BETA-LACTAMS AND THEIR USE AS HERBICIDES

Abstract

The invention relates to compounds of formula (I), and their use as herbicides. In said formula, R.sup.1 to R.sup.9 represent groups such as hydrogen, halo-gen or organic groups such as alkyl, alkenyl, alkynyl, or alkoxy; X is a bond or a divalent unit; Y is hydrogen, cyano, hydroxyl or a linear or cyclic organic group. The invention further refers to a composition comprising such compound and to the use thereof for controlling unwanted vegetation.

##STR00001##

Claims

1. A compound of formula (I) ##STR00283## wherein the substituents have the following meanings: R.sup.1 hydrogen, (C.sub.1-C.sub.3)-alkyl, (C.sub.3-C.sub.4)-cycloalkyl, (C.sub.1-C.sub.3)-haloalkyl, (C.sub.2-C.sub.3)-alkenyl, (C.sub.2-C.sub.3)-haloalkenyl, (C.sub.2-C.sub.3)-alkynyl, (C.sub.2-C.sub.3)-haloalkynyl, (C.sub.1-C.sub.3)-alkoxy-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-alkoxy, (C.sub.1-C.sub.3)-haloalkoxy; R.sup.2 hydrogen, halogen, hydroxyl, cyano, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkyl, (C.sub.1-C.sub.3)-alkoxy, (C.sub.1-C.sub.3)-haloalkoxy; R.sup.3 hydrogen, halogen, nitro, hydroxyl, cyano, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkyl, hydroxy-(C.sub.1-C.sub.3)-alkyl, (C.sub.3-C.sub.5)-cycloalkyl, (C.sub.3-C.sub.5)-halocycloalkyl, hydroxy-(C.sub.3-C.sub.5)-cycloalkyl, (C.sub.1-C.sub.3)-alkoxy, (C.sub.1-C.sub.3)-haloalkoxy, (C.sub.1-C.sub.3)-alkoxycarbonyl, (C.sub.2-C.sub.3) alkenyl, (C.sub.2-C.sub.3)-haloalkenyl, (C.sub.2-C.sub.3) alkynyl, (C.sub.2-C.sub.3)-haloalkynyl, (C.sub.1-C.sub.3)-alkylthio, (C.sub.1-C.sub.3)-alkylsulfinyl, (C.sub.1-C.sub.3)-alkylsulfonyl; R.sup.4 hydrogen, halogen, hydroxyl, cyano, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkyl, (C.sub.3-C.sub.4)-halocycloalkyl, (C.sub.1-C.sub.3)-alkoxy, (C.sub.1-C.sub.3)-haloalkoxy, (C.sub.2-C.sub.3)-haloalkenyl, (C.sub.2-C.sub.3)-haloalkynyl, (C.sub.1-C.sub.3)-alkylthio; R.sup.5 hydrogen, halogen, nitro, hydroxyl, cyano, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkyl, hydroxy-(C.sub.1-C.sub.3)-alkyl, (C.sub.3-C.sub.5)-cycloalkyl, (C.sub.3-C.sub.5)-halocycloalkyl, hydroxy-(C.sub.3-C.sub.5)-cycloalkyl, (C.sub.1-C.sub.3)-alkoxy, (C.sub.1-C.sub.3)-haloalkoxy, (C.sub.1-C.sub.3)-alkoxycarbonyl, (C.sub.2-C.sub.3) alkenyl, (C.sub.2-C.sub.3)-haloalkenyl, (C.sub.2-C.sub.3) alkynyl, (C.sub.2-C.sub.3)-haloalkynyl, (C.sub.1-C.sub.3)-alkylthio, (C.sub.1-C.sub.3)-alkylsulfinyl, (C.sub.1-C.sub.3)-alkylsulfonyl; R.sup.6 hydrogen, halogen, hydroxyl, cyano, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkyl, (C.sub.1-C.sub.3)-alkoxy, (C.sub.1-C.sub.3)-haloalkoxy; R.sup.7 hydrogen, fluorine, cyano, or (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-alkynyl, (C.sub.1-C.sub.6)-alkoxy, each substituted by m radicals from the group consisting of fluorine, chlorine, bromine, iodine, hydroxyl, cyano and (C.sub.1-C.sub.6)-alkoxy; R.sup.8, R.sup.9 each independently hydrogen, halogen, cyano, or (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkoxy, each substituted by m radicals from the group consisting of fluorine, chlorine, bromine, iodine, and cyano; or R.sup.8 and R.sup.9 form, together with the carbon atom to which they are bound, a saturated, partially or fully unsaturated three to five-membered ring containing, in addition to this carbon atom, q carbon atoms and n oxygen atoms; X a bond (X.sup.0) or a divalent unit from the group consisting of (X.sup.1), (X.sup.2), (X.sup.3), (X.sup.4), (X.sup.5), and (X.sup.6): ##STR00284## R.sup.10-R.sup.15 each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, CO.sub.2R.sup.e, CONR.sup.bR.sup.d, NR.sup.bCO.sub.2R.sup.e, R.sup.a, or (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.5)-cycloalkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-alkynyl, each