WO2015162260A1 - Procédé de préparation d'esters et de dérivés d'anthranilamide - Google Patents

Procédé de préparation d'esters et de dérivés d'anthranilamide Download PDF

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WO2015162260A1
WO2015162260A1 PCT/EP2015/058943 EP2015058943W WO2015162260A1 WO 2015162260 A1 WO2015162260 A1 WO 2015162260A1 EP 2015058943 W EP2015058943 W EP 2015058943W WO 2015162260 A1 WO2015162260 A1 WO 2015162260A1
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alkyl
radicals
group
phenyl
alkoxy
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PCT/EP2015/058943
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Karsten Koerber
Christopher Koradin
Thomas Zierke
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to a process for preparing compounds of formula (I) which comprises reacting a compound of formula (II) or ( ⁇ ) with a compound of formula (III).
  • the present invention also relates to a process, which further comprises preparing compounds of formula ( ⁇ ) by converting a compound of formula (II) into a compound of formula ( ⁇ ), and to a process which further comprises preparing compounds of formula (II) by reacting a compound of formula (IV) with a compound of formula (V) or by reacting a compound of formula (VI) with a compound of formula (VII) or by reacting a compound of formula (VI) with a compound of formula (VIII).
  • the present invention relates to a process for preparing compounds of formula (II) by reacting a compound of formula (IV) with a compound of formula (V), and to a process for preparing compounds of formula (I), which comprises said preparation of the compounds of formula (II), an optional conversion to compounds of formula ( ⁇ ), and the reaction with compounds of formula (III). Furthermore, the present invention relates to compounds of formulae ( ⁇ . ⁇ '), ( ⁇ . ⁇ '), (II.A”) and ( ⁇ . ⁇ ”) as precursors for the preparation of certain compounds of formula (I). N-Pyridylpyrazole carboxanilides carrying a sulfiminocarbonyl group in the ortho position with respect to the amide group, which are represented by formula (I) below, are of great interest in terms of their high activity against
  • Anthranilamide insecticides have e.g. been described in WO 2007/006670.
  • the compounds of formula (I) are typically prepared by reacting a substituted isatoic anhydride compound with a sulfimine or a sulfimine salt to give an aniline compound carrying a sulfiminocarbonyl group in the ortho position with respect to the amide group, which is then reacted with a suitable pyrazole derivative to give the compound of formula (I) (see WO 2013/024008).
  • WO 2007/006670 does not disclose an N-(het)arylpyrazole carboxanilide precursor, which can be obtained by only one reaction step, and can then either be directly reacted with a suitable sulfimine or can be converted to another N-(het)aryl pyrazole carboxanilide precursor.
  • WO 2007/006670 omits to mention any further N-(het)arylpyrazole carboxanilide precursors apart from N-(het)aryl pyrazole carboxanilide compounds carrying an activated carboxylic acid anhydride, azolide or halide.
  • N-pyridylpyrazole caboxanilide precursors as versatile reaction tools for the preparation of compounds of formula (I) and anthranilamide insecticides such as cyclaniliprole.
  • X is halogen, OC(0)Ci-C 6 -alkyl, OS(0) 2 Ci-C 6 -alkyl, OS(0) 2 Ci-C 6 -haloalkyl, OS(0) 2 benzyl,
  • p 0, 1 , 2, 3 or 4;
  • R 1 is selected from H, halogen, CN, CBrF 2 , Ci-C6-alkyl, Ci-C6-fluoroalkyl, C 2 -C6-alkenyl, and
  • R 2 is selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-fluoroalkyl, C 2 -C6- alkenyl, C 2 -C6-fluoroalkenyl, wherein the four last mentioned radicals may be substituted by one or more radicals R a ;
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R e , 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 N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R e ;
  • halogen CN , Ci-Cs- alkyl, d-Cs-haloalkyl, C2-Cs-alkenyl, C2-C8-haloalkenyl, C2-Cs-alkynyl, C2-C8-haloalkynyl, wherein the six last radicals may optionally be substituted by one or more radicals R a , Cs-Cs-cycloalkyI, which is unsubstituted, partially or completely halogenated or carries one or more radicals R aa ;
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R e , 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 N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R e , for p > 1 it being possible that R 3 are identical or different,
  • Ci-C6-alkoxy is selected from the group consisting of Ci-C6-alkoxy, Ci-C6-haloalkoxy, Cs-Cs-cycloalkyI,
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R e , 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 N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R e ;
  • R a in the case of more than one R a , R a can be identical or different;
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R e , 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 N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R e ;
  • R c , R d are, independently from one another, selected from the group consisting of H, CN, C1-C6- alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, where the five last mentioned radicals may be unsubstituted, partially or fully halogenated and/or wherein one or two CH2 groups may be replaced by a CO group; and/or may carry 1 or 2 radicals selected from Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylthio, phenyl, benzyl, pyridyl and phenoxy, it being pos- sible for pheny
  • R c and R d 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 N-heterocyclic ring which may contain 1 or 2 further heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2, 3 or 4 substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy; R e is selected from the group consisting of halogen, CN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl and Cs-Cs-cycloalkyl, where the four last-mentioned radicals may be unsubsti- tuted, partially or fully halogenated and/or wherein one or two CH2 groups may be replaced by a CO group, and/or
  • R f , R9 are, independently of each other and independently of each occurrence, selected from the group consisting of Ci-C4-alkyl, C3-C6-cycloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, C3-C8- cycloalkyl-Ci-C4-alkyl, phenyl and benzyl;
  • R h , R k are, independently from one another, selected from the group consisting of H, halogen, CN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cs-cycloalkyl, where the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or oxgenated, and/or may carry 1 or 2 radicals selected from Ci-C4-alkyl; Ci-C4-haloalkyl; Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, C1-C6- haloalkylthio, -OH, -SH, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzy
  • RP is selected from the group consisting of halogen, CN, Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl, said substituents RP being identical or different from one another if more than one substituent RP is present;
  • R q is selected from the group consisting of H, CN, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl and C3-Cs-cycloalkyl-Ci-C4-alkyl;
  • process A The process is hereinafter also referred to as "process A”.
  • the process A is advantageous in terms of the possibility to combine different N- pyridylpyrazole carboxanilide precursors, i.e. compounds of formula (II) or ( ⁇ ), with a variety sulfimines or sulfimine salts, i.e. compounds of formula (III), so that the sulfiminocarbonyl group can easily be varied in the compounds of formula (I), e.g. to find an optimal combination be- tween a N-pyridylpyrazole carboxanilide backbone and a sulfiminocarbonyl group in terms of the activity against invertebrate pests.
  • N- pyridylpyrazole carboxanilide precursors i.e. compounds of formula (II) or ( ⁇ )
  • compounds of formula (II) or ( ⁇ ) allows an optimization of the process in terms of the yields.
