IL37529A - Herbicidally active 1,1,3-trimethyl-3-(5-substituted-1,3,4thiadiazol-2-yl)ureas their manufacture and preparations containing them - Google Patents

Herbicidally active 1,1,3-trimethyl-3-(5-substituted-1,3,4thiadiazol-2-yl)ureas their manufacture and preparations containing them

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Publication number
IL37529A
IL37529A IL37529A IL3752971A IL37529A IL 37529 A IL37529 A IL 37529A IL 37529 A IL37529 A IL 37529A IL 3752971 A IL3752971 A IL 3752971A IL 37529 A IL37529 A IL 37529A
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Israel
Prior art keywords
compound
general formula
urea
treated
th1ad1azol
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IL37529A
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IL37529A0 (en
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Schering Ag
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Priority claimed from DE2044442A external-priority patent/DE2044442C2/en
Priority claimed from DE19702059328 external-priority patent/DE2059328C2/en
Application filed by Schering Ag filed Critical Schering Ag
Publication of IL37529A0 publication Critical patent/IL37529A0/en
Publication of IL37529A publication Critical patent/IL37529A/en

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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)
  • 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)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Description

Herblcldally active 1 ,1 ,3-tr1methyl-3-(5-subst1tuted- 1 ,3,4-th1ad1azol-2-yl )ureas, their manufacture and preparations containing them The present Invention is concerned with new 5-alkyleulph¾yTl and 5-alkylaulphlnyl derivatives of l, 3,4-thiadlazol-2-yl-ur¾s, with processes for their manufacture as well as with herblcldal pj¾>aratlons containing these ureas.
One of the hitherto known urea derivatives having a herblcldal activity is N- ( 3,4-dichlorophenyl)-N,N* -dimeth lurea.
German Offenlegungsschrift Wo. 1,816,696 has already described herblcldally active 1, 3,4-thiadiazolyl-ureas, among them being l-methyl-3- (5-trifluoromethy 1-1, 3,4-thladiazol-2-yl)-urea.Thls active substance has also been mentioned lti German Offenlegungsschrift No. 1,901,672 which has proposed as further active thladlazole ureas, Inter alia, l-methyl-3- (5-methylmercapto 1, 3,4?-thladlazol-2-yl)-urea and l-methyl-3- (5-methyl8ulphonyl-1, 3,4-thiadlazo 1-2-yl)-urea.
Furthermore, German ffenlegungsschrift No. 1,816,567 has described the herblcldal activity of N-acyl derivatives of 5-amlnO 1, 3,4-thladlazoles, for example of l-methyl-3- (5-methylsulphlny 1-l, 3,4-thiadiazol-2-yl)-urea as well as of the corresponding sulphonyl derivative referred to above.
The herblcldal activity of the active substances described in the afore-mentloned publications Is, however, insufficient, especially as they have an insufficient selectivity towards cultivated plants.
There has, therefore, been a need for a compound which combines a considerably improved activity against weeds with a compatibility towards cultivated plants, which need has been satisfied by the present invention.
The present invention provides compounds of the general formula I 1n which R, represents an alkyl group containing 1 to 3 carbon atoms, and n represents 1 or Z: The aforesaid publications have neither specifically mentioned the active compounds of the general formula I nor contained any Indication that these active compounds 1n particular occupy a special position with respect to their herblcldal and herblddal-selectlve properties.
Furthermore, such a special position would not have been expected even when considering their constitution which is analogous to the aforesaid known active substances. It 1s, therefore, all the more surprising that the active compounds of this Invention have a herblcldal activity which 1s far above that of the aforesaid known active substances, and this renders them especially suitable for a total weed control. This suitability as total herbicides 1s partially also due to their surprisingly long active lifetime 1n the soil against germinating and emerging types of plants as compared with similar active substances, whereby the reemergence of a destroyed vegetation can be prevented for a long period of time. The amount required for a total weed control ranges from about 2 to 10 kg of active substance per hectare.
In Israel Patent 33 499 there are described and claimed compounds which at least formally Include within the scope of their general formula the compounds of the present Invention. Said patent however does not disclose the trimethyl -substi tuted 1 ,1 ,3-trlmethyl Al ,3 ,4-th1 ad1 azolyl ureas of the present invention or suggest the unexpectedly superi or herblcldal action evidenced thereby as shown In comparative example 8 hereinafter .
The hew compounds are further characterized by a broader so1l- Thus, when used either In the pre-emergence stage or In the post-emergence stage they will destroy weeds found In tui^ land, for example Slnapls ssp.. Stellarla media, Seneclo vulgaris. Matricaria ohamoml la. Ipomea purpurea. Chrysanthemum segetum.
Lamlum amplexicaule. Centaurea cyanus . Amarantus retroflexus.
