DK171559B1 - Substituted thienyl chloroacetamides, process for their preparation, intermediates, preparation containing the compounds and use of the compounds as herbicides - Google Patents

Substituted thienyl chloroacetamides, process for their preparation, intermediates, preparation containing the compounds and use of the compounds as herbicides Download PDF

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DK171559B1
DK171559B1 DK053583D DK53583D DK171559B1 DK 171559 B1 DK171559 B1 DK 171559B1 DK 053583 D DK053583 D DK 053583D DK 53583 D DK53583 D DK 53583D DK 171559 B1 DK171559 B1 DK 171559B1
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compound
general formula
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chloroacetamide
thien
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DK053583D
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DK53583D0 (en
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Karl Seckinger
Fred Kuhnen
Karlheinz Milzner
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Sandoz Ag
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    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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  • Health & Medical Sciences (AREA)
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  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
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Description

DK 171559 B1DK 171559 B1

Den foreliggende opfindelse angår hidtil ukendte substituerede thie-nyl-chloracetamider, deres anvendelse som herbicider, landbrugspræparater til lettelse af denne anvendelse og fremgangsmåde til fremstillingen af de hidtil ukendte forbindelser samt mellemprodukter.The present invention relates to novel substituted thienyl chloroacetamides, their use as herbicides, agricultural preparations to facilitate this use, and to the method of preparing the novel compounds and intermediates.

5 Der kendes forskellige herbicide N-substituerede a-halogenacetanili-der, men der er behov for endnu mere effektive herbicider. De hidtil ukendte thienyl-chloracetamider er særlig effektive herbicider med en hensigtmæssig jordpersistens.Various herbicidal N-substituted α-haloacetanilides are known, but even more effective herbicides are needed. The novel thienyl chloroacetamides are particularly effective herbicides with a suitable soil persistence.

Den foreliggende opfindelse angår substituerede thienyl-chloracetami-10 der med den almene formel IThe present invention relates to substituted thienyl chloroacetamides of general formula I

/CO-CHjCI/ CO CHjCI

R" u s R· hvor R' og R" uafhængigt af hinanden er C-^-alkyl eller ^.4-alkoxy, 15 A er CH2, CH2-CH2 eller CH(CH3)-CH2, og R er C^.3-alkyl.R "us R · wherein R 'and R" are independently C 1-4 alkyl or C 1-4 alkoxy, A is CH 2, CH 2 -CH 2 or CH (CH 3) -CH 2, and R is C alkyl.

R er fx CH3, C2Hg og nC3H7.For example, R is CH3, C2Hg and nC3H7.

Fra Chemical Abstracts, bind 89 (1978), 42746r kendes chloracetamider, der imidlertid adskiller sig fra de foreliggende forbindelser 20 ved, at de altid er substitueret med både (eventuelt alkylsubstitu-eret)phenyl og med cyclopentyl på amid-nitrogenatomet. Ligeledes beskrives i DE 30 11 084 halogenacetanilider, der også adskiller sig fra de foreliggende forbindelser hvad angår begge amid-nitrogensubs-tituenter.From Chemical Abstracts, Volume 89 (1978), 42746r, chloroacetamides are known, but differ from the present compounds 20 in that they are always substituted with both (optionally alkyl-substituted) phenyl and with cyclopentyl on the amide nitrogen atom. Also disclosed in DE 30 11 084 haloacetanilides which also differ from the present compounds in both amide-nitrogen substituents.

25 1 DK 151011 beskrives brom- eller chloracetanilider med et azolylmet- hylsubstitueret amid-nitrogenatom. Ligesom forbindelserne fra DE 30 11 084 bærer disse kendte forbindelser en phenylsubstituent og en azolylmethylsubstituent på amid-nitrogenatamet og adskiller sig derfor fra de foreliggende forbindelser.25 1 DK 151011 discloses bromine or chloroacetanilides with an azolylmethyl-substituted amide nitrogen atom. Like the compounds of DE 30 11 084, these known compounds carry a phenyl substituent and an azolylmethyl substituent on the amide nitrogen atom and therefore differ from the present compounds.

2 DK 171559 B1 FR 2394538 beskriver herbicide halogenacetamider, hvor substituenterne på amid-nitrogenatoznet bl.a. omfatter forskellige heterocycliske substituenter. Der er imidlertid i arbejdseksempleme kun anført forbindelser, der indeholder usubstituerede furyl-, furfuryl- og 5 thienylgrupper, hvorimod thienylgruppen i de foreliggende forbindelser er substitueret med lineær alkoxyalkyl eller med alkyl eller alkoxy.2 DK 171559 B1 FR 2394538 discloses herbicidal haloacetamides, wherein the substituents on the amide nitrogen atom include e.g. comprises various heterocyclic substituents. However, in the working examples, only compounds containing unsubstituted furyl, furfuryl and thienyl groups are listed, whereas the thienyl group of the present compounds is substituted by linear alkoxyalkyl or by alkyl or alkoxy.

US 4.282.028 beskriver herbicide halogenacetamider, der imidlertid er karakteriseret ved en pyrrolring, som via sit nitrogenatom er bundet 10 direkte til amid-nitrogenatomet.US 4,282,028 discloses herbicidal haloacetamides, however, characterized by a pyrrole ring which, via its nitrogen atom, is bonded directly to the amide nitrogen atom.

Det har vist sig, at forbindelserne ifølge opfindelsen udviser signifikant bedre herbicide egenskaber end kendte substituerede acetani-lidderivater, jfr. eksempel 17 nedenfor, hvor der foretages sammenligning med forbindelsen metolachlor (a-chlor-2'-ethyl-6'-methyl-N-15 (1-methyl-2-methoxyethyl)acetanilid) , der på sit amid-nitrogen bærer en substitueret phenylgruppe i stil med nogle af de ovenfor beskrevne kendte forbindelser.It has been found that the compounds of the invention exhibit significantly better herbicidal properties than known substituted acetanide derivatives, cf. Example 17 below comparing the compound metolachlor (α-chloro-2'-ethyl-6'-methyl-N-15 (1-methyl-2-methoxyethyl) acetanilide) which carries on its amide nitrogen a substituted phenyl group in the style of some of the known compounds described above.

Den foreliggende opfindelse angår også fremgangsmåder til fremstilling af en forbindelse med den almene formel I, hvilke fremgangsmåder 20 er kendetegnet ved, atThe present invention also relates to processes for the preparation of a compound of the general formula I, characterized in that:

a) OH-gruppen hos N-hydroxyacetylgruppen i en forbindelse med den almene formel IIa) the OH group of the N-hydroxyacetyl group in a compound of the general formula II

R* COCHjOHR * COCH 2 OH

|T"SA-0-B| T "SA-0-B

11 25 hvor R, R' , R" og A har den i krav 1 definerede betydning, substitueres med chlor,Wherein R, R ', R "and A are as defined in claim 1, are substituted with chlorine,

b) en forbindelse med den almene formel IIIb) a compound of general formula III

R" IIIR "III

V-nr-NH-COCHjCIV-NR-NH-COCHjCI

S^R‘ 3 DK 171559 B1S ^ R '3 DK 171559 B1

hvor R' og R" har den i krav 1 anførte betydning, omsættes med en forbindelee med den almene formel IVwherein R 'and R "are as defined in claim 1, reacted with a linker of general formula IV

L-A-O-R IVL-A-O-R IV

hvor R og A har den i krav l anførte betydning, og L betegner en fra* 5 spaltelig enhed, der er i stand til at blive fraspaltet under N-alky-leringsreaktionsbetingelseme, c) en forbindelse med den almene formel lawherein R and A are as defined in claim 1, and L represents a cleavable moiety capable of being cleaved under the N-alkylation reaction conditions; c) a compound of general formula Ia

R· -CO-CHjCIR · -CO-CH₂Cl

R' R.,R 'R.,

hvor R"' betegner hydrogen, og R, R' og R" har den i krav 1 anførte betydning fås ved, at en forbindelse med den almene formel Vwherein R "represents hydrogen and R, R 'and R" have the meaning set forth in claim 1 obtained by a compound of the general formula V

R· ^CO-CHjCIR · CO-CH₂Cl

Vt( ^CH-ClVt (^ CH-Cl

15 «Α I15 «Α I

R· έ.,R · έ.,

hvor R', R" og R'1' har den ovenfor anførte betydning, omsættes med et reaktivt derivat af en forbindelse med den almene formel VIwherein R ', R "and R'1' have the meaning set forth above, react with a reactive derivative of a compound of general formula VI

HOR vi 20 hvor R har den i krav 1 anførte betydning,HOW do we have 20 where R has the meaning set forth in claim 1,

d) en forbindelse med den almene formel VII(d) a compound of general formula VII

R" ^-X—NH-A—0 —R vil hvor R, R', R" og A har den i krav l emførte betydning, N*acyleres med chloracetylchlorid eller et reaktivt funktionelt derivat deraf.Wherein R, R ', R' and A have the meaning set forth in claim 1, N * is acylated with chloroacetyl chloride or a reactive functional derivative thereof.

4 DK 171559 B14 DK 171559 B1

Fremgangsmåde a) ifølge opfindelsen kan udføres på kendt måde under betingelser, der er kendte for substitutionen af en OH-gruppe med chlor.Process a) of the invention can be carried out in known manner under conditions known for the substitution of an OH group with chlorine.

En sådan substitution kan fx udføres ved behandling af en forbindelse 5 med den almene formel II med et chloreringsmiddel såsom thionylch-lorid under betingelser, der i sig selv er kendte for analoge reaktioner.Such a substitution can be carried out, for example, by treating a compound of general formula II with a chlorinating agent such as thionyl chloride under conditions known per se for analogous reactions.

I henhold til en variant af denne chloreringsproces, omdannes forbindelserne med den almene formel II først til de tilsvarende sulfonyl-10 oxyderivater, fx ved O-sulfonering ved hjælp af et sulfonylhalogenid, og sulfonyloxyderivaterne omdannes derefter til de ønskede forbindelser med den almene formel I ved nucleofil substitution af sulfony-loxygruppen med chlor.According to a variant of this chlorination process, the compounds of general formula II are first converted to the corresponding sulfonyl-oxy derivatives, for example by O-sulfonation by a sulfonyl halide and the sulfonyloxy derivatives are then converted to the desired compounds of general formula I by nucleophilic substitution of the sulfonyloxy group with chlorine.

