HERBICIDAL COMPOUNDS

Abstract

Use of the compounds of the formula (I) wherein the substituents are as defined herein as herbicides. Compounds of formula (I) are also claimed.

##STR00001##

Claims

1. (canceled)

2. A compound of formula (I) ##STR00222## wherein R.sup.1 is selected from the group consisting of hydrogen, halogen, 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.6haloalkyl, —OR.sup.7, —OR.sup.15a, —N(R.sup.6)S(O).sub.2R.sup.15, —N(R.sup.6)C(O)R.sup.15, —N(R.sup.6)C(O)OR.sup.15, —N(R.sup.6)C(O)NR.sup.16R.sup.17, —N(R.sup.6)CHO, —N(R.sup.7a).sub.2 and —S(O).sub.rR.sup.15; R.sup.2 is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.6alkyl and C.sub.1-C.sub.6haloalkyl, and wherein when R.sup.1 is selected from the group consisting of —OR.sup.7, —OR.sup.15a, —N(R.sup.6)S(O).sub.2R.sup.15, —N(R.sup.6)C(O)R.sup.15, —N(R.sup.6)C(O)OR.sup.15, —N(R.sup.6)C(O)NR.sup.16R.sup.17, —N(R.sup.6)CHO, —N(R.sup.7a).sub.2 and —S(O).sub.rR.sup.15, R.sup.2 is selected from the group consisting of hydrogen and C.sub.1-C.sub.6alkyl, or R.sup.1 and R.sup.2 together with the carbon atom to which they are attached form a C.sub.3-C.sub.6cycloalkyl ring or a 3- to 6-membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O; and Q is (CR.sup.1aR.sup.2b).sub.m; m is 0, 1, 2 or 3; each R.sup.1a and R.sup.2b are independently selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, —OH, —OR.sup.7, —OR.sup.15a, —NH.sub.2, —NHR.sup.7, —NHR.sup.15a, —N(R.sup.6)CHO, —NR.sup.7bR.sup.7c and —S(O).sub.rR.sup.15; or each R.sup.1a and R.sup.2b together with the carbon atom to which they are attached form a C.sub.3-C.sub.6cycloalkyl ring or a 3- to 6-membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O; and R.sup.3, R.sup.4 and R.sup.5 are independently selected from the group consisting of hydrogen, cyano, nitro, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6thioalkyl, C.sub.1-C.sub.6fluoroalkyl, C.sub.1-C.sub.6fluoroalkoxy, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkyl, phenyl and —N(R.sup.6).sub.2; each R.sup.6 is independently selected from hydrogen and C.sub.1-C.sub.6alkyl; each R.sup.7 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; each R.sup.7a is independently selected from the group consisting of —S(O).sub.2R.sup.15, —C(O)R.sup.15, —C(O)OR.sup.15, —C(O)NR.sup.16R.sup.17 and —C(O)NR.sup.6R.sup.15a; R.sup.7b and R.sup.7c are 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, —C(O)NR.sup.16R.sup.17 and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; or R.sup.7b and R.sup.7c 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; and R.sup.8a is selected from the group consisting of hydrogen, —OH, —S(O).sub.rR.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, —NR.sup.7dR.sup.7e, R.sup.15S(O).sub.rC.sub.1-C.sub.3alkyl-, R.sup.16R.sup.17NS(O).sub.2C.sub.1-C.sub.3alkyl-, R.sup.15C(O)C.sub.1-C.sub.3alkyl-, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkoxy, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.3alkoxy-, 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-, cyanoC.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, —C(R.sup.6)═NOR.sup.6, phenyl, phenylC.sub.1-C.sub.2alkyl-, heterocyclyl, heterocyclylC.sub.1-C.sub.2alkyl-, wherein the heterocyclyl moiety is a 4- to 6-membered saturated or partially saturated ring which comprises 1, 2 or 3 heteroatoms individually selected from N, O and S(O).sub.r, heteroaryl and heteroarylC.sub.1-C.sub.2alkyl-, wherein the heteroaryl is a 5- or 6-membered aromatic ring, which comprises 1, 2, 3 or 4 heteroatoms independently selected from N, O and S, and wherein said C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.3alkyl-, phenyl, phenylC.sub.1-C.sub.2alkyl-, heterocyclyl, heterocyclylC.sub.1-C.sub.2alkyl-, heteroaryl or heteroarylC.sub.1-C.sub.2alkyl-, are optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; R.sup.8b is selected from the group consisting of hydrogen, —OR.sup.7, 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 and C.sub.3-C.sub.6alkynyloxy; or R.sup.8a and R.sup.8b together with the nitrogen atom to which they are attached form a 4- to 6-membered heterocyclyl, which optionally comprises 1 or 2 additional heteroatoms independently selected from N, O and S(O), and wherein said heterocyclyl moiety is optionally substituted by 1 or 2 R.sup.9 substituents, which may be the same or different; and R.sup.7d and R.sup.7e are independently selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.3alkyl-, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkyl-, C.sub.2-C.sub.6alkynyl, —S(O).sub.2R.sup.15, —C(O)R.sup.15, —C(O)OR.sup.15, —C(O)NR.sup.16R.sup.17 and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents; each R.sup.9 is independently selected from the group consisting of —OH, halogen, cyano, —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; X is selected from the group consisting of C.sub.3-C.sub.6cycloalkyl, phenyl, a 5- or 6-membered heteroaryl, which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and a 4- to 6-membered heterocyclyl, which comprises 1, 2 or 3 heteroatoms individually selected from N, O and S, and wherein said cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties are optionally substituted by 1 or 2 R.sup.9 substituents, and wherein the aforementioned CR.sup.1R.sup.2, Q and Z moieties may be attached at any position of said cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties; n is 0 or 1; Z is selected from the group consisting of —C(O)OR.sup.10, —CH.sub.2OH, —CHO, —C(O)NHOR.sup.11, —C(O)NHCN, —OC(O)NHOR.sup.11, —OC(O)NHCN, —NR.sup.6C(O)NHOR.sup.11, —NR.sup.6C(O)NHCN, —C(O)NHS(O).sub.2R.sup.12, —OC(O)NHS(O).sub.2R.sup.12, —NR.sup.6C(O)NHS(O).sub.2R.sup.12, —S(O).sub.2OR.sup.10, —OS(O).sub.2OR.sup.10, —NR.sup.6S(O).sub.2OR.sup.10, —NR.sup.6S(O)OR.sup.10, —NHS(O).sub.2R.sup.14, —S(O)OR.sup.10, —OS(O)OR.sup.10, —S(O).sub.2NHCN, —S(O).sub.2NHC(O)R.sup.18, —S(O).sub.2NHS(O).sub.2R.sup.12, —OS(O).sub.2NHCN, —OS(O).sub.2NHS(O).sub.2R.sup.12, —O S(O).sub.2NHC(O)R.sup.18, —NR.sup.6S(O).sub.2NHCN, —NR.sup.6S(O).sub.2NHC(O)R.sup.18, —N(OH)C(O)R.sup.15, —ONHC(O)R.sup.15, —NR.sup.6S(O).sub.2NHS(O).sub.2R.sup.12, —P(O)(R.sup.13)(OR.sup.10), —P(O)H(OR.sup.10), —OP(O)(R.sup.13)(OR.sup.10), —NR.sup.6P(O)(R.sup.13)(OR.sup.10) and tetrazole; 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.9 substituents, which may be the same or different; R.sup.11 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; R.sup.12 is selected from the group consisting of C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, —OH, —N(R.sup.6).sub.2 and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; R.sup.13 is selected from the group consisting of —OH, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy and phenyl; R.sup.14 is C.sub.1-C.sub.6haloalkyl; 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.9 substituents, which may be the same or different; R.sup.15a phenyl, wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; 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 independently selected from N, O and S; and R.sup.18 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, —N(R.sup.6).sub.2 and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; and r is 0, 1 or 2, or an agronomically acceptable salt or zwitterionic species thereof, with the proviso that the compound of formula (I) is not: i) the compound: ##STR00223## or ii) the compound: ##STR00224## or iii) the compound: ##STR00225##

3. The compound of formula (I) according to claim 2, wherein R.sup.1 and R.sup.2 are independently selected from the group consisting of hydrogen and C.sub.1-C.sub.6alkyl.

4. The compound of formula (I) according to claim 2, wherein each R.sup.1a and R.sup.2b are independently selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, —OH and —NH.sub.2.

5. compound of formula (I) according to claim 2, wherein m is 1 or 2.

6. The compound of formula (I) according to claim 2, wherein R.sup.3, R.sup.4 and R.sup.5 are independently selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl and phenyl.

7. The compound of formula (I) according to claim 2, wherein R.sup.3, R.sup.4 and R.sup.5 are hydrogen.

8. The compound of formula (I) according to claim 2, wherein R.sup.8a is selected from the group consisting of C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.3alkyl-, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkyl-, hydroxyC.sub.1-C.sub.6alkyl-, cyanoC.sub.1-C.sub.6alkyl-, phenyl, phenylC.sub.1-C.sub.2alkyl-, heterocyclyl, heterocyclylC.sub.1-C.sub.2alkyl-, wherein the heterocyclyl moiety is a 4- to 6-membered saturated or partially saturated ring which comprises 1, 2 or 3 heteroatoms individually selected from N, O and S(O)r, heteroaryl and heteroarylC.sub.1-C.sub.2alkyl-, wherein the heteroaryl is a 5- or 6-membered aromatic ring, which comprises 1, 2, 3 or 4 heteroatoms independently selected from N, O and S, and wherein said C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.3alkyl-, phenyl, phenylC.sub.1-C.sub.2alkyl-, heterocyclyl, heterocyclylC.sub.1-C.sub.2alkyl-, heteroaryl or heteroarylC.sub.1-C.sub.2alkyl-, are optionally substituted by 1 R.sup.9 substituent.

9. The compound of formula (I) according to claim 2, wherein R.sup.8a is selected from the group consisting of C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkyl-, cyanoC.sub.1-C.sub.3alkyl-, phenyl and heterocyclyl, wherein the heterocyclyl moiety is a 4- to 6-membered saturated or partially saturated ring which comprises 1 S(O).sub.r heteroatom, and wherein said phenyl is optionally substituted by 1 R.sup.9 substituent.

10. The compound of formula (I) according to claim 2, wherein R.sup.8b is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl and C.sub.2-C.sub.3alkynyl.

11. The compound of formula (I) according to claim 2, wherein R.sup.8a and R.sup.8b together with the nitrogen atom to which they are attached form a 5- to 6-membered heterocyclyl, which optionally comprises 1 additional O heteroatom.

12. The compound of formula (I) according to claim 2, wherein Z is selected from the group consisting of —C(O)OR.sup.10, —S(O).sub.2OR.sup.10, —OS(O).sub.2OR.sup.10, —NR.sup.6S(O).sub.2OR.sup.10 and —NHS(O).sub.2R.sup.14.

