CA2026131A1

CA2026131A1 - Oxazole- and thiazolecarboxamides

Info

Publication number: CA2026131A1
Application number: CA002026131A
Authority: CA
Inventors: Klaus Ditrich; Volker Maywald; Gerhard Hamprecht; Albrecht Harreus; Bruno Wuerzer; Karl-Otto Westphalen
Original assignee: Individual
Current assignee: BASF SE
Priority date: 1989-09-26
Filing date: 1990-09-25
Publication date: 1991-03-27
Also published as: HUT56084A; EP0419944B1; HU906212D0; BR9004803A; IL95775A0; DE59008702D1; EP0419944A3; JPH03145478A; HU207058B; DE3932052A1; EP0419944A2; KR910006254A

Abstract

O.Z. 0050/41126 ABSTRACT OF THE DISCLOSURE: Oxazole- and thiazolecarboxamides of the formulae Ia and Ib Ia Ib where the substituents have the following meanings:
X oxygen or sulfur;
R1 hydrogen; halogen; substituted or unsubstituted C1-C6-alkyl, benzyl, cycloalkyl, alkenyl, alkynyl, phenyl, phenoxy or phenyl-thio; alkoxy; alkylthio; haloalkoxy; haloalkylthio; or a sub-stituted or unsubstituted 5- or 6-membered heterocyclic radical;
R2 formyl, 4,5-dihydrooxazol-2-yl or -COYR5;
Y oxygen or sulfur;
R5 hydrogen; cycloalkyl; substituted or unsubstituted alkyl, phenyl, benzyl, alkenyl, cycloalkenyl or alkynyl;
a substituted or unsubstituted 5- or 6-membered heterocyclic radical; phthalimido; tetrahydrophthalimido; succinimido;
maleiimido;
one equivalent of a cation;
or -N=CR6R7;
R6, R7 hydrogen; alkyl; cycloalkyl; phenyl; furyl or together a methylene chain of 4 to 7 members;
R3 hydrogen or substituted or unsubstituted alkyl or cycloalkyl;

O. Z . 0050/41126 R4 hydroxy; alkoxy;
substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, phenyl or naphthyl;
a substituted or unsubstituted 5- or 6-membered heterocyclic radical; or R3 and R4 together are -(CH2)n-Yp-(CH2)q-, where n and q are 1, 2 or 3, p is 0 or 1 and Y is oxygen, sulfur or N-methyl, or form a radical of the formula -(CH2)3-CO- , and their environmentally tolerated salts, X in formula Ib not being sulfur when R1 is 3-pyridyl, R2 is CO2CH2CH3 or R3 is hydrogen, and X in formula Ia X not being sulfur and R1 not being thien-2-yl when YR5 is OH, R3 is hydrogen and R4 is methyl, processes for manufacturing such compounds and herbicidal agents containing compounds of the formulae Ia or Ib as active ingredients.

Description

~ v ~
O.Z. 0050/41126 Oxazole- and thiazolecarboxamide~

The present invention relates to oxazole- and thiazolecarboxamides of the formulae Ia and Ib O R3 ~ R2 R3 NJI`N~ R ~
RI~X~R2 R4 R4 Ia Ib wher~
X i8 oxygen or Rulfur;
Rl is hydrogen; halogen; Cl-C6-alkyl which can carry from one to five halogen atoms and/or one or two of the following: C3-C~-cycloalkyl, Cl-C4-alkoxy, C1-C4-haloalkoxy, Cl-C4-alkylthio, Cl-C4-haloalkylthio or cyano;
benzyl which can carry fro~ one to three of the following: Cl-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy, Cl-C4-alkylthio, Cl-C4-haloalkylthio, halogen, cyano or nitro;
C3-C~ cycloalkyl which can carry from one to three of the following: Cl-C4-alkyl or halogen;
C2-C6-alkenyl which can carry from ons to three of the following: halogen, Cl-C3-alkoxy and/or one phenyl which in turn can carry from one to three of the following: Cl-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy, Cl C4-alkylthio, Cl-C4-haloalkylthio, halogen, cyano or nitro;
C2-C6-alkynyl which can carry from one to three of the following: halogen, Cl-C3-alkoxy and/or one phenyl which in turn can carry from one to three of the following: Cl-C4-alkyl, C,-C4-haloalkyl, Cl-C~-alkoxy, Cl-C4-haloalkoxy, Cl-C4-alkylthio, Cl-C4-haloalkylthio, halogen, cyano or nitro;
Cl-C~-alkoxy; Cl-C4-alkylthio; Cl-C4-haloalkoxy; Cl-C4-haloalkylthio;

- 2 - O.Z. 0050/41126 phenoxy or phenylthio, which can carry from one to three of the following: Cl-C~-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy, Cl-C4-alkylthio, Cl-C4-haloalkylthio, halogen, cyano or nitro;
a 5- to 6-membered heterocyclic radical containing one or two hetero atoms selected from the group comprising oxygen, sulfur and nitrogen, it being possible for the ring to carry one or two of the following: Cl-C3-alkyl, halogen, Cl-C3-alkoxy or Cl-C3-alkoxycarbonyl;
phenyl which can carry from one to three of the following: Cl-C6-alkyl, C~-C6-haloalkyl, Cl-C6-alkoxy, Cl-C6-haloalkoxy, Cl-C6-alkylthio, Cl-C6-haloalkylthio, halogen, nitro and cyano;
R2 is formyl, 4,5-dihydro-2-oxazolyl or -CoYR5;
Y is oxygen or sulfur;
Rs is hydrogen;
Cl-C6-alkyl which can carry from one to five halogen atoms or hydroxyl groups and/or one of the follow-ing: Cl-C4-alkoxy, C2-C4-alkoxy-Cl-C4-alkoxy, cyano, trimethylsilyl,C1-C3-alkylthio,C1-C3-alkylamino,di-Cl-C3-alkyl~mino, C3-C7-cycloalkylamino, Cl-C3-alkyl-sulfinyl,C1-C3-alkylsulfonyl,carboxyl,Cl-C3-alkoxy-carbonyl, di-Cl-C3-alkylaminocarbonyl, di-Cl-C3-alkoxyphosphoryl, alkaneiminoxy, thienyl, furyl, tetrahydrofuryl, phthalimido, pyridyl, benzyloxy or benzoyl, it being po~3ible for the cyclic radicals in turn to carry from one to three of the following:
C1-C3-alkyl, C1-C3-alkoxy or halogen;
benzyl which can carry from one to three of the following: Cl-C3-alkyl, Cl-C3-alkoxy, Cl-C3-haloalkyl, halogen, nitro and cyano;
C3-Ca-cycloalkyl;
phenyl, which can carry from ono to three of the following: Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-haloalkyl, C1-C4-haloalksxy,C1-C4-alkoxycarbonyl,halogen,nitro and cyano;

2026~31 _ 3 - O.Z. 0050/41126 C3-Cg-alkenyl, C5-C~-cycloalkenyl or C3-C8-alkynyl, it being possible for these radicals to carry one of the following: hydroxyl, Cl-C4-alkoxy, halogen or a phenyl ring which in turn can carry from one to three of the following: Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-haloalkyl, halogen, nitro and cyano;
a 5- to 6-membered heterocyclic radical containing one or ~wo hetero atom~ selected from the group comprising oxygen, sulfur and nitrogen or a benzo-triazolyl radical;
phthalimido; tetrahydrophthalimido; succinimido;
maleimido;
one equivalent of a cation from the group compri~ing the alkali metal~ or alkaline earth metals, man-ganese, copper, iron, ammonium and substituted ammonium;
-N=CR6R7;
R5 and R7 are hydrogen; Cl-C4-alkyl; C3-C6-cycloalkyl;
phenyl or furyl, or together form a methylene chain -(CH2)~- with ~ = 4 to 7;
R3 is hydrogen; Cl-C6-alkyl which can carry from one to three of the following: hydroxyl, halogen, Cl-C4-alkoxy, Cl-C4-alkylthio or di-Cl-C3-alkylamino;
C3-C~-cycloalkyl which can carry from one to three of the following: Cl-C4-alkyl, halogen and C1-C4-halo-alkyl;
R4 is hydroxyl, Cl-C4-alkoxy;
Cl-C8-alkyl which can carry from one to three of the following: Cl-C4-alkoxy, Cl-C4-haloalkoxy, Cl-C4-alkylthio, Cl-C4-haloalkylthio, di-Cl-C4-alkylamino, halogen, C3-C8-cycloalkyl or phenyl which in turn can carry from one to three of the following: halogen, cyano, nitro, Cl-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy, Cl~C4-alkylthio or Cl-C4-haloalkylthio;
C3-C8-cycloalkyl which can carry from one to three of the following: Cl-C6-alkyl, Cl-C6-haloalkyl, Cl-C~-202~131 - 4 - O.Z. 0050/41126 alkoxy, C~-C4-haloalkoxy, halogen, nitro or cyano;
C3-C6-alkenyl or C3-C6~alkynyl, which can be sub-stituted from once to three times by halogen and/or once by phenyl which in turn can carry from one to three of the following: Cl-C4-alkyl, C,-C4-haloalkyl, C~-C~-alkoxy, C~-C4-haloalkoxy, C~-C4-alkylthio, C~-C4-haloalkylthio, halogen, cyano or nitro;
a 5- to 6-membered heterocyclic radical which contains one or two hetero atoms selected from the group comprising oxygen, sulfur or nitrogen, and which can carry from one to three of the following:
C~-C4-alkyl or halogen;
phenyl which can carry from one to four of the following: C~-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, Cl-C4-haloalkoxy, Cl-C4-alkylthio, Cl-C4-haloalXylthio, halogen, nitro, cyano, formyl, Cl-C4-alkanoyl, Cl-C4-haloalkanoyl or C1-C4-alkoxycarbonyl;
naphthyl which can be sub~tituted from once to three time~ by C,-C4-alkyl or halogen, or R3 and R4 together form -(CH2)n-Yp-(CH2)q- where n and q are each 1, 2 or 3, p is 0 or 1 and Y is oxygen, sulfur or N-methyl, or -(CH2)3-CO-, and the environ-mentally compatible salts thereof, where X in the formula Ib is not sulfur when R1 is 3-pyridyl, R2 is CO2CH2CH3 or R3 i~ hydrogen, and where X
in the formula Ia is not sulfur and R1 i5 not 2-thienyl when YR5 i8 OH and R3 is hydrogen and R4 is methyl.
The invention also relates to processes for preparing these compounds, and to herbicides which contain at least one compound Ia' or Ib' in which the substituents have the abovementioned meanings and ~ can be sulfur when R1 is 3-pyridyl, R2 i5 CO2CH2CH3 and R2 is hydrogen, or when R1 is 2-thienyl, YR5 is hydroxyl, R3 is hydrogen and R4 i~ methyl.
Oxazole- and thiazolecarboxylic acids and deriva-tives thereof ara known (DE-A 2,254,944, Bnll. Soc. Chim.

- 5 - O.Z. 0050/41126 Fr., 1969, 2152 and DE-A 2,221,647). Possible uses of these ~ubstanc~s as herbicides have not been described.
It is an object of the present invention to find and synthesize novel herbicidal compounds.
We have found that this object is achieved by the oxazole- and thiazolecarboxamides Ia and Ib defined in the first paragraph.
We have alse found processeq for preparing them and herbicides which contain oxazole- and thiazole-carboxamides Ia' and Ib' in which the substituent~ have the abovementioned meanings The oxazole- and thiazolecarboxamides Ia and Ib according to the invention can be prepared in a variety of ways. They are obtained, for example, by the following processes:
1. Process for preparing compounds Ia and Ib where R2 is Co2R5 and R5 is Cl-C5-alkyl Rll~ `R4 R tl~,R 3 Ia Ib (R5 = C~-CB_a1kY1 ) These oxazole- and thiazolecarboxamides Ia and Ib are obtained by hydrolyzing a die~ter of the formula II in a conventional manner with one equivalent of an aqueous base to give the monoesters IIIa and IIIb and then separating IIIa and IIIb or initially converting the mixture to the halide or another active form of the carboxylic acid and subsequently amidating these deriva-tives with an amine IV.
o o o NJ~OR 5 A . NJ~OH NJ~OR S
Il 11 . Il 11' 11 11 Rl~X~RS Rl~X~ORS Rl~X~OH
O O O
II IIIa IIIb 1~ U ~ ~J ! ~ i - 6 - O.Z. OOSOt41126 O R3 o HhR3R~ Rll~R5 Rll~o~R3 O O