substituted by m radicals from the group consisting of fluorine, chlorine, bromine, iodine, hydroxyl and cyano, or (C.sub.1-C.sub.6)-alkoxy, (C.sub.3-C.sub.6)-cycloalkoxy, (C.sub.3-C.sub.6)-alkenyloxy, (C.sub.3-C.sub.6)-alkynyloxy, (C.sub.1-C.sub.3)-alkylthio, (C.sub.1-C.sub.3)-alkylsulfinyl, (C.sub.1-C.sub.3)-alkylsulfonyl, each substituted by m radicals from the group consisting of fluorine, chlorine, bromine, iodine, cyano and (C.sub.1-C.sub.2)-alkoxy; Y hydrogen, cyano, hydroxyl, Z,  or  (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.8)-cycloalkyl, (C.sub.2-C.sub.12)-alkenyl or (C.sub.2-C.sub.12)-alkynyl, each substituted by m radicals from the group consisting of fluorine, chlorine, bromine, iodine, cyano, hydroxyl, OR.sup.d, Z, OZ, NHZ, S(O).sub.nR.sup.a, SO.sub.2NR.sup.bR.sup.d, SO.sub.2NR.sup.bCOR.sup.e, CO.sub.2R.sup.e, CONR.sup.bR.sup.h, COR.sup.b, CONR.sup.eSO.sub.2R.sup.a, NR.sup.bR.sup.e, NR.sup.bCOR.sup.e, NR.sup.bCONR.sup.eR.sup.e, NR.sup.bCO.sub.2R.sup.e, NR.sup.bSO.sub.2R.sup.e NR.sup.bSO.sub.2NR.sup.bR.sup.e, OCONR.sup.bR.sup.e, OCSNR.sup.bR.sup.e, POR.sup.fR.sup.f and C(R.sup.b)═NOR.sup.e; Z a three-, four-, five- or six-membered saturated, partly unsaturated, fully unsaturated or aromatic ring, except phenyl, which is formed from r carbon atoms, n nitrogen atoms, n sulfur atoms and n oxygen atoms, and which is substituted by m radicals from the group consisting of CO.sub.2R.sup.e, CONR.sup.bR.sup.h, S(O).sub.nR.sup.a, SO.sub.2NR.sup.bR.sup.d, SO.sub.2NR.sup.bCOR.sup.e, COR.sup.b, CONR.sup.eSO.sub.2R.sup.a, NR.sup.bR.sup.e, NR.sup.bCOR.sup.e, NR.sup.bCONR.sup.eR.sup.e, NR.sup.bCO.sub.2R.sup.e, NR.sup.bSO.sub.2R.sup.e NR.sup.bSO.sub.2NR.sup.bR.sup.e, OCONR.sup.bR.sup.e, OCSNR.sup.bR.sup.e, POR.sup.fR.sup.f, C(R.sup.b)═NOR.sup.e, R.sup.b, R.sup.c, R.sup.e and R.sup.f, and where the sulfur atoms and carbon atoms bear n oxo groups; R.sup.a (C.sub.1-C.sub.6)-alkyl or (C.sub.3-C.sub.6)-cycloalkyl, each of which is substituted by m radicals selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, hydroxy, and (C.sub.1-C.sub.3)-alkoxy; R.sup.b hydrogen, (C.sub.1-C.sub.3)-alkoxy or R.sup.a; R.sup.c fluorine, chlorine, bromine, iodine, cyano, hydroxyl, S(O).sub.nR.sup.a or (C.sub.1-C.sub.6)-alkoxy, (C.sub.3-C.sub.6)-alkenyloxy or (C.sub.3-C.sub.6)-alkynyloxy, each of which is substituted by m radicals selected from the group consisting of fluorine, chlorine, bromine, cyano and (C.sub.1-C.sub.2)-alkoxy; R.sup.d hydrogen or (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.2-C.sub.4)-alkenyl, (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.3)-alkyl, phenyl-(C.sub.1-C.sub.3)-alkyl, furanyl-(C.sub.1-C.sub.3)-alkyl or (C.sub.2-C.sub.4)-alkynyl, each of which is substituted by m radicals selected from the group consisting of fluorine, chlorine, bromine, cyano, CO.sub.2R.sup.a, CONR.sup.bR.sup.h, (C.sub.1-C.sub.2)-alkoxy, (C.sub.1-C.sub.3)-alkylthio, (C.sub.1-C.sub.3)-alkylsulfinyl, (C.sub.1-C.sub.3)-alkylsulfonyl, phenylthio, phenylsulfinyl, and phenylsulfonyl; R.sup.e R.sup.d; R.sup.f (C.sub.1-C.sub.3)-alkyl or (C.sub.1-C.sub.3)-alkoxy; R.sup.h hydrogen or (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.2)-alkoxy, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.2-C.sub.4)-alkenyl, (C.sub.1-C.sub.6)-alkoxycarbonyl-(C.sub.1-C.sub.6)-alkyl, or (C.sub.2-C.sub.4)-alkynyl each of which is substituted by m radicals selected from the group consisting of fluorine, chlorine, bromine, cyano, CO.sub.2R.sup.a and (C.sub.1-C.sub.2)-alkoxy; m 0, 1, 2, 3, 4 or 5; n 0, 1 or 2; q 1, 2, 3, or 4; r 1, 2, 3, 4, 5 or 6; including their agriculturally acceptable salts, amides, esters or thioesters, provided the compounds of formula (I) have a carboxyl group.

