbazoyl-imino)-1,3,4-thiadiazolin-3-ide 4 4 4 4 Lithium salt of 2-(dimethyl-carbamoyllmino)-5-methylthio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-isopropyl-thio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-isoDropyl-thio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Potassium salt of 5-butylthio-2-(dimethylcarbamoylimino)~
3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-(2-methyl-2-propenylthio)-1,3,4-thia-diazolin-3-ide 4 4 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-(2-methyl-2-propenylthio)-1,3,4-thia-diazolin-3-ide 4 4 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5- hexylsul-phonyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 ~~
Sodium salt of 2-(dimethyl- ~.
carbamoylimino)-5-hexyl- t sulphinyl-1,3,4-thiadiazolin- j:
3-ide 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-hexylsulph-inly-1,3,4-thiadiazolin-3-ide 4 - 4 4 Lithium salt of 2-(dimethyl-carbamoylimino)-5-hexyl-sulphinyl-1,3,4-thiadiazolin-3-ide 4 3 4 3 Lithium salt of 2-(dimethyl-carbamoylimino)-5-isopropyl-thio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Lithium salt of 2-(dimethyl-carbamoylimino)-5-(2-methyl-2-propenylthio)-1,3,4-thia-diazolin-3-ide 4 4 4 4 1(~7704~
Compound of the present Pre-emergence Post-emergence invention Mustard Tomato Mustard Tomato -Sodium salt of 2-(dimethyl-carbamoylimino)-5-isobutyl-thio-1,3,4-thiadiazolin-3-ide 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-isobutvl- r thio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-isopropyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-isopropynyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-isopropyl-sulphinyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-isopropyl-sulphinyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 Lithium salt of 2-(dimethyl-carbamoylimino)-5-isopropyl-sulphinyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 .
Lithium salt of 2-(dimethyl- ~;
carbamoylimino)-5-propyl-sulphonyl-1,3,4-thiadiazolin- :;
3-ide 4 Lithium salt of 2-(dimethyl- ~:
carbamoylimino)-5-pentylthio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Lithium salt of 2-(dimethyl-carbamoylimino)-5-isobutyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 Lithium salt of 2-(dimethyl-carbamoylimino)-5-isobutyl-thio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Lithium salt of 2-(dimethyl- ~
carbamoylimino)-5-propylthio- -1,3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-propyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 ~771)4~
Compound of the present Pre-emergencePost-emergence invention Mustard TomatoMustard Tomato Lithium salt of 2-(dimethyl-carbamoylimino)-5-isopropyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-isobutyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-isobutyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 a 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-pentylthio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-pentyl-thio-1,3,4-thiadiazolin-3-ide 4 4 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-propyl-sulphonyl-1,3,4-thiadiazolin-3-ide a 4 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-pentyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 "
Potassium salt of 2-(dimethyl-carbamoylimino)-5-pentyl- ,.
sulphonyl-1,3,4-thiadiazolin- ~;
3-ide 4 4 4 4 Lithium salt of 2-(dimethyl-carbamoylimino)-S-isobutyl-sulphinyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 Lithium salt of 2-(dimethyl-carbamoylimino)-5-pentyl-sulphonyl-1,3,4-thiadiazolin-3-ide 4 ~ 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-isobutyl-sulphinyl-1,3,4-thiadiazolin-3-ide 4 L
Potassium salt of 2-(dimethyl- ,l carbamoylimino)5-isobutyl-sulphinyl-1,3,4-thiadiazolin-3-ide 4 4 4 4 1(~770~
Compound of the present rre-emergence Post-emergence invention Mustard TomatoMustard Tomato ..
