CA2025939C - Carboxamides of isoxazole- and isothiazole-carboxylic acids - Google Patents

Carboxamides of isoxazole- and isothiazole-carboxylic acids Download PDF

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CA2025939C
CA2025939C CA002025939A CA2025939A CA2025939C CA 2025939 C CA2025939 C CA 2025939C CA 002025939 A CA002025939 A CA 002025939A CA 2025939 A CA2025939 A CA 2025939A CA 2025939 C CA2025939 C CA 2025939C
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alkyl
alkoxy
halogen
partially
substituted
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CA2025939A1 (en
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Volker Maywald
Wolfgang Freund
Gerhard Hamprecht
Thomas Kuekenhoehner
Peter Plath
Bruno Wuerzer
Karl-Otto Westphalen
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BASF SE
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BASF SE
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Priority claimed from DE19893933898 external-priority patent/DE3933898A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D261/12—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D261/18—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Carboxamides Ia, Ib, Ic and Id (X = 0, S; R1 = H, halogen, substituted or unsubstituted alkyl, substi-tuted or unsubstituted benzyl, alkoxy, alkylthio, haloalkoxy, haloalkyl-thio, substituted or unsubstituted phenyl, substituted or unsubstituted phenoxy or phenylthio, a substituted or unsubstituted 5- or 6-membered heterocyclic radical containing one or two heteroatoms, cycloalkyl-substituted alkyl, substituted or unsubstituted alkenyl which may be epoxidized, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl or cycloalkenyl; R1' - cycloalkyl-substituted alkyl, substituted or unsubstituted alkenyl which may be epoxidized, substituted or unsubstituted cycloalkenyl; R2 = CHO, 4,5-dihydrooxazol-2-yl, COYR5, CONR6R7; Y = 0, S; R5 = H, substituted or unsubstituted alkyl, cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsub-stituted cycloalkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted phenyl, a 5- or 6-membered heterocyclic radical contain-ing up to 3 heteroatoms, benzotriazole, N-phthalimido, tetrahydrophthal-imido, succinimido, maleiimido, 2,2-dimethyl-1,3-dioxolan-4-ylmethyl, 1,3-dioxolan-2-on-4-ylmethyl, and when Y = 0: one equivalent of a cation from the group of the alkali or alkaline earth metals, Mn, Cu, Fe, ammonium and substituted ammonium, a radical -N=CR8R9 or -W-Z; R8, R9 = H, substituted or unsubstituted alkyl, substituted or unsubstituted halo-alkyl, cycloalkyl, alkoxy, furanyl, substituted or unsubstituted phenyl;
R8+R9 = 4-7-membered methylene chain; W = alkylene chain, ethoxyethylene chain, butylene, butynylene chain; Z = a molecular moiety bonded to W in the .omega.-position and is the same as that linked to W in the .alpha.-position of W;
R6=H, alkyl, cycloalkyl; R7=H; alkyl; -C(0-alkyl)=N-H or -C(0-alkyl)=N-alkyl; R6+R7 = 4-5-membered methylene chain; R3 = H, substituted or unsub-stituted alkyl, substituted or unsubstituted cycloalkyl; R4 = H, OH, alkoxy, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsub-stituted alkynyl, di-(C1-C4)-alkylamino, a substituted or unsubstituted 5-or 6-membered heterocyclic radical containing one or two heteroatoms, sub-stituted or unsubstituted phenyl, substituted or unsubstituted naphthyl;
R3+R4 = 4-7-membered methylene chain which may be interrupted by 0, S or N-CH3, or -(CH2) 3-CO-) and their environmentally tolerated salts.
40 The compounds Ia to Id are suitable as herbicides.

Description

CARBOXAMIDES OF ISOXAZOLE- AND ISOTHIAZOLE-CARBOXYLIC ACIDS
The present invention relates to carboxamides of the formulae Ia, Ib, Ic or Id R4 R4 j4 3 R1 CO-N-R3 R1~ R2 I I I ( 3 ~ ~

N~ 1 I
R 1 N~
R

Ia Ib Ic Id where X is oxygen or sulfur;
R1 is - hydrogen, halogen, C1-C6-alkyl which may carry from one to five halogen atoms and/or a cyano radical and/or up to two of the following radi-cals : C'1-C4-alkoxy, partially or fully halo-genated C1-C4-alkoxy, C1-C,-alkylthio or parti-ally or fully halogenated C1-C,-alkylthio;
- C1-C4-alkoxy or C1-C4-alkylthio, partially or fully halogenated C1-C4-alkoxy, partially or fully halogenated C1-C,-alkylthio;
- benzyl which may be monosubstituted, disubsti-tuted or trisubstituted by C1-C4-alkyl, partially or fully halogenated C1-C,-alkyl, C1-C~-alkoxy, partially or fully halogenated C1-C~-alkoxy, C1-C~-alkylthio, partially or fully halogenated C1-C"-alkylthio, halogen, cyano or vitro;
- phenyl which may also carry from one to three of the following radicals: cyano, vitro, halogen, C1-C6-alkyl, partially or fully halo-genated C1-Ce-alkyl, C1-CB-alkoxy, partially or fully halogenated C1-Ce-alkoxy, C1-C6-alkylthio and/or partially or fully halogenated C1-Cs-alkylthio;
2 0 2 5 9 3 g 2 O. Z . 0050/41111 - phenoxy or phenylthio, each of which may be monosubstituted, disubstituted or trisubsti-tuted by C1-C,-alkyl, partially or fully halo-genated C1-C,-alkyl, C1-C4-alkoxy, partially or fully halogenated C1-C4-alkoxy, C1-C4-alkylthio, partially or fully halogenated C1-C4-alkylthio, halogen, cyano or vitro;
- a 5- to 6-membered saturated or aromatic heterocyclic radical containing one or two heteroatoms selected from the group comprising oxygen, sulfur and nitrogen which may carry one or two of the following substituentss halogen, C1-C3-alkyl, C1-C3-alkoxy and C1-C3-alkoxy-carbonyl;
- C3-CB-cycloalkyl-substituted C1-Ce-alkyl;
- C2-Ce-alkenyl whose double bond may be epoxidized, or CZ-CB-alkynyl, it being possible for both groups to be monosubstituted, disub-stituted or trisubstituted by halogen, C1-C3-alkoxy and/or monosubstituted by cyclopropyl or phenyl, it also being possible for the phenyl radical to carry up to three of the following substituentss halogen, cyano, vitro, C1-C,-alkyl, which may be unsubstituted or partially or fully halogenated, C1-C,-alkoxy or C1-C,-alkylthio, both of which may be unsubstituted or partially or fully halogenated;
- C3-C8-cycloalkyl or C3-CB-cyeloalkenyl, it being possible for both groups. to be monosubstituted, disubstituted or trisubstituted by Cl-C,-alkyl or halogen;
R1' is - C3-Ce-cycloalkyl-substituted Cl-CB-alkyl; _.
- 3 - O.Z. 0050/41111 - C22C°-~~enyl whose double bond may be epoxidized, or CZ-C6-alkynyl, it being possible for both groups to be monosubstituted, disub-stituted or trisubstituted by halogen, C1-C3-alkoxy and/or monosubstituted by cyclopropyl or phenyl, it also being possible for the phenyl radical to carry up to three of the following substituents: halogen, cyano, nitro, C1-C,-alkyl, which may be unsubstituted or partially or fully halogenated, C1-C4-alkoxy or C1-C4-alkylthio, both of which may be unsubstituted or partially or fully halogenated;
- C3-C6-cycloalkenyl, which may be monosub-stituted, disubstituted or trisubstituted by halogen or C1-C~-alkyl;
RZ is - formyl, 4,5-dihydrooxazol-2-yl, - COYRS or CONReR', where Y is oxygen or sulfur;
R5 is - hydrogen;
- C1-Ce-alkyl which may carry from one to five halogen atoms and/or up to three hydroxyl and/or C1-C,-alkoxy groups and/or one of the following radicals:
cyano, - C1-C,-alkoxy-CZ-C,-alkoxy, - C1-C3-alkylthio, .
- C1-C3-alkylamino, di ( C~-C3 ) -alkyl-amino, C3-Ce-cycloalkylamino or di ( C3-Cs ) -cycloalkylamino-, - trimethylsilyl, - C1-C3-alkylsulfinyl or C1-C3-alkyl-sulfonyl, - carboxyl, C1-C3-alkoxycarbonyl, _ 2025939 - 4 - O.Z. 0050/41111 C1-C3-alkoxycarbonyl-C1-C3-alkoxy or C1-C3-alkoxycarbonyl-C1-C3-alkoxy-C1-C3-alkoxycarbonyl, - di ( C1-C3 ) -alkylaminocarbonyl, - di ( C1-C3 ) -alkoxyphosphonyl, - C1-CB-alkaneiminoxy or CS-CB-cyclo-alkaneiminoxy, - N-phthalimido, N-succinimido, benzyloxy, benzoyl, it being possible for these cyclic radicals to additionally carry from one to three of the following groups:
halogen, C1-C3-alkyl or C1-C3-alkoxy, - a 5- or 6-membered saturated heterocyclic radical or a 5- or 6-membered heteroaromatic radical, each of which has up to three heteroatoms selected from the group comprising oxygen, sulfur and nitrogen, where two oxygen and/or sulfur atoms must not be directly adjacent and where the heterocyclic rings may also carry one or two of the following substituents:
halogen, C1-C3-alkyl, CI-C3-alkoxy or C1-C3-alkoxycarbonyl ;
- phenyl, which may also carry up to three of the following substitu-ents s halogen, nitro, cyano, C1-C3-alkyl, partially or fully halo-genated C1-C3-alkyl, C1-C3-alkoxy or partially or fully halogenated C1-C3-a~lkoxy;
- -CRl°=N-Rll, where Ri° is hydrogen or C1-Ca-alkyl and Rll is Ci-Cs-alkoxy, C3-Ca-alkenyloxy orvC3-Cs-alkynyloxy,- each of which may carry up to 3 halogen atoms and/or a phenyl radical with or without up to three of the following radicals: halogen, vitro, cyano, C1-C3-alkyl or C1-C3-alkoxy; phenoxy, which may also carry up to three of the following substituents:

halogen, vitro, cyano, C1-C3-alkyl or C1-C3-alkoxy; C1-C6-a 1 k y 1 a m i n o , di ( C1-C6 ) alkylamino or phenyl-amino, it being possible for the aromatic ring to addi-tionally carry up to three of the following radicals:

halogen, vitro, cyano, C1-C3-alkyl or C1-C3-alkoxy;

- C3-Ce-cycloalkyl;

- C3-C6-alkenyl, C5-C6-cycloalkenyl, C3-C6-alkynyl, it being possible for these radicals to carry one of the following groups: hydroxyl, halogen, C1-C,-alkoxy or phenyl, it being possible for the aromatic radical to itself carry from one to three of the follow-ing groups: halogen, vitro, cyano, C1-C,-alkyl, partially or fully halo-genated C1-C,,-alkyl or C1-C4-alkoxy;

- phenyl, which may carry from one to three of the following groups:

halogen, vitro, cyano, C1-C,,-alkyl, partially or fully halogenated C1-C,-alkyl, C1-C~-alkoxy, partially or fully halogenated C1-C,-alkoxy or C1-C~-alkoxycarbonyl;

202593_9s -O.Z. 0050/41111 a five- or six-membered heterocyclic radical having up to three heteroatoms selected from the group comprising oxygen, sulfur and nitrogen, where two oxygen and/or sulfur atoms must not be directly adjacent and where the heterocyclic rings may also carry one or two of the following substituents:

halogen, C1-C3-alkyl, C1-C3-alkoxy or C 1-C3-alkoxyc arbonyl ;

- benzotriazolyl;

N-phthalimido, tetrahydrophthalimido, succinimido, maleiimido;

- 2,2-dimethyl-1,3-dioxolan-4-ylmethyl or 1,3-dioxolan-2-on-4-ylmethyl;

- in the case where Y - Os one equivalent of a cation from the group comprising the alkali and alkaline earth metals, manganese, copper, iron, ammonium and ammonium which is sub-stituted by up to 4 C1-C3-alkyl groups;

or - -N=CReR, where R8 and R are hydrogen; C1-C,-alkyl, which may be unsubstituted or partially or fully halogenated and may carry a C1-C3-alkoxy or phenyl radical, it being possible for the aromatic _. radical to itself also be monosubstituted,..disubstituted or trisubstiuted by halogen, nitro, cyano, C1-C3-alkyl, partially or fully halogenated C1-C3-alkyl, C1-C3-alkoxy or partially or fully halogenated C1-C3-alkoxy; C3-Cg-cycloalkyl;

2 0 2 5 9 3 9~ ~ - o.Z. ooso~41111 C1-C,-alkoxy; furanyl or phenyl, which may additionally carry up to three of the following substituentss halogen, vitro, cyano, C1-C3-alkyl, partially or fully halogenated C1-C3-alkyl, C1-C3-alkoxy or partially or fully halogenated C1-C3-alkoxy;
or Re and R° together are a methylene chain having from 4 to 7 members;
- -W-Z , where W is C2-C4-alkylene, ethoxyethylene, but-2-enylene or but-2-ynylene, and Z is a molecular moiety which is bonded to W in the w-position and is the same as that linked to W in the a-position of W;
Rg is - hydrogen, C1-Cg-alkyl or C3-Ce-cyclo-alkyl, and 2 0 R' is - hydrogen, C1-Cg-alkyl , -C ( OR1Z ) =N-H or -C ( oRl2 ) =N- ( C1-C, ) -alkyl , where Ri2 is Cl-C~-alkyl, or R° and R' together are methylene having 4 or 5 members;
R3 is - hydrogen;
- Cl-CQ-alkyl, which may carry from one to three of the following substituentss hydroxyl, halogen, C1-C~-alkoxy, C1-C,-alkylthio or di ( C1-C, ) -alkylamino;
- C3-Ce-cycloalkyl, which may be monosubstituted, 2 p 2 5 9 3 9' 8 - o. z . 0050/41111 disubstituted or trisubstituted by halogen, C1-C'-alkyl or partially or fully halogenated C1-C'-alkyl;
R' is - hydrogen, hydroxyl, C1-C'-alkoxy;
- C1-Cg-alkyl, which may carry from one to three of the following radicals: halogen, cyano, C1-C'-alkoxy, partially or fully halogenated C1-C'-alkoxy, C1-C'-alkylthio, partially or fully halogenated Cl-C'-alkylthio, di-Cl-C'-alkylamino, C3-Ce-cycloalkyl or phenyl, it being poossible for the phenyl ring to itself carry from one to three of the following radicals: halogen, cyano, nitro, C1-C'-alkyl, partially or fully halogenated Cl-C'-alkyl, Cl-C'-alkoxy, partially or fully halogenated C1-C'-alkoxy, C1-C'-alkyl-thio or partially or fully halogenated Cl-C'-alkylthio;
- C3-C8-cycloalkyl, which may carry from one to three of the following radicals: halogen, nitro, cyano, C1-Ce-alkyl, partially or fully halogenated C1-Ce-alkyl, C1-C'-alkoxy or partially or fully halogenated C1-C'-alkoxy;
C3-Cs-alkenyl or C3-Ce-alkynyl, each of which may be monosubstituted, disubstituted or trisubsti-tuted by halogen and/or monosubatituted by phenyl, it being possible for the phenyl radical to itself carry. from one to three of the following groups: C1-C'-alkyl, C1-C'-halo-alkyl, C1-C'-alkoxy, . C1-C'-haloal~COUy, C1-C'-alkylthio, C1-C'-haloalkylthio, halogen, cyano or nitro~
- di ( C1-C' ) -alkylamino;

_ g _ - a 5- or 6-membered heterocyclic saturated or aromatic radical having one or two heteroatoms selected from the group comprising oxygen, sulfur and nitrogen, which may be monosub-stituted, disubstituted or trisubstituted by C1-C4-alkyl or halogen;
- phenyl, which may carry from one to four of the following groups : C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-Ca-alkylthio, C1-C4-haloalkylthio, halogen, nitro, cyano, formyl, C1-C4-alkanoyl, C1-C4-haloalkanoyl or C 1-C4-a lkoxyc arbonyl ;
- naphthyl, which may be monosubstituted, disub stituted or trisubstituted by C1-C4-alkyl or halogen;
or R3 and R" together are methylene having from 4 to 7 members which may be interrupted by oxygen, sulfur or N-methyl, or are 2 0 - ( CHa ) 3-CO
R3 and R4 in the compound. Ia, Ib or Ic not simultaneously being hydrogen if - R1 is hydrogen, methyl or phenyl and RZ is CONHZ, COOH or COOCH3, or if 2 5 - X is oxygen, Rl is CH ( OCHZCH3 ) 2 and RZ is CONHZ, or if - X is oxygen and R2 is formyl, and the agriculturally acceptable salt of the compound Ia, Ib, Ic or Id.
The present invention also relates to herbicides which contain compounds Ia to Id as active ingredients 30 and to herbicides which. contain at -least one compound Ia', Ib' or Ic' in which the substituents are as defined above and R3 and R4 may simultaneously be hydrogen if ,,...., 2p2593~ to -O.Z. 0050/41111 R1 is hydrogen, methyl or phenyl and R2 is CONHZ, C02H
or COZCH3, or if X is oxygen, Rl is CH(OCH2CH3)2andRZ is CONHZ.

Isoxazole- and isothiazole-carboxylic acids and der ivatives thereofare known. These the following are carboxamides type Ia', Ib' and c' of the I

I I I
NI I I

R X N
R X

Ia~ Ib~ Ic Ia' X R1 RZ R3 R' Ref .

1. 0 CH ( OCH2CH3 CONHZ H H 1 ) Z

2. S H CONH2 H H 2 3. S H COOH H H 2 Ib' X R1 R2 R3 R' Ref .

1. S H COOH H H 2 I c ' X R1 RZ R3 R' Re f .

1. S H ~ COOH H H 3 2. 0 Ph COOH H H 4 3. 0 Ph COOCH3 H H 4 4. 0 CH3 COOH H H 5 1) K. Butler; L.H. Conover, R.H. Woodward, U.S., US Patent 3,699,117, 17 Oct. 1972, 40 pp; CA 78(1)s 4027x, CA 73(23)s 120 602b, CA 73(3)s 14574j, CA 70(15)s 68002c 2) J. Chem. Soc., (1965) 7277 3) J. Chem. Soc., (1959) 3061 4) G. Deeimoni, P. Gruenager, Gazz.Chim.Ital., 97(1), ( 1967 ) 25-3~3 5) A. Camparini; F.Ponticelli, P. Tedeschi;
J.Chem.Soc., Perkin Trans l, (10), (1982) 2391-4 Of the type Id, these are 5-aminocarbonyl-3-- ~ ~ 2 5 g 3 ~ 11 - O.Z. 0050/41111 methyl-4-isoxazolecarboxylic acid, ethyl 5-aminocarbonyl-3-methyl-4-isoxazolecarboxylate, isothiazole-4,5-dicar-boxamida and 5-carbamoyl-4-isothiazolecarboxylic acid (J. Chem. Soc. Perkin Trans. I, 1982, 2391;
J. Heterocyclic Chem. 22, (1985), 1561 and J. Chem. Soc.
1 5 , 3061).
However, the use of these compounds as herbicides is not known.
It is an object of the present invention to provide novel herbicidally active compounds.
We have found that this object is achieved by the carboxamides Ia, Ib, Ic and Id defined at the outset.
In addition, the present invention relates to processes for the preparation of these compounds, and to herbicides which contain compounds Ia, Ib, Ic and/or Id.
The novel carboxamides Ia, Ib, Ic and Id can be prepared by various processes, preferably by the follow-ing:
1. A process for the preparation of a compound of the formula Ia or Ib in which R2 is C02CH3 and X is oxygen R~ R4 R3-N-C I I CO-OCN3 H3C0-C ' ( CO-N-R3 Q~~~R1 0~R1 Ia Ib The carboxamide Ia or Ib is obtained by reacting the hydroxamyl chloride II in a conventional manner with a ~9-keto ester III in the presence of a base, subsequent ly first hydrolyzing the resultant dimethyl diester IV
using one equivalent of an aqueous base to give the monoester Va or Vb, and then converting Va or Vb, sepa-rately or as a mixture, first into the halide or another activated form of the carboxylic acid in a conventional manner and subsequently amidating this derivative using an amine VIa.