Alopecurus myoeuroIdes. Echlnochloa crus-galll. Setarla ltalioa. Sorghum h lepense, Lollum perenne4 Qallnsoga pary flora. Galium aparlne and Agropyron repens> When used In the surprisingly low proportions sufficient to achieve satisfactory control of seed weeds (about 0.g5 to 1 kg per hectare) most of the active compounds of the present invention have also proved to be selective t;owards crops of useful plants, for example maize, potatoes and groundnuts, so that they may be used for combating undesired plants growing these cultivated pl nte The present invention accordingly also provides a herblcldal preparation which comprise? 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 compound of the general formula 1.
The present Invention further provides a method of protecting a crop area against weeds, wherein a orop area is treated with a The new active compounds may be applied as the sole ac ^e substance or in the form of mixtures of several active stostances.
If desired, other plant protective or weed control agents, for example ifunglcideo, hematocldes or other agents, depending on the desired effect, may be further added; thus, for example,, fertilizers may also be added.
When it is desired to broaden the activity spectrum further herbicides may also be added., but in such a case the selectivity Is, of course, not always preserved. Examples of suitable herblcl-dal co-cpmponente are active substances belonging to the group of the triazlnes, aminotrlazoles, diazines, for e ampl uracils., aliphatic carbox lie acids and halocarbox lie acids, halogenated benzoic acids and phenylacetlc acids, arylhydroxyearboxylic acids., hydrazldes* amides, nltriles, esters of such carboxyllc acids* carbamic and thiocarbamic acid esters, ureas, 2, 3*6-trlchloroben-zyloxypropanol and agents containing thlocyanatee. Suitable other additives are* fo example., no -phytotoxie additives which in combinatio with herbicides produce a synergistic activity ncrease, for example wetting agents, emulsiflers, solvents, and oily additives.
It Is advantageous to apply the active compounds of the general formula I In the form of herbleidal preparations, for example powders, spraying or dusting agents, granules, solutfcns, emulBlons or suspensions -with the addition of liquid and/or solid vehicles or diluents and, if desired, of surface-active agents,, for exampel v/etting agent, adhesives, emulsiflers and/or dispersing agents*.
Suitable liquid vehicles are, for example, water, aliphatic and aromatic hydrocarbons, for example benzene, toluene, xylene, cyclohexanone and lsophorone, and also petroleum fractions* Suitable solid vehicles are mineral earths, for example As surface-aotive agents there may be mentioned, for pimple calcium lignin sulphonate, polyoxyethylene octylphenol ether, naphthalene3 lphonic acids, phenolsulphonlc acids, formaldehyde condensates, fatty alcohol sulphates and alkali and alkaline eartn metal salts of fatty acids.
The proportions) of active compound(s) In the herbicide! preparations may vary within wide limits. The preparations may contain, for example, about 20 to 80 by weight of active compound(s) , about 80 to 20% by weight of liquid or solid vehicle and, If desired, up to 20% by weight of su face-active agen^e) The preparations may be applied in the usual manner, for example with water as vehicle in spray broths in an amount of from £00 to 1000 lltre¾per hectare. For a total weed control it is also possible to apply, without any further treatment, the usual partial quantities of spray broth of more than 1000 litres per hectare. The preparations may also be applied in the so-called "ultra-low-volume process". They may furthermore be used in theform of microgranules.
The present inventio further provides a process for the manufacture of compounds of the general formula (I), wherein a compound of the general formula II Is treated with an oxidizing agent, preferably an organic hydroperoxide, for example tertiar -butylhydroperoxide, a per-acid, for exampl meta-chloroperbenzoic acid, or an H-hydrohalic acid amide, for example N«*broraosucelnimlde or an Inorganic compound, for example hydrogen peroxide or sodium mota^perlodate.
When n * 1, it Is advantageous to use^ for this purpose 2 oxidation four equivalents, and when n *» 2,4 oxidation equivalents of the oxidizing agent or a slight excess per mole of the thlo compound at a tempe-, rature within the range of from about 0° to 60°C» mentioned Apart from the oxidizing agents me nijoned above there may also be used other inorganic agents , for example potassium permanganate, chromic acid or its salts or nitric acid, within the temperature range of from 0° to 120° C.
Fo this purpose it is likewise advantageous to use per mole of the thlo compound two or four oxidation equivalents or, if desired, an. excess thereof* A reaction media there may be mentioned organic solvents, for example carbox llc acids, for example aceti£ acid, ethers, fo example dioxan, ketones, for example acetone, acid amides, for example dimeth lformamide, nltrlles, for example acetonltrlle, or others, either -ae such or in the form of mixtures with water.
The present invention further provides a process for the manufacture of compounds of the general formula (I), wherein a compound of the general formula III ■ N — K S.% - β(0)ή~^3'^ NH - CH3 (III), is reacted (a) with a carbamoy^halide of the general formula IV Hal - CO - K. (IV) 1n the presence of an add acceptor, or b) 1n the presence of an add acceptor with a carbonic add ester hallde or with phosgene to form a derivative of the carbamlc acid which 1s then reacted with an amine of the general formula V Preferred carbonic add es:.er halldes are carbonic add phenyl ester chloride and thiocarbonic acld-S^phenyl ester chloride, which lead, for example, to the N-(5-alkyl-sulphonyl-l,3,4-th1ad1azol-2-yl)-th1ocarbam1c a d-S-phenyl esters which are then reacted with secondary amines.
