Fungicidal 5-alkyl-6-phenylpyrazolopyrimidin-7-ylamines

A compound of formula I

• wherein:
• L1 and L3 independently of one another are hydrogen, halogen, hydroxyl, mercapto, nitro, NRARB, C1-C4-haloalkyl, C1-C10-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C8-alkoxy, phenyl, phenoxy, phenylthio, benzyloxy or benzylthio;
• wherein RA and RB are hydrogen or C1-C6-alkyl;
• L2 is hydrogen, halogen, hydroxyl, mercapto, nitro, NRARB, C1-C4-haloalkyl, CH2—C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C8-alkoxy, phenyl, phenoxy, phenylthio, benzyloxy or benzylthio;
• wherein two adjacent groups from the group consisting of L1, L2 and L3 together may be a C1-C4-alkylene, C1-C4-oxyalkylene, C1-C4-oxyalkyleneoxy or butadienyl group;
• wherein the groups L1, L2 or L3 are unsubstituted or substituted by one to four identical or different groups Ra:
• Ra is halogen, cyano, hydroxyl, mercapto, C1-C10-alkyl, C1-C10-haloalkyl, C3-C8-cycloalkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkoxy-C1-C6-alkyl or NRARB;
• R1 is ethyl or n-propyl;
• R2 is hydrogen, halogen, cyano, NRARB, hydroxyl, mercapto, C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, C1-C6-alkoxy, C1-C6-alkylthio, C3-C8-cycloalkoxy, C3-C8-cycloalkylthio, carboxyl, formyl, C1-C10-alkylcarbonyl, C1-C10-alkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10-alkenyloxycarbonyl, phenyl, phenoxy, phenylthio, benzyloxy, benzylthio, C1-C6-alkyl-S(O)m— or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group consisting of O, N and S;
• m is 0, 1 or 2;
• wherein the cyclic groups in L1, L2, L3, Ra and/or R1 are unsubstituted or substituted by one to four groups Rb:
• Rb is halogen, cyano, hydroxyl, mercapto, nitro, NRARB, C1-C10-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group consisting of O, N or S which may be unsubstituted or substituted by one or more halogen and/or C1-C4-alkyl groups;
• provided that at least one group L1, L2 or L3 is not hydrogen.

A process for preparing a compound of formula I

• wherein:
• L1 and L3 independently of one another are hydrogen, halogen, hydroxyl, mercapto, nitro, NRARB, C1-C4-haloalkyl, C1-C10-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C8-alkoxy, phenyl, phenoxy, phenylthio, benzyloxy or benzylthio;
• wherein RA and RB are hydrogen or C1-C6-alkyl;
• L2 is hydrogen, halogen, hydroxyl, mercapto, nitro, NRARB, C1-C4-haloalkyl, CH2—C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C8-alkoxy, phenyl, phenoxy, phenylthio, benzyloxy or benzylthio;
• wherein two adjacent groups from the group consisting of L1, L2 and L3 together may be a C1-C4-alkylene, C1-C4-oxyalkylene, C1-C4-oxyalkyleneoxy or butadienyl group;
• wherein the groups L1, L2 or L3 are unsubstituted or substituted by one to four identical or different groups Ra:
• Ra is halogen, cyano, hydroxyl, mercapto, C1-C10-alkyl, C1-C10-haloalkyl, C3-C8-cycloalkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkoxy-C1-C6-alkyl or NRARB;
• R1 is ethyl or n-propyl;
• R2 is hydrogen, halogen, cyano, NRARB, hydroxyl, mercapto, C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, C1-C6-alkoxy, C1-C6-alkylthio, C3-C8-cycloalkoxy, C3-C8-cycloalkylthio, carboxyl, formyl, C1-C10-alkylcarbonyl, C1-C10-alkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10-alkenyloxycarbonyl, phenyl, phenoxy, phenylthio, benzyloxy, benzylthio, C1-C6-alkyl-S(O)m— or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group consisting of O, N and S;
• m is 0, 1 or 2;
• wherein the cyclic groups in L1, L2, L3, Ra and/or R1 are unsubstituted or substituted by one to four groups Rb:
• Rb is halogen, cyano, hydroxyl, mercapto, nitro, NRARB, C1-C10-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group consisting of O, N or S which may be unsubstituted or substituted by one or more halogen and/or C1-C4-alkyl groups;
• provided that at least one group L1, L2 or L3 is not hydrogen;
• comprising
• reacting a compound of formula II
• wherein R is C1-C4-alkyl and L1, L2, L3 and R1 are as described above, with a compound of formula III
• wherein R2 is as described above, to give a compound of formula IV,
• wherein L1, L2, L3, R1 and R2 are as described above;
• halogenating the compound of formula IV to give a compound of formula V;
• wherein Hal is chlorine or bromine and L1, L2, L3, R1 and R2 are as described above;
• and
• reacting the compound of formula V with ammonia;
• wherein a compound of formula I is prepared.

