HERBICIDAL COMPOUNDS

Abstract

The present invention relates to herbicidally active cinnolinium derivatives and formulations comprising such derivatives. The invention further extends to herbicidal mixtures comprising a cinnolinium derivative as described herein and at least one additional herbicidal active ingredient. The use of the afore-mentioned cinnolinium derivatives, formulations and/or herbicidal mixtures in controlling undesirable plant growth: in particular the use for the post-emergence control of weeds, also falls within the scope of the present invention.

Claims

1. A liquid agrochemical composition comprising: (i) a herbicidally effective amount of a compound of Formula (I) or an agrochemically acceptable salt or zwitterionic species thereof: ##STR00066##  wherein R.sup.1 is selected from the group consisting of: C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkyl, —C.sub.1-C.sub.3alkylC.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6haloalkyl, —C.sub.1-C.sub.3alkylC.sub.1-C.sub.6haloalkoxy, —(CR.sup.8.sub.2).sub.qC(O)R.sup.15, —(CR.sup.8.sub.2).sub.qC(O)OR.sup.10, —(CR.sup.8.sub.2).sub.qC(O)NR.sup.16R.sup.17, —(CR.sup.8.sub.2).sub.qNH.sub.2, —(CR.sup.8.sub.2).sub.qNHR.sup.7, —(CR.sup.8.sub.2).sub.qN(R.sup.7).sub.2, —(CR.sup.8.sub.2).sub.qOH, —(CR.sup.8.sub.2).sub.qOR.sup.7, —(CR.sup.8.sub.2).sub.qSR.sup.15, —(CR.sup.8.sub.2).sub.qS(O)R.sup.15, —(CR.sup.8.sub.2).sub.qS(O).sub.2R.sup.15, —(CR.sup.8.sub.2).sub.qS(O).sub.2NR.sup.16NR.sup.17, C.sub.5- or C.sub.6-heterocyclyl, —C.sub.1-C.sub.3alkylC.sub.5-C.sub.6heterocyclyl, C.sub.5- or C.sub.6-heteroaryl, —C.sub.1-C.sub.3alkylC.sub.5-C.sub.6heteroaryl, phenyl or —C.sub.1-C.sub.3alkylphenyl, wherein said heteroaryl moiety comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, said heterocyclyl moiety comprises 1, 2 or 3 heteroatoms individually selected from N, O and S, and said phenyl, heteroaryl and heterocyclyl moieties are optionally substituted by 1 or 2 R.sup.2 substituents; q is an integer of 0, 1, 2, or 3; each R.sup.2 is independently selected from the group consisting of halogen, nitro, cyano, —NH.sub.2, —NHR.sup.9, —N(R.sup.9).sub.2, —OH, —OR.sup.9, —S(O).sub.rR.sup.15, —NR.sup.6S(O).sub.2R.sup.15, —C(O)OR.sup.10, —C(O)R.sup.15, —C(O)NR.sup.16R.sup.17, —S(O).sub.2NR.sup.16R.sup.17, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkoxy, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkyl-, hydroxyC.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkoxy-, C.sub.1-C.sub.6haloalkoxy, C.sub.1-C.sub.3haloalkoxyC.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6alkenyloxy, C.sub.3-C.sub.6alkynyloxy, N—C.sub.3-C.sub.6cycloalkylamino-, and —C(R.sup.6)═NOR.sup.6; R.sup.3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, —S(O).sub.rR.sup.4, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6haloalkoxy, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkyl, —N(R.sup.6).sub.2, phenyl, a 5- or 6-membered heteroaryl comprising 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and a 4- to 6-membered heterocyclyl comprising 1, 2 or 3 heteroatoms individually selected from N, O and S, and wherein said phenyl, heteroaryl or heterocyclyl moieties are optionally substituted by 1 or 2 R.sup.2 substituents; R.sup.4 is selected from the group consisting of C.sub.1-C.sub.6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.2 substituents; r is an integer of 0, 1, or 2; k is an integer of 0, 1, 2, 3, or 4; when k is 1 or 2, each R.sup.5 is independently selected from the group consisting of halogen, nitro, cyano, —NH.sub.2, —NHR.sup.9, —N(R.sup.9).sub.2, —OH, —OR.sup.9, —S(O).sub.rR.sup.15, —NR.sup.6S(O).sub.2R.sup.15, —C(O)OR.sup.10, —C(O)R.sup.15, —C(O)NR.sup.16R.sup.17, —S(O).sub.2NR.sup.16R.sup.17, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkoxy, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkyl-, hydroxyC.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkoxy-, C.sub.1-C.sub.6haloalkoxy, C.sub.1-C.sub.3haloalkoxyC.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6alkenyloxy, C.sub.3-C.sub.6alkynyloxy, —N—C.sub.3-C.sub.6cycloalkylamino, —C(R.sup.6)═NOR.sup.6, phenyl, a 3- to 6-membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O, and a 5- or 6-membered heteroaryl, which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein said phenyl, heterocyclyl or heteroaryl are optionally substituted by 1, 2 or 3 R.sup.11 substituents; when k is 3 or 4, each R.sup.5 is independently selected from the group consisting of halogen, —NH.sub.2, —NHR.sup.9, —N(R.sup.9).sub.2, —OH, —OR.sup.9, —C(O)NR.sup.16R.sup.17, —S(O).sub.2NR.sup.16R.sup.17, C.sub.1-C.sub.6alkyl and C.sub.1-C.sub.6haloalkyl; each R.sup.6 is independently selected from hydrogen and C.sub.1-C.sub.6alkyl; each R.sup.7 is independently hydrogen or C.sub.1-C.sub.6alkyl; each R.sup.8 is independently hydrogen or C.sub.1-C.sub.6alkyl, each R.sup.9 is independently selected from the group consisting of C.sub.1-C.sub.6alkyl, —S(O).sub.2R.sup.15, —C(O)R.sup.15, —C(O)OR.sup.15 and —C(O)NR.sup.16R.sup.17; R.sup.10 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, phenyl and benzyl, and wherein said phenyl or benzyl are optionally substituted by 1, 2 or 3 R.sup.11 substituents; each R.sup.11 is independently selected from the group consisting of halogen, cyano, hydroxyl, —N(R.sup.6).sub.2, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkyl and C.sub.1-C.sub.4haloalkoxy; R.sup.15 is selected from the group consisting of C.sub.1-C.sub.6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.11 substituents; R.sup.16 and R.sup.17 are independently selected from the group consisting of hydrogen and C.sub.1-C.sub.6alkyl; or R.sup.16 and R.sup.17 together with the nitrogen atom to which they are attached form a 4- to 6-membered heterocyclyl ring which optionally comprises one additional heteroatom individually selected from N, O and S; (ii) at least one anionic surfactant that is an alkyl ether sulfate of Formula
R(OCH.sub.2CH.sub.2).sub.nOSO.sub.3.sup.−, wherein R is a C.sub.10-C.sub.16alkyl group and n is an integer of 2-30; and, (iii) at least one solvent.

