NL8900243A - DION COMPOUNDS AND METHODS FOR PREPARING AND USING THESE COMPOUNDS. - Google Patents

Description

£ i - Dione compounds and methods of preparing and using these compounds -

The present invention relates to new dion compounds, to the use of such compounds to control weeds, to new herbicidal compositions containing such dion compounds and to a method of preparing such new compounds.

More particularly, the invention relates to new compounds of formula I, wherein 20 R 2 'R 2' R 3 and R 4 'independently of one another, an unsaturated aliphatic hydrocarbon group having up to 6 carbon atoms, a cycloalkyl group having up to 6 carbon atoms, Ar or a (A .) X group, where ± one of the substituents R, R, R and R is also a

• L Cm J

C 2-5 alkoxycarbonyl group may be, at least one of the substituents on R 1, R 4, R 0 and R is (A 1) X, R, together with R 1 or R 12 12 34 Inl 2 3 together with R 2 also an alkylene group with 2-5 carbon atoms and R 1 and R 2 together may also form the oxo or an alkylidene group having 1 to 5 carbon atoms, Ar represents an a * * or n; * - substituted heteroaryl 5- or 6- ring with 1-3 heteroatoms selected from oxygen, nitrogen and sulfur and represented by a carbon atom of the ring connected to ring A, n = 0 or 1.25 X is H, ORg, S.R7, NR8Rgr NO, halogen, CN, CF, CHF, S (0) R, CO-NHR .., C0-R..r CR R -C00 (C-alkyl> 32 m 10 11 12 13 14 1-6 or benzyl, A ^ a methylene or ethylene group which is unsubstituted or substituted by one or more alkyl groups 3q with 1 to 5 carbon atoms, R and R independently represent D 7 a hydrogen atom, a hydrocarbon group, a haloalkyl group, a heteroaryl group, or a CO- R group displays, 15 R ee n hydrogen atom, a hydrocarbon group,

O

89002A3 '* Λ - 2 - represents a heteroaryl group or a CO-R ^ ^ group,

R8, R10, R13 and R14 'are independently of one another, a hydrogen atom, an alkyl group of 1-6 carbon atoms or an aryl group, R is a hydrogen atom or a hydrocarbon group, R 2 and R 4 independently of each other, a hydrogen atom, a hydrocarbon group or a heteroaryl group, m = 1 or 2, A „represents a bond or CR, R, CR, R, -2 16 17 16 17 CR R, 0, S, NR or CO, 18 19 20 R and R18f independently represents a hydrogen atom, a hydrocarbon group or a carboxyl group in free form, salt form or esterified form, wherein R together with R at the adjacent carbon atom can form a 16 L bond, R and R independently of each other,

a hydrogen atom, a hydrocarbon group or an (A ^) X

represents group, in which A, n and X have the meanings indicated above, where R, _ and R, or R, „and R,„ 16 17 18 19 together can also form a (CH) group, so 2 2-5 under formation of a spiro compound, and / or R together with R at the adjacent carbon atom, or R together 1 18 ρ ς with R ^ at the adjacent carbon atom can form a (CH ^) ^ 5 group, thus forming a bicyclic ring, R20 eSn hydrogen atomic hydrocarbon group or a CO-R group, wherein R has a previously defined meaning, A ^ --- A ^ is C = C (0Ra) (Group A) or C (X ^) - C (0) (Group B), X ^ represents a fluorine or chlorine atom,

Ra represents a hydrogen atom, a salt-forming portion, or together with the oxygen atom to which this substituent is bonded, represents an ether or ester portion, Y represents a phenyl group substituted by R 21 'R22 and R23' or Ar ', 8900243s-3 - » ί

Ar 'is a 5- or 6-membered group with 1,2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen, which heteroatomatic group is unsubstituted or substituted and is connected via a carbon atom of the ring to the CO- group to which it is attached, R Sn R22 'independently * 3k from each other, a hydrogen atom, halogen atom, alkyl group with 1-4 carbon atoms, alkoxy group with 1-4 carbon atoms, haloalkyl group with 1-4 carbon atoms, Cn, NC> 2 <CF 0 , 10 represent RfaS (0), NRCRd, C (0) -R °, SO -NRCRd or NR ° -C (0) -Rd, p 2 where R and R 22 together may form the methylenedioxy group, p = 0, 1 or 2, R represents an alkyl group of 1 to 4 carbon atoms, which is optionally substituted by halogen, cyano, phenyl or benzyl, Cl R and R, independently, represent a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, 20 R ° an alkyl group with 1-4 carbon atoms or an alkoxy group with 1-4 carbon atoms, R22 is a halogen atom, nitro group, cyano group, alkyl call with 1 or 2 carbon atoms, alkoxy group with 1 or 2 carbon atoms, haloalkyl group with 1 or 2 carbon atoms or C, alkyl-S (0) group and 1-4 qq = 0, 1 or 2, where, if Y represents a has other meaning than an optionally substituted pyrimidinyl group, one of the substituents R 1, R 2, and also a phenyl group or a substituted phenyl group 30, and under the conditions that a) X in one of the substituents R 1, R 2 and only is a hydrogen atom if at least one of the following conditions is met: i) CRxR2-A2 is C (R2) = C {R1?) or 35 CR R -CR, R -CR „„ R, „, 12 16 17 18 19 ii) Y has a meaning other than an optionally substituted phenyl group or an optionally substituted βδ 00 243 "- 4 - substituted pyrimidinyl group, iii) R 1 and R 2 together form the oxo group or an alkylidene group of 1 to 5 carbon atoms, 5 iv ) at least one of the other substituents R ^, R ^, R ^ and R is an unsaturated aliphatic hydrocarbon group, a cycloalkyl group an al or unsubstituted phenyl group or Ar, v) at least one of the other substituents R ^, R ^, R ^, R ^, R ^ ^ and R is an (A ^ JnX group, where X has a meaning other than hydrogen, or vi) Ag --- A ^ is CiX ^ J-CfO), b) if CR1R2-A2 is C (R2) = C (R17 * ', R ^ and R ^ are both not hydrogen, and c) if R 2 and R 2 together form the oxo group, A2 does not represent 0, S, NR, ^ or CO.

The compounds of formula I can be obtained by reacting a compound of formula II, wherein R 1, R 2, R 1, R 1, and A2 have the previously defined meanings, with a compound of formula III, wherein Y is a previously has defined meaning and Hal is a halogen atom, followed by rearrangement of the ester of formula IV thus obtained, wherein Y, R 2, R 2, R 2, R 2 and A 2 have the previously defined meanings, to give compounds of the formula Ib, wherein Y, A, R 2, R 2, R 3 and R 3 have the meanings defined above and M represents a hydrogen atom or a salt-forming part and, if desired, etherification, esterification or halogenation of the compounds of formula Ib thus obtained to the corresponding 2- (Y-CO) -2-en-1-on-3-20 olethers, 2- (Y-CO) -2-en-1-on-3-olesters or 2-X ^ -2- (YC0) - 1,3-dione compounds.

The esterification of the 1-on-3-ol compounds with the halide can be carried out in a manner known per se for preparing esters from an alcohol and an acid halide. The reaction is suitably carried out in a solvent which is inert under the reaction conditions, such as dichloromethane, preferably in the presence of a 89 00 243; to *. Acid-binding agent / for example triethylamine. A suitable reaction temperature is in the range from 0 to 40 ° C and is, for example, 20 C.

The rearrangement of the thus obtained esters of formula IV into the desired compounds of formula I can be carried out under the conditions known for the preparation of α-acylated 8-diketones from β-ketoenol esters. For that purpose, it is generally not necessary to isolate the esters from the reaction mixture in which they are formed.

Such rearrangement can be performed in the presence of a catalyst, such as 4-dimethylamino-pyridine, a Lewis acid catalyst, or a source of cyanide, such as acetone cyanohydrin with a moderate base, for example, a tertiary amine base, such as triethylamine.

Suitable Lewis acid catalysts for such a rearrangement reaction are, for example, aluminum chloride, zinc chloride or tin (IV) chloride.

Examples of suitable solvents are methylene chloride, acetonitrile and toluene. The reaction temperature is suitably between 0 C and the reflux temperature, preferably at room temperature (about 20 ° C).

The compounds of formula Ib can be recovered from the reaction mixture in which they are formed by working up according to established methods.

Depending on the reaction conditions, the compounds of formula Ib can be obtained in free acid form (fM = hydrogen) or in salt form.

When the compounds of formula I b 30 are in free acid form, they can exist in various tautomeric forms. Such acids can be converted into the corresponding salts in a manner known per se and vice versa.

If the compounds of formula 35 Ib are in salt form (M is a salt-forming part), then M may be inorganic (for example a metal equivalent of sodium, 8900243. - 6 - calcium, iron or copper) or organic, for example the ammonium salt part from an amine (such as 1- (methylaminomethyl) naphthalene), a sulfonium; sulfoxonium or phosphonium portion.

Depending on the nature of M, the salt may exist in chelated form.

The ester and ether forms of the compounds of the formula I are also obtained in a manner known per se from the corresponding compounds of the formula I in free acid or salt form.

Compounds of formula la, wherein OR'a is an ether or ester moiety and Y, A ^ and R ^, R ^, R ^ and R ^ have the meanings defined above, are thus obtained from the corresponding compounds of formula Ib by reaction with a) the compound R'^ OH and a catalyst, b) the compound R'Q and a moderate a base, wherein Q is a halogen atom, or c) the compound R'NHCOCl and a functionally reactive derivative thereof.

2g. The aforementioned reaction a) is carried out in the presence of a catalyst, such as concentrated sulfuric acid. The reaction is conveniently conducted in a solvent, which is also a reactant, such as methanol, and at an elevated temperature.

The aforementioned reaction b) is carried out in the presence of a moderate base, such as triethyl amine or pyridine, and conveniently proceeds at room temperature or a lower temperature. For the preparation of ether compounds, this reaction b) can also be carried out in a manner known per se using a compound of formula Ib in silver salt form.

The aforementioned reaction c) is carried out under the conditions known for preparing carbamates by reacting an optionally N-25 substituted carbamoyl chloride or a corresponding isocyanate with an alcohol. It will be appreciated that such carbamates can also be obtained via the corresponding carbonates by reaction with 89 0 O 243: 7-NH ^ or primary amines.

Examples of suitable ether groups OR'a are hydrocarbonoxy groups such as O-C 1-6 alkyl, O-C 1-6 alkenyl, O-C alkynyl, O-benzyl, O-phenyl, O-tolyl and benzoyl-2 * 6 * methoxy.