When a process 1s chosen 1n which a hydrohallc add s evolved, an organic base, for example a tertiary amine, for example tr1ethylam1ne or dimethyl an111 ne , a pyridine base or a suitable Inorganic base, for example an oxide or hydroxide of an alkali or alkaline earth metal, 1s added to bind 1t.
The reaction with the carbonic add chloride 1s carried out between about -10° and 150°C, and the subsequent reaction with the primary or secondary amine of the formula (V) between about -10°C and 100°C, although 1n general at room temperature.
Those reaction media are suitable which are solvents Inert towards the reactants; as such solvents there may be mentioned, for example, aliphatic and aromatic hydrocarbons and halogenated hydrocarbons, for example benzene, toluene, xylene, methyle. chloride, chloroform, carbon tetrachloride, chlorinated ethylenes, ketones, ether-like compounds, Ν,Ν-dlalkylated amides and nltrlles.
The present invention further provides a process for the manufacture of the 5-alkylsu phonyl—l,3»4-thiadiazolyl-ur aB falling tilthin the scope of the general formula I, wherein a 5»carbamoylamlno-l, 3, -thiadiazol-2-.yl-sulphinate of the general formula VI s treated Hal - ¾ (VII); Instead of compounds of he general formula VII other alkylating agents may be used, for example esters of sulphuric acid or esters o aromatic sulphonlc acids, for example dimethylsulphate* In the above genejal formulae II to VII the symbols Rj R/ganfi n have the same meanings as defined for the general formula I, Hal represents a chlorine, bromine or iodine atom and B represents a hydrogen atom, a monovalent metal equivalent, preferably an alkali metal or a monovalent alkaline earth metal equivalent, or a tertiary organic base.
The starting materials needed for the performance of the processes of the present invention are known per s or may be prepared by known methods.
' Most of the compounds of the present Invention of the general formula I are crystalline, colourless substances are soluble In organic solvents, for example In methylene chloride, chloroform, dimethyl formamlde , dimethyl sulphoxlde, xylene, toluene, cyclohexanone and Isophorone and slightly soluble 1n water.
The following Examples Illustrate the Invention. Example I described the manufacture of sulph nyl derivatives oi the present Invention and Example 2 ' describes the manufacture of sul- 3 phonyl derivatives of the present Invention. Examples 4 to la describe the excellent herblddal activity of compounds of the present Invention as compared with similar known active agent; 3 the results given 1n Examples 4 to 10 are expressed by a numerical scale extending from 0 to 10, the value 0 being equivalent to total destruction and the value 10 being equivalent to no damage. Example 1 26.3 Grams of 1 ,1 ,3-tr1methyl -3- (5-methyl th1o-l ,3 ,4-thladlazol -2-yl )urea were dissolved 1n 200 ml of glacial acetic add, and 12.8 g of hydrogen peroxide of 30¾ strength were reacted 1n this mixture overnight. The glacial acetic add was then distilled off and the 1 ,1 ,3-tr1methyl -3- (5-methyl sul phi nyl -1 ,3,4-th1 ad1 azol -2-yl )-urea remaining behind was recrystall 1 zed from acetonl trile.
Melting point: 106°C.
The following compounds may be manufactured 1n an analogous manner: ■ Name of Compound Physical constant -l-rT-^a— T-r»tfn^h 1^3^(5- nethy-l-s-a1iT-tny1 --¾-Γ3· I 4-4r a4+*z e-l— 2~y-l-)-u r ea » iooft 1.1.3- Tr1methyl-3-(5-ethylsulph1nyl- 1.3.4- th1 adi azol -2-yl )-urea m.p. 85°C 1.1.3- Tr1methyl-3-(5-ji-propylsulph1nyl- 1.3.4- th1ad1 azol -2-yl )- urea mp. 72°C 1 ,1 ,3-Tr1 methyl -3-(5- sopropyl sul phlnyl -1 ,3,4-thiad azol -2-yl )-urea oil / Example 2 j 24.6 Grams of 1 ,1 ,3-tr1methyl-3-(5-n-propylth1o-l ,3,4-th1ad1azol-2-yl )-urea were suspended 1n 150 ml of glacial acetic add and 50 ml of water, and 21.1 g of potassium permanganate were stirred Into this mixture at such a rate that the reaction took place at 70°C. The reaction mixture was stirred for another 30 minutes, then 300 ml of 1ce water were added and the precipitated manganese dioxide was reduced at 0°C with a solution of 19 g of sodium metablsul phi te 1n 150 ml of water. The resulting crystalline 1 ,1 ,3-tr1methy 1-3- (5- n- propyl sul phony 1-1 ,3 ,4-thi ad1 azol -2-yl )-urea was filtered off and recrystal 11zed from benzene.
Melting point: 75°C. 37529/2 1 4 The yields from the processes described 1n Examples 1 to 2 vary from 20 to 90% of the theoretical yield.