2. The liquid agrochemical composition of claim 1, wherein in the anionic surfactant of (ii), n is an integer of 2-4.

3. The liquid agrochemical composition of claim 1, wherein in the anionic surfactant of (ii), n is an integer of 3.

4. The liquid agrochemical composition of claim 1, which is an emulsion concentrate (EC), and emulsion in water (EW), a microcapsule formulation (CS), a dispersion concentrate (DC), a suspension of particles in an emulsion (SE), a suspension of particles in oil (OD), or a soluble liquid (SL).

5. A compound of Formula (IA) or an agrochemically acceptable salt or zwitterionic species thereof, ##STR00067## wherein, R.sup.1 is selected from the group consisting of: C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkyl, —C.sub.1-C.sub.3alkylC.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6haloalkyl, —C.sub.1-C.sub.3alkylC.sub.1-C.sub.6haloalkoxy, —(CR.sup.8.sub.2).sub.qC(O)R.sup.15, —(CR.sup.8.sub.2).sub.qC(O)OR.sup.10, —(CR.sup.8.sub.2).sub.qC(O)NR.sup.16R.sup.17, (CR.sup.8.sub.2).sub.qNH.sub.2, —(CR.sup.8.sub.2).sub.qNHR.sup.7, —(CR.sup.8.sub.2).sub.qN(R.sup.7).sub.2, —(CR.sup.8.sub.2).sub.qOH, —(CR.sup.8.sub.2).sub.qOR.sup.7, —(CR.sup.8.sub.2).sub.qSR.sup.15, —(CR.sup.8.sub.2).sub.qS(O)R.sup.15, —(CR.sup.8.sub.2).sub.qS(O).sub.2R.sup.15, —(CR.sup.8.sub.2).sub.qS(O).sub.2NR.sup.16NR.sup.17, C.sub.5- or C.sub.6-heterocyclyl, —C.sub.1-C.sub.3alkylC.sub.5-C.sub.6heterocyclyl, C.sub.5- or C.sub.6-heteroaryl, —C.sub.1-C.sub.3alkylC.sub.5-C.sub.6heteroaryl, phenyl or —C.sub.1-C.sub.3alkylphenyl, wherein said heteroaryl moiety comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, said heterocyclyl moiety comprises 1, 2 or 3 heteroatoms individually selected from N, O and S, and said phenyl, heteroaryl and heterocyclyl moieties are optionally substituted by 1 or 2 R.sup.2 substituents; q is an integer of 0, 1, 2, or 3; each R.sup.2 is independently selected from the group consisting of halogen, nitro, cyano, —NH.sub.2, —NHR.sup.9, —N(R.sup.9).sub.2, —OH, —OR.sup.9, —S(O).sub.rR.sup.15, —NR.sup.6S(O).sub.2R.sup.15, —C(O)OR.sup.10, —C(O)R.sup.15, —C(O)NR.sup.16R.sup.17, —S(O).sub.2NR.sup.16R.sup.17, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkoxy, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkyl-, hydroxyC.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkoxy-, C.sub.1-C.sub.6haloalkoxy, C.sub.1-C.sub.3haloalkoxyC.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6alkenyloxy, C.sub.3-C.sub.6alkynyloxy, N—C.sub.3-C.sub.6cycloalkylamino-, and —C(R.sup.6)═NOR.sup.6; R.sup.3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, —S(O).sub.rR.sup.4, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6haloalkoxy, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkyl, —N(R.sup.6).sub.2, phenyl, a 5- or 6-membered heteroaryl comprising 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and a 4- to 6-membered heterocyclyl comprising 1, 2 or 3 heteroatoms individually selected from N, O and S, and wherein said phenyl, heteroaryl or heterocyclyl moieties are optionally substituted by 1 or 2 R.sup.2 substituents; R.sup.4 is selected from the group consisting of C.sub.1-C.sub.6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.2 substituents; r is an integer of 0, 1, or 2; k is an integer of 0, 1, 2, 3, or 4; when k is 1 or 2, each R.sup.5 is independently selected from the group consisting of halogen, nitro, cyano, —NH.sub.2, —NHR.sup.9, —N(R.sup.9).sub.2, —OH, —OR.sup.9, —S(O).sub.rR.sup.15, —NR.sup.6S(O).sub.2R.sup.15, —C(O)OR.sup.10, —C(O)R.sup.15, —C(O)NR.sup.16R.sup.17, —S(O).sub.2NR.sup.16R.sup.17, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkoxy, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkyl-, hydroxyC.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkoxy-, C.sub.1-C.sub.6haloalkoxy, C.sub.1-C.sub.3haloalkoxyC.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6alkenyloxy, C.sub.3-C.sub.6alkynyloxy, —N—C.sub.3-C.sub.6cycloalkylamino, —C(R.sup.6)═NOR.sup.6, phenyl, a 3- to 6-membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O, and a 5- or 6-membered heteroaryl, which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein said phenyl, heterocyclyl or heteroaryl are optionally substituted by 1, 2 or 3 R.sup.11 substituents; when k is 3 or 4, each R.sup.5 is independently selected from the group consisting of halogen, —NH.sub.2, —NHR.sup.9, —N(R.sup.9).sub.2, —OH, —OR.sup.9, —C(O)NR.sup.16R.sup.17, —S(O).sub.2NR.sup.16R.sup.17, C.sub.1-C.sub.6alkyl and C.sub.1-C.sub.6haloalkyl; each R.sup.6 is independently selected from hydrogen and C.sub.1-C.sub.6alkyl; each R.sup.7 is independently hydrogen or C.sub.1-C.sub.6alkyl; each R.sup.8 is independently hydrogen or C.sub.1-C.sub.6alkyl, each R.sup.9 is independently selected from the group consisting of C.sub.1-C.sub.6alkyl, —S(O).sub.2R.sup.15, —C(O)R.sup.15, —C(O)OR.sup.15 and —C(O)NR.sup.16R.sup.17; R.sup.10 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, phenyl and benzyl, and wherein said phenyl or benzyl are optionally substituted by 1, 2 or 3 R.sup.11 substituents; each R.sup.11 is independently selected from the group consisting of halogen, cyano, hydroxyl, —N(R.sup.6).sub.2, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkyl and C.sub.1-C.sub.4haloalkoxy; R.sup.15 is selected from the group consisting of C.sub.1-C.sub.6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.11 substituents; R.sup.16 and R.sup.17 are independently selected from the group consisting of hydrogen and C.sub.1-C.sub.6alkyl; or R.sup.16 and R.sup.17 together with the nitrogen atom to which they are attached form a 4- to 6-membered heterocyclyl ring which optionally comprises one additional heteroatom individually selected from N, O and S.