A compound of formula IV

• wherein:
• L1 and L3 independently of one another are hydrogen, halogen, hydroxyl, mercapto, nitro, NRARB, C1-C4-haloalkyl, C1-C10-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C8-alkoxy, phenyl, phenoxy, phenylthio, benzyloxy or benzylthio;
• wherein RA and RB are hydrogen or C1-C6-alkyl;
• L2 is hydrogen, halogen, hydroxyl, mercapto, nitro, NRARB, C1-C4-haloalkyl, CH2—C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C8-alkoxy, phenyl, phenoxy, phenylthio, benzyloxy or benzylthio;
• wherein two adjacent groups from the group consisting of L1, L2 and L3 together may be a C1-C4-alkylene, C1-C4-oxyalkylene, C1-C4-oxyalkyleneoxy or butadienyl group;
• wherein the groups L1, L2 or L3 are unsubstituted or substituted by one to four identical or different groups Ra:
• Ra is halogen, cyano, hydroxyl, mercapto, C1-C10-alkyl, C1-C10-haloalkyl, C3-C8-cycloalkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkoxy-C1-C6-alkyl or NRARB;
• R1 is ethyl or n-propyl;
• R2 is hydrogen, halogen, cyano, NRARB, hydroxyl, mercapto, C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, C1-C6-alkoxy, C1-C6-alkylthio, C3-C8-cycloalkoxy, C3-C8-cycloalkylthio, carboxyl, formyl, C1-C10-alkylcarbonyl, C1-C10-alkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10-alkenyloxycarbonyl, phenyl, phenoxy, phenylthio, benzyloxy, benzylthio, C1-C6-alkyl-S(O)m— or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group consisting of O, N and S;
• m is 0, 1 or 2;
• wherein the cyclic groups in L1, L2, L3, Ra and/or R1 are unsubstituted or substituted by one to four groups Rb:
• Rb is halogen, cyano, hydroxyl, mercapto, nitro, NRARB, C1-C10-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group consisting of O, N or S which may be unsubstituted or substituted by one or more halogen and/or C1-C4-alkyl groups;
• provided that at least one group L1, L2 or L3 is not hydrogen.

A compound of formula V

• wherein:
• Hal is chlorine or bromine;
• L1 and L3 independently of one another are hydrogen, halogen, hydroxyl, mercapto, nitro, NRARB, C1-C4-haloalkyl, C1-C10-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C8-alkoxy, phenyl, phenoxy, phenylthio, benzyloxy or benzylthio;
• wherein RA and RB are hydrogen or C1-C6-alkyl;
• L2 is hydrogen, halogen, hydroxyl, mercapto, nitro, NRARB, C1-C4-haloalkyl, CH2—C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C8-alkoxy, phenyl, phenoxy, phenylthio, benzyloxy or benzylthio;
• wherein two adjacent groups from the group consisting of L1, L2 and L3 together may be a C1-C4-alkylene, C1-C4-oxyalkylene, C1-C4-oxyalkyleneoxy or butadienyl group;
• wherein the groups L1, L2 or L3 are unsubstituted or substituted by one to four identical or different groups Ra:
• Ra is halogen, cyano, hydroxyl, mercapto, C1-C10-alkyl, C1-C10-haloalkyl, C3-C8-cycloalkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkoxy-C1-C6-alkyl or NRARB;
• R1 is ethyl or n-propyl;
• R2 is hydrogen, halogen, cyano, NRARB, hydroxyl, mercapto, C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, C1-C6-alkoxy, C1-C6-alkylthio, C3-C8-cycloalkoxy, C3-C8-cycloalkylthio, carboxyl, formyl, C1-C10-alkylcarbonyl, C1-C10-alkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10-alkenyloxycarbonyl, phenyl, phenoxy, phenylthio, benzyloxy, benzylthio, C1-C6-alkyl-S(O)m— or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group consisting of O, N and S;
• m is 0, 1 or 2;
• wherein the cyclic groups in L1, L2, L3, Ra and/or R1 are unsubstituted or substituted by one to four groups Rb:
• Rb is halogen, cyano, hydroxyl, mercapto, nitro, NRARB, C1-C10-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group consisting of O, N or S which may be unsubstituted or substituted by one or more halogen and/or C1-C4-alkyl groups;
• provided that at least one group L1, L2 or L3 is not hydrogen.

