US 11,053,175 B2
Thioether compounds as nitrification inhibitors
Barbara Nave, Ruppertsberg (DE); Joachim Dickhaut, Heidelberg (DE); Peter Nesvadba, Marly (CH); Mihiret Tekeste Sisay, Mannheim (DE); Alexander Wissemeier, Speyer (DE); Wolfram Zerulla, St Martin (DE); Gregor Pasda, Neustadt (DE); Olof Wallquist, Basel (CH); and Allan F. Cunningham, Magden (CH)
Assigned to BASF SE, Ludwigshafen (DE)
Appl. No. 15/573,224
Filed by BASF SE, Ludwigshafen am Rhein (DE)
PCT Filed May 11, 2016, PCT No. PCT/EP2016/060517
§ 371(c)(1), (2) Date Nov. 10, 2017,
PCT Pub. No. WO2016/180859, PCT Pub. Date Nov. 17, 2016.
Claims priority of application No. 15167357 (EP), filed on May 12, 2015.
Prior Publication US 2018/0134633 A1, May 17, 2018
Prior Publication US 2018/0346392 A9, Dec. 6, 2018
Int. Cl. C05G 3/90 (2020.01); C07C 337/08 (2006.01); C05C 3/00 (2006.01); C05C 9/00 (2006.01); C05F 11/00 (2006.01); C07C 317/08 (2006.01); C07D 221/04 (2006.01); C07D 233/42 (2006.01); C05D 9/00 (2006.01); C07C 317/10 (2006.01); C07C 317/18 (2006.01); C07C 321/20 (2006.01); C07C 321/28 (2006.01); C07C 323/07 (2006.01); C07C 323/47 (2006.01); C07C 323/48 (2006.01); C07D 235/28 (2006.01); C07D 239/38 (2006.01); C07D 241/18 (2006.01); C07D 241/44 (2006.01); C07D 249/12 (2006.01); C07D 277/74 (2006.01); C07D 285/125 (2006.01); C07D 285/135 (2006.01); C07D 401/04 (2006.01); C07D 405/04 (2006.01); C07D 417/04 (2006.01); C07D 495/04 (2006.01)
CPC C05G 3/90 (2020.02) [C05C 3/00 (2013.01); C05C 9/00 (2013.01); C05D 9/00 (2013.01); C05F 11/00 (2013.01); C07C 317/08 (2013.01); C07C 317/10 (2013.01); C07C 317/18 (2013.01); C07C 321/20 (2013.01); C07C 321/28 (2013.01); C07C 323/07 (2013.01); C07C 323/47 (2013.01); C07C 323/48 (2013.01); C07C 337/08 (2013.01); C07D 221/04 (2013.01); C07D 233/42 (2013.01); C07D 235/28 (2013.01); C07D 239/38 (2013.01); C07D 241/18 (2013.01); C07D 241/44 (2013.01); C07D 249/12 (2013.01); C07D 277/74 (2013.01); C07D 285/125 (2013.01); C07D 285/135 (2013.01); C07D 401/04 (2013.01); C07D 405/04 (2013.01); C07D 417/04 (2013.01); C07D 495/04 (2013.01); Y02E 50/30 (2013.01); Y02P 60/21 (2015.11); Y02W 30/40 (2015.05)] 30 Claims
 
1. At least one thioether compound of formula I1,

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or a stereoisomer thereof, a salt thereof, a tautomer thereof, or an N-oxide thereof as nitrification inhibitor,
wherein
R1 and R2 are independently selected from the group consisting of H and C1-C2-alkyl;
and wherein
R3 is selected from the group consisting of (i) C(═N—OH)Ra and C(═N—Rx)NRcRd;
wherein
Ra is selected from the group consisting of H and C1-C2-alkyl;
Rc and Rd are independently selected from the group consisting of H and C1-C2-alkyl; and
Rx is

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wherein § marks the connection to the atom to which Rx is bonded; and
wherein V, W, Y, and Z each represent CH, and X is selected from the group consisting of CH and CRy,
wherein RY is selected from the group consisting of halogen, CN, C1-C2-alkyl, and C1-C2-alkoxy;
and wherein
m is one of 0, 1, and 2;
p is one of 1 and 2.
 