6. A compound of Formula (TB) or an agrochemically acceptable salt or zwitterionic species thereof ##STR00068## wherein R.sup.1 is selected from the group consisting of: C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkyl, —C.sub.1-C.sub.3alkylC.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6haloalkyl, —C.sub.1-C.sub.3alkylC.sub.1-C.sub.6haloalkoxy, —(CR.sup.8.sub.2).sub.qC(O)R.sup.15, —(CR.sup.8.sub.2).sub.qC(O)OR.sup.10, —(CR.sup.8.sub.2).sub.qC(O)NR.sup.16R.sup.17, —(CR.sup.8.sub.2).sub.qNH.sub.2, —(CR.sup.8.sub.2).sub.qNHR.sup.7, —(CR.sup.8.sub.2).sub.qN(R.sup.7).sub.2, —(CR.sup.8.sub.2).sub.qOH, —(CR.sup.8.sub.2).sub.qOR.sup.7, —(CR.sup.8.sub.2).sub.qSR.sup.15, —(CR.sup.8.sub.2).sub.qS(O)R.sup.15, —(CR.sup.8.sub.2).sub.qS(O).sub.2R.sup.15, —(CR.sup.8.sub.2).sub.qS(O).sub.2NR.sup.16NR.sup.17, C.sub.5- or C.sub.6-heterocyclyl, —C.sub.1-C.sub.3alkylC.sub.5-C.sub.6heterocyclyl, C.sub.5- or C.sub.6-heteroaryl, —C.sub.1-C.sub.3alkylC.sub.5-C.sub.6heteroaryl, phenyl or —C.sub.1-C.sub.3alkylphenyl, wherein said heteroaryl moiety comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, said heterocyclyl moiety comprises 1, 2 or 3 heteroatoms individually selected from N, O and S, and said phenyl, heteroaryl and heterocyclyl moieties are optionally substituted by 1 or 2 R.sup.2 substituents; q is an integer of 0, 1, 2, or 3; each R.sup.2 is independently selected from the group consisting of halogen, nitro, cyano, —NH.sub.2, —NHR.sup.9, —N(R.sup.9).sub.2, —OH, —OR.sup.9, —S(O).sub.rR.sup.15, —NR.sup.6S(O).sub.2R.sup.15, —C(O)OR.sup.10, —C(O)R.sup.15, —C(O)NR.sup.16R.sup.17, —S(O).sub.2NR.sup.16R.sup.17, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkoxy, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkyl-, hydroxyC.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkoxy-, C.sub.1-C.sub.6haloalkoxy, C.sub.1-C.sub.3haloalkoxyC.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6alkenyloxy, C.sub.3-C.sub.6alkynyloxy, N—C.sub.3-C.sub.6cycloalkylamino-, and —C(R.sup.6)═NOR.sup.6; R.sup.3 is selected from the group consisting of halogen, cyano, nitro, —S(O).sub.rR.sup.4, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6haloalkoxy, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkyl, —N(R.sup.6).sub.2, phenyl, a 5- or 6-membered heteroaryl comprising 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and a 4- to 6-membered heterocyclyl comprising 1, 2 or 3 heteroatoms individually selected from N, O and S, and wherein said phenyl, heteroaryl or heterocyclyl moieties are optionally substituted by 1 or 2 R.sup.2 substituents; R.sup.4 is selected from the group consisting of C.sub.1-C.sub.6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.2 substituents; r is an integer of 0, 1, or 2; k is an integer of 0, 1, 2, 3, or 4; when k is 1 or 2, each R.sup.5 is independently selected from the group consisting of halogen, nitro, cyano, —NH.sub.2, —NHR.sup.9, —N(R.sup.9).sub.2, —OH, —OR.sup.9, —S(O).sub.rR.sup.15, —NR.sup.6S(O).sub.2R.sup.15, —C(O)OR.sup.10, —C(O)R.sup.15, —C(O)NR.sup.16R.sup.17, —S(O).sub.2NR.sup.16R.sup.17, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkoxy, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkyl-, hydroxyC.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkoxy-, C.sub.1-C.sub.6haloalkoxy, C.sub.1-C.sub.3haloalkoxyC.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6alkenyloxy, C.sub.3-C.sub.6alkynyloxy, —N—C.sub.3-C.sub.6cycloalkylamino, —C(R.sup.6)═NOR.sup.6, phenyl, a 3- to 6-membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O, and a 5- or 6-membered heteroaryl, which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein said phenyl, heterocyclyl or heteroaryl are optionally substituted by 1, 2 or 3 R.sup.11 substituents; when k is 3 or 4, each R.sup.5 is independently selected from the group consisting of halogen, —NH.sub.2, —NHR.sup.9, —N(R.sup.9).sub.2, —OH, —OR.sup.9, —C(O)NR.sup.16R.sup.17, —S(O).sub.2NR.sup.16R.sup.17, C.sub.1-C.sub.6alkyl and C.sub.1-C.sub.6haloalkyl; each R.sup.6 is independently selected from hydrogen and C.sub.1-C.sub.6alkyl; each R.sup.7 is independently hydrogen or C.sub.1-C.sub.6alkyl; each R.sup.8 is independently hydrogen or C.sub.1-C.sub.6alkyl, each R.sup.9 is independently selected from the group consisting of C.sub.1-C.sub.6alkyl, —S(O).sub.2R.sup.15, —C(O)R.sup.15, —C(O)OR.sup.15 and —C(O)NR.sup.16R.sup.17; R.sup.10 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, phenyl and benzyl, and wherein said phenyl or benzyl are optionally substituted by 1, 2 or 3 R.sup.11 substituents; each R.sup.11 is independently selected from the group consisting of halogen, cyano, hydroxyl, —N(R.sup.6).sub.2, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkyl and C.sub.1-C.sub.4haloalkoxy; R.sup.15 is selected from the group consisting of C.sub.1-C.sub.6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.11 substituents; R.sup.16 and R.sup.17 are independently selected from the group consisting of hydrogen and C.sub.1-C.sub.6alkyl; or R.sup.16 and R.sup.17 together with the nitrogen atom to which they are attached form a 4- to 6-membered heterocyclyl ring which optionally comprises one additional heteroatom individually selected from N, O and S.

