Thiophene based apyrase inhibitors

A composition, comprising

• a fungicide;
• a compound of the formula
• or an agriculturally acceptable salt, solvate and/or N-oxide thereof, wherein
• Z1 and Z2 are each independently selected from a group consisting of hydrogen, C1-6 alkyl;
• or Z1 together with Z2 and the atoms to which Z1 and Z2 are attached, forms a 5- or 6-membered ring optionally substituted with one or more of Ra;
• wherein the 5- or 6-membered ring is optionally a heterocyclyl ring with one or more heteroatom groups selected from O, N, —N(Re)—, S, —S(O)—, —SO2—;
• R1 is independently selected from a group consisting of hydrogen, C1-6 alkyl, optionally substituted with one or more Ra;
• R2 is selected from hydrogen and C1-6 alkyl;
• X is —(CRaRb)n—Y;
• Y is selected from the group consisting of Ra, Rb, Ra substituted with one or more of the same or different R8, Ra or Rb, —ORa substituted with one or more of the same or different Ra or Rb;
• —S(O)R8, —S(O)2R8, —N(Rd)S(O)2R8, —S(O)NRcRc, —S(O)2—NRcRc, —OS(O)Rd, —OS(O)2Rd, —OS(O)2ORd, —C(O)OR8, —C(O)R8, —OC(O)R8, —C(O)NRcRc, —NRcRc, —N(Rd)—C(O)R8, —N(Rd)—C(O)OR8, N(Rd)—C(O)NRcRc, —SR8, —(CH2)mR8, —OC(O)—(CH2)m—C(O)R8, —CHRcRc;
• R8 is selected from the group consisting of Ra, Rb, Ra substituted with one or more of the same or different Ra or Rb, —CH2Ra substituted with one or more of the same or different Ra or Rb, —ORa substituted with one or more of the same or different Ra or Rb;
• each Ra is independently selected from hydrogen, C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C1-6 haloalkyl, C3-8 cycloalkyl, C6-10 aryl, C5-10 heteroaryl, C6-16 arylalkyl, 2-6 membered heteroalkyl and 3-8 membered heterocyclylalkyl;
• Rb is independently selected from the group consisting of ═O, —ORa, halogen, C1-3 haloalkyloxy, —OCF3, ═S, —SRd, =NRd, =NORd, —NRcRc, —SF5, halogen, —CF3, —CN, —NO2, —S(O)Rd, —S(O)2Rd, —S(O)2ORd, —N(H)S(O)2Rd, —S(O)NRcRc, —S(O)2NRcRc, —OS(O)Rd, —OS(O)2Rd, —OS(O)2ORd, —OS(O)2NRcRc, —C(O)Rd, —C(O)ORd, —C(O)NRcRc, —C(NH)NRcRc, —C(NRa)NRcRc, —C(NOH)Ra, —C(NOH)NRcRc, —OC(O)Rd, —OC(O)ORd, —OC(O)NRcRc, —OC(NH)NRcRc, —OC(NRa)NRcRc, —[NHC(O)]nRd, —[NRaC(O)]nRd, —[NHC(O)]nORd, —[NRaC(O)]&ORd, —[NHC(O)]nNRcRc, —[NRaC(O)]nNRcRc, —[NHC(NH)]nNRcRc and —[NRaC(NRa)]nNRcRc;
• each Rc is hydrogen, R8, or, alternatively, two Rc are taken together with the atom to which they are bonded to form a 5 to 10-membered cycloalkyl or heterocyclylalkyl which may optionally be substituted with one or more of the same or different Re groups;
• each Rd is independently hydrogen or C1-6 alkyl;
• each Re is independently Rb or Rd;
• each m is independently an integer from 0 to 2;
• and
• each n is independently an integer from 0 to 2;
• and
• a phytologically acceptable carrier.

A pesticidal composition, comprising

• a pesticide;
• a compound of the formula
• or an agriculturally acceptable salt, solvate and/or N-oxide thereof, wherein
• Z1 and Z2 are each independently selected from a group consisting of hydrogen, C1-6 alkyl;
• or Z1 together with Z2 and the atoms to which Z1 and Z2 are attached, forms a 5- or 6-membered ring optionally substituted with one or more of Ra;
• wherein the 5- or 6-membered ring is optionally a heterocyclyl ring with one or more heteroatom groups selected from O, N, —N(Re)—, S, —S(O)—, —SO2—;
• R1 is independently selected from a group consisting of hydrogen, C1-6 alkyl, optionally substituted with one or more Ra;
• R2 is selected from hydrogen and C1-6 alkyl;
• X is —(CRaRb)n—Y;
• Y is selected from the group consisting of Ra, Rb, Ra substituted with one or more of the same or different R8, Ra or Rb, —ORa substituted with one or more of the same or different Ra or Rb;
• —S(O)R8, —S(O)2R8, —N(Rd)S(O)2R8, —S(O)NRcRc, —S(O)2—NRcRc, —OS(O)Rd, —OS(O)2Rd, —OS(O)2ORd, —C(O)OR8, —C(O)R8, —OC(O)R8, —C(O)NRcRc, —NRcRc, —N(Rd)—C(O)R8, —N(Rd)—C(O)OR8, N(Rd)—C(O)NRcRc, —SR8, —(CH2)mR8, —OC(O)—(CH2)m—C(O)R8, —CHRcRc;
• R8 is selected from the group consisting of Ra, Rb, Ra substituted with one or more of the same or different Ra or Rb, —CH2Ra substituted with one or more of the same or different Ra or Rb, —ORa substituted with one or more of the same or different Ra or Rb;
• each Ra is independently selected from hydrogen, C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C1-6 haloalkyl, C3-8 cycloalkyl, C6-10 aryl, C5-10 heteroaryl, C6-16 arylalkyl, 2-6 membered heteroalkyl and 3-8 membered heterocyclylalkyl;
• Rb is independently selected from the group consisting of ═O, —ORa, halogen, C1-3 haloalkyloxy, —OCF3, ═S, —SRd, =NRd, =NORd, —NRcRc, —SF5, halogen, —CF3, —CN, —NO2, —S(O)Rd, —S(O)2Rd, —S(O)2ORd, —N(H)S(O)2Rd, —S(O)NRcRc, —S(O)2NRcRc, —OS(O)Rd, —OS(O)2Rd, —OS(O)2ORd, —OS(O)2NRcRc, —C(O)Rd, —C(O)ORd, —C(O)NRcRc, —C(NH)NRcRc, —C(NRa)NRcRc, —C(NOH)Ra, —C(NOH)NRcRc, —OC(O)Rd, —OC(O)ORd, —OC(O)NRcRc, —OC(NH)NRcRc, —OC(NRa)NRcRc, —[NHC(O)]nRd, —[NRaC(O)]nRd, —[NHC(O)]nORd, —[NRaC(O)]nORd, —[NHC(O)]nNRcRc, —[NRaC(O)]nNRcRc, —[NHC(NH)]nNRcRc and —[NRaC(NRa)]nNRcRc;
• each Rc is hydrogen, R8, or, alternatively, two Rc are taken together with the atom to which they are bonded to form a 5 to 10-membered cycloalkyl or heterocyclylalkyl which may optionally be substituted with one or more of the same or different Re groups;
• each Rd is independently hydrogen or C1-6 alkyl;
• each Re is independently Rb or Rd;
• each m is independently an integer from 0 to 2;
• and
• each n is independently an integer from 0 to 2;
• and
• a phytologically acceptable carrier.