WO1998047864A2

WO1998047864A2 - N-acetalalkylcarbamates, processes for their preparation and their use as herbicides

Info

Publication number: WO1998047864A2
Application number: PCT/EP1998/002288
Authority: WO
Inventors: Hermann Rempfler; Michel Mühlebach; William Lutz; Christoph Lüthy
Original assignee: Novartis Ag; Novartis-Erfindungen Verwaltungsgesellschaft Mbh
Priority date: 1997-04-21
Filing date: 1998-04-17
Publication date: 1998-10-29
Also published as: AU7645298A; WO1998047864A3

Abstract

Compounds of formula (I) wherein R signifies halogen C1-C3-halogenalkyl, C1-C3-halogenalkoxy, cyano or nitro; Z is hydrogen or halogen; or Z and R in 2- and 3-position of the phenyl ring together form a group -O-CF2-O-; R1 signifies C1-C5-alkyl or C3-C6-cycloalkyl; R2 signifies hydrogen or C1-C4-alkyl; Q is a group (Q1) or (Q2); R3 and R4 independently of one another, signify C1-C4-alkyl, C1-C4-halogenalkyl, or benzyl which is optionally substituted on the phenyl ring; or R3 and R¿4? together signify a group (1); R5 signifies hydrogen, C1-C4-alkyl, C1-C4-halogenalkyl or optionally substituted phenyl; n is 2, 3, or 4; R6 and R7, indenpendently of one another, are hydrogen or C1-C4-alkyl; R10 is hydrogen or C1-C3-alkyl; R11 and R12, independently of one another, are hydrogen or C1-C4-alkyl; R13 signifies hydrogen, C1-C4-alkoxy; C1-C6-alkyl optionally substituted by halogen, C1-C3-alkoxy, C1-C3-alkylthio, C1-C3-alkylsulphinyl or C1-C3-alkylsulphonyl; C2-C6-alkenyl or C3-C6-cycloalkyl optionally substituted by halogen or methyl; or phenyl or thienyl optionally substituted by halogen, methyl, trifluoromethyl or methoxy; R14 is hydrogen, C1-C6-alkyl optionally substituted by halogen, C1-C3-alkoxy, C1-C3-alkylthio, C1-C3-alkylsulphinyl; or C1-C3-alkylsulphonyl; or C3-C6-cycloalkyl optionally substituted by halogen or methyl; or R13 and R14 together form a group (2), (3), (4), (5), (6) or (7); R21 and R22, independently of one another, are hydrogen or methyl; R23 signifies hydrogen, halogen or C1-C3-alkyl; m signifies 1, 2, 3 or 4; W signifies -O-, -S-, -S(O)- or -S(O)2-; o signifies 3 or 4; p signifies 1, 2 or 3; q signifies 2 or 3; and r signifies 1 or 2, as well as the diastereoisomers and enantiomers of these compounds, are suitable for use as herbicides.

Description

Novel herbicides

The present invention relates to novel herbicidally active N-acetalalkylcarbamates, to their preparation, to compositions comprising said compounds, and to the use thereof for controlling weeds, in particular in crops of cultivated plants, such as cereals, maize, rice, cotton, soy, rape, sorghum, sugar cane, sugar beet, sunflower, vegetables, orchards and fodder plants, or for inhibiting plant growth.

Herbicidally active substituted N-alkylcarbamates are disclosed, for example, in

WO 94/10132 and WO 96/16941.

Novel N-acetalalkylcarbamates having herbicidal and growth-inhibiting properties have now been found.

Accordingly, the invention relates to compounds of formula I

wherein

R signifies halogen, Cι-C₃-halogenalkyl, C C₃-halogenalkoxy, cyano or nitro;

Z is hydrogen or halogen; or

Z and R in 2- and 3-position of the phenyl ring together form a group -O-CF₂-O-

Ri signifies Cι-C₅-alkyl or C₃-C₆-cycloalkyl;

R₂ signifies hydrogen or C C₄-alkyl;

Q is a group ^"~ (Qz)

R₃ and R₄, independently of one another, signify Cι-C₄-alkyl, d-C -halogenalkyl, or benzyl which is optionally substituted on the phenyl ring; or ^R ι 6⁶

R₃ and R₄ together signify a group -C-

R,

R₅ signifies hydrogen, CrC -alkyl, C C -halogenalkyl or optionally substituted phenyl; n is 2, 3 or 4;

R₆ and R₇, independently of one another, are hydrogen or d-C₄-alkyl;

Rio is hydrogen or C C₃-alkyl;

Rn and R₁₂, independently of one another, are hydrogen or C C₄-alkyl;

Ri3 signifies hydrogen, C-ι-C₄-alkoxy; d-C₆-alkyl optionally substituted by halogen, d-C₃- alkoxy, CrC₃-alkylthio, CrC₃-alkylsulphinyl or C C₃-alkylsulphonyI; C₂-C₆-alkenyl or C₃-C₆- cycloalkyl optionally substituted by halogen or methyl; or phenyl or thienyl optionally substituted by halogen, methyl, trifluoromethyl or methoxy;

R14 is hydrogen, d-C₆-alkyl optionally substituted by halogen, d-Qralkoxy, d-C₃-alkylthio,

CrC₃-alkylsulphinyl or d-C-₃-alkylsulphonyl; or C₃-C₆-cycloalkyl optionally substituted by halogen or methyl; or

R₁₃ and R₁₄ together form a group

^R21 ^R21 21 ^R21 R 21 or — C — C-C=C-

I I

R₂₃ n₂₂ 22

R₂₁ and R₂₂, independently of one another, are hydrogen or methyl;

R₂3 signifies hydrogen, halogen or C C₃-alkyl; m signifies 1 , 2, 3 or 4;

W signifies -O-, -S-, -S(O)- or -S(O)₂- ;

0 signifies 3 or 4; p signifies 1 , 2 or 3; q signifies 2 or 3; and r signifies 1 or 2, as well as the diastereoisomers and enantiomers of these compounds.

The alkyl groups occurring in the above definitions of the substituents may be straight-chain or branched and are typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, as well as the isomeric pentyls and hexyls.

Halogen signifies fluorine, chlorine, bromine or iodine. The same applies also to halogen in connection with other significances, such as halogen-alkyl or halogen-alkoxy.

Alkyl groups which may be considered as halogen-alkyl are those which are substituted by halogen once or several times, especially once to three times, whereby halogen signifies in detail bromine or iodine and especially fluorine or chlorine, for example fluoromethyl, difluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, difluorochloromethyl, 2-fluoro- ethyl, 2,2,2-trichloroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl and especially trifluoromethyl.

Alkoxy signifies for example methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy and tert.-butoxy, preferably methoxy, ethoxy and iso-propoxy.

Alkylthio signifies for example methylthio, ethylthio, propylthio and iso-propylthio.

Alkylsulphinyl signifies for example methylsulphinyl, ethylsulphinyl, propylsulphinyl and iso- propylsulphinyl.

Alkylsulphonyl signifies for example methyisulphonyl, ethylsulphonyl, propylsulphony! and isopropylsulphonyl.

Halogen-alkoxy may be for example fluoromethoxy, difluoromethoxy, trifluoromethoxy,

2-fluoroethoxy, 2-chloroethoxy, 2,2,2-trichloroethoxy, 2,2,2-trifluoroethoxy and 1 ,1 ,2,2- tetrafluoroethoxy; preferably difluoromethoxy and trifluoromethoxy.

Cycloalkyl is for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Alkenyl signifies for example vinyl, allyl, methallyl, 1-methylvinyl, but-2-en-1 -yl, pentenyl and

2-hexenyl, preferably alkenyl radicals with a chain length of 3 to 5 carbon atoms.

If not explicitly mentioned, Optionally substituted phenyl' or 'benzyl optionally substituted on the phenyl ring' signifies that the phenyl ring may be present in substituted form, whereby the substituents are then in ortho-, meta- or para-position of the phenyl ring. Substituents are e.g. halogen, d-C₄-alkyl, C C₄-halogen-alkyl, C C₄-alkoxy, C C₄-halogen-alkoxy, d-

C -alkylthio, C C₄-halogen-alkylthio, cyano or nitro. Corresponding significances may also be assigned to the substituents in compound definitions such as alkoxy-alkyl, alkylthio-alkyl, halogen-alkylthio, alkyisulphinyl-alkyl and alkylsulphonyl-alkyl.