7. A compound of Formula (IC) or an agrochemically acceptable salt or zwitterionic species thereof ##STR00069## wherein, R.sup.1 is selected from the group consisting of: C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkyl, —C.sub.1-C.sub.3alkylC.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6haloalkyl, —C.sub.1-C.sub.3alkylC.sub.1-C.sub.6haloalkoxy, —(CR.sup.8.sub.2).sub.qC(O)R.sup.15, —(CR.sup.8.sub.2).sub.qC(O)OR.sup.10, —(CR.sup.8.sub.2).sub.qC(O)NR.sup.16R.sup.17, —(CR.sup.8.sub.2).sub.qNH.sub.2, —(CR.sup.8.sub.2).sub.qNHR.sup.7, —(CR.sup.8.sub.2).sub.qN(R.sup.7).sub.2, —(CR.sup.8.sub.2).sub.qOH, —(CR.sup.8.sub.2).sub.qOR.sup.7, —(CR.sup.8.sub.2).sub.qSR.sup.15, —(CR.sup.8.sub.2).sub.qS(O)R.sup.15, —(CR.sup.8.sub.2).sub.qS(O).sub.2R.sup.15, —(CR.sup.8.sub.2).sub.qS(O).sub.2NR.sup.16NR.sup.17, C.sub.5- or C.sub.6-heterocyclyl, —C.sub.1-C.sub.3alkylC.sub.5-C.sub.6heterocyclyl, C.sub.5- or C.sub.6-heteroaryl, —C.sub.1-C.sub.3alkylC.sub.5-C.sub.6heteroaryl, phenyl or —C.sub.1-C.sub.3alkylphenyl, wherein said heteroaryl moiety comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, said heterocyclyl moiety comprises 1, 2 or 3 heteroatoms individually selected from N, O and S, and said phenyl, heteroaryl and heterocyclyl moieties are optionally substituted by 1 or 2 R.sup.2 substituents; q is an integer of 0, 1, 2, or 3; each R.sup.2 is independently selected from the group consisting of halogen, nitro, cyano, —NH.sub.2, —NHR.sup.9, —N(R.sup.9).sub.2, —OH, —OR.sup.9, —S(O).sub.rR.sup.15, —NR.sup.6S(O).sub.2R.sup.15, —C(O)OR.sup.10, —C(O)R.sup.15, —C(O)NR.sup.16R.sup.17, —S(O).sub.2NR.sup.16R.sup.17, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkoxy, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkyl-, hydroxyC.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkoxy-, C.sub.1-C.sub.6haloalkoxy, C.sub.1-C.sub.3haloalkoxyC.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6alkenyloxy, C.sub.3-C.sub.6alkynyloxy, N—C.sub.3-C.sub.6cycloalkylamino-, and —C(R.sup.6)═NOR.sup.6; R.sup.3 is selected from the group consisting of halogen, cyano, nitro, —S(O).sub.rR.sup.4, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6haloalkoxy, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkyl, —N(R.sup.6).sub.2, phenyl, a 5- or 6-membered heteroaryl comprising 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and a 4- to 6-membered heterocyclyl comprising 1, 2 or 3 heteroatoms individually selected from N, O and S, and wherein said phenyl, heteroaryl or heterocyclyl moieties are optionally substituted by 1 or 2 R.sup.2 substituents; R.sup.4 is selected from the group consisting of C.sub.1-C.sub.6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.2 substituents; r is an integer of 0, 1, or 2; k is an integer of 0, 1, 2, 3, or 4; when k is 1 or 2, each R.sup.5 is independently selected from the group consisting of halogen, nitro, cyano, —NH.sub.2, —NHR.sup.9, —N(R.sup.9).sub.2, —OH, —OR.sup.9, —S(O).sub.rR.sup.15, —NR.sup.6S(O).sub.2R.sup.15, —C(O)OR.sup.10, —C(O)R.sup.15, —C(O)NR.sup.16R.sup.17, —S(O).sub.2NR.sup.16R.sup.17, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkoxy, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkyl-, hydroxyC.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkoxy-, C.sub.1-C.sub.6haloalkoxy, C.sub.1-C.sub.3haloalkoxyC.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6alkenyloxy, C.sub.3-C.sub.6alkynyloxy, —N—C.sub.3-C.sub.6cycloalkylamino, —C(R.sup.6)═NOR.sup.6, phenyl, a 3- to 6-membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O, and a 5- or 6-membered heteroaryl, which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein said phenyl, heterocyclyl or heteroaryl are optionally substituted by 1, 2 or 3 R.sup.11 substituents; when k is 3 or 4, each R.sup.5 is independently selected from the group consisting of halogen, —NH.sub.2, —NHR.sup.9, —N(R.sup.9).sub.2, —OH, —OR.sup.9, —C(O)NR.sup.16R.sup.17, —S(O).sub.2NR.sup.16R.sup.17, C.sub.1-C.sub.6alkyl and C.sub.1-C.sub.6haloalkyl; each R.sup.6 is independently selected from hydrogen and C.sub.1-C.sub.6alkyl; each R.sup.7 is independently hydrogen or C.sub.1-C.sub.6alkyl; each R.sup.8 is independently hydrogen or C.sub.1-C.sub.6alkyl, each R.sup.9 is independently selected from the group consisting of C.sub.1-C.sub.6alkyl, —S(O).sub.2R.sup.15, —C(O)R.sup.15, —C(O)OR.sup.15 and —C(O)NR.sup.16R.sup.17; R.sup.10 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, phenyl and benzyl, and wherein said phenyl or benzyl are optionally substituted by 1, 2 or 3 R.sup.11 substituents; each R.sup.11 is independently selected from the group consisting of halogen, cyano, hydroxyl, —N(R.sup.6).sub.2, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkyl and C.sub.1-C.sub.4haloalkoxy; R.sup.15 is selected from the group consisting of C.sub.1-C.sub.6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.11 substituents; R.sup.16 and R.sup.17 are independently selected from the group consisting of hydrogen and C.sub.1-C.sub.6alkyl; or R.sup.16 and R.sup.17 together with the nitrogen atom to which they are attached form a 4- to 6-membered heterocyclyl ring which optionally comprises one additional heteroatom individually selected from N, O and S; with the proviso that (i) when R.sup.3 is hydrogen, and k is 0, R.sup.1 is not methyl, ethyl, isopropyl, n-butyl, 2, 2,2 trichloroethyl, or cylcohexyl; (ii) when R.sup.3 is hydrogen, k is 1, and R.sup.5 is 5-chloro, 5-methyl, 5-methoxy, 6-chloro, 6-fluoro, 6-trifluoromethyl, 6-cyano, 6-nitro, 6-methoxy, 6-ethoxy, 6-isopropoxy, 6-methylsulfonyl, 6-methylthio, 7-trifluoromethyl, 7-methoxy, 7-nitro, 8-fluoro, 8-chloro, 8-trifluoromethyl, 8-nitro, 8-methoxy, 8-ethoxy, 8-isopropoxy, 8-methylsulfonyl, or 8-methylthio, then R.sup.1 is not methyl; and (iii) when R.sup.1 is methyl, R.sup.3 is hydrogen, k is 2 and the two R.sup.5 substituents are either at positions 6 and 7, or positions 7 and 8 of the cinnolinium ring, then the two R.sup.5 substituents are not both methyl.