Examples of suitable ester groups OR'a are acyloxy groups, for example the groups 0-C00-hydrocarbon, 0-C0-hydrocarbon and O-SO2-hydrocarbon groups, such as O-acetyl, O-mesyl, O-tosyl, O-benzoyl, O -COOC alkyl lo (e.g. O-COOCHg), 0-C00phenyl, 0-C0-benzyl and O-CONHR. ^ (E.g.

O-CONH and O-CONH-C, alkyl).

2 1—6

The compounds of formula I in which A ^ --- A ^ is group B are obtained by chlorination or fluorination of compounds of formula Ib with a chlorinating or fluorinating agent.

The choice of the chlorinating or fluorinating agent will depend on the special substituents present in the compound of formula Ib. Suitable chlorinating agents include chlorine cations donors, such as an alkali metal hypochlorite (e.g., Na or KC10) or N-Cl succinimide. It is desirable to carry out the chlorination with the compound of formula Ib in anion form to avoid chlorination of an optional substituent present in the compound of formula Ib.

Suitable fluorination / agents include fluorocation donors, such as PCIO4 or p-tosyl-NfFjCH4.

The fluorination is conveniently carried out with the compound of formula Ib in anion form.

The compounds of formula I30 are generally obtained in the form of cis-transmitters and, if they contain one or more chiral centers, in the form of racemic or diastereoisomeric mixtures.

Examples of recommended subgroups of compounds of formula I are: ^ compounds of formula I wherein R ^ (A ^ JnX ', X' has a meaning defined above for X, excluding hydrogen and * - 8 - A, η, H R3, R4, A2 'Α3 —-- * 4 and Υ have the meanings defined above (hereinafter compounds of formula Iz), compounds of formula I, wherein R ^ is an unsaturated aliphatic hydrocarbon group with up to 6 carbon atoms, a cycloalkyl group with up to 6 carbon atoms or Ar [and Ar, R ^, R ^, R ^, A ^, A ^ --- A ^ and Y have the previously defined meanings (hereinafter compounds of formula Iy)], compounds of formula I, wherein CR ^ R ^ A ^ ^ R2 ^ = <"Ri7 ^ and R2, R ^ 7'RpgfR19, R3'R4 * A3 A4 and Y have the previously defined meanings (hereinafter compounds of formula 1x)], compounds of formula I wherein R ^ and R ^ together represent oxo or an alkylidene group having 1 to 5 carbon atoms [and A ^, A ^ --- A ^, R ^ fR ^ and Y the previously defined have meanings (hereinafter compounds of formula Iw)], compounds of formula I, wherein A ----- A ^ is C (X ^) - C (O) [and X ^, RL, R2, R3, R ^, A2 and Y have the previously defined meanings (hereinafter compounds 20 of formula Iv]), compounds of formula I, wherein A is C (CF) R or C (CF) R -CR R [and R-, fR, QfR, Q »R ·,, 2 3 16 3 16 18 19 16 18 19 1 R2, R3, R4fA3 --- A4 and Y k - * - 61 ^ 00 * 'have defined meanings (hereinafter compounds of formula Iu)], 25 compounds of formula I, wherein Y is an optionally substituted thienyl group, pyridyl group, pyrazolyl group, isothiazolyl group, 1,2,3-thiadiazolyl group or pyrazinyl group (especially an optionally substituted thienyl group, pyridyl group or pyrazolyl group, especially an optionally substituted pyridyl group, or the most preferred pyrazolyl group 1-CH 2 -NO -pyrazol-5-yl or 1-CH 3-4-NO 2 -pyrazol-3-yl), represents and [and R 2, R 2, R 2, ^ 4, A2 and A3-- -A4 have previously defined meanings (hereinafter compounds of the formula It)], compounds of the formula I, wherein Y is a phenyl group substituted by R 2, R 22 and R or an optionally substituted heteroaryl 5- or 6-ring with 1-3 heteroatoms selected from oxygen, nitrogen and sulfur, with exception of an optionally substituted 8900243.

Pyrimidinyl group, which heteroaryl group is bonded to ring A via a ring carbon atom, wherein one of the substituents ^ i ^ 2, R3 and R4 is an eny ^ p or a substituted phenyl group and the other substituents 5 R, R, R, and R, independently, an unsaturated one

J. Z O

aliphatic hydrocarbon group with up to 6 carbon atoms, a cycloalkyl group with up to 6 carbon atoms, Ar or an (A ^) nX group, [where R ^, A ^; - A ^, and R. have the meanings defined above (hereinafter 4 compounds of formula Is)], and compounds of formula I, wherein

CV2-A2 1S CR1R2 ~ CR16R17_CR18R19 i <5n Rl'R2, R16rR17, R18'RW

R., R ", A" --- A. and Y have the previously defined meanings 3 4 3-4 (hereinafter compounds of formula Ir)].

15 In the connections with formulas

Ir, Iu, Iv, Iw, 1x, Iy and Iz, Y is a preferably substituted phenyl, pyridyl, thienyl, pyrazolyl or pyrimidinyl group, more preferably a substituted phenyl, pyridyl, pyrimidynyl, or pyrazolyl group, the most commendably a substituted phenyl, pyridyl or pyrazolyl group, especially a substituted phenyl group, 1-CH 2 -é-NC 2 -pyrazol-5-yl or 1-CH 2 -é-NO-pyrazol-S-yl.

In the compounds of formula Is, Y is preferably a phenyl group substituted by R21, R22, βΩ R23 *, a sex-substituted pyridyl, thienyl or pyrazolyl group, more preferably a substituted phenyl, pyridyl or pyrazolyl group, and most preferably a substituted phenyl group, 1-CH 3-4-NC> 2-pyrazol-5-yl or 1-CH 2 -é-NC 1 -pyrazol-S-yl group.

30

If in the compounds of formula

When R 1 represents a phenyl group or a substituted phenyl group, each (A 1) n X group is preferably a hydrogen atom or an alkyl group of 1-4 carbon atoms.

35 If one or more R, R, R

12 3 and R 2 substituents is an unsaturated aliphatic hydrocarbon group of up to 6 carbon atoms, it conveniently contains one 8900143.

- 10 - double bond or a triple bond

If one or more substituents R 1, R 2, R 3 and R 4 represent an unsaturated aliphatic hydrocarbon group with a maximum of 6 carbon atoms, it preferably contains a maximum of 4 carbon atoms, examples of the recommended groups of this category being vinyl , allyl and propargyl.

Each of the substituents R, R, R, and R represents a cycloalkyl group, this is preferably the cyclopropyl group.

If one of the substituents R 1, R 2, R 3 and R 3 is a substituted phenyl group, such a phenyl group suitably contains 1,2 or 3 substituents selected from alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms, halogen and CF and is preferably monosubstituted or disubstituted, especially monosubstituted, especially by halogen.

If one of the substituents R, R, R, R, R, R, R, R and R represents a heteroaryl group, 1334678 12 15, such a group is suitably selected from thienyl, furyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, 1,2,3-thiadiazolyl, pyridyl, pyrimidinyl, pyrazinyl and pyridazinyl, which groups may be unsubstituted or substituted.

Examples of suitable substituents of such heteroaryl groups and of Ar '(wherein Ar' 25 is a substituted heteroaryl group) are halogen (e.g. fluorine, chlorine or bromine), alkyl groups of 1-4 carbon atoms which are unsubstituted or substituted by halogen (e.g. fluorine, chlorine or bromine), phenyl, SC1-alkyl or alkoxy of 1-4 carbon atoms, nitro, cyano, alkoxy of 1-4 carbon atoms, formyl or alkanoyl of 2-4 carbon atoms and functional derivatives such as oximes, acetals and ketals thereof (e.g. C (= NOC ^ _ ^ alkyl) -C ^ _2alkyl, C (0-C ^ _ ^ alkyl) 2- C ^ ^ alkyl, CH (0-C ^ _ ^ alkyl) 2, etc. ); C 1-4 alkyl-S, C 1-4 alkyl-SO 2, -alkyl-SO 2; C 1-4 alkoxy-carbonyl.

35 If one of the substituents R, R, R ,, R., R, R, R, R and R represents a heteroaryl group, then X λ ó 4 b 7 o L2. This is preferably a thienyl or furyl group which is unsubstituted 88 00243, -Ills or monosubstituted by halogen, nitro, alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms or alkylthio of 1-4 carbon atoms, however, it is preferably unsubstituted.

If one of the substituents represents an optionally substituted phenyl group, this group is preferably unsubstituted.

When R 2 together with R 2 forms an alkylidene group with 1 to 5 carbon atoms, this is preferably a group 10 with 1 to 4, especially with 1 or 2, carbon atoms.

It is recommended that no more than one of the substituents and R 4 be an ether or an optionally substituted phenyl group. It is even more recommended that ring A is unsubstituted by more than one group selected from aromatic hydrocarbon, araliphatic hydrocarbon, or heteroaryl.

If one or more of the substituents V * 7'V * 11'E12'E15'E16'B17'B18 'R19 * "R20 represents a hydrocarbon group, such 2Q hydrocarbon group may be aliphatic, aromatic or araliphatic and suitably contains up to 8 carbon atoms If such a hydrocarbon group is aliphatic, this group preferably contains a maximum of 5 carbon atoms and may be saturated or unsaturated. In the case of unsaturation, this group suitably contains one double or one triple bond. Such a hydrocarbon group is aromatic or araliphatic then its aroamatic ring may be substituted by one or more substituents, which are suitably selected from halogen, alkoxy of 1-4 carbon atoms, and alkyl of 1-4 carbon atoms and CF ^

Each of the substituents R and R denote a haloalkyl group, for example O 7 is a chloroalkyl group and preferably contains 1-4 carbon atoms

If one or more of the substituents R-, R1 (., R._ and R1. Represents an alkyl group with 1-6 carbon atoms, this is preferably an alkyl group with 1-4 carbon atoms, for example the methyl group.

89 00143 - 12 -

Preferably, one of the substituents R -R_ represents an aryl group, this is preferably the 6 phenyl group which is unsubstituted or substituted by 1-3 substituents selected from halogen, alkoxy of 5 1-4 carbon atoms, alkyl of 1-4 carbon atoms and CF ^ r especially preferred that it contains less than 3 substituents.

