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HERBICIDAL MALONAMIDES

20230406833 ยท 2023-12-21

    Inventors

    Cpc classification

    International classification

    Abstract

    The present invention relates to malonamide compounds of the formula (I) wherein the variables are as defined in the claims and the description, and to compositions comprising these compounds. The invention also relates to the use of said malonamide compounds or the corresponding compositions for controlling unwanted vegetation. Furthermore, the invention relates to methods for controlling unwanted vegetation wherein said malonamide compounds or the corresponding compositions are applied.

    ##STR00001##

    Claims

    1. A compound of formula (I) ##STR00708## wherein the substituents have the following meanings: R.sup.1 is 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, or (C.sub.1-C.sub.3)-haloalkoxy; R.sup.2 is 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, or (C.sub.1-C.sub.3)-haloalkoxy; R.sup.3 is 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, or (C.sub.1-C.sub.3)-alkylsulfonyl; R.sup.4 is hydrogen, halogen, hydroxyl, cyano, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkyl, (C.sub.3-C.sub.4)-cycloalkyl, (C.sub.3-C.sub.4)-halocycloalkyl, (C.sub.1-C.sub.3)-haloalkoxy, (C.sub.2-C.sub.3)alkenyl, (C.sub.2-C.sub.3)-haloalkenyl (C.sub.2-C.sub.3)-alkynyl, or (C.sub.2-C.sub.3)-haloalkynyl; R.sup.5 is 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, or (C.sub.1-C.sub.3)-alkylsulfonyl; R.sup.6 is 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, or (C.sub.1-C.sub.3)-haloalkoxy; R.sup.7 and R.sup.8 form, together with the carbon atom to which they are bound, a saturated or partially unsaturated three-, four-, five-, six-, seven- or eight-membered monocyclic or bicyclic heterocyclic ring W, containing, in addition to this carbon atom, q carbon atoms, u oxygen atoms, v nitrogen atoms, w sulfur atoms, and x elements selected from the group consisting of NR.sup.d, NCOR.sup.d, and NC(O)OR.sup.d, where one carbon ring atom bears p oxo groups, and where the ring is substituted by n radicals R.sup.g; R.sup.9 is hydrogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.4)-cycloalkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.3)-alkoxy-(C.sub.1-C.sub.3)-alkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-haloalkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.2-C.sub.6)-haloalkynyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-haloalkoxy, or (C.sub.1-C.sub.3)-alkoxy-(C.sub.1-C.sub.3)-alkoxy; X is a bond (X.sup.0) or a divalent unit selected from the group consisting of (X.sup.1), (X.sup.2), (X.sup.3), (X.sup.4), (X.sup.5), and (X.sup.6): ##STR00709## R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, and R.sup.15, independently of each other and independently of each occurrence, are hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, CO.sub.2R.sup.e, CONR.sup.bR.sup.d, 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, where the four last-mentioned aliphatic and cycloaliphatic radicals are each substituted by m radicals selected 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 or (C.sub.3-C.sub.6)alkynyloxy, where the aliphatic and cycloaliphatic moieties in the four last-mentioned radicals are each substituted by m radicals selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, and (C.sub.1-C.sub.2)-alkoxy; Y is hydrogen, cyano, hydroxyl, Z, or is (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, where the four last-mentioned aliphatic and cycloaliphatic radicals are each substituted by m radicals selected 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 is a three-, four-, five-, six-, seven- or eight-membered saturated, partly unsaturated, fully unsaturated or aromatic monocyclic, bicyclic, or polycyclic ring, except phenyl, which is formed from r carbon atoms, k nitrogen atoms, n sulfur atoms, and n oxygen atoms, and which is substituted by m radicals selected 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, and C(R.sup.b)NOR.sup.e, R.sup.b, R.sup.c, R.sup.e and R.sup.f, and where the sulfur and carbon ring atoms bear n oxo groups; each R.sup.a is independently (C.sub.1-C.sub.6)-alkyl, (C.sub.2-C.sub.4)-alkynyl, 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; each R.sup.b is independently hydrogen or has one of the meanings given for R.sup.a; each R.sup.c is independently 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, where the aliphatic and cycloaliphatic moieties in the three last-mentioned radicals are each substituted by m radicals selected from the group consisting of fluorine, chlorine, bromine, cyano, and (C.sub.1-C.sub.2)-alkoxy; each R.sup.d is independently hydrogen or (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.3)-alkyl, (C.sub.2-C.sub.4)-alkenyl, phenyl-(C.sub.1-C.sub.3)-alkyl, or (C.sub.2-C.sub.4)-alkynyl, where the six last-mentioned radicals are each substituted by m radicals selected from the group consisting of fluorine, chlorine, bromine, cyano, COOR.sup.a, (C.sub.1-C.sub.2)-alkoxy, (C.sub.1-C.sub.3)alkylsulfinyl, (C.sub.1-C.sub.3)-alkylsulfonyl, (C.sub.1-C.sub.3)-alkylthio, phenylsulfinyl, phenylsulfonyl, and phenylthio, where the aliphatic or aromatic moieties in the seven last-mentioned radicals are each substituted with m radicals selected from the group consisting of fluorine, chlorine, and bromine; and a 5- or 6-membered heteroaromatic ring containing 1, 2, or 3 heteroatoms selected from N, O, and S as ring members; each R.sup.e is independently hydrogen or (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.3)-alkyl, (C.sub.2-C.sub.4)-alkenyl, phenyl-(C.sub.1-C.sub.3)-alkyl, or (C.sub.2-C.sub.4)-alkynyl, where the six last-mentioned radicals are each substituted by m radicals selected from the group consisting of fluorine, chlorine, bromine, cyano, COOR.sup.a, (C.sub.1-C.sub.2)-alkoxy, (C.sub.1-C.sub.3)alkylsulfinyl, (C.sub.1-C.sub.3)-alkylsulfonyl, (C.sub.1-C.sub.3)-alkylthio, phenylsulfinyl, phenylsulfonyl, and phenylthio, where the aliphatic or aromatic moieties in the seven last-mentioned radicals are each substituted with m radicals selected from the group consisting of fluorine, chlorine, and bromine; and a 5- or 6-membered heteroaromatic ring containing 1, 2, or 3 heteroatoms selected from N, O and S as ring members; each R.sup.f is independently (C.sub.1-C.sub.3)-alkyl or (C.sub.1-C.sub.3)-alkoxy; each R.sup.g is independently 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, or (C.sub.1-C.sub.3)-alkylsulfonyl; or two R.sup.g, bound on the same carbon atom, form together a methylene group (CH.sub.2); each R.sup.h is independently 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, where the six last-mentioned radicals are each substituted by m radicals selected from the group consisting of fluorine, chlorine, bromine, cyano, and (C.sub.1-C.sub.2)-alkoxy; k is 0, 1, 2, 3, or 4; each m is independently 0, 1, 2, 3, 4, or 5; each n is independently 0, 1, or 2; p is 0 or 1; q is 1, 2, 3, 4, 5, or 6; r is 1, 2, 3, 4, 5, 6, 7, or 8; u is 0, 1, or 2; v is 0, 1, 2, or 3; w is 0, 1, or 2; x is 0, 1, or 2; with the proviso that at least one of u, v, w, and x is not 0; including agriculturally acceptable salts, stereoisomers, and tautomers thereof.

    2. The compound as claimed in claim 1, wherein the substituents have the following meaning: R.sup.1 is hydrogen; R.sup.9 is hydrogen or (C.sub.1-C.sub.4)-alkyl.

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

    4. The compound as claimed in claim 3, wherein the substituents have the following meaning: R.sup.2 hydrogen or halogen; R.sup.6 is hydrogen.

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

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

    7. The compound as claimed in claim 6, wherein the substituents have the following meaning: R.sup.3 is halogen, cyano, or (C.sub.1-C.sub.3)-haloalkoxy; R.sup.5 is hydrogen or halogen.

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

    9. The compound as claimed in claim 1, wherein the substituents have the following meaning: R.sup.7 and R.sup.8 form, together with the carbon atom to which they are bound, a saturated or partially unsaturated three- to eight-membered monocyclic or bicyclic heterocyclic ring W, containing, in addition to this carbon atom, q carbon atoms, u oxygen atoms, v nitrogen atoms, w sulfur atoms, and x elements selected from the group consisting of NR.sup.d and NC(O)OR.sup.d, and where the ring is substituted by n radicals R.sup.g and by p oxo groups.

    10. The compound as claimed in claim 1, where u is 1 or 2, v is 0, w is 0, and x is 0; or u is 0 or 1, v is 1, w is 0, and x is 0; or u is 0 or 1, v is 0, w is 1, and x is 0; or u is 0, v is 0, w is 0, and x is 1.

    11. The compound as claimed in claim 1, wherein the substituents have the following meaning: R.sup.7 and R.sup.8 form, together with the carbon atom to which they are bound, a saturated or partially unsaturated four- to five-membered monocyclic heterocyclic ring W, containing, in addition to this carbon atom, q carbon atoms and u oxygen atoms, and where the ring is substituted by n radicals R.sup.g, where u is 1 or 2 and q is 1, 2.sub.1 or 3.

    12. The compound as claimed in claim 1, where each R.sup.g is independently (C.sub.1-C.sub.3)-alkyl or (C.sub.1-C.sub.3)-haloalkyl; or two R.sup.g, bound on the same carbon atom, form a methylene group (CH.sub.2).

    13. The compound as claimed in claim 1, where each R.sup.d in the elements selected from the group consisting of NR.sup.d, NCOR.sup.d, and NC(O)OR.sup.d as a ring member of the ring formed by R.sup.7 and R.sup.8 is independently hydrogen or (C.sub.1-C.sub.3)-alkyl.

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

    15. The compound as claimed in claim 1, wherein the substituents have the following meaning: X is a bond; Y is (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 selected 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.f1 and C(R.sup.b)NOR.sup.e.

    16. The compound as claimed in claim 15, where Y is (C.sub.1-C.sub.8)-alkyl or (C.sub.2-C.sub.8)-alkenyl, each substituted by one radical selected from the group consisting of CO.sub.2R.sup.e, CONR.sup.bR.sup.h, CONR.sup.eSO.sub.2R.sup.a, and Z, and also by 0 or 1 OR.sup.d substituents; or Y is (C.sub.2-C.sub.8)-alkynyl, where Z is a 3-, 4-, 5-, or 6-membered saturated or partly unsaturated monocyclic ring which is formed from 3 to 6 carbon atoms and 0 or 1 oxygen atoms, where the ring is substituted by a CO.sub.2R.sup.e radical.

    17. The compound as claimed in claim 16, where Y is (C.sub.1-C.sub.5)-alkyl substituted by one radical selected from the group consisting of CO.sub.2R.sup.e, CONR.sup.bR.sup.h, and CONR.sup.eSO.sub.2R.sup.a, and also by 0 or 1 OR.sup.d substituents; or Y is (C.sub.2-C.sub.8)alkynyl,

    18. The compound as claimed in claim 1, wherein the substituents have the following meaning: X is X.sup.6, wherein R.sup.10 to R.sup.13 are independently hydrogen or methyl; and Y is (C.sub.1-C.sub.8)-alkyl substituted by one radical selected from the group consisting of CO.sub.2R.sup.e, CONR.sup.bR.sup.h, and CONR.sup.eSO.sub.2R.sup.a.

    19. The compound as claimed in claim 1, wherein the substituents have the following meaning: X is a bond; Y is Z; Z is a 3-, 4-, 5-, 6-, 7-, or 8-membered saturated, partly unsaturated or aromatic monocyclic, bicyclic, or polycyclic ring, which is formed from r carbon atoms, n oxygen atoms, n sulfur atoms and k nitrogen atoms, each substituted by m radicals selected 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.

    20. The as claimed in claim 19, where Z is a 4-, 5-, 6-, 7-, or 8-membered saturated or partly unsaturated monocyclic, bicyclic, or polycyclic ring, which is formed from 4 to 8 carbon atoms, 0 or 1 oxygen atoms and 0 or 1 sulfur atoms and which is substituted by a group CO.sub.2R.sup.e, by 0 or 1 fluorine atoms and by 0 or 1 (C.sub.1-C.sub.4)-alkyl groups; or Y is a 5- or 6-membered heteroaromatic ring containing 1, 2, 3, or 4 heteroatoms selected from N, O, and S as ring members and which is substituted by y 0 or 1 groups CO.sub.2R.sup.e, by 0 or 1 fluorine atoms, and by 0 or 1 (C.sub.1-C.sub.4)-alkyl groups.

    21. The compound as claimed in claim 19, where Z is a 3-, 4-, 5-, 6-, 7-, or 8-membered saturated or partly unsaturated monocyclic carbocyclic ring substituted by a group CO.sub.2R.sup.e, by 0 or 1 fluorine atoms, and by 0 or 1 (C.sub.1-C.sub.4)-alkyl groups; or Z is a 5-, 6-, 7-, or 8-membered saturated or partly unsaturated bicyclic carbocyclic ring substituted by a group CO.sub.2R.sup.e, and by 0 or 1 (C.sub.1-C.sub.4)-alkyl groups; or Z is an 8-membered saturated polycyclic carbocyclic ring substituted by a group CO.sub.2R.sup.e and by 0 or 1 (C.sub.1-C.sub.4)-alkyl groups; or Z is a 5- or 6-membered saturated or partly unsaturated monocyclic heterocyclic ring containing one oxygen atom or one sulfur atom as ring member, where the heterocyclic ring is substituted by a group CO.sub.2R.sup.e and by 0 or 1 (C.sub.1-C.sub.4)-alkyl groups; or Z is a 5- or 6-membered heteroaromatic ring containing 1, 2, 3, or 4 heteroatoms selected from N, O, and S as ring members, where the heteroaromatic ring is substituted by 0 or 1 (C.sub.1-C.sub.4)-alkyl groups.

    22. The compound as claimed in claim 1, wherein the substituents have the following meaning: R.sup.1 is 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, or (C.sub.1-C.sub.3)-haloalkoxy; R.sup.2 is 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, or (C.sub.1-C.sub.3)-haloalkoxy; R.sup.3 is 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, or (C.sub.1-C.sub.3)-alkylsulfonyl; R.sup.4 is 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, or (C.sub.2-C.sub.3)-haloalkynyl; R.sup.5 is 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, or (C.sub.1-C.sub.3)-alkylsulfonyl; R.sup.6 is 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, or (C.sub.1-C.sub.3)-haloalkoxy; R.sup.7 and R.sup.8 form, together with the carbon atom to which they are bound, a saturated or partially unsaturated four- to eight-membered monocyclic or bicyclic heterocyclic ring W, containing, in addition to this carbon atom, q carbon atoms, u oxygen atoms, v nitrogen atoms, w sulfur atoms, and x elements selected from the group consisting of NR.sup.d and NC(O)OR.sup.d, where one carbon atom bears p oxo groups and where the ring is substituted by n radicals R.sup.g; R.sup.9 is hydrogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.4)-cycloalkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.1-C.sub.3)-alkoxy-(C.sub.1-C.sub.3)-alkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-haloalkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.2-C.sub.6)-haloalkynyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-haloalkoxy, or (C.sub.1-C.sub.3)-alkoxy-(C.sub.1-C.sub.3)-alkoxy; X is a bond or X.sup.6, wherein R.sup.10 to R.sup.13 are independently hydrogen or methyl; Y is 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 selected from the group consisting of fluorine, OR.sup.d, Z, CONR.sup.eSO.sub.2R.sup.a, CONR.sup.bR.sup.h, and CO.sub.2R.sup.e; Z is a three to eight-membered saturated or partly unsaturated mono-, bi-, or polycyclic ring which is formed from r carbon atoms, n oxygen atoms, n sulfur atoms and k nitrogen atoms, and which is substituted by m radicals selected 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 is (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.b is 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 is 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; each R.sup.d is independently 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, COOR.sup.a, (C.sub.1-C.sub.2)-alkoxy, (C.sub.1-C.sub.3)alkylsulfinyl, (C.sub.1-C.sub.3)-alkylsulfonyl, and (C.sub.1-C.sub.3)-alkylthio; each R.sup.e is independently hydrogen or (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.3)-alkyl, (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, (C.sub.1-C.sub.2)-alkoxy, (C.sub.1-C.sub.3)-alkylsulfinyl, (C.sub.1-C.sub.3)-alkylsulfonyl, (C.sub.1-C.sub.3)alkylthio, phenylsulfonyl, phenylsulfinyl, phenylthio, and furanyl; R.sup.f is (C.sub.1-C.sub.3)-alkyl or (C.sub.1-C.sub.3)-alkoxy; R.sup.g is 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, or (C.sub.1-C.sub.3)-alkylsulfonyl; or two R.sup.9, bound on the same carbon atom, form together a methylene group (CH.sub.2); R.sup.h is 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, and (C.sub.1-C.sub.2)-alkoxy; m is 0, 1, 2, 3, 4, or 5; n is 0, 1, 2, 3, or 4; p is 0 or 1; q is 2, 3, 4, 5, or 6; r is 1, 2, 3, 4, 5, 6, 7, or 8; u is 0, 1, or 2; v is 0 or 1; w is 0 or 1; x is 0 or 1; with the proviso that at least one of u, v, w, and x is not 0.