  • the use of the compounds of formula (II) as N- pyridylpyrazole carboxanilide precursors has the particular advantage that these compounds are readily available from easily accessible starting materials.
  • the compounds of formula ( ⁇ ) can be advantageous in terms of their reactivity, and can be easily obtained from compounds of formula (II).
  • certain preferred embodiments of the invention relate to a process A, wherein the compound of formula ( ⁇ ) is provided by converting a compound of formula (II) into a compound of formula ( ⁇ ). Furthermore, certain preferred embodiments of the invention relate to a process A, wherein the compound of formula (II) is provided by reacting a compound of formula (IV) with a compound of formula (V),
  • the variables p, R 1 , R 2 and R 3 in the compounds of formulae (IV), (V), (VI), (VII), (VIII) are as defined above, and wherein M in the compounds of formula (V) is Li, MgY or ZnY with Y being halogen, and wherein L in the compounds of formula (VII) is halogen, OC(0)Ci-C6-alkyl, OS(0)2Ci-C6-alkyl or OH.
  • M in the compounds of formula (V) is Li, MgY or ZnY with Y being halogen
  • L in the compounds of formula (VII) is halogen, OC(0)Ci-C6-alkyl, OS(0)2Ci-C6-alkyl or OH.
  • M is Li, MgY or ZnY with Y being halogen
  • R x is Ci-C6-alkyl, benzyl or phenyl, wherein the phenyl radical may be substituted by one or more radicals selected from halogen and NO2;
  • p 0, 1 , 2, 3 or 4;
  • R 1 is selected from H, halogen, CN, CBrF2, Ci-C6-alkyl, Ci-C6-fluoroalkyl, C2-C6-alkenyl, C2- C6-fluoroalkenyl, wherein the four last mentioned radicals may be substituted by one or more radicals R a ;
  • R 2 is selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-fluoroalkyl, C2-C6- alkenyl, C2-C6-fluoroalkenyl, wherein the four last mentioned radicals may be substituted by one or more radicals R a ;
  • R 3 if present, are independently selected from the group consisting of halogen, CN, Ci-Cs- alkyl, Ci-Cs-haloalkyl, C2-Cs-alkenyl, C2-C8-haloalkenyl, C2-Cs-alkynyl, C2-C8-haloalkynyl, wherein the six last radicals may optionally be substituted by one or more radicals R a , Cs-Cs-cycloalkyI, which is unsubstituted, partially or completely halogenated or carries one or more radicals R aa ;
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R e , 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 N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R e , for p > 1 it being possible that R 3 are identical or different,
  • R a is selected from the group consisting of Ci-C6-alkoxy, Ci-C6-haloalkoxy, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, C 2 -C 6 -alkenyl, -OR b , -SR b , -S(0) m R b , -N(R c )R d ,
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R e , 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 N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R e ;
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R e , 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 N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R e ;
  • R c and R d 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 N-heterocyclic ring which may contain 1 or 2 further heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2, 3 or 4 substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;
  • halogen is selected from the group consisting of CN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl and Cs-Cs-cycloalkyl, where the four last-mentioned radicals may be
  • R e in the case of more than one R e , R e can be identical or different;
  • process B is 1 or 2, wherein, in the case of several occurrences, m may be identical or different; is 0, 1 or 2; wherein, in the case of several occurrences, n may be identical or different.
  • process B is hereinafter also referred to as "process B".
  • the present invention also relates to a process for preparing a compound of formula (I) comprising the steps of preparing a compound of formula (II) as defined above, optionally converting said compound into a compound of formula ( ⁇ ),
  • R x is Ci-C6-alkyl, benzyl or phenyl, wherein the phenyl radical may be substituted by one or more radicals selected from halogen and NO2;
  • X is halogen, OC(0)Ci-C 6 -alkyl, OS(0) 2 Ci-C 6 -alkyl, OS(0) 2 Ci-C 6 -haloalkyl, OS(0) 2 benzyl, OS(0) 2 tolyl or OH;
  • R 1 is selected from H, halogen, CN, CBrF 2 , Ci-C6-alkyl, Ci-C6-fluoroalkyl, C 2 -C6-alkenyl, and C 2 -C6-fluoroalkenyl, wherein the four last mentioned radicals may be substituted by one or more radicals R a ;
  • R 2 is selected from the group consisting of C 2 -C6-alkyl, Ci-C6-fluoroalkyl, C 2 -C6-alkenyl, C 2 - C6-fluoroalkenyl, wherein the four last mentioned radicals may be substituted by one or more radicals R a ; Cs-Cs-cycloalkyI, which is unsubstituted, partially or completely halogenated or carries one or more radicals R aa ;
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R e , 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 N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R e ;
  • R 3b are independently selected from the group consisting of halogen, CN, d-Cs-alkyl, Ci- Cs-haloalkyl, C2-Cs-alkenyl, C2-C8-haloalkenyl, C2-Cs-alkynyl, C2-C8-haloalkynyl, wherein the six last radicals may optionally be substituted by one or more radicals R a ,
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R e , 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 N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R e , is selected from the group consisting of Ci-C6-alkoxy, Ci-C6-haloalkoxy, Cs-Cs-cycloalkyI, Cs-Cs-halocycloalkyl, C 2 -C 6 -alkenyl, -OR b , -SR b , -S(0) m R b , -N(R c )R d ,
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R e , 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 N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R e ;
  • Ci-C6-alkyl Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci- C6-haloalkoxy, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, -Si(R f ) 2 R9, -OR , -SR , -S(0) m R , -N(R c )R d ;
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R e , 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 N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R e ;
  • Ci-C6-alkyl is selected from the group consisting of H, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3- Ce-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, where the five last mentioned radicals may be unsubstituted, partially or fully halogenated and/or wherein one or two CH2 groups may be replaced by a CO group; and/or may carry 1 -2 radicals selected from Ci-C6-alkoxy, C1-C6- haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, phenyl, benzy
  • R d are, independently from one another, selected from the group consisting of H, CN, C1-C6- alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, where the five last mentioned radicals may be unsubstituted, partially or fully halogenated and/or wherein one or two Chb groups may be replaced by a CO group; and/or may carry 1 or 2 radicals selected from Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylthio, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyri
  • R c and R d 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 N-heterocyclic ring which may contain 1 or 2 further heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2, 3 or 4 substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;
  • halogen is selected from the group consisting of CN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl and Cs-Cs-cycloalkyl, where the four last-mentioned radicals may be
  • R e in the case of more than one R e , R e can be identical or different;
  • R9 are, independently of each other and independently of each occurrence, selected from the group consisting of Ci-C4-alkyl, C3-C6-cycloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, C3-C8- cycloalkyl-Ci-C4-alkyl, phenyl and benzyl;