If one of the substituents R 1, R 6, R 0, R,., R ..,., R, - R "represents an araliphatic hydrocarbon group / o 1 ± ± 2 15 20 10, then this group is preferably a benzyl or α-methylbenzyl group, the phenyl ring of which is unsubstituted or substituted by 1-3, preferably 1 or 2, substituents selected from halogen, alkoxy of 1-4 carbon atoms, alkyl of 1-4 carbon atoms and CF ^ 51 If Ar 'represents a substituted heteroaryl group, such a heteroaryl group may contain 1-3 substituents selected from halogen, CF1, HOalkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms (where two adjacent substituents together form the methylenedioxy-20 group), C 1 -alkyl-S, C 1-6 -alkyl-S-C 2 -alkyl, C 1 -alkyl-SO 2 and benzyl. The alkyl groups in such substituents preferably contain 1 or 2, especially 1, carbon atom.

Ar 'is preferably a substituted heteroaryl group.

Recommended meanings of Ar 'include substituted thienyl, pyrazolyl, isothiazolyl, 1,2,3-thiadiazolyl, pyridyl, pyrazinyl, and pyrimidinyl, especially substituted thienyl, pyrazolyl, pyrimidinyl, and pyridyl, and especially substituted pyrazolyl, pyrimidinyl, and pyridyl.

Preferably, one substituent of Ar 'is present in the ortho position relative to the CO group in which Ar' is bonded and / or methylenedioxy, wherein additional substituents (1 or 2) may be present.

89 0 0 243 .i -13-

Suitable examples of aryl groups substituted by methylene dioxide Ar 'are: 5,6-methylenedioxy-3-pyridyl, 4,5-methylenedioxy-3-pyridyl and 4,5-methylenedioxypyrimidinyl. Recommended examples of orthosubstituents of Ar 'are 5 (except methylenedioxy) NO2, halogen, CN, CF ^, CH ^ -SO ^ and CH3SCH2 ·

Recommended examples of additional substituents are halogen and alkyl of 1-4 carbon atoms when bonding to a ring carbon atom and alkyl of 1-4 carbon atoms, benzyl and C 1-6 alkyl-thio-C 1-6 alkyl when bonding to a ring nitrogen atom.

Specially recommended meanings of Ar1 include 1-CH 3 ~ 4-NC> 2-pyrazol-5-yl and 1-CH 2 -é-NO 2 -pyrazol-3-yl.

Ar 'represents a substituted pyridyl group, this is preferably the 3,5-dichloro-2-pyridyl group.

When A 1 is a methylene or ethylene group substituted by one or more alkyl groups of 1 to 5 carbon atoms, such alkyl substituents preferably contain up to 4 carbon atoms and are especially methyl.

If R23 represents an alkoxy group with 1-6 carbon atoms or an alkylthio group with 1-6 carbon atoms, such a group suitably contains 1-4, preferably 1, carbon atom.

If one or more of the substituents R 21, R 22 and R 23 is a ylsulfonyl group with 1-6 carbon atoms, such a group suitably contains 1-4, preferably 1, carbon atom.

R22 is preferably in the p-position and R23 is preferably in the ortho-position relative to the carbonyl group.

R22 is preferably a hydrogen or halogen atom (fluorine, chlorine or bromine), alkyl-S, C3-alkyl-SC> 2 or together with R forms the methylenedioxy group.

R23 is preferably a hydrogen or halogen atom or the methyl group.

It is recommended that R23 be a halogen atom (e.g. Cl), CF, NO, CN, or CH 2 -SO-.

8900243.

- 14 -

Examples of recommended groups CR1R2-A2 Include: CR1R2 'CR1R2-CH2' ^ 1 ^ 2_CH (CH3 ^ 'CR1R2 ~ C (CH3} 2' CR1R2 ~ C0 'CRxR2 “°' <" R1R2 ™ CRCP3 'CR1R2 ~ CH2 ~ CH2 cr1r2_CH (CH3} ~ CH (CH3) and C (R2) = CH.

It is recommended that R 1 vinyl, allyl, propargyl, cyclopropyl, optionally substituted phenyl, furyl or thionyl, CH 2 OH; CH (OH) CH3; CH CH2OH ^ represents the (A ^) nX 'group, in which A ^ and n have the previously defined meanings and X' has one meaning defined for X, with the exception of hydrogen, or together with R2 oxo, CH2 or CH-CH3 group or together with R is a bond. In addition, R 1 preferably represents an alkyl group of 1 to 4 carbon atoms, in particular a methyl or ethyl group, especially the methyl group, if Y has a meaning other than the optionally substituted phenyl or pyrimidinyl group.

When R ^ represents an (A ^) X 'group, then A is preferably CH2 or (CH2) 2, optionally substituted by 1 or 2 methyl groups.

If A 1 represents a methylene or ethylene group substituted by one or more alkyl groups of 1 to 5 carbon atoms, such alkyl substituents preferably contain up to 4 carbon atoms and are especially the methyl group.

Examples of recommended groups X 'are alkylthio of 1-4 carbon atoms, phenylthio, alkoxy of 1-4 carbon atoms, phenoxy, CHO, alkanoyl of 2-5 carbon atoms, hydroxyl and esters thereof with a C 1-4 aliphatic carboxylic acid 2-5 or with optionally substituted benzoic acid, C-carbalkoxy-2-5 CH2 'C2 -C5 Carba - koxii'-CH ^ CH3 Cyan, F, Cl, CHF2, CF3, NO3, CONH2, CO-NHCC alkyl), diCC ^ alkyDN or benzyl, especially alkylthio with 1-4 carbon atoms.

(A ^) X1 is preferably an alkylthio group of 1-4 carbon atoms.

Examples of recommended groups R 2, R 3 and R 3 are hydrogen, alkyl of 1-4 carbon atoms, 8900243, 5-15 alkoxy of 1-4 carbon atoms, alkylthio of 1-4 carbon atoms, OH, C. alkyl-CO-O , C „_carbalkoxy, thienyl and furyl, especially 1—4 2 *“ 5 H, CH, OCH, SCH, OH, CH CO-O and COOCH, in particular • 3 y O <3 H or CH3-5 A “ is preferably CR, _RT_ or 0.

2 16 17

Examples of recommended meanings of R are hydrogen, alkyl of 1-4 carbon atoms, optionally 16 substituted phenyl or benzyl, thienyl, furyl, carboxyl (in acid, salt or esterified form) and as indicated above, together with R ^ a bond, preferably a hydrogen atom or the methyl group, especially hydrogen.

Examples of recommended meanings of R 7 7 are hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkyl of C 3 to 3 alkylthio-C 1 to 3 and CF 1, especially hydrogen , SCH3, methyl and CF4, especially hydrogen or the trifluoromethyl group.

R18 and R19 independently of one another prefer hydrogen or an alkyl group of 1-4 carbon atoms, especially a hydrogen atom or the methyl group.

Specially recommended compounds of formula I have one or more of the following characteristics: R 1 is H, CH 3, SCH 3, S (O) CH 3, SC 1 CH 3 phenyl or phenyl monosubstituted by alkyl of 1-4 carbon atoms, alkoxy with 1-4 carbon atoms, halogen or CF3 or is alkenyl or alkynyl with up to 4 carbon atoms, R ^, R3 and R ^ are independently hydrogen or the methyl group, one of the substituents RR ^ and R ^ also being SCH3, S (0 ) CH 3 or SO 2 CH 3, provided that only one of the substituents R 1 -R 1 SCH 3 represents S (O) CH 3 or SQ 1 CH 3.

A2 is CH {CF3), CH2 or 0.

Y is 3,5-dichloro-2-pyridyl, 1-CH3 ~ 4-NO2-pyrazol-5-yl, 1-CH3-4-NO2-pyrazol-3-yl or phenyl substituted by R, R and R, wherein said phenyl substituents have bJL tob relative to the aforementioned recommended meanings.

Examples of such specially recommended compounds of formula I include: 89 00143.

- 16 -

Compounds of formula I, wherein R 1 is SCH, S (O) CH or SO, CH 2; R ', R' and R, independently 1 3 323234, are H or CH 2? is CH ^, 0 or CH (CF ^) and Y is 3,5-dichloro-2-pyridyl, 1-CH ^ -4-NO2-pyrazol-5-yl, -1-01 ^ -4 ^ 5 NO2 " pyrazol-3-yl or phenyl substituted by R 1, R 2 and R 2.

23

Compounds of formula I wherein R ^ is SCH ^, S (O) CH ^ or SO ^ CH ^; R ^, Ren R ^ are independently H or CH ^; A2 is CH (CF ^) or 0; Y is phenyl substituted by R 1, R 22 and R 23 * 15

Compounds of formula I in which R ^ represents an alkenyl or alkynyl group with up to 4 carbon atoms, R, R ^ and R ^, independently of one another, are H, CH, SCH, S (0) CH or S0 CH, provided only one of The substituents R 2 ~ R 6 are selected from the group consisting of 3

from SCH3, S (O) CH3 and SC ^ CH; A2 is CH2, O or CH (CF3) and Y

3,5-dichloro-2-pyridyl, 1-CH3-4-NO-pyrazol-5-yl, 1-CH3-4-NO2-pyrazol-3-yl or phenyl is substituted by R 2, R 22 and R 4.

Compounds of formula I wherein R ^ is a phenyl group or a phenyl group monosubstituted by alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms, halogen or CF3, R2, R3 and R4 independently of one another, a hydrogen atom or the methyl group , A2 CH {CF3), represents 30 CH or 0 and Y is 3,5-dichloro-2-pyrid / 1,1-CH-2-4-NO-pyrazol-5-yl, 1-CH -4-NO -pyrazole — 3-yl or phenyl substituted by R, R and R, most preferably phenyl substituted by R21, R22 and R23 *

The compounds of formula II, which are used as starting materials, can be obtained in a manner known per se.

Many compounds of formula Ha, which are also in their tautomeric form of formula Ilb, can be 8900243.

- occurrences (see A on the formula sheet), in which n, A, AX, R ^, and R ^ have the meanings defined above, are conveniently obtained by γ-substitution of dianions of the β-dicarbonyl compounds of formula V, 5 wherein AR ^, R ^ and R4 have previously defined meanings, using electrophilic agents suitable for entering an (A ^) nX group.

Electrophilic agents suitable for introducing (A ^) nX group by γ-substitution of dianions of the β-dicarbonyl compounds of formula V are known from the literature. Their nature will depend on the meaning of (A ^ JnX.

