IE55108B1 - Herbicidal chloroacetamides - Google Patents

Herbicidal chloroacetamides

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Publication number
IE55108B1
IE55108B1 IE247/83A IE24783A IE55108B1 IE 55108 B1 IE55108 B1 IE 55108B1 IE 247/83 A IE247/83 A IE 247/83A IE 24783 A IE24783 A IE 24783A IE 55108 B1 IE55108 B1 IE 55108B1
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IE
Ireland
Prior art keywords
compound according
group
compound
thien
alkyl
Prior art date
Application number
IE247/83A
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IE830247L (en
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Sandoz Ltd
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Publication date
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Publication of IE830247L publication Critical patent/IE830247L/en
Publication of IE55108B1 publication Critical patent/IE55108B1/en

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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—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
    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—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
    • A01N43/74—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 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—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
    • A01N43/74—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 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—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
    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—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
    • A01N43/82—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 three ring hetero atoms
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
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    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/38—Nitrogen atoms
    • C07D231/40—Acylated on said nitrogen atom
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    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D275/03—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Furan Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Pyrrole Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

(A)A5-membered heteroaromatic chloroacetamide deriv. of formula (I) is new. (where Ar is a 5-membered heteroaromatic gp. contg. 1 or 2 ring heteroatoms chosen from O, S and N, and bonded via a ring C atom to the N atom of the N(Y)COCH2Cl gp., and where if Ar is pyrazolyl, N(Y)COCH2Cl is in the 4-position; Y is allene, CH2CH=C=CH2, 1-8C alkyl, 3-8C alkenyl, 3-8C alkinyl, 3-8C cycloalkyl, 5-8C cycloalkenyl, 3-8C cycloalkyl, 1-5C alkyl, these hydrocarbyl gps. being opt. substd. by F, Cl, or Br; or Y is CGR1COY1, R2A3, A-OR3, CHR5CHR5=NOR4 or CHR6NMeCOMe; R1 is H or 1-5C alkyl; Y1 together with the CO gp. to which it is attached forms an ester or amide gp.; R2 is CH2 or CH2CH2 each opt. substd. by 1-5C alkyl (Editor - not in spec. have assumed alkyl) A3 is a heteroaromatic ring chosen from a di- or tri-azole bonded via a ring N to R2, a5-membered heteroring contg. 1-3, O, S and/or N heteroatoms, and bonded via a ring C to R2, pyrimidine, 2-oxo-1-pyrrolidinyl in which a CH2 gp. is opt. replaced by O, S or NMe, and 5-oxo and/or bicyclic benz(c) bonded derivs. such as 2-oxo-1-pyrrolidinyl gps.; R3 is H, 1-8C alkyl, 3-8C alkenyl, 3-8C alkinyl, 3-8C cycloalkyl, 5-8C cycloalkenyl, 3-8C cycloalkyl 1-5C alkyl (these hydrocarbyl gps. being opt. substd.) or N=CR4R4' R4 is 1-5C alkyl, 3-5C alkenyl, 3-5C alkinyl, 3-8C cycloalkyl, 3-8C cycloalkenyl, 3-8C cycloalkyl, 1-5C alkyl (these hydrocarbyl gps. being opt. substd. by F, Cl, or Br) or allene; R4' is H or as R4; A is hydrocarbyl gp. bonded with R3 to form heteroring contg. 1 or 2 O heteroatoms so that the N and O atoms are joined by A and are sepd. by up to 3C atoms; R5 and R5' are each H or Me or together form (CH2)3 or (CH2)4; R6 is H or 1-3C alkyl). (B) The intermediate heterocyclic cpds. (II) and (III) are also new (where R7 is COCH2OH or H). (I) are selective herbicides used in e.g. soya, cotton, etc. [FR2523967A1]

Description

55108 - la - HEBBXCIDM. CSLOROACETAMIDES The present invention relates to novel 5-membered heteroaromatic compounds bearing at one ring C-atom a N-substituted chloroacetyl-amino group, their use as herbicides, agricultural compositions for g facilitating such use and the preparation of the novel compounds of the invention.
Various herbicidal N-substituted cc-halogenacetanilides are known.
The U.S. Patent Spec. 4,282,028 discloses N-substituted-N-2,5-10 di-alkyl-pyrrol-l-yl)haloacetamldes having herbicidal and plant- growth-regulating activity. The need exists for still more effective herbicides. The novel 5-membered heteroaromatic compounds are particularly effective herbicides having an appropriate soil persistence.
The present invention provides compounds of formula I ^/C0C82C1 Ar - N^ 'Y 25 wherein Ar is a 5-membered heteroaromatic group, unsubstituted or substituted^lo^rlWroM^rlti heteroatoms selected from 0, S and N, and linked by a C-ring atom to the N-atom of the N(Y)C0CHjCl group to which it is bound, whereby, where Ar is pyrazolyl, said N(Y)C0CH2C1 group is in the 4-position, and Y is allenyl, CH2-CH=C«CH2 or is a hydrocarbon selected from C3_3alkenyl, C3_8alkynyl, C3_ecycloalkyl, C5-8cycloalkenyl, C3_8cyclo-alkyl-Ci_5alkyl, whereby such hydrocarbon is unsubstituted or substituted by halogen selected from F, Cl or Br; or is Cj._aalkyl substituted by Cl, Br or F; or is a group CH(Hi)-C0Yj., wherein is H or Ci_5alkyl and Yi forms together with the CO-group to which it is bound an ester or amide function, as hereinafter defined; 30 - 2 - 5510S or is a group R2-Az> wherein R2 is CH2 or CH^-CHg unsubstituted or substituted by Chalky! and 5 Az is an aromatic heteroring selected from a di-or triazole linked by one of its nitrogen atoms to R2> a 5-membered heteroring linked by a C-atom of said ring to R2 and having 1 to 3 10 heteroatoms selected from the group consisting of 0, S or N, and a pyrimidine group· or is a 2-oxo-l-pyrrolidinyl group in which one CH2 group can be replaced by 0, S or NCH3 and 5-oxo- and/or bicyclic benz[c] fused derivatives of such 2-oxo-l-pyrrolidinyl group or is a group A-O-Rg, wherein R3 is H, hydrocarbon selected from the group consisting of Clgalkyl, C3_galkenyl, C3_g- alkynyl, C3_8cycloalkyl, Cg gcycloalkenyl or Cg.ocycloalkyl-C, -alkyl, whereby the hydrocarbon . i. i.··. - j 3 L hereinafter defined is unsubstituted or substituted; or a group wherein is hydrocarbon selected from C^g-alkyl, C3_galkenyl, C3_galkynyl, C^cycloalkyl, Cg_gcycloalkenyl, C3_8cycloalkyl-Ci-galkyl, whereby the hydrocarbon is unsubstituted or substituted by halogen selected from F, Cl or Br; or allenyl, R4' is H or has one of the meanings defined for R^ 25 - 3 - - 3 - 55108 and A is a hydrocarbon moiety as hereinafter defined unsubstituted or substituted by Ci_salkoxy, which may be linked with S3 to form a saturated oxygen containing heterocyclic ring comprising 1 or 2 oxygen as heteroatom(s), and whereby the N 5 and 0 atoms to which it is bound are separated by up to 3 C-atoms; or a group CH - C » N0R4, R5 Rs' wherein R4 is as defined above, R; and Rj' are independently B or CH3 or Rs together with Rs' are (CH2)3 or (CH2)4 or a group CH-N(CH3)C0CH3 Re wherein R$ is H or Ci_3alkyl.
The Ar group may be unsubstituted or substituted. Where Ar is substituted it may bear substituents in any possible position; preferred positions of such substituents are in o-position, 15 particularly in ο,ο'-position with respect to the chloroacetamide group, whereby additional substituents may be present. Examples of suitable substituents of Ar are halogen selected from F, Cl and Br; Ci_4alkyl unsubstituted or substituted by halogen (F, Cl, Br), Ci_4alkoxy or C3_6cyloalkyl; C2_4alkenyl unsubstituted or substituted 20 by Cl_4alkoxy; C3_6cycloalkyl; formyl or C2_4alkanoyl and functional derivatives thereof (i.e.
C(=N0Cl.4alkyl)-C1_3alkyl, C(0-C1.4alkyl)2-C3.3alkyl, CH(0-Cj._4alkyl)2; Ci_4alkyl-S, Ci_4alkyl-S0, Ci_4alkyl-S02; Ci_4alkoxy-carbonyl; C3_4alkoxy unsubstituted or substituted by 25 halogen or C1_4alkoxy; C2.4alkenyloxy, C2_4alkynyloxy; hydroxy and hydroxymethyl and esters thereof (i.a esters with an organic carboxylic acid, for example formic acid, a C2.5alkane carboxylic acid or an halogenated derivative thereof, such as acetic acid or chloroacetic acid). - 4 - - 4 -55108 Any optional substituent(s) of Ar which is not in o-position of the N-substituted chloroacetylamino group is · selected from Ci„4alkyl (e.g. CH3), halogen (F, Cl, Br) and Ci.4alkoxycarbony1 (e.g. COOCH3).
Where Ar contains 2 ring heteroatoms, one of them is N; the other is preferably selected from 0 or S.
A preferred sub-group of compounds of formula I, are compounds wherein Ar contains either one ring heteroatom (pyrrolyl, thienyl, furanyl) or 2 adjacent ring heteroatoms (isoxazolyl, isothiazolyl, 10 pyrazolyl). The N-substituted chloroacetylamino group is preferably tied to the ring C-atom in β-position of the ring heteroatom(s); thus in the 3-position where Ar is pyrrole, thiophene or furan and in the 4-position where Ar is isoxazole, isothiazole or pyrazole. A preferred sub-group of the latter group are those compounds wherein 15 the Ar-group is substituted in ortho-, more preferably in ortho-ortho'-position of the N-substituted acetylamino group, especially when the substituent(s) are selected from the group specified hereinbefore. Any ring N-atom may be unsubstituted or substituted; where it is substituted, it is preferably substituted by 20 Ci-4alkyl, especially CH3 or CjH5. Ar signifies preferably a thiophene, isothiazole and isoxazole, more preferably isothiazole or thiophene ring. A particularly preferred sub-group of compounds of formula I, are compounds wherein Ar is thiophene, particularly 3-thienyl which is at least 2,4-disubstituted, especially those 25 3-thienyl compounds wherein the substituents in 2- and 4-position are selected from Cj.4alkyl and Ci-4alkoxy.
Where T, S3, K4 and R4' are hydrocarbon substituted by halogen, such halogen is preferably Cl or Br; any such substituted hydrocarbon is particularly monosubstituted. Where Y is halogen substituted 30 hydrocarbon, the halogen is in general preferably not in the 1-position where the use as herbicide is intended (such 1-halogenated - 5 - compounds are in general unstable; they are however useful as valuable intermediates for the production of other compounds of formula I, e.g. for those wherein Y is alkoxyalkyl or pyrazolyl-methyl); a suitable example of such significance of Y is 2-Cl-ethyl.
Preferred Ci_»alkyl, C3.aalkenyl or C3-jalkynyl groups have up to 5 C-atoras, Where Y, Rj, R4 and/or R4' are or contain cycloalkyl or cycloalkenyl Such cyclic hydrocarbon groups contain preferably up to 6 C-atoms.