Reaktanter, der afgiver de chloranioner, der kræves til en sådan nuc-15 leofil substitution, er fx alkalimetalchlorider såsom natriumchlorid, kvaternært tetrabutylammoniumchlorid eller 4-dimethylaminopyridin-hy-drochlorid. Substitutionen udføres hensigtsmæssigt i CH2CI2 eller i et vandigt/organisk tofasesystem, hvor den organiske fase fx er et carbonhydrid såsom toluen, i nærværelse af en hensigtsmæssig fase-20 overførselskatalysator og fortrinsvis under opvarmning ved fx 40-120°C.Reactants which release the chloro anions required for such a nucleophilic substitution are, for example, alkali metal chlorides such as sodium chloride, quaternary tetrabutylammonium chloride or 4-dimethylaminopyridine hydrochloride. The substitution is conveniently carried out in CH 2 Cl 2 or in an aqueous / organic two-phase system where the organic phase is, for example, a hydrocarbon such as toluene, in the presence of an appropriate phase-transfer catalyst and preferably under heating at, for example, 40-120 ° C.

Fremgangsmåde b) kan udføres på kendt måde under betingelser, der kendes for N-alkyleringen af amider. Reaktionen udføres fordelagtigt i et opløsningsmiddel, der er inert under reaktionsbetingelseme, fx 25 dimethoxyethan eller acetonitril, eller i et vandigt/organisk tofasesystem i nærværelse af en faseoverførselskatalysator.Process b) can be carried out in known manner under conditions known for the N-alkylation of amides. The reaction is advantageously carried out in a solvent which is inert under the reaction conditions, for example, dimethoxyethane or acetonitrile, or in an aqueous / organic two-phase system in the presence of a phase transfer catalyst.

Hensigtsmæssige betydninger for L (i formel IV) er chlor, brom eller sulfonyloxydelen af en organisk sulfonsyre såsom mesyloxy eller p-to-syloxy.Suitable meanings for L (in Formula IV) are the chlorine, bromine or sulfonyloxy moiety of an organic sulfonic acid such as mesyloxy or p-to-syloxy.

30 Forbindelserne med den almene formel III anvendes fortrinsvis i form af et salt, især et alkalimetalsalt, fx natriumsaltet. Sådanne salte fås på kendt måde ved reaktion af forbindelsen med den almene formel DK 171559 Bl 5 III med en base såsom et alkalimetalamid, -hydrid, -hydroxid eller -alkoholat.The compounds of the general formula III are preferably used in the form of a salt, especially an alkali metal salt, for example the sodium salt. Such salts are obtained in known manner by reaction of the compound of the general formula DK 171559 B1 III with a base such as an alkali metal amide, hydride, hydroxide or alcoholate.

Til fremstilling af forbindelser med den almene formel la ifølge fremgangsmåde c) anvendes der hensigtsmæssigt forbindelser med den 5 almene formel V i form af alkalimetalsaltet deraf, fx natriumsaltet.For the preparation of compounds of general formula Ia according to process c), compounds of general formula V are suitably used in the form of the alkali metal salt thereof, for example the sodium salt.

Reaktionen i fremgangsmåde d) kan ligeledes udføres på kendt måde under betingelser, der er kendt for N-chloracetyleringen af aminer.The reaction of process d) can also be carried out in known manner under conditions known to the N-chloroacetylation of amines.

Når der anvendes CICOCH2CI som N-chloracetyleringsmiddel, udføres reaktionen hensigtsmæsigt i nærværelse af et syrebindingsmiddel såsom 10 K2C03.When CICOCH 2 Cl is used as N-chloroacetylating agent, the reaction is conveniently carried out in the presence of an acid binding agent such as 10 K 2 CO 3.

Forbindelserne med den almene formel I kan udvindes fra den reaktionsblanding, i hvilken de dannes, ved at arbejde efter kendte metoder .The compounds of general formula I can be recovered from the reaction mixture in which they are formed by working by known methods.

Det er klart, at forbindelserne ifølge opfindelsen kan have ét eller 15 flere asymmetriske centrer og derfor kan findes i form af optisk aktive, diastereomere, racemiske eller geometriske isomerer. Sædvanligvis anvendes forbindelserne som blandinger i herbicidfremgangsmåden og- præparaterne ifølge opfindelsen, selv om adskillelse kan udføres på kendt måde.It is to be understood that the compounds of the invention may have one or more asymmetric centers and can therefore be found in the form of optically active, diastereomers, racemic or geometric isomers. Generally, the compounds are used as mixtures in the herbicide method and compositions of the invention, although separation can be carried out in known manner.

20 Forbindelserne med den almene formel II, III og VII er hidtil ukendte og er omfattet af opfindelsen.The compounds of general formulas II, III and VII are novel and are encompassed by the invention.

Forbindelserne med den almene formel II kan fås ved ammonolyse af en ester af en forbindelse med den almene formel VIIIThe compounds of general formula II can be obtained by ammonolysis of an ester of a compound of general formula VIII

R"R "

V—nr— nhcoch2oh VIIIV — no— nhcoch2oh VIII

25 hvor R' og R" har de ovenfor anførte betydninger, med en carboxylsyre efterfulgt af indføring af gruppen A-O-R (med den ovenfor anførte betydning) i forbindelserne med den almene formel VIII ved N-alkyle- 6 DK 171559 B1 ring. Sådanne estere fås ved acylering af de tilsvarende forbindelser med den almene formel V'- hvor R' og R" har de ovenfor anførte betydninger, med den egnede 5 ester af HO-CH2COC1, fx CH3CO-OCH2-COCl.Wherein R 'and R "have the above meanings, with a carboxylic acid followed by the introduction of the group AOR (of the meaning given above) into the compounds of the general formula VIII by N-alkyl ring. Such esters are obtained. by acylating the corresponding compounds of general formula V'- wherein R 'and R "have the meanings set forth above, with the appropriate ester of HO-CH 2 COOC, e.g. CH 3 CO-OCH 2 -COCl.

Forbindelserne med den almene formel III kan også fås ved acylering af en forbindelse med den almene formel IX med chloracetylchlorid.The compounds of general formula III can also be obtained by acylating a compound of general formula IX with chloroacetyl chloride.

Forbindelser med den almene formel V (der i realiteten udgør en undergruppe af forbindelser med den almene formel I) kan fås ved 10 omsætning af en forbindelse med den almene formel IX med et hensigtsmæssigt aldehyd og omsætning af den således vundne Schiffske base med chloracetylchlorid.Compounds of general formula V (which in effect constitute a subgroup of compounds of general formula I) can be obtained by reacting a compound of general formula IX with an appropriate aldehyde and reacting the thus obtained Schiff base with chloroacetyl chloride.

Forbindelserne med den almene formel VII kan fås ved N-alkylering af en forbindelse med den almene formel IX. En sådan alkylering kan 15 udføres på kendt måde med de tilsvarende alkyleringsmidler (fx halo-genider) eller, hvor dette er hensigtsmæssigt, reduktivt via den Schiffske base eller amidet.The compounds of general formula VII can be obtained by N-alkylation of a compound of general formula IX. Such alkylation may be carried out in known manner with the corresponding alkylating agents (e.g. halogenides) or, where appropriate, reductively via the Schiff base or the amide.

Mange af forbindelserne med den almene formel IX er hidtil ukendte.Many of the compounds of general formula IX are novel.

Forbindelserne med den almene formel IX kan fås ved reduktion af de 20 tilsvarende N02-forbindelser, fx ved katalytisk hydrogenering tinder hydrogentryk i nærværelse af palladium. Forbindelser med den almene formel iXa med en CH3-gruppe i 2- eller 4-stillingen kan fås ved reduktion af det tilsvarende thiophencarboxylat ved hjælp af et com-plext hydrid såsom natrium-bis(methoxyethoxy)aluminiumhydrid. Om 25 ønsket kan forbindelserne med den almene formel IX også fås ud fra de tilsvarende carbamatestere, fx benzylcarbamatet, ved hydrolyse. De carbaxnater, der anvendes som udgangsmaterialer, kan fx fås ud fra de tilsvarende syrer, via azideme deraf efterfulgt af en Curtius-reaktion.The compounds of general formula IX can be obtained by reducing the 20 corresponding NO2 compounds, for example, by catalytic hydrogenation, hydrogen pressure in the presence of palladium. Compounds of the general formula iXa with a CH 3 group at the 2- or 4-position can be obtained by reducing the corresponding thiophene carboxylate by a complex hydride such as sodium bis (methoxyethoxy) aluminum hydride. If desired, the compounds of general formula IX may also be obtained from the corresponding carbamate esters, e.g., the benzylcarbamate, by hydrolysis. For example, the carbaxnates used as starting materials can be obtained from the corresponding acids, via the azides thereof, followed by a Curtius reaction.

7 DK 171559 B17 DK 171559 B1

Por så vidt som fremstillingen af udgangsmaterialer ikke er beskrevet i nærværende beskrivelse, er disse forbindelser kendte eller kan fremstilles og renses i henhold til kendte metoder eller analogt med fremgangsmåder, der er beskrevet i nærværende beskrivelse, eller 5 analogt med kendte metoder.As far as the preparation of starting materials is not described in this specification, these compounds are known or can be prepared and purified according to known methods or analogous to methods described in this specification or analogous to known methods.

Forbindelserne med den almene formel I er nyttige, fordi de regulerer eller modificerer*væksten af planter. Udtrykket "planter" betegner spirende frø, kimplanter og udvokset vegetation, herunder de dele, der befinder sig under jorden.The compounds of general formula I are useful because they regulate or modify * the growth of plants. The term "plants" means germinating seeds, seedlings and mature vegetation, including those parts that are underground.

10 Forbindelserne er især nyttige som herbicider, hvilket bl.a. er vist ved den skade, der forårsages på såvel enkimbladede som tokimbladede planter, såsom Lepidium sativum, Avena sativa, Agrostis alba og Lolium perenne, i tests ved testdoser, der svarer til en påføringsmængde på 1,4-5,6 kg/ha, efter påføring før og efter spiring. I 15 betragtning af deres herbicide virkning anbefales det at anvende forbindelserne ifølge opfindelsen til bekæmpelse af tokimbladet ukrudt og ukrudtsgræs, hvilket bekræftes af yderligere undersøgelser med repræsentative forbindelser i testdoser, der svarer til en påføringsmængde på 0,2-5,0 kg aktiv bestanddel, fx testdoser, der 20 svarer til en mængde på 0,2, 1,0 og 5,0 kg aktiv bestanddel pr. ha, hvilke undersøgelser er udført under anvendelse af tokimbladet ud-krudt såsom Amaranthus retroflexus, Capsalle bursa-pastoris, Chenopo-dium alba, Stellaria media, Senecio vulgaris og Galium aparine og især ukrudtsgræsser såsom Agropyron repens, Agrostis alba, Alopecurus 25 myosuroides, Apera spica-venti, Avena fatua, Echinochloa crus-galli, Bromus tectorum, Sorghum halepense, Digitaria spp og Setaria spp. yderligere tests viser en gunstig jordpersistens af forbindelserne ifølge opfindelsen.The compounds are particularly useful as herbicides, which include is shown by the damage caused to both single-seeded and two-seeded plants, such as Lepidium sativum, Avena sativa, Agrostis alba and Lolium perenne, in tests at test doses corresponding to an application rate of 1.4-5.6 kg / ha, after application before and after germination. In view of their herbicidal action, it is recommended to use the compounds of the invention to control the two-leaf weeds and weeds, which is confirmed by further studies with representative compounds at test doses corresponding to an application rate of 0.2-5.0 kg of active ingredient. eg test doses corresponding to an amount of 0.2, 1.0 and 5.0 kg of active ingredient per day. ha, which studies have been carried out using the two-leaf leaf weeds such as Amaranthus retroflexus, Capsalle bursa-pastoris, Chenopodium alba, Stellaria media, Senecio vulgaris and Galium aparine and especially weeds such as Agropyron repens, Agrostis alba, Alopecurus 25 myosuro spica-venti, Avena fatua, Echinochloa crus-galli, Bromus tectorum, Sorghum tailpipe, Digitaria spp and Setaria spp. further tests show a favorable soil persistence of the compounds of the invention.