12 - O.Z. 0050/41111 2p2593g_ A.
H;CO-CO~C1 + CO-OCH; --~ H3C0-C CO-OCH;
INfOH O~R 1 NI 0 I R 1 II III IV
B.
HOOC I I CO-OCH; + H3C0-CO I I COOH
N~~R1 N~ R1 ya yb --~ R3-N-CO CO-OCH; + H;CO-C CO-N-R3 N) ~ R1 NI 0 I R1 Ia Ib The individual reaction steps A, B and C of this synthesis can be carried out as follows:
Reaction step A:
The reaction is generally carried out at from 0 to 50°C, preferably from 10 to 30°C, in an inert, aprotic, polar organic solvent in the presence of a base.
The solvent used is expediently a hydrocarbon, such as, in particular, benzene, toluene, o-, m- or p-xylene, or an ether, such as diethyl ether, tert-butyl methyl ether, tetrahydrofuran, dimethoxyethane, ethylene glycol dimethyl ether or dioxane.
A particularly suitable base-'is sodium hydride.
The reaction is usually carried out by first converting the ~-keto ester III into the anion in the solvent containing from 1 to 2 mol equivalents of the base. This solution of the anion of III is subsequently treated with a solution of II, and the mixture is kept at the reaction temperature: The reaction is generally complete after from 4 to 12 hours.
Before work-up of the products, it is advisable to remove the water of reaction by azeotropic distil-lation.

13 - O.Z. 0050/41111 Reaction step B:
The partial hydrolysis of the dimethyl diester IV
to give the monoester Va or Vb is usually carried out at from -40 to 20°C, preferably from -20 to 0°C, in an inert, water-miscible organic solvent in the presence of from 1 to 1.1 mol equivalents of a base.
Particularly suitable bases are hydroxides of alkali metal cations. The base is generally added as a 5 to 10 percent strength aqueous solution.
Examples of preferred solvents for this reaction are tetrahydrofuran and dioxane.
For work-up, the reaction mixture is usually acidified, the desired product separating out as a solid or oil, and being isolated in a conventional manner by filtration or extraction.
The mixture of the two isomeric monoesters Va and Vb can be resolved by fractional crystallization or by chromatography or the reaction sequence can be continued without resolving the isomers.
Reaction step Cs The compound Ia or Ib is obtained form the monoester Va or Vb respectively by converting Va or Vb first into the halide or another activated form of the carboxylic acid function in a conventional manner and subsequently aminating this derivative using an amine VIa.
In addition to the halides, such as, in par-ticular, the chlorides and the bromides, examples of activated forms of the carboxylic acid are also imidazol-ides. In general, the halides are preferred.
They are obtained by reacting the carboxylic acid Va or Vb with a halogenating agent, such as phosgene, thionyl chloride, thionyl bromide, phosphorus oxychlo-ride, phosphorus oxybromide, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide, phos-phorus pentabromide, elemental chlorine or elemental bromine.

2 ~ 2 5 g 3 g- 14 - o. z . 0050/41111 The halogenating agent is employed in an amount of from 1 to 5 mol equivalents, preferably from 1 'to 2 mol equivalents.
The reaction proceeds at from 20°C to the boiling point of the halogenating agent or, if using an inert organic solvent, to its boiling point.
Examples of suitable solvents are hydrocarbons, such as benzene, toluene, o-, m- and p-xylene, halo-genated hydrocarbons, such as dichloromethane, chloro-form, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene and 1,2-dichlorobenzene, and mixtures of these.
The activated carboxylic acid derivative is usually isolated, for example by removing the halogenat-ing agent and, if present, the solvent by distillation and only then reacted with the amine VIa.
In this case, the amidation is carried out at from -20 to 50°C, preferably from 0 to 30°C, in an inert, aprotic, polar organic solvent.
Particularly suitable solvents for this reaction are hydrocarbons, such as benzene, toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as dichloro-methane, and ethers, such as dimethyl ether and tert-butyl methyl ether.
Since hydrogen halide is formed during the amidation of acyl halidea, it is advisable to add the amine VIa in an excess of from 2 to 5 mole equivalents, preferably from 2 to 3 mole equivalents. If the amine is employed in an equimolar amount (from 1 to 1.2 mol equivalents), a base, in particular a tertiary amine, such as triethylamine or pyridine, should be added to bind the hydrogen halide.
If starting from a mixture of the monoesters Va and Vb, a mixture of the isomeric.carhoxamides Ia and Ib is obtained in the reaction. This mixture can be sepa rated into the individual components in a conventional manner, for example by fractional crystallization or 2p25939- 15 -O.Z. 0050/41111 chromatography.
2. A process for the preparation of a compound Ia in which X is oxygen, R2 is CO-ORS and RS is not hydrogen or methyl:

R 3-N-C I I CO~R 5 ~R1 Ia (RS:H, CH;) In a similar manner to that outlined under 1. , this compound Ia is obtained by reacting the hydroxamyl chloride II with a ~9-keto ester of the formula IIIa in the above-outlined manner, subsequently cleaving the resultant diester IVa using a hydrolyzing agent to give the monoester Va', activating the latter and amidating product to give Ia.
A.
H CO-COYCI + CO-ORS ~ H CO-CO I I CO-OR5 INIOH O~R 1 3 N~R 1 II IIIa IVa HOOC , CO-ORS --~ R3-N-CO CO-OR5 Va~ Ia Reaction steps A and C are carried out in general and specific terms under the conditions outlined for processes IA and IC.
Reaction step 8s The partial hydrolysis of the mixed diester IVa to give the monoester Va' is usually carried out at from -40 to 20°C, preferably from---20 to 0°C, in an inert organic solvent.
These processes are known in general terms and can be carried out under the conditions described in the literature.
If, in a synthesis of this type, a hydroxamyl - ., ., - 16 - O.Z. 0050/41111 chloride IIa is reacted with a p-keto ester III, it is also possible specifically to prepare the compound Ib where X is oxygen, RZ is COZRS and RS is not hydrogen or methyl by the same route.
A.
R50-CO~CI + ~CO-OCH3 --~ R50-CO ( I CO-OCH3 NOH 0 R1 N~0 RI
IIa III IVb R50-CO COOH -~ R50-CO CO-N-R3 NI 0 I R 1 NI 0 I R i Vb' Ib (R5#H; CHj) The last-mentioned process for the specific preparation of an isomer of the two carboxamides Ia and Ib is based on the possibility of selectively cleaving one ester group of the two dif ferent ester groups in a compound by using only one mole equivalent of hydrolyzing agent under mild reaction conditions.
Examples of suitable hydrolyzing agents are hydroxides of alkali metal cations in the case of un-branched alkyl esters, mineral acids in the case of a-branched alkyl esters, and hydrogen in the case of hydrogenolysis of benzyl and allyl esters.
3. A process for the preparation of a compound Ia or Ic in which Rl is not hydrogen, and RZ is carboxyl or formyl and R3 is hydrogens Rø R4 H-N-C I I R1 R1 ( I CO-N-H
N\X~R1 ~R1 Ia (R1#H; R1=COZH, CHO) Ic (R1#H; R1=C01H, CHO) These isomeric carboxamides Ia and Ic are ob-tained by activating and amidating a carboxylic acid Vc or Vd under the conditions outlined under 1C, and - 17 - O.Z. 0050/41111 subsequently reacting the resultant amide VIIa or VIIb in a conventional manner in the presence of a carboxylating or formylating agent.

HOOC A~ I
I I R I COOH ---~ H-N-CO
NIX R1 Or I I I I Or Vc Vd VIIa R1 I I CO-N-H -~ H-N-CO I I RZ Or RI ~( I CO-N-R4 N\X/ N~R1 N~~RZ
VIIb Ia (Ri#H; RZ=COZH,CHO) Ic (R1#H; RZ=COZH,CHO) Reaction step A is carried out in general and specific terms under the conditions described under point C in process 1.
Reaction step Bs The formylation or carboxylation of the car-boxamide VIIa (X = 0 or S) or VIIb (X = S) is generally carried out at from -100 to 0°C, preferably from -80 to -20°C, and the formylation or'carboxylation of the carboxamide VIIb (X = 0) is advantageously carried out at <-80°C. The reaction is preferably carried out in an aprotic, polar, inert organic solvent with exclusion of moisture and in the presence of a base.
Particularly suitable formylating agents are dimethylformamide and N-formylmorpholine, and the prefer red carboxylating agent is carbon dioxide.
Particularly suitable solvents are diethyl ether, tart-butyl methyl ether, tetrahydrofuran and dioxane.
Preferred bases are alkali metal hydrocarbons, such as methyllithium, n-butyllithium, tart-butyllithium and phenyllithium.
The reaction is usually carried out by first 2 0 2 5 9 3 9 is - o. z . 0050/41111 adding from 2 to' 2.5 mole equivalents of the dissolved base to a solution of the carboxamide VIIa or VIIb to produce a ring-metallated carboxamide derivative, which, on subsequent addition of the electrophilic formylating or carboxylating agent, reacts to form the desired product Ia or Ic.
The carboxylic acids Vc and Vd required for this process are known from the literature (Beilstein, main work and supplements 1-5, volume 27; R.W. Wiley, The Chemistry of Heterocyclic Compounds, Five- and Six-Membered Compounds with Nitrogen and Oxygen, Interscience Publishers, New York, London (1962), or can be prepared by methods known in general terms from the literature, for example by oxidizing the corresponding alcohol or aldehyde or by hydrolyzing the corresponding nitrile.
4. A process for the preparation of a compound of the formula Id in which RZ is COORS and RS is hydrogen or C1-Cs-alkyl, by hydrolyzing a dialkyl isoxazole- or isothiazole-4,5-dicarboxylate X (RS' - C1-Ce-alkyl), converting the product into an acyl halide XII, and amidating the acyl chloride:
R1~ COORS R1~ COORS
1) 1 equiv. of aqueous base I I
N~~COORS~ 2 8Cid NIX COOH
) X XI
(RS = RS' _ C1_C6_plkyl) SOCla _ Or R1~ COORS HNRjR4 R1~ ~ I COORS
NI X I CO-Ha 1 V I a N\X CO-N-R 3 PHal3, PHals R4 XII Id 1 ) aqueous base R 1 ~ NI X ( COON
2) acid ~ CO-N-R3 Id R4 Particularly suitable isoxazole- or isothiazole-2 0 2 5 9 3 ~ lg - o.z. 005041111.
4, 5-dicarboxylates X are lower alkyl esters ( RS - RS' -C1-C4-alkyl), dimethyl and diethyl esters being 'par-ticularly preferred.
The reaction is carried out by treating a dialkyl isoxazole- or isothiazole-4,5-dicarboxylate X in an organic solvent, eg. methanol or ethanol, at from about 0 to 80°C, preferably from 0 to 50°C, with in general about one equivalent of a strong base, eg. NaOH, KOH or Ca(OH)Z, in aqueous solution. When the reaction is com plate, the mixture is cooled and acidified with a strong mineral acid, eg. hydrochloric acid or sulfuric acid. The resultant carboxylic acid XI can be isolated in a conven-tional manner, for example by suction filtration or by extraction with an organic solvent.
For conversion into the acyl halide XII, the carboxylic acid XI is reacted in a conventional manner with an inorganic acid halide, such as thionyl chloride, phosphorus trihalide or phosphorus pentahalide, the chlorides being preferred. The inorganic acid halide is expediently employed in an amount of from 1 to 5 mole equivalents, preferably from 1 to 2 mole equivalents. The reaction can be carried out without a solvent or in the presence of an inert organic solvent, eg. benzene or toluene, at from room temperature to the boiling point of the inorganic acid halide or the inert organic solvent.
In some cases, the addition of a catalyst, such as dimethylformamide or 4-dimethylaminopyridine, may be advantageous. When the reaction is complete, the acyl halide XII can be isolated in a conventional manner, for example by removing the excess inorganic acid halide and organic solvent by distillation and subsequently distil-ling the acyl chloride XII at atmospheric pressure or reduced pressure.
The carboxamide of the formula Id in which RZ is COORS and RS is C1-Cs-alkyl is obtained from the acyl halide XII by reaction with an amine VIa, the acyl halide generally being reacted in an inert organic solvent, such 2 0 2 5 9 3 $ 20 - o.z. 0050/41111 as dichloromethane, or an ether, such as diethyl ether or methyl tart-butyl ether, with an amine VIa, likewise dissolved in an organic solvent. The amine VIa is ex-pediently employed in from 2- to 5-times the molar amount, preferably from 2- to 3-times the molar amount, in order to bind the hydrogen halide produced. The reaction can also be carried out in the presence of an auxiliary base, such as a tertiary amine, eg. triethyl-amine. In this case, from 1 to 1.5 mole equivalents of the amine VIa are sufficient. The reaction temperature can be, for example, from 0 to 50°C, preferably from 0 to 20°C. The reaction is generally complete after from 1 to 12 hours. The mixture can be worked up in a customary manner, for example by hydrolyzing with water and sub-sequently extracting of the product of the formula Id (R2 = COORS, RS = C1-Cs-alkyl ) with an organic solvent and then evaporating the latter. The product of the formula Id (RZ
- COORS, RS = C1-Ce-alkyl ) can be purif ied, for example, by recrystallization or chromatography.
The acid amide Id (R2 = COORS, RS = C1-CB-alkyl) can advantageously also be prepared from the carboxylic acid XI in one step, the carboxylic acid XI being reacted with an amine VIa at from 0 to 50°C, preferably from 5 to 25°C, in an inert solvent, such as dichloromethane, tetrahydrofuran, toluene or ethyl acetate, in the presence of a dehydrating agent, for example propanephos-phonic anhydride (PPA) or dicyclohexylcarbodiimide (DCC).
The 4-alkoxycarbonylisoxazole-5-carboxamide or 4-alkoxycarbonylisothiazole-5-carboxamide Id (RZ = COORS
where RS - C1-Cs-alkyl) can be converted into the free carboxylic acid Id ( RZ = COON) , for example, by hydrolysis using an aqueous base and subsequently neutralizing the product using a mineral acid. The reaction is carried out by treating the ester Id ( RZ = COORS, RS = C1-Ce-alkyl ) in an organic solvent, eg. methanol or ethanol, at from 0 to 80°C, preferably from 0 to 50°C, with a base, eg. NaOH, KOH or Ca ( OH ) Z . In general , from about 1 to 3 equivalents , -- 2 p 2 5 9 3 ~ 21 - o.z. 0050/41111 preferably from 1 to 1.5 equivalents, of the strong base are employed in aqueous solution. When the reaction is complete, the mixture is acidified using a strong mineral acid, eg. hydrochloric acid or sulfuric acid, with cooling. The resultant carboxylic acid Id (RZ = COON) can be isolated by suction filtration or by extraction with an organic solvent and evaporation of the latter. The product is further purified, for example, by recrystal-lization or chromatography.
5. A process for the synthesis of a dicarboxamide of the formula Ic in which RZ = CO-NR'R' (R3 and R' ~~ H), by reacting the acid Id' with a primary amine VIa in the presence of a dehydrating agent:
R4 i4 R1 I ' COOH HZN-R4 R1 I ~ CO-N-H R1 CO-N-H
~ .. b8se N~ X I COOH
N\X~CO-N-R3 VIa NCO-N-R3 I I~ Ic (Id~: RZ=COOH) (RZ=CO-NR3R~) (R~=COOH) Examples of suitable dehydrating agents are propanephosphonic anhydride and dicyclohexylcarbodiimide.
In general, the process is carried out at from -20 to 50°C, preferably from 20 to 40°C, in an inert organic solvent, such as dichloromethane or an ether, such as diethyl ether or methyl tart-butyl ether. The starting materials are reacted in approximately stoichiometric amounts. The mixture can be worked up in the cutomary manner, for example by hydrolysis using water, extraction of the product of the formula Ic (RZ = CO-NR3R') with an organic solvent, and evaporation of the latter. The product of the formula Ic (RZ = CO-NR3R') can be further purified, for example, by recrystallization or chromatography.
The resultant isoxazole-4,5-dicarboxamide of the formula Ic in which X is oxygen- and RZ is CO-NR3R' (R3 and R'~H) can be used to prepare the carboxylic acid Ic 2 0 2 5 9 3 ~ 22 - 0. Z . 0050/41111 (RZ=COOH) by reaction with excess potassium tart-butoxide.
This reaction is expediently carried out by treating the diamide Ic ( R2 - CO-NR3R4 ) in an inert organic solvent, such as diethyl ether or tetrahydrofuran, at from 0 to 30°C, preferably at room temperature, with potassium tert-butoxide in water (ratio 3 to 6:1). The reaction is generally complete after from 1 to 12 hours. The free carboxylic acid Ic (R2 - COOH) can be isolated, after acidification using a mineral acid, either by suction filtration or by extraction with an organic solvent and evaporation of the latter. The acid Ic (R2=COOH) can be further purified by either recrystallization or chromatography.
The isothiazole-4,5-dicarboxylates X (X=sulfur) required as starting material for this process are known (R. M. Paton, J. Stobie, R. M. Mortier, Phosphorus Sulfur, 15 (2), (1983), 137, or can be prepared by conventional methods.
The dialkyl isoxazole-4,5-dicarboxylates X (X =
oxygen) required as starting material for this process are known from the literature [J. Org. Chem. 43, (1978), 3736; Chem. Pharm. Bull. 28, (1980), 3296; Tetrahedron 30, (1974), 1365] or can be prepared by methods which are known in general terms from the literature [cf., for example, DE-A 27 54 832, and Synthesis, (1982), 508], for example from the aldoxime XIII and the acetylenedicar-boxylate XIV:
COORS
R 1 H c~ hypohal ite + ~~~ R1 COORS
N~OH C\ 8 NI ~ COORe COOK
XIII XIV X
In this process, the aldoxime XIII is oxidized in the reaction medium by the hypohalite to give the cor-responding nitrile oxide, which is a very reactive 1,3-dipole. This nitrile oxide is continuously scavenged, as it is produced, by the acetylene dicarboxylate XIV, 23 - O.Z. 0050/41111 likewise present in the reaction medium, in a 1,3-dipolar cycloaddition reaction with formation of the isoxazole compound X.
Expediently, equimolar amounts of the aldoxime XIII and of the acetylenedicarboxylate XIV are reacted with the hypohalite, which can be added to the reaction mixture in a stoichiometric amount. However, it is usually metered into the reaction batch in a slight excess, up to a two-fold excess. For technical reasons, it may be advantageous to limit the conversion by using sub-stoichiometric amounts of hypohalite, from about 50 to 90 mol-% per mole of XIII. It is also possible to use sub- or super-stoichiometric amounts of the reactants XIII and XIV.
The hypohalites used are generally hypobromites or hypochlorites, of which the latter are preferred. For this purpose, aqueous solutions of hypochlorous or hypobromous acid may be employed, but alkali metal or alkaline earth metal hypochlorites or hypobromites, for example sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, magnesium hypochlorite, strontium hypochlorite, barium hypochlorite or the corresponding hypobromides, are preferred. Particular preference is given to sodium hypochlorite, potassium hypochlorite and calcium hypochlorite, in the form of their commercially available, aqueous solutions.
Examples of suitable solvents for the process are alcohols, such as methanol, ethanol, propanol and isopro-panol, ketones, such as acetone and methyl ethyl ketone, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran and dioxane, hydrocarbons, such as pentane, hexane, cyclohexane, petroleum ether, white oils and ligroin, halogenated aliphatic hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, dichlorethane, trichloroethane, tetrachloroethane and perchloroethane, aromatic compounds, such as benzene, toluene, xylenes and chlorobenzenes, esters, such as - 24 - O.Z. 0050/41111 ethyl acetate, and dimethylformamide, N-methylpyr-rolidone, dimethyl sulfoxide, sulfolane, etc.
The temperature at which the reaction is carried out can be varied within broad limits. In general, it takes place even at -15°C and lower, and the upper limit is in principle set only by the boiling point of the solvent used, since the reaction is expediently carried out at atmospheric pressure. The preferred temperature range is from 0 to 40°C. The reaction can also be carried out under superatmospheric pressure, in particular under autogenous pressure, but atmospheric pressure is preferred.
The aldoximes XIII required for this process are either known or can be prepared in a conventional manner (eg. Houben-Weyl, Methoden der organischen Chemie, Vol.
10/4, pages 55 to 56, Thieme Verlag, Stuttgart, 1968) by reacting the corresponding aldehydes with hydroxylamine.
The aldoximes XIII can of course be used either in the form of their E- or Z-isomers or as mixtures of these.
The acetylenedicarboxylates are commercially available or can be prepared by conventional methods (eg. Organic Syntheses Coll. Vol. 4, page 329).
6. A process for the preparation of compounds Ia and Ib, in which Rz is carboxyl and X is sulfur:

Ia (X=S; R~=COOH) Ib (X=S; RZ=COOH) These carboxamides Ia and Ib are particularly advantageously obtained by reacting an isothiazoledicar-boxylic anhydride VIII in a conventional manner with an amine VIa, and separating the resultant mixture of isomers Ia and Ib into the individual components.