Where Ri is Ci_salkyl it is preferably CH3 or CjH5, particularly 10 CH3, The term ester or amide function used in connection with the meaning of Yi is intended to embrace any function obtainable by the reaction of the C00B group of an acid with any organic compound reacting with such acid with the elimination of water e.g. an alcohol, an amine, a mercaptan, an oxime, a hydrazine, hydrazide or 15 hydrazone. Examples of suitable ester significances of Yi are Cj-jalkoxy-CO and C3-3alkyny1-0-C0. Examples of suitable amide significances of Yi are Ci_4alkylamino-C0, di(Cl_4alkyl)amino-CO, CO-NHNHj and CO-NH-S»C(Ci_3alkyl)2.
Where R2 is CH2 it may be substituted by 1 or 2, preferably 1 20 Ci_5alkyl. Where R2 is CHjCHj it may be substituted by up to 4 Ci.5alkyl group and is preferably mono- or disubstituted. Where CH2CHj is disubstituted, the Substituents are preferably at different C-atoms.
Preferred Cj._5alkyl substituents of R2 are CH3 and C2H5, 25 particularly CH3. where R2 is substituted by Ci.salkyl, it is preferably monosubstituted. Rj is especially CH2 or CB(CH3>. - 6 - - 6 -55108 Where Az is one of the above defined aromatic heterorings, such ring may be unsubstituted or substituted; suitable substituents of such Az significances are e.g. one or more Ci-5alkyl (such as CH3, C2H5) groups; such substituted aromatic heterorings are preferably 5 mono- or di-substituted.
Where Az is di- or triazole it is preferably 1-pyrazolyl, 1- imidazolyl, 1,2,3-triazol-l-yl or 1,2,4-triazol-l-yl, unsubstitued or substituted, particularly 1-pyrazolyl, 3,5-di-CHj-l-pyrazolyl.
Where Az is the above defined 5-membered heteroring linked by a 10 ring C-atom to R2, such ring is e.g. a furyl, a thienyl, a thiazolyl, an isothiazolyl, an oxazolyl, an isoxazolyl, a 1,2,4- or 1,3,4-thia-or oxadiazol or a 1,3,4-triazolyl group, unsubstituted or substituted, by one or two substituents of the group C2_4alkyl, C3_4alkylthio, C1_4alkoxy; typical examples of such significances are 2-furyl, 15 2-thienyl, 2-CH3-4-thiazolyl, 3-CH3-5-isoxazolyl, 2-C2Hs-l,3,4-oxa-diazol-5-yl, 3-CH3-l,2,4-oxadiazol-5-yl, l-CH3-2-CH3S-l,3,4-triazol-5-yl and 2-CH3-l,3,4-triazol-5-yl.
Where Az is a pyrimidine group, this may be linked by its 2-, 4-or 5-C-atom to R2, and is e.g. 2-pyrimidinyl.
Where Az is the above defined bicyclic 2-oxo-l-pyrrolidinyl derivative, the benzo-moiety may be unsubstituted or substituted, e.g. by halogen; a suitable example of such significance is 2- oxo-l,3-benzothiazol-3-yl and the 4-chloro derivative thereof.
Where R3 is the above defined hydrocarbon, such hydrocarbon may 25 be unsubstituted or substituted, by halogen, cyano, an azole group such as 2-pyrazolyl and/or by Cx^alkoxy; such substituted hydrocarbon significances of R3 are preferably monosubstituted. Examples of such R3 significances are CH2H2C1, (l-pyrazolyl)-CH2, CH2CH2CN.
Suitable meanings of A-0-R3, when A is linked with R3 to - 7 - &S1Q8 form a ring, are e.g. 1,3-dioxolan-4-y1-Ci_3alkylene, 1,3-dioxolan-2-y1-Cj_3alkylene and 2- or 3-tetrahydrofuryi-Cj._3aIkylene.
Where A is not linked with R3 to form a ring, A is a non-aromatic, particularly a C1-0alkylene moiety separating the 0-5 and N-atom to which it is bound by 1 to 3, preferably 1 or 2 C-atoms. A suitable significance of A is a CHj or CH2-CH2 group or mono-methylated derivatives thereof, particularly CH2, CH(CH3), CH2CH2 and CH(CH3)CH2; R3 is then especially Cj.-3alkyl, such as CR3, C2Hb and nC3H7.
A may be unsubstituted or substituted by Ci_5alkoxy. Any substituted A significance is preferably mono-substituted.
The present invention also provides processes for producing a compound of formula I comprising a) substituting in a compound-of formula II ^COCHiOH Ar - N II wherein Ar and Y are as defined above, the HO group of the H-hydroxyacetyl group by Cl, b) reacting a compound of formula III Ar-HH-C0CH2C1 III wherein Ar is as defined above, with a compound of formula IV LY IV wherein Y is as defined above, and L is a leaving group capable of being split off under the N-alkylation reaction conditions, - 8 - 5 510 8 la c) obtaining a compound of formula la X0-CH,C1 Ar - NC_ 2 CH - Y, t c R' wherein R' is H or Chalky!, Y2 is Az\ 0R3>N(CH3)C0CH3 and Az' is a di- or triazole linked by one of its nitrogen atoms to CHR' and Ar and R3 are as defined above, by reacting a compound of formula V Ar - N ^CO-CHgCl VCH - Cl V I R* wherein Ar and R‘ are as defined above, with a reactive derivative of a compound of formula VI hy2 VI wherein Y2 is as defined above, d) N-acylation of a compound of formula VII Ar - NH - Y VII wherein Ar and Y are as defined above, with chloroacetyl chloride, or a reactive functional derivative thereof.
Process a) of the invention can be carried out by conventional 15 manner under conditions known for the substitution of an OH group by a Cl. -9-- -9-- 5 5 10 8 Such substitution can for example be effected by treating a compound of formula II with a chlorinating agent, such as thionyl chloride under conditions known per se for analogous reactions.
According to a variant of this chlorination process, the 5 compounds of formula II are first converted into the corresponding sulphonyloxy derivatives, e.g. by O-sulphonation with the aid of a sulphonyl halide, and such sulphonyloxy derivatives then converted into the desired compounds of formula I by nucleophilic substitution of the sulphonyloxy group by chlorine.
Reactants supplying the Cl anions required for such nucleophilic substitution are e.g. alkalimetal chlorides such as NaCl, quaternary tetrabutylammonium chloride or 4-dimethylaminopyridine-hydrochloride. Such substitution is conveniently carried cut in CHgClg or in an aqueous/organic two-phase system, wherein the 15 organic phase is e.g. a hydrocarbon such as toluene, in the presence of a suitable phase transfer catalyst, preferably with heating e.g. at 40° to 120eC.
Process b) may be carried out by conventional manner under conditions known for the ff-alkylation of amides. The reaction is 20 advantageously carried out in a solvent which is inert under the reaction conditions e.g. dimethoxyethane or acetonitrile or in an aqueous/organic two-phase system in the presence of a phase transfer catalyst.
Suitable meanings of L (in formula IV) are Cl, Br or the 25 sulphonyloxy moiety of an organic sulphonic acid such as mesyloxy or p-tosyloxy. . - 10 - - 10 -551 08 The compounds of formula III are preferably used in salt form, more preferably in alkali metal salt form, e.g. the sodium salt form. Such salts are obtained in conventional manner by reaction of the compound of formula III with a base such as an alkali metal amide, 5 hydride, hydroxide or alcoholate.
For the preparation of compounds of formula la according to process c), the compounds of formula V are suitably used in the form of the alkali metal salt, e.g. as sodium salt. Where Y2 is a di- or triazole, the compound of formula V may also be used as N-trialkyl-10 silyl (e.g. N-trimethylsilyl) compound. The reaction can be effected in conventional manner.
The reaction of process d) can likewise be effected in conventional manner, under conditions known for the N-ohloroacetyl-ation of amines. Where CICOCHjCl is used as N-chloroacetylation agent 15 such reaction is conveniently carried out in the presence of an acid binding agent, such a K2CO3.
The compounds of formula I may be recovered from the reaction mixture in which it is formed by working according to established procedures. it will will be appreciated that interconversion of one compound of the invention to another, e.g. conversion of an acid group to an ester group, of a carbonyl group to an oxime, of a haloalkyl group to an ether group (or vice versa) etc., may be carried out in conventional manner. AS will also be appreciated, the compounds of 25 the invention may possess one or more asymmetric centres and may therefore exist in optically active, diastereomeric, racemic or geometric isomer forms. In general such compounds are employed as mixtures in the herbicide method and compositions of the invention, even though separation may be effected by known procedures. - π - The compounds of formulae II, III, V and VII are novel.
The compounds of formula II may be obtained by ammonolysis of an ester of the compounds of formula VIII Ar HHCOCHgOH VIII wherein Ar is as defined above, with a carboxylic acid, and subsequent introduction of the group Y (as defined above) in the compounds of formula VIII by N-alkylation. Such esters are obtained by acylation of the corresponding compounds of formula IX ArNH2 IX wherein Ar is as defined above, with the appropriate ester of HO-CH^COCl, e.g. with CHjCO-OCHg-COCl.
The compounds of formula III may also be obtained by acylation of a compound of formula IX with chloroacetyl chloride.
Compounds of formula V (which are in fact a sub-group of compounds 15 of formula I) may be obtained by reaction of a compound of formula IX with an appropriate aldehyde and reaction of the Schiff base thus obtained with chloroacetyl chloride.
The compounds of formula VII may be obtained by N-alkylation of a compound of formula IX. Such alkylation can be carried out in 20 conventional manner, with the corresponding alkylating agents (e.g. halogenides), or where appropriate, reductively via the Schiff base or amide.
Many of the compounds of formula IX are novel.
A particular group of valuable novel compounds of formula IX 25 are 3-ami nothiophenes substituted in 2- and 4-position by a group selected from C^alkyl and C^alkoxy (compounds of formula IXa). - 12 - 55108 The compounds of formula IX may be obtained by reduction of the corresponding NOg compounds, e.g. by catalytic hydrogenation under hydrogen pressure in the presence of palladium. Compounds of formula IXa having a CH3 group in 2- or 4-position may be obtained 5 by reduction of the corresponding thiophene-carboxyl ate with the aid of a complex hydride such as sodium bis(methoxyethoxy)aluminium hydride. Where appropriate, the compounds of formula IXa may also be obtained from the corresponding carbamates esters, e.g. the benzyl carbamate, by hydrolysis. The carbamates, used as starting 10 material, may for example be obtained starting from the corresponding acids, via their azides followed by a Curtius reaction.
Insofar as the production of starting material is not described herein, these compounds are known, or may be produced and purified in accordance with known processes or in a manner analogous to 15 processes described herein or to known processes.
The compounds of formula I are useful because they control or modify the growth of plants. By plants it is meant germinating seeds, emerging seedlings and established vegetation including underground portions.
In particular, the compounds are useful as herbicides as indicated by i.a. the damage caused to both monocotyledoneous and di-cotyledoneous plants such as Lepidium sativum, Avena sativa, Agrostis alba and Lolium perenne in tests by test dosages equivalent to an application rate of from 1.4 to 5.6 kg/ha after pre- or post-25 emergence application. In view of their herbicidal effect the compounds of the invention are indicated for use in combatting dicotyledoneous and grassy weeds, as confirmed by further evaluation with representative compounds with test dosages equivalent to an application rate of from 0.2 to 5.0 kg active 30 ingredient, e.g. test dosages equivalent to a rate of 0.2, 1.0 - 13 - 55108 and 5.0 kg active ingredient/ha, in dicotyledoneous weeds such as Amarantus retroflexus. Capsella bursa-pastoris. Chenooodium alba. Stellaria media. Senecio vulgaris and Galium anarine. and, especially, grassy weeds such as Aaropvron repens. Aarostis alba. Alopecurus 5 mvosuroides. Apera spica-venti. Avena fatua. Echinochloa crus-oalli. Bromus tectorum. Sorghum halepense. Diaitaria spp and Setaria spp. Additional tests indicate a favourable soil persistence of the compounds of the invention.
