Use of 4-Aminopyrimidines for Controlling Harmful Fungi, Novel 4-Aminopyrimidines, Processes for Their Preparation and Compositions Comprising Them

A method for controlling phytopathogenic harmful fungi, wherein the fungi or materials, plants, soil, or seed to be protected against fungal attack are treated with an effective amount of a compound of formula I:

• wherein:
• R1 is hydrogen, halogen, cyano, C1-C14-alkyl, C1-C14-haloalkyl, C2-C12-alkenyl, C2-C12-alkynyl, C3-C8-cycloalkyl, C1-C12-alkoxy, C1-C12-alkoxy-C1-C12-alkyl, benzyloxy-C1-C12-alkyl, C1-C12-alkoxy-C2-C12-alkenyl, or C1-C12-alkoxy-C2-C12-alkynyl;
• R2 is hydrogen, halogen, cyano, C1-C12-alkyl, C1-C12-haloalkyl, C2-C12-alkenyl, C2-C12-alkynyl, C3-C8-cycloalkyl, C1-C12-alkoxy, C1-C12-alkoxy-C1-C12-alkyl, or C1-C12-alkylthio-C1-C12-alkyl,
• wherein the carbon chains in R1 and/or R2 may be substituted by one to four identical or different groups Rα:
• Rα 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, NRaRb, phenyl, or C1-C6-alkylphenyl;
• Ra, Rb are independently of one another hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, or C4-C6-cycloalkenyl;
• wherein the groups Rα may be substituted by one to four groups Rβ:
• Rβ is halogen, cyano, hydroxyl, mercapto, C1-C10-alkyl, C1-C10-haloalkyl, C2-C10-alkenyl, C2-C10-alkynyl, or C1-C6-alkoxy;
• R1 and R2 together with the carbon atoms to which they are attached may form a five- to seven-membered ring which may contain one to three identical or different heteroatoms from the group consisting of O, N and S;
• R3 is hydrogen, halogen, cyano, hydroxyl, mercapto, azido, C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C1-C6-haloalkyl, —O-D, —S(O)m-D, —ON═CRaRb, —CRc═NORa, —NRcN═CRaRb, —NRaRb, —NRcNRaRb, —NORa, —NRcC(═NRc)NRaRb, —NRcC(═O)NRaRb, NRaCN, NRaC(═O)Rc, —NRaC(═NORc)Rc′, —OC(═O)Ra, —C(═NORc)NRaRb, —CRc(═NNRaRb), —C(═O)NRaRb, —C(═O)Ra, —CO2Ra, —C(═O)NRzRb, —C(═O)—N—ORb, —C(═S)—NRzRb, C(═NORa)NRzRb, C(═NRa)NRzRb, —C(═O)NRaNRzRb, —C(═N—NRzRc)NRaRb, —C(═NORb)Ra, —C(═N—NRzRb)Ra, —CRaRb—ORz, —CRaRb—NRzRc, —ON(═CRaRb), —NRa(C(═O)Rb), —NRa(C(═O)ORb), —NRa(C(═O)—NRzRb), —NRa(C(═NRc)Rb), NRa(N═CRcRb), NRa—NRzRb, —NRz—ORa, —NRa(C(═NRc)—NRzRb), or —NRa(C(═NORc)Rb),
• D is C1-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C1-C6-haloalkyl, or C3-C8-cycloalkyl;
• m is 0, 1 or 2;
• Rz is a group Ra which may be attached directly or via a carbonyl group;
• Rc is one of the groups as defined by Ra or Rb;
• a five- or six-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocycle which contains one to four heteroatoms from the group consisting of O, N and S,
• one of the groups G1 or G2
• wherein:
• x is 0 or 1;
• Ra, Rb are as defined above and, in group G1, together with the nitrogen atom to which they are attached may additionally have the meaning Rc-Z-C(Rd)═N;
• Rd is halogen, cyano, one of the groups as defined by Ra, Rb or, together with the carbon to which it is attached, may be a carbonyl group;
• Z is oxygen or N—Rc;
• Y is C(H)—Re, C—Re, N—N(H)—Rc or N—Rc;
• Re is halogen, cyano or one of the groups as defined by Ra or Rb;
• is a double or a single bond;
• wherein the aliphatic, alicyclic or aromatic groups R3, Ra, Rb, Rc, Rd, or Re may be partially or fully halogenated or may carry one to four groups RA:
• RA is halogen, cyano, C1-C8-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C6-alkoxy, C2-C10-alkenyloxy, C2-C10-alkynyloxy, OH, SH, two vicinal groups RA may be (═O) or (═S), C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C3-C6-cycloalkoxy, C3-C6-cycloalkenyloxy, —C(═O)-A, —C(═O)—O-A, —C(═O)—N(A′)A, C(A′)(═N—OA), N(A′)A, N(A′)—C(═O)-A, N(A″)—C(═O)—N(A′)A, S(═O)m-A, S(═O)m—O-A, or S(═O)m—N(A′)A,
• A, A′, A″ independently of one another are hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, or C3-C8-cycloalkenyl, wherein the groups may be partially or fully halogenated or may be substituted by cyano or C1-C4-alkoxy, or A and A′ together with the atoms to which they are attached are 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;
• wherein the aliphatic, alicyclic, or aromatic groups RA, A, A′ and A″ may be partially or fully halogenated or may carry one to three groups Rb.

