DK145717B - ISOXAZOLYLMETHYLTHIOL CARBAMATE WITH HERBICIDE EFFECT - Google Patents
ISOXAZOLYLMETHYLTHIOL CARBAMATE WITH HERBICIDE EFFECT Download PDFInfo
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- DK145717B DK145717B DK338577AA DK338577A DK145717B DK 145717 B DK145717 B DK 145717B DK 338577A A DK338577A A DK 338577AA DK 338577 A DK338577 A DK 338577A DK 145717 B DK145717 B DK 145717B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
- C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
- C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
- C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- 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
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
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- 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
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic ring
-
- 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
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
- C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
- C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
- C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (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)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
(19) DANMARK J(19) DENMARK J
^ (12) FREMLÆGGELSESSKRIFT (ιυ 145717 B^ (12) SUBMISSION WRITING (ιυ 145717 B
DIREKTORATET FOR PATENT- OG VAREMÆRKEVÆSENETDIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM
(21) Ansøgning nr. 3385/77 (51) IntCI.3 C 07 D 261/06 (22) Indleveringsdag 27· jul. 1977 C 07 D 413/12 (24) Løbedag 27· jul. 1977 A 01 || A7 /10 (41) Aim. tilgængelig 29. jan. 1978 (44) Fremlagt 7. feb. 1983 (86) International ansøgning nr.(21) Application No. 3385/77 (51) IntCI.3 C 07 D 261/06 (22) Filing date 27 · Jul. 1977 C 07 D 413/12 (24) Race day 27 · Jul. 1977 A 01 || A7 / 10 (41) Aim. available Jan 29 1978 (44) Posted Feb 7 1983 (86) International application no.
(86) International indleveringsdag (85) Videreførelsesdag -(62) Stamansøgning nr. -(86) International filing day (85) Continuation day - (62) Master application no. -
(30) Prioritet 28. jul. 1976, 2633790, DE(30) Priority 28 Jul. 1976, 2633790, DE
(71) Ansøger BASF AKTIENGESELLSCHAFT, 6700 Ludwigshafen, DE.(71) Applicant BASF AKTIENGESELLSCHAFT, 6700 Ludwigshafen, DE.
(72) Opfinder Karl Eicken, DE: Hans Theobald, DE: Hanspeter Hansen, DE: Bruno Wuerzer, DE: Kurt Fett, DE.(72) Inventor Karl Eicken, DE: Hans Theobald, DE: Hanspeter Hansen, DE: Bruno Wuerzer, DE: Kurt Fett, DE.
(74) Fuldmægtig Ingeniørfirmaet Hofman-Bang & Boutard.(74) Associate Engineer Hofman-Bang & Boutard.
(54) Isoxazolylmethylthiolcarbamat med herbicid virkning.(54) Isoxazolylmethylthiol carbamate with herbicidal activity.
Opfindelsen angår nye, værdifulde isoxazolylmethylthiolcarbamater med herbicid aktivitet.This invention relates to novel valuable isoxazolylmethylthiol carbamates with herbicidal activity.
Fra fransk patentskrift nr. 2.205·514 er det kendt, at thiolcar-baminsyreestere af imidazoler er herbicidt aktive.From French Patent Specification No. 2,205 · 514 it is known that thiol carbamic acid esters of imidazoles are herbicidal active.
gQ Om arten af den herbicide aktivitet, f.eks. selektivitet og for- >. ligelighed overfor kulturplanter samt anvendte mængder, er der ^ intet beskrevet. De kendte aktive stoffer har kun en ringe herbi- _f) c id virkning.gQ About the nature of the herbicidal activity, e.g. selectivity and for->. similarity to culture plants and quantities used, nothing is described. The known active substances have only a slight herbicidal effect.
* □ 145717 2* □ 145717 2
Talrige thiolcarbamater er kendt som herbicider. Nogle af disse opnåede i den agrikulturelle og hortikulturelle praksis stor betydning til fjernelse af uønsket plantevækst. Disse stoffer udmærker sig på fælles måde ved deres gode virkning mod uønskede græsser. De adskiller sig dog hvad angår deres virkning mod enkelte arter af denne familie. Således bekæmpes flyvehavre af ethyl-N,N-dipropylthiolcarbamat (DE-fremlaeggelsesskrift 1.031.571), mens denne art ved propyl-N,N-dipropylthiolcarbamat (DE-fremlæg-gelsesskrift 1.031.571), ikke opføres i fabrikantens anbefaling.Numerous thiol carbamates are known as herbicides. Some of these, in the agricultural and horticultural practice, achieved great importance in removing unwanted plant growth. These substances are distinguished in common by their good action against unwanted grasses. However, they differ in their effect on individual species of this family. Thus, fly oats of ethyl N, N-dipropylthiol carbamate (DE presentation 1,031,571), while this species by propyl N, N-dipropylthiol carbamate (DE presentation 1,031,571), are not listed in the manufacturer's recommendation.
Om ethyl-N,N-dipropylthiolcarbamat berettes en god virkning mod Setaria spp., mens virkningen af 2,3-dichlorallyl-N,N-diisopro-pylthiolcarbamat (DE-fremlaeggelsesskrift 1.142.464) herved svigtede. Ved siden af bekæmpelsen af uønskede græsser kan også Cyperaceae og nogle bredbladede ukrudtsarter tilintetgøres af nogle forbindelser af denne klasse. Således udviser for eksempel propyl-N,N-dipropyl-thiolcarbamat mod Cyperus spp. en udmærket virkning, mens 2,3-dichlorallyl-N,N-dipropylthiolcarbamat næsten ikke har nogen effekt på disse arter. Et væsentligt kriterium for anvendelsen af disse midler er deres forskelle hvad angår selektiviteten for de enkelte kulturplanter. Således anvendes ethyl-N-ethyl-N-cyclohexyl-thiolcarbamat (GB-patentskrift 995.316) overvejende i beta-roer. Den vigtigste kulturplante for ethyl-N,N-diisobutyl-thiolcarbamat (DE-fremlæggelsesskrift 1.031.571) er majs. Særligt overraskende er denne forskel også ved 2,3-dichlor-allyl-N,N-diisopropyl-thiolcarbamat og 2,3,3-trichlorallyl-N,N-diisopropyl-thiolcarbamat (DE-fremlæggelsesskrift 1.142.464).Ethyl N, N-dipropylthiol carbamate is reported to have a good effect on Setaria spp., While the effect of 2,3-dichloroallyl-N, N-diisopropylthiol carbamate (DE disclosure no. 1,142,464) failed. Alongside the control of unwanted grasses, Cyperaceae and some broadleaf weeds may also be destroyed by some compounds of this class. Thus, for example, propyl N, N dipropyl thiol carbamate against Cyperus spp. an excellent effect, while 2,3-dichloroallyl-N, N-dipropylthiol carbamate has almost no effect on these species. An important criterion for the use of these agents is their differences in the selectivity of the individual crops. Thus, ethyl-N-ethyl-N-cyclohexyl-thiol carbamate (GB patent 995,316) is used predominantly in beta-beets. The most important culture plant for ethyl N, N-diisobutyl-thiol carbamate (DE Publication No. 1,031,571) is maize. Particularly surprising is this difference also with 2,3-dichloro-allyl-N, N-diisopropyl-thiolcarbamate and 2,3,3-trichloro-allyl-N, N-diisopropyl-thiolcarbamate (DE disclosure no. 1,142,464).
Begge produkter kan anvendes problemløst i bredbladede kulturer som roer og raps. For korn anbefales af fabrikanterne og distributørerne kun 2,3,3-trichlorallyl-N,N-diisopropyl-thiolcar-bamat, da dette er mindre aggressivt for disse kulturer.Both products can be used without problems in broad-leaf cultures such as beets and canola. For cereals, only 2,3,3-trichloroallyl-N, N-diisopropyl-thiolcar-bamate is recommended by the manufacturers and distributors as this is less aggressive for these cultures.
Kendte thiolcarbamater har i almindelighed et højt damptryk, hvad den følgende liste viser: 3 145717 sKnown thiol carbamates generally have a high vapor pressure, as the following list shows: 3 145717 s
Aktivt stof _Damptryk mm/Hg ved °CActive substance _ Vapor pressure mm / Hg at ° C
Ethyl-N,N-dipropyl-thiolcarbamat 34 x 10 25Ethyl N, N dipropyl thiol carbamate 34 x 10 25
Ethyl-N,N-diisobutyl-thiolcarbamat 13 x 10”^ 25Ethyl N, N-diisobutyl thiol carbamate 13 x 10
Propyl-N,N-dipropyl-thiolcarbamat 10,4 x 10 25Propyl N, N dipropyl thiol carbamate 10.4 x 10 25
Ethyl-N-ethyl-N-cyclohexyl-thiolcarbamat 6,2 x 10“^ 25 2.3- dichlorallyl-N,N-diisopropyl-thiol- , carbamat 1,5 x 10 25 2.3.3- trichlorallyl-N,N-diisopropyl-thiol- carbamat 1,2 x 10“ 25Ethyl N-ethyl-N-cyclohexyl-thiol carbamate 6.2 x 10 10 ^ 2.3-dichloroallyl-N, N-diisopropyl-thiol, carbamate 1.5 x 10 2.3.3-trichloro-ll-N, N-diisopropyl -thiol-carbamate 1.2 x 10 “25
Hexahydro-lH-azepin-1-thiolcarboxylsyre- , ethylester 5,6 x 10“ 25 (DE-patentskri ft 1.300.947)Hexahydro-1H-azepine-1-thiol carboxylic acid, ethyl ester 5.6 x 10 6 (DE patent file 1,300,947)
Alle disse aktive stoffer må indarbejdes i jordbunden for at undgå fordampningstab. Det samme formål turde ved siden af indarbejdningen opnås ved opstuvningen af vandet i rismarker.All these active substances must be incorporated into the soil to avoid evaporation losses. The same purpose, besides incorporation, should be achieved by the sputtering of the water in rice fields.