The compounds of the invention are relatively less toxic towards crops than towrads weeds. Selective herbiciaT activity is i.a. observed in corn (maize), soybean, cotton, sugar beet, potato, alfalfa, sunflower, rape, peanuts or flax, depending i.a. on the compound involved and on the application rate. The compounds of the invention 15 are therefore also indicated for use as selective herbicides in a crop locus.
The present invention therefore also provides a method of combatting weeds in a locus, preferably in a crop locus, particularly 20 2n a crop locus as mentioned above, which comprises applying to the locus a herbicidally effective amount (a selective herbicidally effective amount where the locus is a crop locus) of a compound of the invention. A particularly preferred and advantageous embodiment of the invention is the pre-emergence (both crops and weeds) use of a compound 25 of formula I in selectively combatting weeds in a crop locus.
For general herbicidal as well as for selective herbicidal use of compounds of the invention, the amount to be applied to attain the desired effect will vary depending on the particular crop if employed 35 for selective use and other standard variables such as the compound employed, mode of application, conditions of treatment and the like.
The appropriate application rates can be determined by routine procedures by those skilled in the art, or by comparing the activity of the compounds of the invention with standards.for which the application 5 S1 Ο 8 ' - 14 - rate is known, e.g. in greenhouse tests. However, in general, satisfactory resutls are usually obtained when the compound is applied at a rate in the range of from 0.1 to 5 kg/ha, preferably from 0.2 to 4 kg/ha, more preferably from 0.5 to 3.0 kg/ha, 5 the application being repeated as necessary. When used in a crop locus, the application rate should preferably not exceed 3 kg/ha.
The compounds of formula I may be and preferably are employed as herbicidal compositions in association with herbicidally acceptable diluent(s). Suitable formulations contain 0.01¾ to 89¾ by 10 weight of active ingredient, from 0 to 20¾ herbicidally acceptable surfactant and 1 to 99.99¾ solid or liquid diluent(s). Higher ratios of surfactant to active ingredient are sometimes desirable and are achieved by incorporation into the formulation or by tank mixing. Application forms of composition generally contain between 15 o.Ol and 25¾ by weight of active ingredient. Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Concentrate forms of composition intended to be diluted before use generally contain between 2 and 90¾. preferably between 10 and 2D 80S by weight of active ingredient.
Useful formulations of the compounds of the invention include dusts, granules, pellets, suspension concentrates, wettable powders, emulsifiable concentrates and the like. They are obtained by conventional manner, e.g. by mixing the compounds of the invention 25 with the diluent(s). More specifically liquid compositions are obtained by mixing the ingredients, fine solid compositions by blending and, usually grinding, suspensions by wet milling and granules and pellets by impregnating or coating (preformed) granular carriers with the active ingredient or by agglomeration techniques. - 15 - - 15 - 55108 Alternatively, the compounds of the invention may be used in microencapsulated form.
Herbicidally acceptable additives may be employed in the herbicidal compositions to improve the performance of the active 5 ingredient and to reduce foaming, caking and corrosion.
Surfactant as used herein means a herbicidally acceptable material which imparts emu!siflability, spreading, wetting, dispersibility or other surface-modifying properties. Examples of surfactants are sodium lignin sulphonate and lauryl sulphate.
Diluents as used herein mean a liquid or solid herbicidally acceptable material used to dilute a concentrated material to a usable or desirable strength. For dusts or granules it can be e.g. talc, kaolin or diatomaceous earth, for liquid concentrate forms, for example a hydrocarbon such as xylene or an alcohol such as 15 isopropanol, and for liquid application forms i.a. water or diesel • oil.
The compositions of this invention can also comprise other compounds having biological activity, e.g. compounds having similar or complementary herbicidal activity or compounds having antidotal, 20 fungicidal or insecticidal activity. - 16 - 55108 Specific Examples of herbicidal compositions will now be described. Parts are by weight.
EXAMPLE A : Wettable^Pgwder 25 Parts of a compound of formula I, e.g. Compound No. 25 5 hereinafter given, are mixed and milled with 25 parts of synthetic fine silica, 2 parts of sodium lauryl sulphate, 3 parts of sodium ligninsulphonate and 45 parts of finely divided kaolin until the mean particle size is about 5 micron. The resulting wettable powder is diluted with water before use to a spray liquor with the desired 10 concentration.
EXAMPLE B : Emuision_Concentrate 20 Parts of a compound of formula I, e.g. Compound No. 25 hereinafter given, 40 parts of xylene, 30 parts of dimethyl formamide and 10 parts of emulsifier (e.g. ATLOX 4851 B, a Trade Mark for a blend of 15 Ca alkylarylsulphonate and a polyethoxylated triglyceride of Atlas Chemie GmbH) are throughly mixed until a homogeneous solution is obtained. The resulting emulsion concentrate is diluted with water before use.
EXAMPLE C : Granules 20 5 Kg of a compound of formula I, e.g. Compound No. 25 herein after given, are dissolved in 25-^ methylene chloride. The solution is then added to 95 kg of granulated attapulgite (mesh size 24/48 mesh/ inch) and thoroughly mixed. The solvent is then evaporated off under reduced pressure.
The invention is further illustrated by the following Examples wherein temperatures are in °C, pressures are in Torr and Rf values are on silica gel, so far not otherwise indicated.
FINAL COMPOUNDS Example 1 30 N-I^^q-dinrieth^l; thi oxol an^-g-^lmg th.vl ^-chl oro- - 17 - - 17 - S 5 1 0 s To the well stirred mixture of 1.7 g (0.0063 mol) of N-(2,4-dimethyl -thien-3-yl)-N-(1,3-dioxolan -2-ylmathyl)-hydroxyacetamide, 58 mg of benzyl triethyl ammonium chloride, 7 ml of toluene and 7 ml of 302 NaOH are added dropwise without cooling 1.31 g (0.0069 mol) 5 of p-toluene sulfonyl chloride in 3.5 ml of toluene. After the exothermic reaction has subsided, stirring is continued for a further 20 hours at ambient temperature.
The toluene layer is then separated, washed with water and dried over anhydrous NagSO^.
The crude residue left on rotevaporation of the solvent is recrystallised from diethyl ether to give N-(2,4-dimethyl-thien-3-yl)-N-(l,3-dioxolan -2-ylmethyl)-tosyloxyacetamide ("tosylate") having a m.p. of 101-103° A stirred mixture of 2.16 g (0.0051 mol) of said tosylate, 1.84g B (0.0066 mol) of tetrabutylammonium chloride, 8 ml of water and 16 ml of toluene is heated at 90° over a period of 6 hours. The toluene layer is then separated, dried (HagSO^) and evaporated in vacuo.
The residue is chromatographed on a silica gel column.; Elution 20 viith hexane-ethyl acetate 2:1 affords the title compound as analytically pure crystals, having a m.p. of 76-78°.
Example 2 (process a) To a stirred solution of. 2.0 g (0.008 mol) of N-(2,4-dimethyl-25 thien-3-y1)-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) of mesyl chloride in 20 ml of dry CHgClg.
The resulting mixture containing DMAP-hydrochloride and the - 18 - - 18 - 55108 methanesulphonate of the starting compound is heated under reflux for 25 hours and then evaporated in vacuo.
The residual oil, after column chromatography on silica gel (elution with diethylether), solidified on chilling at -20°, m.p. 54-55°.
Example 3 : N;(chlorgacetYl};N;(2;carbomethgxy;4;methyl;tliien; Saifcsls" in§;ethyl§ster (process b) To a well stirred suspension of 1>5 g (0.05 mol) sodium hydride (80 % dispersion in mineral oil) in 250 ml of dry 1,2-10 dimethoxyethane (=DME) are added portionwise, 9.9 g (0.04 mol) of solid N-(2-carbomethoxy-4-methyl-thien-3iyl)-chloroacetamide.
After the addition is completed the resulting solution of the Na-salt is stirred an additional hour at 50°, then allowed to reach room temperature and treated with the solution of 7.25 g (0.04 mol) 15 of ethyl-2-bromopropionate in 50 ml of dry DME.
After a reaction period of 4 hours at 50°, the mixture is filtered and evaporated in vacuo (50°/0.01 Torr.). The residual brown oil, after chromatography on silica gel (elution with diethyl ether-hexane 2:1),is subjected to ball tube distillation, giving the 20 analytically pure.title compound, b.p. 135°/0.005 Torr.
Example 4 : {|;iIH;eycaz?l;l:il?ethyl];N;(2,4;dimfthyl;thien;3;yl)- (process b) To a well stirred mixture of 19.35 g (0.095 mol) of N-(2,4~di-methyl-thien-3-yl)-chloroacetamide, 4.15 g (0.01 mol) of benzyldi- -19 - methylhexadecyl-arnmonium chloride, 40 g (1 mol) of sodium hydroxide, 200 ml of methylene chloride and 40 ml of water are added 17 g (0.11 mol) of solid 1-chloromethyl pyrazolehydrochloride at such a rate, that the temperature does not rise above 25°.
When the addition is completed, the reaction mixture is stirred an additionar2^/2 hours at amhient temperature. Then 100 ml of water are added. The organic layer is separated, washed with three 200 ml portions of water, dried over Na2S0^ and evaporated to dryness. The residue is chromatographed on a silica gel column. Elution with hexane-diethylether 1:1 affords the title compound as an analytically pure syrup which crystallized on chilling overnight at -20°, m.p. 88-89° (recrystallized from diethyl ether).
Example 5 : N-(chloroacetvl 1-11-(3.5-dimethvl-isoxazoT-4-vl1-alanineethvlester (process b) 9.4 g (0.05 mol) of 11-(3,5-dimethyl-isoxazol-4-y1)-chloro-acetamide in 150 ml of dry acetonitrile (CH^CN) are added drop-wise to a well stirred suspension of 1.8 g (0.05 mol) of sodium hydride (80% dispersion in mineral oil) in 25 ml of dry CHgCN.
After the exothermic reaction (34°) has subsided the solution of the sodium salt is allowed to reach room temperature and then treated with the solution of 9.05 g (0.05 mol) of ethyl 2-bromo-propionate in 25 ml of dry ch3cn.
After the addition is completed the reaction mixture is heated at 50° for three hours and then evaporated to dryness. The residue, is taken up with 100 ml of diethyl ether and filtered. The residual oil left on evaporating the filtrate is chromatographed on a silica gel column. Elution with diethylether-hexane 1:1 affords the title compound, having a m.p. of 49-50°. - 20- - 20- 55108 Example 6 : ΝχtlrX!Ur!2Yr522ln!r^!^.ΟίίΐΥΐΙΙΐίίζί £bl2!T92£§i§!I!i^g (process c) To a stirred solution of 12.7 g (0.1 mol) of 2,4-dimethyl-3-araino-thiophene in 100 ml of dry benzene, which contains 16 g of o 5 molecular sieves (3A) and two drops of cone. HgSO^, are added dropwise 8.5 ml (0.15 mols) of acetaldehyde, taking care that the temperature does not rise above 25°.
When all the acetaldehyde has been introduced, the reaction mixture is stirred 24 hours longer at ambient temperature and is 10 then filtered. Removal of the solvent leaves the Schiff base os a light brown liquid.