The presence of one or more asymmetrical carbon atoms in the compounds of formula I, e.g. in β-position to the phenoxy group and on the γ-carbon atom, if R₂ is different from hydrogen, and in the group Q_ if R₃ is different from R₄, and in the group Q₂ on the δ-carbon atom and additionally if e.g. R₁0 and Rn and/or R-,₃ and R₁₄ (on the ε-carbon atom) are different, has the consequence that the compounds may occur both as optically active isomers and in the form of racemic mixtures (rac). The optically active compounds of formula I may be obtained from the racemic mixtures according to known separation processes, e.g. fractional crystallisation or column chromatography on the chiral (e.g. cellulose triacetate) or achiral phase (e.g. silica gel), or by means of enantio-selective synthesis. In the present invention, therefore, the active ingredients of formula I are understood to include both the pure optical antipodes and the racemates of all possible isomeric mixtures. If there is no specific reference to the individual optical antipodes (e.g. isomer I or isomer II in Table 5), then, under the indicated formula, those racemic mixtures which are obtained in the indicated preparation process are to be understood. By the enantiomers A (enant.A) in Tables 1 -6, such as compound no. 1.06 and no. 1 .25 in Table 1 , compound no. 5.10 in Table 5 or compound no. 6.02 in Table 6, are understood those optically active compounds of formula I or of formula X which are produced from the corresponding optically active alcohols of formula lla [(-)-enantiomers].

Preferred compounds are those of formula l₀

wherein

R signifies halogen, d-C₃-halogen-alkyl, Cι-C₃-halogen-alkoxy, cyano or nitro;

Z is hydrogen or halogen; or

Z and R together form a group -O-CF₂-O- in the 2- and 3-positions of the phenyl ring; Ri signifies Ci-Cs-alkyl or C₃-C₆-cycloalkyl;

R₂ is hydrogen or C C₄-alkyl;

R₃ and R₄, independently of one another, signify d-C₄-alkyl, d-C₄-halogen-alkyl, or benzyl which is optionally substituted on the phenyl ring; or

R₃ and R₄ together signify a group

R₅ signifies hydrogen, Cι-C₄-alkyl, d-C₄-halogen-alkyl or optionally substituted phenyl; n is 2, 3 or 4;

R₆, independently of one another, signify hydrogen or C C₄-alkyl; and

R₇₎ independently of one another, signify hydrogen or C C₄-alkyl.

Preference is given to compounds of formula I, wherein Z denotes hydrogen.

Preference is similarly given to compounds of formula I, wherein R denotes trifluoromethyl or trifluoromethoxy; and R_T denotes methyl or ethyl.

Also preferred are compounds of formula I, wherein R₂ is hydrogen.

OR-

/ ³

Equally preferred are compounds of formula l, wherein Q is a group — \""OR 4 (Qι); 5 and R₃ and R₄, independently of one another, are C C₄-alkyl.

OR, Suitable compounds are those of formula I, wherein Q is a group — "OR (Qi); and

\ 4

^R5

R5 is hydrogen, d-C₄-alkyi or phenyl. Also suitable are compounds of formula

wherein R is trifluoromethyl, pentafluoroethyl, trifluoromethoxy, chlorine or cyano; R₁ is methyl or ethyl; R₂ is hydrogen or methyl; R₃ is d-C₃-alkyl; and R₄ is C C₄-alkyl or benzyl. Equally suitable are compounds of formula l₂

wherein R is trifluoromethyl, pentafluoroethyl or trifluoromethoxy; R_. is ethyl; R₃ is methyl; R₄ is methyl or ethyl; and R₅ is C C -alkyl, phenyl or phenyl substituted by chlorine, methyl or methoxy.

Also suitable are compounds of formula l₃

wherein R is trifluoromethyl or trifluoromethoxy; Rj is ethyl; R₂ is hydrogen or methyl; R₅ is hydrogen, C C₄-alkyl or phenyl; R₆ is hydrogen or methyl; and R₇ is hydrogen or C C₄- alkyl.

Also suitable are those compounds of formula l

wherein R is trifluoromethyl or trifluoromethoxy; R^ is ethyl; R₅ is hydrogen, d-C₄-alkyl, phenyl or phenyl substituted by chlorine; R₆ is hydrogen or methyl; and R₇ is hydrogen, methyl or ethyl.

The compounds of formula I, wherein Q signifies a group (Q₂) are

important. Of these compounds of formula I, the ones that are especially important are those in which R₁0, Rn and R₁₂ signify hydrogen; R₁₃ signifies hydrogen, d-C₆-alkyl, C or C₂-alkoxy, C₃-C₆-cycloalkyi, or C C₄-alkyl which is substituted by halogen, d- or C -alkoxy, C or C₂-alkylthio, d- or C -alkylsulphinyl, C or C₂-alkylsulphonyl; R₁₄ signifies hydrogen, d-C₄-alkyl or d-C₄-halogen-alkyl; or

R₁₃ and R together signify a group

^R21 ^R21 ^R21 21 ^R21 or -C — C-C=C — C- R₂1, R22 and R₂₃ signify hydrogen; r is 2; and m is 3 or 4.

H '23 r *' 22 R 2. 2

The compounds of formula I can be prepared by processes known per se, for example, by converting a compound of formula II

wherein R, Z and R. have the significances indicated under formula I, using a chioroformylation agent, into the compound of formula IV

wherein R, Z and Ri have the significances indicated, and reacting this compound with a compound of formula V

R,

(V),

H₂N-CH— Q

wherein R₂ and Q have the significances indicated under formula I.

Processes of this type are described for example in US-A-5 399 545 and WO 96/16941. A further process according to the invention for the production of compounds of formula I,

wherein Q is a group (Q₂), and Rio to R ₄ have the significances

indicated under formula I, is carried out analogously to known processes and comprises reacting a compound of formula IV

wherein R, Z and R^ have the significances indicated under formula I, with a compound of formula Va

^R2 R | 12

H₂N— CH-C-OH _{Λ /} ,

² I (Va),

R^C-OH 11 wherein R₂ and R₁₀ to Rι₂ have the significances indicated under formula I, to form the compound of formula X

and subsequently a) further reacting this compound under acid catalysis with the compound of formula XI or XIa

^{Rl3 (χia)}-

wherein R₁3 and R₁₄ have the significances indicated under formula I, except for R₁₃ d-C₄- alkoxy in the compound of formula XI, and R₃₀ is C C₄-alkyl, or b) further reacting it under acid catalysis with the compound of formula XII

R '2,3

OR 3.0

(XII),

R '3_5- ^c

R. wherein R₂₃ is hydrogen or d-C₃-alkyl, R₃₀ is C C₄-alkyl, R₃₅ is hydrogen, C C₅-alkyl optionally substituted by halogen, d-d-alkoxy, d-d-alkylthio, CrC₃-alkyisulphinyl or CrC₃-alkylsulphonyl, or C₂-C₅-alkenyl optionally substituted by halogen or methyl, and R₁₄ has the significance indicated under formula I, or R₁₄ and R₃₅ together form a group

m is 2, 3 or 4; and R₂ι, R₂₂, W and r have the significances indicated under formula I, or c) firstly converting it with a compound of formula Xlla

R ,'21

OR ',30

R (Xlla), '35

R. wherein R₂₁ is hydrogen or methyl; and R₁₄, R₃₀ and R₃₅ have the significances indicated, or

Rι₄ and R₃₅ together form a group

^R21 ^R21 ^R21 | 21

^■C-C=C — C , and m, R₂ι, R₂2_> W and r have the significances indicated, 22 ^R22 in the presence of an equimolar quantity of a N-halogen-imide, to form the compound of formula XIII

wherein R, Z, R_{1 (} R₂, Rio to Rι₂, Ru, R21, R30 and R₃₅ have the significances indicated, and Hal is halogen, and subsequently further reacting this compound under acid catalysis.

The above process variants follow reaction schemes 1 and 2.