Forbindelserne ifølge opfindelsen er relativt mindre toxiske over for 30 afgrøder end over for ukrudt. Der er bl.a. observeret en selektiv herbicid virkning for majs, sojabønne, bomuld, sukkerroer, kartoffel, lucerne, solsikke, raps, jordnødder og hør afhængig af bl.a. den anvendte forbindelse og påføringsmængden. Forbindelserne ifølge opfindelsen kan derfor også anvendes som selektive herbicider i et 35 afgrødeområde.The compounds of the invention are relatively less toxic to 30 crops than to weeds. There are observed a selective herbicide effect for maize, soybean, cotton, sugar beet, potato, alfalfa, sunflower, rapeseed, peanuts and flax depending on i.a. the compound used and the amount of application. Therefore, the compounds of the invention can also be used as selective herbicides in a crop area.

8 DK 171559 B18 DK 171559 B1

Opfindelsen angår derfor også anvendelse af forbindelser ifølge opfindelsen som herbicid og herbicide præparater indeholdende forbindelserne .The invention therefore also relates to the use of compounds of the invention as herbicide and herbicidal compositions containing the compounds.

Til generel herbicid såvel som selektiv herbicid anvendelse af for-5 bindeiser ifølge opfindelsen vil den mængde, der skal påføres for at opnå den ønskede virkning, variere afhængig af den bestemte afgrøde, hvis forbindelsen- anvendes selektivt, og andre standardvariabler såsom den anvendte forbindelse, påføringsmåde, behandlingsbetingelser og lignende. De hensigtmæssige påføringsmængder kan bestemmes af 10 fagfolk ved rutinemetoder eller ved at sammenligne virkningen af forbindelserne ifølge opfindelsen med standardpræparater, hvis påføringsmængde er kendt, fx i drivhustests. Sædvanligvis fås imidlertid tilfredsstillende resultater, når forbindelsen påføres i en mængde i området ca. 0,1-5 kg/ha, fortrinsvis ca. 0,2-4 kg/ha, især 0,5-3,0 15 kg/ha, idet påføringen gentages efter behov. Når forbindelsen anvendes i et afgrødeområde, bør påføringsmængden fortrinsvis ikke overstige 3 kg/ha.For general herbicide as well as selective herbicide use of compound according to the invention, the amount to be applied to achieve the desired effect will vary depending on the particular crop if the compound is used selectively and other standard variables such as the compound used. mode of application, treatment conditions and the like. The appropriate amounts of application can be determined by 10 skilled in the art by routine methods or by comparing the effect of the compounds of the invention with standard compositions whose application amount is known, for example, in greenhouse tests. However, usually satisfactory results are obtained when the compound is applied in an amount in the range of approx. 0.1-5 kg / ha, preferably approx. 0.2-4 kg / ha, in particular 0.5-3.0 15 kg / ha, repeating the application as needed. When applied in a crop area, the application rate should preferably not exceed 3 kg / ha.

Forbindelserne med den almene formel 1 kan anvendes og anvendes fortrinsvis som herbicide præparater sammen med ét eller flere herbi-20 cidt acceptable fortyndingsmidler. Hensigtsmæssige formuleringer indeholder 0,01-99 vægtprocent aktiv bestanddel, 0-20% herbicidt acceptabelt overfladeaktivt middel og 1-99,99% af ét eller flere faste eller flydende fortyndingsmidler. Større mængder af overfladeaktive middel i forhold til den aktive bestanddel er somme tider ønskelige 25 og opnås ved inkorporering af de overfladeaktive midler i formuleringen eller ved blanding i en tank. Påføringsformer for præparatet indeholder sædvanligvis mellem 0,01 og 25 vægtprocent aktiv bestanddel. Lavere eller højere niveauer af aktiv bestanddel kan naturligvis være til stede afhængig af den påtænkte anvendelse og forbindelsens 30 fysiske egenskaber. Koncentratformer af præparater, der skal fortyndes før brugen, indeholder sædvanligvis mellem 2 og 90 vægtprocent, fortrinsvis mellem 10 og 80 vægtprocent, aktiv bestanddel.The compounds of general formula 1 may be used and preferably used as herbicidal compositions together with one or more herbicidally acceptable diluents. Suitable formulations contain 0.01-99% by weight of active ingredient, 0-20% herbicide-acceptable surfactant, and 1-99.99% of one or more solid or liquid diluents. Larger amounts of surfactant relative to the active ingredient are sometimes desirable and are obtained by incorporating the surfactants into the formulation or by mixing in a tank. Formulations of the composition usually contain between 0.01 and 25% by weight of active ingredient. Naturally, lower or higher levels of active ingredient may be present depending on the intended use and the physical properties of the compound. Concentrate forms of compositions to be diluted prior to use usually contain between 2 and 90% by weight, preferably between 10 and 80% by weight, of active ingredient.

Nyttige formuleringer af forbindelserne ifølge opfindelsen omfatter puddere, granuler, pellets, suspensionskoncentrater, befugtelige 35 pulvere, emulgerbare koncentrater og lignende. De fås på kendt måde, 9 DK 171559 B1 fx ved blanding af forbindelserne ifølge opfindelsen med ét eller flere fortyndingsmidler. Nærmere bestemt fås flydende præparater ved blanding af bestanddelene, fine faste præparater ved blanding og sædvanligvis formaling, suspensioner ved vådformaling og granuler og 5 pellets ved imprægnering eller overtrækning af (fordannede) granulære bærere med den aktive bestanddel eller ved agglomereringsteknikker.Useful formulations of the compounds of the invention include powders, granules, pellets, suspension concentrates, wettable powders, emulsifiable concentrates and the like. They are obtained in known manner, for example by mixing the compounds of the invention with one or more diluents. Specifically, liquid compositions are obtained by mixing the ingredients, fine solid compositions by mixing and usually milling, suspensions by wet milling and granules and 5 pellets by impregnating or coating (pre-formed) granular carriers with the active ingredient or by agglomeration techniques.

Alternativt kan forbindelserne ifølge opfindelsen anvendes i mikro-indkapslet form.Alternatively, the compounds of the invention may be used in microencapsulated form.

Herbicidt acceptable tilsætningsstoffer kan anvendes i de herbicide 10 præparater for at forbedre den aktive bestanddels ydeevne og for at nedsætte skumning, sammenbagning og korrosion.Herbicidally acceptable additives can be used in the herbicidal compositions to improve the performance of the active ingredient and to reduce foaming, baking and corrosion.

Udtrykket "overfladeaktivt middel" i nærværende beskrivelse betegner et herbicidt acceptabelt materiale, der meddeler emulgerbarhed, spredning, befugtning, dispergerbarhed eller andre overflademodifi -15 cerende egenskaber. Eksempler på overfladeaktive midler er natrium-ligninsulfonat og natriumlaurylsulfat.The term "surfactant" in this specification refers to a herbicide-acceptable material which discloses emulsifiable, dispersion, wetting, dispersibility or other surface modifying properties. Examples of surfactants are sodium lignin sulfonate and sodium lauryl sulfate.

Udtrykket "fortyndingsmidler" i nærværende beskrivelse og krav betegner et flydende eller fast herbicidt acceptabelt materiale, der anvendes til at fortynde et koncentreret materiale til en anvendelig 20 eller ønskelig styrke. Til puddere eller granuler kan det fx være talkum, kaolin eller diatoméjord, til flydende koncentratformer fx et carbonhydrid såsom xylen eller en alkohol såsom isopropanol og til flydende påføringsformer bl.a. vand eller dieselolie.The term "diluents" in the present specification and claims refers to a liquid or solid herbicide acceptable material used to dilute a concentrated material to a useful or desirable strength. For powders or granules it may be, for example, talc, kaolin or diatomaceous earth, for liquid concentrate forms, for example a hydrocarbon such as xylene or an alcohol such as isopropanol, and for liquid applications, e.g. water or diesel fuel.

Præparaterne ifølge opfindelsen kan også omfatte andre forbindelser 25 med biologisk virkning, fx forbindelser med en tilsvarende eller en komplementær herbicid virkning eller forbindelser med modgifts-, fungicid eller insecticid virkning.The compositions of the invention may also comprise other compounds having a biological effect, for example, compounds having a corresponding or a complementary herbicidal action or compounds having an antidote, fungicide or insecticidal effect.

I det følgende beskrives specifikke eksempler på herbicide præparater.Specific examples of herbicidal preparations are described below.

10 DK 171559 B1 EKSEMPEL A:EXAMPLE A:

Befugteligt pulver 25 dele af en forbindelse med den almene formel I, fx forbindelse nr.Wettable powder 25 parts of a compound of general formula I, e.g.

6 nedenfor, blandes og formales med 25 dele af syntetisk fint silici-5 umdioxid, 2 dele natriumlaurylsulfat, 3 dele natriumligninsulfonat og 45 dele findelt kaolin, indtil den gennemsnitlige partikelstørrelse er ca. 5 μιη. Det resulterende befugtelige pulver fortyndes med vand før anvendelsen til en sprayvæske med den ønskede koncentration.6 below, are mixed and ground with 25 parts of synthetic fine silicon dioxide, 2 parts sodium lauryl sulfate, 3 parts sodium lignin sulfonate and 45 parts finely divided kaolin until the average particle size is approx. 5 μιη. The resulting wettable powder is diluted with water before use to a spray liquid of the desired concentration.