To the stirred solution of 13 g (0.085 mols)of this material in 75 ml of dry toluene are added dropwise at -30° 9.7 g (0.085 mols) of chloroacetyl chloride.
When the addition is complete, the reaction solution is stirred for a further 30 minutes at -30° and then treated dropwise at the same temperature with 12 g (0.085 mols) of l-trimethylsilyl~ pyrazole. After the addition, the solid CO^/acetom; bath is removed, the mixture allowed to warm to ambient temperature and 2o left to stir for a further period of 20 hours.
The reaction mixture is then filtered and evaporated in vacuo.
The residual syrup is chromatographed on a silica gel column.
Elution with hexane/diethyl ether 3 : 2 affords colourless crystals of the title compound which, upon recrystallization from diethyl 25 ether have a melting point of 76-78°.
Example 7 : N;i2;roethQXi';2;meth^1;thien;3;^l];ij-[2-ethoxjfethYl]-ί1ΐΐ2ϊ2§9§ί§!!!Ϊ^§ (process d) To a well stirred mixture of 6,05 g (0.03 mol) H-(2-ethoxyethyl)-4-methoxy-2-methyl-thiophene-3-amine, 4.15 g (0.03 mol) of KgCO^, 5 10 ml of water and 100 ml of CH2C12 is added dropwise without cooling the solution of 3.4 g (0.03 mol) of chlcroacetyl chloride in 10 ml of CHjjClg. After the exothermic reaction (27°) has subsided, stirring is continued for a further hour at ambient temperature.
The methylene chloride layer is then separated, washed twice 10 with 100 ml of water, dried (Ka^SO^) and evaporated in vacuo. The residual crude title compound is analytically pure; RF= 0.23 (hexane-diethyl ether 1:2). A small portion of this material was subjected to ball tube distillation : b.p. »68-170° / 0.05 Torr.
The following compounds of formula I are obtained according to one or more of the procedures of the Examples 1 to 7, as indicated hereinbefore: (Me is CH^ and Et is CgHg) TABLE A (see next page). - 22 - 55108 Cmpd. No. Ar Y Characterization 1 4-Me-thien*3-yl CH?0C?H,. m.p. 25-26° 2 II CH2CH20CH3 Rf=0.45(cyclohexane/ ethyl acetate 1:1) 3 2-Me-thien-3-yl ch2ch2och3 Rf*0.3(cyclohexane/ ethylacetate 6:4) 4 2,4-diMe-thien-3-yl ch2-ch»ch2 5 II CH2C(CH3)»CH2 m.p. 85-86° 6 II CH2-C3CH m.p. 95-96° 7 8 tl II C(CH3)z-CSCH CH2C6H5 Πρ°*1.5479 9 II ch2cf3 m.p. 60-61° 10 II CH2-C(C1)*CH2 11 II CH2-C(Br)=CH2 m.p. 45-46° 12 II ch2-cooh m.p. 145-48° 13 n CHgCOOMe m.p. 48-49° 14 u CHgCOOEt njj0«1.5345 15 n CH2COOC3H7i b.p.H8-21°/0.005 Torr 16 It CH?-COOC(CH,),CsCH m.p. 77-79° 17 u ch(ch3)cooch3 ngO.i.5342 18 N ch{ch3)cooc3h7i n|°-1.5l92 19 N CH2C0N(CH3)2 m.p. 82-84° 20 N ch?conhc,h7i m.p.135-137° 21 N CH9CONHN*C(CH,)9 m.p. 141° 22 u CH2-(l-pyra2olyl) m.p. 88-89° 23 II CH(CH3)(l-pyrazoly1) m.p. 76-78e 24 M CHj,-{3,5-diMe*pyra- zol-1-yl) m.p.143-144° - 23 - S 5 1 Ο 8 Cmpd. No. Ar Y Characterization 25 2,4-diMe-thien-3-yl CH(CH3)-Q 25 n CH2-0J 27 u ch(ch3hI] m.p. 132-1339 28 II CHrd 29 IS CH(He)-T] Mef 0. 30 II CH,-N1 20^-S Q 31 II 32 II CH(Ke)-p 33 II CH2(2-furyl) m.p. 78-79° 34 It CHz-(2-thienyl) m.p. 57-59° 35 11 XU m.p. 66-67° 36 n 3-Me-i s oxazol-5-y1- ch2 m.p. 77-78° N-N 37 CH2-<0H-Et m.p. 54-56° 38 II CHjJtpT* - m.p. 71-72° 5 510 8 Cmpd. No. Ar - 24 - Y Characterization 39 2,4-diMe-thien-3-y1 N — N CHgAjJI-Me m.p. 110-15° 40 11 N-N CH2-iLNJ)-He H N-N m.p. 119-25° 41 II CH^jL SMe Me m.p. 120-22° 42 II "20 m.p. 68-70° 43 II CHzCH2OH m.p. 79-80 44 II CH20Et b.p. 11570.001 Torr 45 II CH20C3H7n n^*1.5280 46 II CH20C4Hgn b.p.ll0-n°/0.001 Torr 47 II CH(Me)OMe m.p. 48-50° 48 II CH(Et)0Me m.p. 55-57° 49 II CH2CH20Me m.p. 54-55° 50 II CH2CH20Et b.p.Π0°/0.01 Torr 51 II CH2CH20C3H7n Rf=0.36(diethylether/ hexane 1:1) 52 (1 CH(Me)CH20Me b.p. 148-150°/0.03 Torr 53 II C(Me)2CH20Me 54 II CH^O^ 55 It m.p. 76-78° Cmpd. No. Ar " Y Characterization 56 2,4-diMa=thi en-3-yl CH(He)0CH2CH2Cl m.p. 62-64° 57 « CH(0He)CH'20He Rf=0.3(diethylether/ hexane 1:1) 58 <3 CH,0CH,CH,0M8 b.p.117-1870.005 Torr 59 11 CH(He)0CH2CH2CN m.p.· 59-64° 60 (1 CH?QCH2-f{^j 61 u CH(He)0CH2-lfj 62 11 CH{Me)0-N=«CH-Me 63 u CH(He)0-N*C(He)2 64 n CH2-CH=NOHs Rf=0.31(hexane/ethyl-acetate 3:2) 65 n CH2-CH=N0Et Rf=0.23(hexane/ethyl-acetate 4:1) 66 It CH2-C(Me)=N0He m.p. 76-78° 67 IT CH2-C(Me)=>N0Et m.p. 57-59° 68 It CH(Hs)CH=N0Me m.p. 68-70° 69 n CH(Me)CH*N0Et Rf=0.4(hexane/ethy1--acetate 4:1) 70 H CH(Me)-N(Me)-COMe 71 2- Me-4-Et-thien- 3- yl CH(Me)CH20Me b.p. 142-4470.2 Torr 72 73 a a CHgOEt pyrazol-1-yl~CH? m.p. 49-50° m.p. 53-54° 74 2- Et-4-Me-thien- 3- yl CH20C2H5 Rf=0.47(dtethyl ether/ hexane 7:3) 75 11 CHCMe)CH20Me Rf=0.47(di ethyl ether/ hexane 7:3) .76 2,4-diEt-thien-3-y1 pyrazol-1-yl-CHz m.p’. 63-65° 77 u CH2-0Et n|®*t..5242 SS108 - 26 - Cmpd. NO. Ar Y Character!zation 79 2-_iC2Hj-4-Me-th1en- 80 4-0H-2-Me-thien- 3-yl CH(Me)CH20Me 81 2- Me-4-Me0-thien- 3- yi pyrazo1-1-y1-CH2 m.p. 90-92" 82 II CH2-0Et m.p. 24" 83 II CH2CH2-0Et b.p.168-170"/0.05 Torr 84 2- Me-4-Et0-thien- 3- yl pyrazo1-1-y1-CH2 85 2-Me-4-i-C,H7- thien-3-yi II 86 2- MeS0,-4-Me-thien- 3- yi 2 CHgOEt 87 2-Ke-4-0CH,-CH=CH?- thien-3-yf pyrazol*1-y1-CH2 88 2-Me-4-0CH2-C*CH thien-3-yr 1» 89 2-HeOCH2-4-HeO- thien-3-yl If 90 2- MeS-4-Me-thien- 3- yl It b. p.18070.001 Torr 91 » CHgOEt b. p.13570.001 Torr 92 II CHgCHjOHe b.p.148-150®/0.001 Torr 93 2- MeS{0)-4-Me-thien- 3- yl CH20Et m.p. 100" 94 2-MeC0-4-Me-thien- 3-yl CHgOEt m.p. 37-38" 95 2- MeC0-4-Et-thien- 3- yi pyrazo1-1-y1-CH2 96 2-MeC0-4,5-diMe- thien-3-yl pyrazo1-1-yl-GH2 97 2-MeC(=N0Me)-4-Me-thlen-3-yl CH,OEt syn : m.p. 89-91° c anti: m.p. 75-76" 5510 - 27 - Cinpd. No. Ar Y Characterization 98 2-MeC(=N0Me)-4-He- thien-3-yl pyrazoH-yl-CHg syn : m.p. 123° 99 2-MeC(0Et),-4-Me- thien-3-yr CHgOEt m.p. 46-47° 100 2- Me-4-O-C0Ma-thien- 3- yl CH(He)CH20Ke 101 2- C00Me-4-Me-thien- 3- yl ch2-csch m.p.l19-21° 102 M CH20Et m.p.20-22° 103 1« CH(Me)C00Et b.p.l35°/0.0Q5 Torr 104 2-iC3H7-4*C00Me- thien-3-yl pyrazol-1-yl-CH2 105 2-Et-4,5-diHe- thien-3-yl CHgOEt 0^=.1.5273 106 *» CH2C00C3H7i η|°=1.5Π2 107 U pypazol-l-yl-CH2 njj°=1.5509 108 2,4-diMe-5-C1- thien-3-yl CH20Et n|°-l.S412 109 «1 CH,0CH?CH,0CH, n*1 =1.5321 no tetrahydrofuryl-2-ch2 Rf*0.35(cyclohexane/ ethylacetate 7:3) 111 m pyrazol-1-yl-CH2 m.p. 68-73* 112 2,5-diSr-4-Me- thien-3-yl CHgOEt m.p. 75-77° 113 2-Me-4-HeQ-5-Br- thien-3-yl pyrazol-l-yl-CH2 m.p. 98-99° 114 2,4-diMe-5-CQOHe-thfen-3-yl CHgOEt b.p. 140/Ό.005 Torr 115 2,4- di He- furan- 3-yl CHgOEt Rf*0.5(dtethy1 ether) - 28- 55108 Cmpd. No. Ar Y Characterization 116 2,4-d1Me-furan-3-y1 CHgCHgOMe 117 1* CHg-CH’NOMe Π8 II CH2-C(He)*NOHe 119 U pyrazol-i-yi-cH 120 1,2,4-triMe-pyrrol- 3-yl CH2-0Et 121 N CH2CH2OHe 122 « pyrazoT-i-yi-CH2 123 •I CH2-C(Me)*CH2 124 2—COOE t-N,3,5-tri-Mepyrrol-4-yl pyrazo1-1-yl-CH2 n|4-l.5422 125 3,5-diMe-isoxazol- 4-yl CH(Me)COOEt m.p. 49-50® 126 II CH2CH2OHe 127 w CH20Et ra.p. 45-46* 128 tl pyrazo1-1-yl-C'H2 129 3,5-diEt-lsoxazol- 4-yl CH2-C(Ke)*CH2 T30 II ch2-c*ch b.p. 118®/0.001 Torr 131 H CH2-0Et [b.p. 107-108®/0.001 { 20 Torr |Πρ *1.4908 132 3,5-diMe-isothia- zol-4-yl CH20Et m.p. 43-45* 133 II CH2CH20Me 134 H pyrazol-i-yi-CH2 m.p. 109-14" 135 N CHgCSCH m.p. 109-12* 136 3-Me-5-EtO-pyra- zo1*4-y1 CHjCHjOHe m.p. 111-113* 137 1,3,5-triMe-pyra- zol-4-yl CHjOEt b.p.!30*/0.001 Torr 55108 - 29 - Cmpd. Ho. Ar Y Characterization 138 1,3,5-triMe-pyra- ΖθΙ-4-yl CHgCHgOHe m.p. 66-67° 139 tt CH2-OC3H7n b.p.135°/0.001 Torr 140 tt ch2-c*ch m.p. 115-117° 141 H pyrazol-l-yVCHg m.p. 96-97° 142 1-Me-3,5-di Et-pyra-zo1-4-yl CH2-0C3H7n n*°=»T.5008 143 It CH2CH2OMe b.p. 130°/0.001 Torr 144 l,3-diMe-5-EtO- pyrazol-4-yl CH20Et m.p. 54-56° -30 - 5 510 8 INTERMEDIATES Example 8 : Methyl_^S^direth^T^^amir.o^thioDhene^Z^carboxi;!ate A solution of 45.2 g (0.21 mol) methyl 3,5-dimethyl-4-nitro-thiophene-2-carboxylate in 1000 ml methanol is hydrogenated for two hours at 10 bar in the presence of 4.5.g palladium (10 % on carbon).