Suitable electrophilic agents are, for example, for γ-substitution: 15 - by Cl: Cl C-CC1 or N-Cl succinimide - by Br: Br ^ - by S-hydrocarbon: disulfides, such as alkyl-SS-alkyl and phenyl-SS- phenyl - by SH: sulfur 20 - by OH: 0 ^ - by COOH: carbon dioxide - by C (OH) RR '(e.g. C (0H) (phenyl) ^): aldehydes or ketones (such as phenyl) CO) by carbonyl addition 2 - by NO 2: isopentyl nitrate 25 - by an aliphatic or araliphatic hydrocarbon: the corresponding hydrocarbon halides.

If desired, imported functional groups can be converted into other functional groups in a manner known per se.

Compounds of formula II in which R1 and R1 together form a bond can be obtained by dehydrohalogenation of corresponding halogenated compounds. Thus, the compounds of formula II obtained in this way can also be used in an addition reaction with, for example, methanol, acetic acid and z., To obtain 89 00 243.

t - 18 - saturated Compounds of formula II substituted by, for example, methoxy, acetoxy, etc.

Many compounds of formula V can be cyclized, using the Dieckmann condensation reaction, see b

Examples of reaction schemes with which it is possible to prepare compounds of formula VI are reaction schemes C, D, E and F shown on the formula sheet.

Compounds of formula II, which represents the vinyl group, can be obtained, for example, by dehydration, conveniently via the tosylate, from the corresponding compound of formula II, wherein R 1 represents the CH 2 CH 2 OH group.

Such vinyl compounds can be converted to the corresponding cyclopropyl compounds, for example, according to Simmon / Smith using Zn / CI ^^

Compounds of formula II in which R1 and RJ together form the CH2 group can be obtained by reacting the corresponding compounds of formula II in which R1 and R2 represent a hydrogen atom in dianion form with CICH ^ SCH, S-oxidation of the obtained compound of formula II in which R 1 represents the CH 2 SCH group and conversion of this CH 2 S (O) CH group into the CH 2 group.

Compounds of formula II in which R 1 and R 2 together form a C 2 alkylidene group are obtained by reacting the corresponding compound of formula II, wherein R 1 and R 2 are hydrogen in dianion form with an aliphatic aldehyde of 2-5 carbon atoms or ketone with 3-5 carbon atoms, followed by dehydration of the alcohol thus obtained.

It will be appreciated that the choice of the appropriate reaction pathway and the most suitable sequence of the reaction steps necessary to prepare the compounds of formula II will depend to a great extent on the desired combination of substituents. Such a choice can easily be made by an experienced chemist.

89 00 243 / - 19 -

Insofar as the preparation of the starting materials has not been described, such materials are known, or, if they are new, can be prepared according to methods analogous to the methods described herein or known methods.

The compounds of the formula I, in free acid form or in the form of an ether, ester or salt form acceptable for agricultural purposes, exhibit an interesting broad spectrum herbicide activity. They offer valuable alternatives to known dion herbicides in terms of, for example, their interesting crop safety and / or environmental acceptability (as a result of, for example, optimal soil mobility).

The invention therefore also relates to a method of controlling weeds, which method comprises applying a herbicidally effective amount of a compound of formula I in free form and / or in the form of a salt form acceptable for agricultural purposes in an area where weeds are growing.

// 20 The action before and after hatching can be carried out in tests in greenhouses with dosages to be tested equivalent to administration amounts of 0.33; 1.0 and 3 kg per ha are detected. The amount of the compound of the formula I to be used will depend on the special weeds to be controlled, the compound used, the method of administration thereof, the conditions of the treatment, etc. The appropriate administration amount can be determined according to routine determinations carried out by experts in the field. , or by comparing the action of the desired compound of Formula 30 I with standards for which the amount of administration is known, for example, from tests in greenhouses.

In general, however, satisfactory results are obtained when a compound of formula I is used in an amount ranging from about 0.03 to 3.0 kg per hectare of plant area. Many compounds of formula I exhibit an interesting selective herbicidal activity within this range. For example, the compound exhibits 2.82 (hereinafter 8900243.

t-20 - following table A) excellent selectivity for soybeans and very good control broad-leaved weeds, especially if they are applied at about 1 to 2 kg per ha after emergence.

The compounds of formula I can and preferably are used as herbicidal preparations together with diluent (s) acceptable for agricultural purposes. Suitable formulations contain 0.01-99% by weight of active ingredient, 0-20% surfactant and 1-99% solid or liquid diluent (s). Larger surfactant to active ingredient ratios are sometimes desirable and are achieved by incorporating the surfactant ingredient into the composition or by mixing in a tank. Usage forms of a preparation generally contain 0.01-25% by weight of active ingredient. Lower or higher levels of active ingredient may of course be present depending on the intended use, the physical properties of the compound and the mode of administration. Concentrated forms of a composition to be diluted before use generally contain between 2 and 90% by weight, preferably between 10 and 80% by weight, of the active ingredient.

Useful preparations of the compounds of formula I include powders, granules, concentrated suspensions, wettable powders, emulsifiable,. concentrated preparations, liquid preparations, etc. They are obtained in a usual manner, for example by mixing a compound of formula I with the diluent (s) and, if desired, with other ingredients.

It is also possible to use the compounds of formula I in a microencapsulated form.

Additives acceptable for agricultural purposes can be used in the herbicidal compositions to enhance the activity of the active ingredient and to reduce, for example, foaming, caking, and corrosion.

The term "surfactant" used herein refers to a material acceptable for agricultural purposes which imparts emulsifiability, spreading, wetting, 89 00243, - 21 - dispersibility or other surface modifying properties. Examples of surfactants are sodium lignin sulfonate and lauryl sulfate.

The designation "diluent" used herein denotes a liquid or solid, acceptable for agricultural purposes, material used to dilute a concentrated material to a useful or desired strength. For powders or granules, it may be, for example, talc, kaolin or diatomaceous earth, for liquid concentrated forms, for example, a hydrocarbon, such as xylene, or an alcohol, such as isopropanol, and for liquid applications, such as water or diesel oil.

The compositions of this invention may also contain other compounds with a biological activity, for example compounds with a corresponding or complementary herbicidal activity or compounds with an antidotal, fungicidal or insecticidal activity.

The following examples are provided to illustrate the practice of the invention. The 20 parts and percentages are parts by weight and percentages by weight, respectively.

Herbicidal preparations

Example A; wettable powder 25 parts of a compound of formula I, for example the compound of Example 1 below, were mixed and comminuted with 25 parts of synthetic fine silica, 2 parts of sodium lauryl sulfate, 3 parts of sodium lignin sulfonate and 45 parts of finely divided kaolin. average particle size was about 5 microns.

Example B: concentrated emulsion 35

25 parts of a compound of formula I, for example the compound of Example 1 below, were intimately mixed, 25 parts of xylene, 15 parts of 8900243.

* - 22 - dimethylformamide and 10 parts emulsifier until a homogeneous solution was obtained.

Herbicidal research 5 Research example 1; treatment before hatching.

Seed pots were filled with a substrate equivalent to sandy loam. In each pot, seeds of Abutilon theophrasti (hereinafter At), Amaranthus 10 retroflexus (Ar), Sinapis alba (Sa), Solanum nigrum (Sn,

Bromus tectorum (Bt), Setaria viridis (Sv), Avena fatua (Af),

Sow Echinochloa crus-galli (Ec).

Then the material of formula I to be tested was in an amount corresponding to 0.25; 15 1 and / or 4 kg of active ingredient per ha. using a volume to be applied corresponding to 10001 per ha (sprayed with an aqueous liquid to be tested, for example formulated according to example B). Then the seeds were covered with a thin layer (about 0.5 cm) of substrate. 20 0

The pots were kept at room temperature (30-24 ° C) for 21 days with 14-17 hours of light (daylight or equivalent) per day.

The herbicidal activity was tested after the 21 day period. This assay involved visual assessment of the extent and quality of damage inflicted on different seeded plants.

A herbicidal action was observed.

Examine example 2: post-hatch treatment.

A procedure analogous to that used in study Example 1 was followed, except that the test compounds were applied when the plants were in the 2-4 leaf stage. The other experimental conditions (amount to be used, volume used, temperature, light) and evaluation method (21 days after application) were those as stated in study Example S900243.

- 23 -

A herbicidal action was observed.

Research example 3

Corresponding tests as described in Study Examples 1 and 2 were performed with a selection of compounds of formula I on various monocotyledonous and dicotyledonous weeds selected from the broadleaf weed species Abutilon theophrasti, Capsella bursa pastoris, Cassia obtusifolia, Chenopodium album. Datura stramonium, Calium aparine, Ipomoea purpurea, Polygonum 10 pensylvanicum, Portulaca oleracea, Senecio vulgaris, Sida spinosa,

Solanum nigrum, Stellaria media, Xanthium strumarium, the grassy weed species Agropyron repens, Cyperus rotundus, Alopecurus myosuroides, Apera spica-venti, Avena fatua, Brachiaria plantaginea, Bromus tectorum, Digitaria sanguinalis, Echinochloa crus-galli, 15 Panlorlorum Setaria faberi and Sorghum halepense and crops such as the broadleaf washed cotton, soybeans, sugar beets, sunflowers and the grassy crops of rice, maize (Zea maize) and milo 2 colored sorghum, using different concentrations of the liquid to be investigated, the concentrations being so selected that the desired amounts to be administered (generally corresponding to application ratios of 0.11; 0.33 and 1.0 kg of compound of formula 1 per ha) were obtained. The applied volume corresponds to 600 l per ha.

The evaluation took place 28 days after the administration. A herbicidal action was observed in the application range of 30-1000 g per ha.

A particularly interesting herbicidal activity has been observed, inter alia, in the following group of compounds of formula I;

Compounds of formula Ib, wherein A ^ = CH ^, represents a phenyl group or a substituted phenyl group (preferably phenyl, 2-F-phenyl or 4-F-phenyl), R ^ -R ^, independently, of a hydrogen atom or represent the methyl group and Y represents a phenyl group substituted by ^ 21 'K22 and ^ 23 as the beer denoted compounds 8900243.

- 24 - 2.82, 2.88 and 2.89.

Compounds of formula Ib, wherein A2 is CH (CF ^) and R ^ -R, independently, represent a hydrogen atom or the methyl group, for example compounds of formula Ib, wherein A2 = CH (CF ^), R - R ^ represent a hydrogen atom or the methyl group and Y is a phenyl group substituted by R, R and R, such as the compounds J. & quot. 4 * 3 2-177, 2-192, 2-195 and 2-248 listed below.