13. The compound of formula (I) according to claim 2, wherein Z is —C(O)OH or —S(O).sub.2OH.

14. The compound of formula (I) according to claim 2, wherein n is 0.

15. An agrochemical composition comprising a herbicidally effective amount of a compound of formula (I) ##STR00226## wherein R.sup.1 is selected from the group consisting of hydrogen, halogen, 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.6haloalkyl, —OR.sup.7, —OR.sup.15a, —N(R.sup.6)S(O).sub.2R.sup.15, —N(R.sup.6)C(O)R.sup.15, —N(R.sup.6)C(O)OR.sup.15, —N(R.sup.6)C(O)NR.sup.16R.sup.17, —N(R.sup.6)CHO, —N(R.sup.7a).sub.2 and —S(O).sub.rR.sup.15; R.sup.2 is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.6alkyl and C.sub.1-C.sub.6haloalkyl, and wherein when R.sup.1 is selected from the group consisting of —OR.sup.7, —OR.sup.15a, —N(R.sup.6)S(O).sub.2R.sup.15, —N(R.sup.6)C(O)R.sup.15, —N(R.sup.6)C(O)OR.sup.15, —N(R.sup.6)C(O)NR.sup.16R.sup.17, —N(R.sup.6)CHO, —N(R.sup.7a).sub.2 and —S(O).sub.rR.sup.15, R.sup.2 is selected from the group consisting of hydrogen and C.sub.1-C.sub.6alkyl, or R.sup.1 and R.sup.2 together with the carbon atom to which they are attached form a C.sub.3-C.sub.6cycloalkyl ring or a 3- to 6-membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O, and Q is (CR.sup.1aR.sup.2b).sub.m; m is 0, 1, 2 or 3; each R.sup.1a and R.sup.2b are independently selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, —OH, —OR.sup.7, —OR.sup.15a, —NHR.sup.7, —NHR.sup.15a, —N(R.sup.6)CHO, —NR.sup.7bR.sup.7c and —S(O).sub.rR.sup.15; or each R.sup.1a and R.sup.2b together with the carbon atom to which they are attached form a C.sub.3-C.sub.6cycloalkyl ring or a 3- to 6-membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O; and R.sup.3, R.sup.4 and R.sup.5 are independently selected from the group consisting of hydrogen, cyano, nitro, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6thioalkyl, C.sub.1-C.sub.6fluoroalkyl, C.sub.1-C.sub.6fluoroalkoxy, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkyl, phenyl and —N(R.sup.6).sub.2; each R.sup.6 is independently selected from hydrogen and C.sub.1-C.sub.6alkyl; each R.sup.7 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; each R.sup.7a is independently selected from the group consisting of —S(O).sub.2R.sup.15, —C(O)R.sup.15, —C(O)OR.sup.15, —C(O)NR.sup.16R.sup.17 and —C(O)NR.sup.6R.sup.15a; R.sup.7b and R.sup.7c are 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, —C(O)NR.sup.16R.sup.17 and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different or R.sup.7b and R.sup.7c 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; and R.sup.8a is selected from the group consisting of hydrogen, —OH, —OR.sup.7, —S(O).sub.rR.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, —NR.sup.7dR.sup.7e, R.sup.15, S(O).sub.rC.sub.1-C.sub.3alkyl-, R.sup.16R.sup.17NS(O).sub.2C.sub.1-C.sub.3alkyl-, R.sup.15C(O)C.sub.1-C.sub.3alkyl-, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkoxy, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.3alkoxy-, 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-, cyanoC.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, —C(R.sup.6)═NOR.sup.6, phenyl, phenylC.sub.1-C.sub.2alkyl-, heterocyclyl, heterocyclylC.sub.1-C.sub.2alkyl-, wherein the heterocyclyl moiety is a 4- to 6-membered saturated or partially saturated ring which comprises 1, 2 or 3 heteroatoms individually selected from N, O and S(O).sub.r, heteroaryl and heteroarylC.sub.1-C.sub.2alkyl-, wherein the heteroaryl is a 5- or 6-membered aromatic ring, which comprises 1, 2, 3 or 4 heteroatoms independently selected from N, O and S, and wherein said C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.3alkyl-, phenyl, phenylC.sub.1-C.sub.2alkyl-, heterocyclyl, heterocyclylC.sub.1-C.sub.2alkyl-, heteroaryl or heteroarylC.sub.1-C.sub.2alkyl-, are optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; R.sup.8b is selected from the group consisting of hydrogen, —OR.sup.7, 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 and C.sub.3-C.sub.6alkynyloxy; or R.sup.8a and R.sup.8b together with the nitrogen atom to which they are attached form a 4- to 6-membered heterocyclyl, which optionally comprises 1 or 2 additional heteroatoms independently selected from N, O and S(O), and wherein said heterocyclyl moiety is optionally substituted by 1 or 2 R.sup.9 substituents, which may be the same or different; and R.sup.7d and R.sup.7e are independently selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.3alkyl-, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkyl-, C.sub.2-C.sub.6alkynyl, —S(O).sub.2R.sup.15, —C(O)R.sup.15, —C(O)OR.sup.15, —C(O)NR.sup.16R.sup.17 and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents; each R.sup.9 is independently selected from the group consisting of —OH, halogen, cyano, —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; X is selected from the group consisting of C.sub.3-C.sub.6cycloalkyl, phenyl, a 5- or 6-membered heteroaryl, which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and a 4- to 6-membered heterocyclyl, which comprises 1, 2 or 3 heteroatoms individually selected from N, O and S, and wherein said cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties are optionally substituted by 1 or 2 R.sup.9 substituents, and wherein the aforementioned CR.sup.1R.sup.2, Q and Z moieties may be attached at any position of said cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties; n is 0 or 1; Z is selected from the group consisting of —C(O)OR.sup.10, —CH.sub.2OH, —CHO, —C(O)NHOR.sup.11, —C(O)NHCN, —OC(O)NHOR.sup.11, —OC(O)NHCN, —NR.sup.6C(O)NHOR.sup.11, —NR.sup.6C(O)NHCN, —C(O)NHS(O).sub.2R.sup.12, —OC(O)NHS(O).sub.2R.sup.12, —NR.sup.6C(O)NHS(O).sub.2R.sup.12, —S(O).sub.2OR.sup.10, —OS(O).sub.2OR.sup.10, —NR.sup.6S(O).sub.2OR.sup.10, —NR.sup.6S(O)OR.sup.10, —NHS(O).sub.2R.sup.14, —S(O)OR.sup.10, —OS(O)OR.sup.10, —S(O).sub.2NHCN, —S(O).sub.2NHC(O)R.sup.18, —S(O).sub.2NHS(O).sub.2R.sup.12, —OS(O).sub.2NHCN, —OS(O).sub.2NHS(O).sub.2R.sup.12, —O S(O).sub.2NHC(O)R.sup.18, —NR.sup.6S(O).sub.2NHCN, —NR.sup.6S(O).sub.2NHC(O)R.sup.18, —N(OH)C(O)R.sup.15, —ONHC(O)R.sup.15, —NR.sup.6S(O).sub.2NHS(O).sub.2R.sup.12, —P(O)(R.sup.13)(OR.sup.10), —P(O)H(OR.sup.10), —Op(O)(R.sup.13)(OR.sup.10), —NR.sup.6P(O)(R.sup.13)(OR.sup.10) and tetrazole; 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.9 substituents, which may be the same or different; R.sup.11 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; R.sup.12 is selected from the group consisting of C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, —OH, —N(R.sup.6).sub.2 and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; R.sup.13 is selected from the group consisting of —OH, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy and phenyl; R.sup.14 is C.sub.1-C.sub.6haloalkyl; 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.9 substituents, which may be the same or different; R.sup.15a phenyl, wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; 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 independently selected from N, O and S; and R.sup.18 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, —N(R.sup.6).sub.2 and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different and r is 0, 1 or 2, or an agronomically acceptable salt or zwitterionic species thereof and an agrochemically-acceptable diluent or carrier.

16. A method of controlling unwanted plant growth, comprising applying a compound of formula (I) ##STR00227## wherein R.sup.1 is selected from the group consisting of hydrogen, halogen, 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.6haloalkyl, —OR.sup.7, —OR.sup.15a, —N(R.sup.6)S(O).sub.2R.sup.15, —N(R.sup.6)C(O)R.sup.15, —N(R.sup.6)C(O)OR.sup.15, —N(R.sup.6)C(O)NR.sup.16R.sup.17, —N(R.sup.6)CHO, —N(R.sup.7a).sub.2 and —S(O).sub.rR.sup.15; R.sup.2 is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.6alkyl and C.sub.1-C.sub.6haloalkyl, and wherein when R.sup.1 is selected from the group consisting of —OR.sup.7, —OR.sup.15a, —N(R.sup.6)S(O).sub.2R.sup.15, —N(R.sup.6)C(O)R.sup.15, —N(R.sup.6)C(O)OR.sup.15, —N(R.sup.6)C(O)NR.sup.16R.sup.17, —N(R.sup.6)CHO, —N(R.sup.7a).sub.2 and —S(O).sub.rR.sup.15, R.sup.2 is selected from the group consisting of hydrogen and C.sub.1-C.sub.6alkyl; or R.sup.1 and R.sup.2 together with the carbon atom to which they are attached form a C.sub.3-C.sub.6cycloalkyl ring or a 3- to 6-membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O, and Q is (CR.sup.1aR.sup.2b).sub.m; m is 0, 1, 2 or 3; each R.sup.1a and R.sup.2b are independently selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, —OH, —OR.sup.7, —OR.sup.15a, —NH.sub.2, —NHR.sup.7, —NHR.sup.15a, —N(R.sup.6)CHO, —NR.sup.7bR.sup.7c and —S(O).sub.rR.sup.15; or each R.sup.1a and R.sup.2b together with the carbon atom to which they are attached form a C.sub.3-C.sub.6cycloalkyl ring or a 3- to 6-membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O; and R.sup.3, R.sup.4 and R.sup.5 are independently selected from the group consisting of hydrogen, cyano, nitro, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6thioalkyl, C.sub.1-C.sub.6fluoroalkyl, C.sub.1-C.sub.6fluoroalkoxy, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkyl, phenyl and —N(R.sup.6).sub.2; each R.sup.6 is independently selected from hydrogen and C.sub.1-C.sub.6alkyl; each R.sup.7 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; each R.sup.7a is independently selected from the group consisting of —S(O).sub.2R.sup.15, —C(O)R.sup.15, —C(O)OR.sup.15, —C(O)NR.sup.16R.sup.17 and —C(O)NR.sup.6R.sup.15a; R.sup.7b and R.sup.7c are 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, —C(O)NR.sup.16R.sup.17 and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; or R.sup.7b and R.sup.7c 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; and R.sup.8a is selected from the group consisting of hydrogen, —OH, —OR.sup.7, —S(O).sub.rR.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, —NR.sup.7dR.sup.7e, R.sup.15S(O).sub.rC.sub.1-C.sub.3alkyl-, R.sup.16R.sup.17Ns(O).sub.2C.sub.1-C.sub.3alkyl-, R.sup.15C(O)C.sub.1-C.sub.3alkyl-, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkoxy, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.3alkoxy-, 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-, cyanoC.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, —C(R.sup.6)═NOR.sup.6, phenyl, phenylC.sub.1-C.sub.2alkyl-, heterocyclyl, heterocyclylC.sub.1-C.sub.2alkyl-, wherein the heterocyclyl moiety is a 4- to 6-membered saturated or partially saturated ring which comprises 1, 2 or 3 heteroatoms individually selected from N, O and S(O)r, heteroaryl and heteroarylC.sub.1-C.sub.2alkyl-, wherein the heteroaryl is a 5- or 6-membered aromatic ring, which comprises 1, 2, 3 or 4 heteroatoms independently selected from N, O and S, and wherein said C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.3alkyl-, phenyl, phenylC.sub.1-C.sub.2alkyl-, heterocyclyl, heterocyclylC.sub.1-C.sub.2alkyl-, heteroaryl or heteroarylC.sub.1-C.sub.2alkyl-, are optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; R.sup.8b is selected from the group consisting of hydrogen, —OR.sup.7, 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 and C.sub.3-C.sub.6alkynyloxy; or R.sup.8a and R.sup.8b together with the nitrogen atom to which they are attached form a 4- to 6-membered heterocyclyl, which optionally comprises 1 or 2 additional heteroatoms independently selected from N, O and S(O), and wherein said heterocyclyl moiety is optionally substituted by 1 or 2 R.sup.9 substituents, which may be the same or different; and R.sup.7d and R.sup.7e are independently selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.3alkyl-, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkyl-, C.sub.2-C.sub.6alkynyl, —S(O).sub.2R.sup.15, —C(O)R.sup.15, —C(O)OR.sup.15, —C(O)NR.sup.16R.sup.17 and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents; each R.sup.9 is independently selected from the group consisting of —OH, halogen, cyano, —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; X is selected from the group consisting of C.sub.3-C.sub.6cycloalkyl, phenyl, a 5- or 6-membered heteroaryl, which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and a 4- to 6-membered heterocyclyl, which comprises 1, 2 or 3 heteroatoms individually selected from N, O and S, and wherein said cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties are optionally substituted by 1 or 2 R.sup.9 substituents, and wherein the aforementioned CR′R.sup.2, Q and Z moieties may be attached at any position of said cycloalkyl, phenyl, heteroaryl or heterocyclyl moieties; n is 0 or 1; Z is selected from the group consisting of —C(O)OR.sup.10, —CH.sub.2OH, —CHO, —C(O)NHOR.sup.11, —C(O)NHCN, —OC(O)NHOR.sup.11, —OC(O)NHCN, —NR.sup.6C(O)NHOR.sup.11, —NR.sup.6C(O)NHCN, —C(O)NHS(O).sub.2R.sup.12, —OC(O)NHS(O).sub.2R.sup.12, —NR.sup.6C(O)NHS(O).sub.2R.sup.12, —S(O).sub.2OR.sup.10, —OS(O).sub.2OR.sup.10, —NR.sup.6S(O).sub.2OR.sup.10, —NR.sup.6S(O)OR.sup.10, —NHS(O).sub.2R.sup.14, —S(O)OR.sup.10, —OS(O)OR.sup.10, —S(O).sub.2NHCN, —S(O).sub.2NHC(O)R.sup.18, —S(O).sub.2NHS(O).sub.2R.sup.12, —OS(O).sub.2NHCN, —OS(O).sub.2NHS(O).sub.2R.sup.12, —O S(O).sub.2NHC(O)R.sup.18, —NR.sup.6S(O).sub.2NHCN, —NR.sup.6S(O).sub.2NHC(O)R.sup.18, —N(OH)C(O)R.sup.15, —ONHC(O)R.sup.15, —NR.sup.6S(O).sub.2NHS(O).sub.2R.sup.12, —P(O)(R.sup.13)(OR.sup.10), —P(O)H(OR.sup.10), —OP(O)(R.sup.13)(OR.sup.10), —NR.sup.6P(O)(R.sup.13)(OR.sup.10) and tetrazole; 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.9 substituents, which may be the same or different; R.sup.11 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; R.sup.12 is selected from the group consisting of C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, —OH, —N(R.sup.6).sub.2 and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; R.sup.13 is selected from the group consisting of —OH, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy and phenyl; R.sup.14 is C.sub.1-C.sub.6haloalkyl; 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.9 substituents, which may be the same or different; R.sup.15a is phenyl, wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; 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 independently selected from N, O and S; and R.sup.18 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, —N(R.sup.6).sub.2 and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; and r is 0, 1 or 2, or an agronomically acceptable salt or zwitterionic species thereof to the unwanted plants or to the locus thereof.

Description

EXAMPLES

[0275] The Examples which follow serve to illustrate, but do not limit, the invention.

Formulation Examples

[0276]

TABLE-US-00006 Wettable powders a) b) c) active ingredients 25%  50% 75% sodium lignosulfonate 5%  5% — sodium lauryl sulfate 3% —  5% sodium diisobutylnaphthalenesulfonate —  6% 10% phenol polyethylene glycol ether —  2% — (7-8 mol of ethylene oxide) highly dispersed silicic acid 5% 10% 10% Kaolin 62%  27% —

[0277] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.

Emulsifiable Concentrate

[0278]

TABLE-US-00007 active ingredients 10% octylphenol polyethylene glycol ether  3% (4-5 mol of ethylene oxide) calcium dodecylbenzenesulfonate  3% castor oil polyglycol ether  4% (35 mol of ethylene oxide) Cyclohexanone 30% xylene mixture 50%

[0279] Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

TABLE-US-00008 Dusts a) b) c) Active ingredients  5%  6%  4% Talcum 95% — — Kaolin — 94% — mineral filler — — 96%

[0280] Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill.

Extruder Granules

[0281]

TABLE-US-00009 Active ingredients 15% sodium lignosulfonate  2% carboxymethylcellulose  1% Kaolin 82%

[0282] The combination is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

Coated Granules

[0283]

TABLE-US-00010 Active ingredients 8% polyethylene glycol (mol. wt. 200) 3% Kaolin 89% 

[0284] The finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

Suspension Concentrate

[0285]

TABLE-US-00011 active ingredients 40% propylene glycol 10% nonylphenol polyethylene glycol ether  6% (15 mol of ethylene oxide) Sodium lignosulfonate 10% carboxymethylcellulose  1% silicone oil (in the form of a 75% emulsion in water)  1% Water 32%

[0286] The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.

Slow Release Capsule Suspension

[0287] 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.

[0288] The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns.

[0289] The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.

LIST OF ABBREVIATIONS

[0290] Boc=tert-butyloxycarbonyl
br=broad
CDCl.sub.3=chloroform-d
CD.sub.3OD=methanol-d
° C.=degrees Celsius
D.sub.2O=water-d
DCM=dichloromethane
d=doublet
dd=double doublet
dt=double triplet
DMSO=dimethylsulfoxide
EtOAc=ethyl acetate
h=hour(s)
HCl=hydrochloric acid
HPLC=high-performance liquid chromatography (description of the apparatus and the
methods used for HPLC are given below)
m=multiplet
M=molar
min=minutes
MHz=mega hertz
mL=millilitre
mp=melting point
ppm=parts per million
q=quartet
quin=quintet
rt=room temperature
s=singlet
=triplet
THF=tetrahydrofuran

LC/MS=Liquid Chromatography Mass Spectrometry

Preparative Reverse Phase HPLC Method:

[0291] Compounds purified by mass directed preparative HPLC using ES+/ES− on a Waters FractionLynx Autopurification system comprising a 2767 injector/collector with a 2545 gradient pump, two 515 isocratic pumps, SFO, 2998 photodiode array (Wavelength range (nm): 210 to 400), 2424 ELSD and QDa mass spectrometer. A Waters Atlantis T3 5 micron 19×10 mm guard column was used with a Waters Atlantis T3 OBD, 5 micron 30×100 mm prep column.