IV Ia Ib The individual steps A and B in this reaction sequence can be carried out as follows:
Step A:
The partial hydrolysis of the diester II to the monoesters IIIa and IIIb is normally carried out at from -20 to 60CC~ preferably -10 to 30C, in an inert organic solvent which is miscible with water, in the pre~ence of from 1.0 to 1.2 mole eguivalent~ of a base.
Particularly quitable ba~es are alkali metal hydroxides. The ba~e is generally added as an aqueous solution which is from S to 20% strength.
Examples of preferred solvents for this reaction are dioxane or the alcohol corresponding to the ester component in the formula II.
The reaction mixture i5 normally worked up by acidification, when the desired product separates out as a solid or oil. Isola$ion is carried out in a conven-tional manner by filtration or extraction.
The mixture of the two isomeric monoesters IIIa and IIIb can be separated by fractional cry3tallization or chromatography, or it can be reacted further without separation.
Step B:
The compounds Ia and Ib are obtained from the monoesters IIIa and IIIb by initially converting the ~ V r~.l J ~
- 7 - O.Z. OOS0/41126 latter in a conventional manner into the halide or another active form of the carboxyl group and sub-sequently amidating these derivatives with an amine IV.
Examples of active forms of carboxylic acidq are, 5 besides the halides such as, in particular, the chlorides and bromides, also the Lmidazolides. The halides are generally preferred.
They are obtained by reacting the carboxylic acids IIIa and IIIb with a halogenating agent such as thionyl chloride or bromide, phosphorus oxychloride or oxybromide, ~richloride or trib~omide or pentachloride or pentabromide, phosgene and elemental chlorine and bromine.
From 1 to 5 mole equivalents, preferably from 1 lS to 2 mole equivalents, of halogenating agent are used.
The reaction is carried out at from ODC to the boiling point of the halogenating agent or, if an inert organic solvent is used, the boiling point thereof, preferably at from 20 to 120C.
Examples of suitable solvent~ are hydrocarbons and halohydrocarbons such as tetrachloroethane, methylene chloride, chloroform, dichloroethane, chlorobenzene, 1,2-dichlorobenzene, benzene, toluene and xylene.
The active carboxylic acid derivatives are normally isolated, for example by removing the halogenat-ing agent and, where present, the solvent by distillation and only then reacting them with the amines IV.
In this case, the amidation is carried out from -20 to 100C, preferably at -10 to 20C, in an inert aprotic polar organic solvent.
Particularly ~uitable solvents for thi~ reaction are halohydrocarbon~ such as dichloromethane, and ether~
such as diethyl ether and tert-butyl methyl ether.
Since hydrogen halide is formed in the amidation of acid halides, it is advisable to add the amine IV in an excess of from 2 to 5 mole equivalent~, preferably 2 to 3 mole equivalen~s. If the amine i3 u~ed in equimolar - 8 - O.z. 0050/41126 amount (from 1 to 1.2 mole equivalents), a base should be added, especially a tertiary amine such as triethylamine or pyridine, to bind the hydrogen halide.
When a mixture of the monoesters IIIa and IIIb i~
used as starting material, the reaction results in a mixture of the isomeric carboxamide~ Ia and Ib. This mixture can be fractionated into the individual com-ponents in a conventional manner, for example by fractional crystallization or chromatography.
The precursors II required for this synthesis are known (Bull. Soc. Chim. Fr. 1974, 2079) or can be ob-tained by known methods (Bull. Soc. Chim. Fr. 1969, 1762;
J. Chem. Soc., 1953, 93).
2. Process for preparing compounds Ia and Ib where X is sulfur and R2 is CO2H

R 11~2H R 1 ~N~HRR 43 Ia Ib These thiazolecarboxamide~ Ia and Ib are obtained particularly advantageously by reacting a dicarboxylic anhydride of the formula V in a conventional manner with an amine of the formula IV to give the isomers Ia and Ib and subsequently fractionating the mixture to give the isomers O O
N ~ o /1 ~ N~R4 + 1 ~ co2HR3 ~ \R4Rl C02H Rl ~ N~

V IV Ia Ib The reaction i~ normally carried out at from -10 to 150C, preferably 20 to 120C, in an inert aprotic - 9 - O.Z. 0050/41126 polar organic solvent.
Particularly suitable solvents are halohydro-carbons, eg. tetrachloroethane, methylene chloride, chloroform, dichloroethane, chlorobenzene and 1,2-di-chlorobenzene; ethers, eg. diethyl ether, methyl tert-butyl ether, dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran and dioxan; dipolar aprotic solvents, eg. acetonitrile, dimethylformamide, dimethyl-acetamide, dimethyl sulfoxide, N-methylpyrrolidone, 1,3-dimethyltetrahydro-2(lH)-pyrimidinone and 1,3-di-methylimidazolidin-2-one; aromatic compounds, eg. ben-zene, toluene, xylene, pyridine and quinoline; ketones, eg. acetone, methyl ethyl ketone or mixtures thereof.
The amine IV is generally used in equimolar amounts or in an excess, preferably in amounts of from 1.0 to 5.0 mole equivalents based on V.
The dicarboxylic anhydrides required for this process as known or can be prepared by known methods (Bull. Soc. Chim. Fr. 1969, 1762; CS-A-195,369;
CS-A-195,370).
3. Proce~s for p~eparing compounds Ia and Ib where Rl is not halogen and R2 is carboxyl or formyl O R3 N ~R2 R3 NJ~N\ R l~X~N
Rl~X~R2 R4 R4 Ia Ib (Rl ~ Hal; R2 = CO2H, CHO) These isomeric oxazole- and thiazolecarboxamides are obtained by activating and amidating a carboxylic acid IIIc or IIId under the conditions described in lB, and then reacting the resulting amides VIa and VIb in a conventional manner in the presence of a carboxylating or formylating reagent.

20261~
- 10 - O.Z. 0050/41126 ~ R .1~
IIIc IIId VIa R11~ ~ R3 VIb Ia Ib Step A in this reaction sequence is generally carried out under the conditions described in Section B
in Proces~ 1.
Step B.
The carboxylation or formylation of the oxazole-and thiazolecarboxamides VIa and VIb is usually carried out at from 0 to -100C, preferably -50 to -80C, in an inert aprotic polar organic solvent in the pre ence of a base with exclusion of moisture.
The preferred carboxylating agent is gaseous or solid carbon dioxide, and dimethylformamide or N-formyl-morpholine is used, in particular, as formylating reagent.
Suitable ~olvent~ are, in particular, ethers, eg.
diethyl ether, methyl tert-butyl ether, dLmethoxyethane, dLethylene glycol dimethyl ether, tetrahydrofuran and dioxan.
The ba3es which ars preferably used are organo-metallic compound~, eg. methyllithium, n-butyllithium, s-butyllithium, t-butyllithium or phenyllithium.
The reaction is normally carried out by first adding up to 3 mole equivalents of the dissolved base to a solution of the oxazole- or thiazolecarboxamide VIa or VIb, resulting in a derivative which i8 metalated on the heterocycle and i~ then converted into the desired ~ v ~ ~ 1 ~ O.Z. 0050/41126 product Ia or Ib by addition of the electrophilic carboxylating or formylating reagent.
When R3 is hydrogen, correspondingly more mole equivalents of the base are required because, in this case, the amide nitrogen is initially deprotonated.
Hence, from 2 to 2.5 mole equivalents of the base are preferably used for the reaction of carboxamides VIa or VIb where R3 is hydrogen.
Compounds VIa and VIb where Rl is hydrogen react with the base initially to metalate the 2-position of the heterocycle ring.
In order to introduce the carboxyl or formyl radical adjacent to the carbamoyl group in this case, it is necessary to start from oxazole- or thiazolecarbox-amides VIa or VIb where R3 is hydrogen.
Oxazole- and thiazolecarboxamides Ia and Ib where R1 is hydrogen and R3 is not hydrogen are obtained from the compounds which can be obtained by $he abovementioned process and in which Rl and R3 are hydrogen in a conven-tional manner by subsequent alkylation or cycloalkyl-ation.
The carboxylic acids IIIc and IIId required for the abovementioned process are known from the literature (Beilstein, Volume 27, Supplements 1-53 or can be pre-pared by conventional methods, for axample by oxidationof the corresponding alcohols or aldehyde~ or by hydro-lysis of the corresponding nitriles (J.V. Metzger in "The Chemistry of Heterocyclic Compounds, Vol. 34, Part 1, Thiazole and it~ Derivatives", Arnold Wei~sberger and Edward C. Taylor (Editors), John Wiley and Sons, page~
519 et sec., I.J. Turchi in ~'The Chemistry of Heterocyclic Compounds, Vol. 45, Oxazoles", Arnold Weissberger and Edward C. Taylor (Editors), John Wiley and Sons).

4. Process for preparing compounds Ia and Ib where R2 is carboxyl - 12 - O.Z. 0050/41126 R 1 ~2H R 1 J~o'N~HRR 3 Ia Ib These oxazole- and thiazolecarboxamides Ia and Ib are obtained, for example, by hydrolyzing an appropriate carboxamide Ia or Ib where R2 is Co2R5 and R5 is Cl-C6-alkyl in a conventional manner with one equivalent of an aqueous base. The reaction is shown in the following diagram only for the carboxamides Ia. It takes place similarly with the corresponding carboxamides Ib.

N~N'R 3 R 11~ 2H

Ia (R5 = Cl-C6-alkyl) Ia This synthesis is generally carried out under the condition~ described in Section A in Proces~ 1.

5. Process for preparing compounds Ia and Ib where R2 ig CoYR5 Rl~rRS Rl~o RR3 Ia Ib These carboxamides Ia and Ib are obtained by activating a corresponding carboxylic acid Ia or Ib (R2 = CO2H) and subsequent reaction in a conventional manner with a compound VII.

~ ù ~
- 13 - O.Z. 0050/41126 or Rl l ~ `R4 + HYR
Rl X C02H O

Ia Ib VII

R 1 1~YR 5 ~;~Y R 5 3 Ia Ib The reaction can be carried out at from -20C to the reflux temperature of the solvent or mixture thereof, preferably at from 0 to 60C.
Solvents expediently used for these reactions are halohydrocarbons, eg. tetrachlorosthane, methylene chloride, chloroform, dichloroethane, chlorobenzene and 1,2-dichlorobenzene; ethers, eg. diethyl ether, methyl tert-butyl ether, dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran and dioxan; aromatic compounds, eg. benzene, toluene or xylene; or mixtures thereof.
Suitable condensing agents are dicyclohexylcarbo-diimide or propanephosphonic anhydride.
The molar ratios of the starting compounds in the reaction are generally from 0.5:1 to 2:1 for the ratio of carboxylic acid VIa to alcohol or thiol and from 1:1 to 1;3 for the ratio of carboxylic acid IVa to condensing agent.
The concentration of the precursor3 in the solvent is generally from 0.1 to 5 mol/l, preferably 0.2 to 2 mol/l.
It is particularly preferred to use ethers such as die~hyl ether, tetrahydrofuran or dioxan with propane-phosphonic anhydride as condensing agent at from 20 to 2026~31 - 14 - O.Z. 0050/41126 60C.

6. Process for preparing compounds Ia and Ib where R2 is 4,5-dihydro-2-oxazolyl R~ 4 ,~ ~3 o Ia Ib These compound~ are obtained by reacting an appropriate carboxylic acid derivative Ia or Ib where R2 is CO2R' or COOH and R' i5 Cl-C4-alkyl in a conventional manner with an amino alcohol of the formula VIII.

R 1~2H or 1 ~ ,R 3 10 Ia Ib VIII

R1~4 or Rl ~ 13 Ia Ib The reaction is carried out at from 0 to 180C, preferably at the reflux temperature of the mixture with an amino alcohol VIII, in the pre~ence or absence of an inert solvent. The ratio of ester or carboxylic acid Ia or Ib to amino alcohol VIII in this reaction is from 1:1 to 1:2.5, preferably 1:1 to 1:1.5.
The ~olvents expediently used arQ halohydro-carbons such as chlorobenzenH and 1,2-dichlorobenzene, ether~, eg. methyl tert-butyl ether~ 1,2-dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran and ~J IJ r~ v ~
15 ~ O~ Z ~ 0050/41126 dioxan; alcohols such a~ methanol, ethanol, propanol or ethylene glycol, dipolar aprotic solvents, eg. aceto-nitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, 1,3-dimethyltetrahydro-2(1H)-pyrimidinone and 1,3-dimethylimidazolin-2-one, or aromatic compounds, eg. benzene, toluene and xylene. The concentration of the precurqors in these solvents is generally from 0.1 to 5 ~ 0 mol/l, preferably 0.2 to 2.0 mol/l.
The reaction is generally complete after 14 hours; the carboxamides Ia and Ib are then precipi-tated, where appropriate by adding water, filtered off with suction or extracted with an organic solvent, and purified by conventional methods such as recrystal-lization or chromatography.
Compounds of the formula VIa where R1 is _ZR8 are obtained in a conventional manner (Xelv. Chim. Acta, 37 (1954) 2059) by reaeting a 2-halothiazole-4-carboxamide VIa (DE 2,241,035) with an alcohol or thiol H-ZRa in the presence of a base in an inert organic solvent.

1~ \ + H--ZRa , 1~ ~

VIa (R1 = Hal) YIa' Hal in formula VIa is a halogen sueh as fluorine, ehlorine, bromine or iodine; particularly suitable compounds VIa are those where Hal i~ chlorine or bromine.
R8Z in formula VIa' is Cl-C~-alkoxy, Cl-C4-alkyl-thio, each of-which can be substitu~ed up to three time~
by halogen, in particular methoxy, ethoxy, l-methyl-ethoxy, 1,l-dimethyletho~, trifluoromethoxy, methylthio, ethylthio~ difluoromethylthio; or phenoxy or phenylthio, eaeh of whieh ean be substitute~ up to three time~ by Cl-C4-alkyl, Cl-C"-haloalkyl, Cl-C~-alkylthio, Cl-C4-halo-- 16 - O.Z. 0050/41126 alkylthio, halogen, cyano or nitro, in particular 2,4-di-chlorophenoxy, 2,4-difluorophenoxy, 2,4,6-trifluoro-phenoxy, p-trifluoromethylphenoxy, 2-chloro-4-trifluoro-phenoxy, 3-cyanophenoxy, 4-cyano-2-methoxyphenoxy, 4-nitrophenoxy, 2-fluorophenylthio, 4-trifluoromethyl-phenylthio and 3-cyanophenylthio.
The solvents expediently used for these reactions are halohydrocarbons, eg. tetrachloroethane, methylene chloride, chloroform, dichloroethane, chlorobenzene and 1,2-dichlorobenzene; ethers, eg. diethyl ether, methyl tert-butyl ether, dLmethoxyethanè, diethylene glycol dimethyl ether, tetrahydrofuran and dioxan; dipolar aprotic solvents, eg. acetonitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrol-idone, 1,3-dimethyltetrahydro-2(1H)-pyrimidinone and 1,3-dimethylimidaæolidin-2-one; aromatic compounds, eg.
benzene, toluene, xylene, pyridine and quinoline;
ketones, 2g. acetone, methyl ethyl ketone; alcohols, eg.
methanol, ethanol, iso-propanol and tert-butanol or mix-tures thereof.
The reaction can be carried out at from -100C to the reflux temperature of the solvent or mixture thereof, preferably at from -60~ to 150C.
The bases used are hydrides and alkoxides of alkali metals and alkaline earth metals, in particular NaH, RH, CaH2, LiH and RO-tBu. It is also beneficial on occasion to use combinations of the bases listed.
The molar ratios of the starting compounds in the reaction are generally from 3:1 to 1:1 for the ratio of alcohol or thiol to 2-halothiazole-4-carboxamide VIa and from 1:1 to 1:3 for the ratio of alcohol or thiol to the base.
The concentration of the precursor~ in the solvent is generally from 0.1 to 5 mol/l, preferably 0.2 to 2 mol~l.
It is particularly preferable to use aprotic dipolar solvents such as acetonitrile~ dimethylformamide, - 17 - O.Z. 0~50i41126 dimethyl sulfoxide, N-methylpyrrolidone, 1,3-dimethyl-tetrahydro-2(1~I)-pyrimidinone and 1,3-dLmethylimidazo-lidin-2-one or ethers such as 1,2-dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran or dioxan at from 50C to 150C with NaH or RO-tBu as base.
The 2-halothiazole-4-carboxamides of the formula - VIa required for the reaction can be obtained by methods known from the literature from the corresponding carbonyl halides by reaction with amines (DE-A 2,241,035).
10The alcohols or thiols which are used are com-mercially available in many cases or thPy can be prepared in a conventional manner.
Furthermore, the compounds of the formula Vlb are obtained in a conventional manner (Helv. ChLm. Acta, 37, 15(1954) 2Q59) by reacting a 2-halothiazole-5-carboxamide VIb with an alcohol or thiol in an inert organic solvent in the presence of a base a~ shown in the scheme:

N~ R3 N~ R3 Il 11 ~ ~ H-zR8 . Il ll Ha I~X~N\ . . R8;~X~N~
Q R~ o R~
VIb VIb' Hal in VIb is a halogen such a~ fluorine, chlorine, bromine or iodine; particularly uitable compounds VIb are those where Hal is chlorine or bromine.
R9Z in formula VIb' is Cl-C4-alkoxy, Cl-C~-alkyl-thio, each of which can be substitutad up to three time~
by halogen, in particular methoxy, ethoxy, 1-methyl-ethoxy, 1,l-dimethylethoxy, trifluoromethoxy, methylthio, ethylthio, difluoromethylthio; or phenoxy or phenylthio, each of which can be=~ubstituted up to three times by Cl-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkylthio, C1-C4-halo-alkylthio, halogen, cyano or nitro, in par-ticular 2,4-dichlorophenoxy, 2,4-difluorophenoxy, 2,4,6-trifluorophenoxy, p-trifluoromethylphenoxy, ~ J ~
- 18 - O.Z. 0050/41126 2-chloro-4-trifluorophenoxy, 3-cyanophenoxy, 4-cyano-2-methoxyphenoxy, 4-nitrophenoxy, 2-fluorophenylthio, 4-trifluoromethylphenylthio and 3-cyanophenylthio.
The solvents expediently used for these reactions are halohydrocarbons, eg. tetrachloroethane, methylene chloride, chloroform, dichloroethane, chlorobenzene and 1,2-dichlorobenzene; ethers, eg. diethyl ether, methyl tert-butyl ether, dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran and dioxan; dipolar 10 aprotic solvents, eg. acetonitrile, dimethylformamide, dimethylacetamide, dLmethyl sulfoxide, N-methylpyrrol-idone, 1,3-dimethyltetrahydro-2(1H)-pyrimidinone and 1,3- dimethylimidazolidin-2-one; aromatic compounds, eg.
benzene, toluene, xylene, pyridine and quinoline;
lS ketone~, eg. acetone, methyl ethyl ketone; alcohols, eg.
methanol, ethanol, iso-propanol and tert-butanol or mix-tures thereof.
The reaction can be carried out at from -100C to the reflux temperature of the solvent or mixture thereof, 20 preferably at from -60C to 150C.
The ba es used are hydrides and alkoxide~ of alkali metals and alkaline earth metal~, in particular NaH, KH, CaH2, LiH and KO-tBu. It i~ also beneficial on occasion to use combinations of the bases listed.
The molar ratios of the starting compounds in the reaction are generally from 3:1 to 1:1 for the ratio of alcohol or thiol to 2-halothiazole-5-carboxamide VIb and from 1:1 to 1:3 for the ratio of alcohol or thiol to the base.
The concentration of the precursors in the solvent i~ generally from 0.1 to 5 mol/l, preferably 0.2 to 2 mol/l.
It is particularly preferable to use aprotic dipo~ar solvents such as acetonitrile, dimethylforma~ide, 35 dimethyl sulfoxide, N-methylpyrrolidone, 1,3-dimethyl-tetrahydro-2(lH)-pyrimidinone and 1,3-dimethylimidazo-lidin-2-one or ethers such a~ 1,2-dimethoxyethane, di-- 19 - o.z. 00~0~41126 ethylene glycol dimethyl ether, tetrahydrofuran or dioxan at from 50C to 150C with NaH or KO-tBu a~ base.
The 2-halothiazole-5-carboxamides of the formula VIb required for the reaction can be obtained by methods known from the literature from the correspondin~ carbonyl halides by reaction with amines (US-A-4,001,421 Compounds of the formula Ib can be obtained by reacting dicarboxylic esters of the formula II with amines in a conventional manner, and hydrolyzing the resulting amides Ib as shown in the scheme:

~1 l~R 5 + -- R 1 l~R 3 b ~ R 3 I I ( R2 = Co2R5 ) Ib ( R2 =C02H ) The procedure for this is expediently to dissolve the diester II in an inert organic solvent and react with an amine.
The solvents used for these reactions are ethers, eg. diethyl ether, me~hyl tert-butyl ether, dLmethoxy-ethane, diethylene glycol dimethyl ether, tetrahydrofuran and dioxan; aromatic compounds, eg. benzene, toluene, xylene or mesitylene; alcohols, eg. methanol, ethanol, iso-propanol and tert-butanol, or mixtures thereof.
The reaction can be carried out at from -100C to the reflux temperature of the solvent or mixture thereof, preferably at from -60 4C to 150C.
The molar ratio of diester II to amine is from 1:1 to 1:2, preferably from 1:1 to 1:1.2.
The concentration of the precursors in the solvent is generally from 0.1 to S mol/l, preferably 0.2 to 2.0 mol/l.
It i~ particularly preferable to use alcohols - 20 - O.Z. 0050/41126 such a~ ethanol in the presence of one equivalent of amine at from ~0 to 100C. The diester~ II required for the reaction are known from the literature or can be prepared by conventional methods (Bull. Soc. ChLm. Fr., 1969, 1762; J. Chem. Soc., 1953, 93).
Beside~ Processes 1-6 which have been described above for preparing compounds Ia and Ib, there are further po~ible syntheses which can be found in the following references:
Beilstein, main serie~ and supplement3 1-5, volume 27; R.W. Wiley, The Chemistry of Heterocyclic Compounds, Five- and Six-Membered Compounds with Nitrogen and Oxygen, Interscience Publisher~, New York, London (1962), Heterocyclic Chemistry, Vol. 6, ~ive-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 and X.
With a view to the intended use of the compounds Ia' and Ib', the following sub3tituents are preferred:
X i9 oxygen or sulfur R1 is hydrogen;
halogen such a~ fluorine, chlorine, bromine and iodine, especially fluorine and chlorine;
Cl-C~-alkyl, such ~8 methyl, ethyl, n-propyl, iso-propyl, n-butyl, ~ec-butyl, i~o-butyl and tert-butyl, pentyl, l-methylbutyl, 2-methylbutyl, 3-methylbutyl, l,l-dimethylpropyl, 1,2-dimethyl-propyl, 2,2-dimethylpropyl, l-ethylpropyl, hexyl, l-methylpentyl, 2-methylpen~yl, 3-methylpentyl, 4-methylpentyl, l,l-dimethylbutyl, 1,2-dimethyl-butyl, 1,3-dimethylbutyl, 2,2-dLmethylbutyl, 2,3-~ dimethylbutyl, 3,3-dLmethylbutyl, l-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-tri-methylpropyl, l-ethyl-l-methylpropyl and l-ethyl-2-met~ylpropyl, e~pecially methyl, ethyl, propyl and 1~ V r~ ~ ~ JL
- 21 - O.Z. 0050/41126 iso-propyl, which can carry from one to five halogen atoms, in particular fluorine and/or chlorine or one or two of the following: cycloalkyl such as cyclo-propyl, cyclobutyl, cyclopentyl and cyclohexyl, especially cyclopropyl; alkoxy ~uch a~ methoxy, ethoxy, n-propoxy, 2-methylethoxy, n-butoxy, l-methylpropoxy, 2-methylpropoxy and 1,l-dimethyl-ethoxy, especially methoxy, ethoxy, 1-methylethoxy and 1,1-dimethylethoxy; haloalkoxy such as difluoro-methoxy, trifluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, 1-fluoroethoxy, 2-fluoro-ethoxy, 2,2-difluoroethoxy, 1,1,2,2-tetrafluoro-ethoxy, 2,2,2-trifluoroethoxy, 2-chloro-1,1,2-trifluoroethoxy and pentafluoroethoxy, especially trifluoromethoxy and pentafluoroethoxy; alkylthio such as methylthio, ethylthio, propylthio, 1-methyl-ethylthio, butylthio, 1-methylpropylthio, 2-methyl-propylthio and 1,1-dimethylethylthio, especially methylthio and ethylthio; haloalkylthio such as difllloromethylthio, trifluoromethylthio, chlorodi-fluoromethylthio, l-fluoroethylthio, 2-fluoroethyl-thio, 2,2-difluoroethylthio, 2,2,2-trifluoroethyl-thio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio and pentafluoroethylthio, especially difluoromethylthio and pentafluoroethylthio or cyano;
benzyl which can carry from one to three of the following: alkyl as mentioned above, especially methyl, ethyl and i~o-propyl; haloalkyl as mentioned above, especially trifluoromethyl and chlorodi-fluoromethyl; alkoxy as mentioned above, especially methoxy and ethoxy; haloalkoxy as mentioned above, especially trifluoromethoxy, pentafluoroethoxy and trichloromethoxy; alkylthio as mentioned above, especially methylthio and ethylthio; haloalkylthio ac mentioned above, e~pecially difluoromethylthio, pentafluoroethylthio and trifluoromethylthio;

~ V r~ V ~ c~ 1 - 22 - O.Z. 0050/41126 h~lo~en as mentioned above, especially fluorine and chlorine; cyano or nitro;
cycloalkyl such as cyclopropyl, cyclobutyl, cyclo-pentyl, cyclohexyl, cycloheptyl and cyclooctyl, especially cyclopropyl, cyclopentyl and cyclohexyl, which can carry from one to three of the following:
alkyl as mentioned above, especially methyl, or halogen as mentioned above, especially chlorine and fluorine;
alkenyl such as ethenyl, l-propenyl, 2-propenyl, l-methylethenyl, l-butenyl, 2-butenyl, 3-butenyl, l-methyl-l-propenyl, l-methyl-2-propenyl, 2-methyl-l-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, l-methyl-l-butenyl, 2-methyl-1-butenyl, 3-methyl-2-butenyl, 1-methyl-2-butenyl, 2-methyl-2-bu~enyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1,-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, l-ethyl-l-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, l-methyl-l-pentenyl, 2-methyl-l-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, l-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, l-methyl-3-pentenyl, 2-methyl-3-p~ntenyl, 4-methyl-2-pentenyl, l-methyl-3-pentenyl, 2-methyl-3-psntenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, l-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dLmethyl-2-butenyl, 1,1-dLmethyl-3-butenyl, 1,2-dLmethyl-l-butenyl, 1,2-dLmethyl-2-butenyl, 1,2-dLmethyl-3-butenyl, 1,3-dLmethyl-l-butenyl, 1,3-dLmethyl-2-butenyl, 1,3-dLmethyl-3-butenyl, 2,2-dLmethyl-3-butenyl, 2,3-dLmethyl-l-butenyl, 2,3-dLmethyl-2-butenyl, 2,3-dLmethyl-3-butenyl, 3,3-dLmethyl-l-butenyl, l-ethyl-l-butenyl, l-ethyl-2-butenyl, 1-ethyl-3-buten~l, 2-ethyl-1-butenyl, 2-ethyl-2-~ ~ r.~
- 23 - O.Z. 0050/41126 butenyl, 2-ethyl-3-butenyl, 1,1,2-trLmethyl-2-propenyl, l-ethyl-l-methyl-2-propenyl, 1-ethyl-2-methyl-l-propenyl and l-ethyl-2-methyl-2-propenyl, especially allyl which can carry from one to three s of the following: halogen as mentioned above, especially fluorine and chlorine; alkoxy as mentioned above, especially methoxy and ethoxy, and/or one phenyl which in turn can carry from one to three of the following: alkyl as mentioned above, especially methyl, ethyl and iso-propyl; haloalkyl as mentioned above, especiall`y trifluoromethyl and chlorodifluoromethyl; alkoxy as mentioned above, especially methoxy and ethoxy; haloalkoxy as mentioned above, especially trifluoromethoxy, pentafluoroethoxy and trichloromethoxy; alkylthio as mentioned above, especially methylthio and ethyl-thio; haloalkylthio as mentioned above, especially difluoromethylthio, pentafluoroethylthio and tri-fluoromethylthio; halogen as mentioned above, especially fluorine and chlorine; cyano or nitro;
alkynyl such as ethynyl, l-propynyl, propargyl, l-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, l-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl, 3-methyl-1-butynyl, l,l-di-methyl-2-propynyl, 1-ethyl-2-propynyl, l-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-l-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1~2-dimethyl-3-butynyl, 2,2-dLme-~hyl-4-butynyl, 3,3-dLmethyl-l-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl, especially propargyl, which can carry from one to three of the following: halogen as mentioned above, ~ V rJ ;J ~
- 24 - o.Z. 0050/41126 especially iodine; alkoxy as mentioned above, especially methoxy and ethoxy, and/or one phenyl which in turn can carry from one to three of the following: alkyl as mentioned above, especially methyl, ethyl and iso-propyl; haloalkyl as mentioned above, especially trifluoromethyl and chlorodi-fluoromethyl; alkoxy as mentioned above, especially methoxy and ethoxy; haloalkoxy as mentioned above, especially trifluoromethoxy, pentafluoroethoxy and trichloromethoxy; alkylthio a3 mentioned above, e~pecially methylthio and ethylthio; haloalkylthio a~ mentioned above, especially difluoromethylthio, pentafluoroethylthio and trifluoromethylthio;
halogen as mentioned above, e~pecially fluorine and chlorine; cyano or nitro;
Cl-C4-alkoxy as mentioned above, e~pecially methoxy and ethoxy;
Cl-C4-haloalkoxy as mentioned above, especially trifluoromethoxy, pentafluoroethoxy and trichloro-methoxy;
Cl-C4-alkylthio a~ mentioned above, especially methylthio and ethylthio;
C1-C4-haloalkylthio as mentioned above, especially difluoromethylthio, pentafluoroethylthio and tri-fluoromethylthio;
phenoxy or phenylthio, each of which can carry from one to three of the following: alkyl aæ mentioned above, especially methyl, ethyl and iso-propyl;
haloalkyl as mentioned above, especially trifluoro-methyl and chlorodifluoromethyl; alkoxy as mentioned above, especially methoxy and ethoxy; haloalkoxy as msntioned above, e~pecially trifluoromethoxy, pentafluoroethoxy and trichloromethoxy; alkylthio as mentioned above, e~pecially methylthio and ethylthio; haloalkylthio as mentioned above, especi-ally difluoromethylthio, pentafluoroethylthio and trifluoromathylthio; halogen a~ mentioned above, ~ v l ~ ~
- 25 - O.Z. 0050/41126 especially fluorine and chlorine; cyano or nitro;
a 5- to 6-membered heterocyclic radical containing one or two hetero atoms selected from the group . comprising oxygen, sulfur and nitrogen, such as 2-S tetrahydrofuryl, 3-tetrahydrofuryl, 4-tetrahydro-pyranyl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 3-furyl, 2-thienyl, 3-thienyl, 2-furyl, 3-tetra-hydrothienyl, 2-tetrahydropyranyl, 5-isoxazolyl, 3-isoxazolyl, 4-iscxazolyl, 5-isothiazolyl, 4-isothia-zolyl, 3-isothiazolyl, 2-oxazolyl, 4-thiazolyl, 4-oxazolyl, 2-thiazolyl, 5-oxazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-pyrrolyl, 2-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 4-pyridyl, 3-pyridyl and 2-pyridyl, it being pos-sible for this ring to carry one or two of the followings alkyl as mentioned above, especially methyl; halogen a~ mentioned above, especially fluorine and chlorns; alkoxy as mentioned above, especially methoxy and ethoxy, or alkoxycarbonyl such a methoxycarbonyl and ethoxycarbonyl, especially methoxycarbonyl;
phenyl which can carry from one to three of the following: alkyl a-~ mentioned for Rl, especially methyl, ethyl and iso-propyl; haloalkyl ac mentioned above, especially trifluoromethyl and chlorodi-fluoromethyl; alkoxy as mentioned above, e pecially methoxy and ethoxy; haloalkoxy as mentioned above, especially trifluoromethoxy, pentafluoroethoxy and trichloromethoxy; alkylthio as mentioned above, especially methylthio and ethylthio; haloalkylthio as mentioned above, especially difluoromethylthio, pentafluoroe~hylthio and trifluoromethylthio;
halogen as mentioned above, especially fluorine and chlorine; cyano or nitro;
R2 is formyl, 4,5-dihydro-2-oxazolyl or -CoYR5 and Y i~ oxygen or ~ulfur;

