CHLORACETAMIDE.

The available invention concerns new 5-gliedñge heteroaromatic connections, which carry a N-substituted Chloracetamido group at a ring carbon atom, their application as herbicide, preparations, to facilitate around this application in the agriculture and the production of the new Verbindungen.

Some herbicide N-substituted ct-Halogenacetanilide is well-known. The US-Patentschñft 4,282,028 describes Nsubstituierte N-2,5-Dialkyl-pyrro1-1yl) haloacetamide, which possesses a herbicide and plant growth the adjusting Wir6s kung. There is the need according to more effective herbicides. The new 5-gliedfigen heteroaromatisehen connections is particularly effective herbicides, one suitable ground persistence aufweisen.

655,312 the available invention connections of the formula I/COCH2 c1 ArN/I Y betñfft where acre a 5-gliedriger heteroaromatic ring, which contains 1 or 2 ring hetero atoms selected from O, S and N, and by a ring carbon atom at the N-atom of the N (Y) COCH2 C1Gruppe is bound, whereby, if acre Pyrazolyl means, which N (Y) COCH2C1-Gruppe in 4-Stellung stands, and Y Allenyl, CH2 - CH = C = CH2, a hydrocarbonist selected from the row CI alkyl, C3 alkenyl, C3 _sAlkinyl, C38 Cycloalkyl, C58 Cycloalkenyl, C38 Cycloalkyl-C15 alkyl, whereby the hydrocarbon unsubstituiert or by halogen, selected from the row F, c1 or Br, are substituted; or a group of CHRI-COY1 means, in which R-S stands for H or C15 alkyl, and Y1 as well as the group of CO bound to the YI is a Esteroder amide function forms; or a group of RZ-Az means, in which R2 for unsubstituiertes or by C15 substituted CH2 or CH2 - CH2 stands, and Az a heteroaromafisehen ring meant selected from a Dioder Triazol, with a ring carbon atom at R2 bound 5-gliedrigen hetero ring, bound with a ring ticking off atom at R2, of the 1 to 3 Heteroatome contains, selected from O, S and N, and a PyrimidinGruppe; or a 2-Oro-1-pyrrolidinyl-Gruppe means in some CH2 - as well as group to be replaced by O, S or NCH3 knows 5-Oxound/oder bicyclische Benz of linked derivatives of such 2-Oxo-l-pyrrolidinyl-Gruppe, or a group of A-OR3 means, where R3 stands for H or a hydrocarbon is selected of the row consisting of CI alkyl, Ca_sAlkenyl, Ca_sAlkinyl, C3 _8 Cycloalkyl, Cs_8 Cycloalkenyl and Ca_8 Cyeloalkyl C 5-alkyl, whereby this Kohlenwasserstoffunsubstituiert is substituted or; or for a group of N = CjR4 R4 'stands, in which RA a hydrocarbon means selected of the row consisting of CI_5 AIkyl, C3 _5 alkenyl, C3 _5 Alkinyl, Ca_sCycloalkyl, approx. Cycloalkenyl and Ca_sCyeloalkyl-C1 _salkyl, whereby the Kohlenwasserstoffunsubsfituiert or by Chloracetamid group, whereby additional substituents can be present. Examples of suitable substituents of acre are selected halogen from F, c1 and Br; C1 qAlkyl, unsubstituiert or by halogen (F, Cl, Br), c1 _4 Alkoxy or c1 -6 s Cycloalkyl substitutes; Ci4Alkenyl unsubstituiert or replaces with CI4Alkoxy; C36 Cycloalkyl; CHO or C2 q Alkanoyl and functional derivatives of it like Opime, acetals, Ketale (e.g. C (= NOC 4 alkyl) - c1 _aalkyl; C (OCI AIkyl) z-C1_aalkyl; CH (OC1 alkyl) z etc.); C1 ù alkyl s, CI A1lokyl-SO, C14 alkyl SOz, c1 _5 Alkoxy carbonyl; C1 _4 Alkoxy, unsubstituiert or by halogen or c1 _4 Alkoxy substitutes; C2 “Alkenyloxy, C2 Alkinyloxy; HO and CH2 OH and ester of it (e.g. ester with organic carbonic acids, like formic acid, C2 _sAlkancarbonsäure or a halogenìertes 1 derivative of it, e.g. acetic acid or chlorine acetic acid).

Possible substituents of acre in zero position of the Chloracetamid group do not stand are preferably selected from the row CI_4 alkyl (e.g. CHa), halogen (e.g. Cl, Br) and C1_4Alkoxy-carbonyl (e.g. COOCHa).

If acre contains 2 Heteroatome, one of it is N; the other one is preferably O or S.

A preferential sub-group of connections of the formula I are connections where acre either a hetero ring atom (as in Pyrrolyl, Thienyl, Furanyl) or 2 neighbouring zs hetero ring atoms (as in Isoxazolyl, Isothiazolyl, Pyrazolyl) has. The Chloracetamid group is preferably at the ring carbon atom binds in 13-Stellung () hetero ring atoms (s) stands; so in 3-Stellung if acre Pyrrol, Thiophen or Furan means meant and in 4-Stellung if acre a0 Isoxazol, Isothiazol or Pyrazol. A preferential sub-group of latter group are the connections where the group of acres in orthomehr preferentially in ortho ortho' position the Acetamid group is located, in particular if the substituents from the before defined group are selected. Each ring N atom with a free valence can be unsubstituiert (i.e. for NH to stand) or substituted; if it is substituted, it is replaced, in particular vorzugsweíse with C ù alkyl by CH3 or Cz--” Acre stands in particular for a thiophen, a Isothiazoloder Isoxazol, preferably for a Isothiazoloder Thíophenring. A particularly preferred sub-group of the connections of the formula I connections are where acre Thiophen meant, in particular that woñn acre in 2,4-Stellung meant, more in particular the 3-Thienyl-Verbindungen 4 is selected substituted 3-Thienyl at least where the substituents in 2und 4-Stellung from C1Alkyl and c1 ù Alkoxy.

If Y, RA, RA and/or Ra' by Ha_logen substituted hydrocarbon mean one, then halogen stands in particular for c1 or Br; such substituted coal which halogens, selected from F, Clund Br, substituted is; or Alleo serstoffist in particular monosubstitutes. If y means one nyl, with halogen are hydrocarbon-meant Ra' replaced H or one for R4 indicated of the meanings bedie halogen substitution generally preferably not in sits, and 1-Stellung if application as herbicide is intended A a hydrocarbon remainder meant, which with R3 en (such 1-halogenierten connections are generally attaches to be can, under education of one 1 or 2 O-heteroatome ss not stably, they are however valuable intermediate products for containing hetero ring, whereby the Nund of O-atoms the production of those is connected for Y Alkoxyalkyl or Pyrazolylmittels A where through up to 3 carbon atoms from each other separated is; or a group of CHRs CHRs' = = NORa meant where RA above meaning possesses, R-S and Rs' mean independently H or CHa or together (CHz) 3 or (CH2) 4, or COCH3 means a group of CHR6-N (CHa), where R6 for H or CI-3 alkyl steht.

methyl is); a suitable example of such a meaning of Y is 2-Cl-ethyl.

If Y, RA, Æ and/or R4 “CI-sAlkyl, mean CsAlkenyl or Ca_8 Alkinyl, they have in particular up to 5 CAtome. If Y, RA, RA and/or RA” Cycloalkyl or Cycloalkenyl mean and/or contain such group, this cycloaliphatisehe group preferably contains up to 6 C-Atome.

If RI C 5Alkyl means, it stands in particular for CH3 the group of acres can unsubstituiert or substituted be. 6s or C2 H5 preferably for CHa. The expression ester or case acre is substituted can it for Substítuenten in each mögAmid function in connection with the meaning of lichen position carry: preferential positions of such SubstiY each function covers by conversion of a COOHtuenten is in zero position, in particular to o, o' Stellnng of the group of an acid with an organic compound re655 312 acted under splitting off from water, e.g. by conversion with an alcohol, an amine, a Merkaptan, a Oxim, a hydrazine, Hydrazid or Hydrazon. Examples of such ester meanings of YI are c1 _sAlkoxy-CO, C3_sAlkinyl-O-CO etc. of examples of suitable amide function meanings of Y1 are c1 _4 Alkylamino CO, Di (Ct_4 alkyl) - amino CO, of” case RZ CH2 meant CONHNH2 and CONH-N = C (CI_3 AIkyl), can carry it for 1 or 2 in particular 1 C1_sAlkyl. If RZ CH2 CHz means, it can up to 4 C zAlkylgruppen to carry, and is preferably more monooder disubstituiert. If CHzCH2 is disubstituiert, the substituents are zweekmässig to different C-Aromen.

Preferential c1 _sAlkyl-Substituenten from R2 are CH3 and C Hs, in particular CH3. If R2 is replaced, is with Cv alkyl it preferably monosubstituted. RZ means in particular CHE or CH (CH3).

If Az stands for one of the aromatic hetero rings defined above, this ring can be unsubstituiert or substituted, suitable substituents of such Az-meanings e.g. is one or more c1 _sAlkylgruppen (like CH3, C2H5); such substituted aromatic hetero rings are in particular more monooder disubstituiert.

If AZ stands for a Dioder Triazolrest, are this in particular unsubstituiertes or substituted 1-Pyrazolyl, I-Imidazolyl, 1,2,3-TriazoI-l-yl or 1,2,4-Triazol-l-yl, preferably 1-Pyrazolyl or 3,5-Di-CHr 1-pyrazolyl.

If AZ stands for bound hetero ring for one the 5-gliedrigen defined above, by means of an ring C atom at R2, this is e.g. e.g. selected a Furyl, Thienyl, Thiazolyl, Isothiazolyl, Oxazolyl, Isoxazolyl, 1,2,4oder 1,2,3-Thiaoder Oxadiazolyl, or a 1,3,4-Triazolylgruppe, whereby the hetero ring unsubstítuiert or can be substituted, by or two substituents from the row a C14 alkyl, C 4AIkylthio and C 4 Alkoxy; suitable examples of such meanings are 2-Furyl, 2-Thienyl, 2-CHr4-Thiazolyl, 3-CH3-5-Isoxazolyl, 2-C2 H5 -1,3,4-Oxadiazol-5-yl, 3-CH3 - 1,2,4-Oxadiazol-5-yI, 1-CH3 -2-CH3 S1,3,4-triazoI-5-yl and 2-CH3-1,3,4-Tñazol-5-yI.