A process for preparing a compound of formula I:

• wherein:
• R1 is C4-C10-alkyl, C4-C10-haloalkyl, C4-C10-cyanoalkyl, C1-C12-alkoxy-C1-C12-alkyl, or phenyl-C1-C8-alkyl;
• R2 is C1-C4-alkyl or C1-C8-alkoxy-C1-C4-alkyl;
• R3 is cyano or a group attached via a heteroatom,
• the process comprising:
• a) reacting substituted β-ketoesters of formula II
• with thiourea of the formula III
• to yield a 2-thio-4-hydroxypyrimidine of formula IV
• b) reacting said 2-thio-4-hydroxypyrimidine of formula IV with alkylating agents D-X,
• wherein D is C1-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C1-C6-haloalkyl, or C3-C8-cycloalkyl, to yield a thioether of formula V
• c) halogenating said thioether of formula V to yield a compound of formula VI
• in which Hal is a halogen atom,
• d) contacting said compound of formula VI with ammonia to yield a 4-aminopyrimidine of formula I.1,
• wherein said 4-aminopyrimidine of formula I.1 is optionally oxidized to yield a sulfoxide or a sulfone of formula I.2, and
• e) reacting a compound of formula I.2 with a compound of formula VII
• R3—H VII
• or alkali metal, alkaline earth metal or ammonium salts thereof, to yield a compound of formula I, wherein R3 is cyano or a group attached via a heteroatom.

A process for preparing a compound of formula I:

• wherein:
• R1 is C4-C10-alkyl, C4-C10-haloalkyl, C4-C10-cyanoalkyl, C1-C12-alkoxy-C1-C12-alkyl, or phenyl-C1-C8-alkyl;
• R2 is C1-C4-alkyl or C1-C8-alkoxy-C1-C4-alkyl;
• R3 is C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C1-C6-haloalkyl,
• the process comprising:
• a) reacting substituted β-ketoesters of formula II
• with amidines of formula IIIa
• to yield a hydroxypyrimidine of formula Va
• b) halogenating said compound of formula Va to yield a compound of formula VIa;
• and
• c) reacting said compound of formula VIa with ammonia to yield a compound of formula I.

A process for preparing a compound of formula I:

• wherein:
• R1 is C4-C10-alkyl, C4-C10-haloalkyl, C4-C10-cyanoalkyl, C1-C12-alkoxy-C1-C12-alkyl, or phenyl-C1-C8-alkyl;
• R2 is C1-C4-alkyl or C1-C8-alkoxy-C1-C4-alkyl;
• R3 is a group attached via nitrogen,
• the process comprising:
• a) reacting substituted β-ketoesters of formula II
• with urea of formula IIIb
• to yield a hydroxypyrimidine of formula Vb
• b) halogenating said hydroxypyrimidine of formula Vb to yield a compound of formula VIb
• c) reacting said compound of formula VIb with ammonia to yield a diaminopyrimidine;
• and
• d) alkylating or acylating said diaminopyrimidine of step c) to yield a 4-aminopyrimidine of formula I, wherein R3 is a group attached via nitrogen.