EKSEMPEL B: 10 Emulsionskoncentrat 20 dele af en forbindelse med den almene formel X, fx forbindelse nr. 6 nedenfor, 40 dele xylen, 30 dele dimethylformamid og 10 dele af et emulgeringsmiddel (fx ATLOX®4851 B, som er en blanding af cal-ciumalkylarylsulfonat og et polyethoxyleret triglycerid fra Atlas 15 Chemie GmbH) blandes grundigt, indtil der fås en homogen opløsning.EXAMPLE B: 10 Emulsion Concentrate 20 parts of a compound of general formula X, e.g. compound # 6 below, 40 parts xylene, 30 parts dimethylformamide and 10 parts of an emulsifier (e.g. ATLOX® 4851 B, which is a mixture of cium alkylarylsulfonate and a polyethoxylated triglyceride from Atlas 15 Chemie GmbH) are thoroughly mixed until a homogeneous solution is obtained.

Det resulterende emulsionskoncentrat fortyndes med vand før brugen.The resulting emulsion concentrate is diluted with water before use.

EKSEMPEL C:EXAMPLE C:

Granuler 5 kg af en forbindelse med den almene formel I, fx forbindelse nr. 6 20 nedenfor, opløses i 25 liter methylenchlorid. Opløsningen sættes derefter til 95 kg granuleret attapulgit (maskestørrelse 24/48 ma-sker/tomme) og blandes grundigt. Opløsningsmidlet afdampes derefter under reduceret tryk.Granules 5 kg of a compound of the general formula I, eg compound No. 6 20 below, are dissolved in 25 liters of methylene chloride. The solution is then added to 95 kg of granulated attapulgite (mesh size 24/48 mesh / inch) and mixed thoroughly. The solvent is then evaporated under reduced pressure.

Opfindelsen belyses nærmere ved nedenstående eksempler, hvor tryk er 25 angivet i mm Hg, og Rf-værdier er på silicagel, medmindre andet er angivet.The invention is further illustrated by the following examples, where pressure is given in mm Hg and Rf values are on silica gel, unless otherwise stated.

11 DK 171559 B1 SLUTFORBINDELSER EKSEMPEL 1 N-(2,4-Dimethyl-thien-3-yl)-N-methoxyethyl-chloracetamid (fremgangsmåde a) 5 Til en omrørt opløsning af 2,0 g (0,008 mol) N-(2,4-dimethyl-thien-3-yl)-N-methoxyethyl-hydroxyacetamid og 0,92 g (0,008 mol) 4-dime-thylaminopyridin (DMAP) i 80 ml tørt methylenchlorid sættes uden afkøling 0,93 g (0,008 mol) mesylchlorid i 20 ml tørt methylenchlorid.EXAMPLE 1 N- (2,4-Dimethyl-thien-3-yl) -N-methoxyethyl chloroacetamide (Method a) To a stirred solution of 2.0 g (0.008 mol) N- (2) , 4-Dimethyl-thien-3-yl) -N-methoxyethyl-hydroxyacetamide and 0.92 g (0.008 mol) of 4-dimethylaminopyridine (DMAP) in 80 ml of dry methylene chloride are added without cooling 0.93 g (0.008 mol) mesyl chloride in 20 ml of dry methylene chloride.

Den resulterende blanding, som indeholder DMAP-hydrochlorid og met-10 hansulfonatet af udgangsforbindelsen, opvarmes under tilbagesvaling i 25 timer og inddampes derefter i vakuum.The resulting mixture containing DMAP hydrochloride and the methanesulfonate of the starting compound is heated under reflux for 25 hours and then evaporated in vacuo.

Efter søjlechromatografi på silicagel (eluering med diethylether) størknede den tilbageværende olie ved afkøling ved -20°C, smeltepunkt 54 - 55 °C.After column chromatography on silica gel (eluting with diethyl ether), the residual oil solidified on cooling at -20 ° C, mp 54-55 ° C.

15 EKSEMPEL 2 N-(4-Methoxy-2-methyl-thien-3-yl)-N-(2-ethoxyethyl)-chloracetamid (fremgangsmåde d)EXAMPLE 2 N- (4-Methoxy-2-methyl-thien-3-yl) -N- (2-ethoxyethyl) chloroacetamide (process d)

Til en grundigt omrørt blanding af 6,05 g (0,03 mol) N-(2-ethoxy-ethyl)-4-methoxy-2-methyl-thiophen-3-amin, 4,15 g (0,03 mol) K2C03, 20 10 ml vand og 100 ml CH2C12 sættes dråbevis uden afkøling en opløs ning af 3,4 g (0,03 mol) chloracetylchlorid i 10 ml CH2C12. Efter at den exoterme reaktion (27°C) er ophørt, fortsættes omrøringen i yderligere 1 time ved omgivelsestemperatur.To a thoroughly stirred mixture of 6.05 g (0.03 mole) of N- (2-ethoxy-ethyl) -4-methoxy-2-methyl-thiophene-3-amine, 4.15 g (0.03 mole) K2CO3, 20 ml of water and 100 ml of CH2 Cl2 are added dropwise without cooling a solution of 3.4 g (0.03 mole) of chloroacetyl chloride in 10 ml of CH2 Cl2. After the exothermic reaction (27 ° C) has ceased, stirring is continued for an additional hour at ambient temperature.

Methylenchloridfasen fraskilles derefter, vaskes to gange med 100 ml 25 vand, tørres (Na2S04) og inddampes i vakuum. Den tilbageblevne rå titelforbindelse er analytisk ren, Rf-værdi 0,23 (hexan/diethylether, 12 DK 171559 B1 1:2). En lille portion af dette materiale blev udsat for kuglerørsdestillation: kogepunkt 168-170°C/0,05 mm Hg.The methylene chloride phase is then separated, washed twice with 100 ml of water, dried (Na 2 SO 4) and evaporated in vacuo. The crude title compound remaining is analytically pure, Rf value 0.23 (hexane / diethyl ether, 1: 2). A small portion of this material was subjected to ball-tube distillation: boiling point 168-170 ° C / 0.05 mm Hg.

De følgende forbindelser med den almene formel I fås i henhold til én eller flere af de i eksempel 1 eller 2 beskrevne fremgangsmåder (Me 5 betegner CH3 og Et betegner C2H5).The following compounds of general formula I are obtained according to one or more of the methods described in Examples 1 or 2 (Me 5 represents CH 3 and Et represents C 2 H 5).

- Tabel A- Table A

For- R" -A-O-R Karakterisering bin‘ \_/ 10 del* (Pk nr. S R.For- R "-A-O-R Characterization bin '\ _ / 10 part * (Pk No. S R.

1 2,4-diMe-thien-3-yl CH2OEt b.p. 115°C/0,001 15 mm Hg 20 2 2,4-diMe-thien-3-yl CH2OC3H7n n D = 1,52801 2,4-diMe-thien-3-yl CH 2 OE b.p. 115 ° C / 0.001 15 mm Hg 2 2,4-diMe-thien-3-yl CH2OC3H7n n D = 1.5280

3 2,4-diMe-thien-3-yl CH2CH2OMe m.p. 54-55eC3 2,4-diMe-thien-3-yl CH 2 CH 2 Ome m.p. 54-55eC

4 2,4-diMe-thien-3-yl CH2CH20Et b.p. 110°C/0,0l mm Hg 20 5 2,4-diMe-thien-3-yl CH2CH2OC3H7n Rf = 0,36 (diethyl- ether/hexan 1:1) 6 2,4-diMe-thien-3-yl CH(Me)CH2OMe b.p. 148-150°C/0,03 mm Hg 7 2-Me-4-Et-thien- 25 3-yl CH(Me)CH2OMe b.p. 142-144°C/0,2 mm Hg 8 2-Me-4-Et-thien-4 2,4-DiMe-thien-3-yl CH2 CH2 OE b.p. 110 ° C / 0.01 mm Hg 5 2,4-diMe-thien-3-yl CH2 CH2 OC3 H7 Rf = 0.36 (diethyl ether / hexane 1: 1) 6 2,4-diMe-thien-3-yl CH (Me) CH2OMe bp 148-150 ° C / 0.03 mm Hg 7 2-Me-4-Et-thien-3-yl CH (Me) CH2OMe b.p. 142-144 ° C / 0.2 mm Hg 8 2-Me-4-Et-thienes

3-yl CH2OEt m.p. 49-50°C3-yl CH2 OEt m.p. 49-50 ° C

9 2-Et-4-Me-thien- 30 3-yl CH2OC2H5 Rf = 0,47 (diethyl- ether/hexan 7:3) 10 2-Et-4-Me-thien- 3-yl CH(Me)CH2OMe Rf - 0,47 (diethyl- ether/hexan 7:3) 20 35 11 2,4-diEt-thien-3-yl CH2-OEt n D . 1,5242 12 2,4-diEt-thien-3-yl CH2CH2OMe n2p « 1,5328 13 2-Me-4-MeO-thien-9 2-Et-4-Me-thien-3-yl CH 2 OC 2 H 5 Rf = 0.47 (diethyl ether / hexane 7: 3) 10 2-Et-4-Me-thien-3-yl CH (Me) CH 2 Ome Rf - 0.47 (diethyl ether / hexane 7: 3) 2,4-diEt-thien-3-yl CH 2 -OEt n D. 1,5242 12 2,4-Dieth-thien-3-yl CH2CH2OMe n2p «1,5328 13 2-Me-4-MeO-thienyl

3-yl CH2-OEt m.p. 24eC3-yl CH2-OEt m.p. 24eC

13 DK 171559 B113 DK 171559 B1

Tabel fortsat 14 2-Me-4-MeO-thien- 3-yl CH2CH2-OEt b.p. 168 -170°C/ 0,05 mm Hg 5 15 2-Me-4-nC4H90-Table continued 14 2-Me-4-MeO-thien-3-yl CH2CH2-OEt b.p. 168-170 ° C / 0.05 mm Hg 2-Me-4-nC4H90-

thien- CH2OEt m.p. 44-46°Cthien- CH2OEt m.p. 44-46 ° C

m.p. = smeltepunkt, Rf = Rf-værdi, b.p. = kogepunkt MELLEMPRODUKTER 10 EKSEMPEL 3 2,4-Dimethyl-3-amino-thiophenm.p. = melting point, Rf = Rf value, b.p. = boiling point INTERMEDIATES EXAMPLE 3 2,4-Dimethyl-3-amino-thiophene

Til 890 ml (3 mol) natrium-bis(2-methoxyethoxy)aluminiumhydrid (70%'s opløsning i toluen) og 600 ml tørt toluen sættes dråbevis under kraftig omrøring en opløsning af 100 g (0,58 mol) methyl-3-amino-4-me-15 thyl-thiophen-2-carboxylat i 700 ml tørt toluen ved en sådan hastighed, at temperaturen ikke overstiger 55°C.To 890 ml (3 mol) of sodium bis (2-methoxyethoxy) aluminum hydride (70% solution in toluene) and 600 ml of dry toluene are added dropwise with vigorous stirring a solution of 100 g (0.58 mol) of methyl-3 amino-4-methyl-thiophene-2-carboxylate in 700 ml of dry toluene at a rate such that the temperature does not exceed 55 ° C.