Reaction scheme 1

IV

H₂N-CH-Q

V

Reaction scheme 2

In the process variant of reaction scheme 1 , the alcohol of formula II is firstly chloro- formylated under standard conditions, e.g. as described in US-A 5 099 059, US-A 5 078 783, WO 94/10132 and WO 96/16941 , preferably with phosgene or diphosgene, to form the compound of formula IV. The chloroformate of formula IV obtained is allowed to react with the amine of formula V, at temperatures of between -20°C and +40°C, preferably between +5°C and +20°C, advantageously in an inert aprotic organic solvent, such as an aliphatic or cyclic ether, for example diethyl ether, 1 ,2-dimethoxyethane, tetrahydrofuran or dioxane, or a chlorinated aliphatic hydrocarbon, for example methyiene chloride, or an aromatic substance, for example toluene or xylenes, or an aliphatic ester, for example ethyl acetate, as well as in the presence of an organic base, for example triethylamine, pyridine, 4-N,N-dimethylaminopyridine, picoline or N,N-dimethylaniline, or sodium carbonate or potassium carbonate. During working up, the reaction mixture obtained is washed preferably with water and diluted acid in order to remove amine by-products as salts. In the process variant of reaction scheme 2, the chloroformate of formula IV is reacted with the amine of formula Va, analogously to the manner described under reaction scheme 1 , in an inert, organic solvent or in a two-phase system consisting of water and a solvent which is immiscible with water, e.g. a halogenated hydrocarbon such as dichloromethane, or an ester such as ethyl acetate, to form the compound of formula X (1 ,2-glycol derivative). Subsequently, the compound of formula X is converted e.g. under acid catalysis in the presence of sulphuric acid, p-toluenesulphonic acid, trifluoroacetic acid, acetic acid, formic acid or phosphorus oxychloride either a) with a ketone or aldehyde of formula XI, or with an acetal or ketal of formula XIa, for example 2,2-dimethoxypropane, or with an ortho acid alkyl ester of formula XIa, wherein R₁3 is d-d-alkoxy, or b) with an enol ether of formula XII, for example butylvinyl ether, to the desired cyclic ketals of formulae l₅ and l₆. According to method c) in reaction scheme 2, the compound of formula X is reacted with an enol ether of formula Xlla in the presence of a N-halogen-imide, for example N-bromo- or N- chlorosuccinimide, to the compound of formula XIII and subsequently converted analogously to the manner described under methods a) and b), under acid catalysis, to the desired cyclic ketal of formula l₇.

Such reactions are described for example in Synth. Communic. 19, 21 (1989). The compounds of formulae XI, XIa, XII and Xlla are suitably employed in an excess, optionally in the presence of an inert, organic solvent, e.g. an ether, for example diethyl ether or tetrahydrofuran, an aromatic hydrocarbon, for example toluene or xylenes, a halogenated hydrocarbon, for example dichloromethane, an ester, for example ethyl acetate, or an alcohol, for example methanol or ethanol. In the reactions of compounds of formula X with the acetal or ketal, or ortho acid alkyl ester of formula XIa, or the enol ether of formula XII or Xlla, instead of the above-mentioned acids, metal catalysts such as cobalt(ll)-chloride or copper(ll)-bromide may also be suitably employed. Such reactions are described e.g. in Synth. Comminic. 19, 901 (1989) or ibid. 13, 629 (1983).

These reactions are suitably carried out at temperatures of -40°C to boiling point of the respective solvent, or in an excess of the compounds of formulae XI, XIa, XII or Xlla employed; preferably at temperatures of 0° to 40°C.

If required, the acid-catalysed reactions according to method a), b) or c) in reaction scheme 2 may be effected in the presence of a water-binding reagent, e.g. an alkali or alkaiine earth metal sulphate, for example sodium or magnesium sulphate, or in the presence of a suitable molecular sieve. When using solvents which form an azeotropic mixture with water, such as benzene or toluene, the reaction water formed may also be removed azeotropically using a water separator.

The alcohols of formula II may be produced by known standard processes (e.g. US-A

5 099 059, WO 94/10132 and WO 96/16941), for example in accordance with the following reaction scheme 3.

Production of the intermediate product of formula II may also take place in the presence of lithium hydroxide monohydrate and in the absence of solvents under pressure, as described in WO 94/10132.

The alcohols of formula II may be separated into the enantiomers e.g. using liquid chromatography on chiral carriers, for example with HPLC on Chiracel-OD-H (Daicel) and

2% isopropanol in n-hexane as the eluant.

A further possibility of obtaining enantiomer-pure alcohols of formula II is the enantio- selective hydrogenation of α-phenoxyketones with BINAP-Ru(ll) catalyst complexes.

By the (-)-enantiomer of the compounds of formula II is understood the optical antipode of formula lla which is eluted first, i.e. before the (+)-enantiomer, by means of HPLC on a Chiracel-OD-H column from Daicel with a mixture of n-hexane and 2% isopropanol as eluant, or the one which is formed in predominant quantities (enantiomer excess of up to > 96%) in the enantio-selective hydrogenation of α-phenoxyketones with a Ru₂CI₄[(R)- BINAP]₂[N(C₂H₅)₃] catalyst complex.

The process for the production of optically active compounds of formula lla

wherein R, Ri and Z have the significances indicated under formula I, and the β-carbon atom is present in optically pure form as the (-)-enantiomer, emanates e.g. from the α- phenoxyketones of formula VIII

wherein R, Ri and Z have the significances indicated. These undergo a (R)-BINAP-Ru(ll)- catalysed hydrogenation, analogously to the method described in detail in WO 96/16941 , pages 9-1 1.

The enantio-selective synthesis of the optically active compounds of formula I (enantiomer A) in β-position to the phenoxy group from the corresponding optically active alcohols of formula lla ((-)-enantiomers) may be effected e.g. analogously to the process variant described (reaction scheme 1).

The amines of formula V and Va are either commercial or may be produced analogously to known processes, e.g. in accordance with the Gabriel synthesis. The following are described e.g.: (rac)- or (S)-3-amino-1 ,2-dihydroxypropane in Beilstein's Handbuch der Organischen Chemie E IV, Vol. 4/2, page 1865, Springer Verlag Berlin 1979, or in Tetrahedron Asym. 5, 1 181 (1995), 3-amino-1 ,2-dihydroxy-2-methylpropane in Beilstein's Handbuch der Organischen Chemie E III, Vol. 4, page 847, Springer Verlag Berlin 1962, 3-(R,R)-amino-1 ,2-butanediol in Tetrahedron Asym. 6, 2329 (1995), and 3-(R,R)-amino-1 ,2- hexanediol in Tetrahedron Lett. 32, 6931 (1991). 3-amino-1 ,2-pentanediol has the CAS registration number RN 89282-72-4. By way of example, reference may be made to the following standard processes, e.g. in Houben-Weyl, "Methoden der Organischen Chemie", Volume XI/1 , Thieme-Verlag Stuttgart, 1957, on pages 24 ff., 79 ff., 105 ff., 539 ff., 545 ff. and 853 ff.: e.g.

a)

2) HCI aq. or NH₂NH₂ , T

X= leaving group e.g. halogen, for example chlorine, bromine or iodine or

b)

R 0

1 ² II via Hofmann, Curtius or

— ►

Q-CH-C-R_{100 Schmidt degradation} Q-CH-NH₂

V

R₁₀₀= e.g. NH₂, OH or OR₁₀₁

R₁₀₁ = e.g. alkyl

The compounds of formulae XI, XIa, XII and Xlla (reaction scheme 2) are known or may be produced by processes that have been disclosed.

The 1 ,2-glycol derivatives of formula X and XIII are new and similarly have herbicidal properties. In addition, they are important intermediate products for the synthesis of the compounds of formula I, wherein Q is a group Q₂. They therefore similarly form an object of the present invention.

All remaining functionalisation, e.g. of substituents R₁₃ and R₁₄ in group Q₂, may be produced analogously to known standard processes. The nucleophilic substitution of halogen on haiogenalkyl groups with sodium mercaptides for example and the oxidation of the thioether derivatives with hydrogen peroxide (H₂O₂) or m-chloroperbenzoic acid in acetic acid to sulphones or sulphoxides are described e.g. in Org. Synth. 64, 157 (1985) and J. Am. Chem. Soc. 87, 1109 (1965). The compounds of formulae I, II, IV, X and XIII may be isolated and purified by methods known per se. The person skilled in the art is also familiar with the order in which certain reactions in the process variants according to reaction schemes 1 and 2 have to be suitably carried out in order to avoid possible secondary reactions.

Insofar as no targeted synthesis is carried out to isolate pure isomers, the product may be obtained as a mixture of two or more isomers. The isomers can be separated by methods known per se. For example, if desired, pure optically active isomers may also be produced by synthesis from the corresponding optically active starting materials, such as optically active alcohols of formula lla. The intermediate products of formula lid

wherein Ri has the significance indicated under formula I, are known from WO 94/10132. The starting compounds of formulae VI and VII (reaction scheme 3) required for the preparation processes are either known or may be produced by various processes that are known in literature, for example for the compounds of formula Via, in accordance with the following reaction scheme 4.

