Heterocyclic compounds such as pesticides, composition comprising them and their uses, as well as me

专利摘要:
new heterocyclic compounds as pesticides. The present application relates to novel amides and thioamides, processes for their preparation and their use for the control of animal pests, in particular arthropods and in particular insects.
公开号:BR112012026530B1
申请号:R112012026530-0
申请日:2011-04-11
公开日:2018-03-20
发明作者:Bretschneider Thomas；Köhler Adeline；Fischer Reiner；FÜßLEIN MARTIN；Jeschke Peter；Kluth Joachim；August Mühlthau Friedrich；Voerste Arnd；Malsam Olga；Görgens Ulrich；Sato Yoshitaka
申请人:Bayer Intellectual Property Gmbh；
IPC主号:

专利说明:

(54) Title: HETEROCYCLIC COMPOUNDS AS PESTICIDES, COMPOSITION OS
UNDERSTANDING AND ITS USES, AS WELL AS A METHOD FOR PEST PEST CONTROL (51) Int.CI .: C07D 401/04; C07D 417/04; C07D 417/14; A01N 43/78; A01N 47/02 (52) CPC: C07D 401/04, C07D 417/04, C07D 417/14, A01N 43/78, A01N 47/02 (30) Unionist Priority: 4/16/2010 US 61 / 325,094, 16 / 04/2010 EP 10160189.6 (73) Holder (s): BAYER INTELLECTUAL PROPERTY GMBH (72) Inventor (s): THOMAS BRETSCHNEIDER; ADELINE KÕHLER; REINER FISCHER; MARTIN FÜSSLEIN; PETER JESCHKE; JOACHIM KLUTH; FRIEDRICH AUGUST MÜHLTHAU; ARND VOERSTE; OLGA MALSAM; ULRICH GÓRGENS; YOSHITAKA SATO
1/42
Invention Patent Descriptive Report for: HETEROCYCLIC COMPOUNDS AS PESTICIDES, COMPOSING UNDERSTANDING THEM AND THEIR USES, AS WELL AS A METHOD FOR PEST CONTROL.
The present application relates to new amides and thioamides, processes for their preparation and their use to control animal pests, which include arthropods and especially insects.
Particular amides and thioamides have already become known as active compounds against insects (see DE 2221647, WO 2009/149858, WO 2010/129497).
In addition, the formula compound,
CH has already become known (CAS Registry No. 262855-20-9), but no use has been described for it.
Modern crop protection compositions have to meet many requirements, for example, regarding the level, duration and scope of their action and their possible use. Issues of toxicity and combinability with other active ingredients or auxiliary formulations play a role, as does the question of cost that synthesis of an active ingredient requires. In addition, resistance may occur. For all these reasons, the search for new crop protection compositions cannot be considered completed, and there is a constant need for new compounds that have properties that, compared to known compounds, are better at least in relation to individual aspects. .
It was an objective of the present invention to provide compounds that increase the spectrum of pesticides in several aspects.
This objective and other objectives that are not explicitly indicated, but that can be perceived or derived from the sequences discussed here, are achieved by new compounds of formula (I)
G ¹
Is
A ²
A ¹
(I) in which
A ¹ and A ² are each, independently, hydrogen, halogen, cyano, nitro, alkyl, cycloalkyl or alkoxy,
G ¹ is N or CA ¹ and
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G ² is a radical of the group of