[0292] Ionisation method: Electrospray positive and negative: Cone (V) 20.00, Source Temperature (° C.) 120, Cone Gas Flow (L/Hr.) 50

[0293] Mass range (Da): positive 100 to 800, negative 115 to 800.

[0294] The preparative HPLC was conducted using an 11.4 minute run time (not using at column dilution, bypassed with the column selector), according to the following gradient table:

TABLE-US-00012 Solvent A Solvent B Flow Time (mins) (%) (%) (ml/min) 0.00 100 0 35 2.00 100 0 35 2.01 100 0 35 7.0 90 10 35 7.3 0 100 35 9.2 0 100 35 9.8 99 1 35 11.35 99 1 35 11.40 99 1 35

[0295] 515 pump 0 ml/min Acetonitrile (ACD)

[0296] 515 pump 1 ml/min 90% Methanol/10% Water (make up pump)

[0297] Solvent A: Water with 0.05% Trifluoroacetic Acid

[0298] Solvent B: Acetonitrile with 0.05% Trifluoroacetic Acid

Preparation Examples

[0299] Additional compounds in Table A (below) were prepared by analogues procedures, from appropriate starting materials. The skilled person would understand that the compounds of formula (I) may exist as an agronomically acceptable salt, a zwitterion or an agronomically acceptable salt of a zwitterion as described hereinbefore. Where mentioned the specific counterion is not considered to be limiting, and the compound of formula (I) may be formed with any suitable counter ion.

[0300] NMR spectra contained herein were recorded on either a 400 MHz Bruker AVANCE III HD equipped with a Bruker SMART probe unless otherwise stated. Chemical shifts are expressed as ppm downfield from TMS, with an internal reference of either TMS or the residual solvent signals. The following multiplicities are used to describe the peaks: s=singlet, d=doublet, t=triplet, dd=double doublet, dt=double triplet, q=quartet, quin=quintet, m=multiplet. Additionally br. is used to describe a broad signal and app. is used to describe and apparent multiplicity.

Example 1: Preparation of 2-[4-(methylcarbamoyl)pyridazin-1-ium-1-yl]ethanesulfonate A1

[0301] ##STR00047##

Step 1: Preparation of methyl pyridazine-4-carboxylate

[0302] ##STR00048##

[0303] To a solution of pyridazine-4-carboxylic acid (200 mg) in methanol (2 mL) at 0° C. under a nitrogen atmosphere was added thionyl chloride (0.49 mL) drop wise. The reaction mixture was stirred at 65° C. for 2 hours. The reaction mixture was concentrated and partitioned between ethyl acetate (100 mL) and saturated aqueous sodium bicarbonate solution (50 mL). The aqueous was extracted with further ethyl acetate (2×100 mL). The combined organic layers were concentrated to afford methyl pyridazine-4-carboxylate as a pale brown solid.

[0304] .sup.1H NMR (400 MHz, DMSO-d6) 9.58-9.60 (m, 1H) 9.51-9.53 (m, 1H) 8.11 (dd, 1H) 3.93 (s, 3H)

Step 2: Preparation of N-methylpyridazine-4-carboxamide

[0305] ##STR00049##

[0306] A mixture of pyridazine-4-carboxylate (50 mg) in methylamine solution (2M in methanol, 1 mL) was heated at 100° C. for 2 hours in a sealed vessel. The reaction mixture was cooled, concentrated and purified by chromatography on silica eluting with 80% ethyl acetate in hexanes to give N-methylpyridazine-4-carboxamide as a brown solid.

[0307] .sup.1H NMR (400 MHz, DMSO-d6) 9.51-9.53 (m, 1H) 9.41-9.43 (m, 1H) 8.97 (brs, 1H) 7.96-7.98 (m, 1H) 2.83 (d, 3H)

Step 3: Preparation of 2-[4-(methylcarbamoyl)pyridazin-1-ium-1-yl]ethanesulfonate A1

[0308] To a mixture of N-methylpyridazine-4-carboxamide (200 mg) in water (4 mL) was added sodium 2-bromoethanesulfonate (0.461 g). The mixture was heated at 100° C. for 30 hours. The reaction mixture was concentrated and triturated with methyl tert-butyl ether to afford a crude solid. This crude solid was purified by preparative reverse phase HPLC to give 2-[4-(methylcarbamoyl)pyridazin-1-ium-1-yl]ethanesulfonate as white solid.

[0309] 1H NMR (400 MHz, D.sub.2O) 9.88 (d, 1H), 9.68 (d, 1H), 8.74 (d, 1H), 5.20-5.25 (m, 2H), 3.55-3.66 (m, 2H), 2.91 (s, 3H) (NH proton missing)

Example 2: Preparation of 3-[4-(methylcarbamoyl)pyridazin-1-ium-1-yl]propanoic Acid trifluoroacetate A4

[0310] ##STR00050##

[0311] To a mixture of N-methylpyridazine-4-carboxamide (200 mg) in water (4 mL) was added 3-bromopropanoic acid (0.401 g). The mixture was heated at 110° C. for 18 hours, then cooled and concentrated. The crude product was washed with methyl tert-butyl ether and the resulting crude product was purified by preparative reverse phase HPLC to afford 3-[4-(methylcarbamoyl)pyridazin-1-ium-1-yl]propanoic acid trifluoroacetate as white solid.

[0312] 1H NMR (400 MHz, D.sub.2O) 9.94 (d, 1H), 9.72 (d, 1H), 8.80 (dd, 1H), 5.16 (t, 2H), 3.25 (t, 2H), 2.98 (s, 3H) (NH and CO2H protons missing)

Example 3: Preparation of 3-[3-methyl-4-(methylcarbamoyl)pyridazin-1-ium-1-yl]propanoic Acid 2,2,2-trifluoroacetate A57

[0313] ##STR00051##

Step 1: Preparation of (2,3,4,5,6-pentafluorophenyl) 3-methylpyridazine-4-carboxylate

[0314] ##STR00052##

[0315] To a solution of 3-methylpyridazine-4-carboxylic acid (500 mg) in dichloromethane (5 mL), at room temperature under a nitrogen atmosphere, was added 4-dimethylaminopyridine (89 mg) and pentafluorophenol (0.37 mL) drop wise. The reaction mixture was stirred at room temperature for 16 hours, then quenched with ice cold water (50 mL) and extracted with ethyl acetate (3×100 mL). The combined organic layers were concentrated to afford (2,3,4,5,6-pentafluorophenyl) 3-methylpyridazine-4-carboxylate as a pale white solid, which was used without further purification.

Step 2: Preparation of N,3-dimethylpyridazine-4-carboxamide

[0316] ##STR00053##

[0317] A mixture of (2,3,4,5,6-pentafluorophenyl) 3-methylpyridazine-4-carboxylate (800 mg) and methylamine solution (4M in THF, 3.3 mL), under a nitrogen atmosphere, was heated at 80° C. for 16 hours. The reaction mixture was cooled, concentrated and purified by chromatography on silica eluting with 45% ethyl acetate in hexanes to afford N,3-dimethylpyridazine-4-carboxamide as a brown oil.

[0318] .sup.1H NMR (400 MHz, DMSO-d6) 9.19 (d, 1H) 8.72 (br s, 1H) 7.57 (d, 1H) 2.79 (d, 3H) 2.65 (s, 3H)

Step 3: Preparation of ethyl 3-[3-methyl-4-(methylcarbamoyl)pyridazin-1-ium-1-yl]propanoate Bromide

[0319] ##STR00054##

[0320] To a solution of N,3-dimethylpyridazine-4-carboxamide (300 mg) in acetonitrile (6 mL) was added ethyl 3-bromopropanoate (0.381 mL). The mixture was heated at 90° C. for 16 hours, then cooled and concentrated. The crude product was triturated with methyl tert-butyl ether to afford crude ethyl 3-[3-methyl-4-(methylcarbamoyl)pyridazin-1-ium-1-yl]propanoate bromide as yellow gum which was used without further purification in the next step.

Step 4: Preparation of 3-[3-methyl-4-(methylcarbamoyl)pyridazin-1-ium-1-yl]propanoic Acid 2,2,2-trifluoroacetate A57

[0321] ##STR00055##

[0322] A solution of crude ethyl 3-[3-methyl-4-(methylcarbamoyl)pyridazin-1-ium-1-yl]propanoate bromide (0.3 g) in 2M aqueous hydrochloric acid (10 mL) was stirred at room temperature for 16 hours. The reaction mixture was concentrated and purified by preparative reverse phase HPLC (trifluoroacetic acid is present in the eluent) to afford 3-[3-methyl-4-(methylcarbamoyl)pyridazin-1-ium-1-yl]propanoic acid 2,2,2-trifluoroacetate.

[0323] .sup.1H NMR (400 MHz, D.sub.2O) 9.68 (d, 1H) 8.42 (d, 1H) 5.01 (t, 2H), 3.18 (t, 2H), 2.90 (s, 3H), 2.73 (s, 3H) (NH and CO.sub.2H protons missing)

Example 4: Preparation of 3-[4-[methyl(phenyl)carbamoyl]pyridazin-1-ium-1-yl]propanoic Acid trifluoroacetate A38

[0324] ##STR00056##

Step 1: Preparation of N-methyl-N-phenyl-pyridazine-4-carboxamide

[0325] ##STR00057##

[0326] To a solution of pyridazine-4-carboxylic acid (1.5 g) in N,N-dimethylformamide (30 mL) at room temperature under a nitrogen atmosphere was added 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (5.20 g) followed by N,N-diisopropylethylamine (9.4 g) drop wise. After 30 minutes stirring N-methylaniline (1.9 g) was added and stirring was continued for a further 16 hours. The reaction mixture was quenched with water (50 mL) and extracted with ethyl acetate (3×100 mL). The organic phases were combined, washed with saturated aqueous lithium chloride (2×100 ml) and concentrated. The crude product was purified by chromatography on silica eluting with 45% ethyl acetate in hexanes to afford N-methyl-N-phenyl-pyridazine-4-carboxamide as a brown oil.

[0327] .sup.1H NMR (400 MHz, DMSO-d6) 9.13 (br d, 1H) 9.08-8.95 (m, 1H) 7.48 (br s, 1H) 7.35-7.20 (m, 5H) 2.68 (s, 3H)

Step 2: Preparation of methyl 3-[4-[methyl(phenyl)carbamoyl]pyridazin-1-ium-1-yl]propanoate bromide

[0328] ##STR00058##

[0329] To a solution of N-methyl-N-phenyl-pyridazine-4-carboxamide (800 mg) in acetonitrile (16 mL) was added methyl 3-bromopropanoate (0.939 g). The mixture was heated at 90° C. for 18 hours, then concentrated and washed with tert-butyl methyl ether to give crude methyl 3-[4-[methyl(phenyl)carbamoyl]pyridazin-1-ium-1-yl]propanoate bromide as yellow gum which was used without further purification.

Step 3: Preparation of 3-[4-[methyl(phenyl)carbamoyl]pyridazin-1-ium-1-yl]propanoic Acid 2,2,2-trifluoroacetate A38

[0330] A solution of crude methyl 3-[4-[methyl(phenyl)carbamoyl]pyridazin-1-ium-1-yl]propanoate bromide (0.6 g) in 2M aqueous hydrochloric acid (10 mL) was stirred at room temperature for 16 hours. The reaction mixture was concentrated and purified by preparative reverse phase HPLC (trifluoroacetic acid is present in the eluent) to afford 3-[4-[methyl(phenyl)carbamoyl]pyridazin-1-ium-1-yl]propanoic acid trifluoroacetate as a solid.

[0331] .sup.1H NMR (400 MHz, D.sub.2O) 9.57 (dd, 1H), 9.19 (s, 1H), 8.32 (dd, 1H), 7.22-7.35 (m, 5H), 4.73-4.95 (t, 2H), 3.45 (s, 3H), 3.06 (t, 2H) (CO.sub.2H proton missing)

Example 5: Preparation of 3-[4-(piperidine-1-carbonyl)pyridazin-1-ium-1-yl]propanoic Acid trifluoroacetate A24

[0332] ##STR00059##

Step 1: Preparation of 1-piperidyl(pyridazin-4-yl)methanone

[0333] ##STR00060##

[0334] To a solution of pyridazine-4-carboxylic acid (0.6 g) in acetonitrile (25 mL) at room temperature under a nitrogen atmosphere was added triethylamine (2.04 mL), propylphosphonic anhydride (6.15 g) and piperidine (0.52 mL). The reaction mixture was stirred at room temperature for 16 hours, then concentrated, diluted with water (50 mL) and extracted with ethyl acetate (3×100 mL). The combined organic layers were concentrated and purified by chromatography on silica eluting with 45% ethyl acetate in hexanes to afford 1-piperidyl(pyridazin-4-yl)methanone as a white solid.

[0335] .sup.1H NMR (400 MHz, D.sub.2O) 9.33 (dd, 1H) 9.26 (dd, 1H) 7.71 (dd, 1H) 3.63-3.57 (m, 2H) 3.24-3.18 (m, 2H) 1.66-1.44 (m, 6H)

Step 2: Preparation of methyl 3-[4-[methyl(phenyl)carbamoyl]pyridazin-1-ium-1-yl]propanoate

[0336] ##STR00061##

[0337] To a solution of 1-piperidyl(pyridazin-4-yl)methanone (300 mg) in acetonitrile (6 mL) was added methyl 3-bromopropanoate (0.324 g). The mixture was heated at 90° C. for 18 hours, then cooled and concentrated. The crude product was washed with methyl tert-butyl ether (50 mL) to afford crude methyl 3-[4-[methyl(phenyl)carbamoyl]pyridazin-1-ium-1-yl]propanoate bromide as yellow gum, which was used without further purification.

Step 3: Preparation of 3-[4-(piperidine-1-carbonyl)pyridazin-1-ium-1-yl]propanoic Acid trifluoroacetate A24

[0338] A solution of crude methyl 3-[4-[methyl(phenyl)carbamoyl]pyridazin-1-ium-1-yl]propanoate bromide (485 mg) in 2M aqueous hydrochloric acid (10 mL) was stirred at room temperature for 24 hours. The reaction mixture was concentrated and purified by preparative reverse phase HPLC (trifluoroacetic acid is present in the eluent) to afford 3-[4-(piperidine-1-carbonyl)pyridazin-1-ium-1-yl]propanoic acid trifluoroacetate.