Reaction scheme 4

1) Diazotisation

2) Phenolic transformation

by boiling

IX Via

Production of the required starting compound of formula IX is described in EP-A 0 198 797. The end products of formula I may be isolated in the usual manner by concentration and/or evaporation of the solvent, and purified by recrystallisation or trituration of the solid residue in solvents in which they do not dissolve well, such as ether or aliphatic hydrocarbons, or by means of column chromatography with an appropriate eluant.

The compounds of formula I or compositions containing them may be used according to this invention by all standard methods of application used in agriculture, including preemergence application, postemergence application and seed dressing, as well as by different methods and techniques such as controlled release. For controlled release, a solution of the herbicide is applied to a mineral granular carrier or to a polymerised granulate (urea/formaldehyde) and then dried. A coating can then be additionally applied (coated granules) that allows the herbicide to be released at a controlled rate over a specific period of time.

The compounds of formula I may be used in unmodified form, i.e. as obtained in the synthesis. They are preferably processed in conventional manner to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates or microcapsules with the formulation assistants customarily employed in formulation technology. Such formulations are described, for example, in WO 97/34485, pages 9 to 13. As with the type of agents, the methods of application such as spraying, misting, dusting, wetting, scattering or pouring, are selected in accordance with the intended objectives and the prevailing circumstances. The formulations, i.e. the agents, preparations, or compositions comprising the compound of formula I or at least one compound of formula I and usually one or more than one liquid or solid formulation assistant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the herbicide with said formulation assistants, typically solvents or solid carriers. Surface-active compounds (surfactants) may additionally be used for preparing the formulations. Examples of solvents and solid carriers are described in said WO 97/34485, page 6.

Depending on the herbicide of formula I to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, nonionic, and cationic surfactants are listed in said WO 97/34485, pages 7 and 8. Also the surfactants customarily used for the art of formulation and described, inter alia, in "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch" (Handbook of Surfactants), Carl Hanser Verlag, Munich/Vienna, 1981 , and M. and J. Ash, "Encyclopedia of Surfactants", Vol l-lll,

Chemical Publishing Co., New York, 1980-81 are suitable for manufacture of the herbicides according to the invention.

The herbicidal compositions will as a rule contain from 0.1 to 99 % by weight, preferably from 0.1 to 95% by weight, of herbicide, from 1 to 99.9% by weight, preferably from 5 to

99.8 % by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from

0.1 to 25% by weight, of a surfactant.

Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.

The compositions may also contain further ingredients, such as: stabilisers, e.g. where appropriate epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil, or soybean oil); antifoams, typically silicone oil; preservatives; viscosity regulators; binders; and tackifiers; as well as fertilisers or other chemical agents.

The compounds of formula I are usually applied with success to the plants or the locus thereof in rates of application of 0.001 to 4 kg/ha, preferably 0.005 to 2 kg/ha. The rate of application required to achieve the desired action can be determined by experimentation. It will depend on the type of action, the development stage of the cultivated plant and of the weed, as well as on the application (locus, time, method), and as a result of these variables can vary over a wide range.

The compounds of formula I have excellent herbicidal and growth inhibiting properties, which make them suitable for application in crops of cultivated plants, especially in cereals, cotton, soybeans, sunflowers, sugar beet, sugar cane, plantations such as fruit and citrus orchards, rape, sorghum, vegetables, maize, and rice, and for the non-selective control of weeds.

Crops will also be understood as meaning those crops that have been made tolerant to herbicides or classes of herbicides by conventional breeding or genetic engineering methods. The weeds to be controlled may be monocot as well as dicot weeds, typically

Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum,

Phaseolus, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboillia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium,

Ipomoea, Chrysanthemum, Galium, Viola, and Veronica.

The invention is illustrated by the following non-limitative Examples. Preparative Examples:

Example P1 : Preparation of O-ri -(3-trifluoromethylphenoxy)-2-butyll-N-(2.2-dimethoxyethvπ- carbamate

23.7 g of O-(3-trifluoromethylphenoxy)-2-butylchloroformate (prepared from the (-)- enantiomeric alcohol of formula lla) are added dropwise at 0°C to 8.4 g of amino- acetaldehyde-dimethylacetal and 9.1 g of triethylamine in 400 ml of methylene chloride. The reaction mixture is held at 22°C for 2 hours and then poured onto cold, diluted hydrochloric acid. The organic phase is separated, dried over sodium sulphate and concentrated in a vacuum. The residue is chromatographed on silica gel (eluant: ethyl acetate/hexane = 1/3). 28.0 g (96% of theory) of the desired product are obtained as enantiomer A with a refractive

index of n² _D ⁵ 1.4635 .

Example P2: Preparation of ((2,2-dimethyl-f1 ,3l-dioxolan-4-yl)methyl)-carbamic acid-103- trifluoromethyl-phenoxymethvD-propyl-ester

a) 10.9 g of 3-aminopropane-1 ,2-diol are introduced into a two-phase system consisting of 50 ml of 2N sodium hydroxide solution and 50 ml of dichloromethane. Then, with good stirring, at 5-10°C, 29.6 g of O-(3-trifluoromethylphenoxy)-2-butylchloroformate, dissolved in 50 ml of dichloromethane, are added dropwise. Stirring is effected for 1 hour at 22°C, the organic phase is separated and dried over magnesium sulphate. The crude product which has been concentrated by evaporation is purified by chromatography on silica gel (eluant: hexane/ethyl acetate/triethylamine 50/49/1). The intermediate product (2,3-dihydroxy- propyl)-carbamic acid-1 -(3-trifluoromethyl-phenoxymethyl)-propyl-ester (compound no. 6.01) is obtained as an oil. b) 1.36 g of the above product are heated for 1 hour to reflux temperature together with 1.0 g of sodium sulphate, a spatula tip of p-toluenesulphonic acid and 0.232 g of acetone. The solids are filtered off and the product purified by chromatography on silica gel (eluant: ethyl acetate/hexane 1/4). The desired product is obtained as an oil.

¹H-NMR (300MHz, CDCI₃): 7.38 ppm (t, 1 H); 7.22 ppm (d, 1 H); 7.15 ppm (s, 1 H); 7.08 ppm (d, 1 H); 5.05 ppm (m, 2H); 4.27 ppm (m, 1 H); 4.08 ppm (m, 2H); 4.05 ppm and 3,68 ppm (m, 2H); 3.45 ppm and 3.28 ppm (m, 2H); 1.78 ppm (m, 2H); 1.43 ppm and 1.41 ppm (2xs, 3H; 2 isomers); 1.35 ppm (s, 3H); 1.00 ppm (t, 3H).

Example P3: Preparation of f(2-methoxy-H ,31-dioxolan-4-yl)methyl)-carbamic acid-1 -(3- trifluoromethyl-phenoxymethvD-propyl-ester

1.05 g of (2,3-dihydroxy-propyl)-carbamic acid-1 -(3-trifluoromethyl-phenoxymethyl)-propyl- ester (comp. no. 6.02, enantiomer A) are dissolved in 5 ml of orthoformic acid methyl ester and left to stand for 1 hour at 70°C in the presence of a spatula tip of p-toluenesulphonic acid. The mixture is subsequently concentrated by evaporation and the isomeric mixture is partially separated by column chromatography on silica gel (eluant: ethyl acetate/hexane 1/4). The first fraction eluted is a mixture of two isomers in oil form ((2-methoxy-[1 ,3]- dioxolan-4-yl)methyl)-carbamic acid-1 -(3-trifluoromethyl-phenoxymethyl)-propyl-ester (comp. no. 5.43); ⁿH-NMR (300MHz, CDCI₃): 7.38 ppm (t); 7.20 ppm (d); 7.16 ppm (s); 7.08 ppm (2xd, 4H); 5,70 ppm (s, 1 H); 5.32 ppm (broad signal, NH); 5.02 ppm (m, 1 H); 4.82 ppm (m, 1 H); 4.07 ppm (m, 2H); 4.09 ppm and 3.77 ppm (2xm, 2H); 3.7 to 3.3 ppm (m, 2H); 3.34 ppm and 3.31 ppm (2xs, 3H); 1.80 ppm (m, 2H); 1.00 ppm (t, 3H).