9- 25 - O.Z. 0050/41111 2p2593 0~ 0 ,0 R4 R4 + HNR3R4 ~ R3-N-C COOH + HOOC CO-N-R3 NhSI R1 NISI R1 NISI R1 VIII VIa Ia (X=S; RZ=COOH) Ib (X=S; Rz=COOH) The reaction is usually carried out at from -10 to 50°C, preferably from 0 to 30°C, in an inert, aprotic, polar organic solvent.
Particularly preferred solvents are halogenated hydrocarbons, such as methylene chloride, and ethers, such as diethyl ether, tart-butyl methyl ether and tetrahydrofuran.
The amine VIa is generally employed in an equi molar amount or in an excess, preferably in an amount of from 1 to 1.2 mol equivalents, based on VIII.
In this process, the isomeric carboxamides of the formulae Ia and Ib (RZ = COON) are produced in different amounts. The isomer mixture is resolved either by frac-tional crystallization or by chromatography.
The isothiazoledicarboxylic anhydrides VIII
required for this process are known or can be prepared by conventional methods (Beilstein, Main Work and Supple-ments 1-5, Volume 27).
7. A process for the preparation of a compound Ia, Ib, Ic or Id, in which RZ is COZHs R3-N-C ' I COOH HOOC I I CO-N-R3 N~R i N\X~R 1 Ia Ib R1 CO-N-R3 R1~ ' I COOH
N X I ~COOH NCO-N-R 3 I
Ic Id R4 These compounds Ia, Ib, Ic and Id are obtained by -- 2 0 2 5 9 3 ~ 2s - o. z . 0050/41111 hydrolyzing the corresponding ester Ia, Ib, Ic or Id in which R2 is COZRS and RS is C1-C4-alkyl in a conventional manner in the presence of an aqueous base.
This ester hydrolysis is carried out under the general and specific conditions outlined for process 2 under point B.
8. A process for the preparation of compounds Ia, Ib, Ic and Id in which R2 is COYRS or CONR6R' ( shown as an example for the carboxamide Ia):

R3-N-CO COOH HY R5 R3-N-CO ' I COYRS Ia NI X I R1 IX (Y=0, S) NIX R1 (RZ=COYRS) Ia (R1=COOH) HNVIb' R3 N-C ~ I CONR6R~
N\X~R1 (RZ=CONR6R~) Expediently, a carboxylic acid Ia, Ib, Ic or Id (R2=COON) is reacted with an alcohol or thiol IX or with an amine VIb in the presence of a dehydrating agent, for example propane phosphoric anhydride (PPA) or dicyclo-hexylcarbodiimide (DCC), at from -20 to 50°C, preferably from 0 to 40°C, in particular from 20 to 30°C.
All the starting compounds are advantageously employed in an approximately stoichiometric ratio, but an excess of one or other component, approximately up to 10 mol-%, may also be advisable in some cases.
Expedient solvents are hydrocarbons, such as toluene and o-, m- and p-xylene, halogenated hydro-carbons, such as dichloromethane, and ethers, such as diethyl ether, tart-butyl methyl ether and tetrahydro-furan.
A variant of the process comprises activating the carboxylic acid Ia, Ib, Ic or Id (RZ = COON) as described for process 1C, and subsequently eaterifying.or amidating the product without using a dehydrating agent.
The process is normally carried out at 2 0 2 5 9 3 9 - 2' - o.Z. 0050/41111 atmospheric pressure.
The amines VIb are known or can be prepared by conventional processes. Some of the alcohols and thiols HY-RS are known. If RS is -CR1°=N-R11-substituted C1-CB-alkyl (iminoalcohols XVI), these alcohols and thiols are novel; however, they can be prepared by one of the following known processes (shown as an example for Y = O
and RS = -CHZ-CR1°=N-R11 where R1° = H and R11 = C2H5 ) + C1HZC-CHQ
H aN--0C ZH s C 11i =C-C1~N-OC ZH 5 + OHC-CHO + ACO--CH z-CHO + ACOK f 18-crown-6 OHC-CH=N-0C yHS + HO-CH xwCHO
ACo-CH r-CHIN-OC 1H5 HaBH4 KOH
HO-CH I-CHaN--0C ZH~
(E/Z isomer mixture) b.p. (30 mbar) - 72-76°C
Ac = CH3C0 nD° = 1.4340 The following alcohols, for example, were prepared by the process mentioned:
HO-CHZ-CH=N-OCH3 HO-CHZ-C ( CH3 ) =N-OCH3 HO-CHZ-CH=N-OCHZ-CH=CHC 1 HO-CHz-CH=N-OCHZ-C6Hs HO-CHZ-C ( CH3 ) =N-OCZHs 2 0 HO-CHZ-CH=N-OCH2-CH=CH2 HO-CH2-C ( CH3 ) =N-OCH2-Cells HO-CHZ-C ( CH3 ) =N-OCHZ-CH=CHZ
9. A process for the preparation of a compound Ia, Ib, Ic or Id in which Rz is 4,5-dihydrooxazol-2-yl, by the conventional reaction of a carboxamide Ia, Ib, Ic or Id where RZ is COOH or COORS ( Rs = unsubsti-tuted or substituted C1-C,-alkyl, as indicated under the radicals R') , with an aminoalcohol of the formula XV [cf . Wehrmeister, J. Org. Chem. 26, ( 1961) , 3821] s - 28 - O.Z. 0050/41111 R1~ CO-ORS HZN-CHZ-CH2-OH N~
NI X I CO-N-R 3 X V R 1 , ~ ~ 0 Id ( RZ = CO-ORs Id ( R2 = dihydrooxazol-2-yl ) The reaction is carried out by reacting the compound at from 0 to 180°C, preferably under reflux temperature of the mixture used, with an aminoalcohol XV, if desired in the presence of an inert solvent. The ester or carboxylic acid and the aminoalcohol XV are employed in a ratio of from 1:1 to 1:2.5, preferably from lsl to 1:1.5.
The solvents expediently used are halogenated hydrocarbons, such as chlorobenzene and 1,2-dichloroben-zene, ethers, eg. methyl tart-butyl ether, 1,2-dimethoxy-ethane, diethylene glycol dimethyl ether, tetrahydrofuran and dioxane, alcohols, such as methanol, ethanol, propanol and ethylene glycol, dipolar aprotic solvents, eg. acetonitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, 1,3-dimethyl-tetrahydro-2(1Fi)-pyrimidinone andl,3-dimethylimidazolin-2-one, or aromatic compounds, eg. benzene, toluene and xylene. The concentration of the starting materials in the solvent is generally from 0.1 to 5.0 mol/1, prefer-ably from 0.2 to 2.0 mol/1.
The reaction is generally complete after 14 hours; the carboxamide Ia, Ib, Ic or Id (where RZ = 4,5-dihydrooxazol-2-yl) is then precipitated, if necessary, by adding water, and filtered off with suction or ex-tracted with an organic solvent, and' purified by customary standard methods, such as recrystallization or chromatography. -The process is generally carried oat at atmospheric pressure or under the autogenous pressure of the particular solvent.

2 p 2 5 g 3 g - 29 - o. z . 0050/41111 10. A process for the preparation of a compound Ia; Ib, Ic or Id in which R2 is formyl:

Rj-N-CO CHO OHC CO-N-R3 Ia Ib R1 I I CO-N-R3 R1~ I I CHO
N\X~CHO N\X~CO-N-R3 I
Ic Id R4 The compound Ia, Ib,Ic or Id is obtained, for example, by activating a corresponding carboxamide of the formula Ia, Ib, Ic or Id where R2 is C02H, under the conditions outlined in the case of process 1, and reduc-ing the resultant activated form of the carboxylic acid in a conventional manner.
The carboxylic acid is preferably converted into the corresponding chloride, which is reduced at from -100 to 0°C, in particular from -80 to -50°C, using a complex hydride, such as, in particular, lithium tri-t-butoxy aluminum hydride. Particularly preferred solvents in this case are ethers, such as dimethyl ether, diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, diethylene glycol dimethyl ether and dioxane (J. Am. Chew. Soc. 80, (1958), 5372; J. Am. Chem. Soc. 80, (1958), 5377).
11. A compound of the formula Ia, Ib, Ic or Id in which Rl or R1' is epoxidized Cz-C6-alkenyl, which may be monosubstituted, disubstituted or trisubstituted by halogen, C1-C3-alkoxy and/or monosubstituted by cyclopropyl or unsubstituted or substituted phenyl as mentioned under Rl, is obtained, for example, by epoxidizing a carboxamide of the formula Ia, Ib, Ic or Id where Rl or R1' is CZ-Cs-alkenyl, which may carry the abovementioned substituents, in a con-ventional manner using a suitable oxidant (eg. J.

2p25939 - 30 - O.Z. 0050/41111 March, Advanced Organic Chemistry, Third Edition, John Wiley and Sons, 1985, pp. 735ff.).
In addition to processes 1-11 outlined above for the preparation of compounds Ia, Ib, Ic and Id, there are further possible syntheses, which are given in the following literatures Beilstein, Main Work and supplements 1-5, Volume 27; R.W. Wiley, The Chemistry of Heterocyclic Compounds, Five- and Six-Membered Compounds with Nitrogen and Oxygen, Interscience Publishers, New York, London (1962);
A.R. Ratritzky, C.W. Rees, Comprehensive Heterocyclic Chemistry, Vol. 6, Five-membered Rings with Two or More Oxygen, Sulfur or Nitrogen Atoms,~Pergamon Press, 1984;
J. March, Advanced Organic Chemistry, Third Edition, John Wiley and Sons, 1985;
Houben-Weyl, Methoden der organischen Chemie, 4th Edition, Thieme Verlag, Volumes IV, VI, VII, VIII, X.
In detail, these substituents in compounds Ia, Ib, Ic and Id have the following meanings:
R1 is - hydrogen;
- halogen, such as fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine;
linear or branched Cl-CB-alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methyl-butyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethyl-butyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl-butyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl, in particular methyl, 2 0 2 5 9 3 ~ 31 - o. z . 0050/41111 ethyl, propyl, 1-methylethyl or 1,1-dimethyl-ethyl, which may carry from one to five halogen atoms, such as fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine, and/or a cyano radical and/or up to two of the following radicals:
- C1-C4-alkoxy, such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpro-poxy, 2-methylpropoxy and 1,1-dimethylethoxy, in particular methoxy, ethoxy, 1-methylethoxy and 1,1-dimethylethoxy;
- partially or fully halogenated Cl-C~-alkoxy, such as difluoromethoxy, trifluormethoxy, chlorodifluoromethoxy,dichlorofluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoro-ethoxy, 1,1,2,2-tetrafluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-1,1,2-trifluoro-ethoxy and pentafluoroethoxy, in particular trifluoromethoxy and pentafluoroethoxy;
- Cl-C,-alkylthio, such as methylthio, ethyl-thio, propylthio, 1-methylethylthio, n-butyl-thio, 1-methylprophylthio, 2-methylpropylthio and 1,1-dimethylethylthio, in particular methylthio and ethylthio;
- partially or fully halogenated C1-C~-alkyl-thio, such as difluoromethylthio, trifluoro-methylthio, chlorodifluoromethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2,2-difluoroethylthio,2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio and pentafluoroethylthio, in particular trifluoromethylthio and pentafluoroethylthio;

2 0 2 5 9 3 ~ 32 - o. z . 0050/41111 - C1-C4-alkoxy as mentioned above, in particular methoxy or ethoxy;
- partially or fully halogenated C1-C4-alkoxy as mentioned above, in particular trifluoromethoxy, trichloromethoxy or pentafluoroethoxy;
- C1-C4-alkylthio as mentioned above, in particular methylthio or ethylthio;
- partially or fully halogenated C1-C,-alkylthio as mentioned above, in particular difluoromethyl-thio, trifluoromethylthio or pentafluoroethyl-thio;
benzyl which may be monosubstituted, disubsti-tuted or trisubstituted by alkyl having from 1 to 4 carbon atoms as mentioned above, in particular methyl, ethyl or 1-methylethyl; haloalkyl zs mentioned above, in particular trifluoromethyl or chlorodifluoromethyl; alkoxy as mentioned above, in particular methoxy or ethoxy; haloalkoxy as mentioned above, in particular trifluoromethoxy, trichloromethoxy or pentafluoroethoxy; alkylthio as mentioned above, in particular methylthio or ethylthio; haloalkylthio as mentioned above, in particular difluoromethylthio, trifluoromethyl-thio or pentafluoromethylthio; halogen as men-tinned above, in particular fluorine or chlorine;
cyano or nitro;
- phenyl which may also carry from one to three of the following radicals: cyano; vitro; halogen, such as fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine; C1-Ca-alkyl as mentioned above, in particular methyl, ethyl or 1-methylethyl; partially or fully halogenated 2 0 2 5 9 3 9- 33 - o. z . 0050/411 C1-Ce-alkyl as mentioned above, in particular trifluoromethyl or chlorodifluoromethyl; C1-C6-alkoxy as mentioned above, in particular methoxy or ethoxy; partially or fully halogenated C1-Cg-alkoxy as mentioned above, in particular tri-fluoromethoxy, trichloromethoxy or pentafluoro-ethoxy; C1-C4-alkylthio as mentioned above, in particular methylthio or ethylthio and/or par-tially or fully halogenated C1-Ce-alkylthio as mentioned above, in particular difluoromethyl-thio, trifluoromethylthio or pentafluoro-methylthio;
- C3-C8-cycloalkyl-C1-CB-alkyl, preferably C3-Ce-cycloalkyl-Cl-C,-alkyl, such as cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl, 1-cyclo-propylethyl, 2-cyclopropylethyl, 1-cyclopropyl-1-methylethyl, 2-cyclopropyl-1-methylethyl or 4-cyclohexyl-n-butyl;
CZ-Ce-alkenyl , whose double bond may be epoxidized, preferably C2-C~-alkenyl, such as ethenyl, prop-2-en-1-yl, 1-methylethenyl, but-2-en-1-yl or 1-methylprop-2-en-1-yl, which may be monosubstituted, disubstituted or trisub-stituted by halogen, such as fluorine, chlorine, bromine or iodine, C1-C3-alkoxy, such as methoxy, ethoxy or isopropoxy, and/or monosubstituted by cyclopropyl or phenyl, it being possible for the phenyl radical to itself carry from one to three of the following groups: cyano, nitro, alkyl as mentioned above, in particular methyl, ethyl or 1-methylethyl; haloalkyl as mentioned above, in particular trifluoromethyl or chlorodifluoro-methyl; alkoxy as mentioned above, in particular methoxy or ethoxy; haloalkoxy as mentioned above, in particular trifluoromethoxy, trichloromethoxy 2 p 2 5 g 3 g- 34 - o. Z . 0050/41111 or pentafluoroethoxy; alkylthio as mentioned above, in particular methylthio or ethylthio;
partially or fully halogenated alkylthio as mentioned above, in particular difluoromethyl-thio, trifluoromethylthio or pentafluoromethyl-thio or halogen as mentioned above, in particular fluorine or chlorine;
- CZ-Ce-alkynyl, preferably CZ-C4-alkynyl, such as ethynyl, propyn-1-yl, 1-methyl-2-propynyl or n-butynyl, which may be monosubstituted, disub-stituted or trisubstituted by halogen, such as fluorine, chlorine, bromine or iodine, C1-C3-alkoxy, such as methoxy or isopropoxy, and/or monosubstituted by cyclopropyl or phenyl, it being possible for the phenyl radical to itself carry from one. to three of the following groups:

cyano, vitro, alkyl as mentioned above, in particular methyl, ethyl or 1-methylethyl;

haloalkyl as mentioned above, in particular trifluoromethyl or chlorodifluoromethyl; alkoxy as mentioned above, in particular methoxy or ethoxy; haloalkoxy as mentioned above, in par-ticular trifluoromethoxy, trichloromethoxy or pentafluoroethoxy; alkylthio as mentioned above, in particular methylthio or ethylthio; partially or fully halogenated alkylthio as mentioned above, in particular difluoromethylthio, tri-fluoromethylthio or pentafluoromethylthio or halogen as mentioned above, in particular fluorine or chlorine;