Compounds of formula Ib, wherein 10 y is a substituted. pyrazolyl group (especially 1-CH2-4-NO2-pyrazol-5-yl or 1-CH2-4-NO2 "represents pyrazol-3-yl ^ and A2 = CH2 or O, including such compounds wherein R ^ -R ^ , independently, represent a hydrogen atom or the methyl group, and esters or salts thereof, such as compounds 2-165, 2-167, 2-169, 2-172, 2-173, 2-174, 8-21 , 9-1 and 9-2.

Compounds of formula Ib, wherein --- A ^ is C (C1) = C (0) and A is CH2, including such compounds wherein Y is a phenyl group substituted by R1, R22 and R23 and R -R, independently of each other, a hydrogen atom or the methyl group, such as compounds 10.1 and 10.2 mentioned below.

Compounds of formula If, wherein A2 = CH, including such compounds wherein Y represents a phenyl group substituted by R, R22 and ^ 23: el't: and wherein R ^ independently represents a hydrogen atom or the methyl group, such as compound 2-156.

Test Results 1 The values in the following Table I illustrate the herbicidal activity of a selection of compounds of formula I, tested according to the above test Examples 1 and 2 at an amount used corresponding to 1 kg per ha.

The evaluation of the herbicidal activity was performed on a decimal scale, 1 corresponding to 0-10% and 10 corresponding to 90-100% herbicidal activity.

8900243- - 25 -

Before - After emergence After emergence bond „„ _At Ar Sa Sn Bt Sv Af __ Ec At Ar SA Sn Bt fiv Af En 2.1 9 10 10 10 10 10 10 10 10 9 9 9 9 10 9 9 8 5 2.5 10 10 9 9 5 7 1 9 8 6 9 10 1 1 1 8 2.9 10 10 9 10 4 10 1 10 9 10 10 10 4 8 6 9 2.15 10 10 9 10 9 10 7 9 9 8 8 9 6 7 7 8 2.24 10 10 8 10 4 9 499 9991193 2.65 10 10 10 10 10 9 7 10 8 7 7 10 5 5 6 8 10 2.82 10 10 10 10 1 9 2 9 10 8 10 9 1 3 6 9 2.84 999 9 111199991118 2.85 959911119999311 8 2,168 10 10 9 10 8 9 1 9 9 9 9 9 8 8 1 9 2,170 10 10- 196919999 9 '1417 15 2,171 10 9S 8 10 1 8 1 8 9 9 9 10 10 9 8 9 2,172 10 93 10 491998794436 2,173 10 10 10 10 10 10 4 10 9 9 9 10 10 9 9 9 2,174 10 10 6 10 8 9 1 9 9 9 9 9 9 8 8 9 2,203 98 8 839 199 8 991119 2Q 2,204 10 98949 1 994993318 8.21 10 10 10 91519988911 1 4

Research results 2

The values in the following Table II illustrate the herbicidal activity of a solution of compounds of formula I tested according to the previous study. Example 3 with the amount and time used (before or after emergence) specified in said table. As in Table I, the rating is expressed on a decimal scale.

30 8900243, - 26 -

The following abbreviations are shown in Table II

used:

5 for Abutilon theophrasti ABUTH Agropyron repens AGRRE

Capsella bursa pastoris CAPBP Cyperus rotundus CYPRO

Cassia obtusiflolia CASOB Alopecurus myosuroides ALOMY

Chenopodium album CHEAL Apera spica-venti AGSSV

Datura stramonium DATST Avena fatua AVEFA

10 Galium aparine GALAP Brachiaria plantaginea BRAPL

Ipomoea purpurea IPOMO Bromus tectorum BROTE

Polygonium pensylvanicum POLPY Digitaris sanguinalis DIGSA

Portulaca oleracea POROL Echinochloa crus-galli ECHCG

Senecio vulgaris SENVU Panicum dichotomiflorum PANDI

Sida spinosa SIDSP Poa annua POAAN

Solanum nigrum SOLNI Setaria fab «» ri SETFA

Stellaria media STEME Sorghum halepense SORHA

Xanthium goiter XANSP Echinochloa crus-galli wet ECHvet

Soybeans soybea 20 sugar beets sugarb sunflowers sunflo application before emergence pre 25 application after emergence po 30 89 00243.

-27 -

Table II

ff

Herbicide action Time - applies pre po po pre po po pre po pre po

Amount used 0.33 0> 33 1 0 ^ 3 1 1 1 1 1 1

Compound No. 2.1 2.1 2.82 11 11 2 ^ 203 2 ^ 173 2.173 1, 174 2y175

Investigated plants ABUTH 10 10 10 10 10 10 10 10 10 10 CAPBP 10 10 10 9 10 10 10 10 10 10 CASÖB 175 6 64 1 7 2 8 CHEAL 10 10 9 10 10 9 10 10 10 10 DATE 10 10 10 10 4 10 10 10 9 10 GALAP 4 5 6 10 10 5 7 9 6 9 ΙΡ0Μ0 67 10 10 86 5 9 6 9 POLPY 10 10 10 10 10 10 10 10 10 10 P0R0L 10 10 10 10 6 10 10 10 10 10 SENVU 10 10 10 10 10 10 10 10 10 10 SIDSP 10 9 9 10 10 8 9 6 10 10 S0LNI 10 10 10 10 10 10 10 10 10 10 STEHE 10 10 9 8 8 10 10 10 10 10 XANSP - -9 10 10 8 cotton 1 3 5 8 8 4 3 5 4 4 soybeans 5902 64 8 10 7 7 sugarb 10 10 10 10 10 10 10 10 10 10 sunflo 6 7 6 - - 2 7 9 7 9 AGRRE 93 - 10 81 8 1 2 1 CYPR0 916 - - 2 10 5 10 3 AL0HY 8318 10 0 8 3 5 2 AGSSV 10 9 3 10 4 2 10 10 10 9 AVEFA 8716 40 7 4 4 1 BRAPL 10 8 6 10 10 3 10 9 10 10 BR0TE 10 704 6 1 9 9 6 1 DIGSA 10 10 9 10 10 8 10 10 10 10 ECHCG 10 · 7 6 10 8 3 10 6 10 9 PANDI 10 10 1 10 10 2 10 9 7 9 83 00 243.

- 28 - POAAN 941 10 819 9 3 ι SETFA 10 10 1 4 8 2 10 9 7 a SORHA 10 10 1 4 10 2 6 9 6 4 ECHvet 10 10 9 - - 10 10 10 10 10 5 rice 10 10 5 2 8 1 10 10 '10 10 corn 6102603 0 1 1 wheat 8104206 1 5 l mil ° 98 2 4 52 10 710 2 10

Finished products

Example 1; 2 - [(4-Chloro-2-nitro) benzoyl] -4,4,6-trimethyl-6-methylthio-1,3-cyclohexanedione.

15

8.07 g (0.021 mol) of 3- [4-chloro-2-nitro) benzoyloxy] -4,4,6-trimethyl-6-methylthio-2-cyclohexen-1-one were dissolved in the warm (45 ° C) mixture of 3.5 ml (0.025 mol) of triethylamine, 0.4 ml of acetone cyanohydrin and 60 ml of dry acetonitrile.

After stirring at room temperature for 3 hours, the reaction solution was diluted with 200 ml diethyl ether, washed successively with 35 ml 10% hydrochloric acid and 150 ml water and dried over anhydrous sodium sulfate.

The residue which remained after the solvents had been rotary evaporated was chromatographed on a column of silica gel. Elution with a mixture of equal parts of hexane and diethyl ether gave the analytically pure title compound, mp 111-112 ° C.

9 900 243, - 29 - Example 2.

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Table A: the compounds of formula

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Example 3: 2- (2-Nitrobenzoyl) -4-phenoxy-1,3-cyclohexanedione

A mixture of 4.1 g (0.02 mol) of 4-phenoxy-1,3-cyclohexanedione, 3.7 g (0.02 mol) of 2-nitro-5-benzoyl chloride, 2.0 g (0.02) was stirred mol) triethylamine and 60 ml of toluene under reflux for 1 hour. The mixture was then cooled and 200 ml of ether was added. The precipitated triethylamine hydrochloride was filtered off and washed with ether. The filtrate was successively extracted with 10 ml of 2N hydrochloric acid, 20 ml of water, 10 ml of a 2N solution of sodium hydroxide and 50 ml of water. The organic layer was dried over magnesium sulfate. Evaporation of the ether under reduced pressure at 30 ° C left a toluene solution of the intermediate, which was rearranged by adding 1 g (0.012 mole) of acetone cyanohydrin and 2 g (0.02 mole) of triethylamine and stirring at room temperature for 3 hours .

The reaction mixture was dissolved in 200 ml of ether and extracted successively with 15 ml of 2N hydrochloric acid, 20 ml of water, 20 ml of a 2 N sodium hydroxide solution and 50 ml of water. The last two aqueous extracts were combined, washed with ether and then, with stirring, acidified with 30 ml of 2N hydrochloric acid. After 30 min, the precipitate was aspirated and washed with methanol to give 2.8 g of a white powder, mp 109-115 ° C. Recrystallization from ethanol gave 1.7 g of crystals of the title compound with a melting point of 115-116 ° C.

Example 4

Analogous to the method of Example 30, the compounds of Tables A, B, C and D above were obtained from the corresponding compounds of formulas II and III, without isolation of the esters of formula IV.

Example 5: 35 2- (2,4-Dichlorobenzoyl) -3-methoxy-4-allyl-4,6,6-trimethyl-2-cyclohexen-1-one -

3.67 g (0.01 mol) of 2 - [(2,4-dichloro) benzoyl] -4-allyl-4,6,6-trimethyl-1,3-cyclohexanedione 8800243 were dissolved.

- 47 - in 10 ml of a 0.1 N sodium hydroxide solution and then treat the resulting sodium salt solution with 1.7 g {0.01 mol) of silver nitrate in 10 ml of water.

The precipitate of the silver salt 5 formed was diluted with 10 ml of water, filtered with suction and dried in a volume desiccator over phosphorus pentoxide.

The dry silver salt thus obtained was suspended in 100 ml dry diethyl ether and treated with 1 ml {0.016 mol) methyl iodide.

After a reflux period of 3 hours, the reaction mixture was allowed to cool to ambient temperature and filtered.