    23. The compound as claimed in claim 22, wherein the substituents have the following meaning: R.sup.1 is hydrogen; R.sup.2 is hydrogen or halogen; R.sup.3 is hydrogen, halogen, cyano, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkyl, (C.sub.1-C.sub.3)alkoxy, or (C.sub.1-C.sub.3)-haloalkoxy; R.sup.4 is hydrogen or halogen; R.sup.5 is hydrogen, halogen, cyano, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-haloalkyl, (C.sub.1-C.sub.3)alkoxy, or (C.sub.1-C.sub.3)-haloalkoxy; R.sup.6 is hydrogen; R.sup.7 and R.sup.8 form, together with the carbon atom to which they are bound, a saturated or partially unsaturated 3-, 4-, 5-, or 6-membered monocyclic heterocyclic ring W or a 6-, 7-, or 8-membered bicyclic heterocyclic ring W, the ring containing, in addition to said carbon atom, q carbon atoms, u oxygen atoms, v nitrogen atoms, w sulfur atoms, and x elements selected from the group consisting of NR.sup.d and NC(O)OR.sup.d, where one carbon atom bears p oxo groups and where the ring is substituted by n radicals R.sup.g; R.sup.9 is hydrogen or (C.sub.1-C.sub.4)-alkyl; X is a bond and Y is Z, where Z is a 3-, 4-, 5-, 6-, 7-, or 8-membered saturated or partly unsaturated monocyclic carbocyclic ring substituted by a group CO.sub.2R.sup.e, by 0 or 1 fluorine atoms and by 0 or 1 (C.sub.1-C.sub.4)-alkyl groups; or Z is a 5-, 6-, 7-, or 8-membered saturated or partly unsaturated bicyclic carbocyclic ring substituted by a group CO.sub.2R.sup.e, and by 0 or 1 (C.sub.1-C.sub.4)-alkyl groups; or Z is an 8-membered saturated polycyclic carbocyclic ring substituted by a group CO.sub.2R.sup.e and by 0 or 1 (C.sub.1-C.sub.4)-alkyl groups; or Z is a 5- or 6-membered saturated or partly unsaturated monocyclic heterocyclic ring containing one oxygen atom or one sulfur atom as ring member, where the heterocyclic ring is substituted by a group CO.sub.2R.sup.e and by 0 or 1 (C.sub.1-C.sub.4)-alkyl groups; or Z is a 5- or 6-membered heteroaromatic ring containing 1, 2, 3, or 4 heteroatoms selected from N, O, and S as ring members, where the heteroaromatic ring is substituted by 0 or 1 (C.sub.1-C.sub.4)-alkyl groups; or X is a bond and Y is (C.sub.1-C.sub.6)-alkyl or (C.sub.2-C.sub.6)-alkenyl, where the two last-mentioned radicals are substituted by a group CO.sub.2R.sup.e, CONR.sup.bR.sup.h, or CONR.sup.eSO.sub.2R.sup.a and by 0 or 1 (C.sub.1-C.sub.4)-alkoxy groups; or X is a bond and Y is (C.sub.1-C.sub.6)-alkyl substituted by Z, where Z is a 3-, 4-, 5-, or 6-membered saturated monocyclic carbocyclic ring substituted by a group CO.sub.2R.sup.e and by 0 or 1 (C.sub.1-C.sub.4)-alkyl groups or is a 5- or 6-membered saturated monocyclic heterocyclic ring containing 1 oxygen atom as ring member, where the heterocyclic ring is substituted by a group CO.sub.2R.sup.e and by 0 or 1 (C.sub.1-C.sub.4)-alkyl groups; or X is a bond and Y is (C.sub.2-C.sub.8)-alkynyl; or X is X.sup.6, wherein R.sup.10 to R.sup.13 are independently hydrogen or methyl; and Y is (C.sub.1-C.sub.6)-alkyl substituted by a group CO.sub.2R.sup.e and by 0 or 1 (C.sub.1-C.sub.4)-alkoxy groups; R.sup.a is (C.sub.1-C.sub.6)-alkyl; R.sup.b is hydrogen or (C.sub.1-C.sub.6)-alkyl; each R.sup.d is independently hydrogen or (C.sub.1-C.sub.6)-alkyl; each R.sup.e is independently hydrogen, (C.sub.1-C.sub.6)-alkyl which is unsubstituted or substituted by 1, 2, or 3 fluorine or chlorine atoms or by 1 radical selected from the group consisting of (C.sub.1-C.sub.2)-alkoxy, (C.sub.1-C.sub.3)alkylsulfonyl, (C.sub.1-C.sub.3)-alkylthio, phenylthio, phenylsulfonyl, and furanyl; or is (C.sub.2-C.sub.4)-alkynyl, (C.sub.3-C.sub.6)-cycloalkyl, or (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.3)alkyl; R.sup.g is (C.sub.1-C.sub.3)-alkyl or (C.sub.1-C.sub.3)-haloalkyl, or two R.sup.g, bound on the same carbon atom, form together a methylene group (CH.sub.2); R.sup.h is hydrogen, (C.sub.1-C.sub.6)-alkyl substituted by 0 or 1 cyano groups; or (C.sub.2-C.sub.4)-alkynyl; n is 0, 1, or 2; p is 0 or 1; q is 1, 2, 3, 4, 5, or 6; u is 0, 1, or 2; v is 0 or 1; w is 0 or 1; x is 0 or 1; with the proviso that the sum of u, v, w, and x is 1 or 2.

    24. The compound as claimed in claim 23, wherein the substituents have the following meaning: R.sup.1 is hydrogen; R.sup.2 is hydrogen; R.sup.3 is halogen, cyano, or (C.sub.1-C.sub.3)-haloalkoxy; R.sup.4 is hydrogen or halogen; R.sup.5 is hydrogen, halogen, or (C.sub.1-C.sub.3)-alkyl; R.sup.6 is hydrogen; R.sup.7 and R.sup.8 form, together with the carbon atom to which they are bound, a saturated or partially unsaturated 3-, 4-, 5-, or 6-membered monocyclic heterocyclic ring W or a 6-, 7-, or 8-membered bicyclic heterocyclic ring W, the ring containing, in addition to said carbon atom, q carbon atoms, u oxygen atoms, v nitrogen atoms, w sulfur atoms, and x elements selected from the group consisting of NR.sup.d and NC(O)OR.sup.d, where the ring is substituted by n radicals R.sup.g; R.sup.9 is hydrogen; X is a bond and Y is Z, where Z is a 4-, 5-, 6-, 7-, or 8-membered saturated or partly unsaturated monocyclic carbocyclic ring substituted by a group CO.sub.2R.sup.e and by 0 or 1 fluorine atoms; or Z is a 5-, 6-, 7-, or 8-membered saturated or partly unsaturated bicyclic carbocyclic ring substituted by a group CO.sub.2R.sup.e and by 0 or 1 (C.sub.1-C.sub.4)-alkyl groups; or Z is a 5- or 6-membered saturated or partly unsaturated monocyclic heterocyclic ring containing 1 oxygen atom or one sulfur atom as ring member, where the heterocyclic ring is substituted by a group CO.sub.2R.sup.e; or Z is a 5-membered heteroaromatic ring containing 1, 2, 3, or 4 nitrogen atoms as ring members, where the heteroaromatic ring is substituted by 0 or 1 (C.sub.1-C.sub.4)-alkyl groups; or X is a bond and Y is (C.sub.1-C.sub.6)-alkyl substituted by a group CO.sub.2R.sup.e, CONR.sup.bR.sup.h, or CONR.sup.e1SO.sub.2R.sup.a and by 0 or 1 (C.sub.1-C.sub.4)-alkoxy groups; or X is a bond and Y is (C.sub.2-C.sub.8)-alkynyl; or X is X.sup.6, wherein R.sup.10 to R.sup.13 are independently hydrogen; and Y is (C.sub.1-C.sub.4)alkyl substituted by a group CO.sub.2R.sup.e; R.sup.a is (C.sub.1-C.sub.6)-alkyl; R.sup.b is hydrogen; each R.sup.d is independently hydrogen or (C.sub.1-C.sub.6)-alkyl; R.sup.e1 is hydrogen or (C.sub.1-C.sub.4)-alkyl; each R.sup.e is independently hydrogen, (C.sub.1-C.sub.6)-alkyl which is unsubstituted or substituted by 1, 2, or 3 fluorine or chlorine atoms or by 1 radical selected from the group consisting of (C.sub.1-C.sub.2)-alkoxy, (C.sub.1-C.sub.3)alkylsulfonyl, (C.sub.1-C.sub.3)-alkylthio, phenylsulfonyl, phenylthio, and furanyl; or is (C.sub.2-C.sub.4)-alkynyl or (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.3)-alkyl; R.sup.g is (C.sub.1-C.sub.3)-alkyl, or two R.sup.g, bound on the same carbon atom, form together a methylene group (CH.sub.2); R.sup.h is (C.sub.1-C.sub.6)-alkyl substituted by 0 or 1 cyano groups; or is (C.sub.2-C.sub.4)alkynyl; n is 0, 1, or 2; q is 1, 2, 3, 4, 5, or 6; u is 0, 1, or 2; v is 0 or 1; w is 0 or 1; x is 0 or 1; with the proviso that the sum of u, v, w, and x is 1 or 2.

    25. 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.

    26. The composition as claimed in claim 25, comprising a further herbicide.

    27. (canceled)

    28. A method for controlling unwanted vegetation which comprises contacting plants, their seed, and/or their habitat with an herbicidally effective amount of at least one compound as claimed in claim 1.

    Description

    EXAMPLES

    A Chemistry Examples

    [1045] Chemical bonds, drawn as bars in chemical formulae, indicate the relative stereochemistry on the ring system.

    Example 1: Synthesis of 2-[(3,5-dichlorophenyl)carbamoyl]oxetane-2-carboxylic acid (Inter A)

    [1046] ##STR00195##

    [1047] A solution of lithium hydroxide (118 mg, 4.95 mmol) in water was added dropwise to mixture of 2,2-diethoxyoxetane-2,2-dicarboxylate (1) (CAS [1384465-73-9]) (1000 mg, 4.95 mmol), tetrahydrofuran (THF) (50 ml) and water (50 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) (740 mg, 86% yield). 1H NMR (500 MHz, Deuterium Oxide) 4.55 (t, 2H), 4.28 (m, 2H), 3.13 (m, 1H), 2.91 (m, 1H), 1.29 (t, 3H).

    ##STR00196##

    [1048] To a solution of ethyl 2-[(3,5-dichlorophenyl)carbamoyl]oxetane-2-carboxylate (2) (3.52 g, 19.6 mmol) in dimethylformamide (DMF) aniline 3 (3.17 g, 19.6 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]), (8.18 g, 21.5 mmol) and then diisopropylethylamine (16.6 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 ethyl 2-[(3,5-dichlorophenyl)carbamoyl]oxetane-2-carboxylate (4) (1.6 g, 26%). 1H NMR (500 MHz, Chloroform-d) 8.71 (s, 1H), 7.61 (d, 2H), 7.16 (d, 1H), 4.74 (dt, 1H), 4.66 (m, 1H), 4.31 (q, 2H), 3.42 (ddd, 1H), 2.95 (ddd, 1H), 1.32 (t, 3H).

    ##STR00197##

    [1049] A solution of lithium hydroxide (23 mg, 3.8 mmol) in water was added dropwise to mixture of ethyl 2-[(3,5-dichlorophenyl)carbamoyl]oxetane-2-carboxylate (4) (150 mg, 0.472 mmol), tetrahydrofuran (THF) (10 ml) and water (10 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 (MTBE). The aqueous solution was concentrated in vacuo and the remainder dried to give the carboxylic acid Inter A (130 mg, 95% yield). 1H NMR (500 MHz, Methanol-d4) 7.76 (d, 2H), 7.21 (t, 1H), 6.56 (m, 1H), 4.67 (t, 2H), 3.31 (m, 1H), 2.94 (dt, 1H).

    Example 2

    Synthesis of methyl (1S,4R)-4-[[2-[(3,5-dichlorophenyl)carbamoyl]oxetane-2-carbonyl]amino]cyclopent-2-ene-1-carboxylate (1:1 mixture of diastereomers)Compound I.6

    [1050] ##STR00198##

    [1051] To a solution of carboxylic acid Inter A (330 mg, 1.14 mmol) in dimethylformamide (DMF) methyl (1S,4R)-4-aminocyclopent-2-ene-1-carboxylate hydrochloride (7, CAS [180196-56-9]) (202 mg, 1.14 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]), (476 mg, 1.25 mmol) and then diisopropylethylamine (0.76 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 compound I.6 (62 mg, 13%, 1:1 mixture of diastereomers). 1H NMR (400 MHz, Chloroform-d) 9.37 (s, 1H), 9.25 (s, 1H), 7.59 (m, 4H), 7.12 (m, 2H), 5.94 (m, 4H), 5.08 (m, 2H), 4.73 (m, 4H), 3.74 (s, 3H), 3.73 (s, 3H), 3.56 (m, 2H), 3.05 (m, 4H), 2.51 (m, 2H), 2.05 (dt, 1H), 1.95 (dt, 1H).

    Example 3

    Synthesis of methyl (3S)-3-[[2-[(3,5-dichlorophenyl)carbamoyl]oxetane-2-carbonyl]amino]butanoate (1:1 mixture of diastereomers)Compound I.7

    [1052] ##STR00199##

    [1053] To a solution of carboxylic acid Inter A (130 mg, 0.448 mmol) in dimethylformamide (DMF, 5 mL) (3S)-3-aminobutanoate (S-homoalanine) hydrochloride (89 mg, 0.081 mmol) (CAS [139243-55-3]) 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]), (187 mg, 0.493 mmol) and then triethylamine (0.22 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 compound I.7 (102 mg, 58%, 1:1 mixture of diastereomers). 1H NMR (400 MHz, Chloroform-d) 9.68 (s, 1H), 9.48 (s, 1H), 7.76 (m, 6H), 7.15 (m, 2H), 4.57 (m, 5H), 4.32 (dqd, 2H), 3.62 (s, 3H), 3.58 (s, 3H), 2.97 (m, 4H), 2.55 (m, 4H), 1.24 (d, 3H), 1.21 (d, 3H).

    Example 4

    Synthesis of methyl (1S,4R)-4-[[2-[(3,5-difluorophenyl)carbamoyl]oxetane-2-carbonyl]amino]cyclopent-2-ene-1-carboxylate (1:1 mixture of diastereomers)Compound I.1

    [1054] In a similar way to the synthesis for Inter A described above starting from ethyl 2-[(3,5-dichlorophenyl)carbamoyl]oxetane-2-carboxylate, Inter B was obtained as an off-white solid by saponification of ethyl 1-(3,5-fluorophenyl)-3-methyl-2-oxo-azetidine-3-carboxylate.