- 26 - O.Z. 0050/41126 R5 i B hydrogen;
alkyl as mentioned for Rl, especially methyl, ethyl, n-propyl, iso-propyl, and n-hexyl, which can carry from one to five halogen atoms as mentioned for Rl, especially fluorine and chlorine, or hydroxyl groups and/or one of the following: alkoxy as mentioned for Rl, especially methoxy and ethoxy; alkoxyalkoxy such as methoxyethoxy, ethoxyethoxy, propoxyethoxy, especially methoxyethoxy; cyano; trimethylsilyl;
alkylthio as mentioned for R1, especially methylthio and ethylthio; alkylamino such as methylamino, ethylamino, propylamino, iso-propylamino, especially methylamino and ethylamino; dialkylamino such as dimethylamino, diethylamino, dipropylamino, diiso-lS propylamino, methylethylamino, especially dimethyl-amino and methylethylamino; cycloalkylamino such as cyclopropylamino,cyclobutylamino,cyclopentylamino, cyclohexylamino and cycloheptylamino, espeeially cyclopropylamino; alkylsulfinyl such as me~hyl-sulfinyl, ethylsulfinyl, propylsulfinyl, iso-propyl-sulfinyl, e~pecially methylsulfinyl and ethyl-sulfinyl; alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, iso-propylsulfonyl, especially methylsulfonyl and ethylsulfonyl;
carboxyl; alkoxycarbonyl as mentioned for R1, especially methoxycarbonyl; dialkylaminocarbonyl such as dim~thylaminocarbonyl, diethylaminocarbonyl, dipropylaminocarbonyl, diisopropylaminocarbonyl, dicyclopropylaminocarbonyl, methylethylamino-carbonyl, especially dimethylaminocarbonyl and diethylaminocarbonyl; dialkoxyphosphoryl such as dimethoxyphosphoryl, diethoxyphosphoryl, dipropoxy-phosphoryl, diisopropoxyphosphoryl, especially dimethoxyphosphoryl and diethoxypho~phoryl;
alkaneLminoxy ~uch as, in particular, 2-propaneiminoxy; thienyl, furyl, tetrahydrofuryl, phthalimido, pyridyl, benzyloxy; benzoyl, it b~ing 2026~31 - 27 - O.Z. 0~50/41126 possible for the cyclic radicals in turn to carry from one to three of the following: alkyl as mentioned for R1, especially methyl and ethyl; alkoxy as mentioned for Rl, especially methoxy and ethoxy, or halogen as mentioned for Rl, especially fluorine and chlorine;
benzyl which can carry from one to three of the following: alkyl as mentioned for Rl, especially methyl and ethyl alkoxy as mentioned for Rl, aspeci-ally methoxy and ethoxy; haloalkyl as mentioned for Rl, especially trifluoromethyl; halogen as mentioned for R1, especially fluorine and chlorine, nitro and cyano;
C3-Ca-cycloalkyl a~ mentioned for Rl, especially cyclopentyl and cyclohexyl;
phenyl which can carry -from one to three of the following: alkyl as mentioned for Rl, especially methyl and ethyl; alkoxy a~ mentioned for R1, especially methoxy and ethoxy; haloalkyl as mentioned for R1, especially trifluoromethyl; halo-alkoxy a~ mentioned for Rl, especially trifluoro-methoxy; alko~ycarbonyl a~ mentioned above, e.?ecially methoxycarbonyl; halogen as mentioned for R1, especially fluorine and chlorine and bromine, nitro and cyano;
C3-C6-alkenyl as mentioned for R1, especially allyl and methallyl, C5-Cs-cycloalkenyl such as 2-cyclo-pentenyl and 2-cyclohexenyl, especially 2-cyclo-hexenyl, or C3-CB-alkynyl a~ mentioned for R1, especially propargyl, it being po~sible for these radical~ to carry one of the following: ~ydroxyl;
alkoxy as mentioned for Rl, especially methoxy and ethoxy; halogen a~ mentioned for Rl, especially iodine, or phenyl which in turn can carry from one to three of the followinq: alkyl a~ mentioned for Rl, e3pecially methyl and ethyl; alkoxy a~ mentioned for Rl, especially methoxy and ethoxy; haloalkyl a~

~ ~ . J J ~
- 28 - O.Z. 0050/41126 mentioned for Rl, especially trifluoromethyl;
halogen as mentioned for Rl, especially fluorine and chlorine, nitro or cyano;
a five- to six-membered heterocyclic radical con-S taining one or two hetero atoms selected from the group comprising oxygen, sulfur and nitrogen as mentioned for Rl, especially tetrahydrofuryl and tetrahydropyranyl or a benzotriazolyl radical;
phthalimido; tetrahydrophthalimido; succinimido;
maleimido;
one equivalent of a cation of an alkali metal or alkaline earth metal, manganese, copper, iron, ammonium or substituted ammonium or -N=CR6R7 where R~ and R7 are, independently of one another, hydrogen, alkyl as mentioned for Rl, especially methyl, ethyl and iso-propyl; cycloalkyl as mentioned for R1, especially cyclopropyl; phenyl or furyl, or together form a methylene chain -(CH2)~-with m = 4 to 7, 20 R3 i~ hydrogen, Cl-C~-alkyl as mentioned for Rl, especially methyl, ethyl or iso-propyl, which can carry from one to three of the following: hydroxyl; halogen as men-tioned for Rl, especially fluorine and chlorine;
alkoxy a~ mentioned for Rl, especially methoxy and ethoxy; alkylthio a~ mentioned for Rl, especially methylthio and ethylthio, or dialkylamino as men-tioned for R5, especially dimethylamino;
cycloa~kyl as mentioned for R1, especially cyclo-propyl, cyclobutyl, cyclopentyl and cyclohexyl, which can carry from one to three of the following:
alkyl as mentioned for Rl, especially methyl, ethyl and isopropyl; halogen as mentioned for Rl, especi-ally fluorine and chlorine, or haloalkyl as mentioned for R1, especially trifluoromethyl;
R4 is hydroxyl;
alkoxy as mentioned for Rl, especially methoxy and J ;~
- 29 - O.Z. 0050/41126 ethoxy;
alkyl as mentioned for R~, especially methyl, ethyl, n-propyl, i~o-propyl, n-butyl, sec-butyl, iso-butyl and tert-butyl, which can carry from one to three of the following: alkoxy as mentioned for R1, especially methoxy and ethoxy; haloalkoxy as mentioned for Rl, especially trifluoromethoxy; alkylthio as mentioned for Rl, especially methylthio and ethylthio; halo-alkylthio as mentioned for Rl, especially trifluoromethylthio; dialkylamino as mentioned for Rl, especially dimethylamino and diethylamino;
halogen as mentioned for R1, especially fluorine and chlorine; cycloalkyl as mentioned for Rl, especially cyclopropyl, cyclopentyl and cyclohexyl, or phenyl which in turn can carry from one to three of the following: halogen as mentioned for R1, especially fluorine and chlorine; cyano; nitro; alkyl as mentioned for R1, especially methyl and ethyl;
haloalkyl as mentioned for Rl, especially trifluoro-methyl, alkoxy as mentioned for R1, e pecially methoxy and ethoxy; haloalkoxy as mentioned for Rl, especially trifluoromethoxy; alkylthio as mentioned for Rl, especi lly methylthio and ethylthio, or haloalkylthio as mentioned for R1, especially tri-fluoromethylthio;
cycloalkyl as mentioned for Rl, especially cyclo-prspyl, cyclobutyl, cyclopentyl and cyclohexyl, which can carry from one to three of the following:
alkyl as mentioned for Rl, especially methyl, ethyl and isopropyl; haloalkyl as mentioned for Rl, especially trifluoromethyl; alkoxy as mentioned for Rl, especially methoxy and ethoxy; haloalkoxy as men-tioned for Rl, especially trifluoromethoxy; halogen as mentioned for R1, e~pecially fluorine and chlorine, nitro or cyano;
alkenyl or C3-Cs-alkynyl as mentioned for Rl, especially allyl, methallyl, propargyl and 1,1-202613~

_ 30 - O.Z. OOS0/41126 dimQthyl-2-propynyl, which can be substituted from once to three time~ by halogen as mentioned for R1, especially fluorine and chlorine, andJor once by phenyl which in ~urn can carry from one to three of S the following: alkyl as mentioned for Rl, especially methyl and ethyl; haloalkyl a~ mentioned for R1, e~pecially trifluoromethyl; alkoxy a~ mentioned for Rl, especially methoxy and ethoxy, haloalkoxy a~ men-tioned for Rl, e4pecially trifluormethoxy; alkylthio as mentioned for R1, e~pecially methylthio and ethylthio; haloalkylthio as mentioned for R1, especially trifluoromethylthio; halogen as mentioned for R1, especially fluorine and chlorine, cyano or nitro;
a 5- to 6-membered heterocyclic radical which contains one or two hetero atoms selected from the group comprising oxygen, sulfur or nitrogen as mentioned for R1 and which can carry from one to three of the following: alkyl as mentioned for Rl, especially methyl, ethyl and iso-propyl, or halogen as mentioned for R1, especially fluorine and chlorins;
phenyl which can carry from one to four of the following: alkyl a~ mentioned for R', especially methyl, ethyl and iso-propyl; haloalkyl as mentioned for Rl, especially trifluoromethyl; alkoxy a~ men-tioned for R1, e~pecially methoxy and ethoxy; halo-alkoxy as mentioned for R1, e~pecially trifluoro-methoxy; alkylthio as mentioned for Rl, especially methylthio and ethylthio; haloalkylthio a~ mentioned for R1, especially trifluoromethylthio; halogen as mentioned for R1, especially fluorine and chlorine;
nitro; cyano; formyl; alkanoyl such a acetyl, propionyl, butyryl, especially acetyl; haloalkanoyl such a~ trifluoroacetyl, trichloroacetyl, penta-fluoropropionyl, e~pecially trifluoroacetyl, or alkoxycarbonyl a~ mentioned for R1, especially - 31 - O.Z. OOS0/41126 methoxycarbonyl;
naphthyl which can be substituted from once to three times by alkyl as mentioned for R1, especially methyl and ethyl, or halogen as mentioned for R1, especially fluorine and chlorine, or R3 and R~ can together form -tcHz)n-yp-(cH2)q-~ where n and q are each l, 2 or 3, p i~ 0 or 1 and Y is oxygen, sulfur or N-methyl, su~h as -(CH2)3-, -(CH2)4--, -(CH2)5-r -(CH2)6-- -CH2-O-CH2-, -CH2-CH2-O-CH2-CH2-, -CH2-S-CH2-, -CH2-CH2-S-CH2-CH2-, -CH2-CH2-N ( CH3 )-CH2-CH2-, especially -(CH2) 5- and -CH2-cH2-o-cH2-cH2-, or -( CH2)3-CO-;
and the environmentally compatible salt~ thereof.
Particularly preferred compounds Ia~ and Ib' are those in which R3 is hydrogen and those in which:
Rl is hydrogen;
methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;
methoxy, ethoxy, propyloxy, l-methylethoxy, butyl-oxy, l-methylpropyloxy, 2-methylpropyloxy and 1,1-dimethylethoxy;
difluoromethoxy and trifluoromethoxy;
methylthio, ethylthio, propylthio, 1-methylethyl-thio, butylthio, 1-methylpropylthio, 2-methylpropyl-thio and l,1-dimethylethylthio;
difluoromethylthio and trifluoromethylthio, R2 i8 --Co~R5;
R5 is hydrogen; phthalimido; ~uccinimido; maleimido or -N=CR6R7;
R~ and R7 are each hydrogen;
methyl, ethyl, propyl, l-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;
cyclopropyl, cyclopentyl, cyclohexyl and cycloheptyl;
or together form a 4- to 7-membered alkylene chain ~uch as -CH2CH2CH2CH2-~ -CH2CH2CHzCH2cH2~~