8. The liquid agrochemical composition of claim 1, wherein the compound of Formula (I) is: the compound of Formula (IA) as defined in claim 5, the compound of Formula (IB) as defined in claim 6, or the compound of Formula (IC) as defined in claim 7.

9. Use of a compound of Formula (IA) as defined in claim 5, as a herbicide.

10. A method of controlling or preventing undesirable plant growth, wherein a herbicidally effective amount of a compound of Formula (IA) as defined in claim 5 as active ingredient, is applied to the plants, to parts thereof or the locus thereof.

11. A method of controlling or preventing undesirable plant growth, wherein a liquid agrochemical composition as defined in claim 1 is applied to the plants, to parts thereof or the locus thereof.

12. Use of a compound of Formula (IB) as defined in claim 6, as a herbicide.

13. Use of a compound of Formula (IC) as defined in claim 7, as a herbicide.

14. A method of controlling or preventing undesirable plant growth, wherein a herbicidally effective amount of a compound of Formula (IB) as defined in claim 6 as active ingredient, is applied to the plants, to parts thereof or the locus thereof.

15. A method of controlling or preventing undesirable plant growth, wherein a herbicidally effective amount of a compound of Formula (IC) as defined in claim 7 as active ingredient, is applied to the plants, to parts thereof or the locus thereof.

Description

PREPARATION EXAMPLES

Example 1 Preparation of (2,8-dimethylcinnolin-2-ium-4-yl)-methoxy-phosphinate A15

[0107] ##STR00026##

Step 1: Preparation of 1-(2-amino-3-methyl-phenyl)ethanone

[0108] ##STR00027##

[0109] A solution of 2-amino-3-methyl-benzoic acid (20 g) in tetrahydrofuran (500 mL) was cooled to 0° C. and methyl lithium (1.6M in diethylether, 413 mL) was added drop wise, keeping the temperature at 0° C., over 30 minutes. The reaction mixture was stirred at 0° C. for a further 4 hours then quenched with saturated aqueous ammonium chloride (100 mL) and extracted with ethyl acetate (400 mL). The organic layer was washed with brine (200 mL), dried over sodium sulfate, then concentrated and purified by silica gel chromatography eluting with 15% ethyl acetate in iso-hexane to give 1-(2-amino-3-methyl-phenyl)ethanone as a pale yellow liquid.

[0110] .sup.1H NMR (300 MHz, DMSO-d.sub.6) 7.65-7.63 (d, 1H), 7.19-7.17 (d, 1H), 7.05 (bs, 2H), 6.52-6.48 (t, 1H), 2.51 (s, 3H), 2.09 (s, 3H)

Step 2: Preparation of 8-methyl-1H-cinnolin-4-one

[0111] ##STR00028##

[0112] To an ice cold solution of 1-(2-amino-3-methyl-phenyl)ethanone (15 g) in glacial acetic acid (12 mL) was added water (40 mL) and concentrated aqueous hydrochloric acid (21 mL) over 15 minutes, maintaining a reaction temperature of 0° C. To this was added an ice cold solution of sodium nitrite (7.61 g) in water (30 mL) over 15 minutes, again maintaining a reaction temperature of 0° C. The reaction mixture was stirred at 0° C. for 1 hour, followed by addition of urea (604 mg) over 10 minutes then further stirring at 0° C. for 1 hour. To this mixture was then added a solution of sodium acetate (103 g) in water (300 mL) and dichloromethane (140 mL) over 30 minutes followed by stirring at room temperature for 16 hours. The reaction mixture was filtered and the resulting solid was washed with dichloromethane (2×100 mL) and dried to afford 8-methyl-1H-cinnolin-4-one as a red solid.

[0113] .sup.1H NMR (400 MHz, DMSO-d.sub.6) 13.09 (s, 1H), 7.91-7.89 (d, 1H), 7.82 (s, 1H), 7.62-7.60 (d, 1H), 7.34-7.31 (t, 1H), 2.54 (s, 3H)

Step 3: Preparation of 4-chloro-8-methyl-cinnoline

[0114] ##STR00029##

[0115] To a mixture of 8-methyl-1H-cinnolin-4-one (5.82 g) in chlorobenzene (150 mL) was added phosphorus oxychloride (5.0 mL) drop wise at room temperature over 10 minutes. To this was added 2-methyl pyridine (1 g) over 5 minutes and the resulting reaction mixture was heated at 140° C. for 1 hour. The reaction mixture was cautiously poured into crushed ice and the resulting mixture basified with saturated aqueous sodium carbonate solution. The reaction mass was extracted with dichloromethane (2×150 mL) and the combined organic phase was dried over sodium sulfate, concentrated then purified by silica gel chromatography eluting with 20% ethyl acetate in iso-hexane to give 4-chloro-8-methyl-cinnoline as a dark brown solid.

[0116] .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.60 (s, 1H), 8.07-8.05 (d, 1H), 7.96-7.89 (m, 2H), 2.96 (s, 3H)

Step 4: Preparation of 8-methyl-4-(p-tolylsulfonyl)cinnoline

[0117] ##STR00030##

[0118] To a mixture of 4-chloro-8-methyl-cinnoline (1.5 g) and N,N-dimethylformamide (20 mL) was added sodium p-toluenesulfinate (1.8 g) at room temperature. The reaction mixture was stirred at room temperature for 4 hours then diluted with water (50 mL) and extracted with ethyl acetate (2×75 mL). The combined organic layers were dried over anhydrous sodium sulfate and concentrated to afford 8-methyl-4-(p-tolylsulfonyl)cinnoline as a pale yellow solid.

[0119] .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.89 (s, 1H), 8.44-8.42 (d, 1H), 8.04-7.90 (m, 4H), 7.46-7.44 (d, 2H), 2.97 (s, 3H), 2.35 (s, 3H)

Step 5: Preparation of 4-dimethoxyphosphoryl-8-methyl-cinnoline

[0120] ##STR00031##

[0121] To a mixture of 8-methyl-4-(p-tolylsulfonyl)cinnoline (2 g), caesium carbonate (4.3 g) and N,N-dimethylformamide (20 mL) was added dimethyl phosphite (0.88 g) at room temperature. The reaction mixture was stirred at room temperature for 2 hours and then diluted with water (50.0 mL) and extracted with ethyl acetate (2×75 mL). The combined organic layers were dried over anhydrous sodium sulfate and concentrated to afford 4-dimethoxyphosphoryl-8-methyl-cinnoline as a pale yellow solid.