2. The compound as claimed in claim 1, wherein wherein the substituents have the following meaning: R.sup.1 hydrogen.

3. The compound as claimed in claim 1, wherein wherein the substituents have the following meaning: R.sup.2 hydrogen, halogen, (C.sub.1-C.sub.3)-alkyl; R.sup.6 hydrogen, halogen, (C.sub.1-C.sub.3)-alkyl.

4. The compound as claimed in claim 1, wherein wherein the substituents have the following meaning: R.sup.3 hydrogen, halogen, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkoxy; R.sup.5 hydrogen, halogen, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkoxy.

5. The compound as claimed in claim 1, wherein wherein the substituents have the following meaning: R.sup.4 hydrogen, halogen.

6. The compound as claimed in claim 1, wherein wherein the substituents have the following meaning: R.sup.7 (C.sub.1-C.sub.2)-alkyl, cyclopropyl, (C.sub.1-C.sub.2)-haloalkyl, (C.sub.2-C.sub.3)-alkenyl, (C.sub.1-C.sub.2)-alkoxy.

7. The compound as claimed in claim 1, wherein wherein the substituents have the following meaning: R.sup.8 hydrogen, halogen, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkyl; R.sup.9 hydrogen, halogen, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkyl.

8. The compound as claimed in claim 1, wherein wherein the substituents have the following meaning: X a bond.

9. The compound as claimed in claim 1, wherein wherein the substituents have the following meaning: X a bond; Y (C.sub.1-C.sub.8)-alkyl, (C.sub.3-C.sub.8)-cycloalkyl, (C.sub.2-C.sub.8)-alkenyl or (C.sub.2-C.sub.8)-alkynyl, each substituted by m radicals from the group consisting of fluorine, chlorine, bromine, iodine, cyano, hydroxyl, OR.sup.d, Z, OZ, NHZ, S(O).sub.nR.sup.a, SO.sub.2NR.sup.bR.sup.d, SO.sub.2NR.sup.bCOR.sup.e, CO.sub.2R.sup.e, CONR.sup.bR.sup.h, COR.sup.b, CONR.sup.eSO.sub.2R.sup.a, NR.sup.bR.sup.e, NR.sup.bCOR.sup.e, NR.sup.bCONR.sup.eR.sup.e, NR.sup.bCO.sub.2R.sup.e, NR.sup.bSO.sub.2R.sup.e NR.sup.bSO.sub.2NR.sup.bR.sup.e, OCONR.sup.bR.sup.e, OCSNR.sup.bR.sup.e, POR.sup.fR.sup.f and C(R.sup.b)═NOR.sup.e.

10. The compound as claimed in claim 1, wherein wherein the substituents have the following meaning: X a bond; Y Z; Z a four- or five-membered saturated or partly unsaturated ring, which is formed from r carbon atoms and n oxygen atoms, each substituted by m radicals from the group consisting of CO.sub.2R.sup.e, CONR.sup.bR.sup.h, CONR.sup.eSO.sub.2R.sup.a, R.sup.b, R.sup.c, R.sup.e and R.sup.f.