    ##STR00200##

    [1055] To a solution of carboxylic acid Inter B (130 mg, 0.506 mmol) in dimethylformamide (DMF) methyl (1S,4R)-4-aminocyclopent-2-ene-1-carboxylate (5, CAS [229613-83-6]) (99 mg, 0.56 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]), (0.21 g, 0.56 mmol) and then diisopropylethylamine (2.5 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 compound I.1 (105 mg, 56%, 1:1 mixture of diastereomers). 1H NMR: (400 MHz, Chloroform-d) 9.39 (s, 1H), 9.28 (s, 1H), 7.58 (s, 2H), 7.23 (d, 4H), 6.58 (t, 2H), 5.99 (d, 2H), 5.08 (s, 2H), 4.75 (m, 3H), 3.74 (s, 3H), 3.73 (s, 3H), 3.57 (m, 2H), 3.04 (dd, 3H), 2.50 (m, 2H), 2.05 (d, 1H), 1.95 (d, 1H).

    Example 5

    Synthesis of methyl (3S)-3-[[2-[(3,5-difluorophenyl)carbamoyl]oxetane-2-carbonyl]amino]butanoate (1:1 mixture of diastereomers)Compound I.2

    [1056] ##STR00201##

    [1057] To a solution of carboxylic acid Inter B (19 mg, 0.074 mmol) in dimethylformamide (DMF) (3S)-3-aminobutanoate (S-homoalanine) hydrochloride (12 mg, 0.081 mmol) (CAS [139243-55-3]) 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]), (31 mg, 0.081 mmol) and then diisopropylethylamine (0.22 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 compound I.2 (17 mg, 65%, 1:1 mixture of diastereomers). 1H NMR (400 MHz, THF-d8) 9.72 (s, 1H), 9.52 (s, 1H), 7.75 (m, 2H), 7.40 (m, 4H), 6.67 (m, 2H), 4.56 (m, 3H), 4.31 (dq, 1H), 3.58 (m, 6H), 2.98 (m, 2H), 2.51 (m, 4H), 1.25 (d, 3H), 1.21 (d, 3H).

    Example 6

    Synthesis of 5-[(3,5-dichlorophenyl)carbamoyl]-hydrofuran-5-carboxylic acid (Inter C)

    [1058] ##STR00202##

    [1059] To a mixture of diethyl malonate (1) (50 g, 310 mmol) (CAS [53051-81-3]) and triethylamine (75 g, 744 mmol) in MeCN (500 ml) was added 4-acetamidobenzenesulfonyl azide (2) (p-ABSA, 12 g, 465 mmol) (CAS [2158-14-7]) at 20 C. The mixture was stirred at 20 C. for 16 h. The reaction was filtered and the filtrate was concentrated. Dichloromethane (100 mL) was added to the filtrate. The mixture was filtered and the filtrate was concentrated. The crude was purified by HPLC (EtOAc/PE=0%100%) to give diethyl 2-diazopropanedioate (2) (62 g, quant.) as yellow oil. 1H NMR (400 MHz, Chloroform-d) 4.31 (q, 4H), 1.32 (t, 6H).

    ##STR00203##

    [1060] To a solution of diethyl 2-diazopropanedioate (3) (62 g, 330 mmol) and propargyl alcohol (4) (18.5 g, 330 mmol) (CAS [107-19-7]) in toluene (600 ml) was added R.sup.h.sub.2(OAc).sub.4 (1.3 g, 2.9 mmol) (CAS [15956-28-2]) at 20 C. The mixture was stirred at 60 C. for 1 h. The reaction was filtered and the filtrated was concentrated. The crude was purified by HPLC (EtOAc/PE=0%100%) to give the diethyl 2-prop-2-ynoxypropanedioate (5) (53 g, 80% over two steps) as yellow oil. 1H NMR (400 MHz, Chloroform-d) 4.82-4.80 (s, 1H), 4.41 (d, 2H), 4.28 (m, 4H), 2.53 (t, 1H), 1.31 (t, 6H).

    ##STR00204##

    [1061] To a solution of diethyl 2-prop-2-ynoxypropanedioate (5) (30 g, 140 mmol) in EtOH/H.sub.2O (200/200 mL) was added KOH (7.85 g, 140 mmol) at 20 C. in portions. The mixture was stirred at 20 C. for 16 h. The mixture was quenched with H.sub.2O and adjusted to pH=3 with 6N HCl, extracted with EtOAc. The combined organics were washed with brine, dried and concentrated to give 2-ethoxycarbonylhydrofuran-2-carboxylic acid (6) (20 g, 77%) as yellow oil. 1H NMR (400 MHz, Chloroform-d) 6.23 (m, 1H), 6.02 (tdd, 1H), 4.93 (m, 1H), 4.87 (m, 1H), 4.29 (q, 2H), 1.32 (t, 3H).

    ##STR00205##

    [1062] In a similar way to the synthesis for Inter A described above, starting with 2-ethoxycarbonylhydrofuran-2-carboxylic acid (20 g, 108 mmol), ethyl 5-[(3,5-dichlorophenyl)carbamoyl]-hydrofuran-5-carboxylate (8) was obtained as a yellow solid (23 g, 66%). 1H NMR (400 MHz, Chloroform-d) 8.32 (brs, 1H), 7.56 (d, J=1.8 Hz, 2H), 7.14 (m, 1H), 6.20 (m, 1H), 6.01 (m, 1H), 4.89-4.86 (m, 1H), 4.81 (s, 1H), 4.28 (m, 4H), 1.32 (t, 3H).

    ##STR00206##

    [1063] To a solution of ethyl 5-[(3,5-dichlorophenyl)carbamoyl]-hydrofuran-5-carboxylate (8) (1.33 g, 4.03 mmol) in EtOH/H.sub.2O (40/20 mL) was added KOH (452 mg, 8.06 mmol) at 20 C. in portions. The mixture was stirred at 20 C. for 16 h. The mixture was quenched with H.sub.2O and adjusted to pH=3 with 6N HCl, extracted with EtOAc. The combined organics were washed with brine, dried and concentrated to give 5-[(3,5-dichlorophenyl)carbamoyl]-hydrofuran-5-carboxylic acid Inter C (950 mg, 78%) as yellow oil. 1H NMR (400 MHz, Chloroform-d) 6.23 (m, 1H), 6.02 (tdd, 1H), 4.93 (m, 1H), 4.87 (m, 1H), 4.29 (q, 2H), 1.32 (t, 3H).

    Example 7

    Synthesis of methyl (1S,4R)-4-[[5-[(3,5-dichlorophenyl)carbamoyl]-2H-furan-5-carbonyl]amino]cyclopent-2-ene-1-carboxylate (1:1 mixture of diastereomers)Compound I.24

    [1064] ##STR00207##

    [1065] In a similar way to the synthesis for Compound I.6 described above, starting with 5-[(3,5-dichlorophenyl)carbamoyl]-hydrofuran-5-carboxylic acid (Inter C) (48 mg, 0.16 mmol), Compound 1.24 was obtained as an off-white solid (49 mg, 73%, 1:1 mixture of diastereomers). 1H NMR (400 MHz, Chloroform-d) 9.60 (s, 1H), 9.51 (s, 1H), 7.56 (m, 6H), 7.09 (m, 2H), 6.13 (m, 2H), 6.07 (m, 2H), 5.96 (m, 2H), 5.88 (m, 2H), 5.02 (m, 6H), 3.74 (m, 3H), 3.73 (s, 3H), 3.54 (m, 2H), 2.47 (dtd, 2H), 1.93 (m, 2H).

    [1066] The two diastereoisomers could be separated by SFC (column: (S,S)-WHELK-O1,506 mm i.D., 3.5 m; mobile phase A: CO2; mobile phase B: IPA (0.1% IPAm, v/v; flow rate: 3.4 mL/min, column temp.: 35 C., ABPR: 1800 psi; gradient: time (A/B): 0.0 (95/5), 0.2 min (95/5), 1.2 min (50/50), 2.2 (50/50), 2.6 min (95/5), 3.0 (95/5). In Table 2 below they are depicted as compounds 1.183 and 1.184. They are characterized as follows:

    [1067] Compound I.183: t.sub.R=1.395 min, 1H NMR (400 MHz, Chloroform-d) 9.52 (s, 1H), 7.56 (m, 3H), 6.13 (m, 1H), 6.07 (m, 1H), 5.96 (m, 1H), 5.88 (m, 1H), 5.02 (m, 3H), 3.75 (s, 3H), 3.55 (m 1H), 2.47 (dtd, 1H), 1.93 (m, 2H).

    [1068] Compound I.184: t.sub.R=1.616 min, 1H NMR (400 MHz, Chloroform-d) 9.63 (s, 1H), 7.56 (m, 3H), 6.13 (m, 1H), 6.07 (m, 1H), 5.96 (m, 1H), 5.88 (m, 1H), 5.02 (m, 3H), 3.74 (s, 3H), 3.55 (m 1H), 2.47 (dtd, 1H), 1.93 (m, 2H).

    Example 8

    Synthesis of 5-[(3,5-dichlorophenyl)carbamoyl]-1,3-dimethylhydrofuran-5-carboxylic acid (1:1 mixture of diastereomers)Inter D

    [1069] ##STR00208##

    [1070] To a solution of diethyl 2-diazopropanedioate (1) (1.13 g, 6.07 mmol) in toluene (25 mL) pent-3-yn-2-ol (0.85 ml, 9.1 mmol) was added. To the resulting solution [R.sup.h(OAc).sub.2].sub.2 (0.12 g, 0.30 mmol) was added and the resulting reaction mixture was stirred at 60 C. for 2 h. After cooling to room temperature the reaction mixture was washed with water, dried (sodium sulfate) and the solvent was evaporated under reduced pressure. The crude product 2 (1.10 g, 75%) was used without further purification in the next step. 1H NMR (400 MHz, Chloroform-d, 1:1 mixture of diastereomers) 4.39 (m, 1H), 4.26 (m, 4H), 1.82 (d, 3H), 1.47 (d, 3H), 1.28 (m, 6H).

    ##STR00209##

    [1071] To a solution of diethyl 2-prop-2-ynoxypropanedioate (2) (1.10 g, 4.54 mmol) in acetonitrile (50 mL) cesium carbonate (2.96 g, 9.08 mmol) were added. The resulting reaction mixture was stirred at room temperature for 4 h. The solvent was evaporated under reduced pressure and the residue was dissolved in ethyl acetate and water. The organic layer was separated, washed with water (2), 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 3 (1.00 g, 59%, 1:1 mixture of diastereomers). 1H NMR (400 MHz, Chloroform-d, 1:1 mixture of diastereomers) 5.71 (t, 1H), 5.07 (dtt, 1H), 4.25 (m, 4H), 1.90 (m, 3H), 1.29 (m, 9H).

    ##STR00210##

    [1072] In a similar way to the synthesis for Inter A described above, starting with diethyl 3,5-dimethylhydrofuran-2,2-dicarboxylate (750 mg, 3.1 mmol), 2-ethoxycarbonyl-3,5-dimethylhydrofuran-2-carboxylic acid (4) was obtained as an oil (580 mg, 87%, 1:1 mixture of diastereomers). 1H NMR (400 MHz, Chloroform-d) 5.71 (t, 1H), 5.07 (dtt, 1H), 4.25 (m, 2H), 1.90 (t, 3H), 1.29 (m, 6H).

    ##STR00211##

    [1073] In a similar way to the synthesis for Inter A described above, starting with 2-ethoxycarbonyl-3,5-dimethylhydrofuran-2-carboxylic acid (305 mg, 1.42 mmol), ethyl 5-[(3,5-dichlorophenyl)carbamoyl]-1,3-dimethylhydrofuran-5-carboxylate was obtained as a yellow solid (250 mg, 49%). 1H NMR (400 MHz, Chloroform-d) 8.69 (s, 1H), 7.56 (d, 2H), 7.12 (m, 1H), 5.71 (m, 1H), 4.27 (m, 2H), 1.34 (d, 3H), 1.30 (t, 3H). 1H NMR (400 MHz, Chloroform-d, minor diastereomer) =8.69 (s, 1H), 7.53 (d, 2H), 7.12 (m, 1H), 5.71 (m, 1H), 4.27 (m, 2H), 1.45 (d, 3H), 1.30 (t, 3H).

    ##STR00212##

    [1074] In a similar way to the synthesis for Inter A described above starting with ethyl 5-[(3,5-dichlorophenyl)carbamoyl]-1,3-dimethylhydrofuran-5-carboxylate (250 g, 0.70 mmol), 5-[(3,5-dichlorophenyl)carbamoyl]-1,3-dimethylhydrofuran-5-carboxylic acid (Inter D) was obtained as a white solid (128 mg, 56%, 1:3-mixture of diastereomers). 1H NMR (400 MHz, Chloroform-d, major diastereomer) 5=8.84 (s, 1H), 7.53 (d, 2H), 7.19 (t, 1H), 5.75 (dt, 1H), 5.29 (dtd, 1H), 1.97 (t, 3H), 1.51 (dd, 3H). 1H NMR (400 MHz, Chloroform-d, minor diastereomer) 5=8.84 (s, 1H), 7.50 (d, 2H), 7.21 (t, 1H), 5.75 (dt, 1H), 5.40 (dt, 1H), 1.95 (t, 3H), 1.51 (dd, 3H).

    Example 9

    Synthesis of methyl (1S,4R)-4-[[5-[(3,5-dichlorophenyl)carbamoyl]-2,4-dimethyl-2H-furan-5-carbonyl]amino]cyclopent-2-ene-1-carboxylate (1:2:3 mixture of diastereomers)Compound I.29

    [1075] ##STR00213##

    [1076] In a similar way to the synthesis for Compound I.6 described above, starting with 5-[(3,5-dichlorophenyl)carbamoyl]-1,3-dimethylhydrofuran-5-carboxylic acid (Inter D) (58 mg, 0.17 mmol), Compound I.29 was obtained as an off-white solid (65 mg, 82%, 1:2:3 mixture of diastereomers). 1H NMR (400 MHz, Chloroform-d) 9.84 (m, 1H), 7.66 (m, 1H), 7.57 (m, 2H), 7.10 (m, 1H), 5.96 (m, 1H), 5.87 (m, 1H), 5.64 (m, 1H), 5.30 (m, 1H), 5.03 (m, 1H), 3.73 (m, 3H), 3.54 (m, 1H), 2.49 (m, 1H), 1.93 (m, 4H), 1.46 (m, 3H).

    Example 10

    Synthesis of methyl (4S)-4-[[5-[(3,5-dichlorophenyl)carbamoyl]-2,4-dimethyl-2H-furan-5-carbonyl]amino]pentanoate (1:1:1:1 mixture of diastereomers) Compound I.30

    [1077] ##STR00214##

    [1078] In a similar way to the synthesis for Compound I.6 described above, starting with 5-[(3,5-dichlorophenyl)carbamoyl]-hydrofuran-5-carboxylic acid (Inter D) (50 mg, 0.15 mmol), Compound 1.30 was obtained as an off-white solid (60 mg, 89%, 1:1:1:1 mixture of diastereomers). 1H NMR (400 MHz, Chloroform-d) 9.99 (s, 1H), 9.92 (s, 1H), 9.87 (s, 1H), 9.80 (s, 1H), 7.56 (m, 8H), 7.15 (m, 4H), 7.10 (m, 4H), 5.64 (m, 4H), 5.30 (m, 4H), 3.99 (m, 4H), 3.67 (m, 12H), 2.33 (m, 8H), 1.93 (m, 12H), 1.86 (m, 4H), 1.78 (m, 4H), 1.50 (m, 6H), 1.43 (t, 6H), 1.19 (m, 12H).