When the reduction is completed the mixture is filtered, the catalyst washed with methanol and the filtrate evaporated to dryness.
The crystalline residue is treated with diethyl ether, yielding the analytically pure title compound m.p. 88-89° Example 9 : ^^Dimethyl^aminothioghene To 890 ml (3 mol) of sodium bis(2-methoxyethoxy)aluminium 15 hydride (70¾ solution in toluene)and 6C0 ml of dry toluene is added,dropwise with vigorous stirring, a solution of 100 g (0.58 mol) of methyl 3-amino-4-methyUhiophene-2-carboxylate in 700 ml of dry toluene at such a rate that the temperature does not rise above 55°.
After the addition is completed stirring is continued for a 20 further 30 minutes and the reaction mixture then cautiously added in small portions at 0° to 1200 ml of 20¾ potassium hydroxide solution.
The toluene layer is separated, dried over MgSO^ and evaporated in vacuo. The residual brown liquid is distilled under 25 diminished pressure, affording the analytically pure title compound, b.p. 49-52° /0.01 Torr. -31 - -31 - 55108 Example 10 : J^'ethoxy^nethyl^amno^thioDhene The well stirred mixture of 55.4 g (0.2 mol) of benzyl N-(4-methoxy-2-methy1-thien-3-y1)carbamate, 40 g (0.7 mol) of KOH, 600 ml of ethanol and 120 ml of water is heated under reflux for two hours. 5 The resulting solution is then evaporated in vacuo and the residue diluted with 500 ml of water. The separating light yellow oil is taken up in 400 ml of diethyl ether and the aqueous phase extracted once with 400 ml of ether.
The combined ethereal solutions are dried (HagSO^) and 10 filtered. A slow current of dry hydrogen chloride is then passed through the filtrate for a period of 30 minutes, taking care - by intermittent colling in an ice bath - that the temperature does not rise above 10°.
The precipitated hydrochloride of the title compound has a 15 m.p. of 230° (the free base a m.p. of 61-63°).
Example 11 : 2;tjeth¥lthio-4;methyl;;3;aminothioghene 6 g (0.22 gram atoms) freshly prepared aluminium amalgam are added over a period of about two minutes to 18.9 g (0.1 mol) of 2-methylthio-4-methyl-3-nitrothiophene dissolved in 200 ml of 20 moist diethvlether. The vigorous reaction which sets in after 5-10 minutes is kept under control by cooling the flask in ice.
After 45 minutes, when the exothermic reaction has subsided and all the aluminium has reacted, another six grams of amalgamated aluminium are added. - 32 - 55108 The reaction mixture is then gently refluxed for 2 hours; during tin's period the formation of the thiophene amine is complete. The organic phase is decanted and the remainder washed with two 50 ml portions of di ethyl ether. The combined ethereal solutions are dried 5 (MgSO^) and evaporated in vacuo. The residual crude title compound is distilled under reduced pressure, having a boiling point of 79-3170.5 Torr.
Examp l_e_l_2 In the following table are listed compounds of formula IX that are obtained according to one or more of the procedures of 10 15 20 Examples 8 to Π. Ex. 12.1 l,3-di-CH,-5-0C9Hr-4-liH9pyre?.olo (Rf = 0.28 tetrahydro· . furane ; hexane 9:1) Ex. 12.2 3,5-di-CH3-4-NK2-isotiiiazo1e (m.p. 82-84°) Ex. 12.3 ^"Cp^-^-CKj-S-amincthiophene, fjf = o.25 (diethylethe: hexane 2:1) Ex. 12.4 4-n-butoxy-2-methy 1 - 3-ami no-tlii opiiene, m. p. 25°; (Rf - 0.25 (diethylether/hexane 2:1) Ex. 12.5 5-C?HgO-3-Ch'3-4-NH2"pyrazole m.p. 81-83° Ex. 12.6 S.S-di-CpHc-i-CH^-A-liHp-pyraxole b.p. 68-7070.001 c J c Torr Ex. 12.7 3,5-di-CpH,.-4-NHp-isoxazole Rf=0.39 (diethyl c b ά ether) Ex. 12.8 (3-KH2-4-Me-thien-2-yl)ethar.ono, m.p. 30-81° Ex. 12.9 (3-NH2-4-Et-thien-2-yl)ethanone, m.p. 68° Ex. 12.10 (3-NH2-4,5-oiMe-thien-2-yl)ethanone, m.p. 120-23° Ex. 12.11 Ex 12.12 Ex. 12.13 2-Et-4-Me-3-MK,-thiGphene, b.p. 74-7670.0! Torr ί on 2,4-diEt-3-NH.-thiophene, Rf - 0.24 (CiUCl,,) ηή =1-5511 C on L c u 2-Et-4,5-diMe-3-HH2-thiophene, n"=1.5581 25 - 33 - - 33 - SS108 Example 13 : ^acetox^anetamide To 12.7 g (0,1 mol) of 2,4-dimethyl-3-aminothioph5ne, 13.8 g (0.1 mol) of KgCOg, 20 ml of water and 150 ml of methylene chloride are added dropwise at ambient temperature 15 g (0.11 mol) of 5 acetoxyacetyl chloride.
After the exothermic reaction has subsided, stirring is continued for a further hour. Then the organic layer is evaporated, washed with water, dried (KgSO^) and evaporated in vacuo. The solid residue is treated with hexane affording the analytically pure title 10 compound, m.p. 110-112°.
Example 14 : N—h^drgxj(acsjan)lde Through a stirred solution of 15,9 g (0.07 mol) ofH-(2,4-di-methyl-thien-3-yl)-acetoxyacetamide in 300 ml of methanol is bubbled a gentle stream of ammonia gas for 30 minutes.
After the exothermic (40°) reaction (moderated by intermittent cooling in cold water) has subsided, stirring is continued for additional 30 minutes and the reaction solution then evaporated to dryness. The resulting solid is recrystallized from ethylacetate, giving the analytically pure title compound as colourless crystals, 20 m.p. 85-87°. - 34 . - 34 . 5 S1 Ο 8 Example 15 : M;i2;ethoxYeth^1};4;m2thgxY;2;meth^l;thioghsne;3;amine To 70 ml (0.245 mol) of sodium bis(2-niethoxyethoxy)aluminium hydride (70¾ solution in toluene) and 30 ml of dry toluene is added dropwise with stirring a solution of 9.4 g (0.041 mol) of 5 N-(4-methoxy-2-methyl-thien-3-yl)-ethoxyacetamide in 125 ml of dry toluene. After the exothermic reaction has subsided, stirring is continued for a further 90 minutes and the reaction solution then cautiously added in small portions at -10° to 100 ml of 20ϊ KOH solution.
The toluene layer is separated and the aqueous phase extracted twice with 100 ml of toluene. The combined toluene solutions are dried (NagSO^) and evaporated in vacuo. The residual light brown liquid is analytically pure, Rf = 0.32 (hexane-diethyl ether 1:2).
Example 16 : N^MethoxymethylJethyl3~2j,4-dimethyl;thioghene;3;amip.e 15 The solution of 6.4 g (0.05 mol) of 2,4-dimethyl-3-amino-thio-phene and 5.3 g (0.06 mol) of methoxyacetone in 100 ml of dry toluene is boiled under reflux until the theoretical amount of water has separated in the water trap (2½ hours). The toluene solution is then allowed to cool to ambient temperature and 20 evaporated in vacuo. The residual crude Schiff base is sufficiently pure for the next step. 9.2 g (0.04& mol) of this material are dissolved in 100 ml of dry toluene and added without cooling to a well stirred solution of 28 ml (0.098 mol) of sodium bis(2-methoxyethoxy)aluminium 25 hydride (70¾ solution in toluene) in 15 ml of dry toluene.
After the exothermic reaction (44°) has subsided, stirring is continued for a further 90 minutes and the brown reaction solution - 35 - 5 S 1 Ο 8 5 10 15 20 25 then cautiously added in small portions at -10° to 40 ml of 20 Hi KOH solution. The toluene layer is then separated, dried (Na2S0<) and evaporated in vacuo. The residual oil, after column chromatography on silica gel (elution with hexane-diethyl ether 3·.1) is distilled under diminshed pressure (ball tube), having a b.p. of 94-95°/ 0.01 Torr. Example 17; N-(5-Ethyl-l,3,4-oxadiazel-2-ylmethyl)-2,4-dimethyl-thiophene-3-amine The mixture of 12.7 g (0.1 mol) of 2,4-dimethyl-3-amino-thiophene, 14.6 g (0.1 mol) of 2-chloromethyl-5-ethyl-l,3,4-oxadiazole and 13.8 g (0.1 mol) of KjC03 in 150 ml of dry dimethylformamide (=DHF) is stirred for 20 hours at 80°. The reaction mixture is then cooled to ambient temperature poured into 400 ml of water and the water-DMF solution extracted with three 150 ml portions of diethyl ether. The combined ethereal extracts are dried over anhydrous Ma^SO^ and evaporated in vacuo. The residual brown oil is chromatographed on a silica gel column, elution with hexane/diethyl ether 1:1 affords the title compound as an analytically pure orange liquid, Rf=0.2 (ether-hexane 1:1). Example 18 : NTiS^dimethyVthien^yllglycine^hYdrazide 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 ml alcohol are stirred for 24 hours at room temperature. The mixture is evaporated in vacuo. After adding 150 ml water the residue is treated with 4 x 500 ml portions of ether. The ether phase is dried over NagSO^ and evaporated to dryness giving the analytically pure title compound, m.p. 68-70°C - 36 - 55108 Example 19 : N;(2,4;dimeth^1;thien;3;Yl};N;[4;rnethj;l-5-mercagto-]i?25:iEi§29];3;yl;meth^1};ainine A mixture of 15 g (0.075 mol) N-(2,4-dimethy1-thien-3-yl)glycine hydrazide and 5.5g (0.075 mol) methyl isothiocyanate in 100 ml ethanol 5 is refluxed for 4 hours. The reaction mixture is cooled to 6°C and the precipitate formed separated by filtration giving the pure compound, m.p. 184-87°C.