11. The compound as claimed in claim 1, wherein wherein the substituents have the following meaning: R.sup.1 hydrogen, (C.sub.1-C.sub.3)-alkyl, (C.sub.3-C.sub.4)-cycloalkyl, (C.sub.1-C.sub.3)-haloalkyl, (C.sub.2-C.sub.3)-alkenyl, (C.sub.2-C.sub.3)-haloalkenyl, (C.sub.2-C.sub.3)-alkynyl, (C.sub.2-C.sub.3)-haloalkynyl, (C.sub.1-C.sub.3)-alkoxy-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-alkoxy, (C.sub.1-C.sub.3)-haloalkoxy; R.sup.2 hydrogen, halogen, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkyl, (C.sub.1-C.sub.3)-alkoxy, (C.sub.1-C.sub.3)-haloalkoxy; R.sup.3 hydrogen, halogen, hydroxyl, cyano, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkyl, (C.sub.3-C.sub.5)-halocycloalkyl, (C.sub.1-C.sub.3)-haloalkoxy, (C.sub.2-C.sub.3)-haloalkenyl, (C.sub.2-C.sub.3)-haloalkynyl; R.sup.4 hydrogen, halogen, hydroxyl, cyano, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkyl, (C.sub.3-C.sub.4)-halocycloalkyl, (C.sub.1-C.sub.3)-haloalkoxy, (C.sub.2-C.sub.3)-haloalkenyl, (C.sub.2-C.sub.3)-haloalkynyl; R.sup.5 hydrogen, halogen, hydroxyl, cyano, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkyl, (C.sub.3-C.sub.5)-halocycloalkyl, (C.sub.1-C.sub.3)-haloalkoxy, (C.sub.2-C.sub.3)-haloalkenyl, (C.sub.2-C.sub.3)-haloalkynyl; R.sup.6 hydrogen, halogen, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkyl, (C.sub.1-C.sub.3)-alkoxy, (C.sub.1-C.sub.3)-haloalkoxy; R.sup.7 (C.sub.1-C.sub.2)-alkyl, cyclopropyl, (C.sub.1-C.sub.2)-haloalkyl, (C.sub.2-C.sub.3)-alkenyl, (C.sub.1-C.sub.2)-alkoxy; R.sup.8 hydrogen, halogen, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkyl; R.sup.9 hydrogen, halogen, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkyl; X a bond; Y Z, or (C.sub.1-C.sub.8)-alkyl, (C.sub.3-C.sub.8)-cycloalkyl, (C.sub.2-C.sub.8)-alkenyl or (C.sub.2-C.sub.8)-alkynyl, each substituted by m radicals from the group consisting of fluorine and CO.sub.2R.sup.e; Z four to five-membered saturated or partly unsaturated ring which is formed from r carbon atoms, n oxygen atoms, and which is substituted by m radicals from the group consisting of CO.sub.2R.sup.e, CONR.sup.bR.sup.h, CONR.sup.eSO.sub.2R.sup.a, R.sup.b, R.sup.c, R.sup.e and R.sup.f; R.sup.a (C.sub.1-C.sub.6)-alkyl or (C.sub.3-C.sub.6)-cycloalkyl, each of which is substituted by m radicals selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, hydroxy, and (C.sub.1-C.sub.3)-alkoxy; R.sup.b hydrogen, or (C.sub.1-C.sub.6)-alkyl or (C.sub.3-C.sub.6)-cycloalkyl, each of which is substituted by m radicals selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano and hydroxy; R.sup.c fluorine, chlorine, bromine, iodine, cyano, hydroxyl, S(O).sub.nR.sup.a or (C.sub.1-C.sub.6)-alkoxy, (C.sub.3-C.sub.6)-alkenyloxy or (C.sub.3-C.sub.6)-alkynyloxy, each of which is substituted by m radicals selected from the group consisting of fluorine, chlorine, bromine, cyano and (C.sub.1-C.sub.2)-alkoxy; R.sup.e hydrogen or (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.2-C.sub.4)-alkenyl, phenyl-(C.sub.1-C.sub.3)-alkyl or (C.sub.2-C.sub.4)-alkynyl, each of which is substituted by m radicals selected from the group consisting of fluorine, chlorine, bromine, cyano and (C.sub.1-C.sub.2)-alkoxy; R.sup.f (C.sub.1-C.sub.3)-alkyl or (C.sub.1-C.sub.3)-alkoxy; R.sup.h hydrogen or (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.2-C.sub.4)-alkenyl, (C.sub.1-C.sub.6)-alkoxycarbonyl-(C.sub.1-C.sub.6)-alkyl, or (C.sub.2-C.sub.4)-alkynyl each of which is substituted by m radicals selected from the group consisting of fluorine, chlorine, bromine, cyano and (C.sub.1-C.sub.2)-alkoxy; m 0, 1, 2, 3, 4 or 5; n 0, 1 or 2; r 1, 2, 3, 4, or 5.

12. A composition comprising at least one compound as claimed in claim 1, and at least one auxiliary, which is customary for formulating crop protection compounds.

13. The composition as claimed in claim 12, comprising a further herbicide.

14. (canceled)

15. A method for controlling unwanted vegetation which comprises allowing a herbicidally effective amount of at least one compound as claimed in claim 1 to act on plants, their seed and/or their habitat.

Description

A CHEMISTRY EXAMPLES

[0631] Chemical bonds, drawn as bars in chemical formulae, indicate the relative stereochemistry on the ring system.

Example 1

Synthesis of 1-(3,5-difluorophenyl)-3-methyl-2-oxo-azetidine-3-carboxylic (Inter A)

[0632] ##STR00222##

[0633] A solution of lithium hydroxide in water was added dropwise to mixture of diethyl 2-methylpropanedioate (1) (100.0 g, 574 mmol), tetrahydrofuran (THF) (200 ml) and water (200 ml) and the reaction mixture was stirred at room temperature overnight. THF was evaporated in vacuo and the remainder washed with methyl t-butyl ether. The aqueous solution was concentrated in vacuo and the remainder dried to give the product (2) (51.8 g, 59% yield). 1H NMR: (400 MHz, D2O) δ=4.2 (t, 2H), 3.35 (q, 1H), 1.35-1.20 (m, 6H).