Selv om indarbejdningen af herbicider af en række grunde i almindelighed må bedømmes positivt, er denne applikationsmetode dog behæftet med betydelige ulemper. Sådanne ulemper er for eksempel den yderligere arbejdsbelastning og nødvendigheden af at måtte anskaffe specielle apparater til indarbejdning. Dette gør sig især bemærket i lidet mekaniserede landbrugsbedrifter. Jordbunden i såningsområdet løsnes extremt meget, således at der for visse frø ved tørhed opstår opvoksningsvanskeligheder. I områder med stærk slagregn bliver især ved skrånende landskab erosionsfaren forstærket på grund af denne yderligere jordbundsbearbejdning. ligeledes bidrager løsnen af jordbunden i meget stormrige og tørre zoner til bortføring af jord på grund af vinden.Although the incorporation of herbicides for a number of reasons generally needs to be evaluated favorably, this application method suffers from considerable disadvantages. Such disadvantages, for example, are the additional workload and the necessity of having to procure special appliances for incorporation. This is especially noticeable in slightly mechanized farms. The soil in the sowing area is loosened extremely much, so that for certain seeds in the event of dryness, growing difficulties arise. In areas with heavy rainfall, the danger of erosion is intensified especially by sloping landscapes due to this additional soil tillage. likewise, the loosening of the soil in very stormy and arid zones contributes to the removal of soil by the wind.
Af disse grunde forsøger man under de ovenfor angivne betingelser at bevæge jorden så lidt som muligt med henblik på dyrkning af markerne (systemet med minimal jordbundsbearbejdning, "reduced tillage").For these reasons, as far as possible, the soil is being moved as little as possible for cultivation of the fields (the system of minimal tillage, "reduced tillage").
Man søger derfor efter aktive stoffer, der frembyder alternativer til indarbejdning. På det område, der omfatter thiolcarba- 4 145717 materne med deres specifikke egenskaber, foreligger der med undtagelse af hexahydro-lH-azepin-l-thiocarboxylsyre-ethylester og S-(4-chlorbenzyl)-N,N-diethylthiolcarbamat endnu ikke sådanne, som anvendes i ris. Forsøg i denne retning blev i den seneste tid udført ved fremstilling af thiolcarbamatsulfoxider.Active substances that offer alternatives for incorporation are therefore sought. In the area comprising the thiol carbamates having their specific properties, with the exception of hexahydro-1H-azepine-1-thiocarboxylic acid ethyl ester and S- (4-chlorobenzyl) -N, N-diethylthiolcarbamate, which is used in rice. Experiments in this direction have recently been carried out in the preparation of thiol carbamate sulfoxides.
Det har nu vist sig, at et isoxazolylmethylthiolcarbamat, der er ejendommeligt ved det i den kendetegnende del af krav 1 angivne, udviser en stærkere herbicid virkning end de fra fransk patentskrift nr. 2.205.514 kendte forbindelser og samtidigt også en selektiv virkning.It has now been found that an isoxazolyl methylthiol carbamate, which is characterized by the characterizing part of claim 1, exhibits a stronger herbicidal effect than the compounds known from French Patent No. 2,205,514 and at the same time also a selective effect.
Disse forbindelser frembyder ved siden af et forøget virkningsområde en fleksibilitet hvad angår anvendelsesmetoden, som hidtil har været ukendt i denne stofkategori.These compounds, in addition to an increased range of efficacy, offer flexibility in the method of use which has hitherto been unknown in this category of substance.
I de grupper R, der foreligger i isoxazolyl-methylthiolcarbamater-ne med den almene formel I, betyder for eksempel R1 methyl, ethyl, n-propyl, i-propyl, og R5 og R6 betyder uafhængigt af hinanden ethyl, n-propyl, i-propyl, n-butyl, sek.-butyl, i- 5 6 butyl, cyclohexyl, 2-methoxyethyl, eller R og R betyder sammen med nitrogenatomet azetidin, 2-methylazetidin, 2,4-dimethylaze-tidin, 2,4,4-trimethylazetidin, pyrrolidin, 2-methylpyrrolidin, 2-ethylpyrrolidin, 2,5-dimethylpyrrolidinin, hexahydroazepin, 2-methylhexahydroazepin, 2,3-dimethylhexahydroazepin.For example, in the groups R present in the isoxazolyl methylthiol carbamates of the general formula I, R 1 represents methyl, ethyl, n-propyl, i-propyl, and R 5 and R 6 independently represent ethyl, n-propyl, -propyl, n-butyl, sec-butyl, 1-6 butyl, cyclohexyl, 2-methoxyethyl, or R and R together with the nitrogen atom means azetidine, 2-methyllazetidine, 2,4-dimethyllazidine, 2.4, 4-trimethyllazetidine, pyrrolidine, 2-methylpyrrolidine, 2-ethylpyrrolidine, 2,5-dimethylpyrrolidinine, hexahydroazepine, 2-methylhexahydroazepine, 2,3-dimethylhexahydroazepine.
Forbindelserne ifølge opfindelsen med den almene formel I kan i henhold til det i det følgende angivne reaktionsskema fremstilles ved omsætning mellem et isoxazolyl-methylhalogenid eller -methyl-alkansulfonat med saltet af et thiolearbamat.The compounds of the invention of the general formula I can be prepared according to the reaction scheme set out below by reaction of an isoxazolyl methyl halide or methyl alkanesulfonate with the salt of a thiol arbamate.
5 1457175 145717
Metode A: R1 R2 R3 0 R5Method A: R1 R2 R3 0 R5
HvnA. i b / 0 N c - x + m-s-c-n' H \r6HvnA. in b / 0 N c - x + m-s-c-n 'H \ r6
II IIIII III
R1 R2 B? 0 R3R1 R2 B? 0 R3
Nx0>\? « /Nx0> \? «/
0 - S-C-N + M-X0 - S-C-N + M-X
H \r6 R1, R2, R3, R3 og R^ har derved de i krav 1 angivne betydninger, X betyder halogen eller alkansulfonat og M et alkalimatalatom eller en eventuelt med to eller tre alkyler substitueret aimnoniumion. De ved metode A anvendte udgangsstoffer med formel II er kendt eller kan fremstilles ved omsætning mellem nitriloxider og acetylen-halogenider. Sådanne stoffer er for eksempel 5-chlormethyl-3-methylisoxazol, 5-brommethyl-3-ethylisoxazol eller 5-chlormethyl- 3-isopropylisoxazol.H 1, R 1, R 2, R 3, R 3 and R 2 have the meanings specified in claim 1, X is halogen or alkanesulfonate and M is an alkali atom atom or an optionally substituted with two or three alkyls of non-ionic ion. The starting materials of Formula II used in Method A are known or can be prepared by reaction between nitrile oxides and acetylene halides. Such substances are, for example, 5-chloromethyl-3-methylisoxazole, 5-bromomethyl-3-ethylisoxazole or 5-chloromethyl-3-isopropylisoxazole.
Forbindelserne 5-chlormethylisoxazol og 5-brommethyl-3-methyl-4-chlor_ (eller 4-brom)isoxazol er kendt fra litteraturen (Kochetkow et al., Chemical Abstracts 47, 2167 (1953); Khim, Geterotsikl.Soe-din.1974. 602). De tilsvarende isoxazolyl-methyl-alkansulfonater kan fremstilles af kendte isoxazolylmethanoler ( (Jazz. chim. ital.The compounds 5-chloromethylisoxazole and 5-bromomethyl-3-methyl-4-chloro (or 4-bromo) isoxazole are known from the literature (Kochetkow et al., Chemical Abstracts 47, 2167 (1953); Khim, Geterotsikl.Soe-din. 1974. 602). The corresponding isoxazolylmethyl alkanesulfonates can be prepared from known isoxazolylmethanols ((Jazz. Chim. Ital.
69, 556 (1959)) på den sædvanlige måde ved omsætning med alkan-sulfonsyrechlorider i nærværelse af hydrogenchloridbindende midler, såsom for eksempel pyridin. Isoxazolylmethylhalogeniderne kan for eksempel fremstilles således; 6 14571769, 556 (1959)) in the usual manner by reaction with alkanesulfonic acid chlorides in the presence of hydrogen chloride binding agents such as, for example, pyridine. For example, the isoxazolyl methyl halides can be prepared thus; 6 145717
Forskrift A1 p==pCH2-BrRegulation A1 p == pCH2-Br
Ar0 ch3 238 g (vægtdele) propargylbromid, 476 g (vægtdele) phenyliso-cyanat og 158 g (vægtdele) nitroethan opløses i 1500 ml toluen og blandes ved 15 til 20°C med 1 ml triethylamin, der tjener til aktivering af phenylisocyanatet. Temperaturen holdes i 3 timer ved 15 til 30°C, og hver time tilsættes der 1 ml triethylamin (i alt 4 ml), herpå foretager man en omrøring i 1 time ved 70°C, og der afkøles. Man foretager en sugning fra det fremkomne bundfald, og remanensen eftervaskes med 1 liter toluen, he forenede filtrater koncentreres, og remanensen destilleres i oliepumpevakuum. Ted 59 til 61°C/0,2 mm Hg destillerer 310 g (= 88$ teoretisk udbytte) 3-brommethyl-5-methylisoxazol over (n^ = 1,5168).Ar0 CH3 238 g (parts by weight) of propargyl bromide, 476 g (parts by weight) of phenyl isocyanate and 158 g (parts by weight) of nitroethane are dissolved in 1500 ml of toluene and mixed at 15 to 20 ° C with 1 ml of triethylamine serving to activate the phenyl isocyanate. The temperature is maintained for 3 hours at 15 to 30 ° C and every hour 1 ml of triethylamine (a total of 4 ml) is added, then stirred for 1 hour at 70 ° C and cooled. Suction is obtained from the resulting precipitate and the residue is washed with 1 liter of toluene, the combined filtrates are concentrated and the residue is distilled in oil pump vacuum. Ted 59 to 61 ° C / 0.2 mm Hg distills 310 g (= 88 $ theoretical yield) of 3-bromomethyl-5-methylisoxazole (n ^ = 1.5168).
C^HgBrNO = (176).C ^HgBrNO = (176).
Beregnet: C 34,2 - H 3,4 - N 7,9 - Br45,5Calculated: C 34.2 - H 3.4 - N 7.9 - Br45.5
Fundet : C 34,0 - H 3,4 - N 8,0 - Br 45,4.Found: C 34.0 - H 3.4 - N 8.0 - Br 45.4.
60 MHz-NMR-spektrum (i ChCl^j δ-'værdier) 2,3 (3H,s) 4,44 (2H,s) 6,15 (1H,s).60 MHz NMR spectrum (in ChCl3 δ values) 2.3 (3H, s) 4.44 (2H, s) 6.15 (1H, s).