2. A method for reducing nitrification, the method comprising:
applying a composition comprising a compound of Formula (I), or a stereoisomer, a salt, a tautomer, or N-oxide thereof, to a locus where nitrification occurs, wherein

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R1 and R2 are independently selected from the group consisting of H and C1-C2-alkyl;
R3 is selected from the group consisting of:
(i) C(═O)Ra, C(═O)ORa, C(═O)NRcRd, C(═N—OH)Ra, C(═N—OH)NRcRd, C(═N—Rb)Ra, C(═N—Rb)NRcRd, C(═N—Rx)Ra, or C(═N—Rx)NRcRd;
(ii) C1-C8-alkyl, C3-C8-cycloalkyl, C2-C8-alkenyl, C3-C8-cycloalkenyl, or C2-C8-alkynyl, wherein the C-atoms of these groups optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, ORa, NO2, NRcRd, NRb(C═O)Ra, C(═O)Ra, C(═O)ORa, C(═O)NRcRd, S(O)nRa, and S(O)nNRcRd;
(iii) C6-C14-aryl, C5-C14-hetaryl, C6-C14-aryl-C1-C2-alkyl, or C5-C14-hetaryl-C1-C2-alkyl, wherein the aromatic moieties optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, Rx, ORa, SRa, NRcRd, NRb(C═O)Ra, NRb(C═O)NRcRd, C(═O)Ra, C(═O)ORa, C(═O)NRcRd, S(O)nRa, S(O)nNRcRd, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkylen-ORa, C1-C4-alkylen-NRcRd, C6-C10-aryl, C6-C10-aryl-C1-C2-alkyl, C5-C10-hetaryl, C5-C10-hetaryl-C1-C2-alkyl, C5-C10-carbocyclyl, C5-C10-carbocyclyl-C1-C2-alkyl, C5-C10-heterocyclyl, and C5-C10-heterocyclyl-C1-C2-alkyl, wherein the C6-C10-aryl, C5-C10-hetaryl, C5-C10-carbocyclyl, and C5-C10-heterocyclyl moieties optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, NO2, OH, SH, NH2, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-dialkylamino, and C1-C4-haloalkyl; and
(iv) C5-C14-carbocyclyl, C5-C14-carbocyclyl-C1-C2-alkyl, C5-C14-heterocyclyl, or C5-C14-heterocyclyl-C1-C2-alkyl, wherein the heterocyclyl rings optionally carry 1, 2, 3, 4, or 5 heteroatoms selected from the group consisting of O, S, and N, of which S and/or N are optionally oxidized, and wherein the carbocyclic or heterocyclic rings optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of ═O, ═S, halogen, CN, Rx, ORa, SRa, NO2, NRcRd, NRb(C═O)Ra, NRb(C═O)NRcRd, C(═O)Ra, C(═O)ORa, C(═O)NRcRd, S(O)nRa, S(O)nNRcRd, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkylen-ORa, C1-C4-alkylen-NRcRd, C6-C10-aryl, C5-C10-hetaryl, C5-C10-hetaryl-C1-C2-alkyl, C5-C10-carbocyclyl, C5-C10-carbocyclyl-C1-C2-alkyl, C5-C10-heterocyclyl, and C5-C10-heterocyclyl-C1-C2-alkyl, wherein the C6-C10-aryl, C5-C10-hetaryl, C5-C10-carbocyclyl, and C5-C10-heterocyclyl moieties optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, NO2, OH, SH, NH2, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-dialkylamino, and C1-C4-haloalkyl;
Ra is selected from the group consisting of H, C1-C8-alkyl, C1-C8-haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, and C5-C10-hetaryl or C6-C10-aryl, wherein the C5-C10-hetaryl or C6-C10-aryl moieties optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, OH, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C5-C6-hetaryl and C6-aryl, wherein said C5-C6-hetaryl and C6-aryl moieties optionally carry 1, 2, 3, 4, or 5 substituents selected from the group consisting of halogen, CN, OH, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C2-C4-alkenyl, and C2-C4-alkynyl;
Rb is selected from the group consisting of H, C1-C4-alkyl, C3-C8-cycloalkyl, C2-C4-alkenyl, C2-C8-alkynyl, and C6-C10-aryl;
Rc and Rd are independently of each other selected from the group consisting of H, C1-C4-alkyl, C1-C4-haloalkyl, C3-C8-cycloalkyl, C6-C10-aryl, and C5-C10-hetaryl;
or Rc and Rd together with the N-atom to which they are bonded form a 5- to 6-membered, saturated or unsaturated heterocycle, which optionally carries a further heteroatom selected from the group consisting of O, S, and N as a ring member atom, of which S and/or N are optionally oxidized, and wherein the heterocyclic ring optionally carries 1, 2, 3, 4, or 5 substituents, which are independently selected from the group consisting of halogen, CN, OH, NO2, C1-C4 alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy;
Rx is