##STR00223##

[0634] A mixture of aniline 3 (61.1 g, 473 mmol), the lithium salt of 3-ethoxy-2-methyl-3-oxo-propanoic acid (2) (60.0 g, 395 mmol) and triethylamine (164 mL, 3 equiv.) in THF (500 mL) was treated with n-propanephosphonic acid anhydride (427 g, 671 mmol, 50% solution in ethyl acetate), (T3P, CAS [68957-94-8]), and stirred overnight at room temperature. Water was added and the reaction mixture extracted with ethyl acetate; the organic layers were washed with aqueous hydrochloric acid solution (1M) and water, dried over sodium sulfate and concentrated in vacuo. The remainder was triturated with di-isopropyl ether and filtered. The residue consists of the product (4) (72.1 g, 71% yield). 1H NMR: (400 MHz, CDCl3) δ=9.9 (br s, 1H), 7.20-7.10 (m, 2), 6.60 (m, 1H), 4.25 (q, 2H), 3.40 (q, 1H), 1.55 (d, 3H), 1.30 (t, 3H).

##STR00224##

[0635] To a solution of ethyl 3-(3,5-difluoroanilino)-2-methyl-3-oxo-propanoate (4) (72.1 g, 280 mmol) in dimethyl formamide (200 mL) and cesium carbonate (75.1 g, 280 mmol) was added diiodomethane (182.6 g, 560 mmol) at room temperature. During this addition the temperature rose to ca. 40° C. The mixture was stirred overnight at 20° C. Water was added and the reaction mixture extracted with ethyl acetate, the organic layers were washed with water, dried over sodium sulfate and concentrated in vacuo. Flash chromatography (cyclohexane/ethyl acetate) gave crude ethyl 1-(3,5-difluorophenyl)-3-methyl-2-oxo-azetidine-3-carboxylate (5) (49.7 g, 66% yield). This product was used without further purification for the next step.

##STR00225##

[0636] A solution of potassium hydroxide (10.4 g, 185 mmol) in water was added dropwise to a mixture of ethyl 1-(3,5-difluorophenyl)-3-methyl-2-oxo-azetidine-3-carboxylate (5) (49.7 g, 185 mmol), THF (125 ml) and water (125 ml) and the reaction mixture stirred at room temperature overnight.

[0637] THF was evaporated in vacuo and the remainder washed with methyl t-butyl ether. The aqueous solution was adjusted to a pH value of ca. 1 with concentrated hydrochloric acid solution and extracted with ethyl acetate, the organic phase dried with sodium sulfate and concentrated in vacuo. The remainder was triturated with di-isopropyl ether and filtered. The residue consisted of the product as an off-white solid (Inter A) (20.5 g, 46% yield). 1H NMR: (400 MHz, DMSO-d6) δ=13.3 (br s, 1H), 7.10-7.00 (m, 3H), 4.05 (d, 1H), 3.65 (d, 1H), 1.50 (s, 3H).

Example 2

Synthesis of methyl (3S)-3-[[1-(3,5-difluorophenyl)-3-methyl-2-oxo-azetidine-3-carbonyl]amino]butanoate (1:1 mixture of diastereomers)—Compound 14

[0638] ##STR00226##

[0639] To a solution of the carboxylic acid Inter A (250 mg, 1.04 mmol) in dimethylformamide (DMF) commercially available methyl (3S)-3-aminobutanoate (S-homoalanine) hydrochloride (160 mg, 1.04 mmol) was added. To the resulting solution was added HATU (2-(7-aza-1H-benzotriazole-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate, CAS [148893-10-1]), (433 mg, 1.14 mmol) and then diisopropylethylamine (0.43 mL). The resulting reaction mixture was stirred at room temperature overnight. To the reaction mixture water and sodium bicarbonate solution were added. The reaction mixture was extracted with ethyl acetate, washed with water, dried (sodium sulfate) and the solvent was evaporated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate as solvent yielding 305 mg (87%) methyl (3S)-3-[[1-(3,5-difluorophenyl)-3-methyl-2-oxo-azetidine-3-carbonyl]amino]butanoate as a 1:1 mixture of diastereomers). 1H NMR (500 MHz, Chloroform-d) δ 6.9 (m, 2H), 6.8-6.65 (m, 1H), 6.6 (m, 1H), 4.35 (m, 1H), 4.1 (m, 1H) 3.75+3.65 (2×s, 3H) 3.5 (m, 1H), 2.55 (m, 2H), 1.7 (s, 3H), 1.25 (m, 3H).