1 3 C-NMR-spektrum (i ChCl^, ppm-værdier i forhold til TMS): 167,2 (C), 160,1 (C), 104,5 (CH), 18,8 (GH2), 11,3 (CH3).13 C-NMR spectrum (in ChCl3, ppm values relative to TMS): 167.2 (C), 160.1 (C), 104.5 (CH), 18.8 (GH 2), 11 , 3 (CH3).
Forskrift A2Regulation A2
CH3 ϋ ΪΤ CHCH3 ϋ ΪΤ CH
WV^CH~C1 93,5 g (vægtdele) acetohydroximoylchlorid (Ber. dtsch. chem.WV CH 2 Cl 93.5 g (parts by weight) acetohydroximoyl chloride (Ber. Dtsch. Chem.
7 1457177 145717
Ges. 40, 1677 (1907)) og 90 g (vægtdele) isobutynylchlorid om-røres i 1500 ml benzen og blandes dråbevis ved 15 til 20°C med 105 g (vægtdele) triethylamin. Derpå efterrøres der 1 time ved 20 til 25°0 og 1 time ved 70°C. Efter afkølingen filtreres, og filtratet koncentreres. Det tilbageblivende destillat destilleres i oliepumpevakuum. Man opnår 133 g (92 % af teoretisk værdi) XI med kogepunkt 48 til 50°0/mm. Hg; n^5= 1,4740.Ges. 40, 1677 (1907)) and 90 g (parts by weight) of isobutynyl chloride are stirred in 1500 ml of benzene and mixed dropwise at 15 to 20 ° C with 105 g (parts by weight) of triethylamine. Then stir for 1 hour at 20 to 25 ° 0 and 1 hour at 70 ° C. After cooling, filter and concentrate the filtrate. The residual distillate is distilled in oil pump vacuum. 133 g (92% of theoretical value) XI are obtained, with a boiling point of 48 to 50 ° 0 / mm. Hg; n ^ 5 = 1.4740.
C6HgN0Cl (145,5)C6HgNOCl (145.5)
Beregnet: C 49,6 - H 5,5 - N 9,7 - Cl 24,5Calculated: C 49.6 - H 5.5 - N 9.7 - Cl 24.5
Fundet : C 49,5 - H 5,7 - N 10,0 - Cl 24,0.Found: C 49.5 - H 5.7 - N 10.0 - Cl 24.0.
60 MHz-NMR-spektrum (i CDClj, δ-værdier) 1,78 (d, 3H); 2,3 (s, 3H); 5.05 (9, 1H); 6,09 (s, 1H).60 MHz NMR spectrum (in CDCl3, δ values) 1.78 (d, 3H); 2.3 (s, 3H); 5.05 (9.1H); 6.09 (s, 1H).
1^C-NMR-spektrum (i CDOl^, ppm-værdier i forhold til IMS): 171.5 (C); 159,8 (C); 102,5 (OH); 47,4 (OH); 23,3 (OH^j 11.5 (CH3).1 C NMR spectrum (in CDO1, ppm values relative to IMS): 171.5 (C); 159.8 (C); 102.5 (OH); 47.4 (OH); 23.3 (OH + 11.5 (CH3)).
Forskrift A3Regulation A3
C2H5. |f {IC2H5. | f {I
Nv0'ACH2-Br 119 g (vægtdele) propargylbromid, 95 g (vægtdele) 1-nitropropan og 440 g (vægtdele) triethylamin opløses i 1200 ml chloroform og blandes dråbevis ved 0°C med 155 g (vægtdele) phosphoroxychlorid.NvO'ACH2-Br 119 g (parts by weight) of propargyl bromide, 95 g (parts by weight) of 1-nitropropane and 440 g (parts by weight) of triethylamine are dissolved in 1200 ml of chloroform and mixed dropwise at 0 ° C with 155 g (parts by weight) of phosphorus oxychloride.
Derpå koger man i 30 minutter ved 20°C, og der koges i 2 timer under tilbagesvaling. Efter afkølingen filtrerer man, man koncentrerer, og remanensen optages i vand. Vandfasen ekstraheres endnu en gang med toluen, og de forenede toluenfaser vaskes med vand og tørres derpå over natriumsulfat. Derpå separerer man natriumsulfatet fra, og filtratet bliver koncentreret; remanensen destilleres i oliepumpevakuum. Den afdestillerer ved 78 til 79° 0/0,1 mm Hg (79 i° af den teoretiske mængde); n^ = 1,5108.Then, boil for 30 minutes at 20 ° C and cook for 2 hours under reflux. After cooling, the filtrate is filtered and the residue is taken up in water. The aqueous phase is extracted again with toluene and the combined toluene phases are washed with water and then dried over sodium sulfate. The sodium sulfate is then separated and the filtrate concentrated; the residue is distilled in oil pump vacuum. It distils at 78 to 79 ° 0 / 0.1 mm Hg (79 in the theoretical amount); n = 1.5108.
CgHgBrNO (190) 8 145717CgHgBrNO (190) 8 145717
Beregnet: C 37,9 - H 4,7 - N 7,4 - Br 42,0Calculated: C 37.9 - H 4.7 - N 7.4 - Br 42.0
Bundet : C 38,0 - H 4,6 - N 7,6 - Br 41,7.Bound: C 38.0 - H 4.6 - N 7.6 - Br 41.7.
På tilsvarende måde fremkommer der: CH2-C1 - 1,4806Similarly: CH2-C1 - 1.4806
CH3TXCH3TX
CH2-J . ni5 = 1,5500CH2-J. ni5 = 1.5500
De med den almene formel III betegnede forbindelser er salte af thi olcarbaminsyr er.The compounds represented by the general formula III are salts of olcarbamic acid.
Fremgangsmåde A kan gennemføres i nærværelse af vilkårlige, indifferente, organiske opløsningsmidler, for eksempel med carbon-hydrider, f.eks. cyclohexan, benzen, toluen; eller halogenerede carbonhydrider, f.eks. methylenchlorid, chloroform, tetrachlor-kulstof, chlorbenzen; eller ethere, f.eks. diethylether, di-isopropylether, tetrahydrofuran, dioxan, glycoldimethylether; eller lavere alkoholer eller ketoner, f.eks. methanol, ethanol, isopropanol, acetone, methylethylketon, cyclohexanon; eller nitriler, f.eks. acetonitril, eller vand. ligeledes man kan anvende blandinger af disse opløsningsmidler.Process A may be carried out in the presence of any inert organic solvents, for example with hydrocarbons, e.g. cyclohexane, benzene, toluene; or halogenated hydrocarbons, e.g. methylene chloride, chloroform, tetrachlorocarbon, chlorobenzene; or ethers, e.g. diethyl ether, di-isopropyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether; or lower alcohols or ketones, e.g. methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, cyclohexanone; or nitriles, e.g. acetonitrile, or water. mixtures of these solvents can also be used.
Til fremstilling af de nye, aktive stoffer foretrækker man fremgangsmåde A.For the preparation of the new active substances, method A. is preferred.
Eventuelt kan man også fremstille isoxazolylmethylthiolcarbama-terne ifølge opfindelsen med den almene formel I i henhold til metode B ved omsætning af isoxazolylmethylmercaptaner eller deres salte med carbaminsyrechlorider.Optionally, the isoxazolylmethylthiol carbamates of the invention of the general formula I according to method B can also be prepared by reacting isoxazolylmethylmercaptans or their salts with carbamic acid chlorides.
9 1457179 145717
Metode B; R1 r2 . R1 H2 >fcv3 “ /r5 -nV3 /r5 0 XC-S-Y + Cl-C-N--*. · C-S-CO-N^ + Y-Cl 'R6 ' \p6Method B; R1 r2. R1 H2> fcv3 “/ r5 -nV3 / r5 0 XC-S-Y + Cl-C-N - *. · C-S-CO-N ^ + Y-Cl 'R6' \ p6
H . K H . RH. K H. R
IV V 1 1 2 ^ ^ 6 I formlerne har R , R , R , R og R de ovenfor angivne betydninger, og Y betyder hydrogen, et alkalimetalatom eller en eventuelt med to eller tre alkyler substitueret ainmoniumion.In the formulas, R, R, R, R and R have the meanings given above, and Y means hydrogen, an alkali metal atom or an optionally substituted ammonium ion with two or three alkyls.
Den almene formel IV repræsenterer udgangsforbindelser, der lader sig fremstille ved gængse metoder ved omsætning med hydrogensulfid eller salte deraf (f.eks. Houben-Weyl, Methoden der Organischen Chemie, bind IX, s. 1-18) og isoxazolylmethylhalogenider med den almene formel II. Følgende mercaptaner med formel IV skal anføres: 3-methylisoxazolyl-5-methylmercaptan og 3-ethylisoxazolyl-5-methyl-mercaptan.The general formula IV represents starting compounds which can be prepared by conventional methods by reaction with hydrogen sulfide or salts thereof (e.g. Houben-Weyl, Methoden der Organischen Chemie, Vol. IX, pp. 1-18) and isoxazolylmethyl halides of the general formula II. The following mercaptans of formula IV should be listed: 3-methylisoxazolyl-5-methylmercaptan and 3-ethylisoxazolyl-5-methylmercaptan.
Som carbamoylchlorider med formel V skal anføres carbamoylchlo-rideme af diethylamin, af di-n-propylamin, af diisopropylamin, af di-n-butylamin, af N-ethyl-n-butylamin, af N-ethyl-n-isopropyl-amin, af azetidin, af pyrrolidin, af hexahydroazepin samt af disses i ringen med en til tre methyl- og/eller ethylgrupper substituerede derivater.As carbamoyl chlorides of formula V, the carbamoyl chlorides of diethylamine, of di-n-propylamine, of diisopropylamine, of di-n-butylamine, of N-ethyl-n-butylamine, of N-ethyl-n-isopropylamine, of azetidine, of pyrrolidine, of hexahydroazepine, and of theirs in the ring with one to three methyl and / or ethyl groups substituted by derivatives.