~ U r~
- 32 - O.Z. 0050/41126 -CH2CH2CH2CH2CH2CH2- and -cH2cH2cH2cH2cH2cH2cH2-;
R3 and R4are each methyl, ethyl, propyl, l-methylethyl, butyl, l-methylpropyl, 2-methylpropyl and 1,1-dimethyle~hyl;
5 `cyclopropyl, cyclopentyl, cyclohexyl and cyclo-heptyl;
or together form a 4- to 7-membered alkylene chain such as -CH2CH2CH2cH2-~ -CH2CH2CH2cH2cH2--CH2CH2CH2CH2CH2CH2- and -CH2CH2CH2CH2CH2CH2CH2-;
10Examples of very active compounds of the formulae Ia and Ib are listed in the Tables which follow:

J ~
33 O.Z. 0050/41126 Table A
,R3 1 ~ N~R4 Ia (X = O or S) R1 X-~

H COOH H tert.-butyl 5 F COOH H tert.-butyl Cl COOH H tert.-butyl methyl COOH H tert.-butyl ethyl COOH H tert.-butyl n-propyl COOH H tert.-butyl 10 iso-propyl COOH H tert.-butyl n-butyl COOH H tert.-butyl iso-butyl COOH H tert.-butyl sec.-butyl COOH H tert.-butyl tert.-butyl COOH H tert.-butyl 15 cyclo-propyl COOH H tert.-butyl cyclo-butyl COOH H tert.-butyl cyclo-pentyl COOH H tert.-butyl cyclo-hexyl COOH H tert.-butyl cyclo-heptyl COOH H tert.-butyl 20 cyclo-octyl COOH H tert.-butyl l-methylcyclopropyl COOH H tert.-butyl trifluoromethyl COOH H tert.-butyl chlorodifluoromethyl COOH H tert.-butyl pentafluoroethyl COOH H tert.-buty~
25 methoxymethyl COOH H tert.-butyl l-methylmethoxymethyl COOH H tert.-butyl 1-methylmethoxyethyl COOH H tert.-butyl ethoxymethyl COOH H tert.-butyl vinyl COOH H tert.-butyl 30 allyl COOH H tert.-butyl methallyl COOH H tert.-butyl crotyl COOH H tert.-butyl ethynyl COOH H tert.-butyl propargyl COOH H tert.-butyl 35 phenylethynyl COOH ~ tert.-butyl methoxy COOH H tert.-butyl ethoxy COOH H tert.-butyl trifluoromethoxy COOH H tert.-butyl methylthio COOH H tert.-butyl 34 O.Z. 0o5o/4ll26 Rl K2 R3 R4 trifluoromethylthio COOH H tert.-butyl phenoxy COOH H tert.-butyl 5 4-CI-phenoxy COOH H tert.-butyl 2,4-(Cl,Cl)-phenoxy COOH H tert.-butyl 4-CF3-phenoxy COOH H tert.-butyl phenyl COOH H tert.-butyl 2-F-phenylthio COOH H tert.-butyl 10 3-F-phenyl COOH H tert.-butyl 2,4-(F,F)-phenyl COOH H tert.-butyl 2-CI-phenyl COOH H tert.-butyl 3-CI-phenyl COOH H tert.-butyl 2,4-(Cl,CI)-phenyl COOH H tert.-butyl 15 2-CH3-phenyl COOH H tert.-butyl 3-CH3-phenyl COOH H tert.-butyl 4-CH3-phenyl COOH H tert.-butyl 2,4-(CH3,CH3)-phenyl COOH H tert.-butyl 2,4,6-(CH3,CH3,CH3)-phenyl COOH H tert.-butyl 20 2-CF3-phenyl COOH H tert.-butyl 2-OCH3-phenyl COOH H tert.-butyl 2,4-(OCH3,OCH3)-phenyl COOH H tert.-butyl 4-OCF3-phenyl COOH H tert.-butyl 4-SCH3-phenyl COOH H tert.-butyl 25 3-SCF3-phenyl COOH H tert.-butyl 2,4-(NO2,NO2)-phenyt COOH H tert.-butyl 4-NO2-phenyl COOH H tert.-butyl 2-thienyl COOH H tert.-butyl 3-thienyl COOH H tert.-butyl 30 2-furanyl COOH H tert.-butyl 3-furanyl COOH H tert.-butyl 2-tetrahydrofuranyl COOH H tert.-butyl 3-tetrahydrofuranyl COOH H tert.-butyl 2-pyridyl COOH H tert.-butyl 35 3-pyridyl COOH H tert.-butyl 4-pyridyl COOH H tert.-butyl 2-tetrahydropyranyl COOH H tert.-butyl 3-tetrahydropyranyl COOH H tert.-butyl 4-tetrahydropyranyl COOH H tert.-butyl 40 iso-propoxy COOH H tert.-butyl H COOH H cyclo-propyl F COOH H cyclo-propyl Cl COOH H cyclo-propyl ~ ù,~

O.Z. 0050/41126 Rl - R2 R3 R4 methyl COOH H cyclo-propyl ethyl COOH H cyclo-propyl 5 n-propyl COOH H cyclo-propyl iso-propyl COOH H cyclo-propyl n-butyl COOH H cyclo-propyl iso-butyl COOH H cyclo-propyl sec.-butyl COOH H cyclo-propyl lQ tert.-butyl COOH H cyclo-propyl cyclo-propyl COOH H cyclo-propyl cyclo-butyl COOH H cyclo-propyl cyclo-pentyl COOH H cyclo-propyl cyclo-hexyl COOH H cyclo-propyl 15 cyclo-heptyl COOH H cyclo-propyl cyclo-octyl COOH H cyclo-propyl l-methylcyclopropyl COOH H cyclo-propyl trifluoromethyl COOH H cyclo-propyl chlorodifluoromethyl COOH H cyclo-propyl 20 pentafluoroethyl COOH H cyclo-propyl methoxymethyl COOH H cyclo-propyl 1-methylmethoxymethyl COOH H cyclo-propyl l-methylmethoxyethyl COOH H cyclo-propyl ethoxymethyl COOH H cyclo-propyl 25 vinyl COOH H cyclo-propyl allyl COOH H cyclo-propyl methallyl COOH H cyclo-propyl crotyl COOH H cyclo-propyl ethynyl COOH H cyclo-propyl 30 propargyl COOH H cyclo-propyl phenylethynyl COOH H cyclo-propyl methoxy COOH H cyclo-propyl ethoxy COOH H cyclo-propyl trifluoromethoxy COOH H cyclo-propyl 35 methylthio COOH H cyclo-propyl trifluoromethylthio COOH H cyclo-propyl phenoxy COOH H cyclo-propyl 4-CI-phenoxy COOH H cyclo-propyl 2,4-(Cl,CI)-phenoxy COOH H cyclo-propyl 40 4-CF3-phenoxy COOH H cyclo-propyl phenyl COOH H cyclo-propyl 2-F-phenylthio COGH H cyclo-propyl 3-F-phenyl COOH H cyclo-propyl 2,4-(F,F)-phenyl COOH H cyclo-propyl 202613~
36 O.Z. 0050/41126 Rl R2 R3 R4 2-Cl-phenyl COOH H cyclo-propyl 3-CI-phenyl COOH H cyclo-propyl 5 2,4-(Cl,CI)-phenyl COOH H cyclo-propyl 2-CH3-phenyl COOH H cyclo-propyl 3-CH3-phenyl COOH H cyclo-propyl 4-CH3-phenyl COOH H cyclo-propyl 2,4-(CH3,CH3)-phenyl COOH H cyclo-propyl 10 2,4,6-(CH3,CH3,CH3)-phenyl COOH H cyclo-propyl 2-CF3-phenyl COOH H cyclo-propyl 2-OCH3-phenyl COOH H cyclo-propyl 2,4-(OCH3,0CH3)-phenyl COOH H cyclo-propyl 4-OCF3-phenyl COOH H cyclo-propyl 15 4-SCH3-phenyl COOH H cyclo-propyl 3-SCF3-phenyl COOH H cyclo-propyl 2,4-(N02,N02)-phenyl COOH H cyclo-propyl 4-N02-phenyl COOH H cyclo-propyl 2-thienyl COOH H cyclo-propyl 20 3-thienyl COOH H cyclo-propyl 2-furanyl COOH H cyclo-propyl 3-furanyl COOH H cyclo-propyl 2-tetrahydrofuranyl COOH H cyclo-propyl 3-tetrahydrofuranyl COOH H cyclo-propyl 25 2-pyridyl COOH H cyclo-propyl 3-pyridyl COOH H cyclo-propyl 4-pyridyl COOH H cyclo-propyl 2-tetrahydropyranyl COOH H cyclo-propyl 3-tetrahydropyranyl COOH H cyclo-propyl 30 4-tetrahydropyranyl COOH H cyclo-propyl iso-propoxy COOH H cyclo-propyl H COOH methyl tert.-butyl F COOH methyl tert.-butyl Cl COOH methyl tert.-butyl 35 methyl COOH methyl tert.-butyl ethyl COOH methyl tert.-butyl n-propyl COOH methyl tert.-butyl iso-propyl COOH methyl tert.-butyl n-butyl COOH methyl tert.-butyl 40 iso-butyl COOH methyl tert.-butyl sec.-butyl COOH methyl tert.-butyl tert.-butyl COOH methyl tert.-butyl cyclo-propyl COOH methyl tert.-butyl cyclo-butyl COOH methyl tert.-butyl 37 O.Z. 0050/41126 Rl R2 R3 R4 cyclo-pentyl COOH methyl tert.-butyl cyclo-hexyl COOH iso-propyl tert.-butyl 5 cyclo-heptyl COOH iso-propyl tert.-butyl cyclo-octyl COOH iso-propyl tert.-butyl l-methylcyclopropyl COOH iso-propyl tert.-butyl trifluoromethyl COOH iso-propyl tert.-butyl chlorodifluoromethyl COOH iso-propyl tert.-butyl lO pentafluoroethyl COOH iso-propyl tert.-butyl methoxymethyl COOH iso-propyl tert.-butyl l-methyImethoxymethyl COOH iso-propyl tert.-butyl l-methylmethoxyethyl COOH iso-propyl tert.-butyl ethoxymethyl COOH iso-propyl tert.-butyl 15 vinyl COOH iso-propyl tert.-butyl allyl COOH iso-propyl tert.-butyl methallyl COOH iso-propyl tert.-butyl crotyl COOH iso-propyl tert.-butyl ethynyl COOH iso-propyl tert.-butyl 20 propargyl COOH iso-propyl tert.-butyl phenylethynyl COOH iso-propyl tert.-butyl methoxy COOH iso-propyl tert.-butyl ethoxy COOH iso-propyl tert.-butyl trifluoromethoxy COOH iso-propyl tert.-butyl 25 H COOH methyl cyclo-propyl F COOH methyl cyclo-propyl Cl COOH methyl cyclo-propyl methyl COOH methyl cyclo-propyl ethyl COOH methyl cyclo-propyl 30 n-propyl COOH methyl cyclo-propyl iso-propyl COOH methyl cyclo-propyl n-butyl COOH methyl cyclo-propyl iso-butyl COOH iso-propyl cyclo-propyl sec.-butyl COOH iso-propyl cyclo-propyl 35 tert.-butyl COOH iso-propyl tert.-butyl cyclo-propyl COOH iso-propyl cyclo-propyl cyclo-butyl COOH iso-propyl cyclo-propyl cyclo-pentyl COOH iso-propyl cyclo-propyl cyclo-hexyl COOH methyl cyclo-propyl 40 cyclo-heptyl COOH methyl cyclo-propyl cyclo-octyl COOH methyl cyclo-propyl 1-methylcyclopropyl COOH methyl cyclo-propyl trifluoromethyl COOH methyl cyclo-propyl chlorodifluoromethyl COOH methyl cyclo-propyl 38 O.Z. 0050/41126 Rl R2 R3 R4 pentafluoroethyl COOH methyl cyclo-propyl methoxymethyl COOH iso-propyl cyclo-propyl 5 l-methyImethoxymethyl COOH iso-propyl cyclo-propyl l-methylmethoxyethyl COOH iso-propyl cyclo-propyl ethoxymethyl COOH iso-propyl cyclo-propyl vinyl COOH iso-propyl cyclo-propyl allyl COOH iso-propyl cyclo-propyl 10 methallyl COOH iso-propyl cyclo-propyl crotyl COOH methyl cyclo-propyl ethynyl COOH methyl cyclo-propyl propargyl COOH methyl cyclo-propyl phenylethynyl COOH methyl cyclo-propyl 15 methoxy COOH methyl cyclo-propyl ethoxy COOH methyl cyclo-propyl trifluoromethoxy COOH methyl cyclo-propyl 39 O.Z. 0050/41126 Table B