Efter at tilsætningen er fuldført, fortsættes omrøringen i yderligere 30 minutter, og reaktionsblandingen sættes derefter i små portioner ved 0°C forsigtigt til 1200 ml af en 20%'s kaliumhydroxidopløsning.After the addition is complete, stirring is continued for an additional 30 minutes and the reaction mixture is then gently added in small portions at 0 ° C to 1200 ml of a 20% potassium hydroxide solution.

20 Toluenfasen fraskilles, tørres over magnesiumsulfat og inddampes i vakuum. Den tilbageblevne brune væske destilleres under reduceret tryk, hvorved fås den analytisk rene titelforbindelse, kogepunkt 49-52°C/0,01 mm Hg.The toluene phase is separated, dried over magnesium sulfate and evaporated in vacuo. The remaining brown liquid is distilled under reduced pressure to give the analytically pure title compound, boiling point 49-52 ° C / 0.01 mm Hg.

EKSEMPEL 4 25 4-Methoxy-2-methyl-3-amino-thiophenEXAMPLE 4 4-Methoxy-2-methyl-3-amino-thiophene

Til en grundigt omrørt blanding af 55,4 g (0,2 mol) benzyl-N-(4-methoxy-2 -methyl-thien-3-yl)carbamat, 40 g (0,7 mol) kaliumhydroxid, 14 DK 171559 B1 600 ml ethanol og 120 ml vand opvarmes under tilbagesvaling i 2 timer. Den resulterende opløsning inddampes derefter i vakuum, og remanensen fortyndes med 500 ml vand. Den udskilte lysegule olie optages i 400 ml diethylether, og den vandige fase ekstraheres én 5 gang med 400 ml ether.To a thoroughly stirred mixture of 55.4 g (0.2 mol) of benzyl-N- (4-methoxy-2-methyl-thien-3-yl) carbamate, 40 g (0.7 mol) of potassium hydroxide, 14 DK 171559 B1 600 ml of ethanol and 120 ml of water are heated under reflux for 2 hours. The resulting solution is then evaporated in vacuo and the residue is diluted with 500 ml of water. The separated pale yellow oil is taken up in 400 ml of diethyl ether and the aqueous phase is extracted once with 400 ml of ether.

De samlede etheropløsninger tørres (Na2S04) og filtreres. En langsom strøm af tørt hydrogenchlorid passeres derefter gennem filtratet i 30 minutter, idet det ved intermitterende afkøling i et isbad påses, at temperaturen ikke overstiger 10°C.The combined ether solutions are dried (Na 2 SO 4) and filtered. A slow stream of dry hydrogen chloride is then passed through the filtrate for 30 minutes, ensuring, by intermittent cooling in an ice bath, that the temperature does not exceed 10 ° C.

10 Det udfældede hydrochlorid af titelforbindelsen har et smeltepunkt på 230°C (den frie base har et smeltepunkt på 61-63°C).The precipitated hydrochloride of the title compound has a melting point of 230 ° C (the free base has a melting point of 61-63 ° C).

EKSEMPEL 5 I nedenstående tabel er der anført forbindelser med den almene formel IX, der fås ved én eller flere af de i eksempel 3 eller 4 beskrevne 15 fremgangsmåder.EXAMPLE 5 The following table lists compounds of general formula IX obtained by one or more of the 15 methods described in Examples 3 or 4.

Eksempel 5.1 4-C2H5-2-CH3-3-aminothiophen, Rf-værdi = 0,25 (diethylether:hexan 2:1) eksempel 5.2 4-n-butoxy-2-methyl-3-amino-thiophen, smelte punkt 25°C; (Rf-værdi = 0,25, diethylether/ 2 0 hexan 2:1) eksempel 5.3 2-Et-4-Me-3-NH2-thiophen, kogepunkt 74- 76°C/0,01 mm Hg eksempel 5.4 2,4-diEt-3-NH2-thiophen, Rf-værdi = 0,24 (CH2C12) n2£ = 1,5511 25 EKSEMPEL 6 N-(2,4-Dimethyl-thien-3-yl)-acetoxyacetamidExample 5.1 4-C2H5-2-CH3-3-aminothiophene, Rf value = 0.25 (diethyl ether: hexane 2: 1) Example 5.2 4-n-butoxy-2-methyl-3-amino-thiophene, melting point 25 ° C; (Rf value = 0.25, diethyl ether / hexane 2: 1) Example 5.3 2-Et-4-Me-3-NH 2 -thiophene, bp 74-76 ° C / 0.01 mm Hg Example 5.4 2, 4-diEt-3-NH2-thiophene, Rf value = 0.24 (CH2 Cl2) n2 = = 1.5511 EXAMPLE 6 N- (2,4-Dimethyl-thien-3-yl) -acetoxyacetamide

Til 12,7 g (0,1 mol) 2,4-dimethyl-3-aminothiophen, 13,8 g (0,1 mol) kaliumcarbonat, 20 ml vand og 150 ml methylenchlorid sættes dråbevis ved omgivelsestempeatur 15 g (0,11 mol) acetoxyacetylchlorid.To 12.7 g (0.1 mole) of 2,4-dimethyl-3-aminothiophene, 13.8 g (0.1 mole) of potassium carbonate, 20 ml of water and 150 ml of methylene chloride are added dropwise at ambient temperature 15 g (0.11 mol) acetoxyacetyl chloride.

15 DK 171559 B115 DK 171559 B1

Efter at den exoterme reaktion er ophørt, fortsættes omrøringen i yderligere 1 time. Derefter inddampes den organiske fase, vaskes med vand, tørres (magnesiumsulfat) og inddampes i vakuum. Den faste remanens behandles med hexan, hvorved fås den analytisk rene titel-5 forbindelse, smeltepunkt 110-112°C.After the exothermic reaction has ceased, stirring is continued for an additional hour. The organic phase is then evaporated, washed with water, dried (magnesium sulfate) and evaporated in vacuo. The solid residue is treated with hexane to give the analytically pure title compound, mp 110-112 ° C.

EKSEMPEL 7 N-(2,4-Dimethyl-thien-3-yl)-hydroxyacetamidEXAMPLE 7 N- (2,4-Dimethyl-thien-3-yl) -hydroxyacetamide

Gennem en omrørt opløsning af 15,9 g (0,07 mol) N-(2,4-dimethyl-thien-3-yl)-acetoxyacetamid i 300 ml methanol bobles en svag strøm af 10 ammoniakgas i 30 minutter.Through a stirred solution of 15.9 g (0.07 mol) of N- (2,4-dimethyl-thien-3-yl) -acetoxyacetamide in 300 ml of methanol, a gentle stream of 10 ammonia gas is bubbled for 30 minutes.

Efter at den exoterme reaktion (40°C) (modereret ved intermitterende afkøling i koldt vand) er ophørt, fortsætter omrøringen i yderligere 30 minutter, og reaktionsopløsningen inddampes derefter til tørhed.After the exothermic reaction (40 ° C) (moderated by intermittent cooling in cold water) is stopped, stirring is continued for a further 30 minutes and the reaction solution is then evaporated to dryness.

Det resulterende faste stof omkrystalliseres af ethylacetat, hvorved 15 fås den analytisk rene titelforbindelse i form af farveløse krystaller, smeltepunkt 85-87°C.The resulting solid is recrystallized from ethyl acetate to give the analytically pure title compound in the form of colorless crystals, mp 85-87 ° C.

EKSEMPEL 8 N-(2-Ethoxyethyl)-4-methoxy-2-methyl-thiophen-3-aminExample 8 N- (2-Ethoxyethyl) -4-methoxy-2-methyl-thiophen-3-amine

Til 70 ml (0,245 mol) natrium-bis(2-methoxyethoxy)aluminiumhydrid 20 (70%'s opløsning i toluen) og 30 ml tørt toluen sættes dråbevis under omrøring en opløsning af 9,4 g (0,041 mol) N-(4-methoxy-2-methyl-thien-3-yl)-ethoxyacetamid i 125 ml tørt toluen. Efter at den exoterme reaktion er ophørt, fortsættes omrøringen i yderligere 90 minutter, og reaktionsopløsningen sættes derefter i små portioner ved 25 -10°C forsigtigt til 100 ml 20%'s kaliumhydroxidopløsning.To 70 ml (0.245 mol) of sodium bis (2-methoxyethoxy) aluminum hydride 20 (70% solution in toluene) and 30 ml of dry toluene are added dropwise with stirring a solution of 9.4 g (0.041 mol) of N- (4). -methoxy-2-methyl-thien-3-yl) -ethoxyacetamide in 125 ml of dry toluene. After the exothermic reaction has ceased, stirring is continued for a further 90 minutes and the reaction solution is then gently added in small portions at 25 -10 ° C to 100 ml of 20% potassium hydroxide solution.

Toluenfasen fraskilles, og den vandige fase ekstraheres to gange med 100 ml toluen. De samlede toluenopløsninger tørres (natriumsulfat) og 16 DK 171559 B1 inddampes i vakuum. Den tilbageblevne lysebrune væske er analytisk ren, Rf-værdi = 0,32 (hexan/diethylether 1:2).The toluene phase is separated and the aqueous phase is extracted twice with 100 ml of toluene. The combined toluene solutions are dried (sodium sulfate) and evaporated in vacuo. The residual light brown liquid is analytically pure, Rf value = 0.32 (hexane / diethyl ether 1: 2).

EKSEMPEL 9 N-[1-(Methoxymethyl)ethyl]-2,4-dimethyl-thiophen-3-amin 5 En opløsning af 6,4 g (0,05 mol) 2,4-dimethyl-3-aminothiophen og 5,3 g (0,06 mol) methoxyacetone i 100 ml tørt toluen koges under tilbagesvaling, indtil den teoretiske mængde vand er blevet fraskilt i vandsamleren (2 1/2 time). Toluenopløsningen lades derefter afkøle til omgivelsestemperatur og inddampes i vakuum. Den tilbageblevne rå 10 Schiffske base er tilstrækkelig ren til det næste trin.EXAMPLE 9 N- [1- (Methoxymethyl) ethyl] -2,4-dimethyl-thiophen-3-amine 5 A solution of 6.4 g (0.05 mol) of 2,4-dimethyl-3-aminothiophene and 5, 3 g (0.06 mol) of methoxyacetone in 100 ml of dry toluene are refluxed until the theoretical amount of water has been separated into the water collector (2 1/2 hours). The toluene solution is then allowed to cool to ambient temperature and evaporated in vacuo. The remaining raw 10 Schiff base is sufficiently clean for the next step.