Lithium salt of 2-(dimethyl-carbamoylimino)-5-hexylthio-1,3,4-thiadiazolin-3-ide - - 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-hexylthio-1,3,4-thiadiazolin-3-ide - - 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-hexylthio-1,3,4-thiadiazolin-3-ide - - 4 4 sodium salt of 2-(dimethyl-carbamoylimino)-5-pentyl~
sulphinyl-1,3,4-thiadiaæolin-3-ide ~ ~ 4 4 Potassium salt of 2-(dimethyl-carbamoylimino)-5-pentyl-sulphinyl-1,3,4-thiadiazolin-3-ide ~ ~ 4 4 Lithium salt of 2-(dimethyl-carbamoylimino)-5-pentyl-sulphinyl-1,3,4-thiadiazolin-3-ide ~ ~ 4 4 Sodium salt of 2-(dimethyl- ~.
carbamoylimino)-5-hexyl-sulphonyl-1,3,4-thiadiazolin- S
3-ide ~ ~ 4 4 Sodium salt of 2-(dimethyl-carbamoylimino)-5-propyl-sulphinyl-1,3,4-thiadiazolin- i.
3-ide 4 4 4 4 ' Lithium salt of 2-(dimethyl-carbamoylimino)-5-propyl-sulphinyl-1,3,4-thiadiazolin-3-ide . 4 4 4 4 n . . .
Example 4 Q
In a series of tests carried out in a greenhouse the plants listed in the following Table were treated before their emergence with the listed agents being tested at the rates of application given. For this purpose the agents were in each case applied uniformly to the soil in the form of an aqueous r solution using 1 kg of active substance per hectare with 500 litres of water per hectare. The results show that the compounds of the 107704~
present invention, in contradistinction to the known compounds used for comparison, have a good selectivity. The results are expressed by a numerical scale extending from O to 10, the value O representing destruction of the plant and the value 10 representing no damage.
F
i 1077~D44 - n o ~ I o ~ o :~ o ~ o W--~t IJ-~S ~ 1'-~ P-` ~ ~ ` ~ P~ O ~ ~ O ~ IJ- ~ ~0 ~ n) u~ P 1'- W I ~ ~ O
r~ O 1' ~ (D IJ- ~ O 1'~ ~ O 1 o 3 ` ~ ~
p~ IJ. p~ ~< ~ ~. ~ IJ. I_ O
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r~ tD O 1-- ~ I tD ~ I
~ 1'-I l_ 0~
kg of active substance/ha ~ o o Bush-bean o o o o Ground-nut o o o Potato I ~ ~ Pea OD O O
o J o ~ Maize ~ ~ R
c~ I o o lce Sorghum $
;aasu~dole~ uln~ OS I I o o e::)FIe~l eF~e~S o o o o ,~1.Ile~; sn~ eolu,~ouF~ ~ ~ o ,~
s~pFolnso~ul snln~adol~ ~ ~ o ~, . ~
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kg of active substance/ha ~ ~ Bush-bean o I ~ Ground-nut ~ I I Potato o I I Pea Maize o ~ I Rice ~ ~ I Sorghum .. ~ , ...
.. . .
asuadole~ wn~51oc O O O
eaFIe~T elle~ac o O o ~I! ' Ille~ snl~ eo~ ouF~ O O O
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snxal~ol~al sn~ueleur~ o o o d snue~a ealne~ua~ o o o ."~ alne~ xaldule umluler o o o ~n~a~as ~n~a~ues~ o O o ealndlnd eaoulodl o o o ~I
. elll~o~e~ e~ e I o O O
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1.
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.,1 11') 1 11') 1 0 h ~
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,~ I -rl I ~ O ~J O
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~ I ~ I ` h a~ r~) t~l ~ ~ ~ 11 11 11 ~
~ ~ ~ I o o ~3 ` ........... ` `, ..
Example S
In a series of tests carried out in a greenhouse the plants listed 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/hectare. For this purpose the agents were in each case sprayed uniformly over the plants.
Also in this case the compound of the present invention exhibited 3 weeks after the treatment a high selectivity coupled with an excellent action against the weeds. The agent used for comparison did not exhibit selectivity. Again, the results are expressed by a numerical scale extending from O to 10, the value O represent-ing destruction of the plant and the value 10 representing no damage.
2 0 r ~ .