Metode B gennemføres hensigtsmæssigt i nærværelse af en hydrogen-chlorid-acceptor. Til dette formål kan man anvende vilkårlige uorganiske baser, f.eks. alkalimetal-bicarbonater, -carbonater eller -hydroxider; eller organiske baser som alkalimetalalkoho-later, f.eks. natriummethylat; eller tertiære aminer, f.eks. tri-ethylamin, Ν,Ν-dimethylcyclohexylamin; eller mættede eller umættede nitrogenheterocycler, f.eks. N-methyl-piperidin, pyridin eller quinolin. Fremgangsmåden gennemføres hensigtsmæssigt under anvendelse af et af de i forbindelse med fremgangsmåde A opreg- 10 145717 nede opløsningsmidler eller "blandinger deraf.Method B is conveniently carried out in the presence of a hydrogen chloride acceptor. For this purpose, any inorganic bases, e.g. alkali metal bicarbonates, carbonates or hydroxides; or organic bases such as alkali metal alcohols, e.g. sodium methylate; or tertiary amines, e.g. triethylamine, Ν, Ν-dimethylcyclohexylamine; or saturated or unsaturated nitrogen heterocycles, e.g. N-methyl-piperidine, pyridine or quinoline. The process is conveniently carried out using one of the solvents or mixtures thereof listed in connection with process A.
Desuden kan isoxazolylmethylthidLcarbamateme ifølge opfindelsen med den almene formel I også fremstilles i henhold til den følgende metode ved omsætning af en i s oxaz olylme thylthi o chlorkul-syreester med en sekundær amin.In addition, the isoxazolylmethylthide carbamates of the invention of general formula I can also be prepared according to the following method by reacting a sulfoxylated thylthio and chloroacetic acid ester with a secondary amine.
Metode GMethod G
1 2- pi'1 to 2 µl
R1 R R RR1 R R R
s /r5_x N^~i\R3 ° ^r5 V V- \ 6 ° C-S-C-N. + HC1 H R ^ VR6 VI VII i 6 I formlerne har R , R , R , R og R de ovenfor definerede betydninger.s / r5_x N ^ ~ i \ R3 ° ^ r5 V V- \ 6 ° C-S-C-N. + HC1 H R ^ VR6 VI VII in 6 In the formulas, R, R, R, R and R have the meanings defined above.
Thiochlorkulsyreesterne med den almene formel VI kan fremstilles i henhold til sædvanlige metoder af isoxazolylmethylmercaptaner med den almene formel IV (Y = hydrogen) og phosgen. Som forbindelser med formel VI skal for eksempel anføres: 3-methyl-isoxa- zolyl-5-niethylthiocarbonylchlorid og 3-ethyl-isoxazolyl-5-methyl-thiocarbonylchlorid. Som sekundære aminer med den almene formel VII er især de velegnede, der ovenfor i forbindelse med fremgangsmåde B.er anført som stamforbindelser til carbaminsyrechloriderne. Fremgangsmåde C kan gennemføres under anvendelse af de ved fremgangsmåde A angivne indifferente opløsningsmidler - mindre fordelagtigt i alkoholer eller vand - og eventuelt under tilsætning af et af de ved fremgangsmåde B angivne hydrogenchloridbindende midler .The thiochloric acid esters of general formula VI can be prepared according to conventional methods of isoxazolylmethylmercaptans of general formula IV (Y = hydrogen) and phosgene. For example, as compounds of formula VI: 3-methyl-isoxazolyl-5-methyl-thiocarbonyl chloride and 3-ethyl-isoxazolyl-5-methyl-thiocarbonyl chloride. As secondary amines of general formula VII, in particular, those which are listed above in connection with process B. are listed as parent compounds of the carbamic acid chlorides. Process C may be carried out using the inert solvents indicated by process A - less advantageously in alcohols or water - and optionally with the addition of one of the hydrogen chloride-binding agents indicated by process B.
Gennemførelsen af fremgangsmåde A sker i detaljer f.eks. på følgende måde: 11 145717The method A is carried out in detail e.g. as follows: 11 145717
Til en opløsning eller suspension af mindst et mol thiolcarbamat med den almene formel III tildryppes eventuelt i et af de angivne opløsningsmidler ved -20° til 50°C et mol af et isoxazolylmethyl-halogenid eller -alkansulfonat med den almene formel II. For at fuldstændiggøre omsætningen rører man i 3 til 12 timer ved 0 til 80°C. Efter afslutning af reaktionen hælder man ud i vand, og produktet bliver eventuelt ekstraheret med et med vand ikke blandbart , organisk opløsningsmiddel og derpå isoleret ved destillation, eller krystallisation.To a solution or suspension of at least one mole of thiol carbamate of the general formula III is optionally added in one of the indicated solvents at -20 ° to 50 ° C a mole of an isoxazolylmethyl halide or alkanesulfonate of the general formula II. To complete the reaction, stir at 0 to 80 ° C for 3 to 12 hours. After completion of the reaction, pour into water and optionally extract the product with an immiscible organic solvent and then isolated by distillation or crystallization.
Fremgangsmåde B gennemføres for eksempel på følgende måde:For example, Method B is carried out as follows:
En opløsning af et mol isoxazolylmethylmercaptan med den almene formel IV omsætter man i et opløsningsmiddel med mindst et mol af et carbaminsyrechlorid med den almene formel V i nærværelse af mindst et mol af en af de ovenfor angivne uorganiske eller organiske baser, hvorved temperaturer på -10°C til 80°C og reaktionstider på 1 til 12 timer er nødvendige. Isoleringen af thiolcarb-amaterne ifølge opfindelsen med den almene formel I foregår på den ovenfor beskrevne måde.A solution of one mole of isoxazolylmethyl mercaptan of the general formula IV is reacted in a solvent with at least one mole of a carbamic acid chloride of the general formula V in the presence of at least one mole of one of the above-mentioned inorganic or organic bases, whereby temperatures of -10 ° C to 80 ° C and reaction times of 1 to 12 hours are required. The isolation of the thiol carbamates of the invention of the general formula I is carried out in the manner described above.
Fremgangsmåde 0 gennemføres for eksempel på den i det følgende angivne måde:For example, process 0 is carried out in the following manner:
En opløsning af et mol af en thiochlorkulsyreester med den almene formel VI i et inert organisk opløsningsmiddel omsættes med mindst et mol af en amin med den almene formel VII, hvorved mindst et mol af de ved fremgangsmåde B angivne uorganiske eller organiske baser kan tjene som syrebindende middel. Reaktionstemperaturen og -tiden andrager henholdsvis -10 til 80°C og 1 til 12 timer som ved metode B i afhængighed af arten af reaktionspartner, basen og opløsningsmidlet. Isoleringen af thiolcarbamateme foregår som beskrevet i det foregående.A solution of a mole of a thiochloric acid ester of the general formula VI in an inert organic solvent is reacted with at least one mole of an amine of the general formula VII, whereby at least one mole of the inorganic or organic bases indicated by process B can serve as acid binding agent. The reaction temperature and time are -10 to 80 ° C and 1 to 12 hours, respectively, as in Method B, depending on the nature of the reaction partner, the base and the solvent. The isolation of the thiol carbamates takes place as described above.
For at tydeliggøre fremgangsmåden til fremstilling af isoxazolyl-methylthiolcarbamaterne ifølge opfindelsen med den almene formel I anføres de følgende eksempler, hvor dele altid er vægtdele.In order to clarify the process for preparing the isoxazolyl-methylthiol carbamates of the invention of general formula I, the following examples are given, wherein parts are always parts by weight.
12 145717 EKSEMPEL 1EXAMPLE 1
Til en blanding af 102 dele N-ethyl-cyclohexylamin, 80,8 dele triethylamin og 700 dele methylenchlorid indførte man ved 0°0 60,0 dele carbonoxisulfid som en gas, og der efterrørtes i 2 timer ved stuetemperatur. Derpå tildryppede man ved 0°C 105,3 dele 3-methyl-5~chlorinethylisoxazol i løbet af 1 time, og der efterrørtes i 10 timer ved stuetemperatur. Efter frasugning af det opståede salt blev filtratet i den angivne rækkefølge vasket med vand, 1 N saltsyre og vand og tørret. Efter fjernelse af opløsningsmidlet fremkom der ved destillationen af remanensen 194,2 dele 3-methyl-5-isoxazolylmethyl-N-ethyl-N-cyclohexylthiocarbamat med kogepunkt 176 - 179°C ved 0,2 mm Hg (smp.: 60 - 62 °C).To a mixture of 102 parts of N-ethyl-cyclohexylamine, 80.8 parts of triethylamine and 700 parts of methylene chloride, 60.0 parts of carbon oxy sulfide were introduced as a gas at 0 ° 0 and stirred for 2 hours at room temperature. Then, 105.3 parts of 3-methyl-5-chloroethylisoxazole were added dropwise at 0 ° C over 1 hour and stirred for 10 hours at room temperature. After suction of the resulting salt, the filtrate was washed with water, 1N hydrochloric acid and water in the order indicated and dried. After removal of the solvent, 194.2 parts of 3-methyl-5-isoxazolylmethyl-N-ethyl-N-cyclohexylthiocarbamate with boiling point 176 - 179 ° C were obtained at 0.2 mm Hg (mp: 60 - 62 °). C).
EKSEMPEL 2EXAMPLE 2
Til en blanding af 21,2 dele diisopropylamin i 100 dele toluen indførtes ved 0°C 8,0 dele carbonoxisulfid som en gas, og man holdt blandingen under omrøring i 0,5 timer ved 0°C og 1 time ved stuetemperatur. Derpå tildryppedes 19,0 dele 3-e.thyl-5-brom-methylisoxazol i 15 minutter, og man rørte i 3 timer ved stuetemperatur. Efter oparbejdningen som under eksempel 1 fremkom der 21,8 dele 3-ethyl-5-isoxazolylmethyl-N,N-diisopropylthiolcarb-amat med kogepunkt 154 - 156°C ved 0,3 mm Hg (n^ = 1,5089).To a mixture of 21.2 parts of diisopropylamine in 100 parts of toluene was introduced at 0 ° C 8.0 parts of carbon oxysulfide as a gas and the mixture was kept under stirring for 0.5 hours at 0 ° C and 1 hour at room temperature. Then, 19.0 parts of 3-ethyl-5-bromomethylisoxazole were added dropwise for 15 minutes and stirred at room temperature for 3 hours. After work-up as in Example 1, 21.8 parts of 3-ethyl-5-isoxazolylmethyl-N, N-diisopropylthiol carbamate were obtained with a boiling point of 154 DEG-156 DEG C. at 0.3 mm Hg (n + = 1.5089).