The second fraction obtained is a further mixture of two isomers in oil form ((2-methoxy- [1 ,3]-dioxolan-4-yl)methyl)-carbamic acid-1 -(3-trifluoromethyl-phenoxymethyl)-propyl-ester (comp. no. 5.44); ¹H-NMR (300MHz, CDCI₃): 7.39 ppm (t); 7.21 ppm (d); 7.14 ppm (2xs); 7.08 ppm (d, 4H); 5.76 ppm and 5.74 ppm (2xs, 1 H); 5.32 ppm (broad signal, NH); 5.06 ppm (m, 1 H); 4.43 ppm (m, 1 H); 4.08 ppm (m, 2H); 4.14 ppm and 3.72 ppm (2xm, 2H); 3.5 to 3.3 ppm (m, 2H); 3.31 ppm (s, 3H); 1.80 ppm (m, 2H); 1.00 ppm (t, 3H).

Example P4: Preparation of ((2-bromomethyl-[1 ,31-dioxolan-4-yl)methyl)-carbamic acid-1 - (3-trifluoromethyl-phenoxymethyl)-propyl-ester

1.05 g of (2,3-dihydroxypropyl)-carbamic acid-1 -(3-trifluoromethyl-phenoxymethyl)-propyl- ester are dissolved in 15 ml of dichloromethane and reacted at 22°C with 0.33 g of butyl vinyl ether and 1.33 g of N-bromosuccinimide. When the slightly exothermic reaction has died down (after ca. 30 minutes), the solid formed is filtered off and the crude filtrate is purified using a column of silica gel (eluant: ethyl acetate/n-hexane 1/4). (3-(2-bromo-1 - butoxy-ethoxy)-2-hydroxypropyl)-carbamic acid-1 -(3-trifluoromethyl-phenoxymethy.)-propyl- ester is obtained as an intermediate product in oil form.

0.8 g of this intermediate product are then heated to boiling temperature over 20 minutes, in the presence of a catalytic quantity of p-toluenesulphonic acid, subsequently concentrated by evaporation and purified by chromatography on silica gel (eluant: ethyl acetate/n-hexane 1/3). The desired product is obtained as an oil.

¹H-NMR (300 MHz, CDCI₃): 7.38 ppm (t, 1 H); 7.22 ppm (d, 1 H); 7.14 ppm (s, 1 H); 7.08 ppm (d, 1 H); 5.25 ppm and 5.18 ppm (2xm, NH); 5.09 ppm (m, 1 H); 5.03 ppm (m, 1 H); 4.32 ppm (m, 1 H); 4.08 ppm (m, 2H); 4.1 ppm and 3.7 ppm (2xm, 2H); 3.52 ppm and 3.35 ppm (2xm, 2H); 3.46 ppm, 3.44 ppm and 3.36 ppm (3xd, 2H); 1.80 ppm (m, 2H); 1.00 ppm (t, 3H).

The compounds of formula I listed in the following tables are produced in analogous manner. Table 1 : Compounds of formula \_f

Comp. R R R2 R₃ R₄ Enant./rac. phys. data

No.

1.01 CF₃ CH₃ H CH₃ CH₃ rac.

1.02 CF₃ CH₃ H C2H₅ CH₃ rac.

1.03 CF₃ CH₃ H C₂H₅ C₂H₅ rac.

1.04 CF₃ C₂H₅ H CH₃ CH₃ rac. oil

1.05 CF₃ C2H₅ H C2H₅ C2H₅ rac. oil

1.06 CF₃ C2H₅ H CH₃ CH₃ Enant. A 1 .4635

1.07 CF₃ C₂H₅ H CH₃ C2H₅ Enant. A n² _D ⁵ 1 .4580

1.08 CF₃ C₂H₅ H CH₃ n-C₃H₇ Enant. A n² _D ⁵ 1 .4605

1.09 CF₃ C2H₅ H CH₃ i-C₃H₇ Enant. A

1.10 CF₃ C₂H₅ H CH₃ n-C₄H₉ Enant. A

1.11 CF₃ C₂H5 H CH₃ Benzyl Enant. A

1.12 CF₃ C₂H₅ H C2H₅ C₂H_δ Enant. A n² _D ⁵ 1 .4605

1.13 CF₃ C2H₅ H n-C₃H₇ n-C₃H₇ Enant. A

1.14 CF₃ C2H₅ H i-C₃H₇ i-C₃H₇ Enant. A

1.15 CF₃ C2H₅ CH₃ CH₃ CH₃ Enant. A n² _D ⁵ 1 .4628

1.16 CF₃ C₂H₅ CH₃ C₂H₅ C₂H₅ Enant. A

1.17 OCF₃ C₂H_δ H CH₃ CH₃ Enant. A

1.18 OCF₃ C2H₅ H CH₃ C₂H₅ Enant. A

1.19 OCF₃ C2H₅ H C2H₅ C₂H₅ Enant. A

1.20 OCF₃ C2H5 H CH₃ n-C₃H₇ Enant. A

1.21 OCF₃ C₂H5 H CH₃ i-C₃H₇ Enant. A

1.22 OCF₃ C2H₅ H CH₃ n-C₄H₉ Enant. A

1.23 C2F5 C2H₅ H CH₃ CH₃ Enant. A

1.24 C₂F₅ C₂H₅ H CH₃ C₂Hδ Enant. A Comp. R Ri R2 R3 R₄ Enant./rac. phys. data

No.

1.25 C₂F₅ C₂H5 H C₂H₅ C2H₅ Enant. A

1.26 Cl C2H₅ H CH₃ CH₃ rac.

1.27 CN C2H5 H CH₃ CH₃ rac.

1.28 CF₃ C₂H₅ H C2H₅ Benzyl Enant.A n² ₀ ⁵1 .4946

1.29 CF₃ C2H₅ H C₂Hδ i-C₃H₇ Enant.A n²⁵ 1 .4592

1.30 CF₃ C₂H₅ H C2H₅ l-C₄Hg Enant.A

Table 2: Compounds of formula l₂

Comp. R Ri R₃ R₄ R₅ Enant./rac. phys. data

No.

2.01 CF₃ C-2H5 CH₃ CH₃ CH₃ Enant.A n² _D ^S 1 .4658

2.02 CF₃ CH₃ CH₃ C₂H₅ CH₃ Enant.A

2.03 CF₃ C₂H₅ CH₃ CH₃ C2H5 Enant.A n² _D ⁵1 .4664

2.04 CF₃ C₂H₅ CH₃ CH₃ n-C₃H₇ Enant.A

2.05 CF₃ C₂H₅ CH₃ CH₃ i-C₃H₇ Enant.A

2.06 CF₃ C₂H₅ CH₃ CH₃ n-C₄H₉ Enant.A

2.07 CF₃ C2H5 CH₃ CH₃ t-C Hg Enant.A

2.08 CF₃ C₂H₅ CH₃ CH₃ Phenyl Enant.A

2.09 CF₃ C2H₅ CH₃ CH₃ 2-CI-Phenyl Enant.A

2.10 CF₃ C2H5 CH₃ CH₃ 3-CI-Phenyl Enant.A

2.11 CF₃ C₂H₅ CH₃ CH₃ 4-CI-Phenyl Enant.A

2.12 CF₃ C2H₅ CH₃ CH₃ 2-OCH₃-Phenyl Enant.A

2.13 CF₃ C2H₅ CH₃ CH₃ 2-CH₃-Phenyl Enant.A

2.14 OCF₃ C2H₅ CH₃ CH₃ CH₃ Enant.A Comp. R Ri R₃ R₄ R₅ Enant./rac. phys. data

No.