[0339] .sup.1H NMR (400 MHz, D.sub.2O) 9.68-10.04 (m, 1H), 9.32-9.64 (m, 1H), 8.39-8.75 (m, 1H), 5.00-5.22 (m, 2H), 3.56-375 (m, 2H), 3.28-3.34 (m, 2H), 3.18-3.25 (m, 2H), 1.63-1.73 (m, 4H), 1.44-1.61 (m, 2H) (CO.sub.2H proton missing)

Example 6: Preparation of 2-[4-[(2-hydroxyphenyl)carbamoyl]pyridazin-1-ium-1-yl]ethanesulfonate A84

[0340] ##STR00062##

Step 1: Preparation of 2-pyridazin-4-yl-1,3-benzoxazole

[0341] ##STR00063##

[0342] A mixture of 2-aminophenol (0.19 mL), pyridazine-4-carbaldehyde (250 mg), activated charcoal (194 mg) and o-xylene (10 mL) was heated at 120° C. overnight. The reaction mixture was filtered through celite, concentrated and purified by preparative reverse phase HPLC (trifluoroacetic acid is present in the eluent) to give 2-pyridazin-4-yl-1,3-benzoxazole as a beige solid.

[0343] .sup.1H NMR (400 MHz, CD.sub.3OD) 9.93 (dd, 1H), 9.45 (dd, 1H), 8.40 (dd, 1H), 7.89-7.84 (m, 1H), 7.78 (dd, 1H), 7.57-7.46 (m, 2H)

Step 2: Preparation of 2-[4-[(2-hydroxyphenyl)carbamoyl]pyridazin-1-ium-1-yl]ethanesulfonate A84

[0344] A mixture of 2-pyridazin-4-yl-1,3-benzoxazole (100 mg), 2-bromoethanesulfonic acid (131 mg) and water (2 mL) was heated at 100° C. for 20 hours. Further 2-bromoethanesulfonic acid (131 mg) was added and heating continued for a further 6 hours. The reaction mixture was concentrated and purified by preparative reverse phase HPLC (trifluoroacetic acid is present in the eluent) to give 2-[4-[(2-hydroxyphenyl)carbamoyl]pyridazin-1-ium-1-yl]ethanesulfonate as an orange solid.

[0345] .sup.1H NMR (400 MHz, DMSO-d6) 10.60 (s, 1H), 10.11 (d, 1H), 9.99-9.83 (m, 2H), 9.00 (dd, 1H), 7.65 (br d, 1H), 7.16-7.07 (m, 1H), 6.96 (d, 1H), 6.87 (t, 1H), 5.13 (br t, 2H), 3.27-3.20 (m, 2H)

Example 7: Preparation of [(1S)-1-carboxy-2-[4-(ethylcarbamoyl)pyridazin-1-ium-1-yl]ethyl]ammonium 2,2,2-trifluoroacetate A121

[0346] ##STR00064##

Step 1: Preparation of (25)-2-(tert-butoxycarbonylamino)-3-[4-(ethylcarbamoyl)pyridazin-1-ium-1-yl]propanoic Acid 2,2,2-trifluoroacetate

[0347] ##STR00065##

[0348] To a solution of N-ethylpyridazine-4-carboxamide (0.3 g) in dry acetonitrile (6 mL) was added tert-butyl N-[(3S)-2-oxooxetan-3-yl]carbamate (0.668 g) at room temperature, under nitrogen atmosphere. On completion the reaction mixture was concentrated and purified using preparative reverse phase HPLC (trifluoroacetic acid is present in the eluent) to give crude (25)-2-(tert-butoxycarbonylamino)-3-[4-(ethylcarbamoyl)pyridazin-1-ium-1-yl]propanoic acid 2,2,2-trifluoroacetate which was used in the next step without further purification.

[0349] LCMS: retention time 0.29 min, M+339

Step 2: Preparation of [(1S)-1-carboxy-2-[4-(ethylcarbamoyl)pyridazin-1-ium-1-yl]ethyl]ammonium 2,2,2-trifluoroacetate A121

[0350] A mixture of (2S)-2-(tert-butoxycarbonylamino)-3-[4-(ethylcarbamoyl)pyridazin-1-ium-1-yl]propanoic acid 2,2,2-trifluoroacetate (0.06 g) and 2M aqueous hydrochloric acid (4 mL) was stirred at room temperature for 24 hours. The reaction mixture was concentrated under vacuum and purified by preparative reverse phase HPLC (trifluoroacetic acid is present in the eluent) to give of [(1S)-1-carboxy-2-[4-(ethylcarbamoyl)pyridazin-1-ium-1-yl]ethyl]ammonium; 2,2,2-trifluoroacetate.

[0351] .sup.1H NMR (400 MHz, D.sub.2O) 10.00 (d, 1H), 9.80 (d, 1H), 8.90-8.93 (m, 1H), 5.49 (d, 2H), 4.64 (t, 1H), 3.46-3.52 (m, 2H), 1.25 (t, 3H). (NH and CO.sub.2H protons missing)

Example 8: Preparation of [(1S)-1-carboxy-3-[4-(ethylcarbamoyl)pyridazin-1-ium-1-yl]propyl]ammonium dichloride A91

[0352] ##STR00066##

Step 1: Preparation of [(1S)-3-[4-(ethylcarbamoyl)pyridazin-1-ium-1-yl]-1methoxycarbonyl-propyl]ammonium 2,2,2-trifluoroacetate A93

[0353] ##STR00067##

[0354] To a solution of N-ethylpyridazine-4-carboxamide (0.3 g) in dry acetonitrile (6 mL) was added [(1S)-3-bromo-1-methoxycarbonyl propyl]ammonium chloride (0.55 g, preparation as described in WO2019/034757) at room temperature, under nitrogen atmosphere. The reaction mixture was heated at reflux for 16 hours, concentrated and purified by preparative reverse phase HPLC (trifluoroacetic acid is present in the eluent) to give [(1S)-3-[4-(ethylcarbamoyl)pyridazin-1-ium-1-yl]-1methoxycarbonyl-propyl]ammonium 2,2,2-trifluoroacetate as a gum.

[0355] .sup.1H NMR (400 MHz, D.sub.2O) 9.92 (d, 1H), 9.74 (dd, 1H), 8.83 (dd, 1H), 5.16 (t, 2H), 4.33 (dd, 1H), 3.83 (s, 3H), 3.44 (q, 2H), 2.78-2.83 (m, 1H), 2.66-2.76 (m, 1H), 1.20 (t, 3H) (NH protons missing)

Step 2: Preparation of [(1S)-1-carboxy-3-[4-(ethylcarbamoyl)pyridazin-1-ium-1-yl]propyl]ammonium dichloride A91

[0356] A mixture of methyl (2S)-2-amino-4-[4-(ethylcarbamoyl)pyridazin-1-ium-1-yl]butanoate 2,2,2-trifluoroacetate (0.05 g) in 2M aqueous hydrochloric acid (1 mL) was heated at 60° C. for 12 hours. The reaction mixture was concentrated to give [(1S)-1-carboxy-3-[4-(ethylcarbamoyl)pyridazin-1-ium-1-yl]propyl]ammonium dichloride as a gum.

[0357] .sup.1H NMR (400 MHz, D.sub.2O) 9.94 (d, 1H), 9.75 (d, 1H), 8.83 (dd, 1H), 5.18 (t, 2H), 4.11-4.18 (m, 1H), 3.46 (q, 2H), 2.68-2.84 (m, 2H), 1.21 (t, 3H) (NH and CO2H protons missing)

Example 9: Preparation of 3-[4-[2-(5,5-dimethyl-4H-isoxazol-3-yl)ethylcarbamoyl]pyridazin-1-ium-1-yl]propanoic Acid 2,2,2-trifluoroacetate A148

[0358] ##STR00068##

[0359] Step 1: Preparation of tert-butyl N-(3-oxopropyl)carbamate

##STR00069##

[0360] To a solution of 3-(Boc-amino)-1-propanol (5 g) in dichloromethane (150 mL) at 0° C., under nitrogen atmosphere, was added Dess-Martin Periodinane (14.08 g). The reaction mixture was warmed to room temperature and stirred for 2 hours. The reaction mixture was diluted with water (120 mL) and extracted with dichloromethane (3×70 mL). The combined organic layers were washed with 1M aqueous sodium thiosulfate and saturated sodium bicarbonate, dried over sodium sulfate and concentrated to give tert-butyl N-(3-oxopropyl)carbamate as a brown gum, which was used in the next step without further purification.

Step 2: Preparation of tert-butyl N-(3-hydroxyiminopropyl)carbamate

[0361] ##STR00070##

[0362] To a solution of tert-butyl N-(3-oxopropyl)carbamate (5 g) in ethanol (100 mL) was added hydroxylamine hydrochloride (2.82 g) and sodium carbonate (8.26 g) and the resulting mixture was stirred at room temperature for 16 hours. The reaction mixture was diluted with water (120 mL) and extracted with ethyl acetate (3×100 mL). The combined organic layers were washed with water, brine, dried over sodium sulfate and concentrated to give tert-butyl N-(3-hydroxyiminopropyl)carbamate as a brown solid, which was used in the next step without further purification.

Step 3: Preparation of tert-butyl N-[2-(5,5-dimethyl-4H-isoxazol-3-yl)ethyl]carbamate

[0363] ##STR00071##

[0364] To a solution of tert-butyl N-(3-hydroxyiminopropyl)carbamate (4.5 g) in N,N-dimethylformamide (45 ml), at room temperature, was added N-chlorosuccinimide (3.95 g) portion wise. After stirring for 2 hours potassium carbonate (4 g) was added and the reaction mixture was cooled to −40° C. The mixture was purged with isobutylene gas (˜14 g) for ˜30 minutes at −40° C. and then stirred at same temperature for 4 hours. The reaction was slowly warmed to room temperature and stirred for 18 hours. The reaction was quenched with ice water and extracted with ethyl acetate (3×50 mL). The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, concentrated and purified by silica gel column chromatography eluting with a mixture of ethyl acetate in iso-hexane to give tert-butyl N-[2-(5,5-dimethyl-4H-isoxazol-3-yl)ethyl]carbamate as off white solid.

[0365] .sup.1H NMR (400 MHz, CDCl.sub.3) 4.95 (br s, 1H), 3.40 (br d, 2H), 2.70 (s, 2H), 2.46 (t, 2H), 1.42 (s, 9H), 1.37 (s, 6H)

Step 4: Preparation of 2-(5,5-dimethyl-4H-isoxazol-3-yl)ethylammonium 2,2,2-trifluoroacetate

[0366] ##STR00072##

[0367] To a solution of tert-butyl N-[2-(5,5-dimethyl-4H-isoxazol-3-yl)ethyl]carbamate (1 g) in dichloromethane (20 mL), at 0° C., was added 2,2,2-trifluoroacetic acid (2.87 mL). The reaction was warmed to room temperature and stirred for 18 hours. The reaction mass was concentrated and the resulting residue was washed with tert-butyl methyl ether (2×20 mL) and dried under reduced pressure to give 2-(5,5-dimethyl-4H-isoxazol-3-yl)ethylammonium 2,2,2-trifluoroacetate as an off-white solid.

[0368] .sup.1H NMR (400 MHz, DMSO-d6) 7.88 (br s, 3H), 3.00-3.09 (m, 2H), 2.76 (s, 2H), 2.57 (t, 2H), 1.29 (s, 6H)

Step 5: Preparation of N-[2-(5,5-dimethyl-4H-isoxazol-3-yl)ethyl]pyridazine-4-carboxamide

[0369] ##STR00073##

[0370] To a solution of (2,3,4,5,6-pentafluorophenyl) pyridazine-4-carboxylate (0.5 g) in acetonitrile (10 mL) at room temperature was added 2-(5,5-dimethyl-4H-isoxazol-3-yl)ethylammonium 2,2,2-trifluoroacetate (0.48 g) and potassium carbonate (0.6 g). The reaction mass was subjected to microwave irradiation at 100° C. for 1 hour. The reaction was concentrated and purified by silica gel column chromatography eluting with a mixture of methanol in dichloromethane to afford N-[2-(5,5-dimethyl-4H-isoxazol-3-yl)ethyl]pyridazine-4-carboxamide.

[0371] .sup.1H NMR (400 MHz, CD.sub.3OD) 9.49 (dd, 1H), 9.37 (dd, 1H), 8.00 (dd, 1H), 3.67 (t, 2H), 2.88 (s, 2H), 2.65 (t, 2H), 1.35 (s, 6H) (NH proton missing)

Step 6: Preparation of 3-[4-[2-(5,5-dimethyl-4H-isoxazol-3-yl)ethylcarbamoyl]pyridazin-1-ium-1-yl]propanoic acid 2,2,2-trifluoroacetate A148

[0372] To a solution of N-[2-(5,5-dimethyl-4H-isoxazol-3-yl)ethyl]pyridazine-4-carboxamide (0.25 g) in acetonitrile (5 mL) was added 3-bromopropanoic acid (0.32 g) and the mixture was heated at 80° C. for 18 hours. The reaction mass was cooled, concentrated and purified by preparative reverse phase HPLC (trifluoroacetic acid is present in the eluent) to give 3-[4-[2-(5,5-dimethyl-4H-isoxazol-3-yl)ethylcarbamoyl]pyridazin-1-ium-1-yl]propanoic acid 2,2,2-trifluoroacetate as an off-white solid.

[0373] .sup.1H NMR (400 MHz, D.sub.2O) 9.94 (d, 1H), 9.68 (d, 1H), 8.76 (dd, 1H), 5.15 (t, 2H), 3.67 (t, 2H), 3.26 (t, 2H), 2.93 (s, 2H), 2.67 (t, 2H), 1.32 (s, 6H) (NH and CO.sub.2H protons missing)

[0374] For compound A131 synthesis of the amine can be found in WO16071359.