2 4 ~ r i 10:7~4'~
~, .~
o ~ o uln~lOS ~ . ~
~ ~ o ,4 ,~ . o ~ o ;~ ~zle~ ,~ ~
e~d o o ~., e~oS o o o o ~ o o~e~Od ~ ~
o ~ o ~nu-punolg ~ ~
, N ~
I ` O ra O ~) h o I O h 0 ~1 U~
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h Q ~1 0 u~I ~1 sl O rl hu~ I
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.
o ,, ~, ,, O ~~ rl O Ul :~ N OO ~:
rl ~ ~ ~1 g ~ ~
Q) .~ I; ~ h ~ ~ ~rlrl O r~
:~ O ~: O ~ ~:
C~ rl U~ ~ ~ ~
2~
1077~ 144 ~`
e~lle~F elle~aS o o o ealndlnd eao~uodI o o o ~un~ak,as umuall~ues~ o o o auF~ede lunFIe~ o o o 't~ ' ,~
,~ snxal~ol~al sn~ue~eur~ o o o snue~ ea~ne~ua I o o o alne~l, xaldlue lunFIueq o o o ule~:~ eFIe~FI~e~l o O O
sFIe~lnA el~auac o o o eFpaul eF~ella~c o o o ,~ ~ :
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Example S
In a series of tests carried out in a greenhouse the plants listed 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/hectare. For this purpose the agents were in each case sprayed uniformly over the plants.
Also in this case the compound of the present invention exhibited 3 weeks after the treatment a high selectivity coupled with an excellent action against the weeds. The agent used for comparison did not exhibit selectivity. Again, the results are expressed by a numerical scale extending from O to 10, the value O represent-ing destruction of the plant and the value 10 representing no damage.
2 0 r ~ .
2 4 ~ r i 10:7~4'~
~, .~
o ~ o uln~lOS ~ . ~
~ ~ o ,4 ,~ . o ~ o ;~ ~zle~ ,~ ~
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, N ~
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h Q ~1 0 u~I ~1 sl O rl hu~ I
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.
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rl ~ ~ ~1 g ~ ~
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C~ rl U~ ~ ~ ~
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1077~ 144 ~`
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,~ snxal~ol~al sn~ue~eur~ o o o snue~ ea~ne~ua I o o o alne~l, xaldlue lunFIueq o o o ule~:~ eFIe~FI~e~l o O O
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Claims (114)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A 2-dimethylcarbamoylimino-1,3,4-thiadiazolin-3-ide derivative of the general formula I
(I) in which R represents an aliphatic hydrocarbon group selected from an alkyl group containing 1 to 6 carbon atoms, an alkenyl group containing up to 6 carbon atoms, or an alkynyl group containing up to 6 carbon atoms, B represents a alkali metal atom and n represents 0, 1 or 2.
(I) in which R represents an aliphatic hydrocarbon group selected from an alkyl group containing 1 to 6 carbon atoms, an alkenyl group containing up to 6 carbon atoms, or an alkynyl group containing up to 6 carbon atoms, B represents a alkali metal atom and n represents 0, 1 or 2.
2. A compound as claimed in claim 1, wherein R repre-sents an alkyl group containing 1 to 6 carbon atoms.
3. A compound as claimed in claim 1, wherein R repre-sents an alkenyl group containing up to 6 carbon atoms.
4. A compound as claimed in claim 1, wherein R repre-sents an alkynyl group containing up to 6 carbon atoms.
5. A compound as claimed in claim 1, 2 or 3 wherein the alkali metal atom is a lithium, sodium or potassium atom.
6. A compound as claimed in any one of claims 1 to 3, wherein B represents a sodium atom.
7. A compound as claimed in claim 1, which is potassium salt of 5-ethylthio-2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-ide.
8. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-methylsulphonyl-1,3,4-thia-diazolin-3-ide.
9. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-propylthio-1,3,4-thiadiazolin-3-ide.
10. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylcarbamoylimino)-5-propylthio-1,3,4-thiadia-zolin-3-ide.
11. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylcarbamoylimino)-5-methylthio-1,3,4-thiadiazolin-3-ide.
12. A compound as claimed in claim 1, which is potassium salt of 5-ethylsulphonyl-2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-ide.
13. A compound as claimed in claim 1, which is sodium salt of 5-ethylthio-2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-ide.
14. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-methylthio-1,3,4-thiadiazolin-3-ide.