The following compounds of the present Invention may be prepared 1n a manner analogous to that described 1n Example 1 or 2.
Name of the compound Melting point I ,3-£ime*fc 5-e-thy-l-s-u-l boft- J-+r3 ?4-t h i -a-d- 1 a *o-V- 2 -y-H - tH» a 4-5-3- 6- 1.1.3- Tr1methyl -3- (5-methyl sul phonyl - 1.3.4- th1ad1azol-2-yl )-urea 110°C 1.1.3- Tr1methyl-3-(5-ethylsulphonyl- 1.3.4- th1ad1azol-2-yl )-urea 76°C r y ϊ -,-β— T H-me-t hy — 3 -(-5— n -fHfo-p +Hmy J-V 73-,4-t h-l-ertH-a^-o-l— R-y-1- - H^ a 1 ,1 ,3-Tr1methyl-3-(5-1sopropylsulphonyl 1 ,3,4-th1ad1azol-2-yl )-urea 82°C Example 3 In a greenhouse test the plants listed 1n the following Table were treated prior to their emergence 1n a series of experiments with preparations used 1n such amounts that 0.25 kg of active substance was applied per hectare. For this purpose the active substances were 1n each case uniformly sprayed over the soil 1n the form of an aqueous suspension using 500 litres per hectare.
As can be seen from the recorded results the herblcldal effects ) the preparations according to the present Invention against the tough weeds listed in the Table, combined with the sustained selectivity towards the types of cultivated plants listed, were better than those of the control preparation Preparation' of the ,1 2 3 4 5 6 7 8 9* present invention 2 Contro Preparation -methyl-3- (5-me hy1- sulphinyl-l-3,4-thla- diazo1-2-yl5-urea 10 10 10 10 6 6 7 2 10 Untreated 10 10 10 10 10 10 10 10 10 0 a com letely destroyed 10.» undamaged \ -*1 Groundnut 2 Potato 3 Maize 4 Rice 5 Amarantus retro lexus 6 Centaure cyanus 7 Ipomea purpure 8 Seneclo vulgaria 9 e a tua Examp e 5 In a greenhouse test cultivated plants and weeds were treated in a series of experiments at an early stage after having emerged with 0.125 &g ,of active substance per hectare. The compounds of the present invention and the control compound were in each case applied as an aqueous suspension using 500 litres per hectare. As the figures of a check carried out 14 days after the treatment reveal in the following Table the compounds of the present invention combined a good compativility for the cultivated plants tested in this case with a herblcidal effect nqperlor to that of the control compound.
Preparation of the present invention 1 3 + 7 1 ,1, 3-trimethyl- 5- (5-et hyl- s ulp hi- nyl-1 , 3,4-thlad,iazoX-2-yl) -urea 10 lo lo 10 0 0 0 1.1.3- 1 rime thy 1-3- ( -ls o - rop .1- su Iphln 1-1, 3,4- thiadiazol-2-yl) -urea 10 10 10 10 0 1 0 Control preparation l-methyl-3- ( SH-methyl-sulphlnyl- 1.3.4- thiadiazol-2-yl)-urea 10 xo lo 10 9 10 10 Untreated 10 10 10 10 10 10 10 0 »■ totally destroyed 10 » undamaged *1 ~ Groundnut 2 - Potato 3 - Maize 4 ■<*·· Rice 5 - Amarantus retroflexus 6 - Galium aparine 7 - Ipomea purpurea Example 5 ^ The waste flora described 1n Example 3 were treated 1n the post-emergence stage with t.'.e preparations listed below, the preparations being used 1n such amounts that 1.25 kg of active substance were applied per hectare. The active substances were in each case uniformly sprayed over the area treated in the. form of an aqueous suspension using 500 litres per hectare. 3 Weeks after the treatment the results were evaluated.
As the figures show the herbiddal effects of the preparations according to the present invention were better than those of the control preparations also when used in the post-emergence stage.