- C3-C8-cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclo-octyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, or C3-Cs-cycloalkenyl, in particular C5-Ce-cycloalkenyl, such as cyclohexen-1-yl, it 2 0 2 5 9 3 9- 35 - o. z . 0050/41111 being possible for the ring to also be monosub-stituted, disubstituted or trisubstituted by C1-C4-alkyl as mentioned above, in particular methyl or ethyl; or by halogen, such as fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine;
- phenoxy or phenylthio, it being possible for both groups to be monosubstituted, disubstituted or trisubstituted by C1-C,-alkyl as mentioned above, in particular methyl, ethyl or 1-methylethyl;
partially or fully halogenated C1-C,-alkyl as mentioned above, in particular trifluoromethyl or chlorodifluoromethyl; Cl-C,-alkoxy as mentioned above, in particular methoxy or ethoxy; partially or fully halogenated C1-C~-alkoxy as mentioned above, in particular trifluoromethoxy, trichloro-methoxy or pentafluoroethoxy; C1-C,-alkylthio as mentioned above, in particular methylthio or ethylthio; partially or fully halogenated C1-C,-alkylthio as mentioned above, in particular difluoromethylthio, trifluoromethylthio or pentafluoromethylthio; halogen as mentioned above, in particular fluorine or chlorine; cyaao or nitro;
- a 5- or 6-membered saturated or aromatic hetero-cyclic radical containing one or two heteroatoms selected from the group comprising oxygen, sulfur and nitrogen, such as 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-furanyl, 3-furanyl, 2-thienyl, 3-thienyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl,.3-iso-thiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, - 36 - O.Z. 0050/41111 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-pyrrolyl, 3-pyr-rolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-pyridyl, 3-pyridyl and 4-pyridyl, which may carry one or two of the following substituents:
alkyl as mentioned above, in particular methyl;
halogen as mentioned above, in particular fluorine or chlorine; alkoxy as mentioned above, in particular methoxy or ethoxy; or alkoxycar-bonyl, such as methoxycarbonyl or ethoxycarbonyl, in particular methoxycarbonyl;
R1' is - C3-Ce-cycloalkyl-C1-CB-alkyl, preferably C3-CB-cycloalkyl-Cl-C,-alkyl, such as cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl, 1-cyclo-propylethyl, 2-cyclopropylethyl, 1-cyclopropyl-1-methylethyl, 2-cyclopropyl-1-methylethyl or 4-cyclohexyl-n-butyl;
- CZ-CB-alkenyl, whose double bond may be epoxidized, preferably CZ-C,-alkenyl, such as ethenyl, prop-2-en-1-yl and isopropenyl, which may be monosubstituted, disubstituted or trisub-stituted by halogen, such as fluorine, chlorine, bromine or iodine, C1-C3-alkoxy, such as methoxy, ethoxy or isopropoxy, and/or monosubstituted by cyclopropyl or phenyl, it being possible for the phenyl radical to itself carry from one to three of the following groupss cyano, nitro, alkyl as mentioned above, in particular methyl, ethyl or 1-methylethyl; haloalkyl as mentioned above, in particular trifluoromethyl or chlorodifluoro-methyl; alkoxy as mentioned above, in particular methoxy or ethoxy; haloalkoxy as mentioned above, in particular trifluoromethoxy, trichloromethoxy or pentafluoroethoxy; alkyithio as mentioned above, in particular methylthio or ethylthio;
partially or fully halogenated alkylthio as 2 0 2 5 9 3 ~ 3., - o. z . 0050/41111 mentioned above, in particular difluoromethyl-thio, trifluoromethylthio or pentafluoromethyl-thio or halogen as mentioned above, in particular fluorine or chlorine;
- C2-CB-alkynyl, preferably C2-C,-alkynyl, such as ethynyl, propyn-1-yl or n-butynyl, which may be monosubstituted, disubstituted or trisubstituted by halogen, such as fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine, C1-C3-alkoxy, such as methoxy or isopropoxy, and/or monosubstituted by cyclopropyl or phenyl, it being possible for the phenyl radical to itself carry from one to three of the following groups: cyano, nitro, alkyl as mentioned above, in particular methyl, ethyl or 1-methylethyl;

haloalkyl as mentioned above, in particular trifluoromethyl or chlorodifluoromethyl; alkoxy as mentioned above, in particular methoxy or ethoxy; haloalkoxy as mentioned above, in par-ticular trifluoromethoxy, trichloromethoxy or pentafluoroethoxy; alkylthio as mentioned above, in particular methylthio or ethylthio; partially or fully halogenated alkylthio as mentioned above, in particular difluoromethylthio, tri-fluoromethylthio or pentafluoromethylthio or halogen as mentioned above, in particular fluorine or chlorine;

- C3-Ce-cycloalkenyl, preferably Cs-Ca-cycloalkenyl, which may be monosubstited, disubstituted or trisubstituted by halogen, such as fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine, or C1-C,-alkyl, such as methyl, ethyl or tert-butyl; -Rz is - formyl;

2 0 2 5 9 3 9- 3e - o. z . 0050/41111 - 4,5-dihydrooxazol-2-yl;
- COYRs or CONR6R~, where RS is - hydrogen;
- C1-CB-alkyl, preferably C1-Cd-alkyl, such as methyl, ethyl or tert-butyl, which may carry from one to five halogen atoms, such as fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine, and/or up to three hydroxyl and/or C1-C~-alkoxy groups, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or tent-butoxy, and/or one of the following radicals:
- cyano, - C1-C4-alkoxy, in particular methoxyethoxy, ethoxyethoxy or propoxyethoxy, - C1-C3-alkylthio, in particular methylthio or ethylthio, - C1-C3-alkylamino such as methylamino, ethylamino or isopropylamino, 2 0 - di ( C1-C3 ) -alkylamino such as dimethylamino, diethylamino, dipropylamino, di(1-methyl-ethyl)amino or methylethylamino, - C3-Ce-cycloalkylamino or di ( C3-Ce ) -cyclo-alkylamino such as cyclopropylamino or dicyclopropylamino, - trimethylsilyl, - C1-C3-alkylsulfinyl such as methylsulfinyl, 1-methylethylsulfinyl or n-propylsulfinyl, C1-C3-alkylsulfonyl such as methylsulfonyl, ethylsulfonyl or isopropylsulfonyl, - carboxyl, C1-C3-alkoxycarbonyl such as methoxycarbonyl ~or isopropoxycarbonyl, - C1-C~-alkoxycarbonyl-C1-C3-alkoxy such as methoxycarbonylmethoxy, - C1-C3-alkoxycarbonyl-Cl-C3-alkoxy-C1-C3-,.-, 2 0 2 5 9 3 a 39 - o. Z . 0050/41111 alkoxycarbonyl such as methoxycarbonyl-ethoxymethoxycarbonyl, - di(C1-C3)-alkylaminocarbonyl such as dimethylaminocarbonyl,methylethylaminocar-bonyl or diisopropylaminocarbonyl, - di(C1-C3)-alkoxyphosphonyl such as dimethoxyphosphonyl or diisopropoxy-phosphonyl, - C1-C6-alkaneiminoxy such as 2-propaneiminoxy or CS-C6-cycloalkaneiminoxy, such as cyclo-pentaneiminoxy or cyclohexaneiminoxy - N-phthalimido, N-succinimido, benzyloxy or benzoyl, it being possible for these cyclic radicals to carry from one to three of the following groups: halogen as mentioned above, in particular fluorine or chlorine, C1-C3-alkyl, such as methyl, ethyl or isopropyl, in particular methyl, or C1-C3-alkoxy, such as methoxy, ethoxy or iso-propoxy, in particular methoxy;

- a 5- or 6-membered, saturated, heterocyclic radical or a 5- or 6-membered heteroaromatic radical, in each case having from one to three heteroatoms selected from the group compris-ing oxygen, sulfur and nitrogen, where two oxygen or sulfur atoms or one oxygen and one sulfur atom must not be directly adjacent, in particular tetrahydrofuran-2-yl, tetra-hydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl,tetrahydropyran-2-yl, tetrahydropyran-3-yl,tetrahydropyran-4-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, furan-2-yl, furan-3-yl, thien-2-yl, thien-3-yl, pyrrol-2-yl, pyrrol-3-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, 2 0 2 5 9 3 ~ 40 - o. z . 0050/41111 thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, imidazol-2-yl, imidazol-4-yl, imidaxol-5-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, 1,2,3-triazol-1-yl, 1,2,3-triazol-4-yl, 1,2,3-triazol-5-yl, 1,2,4-triazol-1-yl, 1,2,4-triazol-3-yl, 1,2,4-triazol-5-yl, 1,2,3-thiadiazol-4-yl, 1,2,3-thiadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadazol-5-yl, 1,2,5-thiadiazol-3-yl, 1,2,5-thiadiazol-4-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-thiadiazol-5-yl, 1,2,3-oxadi-azol-3-yl, 1,2,3-oxadiazol-5-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,5-oxadiazol-3-yl, 1,2,5-oxadiazol-4-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-oxadiazol-5-yl, pyrid-2-yl, pyrid-3-yl, pyrid-4-yl, pyrimid-2-yl,pyrimid-4-yl or pyrimid-5-yl, it being possible for the heterocyclic rings to also carry one or two of the following substitu-entss halogen, such as fluorine, chlorine, bromine or iodine, in particular chlorine or bromine, Cl-C3-alkyl, such as methyl, ethyl, n-propyl or isopropyl, C1-C3-alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy, and/or Cl-C3-alkoxycarbonyl, such as meth-oxycarbonyl, ethoxycarbonyl or isopropoxy-carbonyl;

- phenyl, which may also carry from one to three of the following substituentss halogen, such as fluorine, chlorine, bromine or iodine, in particular fluorine or chlo-rine, nitro, cyano, C1-C3-alkyl, such as methyl or isopropyl, partially or fully halogenated C1-C3-alkyl, such as trifluoro-methyl, 1,1,2,2-tetrafluoroethyl or tri-chloromethyl, C1-C~-alkoxy, such as methoxy or isopropoxy, and/or partially or fully 41 - O.Z. 0050/41111 halogenated C1-C3-alkoxy, in particular trifluoromethoxy;

- -CR1=N-R11 where Rl is hydrogen or linear or branched C1-C6-alkyl, in particular C1-C4-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl or tent-butyl;

m R is C1-CB-alkoxy, C3-Ce-alkenyloxy or C3-CB-alkynyloxy, in particular C1-C,-alkoxy, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or tert-butoxy, and prop-2-enyloxy, but-2-enyloxy, prop-2-ynyloxy or but-2-ynyloxy, it being possible for these substiutents to also carry from one to three halogen atoms, such as fluorine, chlorine, bromine or iodine, in particular fluo-rine or chlorine, and/or phenyl which may be unsubstituted or monosubstituted, disubstituted or trisubstituted by halogen, as mentioned above, vitro, cyano, Cl-C3-alkyl, such as methyl, ethyl, n-propyl or isopropyl, and/or Ci-C3-alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy; phenoxy, which may also carry from one to three of the following substituentss vitro, cyano, halogen as mentioned above, C1-C3-alkyl as mentioned above, and/or C1-C3-alkoxy as mentioned above;

linear or branched C1-Ce-alkylamino, di ( C1-CB ) -alkylamino or phenylamino, it being possible for the aromatic ring to additionally be monosubstituted, disub-stituted or trisubstitued by vitro, cyano, halogen as mentioned above, C1-C3-alkyl as mentioned above, and/or 2 0 2 5 9 3 .~ 42 - o. z . 0050/41111 C1-C3-alkoxy as mentioned above;
- C3-Ce-cycloalkyl, preferably C3-Ce-cyclo-alkyl, such as cyclopropyl, cyclopentyl or cyclohexyl;
- C3-Cs-alkenyl, preferably C3-C4-alkenyl, such as 2-propenyl or 2-butenyl, CS-C6-cyclo-alkenyl, such as 2-cyclopentenyl or 2-cyclo-hexenyl, C3-C~-alkynyl, preferably C3-C4-alkynyl, such as 2-propynyl, 2-butynyl or 3-butynyl, it being possible for the 3 last-mentioned groups to carry one of the follow-ing radicalss hydroxyl, halogen, such as fluorine, chlorine, bromine or iodine, C1-C,-alkoxy, such as methoxy or tert-butoxy, or phenyl, which may itself carry from one to three of the following groups:
halogen, such as fluorine, chlorine or bromine, nitro, cyano, Cl-C,-alkyl, such as methyl, ethyl or tart-butyl, C1-C,-halo-alkyl, such as fluoromethyl, trifluoro-methyl, chlorodifluoromethyl, pentafluoro-ethyl or 2-chloro-1,1,2-trifluoroethyl, or C1-C,-alkoxy, such as methoxy, isopropoxy or tent-butoxy;
- phenyl, which may carry from one to three of the following groupss - halogen, such as fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine, nitro, cyano, C1-C,-alkyl, such as methyl, ethyl or tent-butyl, partially or fully halogenated C1-C,-alkyl, such as trifluoromethyl, 1,1,2,2-tetrafluoroethyl or trichloromethyl, C1-C,-alkoxy, such as methoxy, ethoxy or isopropoxy, partially or fully halogenated Cl-C,-alkoxy, such as - .~.-.
2 p 2 5 9 3 ~ 43 - 0. Z . 0050/41111 trifluoromethoxy, chlorodifluoromethoxy, 1-fluorothoxy, pentafluoroethoxy or 2-chloro-1,1,2-trifluoroethoxy, or C1-C"-alkoxycarbonyl, such as methoxycarbonyl, n-propoxycarbonyl or tert-butoxycarbonyl;
- a 5- or 6-membered saturated heterocyclic radical or a 5- or 6-membered heteroaromatic radical, in each case having from 1 to 3 heteroatoms selected from the group comprising oxygen, sulfur and nitrogen, where two oxygen or sulfur atoms or one oxygen and one sulfur atom must not be directly adjacent, as men-tioned above, in particular 2-tetrahydro-furanyl, 3-tetrahydrothienyl, 4-tetrahydro-pyranyl, 2-furanyl, 2-thienyl, 4-isoxazolyl, 5-isothiazolyl, 2-oxazolyl, 4-thiazolyl, 2-imidazolyl, 2-pyrrolyl, 3-pyrazolyl and 4-pyridyl, it being possible for the hetero-cyclic rings to also carry one or two of the following substituentss halogen as mentioned above, C1-C3-alkyl as mentioned above, C1-C3-alkoxy as mentioned above and/or C1-C3-alkoxy-carbonyl as mentioned above;

- benzotriazolyl;

- N-phthalimido, tetrahydrophthalimido, N-succinimido or maleiimido;

- 2,2-dimethyl-1,3-dioxolan-4-ylmethyl or 1,3-dioxolan-2-on-4-ylmethyl;

- in the case where Y = Os one equivalent of a cation from the group comprising the alkali metals and alkaline earth metals, such as sodium, potassium and calcium, .manganese, copper, iron, ammonium and ammonium which is - substituted by up to 4 Ci-C3-alkyl groups, such as tetramethylammonium;

- -N=CR8R9 where _ '~ ~ 2025939 - 44 - O.Z. 0050/41111 Re and R are - hydrogen;

- C1-C4-alkyl or partially or fully halogenated C1-C~-alkyl, such as methyl, ethyl, isopropyl, tart-butyl, chloromethyl, fluoromethyl, trifluoromethyl, trichloro-methyl or 1,1,2,2-tetra-fluoroethyl, it being pos-sible for the alkyl or haloalkyl group to also carry one of the following radicals:

- C1-C3-alkoxy as mentioned above, in particular methoxy, - phenyl, which may additionally be monosubsti-tuted, disubstituted or trisubstituted by nitro, cyano, halogen as mentioned above, in particular fluorine or chlorine, Ci-C3-alkyl as mentioned above, in particular methyl or tart-butyl, partially or fully halogenated C1-C3-alkyl as mentioned above, in particular trifluoro-methyl, C1-C3-alkoxy as mentioned above, in par-ticular methoxy, and/or partially or fully halo-genated C1-C3-alkoxy as mentioned above, in par-ticu~lar trifluoromethoxy;

- C3-C8-cycloalkyl, such as ".-,.
2 ~ 2 5 g 3 g. 45 - 0. Z . 0050/41111 cyclopropyl, cyclopentyl or cyclohexyl;

- C1-C4-alkoxy as mentioned above, in particular methoxy;

- furanyl or phenyl, which may additionally be monosubsti-tuted, disubstituted or trisubstituted by vitro, cyano, halogen as mentioned above, in particularfluorine or chlorine, C1-C3-alkyl as mentioned above, in particular methyl or tert-butyl, partially or fully halogenated C1-C3-alkyl as mentioned above, in par-ticular trifluoromethyl, C1-C3-alkoxy as mentioned above, in particular methoxy, and/or partially or fully halo-genated C1-C3-alkoxy as ' mentioned above, in par-ticular trifluoromethoxy;

Re and R are - together are a methylene chain having from 4 to 7 members, preferably 4 or 5 members;

- -W-Z where W is an ethylene, n-propylene, n-butylene, ethoxyethylene, but-2-enylen or but-2 ynylene chain;
Z is a molecular moiety which is bonded to W
in the w-position and is the same as that linked to W in the a-position of W, for example ' - 46 - O.Z. 0050/41111 R~

N\X~R1 R
R6 is - hydrogen;
- Cl-C6-alkyl, preferably C1-C~-alkyl, such as methyl, ethyl, isopropyl or tart-butyl;
- C3-Ce-cycloalkyl, preferably C3-CB-cyclo alkyl, such as cyclopropyl, cyclopentyl or cyclohexyl;
R' is - hydrogen;
- C1-CB-alkyl, preferably C1-C,-alkyl, such as methyl or tart-butyl;
- -C ( OR12 ) =N-H or -C ( OR12 ) =N- ( C1-C,- ) -alkyl , where C1-C4-alkyl is alkyl as mentioned above, in particular methyl, ethyl or tert-butyl, and R12 is likewise C1-C,-alkyl as mentioned above, in particular methyl;
R6 and R' - together are a methylene chain having from 4 to 7 members, preferably 4 or 5 members;
R3 is - hydrogen;
- C1-Ce-alkyl, preferably C1-C4-alkyl, such as 2 0 methyl , ethyl or tart-butyl , which may c arry from one to three of the following substituents:
hydroxyl, halogen, C1-C~-alkoxy, such as methoxy or tart-butoxy, C1-C,-alkylthio, such as methyl thio or tart-butylthio, or di(C1-C,-)-alkylamino, preferably di ( C1-CZ ) -alkylamino, such as dimethyl-amino or diethylamino;
- C3-Ce-cycloalkyl, preferably C3-Ce-cycloalkyl, such as cyclopropyl, cyclopentyl or cyclohexyl, which may be monosubstituted, disubstituted or trisub-stituted by halogen, such as fluorine, chlorine or bromine, C1-C,-alkyl, such as methyl or tert-butyl, or by partially or fully halogenated C1-C,-2 0 2 5 9 3 9 4' - o. z . 0050/41111 alkyl, such as fluoromethyl, trifluoromethyl, chlorodifluoromethyl, pentafluoroethyl or 2-chloro-1,1,2-trifluoroethyl;
R4 is - hydrogen, hydroxyl;
- C1-C,-alkoxy, such as methoxy, ethoxy or tert-butoxy;
- linear or branched C1-CB-alkyl, preferably C1-C,-alkyl, such as methyl, ethyl, isopropyl or tert-butyl, which may carry from one to three of the following radicals: halogen, such as fluorine, chlorine or bromine, cyano, C1-C,-alkoxy, such as methoxy or tert-butoxy, partially or fully halogenated C1-C,-alkoxy, such as fluoromethoxy, trichloromethoxy, 2-chloro-1,1,2-trifluoroethoxy or pentafluoroethoxy, C1-C,-alkylthio, such as methylthio or tert-butylthio, C1-C,-haloalkylthio, such as fluoromethylthio, trichloromethylthio, 2-chloro-1,1,2-trifluoroethylthio or pentafluoro-ethylthio, di(C1-C,)-alkylamino, in particular di(C1-C2)-alkylamino, such as dimethylamino or diethylamino, C3-CB-cycloalkyl, in particular C3-CB-cycloalkyl, such as cyclopropyl, cyclopentyl or cyclohexyl, or phenyl, it being possible for the phenyl radical to itself carry up to three of the following groups: halogen, such as fluorine, chlorine or bromine, cyano, vitro, C1-C,-alkyl, such as methyl or tert-butyl, C1-C,-haloalkyl, such as fluoromethyl, trichloromethyl, 2-chloro-1,1,2-trifluoroethyl or pentafluoro-ethyl, C1-C,-alkoxy, such as methoxy or tert-butoxy, partially or fully halogenated C1-C,-alkoxy, such as fluoromethoxy, trichloromethoxy, 2-chloro-1,1,2-trifluoroethoxy or pentafluoro-ethoxy, C1-C,-alkylthio, such as methylthio or tart-butylthio, or C1-C,-haloalkylthio, such as fluoromethylthio, trichlormethylthio, 2 0 2 5 9 3 9- 48 - o. z . 0050/41111 2-chloro-1,1,2-trifluoroethylthio or pentafluoro-ethylthio;

- C3-C8-cycloalkyl, preferably C3-CB-cycloalkyl, in particular cyclopropyl, cyclopentyl or cyclo-hexyl, each of which may carry from one to three of the following radicals: halogen, such as fluorine, chlorine or bromine, nitro, cyano, C1-C6-alkyl, preferably C1-C~-alkyl, such as methyl or tert-butyl, partially or fully halogenated C1-Cg-alkyl, preferably C1-C4-haloalkyl, such as fluoromethyl, trichloromethyl, 2-chloro-1,1,2-trif luoroethyl or pentaf luoroethyl, C1-C,-alkoxy, such as methoxy or tert-butoxy, or partially or fully halogenated C1-C,-alkoxy, such as fluoromethoxy, trichloromethoxy, 2-chloro-1,1,2-trifluoroethoxy or pentafluoroethoxy;