,R3 Ib (X = O or S) o Rl R2 R3 R4 5 H COOH H tert.-butyl F COOH H tert.-butyl Cl COOH H ` tert.-butyl methyl COOH H tert.-butyl ethyl COOH H tert.-butyl 10 n-propyl COOH H tert.-butyl iso-propyl COOH H tert.-butyl n-butyl COOH H tert.-butyl iso-butyl COOH H tert.-butyl sec.-butyl COOH H tert.-butyl 15 tert.-butyl COOH H tert.-butyl cyclo-propyl COOH H tert.-butyl cyclo-butyl COOH H tert.-butyl cyclo-pentyl COOH H tert.-butyl cyclo-hexyl COOH H tert.-butyl 20 cyclo-heptyl COOH H tert.-butyl cyclo-octyl COOH H tert.-butyl 1-methylcyclopropyl COOH H tert.-butyl trifluoromethyl COOH H tert.-butyl chlorodifluoromethyl COOH H tert.-butyl 25 pentafluoroethyl COOH H tert.-butyl methoxymethyl COOH H tert.-butyl l-methylmethoxymethyl COOH H tert.-butyl 1-methylmethoxyethyl COOH H tert.-butyl ethoxymethyl COOH H tert.-butyl 30 vinyl COOH H tert.-butyl allyl COOH H tert.-butyl methallyl COOH H tert.-butyl crotyl COOH H tert.-butyl ethynyl COOH H tert.-butyl 35 propargyl COOH H tert.-butyl phenylethynyl COOH H tert.-butyl methoxy COOH H tert.-butyl ethoxy COOH H tert.-butyl trifluoromethoxy COOH H tert.-butyl 40 methylthio COOH H tert.-butyl 20261~1 O.Z. 0050/41126 Rl R2 R3 R4 trifluoromethylthio COOH H tert.-butyl phenoxy COOH H tert.-butyl 5 4-Cl-phenoxy COOH H tert.-butyl 2,4-(Cl,CI)-phenoxy COOH H tert.-butyl 4-CF3-phenoxy COOH H tert.-butyl phenyl COOH H tert.-butyl 2-F-phenylthio COOH H tert.-butyl lO 3-F-phenyl COOH H tert.-butyl 2,4-(F,F)-phenyl COOH H tert.-butyl 2-Cl-phenyl COOH H tert.-butyl 3-CI-phenyl COOH H tert.-butyl 2,4-(Cl,Cl)-phenyl COOH H tert.-butyl 15 2-CH3-phenyl COOH H tert.-butyl 3-CH3-phenyl COOH H tert.-butyl 4-CH3-phenyl COOH H tert.-butyl 2,4-tCH3,CH3)-phenyl COOH H tert.-butyl 2,4,6-(CH3,CH3,CH3~-phenyl COOH H tert.-butyl 20 2-CF3-phenyl COOH H tert.-butyl 2-OCH3-phenyl COOH H tert.-butyl 2,4-(OCH3,0CH3)-phenyl COOH H tert.-butyl 4-OCF3-phenyl COOH H tert.-butyl 4-SCH3-phenyl COOH H tert.-butyl 25 3-SCF3-phenyl COOH H tert.-butyl 2,4-(NO2,NO2)-phenyl COOH H tert.-butyl 4-NO2-phenyl COOH H tert.-butyl 2-thienyl COOH H tert.-butyl 3-thienyl COOH H tert.-butyl 30 2-furanyl COOH H tert.-butyl 3-furanyl COOH H tert.-butyl 2-tetrahydrofuranyl COOH H tert.-butyl 3-tetrahydrofuranyl COOH H tert.-butyl 2-pyridyl COOH H tert.-butyl 35 3-pyridyl COOH H tert.-butyl 4-pyridyl COOH H tert.-butyl 2-tetrahydropyranyl COOH H tert.-butyl 3-tetrahydropyranyl COOH H tert.-butyl 4-tetrahydropyranyl COOH H tert.-butyl 40 iso-propoxy COOH H tert.-butyl H COOH H cyclo-propyl F COOH H cyclo-propyl Cl COOH H cyclo-propyl methyl COOH H cyclo-propyl ~:~ v r~

41 O.Z. 0050/41126 Rl R2 R3 R4 ethyl COOH H cyclo-propyl n-propyl COOH H cyclo-propyl 5 iso-propyl COOH H cyclo-propyl n-butyl COOH H cyclo-propyl iso-butyl COOH H cyclo-propyl sec.-butyl COOH H cyclo-propyl tert.-butyl COOH H cyclo-propyl 10 cyclo-propyl COOH H cyclo-propyl cyclo-butyl COOH H cyclo-propyl cyclo-pentyl COOH H cyclo-propyl cyclo-hexyl COOH H cyclo-propyl cyclo-heptyl COOH H cyclo-propyl lS cyclo-octyl COOH H cyclo-propyl l-methylcyclopropyl COOH H cyclo-propyl trifluoromethyl COOH H cyslo-propyl chlorodifluoromethyl COOH H cyclo-propyl pentafluoroethyl COOH H cyclo-propyl 20 methoxymethyl COOH H cyclo-propyl l-methylmethoxymethyl COOH H cyclo-propyl l-methylmethoxyethyl COOH H cyclo-propyl ethoxymethyl COOH H cyclo-propyl vinyl COOH H cyclo-propyl 25 allyl COOH H cyclo-propyl methallyl COOH H cyclo-propyl crotyl COOH H cyclo-propyl ethynyl COOH H cyclo-propyl propargyl COOH H cyclo-propyl 30 phenylethynyl COOH H cyclo-propyl methoxy COOH H cyclo-propyl ethoxy COOH H cyclo-propyl trifluoromethoxy COOH H cyclo-propyl methylthio COOH H cyclo-propyl 35 trifluoromethylthio COOH H cyclo-propyl phenoxy COOH H cyclo-propyl 4-CI-phenoxy COOH H cyclo-propyl 2,4-(Cl,Cl)-phenoxy COOH H cyclo-propyl 4-CF3-phenoxy COOH H cyclo-propyl 40 phenyl COOH H cyclo-propyl 2-F-phenylthio COOH H cyclo-propyl 3-F-phenyl COOH H cyclo-propyl 2,4-(F, F ) -phenyl COOH H cyclo-propyl 2-CI-phenyl COOH H cyclo-propyl 42 O.Z. 0050/41126 Rl R2 R3 R4 3-CI-phenyl COOH H cyclo-propyl 2,4-(Cl,CI)-phenyl COOH H cyclo-propyl 5 2-CH3-phenyl COOH H cyclo-propy1 3-CH3-phenyl COOH H cyclo-propyl 4-CH3-phenyl COOH H cyclo-propyl 2,4-(CH3,CH3)-phenyl COOH H cyclo-propyl 2,4,6-(CH3,CH3,CH3)-phenyl COOH H cyclo-propyl 10 2-CF3-phenyl COOH H cyclo-propyl 2-OCH3-phenyl COOH H ` cyclo-propyl 2,4-(OCH3,0CH3)-phenyl COOH H cyclo-propyl 4-OCF3-phenyl COOH H cyclo-propyl 4-SCH3-phenyl COOH H cyclo-propyl l5 3-SCF3-phenyl COOH H cyclo-propyl 2,4-(N02,N02¦-phenyl COOH H cyclo-propyl 4-N02-phenyl COOH H cyclo-propyl 2-thienyl COOH H cyclo-propyl 3-thienyl COOH H cyclo-propyl 20 2-furanyl COOH H cyclo-propyl 3-furanyl COOH H cyclo-propyl 2-tetrahydrofuranyl COOH H cyclo-propyl 3-tetrahydrofuranyl COOH H cyclo-propyl 2-pyridyl COOH H cyclo-propyl 25 3-pyridyl COOH H cyclo-propyl 4-pyridyl COOH H cyclo-propyl 2-tetrahydropyranyl COOH H cyclo-propyl 3-tetrahydropyranyl COOH H cyclo-propyl 4-tetrahydropyranyl COOH H cyclo-propyl 30 iso-propoxy COOH H cyclo-propyl H COOH methyl tert.-butyl F COOH methyl tert.-butyl Cl COOH methyl tert.-butyl methyl COOH methyl tert.-butyl 35 ethyl COOH methyl tert.-butyl n-propyl COOH methyl tert.-butyl iso-propyl COOH methyl tert.-butyl n-butyl COOH methyl tert.-butyl iso-butyl COOH methyl tert.-butyl 40 sec.-butyl COOH ~ethyl tert.-butyl tert.-butyl COOH methyl tert.-butyl cyclo-propyl COOH methyl tert.-butyl cyclo-butyl COOH methyl tert.-butyl cyclo-pentyl COOH methyl tert.-butyl 43 O.Z. 0050/41126 Rl R2 R3 R4 cyclo-hexyl COOH iso-propyl tert.-butyl cyclo-heptyl COOH iso-propyl tert.-butyl 5 cyclo-octyl COOH iso-propyl tert.-butyl 1-methylcyclopropyl COOH iso-propyl tert.-butyl trifluoromethyl COOH iso-propyl tert.-butyl chlorodifluoromethyl COOH iso-propyl tert.-butyl pentafluoroethyl COOH iso-propyl tert.-butyl 10 methoxymethyl COOH iso-propyl tert.-butyl 1-methylmethoxymethyl COOH iso-propyl tert.-butyl 1-methyImethoxyethyl COOH iso-propyl tert.-butyl ethoxymethyl COOH iso-propyl tert.-butyl vinyl COOH iso-propyl tert.-butyl 15 allyl COOH iso-propyl tert.-butyl methallyl COOH iso-propyl tert.-butyl crotyl COOH iso-propyl tert.-butyl ethynyl COOH iso-propyl tert.-butyl propargyl COOH iso-propyl tert.-butyl 20 phenylethynyl COOH iso-propyl tert.-butyl methoxy COOH iso-propyl tert.-butyl ethoxy COOH iso-propyl tert.-butyl trifluoromethoxy COOH iso-propyl tert.-butyl H COOH methyl cyclo-propyl 25 F COOH methyl cyclo-propyl Cl COOH methyl cyclo-propyl methyl COOH methyl cyclo-propyl ethyl COOH methyl cyclo-propyl n-propyl COOH methyl cyclo-propyl 30 iso-propyl COOH methyl cyclo-propyl n-butyl COOH iso-propyl cyclo-propyl iso-butyl COOH iso-propyl cyclo-propyl sec.-butyl COOH iso-propyl cyclo-propyl tert.-butyl COOH iso-propyl tert.-butyl 35 cyclo-propyl COO~ iso-propyl cyclo-propyl cyclo-butyl COOH iso-propyl cyclo-propyl cyclo-pentyl COOH iso-propyl cyclo-propyl cyclo-hexyl COO~ methyl cyclo-propyl cyclo-heptyl COOH methyl cyclo-propyl 40 cyclo-octyl COOH methyl cyclo-propyl 1-methylcyclopropyl COOH methyl cyclo-propyl trifluoromethyl COOH methyl cyclo-propyl chlorodifluoromethyl COOH methyl cyclo-propyl pentafluoroethyl COOH methyl cyclo-propyl ~;~ v r~
44 O.Z. 0050/41126 Rl R2 R3 R4 methoxymethyl COOH iso-propyl cyclo-propyl 1-methylmethoxymethyl COOH iso-propyl cyclo-propyl 5 1-methyImethoxyethyl COOH iso-propyl cyclo-propyl ethoxymethyl COOH iso-propyl cyclo-propyl vinyl COOH i so-propyl cyclo-propyl allyl COOH iso-propyl cyclo-propyl methallyl COOH iso-propyl cyclo-propyl 10 crotyl COOH methyl cyclo-propyl ethynyl COOH methyl cyclo-propyl propargyl COOH methyl cyclo-propyl phenylethynyl COOH methyl cyclo-propyl methoxy COOH methyl cyclo-propyl 15 ethoxy COOH methyl cyclo-propyl trifluoromethoxy COOH methyl cyclo-propyl ~0 t~ ,L ~) i ~_ OOOOOOOOOOOOOOOOOOO

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91 O.Z. 0050/41126 The oxa~ole- and thiazolecarboxamides la' and Ib', 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 dis-5 persions, pastes, dusts, broadcasting agents, or granules by spraying,atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients accord-ing 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 15 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, 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 25 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.
30 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 35 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-40 ated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycolethers, tributylphenyl polyslycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated ~ iJ

92 O.Z. 0050/41126 castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.
5 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 10 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, fertil kers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable 15 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 20 of 90 to 100, and preferably from 95 to 100, % (according to the NMR
spectrum).
Compounds Ia and Ib according to the invention may be formulated for instance as follows:
I. 90 parts by weight of compound no. 1.003 is mixed with 10 parts by weight of ~-methyl-alpha-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
30 II. 20 parts by weight of compound no. 1.010 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 35 oxide and 1 mole of castor oil. 8y 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. 1.004 is dissolved in a mixture40 consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution ints 100,000 parts by weight of water, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

93 o.z. 0050/41126 IV. 20 parts by weight of compound no. 1.011 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 280C, and 10 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. 1.011 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 15 containing O.i% by weight of the active ingredient.
VI. 3 parts by weight of compound no. 1.003 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3%
by weight of the active ingredient.
VII. 30 parts by weight of compound no. 1.004 is intimately mixed with a mixture consisting of ~2 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 25 having good adherence.
VIII. 20 parts by weight of compound no. 1.010 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-30 sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
~he active ingredients or the herbicidal agents containing the~ may be applied pre- or postemergence. If certain crop plants tolerate the active 35 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 2, kg/ha.

