Process for preparing N-substituted 1H-pyrazole-5-carboxylate compounds and derivatives thereof

A process for preparing a compound of formula (I-A)

• in which
• R1 is selected from the group consisting of hydrogen, halogen, cyano, —SF5, CBrF2, C1-C6-alkyl, C1-C6-fluoroalkyl, C3-C8-cycloalkyl, C3-C8-fluorocycloalkyl, C2-C6-alkenyl, C2-C6-fluoroalkenyl, wherein the six last mentioned radicals may be substituted by one or more radicals Ra;
• —Si(Rf)2Rg, —ORb, —S(O)mRb, —S(O)nN(Rc)Rd, —N(Rc1)Rd1, phenyl which may be substituted by 1, 2, 3, 4 or 5 radicals Re, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1, 2 or 3 heteroatoms or heteroatom groups selected from the group consisting of N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals Re;
• each R2 is independently selected from the group consisting of halogen, SF5, C1-C6-alkyl, C1-C6-fluoroalkyl, C3-C8-cycloalkyl, C3-C8-fluorocycloalkyl, C2-C6-alkenyl, C2-C6-fluoroalkenyl, wherein the six last mentioned radicals may be substituted by one or more radicals Ra;
• —Si(Rf)2Rg, —ORb, —SRb, —S(O)mRb, —S(O)nN(Rc)Rd, —N(Rc1)Rd1, phenyl which may be substituted by 1, 2, 3, 4 or 5 radicals Re, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or completely unsaturated heterocyclic ring containing 1, 2 or 3 heteroatoms or heteroatom groups selected from the group consisting of N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals Re;
• Ra is selected from the group consisting of SF5, C1-C6-alkyl, C1-C6-fluoroalkyl, C1-C6-alkoxy-C1-C6-alkyl, C3-C8-cycloalkyl, C3-C8-fluorocycloalkyl, C2-C6-alkenyl, C2-C6-fluoroalkenyl, —Si(Rf)2Rg, —ORb, —SRb, —S(O)mRb, —S(O)nN(Rc)Rd, —N(Rc1)Rd1, phenyl which may be substituted by 1, 2, 3, 4 or 5 radicals Re, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or completely unsaturated heterocyclic ring containing 1, 2 or 3 heteroatoms or heteroatom groups selected from the group consisting of N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals Re;
• or two geminally bound radicals Ra together form a group selected from the group consisting of ═CRhRi, ═NRc1, ═NORb and ═NNRc1,
• or two radicals Ra, together with the carbon atoms to which they are bound, form a 3-, 4-, 5-, 6-, 7- or 8-membered saturated or partially unsaturated carbocyclic or heterocyclic ring containing 1, 2 or 3 heteroatoms or heteroatom groups selected from the group consisting of N, O, S, NO, SO and SO2, as ring members;
• wherein, in the case of more than one Ra, Ra can be identical or different;
• Rb is selected from the group consisting of C1-C6-alkyl, C1-C6-fluoroalkyl, C2-C6-alkenyl, C2-C6-fluoroalkenyl, C3-C8-cycloalkyl, C3-C8-fluorocycloalkyl, wherein the six last mentioned radicals may optionally carry 1 or 2 radicals selected from the group consisting of C1-C6-alkoxy, C1-C6-fluoroalkoxy, C1-C6-alkylthio, C1-C6-fluoroalkylthio, C1-C6-fluoroalkylsulflnyl, C1-C6-alkylsulfonyl, C1-C6-fluoroalkylsulfonyl, —Si(R)2Rg, phenyl, benzyl, pyridyl and phenoxy, wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1, 2 or 3 substituents selected from the group consisting of C1-C6-alkyl, C1-C6-fluoroalkyl, C1-C6-alkoxy and C1-C6-fluoroalkoxy;
• wherein, in the case of more than one Rb, Rb can be identical or different;
• Rc, Rd are, independently from one another and independently of each occurrence, selected from the group consisting of cyano, C1-C6-alkyl, C1-C6-fluoroalkyl, C2-C6-alkenyl, C2-C6-fluoroalkenyl, C3-C8-cycloalkyl, C3-C8-fluorocycloalkyl, wherein the six last mentioned radicals may optionally carry 1 or 2 radicals selected from the group consisting of C1-C6-alkoxy, C1-C6-fluoroalkoxy, C1-C6-alkylthio, C1-C6-fluoroalkylthio, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, —Si(Rf)2Rg, phenyl, benzyl, pyridyl and phenoxy, wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1, 2 or 3 substituents selected from the group consisting of C1-C6-alkyl, C1-C6-fluoroalkyl, C1-C6-alkoxy and C1-C6-fluoroalkoxy;
• or Rc and Rd, together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6- or 7-membered saturated, partly unsaturated or completely unsaturated heterocyclic ring which may contain 1 or 2 further heteroatoms selected from the group consisting of N, O and S as ring members, where the heterocyclic ring may carry 1, 2, 3 or 4 substituents selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-fluoroalkyl, C1-C4-alkoxy and C1-C4-fluoroalkoxy;
• Rc1 is hydrogen or has one of the meanings given for Rc;
• Rd1 is hydrogen or has one of the meanings given for Rd;
• Re is selected from the group consisting of halogen, C1-C6-alkyl, C1-C6-fluoroalkyl, C2-C6-alkenyl, C2-C6-fluoroalkenyl, C3-C8-cycloalkyl, C3-C8-fluorocycloalkyl, where the six last mentioned radicals may optionally carry 1 or 2 radicals selected from the group consisting of C1-C4-alkoxy;
• C1-C6-alkoxy, C1-C6-fluoroalkoxy, C1-C6-alkylthio, C1-C6-fluoroalkylthio, C1-C6-alkylsulfinyl, C1-C6-fluoroalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-fluoroalkylsulfonyl, —Si(Rf)2Rg, phenyl, benzyl, pyridyl and phenoxy, wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1, 2 or 3 substituents selected from the group consisting of C1-C6-alkyl, C1-C6-fluoroalkyl, C1-C6-alkoxy and C1-C6-fluoroalkoxy;
• wherein, in the case of more than one Re, Re can be identical or different;
• Rf, Rg are, independently of each other and independently of each occurrence, selected from the group consisting of C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl and benzyl;
• Rh, Ri are, independently from one another and independently of each occurrence, selected from the group consisting of hydrogen, halogen, SF5, C1-C6-alkyl, C1-C6-fluoroalkyl, C2-C6-alkenyl, C2-C6-fluoroalkenyl, C3-C8-cycloalkyl, C3-C8-fluorocycloalkyl, where the six last mentioned radicals may optionally carry 1 or 2 radicals selected from the group consisting of C1-C4-alkyl and C1-C4-fluoroalkyl;
• C1-C6-alkoxy, C1-C6-fluoroalkoxy, C1-C6-alkylthio, C1-C6-fluoroalkylthio, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, —Si(Rf)2Rg, phenyl, benzyl, pyridyl and phenoxy, wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1, 2 or 3 substituents selected from the group consisting of C1-C6-alkyl, C1-C6-fluoroalkyl, C1-C6-alkoxy, C1-C6-fluoroalkoxy, (C1-C6-alkoxy)carbonyl, (C1-C6-alkyl)amino and di-(C1-C6-alkyl)amino;
• m is 1 or 2, wherein, in the case of several occurrences, m may be identical or different;
• n is 0, 1 or 2;
• wherein, in the case of several occurrences, n may be identical or different;
• r is 0, 1, 2, 3 or 4;
• M+ is a cation or cation equivalent compensating the charge of the carboxylate;
• comprising
• i) deprotonating a compound of the formula (II)
• in which the variables R1, R2 and r are each as defined above,
• with a magnesium-organic base having a carbon bound magnesium;
• and
• ii) subjecting the product obtained in step (i) to a carboxylation by reacting it with carbon dioxide or a carbon dioxide equivalent, to obtain a compound of formula (I-A).