Rotary evaporation of the filtrate gave the crude title compound as a pale yellow viscous oil which was purified by chromatography on a silica gel column (elution with a mixture of diethyl ether and hexane 1: 5).

Example 6: 2 - [(2-Chloro-4-methyisulfonyl) benzoyl] -3-acetoxy-4-methylthio-4,6,6-trimethyl-2-cyclohexen-1-one.

To a well stirred solution of 4.87 g (0.0117 mol) 2 - [(2-chloro-4-methylsulfonyl) benzayl] -4-methylthio-4,6,6-trimethyl-1,3-cyclohexanedione was added in 25 ml of dry dimethylformamide add 0.35 g (0.0117 mol) of sodium hydride (80% dispersion in mineral oil) at once.

After the exothermic (42 ° C) reaction had ceased, the resulting sodium salt solution was stirred for an additional hour at room temperature and then treated.

with 0.93 ml (0.013 mol of 1 acetyl chloride.) After a reaction period of 18 hours at room temperature, 300 ml of water were added.

The precipitated light yellow enol acetate was filtered off under suction, washed with water, well drained and dried at 60 ° C.

35

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By elution with a mixture of diethyl ether and hexane (4: 1) 8300243 /

V

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5 Example 7

Analogous to the procedure of Example 5, using the corresponding starting materials of formula Ib and a compound R1 ', the following cl compounds of formula Ia were obtained: Table E.

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Example 9: Preparation of an ammonium salt of 2 - [(2-nitro-4-chloro) -benzoyl] -4-methylthio-4-methyl-1,3-cyclohexanedlon.

A solution of 0.96 g (0.0056 mol) of 5 l- (methylaminomethyl) -naphthalene in 10 ml of methylene chloride was added to a suspension of 2.0 g (0.0056 mol) 2- [(2-nitro-4 -chloro-benzoyl] -4-methylthio-4-methyl-1,3-cyclohexanedione in 30 ml of methylene chloride. After 1 hour, the solvent was evaporated and the resulting solid residue was dried under reduced pressure at 10 ° C to 40 ° C, whereby 2.95 g of the salt were obtained as yellow crystals having a melting point of 75-80 ° C.

Analogous to the procedure of Example 9: 9.1 - the triethylammonium salt of 2- (1-methyl-4-NO2-pyrazol-5-oyl) -1,3-cyclohexanedione, mp: 87-99 C and 9.2 - the triethylammonium salt of 2- (1-methyl-4-NO2-pyrazol-5-oyl) -4,4,6,6-tetramethyl-1,3-cyclohexanedione, mp: 144-145 ° C.

20

Example 10: 2-Chloro-2 - [(2-nitro-4-chloro) benzoyl] - 5,5-dimethyl-1,3-cyclohexanedione

A mixture of 3.25 g (0.01 mole) of 2 - [(2-nitro-4-chloro) benzoyl] -5,5-dimethyl-1,3-cyclohexanedione and 1.3 g (0.15 g) was boiled. 01 mol) N-chlorosuccinimide in 40 ml of methylene chloride under reflux for 2 days. The solvent was then evaporated. Diethyl ether was added to the residue and the undissolved material was filtered off (0.5 g crystals of succinimide, mp: 123-125 ° C). The filtrate was evaporated on a rotary evaporator and the resulting product was chromatographed on a silica gel column with a mixture of cyclohexane and ethyl acetate (8: 2) to give the title compound as yellow crystals, m.p. 135-138 ° C. were obtained.

Analogous to the procedure of Example 10, using the desired 2-aroyl-1,3-cyclic 89 00243. - 54 - dione and N-chlorosuccinimide, the following compounds are obtained: 10.1 - 2-chloro-2- (4-chloro-2-nitrobenzoyl) -4,4,6-trimethyl-1,3-cyclohexanedione, m.p .: 77-78 C and 10.2 - 2-chloro-2- (4-chloro-2-nitrobenzoyl) -4,4,6,6-tetramethyl-5 o 1.3-cyclohexanedione, M.p .: 87-99 C.

Example 11 2- (4-Chloro-2-nitrobenzoyl) -1,3-cycloheptanedione.

10

To a solution of 5.95 g of cycloheptane-1,3-dione (0.472 mole) in 50 ml of CH2 Cl2 in one portion was first added 9.51 g (0.472 mole) of 4-chloro-2-nitrobenzoic acid, then 6.21 g (1.3 eq) of triethylamine were added dropwise.

The reaction mixture was then stirred for 2 hours at room temperature, diluted with CH and washed with water (30 ml). The nearly pure enol ester 3- (4-chloro-2-nitrobenzoyl-oxy) -2-cycloheptic-1-one was obtained by evaporation.

14.62 g (0.0472 mol) of the said enol ester were dissolved in 50 ml of acetonitrile and 9.55 g of triethylamine were added in one portion.

1.5 ml of acetone cyanohydrin was then added via a syringe and the mixture was stirred overnight at room temperature. The acetonitrile was removed under reduced pressure and the residue was dissolved in diethyl ether.

25

The solution was washed with 2N hydrochloric acid, separated, dried over magnesium sulfate and evaporated to give a residue which was chromatographed to give the title compound, mp 112 ° C.

Example 12 2 - [(2-Nitro-4-chloro) benzoyl] -4-chloromethylthio-4-methyl-1,3-cyclohexanedione 35 A mixture of 3.6 g (0.01 mol) 2 - [(2— nitro-4-chloro-benzoyl] -4-methylthio-4-methyl-1,3-cyclohexanedione and 1.3 g (0.01 mol) of N-chlorosuccinimide in 50 ml of methylene chloride 3900243.

55 was heated under reflux for 5 days. The solvent was evaporated and the residue was chromatographed on a silica gel column using methylene chloride to afford the title compound as yellow crystals, mp 143-144 ° C.

Intermediates (compounds of formula IV)

Example 13 10 3 - [(4-Chloro-2-nitro) benzoyloxy] -4,4,6-trimethyl-6-methylthio-2-cyclohexen-1-one:, o

At 5 ° C, 6 ml (0.043 mol) of dry triethylamine were added dropwise to a well-stirred, cooled solution of 7.05 g (0.032 mol) of 4-chloro-2-nitrobenzoyl chloride and 6.4 g (0.032 mol) of 4 for 5 min. methylthio-4,6,6-trimethyl-1,3-cyclohexanedione in 70 ml dry methylene chloride.

Once everything was added, the ice bath was removed. The temperature of the reaction mixture was then allowed to rise to ambient temperature, the reaction mixture was kept at this temperature for 3 hours and then treated with 150 ml of water. The organic phase was separated, washed successively with 100 ml of 2N hydrochloric acid, 150 ml of water, 100 ml of a 5% potassium carbonate solution and 150 ml of a sodium chloride solution and then dried over anhydrous sodium sulfate.

Removal of the solvent left a viscous oil, which quickly solidified to a crystalline mass. Treatment of this mass with hexane 30 gave the analytically pure enol ester, m.p. 120-122 ° C.

Example 14

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Example 15

Analogous to the procedure of Example 13, using the corresponding starting materials of formulas II and III, the following compounds of formula IV were obtained: Table H.

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- 63 -

Example 16: 4-Methylthio-4,6,6-trimethyl-1,3-cyclohexanedione

In a dry nitrogen atmosphere, 300 ml of a 1.6 M solution of n-butyl lithium in hexane (0.48 mol) was added dropwise with stirring at a rate of 48.5 g (0.48 mol) of diisopropylamine in 420 ml tetrahydrofuran (THF, o dried over a 4 A molecular sieve), that the temperature o did not exceed -68 C. Once everything was added, the reaction mixture (containing lithium diisopropylamide) was stirred for another 30 min at -70 ° C and then at the same temperature, treated with a solution of 30.9 g (0.2 mol) of 4,4,6-trimethyl-1,3-cyclohexanedione in 200 ml of dry tetrahydrofuran.

Once all the dione had been added, the reaction solution was kept at -70 ° C for a further 30 min.

Finally, the solution of 45.2 g (0.48 mol) of dimethyl disulfide in 150 ml of dry tetrahydrofuran was added dropwise at -70 ° C for 15 min.

Then the bath of solid carbon dioxide and acetone was removed, the temperature of the reaction mixture was allowed to rise to -9 ° C and treated with 100 ml of concentrated hydrochloric acid. The residue remaining after rotary evaporation (30 ° C) of the tetrahydrofuran was diluted with 200 ml of water and extracted 2 times with 500 ml of diethyl ether.

25

The combined and dried (sodium sulfate) ethereal extracts were concentrated under reduced pressure to about one third of their volume and the precipitated crystals were filtered off with suction.

Recrystallization from isopropanol 30 gave the analytically pure title dion, m.p. 147 ° C (Rf = 0.24 on silica gel with a mixture of diethyl ether and hexane 2: 1).

Example 17; 4-Methylthio-4-methyl-1,3-cyclohexanedione.

A mixture of 43 g (0.5 mol) of methyl acrylate and 59 g (0.5 mol) of 3-methylthiobutanon-2 was added 8900243.

within 30 minutes, while stirring, to a solution of 100 ml of 5.4 M (0.54 mol) of methanolic sodium methyl ether in 200 ml of dimethyl o-64 sulfoxide. The exothermic reaction was allowed to proceed below 40 ° C. It was then stirred at room temperature overnight. Then, pieces of ice and 60 ml of concentrated hydrochloric acid were added to the reaction mixture, whereby a yellowish precipitate was obtained, which was filtered off and dried at 50 ° C under reduced pressure. The product melts at 120-122 C.

Example 18: 4-Methoxy-4-carbomethoxy-1,3-cyclohexanedione v

A mixture of 58 g (0.358 mol) of dimethyl methoxymalonate and 25 g (0.357 mol) of methyl vinyl ketone was added to a solution of 66 ml of 5.4 ml (0.356 mol) of methanolic sodium methylate in 120 ml of dimethyl sulfoxide with stirring. . The exothermic reaction was allowed to proceed at 35 ° C with cooling with a water bath. After 1 hour, 200 ml of water were added and the mixture was extracted 2 times with methylene chloride. The water layer was acidified with 80 ml of 20% hydrochloric acid and extracted with methylene chloride.

The extract was washed with water, dried over magnesium sulfate and evaporated under reduced pressure to give a viscous oil. This was treated with ether to give o yellow crystals with a melting point of 122-124 ° C.