94 O.Z. 0050/41126 In view of the number of application methods possible, the compounds according to the invention, or agents containing them, may be used in a large number of crops for eliminating unwanted plant growth.
5 To increase the spectrum of action and to achieve synergistic effects, the oxazole- and thiazolecarboxamides Ia and Ib may be mixed wit~, each other, or mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of suitable components are diazines, 4H-3,1-benzoxazine derivatives, benzo-10 thiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazin-ones, uracils, benzofuran derivatives, cyclohexane-1,3-dione derivatives, quinolinecarboxylic acids, thetero)-aryloxyphenoxypropionic acids and salts, esters, amides thereof, etc.
It may also be useful to apply compounds Ia and Ib, 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 20 used to remedy nutritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.
Synthesis examples 25 The directions given in the synthesis examples below were used, after appropriate modification of the starting materials, to obtain further compounds. The compounds thus obtained are given in the following tables with their physical data.
30 1. Methods of manufacturing the intermediates Example 1.1 4(5)-Ethoxycarbonyl-2-methyloxazole-5(4)-carboxylic acid At -10C and under a nitrogen blanket, a solution of 6.0 g (0.15 mol) of sodium hydroxide in 150 ml of water was dripped over a period of 4 hours into 33.8 9 (0.15 mol~ of 2-methyloxazole-4,5-dicarboxylate in 300 ml of ethanol, and the mixture was stirred at -10C for 2 hours. The solution 40 was evaporated down, the residue was taken up in 300 ml of water, the pH
was adjusted to 8 to 9 with hydrochloric acid and the solution was ex-tracted twice, each time with 300 ml of diethyl ether. The mixture was then acidified to a pH of 2 with concentrated hydrochloric acid and the aqueous phase was extracted four times, each time with 250 ml of dichloro-~ u ~
O.Z. 0o5o/4ll26 methane. The combined organic phases were dried over magnesium sulfate andthe solvent was removed under reduced pressure. There was obtained 26.4 9 (88%) of 4(5)-ethoxycarbonyl-2-methyloxazole-5(4)-carboxylic acid as a white solid (isomer ratio: 3:1 ~lH-NMR, HPLC). Fractional crystallization 5 from cyclohexane/ethyl acetate (2:1) or column chromatography using silica gel (toluene, THF, glacial acetic acid (7:3:1)) gave the pure isomer of 4-ethoxycarbonyl-2-methyloxazole-5-carboxylic acid. lH-NMR (250 MHz, D6-DMS0); main isomer: ~ = 1.28 (t; 3H), 2.52 (s; 3H), 4.30 (q; 2H), 14.00 (broad s; lH).
Example 1.2 4-Ethoxycarbonyl-2-methylthiothiazole-5-carboxylic acid 15 At room temperature, a solution of 1.10 9 (27.5 mmol) of sodium hydroxide in 10 ml of water was added over a period of one hour to a solution of 7.00 9 (25 mmol) of diethyl 2-methylthiothiazole-4,5-dicarboxylate in 100 ml of ethanol/water (2:1). The mixture was stirred for one hour, the solvent mixture was then removed under reduced pressure, the residue was 20 taken up in 100 ml of water, the solution was extracted once with 50 ml of diethyl ether, and the aqueous phase was acidified with concentrated hydrochloric acid. The precipitated product was filtered off and dried.
Yield: 4.50 9 (73%). Melting point: 104C.
The carboxylic acids given in the following table were obtained in accord-ance with the above example:

202~131 96 O.Z. 0050/41126 Example Rl R5 X Physical data 1.9(b) phenyl CH3 S mp.: 127-137 5 1.4(a) n-butylthio C2H5 S 0.95 (t;3H), 1.40 (t;3H), 1.50 (sext;2H), 1.80 (quint;2H), 3.40 (t;2H), 4.35 (q;2H) 1.5(b) n-butylthio C2H5 S 0.95 (t;3H), 1.35 (t;3H), 1.50 (sect;2H), 1.80 (quint;2H), 3.30 (t;2H), 4.45 (q;2H) 2.6(b) iso-propylthio C2H5 S 1.50 (d;6H), 1.45 (t;3H), 3.90 (hept;lH), 4.55 (q;2H), 12.50 (s;lH) 1.7(a) iso-propylthio C2H5 S 1.45 (t;3H), 1.50 (d;6H), 4.05 (hept;lH), IS 4.50 (q;2H), 12.50 (s;lH) 1.8(a) methylthio CH3 S 2.80 (S;3H), 4.05 (s;3H) Example 1.9 s Diethyl 2-methylthiothiazole-4,5-dicarboxylate At 0C, a solution of 2.1 9 (0.03 mol) of sodium methylthiolate in 10 ml of ethanol was dripped into a solution of 9.2 9 (0.03 mol~ of diethyl 25 2-chlorothiazole-4,5-dicarboxylate in 30 ml of ethanol. The mixture was allowed to heat up to 25C and was then stirred for two hours. The solvent was then removed under reduced pressure, the residue was taken up in 100 ml of diethyl ether and the solution washed with 50 ml of 5% strength sodium hydroxide solution and with 50 ml of water. Drying over sodium 30 sulfate and evaporating down gave 7.2 9 t87%) of the product as a color-less oil.
1H-NMR (CDC13, 250 MHz, TMS as internal standard): 1.35 (t, I=7.0 Hz, 3H), 1.45 (t, I=7.0 Hz; 3H), 2.75 (s, 3H), 4.30 (q, 1=7.0 HZ; 2H), 4.50 35 (q, I=7.0 Hz; 2H).

~ . v ~.. ., ~. ~3 1 97 O.Z. 0050/41126 2. Process for manufacturing compounds ~Ia and VIb NI~N RlJ~ N~

Vla VIb Example 2.1 5 2-Methoxythiazole-4-carboxylic acid-tert.-butylamide At 25C, 8.90 9 of a 3~% strength solution (49 mmol) of sodium methanolate in methanol was added to a solution of 12.00 9 (46 mmol) of 2-bromothia-zole-4-carboxylic acid-tert.-butylamide in 150 ml of methanol. The mixture 10 was boiled under reflux for four hours, the clear solution was evaporated down, the residue was taken up in 300 ml of diethyl ether and filtered, and the solvent was removed under reduced pressure. There was obtained 9.60 9 (98%) of the product as a yellow oil.
15 lH-NMR (CDCl3, 250 MHz, TMS as internal standard): 1.45 (s; 9H), 4.10 (s;
3H), 7.00 (s, broad, lH), 7.48 (s; lH).
Example 2.2 20 2-lsopropyloxa~ole-4-carboxylic acid-cyclopropylamide At room temperature, 47.6 9 (0.40 mol) of thionyl chloride was dripped into a solution of 31.0 9 (0.20 mol) of 2-isopropyloxazole-4-carboxylic acid in 200 ml of toluene and 2 ml of dimethylformamide, and the mixture 25 was stirred for one hour at 80C. The solvents were stripped off under reduced pressure, the residue was dissolved in 300 ml of dichloromethane, and 24.0 9 (0.42 mol) of cyclopropylamine in 20 ml of dichloromethane was dripped in at 0 to 10C. The mixture was stirred for 12 hours at room temperature, 150 ml of water was added, the phases were separated, the 30 organic phase was washed once with saturated sodium bicarbonate solution and dried over magnesium sulfate, and the solvent was removed under reduced pressure. There was obtained 37.2 9 (96%) of 2-isopropyl-oxazole-4-carboxylic acid-cyclopropylamide.
35 1H-NMR (CDC13, 250 MHz): ~ = 0.62 (m; 2H), 0.88 (m; 2H), 1.34 (d; 6H), 2.86 (m; lH), 3.09 (m; lH), 6.93 (broad s; lH; NH), 8.09 (s; lH).
The amides listed in the following table were obtained in accordance with the above examples or analogously to the cited literature:

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o 101 O.Z. 0050/41126 3. Methods of manufacturing compounds Ia and Ib Example 1 5 4-Cyclopropylaminocarbonyl-2-isopropyloxazole-5-carboxylic acid At -70C and under a nitrogen blanket, 0.12 mol of n-butyllithium (80.0 ml of a 1.5 molar solution in hexane) was dripped into a solution of 10.4 9 (0.054 mol) of 2-isopropyloxazole-4-carboxylic acid-cyclopropylamide in lO 250 ml of tetrahydrofuran, and the mixture was stirred for 30 minutes at this temperature. The reaction mixture was then`poured onto 500 g of solid C2 and allowed to stand overnight. The residue remaining after evaporat-ing down was taken up in 200 ml of water and 30 ml of 2N NaOH, the sol-ution was extracted twice, each time with 100 ml of diethyl ether, the 15 aqueous phase was acidified to a pH of 2 with concentrated hydrochloric acid and the solution extracted three times, each time with 200 ml of ethyl acetate. Drying over magnesium sulfate and removal of the solvent under reduced pressure gave 10.4 9 (81%) of 4-cyclopropylaminocarbonyl-2-isopropyloxazole-5-carboxylic acid as a white powder of m.p. 109-112C
20 (active ingredient no. 3.007).
Example 2 4-tert-Butylaminocarbonyl-2-methoxythiazole-5-carboXyliC acid At -70C, 65 ml of a 1.5 molar solution (97 mmol) of n-butyllithium in n-hexane was dripped into a solution of 8.00 9 (37 mmol~ of 2-methoxy-thiazole-4-carboxylic acid-tert-butylamide in 150 ml of tetrahydrofuran, and the mixture was stirred for 30 minutes at this temperature. The 30 reaction mixture was then poured onto 500 9 of solid carbon dioxide and allowed to warm up to room temperature over a period of 14 hours. The solvent was removed under reduced pressure, the residue was taken up in a mixture of 150 ml of water and 16 ml of 2N NaOH and filtered, the filtrate was acidified with concentrated hydrochloric acid and the precipitated 35 carboxylic acid was filtered off.
There was obtained 7.80 9 (82%) of 4-tert-butylaminocarbonyl-2-methoxy-thiazole-5-carboxylic acid as a white powder of m.p. 120-122C (active ingredient no. 1.003).

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102 o.Z. 0050/41126 Example 3 5-tert-Butylaminocarbonyl-2-methoxythiazole-4-carboxylic acid 5 At -70C and under a nitrogen blanket, 56 mmol of n-butyllithium (37.3 ml of a 1.5 molar solution in hexane) was dripped into a solution of 5.4 g (25.2 mmol) of 2-methoxythiazole-4-carboxylic acid-tert-butylamide in 150 ml of tetrahydrofuran, and the mixture was stirred for 30 minutes at this temperature. The reaction mixture was then poured onto 500 g of solid lO CO2 and allowed to stand overnight. After concentration the residue was taken up in 150 ml of water and 10 ml of 2N NaOH, the solution was extracted twice, each time with 50 ml of diethyl ether, and the aqueous phase was acidified to a pH of 2 with concentrated hydrochloric acid and extracted three times, each time with 100 ml of ethyl acetate. Drying over 15 magnesium sulfate and removal of the solvent under reduced pressure gave 3.9 g (60~o) of 5-tert-butylaminocarbonyl-2-methoxythiazole-4-carboxylic acid as a white powder of m.p. 105-110C (active ingredient no. 2.001).
Example 4 a) 4-Ethoxycarbonyl-2-methyloxazole-5-carboxylic chloride At 0C, 40 ml of thionyl chloride and 1 ml of dimethylformamide were dripped into 12.2 g (61.3 mmol~ of 4-ethoxycarbonyl-2-methyloxazole-5-carboxylic acid, and the mixture was refluxed for one hour. The excess thionyl chloride ~as stripped off under reduced pressure and the residue was distilled under an oil pump vacuum.
There was obtained 10.9 g (82%) of 4-ethoxycarbonyl-2-methyloxazole-5-carboxylic chloride as a yellow oil of m.p. 103-105C/0.1 mm. lH-NMR
(250 MHz, CDC13): ~ 1.42 (t; 3H~, 2.66 (s; 3H), 4.66 (q; 2H).
b) 4-Ethoxycarbonyl-2-methyloxazole-5-carboxylic acid-tert-butylamide At 0C, a solution of 11.0 9 1150 mmol) of tert-butylamine in 20 ml of dichloromethane was dripped into 10.9 g (50.3 mmol) of 4-ethoxycarbon-yl-2-methyloxazole-5-carboxylic chloride, and the mixture was stirred at this temperature for 12 hours. The reaction mixture was taken up in 200 ml of water, the phases were separated, the organic phase was washed once with saturated sodium bicarbonate solution and once with saturated sodium chloride solution and dried over magnesium sulfate, and the solvent was stripped off under reduced pressure in a rotary evaporator.
There was obtained 11.9 9 (93%) of the title compound as a white solid of m.p. 152-155C (active ingredient no. 4.001).