2.15 OCF₃ C₂H₅ CH₃ CH₃ C2H₅ Enant.A

2.16 OCF₃ C2H₅ CH₃ CH₃ n-C₃H₇ Enant.A

2.17 OCF₃ C₂H₅ CH₃ CH₃ i-C₃H₇ Enant.A

2.18 OCF₃ C₂H₅ CH₃ CH₃ n-C₄H₉ Enant.A

2.19 OCF₃ C₂H₅ CH₃ CH₃ t-C₄Hg Enant.A

2.20 OCF₃ C2H₅ CH₃ CH₃ Phenyl Enant.A

2.21 OCF₃ C₂Hs CH₃ C₂H₅ Phenyl Enant.A

2.22 OCF₃ C2H5 CH₃ C2H₅ CH₃ Enant.A

2.23 C₂F₅ C₂H₅ CH₃ CH₃ CH₃ Enant.A

2.24 C₂F₅ C2H₅ CH₃ CH₃ C₂H₅ Enant.A

2.25 C₂F₅ C2H₅ CH₃ CH₃ i-C₃H₇ Enant.A

2.26 C₂F5 C2H₅ CH₃ CH₃ t-C₄Hg Enant.A

2.27 CF₃ C2H₅ CH₃ C₂H₅ CH3 Enant.A

2.28 CF₃ C2H₅ C2H₅ C₂H CH3 Enant.A n³ _D° 1.4610

2.29 CF₃ C2H₅ C2H₅ i-C₃H₇ CH3 Enant.A

2.30 CF₃ C2H5 C₂H₅ ϊ-C₄Hg CH3 Enant.A

2.31 CF₃ C2H5 C₂H₅ i-C₃H₇ C₂H₅ Enant.A

2.32 CF₃ C₂Hδ C2H₅ i-C₃H₇ i-C₃H₇ Enant.A

2.33 CF₃ C2H₅ C₂H₅ i-C₃H₇ t-C₄Hg Enant.A

Table 3: Compounds of formula l₃

Comp. R Ri R₂ R₅ Re R₇ Enant./rac. phys. data

No.

3.01 CF₃ C₂H₅ H H H H Enant.A n² _D ⁵1.4760

3.02 CF₃ C₂H5 H H H CH₃ Enant.A

3.03 CF₃ C2H₅ H H H C₂H₅ Enant.A n² _D ⁵1.4700

3.04 CF₃ C2H₅ H H H n-C₃H₇ Enant.A n² _D ⁵1.4698

3.05 CF₃ C₂H₅ H H H n-C₄H₉ Enant.A

3.06 CF₃ C2H₅ H H CH₃ CH₃ Enant.A n² _D ⁵1.4686

3.07 CF₃ C₂H₅ H H CH₃ C2H₅ Enant.A

3.08 CF₃ C2H₅ H CH₃ H H Enant.A

3.09 CF₃ C₂H₅ H CH₃ H CH₃ Enant.A

3.10 CF₃ C₂H₅ H CH₃ H C2H₅ Enant.A

3.11 CF₃ C2H₅ H t-C₄Hg H H Enant.A nj 1.4721

3.12 CF₃ C₂H₅ H t-C Hg H C₂H₅ Enant.A

3.13 CF₃ C₂H₅ H Phenyl H H Enant.A n_D ⁵1.5005

3.14 CF₃ C2H₅ H Phenyl CH₃ CH₃ Enant.A

3.15 CF₃ C₂H₅ H Phenyl H C2H5 Enant.A

3.16 OCF₃ C₂H₅ H H H H Enant.A

3.17 OCF3 C₂H₅ H H H C₂H₅ Enant.A

3.18 OCF3 C₂H_S H CH₃ H C2H₅ Enant.A

3.19 OCF₃ C₂H₅ H Phenyl H C2H₅ Enant.A

3.20 OCF₃ C2H₅ H Phenyl H CH₃ Enant.A

3.21 CF₃ C₂H₅ CH₃ CH₃ H H rac. oil (¹H-NMR)

3.22 CF₃ C₂H₅ H t-C₄Hg CH₃ CH₃ Enant.A

3.23 CF₃ C2H₅ H i-C₃H₇ H H Enant.A n³ _D° 1.4722 Comp. R i R2 R₅ Re R₇ Enant./rac. phys. data

No.

3.24 CF₃ C₂H₅ H i-C₃H₇ CH₃ CH₃ Enant.A

3.25 CF₃ C₂H₅ H i-C₃H₇ H CH₃ Enant.A

3.26 CF₃ C₂H₅ H C2H₅ H H Enant.A n² _D ⁵ 1 .4718

3.27 CF₃ C2H5 H C2H₅ H CH₃ Enant.A

3.28 CF₃ C2H₅ H C2H5 CH₃ CH₃ Enant.A

Table 4: Compounds of formula l₄

Table 5: Compounds of formula l₈

Com. R Ri R2 R10 R12 Rl3 Rl4 Enant./rac. phys. data

No.

5.01 CF₃ CH_∑CHs H H H CH₃ H rac Oil (¹H- NMR)

5.02 CF₃ CH₂CH3 H H H CH₂CH₃ H rac Oil ( H- NMR)

5.03 CF₃ CH₂CH₃ H H H CH₂CH₂CH₃ H rac Oil ('H- NMR)

5.04 CF₃ CH₂CH₃ H H H CH(CH₃)₂ H rac Oil ('H- NMR)

5.05 CF₃ CH₂CH₃ H H H C(CH₃)₃ H rac Oil ('H- NMR)

5.06 CF₃ CH₂CH₃ H H H Phenyl H rac Oil ('H- NMR)

5.07 CF₃ CH₂Cπ₃ H H H Thienyl H rac (Isomer Oil ( H- I) N R)

5.08 CF₃ CH₂CH₃ H H H Thienyl H rac (Isomer Oil (¹H- II) NMR)

5.09 CF₃ CH₂CH₃ H H H CH₃ CH₃ rac Oil ('H- NMR)

5.10 CF₃ CH₂CH₃ H H H CH₃ CH₃ Enant. A (2 n_D ²⁵ 1.4695 isomers)

5.11 CF₃ CH₂CH₃ H H H CH2CH3 CH₃ rac Oil ('H- NMR)

5.12 CF₃ CH₂CH₃ H H H CH2CH₃ CH₃ Enant. A (4 Oil ('H- isomers) NMR)

5.13 CF₃ CH₂Cπ₃ H H H CH₂CH₃ CH₂CH₃ rac Oil ('H- NMR)

5.14 CF₃ CH₂CH₃ H H H CH2CH₃ CH_∑CHβ Enant. A (2 Oil ('H- isomers) NMR)

5.15 CF₃ CH₂CH₃ H H H CH(CH₃)₂ CH₃ rac (Isomer Oil ('H- I) NMR)

5.16 CF₃ CH_∑CHs H H H CH₃ CH(CH₃)₂ rac (Isomer Oil ('H-

II) NMR)

5.17 CF₃ CH₂CH₃ H H H CH(CH₃)₂ CH₃ Enant. A (4 Oil ('H- isomers) NMR)

5.18 CF₃ CHsCH₃ H H H C(CH₃)₃ CH₃ rac (Isomer Oil ('H- I) NMR)

5.19 CF₃ CH₂CH₃ H H H CH₃ C(CH₃)₃ rac (Isomer Oil ('H- II) NMR)

5.20 CF₃ CH_∑CHs H H H CH2CI CH₃ rac. Oil ('H- NMR)

5.21 CF₃ CH_∑CHs H H H CH₂CI CH₃ Enant. A (4 Oil ( H- isomers) NMR)

5.22 CF₃ CH₂CH₃ H H H CH₂OCH₃ CH₃ rac. (Isomer Oil (¹H- I) NMR)

5.23 CF₃ CH₂CH₃ H H H CH₃ CH₂OCH₃ rac. (Isomer Oil (¹H- ID NMR)

5.24 CF₃ CH_∑CHs H H H CH2OCH3 CH₃ Enant. A (4 Oil (ⁿH- isomers) NMR) Com. R Ri R2 R10 R12 Rl₃ R14 Enant./rac. phys. data

No.