[0122] .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.57-9.55 (d, 1H), 8.25-8.23 (d, 1H), 7.98-7.90 (m, 2H), 3.81-3.78 (d, 6H), 2.99 (s, 3H)

Step 6: Preparation of (2,8-dimethylcinnolin-2-ium-4-yl)-methoxy-phosphinate A15

[0123] A mixture of 4-dimethoxyphosphoryl-8-methyl-cinnoline (1 g) and methanol (30 mL) was heated at 90° C. for 16 hours. The reaction mixture was cooled to room temperature, concentrated then triturated with acetone (20 mL) to afford (2,8-dimethylcinnolin-2-ium-4-yl)-methoxy-phosphinate as a light green solid.

[0124] .sup.1H NMR (300 MHz, D.sub.2O) 9.46-9.43 (d, 1H), 8.56-8.53 (d, 1H), 8.21-8.16 (t, 1H), 8.08-8.05 (d, 1H), 4.86 (s, 3H), 3.56-3.53 (d, 3H), 2.86 (s, 3H)

Example 2 Preparation of allyloxy-(2-methylcinnolin-2-ium-4-yl)phosphinate A5

[0125] ##STR00032##

Step 1: Preparation of methoxy-(2-methylcinnolin-2-ium-4-yl)phosphinate

[0126] ##STR00033##

[0127] To a suspension of 4-dimethoxyphosphorylcinnoline (5 g) in acetone (100 mL) was added iodomethane (13.1 mL) drop wise and the resulting reaction mixture was stirred for 60 hours at room temperature. The resulting precipitate was filtered, washed with acetone (2×) then dried to give methoxy-(2-methylcinnolin-2-ium-4-yl)phosphinate.

[0128] .sup.1H NMR (400 MHz, D.sub.2O) 9.50 (d, 1H), 8.74 (d, 1H), 8.56 (d, 1H), 8.26-8.37 (m, 2H), 4.87 (s, 3H), 3.56 (d, 3H)

Step 2: Preparation of allyloxy-(2-methylcinnolin-2-ium-4-yl)phosphinate A5

[0129] To a suspension of methoxy-(2-methylcinnolin-2-ium-4-yl)phosphinate (95 mg) in dichloromethane was added oxalyl chloride (160 mg) drop wise. The reaction mixture was warmed to 35° C. followed by addition of allyl alcohol (280 mg). After standing at room temperature overnight, the reaction mixture was concentrated and purified by preparative reverse phase HPLC to give an orange coloured gum which was triturated with diethyl ether to give allyloxy-(2-methylcinnolin-2-ium-4-yl)phosphinate as a cream solid.

[0130] .sup.1H NMR (400 MHz, D.sub.2O) 9.42 (d, 1H), 8.70 (d, 1H), 8.51-8.46 (m, 1H), 8.29-8.19 (m, 2H), 5.81-5.71 (m, 1H), 5.21-5.13 (m, 1H), 5.06-5.01 (m, 1H), 4.80 (s, 3H), 4.34-4.28 (m, 2H)

Example 3 Preparation of (2,3-dimethylcinnolin-2-ium-4-yl)-methoxy-phosphinate A9

[0131] ##STR00034##

Step 1: Preparation of 3-methylcinnolin-4-ol

[0132] ##STR00035##

[0133] To an ice cold solution of 1-(2-aminophenyl)propan-1-one (22 g) in glacial acetic acid (22 mL) was added 2M aqueous hydrochloric acid (66 mL) and water (22 mL). The mixture was cooled to 0° C. and a solution of sodium nitrite (11.192 g) in water (44 mL) was added slowly, keeping the temperature between 0° C. and 5° C. The mixture was stirred at 0° C. for one hour and urea (0.886 g) was added and stirred for another hour. To this was added a solution of sodium acetate (159.19 g) in water (440 mL) followed by dichloromethane (110 mL) at 0° C. and then the mixture was allowed to warm to room temperature and stirred for 15 hours. The reaction mass was filtered and the light brown solid was washed sequentially with water (50 mL), dichloromethane (20 mL) and hexane (20 mL) and dried to give 3-methylcinnolin-4-ol.

[0134] .sup.1H NMR (400 MHz, CDCl.sub.3) 12.50 (br. s., 1H) 8.15 (d, 1H) 7.48-7.60 (m, 1H) 7.39-7.47 (m, 1H) 7.19-7.31 (m, 1H) 2.34-2.35 (m, 3H)

Step 2: Preparation of 4-chloro-3-methyl-cinnoline

[0135] ##STR00036##

[0136] To a mixture of 3-methylcinnolin-4-ol (9 g) and chlorobenzene (90 mL), under a nitrogen atmosphere, was added 2-methylpyridine (1.0466 g) drop wise at room temperature. Phosphorus oxychloride (7.936 mL) was then added drop wise and the resulting mixture was heated at reflux for 2 hours. The reaction mass was poured cautiously into ice cold water and the resulting mixture was basified with saturated aqueous sodium carbonate solution. The reaction mixture was extracted with dichloromethane (3×50 mL) and the combined organic phase were concentrated then purified by silica gel chromatography eluting with a 3:7 ration of ethyl acetate in iso-hexane to give 4-chloro-3-methyl-cinnoline.

[0137] .sup.1H NMR (400 MHz, CDCl.sub.3) 8.48 (m, 1H), 8.12 (m, 1H), 7.74-7.84 (m, 2H), 3.03 (s, 3H)

Step 3: Preparation of 3-methyl-4-(p-tolylsulfonyl)cinnoline

[0138] ##STR00037##

[0139] A mixture of 4-chloro-3-methyl-cinnoline (0.5 g) and acetonitrile (6 mL), under a nitrogen atmosphere, was cooled to 0° C. and sodium p-toluenesulfinate (0.549 g) was added in one portion. The mixture was stirred cold for 1 hour and then allowed to warm to room temperature and stirred overnight. The reaction mixture was partitioned between water and ethyl acetate (100 mL), then extracted further ethyl acetate (2×100 mL). The combined organic layers were dried over sodium sulphate and concentrated to give 3-methyl-4-(p-tolylsulfonyl)cinnoline.

[0140] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.15 (d, 1H), 8.62 (d, 1H), 7.81-7.92 (m, 4H), 7.32 (d, 2H), 3.35 (s, 3H), 2.41 (s, 3H)

Step 4: Preparation of 4-dimethoxyphosphoryl-3-methyl-cinnoline

[0141] ##STR00038##

[0142] A stirred suspension of sodium hydride (0.30 g) in tetrahydrofuran (60 mL), under a nitrogen atmosphere, was cooled to 0° C. and dimethyl phosphite (0.56 mL) was added drop wise. After stirring for 30 minutes at 0° C., a solution of 3-methyl-4-(p-tolylsulfonyl)cinnoline (1.5 g) in tetrahydrofuran (40 mL) was added drop wise. The reaction was slowly warmed to room temperature and stirred overnight. The reaction mixture was diluted with water (50 mL) and extracted twice with dichloromethane (2×20 mL). The organic layers were concentrated then purified by silica gel chromatography eluting with 0-30% ethyl acetate in cyclohexane to give 4-dimethoxyphosphoryl-3-methyl-cinnoline

[0143] .sup.1H NMR (400 MHz, CDCl.sub.3) 8.91-8.96 (m, 1H) 8.56-8.61 (m, 1H) 7.80-7.86 (m, 2H) 3.86 (s, 3H) 3.84 (s, 3H) 3.26 (s, 3H)

Step 5: Preparation of (2,3-dimethylcinnolin-2-ium-4-yl)-methoxy-phosphinate A9

[0144] To a mixture of 4-dimethoxyphosphoryl-3-methyl-cinnoline (0.5 g) and acetone (10 mL) was added iodomethane (2.5 mL) drop wise. The reaction mixture was stirred at room temperature for 60 hours. The resulting precipitate was filtered off and dried to give (2,3-dimethylcinnolin-2-ium-4-yl)-methoxy-phosphinate.