  • R k are, independently from one another, selected from the group consisting of H, halogen, CN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cs-cycloalkyl, where the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or oxgenated, and/or may carry 1 or 2 radicals selected from Ci-C4-alkyl; Ci-C4-haloalkyl; Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, C1-C6- haloalkylthio, -Si(R f )2R g , -OH, -SH, phenyl, benzyl, pyridyl and phenoxy, it
  • Ci-C6-alkyl is Ci-C6-alkyl, benzyl or phenyl, wherein the phenyl radical may be substituted by one or more radicals selected from halogen and NO2;
  • halogen is halogen, OC(0)Ci-C 6 -alkyl, OS(0) 2 Ci-C 6 -alkyl, OS(0) 2 Ci-C 6 -haloalkyl, OS(0) 2 benzyl, OS(0) 2 tolyl or OH;
  • radicals R a is selected from H, halogen, CN, CBrF 2 , Ci-C6-alkyl, Ci-C6-fluoroalkyl, C 2 -C6-alkenyl, and C 2 -C6-fluoroalkenyl, wherein the four last mentioned radicals may be substituted by one or more radicals R a ;
  • halogen is selected from the group consisting of halogen, Ci-C6-alkyl, Ci-C6-fluoroalkyl, C 2 -C6- alkenyl, C 2 -C6-fluoroalkenyl, wherein the four last mentioned radicals may be substituted by one or more radicals R a ;
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R e , 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 N, O, S, NO, SO and S0 2 , as ring members, where the heterocyclic ring may be substituted by one or more radicals R e ;
  • R 3b are independently selected from the group consisting of halogen, CN, Ci-Cs-alkyl, Ci- Cs-haloalkyl, C 2 -Cs-alkenyl, C 2 -C8-haloalkenyl, C 2 -Cs-alkynyl, C 2 -C8-haloalkynyl, wherein the six last radicals may optionally be substituted by one or more radicals R a ,
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R e , 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 N, O, S, NO, SO and S0 2 , as ring members, where the heterocyclic ring may be substituted by one or more radicals R e , is selected from the group consisting of Ci-C6-alkoxy, Ci-C6-haloalkoxy, Cs-Cs-cycloalkyI, Cs-Cs-halocycloalkyl, C 2 -C 6 -alkenyl, -OR b , -SR b , -S(0) m R b , -N(R c )R d ,
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R e , 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 N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R e ;
  • R a in the case of more than one R a , R a can be identical or different;
  • Ci-C6-alkyl Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci- C6-haloalkoxy, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, - Si(R f ) 2 R9, -OR b , -SR b , -S(0) m R b , -N(R c )R d ;
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R e , 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 N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R e ;
  • Ci-C6-alkyl is selected from the group consisting of H, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs- Cs-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, where the five last mentioned radicals may be unsubstituted, partially or fully halogenated and/or wherein one or two CH2 groups may be replaced by a CO group; and/or may carry 1 -2 radicals selected from Ci-C6-alkoxy, C1-C6- haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, Ci-C6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, phenyl, benz
  • R d are, independently from one another, selected from the group consisting of H, CN, C1-C6- alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, where the five last mentioned radicals may be unsubstituted, partially or fully halogenated and/or wherein one or two CH2 groups may be replaced by a CO group; and/or may carry 1 or 2 radicals selected from Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylthio, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyri
  • R c and R d 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 N-heterocyclic ring which may contain 1 or 2 further heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2, 3 or 4 substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;
  • halogen is selected from the group consisting of CN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl and Cs-Cs-cycloalkyl, where the four last-mentioned radicals may be
  • R e in the case of more than one R e , R e can be identical or different;
  • R f , R9 are, independently of each other and independently of each occurrence, selected from the group consisting of Ci-C4-alkyl, C3-C6-cycloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, C3-C8- cycloalkyl-Ci-C4-alkyl, phenyl and benzyl;
  • the compounds of formulae ( ⁇ . ⁇ '), ( ⁇ . ⁇ '), (II.A”) and ( ⁇ . ⁇ ”) represent versatile reaction tools for the preparation of compounds of formula (I).
  • the compounds of formulae (II.A) and ( ⁇ . ⁇ ') may advantageously be used in the preparation of compounds of formula (I), wherein R 1 is CI, R 2 is CF 3 , R 3a is CH 3 and R 3b is CI.
  • the compounds of formulae (II.A”) and (ll * .A”) may advantageously be used in the preparation of compounds such as cyclaniliprole, which is a well known anthranilamide insecticide.
  • halogen denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.
  • alkyl as used herein (and in the alkyl moieties of other groups comprising an alkyl group, e.g.
  • alkoxy, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl and alkoxyalkyl denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms and in particular from 1 to 3 carbon atoms.
  • alkylene (or alkanediyl) as used herein in each case denotes an alkyl radical as de- fined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.
  • haloalkyl as used herein (and in the haloalkyl moieties of other groups comprising a haloalkyl group, e.g. haloalkoxy and haloalkylthio) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms.
  • fluoroalkyl as used herein (and in the fluoroalkyl units of fluoroalkoxy,
  • fluoroalkylthio, fluoroalkylsulfinyl and fluoroalkylsulfonyl denotes in each case straight-chain or branched alkyl groups having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms and in particular 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with fluorine atoms. Examples thereof are fluoromethyl, difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,
  • cycloalkyl as used herein (and in the cycloalkyl moieties of other groups comprising a cycloalkyl group, e.g. cycloalkoxy and cycloalkylalkyl) denotes in each case a mono- or bicy-mann cycloaliphatic radical having usually from 3 to 10 carbon atoms, 3 to 8 carbon atoms or 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.1 .1 ]hexyl, bicyclo[3.1 .1 ]heptyl, bicyclo[2.2.1]heptyl, and bicyclo[2.2.2]octyl.
  • halocycloalkyi as used herein (and in the halocycloalkyi moieties of other groups comprising an halocycloalkyi group, e.g. halocycloalkylmethyl) denotes in each case a mono- or bicyclic cycloaliphatic radical having usually from 3 to 10 carbon atoms, 3 to 8 carbon atoms or 3 to 6 carbon atoms, wherein at least one, e.g. 1 , 2, 3, 4 or 5 of the hydrogen atoms are replaced by halogen, in particular by fluorine or chlorine.
  • Examples are 1 - and 2-fluorocyclopropyl, 1 ,2-, 2,2- and 2,3-difluorocyclopropyl, 1 ,2,2-trifluorocyclopropyl, 2,2,3,3-tetrafluorocyclpropyl, 1 - and 2-chlorocyclopropyl, 1 ,2-, 2,2- and 2,3-dichlorocyclopropyl, 1 ,2,2-trichlorocyclopropyl, 2,2,3,3-tetrachlorocyclpropyl, 1 -,2- and 3-fluorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5- difluorocyclopentyl, 1 -,2- and 3-chlorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-,
  • cycloalkylalkyl denotes in each case alkyl as defined above, usually comprising 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein 1 carbon atom carries a cycloalkyl radical as defined above, usually comprising from 3 to 10 carbon atoms, 3 to 8 carbon atoms or 3 to 6 carbon atoms as defined above. Examples are cyclopropylmethyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclohexylethyl and the like.