    Example 11

    Synthesis of [(3,5-dichlorophenyl)carbamoyl]tetrahydrofuran-2-carboxylic acid (Inter E)

    [1079] ##STR00215##

    [1080] To a mixture of tetrahydrofuran-2-carboxylic acid (1) (5 g, 43 mmol) in MeOH (15 ml) was added H.sub.2SO.sub.4 (0.2 ml) at 25 C. and stirred at 75 C. for 16 h. The mixture was poured into H.sub.2O, extracted with dichloromethane. The combined organics were washed with aq. NaHCO.sub.3, dried and concentrated. The crude was purified by distillation to give methyl tetrahydrofuran-2-carboxylic acid (2) (3.5 g, 62.5%) as a yellow oil. 1H NMR (400 MHz, Chloroform-d) 4.48 (m, 1H), 3.97 (m, 2H), 3.74 (s, 3H), 2.28 (m, 2H), 2.10 (m, 1H), 1.96 (m, 1H).

    ##STR00216##

    [1081] To a mixture of methyl tetrahydrofuran-2-carboxylic acid (2) (3 g, 23 mmol) in THF (50 ml) was added lithium diisopropylamide (LDA) (17 ml, 34.5 mmol) dropwise at 78 C. The mixture was stirred at 78 C. for 0.5 h before adding benzyl chloroformate (3) (15.7 g, 92 mmol). The mixture was stirred at 78 C. to 20 C. for 1 h. The mixture was poured into H.sub.2O, adjusted pH=3, extracted with EtOAc. The combined organics were washed with brine, dried and concentrated. The crude was purified by column using ethyl acetate and hexane to give benzyl methyl tetrahydrofuran-2,2-dicarboxylate (4) (2.5 g, 33%) as yellow oil. 1H NMR (400 MHz, Chloroform-d) 7.35 (m, 5H), 5.24 (d, 2H), 4.07 (t, 2H), 3.75 (s, 3H). 2.46 (m, 2H), 2.01 (m, 2H).

    ##STR00217##

    [1082] To a mixture of Pd/C (200 mg) was added to a solution of benzyl methyl tetrahydrofuran-2,2-dicarboxylate (4) (2.2 g, 8.33 mmol) in MeOH (200 ml) and stirred at 25 C. under H.sub.2 (50 psi) for 2 h. The mixture was filtered and concentrated give compound 2-methoxycarbonyltetrahydrofuran-2-carboxylic acid (5) (1.4 g, 97%) as yellow oil. 1H NMR (400 MHz, Chloroform-d) 4.12 (quin, 2H), 3.82 (s, 3H), 2.47 (m, 2H), 2.05 (m, 3H).

    ##STR00218##

    [1083] To a mixture of carboxylic acid 5 (1 g, 5.75 mmol) in DMF (20 mL) was added 3,5-dichloroaniline (6) (1.4 g, 8.6 mmol) and HATU (2.6 g, 6.9 mmol) at 15 C. and stirred at 15 C. for 24 h. The mixture was poured into ice water and extracted with methyl tert-butyl ether. The combined organics were washed with brine, dried and concentrated. The crude was purified by prep-HPLC (TFA-ACN-H.sub.2O) to give methyl 2-[(3,5-dichlorophenyl)carbamoyl]tetrahydrofuran-2-carboxylate (7) (900 mg, 49%) as a white solid. 1H NMR (400 MHz, Chloroform-d) 8.61 (br s, 1H), 7.58 (d, 2H), 7.14 (t, 1H), 4.12 (m, 2H), 3.81 (s, 3H), 2.75 (td, 1H), 2.44 (ddd, 1H), 2.11 (m, 1H), 1.99 (m, 1H).

    ##STR00219##

    [1084] A solution of lithium hydroxide (133 mg, 5.56 mmol) in water was added dropwise to mixture of methyl 2-[(3,5-dichlorophenyl)carbamoyl]tetrahydrofuran-2-carboxylate (7) (885 mg, 2.78 mmol), tetrahydrofuran (THF) (50 ml) and water (50 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 [(3,5-dichlorophenyl)carbamoyl]tetrahydrofuran-2-carboxylic acid (Inter E) (750 mg, 89% yield). 1H NMR: (400 MHz, Chloroform-d) 8.77 (s, 1H), 7.55 (d, 2H), 7.18 (t, 1H), 4.29 (tq, 2H), 2.63 (ddd, 1H), 2.46 (ddd, 1H), 2.16 (tt, 1H), 2.05 (m, 1H).

    Example 12

    Synthesis of methyl (1S,4R)-4-[[2-[(3,5-dichlorophenyl)carbamoyl]tetrahydrofuran-2-carbonyl]amino]cyclopent-2-ene-1-carboxylate (1:1 mixture of diastereomers)Compound I.16

    [1085] In a similar way to the synthesis of methyl (1S,4R)-4-[[2-[(3,5-dichlorophenyl)carbamoyl]oxetane-2-carbonyl]amino]cyclopent-2-ene-1-carboxylate (Compound I.6) commencing from Inter A, Inter E was converted to Compound I.16

    ##STR00220##

    [1086] To a solution of [(3,5-dichlorophenyl)carbamoyl]tetrahydrofuran-2-carboxylic acid (Inter E) (100 mg, 0.329 mmol) in dimethylformamide (DMF) methyl (1S,4R)-4-aminocyclopent-2-ene-1-carboxylate (5, CAS [229613-83-6]) (76 mg, 0.43 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]), (162 mg, 0.427 mmol) and then diisopropylethylamine (0.17 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 compound I.16 (119 mg, 85%, 1:1 mixture of diastereomers). 1H NMR: (400 MHz, Chloroform-d) 9.71 (s, 1H), 9.66 (s, 1H), 7.73 (m, 4H), 7.54 (m, 2H), 7.11 (m, 2H), 5.90 (dq, 2H), 5.81 (tq, 2H), 4.95 (m, 2H), 4.08 (m, 4H), 3.65 (s, 3H), 3.65 (s, 3H), 3.50 (m, 2H), 2.45 (m, 5H), 2.35 (m, 1H), 1.90 (m, 5H), 1.84 (dd, 1H).

    Example 13

    Synthesis of (1S,4R)-4-[[2-[(3,5-dichlorophenyl)carbamoyl]tetrahydrofuran-2-carbonyl]amino]cyclopentane-1-carboxylate (1:1 mixture of diastereomers)Compound I.15

    [1087] In a similar way to the synthesis of methyl (1S,4R)-4-[[2-[(3,5-dichlorophenyl)carbamoyl]tetrahydrofuran-2-carbonyl]amino]cyclopent-2-ene-1-carboxylate (Compound I.16), Inter E was converted to Compound I.15.

    ##STR00221##

    [1088] [(3,5-dichlorophenyl)carbamoyl]tetrahydrofuran-2-carboxylic acid Inter E (100 mg, 0.329 mmol) was treated with (1S,4R)-4-aminocyclopentane-1-carboxylate hydrochloride (CAS [222530-29-2]) (84 mg, 0.43 mmol) to give (1S,4R)-4-[[2-[(3,5-dichlorophenyl)carbamoyl]tetrahydrofuran-2-carbonyl]amino]cyclopentane-1-carboxylate (Compound I.15) as a colorless oil (82 mg, 58%, 1:1 mixture of diastereomers). 1H NMR: (400 MHz, Chloroform-d) 9.75 (s, 1H), 9.69 (s, 1H), 7.71 (d, 2H), 7.70 (d, 2H), 7.55 (m, 2H), 7.12 (t, 2H), 4.23 (m, 3H), 4.09 (m, 5H), 3.62 (s, 4H), 3.62 (s, 3H), 2.86 (m, 2H), 2.38 (m, 6H), 2.14 (m, 2H), 1.90 (m, 7H), 1.72 (m, 1H), 1.62 (m, 1H).

    Example 14

    Synthesis of methyl 4-[[2-[(3,5-dichlorophenyl)carbamoyl]tetrahydrofuran-2-carbonyl]amino]butanoateCompound I.18

    [1089] In a similar way to the synthesis of methyl (1S,4R)-4-[[2-[(3,5-dichlorophenyl)carbamoyl]tetrahydrofuran-2-carbonyl]amino]cyclopent-2-ene-1-carboxylate (Compound I.16), Inter E was converted to Compound I.18.

    ##STR00222##

    [1090] [(3,5-dichlorophenyl)carbamoyl]tetrahydrofuran-2-carboxylic acid (Inter E) (100 mg, 0.329 mmol) was treated with methyl 3-aminopropanoate to give methyl 4-[[2-[(3,5-dichlorophenyl)carbamoyl]tetrahydrofuran-2-carbonyl]amino]butanoate (Compound I.18) as a colorless oil (96 mg, 72%). 1H NMR: (400 MHz, Chloroform-d) 9.43 (s, 1H), 7.55 (d, 2H), 7.24 (m, 1H), 7.10 (t, 1H), 4.23 (dp, 2H), 3.68 (s, 3H), 3.34 (tt, 2H), 2.47 (m, 1H), 2.44 (m, 1H), 2.36 (t, 2H), 2.04 (dt, 1H), 1.98 (m, 1H), 1.87 (m, 2H).

    Example 15

    Synthesis of (3S)-3-[[2-[(3,5-dichlorophenyl)carbamoyl]tetrahydrofuran-2-carbonyl]amino]butanoate (1:1 mixture of diastereomers)Compound I.17

    [1091] In a similar way to the synthesis of methyl (1S,4R)-4-[[2-[(3,5-dichlorophenyl)carbamoyl]tetrahydrofuran-2-carbonyl]amino]cyclopent-2-ene-1-carboxylate (Compound I.16), Inter E was converted to Compound I.17.

    ##STR00223##

    [1092] [(3,5-dichlorophenyl)carbamoyl]tetrahydrofuran-2-carboxylic acid Inter E (100 mg, 0.329 mmol) was treated with methyl (3S)-aminobutanoate hydrochlorid to give methyl (3S)-3-[[2-[(3,5-dichlorophenyl)carbamoyl]tetrahydrofuran-2-carbonyl]amino]butanoate (Compound I.17) as a colorless oil (120 mg, 90%, 1:1 mixture of diastereomers). 1H NMR: (400 MHz, Chloroform-d) 9.48 (s, 1H), 9.28 (s, 1H), 7.58 (d, 2H), 7.56 (d, 2H), 7.48 (m, 2H), 7.08 (m, 2H), 4.33 (qd, 2H), 4.20 (tdd, 4H), 3.69 (s, 3H), 3.67 (s, 3H), 2.50 (m, 8H), 2.00 (m, 4H), 1.26 (m, 6H).

    Example 16

    2-[(3,5-dichlorophenyl)carbamoyl]-1,3-oxathiolane-2-carboxylic acid (Inter F)

    [1093] ##STR00224##

    [1094] To a mixture of 2-hydroxyethanthiol (2) (23.4 g, 0.3 mol) in THF (2 L) was added sodium hydride (26 g, 0.65 mol) at 20 C., stirred for 2 h. and then added dropwise to a solution of diethyl dibromomalonate (1) (75.4 g, 0.3 mol) in THF (100 ml) at 20 C. for 4 h. The mixture was stirred at 20 C. for 16 h under N.sub.2. The mixture was poured into ice water (1.5 L), adjusted to pH=7, concentrated, extracted with EtOAc (1.5 L). The combined organic layer was washed with brine, dried over Na.sub.2SO.sub.4, concentrated and purified by prep-HPLC (TFA-MeCNH2O) to give diethyl 1,3-oxathiolane-2,2-dicarboxylate (3) (1.8 g, 2.5%) as yellow solid. 1H NMR (400 MHz Chloroform-d) 4.40 (t, 2H), 4.29 (m, 4H), 3.19 (t, 2H), 1.31 (t, 6H).

    ##STR00225##

    [1095] To a mixture of compound diethyl 1,3-oxathiolane-2,2-dicarboxylate (3) (800 mg, 3.42 mmol) in EtOH (8 mL) and H.sub.2O (8 ml) was added KOH (191 mg, 3.418 mmol) at 0 C. The mixture was stirred at 0 C. for 2 h. The mixture was quenched with H.sub.2O (50 ml) and adjusted to pH=3 with 6N HCl, extracted with EtOAc (100 ml). The combined organics were washed with brine, dried and concentrated to give 2-ethoxycarbonyl-1,3-oxathiolane-2-carboxylic acid (4) (350 mg, 50%) as yellow oil. 1H NMR (400 MHz, Chloroform-d) 9.20 (br s, 1H), 4.45 (m, 2H), 4.33 (q, J=7.1 Hz, 2H), 3.23 (t, J=5.8 Hz, 2H), 1.33 (t, J=7.2 Hz, 3H).

    ##STR00226##

    [1096] To a solution of compound 2-ethoxycarbonyl-1,3-oxathiolane-2-carboxylic acid (4) (350 mg, 1.7 mmol) and 3,5-dichloroaniline (328.25 mg, 2.04 mmol) in THF (5 mL) was added HATU (775.2 mg, 2.04 mmol), triethylamine (0.47 ml, 3.4 mmol) at 20 C. The mixture was stirred at 20 C. for 4 h. The mixture was quenched with H.sub.2O (20 ml) and extracted with methyl ter-butyl ether (MTBE) (50 ml). The combined organic layers were washed with brine, dried and concentrated. The crude was purified by prep-HPLC (MeCN-TFA-H.sub.2O) to give ethyl 2-[(3,5-dichlorophenyl)carbamoyl]-1,3-oxathiolane-2-carboxylate (5) (320 mg, 51%) as white solid. 1H NMR (400 MHz, Chloroform-d) =8.56 (br s, 1H), 7.56 (d, J=1.8 Hz, 2H), 7.14 (t, J=1.8 Hz, 1H), 4.53 (td, J=5.2, 9.2 Hz, 1H), 4.42-4.27 (m, 3H), 3.29-3.17 (m, 2H), 1.34 (t, J=7.1 Hz, 3H)

    ##STR00227##

    [1097] In a similar way to the synthesis of diethyl 1,3-oxathiolane-2,2-dicarboxylate (4), commencing with ethyl 2-[(3,5-dichlorophenyl)carbamoyl]-1,3-oxathiolane-2-carboxylate (5), 2-[(3,5-dichlorophenyl)carbamoyl]-1,3-oxathiolane-2-carboxylic acid (Inter F) was obtained as an off-white solid (Inter F). 1H NMR (500 MHz, THF-d8) 9.98 (s, 1H), 9.50 (s, 1H), 7.75 (d, 2H), 7.15 (t, 1H), 4.42 (dt, 1H), 4.36 (dt, 1H), 3.19 (m, 2H).

    Example 17

    Synthesis of methyl (1S,4R)-4-[[2-[(3,5-dichlorophenyl)carbamoyl]-1,3-oxathiolane-2-carbonyl]amino]cyclopent-2-ene-1-carboxylate (1:1 mixture of diastereomers)Compound I.20

    [1098] ##STR00228##

    [1099] In a similar way to the synthesis for Compound I.6 described above, starting with 2-[(3,5-dichlorophenyl)carbamoyl]-1,3-oxathiolane-2-carboxylic acid (Inter F), Compound I.20 was obtained as an off-white solid (0.1 g, 72%, 1:1 mixture of diastereomers). 1H NMR (400 MHz, Chloroform-d) 9.85 (s, 1H), 9.76 (s, 1H), 7.56 (m, 6H), 7.09 (m, 2H), 5.98 (m, 2H), 5.93 (dt, 1H), 5.88 (dt, 1H), 5.03 (m, 2H), 4.63 (m, 4H), 3.73 (d, 7H), 3.55 (m, 2H), 3.23 (m, 4H), 2.49 (dtd, 2H), 1.97 (ddt, 2H).