Preparation of the present Invention Weed destruction 1.1.3- trimethyl -3- (5-m*thyl sul phonyl - 1 ,3,4-thiad1azol-2-yl )-urea 5 Control preparations l-Methyl-3-(5-tr1fluoromethyl- 1.3.4- th1ad1azol-2-yl )-urea 9 1 -methyl -3- (5-methyl sulphonyl - 1 ,3,4-th1ad1azol-2-yl )-urea 8 0 « totally destroyed 10 ■ undamaged Example 6 Before having emerged the plants listed below were treated 1n a series of experiments 1n a greenhouse with the following preparations, the preparations being used 1n such amounts that 0.25 kg of active substance wes applied per hectare. For this purpose the active substances were 1n each case uniformly sprayed over the soil 1h the form of an aqueous suspension using 500 litres per hectare. As the figures show the herblddal activity of the preparations accordin to the present Invention against the tough weeds, combined with the retention of their selectivity towards the types of plants listed, was better than that of the^control preparations* Preparation of the present Invention 1 4 5 6 7 8* / An 1.1.3- tr1me hyl -3-(5-methyl-sul phony! - 1.3.4- th1ad1azol-2-y1 )-urea 10 10 10 0 0 0 0 0 Control preparations l-Methyl-3-(5-tr1f luoromethyl-1 ,3,4- thladiazol -2-yl ) -urea 8 10 1 -methyl -3- (5-mithylsul phonyl -1 ,3 , thladiazol -2-yl )-urea 10 10 1 -methyl -3- (5 -methyl sul phlnyl 1 ,3,4- thladiazol -2-yl )-urea 10 10 10 10 8 5 10 10 Untreated 10 10 ,10 10 10 10 10 10 0 = totally destroyed 10 = undamaged 1 - Potato 5 - Centaurea cyanus 2 - Maize 6 - Senecio vulgaris 3 - Groundnut 7 - I pome a purpurea 4 - Amarantus retroflexus 8 - Avena fatua Example 7 In a greenhouse test cultivated plants and weeds at an early stage of their development after emerging were treated with 0.125 kg of active substance per hectare, the compounds of the present Invention as well as the known control compounds being 1n each case applied 1n the form of an aqueous suspension using 600 litres per hectare. As 1s revealed by the test results the compounds of the present Invention were well tolerated by the cultivated plants tested and were superior 1n their herblcldal activity to the control compounds .
Preparation of the present Invention 1 1.1.3- tr1methyl-3-(5-methyl-sulphonyl- 1.3.4- th1ad1azol-2-yl )0-urea 10 10 10 0 1.1.3- tr1 me thy 1-3- (5-ethyl -sulphonyl - 1.3.4- th1ad1azol-2-yl )-urea 10 10 10 0 Control preparations l-Methyl-3-(5-tr1fluoromethyl 1 ,3,4-th1ad azol-2-yl )-urea 10 10 10 10 10 7 10 1 -methyl -3- (5 -methyl sul phony 1 1 ,3,4-th1ad azol-2-yl )-urea 10 10 10 5 8 6 10 1 -methyl -3- (5 -methyl sul ph 1 nyl 1 ,3,4-th1ad1azol-2-yl )-urea 10 10 10 9 9 8 10 Untreated 10 10 10 10 10 10 10 0 = totally destroyed 10 a undamaged * 1 » Potato 2= Maize 3 s Groundnut 4 B Amarantus retroflexus 5 a Galium aparine 6 ■ Setarla itallca 7 = Ipomea purpurea EXAMPLE .a; In a greenhouse the plants mentioned were treated after emergence with the agents at the rate of 0.125 kg of active substance per hectare. For this purpose the agents were sprayed uniformly over the plants 1n the form of aqueous suspensions 1n 500 litres of water per hectare. The results 2 weeks after the treatment show that the compounds of the present Invention have a herblcldal effect superior to that of the control compounds.
Alopecurus Preparations ^of the present Invention Avena fatua myosuroldes 1.1.3- Tr1methyl-3-(5-methyl-sulphonyl- 1.3.4- th1ad1azol-2-yl )-urea 4 5 1.1.3- Tr1methyl-3- (5-ethyl -sulphonyl - 1.3.4- th1ad1azol-2-yl)-urea 1 1 1.1.3- Trimethyl -3- (5-n-propyl -sul phonyl - 1.3.4- th1ad1azol-2-yl )-urea 1.1.3- Tr1methyl -3- (5-1sopropyl -sulphonyl - 1.3.4- th1ad1azol-2-yl )-urea 0 1.1.3- Tr1methyl-3-(5-methylsulph1nyl- 1.3.4- th1ad1azol-2-yl )-urea 0 2 1.1.3- Tr1methyl-3-(5 ethyl-sulphlnyl- 1.3.4- th1ad1azol-2-yl )-urea 0 2 1.1.3- Tr1methyl -3- (5-n-propyl -sulphinyl- 1.3.4- th1ad1azol-2-yl)-urea - 4 Control preparations (Israel Patent application 33499, British Patent 1195672 and analogous compounds) 1 -Methyl -3- (5-methyl sul phony 1 -1 ,3 ,4-th1ad1azol-2-yl )-urea 10 10 1 -Methyl -3- (5-ethyl sul phonyl -1,3,4-th1ad1azol-2-yl )-urea 10 10 1 -Methyl -3- (5-n-propyl sul phonyl -1 ,3,4-th1ad1azol-2-yl)-urea 10 10 l-Methyl-3-(5-lsop;r*pylfiis?.p onyl-1 ,3,4-th1ad1azoi-2-yl )-urea 10 10 1 ,3-D1methyl -3- (5-n-propylsul phonyl - Alopecurus Control preparations . Avena fatug myosuroldes 1 , 3-D1methyl-3- (5-1 sopropyl sul phon l -l,3,4-th1ad1azol-2-yl)-urea 10 10 Untreated 0 = totally destroyed 10 ° undamaged Example 9 : In a green-house the plants mentioned were treated after emergence with the agents at the rate of 0,125 kg of active substance per hectare. For this purpose the agents were sprayed uniformly over the plants 1n the form of aqueous suspensions 1n 500 litres of water per hectare. The result 2 weeks after the treatment show that the compounds of the present Invention have a herblcldal effect superior to that of the control compounds. * Preparations of the present Invention Ipomea purpurea Galium aparlne 1.1.3- Tr1methyl-3-(5-methylsulphonyl- 1.3.4- th1ad1azol-2-yl)-urea 0 0 1.1.3- Tr1methyl-3-(5-ethylsulphonyl- 1.3.4- th1ad1azol-2-yl)-urea 0 3 1.1.3- Tr1methyl-3-(5-1sopropylsulphonyl- 1.3.4- th1ad1azol-2-yl)-urea 0 0 1 ,1 ,3-Tr1methyl -3- ( 5-methyl sulphl nyl -1 ,3,4-th1ad1azol-2-yl)-urea 0 0 1 ,1 ,3-Tr1methyl-3-(5-ethylsulph1nyl-l ,3,4-th1ad1azol-2-yl)urea 0 0 1.1.3- Tr1methyl-3-(5-n-propylsulph1nyl- 1.3.4- th1ad1azol-2-yl)-urea 3 4 1.1.3- Tr1methyl-3-(5-1sopropylsulph1nyl- 1.3.4- th1ad1azol-2-yl)-urea 2 Control preparations (British patent No. 1195672 and analogous compounds. 1 -Methyl -3- (5-methyl sul phonyl -1 ,3,4-th1ad1azol-2-yl)-urea 10 10 1 -Methyl -3- (5-methyl sul phi nyl -1 , 3 ,4-th1ad1azol-2-yl)-urea 10 9 Control preparations (cont.) l-Methyl-3-(5-ethylsulphonyl-l ,3,4-th1ad1azol-2-yl)-urea 10 7 1 -Methyl -3- (5-n-propy 1 sul phonyl -1 ,3,4-th1ad1azol-2-yl)-urea 10 9 1 -Methyl -3- ( 5-1 sopropy 1 sul phonyl -l,3,4-th1ad1azol-2-yl)-urea 10 9 1 ,3-D1methyl -3- (5-1sopropyl sul phonyl -l,3,4-th1ad1azol-2-yl)-urea - 9 Untreated 0 = totally destroyed 10 = undamaged EXAMPLE 10, In a greenhouse the plants mentioned were treated after emergence with the agents at the rate of 0,125 kg of active substance per hectare. For this purpose the agents were sprayed uniformly over the plants 1n the form of aqueous suspensions 1n 500 litres of water per hectare. The result 2 weeks after the treatment show that the compounds of the present Invention have a herblddal effect superior to that of the control compounds.
D1g1tar1a Preparations of the present Invention SetaHa 1tal1ca sanguineus 1 ,1 ,3-Tr1methyl -3- (5-methyl sul phonyl -1 ,3,4-th1ad1azol-2-yl)-urea 2 1.1.3- Tr1 methyl -3- (5-ethyl sul phonyl - 1.3.4- th1adiazol-2-yl )-urea 0 1.1.3- Tr1methyl-3-(5-n-propylsulphonyl- 1.3.4- th1ad1azol-2-yl )-urea 2 1.1.3- Tr1 methyl -3- (5-1 sopropy 1 us 1 hony 1- 1.3.4- th1ad1azol-2-yl )-urea 2 1 1.1.3- Tr1methy -3- (5-methyl sul phlnyl- 1.3.4- th1ad1azol-2-yl )-Urea 4 3 1.1.3- Tr1methyl -3- (5-ethyl sul phlnyl - 1.3.4- th1ad1azol-2-yl)-urea 4 3 Control preparations (British patent Π 95672 and analogous compounds) f 1 -Methyl -3- (5-methylsulphonyl -l,3,4-thiad1azol-2-y1)-urea 10 10 1 -Methyl -3- (5-ethyl sul phi nyl - !,3,4-th1ad1azol-2-yl)-urea 10 lo 1 -Methyl -3- (5-Ethyl sulphonyl - / l,3,4-th1ad1azo1-2-yl)-urea 10 10 1 ,3-D1methyl-3-(5-ethylsulphonyl-l,3,4-th1ad1azol-2-yl)-urea - 10 1 -Methyl -3- (5-methyl sul phi nyl -l,3,4-th1ad1azol-2-yl)-urea 10 10 1 ,3-D1methyl -3- (5-1sopropyl sul phonyl -l,3.4-th1ad1azol-2-yl)-urea 10 10 0 β totally destroyed 0 = undamaged - 20b -

Claims (16)

1. 37529/2 WHAT WE CLAIM IS: 1. Compounds of a general formula I in which R-j represents an alkyl group containing 1 to 3 carbon atoms and n represents 1 or 2.
2. A compound of the general formula 1n which R- represents an alkyl group containing 1 to 3 carbon atoms.
3. A compound of the general formula 1n which R-j represents an alkyl group containing 1 to 3 carbon atoms.
4. 1 ,1 ,3-Tr1methyl-3-(5-methylsulph1nyl-l ,3 ,4-th1ad1azol -2-yl )- urea. 5-
5. 1 ,1 ,3-Tri methyl -3- Cethyl sul phi nyl -1 ,3 ,4-th1ad1azol -2-yl )-urea.