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V, W, X, Y, and Z are independently selected from the group consisting of N, CH and CRy,
RY is selected from the group consisting of halogen, CN, NO2, OH, SH, NH2, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-dialkylamino, and C1-C4-haloalkyl;
m is 0, 1, or 2;
n is 0, 1, or 2; and
p is 0, 1, or 2.
 
19. A method for reducing nitrification, the method comprising:
applying a composition comprising a compound, or a stereoisomer, a salt, a tautomer, or N-oxide thereof, to a locus where nitrification occurs, wherein the compound is selected from the the group consisting of A-1, A-2, A-3, A-4, A-5, A-6, A-7, A-8, A-9, A-10, A-11, A-12, A-13, A-14, A-15, A-16, A-17, A-18, A-19, A-20, A-21, A-22, A-23, A-24, A-25, A-26, A-27, A-28, A-29, A-30, A-31, A-32, and A-33 as shown below:
 
 
 
No. Compound
 
 
 
A-1
 

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A-2
 

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A-3
 

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A-4
 

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A-5
 

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A-6
 

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A-7
 

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A-8
 

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A-9
 

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A-10
 

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A-11
 

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A-12
 

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A-13
 

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A-14
 

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A-15
 

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A-16
 

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A-17
 

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A-18
 

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A-19
 

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A-20
 

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A-21
 

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A-22
 

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A-23
 

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A-24
 

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A-25
 

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A-26
 

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A-27
 

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A-28
 

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A-29
 

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A-30
 

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A-31
 

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A-32
 

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A-33
 

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21. An agrochemical mixture comprising (i) at least one fertilizer; and (ii) at least one compound, or a stereoisomer, a salt, a tautomer, or N-oxide thereof, wherein the compound is selected from the group consisting of A-1, A-2, A-3, A-4, A-5, A-6, A-7, A-8, A-9, A-10, A-11, A-12, A-13, A-14, A-15, A-16, A-17, A-18, A-19, A-20, A-21, A-22, A-23, A-24, A-25, A-26, A-27, A-28, A-29, A-30, A-31, A-32, and A-33 as shown below:
 
 
 
No. Compound
 
 
 
A-1
 

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A-2
 

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A-3
 

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A-4
 

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A-5
 

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A-6
 

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A-7
 

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A-8
 

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A-9
 

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A-10
 

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A-11
 

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A-12
 

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A-13
 

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A-14
 

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A-15
 

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A-16
 

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A-17
 

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A-18
 

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A-19
 

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A-20
 

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A-21
 

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A-22
 

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A-23
 

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A-24
 

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A-25
 

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A-26
 

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A-27
 

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A-28
 

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A-29
 

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A-30
 

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A-31
 

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A-32
 

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A-33
 

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24. A method for treating a fertilizer, the method comprising:
applying a compound of Formula (I), or a stereoisomer, salt, tautomer or N-oxide thereof, to the fertilizer, wherein