25

Example 19; 4-Methylthio-6,6-dimethyl-4-cyclohexen-1,3-dione-2Q 5.3 g (0.0169 mol) m-chloroperbenzoic acid (55%), without cooling and in portions, was added to a solution of 2.8 g (0.015 mol) of 4-methylthio-6,6-dimethyl-1,3-cyclohexanedione in 50 ml of methylene chloride. Once all the peracid was added, 1 ml (0.0175 mol) of glacial acetic acid was added and the mixture was refluxed for 18 hours. Then 8960243.

The reaction mixture was allowed to cool to ambient temperature and filtered.

Rotary evaporation of the filtrate gave the title compound as a crystalline mass, which was chromatographed on silica gel (eluting with a mixture of diethyl ether and hexane 3: 1); Rf = 0.28 (over silica gel with diethyl ether), mp .: 163-165 ° C, was purified.

Example 20

Starting from the cyclohexane compound of Example 17, the following compounds were obtained by an addition reaction: 4-methoxy-4-methylthio-6,6-dimethyl-1,3-cyclohexanedione (addition of methanol) - 4-acetoxy-4-methylthio -6,6-dimethyl-1,3-cyclohexanedione (addition of acetic acid)

Example 21

Analogous to the procedure of Example 17, using suitable methyl ketones and carboxylic acid esters as starting materials, the following compounds of formula II were obtained: Table J.

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Example 22

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Example 23 4,4-Dimethyl-6-methylene-1,3-cyclohexanedione (a) and 4,4-Dimethyl-6-methoxymethyl-1,3-cyclohexanedione (b)

The mixture of 26 g (0.2 mol) of the ethyl ester of 2-hydroxymethyl-2-propenoic acid and 17.2 g (0.2 mol) of 3-methyl-2-butanone was added dropwise with stirring at such a rate. solution of 40 ml of 5.4 M methanolic sodium methoxide in 80 ml of dry dimethyl sulfoxide, o that the temperature rose to above 40 ° C. After the addition, the brown reaction solution was stirred for 2 hours at room temperature and then treated with 300 ml of water. The aqueous solution was extracted 2 times with 100 ml CH and the organic extracts were dried over anhydrous sodium sulfate and evaporated under reduced pressure. The crude mixture of the two title compounds obtained was separated by chromatography with a mixture of hexane and diethyl ether as mobile phase: first eluted (a mixture of hexane 2Q and ether 3: 1), the 6-methylene substituted dione a (mp: 144-146 ° C, R £ = 0.35, ether on silica gel), which is the retro Michael reaction product of the 6-hydroxymethyl derivative initially formed. Continued elution of the silica gel column (hexane-ether 2: 1) provided the 6-methoxyethyl-substituted cyclohexanedione 25b, m.p. 108-110 ° C (Rf = 0.24, ether over silica gel).

Example 24 4-Methyl-5-trifluoromethyl-1,3-cyclohexanedione.

A mixture of 7.2 g (0.1 mol) of 2-butanone and 16.8 g (0.1 mol) of ethyl (3- (trifluoromethyl) -acrylate) was added dropwise to a solution of 2 while stirring. .7 g of sodium dissolved in 20 ml of methanol and 60 ml of dry xylene The reaction mixture was then refluxed for 3 hours and evaporated to dryness The residue was dissolved in 50 ml of water and treated with concentrated hydrochloric acid The precipitated crystals were filtered off with suction, washed with o water and diethyl ether and dried, mp .: 122-128 C.

83 00243.

- 75 -

Analogous to the procedure of Example 24, 5-trifluoromethyl-1,3-cyclohexanedione, m.p .: 143-144 ° C and 4,4-dimethyl-5-trifluoromethyl-1,3-cyclohexanedione, mp .: 122- 5 128 ° C.

8900243.

Claims (35)