5.25 CF₃ CH₂CH₃ H H H -CH2CH20CH2CH2- rac Oil (ⁿH-

NMR)

5.26 CF₃ CH₂CH3 H H H -CH2CH2SCH2CH2- rac Oil (Η-

NMR)

5.27 CF₃ CH₂CH₃ H H H -CH2CH2CH2CH2CH2- rac Oil (¹H-

N R)

5.28 CF₃ CH₂Cπ₃ H H H -CH2CH2CH2CH2CH2- Enant. A (2 Oil (ⁿH- isomers) NMR)

5.29 CF₃ CH₂CH₃ H H H -CH2CH₂CH₂CH₂- Enant. A (2 Oil ('H- isomers) N R)

5.30 CF₃ CH₂Cπ₃ H H H Cyclopropyl CH₃ Enant. A (4 Oil (¹H- isomers) NMR)

5.31 CF₃ CH₂Cπ₃ H H H CH2SCH₃ CH₃ Enant. A (4 Oil ('H- isomers) NMR)

5.32 CF₃ CH₂CH3 H H H CH₂S(0)CH₃ CH₃ Enant. A (8 Oil (ⁿH- isomers) NMR)

5.33 CF₃ CH₂CH₃ H H H CH2Sθ₂CH₃ CH₃ Enant. A (2 Oil H- isomers) NMR)

5.34 CF₃ CH₂CH3 H H H CH₃ CH₂S0₂CH₃ Enant. A (2 Oil (¹H- isomers) NMR)

5.35 CF₃ CH₂CH₃ H H H C(CH₃)₂Br CH₃ Enant. A (4 Oil H- isomers) NMR)

5.36 CF₃ CH₂ϋH₃ H H H H CH₃ Enant. A (4 Oil ('H- isomers) NMR)

5.37 CF₃ CH₂CH₃ H H H H CH(CH₃)₂ Enant. A (4 Oil ('H- isomers) NMR)

5.38 CF₃ CH₂CH₃ H H H Cyclopropyl CH Br Enant. A (4 Oil H- isomers) NMR)

5.39 CF₃ CH₂CH₃ H H H Cyclopropyl CH₂SCH₃ Enant. A (4 Oil ('H- isomers) NMR)

5.40 CF₃ CH₂CH3 H H H CH(CH₃)SCH₃ CH₃ Enant. A (8 Oil ('H- isomers) NMR)

5.41 CF₃ CH₂CH3 H H H CH(CH₃)Br CH₃ Enant. A (8 Oil ('H- isomers) NMR)

5.42 CF₃ CH₂CH3 H H H CH₂CH₃ CH₂Br Enant. A (4 Oil ('H- isomers) N R)

5.43 CF₃ CH₂CH3 H H H OCH3 H Enant.A (2 Oil ('H- isomers) R)

5.44 CF₃ CH_∑CHs H H H OCH₃ H Enant.A (2 Oil (¹H- isomers) NMR)

5.45 CF₃ CH₂CH₃ H H H OCH₂H₃ H Enant.A (4 Oil ('H- isomers) NMR)

5.46 CF₃ CH₂CH₃ H H H OCH3 CH₃ Enant.A (4 Oil (¹H- isomers) NMR)

5.47 CF₃ CH₂CH3 H H H OCH₂H₃ CH₃ Enant.A (4 Oil ( H- isomers) NMR)

5.48 CF₃ CH₂CH₃ H H H CH₂CH₃ H Enant.A (4 Oil ('H- isomers) NMR)

5.49 CF₃ CH2CH3 H H H -CH₂CH=CH(CH₂)₂- rac. Oil (¹H-

NMR)

5.50 CF₃ CH₂CH₃ H H H -CHBrCH CH=CHCH₂-

5.51 CF₃ CH₂CH₃ H H H (CH₂)3CH₃ H

5.52 CF₃ CH2CH3 H H H (CH₂)₄CH₃ H

5.53 CF₃ CH₂CH₃ H H H (CH₂)₅CH₃ H

5.54 CF₃ CHaCH₃ H H H iso-butyl H Com. Ri Enant./rac. phys. data

No.

5.55 CF₃ Cπ₂CH₃ H H H sec-butyl H

5.56 CF₃ CH₂CH₃ H H H H H

5.57 CF₃ CH₂CH₃ H H H CF₃ H

5.58 CF₃ Cπ2CH₃ H H H CF₃ CH₃

5.59 CF₃ Cπ₂CH₃ H H H CH2CI H

5.60 CF₃ CH₂CH₃ H H H CH₂Br H rac. Oil (example P4)

5.61 CF₃ CH2CH₃ H H H CH₂I H

5.62 CF₃ CH2CH3 H H H CH2Cπ2CH₃ CH₃

5.63 CF₃ CH2CH₃ H H H CH=CH₂ CH₃

5.64 CF₃ CH2CH₃ H H CH₃ CH₃ CH₃

5.65 CF₃ Cπ₂CH₃ H CH₃ H CH₃ CH₃

5.66 CF₃ CH2CH₃ CH₃ H H CH₃ CH₃

5.67 CF₃ CH₃ H H H CH₃ CH₃

5.68 OCF₃ CH₂CH₃ H H H CH₃ CH₃

5.69 C₂F₅ CH2CH₃ H H H CH₃ CH₃

5.70 OCF₃ CH2CH3 H H H CH₃ H

5.71 C2F5 CH_∑CHs H H H CH₃ H

5.72 OCF₃ CH2CH₃ H H H CH2CH₃ H

5.73 C2F5 CH2CH₃ H H H CH2CH₃ H

5,74 OCF₃ CH_∑CHs H H H CH_∑CHsCHs H

5.75 C₂F₅ Cπ₂CH₃ H H H CH2CH2CH₃ H

5,76 OCF₃ CH2CH₃ H H H CH2CI CH₃

5.77 C2F5 CH₂CH₃ H H H CH2CI CH₃

5.78 OCF₃ CH2CH₃ H H H CH2CH₃ CH₃

5.79 C2F5 CH2CH3 H H H CH2CH3 CH₃

5.80 OCF₃ CH2CH₃ H H H CH(CH₃)₂ CH₃

5.81 C2F5 Cπ₂Cπ₃ H H H CH(CH₃)₂ CH₃

5.82 CF₃ CH2CH3 H H H CH(CH₃)S0₂CH₃ CH₃

Table 6: Compounds of formula Xa

Comp. R Z Ri R2 R10 R11 R12 Enant./rac. phys. data

No.

6.01 CF₃ H CH₂CH3 H H H H rac. Example P2 a)

6.02 CF₃ H CH₂CH₃ H H H H Enant. A (2 oil ('H-NMR) isomers)

6.04 CF₃ H CH₂CH₃ H H CH₃ H

6.05 CF₃ H CH_∑CHs H CH₃ CH₃ H

6.06 CF₃ H CH2CH3 H CH∑CHs H H

6.08 CF₃ H CH2CH3 CH₂CH₃ H H H

6.09 CF₃ H CH₃ H H H H

6.12 -OCF₂O- CH₂CH₃ H H H H

(¹H-NMR) in Tables 5 and 6 (last column) signifies that the structures of the compounds are in accord with the ¹H-NMR (300MHz, CDCI₃)-spectra.

Examples of specific formulations for compounds of formula I, such as emulsifiable concentrates, solutions, wettabie powders, coated granulates, extrusion granulates, dusts and suspension concentrates, are described in WO 97/34485 on pages 9-13.

Biological Examples

Example B1 : Pre-emerqence herbicidal action

Monocot and dicot test plants are sown in standard soil in plastic pots. Immediately after sowing, the plants are sprayed at a concentration of 2 kg active substance/ha with an aqueous suspension of the test compound prepared from a 25% wettabie powder (Example F3, b) as described for example in WO 97/34485) or an emulsion of the test compound prepared from a 25% emulsifiable concentrate (Example F1 c) as described for example in WO 97/34485) (500 I of water/ha). The test plants are then cultivated in the greenhouse under optimum conditions. The test is evaluated 3 weeks later on a rating scale of 1-9 (1 = total damage, 9 = no action). Ratings of 1 to 4 (especially of 1 to 3) denote good to very good herbicidal action. In this test, the compounds of formula I exhibit a pronounced herbicidal action.

Examples of the good herbicidal action are listed in Table B1.

Table B1 : Pre-emerqence action:

Test plant: S Seettaarriiaa Sinapis Solanum Stellaria

Compound no.

1.04 1 2 1

1.05 2 1 2

1.06 1 2 2

1.07 1 1

1.08 3 2

1.29 1 1

2.01 1 1

3.06 1 1

3.1 1 2 1

3.13 2 1

3.21 1 1

4.01 1 3

5.01 1 1

5.02 2 2

5.09 1 1

5.10 1 1

5.11 1 1

5.12 1 1 5.14 1 1 1 5.16 3 1 1 5.20 1 1 1 5.21 1 2 1 1 5.22 2 1 1 5.23 2 1 2 5.24 2 1 1 5.29 3 3 1 5.36 1 1 1 5.37 2 1 1 5.41 2 3 1

The same results are obtained by formulating the compounds of formula I in accordance with Examples F2 and F4 to F8 as described for example in WO 97/34485.