6. 1 ,1 ,3-Tr1methyl-3-(5-n-propylsu1ph1nyl-l ,3 ,4-th1ad1azol -2-yl )- urea.
7. 1 ,1 ,3-Tr1 methyl -3- ( 5-1 sopropyl sulphl nyl -1 ,3,4-th1ad1azol-2-yl )· urea. - 21 -
8. 1,1 ,3-Tr1methy1-3- (5-methyl sul honyl-! ,3,4-th1ad1azol- %.. A 2-yl )-urea. '
9. 1,1 ,3-Tr1methyl-3-(5-ethylsulphonyl-l ,3 ,4-th1ad1azol -2-yl )-urea .
10. 1,1 ,3-Tr1methyl-3-(5-n_-propylsulphonyl-l ,3,4-th1adiazol-2-yl)-u.rea.
11. 1,1 ,3-Tr1methyl-3-(5-1sopropylsulphonyl-l ,3,4-t ladiazol-2-yl )-urea.
12. A process for the manufacture of a compound as claimed in claim 1, wherein a compound of the general formula in which has the meaning given in claim 1, is treated in a solvent with an oxidizing agent.
13. A process as claimed in claim 12, wherein the oxidizing agent 1s an organic hydroperoxide, a per-add or an inorganic oxidizing agent.
14. A. process for the manufacture of a compound claimed 1n claim 1, wherein a compound of the general formula in which and n^ have the meanings given in claim 1, 1s reacted (a) with a carbamoyl halide of the general formula 37 529/2 1n which Hal represents a chlorine, bromine or Iodine atom, 1n an Inert solvent and 1n the presence of an add acceptor,' or b) In an Inert solvent and in thapresence of an add acceptor with a carbonic add ester halide or with phosgene and the resulting product is then reacted with an amine of the general formula
15. A process as claimed 1n claim 14 wherein the carbonic add ester halide 1s carbonic add phenyl ester chloride, or thlocarbonlc aci d-S-phenyl ester chloride.
16. A process for the manufacture of a compound as claimed 1n claim 3 wherein a compound of the general formula 1n which B represents a hydrogen atom, a monovalent metal equivalent or a tertiary organic base, 1s treated with an alkylating agent of the general formula Hal - R1 in which R-j has the meaning given 1n claim 3 and Hal represents a chlorine, bromine or Iodine atom, or with an ester of sulphuric acid or an ester of an aromatic sulphonlc acid. - 23 - 1 7 . 23. A process for the manufacture of a compound as claimed In claim 2 , conducted substantially as described In Example 1 here -ivn. 18. -24· A process for the manufacture of a compound as claimed in claim 3, oonducted substantially as described In Example 2 herein* 1 9 · 25» A herblcldal preparation which comprises a compound of the general formula I , as defined in claim 1, in admixture or conjunction with a suitable carrier. 20 · 26* . A herblcldal preparation which comprises a compound ad claimed i claim , in admixture or conjunction with suitable carrier. 21 . 27· A herblcldal preparation which comprises a compound as claimed in claim 3, in admixture or conjunction with a suitable carrier. 22 . 2&-» A herblcldal preparatio which comprises the compound claimed 7 . in any one of claims 4 to 40-, in admixture or conjunction with a suitable carrier . q x hlch comprises the compound claimed in admixture or conjunction with a suitable carrier. 1 9 23 24. 5o> . preparation as claimed in any one of claims 2-5 to 29, which is in the form of a powder , spraying or duBtlng agent , granule , solution,, emulsion or suspension. c 1 9 24 ' 25 · 31. A preparation as claimed in any one of claims 25 to 30 , which contains a single compound of the general formul I in a concentration of about 20 to 80$ by weight . 1 9 24 26 · 32. A preparation as c laimed in any one of claims 25-to 30, which contains tv/o or more compounds of the general formula I in a total concentration of about 20 to Q0 by weight. 1 9 86 26 Ll - Τ5· A preparation as claimed In any one of c laims 25 to 32¾ vjhlch contains a single surface-active agent in a concentration of up to 20% by weight. 1 9 26 28. ·¾-· A preparation as claimed in any one of claims 25 to 329 which contains two or more surface-active agents in a total concentration of up to 20 by weight. 37529/2 29. Any one of the herblcidal preparations as claimed In cla^jn 20 and substantially as described 1n Examples 3 and 4 herein. 30. Any one of the herblcidal preparations as claimed 1n claim 21 and substantially as described 1n Examples 5 to 10 herein. 31. A method of protecting a living plant against weeds, wherein the area 1n the vicinity of a living plant Is treated with a compound of the general formula I, as defined 1n claim 1. 32. A method of protecting a living plant against weeds, wherein the area In the vicinity of a living plant 1s treated with a compound as claimed 1n claim 2. 