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R1 and R2 are independently selected from the group consisting of H and C1-C2-alkyl;
R3 is selected from the group consisting of
(i) C(═O)Ra, C(═O)ORa, C(═O)NRcRd, C(═N—OH)Ra, C(═N—OH)NRcRd, C(═N—Rb)Ra, C(═N—Rb)NRcRd, C(═N—Rx)Ra, and C(═N—Rx)NRcRd;
(ii) C1-C8-alkyl, C3-C8-cycloalkyl, C2-C8-alkenyl, C3-C8-cycloalkenyl, or C2-C8-alkynyl, wherein the C-atoms of these groups optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, ORa, NO2, NRcRd, NRb(C═O)Ra, C(═O)Ra, C(═O)ORa, C(═O)NRcRd, S(O)nRa, and S(O)nNRcRd;
(iii) C6-C14-aryl, C5-C14-hetaryl, C6-C14-aryl-C1-C2-alkyl, or C5-C14-hetaryl-C1-C2-alkyl, wherein the aromatic moieties optionally carry 1, 2, 3, 4, or 5 identical or different substituents, selected from the group consisting of halogen, CN, Rx, ORa, SRa, NRcRd, NRb(C═O)Ra, NRb(C═O)NRcRd, C(═O)Ra, C(═O)ORa, C(═O)NRcRd, S(O)nRa, S(O)nNRcRd, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkylen-ORa, C1-C4-alkylen-NRcRd, C6-C10-aryl, C6-C10-aryl-C1-C2-alkyl, C5-C10-hetaryl, C5-C10-hetaryl-C1-C2-alkyl, C5-C10-carbocyclyl, C5-C10-carbocyclyl-C1-C2-alkyl, C5-C10-heterocyclyl, and C5-C10-heterocyclyl-C1-C2-alkyl, wherein the C6-C10-aryl, C5-C10-hetaryl, C5-C10-carbocyclyl, and C5-C10-heterocyclyl moieties that optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, NO2, OH, SH, NH2, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-dialkylamino, and C1-C4-haloalkyl; and
(iv) C5-C14-carbocyclyl, C5-C14-carbocyclyl-C1-C2-alkyl, C5-C14-heterocyclyl, or C5-C14-heterocyclyl-C1-C2-alkyl, wherein the heterocyclyl rings optionally carry 1, 2, 3, 4, or 5 heteroatoms selected from the group consisting of O, S, and N, of which S and/or N may optionally be oxidized, and wherein the carbocyclic or heterocyclic rings optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of ═O, ═S, halogen, CN, Rx, ORa, SRa, NO2, NRcRd, NRb(C═O)Ra, NRb(C═O)NRcRd, C(═O)Ra, C(═O)ORa, C(═O)NRcRd, S(O)nRa, S(O)nNRcRd, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkylen-ORa, C1-C4-alkylen-NRcRd, C6-C10-aryl, C6-C10-aryl-C1-C2-alkyl, C5-C10-hetaryl, C5-C10-hetaryl-C1-C2-alkyl, C5-C10-carbocyclyl, C5-C10-carbocyclyl-C1-C2-alkyl, C5-C10-heterocyclyl, and C5-C10-heterocyclyl-C1-C2-alkyl, wherein the C6-C10-aryl, C5-C10-hetaryl, C5-C10-carbocyclyl, and C5-C10-heterocyclyl moieties optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, NO2, OH, SH, NH2, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-dialkylamino, and C1-C4-haloalkyl;
Ra is selected from the group consisting of H, C1-C8-alkyl, C1-C8-haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl; C5-C10-hetaryl or C6-C10-aryl, wherein the C5-C10-hetaryl or C6-C10-aryl moieties optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, OH, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C5-C6-hetaryl and C6-aryl, wherein said C5-C6-hetaryl and C6-aryl moieties optionally carry 1, 2, 3, 4, or 5 substituents selected from the group consisting of halogen, CN, OH, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C2-C4-alkenyl, and C2-C4-alkynyl;
Rb is selected from the group consisting of H, C1-C4-alkyl, C3-C8-cycloalkyl, C2-C4-alkenyl, C2-C8-alkynyl, and C6-C10-aryl;
Rc and Rd are independently of each other selected from the group consisting of H, C1-C4-alkyl, C1-C4-haloalkyl, C3-C8-cycloalkyl, C6-C10-aryl, and C5-C10-hetaryl;
or Rc and Rd together with the N-atom to which they are bonded form a 5- to 6-membered, saturated or unsaturated heterocycle, which optionally carries a further heteroatom being selected from the group consisting of O, S, and N as a ring member atom, of which S and/or N are optionally oxidized, and wherein the heterocyclic ring optionally carries 1, 2, 3, 4, or 5 substituents, which are independently selected from the group consisting of halogen, CN, OH, NO2, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy;
Rx is

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V, W, X, Y, and Z are independently selected from the group consisting of N, CH and
CRy,
RY is selected from the group consisting of halogen, CN, NO2, OH, SH, NH2, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-dialkylamino, and C1-C4-haloalkyl;
m is 0, 1, or 2;
n is 0, 1, or 2; and
p is 0, 1, or 2.