Example B2: Post-emergence herbicidal action

In a greenhouse, monocot and dicot test plants are sown in standard soil in plastic pots and sprayed in the 4- to 6-leaf stage with an aqueous suspension of the test compounds of formula I prepared from a 25 % wettabie powder (Example F3, b) as described for example in WO 97/34485) or with an emulsion of the test compound of formula I prepared from a 25 % emulsifiable concentrate (Example F1 c) as described for example in WO 97/34485) at a concentration of 2 kg active substance/ha (500 I of water/ha). The test plants are then further cultivated in the greenhouse under optimum conditions. The test is evaluated about 18 days later on a rating scale of 1-9 (1 = total damage, 9 = no action). Ratings of 1 to 4 (especially of 1 to 3) denote good to very good herbicidal action. In this test the compounds of formula I exhibit a pronounced herbicidal action. Examples of the good herbicidal action are listed in Table B2. Table B2: Post-emergence action

Test plant: Sinapis Solanum IPpomoea

Compound no.

1.04 2 2 2

1.05 2 2 2

1.06 2 3 2

1.07 2 2 2

1.08 2 2 2

1.15 2 3 3

1.29 2 1 2

2.01 2 2 2

3.01 3 2 2

3.03 2 2 1

3.04 2 3 2

3.06 1 1 1

3.1 1 2 2 1

3.13 2 1

3.21 2 1

4.01 2 2

5.01 2 2

5.02 2 2 2

5.04 2 3

5.09 2 2

5.10 2 2 2

5.1 1 1 2

5.12 2 1

5.13 1 3

5.14 2 1

5.15 1 2

5.17 2 1

5.20 2 3

5.21 2 1 5.22 1 1 2 5.23 1 1 2 5.24 1 2 1 5.25 1 1 2 5.27 1 2 2 5.28 1 2 1 5.29 1 2 2 5.30 1 2 1 5.31 2 2 3 5.32 2 2 2 5.33 1 2 2 5.34 2 2 2 5.35 1 2 2 5.36 2 2 1 5.37 1 2 2 5.38 2 2 2 5.39 2 2 2 5.40 1 2 2 5.41 1 2 1 5.42 1 2 2 6.02 2 2 3

Claims

What is claimed is:

1. Compounds of formula I

wherein

R signifies halogen, CrC₃-halogenalkyl, C C₃-halogenalkoxy, cyano or nitro;

Z is hydrogen or halogen; or

Z and R in 2- and 3-position of the phenyl ring together form a group -O-CF₂-O- ;

Ri signifies C C₅-alkyl or C₃-C₆-cycloalkyl;

R₂ signifies hydrogen or C C -alkyl;

Q is a group ^ΓÇö (Q₂) ;

R₃ and R₄, independently of one another, signify C C₄-alkyl, C C₄-halogenalkyl, or benzyl which is optionally substituted on the phenyl ring; or

^R6

I ⁶

R₃ and R₄ together signify a group -C- 7

R₅ signifies hydrogen, d-C₄-alkyl, C╬╣-C₄-halogenalkyl or optionally substituted phenyl; n is 2, 3 or 4;

R₆ and R₇, independently of one another, are hydrogen or C C -alkyl;

Rio is hydrogen or C C₃-alkyl;

Ru and R₁₂, independently of one another, are hydrogen or d-C₄-alkyl;

R13 signifies hydrogen, C╬╣-C₄-alkoxy; d-Ce-alkyl optionally substituted by halogen, C C₃- alkoxy, C╬╣-C₃-alkylthio, C C₃-alkylsulphinyl or C C₃-alkylsulphonyl; C₂-C₆-alkenyl or C₃-C₆- cycloalkyl optionally substituted by halogen or methyl; or phenyl or thienyl optionally substituted by halogen, methyl, trifluoromethyl or methoxy; R₁₄ is hydrogen, d-Ce-alkyl optionally substituted by halogen, C C₃-alkoxy, d-d-alkylthio, C C₃-alkylsulphinyl or C C₃-alkylsulphonyl; or C₃-C₆-cycloalkyl optionally substituted by halogen or methyl; or

R₁₃ and R₁₄ together form a group

o

R21 and R₂₂, independently of one another, are hydrogen or methyl;

R₂₃ signifies hydrogen, halogen or C C₃-alkyl; m signifies 1 , 2, 3 or 4;

W signifies -O-, -S-, -S(O)- or -S(O)₂- ; o signifies 3 or 4; p signifies 1 , 2 or 3; q signifies 2 or 3; and r signifies 1 or 2, as well as the diastereoisomers and enantiomers of these compounds.

2. Compounds according to claim 1 of formula l₀

wherein R signifies halogen, C╬╣-C₃-halogenalkyl, C C₃-halogenalkoxy, cyano or nitro;

Z is hydrogen or halogen; or

Z and R together form a group -O-CF₂-O- in the 2- and 3-positions of the phenyl ring;

R₁ signifies d-C₅-alkyl or C₃-C₆-cycloalkyl;

R₂ is hydrogen or d-C₄-alkyl;

R₃ and R₄, independently of one another, signify d-C₄-alkyl, C╬╣-C₄-halogenalkyl, or benzyl which is optionally substituted on the phenyl ring; or

R_*

R₃ and R together signify a group

R₇

R₅ signifies hydrogen, C C₄-alkyl, d-C₄-halogenalkyl or optionally substituted phenyl; n is 2, 3 or 4;

R₆, independently of one another, signify hydrogen or d-C₄-alkyl; and

R₇, independently of one another, signify hydrogen or d-C₄-alkyl.

3. Compounds according to claim 1 , wherein Q signifies a group

and R₁₀ to R₁₄ are defined as in claim 1.

4. A method for the preparation of compounds of formula I according to claim I, which comprises converting a compound of formula II

wherein R, Z and Ri have the significances indicated in claim 1 , using a chloroformylation agent into the compound of formula IV

R_

(V),

H₂N-CHΓÇö Q

wherein R₂ and Q have the significances indicated in claim 1.

5. A method for the preparation of compounds of formula I according to claim I, wherein

Q is a group (Q₂) and R₁₀ to R_M are defined as in claim 1 ,

which comprises reacting a compound of formula IV

wherein R, Z and Ri have the significances indicated in claim 1 , with a compound of formula Va

wherein R₂ and R╬╣₀ to R╬╣₂ have the significances indicated in claim 1 , to form the compound of formula X

O R₃₀O. OR₃₀

II \ /

X (XI) or C XIa),

R 13 / \ (

^R14 R 13 R 14 wherein R╬╣₃ and R ₄ have the significances indicated in claim 1 , except for R╬╣₃ C C₄-alkoxy in the compound of formula XI, and R₃₀ is CrC₄-alkyl, or b) further reacting it under acid catalysis with the compound of formula XII

r ,'23

OR ',₃0

(XII), R '3,5- ^c

R 14 wherein R₂s is hydrogen or C C₃-alkyl, R₃₀ is C C₄-alkyl, R₃₅ is hydrogen, d-C₅-alkyl optionally substituted by halogen, C C₃-alkoxy, C C₃-alkylthio, C╬╣-C₃-alkylsulphinyl or CrC-₃-alkylsulphonyl, or C₂-C₅-aikenyl optionally substituted by halogen or methyl, and R₁₄ has the significance indicated in claim 1 , or R₁₄ and R₃₅ together form a group

m is 2, 3 or 4; and R₂╬╣, R22_> W and r have the significances indicated in claim 1 , or c) firstly converting it with a compound of formula Xlla

wherein R₂╬╣ is hydrogen or methyl; and R_M, R₃₀ and R₃₅ have the significances indicated, or

R╬╣₄ and R₃₅ together form a group or

^R21 ^R21 ^R21 ^R21

ΓÇö C-C=C ΓÇö C , and m, R₂₁, R ₂, W and r have the significances indicated, I I

R 'ΓÇ₧2,2 R 22 in the presence of an equimolar quantity of a N-halogen-imide, into the compound of formula XIII

wherein R, Z, R_{1 f} R₂, Rio to R₁₂, R₁ , R₂╬╣, R₃₀ and R₃₅ have the significances indicated, and Hal is halogen, and subsequently further reacting this compound under acid catalysis.

6. Compounds of formula X

wherein R, Z, Ri, R₂ and R ₀ to R╬╣₂ are defined as in claim 1.

7. Compounds of formula XIII

wherein R, Z, R_{1 (} R₂, Rio to R╬╣₂₎ R╬╣₄, R₂╬╣, R₃₀ and R₃₅ are defined as in claim 1 , and Hal is halogen.

8. A herbicidal and plant growth inhibiting composition, which comprises a herbicidally effective amount of the compound of formula I and an inert carrier.

9. A method of controlling undesirable plant growth, which comprises treating the plants or the locus thereof with a herbicidally effective amount of a compound of formula I or of a composition containing such a compound.

10. Use of a composition according to claim 8 for controlling undesirable plant growth.