15. A compound as claimed in claim 1, which is sodium salt of 5-butylthio-2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-ide.
16. A compound as claimed in claim 1, which is sodium salt of 5-ethylsulphonyl-2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-ide.
17. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylcarbamoylimino)-5-methylsulphonyl-1,3,4-thiadiazolin-3-ide.
18. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-methylsulphinyl-1,3,4-thiadiazolin-3-ide.
19. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylcarbamoylimino)-5-methylsulphinyl-1,3,4-thiadiazolin-3-ide.
20. A compound as claimed in claim 1, which is potassium salt of 5-butylthio-2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-ide.
21. A compound as claimed in claim 1, which is lithium salt of 5-butylthio-2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-ide.
22. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-(2-propynylthio)-1,3,4-thiadiazolin-3-ide.
23. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylcarbamoylimino)-5-(2-propynylthio)-1,3,4-thiadiazolin-3-ide.
24. A compound as claimed in claim 1, which is lithium salt of 5-ethylthio-2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-ide.
25. A compound as claimed in claim 1, which is lithium salt of 2-(dimethylcarbamoylimino)-5-methylthio-1,3,4-thiadiazolin-3-ide.
26. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-isopropylthio)-1,3,4-thiadiazolin-3-ide.
27. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylcarbamoylimino)-5-isopropylthio)-1,3,4-thiadiazolin-3-ide.
28. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-(2-methyl-2-propenyl-thio)-1,3,4-thiadiazolin-3-ide.
29. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylcarbamoylimino)-5-(2-methyl-2-propenyl-thio)-1,3,4-thiadiazolin-3-ide.
30. A compound as claimed in claim 1, which is lithium salt of 2-(dimethylcarbamoylimino)-5-isopropylthio-1,3,4-thiadiazolin-3-ide.
31. A compound as claimed in claim 1, which is lithium salt of 2-(dimethylcarbamoylimino)-5-(2-methyl-2-propenyl-thio)-1,3,4-thiadiazolin-3-ide.
32. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-isobutylthio-1,3,4-thiadiazolin-3-ide.
33. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-isopropylsulphonyl-1,3,4-thiadiazolin-3-ide.
34. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylcarbamoylimino)-5-isopropylsulphonyl-1,3,4-thiadiazolin-3-ide.
35. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-isopropylsulphinyl-1,3,4-thiadiazolin-3-ide.
36. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylearbamoylimino)-5-isopropylsulphinyl-1,3,4-thiadiazolin-3-ide.
37. A compound as claimed in claim 1, which is lithium salt of 2-(dimethylcarbamoylimino)-5-isopropylsulphinyl-1,3,4-thiadiazolin-3-ide.
38. A compound as elaimed in claim 1, which is lithium salt of 2-(dimethylcarbamoylimino)-5-propylsulphonyl-1,3,4-thiadiazolin-3-ide.
39. A compound as claimed in claim 1, which is lithium salt of 2-(dimethylcarbamoylimino)-5-isobutylsulphonyl-1,3,4-thiadiazolin-3-ide.
40. A compound as claimed in claim 1, which is lithium salt of 2-(dimethylearbamoylimino)-5-pentylthio-1,3,4-thiadiazolin-3-ide.
41. A compound as claimed in claim 1, which is lithium salt of 2-(dimethylcarbamoylimino)-5-isobutylthio-1,3,4-thiadiazolin-3-ide.
42. A compound as claimed in claim 1, which is lithium salt of 2-(dimethylcarbamoylimino)-5-propylthio-1,3,4-thiadiazolin-3-ide.
43. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-propylsulphonyl-1,3,4-thiadiazolin-3-ide.
44. A compound as claimed in claim 1, which is lithium salt of 2-(dimethylcarbamoylimino)-5-isopropylsulphonyl-1,3,4-thiadiazolin-3-ide.
45. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-isobutylsulphonyl-1,3,4-thiadiazolin-3-ide.
46. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylcarbamoylimino)-5-isobutylsulphonyl-1,3,4-thiadiazolin-3-ide.
47. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylcarbamoylimino)-5-pentylthio-1,3,4-thiadiazolin-3-ide.
48. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-pentylthio-1,3,4-thia-diazolin-3-ide.
49. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylcarbamoylimino)-5-propylsulphonyl-1,3,4-thiadiazolin-3-ide.
50. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-pentylsulphonyl-1,3,4-thiadiazolin-3-ide.
51. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylcarbamoylimino)-5-pentylsulphonyl-1,3,4-thiadiazolin-3-ide.
52. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-propylsulphinyl-1,3,4-thiadiazolin-3-ide.
53. A compound as claimed in claim 1, which is lithium salt of 2-(dimethylcarbamoylimino)-5-propylsulphinyl-1,3,4-thiadiazolin-3-ide.
54. A compound as claimed in claim 1, which is lithium salt of 2-(dimethylcarbamoylimino)-5-isobutylsulphinyl-1,3,4-thiadiazolin-3-ide.
55. A compound as claimed in claim 1, which is lithium salt of 2-(dimethylcarbamoylimino)-5-pentylsulphonyl-1,3,4-thiadiazolin-3-ide.
56. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-isobutylsulphinyl-1,3,4-thiadiazolin-3-ide.
57. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylcarbamoylimino)-5-isobutylsulphinyl-1,3,4-thiadiazolin-3-ide.
58. A compound as claimed in claim 1, which is lithium salt of 2-(dimethylcarbamoylimino)-5-hexylthip-1,3,4-thiadiazolin-3-ide.
59. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-hexylthio-1,3,4-thiadiazolin-3-ide.
60. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylcarbamoylimino)-5-hexylthio-1,3,4-thiadiazolin-3-ide.
61. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-pentylsulphinyl-1,3,4-thiadiazolin-3-ide.
62. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylcarbamoylimino)-5-pentylsulphinyl-1,3,4-thiadiazolin-3-ide.
63. A compound as claimed in claim 1, which is lithium salt of 2-(dimethylcarbamoylimino)-5-pentylsulphinyl-1,3,4-thiadiazolin-3-ide.
64. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-hexylsulphonyl-1,3,4-thiadiazolin-3-ide.
65. A compound as claimed in claim 1, which is lithium salt of 2-(dimethylcarbamoylimino)-5-hexylsulphonyl-1,3,4-thiadiazolin-3-ide.
66. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylcarbamoylimino)-5-hexylsulphonyl-1,3,4-thiadiazolin-3-ide.
67. A compound as claimed in claim 1, which is sodium salt of 2-(dimethylcarbamoylimino)-5-hexylsulphinyl-1,3,4-thiadiazolin-3-ide.
68. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylcarbamoylimino)-5-hexylsulphinyl-1,3,4-thiadiazolin-3-ide.
69. A compound as claimed in claim 1, which is lithium salt of 2-(dimethylcarbamoylimino)-5-hexylsulphinyl-1,3,4-thiadiazolin-3-ide.
70. A compound as claimed in claim 1, which is potassium salt of 2-(dimethylcarbamoylimino)-5-isobutylthio-1,3,4-thiadiazolin-3-ide.
71. 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 given in claim 1, in which R, B and n have the meanings given in claim 1.
72. 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 2, 3 or 4.
73. 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 5, 6 or 7.
74. 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 8, 9 or 10.
75. 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 11, 12 or 13.
76. 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 14, 15 or 16.
77. 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 17, 18 or 19.
78. 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 20, 21 or 22.
79. 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 23, 24 or 25.
80. 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 26, 27 or 28.
81. 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 29, 30 or 31.
82. 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 32, 33 or 34.
83. 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 35, 36 or 37.
84. 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 38, 39 or 40.
85. 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 41, 42 or 43.
86. 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 44, 45 or 46.
87. 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 47, 48 or 49.
88. 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 50, 51 or 52.
89. 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 53, 54 or 55.
90. 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 56, 57 or 58.
91. 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 59, 60 or 61.
92. 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 62, 63 or 64.
93. 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 65, 66 or 67.
94. 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 68, 69 or 70.
95. 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 70.
96. A method as claimed in claim 71, in which the compound is in the form of a preparation in admixture or con-junction with a suitable carrier.