  • fluorocylcoalkyl denotes a halocycloalkyl radical, as defined above, wherein the one or more halogen atoms are fluorine atoms.
  • alkenyl denotes in each case a singly unsaturated hydrocarbon rad- ical, i.e. a hydrocarbon radical having a carbon-carbon double bond, having usually 2 to 10, preferably 2 to 4 carbon atoms, e.g.
  • alkenylene (or alkenediyl) as used herein in each case denotes an alkenyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.
  • haloalkenyl as used herein, which may also be expressed as "alkenyl which may be substituted by halogen", and the haloalkenyl moieties in haloalkenyloxy, haloalkenylcarbonyl and the like refers to unsaturated straight-chain or branched hydrocarbon radicals having 2 to 10 ("C2-Cio-haloalkenyl") or 2 to 6 (“C2-C6-haloalkenyl”) carbon atoms and a double bond in any position, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, for example chlorovinyl, chloroallyl and the like.
  • alkynyl denotes unsaturated straight-chain or branched hydrocarbon radicals having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms and one or two carbon-carbon triple bonds in any position, e.g.
  • ethynyl propargyl (2-propyn-1 -yl), 1 -propyn- 1 -yl, 1 -methylprop-2-yn-1 -yl), 2-butyn-1 -yl, 3-butyn-1 -yl, 1 -pentyn-1 -yl, 3-pentyn-1 -yl, 4-pentyn- 1 -yl, 1 -methylbut-2-yn-1 -yl, 1 -ethylprop-2-yn-1 -yl and the like.
  • alkynylene (or alkynediyl) as used herein in each case denotes an alkynyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.
  • haloalkynyl as used herein, which is also expressed as “alkynyl which may be sub- stituted by halogen”, refers to unsaturated straight-chain or branched hydrocarbon radicals having usually 3 to 10 carbon atoms, frequently 2 to 6, preferably 2 to 4 carbon atoms, and one or two triple bonds in any position (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine.
  • alkoxy denotes in each case a straight-chain or branched alkyl group usually having from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, which is bound to the remainder of the molecule via an oxygen atom.
  • alkoxy group examples are methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2-butyloxy, iso-butyloxy, tert-butyloxy, and the like.
  • haloalkoxy denotes in each case a straight-chain or branched alkoxy group, as defined above, having from 1 to 10 carbon atoms, frequently from 1 to 6 car- bon atoms, preferably 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms, in particular fluorine atoms.
  • Preferred haloalkoxy moieties include Ci-C4-haloalkoxy, in particular halomethoxy, and also in particular Ci-C2-fluoroalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy,
  • alkoxy-alkyl denotes in each case alkyl usually comprising 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 to 10, frequently 1 to 6, in particular 1 to 4, carbon atoms as defined above.
  • Examples are CH 2 OCH 3 , CH2-OC2H5, n-propoxymethyl, CH 2 -OCH(CH 3 )2, n- butoxymethyl, (l -methylpropoxy)-methyl, (2-methylpropoxy)methyl, CH2-OC(CH3)3, 2- (methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n-propoxy)-ethyl, 2-(1 -methylethoxy)-ethyl, 2-(n-butoxy)ethyl,
  • fluoroalkoxy-alkyl denotes in each case alkyl as defined above, usually comprising 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein 1 carbon atom carries an fluoroalkoxy radical as defined above, usually comprising 1 to 10, frequently 1 to 6, in particular 1 to 4, carbon atoms as defined above.
  • haloalkylthio refers to an alkylthio group as defined above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • fluoromethylthio difluoromethylthio, trifluoromethylthio, 1 -fluoroethylthio, 2- fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro- 2,2-difluoro-ethylthio, 2,2-dichloro-2-fluorethylthio, 2,2,2-trichloroethylthio, pentafluoroethylthio and the like
  • alkylsulfinyl and S(0) n -alkyl (wherein n is 1 ) are equivalent and, as used herein, denote an alkyl group, as defined above, attached via a sulfinyl [S(O)] group.
  • alkylsulfinyl and “S(0) n -alkyl” (wherein n is 1 ) are equivalent and, as used herein, denote an alkyl group, as defined above, attached via a sulfinyl [S(O)] group.
  • Si -C6-a I kylsu If i nyl refers to a Ci-C6-alkyl group, as defined above, attached via a sulfinyl [S(O)] group.
  • Examples are methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1 -methylethylsulfinyl (isopropylsulfinyl), butyl sulfinyl, 1 -methylpropylsulfinyl (sec-butylsulfinyl), 2-methylpropylsulfinyl (isobutylsulfinyl), 1 ,1 -dimethylethylsulfinyl (tert-butylsulfinyl), pentylsulfinyl, 1 -methylbutylsulfinyl,
  • haloalkylsulfinyl and "S(0) n -haloalkyl (wherein n is 1 ) as used herein refers to an alkylsulfinyl group as defined above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine. Examples are trifluormethylsulfinyl,
  • alkylsulfonyl and “S(0) n -alkyl” are equivalent and, as used herein, denote an alkyl group, as defined above, attached via a sulfonyl [S(0)2] group.
  • Si-C6-alkylsulfonyl refers to a Ci-C6-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group. Examples are methylsulfonyl, ethylsulfonyl, n-propylsulfonyl,
  • haloalkylsulfonyl and "S(0) n -haloalkyl (wherein n is 2) as used herein refers to an alkylsulfonyl group as defined above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine. Examples are trifluormethylsulfonyl,
  • alkylamino denotes in each case a group -NHR, wherein R is a straight-chain or branched alkyl group usually having from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
  • alkylamino groups are methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, 2-butylamino, iso-butylamino, tert-butylamino, and the like.
  • dialkylamino denotes in each case a group-NRR', wherein R and R', independently of each other, are a straight-chain or branched alkyl group each usually hav- ing from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
  • dialkylamino group examples include dimethylamino, diethylamino, dipropylamino, dibutylamino, methyl-ethyl-amino, methyl- propyl-amino, methyl-isopropylamino, methyl-butyl-amino, methyl-isobutyl-amino, ethyl-propyl- amino, ethyl-isopropylamino, ethyl-butyl-amino, ethyl-isobutyl-amino, and the like.
  • haloalkylcarbonyl alkoxycarbonyl and haloalkoxycarbonyl.
  • aryl refers to a mono-, bi- or tricyclic aromatic hydrocarbon radical having 6 to 14 carbon atoms. Examples thereof comprise phenyl, naphthyl, fluorenyl, azulenyl, anthracenyl and phenanthrenyl. Aryl is preferably phenyl or naphthyl and especially phenyl.