1. Compounds of formula I, wherein R1, R2 'R3 βη R4' is independent of an unsaturated aliphatic hydrocarbon group with up to 6 carbon atoms, a cycloalkyl group with up to 6 carbon atoms, 2 X 2 o 4 35 have the meanings. and M represents a hydrogen atom or a salt-forming 89 00243. * -84- group and optionally etherifying, esterifying or halogenating the compounds of formula Ib thus obtained to the corresponding 2- (Y-CO) -2-en-1-one- 3-ol ethers, 2- (Y-C0) -2-en-1-on-3-ol esters or 2- (2-) (YC0) -1,3-dione compounds. A compound according to claim 1 wherein R 1 represents an unsaturated aliphatic group having up to 6 carbon atoms, a cycloalkyl group having up to 6 carbon atoms or Ar, wherein Ar has a meaning defined in claim 1. A compound according to claim 1, wherein CR, R -A is C (R) = CR .._, wherein R 1 and RT_. 1. r 2 17 2 Ir has a meaning defined in claim 1. A compound according to claim 1, wherein R 1 and R 2 together represent the oxo group or an alkylidene group of 1 to 5 carbon atoms. A compound according to claim 1 wherein A ^ --- A ^ is C (X ^) - C (0), wherein X ^ has a defined meaning in claim! 20 A compound according to claim 1, wherein R 1 is the methyl, ethyl, vinyl, allyl, propargyl, cyclopropyl, an optionally substituted phenyl, furyl or thienyl group, or an (A 2) X 1 group or R ^ together with R the oxo group, CH or CH-CH group, or R together with R 2 2. ό X Xb 25 a bond, n 0 or 1, A ^ CH2 ~ or ^ CH2 ^ 2 'optionally substituted by one or two methyl groups and X 'an alkylthio group with 1-4 carbon atoms, phenylthio group, alkoxy group with 1-4 carbon atoms, phenoxy group, CHO, alkanoyl group with 2-5 carbon atoms, OH and esters thereof with an aliphatic carboxylic acid with 2- 5 carbon atoms or with an optionally substituted benzoic acid, (C-carbalkoxy) -CH0, (CL-carbalkoxy) - 2-5 2 2-5 CH (CH3), cyano, F, Cl, CHF2, CF3, NOC0NH2, CONHfC (alkyl)) , diiC 4 alkyl or benzyl, one of the substituents R 2, R 3 and R 3 a hydrogen atom, alkyl group with 1-4 carbon atoms, alkoxy group with 1-4 carbon atoms, alkylthio group with 1-4 S3 00 JUS. - koo material atoms, OH, alkyl-CO-O, carbalkoxy group of 2-5 carbon atoms, thienyl group or furyl group and any remaining substituent of, R 4 and 4 is a hydrogen atom or the methyl group. Ar or an (A.) X group, wherein one of the substituents in R 1, R-, R, and R is also a C 1-8 alkoxycarbonyl group, 12 3 4 2-5, wherein at least one of the R 1, R f and R4 are substituents (A,) X, R 'together with R. or R 'together with R 1 may also be 1 η 1 2 3 4 an alkylene group with 2-5 carbon atoms and R 1 and R 2 and 10 R 2 together may also be the oxo group or an alkylidene group with 1 to 5 carbon atoms, Ar unsubstituted is whether a substituted heteroaryl 5- or 6-ring with 1-3 heteroatoms selected from oxygen, nitrogen and sulfur and connected by a carbon atom of the ring represents ring A, n = 0 or 1, X is H, OR, SR , NR R, NO, halogen, 6. o 9 2. CN, CF, CHF, S (0) Rin, CO-NHR, CO-R 4, CR R -C00 (C alkyl) 32 m 10 11 12 15 14 l ~ o or benzyl, A compound according to claim 6 wherein a bond CH 2 CH 1 (CH 2), C (CH 2) 2, CO, O, CH (CF 3), CH 2 -CH 2 or CH (CH 3) -CH (CH 3), or A2 together with CR 1 C (R) = C (R), wherein R is H, SCH, CH or CF. 2 17 17 J o o A compound according to claim 1, 10 wherein A2 is. CH 2, CH (CH 3) or C (CH 3) 2, (Al) nX 'is NO 2, represents thienyl or furyl and Y is a phenyl group substituted by R 1, R 1 and R 2. 21 22 23 A compound according to claim 7, wherein n = 1 or 2 and Y is a phenyl group substituted by R 1, is K 22 and R 23. 10. Compounds according to claims 1-7, wherein Y represents a phenyl group substituted by R, R22 and R23 or thienyl, pyrazolyl, isothiazolyl, pyridyl, pyrazinyl or pyrimidinyl, which heteroaromatic group at the ortho position is substituted by methylenedioxy, NO2, halogen, CN, CF3, CH3 -SO2 or CH3SCH2 and optionally one or two additional substituents selected from halogen and alkyl of 1-4 carbon atoms / regions on a carbon atom of the ring and selected from alkyl of 1-4 carbon atoms, benzyl and C1-4. alkyl-25. . thio-C 1-6 alkyl when bonded to a nitrogen atom of the ring, R 22 is in the para site of the carbonyl group and hydrogen, halogen, C 1-6 alkyl-S or C 1-6 alkyl-SO 2, R 23 is in the ortho position of the carbonyl group and is halogen, CF, NO, CN or CHSO and R represents a 30 * 3 ^ <3 ^ hydrogen or halogen atom or the methyl group. A compound according to claim 10, wherein Y represents a phenyl group substituted by R 2, R 22 and R 23. A compound according to claim 10. wherein Y represents a substituted pyrazolyl, pyrimidinyl-35 or pyridyl group. 89 00 243, * - 81 - A compound according to claim 12, wherein Y is a substituted pyrazolyl group. A compound according to claim 12, wherein Y represents a substituted pyridyl group. A compound according to claim 1, wherein RH, CH, SCH, S (O) CH, SO CH, phenyl or phenyl xu J OxO monosubstituted by alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms, halogen or CF ^ or represents an alkenyl or alkynyl group with up to 4 carbon atoms. A compound according to claim 1 or 15, wherein R, R and R., independently of each other, x O rt represent a hydrogen atom, or the methyl group, wherein one of the substituents R 1, R 4 and R 4 also represents SCH 2, S (0) CH2 or SO2CCH2), provided that only one of the substituents is R2_R4 SCH3, SfOjCii ^ or SO2CH3. A compound according to claim 16, wherein A ^ is CHiCF ^), CH2 or O. A compound according to claim 17, wherein Y is 3,5-dichloro-2-pyridyl A compound according to claim 17, wherein Y is 1-CH 3 -4-NG> 2-pyrazol-5-yl or 1-CH 2 -é-NO-pyrazol-3-yl. A compound according to claim 17, wherein Y represents a phenyl group substituted by R 1, R 22 and R 2, wherein R 1, R 22 and R 23 have the meanings defined in claim 1. 20 A ^ represents a methylene or ethylene group, which is unsubstituted or substituted by one or more alkyl groups of 1 to 5 carbon atoms, Rg and R ^, independently of one another, a hydrogen atom, a hydrocarbon group, a haloalkyl group, or a heteroaryl group or a CO-R. group, ± 3 R is a hydrogen atom, hydrocarbon group, O heteroaryl group or a CO-R. group, R9 'R10' R13 and R14f independently, a hydrogen atom, an alkyl group with 1-6 carbon atoms 20 or represent an aryl group, R represents a hydrogen atom or a hydrocarbon group, R, and R, _ independently of each other, 12 15 are a hydrogen atom, hydrocarbon group or heteroaryl group 25, 8000243.-77 -m = 1 or 2, A2 is a bond, CR16R17 'CRieRl7 ~ CRl8R19' O, S, NR2q ° f CO, R and R, independently, 16 18 5 a hydrogen atom, hydrocarbon group or the carboxyl group in free form, salt form or esterified form, where R together 1b with R ^ to hey the adjacent carbon atom can form, represent, R ^ 7 and independently, a hydrogen atom, hydrocarbon group or an (A_) X group, 1 n in which A ^, n and X have the meanings indicated above, wherein R and R or R and R together may also be a (CH) 16 17 18 19 δ 2 ~ 5 group, thus forming a spiro compound, and / or R1C together with R, at the adjacent carbon atom or R.0 16 1 lo 15 together with R ^ at the adjacent carbon atom can form a (CH) .sub.1 group, thus forming a bicyclic ring, 2 to 1-5, R2g represents a hydrogen atom, a hydrocarbon group or a CQ -R. group, wherein R. is a previously defined 15 15 20 has a specific meaning, A „--- A ^ is C = C (0Ra) (Group A) or C (X ^ J- C (0) (Group B), X ^ is a fluorine or chlorine atom, Ra represents a hydrogen atom, a salt-forming group, or together with the oxygen to which it is attached an ether or ester group, Y represents a phenyl group substituted by R21f R22 and R23 represent whether Arr is, Ar 'is a 1, 2 or 3 heteroatoms selected, n containing oxygen, sulfur and nitrogen / 5 or 6 member group, which heteroarornatic group is unsuspended and substituted by a carbon atom of the ring is attached to the CO group to which it is attached, R21 and R22 'depending on one another, 55 a hydrogen or halogen atom, an alkyl group with 1-4 carbon atoms, an alkoxy group with 1-4 carbon atoms, a haloalkyl group of 1 to 4 carbon atoms, CN, NO 2 CF 0, R 2 S (O), 2 y 3 p 0900243.- 78 - NR ° Rd, C (0) -R °, SO 2 ~ NRCRd, or NRC -C (0) HRd, in which R21 and R22 together may form the methylenedioxy group, p = 0, 1 or 2, b R represents an alkyl group of 1-4 carbon atoms, optionally substituted by halogen, cyano, phenyl or benzyl First, represents, CD R and R, independently, represent a hydrogen atom or an alkyl group of 1-4 carbon atoms, o 10. an alkyl group of 1-4 carbon atoms or an alkoxy group of 1-4 carbon atoms, R22 is a halogen atom, a nitro group, cyano group, alkyl group of 1 or 2 carbon atoms, alkoxy group of 1 or 2 carbon atoms, haloalkyl group of 1 or 2 carbon atoms or a C 1-4 alkyl- SfO) 1 group, and g is 0, 1 or 2, where, if Y has any meaning other than an optionally substituted pyrimidinyl group, one of the substituents R 1, R 2, R 3 and R 4 is also a phenyl group or a substituted phenyl group, under the conditions that a) X in one of the substituents R1, R2, R8 and R4 is hydrogen only if at least one of the following conditions is met: i) CR R-A2 is C (R2) = C (R17 ) or A compound according to claim 15, wherein R ^ is SCH ^, S (O) CH3 or SO2Cl3 / R2, R3 and R4f independently, represent a hydrogen atom or the methyl group, A2 is 0 or CHfCF ^) and Y3 , 5-dichloro-2-pyridyl, 1-CH3 ~ 4-NO2-pyrazol-5-yl, 1-CH3-4-NO2 ~ pyrazol-3-yl or phenyl substituted by R21, R22 and R23 22. A compound according to claim 21, wherein A2 is CH 1 CF 2) or O and Y represents a phenyl group substituted by R 1, R 4 and R 4. 21 22 23 A compound according to claim 15, wherein R 1 is an alkenyl or alkynyl group having a maximum of 89 00243. - 82 - represents 4 carbon atoms, R., Ro and R, independently of 2 ° 4, are each other, H, CH ^, SCH ^, S (0) CH ^ or SO ^ CH ^, provided only one of the substituents is R2 ~ R4 is selected from the group consisting of SCH, S (0) CH and SO CH, A is CH, 0 or CH (CP) O u O u ^ o 5 and Y is 3,5-dichloro-2 pyridyl, 1-CH3-4-NO2-pyrazol-5-yl, 1-CH3-4-NO2-pyrazol-3-yl or phenyl substituted by R21, R22 and R23. A compound according to claim 15, wherein R 1 represents a phenyl group or a phenyl group monosubstituted by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, halogen or CF 4, R 2, R 3 and R 4 'independently of one another, hydrogen atom or the methyl group, A ^ is CH (CF ^), CH2 or 0, and Y is 3,5-dichloro-2-pyridyl, 1-CH3 ~ 4-NO2-pyrazol-5-yl, 1-CH3- 4-NO2-pyrazol-3-yl or phenyl 15 substituted by R 1, R 22 and R 23 * A compound according to claim 24, wherein Y is a phenyl group substituted by 2222 and R „_. 23 CRlVCR16R17-CR18R19 'ii) Y has a meaning other than an optionally substituted phenyl group or an optionally substituted pyrimidinyl group, iii) R 1 and R 2 together are the oxo group 30 or an alkylidene group having 1 to 5 carbon atoms, iv) at least one of the others substituents R, R2, R3 and R4 is an unsubstituted, aliphatic hydrocarbon group, a cycloalkyl group, an unsubstituted or substituted phenyl group or Ar, 35 v) at least one of the other substituents R, R, R, R, R and R is an (A) nX group, in which 1 2 3 4 17 19 1 X has a different meaning than hydrogen, or 8900243 <- 79 - vi) & 3 --- A4 is C (X) -C (0), b) if CR ^ R2_A2 is C (R2) = C (Riy ^ 'are R and R, not both a hydrogen atom, and J 3 4 c) if R ^ and R2 together form the oxo group, A2 is not O, S, Ο2ο or C0 ' A compound according to any one of claims 20 to 25, wherein A ^ --- A ^ is C = C (0Ra). A compound according to claim 1 selected from a. 2- (1-Methyl-4-nitro-5-pyrazolylcarbonyl) -1,3-cyclohexanedione. b. 2- (1-Methyl-4-nitro-3-pyrazolylcarbonyl) -1,3-cyclohexanedione. C. 2- (1-Methyl-4-nitro-3-pyrazolylcarbonyl) -5-methyl-1,3-cyclohexane dione. d. 2- (1-Methyl-4-nitro-3-pyrazolylcarbonyl) -4,4,6-trimethyl-1,3-cyclohexanedione. e. 2- (1-Methyl-4-nitro-3-pyrazolylcarbonyl) -4,4,6,6-tetramethyl-1,3-cyclohexanedione. f. 4- (1-Methyl-4-nitro-3-pyrazolylcarbonyl) -2,2,6,6-tetramethyl-3,6-dihydro-2H-pyran-3-one. g. 2- (4-Chloro-2-nitrobenzoyl) -4-phenyl-1,3-cyclohexanedione. h. 2- (4-Chloro-2-nitrobenzoyl) -5-trifluoromethyl-1,3-cyclohexanedione. 35 i. 2- (4-Chloro-2-nitrobenzoyl) -4-methyl-5-trifluoromethyl-1,3-cyclohexanedione. 89 00243, * - 83 - j. 2- (4-Chloro-2-nitrobenzoyl) -4,4-dimethyl-5-trifluoromethyl-1,3-cyclohexanedione. k. 2- (4-Chloro-2-nitrobenzoyl) -4- (2-fluorophenyl-1,3-cyclohexanedione. 1- 2- (4-Chloro-2-nitrobenzoyl) -4- (4-fluorophenyl-1,3- cyclohexanedione. 5 m. 2- (2-Chloro-4-methylsulfonylbenzoyl) -5-trifluororaethyl-1,3-cyclohexanedione.n. 2- (4-Chloro-2-nitrobenzoyl) -4,6,6-trimethyl-4 -cyclohexen- 1,3-dione. o. 2-Chloro-2- (4-chloro-2-nitrobenzoyl) -4,4,6,6-tetramethyl-1,3-cyclohexan-1,3-dione. 2-Chloro-2- (4-chloro-2-nitrobenzoyl) -4,4,6-trimethyl-1,3-cyclohexan-1,3-dione.q. 2- (3,5-Dichloro-2-pyridylcarbonyl 1,3-cyclohexanedione. A compound according to claim 15 26, wherein Ra represents a hydrogen atom, in free form or in the form of a salt. A compound according to claim 27, in free form or in the form of a salt. 30. 2- (1-Methyl-4-nitro-3-pyrazolylcarbonyl-3- (phenoxycarbonyloxy) -2-cyclohexen-1-one. A compound according to claim 26, wherein Ra together with the oxygen atom to which this substituent is bonded represents an ether or ester group. 32. Process for preparing a cyclic compound, characterized in that a compound of formula I as defined in claim 1 is prepared by a compound of formula II, wherein R., R_, R_, R. and A. X 2 6 4 2 have previously defined meanings to be reacted with a compound of formula III, wherein Y has a previously defined meaning and Hal is a halogen atom, followed by rearrangement of the thus obtained ester of formula IV, wherein Y, R2 R2, R3, R4 and A2 have previously defined meanings to obtain a compound of formula Ib wherein Y, A, R, R, R and R have the previously defined 33. Herbicidal preparations containing one or more compounds of formula I according to any one of claims 1-31. A method of controlling weeds, characterized in that a herbicidally effective amount of one or a number of compounds of the formula I according to any one of claims 1-31 is applied to the weeds or the area on which they are present. 35. Compounds, methods and preparations as described in the description and / or examples. 15 -o-o-o-o-o- / ^ 89 00 2.4 3.