    Example 18

    Synthesis of methyl (4S)-4-[[2-[(3,5-dichlorophenyl)carbamoyl]-1,3-oxathiolane-2-carbonyl]amino]pentanoate (1:1 mixture of diastereomers)Compound I.21

    [1100] ##STR00229##

    [1101] In a similar way to the synthesis for Compound I.7 described above, starting with 2-[(3,5-dichlorophenyl)carbamoyl]-1,3-oxathiolane-2-carboxylic acid (Inter F), methyl (4S)-4-[[2-[(3,5-dichlorophenyl)carbamoyl]-1,3-oxathiolane-2-carbonyl]amino]pentanoate (Compound I.21) was obtained as an off-white solid (40 mg, 59%, 1:1 mixture of diastereomers). 1H NMR (400 MHz, Chloroform-d) =9.79 (s, 1H), 9.68 (s, 1H), 7.53 (t, 4H), 7.10 (dt, 2H), 7.01 (m, 2H), 4.64 (m, 4H), 4.01 (m, 2H), 3.69 (s, 3H), 3.66 (s, 3H), 3.27 (m, 2H), 3.21 (m, 2H), 2.39 (m, 4H), 1.86 (m, 4H), 1.22 (t, 6H).

    Example 19

    Synthesis of 4-[(3,5-dichlorophenyl)carbamoyl]-1,3-dioxolane-4-carboxylic acid (Inter G)

    [1102] ##STR00230##

    [1103] To a solution of 3,5-dichloroaniline (1) (10 g, 61.7 mmol) in dichloromethane (200 mL) was added ethyl 3-chloro-3-oxo-propanoate (2) (9.3 g, 61.7 mmol) at 0 C. The mixture solution was stirred for 15 min. After dropwise addition of triethylamine (6.6 g, 64.8 mmol) at 0 C. and then stirred for 5 h at 0 to 15 C. The reaction was poured into water, extracted with DCM. The organic phase was washed with brine and dried over Na.sub.2SO.sub.4. The dried organic phase was filtrated, concentrated and purified by column (pentane/EtOAc=10:1 to 2:1) to give ethyl 3-(3,5-dichloroanilino)-3-oxo-propanoate (3) (19.8 g, 97%) as brown solid. 1H NMR (400 MHz, Chloroform-d) =9.49 (br s, 1H) 7.54 (d, 2H) 7.12 (t, 1H) 4.28 (q, 2H) 3.48 (s, 2H) 1.34 (t, 3H).

    ##STR00231##

    [1104] To a solution of ethyl 3-(3,5-dichloroanilino)-3-oxo-propanoate (3) (4.5 g, 16.3 mmol) in trifluoroethanol (50 mL) was added bis(trifluoroacetoxy)iodo)benzene (PIFA) (9.1 g, 21 mmol) (CAS [2712-78-9]) at 18 C. in several portions. Then the mixture solution was stirred for 16 h. The reaction was quenched with water and diluted with ethyl acetate (EtOAc). The aqueous phase was separated and extracted with EtOAc. The organic phase was washed with brine and dried over Na.sub.2SO.sub.4. The dried organic phase was filtrated, concentrated and purified by column (pentane/EtOAc=10:1 to 1:1) to give ethyl 3-(3,5-dichloroanilino)-2-hydroxy-3-oxo-propanoate (4) (2.3 g, 49%) as brown oil. 1H NMR (400 MHz, Chloroform-d) =8.60 (br s, 1H), 7.55 (d, 2H), 7.27 (s, 1H), 4.76 (s, 1H), 4.30 (m, 2H), 1.40 (t, 3H).

    ##STR00232##

    [1105] To a solution of ethyl 3-(3,5-dichloroanilino)-2-hydroxy-3-oxo-propanoate (4) (1.0 g, 3.4 mmol) in dimethoxymethane (5) (5 mL) was added BF.sub.3 etherate (0.3 g, 1.7 mmol) at 20 C. in one portion. Then the mixture solution was heated to 60 C. and stirred for 4 h. The reaction was quenched with water and extracted with EtOAc. The organic phase was washed with brine and dried over Na.sub.2SO.sub.4. The dried organic phase was filtrated, concentrated and purified by column (pentane/EtOAc=10:1 to 2:1) to give ethyl 3-(3,5-dichloroanilino)-2-(methoxymethoxy)-3-oxo-propanoate (6) (0.6 g, 54%) as a yellow oil. 1H NMR (400 MHz, Chloroform-d) =8.39 (br s, 1H), 7.56 (d, 2H), 7.14 (t, 1H), 4.84 (d, 2H), 4.72 (s, 1H), 4.31 (m, 2H), 3.45 (s, 3H), 1.34 (t, 3H).

    ##STR00233##

    [1106] To a solution of ethyl 3-(3,5-dichloroanilino)-2-(methoxymethoxy)-3-oxo-propanoate (6) (0.3 g, 0.9 mmol) in toluene (3 mL) was added paraformaldehyde (0.27 g, 2.7 mmol) and paratoluenesulfonic acid (PTSA) (16 mg, 0.09 mmol) at 20 C. Then the mixture solution was heated to 90 C. and stirred for 0.5 h. The reaction was concentrated to move toluene and the residue was purified by column (pentane/EtOAc=10:1 to 1:1) to give ethyl 2-[(3,5-dichlorophenyl)carbamoyl]-1,3-dioxolane-2-carboxylate (7) (190 mg, 63%) as white solid. 1H NMR (400 MHz, Chloroform-d) =8.45 (br s, 1H), 7.56 (d, 2H), 7.16 (t, 1H), 5.29 (s, 1H), 5.11 (s, 1H), 4.52 (m, 1H), 4.43 (m, 1H), 4.31 (q, 2H), 1.32 (t, 3H).

    ##STR00234##

    [1107] In a similar way to the synthesis of 2-[(3,5-dichlorophenyl)carbamoyl]-1,3-oxathiolane-2-carboxylic acid (Inter F), starting with ethyl 4-[(3,5-dichlorophenyl)carbamoyl]-1,3-dioxolane-4-carboxylate (0.17 g, 0.50 mmol), 4-[(3,5-dichlorophenyl)carbamoyl]-1,3-dioxolane-4-carboxylic acid (Inter G) was obtained as an off-white solid (111 mg, 72%). LC-MS (M+H).sup.+: 307.8

    Example 20

    Synthesis of methyl (1S,4R)-4-[[4-[(3,5-dichlorophenyl)carbamoyl]-1,3-dioxolane-4-carbonyl]amino]cyclopent-2-ene-1-carboxylate (1:1 mixture of diastereomers)Compound I.22

    [1108] ##STR00235##

    [1109] In a similar way to the synthesis for Compound I.7 described above, starting with 4-[(3,5-dichlorophenyl)carbamoyl]-1,3-dioxolane-4-carboxylic acid (Inter G), methyl (1S,4R)-4-[[4-[(3,5-dichlorophenyl)carbamoyl]-1,3-dioxolane-4-carbonyl]amino]cyclopent-2-ene-1-carboxylate (Compound I.22) was obtained as an off-white solid (55 mg, 68%, 1:1 mixture of diastereomers). 1H NMR (400 MHz, Chloroform-d) 9.47 (s, 1H), 9.28 (s, 0H), 7.57 (d, 1H), 7.55 (m, 2H), 7.13 (m, 1H), 5.33 (d, 1H), 5.25 (d, 1H), 4.30 (m, 2H), 4.22 (d, 1H), 3.70 (s, 2H), 3.69 (s, 1H), 2.55 (m, 2H), 1.29 (d, 1H), 1.27 (d, 1H).

    Example 21

    Synthesis of methyl 4-[[4-[(3,5-dichlorophenyl)carbamoyl]-1,3-dioxolane-4-carbonyl]amino]butanoateCompound I.23

    [1110] ##STR00236##

    [1111] In a similar way to the synthesis for Compound I.7 described above, starting with 4-[(3,5-dichlorophenyl)carbamoyl]-1,3-dioxolane-4-carboxylic acid (Inter G), methyl 4-[[4-[(3,5-dichlorophenyl)carbamoyl]-1,3-dioxolane-4-carbonyl]amino]butanoate (Compound I.23) was obtained as an off-white solid (40 mg, 60%). 1H NMR (400 MHz, Chloroform-d) 9.50 (s, 1H), 7.55 (d, 2H), 7.29 (s, 1H), 7.13 (t, 1H), 5.35 (s, 1H), 5.25 (s, 1H), 4.32 (d, 1H), 4.21 (d, 1H), 3.69 (s, 3H), 3.38 (m, 2H), 2.38 (t, 2H), 1.90 (m, 2H).

    Example 22

    Synthesis of tert-butyl 2-[(3,5-dichlorophenyl)carbamoyl]-2-[[(1R,4S)-4-methoxycarbonylcyclopent-2-en-1-yl]carbamoyl]pyrrolidine-1-carboxylate (1:1 mixture of diastereomers)Compound I.35

    [1112] ##STR00237##

    [1113] To a solution of diethyl 2-diazopropanedioate (1) (5.86 g, 31.5 mmol) and tert-butyl N-(3-bromopropyl)carbamate (5 g, 21 mmol) in toluene (50 mL) bis[Rhodium (,,,-tetramethyl-1,3-benzenedipropionic acid)] ([R.sup.h(esp)].sub.2 CAS [819050-89-0], 100 mg, 0.13 mmol) was added and the mixture was stirred for 2.5 h at 60 C. After cooling to room temperature, tetrabutylammonium bromide (677 mg, 2.1 mmol) and cesium hydroxide monohydrate (7.1 g, 42 mmol) were added and the mixture stirred for 18 h. After filtration through Celite and washing with EtOAc, the filtrate was purified by column chromatography (silica RP18, MeCN/H.sub.2O) to afford compound 3 (3.5 g, 53%, 1:1 mixture of atropisomers) as a colorless oil. 1H NMR (400 MHz, Chloroform-d) 4.26 (m, 4H), 3.56 (m, 2H), 2.48 (m, 2H), 1.86 (m, 2H), 1.47 (s, 9H), 1.41 (s, 9H), 1.29 (m, 6H).

    ##STR00238##

    [1114] To a solution of compound 3 (3.5 g, 11 mmol) in a 1:1 mixture of H.sub.2O and THF (50 mL) lithium hydroxide (266 mg, 11.1 mmol) was added and the mixture stirred for 2 h. After concentrating the mixture, the residue was dissolved in THF (50 mL) and treated with 3,5-dichloroaniline (1.77 g, 10.9 mmol) and triethylamine (4.56 mL, 32.7 mmol). The reaction was quenched with H.sub.2O. The organic layer was separated and extracted with ethyl acetate. The combined filtrates were washed with brine and concentrated. The residue was purified by flash column chromatography (pentane/EtOAc) to afford compound 4 (0.7 g, 15% over two steps) as an off-white solid. 1H NMR (400 MHz, Chloroform-d) 7.86 (m, 2H), 7.28 (m, 1H), 7.25 (m, OH), 3.57 (m, 2H), 2.43 (m, 2H), 2.07 (m, 2H), 1.45 (s, 4H), 1.30 (s, 6H).

    ##STR00239##

    [1115] To a solution of compound 4 (0.7 g, 1.6 mmol) in a 1:1 mixture of H.sub.2O and THE (50 mL) lithium hydroxide (266 mg, 11.1 mmol) was added and the mixture stirred for 2 h. After concentrating the mixture, the residue was dissolved in dimethylformamide (DMF) (10 mL) and treated with [(1R,4S)-4-methoxycarbonylcyclopent-2-en-1-yl]ammonium chloride (329 mg, 1.85 mmol) and HATU (705 mg, 1.85 mmol). After stirring for 18 h, the reaction was quenched with water. The aqueous layer was separated and extracted with ethyl acetate. The combined filtrates were washed with brine and concentrated. The residue was purified by column chromatography (silica RP18, MeCN/H.sub.2O) to afford compound I.35 (380 mg, 48%, 1:1 mixture of diastereomers, mixture of rotamers) as an off-white solid. 1H NMR (400 MHz, Chloroform-d) 11.27 (s, 1H), 11.22 (s, 1H), 7.61 (d, 4H), 7.09 (m, 2H), 5.96 (m, 4H), 5.04 (m, 2H), 3.80 (m, 2H), 3.72 (m, 10H), 3.56 (m, 2H), 2.40 (m, 6H), 1.95 (m, 6H), 1.32 (s, 9H), 1.27 (s, 9H).

    Example 23

    Synthesis of methyl (1S,4R)-4-[[2-[(3,5-dichlorophenyl)carbamoyl]pyrrolidine-2-carbonyl]amino]cyclopent-2-ene-1-carboxylate (1:1 mixture of diastereomers)Compound I.33

    [1116] ##STR00240##

    [1117] A solution of hydrochloric acid (1.25 M in methanol, 2 mL) was added to compound I.35 (350 mg, 0.665 mmol) and the mixture stirred for 1 h under refluxing conditions. After concentrating, the ammonium salt of compound I.33 (280 mg, 99%, 1:1 mixture of diastereomers) was obtained as an off-white solid. 1H NMR (400 MHz, Chloroform-d) 11.04 (s, 1H), 10.96 (s, 1H), 8.41 (s, 2H), 7.77 (d, 4H), 7.11 (s, 1H), 7.09 (s, 1H), 5.95 (m, 4H), 4.94 (s, 2H), 3.71 (m, 8H), 3.53 (m, 2H), 2.94 (s, 2H), 2.74 (s, 2H), 2.45 (m, 2H), 2.10 (m, 8H).

    Example 24

    Synthesis of methyl (1S,4R)-4-[[2-[(3,5-dichlorophenyl)carbamoyl]-1-methyl-pyrrolidine-2-carbonyl]amino]cyclopent-2-ene-1-carboxylate (1:1 mixture of diastereomers)Compound I.34

    [1118] ##STR00241##

    [1119] To a solution of compound I.33 (50 mg, 0.12 mmol) in acetonitrile (2 mL) an aqueous solution of formaldehyde (5 equiv) and sodium cyanoborohydride (12 mg, 0.19 mmol) were added. After stirring for 15 min, the reaction was quenched with acetic acid until pH=7 was reached and the mixture stirred for another 30 min. After concentrating the mixture, the residue dissolved in ethyl acetate, washed with an aqueous saturated solution of sodium bicarbonate (3) and dried over Na.sub.2SO.sub.4. After concentrating, the crude compound I.34 was obtained as a colorless oil (39 mg, 76%, 1:1 mixture of diastereomers). 1H NMR (400 MHz, Chloroform-d) 10.84 (s, 1H), 10.82 (s, 1H), 8.28 (s, 1H), 8.25 (s, 1H), 7.57 (s, 2H), 7.57 (s, 2H), 7.08 (m, 2H), 5.92 (m, 4H), 5.01 (m, 2H), 3.73 (s, 3H), 3.73 (s, 3H), 3.56 (m, 2H), 3.21 (m, 4H), 2.51 (m, 8H), 2.32 (m, 4H), 1.95 (m, 6H).

    Example 25

    Synthesis of methyl (3S)-3-[[3-[(3,5-dichlorophenyl)carbamoyl]-2-oxabicyclo[2.2.2]oct-5-ene-3-carbonyl]amino]butanoate (1:1 mixture of diastereoisomers)Compound I.174

    [1120] ##STR00242##

    [1121] According to the literature J. Org. Chem. 1997, 42, 4095-4103, diethyl ketomalonate (1) (5.0 g, 29 mmol) was added to a solution of hydroguinone (50 mg, 0.45 mmol) and freshly distilled 1,3-cyclohexadiene (2) (5.06 g, 63.2 mmol) in acetonitrile (20 mL). The mixture was placed in a microwave and heated to 130 C. for 4 h. After cooling to room temperature, the mixture was concentrated under reduced pressure and the residue purified by column chromatography (silica RP18, MeCN/H.sub.2O) to yield the title compound 3 (4.5 g, 62%) as a colourless oil. 1H NMR (400 MHz, Chloroform-d) 6.53 (ddd, 1H), 6.46 (ddd, 1H), 4.68 (ddt, 1H), 4.22 (m, 4H), 2.18 (m, 1H), 1.63 (m, 1H), 1.26 (m, 9H).), which is in alignment with the reported literature.