If AZ means a Pyrimidin group, this can be bound at R2 by its 2, 4oder 5-Stellung, and stands e.g. for 2-Pyñmidinyl.

If Az stands for the bicyelise EN 2-Oro-l-pyrolidinyl-Gruppen defined above for one, this can unsubstituiert or, e.g. by halogen, to be substituted; an example of such a meaning is 2-Oro-1,3-benzothiazol-3-yl and the 4-Chlordeñvat davon.

If R3 means one of the hydrocarbon remainders defined above, this can unsubstituiert or e.g. by halogen, CN, a Azolgruppe such as 1-Pyrazolyl and] or Cv4 Alkoxy to be substituted; such substituted hydrocarbon meanings of R3 are CH2 CH2 CI, (1-Pyrazolyl) - CH2, CH2CH2CN and 3,5-Dimethyll-pyrazolyl.

Suitable meanings of A-O-R3, if A is linked to a ring with R3, are e.g. 1,3-Dioxolan-4-yl-C1 _3 alkyls, 1,3-Dioxolan-2-yl-C 3 alkyls and 2oder 3-Tetrahydrofuryl-Ci_3alkylen.

If A is not linked to a ring with R3, A means in particular an non-aromatic, in particular a Cj_sAIkylen-Gruppe those the Ound N-atom at those it is bound with 1 to 3, in particular 1 to 2 carbon atoms separates. A suitable meaning of A is e.g. the CHz or CHz CHz group as well as monomethylierte Deñvate of it, in particular CH2, CH (CH3), CH2 CH2, CH (CH3) CH2; R3 is then in particular c1 3 alkyl such as CH3, C2 H5 and nC3HT.

The group of A is unsubstituiert or substituted, e.g.

by C 5Alkoxy. Substituted meanings of A preferably are monosubstituiert.

The connections of the formula I are manufactured, by a) in a connection of the formula II ICO-CH OH ArN y II where acre and Y above meaning possessing, which HO-group lo the N-Hydroxyaeetylgruppe replaces with c1, b) a connection of the formula III ACRE - NH - COCH2 CI III where acre above meaning possesses, with einêr connection of the formula IV LY IV where Y above meaning possesses and a group split offable under the conditions of a N-Alkylierungsreaktion converts L meant, c) for the production of a connection of the formula Ia ACRE n COCH2 CI - CHY2 R' la where R' H or c1 _3 AlkyI meant, Y2 means Az', OR3 or N (CH3) COCH3, Az' a Dioder Triazol, and acre and R3 above meaning bound with its N-atom at CHR' possess, meant, a connection of the formula V /COCH2C1 ARN. - “CH-CI R' V where acre and R' above meaning possess, with a reactive derivative of a connection of the formula VI HY2 where Y2 above meaning possess, convert, d) a connection of the formula VII ACRE - NH - Y VII where acre and possesses Y above meaning, with Chloracess tylchlorid, or a reactive functional derivative of it, N-acetyliert.

Procedure a) can do similar to that, for the substitution of the OH-group by chlorine of well-known methods accomplished werden.

Such a substitution can e.g. by treatment of a connection of the formula II with a ChlorierungsmitteI, e.g. with Thionylchlorid, under for similar conversions admitted reaction conditions erfolgen.

After a variant of this chlorination procedure the connections can be transferred of the formula II only into an appropriate Sulfonyloxy derivative, e.g. by O-sulphonation with the help of a sulphonyl halide, and this then by nukleophile substitution of the Sulfonyloxy655 312 group by chlorine into the desired connections of the formula I transfers werden.

Reaction means those the c1 anion needed for the nukleophile substitution supply are e.g. alkali metal chloride such as NaC1, quaternãres Tetrabutylammoniumchloird and 4-Dimethylaminopyridinhydrochlorid. Such substitution becomes zweckmãssig in CHIC12 or in a wässfigen organic two-phase system, where the organic phase e.g. a hydrocarbon is such as toluol, in presence of a suitable phase transfer catalyst, preferably under warming up auf40° to 120 °C, durchgeführt.

Procedure b) knows similarly to well-known procedures under for the N-alkylation of amides admitted methods to be accomplished. The conversion becomes appropriately in on the reaction conditions inert solvents, e.g. Dimethoxyäthan or acetonitrile, or in an aqueous/organic Zweiphasensystem in presence of a phase transfer catalyst durchgeführt.

Suitable meanings of L (in the formula IV) are Cl, Br or the Sulfonyloxyrest of an organic sulfone acid such as Mesyloxy or p-Tosyloxy.

The connections of the formula III are preferably used in particular in Salzform, in alkali metal salt form, e.g. in NaSalzform. Such salts know alcoholate in well-known way by conversion of a connection of the formula III with a base as a AlkalimetaUamid, hydride, - hydroxide or - received werden.

For the production of the connections of the formula Ia in accordance with procedure c) the connections of the formula V ACRE NH2 IX become where acre above meaning possess, with a suitable ester of HOCH2 COC1, e.g. with CH3 CO--OCH2 COC1.

The connections of the formula III become by N-Aeylierung of a connection of the formula IX with CH! oracetylchlorid erhalten.

Connections of the formula V (a sub-group of connections of the formula I) one receives e.g. by conversion RST of a connection of the formula IX with an aldehyde and a conversion of in such a way received Schiff'sehen base with Chloracetylchlorid.

Connections of the formula VII know by N-alkylation of connections of the formula IX it A ¿ ten to become. S01che alkylation can according to well-known methods, by suitable alkylating agents (e.g. of halides), or in addition, where appropriately, reductively over a ship 'sche base or over an amide, erfolgen.

Many of the connections of the formula IX are neu.

A particularly valuable group of new connections of the formula IX are 3-Aminothiophene in 2und 4-Stellung the substituents from the row c1 _4 alkyl and c1 _4 Alkoxy carry; they are called in the following connections of the formula IXa. The connections of the formula IXa are likewise article of the Erfindung.

The connections of the formula IX can be received by reduction of the appropriate NO2 - connections, e.g. by catalytic hydrogenation under hydrogen printing in presence of palladium. Used connections of the formula IXa those appropriately as A1kalimetallsalz, e.g. as well salt, so a CHs, group in 2oder 4-Stellung, can through case Y2 for a Diazol or a Triazol carries stands, can the connections of the formula V also as N-Trialkylsilyl (e.g. N-Trimethylsilyl) - connection be used. The conversion effected similar to well-known Methoden.

The conversion in accordance with procedures cl) knows likewise similarly to well-known methods, under for the N-Chloracetylierung of amines admitted conditions, to be accomplished. If C1COCH2 c1 is used as N-Chloracetylierungsmittel, one works appropriately in presence of a acid-binding means such as K2 CO3.

The connections of the formula I can after well-known way from the reaction mixture in an isolated manner and regenerated werden.

The transformation of a connection of the formula I into another connection of the formula I, e.g. transformation of an acid into an ester, a Carbony! - Connection in a Oxim, a halo alkyl connection into an ether connection (or in reverse) etc., can take place likewise similarly to well-known methods. The connections according to invention therefore possess in or several asymetrisehe centers and can in optically active, diastereomeren, racemischen or geometrical isomers forms exist. Generally such connections as mixture in the herbicides procedures and preparations in accordance with the invention used, although isolating similar to well-known methods take place kann.

The connections of the formula II, III, V and VII are neu.

The connections of the formula II know by ammonolysis of the esters of the connections of the formula VIII Acre-NHCOCHzOH VIII where acre above meaning possess, with a carboxyl acid, and by N-alkylation, receive following introduction of a group of Y (defined as above) in connections of the formula Vili, werden.

One receives such esters e.g. by N-acylation of the appropriate connections of the formula IX.

Reduction of the appropriate Thiophencarboxylate by complex hydrides such as Na-bis (methoxyethoxy) alumìnìumhydñd to be received. Wishing case can be received the connections of the formula IXa also by hydrolysis of the appropriate Carbamatester, e.g. the appropriate Benzylcarbamates. The Carbamatester needed thereby as parent compounds can e.g. from the appropriate acids, followed over the azides, received from a Curtius relocation, werden.

If the production of the parent compounds is not descriptive, these are well-known or can similarly to well-known and/or herein descriptive methods manufactured and cleaned werden.

The connections according to invention possess herbicide effect, whereby herbicide is to be understood here in general sense, when a connection permits the one growth inhibition or growth influence of plants. With plants are germinating seeds, Keimlinge and established vegetation including underground parts gemeint.

The valuable herbicide effect of the connections according to invention comes out e.g. from the damage, which is observed with test quantities from 1,4 to 5.6 kg/ha after more preoder post office ere application (Voroder Nachauflauf) with monound dicotylen Planzen such as Lepidium sativum, Avena sativa, Agrostis alba s5 and Lolium perenne. Due to this herbicides effect the connections according to invention come with the fight against dikotylen or monokotylen Unkräutem into consideration, as this by supplementing regulations with representative connections are confirmed with test quantities according to an application quantity from 0,2 to 5.0 kg (e.g. 0.2, 1.0 and 5.0 kg) per ha of a connection according to invention on dicotylen Unkränter such as Amaranthus retroflexus, Capsella bursa pastoñs, Chenopodinm alba, Stellaria media, Senecio vulgaris, Galium aparine, and on grasses such as Agropyron repens, Agrostis alba, Alopeenrus of myosuroides, Apera spica Venti, arena fatua, Echinochloa crus galli, Bromus tectorum, sorghum halepense, Digitaria spp and Setaria spp. Supplementing attempts show 655,312 a favorable ground resistance of the erfíndungsgemässen Verbindungen.