Example 20 : ^(Z^dinKthYVthien^yl^N^^methyl^methYlmercapto; triazgl-3-^T-niethYl j-amine 10 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-triazol-3-yl-methyl)-amine, 1.1g tri-ethyl-benzyl ammonium chloride in 100 ml toluene and 30 ml aqueous 50« sodium hydroxide solution are added 4.7g (0.037 mol) dimethyl-sulfate. The reaction mixture is stirred at room temperature for 5 15 hours, the organic layer is separated, washed with three 100 ml portions of water, dried over NagSO^ and evaporated to dryness. The residue is recrystallized twice from ether giving the pure title compound, m.p. 92-96°C.
Example 21 : N;i2I4;dim§thyl;thien;3;yl];N;i5;methyl;l ,3,4;thiadiazol; 20 ?;yl:methyl];amine To lOg (0.05 mol) N-(2,4-dimethyl-thien-3-yl)-glycine hydrazide in 175 ml methylene chloride is added dropwise 5.5g (0.05 mol) acetic acid anhydride. The mixture is stirred for 1 hour at 20°C and evaporated to dryness. The oily residue is dissolved in 150 ml 5 pyridine and 11.Ig (0.05 mol) phosphorous pentasulfide is added in small portions. During the course of the addition the temperature reached 48°C. The mixture is refluxed for two hours and stirred at room temperature for another 16 hours. After evaporation to dryness - 37 - - 37 - 53108 the residue is dissolved in methylene chloride and the solution treated successively with ice water, diluted cold sodium hydroxide solution and water, dried over Ka^SO^ and evaporated to dryness. Chromatography on a silica gel column afforded the pure compound as 5 an oil, Rf = 0.23 (ethylacetate/hexane 6:4).
Example 22: -Ί ,2^4-trlazol-3- ϊΙ;Κ=ίί!ϊ11§ϋ!Ϊ!3§ To a stirred solution of 2.2g (0.055 mol) NaOH in 125 ml methanol is added 5 g (0.05 mol) acetamidine hydrochloride. After TO 15 minutes 10 g (0.05 mol) N-(2,4-dimethyl-thien-3-yl)-glycine hydrazide is added and the mixture refluxed for 18 hours. After evaporation to dryness the residue is treated with methylene chloride and freed from insoluble by-products by filtration. Evaporation of the methylene chloride gives the title compound, m.p. 85-87°C.
Example 23: ^[Z^dimethyl-thien^Yl^Iydne^isogrogylidene; hydrazide 7g (0.035 mol) N-(2,4-dimathyl-thien-3-yl)-glycine hydrazide in 50 ml acetone is stirred at room temperature for 2 hours. The pure title compound which crystallized was obtained by filtration, m.p. 126-28°C.
Example 24 The following compounds of formula VII are obtained according to one or more of the preceding Examples 13 to 23: 55108 Ex. Ar - 33- Y Characteriza tion 24.1 2,4-di-CH3-thien-3-yl ch2ch2-och3 Rf=0.32( diethyl ether-hexane 3:1) 24.2 C?H,. Rf=0.23(di ethyl ether-hexane 1:1) 24.3 CH2XP Rf=0.38(diethyl ether-hexane 1:1.) 24.4 Rf=0.39 (dietiiyl ether-i;exane 2:1) 24 .5 2 -CH3S-4-CH3-thien-3-yl ch2ch2-och3 b.p.ssvo.ei Torr 24 .6 1,3,5-tri-CH3-py razol-4-y1 II b. p.92-947 0.01 Torr 24 .7 l-CH3-3,5-di-C?Hg- 11 Rf-0.38(acfetone- pyrazol-4-yl hexane 4:6) 24 .8 153,5-tri-CHo-pyrazol-4-yl C2H5 Rf=0.2(ethyl~ 0 aestate-CM,CH 2:1) 24 .9 3-CH3-5-0C2H5-pyrazol-4-yl CH2CH20CH3 Rf=0.25(ethyl- acetaie-CH,CH 9:1) 24.10 2,4-di-CHg-thi en-3-y1 CH2CH20C2H5 Rf"0.48(diethyl ether) 24.11 II CH2CH20C3H7-n Rf=0.57(diethyl ether) 24.12 II ch?cf3 np°=1.4786 24.13 2»4-di-C~H,.-thien-3-yl c. 0 CH2CH20CH3 Πρ°=1.5Ζ38 24.14 2-CH3-4-C2Hs-thien-3-yl CHCii3.CH20CH3 b.p. 98-1007 0.09 forr Ex. Ar Y Character!zati on 2/1.15 2-C2 H g-4-CR3-thien-3-yl /CH3 CH —CHgOCHj Rf-0.52 (ether-hexane 7:3) ch3 24.16 2,4-di -CHj-thien-3-yl ch2-c = CK? Rf=0.55( d.i ethyl ether-hexane 1:1) 24.17 U 24.18 II 24.19 . II Rf=0.15(CH2Cl2) 24.20 tl CH2C0K(CH,)2 η^°-·1.5579 24.21 11 CH2C00CH3 b.p. 82-87°/0.005 Torr Example 25 : K-(2-carboraethoxy~3,5-dimetb/l-thien-4-yl)-chloro-- acetamide §5108 To 12.25 g (0.056 trol) of methyl 3,5-diraethyl-4-aininothiophene-2-carboxylate, 9.1 g (0.066 mol) of K^CC^, 25 ml of water and 150 ml of methylene chloride are added without cooling 7.5 g (0.066 mol) of 15 chloroacetyl chloride.
After the exothermic reaction (36°) has subsided stirring is continued for a further hour. Then the organic layer is separated, washed with water and dried over anhydrous MagSO^,. After removal of the solvent the desired product is obtained as colourless crystals, 20 m.p. 157-58°. - 40 - 5S108 Example 26 : Niii^chlgro^S^dimethyl^thien^ylj^chloroacetamide To the stirred solution of 5.0g (0.0245 mol) of N-(2,4-dimethyl-thien-3-yl)-chloroacetamide in 50 ml of dry CHgClg are added dropwise at 0° 3.3g (0.0245 mol) of sulfuryl chloride.
When the addition is complete, the reaction mixture is allowed to warm to ambient temperature and stirred for a further period of 20 hours. Then the solvent is removed in vacuo and the crystalline residue triturated with hexane, yielding the analytically pure title compound, m.p. 166°, decomp.
Example 27 : N-C2~i 1 jtl^diethgxyJeth^l-^-njeth^l-thien^S-^lD^chlorc; acetamide 15 g (0.065 mol) of N-(2-acetyl-4-methyl-thien-3-yl)-chloro-acetamide are dissolved in the warm (50°) mixture of 60 g of dry ethyl alcohol, 60 g of triethyl orthoformate and 7 drops of concentrated 15 HC1.
Upon standing for 30 hours at room temperature the reaction mixture is evaporated in vacuo (50°/0.01 Torr) and the residual brown syrup chromatographed on a silica gel column. Elution with hexane-diethylether 2:1 affords the title compound as colourless 20 crystals, having a m.p. of 57-58°.
Example 28 : N;[2;il;methoxyiming}ethyl;4;methy];thien;3;yl];chloro; acetamide The solution of 1.5 g (0.0065 mol) of N-(2-acetyl-4-methyl-thien-3-yl)-chloroacetamide and 6.6 g (0.14 mol) of methoxyamine in 50 ml O of dry toluene, which contains 5 g of molecular sieves (3A) is refluxed for 7 hours.
The yellow reaction solution is then filtered and evaporated in vacuo. The resulting crude syn/anti isomer mixture is separated by chromatography with hexane-diethylether as the mobile phase. - 41 _ - 41 _ 55108 First are eluted 0.6g of the pure Isomer (syn isomer) with the m.p. of 101-102° (P.f=0.33, hexane-ether'1:1). Continued elution of the silica gel column affords the other analytically pure anti isomer (0.4 g) having a melting point of 87-89° (Rf=0.21).
Example 29 5 The following compounds of formula- III are obtained according to one or more of the Examples 25 to 28: Ex. Ar Characterization 29.1 2-C00CH3-4-CK3-thien-3-yl m.p. 118-119° 29.2 2-CHjS—4-CK3-thien-3-yl m.p. 105-106° 10 29.3 2,4-di-CH3-thien-3-yl m.p. 128-129° 29.4 3,5-di-CH3-isoxa7.ol-4-yl m.p. 96-98° 29.5 3 , 5-di CgHg-i soxazol-4-yl m.p.- 67-69° 29.6 4-CH3-thien-3-yl m.p. 93-96° 23.7 ?-CH3-4-C2K5-thien-3-yl m.p. 114° 15 29.8 2-CH3~4-0CH3-thien-3-yl m.p. 144-45° 29.9 254-di-CU3-f'uran-3-yl m.p. 95-97° 29.10 3,5-di-CH3-i?othiazol-4-yl m.p. 104-06° 29.11 S-CH^-S-OCgHg-pyrazol-4-yl m.p. 125-27° 29.12 2-COOC,H5-K53,5-tri-CH3- 20 pyrrol-4-yl m.p. 163-65° 29.13 2- CHg- thi en- 3-yl m.p. 105° 29.14 2,4-di-C2Hg-thien-3-y1 m.p. 145° 29.15 2-C0CH3-4-CH3-thien-3-yl m.p. 110° 29.15 2-CH3- 4-0C4Hgii- th i en-3-y 1 m.p. 129-30° 25 29.17 2-C2H5-4,5-diCH3-thien-3-yl m.p. 147-48° - 42 - 55108 Example 30 : N;(2,4;dimethylthien;3^1 ];N;!r.ethox^eth^1;hvdrox^-acetamlde 18.4 g (0.1 mol) of N-(2,4-dimethylthien-3-yl)-hydroxyacetamide in 50 ml of dry dimethylformamide (=DMF) are added dropwise to a well 5 stirred suspension of 3.0 g (0.1 mol) of sodium hydroxide (80* dispersion in mineral oil) in 50 ml of dry DMF.
After the exothermic reaction (50°) has subsided, the solution of the Na-salt is allowed to reach room temperature and then treated with the solution of 10.4 g (0.11 mol) of 2-chloroethyl-10 methylether in 20 ml of dry DMF. When the addition is completed, the resulting mixture is heated at 100" for 4 hours and then evaporated to dryness (40°/0.1 Torr).
The residue is taken up with 200 ml of diethyl ether, washed with 250 ml of water, dried (MgSO^) and filtered. The residual 15 oil left on evaporating the filtrate is chromatographed on a silica gel column. Elution with ether affords the desired product asan analytically pure viscous liquid (Rf=0.25/ether).
Example 31 Following the procedure of Example 30, the following compounds 20 of formula II, in which Ar is 2,4-dimethylthien-3-yl, are obtained.