    ##STR00243##

    [1122] In analogy to example 1, lithium hydroxide (418 mg, 17.4 mmol) was added to a solution of diethyl 2-oxabicyclo[2.2.2]oct-5-ene-3,3-dicarboxylate (3) (4.43 g, 17.4 mmol) in a 1:1-mixture of THE and water (50 mL). After stirring the mixture at room temperature for 2 h, THF was evaporated in vacuo and the remainder dried to give the product (4) (4.0 g, 99% yield). 1H NMR (500 MHz, Deuterium Oxide) 6.56 (m, 1H), 6.47 (m, 1H), 4.60 (m, 1H), 4.14 (m, 2H), 3.37 (m, 1H), 2.08 (m, 1H), 1.60 (m, 1H), 1.26 (m, 5H).

    ##STR00244##

    [1123] In analogy to example 1, 1-propanephosphonic anhydride (16.6 g, 29.3 mmol) was added to a solution of lithium (3-ethoxycarbonyl-2-oxabicyclo[2.2.2]oct-5-ene-3-carboxylate (5) (4.0 g, 17 mmol), 3,5-dichloroaniline (6) (2.8 g, 17 mmol), triethylamine (5.2 g, 52 mmol) in THE (50 mL) at 0 C. 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 (silica RP18, MeCN/H.sub.2O) yielding ethyl 3-[(3,5-dichlorophenyl)carbamoyl]-2-oxabicyclo[2.2.2]oct-5-ene-3-carboxylate (7) (1.3 g, 20%) as a colorless oil. 1H NMR (400 MHz, Chloroform-d) 8.94 (s, 1H), 7.58 (d, 2H), 7.13 (t, 1H), 6.57 (ddd, 1H), 6.47 (ddd, 1H), 4.80 (m, 1H), 4.19 (m, 2H), 3.69 (m, 1H), 2.03 (tt, 1H), 1.66 (ddt, 1H), 1.35 (m, 2H), 1.26 (t, 3H).

    ##STR00245##

    [1124] In analogy to example 1, lithium hydroxide (168 mg, 7.0 mmol) was added to a solution of ethyl 3-[(3,5-dichlorophenyl)carbamoyl]-2-oxabicyclo[2.2.2]oct-5-ene-3-carboxylate (7) (1.3 g, 3.5 mmol) in a 1:1-mixture of THE and water (20 mL). After stirring the mixture at room temperature for 2 h, THE was evaporated in vacuo and the residue was acidified to pH=1 with HCl (1 M). The aqueous acidic phase was extracted with ethyl acetate (310 mL) and the combined extracts were dried over MgSO.sub.4. After concentration, the product (8) (900 g, 99% yield) was obtained as colorless amorphous crystals and was used in the next step without further purification. 1H NMR (400 MHz, Chloroform-d) 8.94 (s, 1H), 7.58 (d, 2H), 7.16 (t, 1H), 6.54 (m, 2H), 4.89 (m, 1H), 3.63 (dd, 1H), 2.08 (m, 1H), 1.71 (ddt, 1H), 1.39 (m, 2H).

    ##STR00246##

    [1125] In analogy to example 3, to a solution of carboxylic acid 8 (150 mg, 0.438 mmol) in dimethylformamide (DMF, 5 mL) (3S)-3-aminobutanoate (9) hydrochloride (80.8 mg, 0.503 mmol) (CAS [139243-55-3]) 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]), (210 mg, 0.526 mmol) and then diisopropyl ethyl amine (0.22 mL, 1.3 mmol). 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 (silica RP18, MeCN/H.sub.2O) yielding compound I.174 (128 mg, 66%, 1:1 mixture of diastereomers). 1H NMR (400 MHz, Chloroform-d) 9.35 (s, 1H), 9.28 (s, 1H), 7.57 (m, 4H), 7.08 (m, 2H), 6.44 (m, 4H), 4.85 (t, 2H), 4.27 (m, 2H), 3.67 (m, 7H), 3.53 (ddd, 1H), 2.55 (m, 2H), 2.47 (dd, 4H), 2.18 (m, 1H), 1.72 (m, 1H), 1.29 (m, 4H), 1.18 (m, 6H).

    Example 26

    Synthesis of methyl (1S,4R)-4-[[5-[(3,5-dichlorophenyl)carbamoyl]-3-methyl-4H-isoxazole-5-carbonyl]amino]cyclopent-2-ene-1-carboxylate (1:1 mixture of diastereoisomers)Compound I.178

    [1126] ##STR00247##

    [1127] To a solution of compound ethyl 2-(hydroxymethyl)prop-2-enoate (1) (CAS: 10029-04-6, 4.3 g, 33 mmol) in dichloromethane (45 mL) was added tert-butyldiphenylsilyl chloride (CAS: 58479-61-1, 9.97 g, 36.3 mmol) and imidazole (2.69 g, 39.6 mmol) at room temperature. The mixture was stirred for 2 h at room temperature. The mixture was filtered and the filtrate was concentrated. The crude was purified by column chromatography (pentane/EtOAc) to afford compound 2 (11.3 g, 93%) as yellow oil. 1H NMR (400 MHz, Chloroform-d) 7.68 (dd, 4H), 7.41 (m, 6H), 6.34 (q, 1H), 6.11 (q, 1H), 4.44 (t, 2H), 4.18 (m, 2H), 1.27 (m, 3H), 1.10 (m, 9H).

    ##STR00248##

    [1128] To a mixture of compound 2 (20 g, 54.3 mmol), di-tert-butyl dicarbonate (CAS: 24424-99-5, 23.7 g, 108.6 mmol) and 4-dimethylaminopyridine (1.3 g, 10.9 mmol) in chloroform (200 mL) was added compound nitroethane (3) (10.2 g, 135.8 mmol) dropwise. The mixture was stirred for 16 h at room temperature. The mixture was poured into the solution of NH.sub.4Cl (aq), extracted with dichloromethane, the organic layers was washed with brine, dried, concentrated. The residue was purified by column chromatography (pentane/EtOAc) to afford compound 4 (17.5 g, 75%) as brown oil. 1H NMR (400 MHz, Chloroform-d) 7.67 (m, 4H), 7.49-7.36 (m, 6H), 4.23 (q, 2H), 3.99 (m, 1H), 3.89 (m, 1H), 3.44 (dd, 1H), 3.50-3.39 (m, 1H), 3.12 (dd, 1H), 1.99 (s, 3H), 1.29 (m, 3H), 1.04 (s, 9H)

    ##STR00249##

    [1129] To a solution of compound 4 (17.5 g, 41.2 mmol) in THF (175 mL) was added tetrabutylammonium fluoride (TBAF, 1 M in THF, 61.8 mL, 61.8 mmol) dropwise at 0 C. The mixture was stirred for 2 h at the same temperature. The mixture was poured into ice water, extracted with ethyl acetate, the organic layers was washed with brine, dried, concentrated. The residue was purified by column chromatography (pentane/EtOAc) to afford compound 5 (4 g, 52%) as brown oil. 1H NMR (400 MHz, Chloroform-d) 4.24 (m, 2H), 3.73 (m, 2H), 3.22 (m, 2H), 2.54 (br s, 1H), 1.98 (s, 3H), 1.29 (t, 3H).

    ##STR00250##

    [1130] The mixture of compound 5 (2 g, 10.7 mmol) and pyridinium dichromate (PDC, CAS: 20039-37-6, 40.2 g, 107 mmol) in DMF (40 mL) was stirred for 16 h at room temperature. The mixture was poured into ice water, adjusted pH=3 with 3N HCl, extracted with EtOAc, the organic layers was washed with brine, dried, concentrated to give compound 6 (1.8 g, Crude) as brown oil.

    ##STR00251##

    [1131] In analogy to example 1, to a solution of compound 6 (1.8 g, 8.0 mmol) in THF (18 mL) was added 3,5-dichloroaniline (1.7 g, 10.8 mmol), HATU (4.1 g, 10.8 mmol), triethylamine (1.8 g, 18 mmol) at room temperature. After stirring for 3 h at the same temperature, the mixture was poured into ice water, extracted with EtOAc, the organic layers was washed with brine, dried, concentrated. The residue was purified by prep-HPLC (NH.sub.4HCO.sub.3, MeCNH.sub.2O) to give compound 7 (651 mg, 28%) as brown solid. 1H NMR (400 MHz, Chloroform-d) 8.65 (br s, 1H), 7.58 (d, 2H), 7.17 (s, 1H), 4.32 (m, 2H), 3.92 (d, 1H), 3.47 (d, 1H), 2.05 (s, 3H), 1.31 (t, 3H).

    ##STR00252##

    [1132] In analogy to example 1, lithium hydroxide (66.2 mg, 2.85 mmol) was added to a solution of compound 7 (575 mg, 1.67 mmol) in a 1:1-mixture of THF and water (5 mL). After stirring the mixture at room temperature for 2 h, THF was evaporated in vacuo and the residue was acidified to pH=1 with HCl (1 M). The aqueous acidic phase was extracted with ethyl acetate (310 mL) and the combined extracts were dried over MgSO.sub.4. After concentration, the product (8) (900 g, 99% yield) was obtained as colorless amorphous crystals and was used in the next step without further purification. LC-MS (M+H).sup.+: 317.1

    ##STR00253##

    [1133] In analogy to example 2, to a solution of carboxylic acid 8 (150 mg, 0.438 mmol) in dimethylformamide (DMF, 5 mL) methyl (1S,4R)-4-aminocyclopent-2-ene-1-carboxylate hydrochloride (CAS: 180196-56-9, 148 mg, 0.833 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]), (316 mg, 0.833 mmol) and then diisopropyl ethyl amine (0.35 mL, 2.1 mmol). 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 (silica RP18, MeCN/H.sub.2O) yielding compound I.178 (245 mg, 80%, 1:1 mixture of diastereomers). 1H NMR (400 MHz, Chloroform-d) 8.86 (s, 1H), 8.74 (s, 1H), 7.61 (d, 2H), 7.56 (d, 2H), 7.35 (d, 1H), 7.27 (m, 1H), 7.12 (m, 2H), 6.01 (dq, 1H), 5.96 (ddd, 1H), 5.91 (m, 2H), 5.00 (m, 2H), 3.73 (m, 6H), 3.61 (m, 2H), 3.54 (m, 2H), 2.45 (dt, 1H), 2.36 (dt, 1H), 2.17 (s, 6H), 2.03 (m, 4H).

    Example 27

    Synthesis of methyl (1S,4R)-4-[[5-[(3,5-dichlorophenyl)carbamoyl]-2H-thiophene-5-carbonyl]amino]cyclopent-2-ene-1-carboxylate (1:1 mixture of diastereoisomers)Compound I.177

    [1134] ##STR00254##

    [1135] To a solution of dimethyl 2-chloropropanedioate (1) (45.5 g, 274 mmol) in THF (300 ml) was added 3-sulfanylpropan-1-ol (2) (19.5 g, 212 mmol) and Na.sub.2CO.sub.3 (67.3 g, 635 mmol) at room temperature. The mixture was stirred at 45 C. for 16 h. The reaction mixture was filtered and the filtrate was concentrated. The crude was purified by column chromatography by applying a gradient (EtOAc/pentane=100:0 to 1:1) to give compound 3 (54 g, 89%) as yellow oil. 1H NMR (400 MHz, Chloroform-d) 4.22 (s, 1H), 3.80 (s, 6H), 3.76 (t, 2H), 2.86 (t, 2H), 1.86 (m, 2H).

    ##STR00255##

    [1136] In two parallel reactions, 4 molecular sieve (27 g*2) and pyridinium chlorochromate (PCC, 39 g*2 g, 182 mmol*2) was added to a solution of compound (27*2 g, 121.6*2 mmol) in dichloromethane (1.5*2 L) at room temperature. The two mixtures were stirred in two different flasks for 4h. The two mixtures were filtered and the combined filtrates were concentrated. The residue was purified by column chromatography by applying a gradient (EtOAc/pentane=100:0 to 1:1) to give compound 4 (21 g, 39%) as yellow oil. 1H NMR (400 MHz, Chloroform-d) 4.80 (br d, 1H), 3.82 (s, 3H), 3.78 (s, 3H), 3.17 (m, 1H), 2.97 (m, 2H), 2.38 (m, 2H).

    ##STR00256##

    [1137] To a solution of compound 4 (19.5 g, 88.6 mmol) and 4-dimethylaminopyridine (54 g, 443 mmol) in dichloromethane (400 mL) was added trifluoromethanesulfonic anhydride (62.5 g, 221.6 mmol) dropwise at 40 C. After warming to room temperature, the mixture was stirred for 16 h at the same temperature before the reaction was quenched with H.sub.2O (500 mL). The aqueous layer was separated and extracted with dichloromethane. The combined extracts were washed with brine, dried over Na.sub.2SO.sub.4 and concentrated. The residue was purified by column chromatography by applying a gradient (EtOAc/pentane=100:0 to 1:1) to give compound 5 (10 g, 55.9%) as yellow solid. 1H NMR (400 MHz, Chloroform-d) 6.11 (td, 1H), 5.98 (td, 1H), 3.88 (t,), 3.80 (m, 6H).

    ##STR00257##

    [1138] To a solution of compound 5 (7.25 g, 35.9 mmol) in MeOH (60 mL) was added lithium hydroxide (1.5 g, 35.9 mmol) in H.sub.2O (60 mL) dropwise at 0 C. The mixture was stirred for 2h at 0 C. The reaction mixture was quenched with H.sub.2O (100 mL) and adjusted to pH=3, extracted with EtOAc (80 mL*2). The combined organics were washed with brine, dried over Na.sub.2SO.sub.4 and concentrated to give compound 6 (6 g, 89%) as yellow solid. 1H NMR (400 MHz, Chloroform-d) 6.15 (m, 1H), 5.99 (td, 1H), 3.92 (t, 2H), 3.83 (m, 4H).

    ##STR00258##

    [1139] To a solution of compound 6 (5 g, 26.6 mmol) in dichloromethane (50 mL) was added DMF (1 drop) and oxalyl chloride (6.9 g, 53.2 mmol) dropwise at 0 C. The mixture was stirred for 2h at 0 C. The mixture was added dropwise to the solution of 3,5-dichloroaniline (6.5 g, 39.9 mmol) and pyridine (8.4 g, 106.4 mmol) in dichloromethane (50 mL) at 0 C. After stirring for 2 h at the same temperature, the reaction was quenched with H.sub.2O (50 mL). The aqueous layer was extracted with EtOAc (50 mL*2). The combined extracts were washed with brine, dried over Na.sub.2SO.sub.4 and concentrated. The crude was purified by column chromatography by applying a gradient (EtOAc/pentane=100:0 to 70:30) to give compound 7 (8 g, 91%) as yellow solid. 1H NMR (400 MHz, Chloroform-d) 9.13 (br s, 1H), 7.56 (d, 2H), 7.15 (t, 1H), 6.13 (m, 2H), 3.99 (m, 2H), 3.82 (s, 3H).

    ##STR00259##

    [1140] To a solution of compound 7 (3.31 g, 10 mmol) in a 1:1 mixture of methanol and water (40 mL) was added lithium hydroxide (420 mmol, 10 mmol) at 0 C. The mixture was stirred for 1 h at 0 C. The reaction was quenched with H.sub.2O (50 mL), washed with EtOAc (50 mL). The aqueous phase was adjusted to pH=3 with 6N HCl and extracted with EtOAc (50 mL*2). The combined organics were washed with brine, dried over Na.sub.2SO.sub.4 and concentrated to give compound 8 (2 g, 63%) as yellow solid. 1H NMR (400 MHz, MeOD) 7.67 (d, 2H), 7.20 (t, 1H), 6.18 (dt, 1H), 6.04 (dt, 1H), 4.97 (m, 2H).