97. A method as claimed in claim 71, in which the preparation is in the form of a powder, a strewable preparation, granules, a solution, an emulsion or a suspension.
98. A method as claimed in claim 71, 96 or 97, in which the preparation contains a single compound of the general formula I in an amount of approximately 10 to 80% by weight.
99. A method as claimed in claim 71, 96 or 97, in which the preparation contains two or more compounds of the general formula I in a total amount of approximately 10 to 80% by weight.
100. A method as claimed in claim 71, 96 or 97, in which the preparation contains a single surface-active agent in an amount of up to 20% by weight.
101. A method as claimed in claim 71, 96 or 97, in which the preparation contains two or more surface-active agents in a total amount of up to 20% by weight.
102. A method as claimed in claim 71, 96 or 97, wherein a single compound of the general formula I is used for the treatment in an amount within the range of from 1 to 5 kg per hectare.
103. A method as claimed in claim 71, 96 or 97, wherein two or more compounds of the general formula I are used for the treatment in a total amount within the range of from 1 to 5 kg per hectare.
104. A method of protecting a crop area against weeds, wherein a crop area is treated with a compound of the general formula I given in claim 1, in which R, B and n have the meanings given in claim 1.
105. A method of protecting a crop area against weeds, wherein a crop area is treated with a compound as claimed in claim 2, 3 or 4.
106. A method of protecting a crop area against weeds, wherein a crop area is treated with a compound as claimed in claim 5, 6 or 7.
107. A method of protecting a crop area against weeds, wherein a crop area is treated with a compound as claimed in claim 8, 9 or 10.
108. A method of protecting a corp area against weeds, wherein a crop area is treated with a compound as claimed in claim 11, 12 or 13.
109. A method as claimed in claim 104, wherein a single compound of the general formula I is used for the treatment in an amount within the range of from 1 to 5 kg per hectare.
110. A method as claimed in claim 104, wherein two or more compounds of the general formula I are used for the treatment in a total amount within the range of from 1 to 5 kg per hectare.
111. A method as claimed in claim 104, wherein the crop is a bush-bean, ground-nut, potato, pea, rice, maize, sorghum or soya crop.
112. 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 given in claim 1, in which R, B and n have the meanings given in claim 1, the compound(s) being used in a total amount of more than 5 kg per hectare.
113. A process for the manufacture of a compound of the general formula I given in claim 1, in which R, B and n have the meanings given in claim 1, wherein (a) dimethylcarbamoyl chloride of the formula II
(II) is reacted in the presence of an acid-binding agent with a 1,3,4-thiadiazolylamine of the general formula III
(III) , in which R and n have the meanings given above, to form a 2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-carboxylic acid dimethylamino derivative of the general formula IV
(IV) , in which R and n have the meanings given above, which is split with a metal compound of the general formula V
BY (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-dimethylurea derivative of the general formula VI
(VI) , in which R and n have the meanings given above, is reacted with a metal compound of the general formula V
BY (V) , in which B and Y have the meanings given above.
(II) is reacted in the presence of an acid-binding agent with a 1,3,4-thiadiazolylamine of the general formula III
(III) , in which R and n have the meanings given above, to form a 2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-carboxylic acid dimethylamino derivative of the general formula IV
(IV) , in which R and n have the meanings given above, which is split with a metal compound of the general formula V
BY (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-dimethylurea derivative of the general formula VI
(VI) , in which R and n have the meanings given above, is reacted with a metal compound of the general formula V
BY (V) , in which B and Y have the meanings given above.