Ex. V Charactcrization 31.1 CH,CK=N0CH, Rf=0.21 (hexane-ethyl- acetate 3:2) 31.2 CH,CH=N0C„H, Rf-0.25 (hexane-ethyl- acetate 3:2) 31.3 CKj,C=K0CH, in.p. 69-71° ch3 31.4 CH2-C=N0C2H5 ch3 Rf=0.27 (hexare-etnyl- acetate 3:2) 31.5 CHCH-iiOCH, Rf=0.31 (hexar.s-ethyl- t «5 CH3 acetate 3:2) 31.6 chch=noc2h5 Rf=0.3 (hexane-ethyl- acetate 3:2) 31.7 CIH°] Rf=0,Ϊ2 (hexane-ethyl-- acetate 3:2) Example 32 : K-(4-Methox.y- 2-methyl-thien~3-y'i lethoxyacetami di 55108 To 9.8 g (0.063 mol) 4-methoxy·· 2-methyl-3-ar>iino-thi opher.e, S.45 g (0.068 mol) (igCOg, 05 ml of water-and 100 nil of CHgClg is-. added without cooling the solution of 8.4 g (0.069 mol) of ethoxy-acetyl chloride in 20 ml of CH.^Clr,· 20 After the exothermic reaction (32°) has subsided, stirring is continued for a further hour. Then the organic layer is. separated, washed twice with 150 ml of water and dried over anhydrous ha,S0^.
The residue left on rotevaporation of the solvent is subjected to column chromatography on silica gel. Elution with hexane-diethyl-25 ether 1:1 affords the analytically pure title compound having a m.p. oF 40-41°. - 44 - - 44 - 55108 Example 33 Analogous to the procedure of Example 34, the following amides of formula ArNHCQYj are obtained.
Ex. Ar Y3 Characterization 33.1 2,4-di-CH3-thien-3-yl -CH2~0CH3 m.p.62-63° 5 33.2 tl -ch3 m.p.158-69° 33.3 tl m.p.140-42° 33.4 II Φ m.p.164-65° 33.5 1,3,5-tri-CH3-pyrazol-4-yl -ch2och3 m.p.85-87° 33.6 l-CH3-3,5-di-C2H5- It b.p.12070.001 Torr 10 33.7 pyrazol-4-yl 3-CH3-5-0C2H5- -CH90CH, m.p.128-30° 33.8 pyrazol-4-yl 2,4-di-CH3-thien-3-yl -CH20C2H5 m.p. 37-38° 33.9 <1 -CH20C3H7-n m.p. 43-45° 15 33.10 II CF3 m.p. 94-97° 33.11 2,4-di-C,,Hg-thien-3-yl -ch2och3 m.p. 48-49° Example 34 : Benzyl^N^methoxy^metlj^Khien^yljcarbamate 63.6 g (0.23 mol) of diphenylphosphoryl azide and 24.4 g (0.23 mol) of triethylamine are added all at once to the stirred 20 suspension of 36.5 g (0.21 mol) of 4-methoxy-2-methyl~thiophene-3-carboxylic acid in 300 ml of dry benzene.
The resulting mixture is refluxed for one hour and then treated with 25 g (0.23 mol) of benzyl alcohol. - 45 - - 45 - 5S108 After a reaction period of 3½ hours at 78° the reaction mixture is cooled to ambient temperature, diluted with diethyl ether (350 ml) and washed successively with 250 ml of 5¾ HC1, 250 ml of saturated NaHCOg solution and 200 ml of saturated ftaCl 5 solution. The crystalline residue left on rotevaporation of the dried (NagSO^) solvent is triturated with pentane, yielding the analytically pure title compound, m.p. 107-108°.
Example 35 Following the procedure of Example 34, employing the appropriate carboxylic acid, the following carbamate is obtained.
Ex. 35.1 Benzyl (N-2,4-di-CH3-furan-3-yl)carbamate, m.p. 103-5°.
Ex. 35.2 Benzyl (N-4-n-butoxy-2-methyT-thien-3-yl)carbamate, m.p. 83°.
Example 36 : 4;Methoxy^2-methyl;thioDhene;3;carboxyli^_acid The title compound is obtained by saponification (KOH) of the corresponding ethyl ester; m.p. 127°.
Example 37 15 Analogous to the procedure of Example 36 is obtained 4-n^butoxy-2-methyl-thiophene-3-carboxylic acid, m.p. 65-68°.
Example 38 : Ethyl_4;methox^2;methyl2thiophene;3-carboxylate. ml of 50¾ sodium hydroxide solution are added dropwise to a mixture of 18.6 g (0.1 mol) of ethyl 4-hydroxy-2-methyl-thiophene-20' 3-carboxylate, 10 ml (0.105 mol) of dimethyl sulphate and 2.3 g (0.01 mol) of benzyltriethyl ammonium chloride in 100 ml of CHgClg» at ambient temperature.
After about 15 minutes of reflux, the reaction mixture is worked up to give the title compound, Rf = 0.36 (diethyl etherthexane 25 2 : I)· -46 - -46 - 55X08 Example 39 : Methyl^S^dimethyl^nitrothioghen§;2;carboxylate To a well stirred, chilled (0°) solution of 51.4 g (0.3 mol) of methyl 3,5-dimethylthiophene-2-carboxylate in 200 ml of glacial 5 acetic acid are added dropwise over a period of 40 minutes, a mixture of 30 ml of fuming nitric acid (specific gravity = 1.5) and 120 ml of acetic anhydride. After the addition is completed the resulting brown solution is stirred a further two hours at 5° and then poured into 3000 ml of ice water.
The aqueous phase is extracted twice with 500 ml of diethyl ether. The ethereal extracts are washed with water and 3¾ sodium bicarbonate solution, dried (Na2S04) and evaporated in vacuo.
The residue is subjected to column chromatography on silica gel. Elution with hexane-diethyl ether (10:1) afforded the title 15 compound having a melting point of 87-88°.
Example 40 Analogous to the process of Example 39 but employing 1.3- dimethyl-5-ethoxypyrazole as starting material is obtained 1.3- dimethyl-5-ethoxy-4-nitropyrazole; Rf = 0.37 with diethylether on silica gel. 55108 - 47 - Hcrbicidal_Jk*sts Example 41 : W§°d.cont.roT_£_Pre;emerc:ence_tre3tinent Seed pots (7 cm diameter) are filled with a mixture of peat culture substrate and sand. The exposed surface of the peat 5 culture substrate and sand mixture is sprayed with a test liquid of a test compound (e.g. formulated in accordance with Example B) and seeds of Leoidium sativum, Agrostis alts, Avena saliva and Lolium perenne are sown in each pot, whereby the Avene saliva and l.olium perenne seeds are, after sowing covered with a thin layer 10 (0.5 cm) of peat culture substrate/sand mixture. The pots are kept for 21 days at room temperature with 14 to 17 hours light .(day!ioh or its equivalent) per day.
Determination of the herbicidal effect of the particular herbicide is made after the 21 day period. The determination 15 involves a visual evaluation of the degree ar.d quality of damage to the various seed plants. -48 - -48 - 5 510 8 The compounds of formula I are applied in the above manner at dosages equivalent to 1.4 and 5.6 kg of active agent/hectare.
Herbicide! activity, that is to say, significant damage to the test plants is observed.
Example 42 : W9ed_control_^_Post;e08rgence_treatent A procedure similar to that employed in Example 41 is followed with the exception that the test compounds (herbicides) are applied when the plants are at the 2-4 leaf stage, the sowing of the plant seeds being staggered to ensure that the plants reach the 2-4 leaf 10 stage at about the same time.
Again the compounds of formula I are applied in the above manner at dosages corresponding to 1.4 kg/ha and 5.6 kg/ha. The determination of the herbicide! effect is made 21 days after application of the test compounds and involves an 15 analogous evaluation as described in Example 41. Kerbicidal activity is observed.
Example 43 Representative compounds of the invention are evaluated ir, the following pre-emergence test procedure.
Seed dishes measuring 30 x 40 cm are filled to a depth of 6 cm 20 with a mixture of peat culture substrate and sand. The exposed surface of the peat culture substrate and sand mixture is sprayed with an aqueous test liquid (e.g. formulated in accordance with Example B) comprising a compound of the invention in a given concentration. The spray volume corresponds to 600-(/ aqueous test liquid/ha. The same 25 test is repeated with various concentrations of test liquid, whereby the concentrations are selected in such a manner that the desired application rates are realized. Six species of seed are then sown-in each dish. The numoer of seeds sown for each plant species depends on the seed germination potential and also the initial growth size of the particular seed plant. After sowing of the seeds, the 5 treated surface is covered with a thin layer about 0.5 cm deep of the peat culture substrate and sand mixture.
The prepared seed dishes are kept for 28 days at a temperature of 20 to 24°C and 14 to 17 hours light each day.
Determination of the herbicidal effect of the particular 10 compound of the invention is made after the 28 day period. The determination involves a visual evaluation of the degree and quality of damage to the various plants. Particular advantageous herbicidal properties are i.a. observed with the Compound Nos. , 25, 47, 48, 55, 75, 84 and 85 of Table A. Some of the results 15 obtained with an application rate corresponding to 1 kg active ingredient/hectare are summarised in the following Table B.
Example 44 : Post-ercergence^Treatment A further evaluation of representative compounds of the formula I is effected in a post-emergence test procedure similar to that of the 20 pre-emergence test described in Example 43, except that the herbicide test liquid is applied when the plants are at a 2 - 4 leaf stage. For that purpose the various plants species are sown in time-staggered relationship. The greenhouse conditions (temperature, light) are as in Example 43. Determination of the herbicidal effect is also effected Z> 28 days after application according to the method of Example 41.
Particular advantageous herbicidal properties are i.a. observed with the Compound Nos. 25, 25, 47, 48, 55, 75, 84 and 86 of Table A. Some of the results obtained with application rates corresponding to 5 kg active ingredient/hectare are summarised in the following 30 Table C. - 50 - 55108 TABU·; H Pre-omt rcjencc applies t i or 1 kg/ha Compound Tested - ΐ damage Plant treated 25 26 47 48 55 75 84 85 Amarsn. retrofl. SO 90 100 100 100 100 80 SO Capssila b.p. 80 100 100 80 90 70 70 90 Chenop. alb. 80 80 90 50 20 50 60 60 Galium aparine 80 10 50 0 10 10 50 10 Sanenlo vulg. 90 80 80 80 80 100 90 ICO Stellaria media 90 70 70 80 50 50 70 90 Λ1 fcilfa 80 60 60 50 80 10 70 90 Usan 0 0 20 20 0 0 10 10 Carrot 80 90 SO 90 70 100 80 90 Cotton 20 0 10 0 0 0 20 0 Flax 80 30 60 50 30 0 20 10 Potato 0 10 10 0 0 0 o 0 Soya 50 10 30 30 0 10 30 30 Sugar beet 50 10 10 0 0 0 20 30 Rape 10 0 20 0 0 0 20 10 Sunflower 0 10 30 50 0 0 o f 10 Agropyron repens 90 100 90 60 80 90 90 70 Agrostis alba 100 100 100 100 100 100 100 100 Alopec. mvos. 90 90 80 20 50 80 80 90 Apera sp.venti. Ϊ00 100 100 100 100 100 100 100 Avena fatua 80 80 80 40 80 90 50 90 Eehinochloa c.g. 90 100 90 90 90 100 90 SO Corn 20 30 50 30 0 50 90 60 Wheat 70 100 SO 90 0 100 60 70 - 51 - 55108 TABLE C Post-emergence application 5 kg/ha ^ _____Compound___ Tc ϋ l ed __ ~_% darn a c.e treated. 25 26 47 48 55* 75 84 CO σ'. H j— Ama ran.retrof1. 90 80 70 50 80 60 80 90 Ccipsella b.p. 80 60 20 20 80 50 80 60 Ctienon. alb. 90 40 40 20 20 40 30 60 Galium aparine 80 60 40 30 80 20 70 60 Oenecio vulg. 80 50 70 80 SO 90 80 90 Stellaria media 90 50 60 10 30 40 60 40 Alfalfa 80 60 20 10 50 20 70 70 Bean 100 20 30 2C 20 30 30 50 Carrot 70 so 30 100 80 100 100 1 80 1 Cotton 70 60 50 40 50 60 70 ( 1 70 IM AX 80 7U 90 100 80 90 40 Γ l 80 Potato 70 30 20 10 10 to 40 10 Soya 90 30 30 30 20 30 30 ! 1 50 Sugar beet 30 20 70 0 10 10 0 10 Rape 40 20 10 10 30 60 50 i ! 40 Sunflower 60 50 30 80 40 .60 90 1 I 50 Agropyron repena 70 3° 70 50 50 50 30 50 Agrostis alba - - - - - - - - Alopec. mycs. 80 90 80 70 60 90 80 90 Apera sp.venti. 90 100 100 100 100 100 90 90 Avena fatua 90 100 90 80 90 100 100 100 Echiriochloa c. q. 1) 80 60 80 80 90 70 80 90 2) 90 80 80 90 100 80 SO 100 Corn 80 60 100 90 30 30 70 80 Wheat 70 90 80 50 10 60 6Q 80 Rice 2) 40 30 10 50 30 30 30 40 * 4 kg/ha 1) upland conditions; 2) paddy conditions - 5? - 55108 Field Test Compound No. 25 has further been evaluated in a pre-emergence Multicrop-Fieldscreening under the following conditions: - Crops Soybean('Steele1)- (So) Cotton (‘Stonevilie 213') - (Cot) Corn (LG 11) - (Co) Wheat (Svenno) - (Wh) - Weeds Alopecurus pratensis - (Al) Echinochlca crus gal 1i - (Ech) Galium aparine ~j 10 di cots flienopediiwi album and polyspeni.u; Amaranthus rctroflexus (All the weeds, except for Alcpecurus pratensis which was sown, were naturally occurring).