    ##STR00260##

    [1141] To a solution of compound 8 (500 mg, 4.58 mmol) and methyl (1S,4R)-4-aminocyclopent-2-ene-1-carboxylate (418 mg, 2.36 mmol) in THF (10 mL) was added triethylamine (478 mg, 9.26 mmol) and 1-propanephosphonic anhydride (636 mg, 5.58 mmol) dropwise at 0 C. The mixture was stirred for 1h at 0 C. The reaction mixture was quenched with H.sub.2O (20 mL) and extracted with EtOAc (20 mL*2). The combined organics were washed with brine, dried over Na.sub.2SO.sub.4 and concentrated. The crude was purified by column chromatography by applying a gradient (EtOAc/pentane=100:0 to 0:100) to give compound I.177 (370 mg, 53%, 1:1 mixture of diastereomers) as yellow solid. 1H NMR (400 MHz, MeOD) 7.65 (m, 4H), 7.18 (m, 2H), 6.20 (m, 8H), 4.95 (m, 2H), 3.99 (m, 4H), 3.72 (s, 3H), 3.71 (s, 3H), 3.59 (m, 2H), 2.51 (m, 2H), 1.96 (m, 2H).

    [1142] High Performance Liquid Chromatography: HPLC-column KinetexXB C18 1.7 (502.1 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).

    [1143] In analogy to the examples described above, the following compounds of formula (I) were prepared, wherein R.sup.1 is hydrogen, and W is formed by R.sup.7 and R.sup.8 together with the carbon atom to which they are bound, starting from commercially available diesters and using commercially available amines:

    ##STR00261##

    TABLE-US-00002 TABLE 2 Cpd. R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 W R.sup.9 N* XY HPLC/MS I.1 H F H F H [00262]embedded image H [00263]embedded image 314.8 I.2 H F H F H [00264]embedded image H [00265]embedded image 379.0 I.3 H F H F H [00266]embedded image H [00267]embedded image 294.8 I.4 H F H F H [00268]embedded image H [00269]embedded image 408.8 I.5 H F F F H [00270]embedded image H [00271]embedded image 357.0 I.6 H Cl H Cl H [00272]embedded image H [00273]embedded image 388.8 I.7 H Cl H Cl H [00274]embedded image H [00275]embedded image 374.6 I.8 H Cl H Cl H [00276]embedded image H [00277]embedded image 388.9 I.9 H Cl H Cl H [00278]embedded image H [00279]embedded image 440.8 I.10 H Cl H Cl H [00280]embedded image H [00281]embedded image 426.9 I.11 H Cl H Cl H [00282]embedded image H [00283]embedded image 440.9 I.12 H Cl H Cl H [00284]embedded image H [00285]embedded image 462.9 I.13 H Cl H Cl H [00286]embedded image H [00287]embedded image 451.1 I.14 H Cl H Cl H [00288]embedded image H [00289]embedded image 374.6 I.15 H Cl H Cl H [00290]embedded image H [00291]embedded image 428.8 I.16 H Cl H Cl H [00292]embedded image H [00293]embedded image 427.0 I.17 H Cl H Cl H [00294]embedded image H [00295]embedded image 402.9 I.18 H Cl H Cl H [00296]embedded image H [00297]embedded image 402.9 I.19 H Cl H Cl H [00298]embedded image H [00299]embedded image 405.0 I.20 H Cl H Cl H [00300]embedded image H [00301]embedded image 444.7 I.21 H Cl H Cl H [00302]embedded image H [00303]embedded image 435.0 I.22 H Cl H Cl H [00304]embedded image H [00305]embedded image 405.0 I.23 H Cl H Cl H [00306]embedded image H [00307]embedded image 404.9 I.24 H Cl H Cl H [00308]embedded image H [00309]embedded image 424.7 I.25 H Cl H Cl H [00310]embedded image H [00311]embedded image 400.9 I.26 H Cl H Cl H [00312]embedded image H [00313]embedded image 414.9 I.27 H Cl H Cl H [00314]embedded image Me [00315]embedded image 438.9 I.28 H Cl H Cl H [00316]embedded image H [00317]embedded image 439.1 I.29 H Cl H Cl H [00318]embedded image H [00319]embedded image 453.1 I.30 H Cl H Cl H [00320]embedded image H [00321]embedded image 442.9 I.31 H Cl H Cl H [00322]embedded image H [00323]embedded image 453.2 I.32 H Cl H Cl H [00324]embedded image H [00325]embedded image 443.2 I.33 H Cl H Cl H [00326]embedded image H [00327]embedded image 425.9 I.34 H Cl H Cl H [00328]embedded image H [00329]embedded image 439.9 I.35 H Cl H Cl H [00330]embedded image H [00331]embedded image 526.1 I.36 H Cl H Cl H [00332]embedded image H [00333]embedded image 466.9 I.37 H Cl H Cl H [00334]embedded image H [00335]embedded image 464.9 I.38 H F H F H [00336]embedded image H [00337]embedded image 421.2 I.39 H F H F H [00338]embedded image H [00339]embedded image 395.2 I.40 H F H F H [00340]embedded image H [00341]embedded image 369.2 I.41 H F H F H [00342]embedded image H [00343]embedded image 379.2 I.42 H F H F H [00344]embedded image H [00345]embedded image 393.3 I.43 H F H F H [00346]embedded image H [00347]embedded image 392.9 I.44 H Cl H Cl H [00348]embedded image H [00349]embedded image 421.2 I.45 H Cl H Cl H [00350]embedded image H [00351]embedded image 452.9 I.46 H F H F H [00352]embedded image H [00353]embedded image 397.1 I.47 H F H F H [00354]embedded image H [00355]embedded image 395 I.48 H F H F H [00356]embedded image H [00357]embedded image 396.9 I.49 H F H F H [00358]embedded image H [00359]embedded image 381.1 I.50 H F H F H [00360]embedded image H [00361]embedded image 393.1 I.51 H F H F H [00362]embedded image H [00363]embedded image 411.1 I.52 H F H F H [00364]embedded image H [00365]embedded image 425.2 I.53 H Cl H Cl H [00366]embedded image H [00367]embedded image 411.2 I.54 H CH.sub.2CH.sub.3 H H H [00368]embedded image H [00369]embedded image 413.3 I.55 H I H H H [00370]embedded image H [00371]embedded image 511 I.56 H Cl Cl Cl H [00372]embedded image H [00373]embedded image 488.9 I.57 H F F F H [00374]embedded image H [00375]embedded image 439 I.58 H OCF.sub.3 H H H [00376]embedded image H [00377]embedded image 469 I.59 H OCF.sub.3 H F H [00378]embedded image H [00379]embedded image 487 I.60 H OCF.sub.3 H Cl H [00380]embedded image H [00381]embedded image 503 I.61 H F H Cl H [00382]embedded image H [00383]embedded image 437.1 I.62 H CN H F H [00384]embedded image H [00385]embedded image 428 I.63 H Cl H H H [00386]embedded image H [00387]embedded image 419.1 I.64 H F H H H [00388]embedded image H [00389]embedded image 403.3 I.65 H CF.sub.3 H H H [00390]embedded image H [00391]embedded image 453 I.66 H CF.sub.3 H Cl H [00392]embedded image H [00393]embedded image 487 I.67 H Cl Cl Cl H [00394]embedded image H [00395]embedded image 447.2 I.68 H Cl Cl Cl H [00396]embedded image H [00397]embedded image 462.8 I.69 H Cl Cl Cl H [00398]embedded image H [00399]embedded image 462.8 I.70 H Cl Cl Cl H [00400]embedded image H [00401]embedded image 448.8 I.71 H OCF.sub.3 H H H [00402]embedded image H [00403]embedded image 431.1 I.72 H OCF.sub.3 H H H [00404]embedded image H [00405]embedded image 417.1 I.73 H OCF.sub.3 H H H [00406]embedded image H [00407]embedded image 441 I.74 H OCF.sub.3 H H H [00408]embedded image H [00409]embedded image 443 I.75 H OCF.sub.3 H H H [00410]embedded image H [00411]embedded image 440.4 I.76 H Cl F Cl H [00412]embedded image H [00413]embedded image 471.3 I.77 H OCHF.sub.2 H H H [00414]embedded image H [00415]embedded image 451.3 I.78 H OCF.sub.3 H CH.sub.3 H [00416]embedded image H [00417]embedded image 483.4 I.79 H OCH.sub.3 H H H [00418]embedded image H [00419]embedded image 415.3 I.80 H OCH.sub.3 H F H [00420]embedded image H [00421]embedded image 433.3 I.81 H CH.sub.3 H F H [00422]embedded image H [00423]embedded image 417.3 I.82 H Cl H Cl H [00424]embedded image H [00425]embedded image 387.2 I.83 H Cl H Cl H [00426]embedded image H [00427]embedded image 401.2 I.84 H Cl H Cl H [00428]embedded image H [00429]embedded image 399.2 I.85 H Cl H Cl H [00430]embedded image H [00431]embedded image 411.2 I.86 H Cl H Cl H [00432]embedded image H [00433]embedded image 547.4 I.87 H Cl H Cl H [00434]embedded image H [00435]embedded image 507.3 I.88 H Cl H Cl H [00436]embedded image H [00437]embedded image 469.3 I.89 H Cl H Cl H [00438]embedded image H [00439]embedded image 547.4 I.90 H Cl H Cl H [00440]embedded image H [00441]embedded image 468.9 I.91 H Cl H Cl H [00442]embedded image H [00443]embedded image 444.8 I.92 H Cl H Cl H [00444]embedded image H [00445]embedded image 440.9 I.93 H Cl H Cl H [00446]embedded image H [00447]embedded image 440.9 I.94 H Cl H Cl H [00448]embedded image H [00449]embedded image 454.9 I.95 H Cl H Cl H [00450]embedded image H [00451]embedded image 452.9 I.96 H Cl H Cl H [00452]embedded image H [00453]embedded image 438.9 I.97 H F H F H [00454]embedded image H [00455]embedded image 423 I.98 H F H F H [00456]embedded image H [00457]embedded image 421 I.99 H F H F H [00458]embedded image H [00459]embedded image 406.9 I.100 H F H F H [00460]embedded image H [00461]embedded image 408.9 I.101 H F H F H [00462]embedded image H [00463]embedded image 408.8 I.102 H F H F H [00464]embedded image H [00465]embedded image 392.9 I.103 H Cl H Cl H [00466]embedded image H [00467]embedded image 300.8 I.104 H F H F H [00468]embedded image H [00469]embedded image 378.9 I.105 H F H F H [00470]embedded image H [00471]embedded image 366.9 I.106 H Cl H Cl H [00472]embedded image H [00473]embedded image 430.8 I.107 H Cl H Cl H [00474]embedded image H [00475]embedded image 430.9 I.108 H Cl H Cl H [00476]embedded image H [00477]embedded image 428.9 I.109 H F H F H [00478]embedded image H [00479]embedded image 394.9 I.110 H F H F H [00480]embedded image H [00481]embedded image 382.9 I.111 H Cl H Cl H [00482]embedded image H [00483]embedded image 415.3 I.112 H Cl H Cl H [00484]embedded image H [00485]embedded image 455 I.113 H Cl H Cl H [00486]embedded image H [00487]embedded image 455.2 I.114 H Cl H H H [00488]embedded image H [00489]embedded image 421.2 I.115 H F H H H [00490]embedded image H [00491]embedded image 405.2 I.116 H OCF.sub.3 H H H [00492]embedded image H [00493]embedded image 471 I.117 H Cl Cl Cl H [00494]embedded image H [00495]embedded image 490.9 I.118 H F F F H [00496]embedded image H [00497]embedded image 441.2 I.119 H Cl H Cl H [00498]embedded image H [00499]embedded image 439.0 I.120 H Cl H Cl H [00500]embedded image H [00501]embedded image 440.8 I.121 H Cl H Cl H [00502]embedded image H [00503]embedded image 426.8 I.122 H Cl H Cl H [00504]embedded image H [00505]embedded image 414.9 I.123 H F H F H [00506]embedded image H [00507]embedded image 371.1 I.124 H F H F H [00508]embedded image H [00509]embedded image 408.9 I.125 H F H F H [00510]embedded image H [00511]embedded image 385 I.126 H F H F H [00512]embedded image H [00513]embedded image 343.2 I.127 H F H F H [00514]embedded image H [00515]embedded image 356.9 I.128 H F H F H [00516]embedded image H [00517]embedded image 382.9 I.129 H F H F H [00518]embedded image H [00519]embedded image 343.2 I.130 H F H F H [00520]embedded image H [00521]embedded image 448.9 I.131 H F H F H [00522]embedded image H [00523]embedded image 417.2 I.132 H F H H H [00524]embedded image H [00525]embedded image 390.9 I.133 H F F F H [00526]embedded image H [00527]embedded image 426.9 I.134 H OCF.sub.3 H H H [00528]embedded image H [00529]embedded image 457 I.135 H F H F H [00530]embedded image H [00531]embedded image 420.3 I.136 H F H F H [00532]embedded image H [00533]embedded image 357.2 I.137 H F H F H [00534]embedded image H [00535]embedded image 343.2 I.138 H F H F H [00536]embedded image H [00537]embedded image 357 I.139 H F H F H [00538]embedded image H [00539]embedded image 370.9 I.140 H F H F H [00540]embedded image H [00541]embedded image 385 I.141 H F H F H [00542]embedded image H [00543]embedded image 393.9 I.142 H F H F H [00544]embedded image H [00545]embedded image 394.9 I.143 H F H F H [00546]embedded image H [00547]embedded image 385.3 I.144 H F H F H [00548]embedded image H [00549]embedded image 371.2 I.145 H F H F H [00550]embedded image H [00551]embedded image 357.2 I.146 H F H F H [00552]embedded image H [00553]embedded image 372.9 I.147 H F H F H [00554]embedded image H [00555]embedded image 343.1 I.148 H F H F H [00556]embedded image H [00557]embedded image 372.8 I.149 H F H F H [00558]embedded image H [00559]embedded image 386.9 I.150 H F H F H [00560]embedded image H [00561]embedded image 381.2 I.151 H F H F H [00562]embedded image H [00563]embedded image 423.3 I.152 H F H F H [00564]embedded image H [00565]embedded image 381.3 I.153 H F H F H [00566]embedded image H [00567]embedded image 420.9 I.154 H F H F H [00568]embedded image H [00569]embedded image 438.9 I.155 H F H F H [00570]embedded image H [00571]embedded image 414.9 I.156 H F H F H [00572]embedded image H [00573]embedded image 383.2 I.157 H F H F H [00574]embedded image H [00575]embedded image 383.3 I.158 H F H F H [00576]embedded image H [00577]embedded image 383.2 I.159 H F H F H [00578]embedded image H [00579]embedded image 369.2 I.160 H F H F H [00580]embedded image H [00581]embedded image 403.3 I.161 H F H F H [00582]embedded image H [00583]embedded image 419.3 I.162 H F H F H [00584]embedded image H [00585]embedded image 387 I.163 H F H F H [00586]embedded image H [00587]embedded image 397 I.164 H F H F H [00588]embedded image H [00589]embedded image 371 I.165 H F H F H [00590]embedded image H [00591]embedded image 384.9 I.166 H F H F H [00592]embedded image H [00593]embedded image 417.1 I.167 H F H F H [00594]embedded image H [00595]embedded image 423.2 I.168 H F H F H [00596]embedded image H [00597]embedded image 370.8 I.169 H F H F H [00598]embedded image H [00599]embedded image 371 I.170 H F H F H [00600]embedded image H [00601]embedded image 398.9 I.171 H F H F H [00602]embedded image H [00603]embedded image 368.9 I.172 H F H F H [00604]embedded image H [00605]embedded image 354.9 I.173 H F H F H [00606]embedded image H [00607]embedded image 382.9 I.174 H Cl H Cl H [00608]embedded image H [00609]embedded image 441.3 I.175 H Cl H Cl H [00610]embedded image H [00611]embedded image 455.3 I.176 H Cl H Cl H [00612]embedded image H [00613]embedded image 412.2 I.177 H Cl H Cl H [00614]embedded image H [00615]embedded image 441 I.178 H Cl H Cl H [00616]embedded image H [00617]embedded image 439.9 I.179 H Cl H Cl H [00618]embedded image H [00619]embedded image 415.9 I.180 H Cl H Cl H [00620]embedded image H [00621]embedded image 416.9 I.181 H Cl H Cl H [00622]embedded image H [00623]embedded image 430.9 I.182* H Cl H Cl H [00624]embedded image H [00625]embedded image 412.9 I.183* H Cl H Cl H [00626]embedded image H [00627]embedded image 424.9 I.184* H Cl H Cl H [00628]embedded image H [00629]embedded image 424.9 I.185* H Cl H Cl H [00630]embedded image H [00631]embedded image 412.9 I.186 H Cl H Cl H [00632]embedded image H [00633]embedded image 400.8 I.187 H Cl H Cl H [00634]embedded image H [00635]embedded image 472.9 I.188 H CN H H H [00636]embedded image H [00637]embedded image 410.1 I.189 H CN H Cl H [00638]embedded image H [00639]embedded image 444.3 I.190 H Cl H Cl H [00640]embedded image H [00641]embedded image 412.9 I.191* H Cl H Cl H [00642]embedded image H [00643]embedded image 425.0 I.192* H Cl H Cl H [00644]embedded image H [00645]embedded image 425.0 I.193* H Cl H Cl H [00646]embedded image H [00647]embedded image 413.0 I.194* H Cl H Cl H [00648]embedded image H [00649]embedded image 411.0 I.195* H Cl H Cl H [00650]embedded image H [00651]embedded image 413.0 I.196* H Cl H Cl H [00652]embedded image H [00653]embedded image 411.0 I.197 H Cl Cl F H [00654]embedded image H [00655]embedded image 470.9 I.198 H F F Cl H [00656]embedded image H [00657]embedded image 455.0 I.199 H Cl H Cl H [00658]embedded image H [00659]embedded image 465.1 I.200 H Cl H Cl H [00660]embedded image H [00661]embedded image 438.8 I.201 H Cl H Cl H [00662]embedded image H [00663]embedded image 410.7.sup.a I.202 H Cl H Cl H [00664]embedded image H [00665]embedded image 410.7.sup.b I.203 H F H CH.sub.3 H [00666]embedded image H [00667]embedded image 417.2 I.204 H OCH.sub.3 H F H [00668]embedded image H [00669]embedded image 433.2 I.205 H OCH.sub.3 H H H [00670]embedded image H [00671]embedded image 415.2 I.206 H OCF.sub.3 H CH.sub.3 H [00672]embedded image H [00673]embedded image 483.2 I.207 H OCHF.sub.2 H H H [00674]embedded image H [00675]embedded image 451.2 I.208 H CF.sub.3 H Cl H [00676]embedded image H [00677]embedded image 487.2 I.209 H CF.sub.3 H H H [00678]embedded image H [00679]embedded image 453.2 I.210 H F H H H [00680]embedded image H [00681]embedded image 403.2 I.211 H Cl F Cl H [00682]embedded image H [00683]embedded image 471.1 I.212 H I H H H [00684]embedded image H [00685]embedded image 511.1 I.213 H CH.sub.2CH.sub.3 H H H [00686]embedded image H [00687]embedded image 413.3 I.214 H Cl H Cl H [00688]embedded image H [00689]embedded image 465.2 I.215 H F Cl F H [00690]embedded image H [00691]embedded image 456.9 I.216 H Cl Cl F H [00692]embedded image H [00693]embedded image 472.9 I.217 H Cl F F H [00694]embedded image H [00695]embedded image 456.9 I.218 H Cl F Cl H [00696]embedded image H [00697]embedded image 472.9 I.219 H F H F H [00698]embedded image H [00699]embedded image 366.9 I.220 H Cl H Cl H [00700]embedded image H [00701]embedded image 427.1 I.221 H F H F H [00702]embedded image H [00703]embedded image 393.0 I.222* H F H F H [00704]embedded image H [00705]embedded image 393.0 I.223* H F H F H [00706]embedded image H [00707]embedded image 393.0 HPLC/MS = MassChargeRatio .sup.amass of the anion only. Salt obtained by neutralizing the corresponding acid with NaOH in aqueous THF and concentration of the reaction mixture. .sup.bmass of the anion only. Salt obtained by neutralizing the corresponding acid with LiOH in aqueous THF and concentration of the reaction mixture. *in context with the compound no.: Stereomerically pure compounds with an unknown absolute configurationen. These were obtained by SFC column chromatography under the indicated conditions: Column: (S,S)-WHELK-O1,50x6 mm i.D., 3.5 m; mobile phase A: CO2; mobile phase B: IPA (0.1% IPAm, v/v); flow rate: 3.4 mL/min, column temp.: 35 C., ABPR: 1800 psi; gradient: time (A/B): 0.0 (95/5), 0.2 min (95/5), 1.2 min (50/50), 2.2 (50/50), 2.6 min (95/5), 3.0 (95/5): Cpd I.182: t.sub.R = 1.384 min Cpd I.183: t.sub.R = 1.395 min Cpd I.184: t.sub.R = 1.616 min Cpd I.185: t.sub.R = 1.508 min Column: Chiralpak AD-3, 50x4.6 mm i.D., 3 m; mobile phase A: CO2; mobile phase B: MeOH (0.1% IPAm, v/v); flow rate: 3.4 mL/min, column temp.: 35 C., ABPR: 1800 psi; gradient: time (A/B): 0.0 (95/5), 0.2 min (95/5), 1.2 min (50/50), 2.2 (50/50), 2.6 min (95/5), 3.0 (95/5): Cpd I.193: t.sub.R = 1.386 min Cpd I.194: t.sub.R = 1.188 min Cpd I.195: t.sub.R = 1.677 min Cpd I.196: t.sub.R = 1.331 min Cpd I.222: t.sub.R = 2.020 min Cpd I.223: t.sub.R = 2.244 min Column: Chiralpak IC-3, 50x4.6 mm i.D., 3 m; mobile phase A: CO2; mobile phase B: IPA (0.1% IPAm, v/v); flow rate: 3.4 mL/min, column temp.: 35 C., ABPR: 1800 psi; gradient: time (A/B): 0.0 (95/5), 0.2 min (95/5), 1.2 min (50/50), 2.2 (50/50), 2.6 min (95/5), 3.0 (95/5): Cpd I.191: t.sub.R = 1.709 min Cpd I.192: t.sub.R = 2.000 min