  • the term "3-, 4-, 5-, 6-, 7- or 8-membered saturated carbocyclic ring” as used herein refers to carbocyclic rings, which are monocyclic and fully saturated. Examples of such rings include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like.
  • 3-, 4-, 5-, 6-, 7- or 8-membered partially unsaturated carbocyclic ring and "5- or 6- membered partially unsaturated carbocyclic ring” refer to carbocyclic rings, which are monocyc- lie and have one or more degrees of unsaturation.
  • examples of such rings include include cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene and the like.
  • heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members
  • ring members [wherein “completely/fully unsaturated” includes also “aromatic”] as used herein denotes monocyclic radicals, the monocyclic radicals being saturated, partially unsaturated or fully unsaturated (including aromatic).
  • the heterocyclic ring may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. Examples of a 3-, 4-, 5-, 6- or 7-membered saturated heterocyclic ring include:
  • oxiranyl aziridinyl, azetidinyl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, pyrazolidin-3-yl, pyrazolidin-4-yl, pyrazolidin- 5-yl, imidazolidin-2-yl, imidazolidin-4-yl, oxazolidin-2-yl, oxazolidin-4-yl, oxazolidin-5-yl, isoxa- zolidin-3-yl, isoxazolidin-4-yl, isoxazolidin-5-yl, thiazolidin-2-yl, thiazolidin-4-yl, thiazolidin-5-yl, isothiazolidin-3-yl, iso
  • Examples of a 3-, 4-, 5-, 6- or 7-membered partially unsaturated heterocyclic ring include: 2,3-dihydrofur-2-yl, 2,3-dihydrofur- 3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4- dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-yl, 3-pyrrolin-
  • 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 N, O, S, NO, SO and SO2, as ring members denotes a saturated or unsaturated 3- to 8- membered ring system which optionally contains 1 to 3 heteroatoms selected from N, O, S, NO, SO and SO2, as defined above, with the exception of the completely unsaturated ring systems.
  • p in the compounds of formulae (I), (II), ( ⁇ ), (IV) and (VI) is 0, 1 or 2, preferably 1 or 2, more preferably 2.
  • R 3 in the compounds of formulae (I), (II), ( ⁇ ), (IV) and (VI) is selected from the group consisting of halogen, CN, Ci-C4-alkyl, and C1-C4- fluoroalkyl, for p > 1 it being possible that R 3 are identical or different.
  • R 3 is selected from the group consisting of halogen, CN, Ci-C4-alkyl and Ci-C4-fluoroalkyl, more preferably from halogen, CN and CH3, for p > 1 it being possible that R 3 are identical or different.
  • p in the compounds of formulae (I), (II), ( ⁇ ), (IV) and (VI) is 2, and one radical R 3 is located ortho with regard to the aminocarbonyl group, while the other is located para with respect to this group.
  • Such compounds are referred to as compounds of formulae (I.A), (I I .A), ( ⁇ . ⁇ ), (IV.A) and (VI.A), respectively.
  • the compounds are depicted below and are preferred according to the present invention.
  • R 3a , R 3b are independently selected from the group consisting of halogen, CN, d-Cs-alkyl, Ci- Cs-haloalkyl, C2-Cs-alkenyl, C2-C8-haloalkenyl, C2-Cs-alkynyl, C2-C8-haloalkynyl, wherein the six last radicals may optionally be substituted by one or more radicals R a , C3-C8-cycloalkyl, which is unsubstituted, partially or completely halogenated or carries one or more radicals R aa ;
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R e , and
  • heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R e .
  • R 3a and R 3b are independently selected from halogen, CN, C1-C4- alkyl, and Ci-C4-fluoroalkyl, and even more preferred that R 3a and R 3b are independently selected from the the group consisting of halogen, CN and CH3. It is most preferred that R 3a is CH3 and R 3b is halogen, preferably CI.
  • R 2 in the compounds of formulae (I), (II), (II * ), (V), (VII) and (VIII) is halogen, Ci-C 4 -alkyl Ci-C 4 -fluoroalkyl or (3,5-bis(trifluoro- methyl)pyrazol-2-yl)methyl.
  • R 2 is Ci-C2-fluoroalkyl.
  • R 2 is CF3.
  • Such compounds are referred to as compounds of formulae (I.CF3), (II.CF3), (IT.CFs), (V.CF3), (VII. CF3) and (VIII.CF3), respectively.
  • the compounds are depicted below and are preferred according to the present invention.
  • the compounds of formulae (I), (II) and ( ⁇ ) are compounds of formulae (I.A), (II.A) and ( ⁇ . ⁇ ), respectively, wherein R 2 is CF3. These compounds are referred to as (I .A.CF3), (I I .A.CF3) and (IT.A.CFs).
  • the compounds are available from the compounds of formula (IV.A) or (VI.A) as defined above and compounds of formula (V.CF3), (VII . CF3) or (VI I I .CF3) as defined above.
  • R 1 in the compounds of formulae (I), (II), (II * ), (V), (VII) and (VIII) is halogen or CF 3 .
  • R 1 is CI.
  • R 4 and R 5 in the compounds of formulae (I) and (III) are independently of each other selected from the group consisting of Ci-C6-alkyl, C3- C7-cylcoalkyl and C3-C8-cycloalkyl-Ci-C4-alkyl, or
  • R 4 and R 5 together represent a C3-C7-alkylene or C3-C7-alkenylene forming together with the sulfur atom to which they are attached a 4-, 5-, 6-, 7- or 8-membered saturated or partially unsaturated ring, wherein 1 or 2 of the CH2 groups in the C3-C7-alkylene chain or 1 or 2 of any of the CH2 or CH groups in the C3-C7-alkenylene chain may be replaced may be replaced by 1 or 2 groups independently selected from the group consisting of O and S.
  • the compounds of formulae (I) are compounds of formula (I.A) or compounds of formula (I.CF3) or compounds of formula (I.A.CF3), wherein R 4 and R 5 are as defined above.
  • salts of the compounds of formula (III) hydrogen sulfate salts and sulfate salts are preferred. Sulfate salts are particularly preferred.
  • the salts of the compounds of formula (III) may be represented by the following formula (Ilia)
  • R 4 and R 5 are as defined above for the compounds of formula (III) and A- is HSCv or
  • variables, if present, are selected as such that R 1 is CI and R 2 is CF3, and the remaining variables are selected as indicated in one of the rows A-1 to A-54 of Table A.
  • the compounds of formulae (I), (II), ( ⁇ ), (IV) and (VI) correspond to compounds of formulae (I.A), (II.A), ( ⁇ . ⁇ ), (IV.A) and (VI.A), and that in the compounds of formulae (I.A), (II.A), (ll * .A), (IV.A) and (VI.A) and (III), (V), (VII) and (VIII), the variables, if present, are selected as such that R 1 is CI, R 2 is CF 3 , R 3a is CH 3 , R 3b is CI, R 4 and R 5 are both CH 2 CH 3 .