The connections according to invention are less toxiseh against useful plants than against weeds. The selective herbicides effect e.g. in corn, soy, cotton, sugar beets, potatoes, Alfalfa, sunflowers, rape, is observed Erdnüs and flax depending upon used substance and application quantity. The connections according to invention are therefore also for the use as selective herbicides in useful plants geeignet.

The available invention concerns therefore also a procedure for the fight against unwanted plants (Unkräutem), in particular in useful plant cultures, vorzugswelse in one of the above-mentioned useful plant cultures, by treatment of the place concerned with a herbicide an effective quantity (with one selectively herbicide effective quantity, if the place which can be treated is a cultural surface).

A particularly preferred and favourable procedure in accordance with those identification, is the pre cm application (pre em know UnDie connections according to invention also in the form of micro caps used werden.

For herbicides akzentable additives can be used likewise in the herbicides preparations e.g. around the effect to improve and over foams, sticking and corrosion too vermeiden.

The term oberfiächenaktive materials, how hieñn uses, means each material, the emulsiveness, acceptable for herbicides, wettability and Dispersionsfåhigkeit ton e.g. lends and/or the improvement of other surface properties like propagation and adhesion on plant parts bewirkt.

Examples of such oberfläehenaktiven materials are Natriumligninsulfonat and Laurylsulfat.

m of the term solvents, how herein uses, means a liquid or a firm for herbicide acceptable material, which is used, in order to dilute the Wirkstoffzu of an useful or desired form. For types of dust means or granulates this is e.g. talc, kaolin or Diatomeenerde, for herbs and useful plants) of a connection of the formula I with 20 liquid concentrated forms e.g. Kohlenwasserstoffwie of the selective fight against weeds in useful plant xylene or an alcohol such as isopropanol, and for liquid Apkulturen.

For those selectively herbicides application of the erflndungsgemässen connections, those will generally vary herbicides like also for those to applizierende quantity depending upon cultivated plant (if selective application is intended) and other variables like the assigned connection, kind of the application, treatment conditions usw.

Specialists can determine the suitable application quantity by routine attempts e.g. by comparison in the greenhouse of the activity of the connection according to invention with a standard, for that the application quantity admit ist.

Generally however satisfying results obtained with a quantity from ungefåhr 0.1 to 5.0 kg/ha, in particular from 0,2 to 4.0 kg/ha, preferably from 0,5 to 3.0 kg/ha whereby the application if necessary repetitive wird.

In the case of use in useful plant cultures the application quantity is not generally over 3 kg/ha.

e.g. plikationsformen water or Dieselöl.

The preparations according to invention can contain also different materials, which possess biological effect, like e.g. connections with similar or complementary herbizider effect or connections with antagonistic, fungicidal or insektizider Wirkung.

In the following specific examples of herbizider preparations will describe. (Parts are parts by weight).

Example A Spritzpulver of parts of a connection according to invention, the connection No. of 25, 25 parts fine, synthetic silicate, 2 parts of Natriumlaurylsulfat, 3 parts of Natriumligninsulfonat and parts finely distributed Kaolinit are e.g. mixed so for a long time and husbands to the middle particle size approx. 5 Micron are. The received Spritzpulver before application with water diluted to a Spritzbrühe with desired Konzentration.

The connections according to invention know and will favourably in form of herbizider preparations together example B also for herbicides acceptable solvent used. GeeigEntulsionskonzentrat nete formulations contain 0.01 to 99 weight % to 20 parts of a connection according to invention, e.g. the active substance, 0 to 20% for herbicides acceptable surface NAK connection No. of 25, 40 parts xylene, 30 parts of Dimethylformtive of materials and 1 to 99.99% of a firm or liquid Ver45 amide and 10 parts of an emulsifying agent (e.g. ATLOX 4851 B, dünners. Higher conditions surface-active materials: a mixture of approx.-Alkylarylsulfonat and polyäthoxylierWirkstoff are sometimes desired and fulfilled by including into the preparation or in tank-mix. Application forms of the preparations contain generally 0.01 to 25 weight % at Wirkstoff.

Smaller quantities of active substance ability naturally present its, depending upon intended application and physical characteristics of the active substance. Concentrated preparation forms, which are diluted before application, preferably contains 2 to 90 weight % 10 to 80 weight % at Wirkstoff.

Suitable formulations of the connections according to invention cover types of dust means, granulates, pellets, suspension concentrates, Spritzpulver (wettable powders), Emultern Triglycerid the Atlas chemistry GmbH) strongly mixed to a homogeneous liquid received are. In such a way received emulsion concentrate becomes before use with water in such a way verdünnt.

Example C granulates kg of a connection according to invention the connection No. 25, are e.g. solved in 25 1 CH2 C12. The solution is then given and mixed to Attapulgit of the granulation 24/48 to 95 kg mesh/inches. The solvent becomes under decreased pressure entfernt.

The invention is läutert by the following examples ersionskonzentrate etc. you according to well-known methods, 60; Temperature specifications take place in °C. Pressure indications e.g. by mixture of the connections according to invention in torr and Rf-values on silicagel, if differently does not anmit solvents received. Liquid preparations become gegeben.

z.B. by mixing the components, fine-grained firm preparations by mixing and grinding, SuspensionskonzenEndverbütdungen trate through to wet meals and granulates and pellets by Im6s example 1 coining/shaping kidneys or Besehichten from submitted carriers with n (2,4-Dimethyl-thien-3-yl) - n (1,3-dioxolan-2-ylmethyl) Wirkstoffoder by agglomeration techniques (fluidized bed - ehloracetamid (procedure a)) e.g.) receive. To a well agitated mixture of 1,7 g (0.0063 mol) of “7,655,312 N (2,4-Dimethylthien-3-yl) - n (1.3 - dioxolan-2-yl-methyl) - hydroxyacetamid, 58 mg benzyle tri ethyl ammonium chloride, 7 valley toluol and 7 valley 30% NaOH are dripped, without cooling, 1.31 g (0.0069 mol) p-Toluolsulfonylchlorid in 3,5 valley toluol. At expiration the exotherms of the reaction still hours agitated with Raumtemperatur.

The toluol phase is then separated, washed with water and dried IN SUCH A WAY over Na2. The solvent is removed by red evaporation and agitated recrystallization rorend of the 21/2 hours at ambient temperature. Then 100 valley H2 0 is admitted. The organic phase is washed separated, with 3,200 valley portions water, evaporated dried over Na2 SO4 and to dry ones. The arrears are chromatographiert at silicagel. Eluierung with HexanDiethyläther 1:1 supplies the analytically pure title connection in form of a syrup crystallized after cooling over night of the up 20 ", stop. 88-89° (crystallization in Diethyläther).

hen arrears in Diethyläther the n (2,4-Dimethylo thien-3-yl) results in - n (1,3-dioxolan-2-ylmethyl) - tosyloxyacetamid (“Tosylat”) of the stop. 101-103o.

An agitated mixture of 2,16 g (0.0051 mol) of the Tosylates, 1.84 g (0.0066 mol) Tetrabutylammoniumehlorid, 8 valley water and 16 ml toluol is heated up during 6 hours on 90°. The toluol phase is separated, restricted dried (Na2SO4) and in the vacuum. The arrears chromatographiert on a silicagel column. Eluierung with hexane ethyl acetate 2:1 supplies the title connection in form of analytically pure crystals of the stop. 76-78.

Beispiel2 n (2,4-Dimethyl-thien-3-yl) - Ne-methoxyethylchloraeetamid (procedures a) 0.93 g (0.008 mol) Mesylchlorid in 20 ml dry CH2C12 become without cooling of a gerùhrten mixture of 2,0 g (0.008 mol) N-2,4 (Dimethyl-thien-3-yl) - N-methoxyethyl-hydroxyacetamid and 0.92 g (0.008 mol) 4-Dimethylaminopyridin (DMPA) in 80 ml dry CH2 C12 zugegeben.

Dic so received mixture, the DMPA hydrochloride and the Methansulfonat of the parent compound contains, is heated up, during 25 hours and then under vacuum eingedampft.

The remaining oil solidifies for 20o after chromatography at silicagel (eluiert with Diethylãther) and cooling -; Stop. 54-55o.

Beispiel5 n (chlorine acetyl) - n (3,5-dimethyMsoxazol-4-yl) - alanine ethyl ester (procedure õ) 9.4 g (0.05 mol) n (3,5-Dimethylisoxazol-4-yl) - chloracetamid in 150 valley dry CH3 CN become one (80% dispersion in Mineralöt) in 25 valley dry CHaCN getropft.

After completion the exotherms of the reaction (34o) the solution of the well salt left untouched to it on ambient temperature cooled down is and then with 9,05 g (0.05 mol) ethyl 2-brompropionat in 25 valley dry CHaCN behandelt.

After terminated addition the reaction mixture is heated up during 3 hours on 50° and evaporated then to dry ones. The arrears are taken up to 100 valley Diethyläther and the LSsung is filtered. After evaporation of the filtrate remains a O1, which is chromatographiert at silicagel. Eluierung with Diethyläther hexane 1:1 results in the title connection of the stop. 49-50o.

Beispiel3 N-Chloraeetyl-n (2-earbomethoxy-4-methyl-thien-3-yl) - alanine ethyl ester (procedure b) 9.9 g (0.04 mol) n (2-Carbomethoxy-4-methy! - thien3-yl) - chloracetamid portionenweise become a well agitated suspension of 1,5 g (0.05 mol) close (80%ige dispersion in mineral oil) in 250 dry Dimethoxyethan (DME) gegeben.

After terminated addition the remaining solution of the well salt still another additional hour with 50° agitated, then left untouched to it on ambient temperature cooled down is following and with a solution of 7,25 g (0.04 mol) Ethyl2-bromopropionat in 50 valley trocknere DME behandelt.

After one reaction period of 4 hours with 50° the mixture is filtered and in the vacuum (50°/0,01 Toro evaporated. The remaining brown oil becomes after chromatography at silicagel (eluiert with Diethyläther hexane 2: 1) a ball tubing distillation subjected, whereby the analytically pure title connection, Sdp. 135°/0,005 torr, receive wird.