EKSEMPEL 3EXAMPLE 3
Til en blanding af 25,8 dele 3-methylisoxazolyl-5-methyl-mercaptan i 100 dele ether og 50 dele pyridin tildryppedes under afkøling 29,8 dele Ν,Ν-diethylcarbaminsyrechlorid, og derpå opvarmedes der i 3 timer under tilbagesvaling. Efter oparbejdningen som under eksempel 1 fremkom der 35,8 dele 3-methyl-5-isoxazolyl-methyl-N,N-diethylthiolcarbamat med kogepunkt 136 - 138°C ved 0,05 mm. Hg.To a mixture of 25.8 parts of 3-methylisoxazolyl-5-methylmercaptan in 100 parts of ether and 50 parts of pyridine was added dropwise with cooling 29.8 parts of diet, Ν-diethylcarbamic acid chloride and then heated at reflux for 3 hours. After the work-up as in Example 1, 35.8 parts of 3-methyl-5-isoxazolyl-methyl-N, N-diethylthiol carbamate with boiling point 136 - 138 ° C were obtained at 0.05 mm. Hg.
I henhold til en af de angivne fremgangsmåder kan man fremstille de følgende isoxazolylmethylthiolcarbamater: 13 145717 o o cc oAccording to one of the methods indicated, the following isoxazolylmethylthiol carbamates can be prepared:
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Ekgempler påherbicid virkning af de nye isoxazolglmethglthiol-carbamaterEkgempler on herbicide effect of the new isoxazolglmethgthiol carbamates
Til bevis for de allerede i forbindelse med disse aktive stoffer angivne udsagn gennemførte man en serie forsøg. Disse omfattede i det væsentlige tre grupper: I. DrivhusforsøgTo prove the statements already made in connection with these active substances, a series of experiments were carried out. These included essentially three groups: I. Greenhouse trials
Paraffinerede papbægre med et indhold på 200 cm tjente som kul-turbeholdere og lerholdig sandjord med cirka 1,5 vægtprocent humus som substrat. I dette substrat fladsåede man frøene af forsøgsplanterne i henhold til arter. Umiddelbart derpå foregik påføringen af aktive stoffer (behandling før opvoksningen).Paraffinized cardboard cups with a content of 200 cm served as culture containers and clay-containing sandy soil with about 1.5% by weight of humus as substrate. In this substrate, the seeds of the experimental plants were seeded according to species. Immediately thereafter, the application of active substances (pre-waking treatment) took place.
Disse suspenderedes eller emulgeredes i vand som fordelingsmiddel og sprøjtedes ved hjælp af fint fordelende dyser på jordoverfladen. Eør den kemiske behandling behandlede man beholderne med en let regn, således at midlerne kom i kontakt med fugtig jord. Efter påføringen af midlerne dækkede man beholderne med gennemsigtige formstofkupler, indtil planterne var vokset til.These were suspended or emulsified in water as a distribution agent and sprayed by means of finely distributing nozzles on the soil surface. After the chemical treatment, the containers were treated with a light rain so that the agents came into contact with moist soil. After application of the agents, the containers were covered with transparent plastic domes until the plants had grown.
Denne dækning forhindrede fordampningen af vand og let flygtige stoffer. Samtidigt frembragte den en regelmæssigere opvoksning af f or s øgsplant eme, når disse ikke var skadet af kemikalier.This coverage prevented the evaporation of water and volatiles. At the same time, it produced a more regular upgrowth of the plant's eggplant when they were not harmed by chemicals.
Ved behandlingen efter opvoksningen fremdrev man først planterne i forsøgsbeholderen til en højde på 3 til 10 cm, i afhængighed af deres vækstform, og behandlede dem derpå. Man undlod en dækning. Svarende til temperaturkravene af forsøgsplanterne opstilledes forsøgene i den koldere (10 - 20°C) eller den varmere (18 - 30°C) del af drivhusanlæggene. Forsøgsperioden strakte sig over 2,5 - 6 uger. I denne tid plejedes planterne, og deres reaktion på de enkelte behandlinger blev evalueret. De undersøgte materialer, de pågældende doseringer i kg aktivt stof/ha og forsøgs-plantearterne står i de her foreliggende tabeller. Bedømmelsen foretoges efter skalaen 0-100. Derved betød 0 ingen beskadigelse eller normal opvoksning og 100 fuldstændig ødelæggelse eller ingen opvoksning af planterne.In the treatment after growing up, the plants in the test container were first propelled to a height of 3 to 10 cm, depending on their growth form, and then treated. One coverage failed. In accordance with the temperature requirements of the experimental plants, the experiments were set up in the colder (10 - 20 ° C) or warmer (18 - 30 ° C) part of the greenhouse plants. The trial period lasted 2.5 - 6 weeks. During this time, the plants were nurtured and their response to the individual treatments evaluated. The materials studied, the dosages concerned in kg of active substance / ha and the experimental plant species are listed in the tables here. The rating was made on the scale of 0-100. Thus, 0 meant no damage or normal waking and 100 complete destruction or no waking of the plants.
19 145717 II. Frilandsforsøg19 145717 II. Open Air attempt
Herved drejede det sig om forsøg i små parceller af forskellig størrelse. Forsøgsstedet var en lerholdig sandjord med pH 5»6 og 1 - l,59é humus. Påføringstidspunkterne lå svarende til såningstidspunkterne af kulturplanterne i det tidlige til det sene efterår samt i det tidlige og sene forår. Påføringen af stofferne foretoges med vand som hære- og fordelingsmedium, emulgeret eller suspenderet ved hjælp af en motordrevet, på en stativhærer monteret parcelsprøjte. Som den hyppigste applikationsmetode gjorde man brug af indarbejdning før såningen og påføring før opvoksnin-gen. Ved enkelte forsøg undersøgte man også virkningen af midlerne ved sprøjtning under opvoksningen af kulturplanterne og ukrudtsplanterne samt i forbindelse med påføring efter opvoksningen efter dannelse af nogle ægte blade. Alle forsøg løb i flere måneder, i hvilket tidsrum man foretog bedømmelsen efter skalaen 0 - 100 med visse afstande.This involved trials in small plots of different sizes. The test site was a clay-containing sandy soil with pH 5 »6 and 1 - 59 g humus. The application times were similar to the sowing times of the culture plants in early to late autumn as well as in early and late spring. The fabrics were applied with water as a cure and distribution medium, emulsified or suspended by means of a motor-driven, mounted on a stand arm mounted spray gun. As the most common application method, incorporation was used before sowing and application prior to growing. In a few experiments, the effect of the agents on spraying during the growth of the culture plants and weeds as well as in connection with the application after the growth after formation of some real leaves was also investigated. All experiments ran for several months, during which time the rating was made on the scale 0 - 100 with certain distances.
III. Herbicid virkning via dampfasenIII. Herbicidal action via the vapor phase
Den bemærkelsesværdige herbicide virkning af isoxazolylmethyl-thiolcarbamater, også når disse stoffer ikke - sådan som det var nødvendigt ved kendte thiolcarbamater - blev indarbejdet i jordbunden, gjorde den konklusion nærliggende, at tabene af aktivt stof ved fordampning af denne forbindelse kun var ringe. For at gå denne overvejelse nærmere efter i sømmene gennemførte man i drivhus følgende forsøg: Man såede, som beskrevet i afsnit IThe remarkable herbicidal action of isoxazolylmethyl-thiol carbamates, even when these substances were not incorporated into the soil - as required by known thiol carbamates - made it obvious that the loss of active substance by evaporation of this compound was only slight. In order to go further into this consideration, the following tests were carried out in the greenhouse:
drivhusforsøg, følsom kulturhavre, og der behandledes med de herbicide, aktive stoffer i forskellige doseringer. Derpå afdækkede man dog ikke beholderne med en formstofkuppel, men stillede disse parvis i en glascylinder med et indhold på 5 liter.greenhouse experiments, sensitive culture oats, and the herbicidal active substances in different dosages were treated. However, the containers were not covered with a plastic dome, but placed in pairs in a glass cylinder with a capacity of 5 liters.
Parrene bestod i hvert tilfælde af en behandlet og en ubehandlet beholder. Kontrolcylindre, der kun indeholdt ubehandlede beholdere, stod selvfølgelig rede til sammenligning. For at forhindre en gasudveksling med den ydre luft bestrøg man randene af cylinderen med vaseline og afdækkede åbningen med en glasplade. Let fordampende materialer kunne på denne måde undvige fra jordoverfladen i de behandlede beholdere i cylinderrummet og muligvis 145717 20 påvirke spiringen og udviklingen af forsøgsplanteme i de parallelle "beholdere, der oprindeligt var frie for aktivt stof. Temperaturen i glascylinderen svingede fra 11°C om morgenen til 30°C ved middagstid ved solbestråling. Når planterne i kontrolcylindrene efter 14 dages forløb udviste en højde på 13 - 15 cm, og forskellene mellem enkelte behandlinger var godt konstaterbare, foretog man bedømmelserne. Ved siden af en visuel bedømmelse bestemte man for hver beholder den friske vægt af de deri frem-voksede havreskud. Dette sidste fremgår af tabel 11.The pairs consisted in each case of a treated and an untreated container. Control cylinders containing only untreated containers were of course ready for comparison. To prevent a gas exchange with the outside air, the edges of the cylinder were coated with vaseline and covered the opening with a glass plate. In this way, slightly evaporating materials could dodge from the soil surface of the treated containers in the cylinder compartment and possibly affect the germination and development of the test plants in the parallel "initially free active substance containers. The temperature of the glass cylinder fluctuated from 11 ° C in the morning. When the plants in the control cylinders showed a height of 13 - 15 cm after 14 days and the differences between individual treatments were well ascertained, the assessments were made, and a visual assessment was made for each container. the fresh weight of the oats produced therein This is shown in Table 11.