A process for preparing a compound formula I:

• wherein:
• R1 is C4-C10-alkyl, C4-C10-haloalkyl, C4-C10-cyanoalkyl, C1-C12-alkoxy-C1-C12-alkyl, or phenyl-C1-C8-alkyl;
• R2 is C1-C4-alkyl or C1-C8-alkoxy-C1-C4-alkyl;
• the process comprising:
• reacting a 2-cyano-4-aminopyrimidine of formula I.3
• with a compound of formula VII
• R3—H VII
• wherein R3 is cyano, mercapto, —O-D, —S(O)m-D, —ON═CRaRb, —CRc═NORa, —NRcN═CRaRb, NRaRb, NRcNRaRb, NORa, —NRcC(═NRc′)NRaRb, —NRcC(═O)NRaRb, —NRaCN, —NRaC(═O)Rc, —NRaC(═NORc)Rc′, —OC(═O)Ra, —C(═NORc)NRaRb, —CRc(═NNRaRb), —C(═O)NRaRb, —C(═O)Ra, —CO2Ra, —C(═O)NRzRb, —C(═O)—N—ORb, —C(═S)—NRzRb, —C(═NORa)NRzRb, —C(═NRa)NRzRb, C(═O)NRa—NRzRb, —C(═N—NRzRc)NRaRb, C(═NORb)Ra, —C(═N—NRzRb)Ra, —CRaRb—ORz, —CRaRb—NRzRc, —ON(═CRaRb), —NRa(C(═O)Rb), —NRa(C(═O)ORb), NRa(C(═O)—NRzRb), NRa(C(═NRc)Rb), —NRa(N═CRcRb), —NRa—NRzRb, —NRz—ORa, —NRa(C(═NRc)—NRzRb), or —NRa(C(═NORc)Rb),
• D is C1-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C1-C6-haloalkyl, or C3-C8-cycloalkyl;
• m is 0, 1, or 2;
• Rz is the group Ra which may be attached directly or via a carbonyl group;
• Rc is one of the groups as defined by Ra, Rb;
• a five- or six-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocycle which contains one to four heteroatoms from the group consisting of O, N and S,
• one of the groups G1 or G2
• wherein
• x is 0 or 1;
• Ra, Rb are as defined above and, in group G1, together with the nitrogen atom to which they are attached may additionally have the meaning Rc-Z-C(Rd)═N;
• Rd is halogen, cyano, one of the groups as defined by Ra, Rb or, together with the carbon to which it is attached, may be a carbonyl group;
• Z is oxygen or N—Rc;
• Y is C(H)—Re, C—Re, N—N(H)—Rc, or N—Rc;
• Re is halogen, cyano or one of the groups as defined by Ra or Rb;
• is a double or a single bond;
• or alkali metal, alkaline earth metal or ammonium salts thereof to yield a compound of formula I.

A process for preparing a compound of formula I:

• wherein:
• R1 is C4-C10-alkyl, C4-C10-haloalkyl, C4-C10-cyanoalkyl, C1-C12-alkoxy-C1-C12-alkyl, or phenyl-C1-C8-alkyl;
• R2 is C1-C4-alkyl or C1-C8-alkoxy-C1-C4-alkyl;
• R3 is cyano or a group R3 attached via a heteroatom,
• the process comprising:
• a) reacting a compound of formula VIII
• with thiourea to yield a 2-thio-4-hydroxypyrimidine of formula IV
• b) reacting said 2-thio-4-hydroxypyrimidine of formula IV with alkylating agents D-X, wherein D is C1-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C1-C6-haloalkyl, or C3-C8-cycloalkyl, to yield a thioether of formula V
• c) halogenating said thioether of formula V to yield a compound of formula VI
• in which Hal is a halogen atom,
• d) contacting said compound of formula VI with ammonia to yield a 4-aminopyrimidine of formula I.1,
• wherein said 4-aminopyrimidine of formula I.1 is optionally oxidized to yield a sulfoxide or a sulfone of formula I.2, and
• e) reacting a compound of formula I.2 with a compound of formula VII
• R3—H VII
• or alkali metal, alkaline earth metal or ammonium salts thereof, to yield a compound of formula I.