33. A method of protecting a living plant against weeds, wherein the area 1n the vicinity of a living plant 1s treated with a compound as claimed In claim 3. 24. A method as claimed 1n claim 32, wherein the area 1s treated with the compound claimed 1n any one of claims 4 to 7. 35. A method as claimed 1n claim 33, wherein the area 1s treated with the compound claimed 1n any one of claims 8 to 11. 36. A method as claimed In claim 31, wherein the area 1s treated with a herblcidal preparation as claimed 1n any one of claims 19 to 30. 37. A method as claimed 1n any one of claims 31 to 36, wherein a single compound of the general formula I 1s used In a concentration of about 2 to 10 kg per hectare. 38. A method as claimed 1n any one of claims 31 to 36, wherein two or more compounds of the general formula I are used 1n a total concentration of about 2 to 10 kg per hectare. 39. A method as claimed 1n claim 32, conducted substantially as described 1n Example 3 or 4 herein. 40. A method as claimed 1n claim 33, conducted substantially as described In any one of Examples 5 to 10 herein. 41 . Αή » _ Α method of protecting a crop area against weeds , herein^ crop area is treated with a compound of the general formu la as defined in claim 1· 42. 6·. A method of protecting a crop area against weeds , wherein a crop area is treated with a compound as claimed in claim 2. 43. 9·· A method of protecting a crop area against weeds , wherein a crop area is treated with a compound as claimed in claim 3· 42 44 · 50. A method as claimed In o.laim 4&, wherein the crop area is 7 treated with the compound claimed in any one of claims to 10. 43 45. 51-· . A method as claimed in claim 49, wherein the crop area is 8 I T treated with the compound claimed in any one of claims to A-?-. 41 46. 53» . A method as claimed in claim 47-, wherein the crop area is steeated with a herblcldal preparation as claimed in any one of 19 30 claims 25 to 36 · 41 46 47. 53» .. A method as claimed in any one of claims -47 to -52,. wfcerein a single compound of the general formula I is used in a concentration of about 2 to 10 ¾g per hectare . 41 46 48. A method as claimed in any one of claims -4-7 to 52,, wherein two or more compounds of the general formula I are used In a total concentration of about 2 to 10 kg per hectare*
IL37529A 1970-09-03 1971-08-19 Herbicidally active 1,1,3-trimethyl-3-(5-substituted-1,3,4thiadiazol-2-yl)ureas their manufacture and preparations containing them IL37529A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2044442A DE2044442C2 (en) 1970-09-03 1970-09-03 1,1,3-Trimethyl-3 - (- 5-Ethylsulfonyl-1,3,4-Thiadiazol-2-yl) -urea with herbicidal action
DE19702059328 DE2059328C2 (en) 1970-11-24 1970-11-24 1,1,3-Trimethyl-3- (5-ethylsulfinyl-1,3,4-thiadiazol-2-YL) urea

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IL37529A0 IL37529A0 (en) 1971-11-29
IL37529A true IL37529A (en) 1977-04-29

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JP (1) JPS5327339B1 (en)
AT (1) AT310497B (en)
BE (1) BE772168A (en)
BR (1) BR7105556D0 (en)
CA (1) CA942751A (en)
CH (1) CH554636A (en)
CS (1) CS167939B2 (en)
DK (1) DK130182B (en)
EG (1) EG10379A (en)
ES (1) ES393478A1 (en)
FI (1) FI55838C (en)
FR (1) FR2107182A5 (en)
GB (1) GB1365556A (en)
HU (1) HU162898B (en)
IE (1) IE35564B1 (en)
IL (1) IL37529A (en)
KE (1) KE2545A (en)
LU (1) LU63804A1 (en)
NL (1) NL174044C (en)
RO (3) RO71809A (en)
SE (1) SE375305B (en)
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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

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RO71694B (en) 1984-03-31
JPS5327339B1 (en) 1978-08-08
RO71694A (en) 1984-03-15
BE772168A (en) 1972-03-03
AT310497B (en) 1973-10-10
SE375305B (en) 1975-04-14
IE35564L (en) 1972-03-03
CH554636A (en) 1974-10-15
NL7112198A (en) 1972-03-07
NL174044C (en) 1984-04-16
HU162898B (en) 1973-04-28
IE35564B1 (en) 1976-03-18
EG10379A (en) 1976-10-31
DK130182C (en) 1975-08-11
CA942751A (en) 1974-02-26
LU63804A1 (en) 1972-01-06
IL37529A0 (en) 1971-11-29
GB1365556A (en) 1974-09-04
CS167939B2 (en) 1976-05-28
RO71809A (en) 1982-05-10
DK130182B (en) 1975-01-13
FR2107182A5 (en) 1972-05-05
BR7105556D0 (en) 1973-02-15
FI55838C (en) 1979-10-10
FI55838B (en) 1979-06-29
YU195871A (en) 1978-12-31
KE2545A (en) 1975-08-01
RO58556A (en) 1975-10-15
ES393478A1 (en) 1974-10-01
YU34419B (en) 1979-07-10

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