ID - Spray volume - Replicates : - Evaluation : - Standards : 750 lt/ha 20 28 days after application A1 a ch 1 o r (=a- ch 1 o ro - 2', 6' - a i c t by 1 - N- me t!i o xy me thy 1 -acetanilide) and Metolachlor t=-a-chloro-2,-ethyl-6‘-methyl -N- (1 -methyl -2-mc-thoxyethyl )acetani Tide]. The following herbicidal activity was observed: Compound kg/ha So Cot Co lih_Al/Fch Dicots No. 25 25 Alachlor Metolachlor 0.6 0 0 10 63 92 43 1.25 3 3 53 80 100 67 2.5 5 7 80 92 100 87 1.25 0 0 0 10 43 43 2.5 0 3 0 53 78 57 1.25 0 0 0 33 100 30 2.5 0 0 0 73 100 43 S 5 1 0 8 - 53 - The above results indicate an herbicidal activity which is equal or superior to that found with commercially available standards against monocotyledonous weeds, and is superior to that of such standards against dicotyledonous weeds. The herbicidal 5 activity is selective in soybean, cotton and at the lowest application rate also in corn.

Claims (5)

1. 55. S 5 1 Ο 8 5-oxo- and/or bi cyclic benz[cl fused derivatives of such 2-oxo-l-pyrrolidinyl group or 1s a group A-O-R3, wherein Rj is H, hydrocarbon selected from the group 5 consisting of C^8alkyl, C3_8alkenyl, C3_3* ally'nyl, C3_8cyc1oa1kyl, C^gCycloalkenyl or ('3-8cyc^oa^,clf^"ci Ralkyl, whereby the hydrocarbon , , ,1 3 , ,, as hereinbefore defined; is unsubstituted or substitutedj or a group 10 15 20 wherein is hydrocarbon selected from C|_g-alkyl, C^alkenyl, C3_ga1kynyl, C3_8cycloalkyl, C5_8cycloalkenyl, Cj-gCycloalky1-C^ _5al kyl, whereby the hydrocarbon is unsubstituted or substituted by halogen selected from F, Cl or Br; or is allenyl, R^' is H or has one of the meanings defined for R^ and A is a hydrocarbon moiely^unsiSsff^ufe^oi'HluDsti-tuted by C^galkoxy, which may be linked with R3 to form a saturated oxygen containing heterocyclic ring comprising 1 or 2 oxygen as heteroatoms ,and whereby the N and 0 atoms to which it is bound are separated by up to 3 C-atoms; 55108 . 56- group CH - C * N0R4, r5 v R4 1$ as defined above, Rg are independently H or CH3 or Rg together with Rg' is (CH2)3 or (CH2)4 group CH-N(CH3)C0CH3 *6 Rg is H or Cj_3alkyl. or Is a wherein Rg and 5 or is a wherein
2. A compound according to Claim 1, wherein Ar is at least substituted in o-position with respect to the chloroacetamide group by a substituent selected from the group consisting of halogen selected from F, Cl 10 and Br; C^^alkyl unsubstituted or substituted by halogen selected from F, Cl ®ndBr, C^alkoxy or C3_gCycloalkyl; C2_4alkenyl unsubstituted or substituted by Cj^alkoxy; C3_gCycloalkyl; formyl or C24alkanoy1; CHOC^alkylK^alkyl; CiOC^lkyl^-C^alkyl; CH(0C1_4alkyl)2; C14alkyl-S; C1_4alkyl-S0; C1_4alkyl-S02; C^alkoxy-carbonyl; C^- 15 alkoxy unsubstituted or substituted by halogen or C^alkoxy; C2_4- alkenyloxy; C, .alkynyloxy; HO and CH,OH and esters thereof (as hereinbefore defined). c
3. A compound according to Claim 2, wherein Ar contains either one ring heteroatom or two adjacent ring heteroatoms, whereby the heteroaromatic ring is at least disubstituted in o,o‘-position with respect 20 to the chloroacetamide group by substituents selected from the group as defined in Claim 2, any optional additional substituent of said heteroaromatic ring being selected from Chalky!, F, Cl, Br and Cj_4-alkoxycarbonyl.
4. A compound according to Claim 3, wherein Ar is a substituted 30 thiophene, isothiazole or isoxazole ring. - 57 - 5. A compound according to Claim 4, wherein Ar is a substituted thiophene or isoxazole ring. β. A compound according to Claim 5, wherein Ar is substituted thiophene. 5 7. A compound according to Claim 6, wherein Ar is 3-thienyl 2,4-disubstituted by substituents selected from C^alkyl and C^^lkoxy. S. A compound according to any one of Claims 1 to 7 wherein Y is a group R2-Az or a group A-0R3 (R2, Az, A and R3 being as 10 defined in Claim 1). 9. A compound according to Claim 8, wherein Y is R2-Az. 10. A compound according to Claim 9, wherein R2 is CH2 or CH(CH3). 11. A compound according to Claim 10, wherein R2 is CH2· 12. A compound according to any one of Claims 9 to 11, wherein Az 15 is a 5-membered heteroring linked by a C-atom of said ring to R2 and having 1 to 3 heteroatoms selected from the group consisting of 0, 5 and N, such heteroring^Seing optionally substituted by one or two substituents of the group Chalky!, C-^alkylthio or C-^alkoxy. 13. A compound according to any one of Claims 9 to 11 wherein Az is 20 1-pyrazolylor 3,5-diCH3-l-pyrazolyl. 14. The compound according to Claim 13, wherein Ar is 2,4-dimethyl-thien-3-yl and Y is pyrazol-1-yl-methyl. 15. The compound according to Claim 13, wherein Ar is 2-methyl-4-methoxy-thien-3-yl and Y is pyrazo1-1-yl-methyl . 15. The compound according to Claim 13, wherein Ar is 2-methyl-4-ethoxy-thien-3-yl and Y is pyrazol-1-yl-methyl. 25 5 510 8 -58- 17. A compound according to Claim 8 wherein Y is a group A-ORg. 18. A compound according to Claim 17 wherein A is CH,,, CH(CH3), Ct^-C^ or CHiCH-jJ-Ct^, unsubstituted or mono-substituted by C^galkoxy. 19. A compound according to Claim 18 wherein A is CHg, CH(CH3), 5 CH2-CH2 or CH(CH3)-CH2. 20. A compound according to Claim 19, wherein R3 is C^alkyl. 21. The compound according to Claim 20, wherein Ar is 2,4-dimethyl-thien-3-yl and Y is CHgOCgHg. 22. The compound according to Claim 20, wherein Ar is 2,4-dimethyl-10 thien-3-yl and Y is CHg-OC^H^n. 23. The compound according to Claim 20, wherein Ar is 2,4-dimethyl-thien-3-yl and Y is CH{CH3)CH2OCH3- 24. The compound according to Claim 20, wherein Ar is 2-methyl-4-ethyl-thien-3-yl and Y is CHgOCgHg. 25. The compound according to Claim 20, wherein Ar is 2-methyl-4- methoxy-thien-3-yl and Y is CHgCHgOCgHg. 26. Processes for the production of a compound of formula I stated in Claim 1, comprising·.....- ---- -59- 55108 a) substituting in a compound of formula II -COCH-OH ; ftr-2 Π wherein Ar and Y are as defined above, the HO group Of the N-hydroxyacetyl group by Cl, b) reacting a compound of formula III Ar-NH-C0CH2C1 III 5 wherein Ar is as defined above, with a compound of formula IV LY IV wherein Y is as defined above, and L is a leaving group capable of being split off under the K-alkylation reaction conditions. 10 c) obtaining a compound of formula la Ar - N la ^CO-CHgCl '"CH - Y, I 6 R' wherein R' is H or Chalky!, Yz is Az\ 0R3,N(CH3)C0CH3 and Az'is a di- or triazole linked by one of its nitrogen atoms to CHR1 15 and Ar and Rg are as defined above, by reacting a compound of formula V Ar ,C0-CH,C1 < 2 CH - Cl R' wherein Ar and R’ are as defined above V -60- 55108 with a reactive derivative of a compound of formula VI HY, 2 VI wherein Y^ is as defined above, d) N-acylation of a compound of formula VII VII Ar - NH - Y wherein Ar and Y are as defined above, 5 with chloroacetyl chloride, or a reactive functional derivative thereof. 27. A compound as stated in Claim 1, whenever obtained by a process claimed in Claim 26. 28. A herbicidal composition comprising a compound of any one of 10 Claims 1 to 25 and 27 in association with an herbicidally acceptable diluent. 29. A composition according to Claim 28 substantially as described herein. 30. A method of combatting weeds in a locus, which comprises 15 applying to the locus a herbicidally effective amount of a compound according to any one of Claims 1 to 25 and 27. 31. A method of combatting weeds in a crop locus, which comprises applying to the crop locus a selective herbicidally effective amount of a compound according to any one of Claims 1 to 25 and 27. 20 32. A method according to Claim 31, wherein the crop locus is a sugar beet, cotton, soybean, corn, peanuts or rape locus. Dated this 8th day of February 1983, BY: TOMKINS & CO.
5. , Dartmouth Road, DUBLIN 6
IE247/83A 1982-02-09 1983-02-08 Herbicidal chloroacetamides IE55108B1 (en)

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PL140272B1 (en) 1987-04-30
ES8503641A1 (en) 1985-03-01
DK171559B1 (en) 1997-01-13
DK53583A (en) 1983-08-10
IT1163085B (en) 1987-04-08
ES519588A0 (en) 1985-03-01
DK53583D0 (en) 1983-02-08
NL350007I2 (en) 2003-01-06
FR2523967A1 (en) 1983-09-30
DE3303388C2 (en) 1994-11-17
CZ86783A3 (en) 1993-01-13
SK277784B6 (en) 1995-01-05
IL67852A (en) 1986-07-31
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