Example 3

Synthesis of 1-(3,5-dichlorophenyl)-3-methyl-2-oxo-azetidine-3-carboxylic (Inter B)

[0640] In a similar way to the synthesis for Inter A described above starting from diethyl 2-methylpropanedioate, Inter B was obtained as an off-white solid by saponification of ethyl 1-(3,5-dichlorophenyl)-3-methyl-2-oxo-azetidine-3-carboxylate.

##STR00227##

[0641] A solution of potassium hydroxide (5.26 g, 93.7 mmol) in water was added dropwise to mixture of ethyl 1-(3,5-dichlorophenyl)-3-methyl-2-oxo-azetidine-3-carboxylate (6) (28.3 g, 93.7 mmol), THF (125 ml) and water (125 ml) and the reaction mixture stirred at room temperature overnight. THF was evaporated in vacuo and the remainder washed with methyl t-butyl ether. The aqueous solution was adjusted to pH 1 with concentrated hydrochloric acid solution and extracted with ethyl acetate, the organic phase dried with sodium sulfate and concentrated in vacuo. The remainder was triturated with di-isopropyl ether and filtered. The residue consisted of the product as an off-white solid (Inter B) (13.0 g, 51% yield) 1H NMR: (400 MHz, deutero-THF) δ=7.4 (s, 2H), 7.15 (s, 1H), 4.1 (d, 1H), 3.55 (d, 1H), 1.55 (s, 3H).

[0642] The pure enantiomers of Inter B, (3S)-1-(3,5-dichlorophenyl)-3-methyl-2-oxo-azetidine-3-carboxylic acid (S-Inter B) and (3R)-1-(3,5-dichlorophenyl)-3-methyl-2-oxo-azetidine-3-carboxylic acid (R-Inter B) were obtained by chiral supercritical fluid chromatography (SFC). Data for S- and R-Inter B:

(3S)-1-(3,5-dichlorophenyl)-3-methyl-2-oxo-azetidine-3-carboxylic acid (S-Inter B)

[0643] ##STR00228##

[00001]$\left[\alpha \right]\frac{20}{D}=-68.8°\left(c=1,\mathrm{Et}\mathrm{OH}\right)$

(3R)-1-(3,5-dichlorophenyl)-3-methyl-2-oxo-azetidine-3-carboxylic acid (R-Inter B)

[0644] ##STR00229##

[00002]$\left[\alpha \right]\frac{20}{D}=+69.°\left(c=1,\mathrm{Et}\mathrm{OH}\right)$

[0645] The absolute stereochemistry was assigned by x-ray crystallography of the reaction product of one of the enantiomers to the compound of example 4 (see reaction example below).

Example 4

Synthesis of Methyl (1S,4R)-4-[[(3R)-1-(3,5-dichlorophenyl)-3-methyl-2-oxo-azetidine-3-carbonyl]amino]cyclopent-2-ene-1-carboxylate

[0646] ##STR00230##

[0647] To a solution of the carboxylic acid (S-Inter B, 10.0 g, 34.5 mmol) in dimethylformamide (DMF) methyl (1S,4R)-4-aminocyclopent-2-ene-1-carboxylate (7, CAS 229613-83-6) was added. To the resulting solution was added HATU (15.0 g, 39.5 mmol)) and then diisopropylethylamine (11.7 mL). The resulting reaction mixture was stirred at room temperature for 2 hours. To the reaction mixture water (10 mL) was added. The resulting mixture was extracted with ethyl acetate, washed with water, dried (sodium sulfate), evaporated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate as solvent yielding methyl (1S,4R)-4-[[(3R)-1-(3,5-dichlorophenyl)-3-methyl-2-oxo-azetidine-3-carbonyl]amino]cyclopent-2-ene-1-carboxylate (8, 7.6 g, 55%).1H NMR (400 MHz, Chloroform-d) δ 7.25 (s, 2H), 7.1 (s, 1H), 6.7 (br d, 1H), 6.0-5.85 (m, 2H), 5.05 (m, 1H), 4.1 (d, 1H), 3.75 (s, 3H), 3.55 (m, 1H), 3.45 (d, 1H), 2.45 (m, 1H), 1.95 (m, 1H), 1.7 (s, 3H).

[0648] High Performance Liquid Chromatography: HPLC-column Kinetex XB C18 1,7μ (50×2.1 mm); eluent: acetonitrile/water+0.1% trifluoroacetic acid (gradient from 5:95 to 100:0 in 1.5 min at 60° C., flow gradient from 0.8 to 1.0 ml/min in 1.5 min).