ResultatResult
De i de forskellige forsøg og tabeller på mosaikagtig måde sammenstillede enkelte værdier udviste følgende billede: 1. Indføringen af i soxazolylmethyIgrupp en i thiolcarbamat førte til en virkningsforskydning, især til en virkningsudvidelse i sammenligning med kendte thiolcarbamater. Således udfoldede for eksempel nogle forbindelser en aktivitet, der omfattede aktiviteterne af 2,3-dichlorallyl-N,N-diisopropyl-thiolcarbamat eller 2,3j3-'fcrichlorallyl-N,N-diisopropyl-thiolcarbamat eller ethyl-N,N-dipropyl-thiolcarbamat (se: tab. 2, 3 og 5). I andre tilfælde konstaterede man en lignende, undertiden noget svagere herbicid aktivitet end ved ethyl-N-ethyl-N-cyclohexylthiolcarbamat. Selektivitetsområdet over for kulturplanterne var dog uforholdsmæssigt meget større (se tabel 6).The individual values compiled in the various experiments and tables in a mosaic-like manner showed the following picture: 1. The introduction of in soxazolyl methyl group one in thiol carbamate led to an effect offset, especially to an effect expansion in comparison with known thiol carbamates. Thus, for example, some compounds exhibited an activity which included the activities of 2,3-dichloroallyl-N, N-diisopropyl-thiol carbamate or 2,3β-chloro-allyl-N, N-diisopropyl-thiolcarbamate or ethyl-N, N-dipropyl thiol carbamate (see: Tables 2, 3 and 5). In other cases, a similar, sometimes somewhat weaker, herbicidal activity was found than with ethyl N-ethyl-N-cyclohexylthiol carbamate. However, the range of selectivity to the culture plants was disproportionately much larger (see Table 6).
På dette sted skal det betones, at de kendte thiolcarbamater kun blev anvendt til forsøgene på grund af deres virkning som herbicider, Forbindelser, der, hvad angår strukturen, ligner forbindelserne ifølge opfindelsen, er ikke hidtil kendt. Et som herbicid kendt thiolcarbamat med en hetero-cyclisk ring udviste en betydningsløs aktivitet (tabel 3).At this point, it should be emphasized that the known thiol carbamates were used only for the experiments because of their effect as herbicides. Compounds which, in terms of structure, are similar to the compounds of the invention, are not known so far. A thiol carbamate known as a herbicide with a heterocyclic ring showed significant activity (Table 3).
Det tilsvarende dithiolcarbamat var fuldstændigt virkningsløst.The corresponding dithiol carbamate was completely ineffective.
Et yderligere eksempel på den herbicide aktivitet af nye isoxazolylmethylthiocarbamater findes i tabel 4.A further example of the herbicidal activity of novel isoxazolylmethylthiocarbamates can be found in Table 4.
21 «,r„4fr 1A5717 2. Mens kendte thiolcarbamater på grund af den inherente phyto-toxicitet og den til den herbicide virkning nødvendige indarbejdning ved siden af spørgsmålet om ukrudtsspektret kun kommer i betragtning til anvendelse ved specifikke kulturplanter eller grupper deraf (for eksempel bredbladede arter), udviste de nye forbindelser for eksempel en forbedret og bredere selektivitet (tabel 3, 5, 6 og 7). Selektiviteten af-forbindelserne ifølge opfindelsen kan derved både være forklarlig i plantefysiologisk henseende og også delvist bero på anvendelsesmetoden. Dette sidste betyder, at ubevægelige, ved jordoverfladen fordelte stoffer ikke kommer i kontakt med de noget dybere liggende frø og rødder af kulturplanterne i phytotoxiske mængder. Denne selektivitet gør sig bemærket ved forbindelser, der efter påføring kan forblive på jordoverfladen. Den ophører, når de aktive stoffer på grund af deres høje damptryk eller af andre årsager må indarbejdes i jordbunden for at undgå fordampningstab.21 ", r" 4fr 1A5717 2. Whereas known thiol carbamates due to the inherent phyto-toxicity and the herbicidal action required alongside the weed spectrum issue are considered only for use with specific culture plants or groups thereof (e.g. broadleaf) species), for example, the new compounds exhibited improved and wider selectivity (Tables 3, 5, 6 and 7). The selectivity of the compounds according to the invention can thereby be both explainable in plant physiological terms and also partly depend on the method of use. This last means that immobile, soil-distributed substances do not come into contact with the somewhat deeper seeds and roots of the culture plants in phytotoxic amounts. This selectivity is noticed by compounds which, after application, can remain on the soil surface. It ceases when the active substances must be incorporated into the soil due to their high vapor pressure or for other reasons to avoid evaporation losses.
3. De nye forbindelser ifølge opfindelsen udviste ved indarbejdning før såningen en lignende aktivitet som de kendte, aktive stoffer. Yed anvendelse uden indarbejdning overgik de de i hvert tilfælde for den pågældende kultur velegnede, kendte thiolcarbamater (tab. 8). I denne forbindelse er det bemærkelsesværdigt, at for eksempel forbindelsen 3-methyl-5-isoxazolylmethyl-N,N-diisopropylthiolcarbamat som thiolcarba-mat ved anvendelse før opvoksningen uden indarbejdning bekæmpede uønskede planter i majs nogenlunde lige så godt som betydende, kendte herbicider beregnet til anvendelse før opvoksningen og med anden struktur (tabel 9). Også bekæmpelser under opvoksningen og efter opvoksningen af de uønskede planter gennemførtes med godt resultat, mens kulturplanterne forblev ubeskadigede (tabel 8, 10).3. The new compounds of the invention exhibited, upon incorporation, prior to sowing, a similar activity to the known active substances. For use without incorporation, they exceeded the known thiol carbamates in each case suitable for that culture (Table 8). In this connection, it is noteworthy that, for example, the compound 3-methyl-5-isoxazolylmethyl-N, N-diisopropylthiolcarbamate as thiolcarbamate, prior to growing without incorporation, treated undesirable plants in maize as well as significant known herbicides intended for application before growing up and with other structure (Table 9). Fights during the growing up and after the growth of the unwanted plants were also carried out with good results, while the cultural plants remained undamaged (Tables 8, 10).
4. Phytotoxiciteten af dampene af 2,3,3-trichlorallyl-N,N-diisopropyl- thiolcarbamat over for' flyvehavre er kendt. Disse resultater kunne bekræftes i egne modelforsøg. Med henblik på de nye forbindelser viste det sig, at for eksempel stoffet 22 145717 3-methyl-5-isoxazolyl-methyl-N ,N-diisopropylthiolcarba:mat ' ved de direkte behandlede beholdere var nøjagtigt så aggressivt over for kulturhavre som forsøgsplante som 2,3-dichlor-allyl-N,N-diisopropyl-thiolcarbamat eller 2,3,3-trichloral-lyl-N,N-diisopropyl-thiolcarbamat. Planterne i de ubehandlede, i den samme glascylinder foreliggende beholdere forblev ved denne nye forbindelse uden beskadigelse, mens væksten deraf ved sammenligningspræparateme havde lidt mere eller mindre (tabel 11). Som følge deraf undveg der fra de direkte behandlede beholdere fra den nye forsøgssubstans mindre aktivt stof end det, der ville have været nødvendigt for en beskadigelse af de tilstødende testplanter via gasfasen. Det faktisk målte damptryk af 3-methyl-5-isoxazolylmethyl-N,N- •*5 o diisopropylthiolcarbamat androg 1,3 x 10 mbar ved 20 C, mens man sammenlignelsesvis for 2,3-dichlorallyl-N,N-diiso-propyl-thiolcarbamat ved den samme temperatur målte 3,7 x 10~4 mbar.4. The phytotoxicity of the vapors of 2,3,3-trichloroallyl-N, N-diisopropylthiol carbamate against oats is known. These results could be confirmed in our own model experiments. For the purposes of the new compounds, it was found that, for example, the substance 3-methyl-5-isoxazolyl-methyl-N, N-diisopropylthiol carbate in the directly treated containers was exactly as aggressive against culture oats as experimental plant as 2 , 3-dichloro-allyl-N, N-diisopropyl-thiolcarbamate or 2,3,3-trichloro-aryl-N, N-diisopropyl-thiolcarbamate. The plants in the untreated, in the same glass cylinder, remained in this new compound without damage, while the growth thereof in the comparator preparations had suffered more or less (Table 11). As a result, the directly treated containers from the new test substance avoided less active substance than would have been necessary to damage the adjacent test plants via the gas phase. The actual measured vapor pressure of 3-methyl-5-isoxazolylmethyl-N, N- * 5 o diisopropylthiol carbamate was 1.3 x 10 mbar at 20 ° C, while comparing 2,3-dichloroallyl-N, N-diisopropyl -thiol carbamate at the same temperature measured 3.7 x 10 ~ 4 mbar.
Naturligvis er de her angivne forsøgsresultater kun eksempler på reaktionen af talrige uønskede og ønskede planter fra de mest forskellige botaniske familier. Også de anvendte mængder kan varieres udover den variation, der fremgår af eksemplerne. De retter sig efter anvendelsesformålet og de lokale betingelser hvad angår voksestedet eller plantestørrelsen og kan for eksempel variere mellem 0,1 og 10 kg aktivt stof/ha.Of course, the experimental results presented here are only examples of the reaction of numerous undesirable and desired plants from the most diverse botanical families. The quantities used can also be varied in addition to the variation shown in the examples. They comply with the purpose and local conditions of the growing site or plant size and may vary, for example, between 0.1 and 10 kg of active substance / ha.
Denne nye gruppe af isoxazolylthiolcarbamater udmærker sig især ved flexibiliteten af anvendelsesmulighederne i sammenligning med kendte thiolearbamater.This new group of isoxazolylthiol carbamates is particularly distinguished by the flexibility of the applications compared with known thiol arbamates.
23 14571723 145717
Forkortelse latinsk navn i tabellerneAbbreviation Latin name in the tables
Alopecurus myosuroides Alooec. myosur.Alopecurus myosuroides Alooec. myosur.
Amaranthus retroflexus Amar. retro.Amaranthus retroflexus Amar. retro.
Avena fatua Avena fat.Avena fatua Avena fat.
Beta vulgaris Beta vulg.Beta vulgaris Beta vulgaris.
Brassica napus Chenopodium albumBrassica napus Chenopodium album
Cynodon dactylon Cynod. dactyl,Cynodon dactylon Cynod. dactyl,
Cyperus esculentus Cvper. escul.Cyperus esculentus Cvper. escul.
Echinochloa grus galli Echin. c.g,Echinochloa gravel bile Echin. c.g,
Eleusine indica Eleus. ind.Eleusine indica Eleus. in.