114. A process as claimed in claim 113, wherein each step is carried out in the presence of a solvent.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762607481 DE2607481A1 (en) | 1976-02-20 | 1976-02-20 | 2-DIMETHYLCARBAMOYLIMINO-1,3,4-THIADIAZOLIN-3-ID DERIVATIVES, PROCESS FOR THE PREPARATION OF THESE COMPOUNDS AND HERBICIDAL AGENTS THESE CONTAINED |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1077044A true CA1077044A (en) | 1980-05-06 |
Family
ID=5970729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA271,481A Expired CA1077044A (en) | 1976-02-20 | 1977-02-10 | Herbicidally active 2-dimethylcarbamoylimino-1,3,4-thiadiazolin-3-ide derivatives, process for their manufacture and their use |
Country Status (32)
| Country | Link |
|---|---|
| JP (1) | JPS52102277A (en) |
| AR (1) | AR217638A1 (en) |
| AT (1) | AT351314B (en) |
| AU (1) | AU2186377A (en) |
| BE (1) | BE851600A (en) |
| BG (1) | BG27713A3 (en) |
| BR (1) | BR7700890A (en) |
| CA (1) | CA1077044A (en) |
| CS (1) | CS193083B2 (en) |
| DD (1) | DD128655A5 (en) |
| DE (1) | DE2607481A1 (en) |
| DK (1) | DK29577A (en) |
| EG (1) | EG12458A (en) |
| ES (1) | ES456051A1 (en) |
| FI (1) | FI770452A (en) |
| FR (1) | FR2341573A1 (en) |
| GB (1) | GB1577523A (en) |
| GR (1) | GR62395B (en) |
| IE (1) | IE44565B1 (en) |
| IL (1) | IL51461A (en) |
| IN (1) | IN155287B (en) |
| IT (1) | IT1118003B (en) |
| LU (1) | LU76741A1 (en) |
| NL (1) | NL7701752A (en) |
| NZ (1) | NZ183378A (en) |
| PL (1) | PL101774B1 (en) |
| PT (1) | PT66210B (en) |
| RO (1) | RO73052A (en) |
| SE (1) | SE7701776L (en) |
| SU (2) | SU648098A3 (en) |
| TR (1) | TR20545A (en) |
| ZA (1) | ZA77985B (en) |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3565901A (en) * | 1969-01-29 | 1971-02-23 | Air Prod & Chem | Certain salts of 1,3,4-thiadiazol-2-ylureas |
| GB1290223A (en) * | 1969-04-21 | 1972-09-20 | ||
| 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 |
| 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 |
| 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 |
| DE2028778A1 (en) * | 1970-06-06 | 1971-12-23 | Thiadiazolyl-urea herbicides - 5 - substd by sulphinyl or sulphonyl | |
| DE2044442C2 (en) * | 1970-09-03 | 1983-11-03 | Schering AG, 1000 Berlin und 4709 Bergkamen | 1,1,3-Trimethyl-3 - (- 5-Ethylsulfonyl-1,3,4-Thiadiazol-2-yl) -urea with herbicidal action |
| JPS5235672B2 (en) * | 1972-05-22 | 1977-09-10 | ||
| DE2246461C2 (en) * | 1972-09-21 | 1985-07-18 | Schering AG, 1000 Berlin und 4709 Bergkamen | 1,1,3-Trimethyl-3- (5-butylsulfonyl-1,3,4-thiadiazol-2-yl) urea and herbicidal agents containing this compound |
| FR2237894A1 (en) * | 1973-06-29 | 1975-02-14 | Velsicol Chemical Corp | Thidiazolyl ureidoacetaldehyde acetals - as herbicies |
| DE2341816A1 (en) * | 1973-08-16 | 1975-02-27 | Schering Ag | HERBICIDES 1,3,4-THIADIAZOL-2-YL URBAN MATERIAL |
| DE2350709A1 (en) * | 1973-10-05 | 1975-04-24 | Schering Ag | 1,3,4-THIADIAZOL-2-YL-UREA WITH SELECTIVE HERBICIDAL EFFECT |
| JPS583585B2 (en) * | 1977-06-10 | 1983-01-21 | 株式会社日立製作所 | Sample room for electron microscopes, etc. |
-
1976
- 1976-02-20 DE DE19762607481 patent/DE2607481A1/en not_active Withdrawn