- C3-CB-alkenyl or C3-CB-alkynyl, preferably C3-C,-alkenyl or C3-C~-alkynyl, such as 2-propenyl, 2-butenyl, 2-propynyl, 1,1-dimethyl-2-propynyl or 3-butynyl, each of which may be up to trisubsti-tuted by halogen, such as fluorine, chlorine or bromine, and/or monosubstituted by phenyl, it being possible for the phenyl radical to itself carry from one to three of the following substi-tuents: halogen, in particular fluorine or chlorine, cyano, nitro, C1-C,-alkyl, such as methyl or tert-butyl, partially or fully halo-genated C1-C,-alkyl, such as fluoromethyl, tri-fluoromethyl, trichloromethyl, 2-chloro-1,1,2-trifluoroethyl or pentafluoroethyl, C1-C,-alkoxy, such as methoxy or tert-butoxy, C1-C,-haloalkoxy, such as fluoromethoxy, trifluoromethoxy, tri-chloromethoxy, 2-chloro-1,1,2-trifluoroethoxy or pentafluoroethoxy, C1-C~-alkylthio, such as methylthio or to=t-butylthio, partially or fully halogenated C1-C,-alkylthio, such as fluoromethyl-thio, trifluoromethylthio, trichloromethylthio, 2 0 2 5 9 3 g 49 - o. z . 005041111 2-chloro-1,1,2-trifluoroethylthio or pentafluoro-ethylthio;
- di ( C1-C4 ) -alkylamino, preferably di ( C1-C2 ) -alkyl amino, such as dimethylamino or diethylamino;
- a 5- or 6-membered, saturated or aromatic hetero-cyclic radical, containing one or two heteroatoms selected from the group comprising oxygen, sulfur and nitrogen, such as 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-furanyl, 3-furanyl, 2-thienyl, 3-thienyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-pyrrolyl, 3-pyr-rolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-pyridyl, 3-pyridyl or 4-pyridyl, which may carry from one to three of the following substituentss C1-C,-alkyl as mentioned above, in particular methyl, or halogen as mentioned above, in par-ticular fluorine or chlorine;
phenyl, which may carry from one to four of the following groups s C1-C~-alkyl as mentioned above, in particular methyl, ethyl or 1-methylethyl;
partially or fully halogenated C1-C~-alkyl as mentioned above, in particular trifluoromethyl or chlorodifluoromethyl; C1-C,-alkoxy as mentioned above, in particular methoxy or ethoxy; partially or fully halogenated Ci-C,-alkoxy as mentioned above, in particular trifluoromethoxy, trichloro-methoxy or pentafluoroethoxy; C1-C,-alkylthio as mentioned above, in particular methylthio or 2 0 2 5 9 3 9" 50 - o. z . 0050/41111 ethylthio; partially or fully halogenated C1-C,-alkylthio as mentioned above, in particular difluoromethylthio, trifluoromethylthio or pentafluoromethylthio, halogen as mentioned above, in particular fluorine or chlorine, cyano, nitro, formyl, C1-C4-alkanoyl, such as acetyl, propionyl, butyryl, in particular acetyl, par-tially or fully halogenated C1-C,-alkanoyl, such as trifluoroacetyl, trichloroacetyl, pentafluoro-propionyl, in particular trifluoroacetyl, C1-C,,-alkoxycarbonyl, such as methoxycarbonyl or tert-butoxycarbonyl;
- naphthyl, which may be monosubstituted, disub-stituted or trisubstituted by C1-C,-alkyl, such as methyl or tert-butyl, in particular methyl or ethyl, or halogen such as fluorine or chlorine;
- R3 and R' together are a C,-C~-methylene chain, which may be interrupted by oxygen, sulfur or N-methyl , such as - ( CHZ ) 3-, - ( CHZ ) ,,-, - ( CH2 ) s-.
2 U - ( CHz ) e- I -CH2-0-CHZ-, -CH2-CHZ-0-CHZ-CH2- ~
-CHZ-S-CH2-, -CH2-CHZ-S-CH2-CHZ-, -CHZ-CH2-N ( CH3 ) -CHZ-CHZ-, in particular - ( CHZ ) s- and -CHZ-CH2-0-CHZ-CH2-;
- or - ( CHs ) 3-CO- .
Preferred compounds of the formulae Ia to Id are those in which RZ is CO-Y-Rs, and Y is oxygen or sulfur:
R4 Ra N~ Ri NI S I R1 Ia (X = 0) Ia (X = S) R 5 Y C I I C 0-N-R 3 R 5-Y-C I I _ C 0-f I-R 3 O~~R 1 ~R 1 Ib (X = 0) Ib (X = S) 2 0 2 5 9 3 ~ 51 - o.z. 0050/41111 R1 I ( CO-N-R3 R1 I I CO N R3 N~~CO-Y-R5 N~~CO-Y-R5 Ic (X = 0) Ic (X = S) R1~ CO-Y-RS R1~ CO-Y-R5 NI I C 0-N-R 5 N' S ~ C 0-N-R 3 Id (X = 0) Id (X = S) Table 1 shows examples of possible substituents R1, R3, R' and RS of the preferred compounds Ia-Ic ( RZ =
CO-Y-Rs), and Table 2 shows possible substituents of the compounds Id (RZ = CO-Y-RS), the carboxamides Ia (R2 = CO-Y-RS) being particularly preferred.

2 0 2 5 9 3 a 52 0.z. 0o5o~4W 11 Table 1 H H tert.-butyl H 0 F H tert.-butyl H 0 Cl H tert.-butyl H 0 methyl H tert.-butyl H 0 ethyl H tert.-butyl H 0 n-propyl H tert.-butyl H 0 iso-propyl H tert.-butyl H 0 n-butyl H tert.-butyl H 0 iso-butyl H tert.-butyl H 0 sec.-butyl H tert.-butyl H 0 tert.-butyl H tert.-butyl H 0 cyclo-propyl H tert.-butyl H 0 cyclo-butyl H tert.-butyl H 0 cyclo-pentyl H tert.-butyl H 0 cyclo-hexyl H tert.-butyl H 0 cyclo-heptyl H tert.-butyl H 0 cyclo-octyl H tert.-butyl H 0 1-methylcyclopropyl H tert.-butyl H 0 chloromethyl H tert.-butyl H 0 1-chloroethyl H tert.-butyl H 0 trifluoromethyl H tert.-butyl H 0 chlorodifluoromethyl H tert.-butyl H 0 pentafluoroethyl H tert.-butyl H 0 methoxymethyl H tert.-butyl H 0 1-methylmethoxymethyl H tert.-butyl H 0 1-methylmethoxyethyl H tert.-butyl H 0 ethoxymethyl H tert.-butyl H 0 vinyl H tert.-butyl H 0 allyl H tert.-butyl H 0 methallyl H tert.-butyl H 0 crotyl H tert.-butyl H 0 ethynyl H tert.-butyl H 0 propargyl H tert.-butyl H 0 phenylethynyl H tert.-butyl H 0 methoxy H tert.-butyl H 0 ethoxy H tert.-butyl H 0 trifluoromethoxy H tert.-butyl H 0 methylthio H tert.-butyl H 0 trifluoromethylthio H tert.-butyl H 0 2 0 2 5 9 3 9 53 O.Z. 0050/41111 phenoxy H tert.-butyl H 0 4-Cl-phenoxy H tert.-butyl H 0 2,4-(C1,C1)-phenoxy H tert.-butyl H 0 4-CF3-phenoxy H tert.-butyl H 0 phenyl H tert.-butyl H 0 2-F-phenylthio H tert.-butyl H 0 3-F-phenyl H tert.-butyl H 0 2,4-(F,F)-phenyl H tert.-butyl H 0 2-Cl-phenyl H tert.-butyl H 0 3-C1-phenyl H tert.-butyl H 0 2,4-(Cl,Cl)-phenyl H tert.-butyl H 0 2-CH3-phenyl H tert.-butyl H 0 3-CH3-phenyl H tert.-butyl H 0 4-CH3-phenyl H tert.-butyl H 0 2,4-(CH3,CH3)-phenyl H tert.-butyl H 0 2, 4, 6-(CH3, CH3, CHg)-phenylH tert.-butyl H 0 2-CFg-phenyl H tert.-butyl H 0 2-OCH3-phenyl H tert.-butyl H 0 2,4-(OCH3,OCH3)-phenyl H tert.-butyl H 0 4-OCF3-phenyl H tert.-butyl H 0 4-SCH3-phenyl H tert.-butyl H 0 3-SCF3-phenyl H tert.-butyl H 0 2,4-(NOZ,NOZ)-phenyl H tert.-butyl H 0 4-NOy-phenyl H tert.-butyl H 0 2-thienyl H tert.-butyl H 0 3-thienyl H tert.-butyl H 0 2-furanyl H tert.-butyl H 0 3-furanyl H tert.-butyl H 0 2-tetrahydrofuranyl H tert.-butyl H 0 3-tetrahydrofuranyl H tert.-butyl H 0 2-pyridyl H tert.-butyl H 0 3-pyridyl H tert.-butyl H 0 4-pyridyl H tert.-butyl H 0 2-tetrahydropyranyl H tert.-butyl H 0 3-tetrahydropyranyl H tert.-butyl H 0 4-tetrahydropyranyl H tert.-butyl H 0 iso-propoxy H tert.-butyl H 0 H H cyclo-propyl H 0 F H cyclo-propyl H 0 C1 H cyclo-propyl H 0 methyl H cyclo-propyl H 0 ethyl H cyclo-propyl H 0 2 0 2 5 9 3 9 54 0. Z . 0050/41111 n-propyl H cyclo-propyl H 0 iso-propyl H cyclo-propyl H 0 n-butyl H cyclo-propyl H 0 iso-butyl H cyclo-propyl H 0 sec.-butyl H cyclo-propyl H 0 tert.-butyl H cyclo-propyl H 0 cyclo-propyl H cyclo-propyl H 0 cyclo-butyl H cyclo-propyl H 0 cyclo-pentyl H cyclo-propyl H 0 cyclo-hexyl H cyclo-propyl H 0 cyclo-heptyl H cyclo-propyl H 0 cyclo-octyl H cyclo-propyl H 0 1-methylcyclopropyl H cyclo-propyl H 0 chloromethyl H cyclo-propyl H 0 1-chloroethyl H cyclo-propyl H 0 trifluoromethyl H cyclo-propyl H 0 chlorodifluoromethyl H cyclo-propyl H 0 pentafluoroethyl H cyclo-propyl H 0 methoxymethyl H cyclo-propyl H 0 1-methylmethoxymethyl H cyclo-propyl H 0 1-methylmethoxyethyl H cyclo-propyl H 0 ethoxymethyt H cyclo-propyl H 0 vinyl H cyclo-propyl H 0 allyl H cyclo-propyl H 0 methallyt H cyclo-propyl H 0 crotyl H cyclo-propyl H 0 ethynyl H cyclo-propyl H 0 propargyl H cyclo-propyl H 0 phenylethynyl H cyclo-propyi H 0 methoxy H cyclo-propyl H 0 ethoxy H cycio-propyl H 0 trifluoromethoxy H cyclo-propyl H 0 methylthio H cyclo-propyl H 0 trifluoromethylthio H cyclo-propyl H 0 phenoxy H cyclo-propyl H 0 4-Cl-phenoxy H cyclo-propyl H 0 2,4-(CI,CI)-phenoxy H cyclo-propyl H

4-CF3-phenoxy H cyclo-propyl H

phenyl H cyclo-propyl H '0 2-F-phenylthio H cyclo-propyl H 0 3-F-phenyl H cyclo-propyl H '0 2,4-(F,F)-phenyl H cyclo-propyl H 0 2 0 2 5 9 3 9 55 0. Z . 0050/41111 2-Cl-phenyl H cyclo-propyl H 0 3-Cl-phenyl H cyclo-propyl H 0 2,4-(Cl,Cl)-phenyl H cyclo-propyl H 0 2-CH3-phenyl H cyclo-propyl H 0 3-CH3-phenyl H cyclo-propyl H 0 4-CH3-phenyl H cyclo-propyl H 0 2,4-(CH3,CH3)-phenyl H cyclo-propyl H 0 2,4,6-(CH3,CH3,CH3)-phenylH cyclo-propyi H 0 2-CF3-phenyl H cyclo-propyl H 0 2-OCH3-phenyl H cyclo-propyi H 0 2,4-(OCH3,OCH3)-phenyl H cyclo-propyl H 0 4-OCF3-phenyl H cyclo-propyl H 0 4-SCH3-phenyl H cyclo-propyl H 0 3-SCF3-phenyl H cyclo-propyl H 0 2,4-(NOZ,NOZ)-phenyl H cyclo-propyl H 0 4-NOZ-phenyl H cyclo-propyl H 0 2-thienyi H cyclo-propyt H 0 3-thienyl H cycio-propyl H 0 2-furanyl H cyclo-propyl H 0 3-furanyl H cyclo-propyl H 0 2-tetrahydrofuranyl H cyclo-propyl H 0 3-tetrahydrofuranyl H cyclo-propyl H 0 2-pyridyl . H cyclo-propyl H 0 3-pyridyl H cyclo-propyl H 0 4-pyridyl H cyclo-propyl H 0 2-tetrahydropyranyi H cyclo-propyl H 0 3-tetrahydropyranyl H cyclo-propyl H 0 4-tetrahydropyranyl H cyclo-propyl H 0 iso-propoxy H cyclo-propyl H 0 H methyl tert.-butyl H 0 F methyl tert.-butyl H 0 Cl methyl tert.-butyl H 0 methyl methyl tert.-butyl H 0 ethyl methyl tert.-butyl H 0 n-propyl methyl tert.-butyl H 0 iso-propyl methyl tert.-butyl H 0 n-butyl methyl tert.-butyl H 0 iso-butyl methyl tert.-butyl H 0 sec.-butyl methyl tert.-butyl H 0 tert.-butyl methyl tert.-butyl H 0 cyclo-propyl methyl tert.-butyl H 0 cyclo-butyl methyl tert.-butyl H 0 cyclo-pentyl methyl tert.-butyl H 0 2 p 2 5 9 3 9 56 0. Z . 0050/41111 cyclo-hexyl iso-propyl tert.-butyl H 0 cyclo-heptyl iso-propyl tert.-butyl H 0 cyclo-octyl iso-propyl tert.-butyl H 0 1-methylcyclopropyl iso-propyl tert.-butyl H 0 trifluoromethyl iso-propyl tert.-butyl H 0 chlorodifluoromethyl iso-propyl tert.-butyl H 0 pentafluoroethyl iso-propyl tert.-butyl H 0 methoxymethyl iso-propyl tert.-butyl H 0 1-methylmethoxymethyl iso-propyl tert.-butyl H 0 1-methylmethoxyethyl iso-propyl tert.-butyl H 0 ethoxymethyl iso-propyl tert.-butyl H 0 vinyl iso-propyl tert.-butyl H 0 allyl iso-propyl tert.-butyl H 0 methallyl iso-propyl tert.-butyl H 0 crotyl iso-propyl tert.-butyl H 0 ethynyl iso-propyl tert.-butyl H 0 propargyl iso-propyl tert.-butyl H 0 phenylethynyl iso-propyl tert.-butyl H 0 methoxy iso-propyl tert.-butyl H 0 ethoxy iso-propyl tert.-butyl H 0 trifluoromethoxy iso-propyl tert.-butyl H 0 H methyl cyclo-propyl H 0 methyl cyclo-propyl H 0 Cl methyl cyclo-propyl H 0 methyl methyl cyclo-propyl H 0 ethyl methyl cyclo-propyl H 0 n-propyl methyl cyclo-propyl H 0 iso-propyl methyl cyclo-propyl H 0 n-butyl iso-propyl cyclo-propyl H 0 iso-butyl iso-propyl cyclo-propyl H 0 sec.-butyl iso-propyl cyclo-propyl H 0 tert.-butyl iso-propyl cyclo-propyl H 0 cyclo-propyl iso-propyl cyclo-propyl H 0 cyclo-butyl iso-propyl cyclo-propyl H 0 cyclo-pentyl iso-propyl cyclo-propyl H 0 cyclo-hexyl methyl cyclo-propyl H 0 cyclo-heptyl methyl cyclo-propyl H 0 cyclo-octyl methyl cyclo-propyl H 0 1-methylcyclopropyl methyl cyclo-propyl H 0 trifluoromethyl methyl cyclo-propyl H 0 chlorodifluoromethyl methyl cyclo-propyl H 0 pentafluoroethyl methyl cyclo-propyl H 0 2 p 2 5 9 3 9 5~ 0. Z . 0050/41111 methoxymethyl iso-propyl cyclo-propyl H 0 1-methylmethoxymethyl iso-propyl cyclo-propyl H 0 1-methylmethoxyethyl iso-propyl cyclo-propyl H 0 ethoxymethyl iso-propyl cyclo-propyl H 0 vinyl iso-propyl cyclo-propyl H 0 allyl iso-propyl cyclo-propyl H 0 methallyl iso-propyl cyclo-propyl H 0 crotyl methyl cyclo-propyl H 0 ethynyl methyl cyclo-propyl H 0 propargyl methyl cyclo-propyl H 0 phenylethynyl methyl cyclo-propyl H 0 methoxy methyl cyclo-propyl H 0 ethoxy methyl cyclo-propyl H 0 trifluoromethoxy methyl cyclo-propyl H 0 >~ O O O O O O O O O O O O O O O O O O O O O O
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NIX CO-N-H R3 = H

R1' R4 RS X

cyclopropyl-CH(CH3)-tert.-butyl H 0 cyclopropyl-CH(C2H5)-tert.-butyl H 0 CNZ=CH- tert.-butyl H 0 E-CH3-CH=CH- tert.-butyl H 0 Z-CH3-CH=CH- tert.-butyl H 0 CHy=CH-CHy- tert.-butyl H 0 CHZ=C(CH3)- tert.-butyl H 0 CZHS-CH=CH- tert.-butyl H 0 CH3-CH=C(CH3)- tert.-butyl H 0 CHZ=C(CZHS)- tert.-butyl H 0 CH3-CH=C(CZHS)- tert.-butyl H 0 (CH3)yC=CH- tert.-butyl H 0 CHZ=C(CH3)-CH(CH3)- tert.-butyl H 0 (CH3)ZC=CH-CHy- tert.-butyl H 0 CH3-CC1=CH- tert.-butyl H 0 C12C=CH- tert.-butyl H 0 cyclopent-1-ene tert.-butyl H 0 cyclohex-1-ene tert.-butyl H 0 1-CH3-cyclohex-2-enetert.-butyl H 0 E-phenyl-CH=CH- tert.-butyl H 0 E-4-(CHgO)-C6H5-CH=CH-tert.-butyl H 0 HC=C- tert.-butyl H 0 CH3-C=C- tert.-butyl H 0 HC=C-CHZ- tert.-butyl H 0 phenyl-C=C- tert.-butyl H 0 CH3-CH ~ CH- tert.-butyl H 0 cyclopropyl-CH(CH3)-cyclopropyl H 0 cyclopropyl-CH(C2H5)-cyctopropyl H 0 CHZ=CH- cyclopropyl H 0 E-CH3-CH=CH- cyclopropyl H 0 Z-CH3-CH=CH- cyclopropyl H 0 CHZ=CH-CHZ- cyclopropyl H 0 CHZ=C(CHg)- cyclopropyl H 0 CZHS-CH=CH- cyclopropyl H 0 2 0 2 5 ~9'S 9 0. Z . 0050 41111 Table 2 (condt.) R1. R4 R5 X