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Poa annuaPoa annua
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Tabel 5 - Selektiv ugræsbekæmpelse i roer med forskellige thiolcarbamater på friland \ V.Table 5 - Selective weed control in beets with various outdoor thiol carbamates \ V
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Hvad angår de applikationsmæssige muligheder kan midlerne ifølge opfindelsen eller blandinger, der indeholder disse, også anvendes i forbindelse med et stort antal kulturplanter foruden de nytteplanter, der er opført i tabellerne, til fjernelse af uønsket plantevækst. Anvendelseskoncentrationen kan derved udgøre mellem 0,1 og 15 kg/ha og derover, i afhængighed af det objekt, som bekæmpes.As to the application possibilities, the compositions of the invention or mixtures containing them can also be used in conjunction with a large number of crop plants in addition to the useful plants listed in the tables for removing unwanted plant growth. The application concentration can thus be between 0.1 and 15 kg / ha and above, depending on the object being combated.
De. nye isoxazolylmethylthiolcarbamater kan blandes med talrige repræsentanter for andre grupper af herbicide, aktive stoffer. Disse kombinationer frembringer en udvidelse af virkningsspektret.The. new isoxazolylmethylthiol carbamates can be mixed with numerous representatives of other groups of herbicidal active substances. These combinations produce an extension of the spectrum of effect.
Det er desuden nyttigt at kunne udbringe de nye forbindelser ifølge opfindelsen alene eller i kombination med andre herbicider, også sammen med yderligere plantebeskyttelsesmidler. I denne forbindelse skal anføres midler til bekæmpelse af skadelige organismer eller phytopatogene svampe eller vækstregulatorer. Af interesse er desuden blandbarheden med mineralske gødningsopløsninger, der anvendes til ophævelse af mangler hvad angår ernæringseller sporgrundstofforsyningen.In addition, it is useful to be able to release the new compounds of the invention alone or in combination with other herbicides, also with additional plant protection products. In this context, means must be provided to control harmful organisms or phytopathogenic fungi or growth regulators. Also of interest is the miscibility with mineral fertilizer solutions used to alleviate deficiencies in nutrition or trace element supply.
Dispenseringen foretages for eksempel under anvendelse af direkte udsprøjtelige opløsninger, pulvere, suspensioner, også højprocentige, vandige, olieagtige eller andre suspensioner eller dispersioner, emulsioner, oliedispersioner, pastaer, pudringsmidler, udstrønings-midler, granulater, hvilke dispenseringsformer fordeles ved udsprøjtning, tågedannelse, udstrøning eller udhældning. Dispenseringsfor-merne retter sig helt efter anvendelsesformålene; de skal i hvert tilfælde sikre den finest muligt fordeling af de aktive forbindelser ifølge opfindelsen.The dispensing is carried out, for example, using directly sprayable solutions, powders, suspensions, also high-percentage, aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, powders, scavengers, granules which dispensing forms are distributed by spraying, spraying, or pouring. The dispensing forms are entirely directed to the uses; in each case they must ensure the finest possible distribution of the active compounds according to the invention.
Til fremstilling af direkte udsprøjtelige opløsninger, emulsioner, pastaer og oliedispersioner kommer mineraloliefraktioner med middelhøjt til højt kogepunkt, såsom kerosin eller dieselolie, desuden kultjæreolier samt olier af vegetabilsk eller animalsk oprindelse, alifatiske, cycliske og aromatiske carbonhydrider, f.eks. benzen, toluen, xylen, paraffin, tetrahydronaphthalen, alkylerede naphthalener eller disses derivater, f.eks. methanol, ethanol, propanol, butanol, chloroform, tetrachlorkulstof, cyclo- 38 145717 hexanol, cyclohexanon, chlorbenzen, isophoron osv*, stærkt polære, opløsningsmidler, såsom f.eks, dime thylformamid, dimethyl-sulfoxid, N~methylpyrrolidon og vand, i betragtning.For the preparation of direct sprayable solutions, emulsions, pastes and oil dispersions, medium to high boiling point mineral oil fractions such as kerosene or diesel oil, in addition coal oils and vegetable or animal origin oils, aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene or their derivatives, e.g. methanol, ethanol, propanol, butanol, chloroform, tetrachlorocarbon, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc. *, highly polar, solvents such as, for example, dime thylformamide, dimethylsulfoxide, N consideration.
Vandige dispenseringsformer kan fremstilles af emulsionskoncentrater, pastaer eller befugtelige pulvere (sprøjtepulvere), oliedispersioner ved tilsætning af vand. Til fremstilling af emulsioner, pastaer eller oliedispersioner kan stofferne som sådanne eller opløst i en olie eller opløsningsmiddel, ved hjælp af be-fugtnings-, adhæsions-, dispergerings- eller emulgeringsmidler, homogeniseres i vand. Man kan også fremstille koncentrater, der består af aktivt stof, adhæsions-, befugtnings-, dispergerings-eller emulgeringsmidler og eventuelt opløsningsmidler eller olie, hvilke koncentrater er velegnede til fortynding med vand.Aqueous dispensing forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders), oil dispersions by the addition of water. For the preparation of emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent, by means of wetting, adhesive, dispersing or emulsifying agents, can be homogenized in water. Concentrates consisting of active substance, adhesive, wetting, dispersing or emulsifying agents and optionally solvents or oil may also be prepared which concentrates are suitable for dilution with water.
Som eksempler på overfladeaktive stoffer kan anføres:Examples of surfactants include:
Alkalimetal-, jordalkalimetal-, ammoniumsalte af ligninsulfonsyre, naphthalensulfonsyrer, phenolsulfonsyrer, alkylarylsulfonater, al-kylsulfater, alkylsulfonater, alkalimetal- og jordalkalimetalsalte af dibutylnaphthalensulfonsyrer, laurylethersulfat, fedtalkohol-sulfater, fedtsyre-alkali- og jordalkalimetalsalte, salte af sul-faterede hexadecanoler, heptadecanoler, octadecanoler, salte af sulfaterede fedtalkoholglycolethere, kondensationsprodukter af sulfoneret naphthalen og naphthalenderivater med formaldehyd, kondensationsprodukter af naphthalen eller naphthalensulfonsyrer med phenol og formaldehyd, polyoxyethylen-octylphenolether, ethoxyleret isooctylphenol-, octylphenol-, nonylphenol-, alkylphenolpolygly-colether, tributylphenolpolyglycolether, alkylarylpolyetheralko-holer, isotridecylalkohol, fedtalkoholethylenoxid-kondensater, ethoxyleret ricinusolie, polyoxyethylenalkylether, ethoxyleret poly-oxypropylen, laurylalkoholpolyglycoletheracetal, sorbitester, lignin, sulfitaffaldslud og methylcellulose.Alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acids, phenylsulfonic acids, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acids, lauryl ether sulfates, lauryl ether sulfates , and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenolpolygly-glycol ether, tributylphenolpolyglycolether, alkylarylpolyetheralko-alcohols , isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitester, lignin, sulfite waste liquor and methyl cellulose.
Pulvere, udstrønings- og pudringsmidier kan fremstilles ved blanding eller fælles formaling af de aktive stoffer med et fast bærestof.Powders, scatters and powders can be prepared by mixing or co-grinding the active substances with a solid carrier.
Granulater, f.eks. omhyllings-, imprægnerings- og homogengranulater, kan fremstilles ved binding af de aktive stoffer til faste bærestoffer. Faste bærestoffer er for eksempel mineraljorder, 39 145717 såsom silicagel, kiselsyrer, kiselgeler, silikater, talkum, kaolin, attapulgit, kalksten, kalk, kridt, talkum, bolus, løss, ler, dolomit, diatomejord, calcium- og magnesiumsulfat, magnesiumoxid, formalede formstoffer, gødningsmidler, såsom for eksempel ammoniumsulfat, ammoniumphosphat, ammoniumnitrat, urinstoffer og vegetabilske produkter, såsom kornmel, træbark-, træ- og nøddeskallemel, cellulosepulver og andre faste bærestoffer.Granules, e.g. envelope, impregnation and homogeneous granules can be prepared by bonding the active substances to solid carriers. Solid carriers are, for example, mineral soils, such as silica gel, silica, silica gels, silicates, talc, kaolin, attapulgite, limestone, lime, chalk, talc, bolus, lime, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, plastics, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and vegetable products such as cereal, wood bark, wood and nut shell flour, cellulose powder and other solid carriers.
Midlerne indeholder mellem 0,1 og 95 vægtprocent aktivt stof, fortrinsvis mellem 0,5 og 90 vægtprocent.The agents contain between 0.1 and 95% by weight of active substance, preferably between 0.5 and 90% by weight.
Til blandingerne eller- de enkelte, aktive stoffer kan man tilsætte olier af forskellige typer, befugtnings- eller adhæsionsmidler, herbicider, fungicider, nematodicider, insekticider, baktericider, sporgrundstoffer, gødningsmidler, skumdæmpende midler (f.eks. sili-coner), vækstregulerende midler, modgifte eller andre berbicidt aktive forbindelser.To the mixtures or individual active substances can be added oils of various types, wetting or adhesive agents, herbicides, fungicides, nematodicides, insecticides, bactericides, trace elements, fertilizers, antifoaming agents (eg silicones), growth regulators , antidotes or other berbicidically active compounds.
Eventuelt kan de også først tilsættes umiddelbart før anvendelsen (tankmix). De sidst angivne herbicide forbindelser kan også bringes i anvendelse før eller efter de enkelte aktive forbindelser ifølge opfindelsen eller blandinger deraf.They may also be added immediately before use (tank mix). The last listed herbicidal compounds may also be used before or after the individual active compounds of the invention or mixtures thereof.
Tilblandingen af disse midler til herbiciderne ifølge opfindelsen kan foregå i vægtforhold fra 1:10 til 10:1.The admixture of these agents to the herbicides of the invention can be in a weight ratio of 1:10 to 10: 1.
EKSEMPEL 4EXAMPLE 4
Man blander 90 vægtdele af forbindelsen 1 med 10 vægtdele N-methyl-a-pyrrolidon og opnår en opløsning, der er velegnet til anvendelse i form af meget små dråber.90 parts by weight of compound 1 are mixed with 10 parts by weight of N-methyl-α-pyrrolidone and a solution suitable for use in the form of very small droplets is obtained.