Beispiel4 n (1H-Pyrazol-l-ylmethyl) - n (2,4-dimethyl-thien-3-yl) - chloraeetamid (procedures b) for a well agitated mixture of t 9.35 g (0.095 mol) n (2,4-Dimethyl-thien-3-yl) chloracetamid, 4.15 g (0.01 mol) Benzyldimethylhexadecylammoniumchlorid, 40 g (1 mol) NaOH, 200 valley CH2 CI2 and 40 valley H2 0 are given in such a manner 17 g (0.11 mol) firm 1-Chtorrnethyl-pyrazol-hydrochlorid that the temperature the 25° not übersteigt.

After terminated addition the reaction mixture wähBeispiel6 n [l (I H-Pyrazol-l-yl) ethyl] becomes - n (2,4-dimethyl-thien-3-yl) ehloraeetamid (procedures c) for an agitated solution of 12,7 g (0.1 mol) 2,4-Dimethyl-3-aminothiophen containing in 100 valley trocknere benzene 16 g molecular sieves (3) and 2 drops H2 SO4 conc., are given 8.5 valley (0.15 mol) to acetaldehyde in such a way that as the reaction temperature 25°nicht übersteigt.

After complete addition of the aldehyde, the reaction mixture is agitated still 24 hours at ambient temperature and filtered then. Distance of the solvent results in the Schiff' base as light brown Flüssigkeit.

The agitated solution of 13 g (0.085 mol) of this material in 75 valley trocknere toluol become - 30° 9.7 g (0.086 mol) chlorine acetyl chloride getropft.

After completed addition the reaction solution becomes still minutes - 30° agitated and in addition, at the same temperature 12 g (0.085 mol) 1-Trimethylsilylpyrazol zugegeben.

After the addition the firm CO2 /Aceton-Bad removed, the mixture left untouched to it the ambient temperature reached and during 20 hours further gerührt.

The reaction mixture is then filtered and evaporated at the Vaso kuum. The syrup staying chromatographiert at silicagel with Hexau/Diethyläther 3:2 as Eluens, and results in then the title connection those, after Rekdstallisation in Diethyläther a stop. of 76-78° hat.

Example 7 N (4-Methoxy-2-methyl-thien-3-yl) - n (2-ethoxyethyl) - ehloraeetamid (procedures d) for a well agitated mixture of 6,05 g (0.03 mol) n (2-Ethoxyethyl) -4-methoxy-2-methylthiophen-3amin, 4.15 g (0.03 mol) K2 CO3, 10 valley H Œ EO and 100 mi CH2 CI are dripped, without cooling of the solution 3.4 g (0.03 mol) chlorine acetyl chloride in 10 valley CH2 C12. After completion the exotherms of the reaction (27o) 1 hour becomes at ambient temperature weitergerührt.

The CH2 Clz phase is washed separated, 2 times with 100 valley H2 0, evaporated dried (Na2 SO4) and in the vacuum. The remaining raw title connection is analytically 655,312 purely; Rf= 0.23 (hexane/Diethyläther 1: 2). A small portion of this Mateñals is subjected to a ball tubing distillation: Sdp. 168-170 " /0.05 Torr.

The following connections of the formula I are received to several of the procedures after or in accordance with the examples 1 to 7: (ME is CH3; Et is CzHs).

Table A verb. Aryl Nr.

Y 1 4-Me-thien-3-yl CH2 OC2 H5 2 DO. CH2 CH2 OCH3 3 2-Me-thien-3-yI CH2 CH2 OCH3 4 2,4-diMe-thien-3-yl CH3 DO. C2 H5 6 DO. iC3 H7 7 DO. CH2 - CH = CH2 8 DO. CH2 C (CI [3) -- CI-I2 9 DO. CHr C - CH DO. C (CH3) 2 - CCH 11 2-MeSO2 -4-Me-thien-3-yI CH2 OEt 12 2,4-diMe-thien-3-yl CH2 CF3 13 DO. CH2 - C (CI) = CH2 14 DO. CH2 - C (Br) = CH2 2-MeCO-4,5-diMe-thien-3-yl pyrazolyl1-CH2 16 2,4-diMe-thien-3-yl CH2 COOMe 17 DO. CH2 COOEt 18 DO. CH2 COOC3 H7i 19 DO. CH2 --COOC (CH3) 2C - = CI {DO. CH (CH3) COOCH3 21 DO. CH (CH3) COOC3 HTi 22 DO. CFI2 CON (CH3) 2 23 DO. CH2 CONHC3 H7i 24 DO. CH2 CONHN = C (CI " I3) 2 DO. CH2 - (l-pyrazolyl) 26 DO. CH (CH3) (1-pyrazolyI) 27 DO. CH2 - (3,5-diMe-pyrazolyl1) 28 2,4-diMe-thien-3-yl CH (CH3) - 4 29 DO. CH2 “- {DO. CH (CH3) - ìt 31 DO. CH2 - N'N = ' 32 do.

33 do.

34 do.

CH (ME) - o CHz_bt) k'] characterisation stop. 25-26-- Rf= 0.45 (cyclohexane/ethyl acetate 1: 1) Rf= 0.3 (cyclohexane/ethyl acetate 6: 4) stop. 45-46'" Smp. 50--51 ° Smp. 60--61 ° Smp. 45-46 " stop. 48-49 “= 1,5345 lp Sdp. 118-21 - 'f0.005 torr stop. 77--79 = 1,5342 lp =1.5192 lp Smp. 82-84ç Smp. 135-137:

Smp. 141Smp. 88-89:

Smp. 76-78 Smp. 143-144Smp. 132-133Verb.

Nr.

36 37 38 39 41 42 43 44 46 47 48 49 51 52 53 54 56 57 58 59 61 62 aryl 2,4-diMe-thien-3-yl do.

do.

do.

do.

DO, do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

2,4-diMe-thien-3-yl do.

do.

do.

9 Y CH (ME} - Æ% CHa (2-furyl) CH2 (2-thienyl) CHz l' s i - ME 3-Me-isoxazol-5-yl-CH2 CHz-- õ e -- Et NN, JH N--N cùz ùX sM, -.

ME CH2CH2OH CH2OEt CH2OC3HTn CH2OC4H9n CH (ME) OMe CH (EOOMe CH2CH2OMe CH2CH2OEt CH2CH2OC3HTn CH (ME) CH2OMe C (ME) 2CH2OMe CII2--L O-Õ CH (ME) OCH2CH2C1 CH (OMe) CH2OMe CHzOCH2CH2OMe CH (ME) OCH2CH2CN characterisation 655312 Smp. 78-79° Smp. 57-59° Smp. 66--67° Smp. 77-78° Smp. 54-56° Smp. 71-72° Smp. 110-15° Smp. 119-25o Smp. 120--22° Smp. 68-70° Smp. 79-80° Sdp. 115°/0,001 peat = 1,5280 lp Sdp. 110-11°/0,001 torr of Smp. 48-50° Smp. 55-57° Smp. 54-55° Sdp. 110 " /0.01 peat Rf= 0.36 (Diethyläther/hexane 1: 1) Sdp. 148-150°/0,03 peat stop. 76-78 " Smp. 62-64° Rf = 0.3 (diethylether/hexane 1: 1) Sdlo. 117-18°/0,005 torr stop. 59-64° 655,312 Verb.

Nr.

63 64 66 67 68 69 71 72 73 74 76 77 78 79 8I 82 83 84 86 87 88 89 90 91 92 93 94 95 96 97 97a 98 99 100,101,102,103,104,105,106,107,108,109,110 aryl Y 2,4-diMe-thien-3-yl do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

2-Me-4-Et-thien-3-yl do.

do.

2-Et-4-Me-thien-3-yl CH (ME) ON = CH-ME CH (ME) ON = C (ME) z CH2-CH = NOMe CH/-CH =NOEt CHz C (ME) = NOMe CHz C (ME) = NOEt CH (ME) CH = NOMe CH (ME) CH = NOEt CH (ME) - N (ME) - COMe CH (ME) CHzOMe CH2OEt pyrazolyl-l-CH2 CH2OC2H5 do.

CH (ME) CH2 OMe 2,4-diEt-thien-3-yl) do.

pyrazolyl-l-CH2 CH2-OEt do.

2-iC3HT-4-Me-thien-3-yl 4-OH-2-Me-thien-3-yl 2-Me-4-MeO-thien-3-yl 2-Me-4-EtO-thien-3-yl 2-Me-4-i-C3HT-thien-3-yl 2-Me-4-nC4HgO-thien-3-yl 2-Me-4-OCH2-CH = CHz-thien-3-yl 2-Me-4-OCH2-C = CH-thien-3-yl 2-MeOCH2-4-MeO-thien-3-yl 2-MeS-4-Me-thien-3-yl 2-MeS (O) - 4-Me-thien-3-yl 2-MeCO-4-Me-thien-3-yl 2-MeCO-4-Et-thien-3-yl 2-MEC (= NOMe) - 4-Me-thien-3-yl CH2CH2OMe pyrazolyl-l-CH2 CH (ME) CH/OMe pyrazolyl-l-CH2 CH2-OEt CH2CHz--OEt pyrazolyl-l-CH2 do.

CH2OEt pyrazolyl-l-CH2 do.

do.

do.

CH/OEt CH2CH2OMe CH2OEt CH2OEt pyrazolyl-l-CH2 CH2OEt 2-MEC (= NOMe) - 4-Me-thien-3-yl 2-MeC (OEt) r4-Me-thien-3-yl 2-Me-4-O-COMe-thien-3-yl 2-COOMe-4-Me-thien-3-yl do.

do.

2-iC3HT-4-COOMe-thien-3-yl 2-Et-4,5-diMe-thien-3-yl pyrazolyl1-CH2 CH2OEt CH (ME) CH2 OMe CH2C CH CH2OEt CH (ME) COOEt pyrazolyl-l-CH2 CH2OEt CH2COOC3HTi pyrazolyl-l-CH2 CH2OEt CH2OCH2CH2OCH3 do.

do.

2,4-diMe-5-Cl-thien-3-yl do.