TABLE-US-00013 TABLE A Physical Data for Compounds of the Invention Compound Number Structure .sup.1H NMR A1 [00074] (400 MHz, D.sub.2O) 9.88 (d, 1H), 9.68 (d, 1H), 8.74 (d, 1H), 5.20-5.25 (m, 2H), 3.55-3.66 (m, 2H), 2.91 (s, 3H) (NH proton missing) A2 [00075] (400 MHz, D.sub.2O) 9.92 (d, 1H), 9.54 (d, 1H), 8.66 (dd, 1H), 5.16 (t, 2H), 3.66 (s, 3H), 3.29 (t, 2H) 3.12 (s, 3H), 2.99 (s, 3H) A3 [00076] (400 MHz, D.sub.2O) 9.83 (d, 1H), 9.53 (d, 1H), 8.63 (dd, 1H), 5.01 (t, 2H), 3.09 (s, 3H), 2.93-3.05 (m, 5H), 2.53-2.58 (m, 2H) (SO3H proton missing) A4 [00077] (400 MHz, D.sub.2O) 9.94 (d, 1H), 9.72 (d, 1H), 8.80 (dd, 1H), 5.16 (t, 2H), 3.25 (t, 2H), 2.98 (s, 3H) (NH and CO2H protons missing) A5 [00078] (400 MHz, D.sub.2O) 9.81-9.96 (m, 1H), 9.64-9.75 (m, 1H), 8.70-8.85 (m, 1H), 5.18-5.29 (m, 2H), 4.07-4.22 (m, 1H), 3.59-3.71 (m, 2H), 1.13- 1.24 (m, 6H) (NH and SO3H protons missing) A6 [00079] (400 MHz, d.sub.6-DMSO) 10.17-10.31 (m, 1H), 9.93-10.03 (m, 1H), 9.69- 9.76 (m, 1H), 9.09-9.19 (m, 1H), 4.97-5.19 (m, 2H), 4.00-4.17 (m, 1H), 3.01-3.17 (m, 2H), 1.11-1.26 (m, 6H) A7 [00080] (400 MHz, d.sub.6-DMSO) 11.18 (s, 1H), 10.12-10.19 (d, 1H), 9.89-9.99 (m, 1H), 8.97-9.07 (s, 1H), 7.67-7.84 (d, 2H), 7.38-7.50 (m, 2H), 7.18-7.27 (m, 1H), 5.09-5.19 (t, 2H), 3.18-3.25 (t, 2H) A8 [00081] (400 MHz, D.sub.2O) 9.55-9.62 (d, 1H), 9.24 (s, 1H), 8.25-8.36 (d, 1H), 7.18- 7.33 (m, 5H), 5.01-5.07 (m, 1H), 4.99-5.05 (m, 1H), 3.49-3.59 (m, 2H), 3.45-3.50 (m, 3H) (SO3H proton missing) A9 [00082] (400 MHz, D.sub.2O) 9.86 (d, 1H), 9.54 (d, 1H), 8.62 (dt, 1H), 5.21-5.26 (m, 2H), 4.64-4.74 (m, 1H), 3.61-3.69 (m, 2H), 2.96 (s, 2H), 2.80 (s, 1H), 1.19 (d, 3H), 1.15 (d, 3H) (SO3H proton missing) A10 [00083] (400 MHz, D.sub.2O) 9.91 (d, 1H), 9.55 (d, 1H), 8.76-8.52 (m, 1H), 5.16 (t, 2H), 3.28 (t, 2H), 3.13 (s, 3H), 3.00 (s, 3H) (CO2H proton missing) A11 [00084] (400 MHz, D.sub.2O) 9.80 (d, 1H), 9.70 (s, 1H), 8.70 (dd, 1H), 5.03 (t, 2H), 2.90- 3.05 (m, 5H), 2.47-2.58 (m, 2H) (NH proton missing) A12 [00085] (400 MHz, D.sub.2O) 9.93 (d, 1H), 9.74 (d, 1H), 8.82 (dd, 1H), 5.17 (t, 2H), 4.14 (dd, 1H), 2.97 (s, 3H), 2.68-2.83 (m, 2H) (three NH and one CO2H protons missing) A13 [00086] (400 MHz, D.sub.2O) 9.82-9.91 (d, 1H), 9.58-9.70 (s, 1H), 8.70-8.80 (d, 1H), 5.18-5.28 (t, 2H), 3.63-3.71(t, 2H), 1.41 (s, 9H) (NH and SO3H protons missing) A14 [00087] (400 MHz, D.sub.2O) 9.79-9.87 (d, 1H), 9.52 (s, 1H), 8.55-8.62 (s, 1H), 5.17- 5.27 (t, 2H), 3.73-3.82 (m, 1H), 3.62- 3.69 (t, 2H), 3.48-3.59 (m, 1H), 1.38- 1.47 (d, 6H), 1.12-1.20 (d, 6H) (SO3H proton missing) A15 [00088] (400 MHz, D.sub.2O) 9.85-9.95 (d, 1H), 9.68(s, 1H), 8.68-8.77 (d, 1H), 5.07- 5.17 (t, 2H), 3.18-3.32 (t, 2H), 1.36 (s, 9H) (NH and CO2H protons missing) A16 [00089] (400 MHz, D.sub.2O) 9.92 (d, 1H), 9.73 (d, 1H), 8.80 (dd, 1H), 5.29-5.22 (m, 2H), 4.18 (d, 2H), 3.71-3.63 (m, 2H), 2.63 (t, 1H) (NH proton missing) A17 [00090] (400 MHz, D.sub.2O) 9.96 (d, 1H), 9.73 (d, 1H), 8.82 (dd, 1H), 5.16 (t, 2H), 4.20 (d, 2H), 3.27 (t, 2H), 2.65 (t, 1H) (NH and CO2H protons missing) A18 [00091] (400 MHz, D.sub.2O) 9.95 (d, 1H), 9.77 (d, 1H), 8.84 (dd, 1H), 5.92 (ddt, 1H), 5.28-5.32 (m, 2H), 5.18-5.28 (m, 2H), 4.05 (d, 2H), 3.67-3.75 (m, 2H) (NH proton missing) A19 [00092] (400 MHz, D.sub.2O) 9.94 (d, 1H), 9.71 (d, 1H), 8.80 (dd, 1H), 5.89 (ddt, 1H), 5.09-5.28 (m, 4H), 4.02 (dt, 2H), 3.25 (t, 2H) (NH and CO2H protons missing) A20 [00093] (400 MHz, D.sub.2O) 9.92 (d, 1H), 9.74 (d, 1H), 8.81 (dd, 1H), 7.30-7.40 (m, 5H), 5.23-5.30 (m, 2H), 4.61 (s, 2H), 3.65-3.71 (m, 2H) (NH proton missing) A21 [00094] (400 MHz, D.sub.2O) 9.92 (d, 1H), 9.71 (d, 1H), 8.79 (dd, 1H), 7.29-7.42 (m, 5H), 5.13 (t, 2H), 4.61 (s, 2H), 3.21 (t, 2H) (NH and CO2H protons missing) A22 [00095] (400 MHz, D.sub.2O) 9.95 (d, 1H), 9.71 (d, 1H), 8.80 (dd, 1H), 7.34-7.40 (m, 2H), 7.05-7.12 (m, 2H), 5.16 (t, 2H), 4.57 (s, 2H), 3.27 (t, 2H) (NH and CO2H protons missing) A23 [00096] (400 MHz, D.sub.2O) 9.93 (d, 1H), 9.74 (d, 1H), 8.80 (dd, 1H), 7.37 (dd, 2H), 7.04-7.12 (m, 2H), 5.24-5.29 (m, 2H), 4.58 (s, 2H), 3.66-3.71 (m, 2H) (NH proton missing) A24 [00097] (400 MHz, D.sub.2O) 9.68-10.04 (m, 1H), 9.32-9.64 (m, 1H), 8.39-8.75 (m, 1H), 5.00-5.22 (m, 2H), 3.56-375 (m, 2H), 3.28-3.34 (m, 2H), 3.18-3.25 (m, 2H), 1.63-1.73 (m, 4H), 1.44- 1.61 (m, 2H) (CO2H proton missing) A25 [00098] (400 MHz, D.sub.2O) 9.87-9.99 (m, 1H), 9.66-9.78 (m, 1H), 8.72-8.88 (m, 1H), 5.20-5.37 (m, 2H), 3.61-3.76 (m, 2H), 3.21-3.36 (m, 2H), 0.99- 1.14 (m, 1H), 0.45-0.61 (m, 2H), 0.16- 0.34 (m, 2H) (NH proton missing) A26 [00099] (400 MHz, D.sub.2O) 9.84-10.01 (m, 1H), 9.46-9.68 (m, 1H), 8.62-8.78 (m, 1H), 5.03-5.22 (m, 2H), 3.56-3.75 (m, 2H), 3.44-3.51 (m, 2H), 3.16- 3.31 (m, 2H), 1.85-2.06 (m, 4H) (CO2H proton missing) A27 [00100] (400 MHz, D.sub.2O) 9.70-9.97 (m, 1H), 9.42-9.62 (m, 1H), 8.53-8.67 (m, 1H), 5.10-5.31 (m, 2H), 3.57-3.78 (m, 4H), 3.16-3.39 (m, 2H), 1.55- 1.66 (m, 6H) A28 [00101] (400 MHz, D.sub.2O) 9.86-9.95 (m, 1H), 9.53-9.64 (m, 1H), 8.63-8.72 (m, 1H), 5.19-5.30 (m, 2H), 3.81-3.86 (m, 2H), 3.77-3.80 (m, 2H), 3.66- 3.73 (m, 4H), 3.42-3.46 (m, 2H) A29 [00102] (400 MHz, D.sub.2O) 9.85-9.98 (m, 1H), 9.47-9.61 (m, 1H), 8.58-8.70 (m, 1H), 5.05-5.19 (m, 2H), 3.73-3.84 (m, 4H), 3.66-3.73 (m, 2H), 3.38- 3.49 (m, 2H), 3.10-3.30 (m, 2H) (CO2H proton missing) A30 [00103] (400 MHz, D.sub.2O) 9.84-9.98 (m, 1H), 9.65-9.76 (m, 1H), 8.69-8.87 (m, 1H), 5.18-5.33 (m, 2H), 3.55-3.75 (m, 2H), 2.75-2.91 (m, 1H), 0.81- 0.90 (m, 2H), 0.63-0.74 (m, 2H) (NH proton missing) A31 [00104] (400 MHz, D.sub.2O) 9.83-10.04 (m, 1H), 9.60-9.82 (m, 1H), 8.64-8.88 (m, 1H), 5.04-5.25 (m, 2H), 3.12-3.38 (m, 2H), 2.74-2.93 (m, 1H), 0.82- 0.97 (m, 2H), 0.67-0.73 (m, 2H) (NH and CO2H protons missing) A32 [00105] (400 MHz, D.sub.2O) 9.87 (d, 1H), 9.52 (d, 1H), 8.58 (dd, 1H), 5.13 (t, 2H), 3.81 (s, 1H), 3.58 (d, 1H), 3.25 (t, 2H), 1.46 (d, 6H), 1.20 (d, 6H) (CO2H proton missing) A33 [00106] (400 MHz, D.sub.2O) 9.98 (d, 1H), 9.81 (s, 1H), 8.92 (dd, 1H), 7.58 (d, 2H), 7.46 (t, 2H), 7.28-7.36 (m, 1H), 5.18 (t, 2H), 3.28 (t, 2H) (NH and CO2H protons missing) A34 [00107] (400 MHz, D.sub.2O) 9.90 (d, 1H), 9.54 (d, 1H), 8.64 (dt, 1H), 5.14 (t, 2H), 4.68- 4.74 (m, 1H), 3.23-3.28 (m, 2H), 2.99 (s, 2H), 2.84 (s, 1H), 1.23 (d, 3H), 1.19 (d, 3H) (CO2H proton missing) A35 [00108] (400 MHz, D.sub.2O) 9.92 (d, 1H), 9.70 (d, 1H), 8.78 (dd, 1H), 5.14 (t, 2H), 3.30- 3.16 (m, 4H), 1.90 (quin, 1H), 0.91 (d, 6H) (NH and CO2H missing) A36 [00109] (400 MHz, D.sub.2O) 9.98 (d, 1H), 9.79 (d, 1H), 8.87 (dd, 1H), 5.34-5.25 (m, 2H), 4.20 (q, 2H), 3.75-3.64 (m, 2H) (NH proton missing) A37 [00110] (400 MHz, D.sub.2O) 9.92 (d, 1H), 9.72 (d, 1H), 8.79 (dd, 1H), 5.33-5.21 (m, 2H), 3.75-3.61 (m, 2H), 3.24 (d, 2H), 1.90 (quin, 1H), 0.91 (d, 6H) (NH proton missing) A38 [00111] (400 MHz D2O)9.57 (dd, 1 H), 9.19 (s, 1 H), 8.32 (dd, 1 H), 7.22-7.35 (m, 5 H), 4.73-4.95 (t, 2 H), 3.45 (s, 3H), 3.06 (t, 2 H) (CO2H proton missing) A39 [00112] (400 MHz D.sub.2O) 9.89 (s, 1H), 9.67 (s, 1H), 7.58-7.72 (m, 5H), 5.18-5.29 (m, 2H), 3.67-3.74 (m, 2H), 2.79 (s, 3H) (NH proton missing) A40 [00113] (400 MHz, D.sub.2O) 9.91 (d, 1H), 9.68 (d, 1H), 8.77 (dd, 1H), 5.12 (t, 2H), 3.65- 3.57 (m, 4H), 3.32 (s, 3H), 3.22 (t, 2H) (NH and CO2H protons missing) A41 [00114] (400 MHz, D.sub.2O) 9.96-10.09 (m, 1H), 9.76-9.92 (m, 1H), 8.91-9.05 (m, 1H), 8.53-8.70 (m, 1H), 6.82-6.98 (m, 1H), 5.08-5.25 (m, 2H), 3.15- 3.37 (m, 2H) (NH and CO2H protons missing) A42 [00115] (400 MHz, D.sub.2O) 9.97 (d, 1H), 9.91 (d, 1H), 9.01 (dd, 1H), 7.54 (d, 1H), 7.25 (d, 1H), 5.18 (t, 2H), 3.67 (s, 3H), 3.31 (t, 2H) (NH proton missing) A43 [00116] (400 MHz, D.sub.2O) 9.92 (d, 1H), 9.69 (d, 1H), 8.77 (dd, 1H), 5.13 (t, 2H), 3.43 (q, 2H), 3.24 (t, 2H), 1.19 (t, 3H) (NH and CO2H protons missing) A44 [00117] (400 MHz, D.sub.2O) 9.94 (d, 1H), 9.73 (d, 1H), 8.82 (dd, 1H), 5.15 (t, 2H), 3.80- 3.74 (m, 2H), 3.61-3.56 (m, 2H), 3.24 (t, 2H) (NH, CO2H and OH protons missing) A45 [00118] (400 MHz, D.sub.2O) 9.93 (d, 1H), 9.69 (d, 1H), 8.77 (dd, 1H), 5.15 (t, 2H), 3.42 (t, 2H), 3.25 (t, 2H), 1.65-1.52 (m, 2H), 1.40-1.28 (m, 2H), 0.88 (t, 3H) (NH and CO2H protons missing) A46 [00119] (400 MHz, D.sub.2O) 9.91 (d, 1H), 9.68 (d, 1H), 8.76 (dd, 1H), 5.12 (t, 2H), 3.36 (t, 2H), 3.21 (t, 2H), 1.59 (sext, 2H), 0.89 (t, 3H) (NH and CO2H protons missing) A47 [00120] (400 MHz, D.sub.2O) 9.96 (d, 1H), 9.74 (d, 1H), 8.84 (dd, 1H), 5.14 (t, 2H), 4.18 (q, 2H), 3.22 (t, 2H) (NH and CO2H protons missing) A48 [00121] (400 MHz, D.sub.2O) 9.94 (d, 1H), 9.75 (d, 1H), 8.82 (dd, 1H), 5.33-5.27 (m, 2H), 3.75-3.68 (m, 2H), 3.47 (q, 2H), 1.22 (t, 3H) (NH proton missing) A49 [00122] (400 MHz, D.sub.2O) 9.95 (d, 1H), 9.77 (d, 1H), 8.85 (dd, 1H), 5.33-5.26 (m, 2H), 3.81-3.75 (m, 2H), 3.74-3.68 (m, 2H), 3.63-3.56 (m, 2H) (NH and OH protons missing) A50 [00123] (400 MHz, D.sub.2O) 9.92 (d, 1H), 9.72 (d, 1H), 8.79 (dd, 1H), 5.32-5.22 (m, 2H), 3.75-3.65 (m, 2H), 3.42 (t, 2H), 1.65-1.53 (m, 2H), 1.35 (qd, 2H), 0.88 (t, 3H) (NH