[0649] In analogy to the examples described above, the following compounds of formula (I), wherein R.sup.1, R.sup.8 and R.sup.9 are hydrogen, were prepared, starting from commercially available diesters and using commercially available amines:

##STR00231##

TABLE-US-00002 TABLE 2 HPLC/ Cpd. R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 N*-X-Y MS I1 H Cl H Cl H CH.sub.3 [00232] 372.7 I2 H Cl H Cl H CH.sub.3 [00233] 358.7 I3 H Cl H Cl H OCH.sub.3 [00234] 402.7 I4 H F H F H CH.sub.3 [00235] 341 I5 H Cl H Cl H CH.sub.3 [00236] 384.9 I6 H Cl H Cl H CH.sub.3 [00237] 398.9 I7 H F H F H CH.sub.3 [00238] 353 I8 H F H F H CH.sub.3 [00239] 366.8 I9 H Cl H Cl H CH.sub.3 [00240] 396.8 I10 H F H F H CH.sub.3 [00241] 340.8 I11 H Cl H Cl H CH.sub.3 [00242] 372.7 I12 H F H F H CH.sub.3 [00243] 364.8 I13 H F H F H OCH.sub.3 [00244] 369 I14 H Cl H Cl H CH.sub.3 [00245] 372.5 I15 H F H F H CH.sub.3 [00246] 355.0 I16 H Cl H Cl H CH.sub.3 [00247] 387 I17 H F H F H CH.sub.3 [00248] 355.0 I18 H Cl H Cl H CH.sub.2CH.sub.3 [00249] 387.0 I19 H F H F H CH.sub.3 [00250] 367.0 I20 H Cl H Cl H CH.sub.3 [00251] 396.7 I21 H Cl H Cl H CH.sub.3 [00252] 396.9 I22 H Cl H Cl H [00253] [00254] 398.9  I23# H Cl H Cl H CH.sub.3 [00255] 372.7 I24 H Cl H Cl H CH.sub.2CH.sub.3 [00256] 410.7 I25 H Cl H Cl H CH.sub.2CH.sub.3 [00257] 386.7 I26 H Cl H Cl H [00258] [00259] 398.9  I27# H Cl H Cl H CH.sub.3 [00260] 372.7  I28# H Cl H Cl H CH.sub.3 [00261] 372.7 I29 H Cl H Cl H CH.sub.2CH.sub.3 [00262] 410.7 I30 H Cl H Cl H CH.sub.2CH.sub.3 [00263] 386.7 I31 H Cl H Cl H H [00264] I32 H F H F H [00265] [00266] 367 I33 H F H F H CH.sub.3 [00267] I34 H Cl H Cl H CN [00268] I35 H Cl H H H CH.sub.3 [00269] 338.8 I36 H Cl H H H CH.sub.3 [00270] 362,9 I37 H F H H H CH.sub.3 [00271] 323 I38 H F H H H CH.sub.3 [00272] 347 I39 H F H Cl H CH.sub.3 [00273] 380.9 I40 H F H Cl H CH.sub.3 [00274] 357.1 I41 H F H CH.sub.3 H CH.sub.3 [00275] 361 I42 H F H CH.sub.3 H CH.sub.3 [00276] 337.2 I43 H Cl H Cl H CH.sub.3 [00277] I44 H OCF.sub.2CHF.sub.2 H H H CH.sub.3 [00278] 420.9 I45 H CN F H H CH.sub.3 [00279] 347.9 I46 H OCF.sub.2CHF.sub.2 H H H CH.sub.3 [00280] 444.9 I47 H CN F H H CH.sub.3 [00281] 371.9 In Table 2, [00282]HPLC/MS = MassChargeRatio #:I23 is a single isomer, prepared from enantiopure S-Inter B. #:I27 is a single isomer, prepared from enantiopure S-Inter B. #:I28 is a single isomer, prepared from enantiopure R-Inter B.

B USE EXAMPLES

[0650] The herbicidal activity of the compounds of formula (I) was demonstrated by the following greenhouse experiments:

[0651] The culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species.

[0652] For the pre-emergence treatment, the active ingredients, which had been suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the test plants had rooted. This cover caused uniform germination of the test plants, unless this had been impaired by the active ingredients. For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment.

[0653] Depending on the species, the test plants were kept at 10-25° C. or 20-35° C., respectively. The test period extended over 2 to 4 weeks. During this time, the test plants were tended, and their response to the individual treatments was evaluated.

[0654] Evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the test plants, or complete destruction of at least the aerial moieties, and 0 means no damage, or normal course of growth. A good herbicidal activity is given at values of 80 to 90 and a very good herbicidal activity is given at values of 90 to 100.

[0655] The test plants used in the greenhouse experiments were of the following species: Bayer code Scientific name

TABLE-US-00003 Bayer code Scientific name ABUTH Abutilon theophrasti ALOMY Alopercurus myosuroides AMARE Amaranthus retroflexus APESV Apera spica-venti AVEFA Avena fatua ECHCG Echinocloa crus-galli SETVI Setaria viridis SETFA Setaria faberi

[0656] At an application rate of 1,000 kg/ha, applied by the pre-emergence method: [0657] compound 11 showed very good herbicidal activity against APESV. [0658] compound 11 showed very good herbicidal activity against SETFA.