[0145] .sup.1H NMR (400 MHz, D.sub.2O) 9.09 (d, 1H), 8.36 (d, 1H), 8.06-8.19 (m, 2H), 6.31 (s, 3H), 3.43 (d, 3H), 3.23 (s, 3H)

[0146] Additional compounds in Table A were prepared by analogous procedures to those described above in Examples 1 to 3, from appropriate starting materials.

TABLE-US-00010 TABLE A Physical data for Compounds Formula (I) Cmpd No. Structure .sup.1H NMR 1 [00039] (400 MHz, CD3OD) 9.65 (d, 1H), 9.05-9.01 (m, 1H), 8.62-8.57 (m, 1H), 8.39-8.30 (m, 2H), 4.98-4.92 (m, 3H), 4.03-3.92 (m, 2H), 1.22 (t, 3H) (POH proton missing) 2 [00040] (400 MHz, CD3OD) 9.64 (d, 1H), 9.02-8.97 (m, 1H), 8.64-8.59 (m, 1H), 8.41-8.31 (m, 2H), 4.94 (s, 3H), 3.93 (q, 2H), 1.63-1.53 (m, 2H), 1.41- 1.29 (m, 2H), 0.86 (t, 3H) (POH proton missing) 3 [00041] (400 MHz, OD3OD) 9.74 (d, 1H), 8.93 (d, 1H), 8.66 (d, 1H), 8.47-8.34 (m, 2H), 4.96 (s, 3H), 4.16-4.06 (m, 2H), 1.29 (t, 3H) (POH proton missing) 4 [00042] (400 MHz, D2O) 9.50 (d, 1H), 8.73-8.69 (m, 1H), 8.53-8.48 (m, 1H), 8.32-8.20 (m, 2H), 4.82 (s, 3H), 4.52 (dd, 2H), 2.59 (t, 1H) 5 [00043] (400 MHz, D2O) 9.42 (d, 1H), 8.70 (d, 1H), 8.51-8.46 (m, 1H), 8.29-8.19 (m, 2H), 5.81-5.71 (m, 1H), 5.21-5.13 (m, 1H), 5.06-5.01 (m, 1H), 4.80 (s, 3H), 4.34-4.28 (m, 2H) 6 [00044] (400 MHz, D2O) 9.45 (d, 1H), 8.67 (d, 1H), 8.52-8.47 (m, 1H), 8.30-8.19 (m, 2H), 4.81 (s, 3H), 4.34-4.24 (m, 2H) 7 [00045] (400 MHz, D2O) 9.43-9.38 (m, 1H), 8.72-8.67 (m, 1H), 8.49-8.44 (m, 1H), 8.28-8.16 (m, 2H), 4.78 (s, 3H), 3.66-3.58 (m, 2H), 0.93-0.81 (m, 1H), 0.30-0.22 (m, 2H), 0.02-0.04 (m, 2H) 8 [00046] (400 MHz, D2O) 9.40 (d, 1H), 8.71-8.67 (m, 1H), 8.51-8.46 (m, 1H), 8.29-8.17 (m, 2H), 4.80 (s, 3H), 4.46-4.36 (m, 1H), 1.06 (s, 3H), 1.05 (s, 3H) 9 [00047] (400 MHz, D2O) 9.09 (d, 1H), 8.36 (d, 1H), 8.06-8.19 (m, 2H), 6.31 (s, 3H), 3.43 (d, 3H), 3.23 (s, 3H) 10 [00048] (400 MHz, D2O) 9.48-9.44 (m, 1H), 8.73-8.69 (m, 1H), 8.54-8.48 (m, 1H), 8.32-8.20 (m, 2H), 4.82 (s, 3H), 3.97-3.91 (m, 2H), 3.49-3.43 (m, 2H), 3.05 (s, 3H) 11 [00049] (400 MHz, D2O) 9.48-9.44 (m, 1H), 8.80-8.75 (m, 1H), 8.56-8.51 (m, 1H), 8.34-8.23 (m, 2H), 7.20-7.14 (m, 2H), 7.09-7.03 (m, 1H), 6.89-6.84 (m, 2H), 4.79 (s, 3H) 12 [00050] (400 MHz, D2O) 9.40 (d, 1H), 8.68 (d, 1H), 8.50-8.44 (m, 1H), 8.28-8.17 (m, 2H), 4.80 (s, 3H), 3.80-3.73 (m, 2H), 1.44-1.36 (m, 2H), 1.19-1.10 (m, 2H), 0.64 (t, 3H) 13 [00051] (400 MHz, CD3OD) 9.42-9.40 (d, 1H), 8.69 (s, 1H), 8.37-8.35 (dd, 1H), 8.09-8.06 (dd, 1H), 4.77 (s, 3H), 3.52-3.49 (d, 3H), 2.68 (s, 3H) 14 [00052] (300 MHz, CD3OD) 9.45-9.42 (d, 1H), 8.83- 8.80 (d, 1H), 8.24 (s, 1H), 8.12-8.10 (d, 1H), 4.79 (s, 3H), 3.52-3.48 (d, 3H), 2.64 (s, 3H) 15 [00053] (300 MHz, D2O) 9.46-9.43 (d, 1H), 8.56-8.53 (d, 1H), 8.21-8.16 (t, 1H), 8.08-8.05 (d, 1H), 4.86 (s, 3H), 3.56-3.53 (d, 3H), 2.86 (s, 3H) 16 [00054] (400 MHz, CD3OD) 9.26-9.24 (d, 1H), 8.33- 8.31 (dd, 1H), 8.13-8.12 (d, 1H), 7.80-7.77 (dd, 1H), 4.67 (s, 3H), 4.09 (s, 3H), 3.52-3.49 (d, 3H) 17 [00055] (400 MHz, CD3OD) 9.369.34 (d, 1H), 8.99-8.97 (d, 1H), 7.76-7.73 (dd, 1H), 7.58 (s, 1H), 4.83 (s, 3H), 4.14 (s, 3H), 3.53-3.51 (d, 3H) 18 [00056] (300 MHz, CD3OD) 9.41-9.38 (d, 1H), 8.39- 8.36 (d, 1H), 8.20-8.15 (t, 1H), 7.56-7.53 (d, 1H), 4.77 (s, 3H), 4.10 (s, 3H), 3.15-3.47 (d, 3H) 19 [00057] (400 MHz, CD3OD) 9.71-9.69 (d, 1H), 9.33 (s, 1H), 8.70-8.68 (d, 1H), 8.41-8.38 (dd, 1H), 4.90 (s, 3H), 3.55-3.52 (d, 3H) 20 [00058] (300 MHz, D2O) 9.64-9.61 (d, 1H), 8.96 (s, 1H), 8.91-8.88 (d, 1H), 8.50-8.47 (d, 1H), 4.91 (s, 3H), 3.563.52 (d, 3H) 21 [00059] (400 MHz, D2O) 9.41 (d, 1H), 8.70 (d, 1H), 8.52-8.46 (m, 1H), 8.30-8.18 (m, 2H), 4.81 (s, 3H), 3.73 (q, 2H), 1.57-1.36 (m, 2H), 0.71 (t, 3H) 22 [00060] (400 MHz, D2O) 9.12 (d, 1H), 8.58-8.53 (m, 1H), 8.37-8.32 (m, 1H), 8.20-8.11 (m, 2H), 6.97-6.81 (m, 5H), 4.89-4.81 (m, 2H), 4.66 (s, 3H) 23 [00061] (400 MHz, D2O) 9.23 (br d, 1H), 8.65-8.48 (m, 1H), 8.48-8.31 (m, 1H), 8.27-8.12 (m, 2H), 7.01-6.93 (m, 2H), 6.67-6.57 (m, 2H), 4.84 (br d, 2H), 4.73 (s, 3H) 24 [00062] (400 MHz, D2O) 9.46 (d, 1H) 8.77 (d, 1H) 8.55 (d, 1H) 8.25-8.35 (m, 2H) 4.87 (s, 3H) 4.16 (dd, 1H) 1.64 (d, 2H) 1.56 (d, 2H) 1.27-1.41 (m, 3H) 1.06-1.20 (m, 3H) 25 [00063] (400 MHz, D2O) 9.53 (d, 1H) 8.77 (d, 1H) 8.57 (d, 1H) 8.26-8.38 (m, 2H) 4.88 (s, 3H) 4.02- 4.05 (m, 1H) 3.88-3.96 (m, 1H) 3.76-3.85 (m, 1H) 3.57-3.67 (m, 2H) 1.74-1.95 (m, 3H) 1.53- 1.63 (m, 1H) 26 [00064] (400 MHz, D2O) 9.48 (d, 1H), 8.78 (d, 1H), 8.58 (d, 1H), 8.27-8.38 (m, 2H), 4.89 (s, 3H), 3.61 (t, 2H), 1.74-1.84 (m, 1H), 0.80 (s, 3H), 0.78 (s, 3H) 27 [00065] (400 MHz, CD.sub.3OD) 9.62 (d, 1H), 9.05-8.98 (m, 1H), 8.62-8.56 (m, 1H), 8.38-8.29 (m, 2H), 4.93 (s, 3H), 3.61 (d, 3H)