Characterisation Rf= 0.31 (hexane/ethyl acetate 3: 2) Rf= 0.23 (hexane/ethyl acetate 4: 1) Smp. 76-78° Smp. 57-59° Smp. 68-70° Rf= 04 (hexane/ethyl acetate 4: 1) Sdp. 142--44°/0,2 torr of Smp. 49-50° Smp. 53-54° Pf= 0.47 (Diethyläther/hexane 7: 3) Rf= 0.47 (diethylether/hexane 7: 3) Smp. 63--65° = 1,5242 lp 23 = 1,5328 lp Smp. 90-92° Smp. 24° Sdp. 168-170°/0,05 torr of Smp. 44-46° Sdp. 180/°/0,001 torr of Sdp. 135°/0,001 torr of Sdp. 148-150°/0,001 peat Smp. 100° Srnp. 37-38° syn: Smp. 89-91° anti: Smp. 75-76° syn: Smp. 123° Smp. 46-47° Smp. 119-21° Smp. 20-22° Sdp. 135°/0,005 peat 1 5273 n D = =1.5112 lp = 1,5509 lp n 2r) ° = 1,5412 21 = 1,5321 lp 11,655,312 verb. Aryl Nr.

110a 2,4-diMe-5-CI-thien-3-yl 11 whether do.

111 do.

112 2,5-dißr-4-Me-thien-3-yl 113 2-Me-4-MeO-5-Br-thien-3-yl 114 2,4-diMe-5-COOMe-thien-3-yl 115 2,4-diMe-furan-3-yl 116 2,4-diMe-furan-3-yl 117 do.

118 do.

119 do.

120 1,2,4-trime-pyrrol-3-yl 121 do.

122 do.

123 do.

Y tetrahydrofuryl-2-CH2 iC3H7 pyrazolyl-l-CH2 CH2OEt pyrazolyl-l-CH2 CH2OEt CH2OEt CH2CH2OMe CH2-CH = NOMe CH2-C (ME) = NOMe pyrazolyl-l-CH2 CH2-OEt CH2CH2OMe pyrazolyl-l-CH2 CH2-C (ME) = CH2 124 2-COOEt-N, 3,5-tri-Mepyrrol-4-yl pyrazolyl1-CH2 125 3,5-diMe-isoxazol-4-yl CH (ME) COOEt 126 DO. CHzCH2 OMe 127 DO. CH2 OEt 128 DO. pyrazolylI-CH2 129 3,5-diEt-isoxazol-4-yl CH2 - C (ME) = CH2 130 DO. CH2 - C = CH 131 DO. CH2 - OEt characterisation Rf= 0.35 (cyclohexane/ethyl acetate 7: 3) Rf= 0.38 (cyclohexane/ethyl acetate 6: 4) Smp. 68-73* Smp. 75-77* Smp. 98-99* Sdp. 140°/0,005 torr of Rf= 0.5 (Diethyläther) n Î = 1,5422 Smp. 49-50 " Smp.45-46 " Sdp. 118 " /0.001 torr b.p. 107-108 " /0.001 torr of 1,4908 nD= 132 3,5-diMe-isothiazol-4-yl CH2 OEt Smp. 43M5° 133 DO. CH2 CH2 OMe 134 DO. pyrazolyl1-CH2 stop. 109-14 " 135 DO. CH2 C= CH stop. 109-12 " 136 3-Me-5-EtO-pyrazol-4-yl CH2 CH2 OMe Smp. 111-113* 137 1,3,5-trime-pyrazol-4-yl CH2 OEt Sdp. 130°/0,001 torr of 138 1,3,5-trime-pyrazol-4-yl CH2 CH2 OMe stop. 66-67* 139 DO. CH2 - OC3 HTn Sdp. 135 " /0.001 torr of 140 DO. Et Smp. 80--82* 141 DO. CH2 - C = CH Smp. 115-117 " 142 DO. pyrazolyl-l-CH2 stop. 96--97° 143 1-Me-3,5-diEt-pyrazol-4-yl CH2 - OC3 H7 n n D = 1,5008 144 DO. CH2 CH2 OMe Sdp. 130 " /0.001 torr of 145 1,3-diMe-5-EtO-pyrazol-4-yl CH2 OEt stop. 54-56° of intermediate products and 600 valley trocknere toluol is course-dripped, under efficient agitating, example 8 a solution by 100 g (0.58 mol) 3-Amino-4-methylthio3,5-Dimethyl-4-aminothiophen-2-carbonsäuremethylester phen-2carbonsäuremethylester in 700 valley dry toluol a solution by 45,2 g (0.21 mol) 3,5-Dimethyl-4-nitroderart that the reaction temperature 55° does not become thiophen-2carbonsäuremethylester in 1000 valley CHaOH 55 übersteigt.

during 2 hours at 10 bar in presence of 4,5 g PallaNach of terminated addition further 30 minutes agitated dium (10% on coal) hydriert.

After terminated hydrogenation the mixture is filtered, the catalyst is washed with CH3 OH and the filtrate up to dry ones eingedampft.

The crystalline arrears are treated with Diethyläther and result in the analytically pure title connection of the Smp. 88-89o.

and the reaction mixture then carefully in small portions, with 0° to 1200 ml 20% a KOH solution gegeben.

The toluol phase is then separated, restricted dried over “o MgSO4 and in the vacuum. The remaining brown liquid is distilled under decreased pressure and results in thus the analytically pure title connection of the Sdp.

49-52°/0,01 Torr.

Example 9 2,4-Dimethyl-3-aminothiophen to a mixture of 890 valley (3 mol) sodium to (2methoxyethoxy) - aluminum hydride (70% solution in toluol) example 4-Methoxy-2-methyl-3-aminothiophen a well agitated mixture of 55,4 g (0.2 mol) BenzylN (4-methoxy-2-rnethyl-thien-3-yl) earbamat, 40 g (0.7 mol) 655,312 KOH, 600 mi ethanol and 120 ml water is heated up 2 hours under Reflux. The developed solution is then restricted in the vacuum and the arrears with 500 are diluted ml water. It separates itself thereby an easily yellow oily phase, which is taken up to 400 ml Dìethyläther. The wässrìge phase becomes likewise with 400 mi ether extrahiert.

The united Äthedösungen is getroeknet (NazSO4) and filtered. During minutes troeknes HCI gas is then led by the filtrate, whereby by ice bath cooling to the fact it is paid attention that the temperature 10° not übersteigt.

The präzipitierte Hydrochloñd of the title connection has a stop. of 230° (the free base melts with 61-63°).

Example 11 2-Methylthio-4-methyl-3-aminothiophet, freshly prepared Aluminiumamalgarn over a Peñode solved from 2 minutes to 18.9 g (0, I mol) 2-Methylthio-4-methyl-3nitrothiophen are given to 6 g (0.22 Gramatome) in 200 ml damp Diethyläther. The violent reaction after 5-10 the minutes begins becomes by ice cooling under control gehalten.

After 45 minutes, after reaction and reacted all aluminum ran off the exotherms, further 6 g become hydrogenite zugegeben.

The Reaktionsgemiseh is held 2 hours under Reflux; during these Peñode the formation of the Thiophenamins becomes vollendet.

The organic phase is decanted and the arrears are washed with two 50 ml portions Diethyläther. The united ethereal solutions are restricted dried (over MgSO4) and in the vacuum. The remaining raw title connection is distilled under decreased pressure, and has a Sdp. of 79-81 °/0,5 Torr.

Beispiel12 in the following list are connections of the formula IX aufgezãhlt in accordance with or several of the procedures in accordance with example 8 to 11 received werden.

Ex. 12,1 1,3-di-CHr5-OCzHs-4NHzpyrazol ex. 12,2 ex.s 12,3 ex.s 12,4 ex.s 12,5 ex.s 12,6 ex.s 12,7 ex.s 12,8 ex.s 12,9 ex.s 12,10 ex.s 12,11 ex.s 12,12 ex.s 12,13 3,5-di-CHr4-NH2-isothiazol 4-CzHs-2-CH3-3-aminothiophen, 4-n-Butoxy-2-methyl-3-aminothiophen (Rf = 0.25 (Diethylether/hexane 2: 1) 5-CzHsO-3-CH3-4-NH2-pyrazol 3,5-di-C2Hs-I-CH3-4-NH2pyrazol 3,5-di-C2Hs-4-NHrisoxazol (3-NHr4-Me-thien-2-yl) ethanon (3-NHr4-Et-thien-2-yl) ethanon (3-NHr4,5-diMe-thien-2yl) ethanon, 2-Et-4-Me-3-NH2-thiophen, 2,4-diEt-3-NHrthiophen, 2-Et-4,5-diMe-3-NH2thiophen, 12 (Rf= 0.28 tetrahydrofurane: Hexane 9: 1) (Smp. 82-84o) Rf=0.25 (Diethyl4s ether: Hexane 2: 1) Smp. 25°; Smp. 81-83° Sdp. 68-70°/0,001 torr of Rf = 0,39 (Diethyläther) Smp. 80-81 ° Smp. 68° Smp. 120-23° Sdp. 74-76°/0,01 torr of Rf= 0.24 (CHzC12) =1.5511 lp = 1,5581 lp example 13 iv (2,4-Dimethyl-thien-3-yl) aeetoxyaeetamid to 12.7 g (0.1 mol) 2,4-Dimethyl-3-aminothiophen, 13.8 g (0.1 mol) KzCO3, 20 valley water and 150 ml CH2 C12 s become at ambient temperature 15 g (0, I 1 mol) Acetoxyacetylchloñd getropft.

At expiration the exotherms of the reaction still 1 hour is agitated. The organic phase is evaporated, restricted washed with water, dried (MgSO4) and in the vacuum lo. The firm arrears are treated with hexane and supply the analytically pure Titelverbindnng of the Stop.

110-112o.

Example 14 N (2,4-Dimethyl-thien-3-yl) hydroxyaeetamid by an agitated solution of 15,9 g (0.07 mol) n (2,4-Dimethyl-thien-3-yl) acetoxyacetamid in 300 ml CH3 OH becomes during 30 minutes of NH3 - gas geleitet.