9,2 g (0,048 mol) af dette materiale opløses i 100 ml tørt toluen og sættes uden afkøling til en grundigt omrørt opløsning af 28 ml (0,098 mol) natrium-bis(2-methoxyethoxy)aluminiumhydrid (70%'s opløsning i toluen) i 15 ml tørt toluen.9.2 g (0.048 mol) of this material is dissolved in 100 ml of dry toluene and added without cooling to a thoroughly stirred solution of 28 ml (0.098 mol) of sodium bis (2-methoxyethoxy) aluminum hydride (70% solution in toluene ) in 15 ml of dry toluene.

15 Efter at den exoterme reaktion (44°C) er ophørt, fortsættes omrøringen i yderligere 90 minutter, og den brune reaktionsopløsning sættes derefter i små portioner ved -10°C forsigtigt til 40 ml af en 20%'s kaliumhydroxidopløsning.After the exothermic reaction (44 ° C) is stopped, stirring is continued for a further 90 minutes and the brown reaction solution is then gently added in small portions at -10 ° C to 40 ml of a 20% potassium hydroxide solution.

Toluenfasen fraskilles derefter, tørres (natriumsulfat) og inddampes 20 i vakuum. Den tilbageblevne olie destilleres efter søjlechromatografi på silicagel (eluering med hexan/diethylether, 3:1) under reduceret tryk (kuglerør) og har et kogepunkt på 94-95°C/0,01 mm Hg.The toluene phase is then separated, dried (sodium sulfate) and evaporated in vacuo. The residual oil is distilled after column chromatography on silica gel (elution with hexane / diethyl ether, 3: 1) under reduced pressure (beads) and has a boiling point of 94-95 ° C / 0.01 mm Hg.

17 DK 171559 B1 EKSEMPEL 10EXAMPLE 10

De følgende forbindelser med den almene formel vil fås ved én eller flere af de i eksempel 6-9 beskrevne metoder: R*The following compounds of the general formula will be obtained by one or more of the methods described in Examples 6-9: R *

Ek- 'S—/ -A-O-R Karakterisering 5 sem- (f \\- Rf = R^-vardiI- S- / -A-O-R Characterization 5 sem- (f \\ - Rf = R

Pel S \ _R_ 10.1 2,4 - di -CH3-thien-3-yl CH2CH2-OCH3 Rf=0,32 (diethylether/ hexan 3:1) 10 10.2 2,4 - di -CH3-thien-3-yl CH2CH2OC2H5 Rf=0,48 (diethylether) 10.3 2,4-di-CH3*thien-3-yl CH2CH2OC3H7-n Rf=0,57 (diethylether) 20 10.4 2,4-di-C2Hg-thien-3-yl CH2CH2OCH3 n D « 1,5238 10.5 2-CH3-4-C2H5*thien- CH3 kogepunkt 3-yl CH-CH2OCH3 98-100cC/0,09 15 mm Hg ch3 10.6 2-C2H5-4-CH3-thien- CH-CH2OCH3 Rf=0,52 (ether/hexan 3-yl 7:3) EKSEMPEL 11 20 Der fås følgende forbindelser med den almene formel III: R*PEL S \ _R_ 10.1 2,4 - di -CH3-thien-3-yl CH2CH2-OCH3 Rf = 0.32 (diethyl ether / hexane 3: 1) 10.2 2.4 - di -CH3-thien-3-yl CH2CH2OC2H5 Rf = 0.48 (diethyl ether) 10.3 2,4-di-CH3 * thien-3-yl CH2CH2OC3H7-n Rf = 0.57 (diethyl ether) 10.4 2,4-di-C2Hg-thien-3-yl CH2CH2OCH3 n D «1,5238 10.5 2-CH3-4-C2H5 * thien-CH3 boiling point 3-yl CH-CH2OCH3 98-100cC / 0.09 15 mm Hg ch3 10.6 2-C2H5-4-CH3-thien-CH-CH2OCH3 Rf = 0.52 (ether / hexane 3-yl 7: 3) EXAMPLE 11 The following compounds of general formula III are obtained: R *

Eksempel te* KarakteriseringExample te * Characterization

S' RS 'R

11.1 2,4 - di-CH3-thien-3-yl smeltepunkt 128-129°C11.1 2,4 - di-CH 3 -thien-3-yl mp 128-129 ° C

11.2 2-CH3-4-C2H5-thien-3-yl smeltepunkt 114eC11.2 2-CH3-4-C2H5-thien-3-yl melting point 114 ° C

25 11.3 2-CH3-4-OCH3-thien-3-yl smeltepunkt 144-145eC11.3 2-CH3-4-OCH3-thien-3-yl mp 144-145 ° C

11.4 2-C2H5-4-CH3-thien-3-yl smeltepunkt 105°C11.4 2-C2H5-4-CH3-thien-3-yl melting point 105 ° C

11.5 2,4-di-C2H5-thien-3-yl smeltepunkt 145eC11.5 2,4-di-C 2 H 5 -thien-3-yl mp 145 ° C

11.6 2-CH3-4-OC4H9n-thien-3-yl smeltepunkt 129-130°C11.6 2-CH3-4-OC4H9n-thien-3-yl mp 129-130 ° C

18 DK 171559 B1 EKSEMPEL 12 N-(2,4-Dimethylthien-3-yl)-N-methoxyethyl-hydroxyacetamid 18,4 g (0,1 mol) N-(2,4-dimethylthien-3-yl)-hydroxyacetamid i 50 ml tørt dimethylformamid (DMF) sættes dråbevis til en grundig omrørt 5 suspension af 3,0 g (0,1 mol) natriumhydroxid (80%'s dispersion i mineralolie) i 50*ml tørt DMF.EXAMPLE 12 N- (2,4-Dimethylthien-3-yl) -N-methoxyethyl-hydroxyacetamide 18.4 g (0.1 mole) of N- (2,4-dimethylthien-3-yl) -hydroxyacetamide in 50 ml dry dimethylformamide (DMF) is added dropwise to a thoroughly stirred suspension of 3.0 g (0.1 mol) of sodium hydroxide (80% dispersion in mineral oil) in 50 * ml dry DMF.

Efter at den exoterme reaktion (50°C) er ophørt, lades opløsningen af natriumsaltet nå stuetemperatur og behandles derefter med en opløsning af 10,4 g (0,11 mol) 2-chlorethylmethylether i 20 ml tørt DMF.After the exothermic reaction (50 ° C) is stopped, the solution of the sodium salt is allowed to reach room temperature and then treated with a solution of 10.4 g (0.11 mol) of 2-chloroethyl methyl ether in 20 ml of dry DMF.

10 Når tilsætningen er fuldført, opvarmes den resulterende blanding ved 100eC i 4 timer og inddampes derefter til tørhed (40°C/0,1 mm Hg).When the addition is complete, the resulting mixture is heated at 100 ° C for 4 hours and then evaporated to dryness (40 ° C / 0.1 mm Hg).

Remanensen optages i 200 ml diethylether, vaskes med 250 ml vand, tørres (magnesiumsulfat) og filtreres. Den olie, der bliver tilbage efter inddampning af filtratet, chromatograferes på en silicagelsøj-15 le. Ved eluering med ether fås det ønskede produkt i form af en analytisk ren viskos væske (Rf-værdi = 0,25/ether).The residue is taken up in 200 ml of diethyl ether, washed with 250 ml of water, dried (magnesium sulfate) and filtered. The oil remaining after evaporation of the filtrate is chromatographed on a silica gel column. Elution with ether gives the desired product in the form of an analytically pure viscous liquid (Rf value = 0.25 / ether).

Herbicide tests EKSEMPEL 13Herbicidal Tests Example 13

Ukrudtskontrol - præ-emergensbehandling 20 Urtepotter (7 cm i diameter) fyldes med en blanding af tørvedyrk- ningssubstrat og sand. Den blottede overflade af tørvedyrkningssubstratet og sandblandingen sprøjtes med en testvæske af en testforbindelse (fx formuleret som beskrevet i eksempel B), og frø af Le pidium sativum, Agrostis alba, Avena sativa og Lolium perenne sås i 25 hver potte, idet Avena sativa- og Lolium perenne-frøene efter såningen dækkes med et tyndt lag (0,5 cm) tørvedyrkningssubstrat/sand-blanding. Potterne holdes ved stuetemperatur i 21 dage med 14-17 timers lys (dagslys eller tilsvarende) pr døgn.Weed Control - Pre-emergence Treatment 20 Herbal pots (7 cm in diameter) are filled with a mixture of peat culture substrate and sand. The exposed surface of the peat growing substrate and sand mixture is sprayed with a test compound test liquid (e.g. formulated as described in Example B), and seeds of Le pidium sativum, Agrostis alba, Avena sativa and Lolium perenne are sown in each pot, with Avena sativa and After sowing, the lolium perenne seeds are covered with a thin layer (0.5 cm) of peat culture substrate / sand mixture. The pots are kept at room temperature for 21 days with 14-17 hours of light (daylight or equivalent) per day.

19 DK 171559 B119 DK 171559 B1

Bestemmelse af den herbicide virkning af det bestemte herbicid foretages efter 21 dages perioden. Bestemmelsen omfatter en visuel bedømmelse af graden og arten af skaden forvoldt mod de forskellige kimplanter.Determination of the herbicidal effect of the particular herbicide is made after the 21 day period. The provision includes a visual assessment of the degree and nature of the damage caused to the various seedlings.

5 Forbindelserne med den almene formel I påføres på ovennævnte måde i doser, der svarer-til 1,4 og 5,6 kg aktiv bestanddel/ha.The compounds of the general formula I are applied in the above manner in doses corresponding to 1.4 and 5.6 kg of active ingredient / ha.

Der iagttages herbicid virkning, dvs. signifikant beskadigelse af testplanterne.Herbicidal action is observed, i.e. significant damage to the test plants.

EKSEMPEL 14 10 Ukrudtsbekæmpelse - post-emergensbehandlingEXAMPLE 14 10 Weed Control - Post-emergence Treatment

Der gås frem på tilsvarende måde som beskrevet i eksempel 13 med undtagelse af, at testforbindelseme (herbiciderne) påføres, når planterne er på 2-4-bladsstadiet, idet såningen af plantefrøene er forskudt for at sikre, at planterne når 2-4-bladsstadiet omtrent sam-15 tidig.Proceed in a similar manner as described in Example 13 except that the test compounds (herbicides) are applied when the plants are at the 2-4 leaf stage, the sowing of the plant seeds being offset to ensure that the plants reach the 2-4 leaf stage. about the same time.

Også i dette tilfælde påføres forbindelserne med den almene formel I på den ovenfor beskrevne måde i doser, der svarer til 1,4 kg/ha og 5,6 kg/ha. Bestemmelsen af den herbicide virkning foretages 21 dage efter påføring af testforbindelserne og omfatter en bedømmelse, der 20 er analog med den i eksempel 13 beskrevne. Den herbicide virkning iagttages.Also in this case, the compounds of the general formula I are applied in the manner described above at doses corresponding to 1.4 kg / ha and 5.6 kg / ha. The herbicidal activity is determined 21 days after application of the test compounds and includes a rating 20 analogous to that described in Example 13. The herbicidal effect is observed.