  • M is MgY with Y being halogen, prefera- bly Br or CI.
  • R x in the compounds of formulae (II), (IV) and (VI) is Ci-C2-alkyl, phenyl (CeH 5 ), p-nitrophenyl ( -NO2-C6H4) or pentafluorophenyl (CeF 5 ), preferably CH3.
  • the compounds of formulae (IV) and (VI) are compounds of formulae (IV.A) and (VI. A), wherein R x is Ci-C2-alkyl, phenyl (CeHs), p-nitrophenyl ( -NO2-C6H4) or pentafluorophenyl (CeFs), preferably CH3, and it is particularly preferred that the compounds of formula (II) are compounds of formula (II.A) or compounds of formula (II.CF3) or compounds of formula (II.A.CF3), wherein R 1 is halogen or CF3, preferably CI, and R x is Ci-C2-alkyl, phenyl (C6H5), p-nitrophenyl ( -NO2-C6H4) or pentafluorophenyl (CeF 5 ), preferably CH3.
  • the compounds of formula (II) correspond to compounds of for- mula (II.A.CFs), wherein R 1 is CI, R 2 is CF 3 , R 3a is CH 3 , R 3b is CI and R x is CH 3 .
  • R 1 is CI
  • R 2 is CF 3
  • R 3a is CH 3
  • R 3b is CI
  • R x is CH 3 .
  • the same sub- stituent definitions are also preferred for the compounds of formula (IV.A), (V), (VI.A), (VII) and (VIII), if the substituents are present.
  • X in the compounds of formula ( ⁇ ) is OH.
  • Such compounds are preferably activated in situ in the presence of a sulfonyl chloride.
  • X is e.g. any one of OS(0) 2 Ci-C 6 -alkyl, OS(0) 2 Ci-C 6 -haloalkyl, OS(0) 2 benzyl, or OS(0) 2 tolyl depending on the choice of the sulfonyl chloride.
  • it is therefore preferred that X is any one of OS(0) 2 Ci-C 6 -alkyl, OS(0) 2 Ci-C 6 -haloalkyl, OS(0) 2 benzyl, or OS(0) 2 tolyl.
  • the compounds of formula ( ⁇ ) are compounds of formula ( ⁇ . ⁇ ) or compounds of formula (IT.CFs) or compounds of formula (IT.A.CFs), wherein X is OH, which may be activated in situ as indicated above.
  • X in the compounds of formula ( ⁇ ) is halo- gen, preferably CI.
  • the compounds of formula ( ⁇ ) are compounds of formula ( ⁇ . ⁇ ) or compounds of formula (IT.CFs) or compounds of formula (IT.A.CFs), wherein X is CI.
  • the variables are selected as such that R 1 is CI and R 2 is CF3, and the remaining variables are selected as indicated in one of the rows C-1 to C-12 of Table C.
  • the compounds of formula ( ⁇ ) correspond to compounds of formula (l l*.A.CF 3 ), wherein R 1 is CI, R 2 is CF 3 , R 3a is CH 3 , R 3b is CI and X is CI or OH, preferably CI.
  • R 1 is CI
  • R 2 is CF 3
  • R 3a is CH 3
  • R 3b is CI
  • X is CI or OH, preferably CI.
  • process B is thus not only suitable for the preparation of compounds of formula (I), but also for the preparation of cyclaniliprole.
  • R 2 in the compounds of formulae ( ⁇ ⁇ . ⁇ ') and ( ⁇ . ⁇ ) is CF 3 . Accordingly, the compounds of formulae (I I .A) and ( ⁇ . ⁇ ') preferably correspond to the compounds of formulae (I I .A.CF 3 ) and (N*.A.CF 3 ) as defined above.
  • R 1 , R 3a and R 3b preferably have the following meanings:
  • R 1 is halogen or CF3
  • R 3a is selected from the group consisting of halogen, CN, Ci-C4-alkyl and Ci-C4-fluoroalkyl
  • R 3b is selected from the group consisting of halogen, CN, Ci-C4-alkyl and Ci-C4-fluoroalkyl; and preferably have the following meanings:
  • R 1 is CI
  • R 3a is selected from the group consisting of halogen, CN and CH3;
  • R 3b is selected from the group consisting of halogen, CN and CH3;
  • R x is Ci-C2-alkyl, phenyl, p-nitrophenyl or pentafluorophenyl, preferably CH3, and that X is halogen or OH, preferably CI.
  • R 3a in the compounds of formulae (II.A") and (II.A") is Br. Furthermore, it is preferred that in such compounds that R 3b is CI and R 2 is Br.
  • R x is Ci-C2-alkyl, phenyl, p-nitrophenyl or pentafluorophenyl, preferably Ci-alkyl, and that X is halogen or OH, preferably CI.
  • reaction vessels customary for such reactions the reactions being carried out in a continuous, semi-continuous or batchwise manner.
  • the temperatures and the duration times of the reactions may be varied in broad ranges, which the person skilled in the art knows from analogous reactions.
  • the temperatures often depend on the reflux temperature of the solvents.
  • Other reactions are preferably performed at room temperature, i.e. at about 25°C, or under ice cooling, i.e. at about 0°C.
  • the end of the re- action can be monitored by methods known to a person skilled in the art, e.g. thin layer chromatography or HPLC.
  • the molar ratios of the reactants, which are used in the reactions are in the range of from 0.2:1 to 1 :0.2, preferably from 0.5:1 to 1 :0.5, more preferably from 0.8:1 to 1 :0.8.
  • equimolar amounts are used.
  • reactants can in principle be contacted with one another in any desired sequence.
  • reaction conditions for step (ii) of the process A depend on whether a compound of formula (II) or a compound of formula ( ⁇ ) is reacted with the compound of formula (III) or a salt thereof.
  • a compound of formula (I I) is reacted with the compound of formula (II I) or a salt thereof.
  • Said reaction can be carried out by analogy to the reaction procedure described in Journal of Medicinal Chemistry, 45(17), 3692- 3702, 2002.
  • reaction may be carried out by a process, wherein the compound of formula (I I I) or a salt thereof is first reacted with a water soluble base in an aqueous solution, the resulting mixture is then dried, and the resulting dry mixture is then reacted with the compound of formula (I I) in a protic solvent.
  • Suitable reaction temperatures for the reaction between the compound of formula (I II) or a salt thereof with the water soluble base are in the range of from -20°C to +20°C, preferably in the range of from -10°C to +10°C, more preferably in the range of from -2°C to +2°C.
  • the water soluble base is used at least in stochiometric amounts.