At expiration that exotherms (40o) reaction (absorbed zo by cooling with ice water) is agitated further 30 minutes and the reaction solution up to dry ones is then evaporated. The remaining arrears recrystallized from ethyl acetate whereby the analytically pure title connection in form of colorless crystals of the Smp. 85-87: received wird.

Example n (2-Ethoxyethyl) -4-methoxy-2-methyl-thiophen-3amin 70 ml (0.245 mol) sodium until (2-methoxyethoxy) aluminum hydride (70% solution in toluol) and 30 ml dry toluol becomes, dripped under agitating, a solution 9,4 g (0.041 mol) n (4-Methoxy-2-methyl-thien-3-yl) ethoxyacetamid in 125 valley trocknere Tolnol. At expiration of the exotherrnen reaction during 90 minutes and the reaction solution is further-agitated then carefully, into small 3s portions, - 10° to I00 valley 20% of a KOH solution gegeben.

The toluol phase is separated and the wässñge phase 2 times with 100 is extracted ml toluol. The united toluol solutions are restricted dried (over Na2 SO4) and in vacuum. The remaining easily brown liquid is analytically pure, Rf = 0,32 (hexane/Diethyläther 1: 2).

Example 16 N [(Methoxymethyl) ethyt-2,4-dimethytthiophen-3-amflt the solution of 6,4 (0.05 mol) 2,4-Dimethyl-3-aminothiophen and 5.3 g (0.06 mol) Methoxyaceton in 100 valley dry toluol under Reflux for simmering heated up up to in such a way the theoretical quantity water of the water cutter separated itself (21/z hours). One lets the toluol phase stand to it the ambient temperature reached and restricts her then in the vacuum. The remaining Schiff' base is sufficient pure for the next Stufe.

ss 9.2 g (0.048 mol) of this arrears are solved in 100 ml dry toluol and without cooling to a well agitated solution from 28 ml (0.098 mol) Natrium-bis (2methoxyethoxy) aluminiumhydñd (70% solution in toluol) in 15 ml dry toluol gegeben.

At expiration the exotherms of the reaction (44 “) still further 90 minutes is agitated and the brown reaction solution then carefully, in small portions, - I0: 'to 40 ml 20% a KOH solution gegeben.

The toluol phase is separated, restricted dried (NazSO4) 6s and in the vacuum. The remaining O1 becomes after Säulenchromatographie at silicagel (Eluens hexane/Diethyläther 3: 1) under decreased pressure distilled (Kugelrohr) and has a Sdp. of 94-95bei 0.01 Torf.

Example 17 iv (5-Ethyl-l, 3,4-oxadiazol-2-ylmethyl) -2,4-dimethyl-thiophen-3-amin the mixture of 12,7 g (0.1 mol) 2,4-Dimethyl-3-aminothiophen, 14.6 g (0.1 mol) 2-Chlormethyl-5-ethyl-l, 3,4oxadiazol and 13.8 g (0.1 mol) K2 CO3 in 150 valley trocknere dimethylformamide (= DMF) becomes during 20 hours with 80° gerührt.

The reaction mixture is cooled up to ambient temperature, poured in 400 valley water and extracted the water DMF solution 3 time with 150 valley portions Diethyläther. The combined ethereal excerpts are dried over Na2 SO4 and restricted in the vacuum. The remaining brown oil is chromatographiert at a silicagel column, using hexane/Diethyläther 1:1 as Eluens, and ergìbt the analytically pure title connection as orange liquid, R, f= 0,2 (Diethyläther/hexane 1: 1).

Example 18 N (2,4-Dimethyl-thien-3-yl) glyeinhydrazid 82 g (0.412 mol) n (2,4-Dimethyl-thien-3-yl) glycine methyl ester and 42 g (1.3 mol) hydrazine hydrate in 350 valley alcohol are agitated 24 hours at ambient temperature. The mixture is restricted in the vacuum. After addition of 150 valley water is extracted the arrears with 4 times 500 valley portions ethers. The ether phases are combined, dried over Na2SO4 and restricted up to dry ones. It remains the title connection of the stop. 68-70o.

Example 19 N (2,4-Dìmethyl-thien-3-yl) - n (4-methyl-5-mercapto-1,2,4triazol-3-yl-methyl) - amine a mixture of 15 g (0.075 mol) n (2,4-Dimethylthien-3-yl) glycinhydrazid and 5.5 g (0.075 mol) Methylisothiocyanat in 100 valley ethanol is heated up 4 hours under Reflux. The reaction mixture is cooled on 6° and the developed precipitate by filtering is separated; the pure title connection melts with 184-87o.

Beispiel20 n (2,4-Dimethyl-thien-3-yl) - n (4-methyl-5-methyhnercapto1,2,4-triazol-3-ylmethyl) amine to a mixture of 9,5 g (0.037 mol) n (2,4-Dimethyl-thien-3-yl) - n (4-methyl-5-mercapto-l, 2,4-tñazol-3-yl) - methyl) arnin, 1.1 g tri ethyl benzyle ammonium chloride in 100 valley toluol and 30 valley more aqueous 50% NaOH solution are given 4.7 g (0.037 mol) to dimethyl sulfate. The reaction mixture is separated, washed at ambient temperature during 5 hours agitated, the organic phase and evaporated 3 time with ever 100 valley water, getroeknet over Na2 SO4 and to 13,655,312 Troekne. The arrears 2 times umkfistallisiert in ethers and results in the title connection of the Smp….

92-96°.

Beispiel21 n (2,4-Dimethyl-thien-3-yl) - n (5-rnethyl-I, 3, 4-thiadiazol2-ylmethy [) - amine to 10 g (0.05 mol) n (2,4-Dirnethyl-thien-3-yl) - glycinlo hydrazid in 175 valley CH2 C12 5.5 g (0.05 mol) are dripped acetic anhydrid. The mixture is agitated during 1 hour with 20° and evaporated to dry ones. The oily arrears will become solved in 150 valley Pyridin and the solution 11.1 g (0.05 mol) Phosphorpentasulfid, in small Portiors to nen, given. The reaction temperature rises thereby to 48o.

The mixture is then heated up during 2 hours under Reflux and further-agitated afterwards at ambient temperature still 16 hours. After evaporation to dry one is solved the arrears in CH2 C12 and the solution is treated successively with ice water, with cold diluted NaOH solution and with water, evaporated dried over Na2 SO4 and to dry ones. Chromatography Rückstau.des at a KJeselgelsäule supplies the title connection as O1, Rf= 0.23 (Eluens: Ethyl acetate/hexane 6: 4).

Beispiel22 n (2,4-Dimethyl-thien-3-yl) - n (5-methyl-l, 2,4-triazol-3.ylmethyl) NaOH in 125 valley CH3 OH 5 g (0.05 mol) are given to amine to an agitated solution of 2,2 g (0.055 mol) Acetamin hydrochloride. 15 minutes after are admitted 10 g (0.05 mol) to n (2,4-Dimethyl-thien-3-yl) - glycinhydrazid and the mixture then during 18 hours under Reflux erhitzt.

The arrears to dry ones evaporated treated with 3s CH2 C12 and liberating from insoluble by-products by filtering. After evaporation of the CH2 C12 the title connection of the stop remains. 85-87o.

Beispiet 2S n (2,4-Dhnethyl-thien-3-yl) glycine isopropyliden hydrazid 7 g (0.035 mol) n (2,4-Dimethyl-thien-3-yl) glycinhydrazid in 50 mi acetone are agitated during 2 hours at ambient temperature. The title connection crystallized is filtered off, stop. 126-28o.

Beispiel24 the following connections of the formula VII are kept similar to several of the above examples 13 to 23 to or:

Verb. Acre Y Nr.

24,1 2,4-di-CH3 - thien-3-yl 24,2 do.

24.3 do.

24.4 do.

24.5 24,6 24,7 24,8 24,9 2-CH3S-4-CH3-thien-3-yl 1,3,5-tri-CH3-pyrazol-4-yl l-CH3-3,5-di-C2Hs-pyrazol-4-yl 1,3,5-tri-CH3-pyrazol-4-yl 3-CH3-5-OC2H5-pymzol-4-yl CH2CH2-OCH3 C2H5 CH2CH2-OCH3 do.

do.

C2H5 CH2CH2OCH3 characterisation Pf-- 0,32 (Diethyläther hexane 3: 1) Pf= 0.23 (Diethyläther hexane 1: 1) Pf= 0.38 (Diethyläther hexane 1: 1) RI'= 0.39 (Diethyläther hexane 2: 1) Sdp. 86°/0,01 torr of Sdp. 92-94°/0,01 torr of Rg= 0.38 (acetone hexane 4: 6) Rf = 0.2 (Ethylacetat-CH3 OH 2: 1) Rf= 0.25 (Ethylacetat-CH3 OH 9: 1) 655,312 14 verb. Acre Nr.

24,10 2,4-di-CH3 - thien-3-yl 24,11 do.

24.12 do.

24,13 2,4-di-C2 Hs-thien-3-yl 24,14 24,15 2-CH3-4-C2Hs-thien-3-yl 2-C2Hs-4-CH3-thien-3-yl 24,16 2,4-di-CH3 - thien-3-yl 24,17 do.

24.18 do.

24.19 do.

Y CHaCH2OC2H5 CH2CH2OC3HT-n CH2CF3 CH2CH2OCH3 /CH3 CH CH2 OCH3 /CH3 CH CHaOCH3 /CH3 CHa C CH2 CHz I - S CH3 24,20 DO. CH2 CON (CH3) 2 24,21 DO. CH2 COOCH3 characterisation Rf= 0.48 (Diethyläther) Rf= 0.57 (Diethyläther) 213 0 = 1,4786 n n D =1 " 5238 Sdp. 98-100 " /0.09 torr of Rf= 0.52 (ether hexane 7: 3) Rf= 0.55 (Diethyläther hexane 1: 1) Rf= 0.15 (CH2 Cla) = 1,5579 lp Sdp. 82-87 " /0.005 torr of fuel element 2S n (2-Carbomethoxy-3,5-dimethyl-thien-4-yl) spiet - chloracetamid to 12.25 g (0.066 mol) 3,5-Dimethyl-4-aminothiophen2-methylcarboxylat, 9.1 g (0.066 mol) K2 CO3, 25 valley water and 150 valley Methylenchlofid become, without cooling, 7.5 g (0.066 mol) chlorine acetyl chloride gegeben.