CH3-CH=C(CH3)- cyclopropyl H 0 CHy=C(CZHS)- cyclopropyl H 0 CH3-CH=C(CyHS)- cyclopropyl H 0 (CH3)pC=CH- cyclopropyl H 0 CH2=C(CH3)-CH(CH3)- cyclopropyl H o (CH3)yC=CH-CHy- cyclopropyl H 0 CH3-CC1=CH- cyclopropyl H 0 C12C=CH- cyclopropyl H 0 cyclopent-1-ene cyclopropyl H 0 cyclohex-1-ene cyclopropyl H 0 1-CH3-cyclohex-2-enecyclopropyl H 0 E-phenyl-CH=CH- cyclopropyl H 0 E-4-(CH30)-CgHS-CH=CH-cyclopropyl H 0 HC=C- cyclopropyl H 0 CH3-C=C- cyclopropyl H 0 HC=C-CHZ- cyclopropyl H 0 phenyl-C=C- cyclopropyl H 0 CH3-CH ~ CH- cyclopropyl H 0 cyclopropyl-CH(CH3)-C(CH3)2C'--CH H 0 cyclopropyl-CH(CyHS)-C(CH3)yC=CH H 0 CHZ=CH- C(CH3)yC'--CH H 0 E-CH3-CH=CH- C(CH3)2C=CH H 0 Z-CH3-CH=CH- C(CH3)yC=CH H 0 CHZ=CH-CHy- C(CH3)2C=CH H 0 CHy=C(CH3)- C(CH3)2C=CH H 0 CZHS-CH=CH- C(CH3)2C=CH H 0 CH3-CH=C(CH3)- C(CH3)yC=CH H 0 CHZ=C(CZHS)- C(CH3)yC=CH H 0 CH3-CH=C(CyHS)- C(CH3)ZC=CH H 0 (CH3)2C=CH- C(CH3)yC'--CH H 0 CHZ=C(CH3)-CH(CH3)- C(CH3)yC=CH H 0 (CH3)ZC=CH-CHZ- C(CH3)yC=CH H 0 CH3-CCl=CH- C(CH3)ZC=CH H 0 C12C=CH- C(CH3)2C=CH H 0 cyclopent-1-ene C(CH3)2C=CH H 0 cyclohex-1-ene C(CH3)ZC=CH H 0 1-CH3-cyclohex-2-eneC(CH3)yC=CH H 0 E-phenyl-CH=CH- C(CH3)2C=CH H 0 2 0 2 5 9 3 ~o o . Z . 0050/41111 Table 2 (condt.) R1. R4 R5 X

E-4-(CH30)-CgHS-CH=CH-C(CH3)2Ce_CH H 0 HC=C- C(CH3)yC=_CH H 0 CH3-C=C- C(CH3)2C'--CH H 0 HC=C-CH2- C(CH3)2C=CH H 0 phenyl-C=C- C(CH3)2C=CH H 0 CH;-CH ~ CH- C(CHg)yC=CH H 0 cyclopropyl-CH(CH3)-C(CH3)2C=N H 0 cyclopropyl-CH(CZHS)-C(CH3)ZC'--N H 0 CHZ=CH- C(CH3)ZC'--N H 0 E-CH3-CH=CH- C(CH3)ZC=N H 0 Z-CH3-CH=CH- C(CH3)yC=N H 0 CHZ=CH-CH2- C(CH3)ZC=N H 0 CH2=C(CH3)- C(CH3)ZC=N H 0 CyHS-CH=CH- C(CH3)yC=N H 0 CH3-CH=C(CH3)- C(CH3)yC=N H 0 CHZ=C(CyHS)- C(CH3)ZC'--N H 0 CH3-CH=C(C2Hg)- C(CH3)2C=N H 0 (CH3)2C=CH- C(CH3)ZC'-__N H 0 CHZ=C(CH3)-CH(CH3)- C(CH3)yC=N H 0 ( CH 3 ) ZC=CH-CH ~ C ( CH; ) ZC=NH 0 CH3-CCl=CH- C(CH3)2C'-_N H 0 C12C=CH- C(CH3)yC'--N H 0 cyclopent-1-ene C(CH3)2C=N H 0 cyclohex-1-ene C(CH3)yC=N H 0 1-CH3-cyclohex-2-eneC(CH3)2C=N H 0 E-phenyl-CH=CH- C(CH3)yC=N H 0 E-4-(CH30)-CgHS-CH=CH-C(CH3)yC=N H 0 HC=C- C(CH3)ZC'--N H 0 CH3-C=C- C(CH3)yC'-_N H 0 HC=C-CH2- C(CH3)yC=N H 0 phenyl-C=C- C(CH3)ZC=N H 0 CH3-CH ~ CH- C(CH3)yC=N H 0 CHy=CH- tert.-butyl H S

E-CH3-CH=CH- tert.-butyl H S

E-C6H5-CH=CH- tert.-butyl H S

CHy=C(CH3)- tert.-butyl H S

91 O.Z. 0050/41111 Table 2 (condt.) 2p2593 R1' R4 R5 X

CHy=CH- cyclopropyl H S

E-CH3-CH=CH- cyclopropyl H S

E-C6H5-CH=CH- cyclopropyl H S

CHZ=C(CH3)- cyclopropyl H S

cyclopropyl-CH(CH3)-tert.-butyl -N=C(CH3)2 0 cyclopropyl-CH(CyHS)-tert.-butyl -N=C(CH3)p 0 CHZ=CH- tert.-butyl -N=C(CH3)y 0 E-CH3-CH=CH- tert.-butyl -N=C(CH3)y 0 Z-CH3-CH=CH- tert.-butyl -N=C(CH3)2 0 CH2=CH-CH2- tert.-butyl -N=C(CH3)2 0 CHZ=C(CH3)- tert.-butyl -N=C(CH3)Z 0 CyH5-CH=CH- tert.-butyl -N=C(CHg)2 0 CH3-CH=C(CH3)- tert.-butyl -N=C(CH3)2 0 CHZ=C(C2Hg)- tert.-butyl -N=C(CH3)2 0 CH3-CH=C(C2H5)- tert.-butyl -N=C(CH3)y 0 (CH3)ZC=CH- tert.-butyl -N=C(CH3)2 0 CHp=C(CH3)-CH(CH3)- tert.-butyl -N=C(CHg)2 0 (CH3)ZC=CH-CHy- tert.-butyl -N=C(CH3)Z 0 CH3-CC1=CH- tert.-butyl -N=C(CH3)y 0 C12C=CH- tert.-butyl -N=C(CH3)2 0 cyclopent-1-ene tert.-butyl -N=C(CH3)y 0 cyclohex-1-ene tert.-butyl -N=C(CH3)y 0 1-CH3-cyclohex-2-enetert.-butyl -N=C(CH3)y 0 E-phenyl-CH=CH- tert.-butyl -N=C(CH3)2 0 E-4-(CH30)-C6H5-CH=CH-tert.-butyl -N=C(CH3)y 0 HC=C- tert.-butyl -N=C(CH3)y 0 CH3-C=C- tert.-butyl -N=C(CH3)2 0 HC=C-CH2- tert.-butyl -N=C(CH3)2 0 phenyl-C=C- tert.-butyl -N=C(CH3)2 0 CH3-CH ~ CH- tert.-butyl -N=C(CH3)2 0 cyclopropyl-CH(CH3)-cyclopropyl -N=C(CH3)2 0 cyciopropyl-CH(CZHS)-cyclopropyl -N=C(CH3)2 0 CHZ=CH- cyclopropyl -N=C(CH3)Z 0 E-CH3-CH=CH- cyclopropyl -N=C(CH3)y 0 Z-CHg-CH=CH- cyclopropyl -N=C(CH3)2 0 CHZ=CH-CH2- cyclopropyl -N=C(CH3)Z 0 CHZ=C(CH3)- cyclopropyl -N=C(CH3)Z 0 CZHg-CH=CH- cyclopropyl -N=C(CH3)Z 0 92 O.Z. 0050/41111 Table 2 (condt.) _ 2 0 2 5 9 3 9 R1. R4 R5 X

CH3-CH=C(CH3)- cyclopropyl -N=C(CH3)y 0 CH2=C(CyHS)- cyclopropyl -N=C(CH3)y 0 CH3-CH=C(CpHS)- cyclopropyl -N=C(CH3)y 0 (CHg)ZC=CH- cyclopropyl -N=C(CH3)2 0 CHZ=C(CH3)-CH(CH3)- cyclopropyl -N=C(CH3)2 0 (CH3)ZC=CH-CH2- cyclopropyl -N=C(CH3)2 0 CH3-CC1=CH- cyclopropyl -N=C(CH3)y 0 CIZC=CH- cyclopropyl -N=C(CH3)2 0 cyclopent-1-ene cyciopropyl -N=C(CH3)2 0 cyclohex-1-ene cyclopropyl -N=C(CH3)2 0 1-CH3-cyclohex-2-enecyclopropyl -N=C(CH3)2 0 E-phenyl-CH=CH- cyclopropyl -N=C(CH3)Z 0 E-4-(CHgO)-CgHS-CH=CH-cyclopropyl -N=C(CH3)y 0 HC-C- cyclopropyl -N=C(CH3)2 0 CH3-C=C- cyclopropyl -N=C(CH3)y 0 HC=C-CHZ- cyclopropyl -N=C(CH3)Z 0 phenyl-C=C- cyclopropyl -N=C(CH3)Z 0 CH3-CH ~ CH- cyclopropyl -N=C(CH3)y 0 CHZ=CH- tert.-butyl -N=C(CH3)y S

E-CHg-CH=CH- tert.-butyl -N=C(CH3)2 S

E-CgHS-CH=CH- tert.-butyl -N=C(CH3)y S

CHZ=C(CH3)- tert.-butyl -N=C(CH3)Z S

CHy=CH- cyclopropyl -N=C(CH3)Z S

E-CH3-CH=CH- cyclopropyl -N=C(CH3)2 S

E-C6H5-CH=CH- cyclopropyl -N=C(CH3)Z S

CHy=C(CH3)- cyclopropyl -N=C(CH3)2 S

3-Cyclopropylaminocarbonyl-5-isopropyl-isoxazole-4-carboxylic acid is particularly preferred.

93 O.Z. 0050/41111 The carboxamides Ia, Ib, Ic and Id, or herbicidal agents containing them, may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broad-casting or watering. The forms of application depend entirely on the pur-pose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vege-table or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphtha-lenes and their derivatives, methanol, ethanol, propanol, butanol, cyclo-hexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.
Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concen-trates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalene-sulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxyl-ated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated ,..., 2~25g~9 O.Z. 0050/41111 castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain meals, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of active ingredient. The active ingredients are used in a purity of 90 to 100, and preferably from 95 to 100, % (according to the NMR
spectrum).
Examples of formulations are as follows:
I. 90 parts by weight of compound no. 3.002 is mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
II. 20 parts by weight of compound no. 3.006 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-sulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dis-persion is obtained containing 0.02% by weight of the active ingredient.
III. 20 parts by weight of compound no. 3.016 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 motes of ethylene oxide and 1 mole of castor oit. By pouring the solution into 100,000 parts by weight of water, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

95 O.Z. 0050/41111 IV. 20 parts by weight of compound no. 3.020 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280°C, and parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole 5 of castor oil. By pouring the solution into 100,000 parts by weight of water, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
V. 20 parts by weight of compound no. 3.029 is well mixed with 3 parts by 10 weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight of the active ingredient.
VI. 3 parts by weight of compound no. 3.047 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3%
b~ weight of the active ingredient.
VII. 30 parts by weight of compound no. 3.048 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
VIII. 40 parts by weight of compound no. 6.04 is dispersed in 10 parts by weight of the sodium salt of a phenosulfonic acid-urea-formaldehyde con densate, 2 parts by weight of silica gel and 48 parts by weight of water.
The mixture may be further diluted.
IX. 20 parts by weight of compound no. 6.06 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenol-sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
x. 10 parts by weight of compound no. 6.08, 4 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 20 parts by weight of the sodium salt of a lignin-sulfonic acid from a sulfite waste liquor, 38 parts by weight of silica gel and 38 parts by weight of kaolin are triturated in a hammer mill. By finely distributing the mixture in 10,000 parts by weight of water a spray liquor is obtained containing O.lwt% of the active ingredient.

96 O.Z. 0050/41111 The active ingredients or the herbicidal agents containing them may be applied pre- or postemergence. If certain crop plants tolerate the active ingredients less well, application techniques may be used in which the herbicidal agents are sprayed from suitable equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by treatment).
The application rates depend on the objective to be achieved, the time of the year, the plants to be combated and their growth stages, and range from 0.001 to 5, and preferably from 0.01 to 1, kg/ha.
In view of the numerous application methods possible, the compounds according to the invention, or agents containing them, may be used in a large number of crops for removing unwanted plants. The crops which follow are given by way of example:
Botanical name Common name Allium cepa onions 20Ananas comosus pineapples Arachis hypogaea peanuts (groundnuts) Asparagus officinalis asparagus Avena sativa oats Beta vulgaris spp. altissima sugarbeets 25Beta vulgaris spp. rapa fodder beets Beta vulgaris spp. esculenta table beets, red beets Brassica napus var. napus rapeseed Brassica napus var. napobrassica swedes Brassica napus var. rapa turnips 30Brassica rapa var. silvestris Camellia sinensis tea plants Carthamus tinctorius safflower Carya illinoinensis pecan trees Citrus limon lemons 35Citrus maxima grapefruits Citrus reticulata mandarins Citrus sinensis orange trees Coffea arabica (Coffea canephora, Coffea liberica) coffee plants 40 Cucumis melo melons Cucumis sativus cucumbers Cynodon dactylon Bermudagrass Daucus carota carrots Elais guineensis oil palms 2 Q 2 5 9 3 ~, o.z. 005041111 Botanical name Common name Fragaria vesca strawberries Glycine max soybeans Gossypium hirsutum (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium) cotton Helianthus annuus sunflowers Helianthus tuberosus Jerusalem artichoke Hevea brasiliensis rubber plants Hordeum vulgare barley 10Humulus lupulus hops Ipomoea batatas sweet potatoes Juglans regia walnut trees Lactuca sativa lettuce Lens culinaris lentils 15Linum usitatissimum flax ~ycopersicon lycopersicum tomatoes Malus spp. apple trees Manihot esculenta cassava Medicago sativa alfalfa (lucerne) 20Mentha piperita peppermint Musa spp. banana plants Nicotiana tabacum (N. rustics) tobacco Olea europaea olive trees Oryza sativa rice 25Panicum mitiaceum millet Phaseolus lunatus limabeans Phaseolus mungo mungbeans Phaseolus vulgaris snapbeans, green beans, dry beans 30Pennisetum glaucum pearl millet Petrosetinum crispum spp. tuberosumparsley Picea abies Norway spruce Abies albs fir trees Pinus spp. pine trees 35Pisum sativum English peas Prunus avium cherry trees Prunus domestics plum trees Prunus dulcis almond trees Prunus persica peach trees 40Pyrus communis pear trees Ribes sylvestre redcurrants Ribes uva-crisps gooseberries Ricinus communis castor-oil plants Saccharum officinarum sugar cane 98 O.Z. 0050/41111 Botanical name Common name Secale cereale rye Sesamum indicum sesame Solanum tuberosum Irish potatoes Sorghum bicolor (s. vulgare) sorghum Sorghum dochna sorgo Spinacia oleracea spinach Theobroma cacao cacao plants Trifolium pratense red clover Triticum aestivum wheat Triticum durum durum wheat vaccinium corymbosum blueberries Yaccinium vitis-idaea cranberries Vicia faba tick beans vigna sinensis (v. unguiculata) cow peas vitis vinifera grapes Zea mays Indian corn, sweet corn, maize To increase the spectrum of action and to achieve synergistic effects, the carboxamides Ia, Ib, Ic and Id may be mixed with each other, or mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of suitable com-ponents are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, Biphenyl ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1,3-dione derivatives, quinolinecar-boxylic acids, (hetero)-aryloxyphenoxypropionic acids and salts, esters, amides thereof, etc.
It may also be useful to apply compounds Ia, Ib, Ic and Id, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phytopathogenic fungi or bacteria. The compounds may also be mixed with solutions of mineral salts used to remedy nutritional or trace element deficiencies.
Non-phytotoxic oils and oil concentrates may also be added.

. ,-- ' 2025939 99 O.Z. 0050/41111 Examples illustrating the synthesis of compounds Ia, Ib, Ic and Id Example 1 3-tert-Butylaminocarbonyl-5-n-propylisoxazole-4-carboxylic acid (no. 3.013 in Table 3) i(CH3)3 H-N-C~COOH

-,~ ~~ n R
Under a nitrogen blanket and at -70'C, 104.6 rtrnol of n-butyllithium (67.7 ml of a 1.5 molar solution in hexane) was dripped into a solution of 10.0 g (47.6 rtanol) of 5-n-propylisoxazole-3-carboxylic acid-tert.-butyl-amide in 250 ml of anhydrous tetrahydrofuran, and the whole was stirred for 30 minutes at this temperature. The reaction mixture was then poured onto 500 g of solid C02 and left to stand overnight. The mixture was evaporated down, the residue was taken up in 300 ml of water and 20 ml of 2N NaOH followed by extraction with two times 100 ml of diethyl ether, the aqueous phase was acidified to pH 2 with 6N hydrochloric acid, followed by extraction four times, each time with 200 ml of ethyl acetate. The ex-tracts were dried over magnesium sulfate and the solvent was removed under reduced pressure. Yield: 80%.
Preliminary stage la 5-n-Propylisoxazole-3-carboxylic acid-tert.-butylamide C~(CH3)3 H-N-C

At 5'C, 9.3 g (126.8 mmol) of tert-butylamine in 20 ml of dichloromethane was dripped into 10.0 g (57.6 mmol) of 5-n-propyl-isoxazole-3-carboxylic chloride in 250 ml of anhydrous dichloromethane. The mixture was stirred for 12 hours at room temperature, 200 m1 of water was added, the phases were separated, the organic phase was washed once with 150 ml of saturated sodium bicarbonate solution and once with 150 ml of saturated sodium chloride solution, followed by drying over magnesium sulfate and stripping off the solvent under reduced pressure. There was obtained 11.5 g (9596) of 5-n-propylisoxazole-3-carboxylic acid-tert-butylamide as a solid of melt-ing point 34 - 37°C.

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Example 2 104 O.Z. 0050/41111 3-tert.-Butylaminocarbonyl-5-n-propyl-isoxazole-4-carboxylic acid acetone oxime ester (No. 3.014 in Table 3) C(CH3) 3 H-N-C I ( C00-N=C(CH3)2 N~C 3H7 At room temperature, 4.9 g (48.1 mmol) of 4-methylmorpholine and 1.6 g (13.0 mmol) of 4-dimethylaminopyridine were dripped into a solution of 3.3 g (13.0 mmol) of 3-tert-butylaminocarbonyl-5-n-propyl-isoxazole-4-carboxylic acid (prepared as in Example 1) and 1.2 g (16.9 mmol) of acetonoxime in 100 ml of dichloromethane, and the mixture was stirred for 5 minutes. Subsequently, 11.3 g of a 50% strength solution of propane-phosphonic anhydride in dichloromethane (= 17.8 mmol) was added and the mixture was refluxed for 12 hours. After concentration, the residue was taken up in 100 ml of ethyl acetate, followed by extraction twice with saturated sodium bicarbonate solution, and once with 59~o strength citric acid solution, once with saturated sodium carbonate solution and once with saturated sodium chloride solution. The organic phase was dried over magnesium sulfate and the solvent was stripped off under reduced pressure.
Yield: 9596.
Example 3 3-tert.-Butylaminocarbonyl-5-phenyl-isothiazole-4-carboxylic acid (No. 3.045 in Table 3) C(CHg)g H-N-C COOH
I I
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with ice cooling, 0.64 g (8.8 mmol) of tent-butylamine was dripped into 2.0 g (8.7 mmol) of 5-phenyl-isothiazole-3,4-dicarboxylic anhydride in 10 ml of dichloromethane, and the whole was stirred for 3 hours at room temperature. The solution was then evaporated down, 25 ml of water was added, and the solution was acidified to a pH of 2 with 6N HC1 and extracted three times, each time with 30 ml of ethyl acetate. The organic phase was washed with 20 ml of saturated sodium chloride solution, dried over magnesium sulfate and evaporated down. The residue was chromatograph-ed on silica gel (developer: ethanol/toluene 2:3).
Yield: 49%.