proton missing) A51 [00124] (400 MHz, D.sub.2O) 9.91 (d, 1H), 9.72 (d, 1H), 8.78 (dd, 1H), 5.30-5.22 (m, 2H), 3.72-3.65 (m, 2H), 3.37 (t, 2H), 1.60 (sext, 2H), 0.90 (t, 3H) (NH proton missing) A52 [00125] (400 MHz, D.sub.2O) 9.94 (d, 1H), 9.75 (d, 1H), 8.82 (dd, 1H), 5.28 (t, 2H), 3.72- 3.68 (m, 2H), 3.68-3.62 (m, 4H), 3.36 (s, 3H) (NH proton missing) A53 [00126] (400 MHz, D.sub.2O) 9.72-9.84 (m, 1H), 9.24-9.37 (m, 1H), 4.93-5.08 (m, 2H), 3.11-3.20 (m, 2H), 2.83-2.96 (m, 3H), 2.49-2.63 (m, 3H) (NH and CO2H protons missing) A54 [00127] (400 MHz, D.sub.2O) 9.80 (d, 1H), 8.60 (d, 1H), 7.51-7.71 (m, 5H), 5.24 (t, 2H), 3.60-3.70 (m, 2H), 2.77 (s, 3H) (NH proton missing) A55 [00128] (400 MHz, D.sub.2O) 9.86 (d, 1H), 8.66 (d, 1H), 7.59-7.74 (m, 5H), 5.20 (t, 2H), 3.27 (t, 2H), 2.85 (s, 3H) (NH and CO2H protons missing) A56 [00129] (400 MHz, D.sub.2O) 9.70 (d, 1H), 8.45 (d, 1H), 5.15 (t, 2H), 3.64 (t, 2H), 2.92 (s, 3H), 2.78 (s, 3H) (NH proton missing) A57 [00130] (400 MHz, D.sub.2O) 9.68 (d, 1H) 8.42 (d, 1H) 5.01 (t, 2H), 3.18 (t, 2H), 2.90 (s, 3H), 2.73 (s, 3H) (NH and CO.sub.2H protons missing) A58 [00131] (400 MHz, D.sub.2O) 9.89 (d, 1H), 9.66 (d, 1H), 8.75 (dd, 1H), 5.11 (t, 2H), 4.09-4.37 (m, 1H), 3.23 (t, 2H), 1.85- 2.07 (m, 2H), 1.44-1.76 (m, 6H) (NH and CO2H protons missing) A59 [00132] (400 MHz, D.sub.2O) 9.91 (d, 1H), 9.67 (d, 1H), 8.76 (dd, 1H), 5.13 (t, 2H), 3.68-3.95 (m, 1H), 3.25 (t, 2H), 1.89 (br d, 2H), 1.64-1.77 (m, 2H), 1.57 (br d, 1H), 1.22-1.41 (m, 4H), 1.06- 1.21 (m, 1H) (NH and CO2H protons missing) A60 [00133] (400 MHz, D.sub.2O) 9.90 (d, 1H), 9.71 (d, 1H), 8.80 (dd, 1H), 5.14 (d, 1H), 4.99 (dd, 1H), 3.39-3.51 (m, 3H), 1.32 (d, 3H), 1.21 (t, 3H) (NH and CO2H protons missing) A61 [00134] (400 MHz, D.sub.2O) 9.97 (d, 1H), 9.74 (d, 1H), 8.78 (dd, 1H), 5.55 (ddd, 1H), 3.45 (q, 2H), 3.29-3.41 (m, 1H), 3.14 (dd, 1H), 1.65-1.71 (m, 3H), 1.21 (t, 3H) (NH and CO2H protons missing) A62 [00135] (400 MHz, D.sub.2O) 9.98 (d, 1H), 9.73 (d, 1H), 8.81 (dd, 1H), 5.16 (t, 2H), 3.26 (t, 2H), 1.66-1.77 (m, 2H), 1.43- 1.50 (m, 2H) (NH and CO2H protons missing) A63 [00136] (400 MHz, D.sub.2O) 9.97 (d, 1H), 9.74 (d, 1H), 8.85 (dd, 1H), 5.16 (t, 2H), 3.26 (t, 2H), 1.79 (s, 6H) (NH and CO2H protons missing) A64 [00137] (400 MHz, D.sub.2O) 9.85 (s, 1H), 9.69 (s, 1H), 7.55-7.76 (m, 5H), 5.23 (t, 2H), 3.68 (t, 2H), 2.95 (s, 3H), 2.59 (s, 3H) (OH proton missing) A65 [00138] (400 MHz, D.sub.2O) 9.93 (d, 1H), 9.72 (s, 1H), 8.79 (d, 1H), 5.14-5.19 (m, 2H), 3.24-3.35 (m, 4H), 1.06-1.09 (m, 1H), 0.50-0.53 (m, 2H), 0.22- 0.28 (m, 2H) (NH and CO.sub.2H proton missing) A66 [00139] (400 MHz, D.sub.2O) 9.85 (d, 1H), 9.49 (d, 1H), 8.56 (dd, 1H), 5.10 (t, 2H), 3.22 (t, 2H), 2.88 (s, 3H), 1.47 (s, 9H) (CO2H proton missing) A67 [00140] (400 MHz, D.sub.2O) 9.99 (d, 1H), 9.77 (d, 1H), 8.88 (dd, 1H), 5.19 (t, 2H), 4.76-4.88 (m, 3H), 4.32-4.50 (m, 2H), 3.30 (t, 2H) (NH and CO2H protons missing) A68 [00141] (400 MHz, D.sub.2O) 9.95 (d, 1H), 9.72 (d, 1H), 8.83 (dd, 1H), 5.15 (t, 2H), 4.59-4.68 (m, 1H), 4.21-4.32 (m, 2H), 3.41-3.54 (m, 2H), 3.26 (t, 2H) (NH and CO2H protons missing) A69 [00142] (400 MHz, D.sub.2O) 9.93 (d, 1H), 9.70 (d, 1H), 8.80 (dd, 1H), 5.23-5.37 (m, 1H), 5.13 (t, 2H), 3.49-3.60 (m, 2H), 3.30-3.42 (m, 2H), 3.22 (t, 2H) (NH and CO2H protons missing) A70 [00143] (400 MHz, D.sub.2O) 9.94 (d, 1H), 9.71 (d, 1H), 8.80 (dd, 1H), 5.15 (t, 2H), 3.66 (t, 2H), 3.26 (t, 2H), 2.77 (t, 2H), 2.11 (s, 3H) (NH and CO2H protons missing) A71 [00144] (400 MHz, D.sub.2O) 9.95 (d, 1H), 9.67 (d, 1H), 8.73 (dd, 1H), 3.39 (d, 2H), 3.28 (s, 2H), 1.86 (s, 6H), 1.15 (t, 3H) (NH and CO.sub.2H proton missing) A72 [00145] (400 MHz, D.sub.2O) 10.06 (d, 1H), 9.81 (d, 1H), 8.91 (dd, 1H), 5.23 (t, 2H), 3.31 (t, 2H), 3.22 (s, 3H), 1.47 (br s, 9H) (NH and CO.sub.2H proton missing) A73 [00146] (400 MHz, D.sub.2O) 9.89 (d, 1H), 9.73 (d, 1H), 8.81 (dd, 1H), 5.03 (t, 2H), 3.96 (t, 2H), 3.40 (q, 2H), 1.16 (t, 3H) (2x NH protons missing) A74 [00147] (400 MHz, D.sub.2O) 9.92 (d, 1H), 9.74 (d, 1H), 8.83 (dd, 1H), 4.99 (t, 2H), 3.48 (q, 2H), 2.54-2.60 (m, 2H), 2.42 (t, 2H), 1.24 (t, 3H) (NH and CO2H protons missing) A75 [00148] (400 MHz, D.sub.2O) 9.91 (d, 1H), 9.75 (d, 1H), 8.83 (dd, 1H), 4.98 (t, 2H), 3.68 (s, 3H), 3.48 (d, 2H), 2.56-2.62 (m, 2H), 2.44 (t, 2H), 1.24 (t, 3H) (NH proton missing) A76 [00149] (400 MHz, D.sub.2O) 9.92 (d, 1H), 9.76 (d, 1H), 8.83 (dd, 1H), 5.09 (t, 2H), 3.44-3.52 (m, 2H), 3.05 (t, 2H), 2.58- 2.63 (m, 2H), 1.25 (t, 3H) (NH proton missing) A77 [00150] (400 MHz, D.sub.2O) 9.96 (d, 1H), 9.72 (s, 1H), 8.81 (d, 1H), 5.12-5.19 (m, 2H), 3.23-3.32 (m, 2H), 2.84 (s, 1H), 1.62-1.70 (s, 6H) (NH and CO.sub.2H proton missing) A78 [00151] (400 MHz, D.sub.2O) 9.98 (d, 1H), 9.74 (s, 1H), 8.84 (d, 1H), 5.10-5.31 (m, 2H), 4.81-4.93 (m, 1H), 3.29 (t, 2H), 2.75 (s, 1H), 1.44-1.56 (d, 3H) (NH and CO.sub.2H protons missing) A79 [00152] (400 MHz, D.sub.2O) 9.90 (d, 1H), 9.81 (d, 1H), 8.89 (dd, 1H), 5.29 (dd, 1H), 5.01 (dd, 1H), 4.70-4.77 (m, 1H), 3.52 (q, 2H), 3.25-3.40 (m, 2H), 1.27 (t, 3H) (NH and OH protons missing) A80 [00153] (400 MHz, D.sub.2O) 9.92 (d, 1H), 9.79 (s, 1H), 8.86 (dd, 1H), 5.26-5.22 (m, 2H), 4.64-4.68 (m, 2H), 3.49 (q, 2H), 1.25 (t, 3H) (NH proton missing) A81 [00154] (400 MHz, D.sub.2O) 9.82 (d, 1H), 9.68- 9.78 (m, 1H), 8.82 (dd, 1H), 4.95- 5.07 (m, 2H), 3.62-3.73 (m, 2H), 3.48 (q, 2H), 1.24 (t, 3H) (2 x NH protons missing) A82 [00155] (400 MHz, D.sub.2O) 9.80 (dd, 1H), 9.71 (dd, 1H), 8.81 (dd, 1H), 5.06 (dd, 1H), 4.67 (dd, 1H), 3.86-3.90 (m, 1H), 3.49 (q, 2H), 1.41 (d, 3H), 1.25 (t, 3H) (2 x NH protons missing) A83 [00156] (400 MHz, D.sub.2O) 9.94 (d, 1H), 9.75 (d, 1H), 8.82 (dd, 1H), 5.09 (t, 2H), 4.15-4.21 (m, 2H), 3.48 (q, 2H), 2.53-2.60 (m, 2H), 1.24 (t, 3H) (NH proton missing) A84 [00157] (400 MHz, d.sub.6-DMSO) 10.60 (s, 1H), 10.11 (s, 1H), 9.99-9.83 (m, 2H), 9.00 (dd, 1H), 7.65 (dd, 1H), 7.16- 7.07 (m, 1H), 6.96 (d, 1H), 6.87 (t, 1H), 5.13 (br t, 2H), 3.27-3.20 (m, 2H) A85 [00158] (400 MHz, D.sub.2O) 10.01 (d, 1H), 9.78 (d, 1H), 8.88 (dd, 1H), 5.19 (t, 2H), 5.06 (q, 1H), 3.29 (t, 2H), 1.69 (d, 3H) (NH and CO.sub.2H protons missing) A86 [00159] (400 MHz, D.sub.2O) 9.94 (d, 1H), 9.67- 9.78 (m, 1H), 8.80 (dd, 1H), 5.14 (t, 2H), 4.13 (q, 2H), 3.22 (t, 2H), 1.76 (t, 3H) (NH and CO.sub.2H protons missing) A87 [00160] (400 MHz, D.sub.2O) 9.99 (d, 1H), 9.82 (d, 1H), 8.89 (dd, 1H), 5.15-5.31 (m, 2H), 4.09-4.30 (m, 4H), 3.51 (q, 2H), 2.88 (td, 2H), 1.28 (td, 9H) (NH proton missing) A88 [00161] (400 MHz, D.sub.2O) 9.93 (d, 1H), 9.76 (d, 1H), 8.86 (dd, 1H), 5.14 (s, 2H), 3.50 (d, 2H), 1.34 (s, 6H), 1.26 (t, 3H) (NH and CO.sub.2H protons missing) A89 [00162] (400 MHz, D.sub.2O) 9.96 (dd, 1H), 9.79 (d, 1H), 8.93 (dd, 1H), 5.92 (s, 2H), 3.87 (s, 3H), 3.49 (q, 2H), 1.21-1.27 (m, 3H) (NH proton missing) A90 [00163] (400 MHz, D.sub.2O) 9.98 (d, 1H), 9.74 (d, 1H), 8.84 (dd, 1H), 5.16 (t, 2H), 4.43 (s, 2H), 3.26 (t, 2H) (NH and CO.sub.2H protons missing) A91 [00164] (400 MHz, D.sub.2O) 9.94 (d, 1H), 9.75 (d, 1H), 8.83 (dd, 1H), 5.18 (t, 2H), 4.11-4.18 (m, 1H), 3.46 (q, 2H), 2.68-2.84 (m, 2H), 1.21 (t, 3H) (NH and CO.sub.2H protons missing) A92 [00165] (400 MHz, D.sub.2O) 9.89 (d, 1H), 9.64 (d, 1H), 8.72 (dd, 1H), 5.12 (t, 2H), 3.23 (t, 2H), 1.36 (s, 3H), 0.79-0.91 (m, 2H), 0.70-0.78 (m, 2H) (NH and CO.sub.2H protons missing) A93 [00166] (400 MHz, D.sub.2O) 9.92 (d, 1H), 9.74 (dd, 1H), 8.83 (dd, 1H), 5.16 (t, 2H), 4.33 (dd, 1H), 3.83 (s, 3H), 3.44 (q, 2H), 2.78-2.83 (m, 1H), 2.66-2.76 (m, 1H), 1.20 (t, 3H) (NH protons missing) A94 [00167] (400 MHz, D.sub.2O) 9.97 (d, 1H), 9.72 (d, 1H), 8.81 (dd, 1H), 5.16 (t, 2H), 3.25 (t, 2H), 1.44-1.48 (m, 2H), 1.24- 1.29 (m, 2H) (NH and CO.sub.2H protons missing) A95 [00168] (400 MHz, D.sub.2O) 9.96 (d, 1H), 9.73 (d, 1H), 8.82 (dd, 1H), 5.16 (t, 2H), 3.47-3.56 (m, 1H), 3.26 (t, 2H), 2.06- 1.96 (m, 1H), 1.65-1.75 (m, 1H) (NH and CO.sub.2H protons missing) A96 [00169] (400 MHz, D.sub.2O) 9.96 (d, 1H), 9.74 (dd, 1H), 8.84 (dd, 1H), 7.72-7.77 (m, 2H), 7.50-7.54 (m, 2H), 5.16 (t, 2H), 4.70 (s, 2H), 3.25 (t, 2H) (NH and CO.sub.2H protons missing) A97 [00170] (400 MHz, D.sub.2O) 9.98 (d, 1H), 9.74 (d, 1H), 8.84 (dd, 1H), 5.16 (t, 2H), 4.25 (t, 2H), 3.25 (t, 2H) (NH and CO.sub.2H protons missing) A98 [00171] (400 MHz, D.sub.2O) 9.96 (d, 1H), 9.73 (d, 1H), 8.83 (dd, 1H), 7.68 (d, 2H), 7.52 (d, 2H), 5.16 (t, 2H), 4.68 (s, 2H), 3.26 (t, 2H) (NH and CO.sub.2H protons missing) A99 [00172] (400 MHz, D.sub.2O) 9.73-9.68 (m, 1H), 9.63-9.58 (m, 1H), 8.68 (dd, 1H), 4.90 (t, 2H), 3.55 (t, 2H), 1.33 (s, 3H), 0.84-0.78 (m, 2H), 0.71-0.65 (m, 2H) (NH protons missing) A100 [00173] (400 MHz, D.sub.2O) 9.84 (d, 1H), 9.62- 9.59 (m, 1H), 8.70 (dd, 1H), 5.08 (t, 2H), 3.69 (s, 2H), 3.22-3.16 (m, 2H), 1.32-1.29 (m, 6H) (NH, OH and CO.sub.2H protons missing) A101 [00174] (400 MHz, D.sub.2O) 9.85 (d, 1H), 9.60 (d, 1H), 8.68 (dd, 1H), 5.07 (t, 2H), 3.19 (t, 2H), 2.52-2.45 (m, 1H), 1.04- 0.97 (m, 4H), 0.80-0.72 (m, 1H), 0.65-0.56 (m, 1H) (NH