  • the amount of the base is preferably in the range of 1 to 3 mole, more preferably 1 .5 to 2.5 mole, most preferably 1 .8 to 2.2 mole per mole of the compound of formula (II I).
  • Suitable bases include, but are not limited to oxo bases.
  • Suitable oxo bases include but are not limited to hydroxides, in particular alkali metal hydroxides such as lithium, sodium or potassium hydroxide, and mixtures thereof. Sodium hydroxide is particularly preferred.
  • Suitable reaction temperatures for the reaction with the pre-treated compound of formula (I II) with the compound of formula (I I) are in the range of from 20°C to 60°C, preferably from 30°C to 50°C, more preferably from 38°C to 42°C.
  • the compound of formula (I I I) is provided in the form of the salt, preferably in the form of a hydrogensulfate salt or a sulfate salt.
  • a compound of formula ( ⁇ ) is reacted with the compound of formula (II I) or a salt thereof.
  • reaction of such compounds of formula ( ⁇ ) with the compounds of formula (II I) or the salts thereof can be carried out by analogy to the reaction procedure described in WO 2000/034368, WO 2000/034238, WO 2000/034260 or WO 2000/034237.
  • step (ii) of the process A of the present invention in situ activation of the carbox- ylic acid group is typically required in step (ii) of the process A of the present invention.
  • In situ activation may e.g. be achieved by adding a reagent, which converts the OH group to a leaving group, such as dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or the like.
  • DCC dicyclohexylcarbodiimide
  • EDC 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide
  • the activated carboxylic acid group may then further be converted into an active ester by adding N-hydroxysuccinimide, 1 -hydroxybenzotriazole (HOBT), 1 - hydroxy-7-azabenzotriazole (HOAT), pentafluorophenol, p-nitrophenyl or the like, before the compound of formula ( ⁇ ) is reacted with the compound of formula (III) or a salt thereof in step (ii) of the process A.
  • N-hydroxysuccinimide 1 -hydroxybenzotriazole (HOBT), 1 - hydroxy-7-azabenzotriazole (HOAT), pentafluorophenol, p-nitrophenyl or the like
  • in situ activation may be achieved by adding a sulfonyl chloride to the reaction mixture in step (ii) of process A of the present invention. It has been found that this in situ activation is particularly effective in terms of increasing the reactivity of compounds of formula ( ⁇ ), wherein X is OH. Accordingly, it is a preferred embodiment of the process A of the present in- vention that X in the compound of formula ( ⁇ ) is OH, and step (ii) is performed in the presence of a sulfonyl chloride.
  • Suitable reaction temperatures for this one pot reaction are in the range of from -20°C to 10°C, preferably in the range of from -10°C to 5°C.
  • a sulfonyl chloride of the formula R S S(0)2CI is used, wherein R s is Ci-C6-alkyl, Ci- C6-haloalkyl, benzyl or phenyl, wherein the phenyl group may be substituted by halogen, C1-C3- alkyl or nitro. More preferably, the sulfonyl chloride is methanesulfonyl.
  • a suitable solvent for the in situ activation and the subsequent amidation reaction is e.g. ace- tonitrile.
  • the compound of formula ( ⁇ ) is provided in step (i) of the process A by converting a compound of formula (II) into a compound of formula ( ⁇ ).
  • the compound of formula ( ⁇ ) is provided by hydrolyzing a compound of formula (II), wherein R x is Ci-C6-alkyl or phenyl, wherein the phenyl radical may be substituted by one or more radicals selected from halogen and NO2, or by hydrogenating a compound of formula (II), wherein R x is benzyl, to give a compound of formula ( ⁇ ) with X being OH, and optionally further activating said compound to give a compound of formula ( ⁇ ), wherein X is halogen, OC(0)Ci-C 6 -alkyl, OS(0) 2 Ci-C 6 -alkyl, OS(0) 2 Ci-C 6 -haloalkyl, OS(0) 2 benzyl, or OS(0) 2 tolyl
  • hydrolysis may be achieved by reacting a compound of formula (II) with a base in an aqueous medium.
  • Suitable reaction temperatures are in the range of from 0°C to 50°C, preferably in the range of from 10°C to 30°C, more preferably in the range of from 20°C to 25°C.
  • the amount of the base is in the range of 1 .0 to 2.0 mole, more preferably 1.0 to 1.3 mole, most preferably 1.0 to 1.1 mole per mole of the compound of formula (II).
  • Suitable bases include but are not limited to hydroxides, in particular alkali metal hydroxides such as lithium, sodium or potassium hydroxide, and mixtures thereof.
  • alkali metal hydroxides such as lithium, sodium or potassium hydroxide, and mixtures thereof.
  • Sodium hydroxide is par- ticularly preferred.
  • Compounds of formula ( ⁇ ), wherein X is CI can be provided by reacting the resulting compound of formula ( ⁇ ), wherein X is OH, with thionylchloride or oxalylchloride, preferably oxalylchloride, optionally in the presence of catalytic amounts of DMF, in an aprotic solvent.
  • thionylchloride or oxalylchloride preferably oxalylchloride, optionally in the presence of catalytic amounts of DMF, in an aprotic solvent.
  • Suitable reaction temperatures are in the range of from 0° to 30°C, preferably from 10°C to 30°C, more preferably in the range of from 20°C to 25°C.
  • Thionylchloride or oxalylchloride is preferably used in an amount in the range of 1.0 to 5.0 mole, more preferably 2.0 to 4.0 mole, most preferably 2.5 to 3.5 mole per mole of the compound of formula ( ⁇ ) with X being OH.
  • Suitable aprotic solvents include aliphatic hydrocarbons, cycloaliphatic hydrocarbons, halo- genated alkanes, aromatic hydrocarbons, open-chained ethers, cyclic ethers, esters, aliphatic or alicyclic carbonates.
  • Preferred aprotic solvents are halogenated solvents, such as methylene chloride, chloroform or 1 ,2-dichlorethane. Methylenechloride is particularly preferred.
  • reaction is carried in the presence of catalytic amounts of DMF.
  • the compound of formula (II) is provided in step (i) of the process A by reacting a 2-isocyanatobenzoate of formula (IV) with a pyrazole metal compound of formula (V)
  • M is Li, MgY or ZnY with Y being halogen.
  • M is MgY with Y being Br, I or CI, preferably Br or CI.
  • the compound of formula (II) is provided in step (i) of the process A by reacting a 2-aminobenzoate of formula (VI) with a pyrazole carboxylic acid derivative of fo
  • L is halogen, OC(0)Ci-C6-alkyl, OS(0)2Ci-C6-alkyl or OH.
  • L is halogen, particularly preferably CI.
  • L may be OH, which is activated by adding a sulfonyl chloride as described above.
  • the compounds of formula (VI) are available from the corresponding 2-aminobenzoic acid derivatives by standard esterification processes known in the art.