in which the arrow indicates the connection with the adjacent ring,
R ¹ in the case of heterocycles (A) and (D) is hydrogen, halogen, cyano, alkyl, alkoxy, amino, alkylamino, dialkylamino, alkylthio or haloalkyl, and
R ¹ in the case of heterocycle (C) is hydrogen, alkyl or haloalkyl,
B is hydrogen, halogen, cyano, nitro, alkyl, cycloalkyl, haloalkyl, amino, alkylamino, dialkylamino, alkylthio or alkoxy and
G ³ is a radical of the group of (E) (F) (G) (H) (O) _n (O) _n , 10
NN 'l ₂ ' e
R R
N = S ^Z
R
Ιγ. '
X (i)
R
I 3 ^N ^ ^R
II (O) n (J) (°) n
II ^S K ^R (K) (°) n 'N (L) in which the arrow indicates the connection with G ² and the radicals (E), (F), (G), (Η), (K) and ( L) can be combined with heterocycles (A), (B), (C) and (D), radical (I) with heterocycle (A) and radical (J) with heterocycles (A), (C ) and (D).
X is oxygen or sulfur, n is 1 or 2,
R ² is a radical of the group of hydrogen, alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, alkenyl, alkoxyalkyl, alkylcarbonyl optionally substituted by halogen, alkoxycarbonyl optionally substituted by halogen, cycloalkylcarbonyl optionally substituted by halogen, alkyl, alkoxy, haloalkyl and cyano or a cation, for example a mono or divalent metal ion, or an ammonium ion optionally substituted by alkyl or arylalkyl,
R ³ and R ⁷ are each, independently, a radical of the alkyl, alkenyl, alkynyl group in each optionally substituted case, cycloalkyl, cycloalkylalkyl, cycloalkenyl in each case optionally substituted, in which the rings may contain at least one heteroatom of the group sulfur, oxygen (where the oxygen atoms cannot be immediately adjacent) and nitrogen, aryl, heteroaryl, arylalkyl and heteroarylalkyl in each case optionally substituted and an amino group optionally
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3/42 replaced,
R ² and R ³ may also form together with the NS (O) n group to which they are attached, a 4- to 8-membered, saturated or unsaturated and optionally substituted ring that may contain one or more other sulfur group heteroatoms, oxygen (where oxygen atoms cannot be immediately adjacent) and nitrogen and / or at least one carbonyl group,
R ⁴ and R ⁵ are each independently a radical of the alkyl, alkenyl, alkoxy, alkynyl group, in each case optionally substituted, cycloalkyl, cycloalkylalkyl, cycloalkenyl in each case optionally substituted, in which the rings may contain at least one heteroatom of the sulfur group, oxygen (where the oxygen atoms cannot be immediately adjacent) and nitrogen, aryl, heteroaryl, arylalkyl and heteroarylalkyl in each case optionally substituted and an optionally substituted amino group,
R ⁸ is a radical of the group of hydrogen, alkyl, alkenyl, alkoxy, alkynyl, in each case optionally substituted, cycloalkyl, cycloalkylalkyl, cycloalkenyl in each case optionally substituted, in which the rings may contain at least one hetero atom of the sulfur group, oxygen (where the oxygen atoms cannot be immediately adjacent) and nitrogen, aryl, heteroaryl, arylalkyl and heteroarylalkyl in each case optionally substituted and an optionally substituted amino group,
R ² and R ⁴ can also form together with the NC (X) group to which they are attached, a 4- to 8-membered, saturated or unsaturated and optionally substituted ring that can contain one or more other sulfur heteroatoms, oxygen (where the oxygen atoms cannot be immediately adjacent) and nitrogen and / or at least one carbonyl group,
R ² and R ⁵ can also form together with the NC (X) group to which they are attached, a 4- to 8-membered, saturated or unsaturated and optionally substituted ring that can contain one or more other sulfur heteroatoms, oxygen (where the oxygen atoms cannot be immediately adjacent) and nitrogen and / or at least one carbonyl group,
R ⁶ is hydrogen or alkyl,
R ² and R ⁶ may also form, together with the nitrogen atom to which they are attached, a 4- to 8-membered, saturated or unsaturated and optionally substituted ring that may contain at least one more sulfur heteroatom, oxygen (where oxygen atoms cannot be immediately adjacent) and nitrogen and / or at least one carbonyl group,
R ² and R ⁷ can also form together with the group NS (O) n in the radical (E) to which they are attached, a 4- to 8-membered ring, saturated or unsaturated and optionally substituted
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R ⁶ and R ⁷ can also form together with the NS (O) n group to which they are attached, 5 a 4- to 8-membered, saturated or unsaturated and optionally substituted ring that may contain one or more other sulfur group heteroatoms , oxygen (where the oxygen atoms cannot be immediately adjacent) and nitrogen and / or at least one carbonyl group,
R ² and R ⁸ may also form, together with the nitrogen atom to which they are attached, a 4- to 8-membered, saturated or unsaturated and optionally substituted ring that may contain one or more other sulfur heteroatoms, oxygen (where oxygen atoms cannot be immediately adjacent) and nitrogen and / or at least one carbonyl group,
L is oxygen or sulfur,
R ⁹ and R ¹⁰ are each independently a radical of the group of alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkyloxy, cycloalkenyloxy, cycloalkylalkoxy, alkylthio, alkenylthio, phenoxy, phenylthio, benzyloxy, benzylthio, hetero, hetero heteroarylalkoxy and heteroarylalkylthio, in each case optionally substituted,
R ⁹ and R ¹⁰ can also form together with the phosphorus atom to which they are attached a 5- to 7-membered, saturated or unsaturated and optionally substituted ring that can contain one or two heteroatoms of the oxygen group (where the oxygen atoms cannot be immediately adjacent) and sulfur, and
R ¹¹ and R ¹² are each independently a radical of the alkyl, alkenyl, alkynyl, phenyl and phenylalkyl group in each optionally substituted case.
and salts and N-oxides of the compounds of formula (I), with the proviso that R ⁷ in the group (F) is not methyl when G ¹ is CH, G ² is the radical (A), R ¹ is methyl, n is 2, X is oxygen and A ¹ , R ² and R ⁶ are each hydrogen.
In addition, it was also discovered that the new compounds of formula (I) can be obtained by the processes described below.
Depending on the G ³ radical, the compounds of formula (I) can be divided into substructures (Ie) to (Il).
Compounds of formula (Ie-g) can be prepared, for example, by reacting heterocyclic carboxylic acids of formula (II1) or acid chlorides thereof with amine derivatives of formula (IIIe-g).
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+ HN (HIe-g) where R ^{Co * * 13} is (O) _r (iii _E ) (O),
N ^ ^S R ⁷ or R ⁶ (lll _F )
L
Compounds of formula (h) can be prepared, for example, by reacting heterocyclic amines of formula ( ₁₂ ) with carboxylic acids of formula (11) or acid chlorides thereof.
Compounds of formula (lj) may be prepared, for example, by reacting heterocyclic amines of the formula (II ₂₎ with sulfonyl chlorides of formula (lllj).
Compounds of formula (1 _K ) can be prepared, for example, by reacting sulfonyl chlorides of formula (11 ₃ ) with amines of formula (11 _K ).
Compounds of formula (1 _L ) can be prepared, for example, by reacting sulfonyl chlorides of formula (11 ₃ ) with amides of formula (11 _{L L} ).
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R ² ι