[0659] At an application rate of 0,500 kg/ha, applied by the pre-emergence method: [0660] compounds 15, 16, 112, 119, 124, 129 showed very good herbicidal activity against AMARE. [0661] compound 13 showed good herbicidal activity against AMARE. [0662] compounds 12, 14, 15, 16, 17, 18, 19, 112, 113, 114, 116, 117, 118, 119, 120, 121, 122, 124, 126, 127, 129 showed very good herbicidal activity against APESV. [0663] compounds 13, 111, 115 showed good herbicidal activity against APESV. [0664] compounds 14, 17, 18, 19, 116, 117, 118, 122, 126, 127, 129 showed very good herbicidal activity against ECHCG. [0665] compounds 12, 121, 126, 127 showed very good herbicidal activity against SETFA.

[0666] At an application rate of 0,250 kg/ha, applied by the pre-emergence method: [0667] compounds 125, 130, 132, 135, 137, 138, 139, 140, 141, 142 showed very good herbicidal activity against APESV. [0668] compound 142 showed good herbicidal activity against ABUTH. [0669] compounds 130, 136 showed very good herbicidal activity against ALOMY. [0670] compounds 136, 137, 138, 139 showed very good herbicidal activity against AMARE. [0671] compounds 132, 142 showed good herbicidal activity against AMARE. [0672] compounds 130, 136, 138, 139 showed very good herbicidal activity against ECHCG. [0673] compound 141 showed good herbicidal activity against ECHCG. [0674] compounds 125, 135, 140 showed very good herbicidal activity against SETFA. [0675] compounds 141 showed good herbicidal activity against SETFA.

[0676] At an application rate of 1,000 kg/ha, applied by the post-emergence method: [0677] compound 131 showed very good herbicidal activity against ABUTH. [0678] compounds 11, 131 showed very good herbicidal activity against AMARE. [0679] compound 11 showed very good herbicidal activity against ECHCG. [0680] compounds 11, 131 showed very good herbicidal activity against SETVI.

[0681] At an application rate of 0,500 kg/ha, applied by the post-emergence method: [0682] compounds 16, 112, 121, 129 showed very good herbicidal activity against ABUTH. [0683] compounds 116, 124 showed good herbicidal activity against ABUTH. [0684] compounds 13, 14, 15, 16, 17, 18, 114, 116, 117, 118, 120, 126 showed very good herbicidal activity against ALOMY. [0685] Compounds 110, 111, 113, 115, 119, 122 showed good herbicidal activity against ALOMY. [0686] compounds 14, 19, 111, 124, 127, 129 showed very good herbicidal activity against AMARE. [0687] compounds 12, 15, 18, 110, 117, showed good herbicidal activity against AMARE. [0688] compounds 15, 115, 117 showed very good herbicidal activity against AVEFA. [0689] compound 13, 16, 111, 113, 114, 119, 120 showed good herbicidal activity against AVEFA. [0690] compounds 12, 14, 19, 112, 118, 121, 122, 126, 127 showed very good herbicidal activity against ECHCG. [0691] compounds 17, 120 showed good herbicidal activity against ECHCG. [0692] compounds 19, 112, 116, 118, 121, 122, 124, 126, 127, 129 showed very good herbicidal activity against SETVI. [0693] compounds 12, 13, 17, 18, 110, 119 showed good herbicidal activity against SETVI.

[0694] At an application rate of 0,250 kg/ha, applied by the post-emergence method: [0695] compound 147 showed very good herbicidal activity against ABUTH. [0696] compounds 130, 138, 139, 141 showed very good herbicidal activity against AMARE. [0697] compound 125 showed good herbicidal activity against AMARE. [0698] compounds 132, 135, 147 showed very good herbicidal activity against ALOMY. [0699] compound 142 showed good herbicidal activity against ALOMY. [0700] compounds 132, 135, 137, 140, 141, 142 showed very good herbicidal activity against AVEFA. [0701] compound 146 showed good herbicidal activity against AVEFA. [0702] compounds 125, 130, 138, 139, 140 showed very good herbicidal activity against ECHCG. [0703] compound 141 showed good herbicidal activity against ECHCG. [0704] compounds 125, 130, 132, 135, 138, 139, 140, 142, 147 showed very good herbicidal activity against SETVI.

[0705] At an application rate of 62.5 g/ha, applied by the post-emergence method: [0706] compound 133 showed good herbicidal activity against ALOMY. [0707] compound 133 showed very good herbicidal activity against AVEFA. [0708] compound 133 showed very good herbicidal activity against SETFA.

[0709] At an application rate of 16.0 g/ha, applied by the post-emergence method: [0710] compound 136 showed very good herbicidal activity against LOLMU. [0711] compound 136 showed very good herbicidal activity against AVEFA. [0712] compound 136 showed very good herbicidal activity against SETVI.