A process for preparing a compound of formula I

• wherein:
• L1 and L3 independently of one another are hydrogen, halogen, hydroxyl, mercapto, nitro, NRARB, C1-C4-haloalkyl, C1-C10-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C8-alkoxy, phenyl, phenoxy, phenylthio, benzyloxy or benzylthio;
• wherein RA and RB are hydrogen or C1-C6-alkyl;
• L2 is hydrogen, halogen, hydroxyl, mercapto, nitro, NRARB, C1-C4-haloalkyl, CH2—C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C8-alkoxy, phenyl, phenoxy, phenylthio, benzyloxy or benzylthio;
• wherein two adjacent groups from the group consisting of L1, L2 and L3 together may be a C1-C4-alkylene, C1-C4-oxyalkylene, C1-C4-oxyalkyleneoxy or butadienyl group;
• wherein the groups L1, L2 or L3 are unsubstituted or substituted by one to four identical or different groups Ra:
• Ra is halogen, cyano, hydroxyl, mercapto, C1-C10-alkyl, C1-C10-haloalkyl, C3-C8-cycloalkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkoxy-C1-C6-alkyl or NRARB;
• R1 is ethyl or n-propyl;
• R2 is hydrogen, halogen, cyano, NRARB, hydroxyl, mercapto, C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, C1-C6-alkoxy, C1-C6-alkylthio, C3-C8-cycloalkoxy, C3-C8-cycloalkylthio, carboxyl, formyl, C1-C10-alkylcarbonyl, C1-C10-alkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10-alkenyloxycarbonyl, phenyl, phenoxy, phenylthio, benzyloxy, benzylthio, C1-C6-alkyl-S(O)m— or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group consisting of O, N and S;
• m is 0, 1 or 2;
• wherein the cyclic groups in L1, L2, L3, Ra and/or R1 are unsubstituted or substituted by one to four groups Rb:
• Rb is halogen, cyano, hydroxyl, mercapto, nitro, NRARB, C1-C10-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group consisting of O, N or S which may be unsubstituted or substituted by one or more halogen and/or C1-C4-alkyl groups;
• provided that at least one group L1, L2 or L3 is not hydrogen;
• comprising
• reacting a compound of formula VI,
• wherein L1, L2, L3 and R1 are as described above, with a compound of formula III,
• wherein R2 is as described above;
• wherein a compound of formula I is prepared.

A fungicidal composition comprising a solid or liquid carrier and a compound of formula I

• wherein:
• L1 and L3 independently of one another are hydrogen, halogen, hydroxyl, mercapto, nitro NRARB, C1-C4-haloalkyl, C1-C10-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C8-alkoxy, phenyl, phenoxy, phenylthio, benzyloxy or benzylthio;
• wherein RA and RB are hydrogen or C1-C6-alkyl;
• L2 is hydrogen, halogen, hydroxyl, mercapto, nitro, NRARB, C1-C4-haloalkyl, CH2—C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C8-alkoxy, phenyl, phenoxy, phenylthio, benzyloxy or benzylthio;
• wherein two adjacent groups from the group consisting of L1, L2 and L3 together may be a C1-C4-alkylene, C1-C4-oxyalkylene, C1-C4-oxyalkyleneoxy or butadienyl group;
• wherein the groups L1, L2 or L3 are unsubstituted or substituted by one to four identical or different groups Ra:
• Ra is halogen, cyano, hydroxyl, mercapto, C1-C10-alkyl, C1-C10-haloalkyl, C3-C8-cycloalkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkoxy-C1-C6-alkyl or NRARB;
• R1 is ethyl or n-propyl;
• R2 is hydrogen, halogen, cyano, NRARB, hydroxyl, mercapto, C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, C1-C6-alkoxy, C1-C6-alkylthio, C3-C8-cycloalkoxy, C3-C8-cycloalkylthio, carboxyl, formyl, C1-C10-alkylcarbonyl, C1-C10-alkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10-alkenyloxycarbonyl, phenyl, phenoxy, phenylthio, benzyloxy, benzylthio, C1-C6-alkyl-S(O)m— or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group consisting of O, N and S;
• m is 0, 1 or 2;
• wherein the cyclic groups in L1, L2, L3, Ra and/or R1 are unsubstituted or substituted by one to four groups Rb:
• Rb is halogen, cyano, hydroxyl, mercapto, nitro, NRARB, C1-C10-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group consisting of O, N or S which may be unsubstituted or substituted by one or more halogen and/or C1-C4-alkyl groups;
• provided that at least one group L1, L2 or L3 is not hydrogen.