At expiration the exotherms of the reaction (36o) still 1 hour is separated agitated, the organic phase, washed with water and dried over Na2 SO4. After distance of the solvent the title connection remains as colorless Kñstalle of the stop. 157-58o.

, 26 N (2-Chlor-3,5-dimethyl-thien-4-yl) chloracetamid to an agitated solution of 5,0 g (0.0245 mol) n (2,4Dimethyl-thien-3-yl) eispiet chloracetamid in 50 ml dry CH2C12 becomes with 0° 3.3 g (0.0245 mol) Sulfurylchlorid getropft.

After terminated addition the reaction mixture left untouched to it reached agitated the ambient temperature and then still 20 hours. That is removed in the vacuum and the crystalline arrears with hexane digested whereby the analytically pure title connection from the Smp.

166° (Zers.) receive wird.

Beispiel27 n [2 (1,1-Diethoxy) ethyl-4methyt-thien-3-yt] - chloracetamid g (0.065 mol) n (2-Acetyl-4-methyl-thien-3-yl) chloracetamid become in a warm (50o) mixture of 60 g trocknere ethanol, 60 g Triethylorthoformat and 7 drops of konzentñerter HC1 gelöst.

One leaves the reaction mixture untouched 30 hours at ambient temperature, evaporates in the vacuum (50°/0,01 torr) and chromatographiert the remaining brown syrup at a silicagel column. Eluierung with hexane/Diethyläther 2:1 supplies the title connection of the Smp. 57-58° (colorless Kñstalle).

so example 28 N [2 (1-Methoxyimino) ethyl-4-methyl-thien-3-yl] - chloracetamid the solution of 1,5 g (0.0065 mol) n (2-Acetyl-4-methyl-thien-3-yl) - chloracetamid and 6.6 g (0.14 mol) Methss oxyamin in 50 ml troeknem toluol, the 5 g molecular sieves (3 A) become 7 hours under Reflux contain erwärmt.

The yellow reaction solution is then filtered and evaporated in the vacuum. The remaining raw syn/anti Isomerengemísch becomes chromatographisch by hexane Diethyläther as mobile phase aufgetrennt.

One eluiert first 0.6 g of pure isomer (syn) with a stop. of 101-102° (Rf= 0.33, hexane/Diethyläther 1: 1). One eluiert at the silicagel column and receives the analytically pure anti-form (0.4 g) of the stop. 87-89° (Rf= 0.21).

Beispiel29 the following connections of the formula III become similar za or several a that examples 25 to 28 erhalten.

Bsp.

Acre characterisation 29,1 29,2 29,3 29,4 29,5 29,6 29,7 29,8 29,9 29,10 29,11 29,12 29,13 29,14 29,15 29,16 29,17 2-COOCH3-4-CH3-thien-3-yl Smp. 118-119° 2-CH3S-4-CH3-thien-3-yl Smp. 105-106° 2,4-di-CH3-thien-3-yl Smp. 128-129° 3,5-di-CH3-isoxazol-4-yl Smp. 96-98° 3,5-diC2Hs-isoxazol-4-yl stop. 67-69° 4-CH3-thien-3-yl Smp. 93-96° 2-CH3-4-C2Hs-thien-3-yl Smp. 114° x0 2-CH3-4-OCHa-thien-3-yl stop. 144-45° 2,4-di-CH3-furan-3-yl Smp. 95-97° 3,5-di-CH3-isothiazol-4-yl stop. 104-06° 3-CH3-5-OC2Hs-pyrazol-4-yl Smp. 125-27° 2-COOC2Hs-N, 3,5-tri-CH3-pyrrol-4-yl Smp. 163-65° 2-C2H5-4-CH3-thien-3-yl Smp. 105° 2,4-di-C2Hs-thien-3-yl Smp. 145° 2-COCH3-4-CH3-thien-3-yl Smp. 110° 2-CH3-4-OC4H9n-thien-3-yl Smp. 129-30° 2-C2Hs-4,5-diCH3-thien-3-yl Smp. 147-48° Beispiel30 n (2,4-Dimethyl-thien-3-yl) - N-methoxyethyl-hydroxyacetamid 18.4 g (0.1 mol) n (2,4-Dimethyl-thien-3-y!) hydroxy2s acetamid in 50 valley trocknere dimethylformamide (DMF_) become a well agitated suspension of 3,0 g (0.1 mol) NaOH (80% dispersion in mineral oil) in 50 valley trocknere DMF getropft.

At expiration of the reaction (50o) one leaves the solution of the Nu-salt on ambient temperature cooling to the exotherms and treats her then with a solution of 10,4 g (0.11 mol) 2Chlorethyl-methyläther in 20 valley trocknere DMF. After terminated addition the Reaktionsgemiseh is heated up during 4 hours on 100° and evaporated then to dry ones (40°/0,1 peat).

The arrears are taken up to 200 ml Diethyläther, filtered washed with 250 valley water, dried over MgSO4 and. The oily arrears after evaporation of the filtrate stay at a silicagel column are chromatographiert. One eluiert with Diethyläther and receives the desired connection as viscous liquid (Rf = 0.25/Diethyläther).

Beispiel31 similar to the procedure in accordance with example 30 are received the following connections of the formula II, where acre stands for 2,4-Dimethylthien-3-yl:

Ex. Y 31,1 CH2 CH = NOCH3 31,2 CH2 CH =NOC2 H5 31,3 CH2 C =NOCH3 I CH3 31,4 CHr C = NOC2 H5 I CH3 31,5 CHCH=NOCH3 I CH3 CHCH = NOC2 H5 CH3 31,6 31,7 CH2 - Ô " -] 655,312 Beispiel32 n (4-Methoxy-2-methyl-thien-3-yl) ethoxyacetamid to 9.8 g (0.068 mol) 4-Methoxy-2-methyl-3-aminothiophen, 9.45 g (0.068 mol) K2 CO3, 35 valley water and 100 ml CH2C12 becomes without cooling the solution of 8,4 g (0.069 mol) Ethoxyacetylchlorid in 20 ml CH2 C12 gegeben.

At expiration the exotherms of the reaction (32o) still another further hour is agitated. The organic phase is washed separated, 2 times rnit to each of 150 ml water, evaporated getroeknet over Na2 IN SUCH A WAY “and by means of red evaporation. The arrears at a silicagel column chromatographiert using hexane/Diethyläther 1:1 as Eluens.

In such a way received title connection has a Smp. of 40--41°.

The following connections of the formula ArNHCOY3 become similar to example 33 to example 32 erhalten.

Ex. acre Y3 characterisation 33,1 2,4-di-CH3 - thien-3-yl-CH2 - OCH3 Smp. 62-63° 33,2 DO. - CH3 stop. 168-69° 33,3 DO. Smp. 140-42° 33,4 DO. - Smp. 164--65° 33,5 33,6 33,7 33,8 33,9 33,10 DO. CF3 33,11 2,4-di-C2 Hs-thien-3-yl - CH2 OCH3 1,3,5-tri-CH3-pyrazol - CH2 OCH3 4-yl I-CH3-3,5-di-C2Hsdo.

pyrazol-4-yl 3-CH3-5-OC2H5 - CH2 OCH3 pyrazol-4-yl 2,4-di-CH3-thien-3-yl - CH2 OC2 H5 do.

Smp. 85-87° Sdp. 120° /0, 001 torr of Smp. 128-30° Smp. 37-38° - CH2OC3Hí--n Smp. 43--45° Smp. 94-97° Smp. 48-49° example 34 benzyle (N-4-methoxy-2-methyl-thien-3-yl) earbamat 63.6 g (0.23 mol) Diphenylphosphorylazid and 24.4 g (0.23 mol) tri ethyl amine becomes in a casting to a suspension of 36 5 g (0 2 mol) 4-Methoxy-2-methylthiophen3 carbon-sour m 300 valley trocknere benzene gegeben.

The received mixture is heated up I hour under Reflux and then with 25 g (0.23 mol) benzyle alcohol behandelt.

After a response time of 3 /2 hours with 78° is cooled that for characterisation s0 reaction mixture on ambient temperature, dilutes Rf= 0.21 (hexane ethyl acetate 3: 2) with Diethyläther (350 valley) and successively with 250 valley 5% - Rf= 0.25 (hexane ethyl acetate 3: 2) iger HC1, with 250 valley of satisfied NaHCO3 - solution, with Smp.69-710 200 valley of satisfied NaC1-Lösung washed, over Na2 SO “dried and evaporated at Rotevaporator. The remaining crystalline arrears are digested with pentane and supply the pure Tltelverbindung of the stop. 107-108o.

Rf= 0.27 (hexane ethyl acetate 3: 2) example Rf= 0.31 (hexane ethyl acetate 3: 2) to 6o similar to example 34 one receives using the appropriate acid the following Carbamate.

Rf=0,3 (hexane ethyl acetate 3: 2) Rf= 0.12 (hexane ethyl acetate 3: 2) Beispiel35.1 benzyle (N-2,4-diCH3 - furan-3-yl) carbamat, Smp. 103-5o.

Example 35,2 benzyle (N-4-n-butoxy-2-methyl-thien-3-yl) carbamat, Smp. 83o.

by soaps (KOH) of the appropriate ethyl ester, stop will receive 655,312 Beispiel36 4-Methoxy-2-methylthiophen-3carbonsà'ure the title connection. 127o.

Example 37 similarly to procedures 36 becomes 4-_n-Butoxy-2-methylthiophen-3carbonsäure, Smp. 66--68° erhalten.