  • the reaction conditions are similar to those described for the reaction between the compounds of formula ( ⁇ ) and the compounds of formula (III).
  • reaction temperatures in the range of from 0°C to 30°C, preferably from 10°C to 30°C , more preferably from 20°C to 25°C are typically applied, and aprotic solvents, preferably methylenechloride, are typically used, if L is CI.
  • aprotic solvents preferably methylenechloride
  • the compound of formula (II) is provided in step (i) of the process A by reacting a 2-aminobenzoate of formula (VI) with a pyrazole aldehyde of formula (VIII)
  • the oxidizing agent is a chloro- and/or CN-substituted benzoquinone or a meta- chloroperbenzoic acid.
  • Suitable reaction temperatures are above 20°C, preferably above 50°C, more preferably in the range of from 70°C to 105°C, most preferably about 100°C.
  • Preferred benzoquinone compounds are selected from the group consisting of 2,3-dichloro- 5,6-dicyano-1 ,4-benzoquinone, tetrachloro-1 ,2-benzoquinone, and tetrachloro-1 ,4- benzoquinone. Tetrachloro-1 ,2-benzoquinone is particularly preferred.
  • benzoquinone compound or the meta-chloroperbenzoic acid is used in an amount in the range of 1.0 to 5.0 mole, more preferably 1 .0 to 2.0 mole, most preferably 1 .0 to 1 .5 mole per mole of the compound of formula (VIII).
  • Preferred solvents for the reaction with benzoquinone compounds as oxidizing agents are high boiling ether compounds such as 1 ,4-dioxane. Acetonitril is preferred as a solvent, if meta- chloroperbenzoic acid is used as oxidizing agent.
  • catalytic amounts of p-toluenesulfonic acid monohydrate, camphor sulfonic acid and/or copper iodide may be added to the reaction mixture.
  • the process B of the present invention for preparing compounds of formula (II) comprises reacting a compound of formula (IV) with a compound of formula (V).
  • the process may be extended to a process for preparing compounds of formula (I) comprising pre- paring compounds of formula (II) by reacting a compound of formula (IV) with a compound of formula (V) and, optionally converting the compound of formula (II) into a compound of formula ( ⁇ ), and reacting the compound of formula (II) or ( ⁇ ) with a compound of formula (III) or a salt thereof.
  • Preferred definitions for the compounds of formulae (II), (IV) and (V) as well as formu- lae (I), (II), ( ⁇ ) and (III) have been provided above.
  • the compound of formula (II) is provided by reacting a 2-isocyanatobenzoate of formula (IV) with a pyrazole metal compound of formula (V)
  • reaction conditions for the preparation of compounds of formula (II) from the compounds of formula (IV) and (V) are as follows. It is preferred that the compounds of formula (V) are pre- pared in situ, for example by reacting a compound of formula (IXa) or (IXb) with Hal meaning halogen, preferably CI or Br, as depicted below with an organometallic reagent. The resulting compounds of formula (V) are then directly reacted with the compounds of formula (IV).
  • the in situ preparation of the compounds of formula (V) is typically performed at temperatures in the range of from -10°C to +5°C, preferably from -5°C to 0°C, more preferably at 0°C.
  • organolithium reagents R Li Li with R Li being Ci-C6-alkyl, such as n- butyllithium, may be used.
  • the organometallic reagent is used in an amount in the range of 1.0 to 3.0 mole, more preferably 1.0 to 2.0 mole, most preferably 1.0 to 1.7 mole per mole of the compound of formula (IXa) or (IXb).
  • Suitable solvents for the in situ preparation of the compounds of formula (V) are cyclic and acyclic ethers, such as diethylether, tetrahydrofuran, 1 ,2-dimethoxyethane and the like. 1 ,2- Dimethoxyethane and tetrahydrofuran are preferred. Mixtures of 1 ,2-dimethoxyethane and tetrahydrofuran are also preferred.
  • both the compound of formula (IXa) or (IXb) and the organometallic reagent are combined with each other in the form of solutions.
  • the addition of the compounds of formula (IV) to the in situ prepared compounds of formula (V) is then performed at a temperature in the range of from -20°C to +20°C, preferably from - 5°C to +5°C, more preferably about 0°C. After about 1 hour at this temperature, the reaction temperature may be increased to a temperature of from 20°C to 25°C.
  • the compound of formula (IV) is also preferably provided in solution, preferably in a solution in a cyclic or acyclic ether or an aromatic solvent or a mixture thereof.
  • the compound of formula (IV) is provided as a solution in tetrahydrofuran or toluene or a mixture thereof.
  • Example P.7 methyl 5-chloro-2-[[2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carbonyl]amino]-3-methyl-benzoate
  • Example P.10 N-[4-chloro-2-[(diethyl- 4 -sulfanylidene)carbamoyl]-6-methyl-phenyl]-2- (3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide
  • Example P.1 1 N-[4-chloro-2-[(diethyl- 4 -sulfanylidene)carbamoyl]-6-methyl-phenyl]-2- (3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide

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Abstract

La présente invention concerne un procédé de préparation de N-pyridylpyrazole carboxanilides portant un groupe sulfiminocarbonyle en position ortho par rapport au groupe amide, qui sont représentés par la formule (I). Le procédé comprend la réaction d'un précurseur de N-pyridylpyrazole carbooxanilide de formule (II) ou (II*) avec une sulfimine de formule (III) ou un sel de cette dernière. De plus, la présente invention concerne un procédé de préparation de précurseurs de N-pyridylpyrazole carbooxanilide de formule (II) par la réaction d'un composé de formule (IV) avec un composé de formule (V). En outre, la présente invention concerne des précurseurs de N-pyridylpyrazole carbooxanilide de formules (II.A'), (II*.A'), (II.A'') et (II*.A'').
PCT/EP2015/058943 2014-04-25 2015-04-24 Procédé de préparation d'esters et de dérivés d'anthranilamide WO2015162260A1 (fr)

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WO2017140563A1 (fr) 2016-02-19 2017-08-24 Basf Se Mélanges à activité pesticide comprenant des composés anthranilamides
WO2020117493A1 (fr) * 2018-12-03 2020-06-11 Fmc Corporation Procédé de préparation de n-phénylpyrazole-1-carboxamides

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017140563A1 (fr) 2016-02-19 2017-08-24 Basf Se Mélanges à activité pesticide comprenant des composés anthranilamides
US11297837B2 (en) 2016-02-19 2022-04-12 Basf Se Pesticidally activi mixtures comprising anthranilamide compounds
WO2020117493A1 (fr) * 2018-12-03 2020-06-11 Fmc Corporation Procédé de préparation de n-phénylpyrazole-1-carboxamides
CN113382984A (zh) * 2018-12-03 2021-09-10 Fmc公司 N-苯基吡唑-1-甲酰胺的制备方法

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