and CO.sub.2H protons missing) A102 [00175] (400 MHz, D.sub.2O) 9.90 (d, 1H), 9.84 (d, 1H), 8.92-8.94 (m, 1H), 7.47 (d, 1H), 7.17 (d, 1H), 5.09 (t, 2H), 3.21 (t, 2H) (NH and CO.sub.2H protons missing) A103 [00176] (400 MHz, D.sub.2O) 9.95 (d, 1H), 9.72 (d, 1H), 8.80 (dd, 1H), 5.15 (t, 2H), 3.86-3.93 (m, 2H), 3.20-3.29 (m, 3H), 3.10-3.19 (m, 1H), 2.74 (s, 3H) (NH and CO.sub.2H protons missing) A104 [00177] (400 MHz, D.sub.2O) 9.96 (d, 1H), 9.71 (d, 1H), 8.79 (dd, 1H), 5.16 (t, 2H), 3.96 (t, 2H), 3.59 (t, 2H), 3.26 (t, 2H), 3.13 (s, 3H) (NH and CO.sub.2H protons missing) A105 [00178] (400 MHz, D.sub.2O) 10.06 (d, 1H), 9.83 (d, 1H), 8.95 (dd, 1H), 5.23 (t, 2H), 3.32 (t, 2H), 2.16 (s, 3H) (NH and CO.sub.2H protons missing) A106 [00179] (400 MHz, D.sub.2O) 10.01 (d, 1H), 9.83 (d, 1H), 8.95 (dd, 1H), 7.63 (dt, 1H), 7.02-7.15 (m, 2H), 5.18 (t, 2H), 3.27 (t, 2H) (NH and CO.sub.2H protons missing) A107 [00180] (400 MHz, D.sub.2O) 9.90 (d, 1H), 9.55 (d, 1H), 8.67 (dd, 1H), 5.10 (t, 2H), 4.55 (s, 2H), 3.15-3.25 (m, 2H), 3.07 (s, 3H) (CO.sub.2H proton missing) A108 [00181] (400 MHz, D.sub.2O) 9.94 (d, 1H), 9.60 (d, 1H), 8.71 (dd, 1H), 5.16 (t, 2H), 4.24 (brs, 2H), 3.84-3.95 (m, 2H), 3.44 (brs, 2H), 3.33 (brs, 2H), 3.27 (t, 2H) (CO.sub.2H proton missing) A109 [00182] (400 MHz, D.sub.2O) 9.90 (d, 1H), 9.55 (d, 1H), 8.65 (dd, 1H), 5.12 (t, 2H), 4.43-4.51 (m, 1H), 3.93-4.03 (m, 1H), 3.79-3.86 (m, 1H), 3.54-3.64 (m, 1H), 3.24 (t, 2H), 2.88-3.15 (m, 4H) (CO.sub.2H proton missing) A110 [00183] (400 MHz, D.sub.2O) 9.96 (d, 1H), 9.71 (d, 1H), 8.79 (dd, 1H), 5.16 (t, 2H), 3.90 (t, 2H), 3.46 (t, 2H), 3.26 (t, 2H), 2.85 (s, 6H) (NH and CO.sub.2H protons missing) A111 [00184] (400 MHz, D.sub.2O) 9.96 (d, 1H), 9.71 (d, 1H), 8.80 (dd, 1H), 5.16 (t, 2H), 3.86 (t, 2H), 3.49 (t, 2H), 3.27 (t, 2H), 2.71 (s, 3H) (NH and CO.sub.2H protons missing) A112 [00185] (400 MHz, D.sub.2O) 9.87 (d, 1H), 9.50 (d, 1H), 8.59 (dd, 1H), 5.10 (t, 2H), 3.98-3.89 (m, 2H), 3.52-3.62 (m, 2H), 3.22 (t, 2H), 2.70-2.78 (m, 2H), 2.58-2.67 (m, 2H) (CO.sub.2H protons missing) A113 [00186] (400 MHz, D.sub.2O) 9.92 (d, 1H), 9.69 (d, 1H), 8.78 (dd, 1H), 5.12 (t, 2H), 3.69 (t, 2H), 3.22 (t, 2H), 2.80 (t, 2H) (NH and CO.sub.2H protons missing) A114 [00187] (400 MHz, D.sub.2O) 9.90 (d, 1H), 9.67 (d, 1H), 8.76 (dd, 1H), 5.11 (t, 2H), 3.54 (t, 2H), 3.22 (t, 2H), 2.49 (dt, 2H), 2.30 (t, 1H) (NH and CO.sub.2H protons missing) A115 [00188] (400 MHz, D.sub.2O) 9.94 (d, 1H), 9.71 (d, 1H), 8.83 (dd, 1H), 8.62 (dd, 1H), 8.48 (td, 1H), 7.97 (d, 1H), 7.89 (t, 1H), 5.11 (t, 2H), 4.95 (s, 2H), 3.21 (t, 2H) (NH and CO.sub.2H protons missing) A116 [00189] (400 MHz, D.sub.2O) 9.97 (d, 1H), 9.78 (d, 1H), 8.92 (dd, 1H), 7.52 (d, 1H), 6.37 (d, 1H), 5.13 (t, 2H), 3.70 (s, 3H), 3.23 (t, 2H) (NH and CO.sub.2H protons missing) A117 [00190] (400 MHz, D.sub.2O) 9.95 (d, 1H), 9.71 (d, 1H), 8.80 (dd, 1H), 5.16 (t, 2H), 3.85-3.93 (m, 2H), 3.27 (t, 2H), 3.14- 3.23 (m, 1H), 3.05-3.14 (m, 1H), 2.91-3.03 (m, 1H), 2.80-2.91 (m, 1H), 1.27 (t, 3H) (NH and CO.sub.2H protons missing) A118 [00191] (400 MHz, D.sub.2O) 9.96 (d, 1H), 9.70 (d, 1H), 8.79 (dd, 1H), 5.15 (t, 2H), 3.94 (t, 2H), 3.53 (t, 2H), 3.20-3.31 (m, 4H), 1.31 (t, 3H) (NH and CO.sub.2H protons missing) A119 [00192] (400 MHz, D.sub.2O) 9.83 (d, 1H), 9.64 (d, 1H), 8.64-8.81 (m, 1H), 4.94-5.09 (m, 2H), 3.32-3.46 (m, 2H), 2.26- 2.46 (m, 2H), 1.14 (t, 3H) (NH and POH protons missing) A120 [00193] (400 MHz, D.sub.2O) 9.99 (d, 1H), 9.75 (d, 1H), 8.84 (dd, 1H), 5.20 (t, 2H), 3.69 (t, 2H) 3.30 (t, 2H) 2.86 (t, 2H) 2.63 (q, 2H) 1.24 (t, 3H) (NH and CO.sub.2H protons missing) A121 [00194] (400 MHz, D.sub.2O) 10.00 (d, 1H), 9.80 (d, 1H), 8.90-8.93 (m, 1H), 5.49 (d, 2H), 4.64 (t, 1H), 3.46-3.52 (m, 2H), 1.25 (t, 3H) (NH and CO.sub.2H protons missing) A122 [00195] (400 MHz, d.sub.6-DMSO) 10.16 (d, 1H), 9.82 (d, 1H), 9.61 (d, 1H), 8.91 (dd, 1H), 5.07 (t, 2H), 4.58 (td, 1H), 3.45 (d, 2H), 3.12 (t, 2H), 3.04 (s, 3H), 1.35 (d, 3H) (CO.sub.2H proton missing) A123 [00196] (400 MHz, D.sub.2O) 9.93 (d, 1H), 9.71 (d, 1H), 8.81 (dd, 1H), 5.14 (t, 2H), 4.20 (dt, 1H), 3.68 (dd, 1H), 3.54- 3.62 (m, 1H), 3.26 (t, 2H), 1.20 (d, 3H) (NH, OH and CO.sub.2H protons missing) A124 [00197] (400 MHz, D.sub.2O) 10.08 (d, 1H), 9.92 (d, 1H), 9.29 (d, 1H), 9.01-9.11 (m, 1H), 8.39-8.57 (m, 2H), 5.24 (t, 2H), 3.34 (t, 2H) (NH and CO.sub.2H protons missing) A125 [00198] (400 MHz, D.sub.2O) 9.96 (d, 1H), 9.78 (d, 1H), 8.84-8.88 (m, 1H), 5.91-6.01 (m, 1H), 5.22-5.33 (m, 2H), 5.10 (t, 2H), 4.18 (t, 2H), 4.06-4.11 (m, 2H), 2.53-2.61 (m, 2H) (NH proton missing) A126 [00199] (400 MHz, D.sub.2O) 9.93 (d, 1H), 9.74 (d, 1H), 8.78-8.82 (m, 1H), 5.09 (t, 2H), 4.16-4.20 (m, 2H), 2.86-2.93 (m, 1H), 2.53-2.60 (m, 2H), 0.88- 0.94 (m, 2H), 0.71-0.77 (m, 2H) (NH proton missing) A127 [00200] (400 MHz, D.sub.2O) 9.98 (d, 1H), 9.74 (d, 1H), 8.82 (dd, 1H), 5.20 (t, 2H), 3.88-3.99 (m, 1H), 3.55 (t, 2H), 3.31 (t, 2H), 1.75-1.86 (m, 2H), 1.22 (d, 3H) (NH, OH and CO.sub.2H protons missing) A128 [00201] (400 MHz, D.sub.2O) 9.98 (d, 1H), 9.76 (s, 1H), 8.86 (dd, 1H), 5.19 (t, 2H), 3.98-4.15 (m, 1H), 3.37-3.61 (m, 2H), 3.31 (t, 2H), 1.23 (d, 3H) (NH, OH and CO.sub.2H protons missing) A129 [00202] (400 MHz, D.sub.2O) 10.01 (d, 1H), 9.79 (d, 1H), 8.90 (dd, 1H), 5.21 (t, 2H), 4.47 (s, 2H), 3.31 (t, 2H), 2.30 (s, 3H) (NH and CO.sub.2H protons missing) A130 [00203] (400 MHz, D.sub.2O) 9.96 (d, 1H), 9.71 (d, 1H), 8.79 (dd, 1H), 5.17 (t, 2H), 3.66 (t, 2H), 3.29 (t, 2H), 2.95 (t, 2H), 2.22 (s, 3H) (NH and CO.sub.2H protons missing) A131 [00204] (400 MHz, D.sub.2O) 10.00 (d, 1H), 9.78 (d, 1H), 8.90 (dd, 1H), 5.18 (t, 2H), 3.21-3.37 (m, 4H), 1.42 (s, 6H) (NH and CO.sub.2H protons missing) A132 [00205] (400 MHz, D.sub.2O) 9.93 (d, 1H), 9.62- 9.75 (m, 1H), 8.79 (dd, 1H), 5.14 (t, 2H), 4.33 (dt, 1H), 3.49-3.58 (m, 1H), 3.46-3.60 (m, 1H), 3.34 (s, 3H), 3.23- 3.29 (m, 2H), 1.20 (d, 3H) (NH and CO.sub.2H protons missing) A133 [00206] (400 MHz, D.sub.2O) 9.90 (d, 1H), 9.54 (d, 1H), 8.64 (dd, 1H), 5.11 (t, 2H), 3.59-3.79 (m, 4H), 3.21-3.52 (m, 2H), 3.12-3.26 (m, 4H), 2.89 (s, 3H) (CO.sub.2H proton missing) A134 [00207] (400 MHz, D.sub.2O) 9.95 (d, 1H), 9.69 (d, 1H), 8.74-8.80 (m, 1H), 5.17 (t, 2H), 3.28 (t, 2H), 1.64 (q, 2H), 0.95 (t, 3H), 0.85-0.89 (m, 2H), 0.77- 0.81 (m, 2H) (NH and CO.sub.2H protons missing) A135 [00208] (400 MHz, D.sub.2O) 9.91 (d, 1H), 9.46- 9.57 (m, 1H), 8.58-8.69 (m, 1H), 5.13 (t, 2H), 3.79-4.14 (m, 2H), 3.53- 3.67 (m, 2H), 3.26 (t, 2H), 3.10- 3.17 (m, 3H), 2.98-3.05 (m, 3H) (CO.sub.2H proton missing) A136 [00209] (400 MHz, D.sub.2O) 9.79-9.74 (m, 1H), 9.66 (d, 1H), 8.74 (dd, 1H), 4.98- 4.90 (m, 2H), 3.91 (t, 2H), 3.60-3.51 (m, 4H), 3.09 (s, 3H) (NH protons missing) A137 [00210] (400 MHz, D.sub.2O) 9.87 (d, 1H), 9.64 (d, 1H), 8.73 (dd, 1H), 5.09 (t, 2H), 3.19 (t, 2H), 2.60-2.54 (m, 1H), 1.05 (s, 3H), 0.98 (s, 3H), 0.85-0.79 (m, 1H), 0.57-0.52 (m, 1H) (NH and CO.sub.2H protons missing) A138 [00211] (400 MHz, D.sub.2O) 9.85 (t, 1H), 9.69- 9.65 (m, 1H), 8.75 (dd, 1H), 5.04- 4.90 (m, 2H), 4.11-4.06 (m, 1H), 3.66-3.55 (m, 5H), 3.31 (s, 3H), 2.52-2.43 (m, 1H), 2.32-2.23 (m, 1H) (NH proton missing) A139 [00212] (400 MHz, D.sub.2O) 9.74 (d, 1H), 9.67- 9.63 (m, 1H), 8.77-8.72 (m, 1H), 4.93 (t, 2H), 3.63-3.54 (m, 6H), 3.30 (s, 3H) (NH protons missing) A140 [00213] (400 MHz, D.sub.2O) 9.75 (d, 1H), 9.68- 9.64 (m, 1H), 8.76 (dd, 1H), 5.92- 5.79 (m, 1H), 5.26-5.11 (m, 2H), 4.93 (t, 2H), 3.98 (br d, 2H), 3.57 (br t, 2H) (NH protons missing) A141 [00214] (400 MHz, D.sub.2O) 9.79-9.74 (m, 1H), 9.69-9.65 (m, 1H), 8.76 (dd, 1H), 4.94 (t, 2H), 4.16 (d, 2H), 3.57 (t, 2H), 2.60 (t, 1H) (NH protons missing) A142 [00215] (400 MHz, D.sub.2O) 9.91-9.85 (m, 1H), 9.70 (d, 1H), 8.78 (dd, 1H), 5.07- 4.94 (m, 2H), 4.17 (d, 2H), 4.09 (t, 1.5H), 3.65 (t, 0.5H), 2.62 (t, 1H), 2.49 (quin, 1.5H), 2.29 (t, 0.5H) (NH proton missing) A143 [00216] (400 MHz, D.sub.2O) 9.89 (d, 1H), 9.60 (d, 1H), 8.69 (dd, 1H), 7.95 (d, 1H), 7.80 (d, 1H), 5.09 (t, 2H), 3.82 (t, 2H), 3.54 (t, 2H), 3.20 (t, 2H) (NH and CO.sub.2H protons missing) A144 [00217] (400 MHz, D.sub.2O) 9.90 (d, 1H), 9.61 (d, 1H), 8.71 (dd, 1H), 8.38 (s, 1H), 5.10 (t, 2H), 3.93 (s, 3H), 3.80 (t, 2H), 3.33 (t, 2H), 3.20 (t, 2H) (NH and CO.sub.2H protons missing) A145 [00218] (400 MHz, D.sub.2O) 9.87 (d, 1H), 9.56 (d, 1H), 8.73 (d, 2H), 8.65 (dd, 1H), 7.47 (t, 1H), 5.09 (t, 2H), 3.84 (t, 2H), 3.19-3.24 (m, 4H) (NH and CO.sub.2H protons missing) A146 [00219] (400 MHz, D.sub.2O) 9.99 (d, 1H), 9.77 (d, 1H), 8.87 (dd, 1H), 7.80 (d, 1H), 7.63 (d, 1H), 5.17 (t, 2H), 5.00 (s, 2H), 3.27 (t, 2H) (NH and CO.sub.2H protons missing) A147 [00220] (400 MHz, D.sub.2O) 9.96 (d, 1H), 9.73 (d, 1H), 8.95 (s, 1H), 8.85 (d, 1H), 5.14 (t, 2H), 4.77-4.79 (m, 2H), 3.93 (s, 3H), 3.25 (t, 2H) (NH and CO.sub.2H protons missing) A148 [00221] (400 MHz, D.sub.2O) 9.94 (d, 1H), 9.68 (d, 1H), 8.76 (dd, 1H), 5.15 (t, 2H), 3.67 (t, 2H), 3.26 (t, 2H), 2.93 (s, 2H), 2.67 (t, 2H), 1.32 (s, 6H) (NH and CO.sub.2H protons missing)