103 O.Z. 0050/41126 Example 5 5-tert-~utylaminocarbonyl-2-methyloxazole-4-carboxylic acid 5 At 0C and under a nitrogen blanket, a solution of 1.2 9 (30.0 mmol) of sodium hydroxide in 50 ml of water was dripped into 7.4 g (29.1 mmol) of 4-ethoxycarbonyl-2-methyloxazole-5-carboxylic acid-tert-butylamide in 150 ml of ethanol and 50 ml of THF. The mixture was stirred for 2 hours at 20C, the solvents were stripped off under reduced pressure in a rotary 10 evaporator, the residue was taken up in 300 ml of water, the pH adjusted to 9, and the aqueous phase was extracted three times, each time with 100 ml of diethyl ether. Acidification was then effected to a pH of 2 with 6N HCI and extraction carried out four times, each time with 150 ml of dichloromethane. The organic phase was dried over sodium sulfate and the 15 solvent stripped off under reduced pressure.
There was obtained 6.1 g (93%) of the title compound as a white solid of m.p. 186-188C (actiYe ingredient no. 4.002).
20 Example 6 a) 4-Ethoxycarbonyl-2-methylthiothiazole-5-carboxylic chloride 3.40 9 (13.7 mmol) of.4-ethoxycarbonyl-2-methylthiothiazole-5-carbox-ylic acid was dissolved in 50 ml of thionyl chloride, and the mixture refluxed until no more gas evolved. Excess thionyl chloride was removed under reduced pressure, leaving 3.55 9 (98~o) of the acyl chloride as a colorless oil.
lH-NMR (CDC13, 250 MHz, TMS as internal standard): 1.50 (t, I=7.0 Hz;
3H), 2.75 (s; 3H), 4.60 (q, I=7.0 Hz; 2H).
b) 4-Ethoxycarbonyl-2-methylthiothiazole-5-carboxylic acid-tert~butyl-amide 3.50 9 (13.2 mmol) of 4-ethoxycarbonyl-2-methylthiothiazole-5-carb-oxylic acid chloride was dissolved in 20 ml of dichloromethane and dripped, at 0C, into a solution of 3.20 9 (44 mmol) of tert-butyl-amine in 50 ml of dichloromethane. The mixture was allowed to warm up to room temperature and was then stirred for 14 hours. 100 ml of lO~o strength hydrochloric acid was added and the organic phase was separ-ated, washed with 50 ml of water and dried over sodium sulfate. The solvent was removed under reduced pressure, leaving 4.00 g (lOOYo) of product as a yellow crystalline slurry.

h~J1 104 o.Z. 0050/41126 lH-NMR (CDC13, 250 MHz, TMS as internal standard): 1.45 (t, I=7.0 HZ; 3H), 1.45 (s; 9H), 2.75 (s; 3H), 4.50 (q; I=7.0 Hz; 2H), 9.90 (s broad; lH).
(Active ingredient no. 2.007) 5 Example 7 5-tert-Butylaminocarbonyl-2-methylthiothiazole-4-carboxylic acid 0.82 9 (14.6 mmol) of potassium hydroxide in 10 ml of water was added to a 10 solution of 4.00 9 (13.2 mmol) of 4-ethoxycarbonyl-2-methylthiothiazole-5-carboxylic acid-tert-butylamide in 50 ml of water/ethanol (2:1), and the mixture was refluxed for 2 hours. The solvent mixture was then removed under reduced pressure and the residue was taken up in 50 ml of water and acidified with concentrated hydrochloric acid. The precipitated product 15 was filtered off and dried.
Yield: 3.40 9 (94%); m.p. 100C (active ingredient no. 2.005).
Example 8 4-tert-Butylaminocarbonyl-2-methoxythiazole-5-carboxylic acid acetoxime ester At room temperature, 4.4 9 (43.6 mmol) of 4-methylmorpholine and 1.5 9 25 (12.3 mmol) of 4-dimethylaminopyridine were dripped into a solution of 3.1 g (12.0 mmol) of 4-tert-butylaminocarbonyl-2-methoxythiazole-5-carb-oxylic acid and 1.2 9 (16.4 mmol) of acetoxime in 100 ml of dichloro-methane, and the mixture was stirred for 5 minutes. Subse~uently, 10.1 9 of a 50% strength solution of propanephosphonic anhydride in dichloro-30 methane (= 15.9 mmol) was added and the mixture was refluxed for 7 hours.After concentration, the residue was taken up in 100 ml of ethyl acetate and the solution was 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 chlor-35 ide solution. The organic phase was dried over magnesium sulfate and thesolvent was stripped off under reduced pressure.
There was obtained 3.1 y (82%) of 4-tert-butylaminocarbonyl-2-methoxythia-zole-5-carboxylic acid-acetoxime ester as a white powder of m.p.
40 128-131C (active ingredient no. 1.011).

105 O.Z. 0050/41126 Example 9 5-tert-8utylaminocarbonyl-2-methyloxazole-4-carboxylic acid acetoxime ester At room temperature, 3.46 9 (16.8 mmol) of dicyclohexylcarbodiimide in 20 ml of tetrahydrofuran was dripped into a solution of 3.80 g (16.8 mmol) of 5-tert-butylaminocarbonyl-2-methyloxazole-4-carboxylic acid and 1.23 g (1~.8 mmol) of acetoxime in 40 ml of tetrahydrofuran. The mixture was 10 stirred for 14 hours, the precipitate was filtered off, the solvent was stripped off under reduced pressure and the residue was chromatographed using silica gel (cyclohexane/ethyl acetate (1:1)). There was obtained 2.7 9 (57%) of 5-tert-butylaminocarbony~-2-methyloxazole-4-carboxylic acid acetoxime ester as a white solid of m.p. 107-111C (active ingredient no.
15 4.003)-The active ingredients listed in the tables below were prepared analogous-ly to the above compounds:

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115 O.Z. 0050/4~126 Use examples The herbicidal action of the oxazole- and thiazolecarboxamides of the formulae la and Ib' 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~O humus. The seeds of the test plants were sown separately, according to species.
10 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 15 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-20 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 35C, and species from moderate climates at 10 to 25C. The experiments were run 25 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., Triticum aestivum and Veronica spp .
35 Active ingredients nos. 1.001~ 1.003, 1.004, 1.009~ 1~010~ 1.011~ 3.002 3. 005 and 3. 024, applied postemergence at a rate of 1.0 kg/ha, provide excellent control of unwanted broadleaved plants. Compounds nos. 1.001~
1.003 and 1.00~ are also tolerated by wheat. Compound no. 3~005 is excel-lently tolerated by Indian corn.

Claims

1. Oxazole- and thiazolecarboxamides of the formulae Ia and Ib Ia Ib where X is oxygen or sulfur;
R1 is hydrogen; halogen; C1-C6-alkyl which can carry from one to five halogen atoms and/or one or two of the following: C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio or cyano;
benzyl which can carry from one to three of the following: C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, halogen, cyano or nitro;
C3-C8 cycloalkyl which can carry from one to three of the following: C1-C4-alkyl or halogen;
C2-C6-alkenyl which can carry from one to three of the following: halogen, C1-C3-alkoxy and/or one phenyl which in turn can carry from one to three of the following: C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, halogen, cyano or nitro;
C2-C5-alkynyl which can carry from one to three of the following: halogen, C1-C3-alkoxy and/or one phenyl which in turn can carry from one to three of the following: C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, halogen, cyano or nitro;
C1-C4-alkoxy; C1-C4-alkylthio; C1-C4-haloalkoxy; C1-C4-haloalkylthio;

117 O.Z. 0050/41126 phenoxy or phenylthio, which can carry from one to three of the following: C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, halogen, cyano or nitro;
a 5- to 6-membered heterocyclic radical containing one or two hetero atoms selected from the group comprising oxygen, sulfur and nitrogen, it being possible for the ring to carry one or two of the following: C1-C3-alkyl, halogen, C1-C3-alkoxy or C1-C3-alkoxycarbonyl;
phenyl which can carry from one to three of the following: C1-C6-alkyl, C1-C6-haloalkyl, C1-C5-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, halogen, nitro and cyano;
R2 is formyl, 4,5-dihydro-2-oxazolyl or -COYR5;
Y is oxygen or sulfur;
R5 is hydrogen;
C1-C5-alkyl which can carry from one to five halogen atoms or hydroxyl groups and/or one of the follow-ing: C1-C4-alkoxy, C2-C4-alkoxy-C1-C4-alkoxy, cyano, trimethylsilyl,C1-C3-alkylthio,C1-C3-alkylamino,di-C1-C3-alkylamino, C3-C7-cycloalkylamino, C1-C3-alkyl-sulfinyl,C1-C3-alkylsulfonyl,carboxyl,C1-C3-alkoxy-carbonyl, di-C1-C3-alkylaminocarbonyl, di-C1-C3-alkoxyphosphoryl, alkaneiminoxy, thienyl, furyl, tetrahydrofuryl, phthalimido, pyridyl, benzyloxy or benzoyl, it being possible for the cyclic radicals in turn to carry from one to three of the following:
C1-C3-alkyl, C1-C3-alkoxy or halogen;
benzyl which can carry from one to three of the following: C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl, halogen, nitro and cyano;
C3-C9-cyC loalkyl;
phenyl, which can carry from one to three of the following: C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy,C1-C4-alkoxycarbonyl,halogen,nitro and cyano;

118 O.Z. 0050/41126 C3-C8-alkenyl, C5-C6-cycloalkenyl or C3-C8-alkynyl, it being possible for these radicals to carry one of the following: hydroxyl, C1-C4-alkoxy, halogen or a phenyl ring which in turn can carry from one to three of the following: C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, halogen, nitro and cyano;
a 5- to 6-membered heterocyclic radical containing one or two hetero atoms selected from the group comprising oxygen, sulfur and nitrogen or a benzo-triazolyl radical;
phthalimido; tetrahydrophthalimido; succinimido;
maleimido;
one equivalent of a cation from the group comprising the alkali metals or alkaline earth metals, man-ganese, copper, iron, ammonium and substituted ammonium;
-N-CR5R7;
R5 and R7 are hydrogen; C1-C4-alkyl; C3-C5-cycloalkyl;
phenyl or furyl, or together form a methylene chain -(CH2)m- with m = 4 to 7;
R3 is hydrogen; C1-C6-alkyl which can carry from one to three of the following: hydroxyl, halogen, C1-C4-alkoxy, C1-C4-alkylthio or di-C1-C3-alkylamino;
C3-C8-cycloalkyl which can carry from one to three of the following: C1-C4-alkyl, halogen and C1-C4-halo-alkyl;
R4 is hydroxyl; C1-C4-alkoxy;
C1-C6-alkyl which can carry from one to three of the following: C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, di-C1-C4-alkylamino, halogen, C3-C8-cycloalkyl or phenyl which in turn can carry from one to three of the following: halogen, cyano, nitro, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio or C1-C4-haloalkylthio;
C3-C8-cycloalkyl which can carry from one to three of the following: C1-C5-alkyl, C1-C6-haloalkyl, C1-C4-119 O.Z. 0050/41126 alkoxy, C1-C4-haloalkoxy, halogen, nitro or cyano;
C3-C6-alkenyl or C3-C6-alkynyl, which can be sub-stituted from once to three times by halogen and/or once by phenyl which in turn can carry from one to three of the following: C1-C4-alkyl, C1-C4-haloalkyl, C1-C4,-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, halogen, cyano or nitro;
a 5- to 6-membered heterocyclic radical which contains one or two hetero atoms selected from the group comprising oxygen, sulfur or nitrogen, and which can carry from one to three of the following:
C1-C4-alkyl or halogen;
phenyl which can carry from one to four of the following: 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 can be substituted from once to three times by C1-C4-alkyl or halogen, or R3 and R4 together form -(CH2)n-Yp-(CH2)q- where n and q are each 1, 2 or 3, p is 0 or 1 and Y is oxygen, sulfur or N-methyl, or -(CH2)3-CO-, and the environ-mentally compatible salts thereof, where X in the formula Ib is not sulfur when R1 is 3-pyridyl, R2 is CO2CH2CH3 or R3 is hydrogen, and where X
in the formula Ia is not sulfur and R1 is not 2-thienyl when YR5 is OH and R3 is hydrogen and R4 is methyl.

120 O.Z. 0050/41126

2. Oxazole- and thiazolecarboxamides of the formulae Ia and Ib as set forth in claim 1, where R3 denotes hydrogen.

3. Oxazole- and thiazolecarboxamides of the formulae Ia and Ib as set forth in claim 1, where the substituents have the following meanings:
R1 hydrogen; C1-C4-alkyl; C1-C4-alkoxy; C1-C4-haloalkoxy;
C1-C4-alkylthio or C1-C4-haloalkylthio;
R2 -COYR5;
R5 hydrogen; phthalimido; succinimido; maleimido or -N=R5R7 R6, R7 hydrogen; C1-C4-alkyl and C3-C6-cycloalkyl or together form a methylene chain -(CH2)m- with m = 4 to 7;
R3 hydrogen and R4 C1-C4-alkyl or C3-C8-cycloalkyl.

4. A process for manufacturing compounds Ia and Ib as set forth in claim 1, R2 denoting CO2R5 and R5 denoting C1-C6-alkyl, wherein a diester of the formula II

II

is hydrolyzed in conventional manner with one equivalent of an aqueous base to give a mixture of the monoesters IIIa and IIIb IIIa IIIb and IIIa and IIIb are then separated or the mixture is initially con-verted to the halide or another active form of the carboxylic acid and these derivatives are subsequently amidated with an amine of the formula IV

IV.

121 O.Z. 0050/41126

5. A process for manufacturing compounds Ia and Ib as set forth in claim 1, where X is sulfur and R2 is CO2H, wherein a dicarboxylic anhydride of the formula V

V

is reacted in conventional manner with an amine of the formula IV as set forth in claim 4 to give the isomers Ia and Ib, and the mixture is subsequently fractionated to give the isomers.

6. A process for manufacturing compounds Ia and Ib as set forth in claim 1, where R1 is not halogen and R2 is carboxyl or formyl, wherein a carboxylic acid of the formula IIIc or IIId IIIc IIId is initially activated in conventional manner as set forth in claim 4, and the resulting amide VIa or VIb VIa VIb is then reacted in the presence of a base with a carboxylating or formylating reagent.

7. A process for the manufacture of compounds Ia and Ib as set forth in claim 1, where R2 is CO2H, wherein a carboxamide Ia or Ib, R2 denoting CO2R5 and R5 denoting C1-C6-alkyl, is hydrolyzed in conventional manner with one equivalent of an aqueous base.

122 O.Z. 0050/41126

8. A process for the manufacture of compounds Ia and Ib, where R2 is COYR5, wherein a corresponding carboxylic acid Ia or Ib (R2 = CO2H) is activated as set forth in claim 4 and then reacted in conventional manner with a compound VII
HYR5 VII.

9. A process for manufacturing compounds Ia and Ib, where R2 is 4,5-di-hydrooxazol-2-yl, wherein a corresponding carboxylic acid Ia or Ib (R2 = CO2H, CO2R' ; R' = C1-C4-alkyl) is reacted in conventional manner with a 2-aminoethanol VIII
VIII.

10. A herbicidal agent containing, in addition to inert additives, at least one oxazole- or thiazolecarboxamide of the formula Ia' or Ib' Ia Ib where the substituents have the meanings given in claim 1, and X may denote sulfur when R1 is 3-pyridyl, R2 is CO2CH2CH3 and R3 is hydrogen, or when R1 is thien-2-yl, YR5 is hydroxy, R3 is hydrogen and R4 is methyl.

11. A herbicidal agent as set forth in claim 10, containing further active constituents in addition to at least one oxazole- or thiazolecarbox-amide of the formula Ia' or Ib' and inert additives.

12. A process for combating unwanted plant growth, wherein the unwanted plants and/or the area to be kept free from unwanted plant growth is treated with a herbicidally effective amount of an oxazole- or thiazolecarboxamide of the formula Ia' or Ib'.