A compound of formula I-A:

• is selected from the group consisting of hydrogen, halogen, cyano, —SF5, CBrF2, C1-C6-alkyl, C1-C6-fluoroalkyl, C3-C8-cycloalkyl, C3-C8-fluorocycloalkyl, C2-C6-alkenyl, C2-C6-fluoroalkenyl, wherein the six last mentioned radicals may be substituted by one or more radicals Ra;
• —Si(Rf)2Rg, —ORb, —SRb, —S(O)mRb, —S(O)nN(Rc)Rd, —N(Rc1)Rd1, phenyl which may be substituted by 1, 2, 3, 4 or 5 radicals Re, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1, 2 or 3 heteroatoms or heteroatom groups selected from the group consisting of N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals Re;
• each R2 is independently selected from the group consisting of halogen, SF5, C1-C6-alkyl, C1-C6-fluoroalkyl, C3-C8-cycloalkyl, C3-C8-fluorocycloalkyl, C2-C6-alkenyl, C2-C6-fluoroalkenyl, wherein the six last mentioned radicals may be substituted by one or more radicals Ra;
• —Si(Rf)2Rg, —ORb, —SRb, —S(O)mRb, —S(O)nN(Rc)Rd, —N(Rc1)Rd1, phenyl which may be substituted by 1, 2, 3, 4 or 5 radicals Re, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or completely unsaturated heterocyclic ring containing 1, 2 or 3 heteroatoms or heteroatom groups selected from the group consisting of N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals Re;
• r is 0, 1, 2, 3 or 4;
• and
• M+ is a cation or cation equivalent compensating the charge of the carboxylate and comprising magnesium.