EKSEMPEL 15EXAMPLE 15

Repræsentative forbindelser fremstillet ved fremgangsmåden ifølge opfindelsen bedømmes ved nedenstående præ-emergenstestmetode.Representative compounds prepared by the process of the invention are evaluated by the following pre-emergence test method.

25 Frøbakker, der måler 30 x 40 cm, fyldes til en dybde på 6 cm med en blanding af tørvedyrkningssubstrat og sand. Den blottede overflade af 20 DK 171559 B1 tørvedyrkningssubstrat/sandblandingen sprøjtes med en vandig testvæ-ske (fx formuleret som beskrevet i eksempel B), der omfatter en forbindelse fremstillet ved fremgangsmåden ifølge opfindelsen i en given koncentration. Sprøjtevolumenet svarer til 600 liter vandig 5 testvæske/ha. Den samme test gentages med forskellige koncentrationer testvæske, idet koncentrationerne vælges på en sådan måde, at der opnås de ønskede påføringsmængder. 6 frøarter sås derefter i hver bakke. Det antal frø, der sås for hver planteart, afhænger af frøspiringsevnen og den indledende vækststørrelse af den bestemte frø-10 plante. Efter såning af frøene dækkes den behandlede overflade med et tyndt lag (ca. 0,5 cm dybt) af tørvedyrkningssubstrat/sandblandin-gen.25 seed trays measuring 30 x 40 cm are filled to a depth of 6 cm with a mixture of peat growing substrate and sand. The exposed surface of the peat culture substrate / sand mixture is sprayed with an aqueous test liquid (e.g. formulated as described in Example B) comprising a compound prepared by the process of the invention at a given concentration. The spray volume corresponds to 600 liters of aqueous 5 test liquid / ha. The same test is repeated with different concentrations of test liquid, the concentrations being chosen in such a way as to obtain the desired application amounts. 6 seed species were then sown in each tray. The number of seeds sown for each plant species depends on the seed germination ability and the initial growth size of the particular seed-10 plant. After sowing the seeds, the treated surface is covered with a thin layer (about 0.5 cm deep) of the peat culture substrate / sand mixture.

De præparerede frøbakker holdes i 2Θ dage ved en temperatur på 20-24°c og 14-17 timer dagslys hver dag.The prepared seed trays are kept for 2Θ days at a temperature of 20-24 ° C and 14-17 hours of daylight each day.

15 Bestemmelsen af den herbicide virkning af den bestemte forbindelse ifølge opfindelsen foretages efter 28 dages perioden. Bestemmelsen omfatter en visuel bedømmelse af graden og arten af beskadigelsen af de forskellige planter. Særlig fordelagtige herbicide egenskaber iagttages bl.a. med forbindelse nr. 1, 2, 6, 8 og 14 i tabel A. Nogle 20 af de resultater, der fås med en påføringsmængde, der svarer til 1 kg aktiv bestanddel/ha, er vist i nedenstående tabel B.The determination of the herbicidal effect of the particular compound of the invention is made after the 28 day period. The provision includes a visual assessment of the degree and nature of the damage to the various plants. Particularly advantageous herbicidal properties are observed. with Compound Nos. 1, 2, 6, 8 and 14 of Table A. Some 20 of the results obtained with an application rate corresponding to 1 kg of active ingredient / ha are shown in Table B.

21 DK 171559 B121 DK 171559 B1

TABEL BTABLE B

Præ-emergenspåføring 1 kg/ha 5 Testet forbindelse - % beskadigelsePre-emergence application 1 kg / ha 5 Compound tested -% damage

Behandlet plante '1 2 6 8 14Treated plant '1 2 6 8 14

Amaran.Amaran.

10 retrofl. 100 100 100 100 9010 retrofl. 100 100 100 100 90

Capsella b.p. 100 80 90 70 90Capsella b.p. 100 80 90 70 90

Chenop.Chenop.

alb. 90 50 20 50 60 15 Galium aparine 50 0 10 10 10alb. 90 50 20 50 60 15 Galium aparine 50 0 10 10 10

Senecio vulg. 80 80 80 100 100Senecio vulg. 80 80 80 100 100

Stellaria 20 media 70 80 50 50 90Stellaria 20 media 70 80 50 50 90

Lucerne 60 50 80 10 90 Bønne 20 20 0 0 10Lucerne 60 50 80 10 90 Bean 20 20 0 0 10

Gulerod 90 90 70 100 90Carrot 90 90 70 100 90

Bomuld 10 0 0 0 0 25 Hør 60 50 30 0 10Cotton 10 0 0 0 0 25 Flax 60 50 30 0 10

Kartoffel 10 0 0 0 0Potato 10 0 0 0 0

Sojabønne 30 30 0 10 30Soybean 30 30 0 10 30

Sukkerroe 10 0 0 0 30Sugar beet 10 0 0 0 30

Raps 20 0 0 0 10 30 Solsikke 30 50 0 0 10Rape 20 0 0 0 10 30 Sunflower 30 50 0 0 10

Agropyron repens 90 60 80 90 70 22 DK 171559 B1Agropyron repens 90 60 80 90 70 22 DK 171559 B1

Tabel B fortsat Agrostis alba 100 100 100 100 100Table B continued Agrostis alba 100 100 100 100 100

Alopec.Alopec.

5 nvyos. 80 20 50 80 905 nvyos. 80 20 50 80 90

Apera sp.Apera sp.

venti. 100 100 100 100 100venti. 100 100 100 100 100

Avena fatua 80 40 80 90 90 10 Echinochloa c.g. 90 90 90 100 90Avena fatua 80 40 80 90 90 10 Echinochloa c.g. 90 90 90 100 90

Majs 50 30 0 50 60Corn 50 30 0 50 60

Hvede 90 90 0 100 70 15 EKSEMPEL 16Wheat 90 90 0 100 70 15 EXAMPLE 16

Post-emergensbehandlingPostemergence

En yderligere bedømmelse af repræsentative forbindelser med den almene formel I udføres ved en post-emergenstestmetode, der svarer til den i eksempel 15 beskrevne præ-emergenstest med undtagelse af, at 20 den herbicide testvæske påføres, når planterne er på 2-4-bladsstadi-et. Til dette formål sås de forskellige plantearter i et tidsforskudt forhold. Drivhusbetingelseme (temperatur, lys) er som beskrevet i eksempel 15. Bestemmelsen af den herbicide virkning udføres også 28 dage efter påføringen i henhold til den i eksempel 13 beskrevne 25 metode.A further evaluation of representative compounds of the general formula I is performed by a post-emergence test method similar to the pre-emergence test described in Example 15 except that the herbicidal test fluid is applied when the plants are on 2-4 leaf stage. one. For this purpose, the different plant species were seen in a time-shifted relationship. The greenhouse conditions (temperature, light) are as described in Example 15. The determination of the herbicidal effect is also carried out 28 days after application according to the method described in Example 13.

Særlig fordelagtige herbicide egenskaber iagttages bl.a. med forbindelse nr. 1, 2, 6, 8 og 14 i tabel A. Nogle af de resultater, der opnås med påføringsmængder, der svarer til 5 kg aktiv bestanddel/ha, er vist i nedenstående tabel C.Particularly advantageous herbicidal properties are observed. with Compound Nos. 1, 2, 6, 8 and 14 of Table A. Some of the results obtained with application rates corresponding to 5 kg of active ingredient / ha are shown in Table C below.

23 DK 171559 B123 DK 171559 B1

TABEL CTABLE C

Post-emergenspåføring 5 kg/ha 5 Testet forbindelse - % beskadigelsePost-emergence application 5 kg / ha 5 Compound tested -% damage

Behandlet plante 1 2 6* 75 14*Treated plant 1 2 6 * 75 14 *

Amaran.Amaran.

10 retrofl. 70 50 80 60 9010 retrofl. 70 50 80 60 90

Capsella b.p. 20 20 80 50 60Capsella b.p. 20 20 80 50 60

Chenop.Chenop.

alb. 40 20 20 40 60 15 Galium aparine 40 30 80 20 60alb. 40 20 20 40 60 15 Galium aparine 40 30 80 20 60

Senecio vulg. 70 80 90 90 90Senecio vulg. 70 80 90 90 90

Stellaria 20 media 60 10 30 40 40Stellaria 20 media 60 10 30 40 40

Lucerne 20 10 50 20 70 Bønne 30 20 20 30 50Lucerne 20 10 50 20 70 Bean 30 20 20 30 50

Gulerod 30 100 80 100 80Carrot 30 100 80 100 80

Bomuld 50 40 50 60 70 25 Hør 90 100 80 90 80Cotton 50 40 50 60 70 25 Flax 90 100 80 90 80

Kartoffel 20 10 10 10 10Potato 20 10 10 10 10

Sojabønne 30 30 20 30 50Soybean 30 30 20 30 50

Sukkerroe 70 0 10 10 10Sugar beet 70 0 10 10 10

Raps 10 10 30 60 40 30 Solsikke 30 80 40 60 50Rapeseed 10 10 30 60 40 30 Sunflower 30 80 40 60 50

Agropyron repens 70 50 50 50 50Agropyron repens 70 50 50 50 50

Agrostis alba ----- 24 DK 171559 B1Agrostis alba ----- 24 DK 171559 B1

Tabel C fortsat Alopec.Table C continued Alopec.

myos. 80 70 60 90 90myos. 80 70 60 90 90

Apera sp.Apera sp.

5 venti. 100 100 100 100 905 venti. 100 100 100 100 90

Avena fatua 90 80 90 100 100Avena fatua 90 80 90 100 100

Echinochloa c.g.l) 80 80 90 70 90 10 2) 80 90 100 80 100Echinochloa c.g.l) 80 80 90 70 90 10 2) 80 90 100 80 100

Majs 100 90 30 30 80Corn 100 90 30 30 80

Hvede 80 50 10 60 80Wheat 80 50 10 60 80

Ris 2) 10 50 30 30 40 15 * 4 kg/ha 1) højlandsbetingelser; 2) rismarksbetingelser (våd) EKSEMPEL 17Rice 2) 10 50 30 30 40 15 * 4 kg / ha 1) Highland conditions; 2) rice field conditions (wet) EXAMPLE 17

Der blev foretaget præ-emergensafprøvninger i drivhus, idet forbindelser ifølge opfindelsen blev sammenlignet med en standardforbindelse. De afprøvede forbindelser og testbetingelserne er anført neden-20 for, ligesom resultaterne er angivet i nedenstående tabel D.Pre-emergence tests were conducted in the greenhouse, comparing compounds of the invention with a standard compound. The tested compounds and test conditions are listed below, as are the results given in Table D.