    B Use Examples

    [1144] The herbicidal activity of the compounds of formula (I) was demonstrated by the following greenhouse experiments:

    [1145] 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.

    [1146] 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 shown 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.

    [1147] 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.

    [1148] 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 70 to <90 and a very good herbicidal activity is given at values of 90 to 100.

    [1149] The test plants used in the greenhouse experiments were of the following species:

    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 LOLMU Lolium multiflorum POLCO Fallopia convolvulus SETVI Setaria viridis SETFA Setaria faberi

    [1150] At an application rate of 0.500 kg/ha, applied by the pre-emergence method: [1151] compound I6 showed very good herbicidal activity against ABUTH. [1152] compounds I2, I7, I9, I17 showed very good herbicidal activity against AMARE. [1153] compounds I2, I6, I7, I9, I15, I16, I17, I18, I19 showed very good herbicidal activity against APESV. [1154] compound I14 showed good herbicidal activity against APESV. [1155] compounds I2, I6, I7, I9, I16 showed very good herbicidal activity against ECHCG. [1156] compound I15 showed good herbicidal activity against ECHCG. [1157] compounds I16, I17, showed very good herbicidal activity against SETFA. [1158] compound I15 showed good herbicidal activity against SETFA.

    [1159] At an application rate of 0.250 kg/ha, applied by the pre-emergence method: [1160] compounds I1, I5, I21, I24, I26, I82, I83, I84, I85, I86, I87, I88, I89, I90, I91, I96, I97, I98, I99, I100, I101, I102, I105, I109, I110, I111, I112, I123, I136, I137, I138, I142, I143, I144, I145, I149, I150, I152, I153, I154, I155, I156, I159, I160, I161, I184, I185, I186, I187, I188, I190, I191 showed very good herbicidal activity against APESV. [1161] compounds I3, I10, I20, I93, I95, I135, I139, I141, I147, I189 showed good herbicidal activity against APESV. [1162] compounds I33, I114, I116 showed good herbicidal activity against ABUTH. [1163] compounds I87, I104, I105, I136, I138, I139, I141, I186, I191, I198, I202 showed very good herbicidal activity against AMARE. [1164] compounds I3, I5, I90, I96, I99, I174, I200, I201 showed good herbicidal activity against AMARE. [1165] compounds I1, I24, I26, I82, I83, I84, I86, I90, I91, I95, I99, I102, I104, I109, I110, I116, I118, I23, I35, I36, I37, I38, I42, I44, I45, I53, I54, I55, I56, I60, I61, I84, I85, I87 showed very good herbicidal activity against SETFA. [1166] compounds I29, I85, I87, I88, I89, I100, I111, I14, I39, I40, I52, I59, I88, I89, I91 showed good herbicidal activity against SETFA. [1167] compound I24 showed very good herbicidal activity against ALOMY. [1168] compound I1, I83, I84, I88, I102, I104, I105, I114, I123, I137, I145, I154, I160, I161, I184, I185, I188 showed very good herbicidal activity against ECHCG. [1169] compounds I26, I28, I82, I85, I91, I109, I110, I115, I142, I143, I144, I149, I153, I156, I159, I187, I189 showed good herbicidal activity against ECHCG. [1170] compound I5 showed very good herbicidal activity against LOLMU. [1171] compounds I200, I202 showed very good herbicidal activity against SETVI. [1172] compound I201 showed good herbicidal activity against SETVI.

    [1173] At an application rate of 0.125 kg/ha, applied by the pre-emergence method: [1174] compound I176 showed very good herbicidal activity against ABUTH. [1175] compounds I30, I36 showed good herbicidal activity against ABUTH. [1176] compound I183 showed good herbicidal activity against APESV.

    [1177] At an application rate of 0.13128 kg/ha, applied by the pre-emergence method: [1178] compound I133 showed very good herbicidal activity against ALOMY. [1179] compound I133 showed very good herbicidal activity against SETFA. [1180] compound I133 showed very good herbicidal activity against LOLMU.

    [1181] At an application rate of 0.0625 kg/ha, applied by the pre-emergence method: [1182] compound I25 showed good herbicidal activity against ALOMY. [1183] compound I25 showed very good herbicidal activity against LOLMU.

    [1184] At an application rate of 1.000 kg/ha, applied by the post-emergence method: [1185] compound I19 showed good herbicidal activity against ABUTH.

    [1186] At an application rate of 0.500 kg/ha, applied by the post-emergence method: [1187] compounds I6, I9, I16 showed very good herbicidal activity against ABUTH. [1188] compounds I14, I15, I19 showed very good herbicidal activity against ALOMY. [1189] compounds I17, I18, I23 showed good herbicidal activity against ALOMY. [1190] compounds I7, I8, I9, I15 showed very good herbicidal activity against AMARE. [1191] compounds I2, I18 showed good herbicidal activity against AMARE. [1192] compounds I7, I14, I15 showed very good herbicidal activity against AVEFA. [1193] compounds I17, I18, I23 showed good herbicidal activity against AVEFA. [1194] compounds I2, I6, I7, I8, I9, I16, I19 showed very good herbicidal activity against ECHCG. [1195] compound I220 showed good herbicidal activity against ECHCG. [1196] compounds I6, I7, I8, I16, I17, I19 showed very good herbicidal activity against SETVI. [1197] compounds I2, I14 showed good herbicidal activity against SETVI.

    [1198] At an application rate of 0.250 kg/ha, applied by the post-emergence method: [1199] compounds I1, I5, I10, I11, I86, I95, I100, I114, I115, I116, I123, I161, I185, I188 showed very good herbicidal activity against ABUTH. [1200] compounds I20, I21, I28, I33, I92, I117, I140, I141, I143, I144, I157, I186, I189 showed good herbicidal activity against ABUTH. [1201] compounds I1, I5, I20, I21, I103, I114, I118, I142, I151, I197, I200, I202 showed very good herbicidal activity against ALOMY. [1202] compound I141, I158, I198, I199, I201 showed good herbicidal activity against ALOMY. [1203] compounds I1, I5, I20, I21, I24, I82, I83, I102, I104, I109, I112, I118, I135, I138, I141, I144, I149, I152, I155, I156, I198, I199, I200, I201 showed very good herbicidal activity against AVEFA. [1204] compound I101, I139, I147, I148, I151, I158, I192, I197, I202 showed good herbicidal activity against AVEFA. [1205] Compound I10, I24, I82, I83, I84, I85, I86, I87, I88, I89, I90, I99, I102, I103, I104, I105, I109, I110, I111, I112, I114, I115, I116, I118, I123, I136, I137, I138, I140, I145, I146, I149, I150, I151, I152, I153, I154, I155, I156, I159, I160, I161, I184, I185, I186, I187, I188, I189, I191, I197, I198, I199, I200, I201, I202 showed very good herbicidal activity against ECHCG. [1206] compounds I26, I91, I92, I96, I100, I139, I178, I190 showed good herbicidal activity against ECHCG. [1207] Compound I10, I24, I26, I82, I83, I84, I85, I86, I87, I89, I90, I100, I103, I105, I109, I110, I111, I112, I116, I123, I135, I136, I137,1138, I139, I140, I142, I145, I146, I149, I150, I152, I153, I154, I155, I156, I159, I160, I184, I187, I189, I190, I191 showed very good herbicidal activity against SETVI. [1208] compounds I88, I91, I96, I99, I144, I147 showed good herbicidal activity against SETVI. [1209] compounds I84, I85, I87, I88, I89, I90, I95, I96, I99, I101, I102, I104, I105, I110, I111, I115, I135, I136, I137, I142, I145, I150, I153, I154, I159, I160, I161, I184, I185, I186, I187, I188, I191, I202 showed very good herbicidal activity against AMARE. [1210] compounds I26, I91, I93, I94, I98, I146, I190, I197, I198, I199, I200, I201 showed good herbicidal activity against AMARE.

    [1211] At an application rate of 0.125 kg/ha, applied by the post-emergence method: [1212] compound I22 showed very good herbicidal activity against AVEFA. [1213] compound I22 showed very good herbicidal activity against ALOMY. [1214] compounds I125, I181 showed good herbicidal activity against ABUTH. [1215] compound I22 showed very good herbicidal activity against LOLMU. [1216] compound I122 showed good herbicidal activity against AMARE.

    [1217] At an application rate of 0.0625 kg/ha, applied by the post-emergence method: [1218] compounds I126, I127, I128, I130, I131, I133, I134 showed very good herbicidal activity against AMARE. [1219] compound I129 showed good herbicidal activity against AMARE. [1220] compounds I25, I126, I131 showed very good herbicidal activity against AVEFA. [1221] compound I130, showed good herbicidal activity against AVEFA. [1222] compounds I128, I129, I130, I131, I132, I134 showed very good herbicidal activity against POLCO. [1223] compounds I106, I108 showed good herbicidal activity against POLCO. [1224] compounds I25, I127, I128, I132, I133 showed very good herbicidal activity against SETVI. [1225] compound I126 showed good herbicidal activity against SETVI. [1226] compounds I25, I108, I127, I129, I132, I133 showed very good herbicidal activity against LOLMU. [1227] compound I134 showed very good herbicidal activity against ECHCG.

    [1228] At an application rate of 0.32 kg/ha, applied by the post-emergence method: [1229] compound I4 showed very good herbicidal activity against POLCO. [1230] compound I4 showed very good herbicidal activity against SETVI. [1231] compound I4 showed very good herbicidal activity against ECHCG.