Seed comprising a compound of formula I

• wherein:
• L1 and L3 independently of one another are hydrogen, halogen, hydroxyl, mercapto, nitro, NRARB, C1-C4-haloalkyl, C1-C10-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C8-alkoxy, phenyl, phenoxy, phenylthio, benzyloxy or benzylthio;
• wherein RA and RB are hydrogen or C1-C6-alkyl;
• L2 is hydrogen, halogen, hydroxyl, mercapto, nitro, NRARB, C1-C4-haloalkyl, CH2—C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C8-alkoxy, phenyl, phenoxy, phenylthio, benzyloxy or benzylthio;
• wherein two adjacent groups from the group consisting of L1, L2 and L3 together may be a C1-C4-alkylene, C1-C4-oxyalkylene, C1-C4-oxyalkyleneoxy or butadienyl group;
• wherein the groups L1, L2 or L3 are unsubstituted or substituted by one to four identical or different groups Ra:
• Ra is halogen, cyano, hydroxyl, mercapto, C1-C10-alkyl, C1-C10-haloalkyl, C3-C8-cycloalkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkoxy-C1-C6-alkyl or NRARB;
• R1 is ethyl or n-propyl;
• R2 is hydrogen, halogen, cyano, NRARB, hydroxyl, mercapto, C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, C1-C6-alkoxy, C1-C6-alkylthio, C3-C8-cycloalkoxy, C3-C8-cycloalkylthio, carboxyl, formyl, C1-C10-alkylcarbonyl, C1-C10-alkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10-alkenyloxycarbonyl, phenyl, phenoxy, phenylthio, benzyloxy, benzylthio, C1-C6-alkyl-S(O)m— or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group consisting of O, N and S;
• m is 0, 1 or 2;
• wherein the cyclic groups in L1, L2, L3, Ra and/or R1 are unsubstituted or substituted by one to four groups Rb:
• Rb is halogen, cyano, hydroxyl, mercapto, nitro, NRARB, C1-C10-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group consisting of O, N or S which may be unsubstituted or substituted by one or more halogen and/or C1-C4-alkyl groups;
• provided that at least one group L1, L2 or L3 is not hydrogen;
• in an amount of from 1 g to 1000 g per 100 kg of seed.

A method for controlling phytopathogenic harmful fungi comprising

• treating fungi or the materials, plants, the soil or seed to be protected from fungal attack with an effective amount of the compound of formula I
• wherein:
• L1 and L3 independently of one another are hydrogen, halogen, hydroxyl, mercapto, nitro, NRARB, C1-C4-haloalkyl, C1-C10-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C8-alkoxy, phenyl, phenoxy, phenylthio, benzyloxy or benzylthio;
• wherein RA and RB are hydrogen or C1-C6-alkyl;
• L2 is hydrogen, halogen, hydroxyl, mercapto, nitro, NRARB, C1-C4-haloalkyl, CH2—C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C8-alkoxy, phenyl, phenoxy, phenylthio, benzyloxy or benzylthio;
• wherein two adjacent groups from the group consisting of L1, L2 and L3 together may be a C1-C4-alkylene, C1-C4-oxyalkylene, C1-C4-oxyalkyleneoxy or butadienyl group;
• wherein the groups L1, L2 or L3 are unsubstituted or substituted by one to four identical or different groups Ra:
• Ra is halogen, cyano, hydroxyl, mercapto, C1-C10-alkyl, C1-C10-haloalkyl, C3-C8-cycloalkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkoxy-C1-C6-alkyl or NRARB;
• R1 is ethyl or n-propyl;
• R2 is hydrogen, halogen, cyano, NRARB, hydroxyl, mercapto, C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, C1-C6-alkoxy, C1-C6-alkylthio, C3-C8-cycloalkoxy, C3-C8-cycloalkylthio, carboxyl, formyl, C1-C10-alkylcarbonyl, C1-C10-alkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10-alkenyloxycarbonyl, phenyl, phenoxy, phenylthio, benzyloxy, benzylthio, C1-C6-alkyl-S(O)m— or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group consisting of O, N and S;
• m is 0, 1 or 2;
• wherein the cyclic groups in L1, L2, L3, Ra and/or R1 are unsubstituted or substituted by one to four groups Rb:
• Rb is halogen, cyano, hydroxyl, mercapto, nitro, NRARB, C1-C10-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy or a five- or six-membered saturated, partially unsaturated or aromatic heterocycle which contains one to four heteroatoms from the group consisting of O, N or S which may be unsubstituted or substituted by one or more halogen and/or C1-C4-alkyl groups;
• provided that at least one group L1, L2 or L3 is not hydrogen;
• wherein the phytopathogenic harmful fungi are controlled.