Biological Examples

Post-Emergence Efficacy

[0375] Seeds of a variety of test species were sown 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 formula (I) 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/l solution which was then diluted to required concentration using 0.25% or 1% Empicol ESC70 (Sodium lauryl ether sulphate)+1% ammonium sulphate as diluent.

[0376] 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).

[0377] 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:

[0378] 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-00014 TABLE B Control of weed species by compounds of formula (I) after post-emergence application Compound Application Number Rate g/Ha AMAPA CHEAL EPHHL IPOHE ELEIN LOLPE DIGSA SETFA ECHCG A1 500 100 70 70 60 70 80 90 80 60 A2 500 10 10 50 20 10 20 50 30 30 A3 500 90 70 90 20 10 10 20 20 20 A4 500 n/a 80 90 80 100 60 100 90 90 A5 500 90 70 30 60 40 50 50 40 60 A6 500 100 100 50 60 70 90 90 90 50 A7 500 100 90 60 10 40 20 20 30 20 A8 500 100 90 80 30 40 0 20 20 10 A9 500 90 90 n/a 30 20 30 50 60 30 A10 500 100 100 100 60 80 10 90 90 70 A11 500 40 80 70 30 10 30 70 20 70 A12 500 90 60 70 40 60 40 90 60 80 A13 500 100 100 70 60 70 60 80 80 60 A14 500 100 70 50 30 10 0 30 10 10 A15 500 100 100 90 30 100 70 90 100 90 A16 500 100 90 80 80 90 60 70 70 90 A17 500 100 100 90 100 100 70 100 90 90 A18 500 100 90 70 70 90 70 80 50 90 A19 500 100 90 90 70 90 80 100 80 80 A20 500 100 100 80 50 80 30 60 90 60 A21 500 90 90 90 60 90 40 70 60 90 A22 500 100 90 90 40 60 40 60 50 50 A23 500 100 70 60 50 60 20 60 70 70 A24 500 100 90 90 30 60 30 70 60 60 A25 500 100 90 80 60 90 60 80 80 70 A26 500 100 100 90 40 80 90 100 100 90 A27 500 70 40 70 30 10 30 40 40 40 A28 500 100 90 80 60 70 60 70 70 50 A29 500 100 90 100 50 90 50 90 90 90 A30 500 100 100 70 70 80 70 70 70 40 A31 500 100 100 100 30 100 70 100 100 70 A32 500 50 20 40 10 10 10 20 30 30 A33 500 100 80 50 30 90 70 60 60 60 A34 500 100 40 70 20 20 30 70 70 30 A35 500 100 90 100 50 100 70 80 90 60 A36 500 100 90 50 40 60 20 60 60 30 A37 500 100 80 70 50 60 50 70 70 50 A38 500 100 90 80 40 60 20 70 90 60 A39 500 70 70 50 20 50 10 40 30 40 A40 500 100 90 100 60 100 70 100 100 90 A41 500 80 90 90 20 60 10 70 90 50 A42 500 20 40 60 10 10 10 10 10 10 A43 500 100 90 100 70 100 50 100 100 60 A44 500 100 100 100 100 30 30 100 100 90 A45 500 80 90 n/a 30 80 60 70 90 70 A46 500 50 70 100 40 10 20 90 100 80 A47 500 100 90 100 90 20 30 100 90 100 A48 500 90 n/a n/a 80 100 70 90 90 70 A49 500 100 80 n/a 70 30 60 100 90 80 A50 500 60 70 40 60 10 20 60 60 40 A51 500 50 70 60 60 20 20 90 60 60 A52 500 100 100 60 60 20 30 90 80 80 A53 500 90 70 60 50 40 20 80 90 70 A54 500 80 70 n/a 10 50 0 60 20 40 A55 500 100 80 n/a 40 30 0 60 40 80 A56 500 100 90 n/a 30 60 40 80 60 90 A58 500 70 60 n/a 30 90 90 90 90 70 A59 500 70 50 10 20 20 20 60 30 20 A60 500 100 20 90 70 100 100 100 100 60 A61 500 100 90 80 70 90 80 100 50 50 A62 500 100 90 100 30 90 70 70 70 80 A64 500 100 30 40 30 40 20 40 30 50 A65 500 90 90 100 20 90 50 100 100 50 A67 500 30 50 n/a 30 90 90 100 100 100 A68 500 100 90 100 100 n/a 90 100 70 100 A69 500 90 60 70 40 30 40 100 100 100 A71 500 100 70 20 60 30 30 60 30 30 A72 500 100 20 20 20 30 20 40 20 20 A73 500 100 90 90 80 90 60 90 60 80 A74 500 100 90 60 40 80 80 80 70 60 A76 500 40 70 100 30 60 70 70 30 30 A77 500 100 90 100 10 n/a 80 n/a 100 n/a A78 500 100 100 70 90 n/a 80 n/a 100 n/a A80 500 100 100 90 70 90 70 90 80 90 A81 500 100 100 100 90 100 90 90 100 100 A83 500 90 90 90 80 90 80 90 60 90 A84 500 0 30 30 10 10 0 50 20 20 A85 500 100 90 100 30 100 60 100 90 90 A86 500 100 90 100 20 90 60 100 100 100 A87 500 100 100 40 30 20 10 10 60 0 A88 500 100 100 90 90 100 60 80 100 90 A89 500 0 0 20 20 0 0 0 0 0 A90 500 100 90 100 80 100 70 100 100 100 A91 500 70 50 20 30 70 60 60 70 0 A92 500 100 100 100 50 90 90 100 100 80 A94 500 100 100 90 60 100 80 90 90 80 A95 500 100 100 100 60 100 60 100 100 80 A96 500 100 80 100 40 50 20 20 30 20 A97 500 100 100 90 30 60 90 90 90 60 A98 500 90 70 100 20 90 0 60 30 50 A99 500 50 40 40 30 70 40 100 90 60 A100 500 60 20 30 20 40 50 70 90 60 A101 500 100 100 50 50 70 80 100 90 90 A102 500 100 60 20 20 0 0 0 10 0 A103 500 90 90 50 50 90 40 90 100 80 A104 500 100 100 100 80 100 70 100 100 70 A105 500 50 70 60 30 30 10 n/a 60 40 A106 500 100 50 60 30 70 50 40 90 10 A107 500 100 20 100 20 20 0 40 60 60 A108 500 100 100 80 70 80 40 90 90 70 A109 500 100 90 90 60 90 30 80 90 70 A110 500 90 50 60 20 30 60 100 90 50 A111 500 100 90 90 40 100 70 100 100 90 A112 500 100 90 90 50 70 30 100 90 40 A113 500 100 80 90 30 100 90 100 100 90 A114 500 100 90 80 60 100 80 100 100 90 A115 500 100 70 70 20 100 70 70 70 70 A116 500 40 20 50 10 40 10 60 40 40 A117 500 100 80 90 40 50 50 100 90 60 A118 500 100 100 90 40 50 50 100 90 40 A119 500 100 100 80 50 30 20 n/a 50 30 A120 500 100 80 90 10 50 40 100 70 50 A121 500 10 20 30 10 10 10 n/a 10 10 A122 500 100 90 70 60 70 60 100 60 90 A123 500 100 90 90 50 100 50 100 100 90 A124 500 20 30 30 20 30 10 70 70 60 A125 500 30 60 60 50 30 60 60 50 70 A126 500 10 60 60 50 40 50 40 70 60 A127 500 100 80 70 30 100 80 100 100 50 A128 500 100 90 100 30 90 80 100 90 40 A129 500 100 100 80 20 90 70 100 100 60 A130 500 100 90 20 10 70 70 100 100 50 A131 500 30 10 90 30 20 0 30 30 30 A132 500 100 100 70 40 100 90 100 100 90 A133 500 20 10 20 10 50 0 90 70 60 A134 500 100 90 40 20 90 90 100 60 100 A135 500 80 60 80 30 40 70 90 100 60 A136 500 0 100 60 30 80 70 100 30 50 A137 500 100 90 10 0 100 100 100 70 100 A138 500 30 70 60 60 60 60 70 80 30 A139 500 90 100 80 40 100 20 90 70 70 A140 500 100 100 90 60 100 20 90 90 70 A141 500 100 100 60 70 90 70 70 40 40 A143 500 100 90 50 40 100 50 60 80 40 A144 500 100 100 90 50 100 60 80 90 60 A145 500 100 100 0 30 100 70 100 80 60 A146 500 80 80 20 20 80 100 100 90 100 A147 500 100 90 80 40 90 90 100 80 90 A148 500 70 90 40 30 30 30 80 50 30