EKSEMPEL 5 20 vægtdele af forbindelsen 2 opløses i en blanding, der består 40 145717 af 80 vægtdele xylen, 10 vægtdele af tillejringsproduktet af 8 til 10 mol ethylenoxid til 1 mol oliesyre-N-monoethanolamid, 5 vægtdele calciumsulfat af dodecylbenzensulfonsyre og 5 vægtdele af tillejringsproduktet af 40 mol ethylenoxid til 1 mol ricinusolie. Ted udhældning og fin fordeling af opløsningen i 100.000 vægtdele vand opnår man en fin dispersion, der indeholder 0,02 vægtprocent af det aktive stof.EXAMPLE 5 20 parts by weight of compound 2 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the preparation product of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium sulfate of dodecylbenzenesulfonic acid and 5 parts by weight of the preparation product. of 40 moles of ethylene oxide to 1 mole of castor oil. Ted pouring and fine distribution of the solution in 100,000 parts by weight of water gives a fine dispersion containing 0.02% by weight of the active substance.
EKSEMPEL· 6 20 vægtdele af forbindelsen 3 opløses i en blanding, der består af 40 vægtdele cyclohexanon, 30 vægtdele isobutanol, 20 vægtdele af tillejringsproduktet af 7 mol ethylenoxid til 1 mol isooctyl-phenol og 10 vægtdele af tillejringsproduktet af 40 mol ethylenoxid til 1 mol ricinusolie. Ved indhældning og fin fordeling af opløsningen i 100.000 vægtdele vand opnår man en vandig dispersion, der indeholder 0,02 vægtprocent af det aktive stof.EXAMPLE 6 20 parts by weight of compound 3 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the product of 7 moles of ethylene oxide to 1 mole of isooctylphenol and 10 parts by weight of the product of 40 moles of ethylene oxide to 1 mole castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion containing 0.02% by weight of the active substance is obtained.
EKSEMPEL· 7 20 vægtdele af forbindelsen 4 opløses i en blanding, der består af 25 vægtdele cyclohexanol, 65 vægtdele af en mineraloliefraktion med kogepunkt 210 til 280°C og 10 vægtdele af tillejrings-produktet af 40 mol ethylenoxid til 1 mol ricinusolie. Ved indhældning og fin fordeling af opløsningen i 100.000 vægtdele vand opnår man en vandig dispersion, der indeholder 0,02 vægtprocent af det aktive stof.EXAMPLE 7 20 parts by weight of compound 4 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280 ° C and 10 parts by weight of the preparation product of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion containing 0.02% by weight of the active substance is obtained.
EKSEMPEL· 8 20 vægtdele af det aktive stof 4 blandes godt med 3 vægtdele af natriumsaltet af diisobutylnaphthalen-a-sulfonsyre, 17 vægtdele af natriumsaltet af en ligninsulfonsyre fra en sulfit-affaldslud og 60 vægtdele pulverformig kiselsyregel og formales i en hammermølle. Ved fin fordeling af blandingen i 20.000 vægtdele vand fremkommer der en sprøjtevæske, der indeholder 0,1 vægtprocent af det aktive stof.EXAMPLE 8 20 parts by weight of the active substance 4 are well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 17 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill. A fine distribution of the mixture in 20,000 parts by weight of water results in a spray liquid containing 0.1% by weight of the active substance.
41 3 vægtdele af forbindelsen 4 blandes grundigt med 97 vægtdele findelt kaolin. På denne måde fremkommer der et pudringsmiddel, der indeholder 3 vægtprocent af det aktive stof.41 3 parts by weight of compound 4 are thoroughly mixed with 97 parts by weight of finely divided kaolin. In this way, a powder containing 3% by weight of the active substance is obtained.
145717 EKSEMPEL 9 EKSEMPEL 10 30 vægtdele af forbindelsen 4 blandes grundigt med en blanding af 92 vægtdele pulverformig kiselsyregel og 8 vægtdele paraffinolie, der blev sprøjtet på overfladen af denne kiselsyregel. På denne måde fremkom der et præparat af det aktive stof med god adhæsionsevne.EXAMPLE 9 EXAMPLE 10 30 parts by weight of compound 4 are thoroughly mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of this silica gel. In this way, a preparation of the active substance with good adhesiveness was obtained.
EKSEMPEL 11 40 vægtdele af det aktive stof 5 blandes grundigt med 10 dele natriumsalte af et phenolsulfonsyre-urinstof-formaldehyd-konden-sat, 2 dele kiselgel og 48 dele vand. På denne måde fremkommer der en stabil, vandig dispersion. 7ed fortynding med 100,000 vægtdele vand opnår man en vandig dispersion, der indeholder 0,04 vægtprocent aktivt stof.EXAMPLE 11 40 parts by weight of the active substance 5 are thoroughly mixed with 10 parts of sodium salts of a phenolic sulfonic acid urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. In this way, a stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion containing 0.04% by weight of active substance.
EKSEMPEL 12 20 dele af det aktive stof 6 blandes med 2 dele calciumsalt af dodecylbenzensulfonsyre, 8 dele fedtalkohol-polyglycolether, 2 dele natriumsalt af et phenolsulfonsyre-urinstof-formaldehyd-kondensat og 68 dele af en paraffinisk mineralolie. Herved fremkommer der en stabil, olieagtig dispersion.EXAMPLE 12 20 parts of the active substance 6 are mixed with 2 parts of calcium salt of dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of a phenolic sulfonic acid urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. This results in a stable, oily dispersion.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19762633790 DE2633790A1 (en) | 1976-07-28 | 1976-07-28 | ISOXAZOLYLMETHYLTHIOLCARBAMATE |
DE2633790 | 1976-07-28 |
Publications (3)
Publication Number | Publication Date |
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DK338577A DK338577A (en) | 1978-01-29 |
DK145717B true DK145717B (en) | 1983-02-07 |
DK145717C DK145717C (en) | 1983-08-01 |
Family
ID=5984086
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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DK338577A DK145717C (en) | 1976-07-28 | 1977-07-27 | ISOXAZOLYLMETHYLTHIOL CARBAMATE WITH HERBICIDE EFFECT |
Country Status (20)
Country | Link |
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JP (1) | JPS5315369A (en) |
AT (1) | AT355862B (en) |
AU (1) | AU511197B2 (en) |
BE (1) | BE857260A (en) |
BR (1) | BR7704931A (en) |
CA (1) | CA1108133A (en) |
CH (1) | CH629080A5 (en) |
DD (1) | DD131068A5 (en) |
DE (1) | DE2633790A1 (en) |
DK (1) | DK145717C (en) |
FR (1) | FR2359833A1 (en) |
GB (1) | GB1581767A (en) |
HU (1) | HU177166B (en) |
IE (1) | IE45532B1 (en) |
IL (1) | IL52365A (en) |
IT (1) | IT1079363B (en) |
NL (1) | NL7707697A (en) |
PL (1) | PL102149B1 (en) |
SU (1) | SU668565A3 (en) |
ZA (1) | ZA774535B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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DE2943965A1 (en) * | 1979-10-31 | 1981-05-27 | Basf Ag, 6700 Ludwigshafen | 1,2-OXAZOLYLALKYLCARBAMATE, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS HERBICIDES |
-
1976
- 1976-07-28 DE DE19762633790 patent/DE2633790A1/en not_active Withdrawn
-
1977
- 1977-06-21 IL IL52365A patent/IL52365A/en unknown
- 1977-06-22 AU AU26333/77A patent/AU511197B2/en not_active Expired
- 1977-07-07 CA CA282,229A patent/CA1108133A/en not_active Expired
- 1977-07-11 NL NL7707697A patent/NL7707697A/en not_active Application Discontinuation
- 1977-07-12 JP JP8263177A patent/JPS5315369A/en active Pending
- 1977-07-20 GB GB30429/77A patent/GB1581767A/en not_active Expired
- 1977-07-22 IE IE1528/77A patent/IE45532B1/en unknown
- 1977-07-25 SU SU772504512A patent/SU668565A3/en active
- 1977-07-25 IT IT50416/77A patent/IT1079363B/en active
- 1977-07-25 CH CH919777A patent/CH629080A5/en not_active IP Right Cessation
- 1977-07-26 AT AT543077A patent/AT355862B/en not_active IP Right Cessation
- 1977-07-26 PL PL1977199854A patent/PL102149B1/en unknown
- 1977-07-26 FR FR7722879A patent/FR2359833A1/en active Granted
- 1977-07-26 DD DD7700200287A patent/DD131068A5/en unknown
- 1977-07-27 ZA ZA00774535A patent/ZA774535B/en unknown
- 1977-07-27 DK DK338577A patent/DK145717C/en not_active IP Right Cessation
- 1977-07-27 BR BR7704931A patent/BR7704931A/en unknown
- 1977-07-28 BE BE179728A patent/BE857260A/en not_active IP Right Cessation
- 1977-07-28 HU HU77BA3562A patent/HU177166B/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
ZA774535B (en) | 1978-07-26 |
AU511197B2 (en) | 1980-07-31 |
FR2359833B1 (en) | 1981-02-20 |
IL52365A0 (en) | 1977-08-31 |
NL7707697A (en) | 1978-01-31 |
IE45532B1 (en) | 1982-09-22 |
DE2633790A1 (en) | 1978-02-02 |
DK145717C (en) | 1983-08-01 |
AU2633377A (en) | 1979-01-04 |
IL52365A (en) | 1980-07-31 |
DK338577A (en) | 1978-01-29 |
CH629080A5 (en) | 1982-04-15 |
PL102149B1 (en) | 1979-03-31 |
IE45532L (en) | 1978-01-28 |
DD131068A5 (en) | 1978-05-31 |
JPS5315369A (en) | 1978-02-13 |
IT1079363B (en) | 1985-05-08 |
FR2359833A1 (en) | 1978-02-24 |
GB1581767A (en) | 1980-12-17 |
PL199854A1 (en) | 1978-03-13 |
HU177166B (en) | 1981-08-28 |
BE857260A (en) | 1978-01-30 |
AT355862B (en) | 1980-03-25 |
SU668565A3 (en) | 1979-06-15 |
BR7704931A (en) | 1978-03-28 |
ATA543077A (en) | 1979-08-15 |
CA1108133A (en) | 1981-09-01 |
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