-
1977
- 1977-01-07 RO RO7788970A patent/RO73052A/en unknown
- 1977-01-13 SU SU772439828A patent/SU648098A3/en active
- 1977-01-25 DK DK29577A patent/DK29577A/en unknown
- 1977-01-29 IN IN127/CAL/77A patent/IN155287B/en unknown
- 1977-02-01 CS CS77664A patent/CS193083B2/en unknown
- 1977-02-02 AR AR266423A patent/AR217638A1/en active
- 1977-02-02 AU AU21863/77A patent/AU2186377A/en not_active Expired
- 1977-02-03 BG BG7735323A patent/BG27713A3/en unknown
- 1977-02-10 CA CA271,481A patent/CA1077044A/en not_active Expired
- 1977-02-10 LU LU76741A patent/LU76741A1/xx unknown
- 1977-02-11 FI FI770452A patent/FI770452A/fi not_active Application Discontinuation
- 1977-02-11 TR TR20545A patent/TR20545A/en unknown
- 1977-02-14 BR BR7700890A patent/BR7700890A/en unknown
- 1977-02-16 IL IL51461A patent/IL51461A/en unknown
- 1977-02-17 SE SE7701776A patent/SE7701776L/en unknown
- 1977-02-18 NZ NZ183378A patent/NZ183378A/en unknown
- 1977-02-18 SU SU772453508A patent/SU605520A3/en active
- 1977-02-18 ZA ZA770985A patent/ZA77985B/en unknown
- 1977-02-18 GR GR52805A patent/GR62395B/en unknown
- 1977-02-18 IT IT20428/77A patent/IT1118003B/en active
- 1977-02-18 PL PL1977196093A patent/PL101774B1/en unknown
- 1977-02-18 IE IE346/77A patent/IE44565B1/en unknown
- 1977-02-18 AT AT111377A patent/AT351314B/en not_active IP Right Cessation
- 1977-02-18 ES ES456051A patent/ES456051A1/en not_active Expired
- 1977-02-18 BE BE175074A patent/BE851600A/en unknown
- 1977-02-18 DD DD7700197438A patent/DD128655A5/en unknown
- 1977-02-18 NL NL7701752A patent/NL7701752A/en not_active Application Discontinuation
- 1977-02-18 PT PT66210A patent/PT66210B/en unknown
- 1977-02-19 EG EG97/77A patent/EG12458A/en active
- 1977-02-21 JP JP1802077A patent/JPS52102277A/en active Pending
- 1977-02-21 GB GB7192/77A patent/GB1577523A/en not_active Expired
- 1977-02-21 FR FR7704886A patent/FR2341573A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| IL51461A0 (en) | 1977-04-29 |
| ATA111377A (en) | 1978-12-15 |
| SU648098A3 (en) | 1979-02-15 |
| EG12458A (en) | 1979-03-31 |
| FR2341573A1 (en) | 1977-09-16 |
| PT66210A (en) | 1977-03-01 |
| TR20545A (en) | 1981-10-15 |
| IN155287B (en) | 1985-01-12 |
| SE7701776L (en) | 1977-08-21 |
| DD128655A5 (en) | 1977-11-30 |
| CS193083B2 (en) | 1979-09-17 |
| BE851600A (en) | 1977-08-18 |
| DE2607481A1 (en) | 1977-08-25 |
| PT66210B (en) | 1978-07-12 |
| NL7701752A (en) | 1977-08-23 |
| GB1577523A (en) | 1980-10-22 |
| AU2186377A (en) | 1978-08-10 |
| SU605520A3 (en) | 1978-04-30 |
| AT351314B (en) | 1979-07-25 |
| ZA77985B (en) | 1977-12-28 |
| NZ183378A (en) | 1979-01-11 |
| LU76741A1 (en) | 1977-06-30 |
| IE44565L (en) | 1977-08-20 |
| IE44565B1 (en) | 1982-01-13 |
| RO73052A (en) | 1982-05-10 |
| IT1118003B (en) | 1986-02-24 |
| FI770452A (en) | 1977-08-21 |
| IL51461A (en) | 1980-03-31 |
| JPS52102277A (en) | 1977-08-27 |
| BR7700890A (en) | 1977-10-18 |
| GR62395B (en) | 1979-04-10 |
| DK29577A (en) | 1977-08-21 |
| AR217638A1 (en) | 1980-04-15 |
| ES456051A1 (en) | 1978-02-16 |
| BG27713A3 (en) | 1979-12-12 |
| PL101774B1 (en) | 1979-01-31 |
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