105 O.Z. 0050/41111 Example 4 5-Piperidinocarbonyl-3-methyl-isoxazole-4-carboxylic acid-tert.-butylamide (No. 5.001 in Table 5) i(CH3)3 NI ~ CO-N
At -5'C, 1.8 g (25.1 mmol) of tert-butylamine, 7.2 g (71.6 mmol) of methylmorpholine, 0.8 g (6.4 mmol) of dimethylaminopyridine and 16.8 g of a 50fo strength solution of propanephosphonic anhydride in dichloromethane (= 26.4 mmol) were added one after the other to 4.6 g (19.3 mmol) of 5-piperidinocarbonyl-3-methyl-isoxazole-4-carboxylic acid in 100 ml of dichloromethane, and the mixture was stirred for 12 hours at room temperature. The solvent was stripped off under reduced pressure, and the residue was taken up in 200 ml of ethyl acetate, followed by extraction twice with saturated sodium bicarbonate solution, and once with 590 strength citric acid solution, once with saturated sodium carbonate solution, and once with saturated sodium chloride solution. The organic phase was dried over magnesium sulfate and the solvent stripped off under reduced pressure. Yield: 90%.
Preliminary stage 4a Methyl 5-piperidinocarbonyl-3-methyl-isoxazole-4-carboxylate ~CO-N~
At -5'C, 3.0 g (35.1 mmol) of piperidine, 10.1 g (100.0 rmnol) of methyl-morpholine, 1.1 g (9 mmol) of dimethylaminopyridine and 22.9 g of a 50%
strength solution of propanephosphonic anhydride in dichloromethane (36.0 mmol) were added one after the other to 5.0 g (27.0 mmol) of 4-methoxycarbonyl-3-methyl-isoxazole-5-carboxylic acid in 100 ml of di-chloromethane, and the mixture was stirred for 12 hours at room tempera-ture. The solvent was stripped off under reduced pressure, and the residue was taken up in 200 ml of ethyl acetate and extracted twice with saturated sodium bicarbonate solution and once with 5% strength citric acid solution and once with saturated sodium chloride solution. The organic phase was dried over magnesium sulfate and the solvent was stripped off under reduced pressure. Yield: 90%; 1H-NMR (250 MHz; CDC13): d = 1.65 ppm (m; 6H), 2.49 ppm (s; 3H), 3.18 ppm (m; 2H), 3.73 ppm (m; 2H), 3.87 ppm (s; 3H).

106 O.Z. 0050/41111 Preliminary stage 4(3 5-Piperidinocarbonyl-3-methyl-isoxazole-4-carboxylic acid CH3 I ~ COOH
\~CO-N
Under a nitrogen blanket and at -15 to -10'C, 1.0 g (25.0 mmol) of sodium hydroxide in 20 ml of water was dripped over a period of 4 hours into a solution of 5.7 g (22.6 mmol) of methyl 5-piperidinocarbonyl-3-methyl-isoxazole-4-carboxylate in 20 ml of methanol, and the mixture was stirred for 12 hours at room temperature. The solution was evaporated down, the residue was taken up in 100 ml of water, the pH was adjusted to 8 - 9, and the mixture was extracted once with 100 ml of diethyl ether. The mixture was acidified to a pH of 2 with 6N HC1, and extracted four times, each time with 100 ml of dichloromethane. The combined organic phases dried over magnesium sulfate and the solvent was stripped off under reduced pressure. Yield: 91%; mp.: 128 - 130°C.
Example 5 4-tert.-Butylaminocarbonyl-3-methyl-isoxazole-5-carboxylic acid (No. 4.001 in Table 4) i (CH3) 3 N~COOH
7.6 g (67.8 mmol) of potassium tert-butylate was added in portions to 3.3 g (11.3 ~nol) of 5-piperidinocarbonyl-3-methyl-isoxazole-4-carboxylic acid-tert-butylamide (prepared as in Example 4) in 150 ml of diethyl ether and 0.4 g (22.2 mmoi) of water, and the mixture was stirred for 6 hours at room temperature. After the addition of 50 ml of water and phase separ-ation, the aqueous phase was acidified to a pH of 2 with 6N HCl and ex-tracted four times, each time with 100 ml of ethyl acetate. The combined organic phases were processed in conventional manner to give the product.
The crude product was recrystallized from cyclohexane/ethyl acetate (5:1).
Yield: 42%; colorless crystals.

...., 890531 w ~ ._ _ 107 O.Z. 0050/41111 Example 6 4-Cyclopropylamino-3-methyl-isothiazole-5-carboxylic acid (No. 4.006 in Table 4) H3c ~ I co-N-H
NHS COOH
At -70'C and under a nitrogen blanket, 60.0 mmol of n-butyllithium (40.0 ml of a 1-5 molar solution in hexane) was dripped into a solution of 5.2 g (28.6 mmol) of 3-methyl-isothiazole-4-carboxylic acid cyclopropyl-amide in 250 ml of tetrahydrofuran, and the mixture was stirred for 30 minutes at this temperature. The reaction mixture was poured onto 500 g of solid COZ and allowed to stand overnight. The mixture was evaporated down, the residue was taken up in 300 ml of water and 15 ml of 2N NaOH, extracted twice, each time with 100 ml of diethyl ether, and the aqueous phase was acidified to a pH of 2 with 6N hydrochloric acid and extracted four times, each time with 200 ml of ethyl acetate. Drying over magnesium sulfate and stripping off of the solvent under reduced pressure gave a yield of 749'0.
Preliminary stage hoc 3-Methyl-isothiazole-4-carboxylic cyclopropylamide NHS
At -5'C, 3.7 g (65.0 mmol) of cyclopropylamine, 18.7 g (185.0 mmol) of methylmorpholine, 2.0 g (16.7 mmol) of dimethylaminopyridine and 43.5 g of a 5096 strength solution of propanephosphonic anhydride in dichloromethane (= 68.4 mol) were dripped one after the other into 7.2 g (50.0 mmol) of 3-methyl-isothiazole-4-carboxylic acid in 200 ml of dichloromethane, and the mixture was stirred for 12 hours at room temperature. The solvent was stripped off under reduced pressure, and the residue was taken up in 250 ml of ethyl acetate and extracted twice with saturated sodium bicar-bonate solution and once with 5% strength citric acid solution, once with saturated sodium carbonate solution and once with saturated sodium chloride solution. The organic phase was dried over magnesium sulfate and the solvent was stripped off under reduced pressure. Yield: 849'0; m.p.:
106 - 108°C.

108 O.Z. 0050/41111 For instance the following isothiazole-4-carboxamides were synthesized analogously:

NI S I
R1 R3 R4 mp(°C) methyl H cyclopropyl 106-108 methyl H tert.-butyl 96- 97 methyl H iso-propyt 100-102 iso-propyl H 3-CF3-phenyl 114-115 iso-propyl H tert.-butyl 158-159 phenyl H cyclopropyl 172-173 phenyl H 4-Cl-phenyl 202-203 Example 7 4-Ethoxycarbonyl-5-methylisoxazole-3-carboxylic acid-tert.-butylamide (No. 3.036 in Table 3) i (CH3) 3 H-N-CO ( I CO-OCyHS
N~CH3 At room temperature, 12.7 g (106.8 mmol) of thionyl chloride was dripped into 10.6 g (53.3 mmol) of 4-ethoxycarbonyl-5-methylisoxazole-3-carboxylic acid in 150 ml of toluene and 2 ml of dimethylformamide, and the mixture was stirred for 1 hour at 80'C. The solvents were stripped off under reduced pressure, the residue was dissolved in 200 ml of anhydrous di-chloromethane, and 10.0 g (137.0 mmol) of tert-butylamine in 20 ml of anhydrous dichloromethane. The mixture was stirred for 12 hours at room temperature, 200 ml of water was added, the organic phase was washed once with 150 ml of saturated sodium bicarbonate solution and once with 150 ml of saturated sodium chloride solution and dried over magnesium sulfate, and the solvent was stripped off under reduced pressure. Yield: 7396.

v 2025939 w"' 890531 109 O.Z. 0050/41111 Preliminary stage 7a Methyl 4-ethoxycarbonyl-5-methyl-isoxazole-3-carboxylate At room temperature, 39.0 g (0.3 mol) of ethyl acetoacetate in 100 ml of toluene was dripped into 9.9 g (0.33 mol) of NaH (80~ strength suspension in white oil), and the mixture was stirred for 3 hours. Subsequently, 41.3 g (0.3 mol) of methyl-a-chloro-a-oximinoacetate in 100 ml of toluene was added and the mixture was stirred for 12 hours at room temperature.
The reaction mixture was then transferred to a Soxhlet apparatus (extrac-tion tube filled with 4 A molecular sieve), 1 g of methanesulfonic acid was added and the mixture was refluxed for 1.5 hours. After the mixture had cooled, the organic phase was washed once with 200 ml of disodium bicarbonate solution and once with 200 ml of saturated sodium chloride solution and dried over magnesium sulfate, and the solvent was stripped off under reduced pressure.
Yield: 6396; yellow oil; 1H-NMR (250 MHz; CDC13): 8 = 1.34 ppm (t; 3H), 2.73 ppm (s; 3H), 4.00 ppm (s; 3H), 4.32 ppm (q; 2H).
For example the following isoxazoledicarboxylic diesters were synthesized analogously:

N~0 R1 R1 R5 1H-NMR (250 MHz; CDC13) 8 in ppm CH3 CHg 2.72 (s;3H), 3.87 (s;3H), 4.00 (s;3H) CH3 C(CH3)3 1.52 (s;9H), 2.70 (s;3H), 4.00 (s;3H) CH3 C2H5 1.34 (t;3H), 2.73 (s;3H), 4.00 (s;3H), 4.32 (q;2H) CF3 CZHS 1.39 (t;3H), 4.06 (s;3H), 4.42 (q;2H) (CHg)yCH CyHg 1.34 (t;3H), 1.37 (d;6H), 3.73 (sp;lH), 4.00 (s;3H), 4.29 (q;2H) ~, 110 O.Z. 0050/41111 Preliminary stage 7(3 4-Ethoxycarbonyl-5-methylisoxazole-3-carboxylic acid HOOC I ~ CO-OC2Hg Ph0 CH3 At -15 to -10'C and under a nitrogen blanket, 4.7 g (0.117 mol) of sodium hydroxide in 80 ml of water was dripped into 25.0 g (0.117 mol) of methyl 4-ethoxycarbonyl-5-methylisoxazole-3-carboxylate in 200 ml of anhydrous tetrahydrofuran, and the mixture was stirred for 12 hours. The solvents were stripped off in a rotary evaporator (bath temperature: 30 - 35°C), the residue was taken up in 250 ml of water, the pH was adjusted to 8 - 9 with hydrochloric acid, and the mixture was extracted twice, each time with 150 ml of diethyl ether. The aqueous phase was acidified to a pH of 2 with 6N HC1 and extracted four times, each time with 250 ml of ethyl acetate. The combined organic phases were dried over magnesium sulfate and the solvent was stripped off under reduced pressure. Yield: 70%; 1H-NMR
(250 MHz; CoCl3): 8 = 1.42 ppm (t; 3H), 2.80 ppm (s; 3H), 4.59 ppm (q; 2H) .
For example the following isoxazole-3-carboxylic acids were synthesized analogously:

N~R1 R1 RS 1H-NMR (250 MHz; CDCl3) 8 in ppm CH3 CZHS 1.42 (t;3H), 2.80 (s;3H), 4.59 (q;2H) CH3 C(CH3)3 1.54 (s;9H), 2.34 (s;3H), 13.80 (bs;lH) CF3 CyH5 1.29 (t;3H), 4.15 (q;2H) 111 O.Z. 0050/41111 Example 8 3-tert.-Butylaminocarbonyl-5-methyl-isoxazole-4-carboxylic acid (No. 3.002 in Table 3) i(CH3)3 H-N-C I I COOH
N~ CH3 At from 5 to 10'C and under a nitrogen blanket, 1.0 g (25.0 mmol) of sodium hydroxide in 50 ml of water was dripped into a solution of 5.4 g (21.3 mmol) of 4-ethoxycarbonyl-5-methyl-isoxazole3-carboxylic acid-tert-butylamide in 100 ml of ethanol, and the mixture was stirred for 12 hours at room temperature. The solution was evaporated down, the residue was taken up in 150 ml of water, the pH was adjusted to 8 - 9, and the mixture was extracted twice, each time with 100 ml of diethyl ether. The aqueous phase was then acidified to a pH of 2 with 6N HC1, followed by extraction four times, each time with 200 ml of ethyl acetate. The combined organic phases were dried over magnesium sulfate and the solvent was stripped off under reduced pressure. Yield: 95%; yellow solid.
Example 9 Methyl 5-cyclopropylaminocarbonyl-3-isopropenylisoxazole-4-carboxylate (No. 6.02 in Table 6) iH3 CHy=C COOCH3 NI I CO-N
H
At 5'C, 3.1 g (0.055 mol) of cyclopropylamine, 16.0 g (0.158 mol) of 4-methylmorpholine, 1.73 g (0.014 mol) of 4-dimethylaminopyridine and 37.0 g (0.058 mol) of a 50% strength solution of propanephosphonic anhydride in dichloromethane were dripped one after the other into a solution of 9.0 g (0.043 mol) of 3-isopropenyl-4-methoxycarbonylisoxazole-5-carboxylic acid in 200 ml of dichloromethane. After the mixture had been stirred for 12 hours at room temperature, the solvent was removed, the residue was taken up in 250 ml of ethyl acetate and the solution is extracted twice with saturated sodium bicarbonate solution and once with 5% strength citric acid solution, once with saturated sodium carbonate solution and once with saturated sodium chloride solution. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure. Yield: 54%.

112 O.Z. 0050/41111 Preliminary stage 9a Dimethyl E-3-styryl-isoxazole-4,5-dicarboxylate I CH=C CO-OCH3 NI ' CO-OCH 3 A mixture, cooled to 0°C, of 14.7 g (0.1 mol) of E-cinnamic aldehyde oxime, 1.8 g (0.01 mol) of disodium biphosphate dehydrate, 1.6 g (0.01 mol) of sodium dihydrogenphosphate dehydrate, 50 ml of dichloro-methane and 50 ml of water was adjusted to a pH of 6.3 with hydrochloric acid/sodium hydroxide solution. After the addition of 14.2 g (0.1 mol) of dimethyl acetylenedicarboxylate, 61.2 g (0.11 mol) of a 13.4% strength aqueous sodium hypochlorite solution was dripped in over a period of one hour at 0-10°C and the pH was also kept constant by adding hydrochloric acid or sodium hydroxide solution. The mixture was then stirred for one hour at room temperature, the phases were separated and the aqueous phase was extracted twice, each time with 100 ml of dichloromethane. The combined organic phases were dried over sodium sulfate, the solvent was removed under reduced pressure and the more readily volatile components were distilled off at 120'C (0.1 mm Hg). Yield: 56%; 1H-NMR (in CDCl3): 8 = 3.9 ppm (s; 3H), 4.0 ppm (s; 3H), 7.2 ppm (d; 1H), 7.3-7.7 ppm (m; 6H).
Analogously to Preliminary stage 9a dimethyl 3-isopropenylisoxazole-4,5-dicarboxylate was synthesized. Yield: 26%; iH-NMR (in CDC13): 6 = 2.2 ppm (s; 3H), 3.9 ppm (s; 3H), 4.0 ppm (s; 3H), 5.45 ppm (m; 2H).
Preliminary stage 9(3 3-Isopropenyl-4-methoxycarbonylisoxazole-5-carboxylic acid iH3 CHZ=C ' ( CO-OCH3 \~~COOH
At 0'C, a solution of 3.6 g (0.09 mol) of sodium hydroxide in 75 ml of water was dripped into 20.0 g (0.09 mol) of dimethyl 3-isopropenylisox-azole-4,5-dicarboxylate (from stage A.1) in 150 ml of methanol, and the mixture was stirred for 14 hours at room temperature. 250 ml of water was added, the pH was adjusted to 8, extraction was effected with 200 ml of 113 O.Z. 0050/41111 dichloroethane, and the aqueous phase was adjusted to a pH of 1-2 with 6N
hydrochloric acid and extracted three times, each time with 250 ml of dichloromethane. The combined organic extracts were dried over magnesium sulfate and the solvent was distilled off under reduced pressure. Yield:
97%; 1H-NMR (in CDC13): d = 2.12 ppm (s; 3H), 4.07 ppm (s; 3H), 5.41 ppm (m; 2H); 8.00 ppm (bs; 1H).
Example 10 5-Cyclopropylaminocarbonyl-3-isopropenylisoxazole-4-carboxylic acid (No. 6.05 in Table 6) iH3 CHy=C ~ I COOH
N~0 CO-i~
~H
At 5 to 10'C, 0.68 g (0.017 mol) of sodium hydroxide was added to a solution of 4.0 g (0.016 mol) of methyl 5-cyclopropylaminocarbonyl-3-iso-propenyl-4-carboxylate (prepared in accordance with Example 9) in 50 ml of methanol. After the mixture had been stirred for 12 hours at room tempera-ture, the solvent was removed, the residue was taken up in 150 ml of water, and the mixture was adjusted to a pH of 8-9 and extracted twice, each time with 100 ml of diethyl ether. The aqueous phase was then acidi-ZO fied to a pH of 2 with 6N HC1 and extracted four times, each time with 200 ml of ethyl acetate, the combined organic phases were dried over mag-nesium sulfate and the solvent was distilled off under reduced pressure.
Yield: 7496.
Example 11 5-tert.-Butylaminocarbonyl-3-isopropenylisoxazole-4-carboxylic acid acetoxime ester (No. 6.08 in Table 6) CHg CH2=C I I C00-N=C(CH3)2 ~CO-N-C(CH3)3 H
At room temperature, 5.9 g (0.059 mol) of 4-methylmorpholine and 1.94 g (0.016 mol) of 4-dimethylaminopyridine were dripped into a solution of 4.0 g (0.016 mol) of 5-tert.-butylaminocarbonyl-3-isopropenylisoxazole-4-carboxylic acid (No. 6.06 in Table 6) and 1.5 g (0.021 mol) of acetoxime in 200 ml of dichloromethane. After the mixture had been stirred for five . 2025939 114 O.Z. 0050/41111 minutes, 13.7 g (0.0215 mol) of a 50% strength solution of propane-phosphonic anhydride in dichloromethane was added. After the mixture had been refluxed for 8 hours, the solvent was removed and the residue was dissolved in 100 ml of ethyl acetate and worked up as in Example 9.
yield: 55%.
The physical data of the end products (Examples 1 to 10) are given in Tables 3 to 7 below, which contain further compounds Ia, Ib, Ic and Id which were obtained (or are obtainable) in the same manner.