Beispiel38 4-Methoxy-2-methylthiophen-3carbonsãureethylester ml 50%ige NaOH solution become a mixture (at ambient temperature) of 18,6 g (0.1 mol) 4-Hydroxy-2methyl-thiophen-3earbonsäureethylester, 10 valley (0.105 mol) dimethyl sulfate and 2.3 g (0.01 mol) benzyle tri ethyl ammonium chloride in 100 ml CH2 C12 getropft.

After 15 minutes with Reflux the reaction mixture is regenerated. The title connection has a Rf-value of 0,36 (Eluens Diethyläther/hexane 2: 1).

Beispiel39 3, 5-Dimethyl-4-nitrothiophen-2-carbonsäurentethylester to a well agitated solution of 51,4 g (0.3 mol), cooled on 0°, 3,5-Dimethylthiophen-2-carbonsäureester in 200 valley glacial acetic acid becomes, over one time interval of 40 minutes, a mixture of 30 mi of fuming nitric acid (spec. Weight = 1.5) and 120 ml acetic anhydrid dripped. After terminated addition the remaining brown solution is agitated further 2 hours with 5° and then in 3000 valley ice water gegossen.

The aqueous phase is extracted 2 times with 500 ml Diethyläther. The ether excerpts are washed, dried with water and 3%iger NaHCO3-Lösung over NazSO4 and in the vacuum eingedampft.

The arrears are subjected to a Kàeselgelsäulenchromatographie, using hexane/Diethyläther (10: 1) as Eluens and the title connection of Smp results in. 87-88o.

Beispiel40 similar to the procedure in accordance with example 39 one erhãlt using 1,3-Dimethyl-5-ethoxypyrazol as parent compound, 1,3-Dimethyl-5-ethoxy4-nitropyrazol with a Rf-value of 0,37 on K.ieselgel, with Diethyläther as Eluens.

16 deh 21 days at ambient temperature with 14 to 17 hours daylight/day stand leave/> The determination the herbicides of the effect takes place at expiration of the 21-Tage-Periode. It covers a visual Abs estimation of the degree and the kind of the Sehadens with the different Pflanzen.

The connections of the formula I are appliziert in above way in quantities according to 1.4 to 5.6 kg active substance/Hektare. It becomes herbicides effect, i.e. significant Schädilo gung, with the test plants beobachtet.

Beispiel42 of herbicides effect after post office eM application one proceeds similar to the procedure in accordance with example 42, whereby the connections according to invention are appliziert with 2 to 4-Blatt-Stadium. (By graduated sowing the test plants reach the 2 at the same time--4 sheet stages).

The connections of the formula I become again in quantities according to 1.4 kg! ha up to 5.6 kg! ha appliziert. The visual determination the herbicides of the effect takes place 21 days after application of the attempt substance. It becomes herbicide Wirktmg beobachtet.

Versuehsergebnisse Beispiel41 of herbicides effect after pre em application of pots (7 cm diameters) are filled with a mixture from peat substrate and sand. The upper surface of the mixture becomes with a test liquid, which a connection according to invention (e.g. in form of the emulsion concentrate in accordance with example B), sprayed, and on that seed of Lepidium contains sativum, Agrostis alba, Avena satira and Lolium ss perenne in each pot sown, according to which the seeds are covered by arena sativa and Lolium perenne with a thin (0.5 cm) layer Torsubstrat sand Misehung. The pots werBeispiel43 a selection of the connections according to invention in the following Voraufkauf attempt becomes closer untersucht.

Containers of 30 x 40 cm become up to a depth of 6 cm with a mixture from peat substrate and sand gefüllt.

The upper surface of the mixture becomes with a test liquid, which a connection according to invention (e.g. in form of the emulsion concentrate in accordance with example B) in a certain concentration contains, sprayed. The Sprühvoluss men corresponds 6001 aqueous Testflüssigkeit/ha. The procedure is repeated with different concentrations, whereby the concentrations are selected in such a way that the desired application quantities are reached. Six plant types are sown per container. The number of seeds, which is sown by each plant type, depends on the germ potential of the seeds and on the initial growth rate of the individual plants. After sowing the seeds the behandere surface with a thin layer (about 0.5 cm) of a dead fsubstrat/sand mixture bedeckt.

4s the containers will then stand 28 days at a temperature from 20 to 24 °C and daily for 14 to 17 hours with daylight (possibly artificial) leave/> The determination the herbicides of the effect of the examined connection according to invention takes place right after completion of the 28Tage-periode. The regulation covers a visual estimation of the degree and the kind of the Sehadens of the different plants. A particularly favourable herbicide effect is observed among other things with the connections No. 25, 26, 47, 48, 55, 75, 84 and 86 of the table A. Some the results with application quantities of 1 kg active substance, obtained with these connections! has are in the following table B zusammengefasst.

Table B treated plant Amaran. retrofl. 90 Capsella b.p.

Chenop. alb.

Galium aparine Pre ero treatment 1 kg/ha connection No./% damage 26 47 48 55 75 84 86 90 100,100,100,100 80 90 100,100 80 90 70 70 90 90 50 20 50 60 50 0 10 10 50 I7 Pre cm treatment 1 kg/ha table B treated plant connection No./% damage Senecio vulg. 90 80 80 80 80 100 90 100 Stellaria media 90 70 70 80 50 50 70 90 Alfalfa 80 60 60 50 80! 0 70 90 Bean 0 0 20 20 0 0 10 Carrot 80 90 90 90 70 100 80 90 Cotton 20 0 10 0 0 0 20 0 Flax 80 30 60 51) 30 0 20 Potato 0 10 10 0 0 0 0 0 Soya 50 10 30 30 0 10 30 Sugar patch 61) 10 10 0 0 1) 20 Rape 10 0 21) 0 0 0 20 Sunflower 0 10 31) 50 0 0 0 Agropyron repens 91) 100 90 60 80 90 91) Agrosfisalba 100,100,100,100,100,100 11) 1) 11) 0 Alopec. myos. 91) 90 80 20 50 81) 81) 90 Aperasp.venti. 101) 101) 100,100,100,100,100,100 arena fatua 81) 80 80 40 80 91) 51) 90 Echinochloa c.g. 90 11) 1) 90 90 90 1O0 90 90 Corn 20 30 50 31) 0 50 91) Wheat 70! 00 90 90 0 100 60 655,312 example 44 post office rh treatment a further examination of a selection of connections according to invention takes place in an Nachauflauf attempt, which is accomplished similarly to 43 Vorauflaufversuch described in example, with the difference that the test liquid appliziert only in the 2bis 4-Blatt-Stadium wird.

For this purpose the different plant types are temporally graduated sown. The greenhouse conditions (temperature, light) are as in example 43. The herbicide effect is determined likewise 28 days according to Applikafion and effected in the procedure in accordance with example 41.

Particularly favourable herbicides characteristics are observed among other things with the connections No. 25, 26, 47, 48, 55, 75, 84 and 86 of the table A. Some the results, which are obtained with the application quantity of 5 kg of Wirkstoff/ha, are in the table C zusammengefasst.

Table C Behanddte Pfanze post office em treatment 5 kg/ha connection No./% damage 26 Amaran. retrofl. 90 Capsella b.p. 80 Chenop. alb. 90 Galium apañne 81) 61) Senecio vulg. 80 51) Stellaria media 91) 51) Alfalfa 80 Bean 100 Carrot 70 90 Cotton 70 61) Flax 81) 71) Potato 70 Soya 90 Sugar patch 30 Rape 41) Sunflower 60 Agropyron repens 71) Agrostis alba - - Alopec. myos. 81) 90 Apera frame venti. 91) 100 Avena fatua 91) 11) 0 Echinochloa c.g. 1) 81) 2) 91) Corn 81) Wheat 70 90 Rice 2) 40 *4 kg/ha 1) “upland” conditions; 47 48 55* 75 84 86* 71) 51) 80 60 80 90 21) 20 80 50 80 41) 20 20 40 30 30 80 21) 70 61) 80 90 91) 80 91) 10 30 41) 60 21) 11) 50 21) 70 20 20 31) 30,100 80 101) 100 81) 40 50 61) 71) 90 11) 0 80 90 41) 10 10 11) 40 30 21) 31) 30 0 10 10 0 10 30 61) 50 80 40 61) 91) 50 50 50 31) 70 60 90 80 90 100 11) 0 11) 0,100 90 91) 90 80 90 11) 0 11) 1) 101) 80 90 71) 81) 90 90 11) 0 80 91) 101) 11) 0 91) 30 30 70 50 10 60 60 81) 50 30 30 31) 2) “paddy” conditions 655,312 field test connection No. 25 MultikulturFeldscreening attempt becomes in one pre ero, under which, further-examines the following conditions:

Cultures: Soy (“Steeleß (so) cotton (“Stoneville 213”) (Cor) corn (LG I 1) (CO) wheat (Svenno) (Wh) of weeds: Alopecurus pratensis (Al) Echinoehloa crus galli - (Ech) Galium aparine Chenopodium album and polyspermum Amaranthus retroflexus Dieots 18 (all weeds, with which exception of Alopecurus pratensis, which was in-sown, were naturally occurring).

- Spraying volumes: 750 I/ha - number of attempts: 3 s - Evaluation: 28 after day the Applikation.

- Standards: Alachlor (= ct-Chlor-2',6' diethyl N METHOXYMETHYL acetanilid) and Metolachlor [= ct-Chlor-2°-ethyl6' methyl n (1-methyl-2-methoxycthyl) aeetanilid].

The following herbicides effect (% Sehaden) became beoblo achtet.

Connection No.

Alachlor Metolaehlor kg/ha in such a way Cot CO Wh AI/Eeh Dicots 0.6 0 0 10 63 92 43 1.25 3 3 53 80 100 67 2.5 5 7 80 92 I00 87 1.25 0 0 0 I0 of 43 43 2.5 0 3 0 53 78 57 1.25 0 0 0 33 100,2.5 0 0 0 73 100 43 above results show herbicides an effect, which the 3o approximately weeds dikotylen are superior. The herbicide we-see in the trade standards present directly or superior kung is in soy and cotton and with the deepest is selective against monokotyle weeds, and to this standards application quantity also in Mais.

C