Biological Examples

Post-Emergence Efficacy

[0147] Seeds of a variety of test species were shown in standard soil in pots. After cultivation for 14 days (post-emergence) under controlled conditions in a glasshouse (at 24/16° C., day/night; 14 hours light; 65% humidity), the plants were sprayed with an aqueous spray solution derived from the dissolution of the technical active ingredient for each of compounds 1 to 26 from Table A above, in a small amount of acetone and a special solvent and emulsifier mixture referred to as IF50 (11.12% Emulsogen EL360 TM+44.44% N-methylpyrrolidone+44.44% Dowanol DPM glycol ether), to create a 50 g/I solution which was then diluted to required concentration using 0.25% or 1% Empicol ESC70 (Sodium lauryl ether sulphate)+1% ammonium sulphate in water as diluent. These spray test compositions are described as composition numbers C1 to C26, with the numerical value corresponding to the compound number from Table A.

[0148] The test plants were then grown in a glasshouse under controlled conditions (at 24/16° C., day/night; 14 hours light; 65% humidity) and watered twice daily. After 13 days the test was evaluated (100=total damage to plant; 0=no damage to plant).

The results are shown in Table B (below). A value of n/a indicates that this combination of weed and test compound was not tested/assessed.

Test Plants:

[0149] Ipomoea hederacea (IPOHE), Euphorbia heterophylla (EPHHL), Chenopodium album (CHEAL), Amaranthus palmeri (AMAPA), Lolium perenne (LOLPE), Digitaria sanguinalis (DIGSA), Eleusine indica (ELEIN), Echinochloa crus-galli (ECHCG), Setaria faberi (SETFA)

TABLE-US-00011 TABLE B Control of weed species by compositions of the invention after post-emergence application Composition Application number Rate g/Ha AMAPA CHEAL EPHHL IPOHE ELEIN LOLPE DIGSA SETFA ECHCG C1  1000 90 100 100 100 90 60 90 80 70 C2  500 60 70 100 80 40 30 60 60 30 C3  1000 90 100 100 100 90 50 100 90 70 C4  1000 100 100 100 100 100 90 100 100 90 C5  500 90 100 90 70 100 60 90 80 90 C6  1000 100 100 100 100 100 80 100 90 100 C7  1000 90 90 100 100 100 60 100 90 80 C8  1000 100 100 100 100 100 50 100 90 100 C9  1000 100 90 50 90 80 50 80 70 40 C10 1000 100 100 100 80 100 20 90 100 70 C11 1000 100 70 60 70 80 30 70 50 20 C12 500 100 100 100 100 100 40 70 70 70 C13 500 100 100 100 70 100 30 100 100 90 C14 1000 100 100 100 100 100 60 80 90 70 C15 1000 40 50 100 20 80 20 70 50 50 C16 1000 100 90 90 70 100 50 80 80 90 C17 1000 10 10 20 10 10 0 10 10 10 C18 1000 100 80 100 80 100 80 100 100 100 C19 500 10 10 0 0 10 10 10 10 10 C20 1000 40 40 30 60 10 10 20 10 10 C21 500 100 100 100 100 100 70 100 100 70 C22 500 10 20 60 20 60 10 60 30 20 C23 125 20 10 40 10 40 10 60 30 30 C24 1000 100 80 100 50 90 30 60 70 40 C25 1000 100 90 80 60 100 60 50 80 90 C26 1000 100 90 100 60 90 40 60 90 60 C27 500 100 100 100 90 100 90 100 100 100