O

N

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T T T T T T T T T T T T O
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M
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t t t T T T T T T T O ~ V

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M a v 2 t V

s ~ ~ II

~-Z ~ ~ Z

E x I

V ~

-z .r .r.r a a a V +~ +~+~

O ~ > >

I i I

~ i~i~

L L i 3 d ~ N

OC +~ +~i~

M
x x x a 0.
O
r L
a a fl.
t s I
+~ +~ O
G7 d N
E E ~~
°' ~ N cr1 o ( O o O
z t' ~ t' 130 O.Z. 0050/41111 use examples The herbicidal action of the carboxamides of the formulae Ia', Ib', Ic' and id is demonstrated in greenhouse experiments:
The vessels employed were plastic flowerpots having a volume of 300 cm3 and filled with a sandy loam containing about 3.0% humus. The seeds of the test plants were sown separately, according to species.
For the preemergence treatment, the active ingredients, suspended or emulsified in water, were applied to the surface of the soil immediately after the seeds had been sown. The vessels were lightly sprinkler-irrigated to induce germination and growth. Transparent plastic covers were then placed on the vessels until the plants had taken root. The cover ensured uniform germination of the plants, insofar as this was not impaired by the active ingredients.
For the postemergence treatment, the plants were grown, depending on growth form, to a height of 3 to 15 cm before being treated with the com-pounds, suspended or emulsified in water. The application rate for post-emergence treatment was 1.0 kg/ha.
The pots were set up in the greenhouse, heat-loving species at 20 to 35°C, and species from moderate.climates at 10 to 25°C. The experiments were run for from 2 to 4 weeks. During this period the plants were tended and their reactions to the various treatments assessed. The assessment scale was 0 to 100, 100 denoting nonemergence or complete destruction of at least the visible plant parts, and 0 denoting no damage or normal growth.
The plants used in the experiments were Cassia tora, Chenopodium album, Chrysanthemum coronarium, Ipomoea spp., Polygonum persicaria, Steltaria media and Triticum aestivum.
Compounds 3.002, 3.005, 3.006, 3.008, 3.016, 3.017, 3.018, 3.019, 3.020, 3.023, 3.028, 3.029, 3.037, 3.052, 3.053, 6.04, 6.05, 6.06 and 6.08, applied postemergence at a rate of 1 kg/ha, provided excellent control of unwanted broadleaved plants. The carboxamides 3.006, 3.016 to 3.020, 3.028, 3.029, 3.037, 3.052, 3.053, 6.04, 6.05, 6.06 and 6.08 were also well tolerated by graminaceous crops such as wheat, Indian corn and rice.

Claims (15)

1. Carboxamide of the formulae Ia, Ib, Ic or Id where X is oxygen or sulfur;
R1 is - hydrogen, halogen, C1-C6-alkyl which may carry from one to five halogen atoms and/or a cyano radical and/or up to two of the following radi-calss C1-C4-alkoxy, partially or fully halo-genated C1-C4-alkoxy, C1-C4-alkylthio or parti-ally or fully halogenated C1-C4-alkylthio;
- C1-C4-alkoxy or C1-C4-alkylthio, partially or fully halogenated C1-C4-alkoxy, partially or fully halogenated C1-C4-alkylthio;
- benzyl which may be monosubstituted, disubsti-tuted or trisubstituted by C1-C4-alkyl, partially or fully halogenated C1-C4-alkyl, C1-C4-alkoxy, partially or fully halogenated C1-C4-alkoxy, C1-C4-alkylthio, partially or fully halogenated C1-C4-alkylthio, halogen, cyano or nitro;
- phenyl which may also carry from one to three of the following radicals: cyano, nitro, halogen, C1-C6-alkyl, partially or fully halo-genated C1-C6-alkyl, C1-C6-alkoxy, partially or fully halogenated C1-C6-alkoxy, C1-C6-alkylthio and/or partially or fully halogenated C1-C6-alkylthio;

- phenoxy or phenylthio, each of which may be monosubstituted, disubstituted or trisubsti-tuted by C1-C4-alkyl, partially or fully halo-genated C1-C4-alkyl, C1-C4-alkoxy, partially or fully halogenated C1-C4-alkoxy, C1-C4-alkylthio, partially or fully halogenated C1-C4-alkylthio, halogen, cyano or nitro;
- a 5- to 6-membered saturated or aromatic heterocyclic radical containing one or two heteroatoms selected from the group comprising oxygen, sulfur and nitrogen which may carry one or two of the following substituents: halogen, C1-C3-alkyl, C1-C3-alkoxy and C1-C3-alkoxy-carbonyl;
- C3-C8-cycloalkyl-substituted C1-C6-alkyl;
- C2-C6-alkenyl whose double bond may be epoxidized, or C2-C6-alkynyl, it being possible for both groups to be monosubstituted, disub-stituted or trisubstituted by halogen, C1-C3-alkoxy and/or monosubstituted by cyclopropyl or phenyl, it also being possible for the phenyl radical to carry up to three of the following substituents: halogen, cyano, nitro, C1-C4-alkyl, which may be unsubstituted or partially or fully halogenated, C1-C4-alkoxy or C1-C4-alkylthio, both of which may be unsubstituted or partially or fully halogenated;
- C3-C8-cycloalkyl or C3-C8-cycloalkenyl, it being possible for both groups to be monosubstituted, disubstituted or trisubstituted by C1-C4-alkyl or halogen;
R1' is - C3-C8-cycloalkyl-substituted C1-C8-alkyl;

- C2-C6-alkenyl whose double bond may be epoxidized, or C2-C6-alkynyl, it being possible for both groups to be monosubstituted, disub-stituted or trisubstituted by halogen, C1-C3-alkoxy and/or monosubstituted by cyclopropyl or phenyl, it also being possible for the phenyl radical to carry up to three of the following substituents: halogen, cyano, nitro, C1-C4-alkyl, which may be unsubstituted or partially or fully halogenated, C1-C4-alkoxy or C1-C4-alkylthio, both of which may be unsubstituted or partially or fully halogenated;
- C3-C6-cycloalkenyl, which may be monosub-stituted, disubstituted or trisubstituted by halogen or C1-C4-alkyl;
R2 is - formyl, 4,5-dihydrooxazol-2-yl, - COYR5 or CONR6R7, where Y is oxygen or sulfur;
R5 is .cndot. hydrogen;
.cndot. C1-C6-alkyl which may carry from one to five halogen atoms and/or up to three hydroxyl and/or C1-C4-alkoxy groups and/or one of the following radicals:
- cyano, - C1-C4-alkoxy-C2-C4-alkoxy, - C1-C3-alkylthio, - C1-C3-alkylamino, di(C1-C3)-alkyl-amimo, C3-C~-cycloalkylamino or di(C3-C~)-cycloalkylamino, - trimethylsilyl, - C1-C3-alkylsulfinyl or C1-C3-alkyl-sulfonyl, - carboxyl, C1-C3-alkoxycarbonyl, C1-C3-alkoxycarbonyl-C1-C3-alkoxy or C1-C3-alkoxycarbonyl-C1-C3-alkoxy-C1-C3-alkoxycarbonyl, - di(C1-C3)-alkylaminocarbonyl, - di(C1-C3)-alkoxyphosphonyl, - C1-C6-alkaneiminoxy or C5-C6-cyclo-alkaneiminoxy, - N-phthalimido, N-succinimido, benzyloxy, benzoyl, it being possible for these cyclic radicals to additionally carry from one to three of the following groups:
halogen, C1-C3-alkyl or C1-C3-alkoxy, - a 5- or 6-membered saturated heterocyclic radical or a 5- or 6-membered heteroaromatic radical, each of Which has up to three heteroatoms selected from the group comprising oxygen, sulfur and nitrogen, where two oxygen and/or sulfur atoms must not be directly adjacent and where the heterocyclic rings may also carry one or two of the following substituents:
halogen, C1-C3-alkyl, C1-C3-alkoxy or C1-C3-alkoxycarbonyl;
- phenyl, which may also carry up to three of the following substitu-ents: halogen, nitro, cyano, C1-C3-alkyl, partially or fully halo-genated C1-C3-alkyl, C1-C3-alkoxy or partially or fully halogenated C1-C3-alkoxy;
- -CR10=N-R11, where R10 is hydrogen or C1-C6-alkyl and R11 is C1-C6-alkoxy, C3-C6-alkenyloxy or C3-C6-alkynyloxy, each of which may carry up to 3 halogen atoms and/or a phenyl radical with or without up to three of the following radicals: halogen, nitro, cyano, C1-C3-alkyl or C1-C3-alkoxy; phenoxy, which may also carry up to three of the following substituents:
halogen, nitro, cyano, C1-C3-alkyl or C1-C3-alkoxy; C1-C6-alkylamino, di( C1-C6) alkylamino or phenyl-amino, it being possible for the aromatic ring to addi-tionally carry up to three of the following radicals:
halogen, nitro, cyano, C1-C3-alkyl or C1-C3-alkoxy;
.cndot. C3-C8-cycloalkyl;
.cndot. C3-C8-alkenyl, C5-C6-cycloalkenyl, C3-C6-alkynyl, it being possible for these radicals to carry one of the following groups s hydroxyl, halogen, C1-C4-alkoxy or phenyl, it being possible for the aromatic radical to itself carry from one to three of the follow-ing groups: halogen, nitro, cyano, C1-C4-alkyl, partially or fully halo-genated C1-C4-alkyl or C1-C4-alkoxy;
.cndot. phenyl, which may carry from one to three of the following groups:
halogen, nitro, cyano, C1-C4-alkyl, partially or fully halogenated C1-C4-alkyl, C1-C4-alkoxy, partially or fully halogenated C1-C4-alkoxy or C1-C4-alkoxycarbonyl;

.cndot. a five- or six-membered heterocyclic radical having up to three heteroatoms selected from the group comprising oxygen, sulfur and nitrogen, where two oxygen and/or sulfur atoms must not be directly adjacent and where the heterocyclic rings may also carry one or two of the following substituents:
halogen, C1-C3-alkyl, C1-C3-alkoxy or C1-C3-alkoxycarbonyl;
.cndot. benzotriazolyl;
.cndot. N-phthalimido, tetrahydrophthalimido, succinimido, maleiimido;
.cndot. 2,2-dimethyl-1,3-dioxolan-4-ylmethyl or 1,3-dioxolan-2-on-4-ylmethyl;
.cndot. in the case where Y = O: one equivalent of a cation from the group comprising the alkali and alkaline earth metals, manganese, copper, iron, ammonium and ammonium which is sub-stituted by up to 4 C1-C3-alkyl groups;
or .cndot. -N=CR8R9, where R8 and R9 are hydrogen; C1-C4-alkyl, which may be unsubstituted or partially or fully halogenated and may carry a C1-C3-alkoxy or phenyl radical, it being possible for the aromatic radical to itself also be monosubstituted, disubstituted or trisubstiuted by halogen, nitro, cyano, C1-C3-alkyl, partially or fully halogenated C1-C3-alkyl, C1-C3-alkoxy or partially or fully halogenated C1-C3-alkoxy; C3-C6-cycloalkyl;

C1-C4-alkoxy; furanyl or phenyl, which may additionally carry up to three of the following substituents: halogen, nitro, cyano, C1-C3-alkyl, partially or fully halogenated C1-C3-alkyl, C1-C3-alkoxy or partially or fully halogenated C1-C3-alkoxy; or R8 and R9 together are a methylene chain having from 4 to 7 members;
.cndot. -W-Z, where W is C2-C4-alkylene, ethoxyethylene, but-2-enylene or but-2-ynylene, and Z is a molecular moiety which is bonded to W in the .omega.-position and is the same moiety group which is bonded to W in the .alpha.-position of W;
R6 is - hydrogen, C1-C6-alkyl or C3-C8-cycloalkyl, and R7 is - hydrogen, C1-C6-alkyl, -C(OR12)=N-H or -C(OR12)=N-(C1-C4)-alkyl, where R12 is C1-C4-alkyl, or R6 and R7 together are methylene having 4 or 5 members;
R3 is - hydrogen;
- C1-C6-alkyl, which may carry from one to three of the following substituents: hydroxyl, halogen, C1-C4-alkoxy, C1-C4-alkylthio or di(C1-C4)-alkylamino;
- C3-C8-cycloalkyl, which may be monosubstituted, disubstituted or trisubstituted by halogen, C1-C4-alkyl or partially or fully halogenated C1-C4-alkyl;
R4 is - hydrogen, hydroxyl, C1-C4-alkoxy;
- C1-C6-alkyl, which may carry from one to three of the following radicals: halogen, cyano, C1-C4-alkoxy, partially or fully halogenated C1-C4-alkoxy, C1-C4-alkylthio, partially or fully halogenated C1-C4-alkylthio, di-C1-C4-alkylamino, C3-C8-cycloalkyl or phenyl, it being poossible for the phenyl ring to itself carry from one to three of the following radicals: halogen, cyano, nitro, C1-C4-alkyl, partially or fully halogenated C1-C4-alkyl, C1-C4-alkoxy, partially or fully halogenated C1-C4-alkoxy, C1-C4-alkyl-thio or partially or fully halogenated C1-C4-alkylthio;
- C3-C6-cycloalkyl, which may carry from one to three of the following radicals: halogen, nitro, cyano, C1-C6-alkyl, partially or fully halogenated C1-C6-alkyl, C1-C4-alkoxy or partially or fully halogenated C1-C4-alkoxy;
- C3-C6-alkenyl or C3-C6-alkynyl, each of which may be monosubstituted, disubstituted or trisubsti-tuted by halogen and/or monosubstituted by phenyl, it being possible for the phenyl radical to itself carry from one to three of the following -groups: C1-C4-alkyl, C1-C4-halo alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, halogen, cyano - or nitro;
- di(C1-C4)-alkylamino;

- a 5- or 6-membered heterocyclic saturated or aromatic radical having one or two heteroatoms selected from the group comprising oxygen, sulfur and nitrogen, which may be monosub-stituted, disubstituted or trisubstituted by C1-C4-alkyl or halogen;
- phenyl, which may carry from one to four of the following groups: C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, halogen, nitro, cyano, formyl, C1-C4-alkanoyl, C1-C4-haloalkanoyl or C1-C4-alkoxycarbonyl;
- naphthyl, which may be monosubstituted, disub-stituted or trisubstituted by C1-C4-alkyl or halogen;
or R3 and R4 together are methylene having from 4 to 7 members which may be interrupted by oxygen, sulfur or N-methyl, or are -(CH2)3-CO-, R3 and R4 in the compound Ia, Ib, or Ic not simultaneously being hydrogen if - R1 is hydrogen, methyl or phenyl and R2 is CONH2, COON or COOCH3, or if - X is oxygen, R1 is CH(OCH2CH3)2 and R2 is CONH2, or if - X is oxygen and R2 is formyl, and the agriculturally acceptable salt of the compound Ia, Ib, Ic or Id.
2. Carboxamide of the formulae Ia, Ib, Ic or Id as set forth in claim 1, where R3 is hydrogen.
3. Carboxamide of the formulae Ia, Ib or Ic as set forth in claim 1, where R1 is hydrogen, C1-C4-alkyl or C3-C6-cycloalkyl;
R2 is COYR5, where Y is oxygen and R5 is hydrogen or -NCR8R9, where R8 and R9 are identical or different and each denotes hydrogen, C1-C4-alkyl or C3-C6-cycloalkyl, or together denote a C4-C7-alkylene chain;
R3 is hydrogen, and R4 is C1-C4-alkyl or C3-C8-cycloalkyl.
4. Carboxamide of the formula Ia as set forth in any one of claims 1 to 3.
5. A method of manufacturing compound Ia or Ib as set forth in claim 1, R2 denoting CO2CH3 and X denoting oxygen, wherein the hydroxamyl chloride of the formula II:
is reacted in the presence of a base with a .beta.-keto ester of the formula III:
wherein R1 is as defined in claim 1, the resultant dimethyl diester IV:~

wherein R1 is as defined in claim 1, is first hydrolyzed using one equivalent of an aqueous base to give the monoester Va or Vb:

wherein R1 is as defined in claim 1, wherein R1 is as defined in claim 1, and Va or Vb is converted, separately or as a mixture, first into the halide or another activated form of the carboxylic acid and this derivative is subsequently amidated using a substituted amine of the formula VIa:

HNR3R4 VIa wherein R3 and R4 are as defined in claim 1.
6. A method of manufacturing compound Ia as set forth in claim 1, R2 denoting CO2R5, X denoting oxygen and R5 not being hydrogen or methyl, wherein the hydroxamyl chloride II as defined in claim 5 is reacted in the presence of a base with a .beta.-keto ester of the formula IIIa:

wherein R1 and R5 are as defined in claim 1, the resultant diester IVa wherein R1 and R5 are as defined in claim 1, is then cleaved using a hydrolyzing agent to give the monoester Va' wherein R1 and R5 are as defined in claim 1, which is converted into the halide or another activated form of the carboxylic acid and this derivative is then amidated with a substituted amine VIa as defined in claim 5.
7. A method of manufacturing compound Ia or Ic as set forth in claim 1, R1 not denoting hydrogen and R2 denoting carboxyl or formyl and R3 denoting hydrogen, wherein a carboxylic acid Vc or Vd:
wherein R1 and X are as defined in claim 1, wherein R1 and X are as defined in claim 1, is converted into the halide or another activated form of the carboxylic acid, this derivative is amidated with a substituted amine VIa as defined in claim 5 and the resultant amide VIIa or VIIb:
wherein R1, R4 and X are as defined in claim 1, wherein R1, R4 and X are as defined in claim 1, is then reacted in the presence of a base with a carboxylating or formylating agent.
8. A method of manufacturing compound Ia or Ib as set forth in claim 1, R2 denoting a carboxyl group and X
denoting sulfur, wherein an isothiazoledicarboxylic anhydride VIII:
wherein R1 is as defined in claim 1, is reacted with an amine VIa as defined in claim 5 to give the isomers Ia and Ib, and the isomers are subsequently separated.
9. A method of manufacturing compound Ia, Ib, Ic or Id as set forth in claim 1, R2 denoting CO2H, wherein a corresponding ester Ia, Ib, Ic or Id, in which R2 is CO2R5 and R5 is C1-C4-alkyl, is hydrolyzed in the presence of an aqueous base.
10. A method of manufacturing compound Ia, Ib, Ic or Id as set forth in claim 1, R2 denoting COYR5 or CONR6R7, wherein a corresponding carboxylic acid Ia, Ib, Ic or Id (R2=CO2H) is first converted to the halide or another activated derivative of the carboxylic acid, and this derivative is then reacted with a compound IX:

HYR5~~~ IX

wherein R5 and Y are as defined in claim 1, or with an amine VIb HNR6R7 ~~~ VIb wherein R6 and R7 are as defined in claim 1.
11. A method of manufacturing compound Ia, Ib, Ic or Id as set forth in claim 1, R2 denoting 4,5-dihydrooxazol-2-yl, wherein a carboxamide of the formulae Ia, Ib, Ic or Id as set forth in claim 1, R2 denoting CO2H or CO2R5 and R5 denoting C1-C4-alkyl, is cyclized with an amino alcohol XV:

12. A method of manufacturing compound Ia, Ib, Ic or Id as set forth in claim 1, R2 denoting formyl, wherein corresponding carboxylic acid of the formula Ia, Ib, Ic or Id (R2 - CO2H) is converted into the halide or another activated form of the carboxylic acid, and this derivative is then reduced.
13. A method of manufacturing compound Ia, Ib, Ic or Id as set forth in claim 1, R1 or R1' denoting an epoxidized C2-C6-alkenyl group, wherein a carboxamide of the formula Ia, Ib, Ic or Id as set forth in claim 1, R1 or R1' denoting C2-C6-alkenyl, is epoxidized with an oxidizing agent.
14. An agent containing inert carriers and a herbicidally effective amount of at least one carboxamide of the formulae Ia, Ib, Ic or Id as set forth in any one of claims 1 to 4.
15. A method of controlling the growth of unwanted plants, wherein a herbicidally effective amount of a carboxamide of tire formula Id as claimed in claim 1 or of a carboxamide of the formula Ia', Ib' or Ic', where Ia', Ib' and Ic' have the meanings of Ia, Ib and Ic as defined in claim 1 without the disclaimer, is allowed to act on plants or their habitat, or on seed.
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