Testforbindelser ^C0-CH2C1 \C~ 'Test compounds ^ C0-CH2 Cl1 \ C ~ '

ForbindelseConnection

med formel IR' R" AORof formula IR 'R "AOR

Forb. nr. 1 CH3 CH3 CH2-0-C2H5 25 Forb. nr. 2 CH3 CH3 CH2-0-C3H7nConn. No. 1 CH3 CH3 CH2-0-C2H5 Forb. No. 2 CH3 CH3 CH2-0-C3H7n

Forb. nr. 14 CH3 0CH3 CH2CH2-OC2H5Conn. No. 14 CH3 OCH3 CH2CH2-OC2H5

Forb. nr. 6 CH3 CH3 CH (CH3) CH20CH3 25 DK 171559 B1Conn. No. 6 CH3 CH3 CH (CH3) CH20CH3 DK 171559 B1

Standard: Metolachlor (a-chlor-2'-ethyl-6'-methyl-N-(l-methyl-2-methoxyethyl)acetanilid) C2H5 _/ ^/COCHjCl xCH(CH3)CH2OCHj CHj (se fx The Pesticide Manual, 9. udg., s. 585)Standard: Metolachlor (α-chloro-2'-ethyl-6'-methyl-N- (1-methyl-2-methoxyethyl) acetanilide) C 2 H 5 _ / 2 / COCH 2 Cl xCH (CH 3) CH 2 OCH 2 CH 2 (see, e.g., The Pesticide Manual, 9th ed., P. 585)

Testprocedure: Ifølge eksempel 15Test procedure: According to Example 15

5 TABEL DTABLE D

Præ-emergensafprøvningerPre-emergensafprøvninger

Forb. nr. 1 2 14 G Metola- 10 chlorConn. No. 1 2 14 G Metola- 10 chloro

Behandlings-mængde, kg a.i./ha. 1,5 1,5 1,5 1,5 1,5 15 _Treatment amount, kg a.i./ha. 1.5 1.5 1.5 1.5 1.5 15 _

Virkning i % Antal af prøvningerEffect in% Number of tests

Alopecurus myos. 2 92 84 94 93 67 20 Poa. annua 2 98 99 99 99 96Alopecurus myos. 2 92 84 94 93 67 20 Poa. annua 2 98 99 99 99 96

Stellaria media 4 90 82 89 89 81Stellaria media 4 90 82 89 89 81

Violoa tricolor 3 58 64 63 46 18Violoa tricolor 3 58 64 63 46 18

Lamium purpureum 3 98 100 98 100 98Lamium purpureum 3 98 100 98 100 98

Matricaria cham. 3 98 99 98 100 96 25 Chenopodium polysp. 3 95 95 93 95 74Matricaria cham. 3 98 99 98 100 96 25 Chenopodium polysp. 3 95 95 93 95 74

Capsella bursa pastoris 2 100 100 87 99 83Capsella bursa pastoris 2 100 100 87 99 83

Chenopodium album 1 100 95 97 100 50Chenopodium album 1 100 95 97 100 50

Galium aparine 1 73 73 72 80 77Galium aparine 1 73 73 72 80 77

Claims (5)

5 Polygonum persic. 1 100 70 80 100 0 Rumex sp. 1 93 70 75 70 40 Senecio vulgaris* 1 99 100 78 97 77 Veronica, hederif. 1 98 99 100 100 98 10 PATENTKRAVPolygonum persic. 1 100 70 80 100 0 Rumex sp. 1 93 70 75 70 40 Senecio vulgaris * 1 99 100 78 97 77 Veronica, hederif. 1 98 99 100 100 98 10 PATENT CLAIM 1. Substituerede thienyl-chloracetamider med den almene formel I /00-CHjCI R" w Ή\-ο-„ s V hvor R' og R" uafhængigt af hinanden er Cj^-alkyl eller 15 alkoxy, A er CH2, CH2-CH2 eller CH(CH3)-CH2, og R er Cj.3-alkyl.1. Substituted thienyl chloroacetamides of the general formula I / O-CH 2 Cl R "w Ή \ -ο-" s V wherein R 1 and R "are independently C 1 -C 6 alkyl or alkoxy, A is CH 2, CH 2 - CH2 or CH (CH3) -CH2 and R is C1-3 alkyl. 2. Forbindelse ifølge krav 1, som er N-(2,4-dimethylthien-3-yl)-N-(1-methoxyprcp-2-yl)-chloracetamid.A compound according to claim 1 which is N- (2,4-dimethylthien-3-yl) -N- (1-methoxyprcp-2-yl) chloroacetamide. 3. Anvendelse af en forbindelse ifølge krav 1 som herbicid.Use of a compound according to claim 1 as herbicide. 4. Anvendelse af et herbicid ifølge krav 3, kendetegnet ved, at forbindelsen er N-(2,4-dimethylthien-3-yl)-N-(l-methoxyprop-2-yl)-chloracetamid.Use of a herbicide according to claim 3, characterized in that the compound is N- (2,4-dimethylthien-3-yl) -N- (1-methoxyprop-2-yl) chloroacetamide. 5. Anvendelse af forbindelserne ifølge krav 3 og 4 som selektive 25 herbicider. 27 DK 171559 B1Use of the compounds of claims 3 and 4 as selective herbicides. 27 DK 171559 B1 6. Anvendelse ifølge krav 5 i sukkerroer, bomuld, kartofler, sojabønner, majs eller jordnødder.Use according to claim 5 in beet, cotton, potatoes, soybeans, maize or peanuts. 7. Herbicidt præparat indeholdende en forbindelse med formlen (I) ifølge krav l i forbindelse med en agrokulturelt acceptabel fortyn- 5 der.A herbicide composition containing a compound of formula (I) according to claim 1 in association with an agro-culturally acceptable diluent. 8. Præparat ifølge krav 7, hvor forbindelsen med formlen I er N-(2,4-dimethylthien-3-yl)-N-(l-methoxyprop-2-yl) -chloracetamid.The composition of claim 7, wherein the compound of formula I is N- (2,4-dimethylthien-3-yl) -N- (1-methoxyprop-2-yl) chloroacetamide. 9. Fremgangsmåde til fremstilling af en forbindelse med den almene formel 1 ifølge krav 1, 10 kendetegnet ved, at a) OH-gruppen hos N-hydroxyacetylgruppen i en forbindelse med den almene formel II R· ^COCHjOH Φ>-0- 15 hvor R, R' , R" og A har den i krav l definerede betydning, substitueres med chlor, b) en forbindelse med den almene formel III R" -COCHjCI 111 ss^R' hvor R' og R" har den i krav 1 amførte betydning, omsættes med en 20 forbindelse med den almene formel IV L-A-O-R IV hvor R og A har den i krav 1 anførte betydning, og L betegner en fraspaltelig enhed, der er i stand til at blive fraspaltet under N-alky-leringsreaktionsbetingelseme, 26 DK 171559 B1 c) en forbindelse med den almene formel la R. -CH2CI ^C'r-0'Process for the preparation of a compound of the general formula 1 according to claim 1, 10, characterized in that a) the OH group of the N-hydroxyacetyl group of a compound of the general formula II R R, R ', R "and A are as defined in claim 1, substituted by chlorine, b) a compound of the general formula III R" -COCH 2 Cl 111 ss ^ R' wherein R 'and R "have the one of claim 1 is represented by a compound of general formula IV LAOR IV wherein R and A are as defined in claim 1, and L represents a leaving group capable of being split off under the N-alkylation reaction conditions. C) a compound of the general formula Ia R. -CH2 Cl2 C'r-O ' 5 R· hvor R"' betegner hydrogen, og R, R' og R" har den i krav 1 anførte betydning fås ved, at en forbindelse med den almene formel v R. ^__CO-CHjCI ! Xcr°R R where R "represents hydrogen and R, R 'and R" have the meaning set forth in claim 1 by obtaining a compound of the general formula v R ^ CO CO-CH₂Cl!. XCR ° 10. R· hvor R’, R" og R"' har den ovenfor anførte betydning, omsættes med et reaktivt derivat af en forbindelse med den almene formel VI HOR VI hvor R har den i krav 1 anførte betydning, 15 d) en forbindelse med den almene formel VII R" V—r-NH A — 0 —R hvor R, R', R" og A har den i krav 1 anførte betydning, N-acyleres med chloracetylchlorid eller et reaktivt funktionelt derivat deraf.R R, wherein R ', R "and R" have the meaning given above, are reacted with a reactive derivative of a compound of general formula VI HOR VI wherein R has the meaning of claim 1, d) a compound with the general formula VII R "V-R-NH A - O-R wherein R, R ', R" and A are as defined in claim 1, N-acylated with chloroacetyl chloride or a reactive functional derivative thereof. 10. Thienylhydroxyacetamid med den almene formel II R· COCHjOH10. Thienyl hydroxyacetamide of the general formula II R · COCH 2 OH 20 Vi—II A-O-R s K hvor R, R', R" og A har den i krav 1 anførte betydning. 29 DK 171559 B1We-II A-O-R s K wherein R, R ', R "and A are as defined in claim 1. 29 DK 171559 B1 11. Thienylchloracetamid med den almene formel III R" ill V-x— NH-COCHjCI hvor R og R" har den i krav 1 anførte betydning. 12. 3-Aminothiophen med den almene formel VII11. Thienyl chloroacetamide of the general formula III R "ill V-x-NH-COCH 2 Cl wherein R and R" have the meaning set forth in claim 1. 12. The 3-Aminothiophene of the general formula VII 5 R·· VII V^_Nh_a-o-r hvor R, R', R" og A har den i krav 1 anførte betydning. 13. 3-Aminothiophen, kendetegnet ved, at det er substitueret i 2- og 4-stillingen med en gruppe valgt blandt C -alkyl og C ^-alkoxy.5 R ·· VII V ^ Nh_a-or wherein R, R ', R "and A are as defined in claim 1. 13. 3-Aminothiophene, characterized in that it is substituted at the 2- and 4-positions by a group selected from C 1-4 alkyl and C 1-4 alkoxy.
DK053583D 1982-02-09 1983-02-08 Substituted thienyl chloroacetamides, process for their preparation, intermediates, preparation containing the compounds and use of the compounds as herbicides DK171559B1 (en)

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NL190919B (en) 1994-06-01
FR2530631B1 (en) 1986-08-01
CZ278361B6 (en) 1993-12-15
MY8700168A (en) 1987-12-31
FR2523967A1 (en) 1983-09-30
CZ86783A3 (en) 1993-01-13
IL67852A (en) 1986-07-31
AU566009B2 (en) 1987-10-08
JPH0645617B2 (en) 1994-06-15
ES8503641A1 (en) 1985-03-01
IT8319474A0 (en) 1983-02-08
JPS58148868A (en) 1983-09-05
PL140272B1 (en) 1987-04-30

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