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

• wherein:
• R1 is C4-C10-alkyl, C4-C10-haloalkyl, C4-C10-cyanoalkyl, C1-C12-alkoxy-C1-C12-alkyl, or phenyl-C1-C8-alkyl;
• R2 is C1-C4-alkyl or C1-C8-alkoxy-C1-C4-alkyl;
• R3 is cyano, mercapto, —O-D, —S(O)m-D, —ON═CRaRb, —CRc═NORa, —NRcN═CRaRb, —NRaRb, —NRcNRaRb, —NORa, —NRcC(═NRc′)NRaRb, —NRcC(═O)NRaRb, —NRaCN, NRaC(═O)Rc, —NRaC(═NORc)Rc′, —OC(═O)Ra, —C(═NORc)NRaRb, —CRc(═NNRaRb), —C(═O)NRaRb, —C(═O)Ra, CO2Ra, —C(═O)NRzRb, —C(═O)—N—ORb, —C(═S)—NRzRb, —C(═NORa)NRzRb, —C(═NRa)NRzRb, —C(═O)NRa—NRzRb, —C(═N—NRzRc)NRaRb, —C(═NORb)Ra, —C(═N—NRzRb)Ra, —CRaRb—ORz, —CRaRb—NRzRc, —ON(═CRaRb), —NRa(C(═O)Rb), —NRa(C(═O)ORb), —NRa(C(═O)—NRzRb), —NRa(C(═NRc)Rb), —NRa(N═CRcRb), —NRa—NRzRb, —NRz—ORa, —NRa(C(═NRc)—NRzRb), or —NRa(C(═NORc)Rb),
• D is C1-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C1-C6-haloalkyl, or C3-C8-cycloalkyl;
• m is 0, 1, or 2;
• Rz is the group Ra which may be attached directly or via a carbonyl group;
• Rc is one of the groups as defined by Ra or Rb;
• a five- or six-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocycle which contains one to four heteroatoms from the group consisting of O, N and S,
• one of the groups G1 or G2
• wherein:
• x is 0 or 1;
• Ra, Rb are as defined above and, in group G1, together with the nitrogen atom to which they are attached may additionally have the meaning Rc-Z-C(Rd)═N;
• Rd is halogen, cyano, one of the groups as defined by Ra, Rb or, together with the carbon to which it is attached, may be a carbonyl group;
• Z is oxygen or N—Rc;
• Y is C(H)—Re, C—Re, N—N(H)—Rc, or N—Rc;
• Re is halogen, cyano or one of the groups as defined by Ra or Rb;
• is a double or a single bond.

Seed comprising the compound of the formula I:

• wherein:
• R1 is C4-C10-alkyl, C4-C10-haloalkyl, C4-C10-cyanoalkyl, C1-C12-alkoxy-C1-C12-alkyl, or phenyl-C1-C9-alkyl;
• R2 is C1-C4-alkyl or C1-C8-alkoxy-C1-C4-alkyl;
• R3 is cyano, mercapto, —O-D, —S(O)m-D, —ON═CRaRb, —CRc═NORa, —NRcN═CRaRb, —NRaRb, —NRcNRaRb, —NORa, —NRcC(═NRc′)NRaRb, —NRcC(═O)NRaRb, —NRaCN, —NRaC(═O)Rc, —NRaC(═NORc)Rc′, —OC(═O)Ra, —C(═NORc)NRaRb, CRc(═NNRaRb), —C(═O)NRaRb, —C(═O)Ra, —CO2Ra, —C(═O)NRzRb, —C(═O)—N—ORb, —C(═S)—NRzRb, —C(═NORa)NRzRb, —C(═NRa)NRzRb, —C(═O)NRa—NRzRb, —C(═N—NRzRc)NRaRb, C(═NORb)Ra, —C(═N—NRzRb)Ra, —CRaRb—ORz, —CRaRb—NRzRc, —ON(═CRaRb), —NRa(C(═O)Rb), NRa(C(═O)ORb), —NRa(C(═O)—NRzRb), —NRa(C(═NRc)Rb), —NRa(N═CRcRb), —NRa—NRzRb, —NRz—ORa, —NRa(C(═NRc)—NRzRb), or —NRa(C(═NORc)Rb),
• D is C1-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C1-C6-haloalkyl, or C3-C8-cycloalkyl;
• m is 0, 1, or 2;
• Rz is the group Ra which may be attached directly or via a carbonyl group;
• Rc is one of the groups as defined by Ra or Rb;
• a five- or six-membered saturated, partially unsaturated or aromatic mono- or bicyclic heterocycle which contains one to four heteroatoms from the group consisting of O, N and S,
• one of the groups G1 or G2
• wherein:
• x is 0 or 1;
• Ra, Rb are as defined above and, in group G1, together with the nitrogen atom to which they are attached may additionally have the meaning Rc-Z-C(Rd)═N;
• Rd is halogen, cyano, one of the groups as defined by Ra, Rb or, together with the carbon to which it is attached, may be a carbonyl group;
• Z is oxygen or N—Rc;
• Y is C(H)—Re, C—Re, N—N(H)—Rc, or N—Rc;
• Re is halogen, cyano or one of the groups as defined by Ra or Rb;
• is a double or a single bond;
• in amounts of 1 to 1000 g per 100 kg of seed.