Finally, it was discovered that the new compounds of formula (I) have very pronounced biological properties and are particularly suitable for controlling animal pests, especially insects, arachnids and nematodes (or nematodes), which are found in agriculture, in forests, in protection products and materials stored and in the hygiene sector.
The compounds of formula (I) may, where appropriate, depending on the nature of the substituents, be in the form of geometric and / or optically active isomers or corresponding mixtures of isomers in different compositions. The invention concerns both pure isomers and mixtures of isomers.
The compounds of the invention can also be present as metal complexes, as described for other amides, for example, in DE 2221647.
Preferred substituents or varieties of the radicals shown in the compounds of formula (I) are elucidated below.
A ¹ and A ² are each independently hydrogen, halogen, cyano, nitro, Ci-Cealkyl, Cs-Ce-cycloalkyl or Ci-Ce-cycloalkoxy.
G ¹ isNouC-A ¹ .
G ²
is a radical of the group of (A) (B)
N-N

in which the arrow indicates the connection to the adjacent ring.
R ¹ in the case of heterocycles (A) and (D) is hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-cycloalkoxy or Ci-Ce-haloalkyl.
R ¹ in the case of heterocycle (C) is hydrogen, Ci-Ce-alkyl or Ci-Ce-haloalkyl.
B is hydrogen, halogen, cyano, nitro, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-CePetição 870170085420, of 11/06/2017, p. 14/56
7/42 alkoxy, C3-C6-cycloalkyl.
G ³ is a radical of the group of
X <O>
(E) / S ^ 7
NR ⁷ '2
R ² (O) n
II
NN ^ R ⁷ l ₂ '6
R ² R ⁶ (F) (G) _R 1 (H) (I)
R ^NR
X
R ¹ 3 ^ < ^R3 (J) (O) n _R 2 (O) n 'V
I 2 _R 2 (K) (O) n (L)> - NR ⁵
I 2 _R 2 in which the arrow indicates the connection with G ² and the radicals (E), (F), (G), (H), (K) and (L) can be combined with heterocycles (A), (B), (C) and (D), the radical (I) with the heterocycle (A) and the radical (J) with the heterocycles (A), (C) and (D),
X is oxygen or sulfur.
n is 1 or 2.
R ² is a radical of the hydrogen group, C1-C6-alkyl, C1-C6-haloalkyl, cyano-C1C6-alkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C2-C6-alkenyl, C1-C6- alkoxy-C1-C6-alkyl, C1-C6alkylcarbonyl optionally substituted by halogen, C1-C6-alkoxycarbonyl optionally substituted by halogen, C3-C6-cycloalkylcarbonyl optionally substituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1- C6-haloalkyl and cyano, or a cation, for example, a mono or divalent metal ion or an ammonium ion optionally substituted by C1-C6-alkyl or aryl-C1-C6-alkyl.
R ³ and R ⁷ are each independently a radical of the group of C1-C6-alkyl, C2-C6alkenyl, C2-C6-alkynyl in each case optionally substituted by halogen, C1-C6alkoxy, C1-C6-haloalkoxy, C1-C6 -alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6-alkylsulfonyl and C1-C6-haloalkylsulfonyl, C3-C6-cycloalkyl, C3-C6-cycloalkenyl each optionally C6-alkyl, C1-C6haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy, in which the rings may contain at least one sulfur group heteroatom, oxygen (where the oxygen atoms cannot be immediately adjacent) and nitrogen (And, especially
The where the arrow in each case indicates the bond to the sulfur atom in the radicals (E), (F) and J)), aryl, heteroaryl, aryl-C1-C6-alkyl, heteroaryl-C1-C6-alkyl in each case optionally
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8/42 substituted by halogen, cyano (including alkyl), nitro, C1-C6-alkyl, C1-C6haloalkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio , C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, amino, C1-C6-alkylamino, di (C1-C6-alkyl) amino, C1 -C6-alkylcarbonylamino, C1-C6alkoxycarbonylamino, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-haloalkoxy-C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl -C1-C6-alkyl, C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl or aminocarbonyl, or NR'R '' in which R 'and R ”are each independently a radical of the hydrogen group, C1-C6-alkyl , C1-C6-haloalkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6alkylcarbonyl and C1-C6-alkoxycarbonyl.
R ² and R ³ can also form together with the NS (O) n group to which they are attached, a 5- to 7-membered ring saturated or unsaturated and optionally substituted by halogen, C1-6 alkyl, C1-6 haloalkyl, C1- C6-alkoxy, Ci-C6-haloalkoxy which can contain one or more other heteroatoms of the sulfur group, oxygen (where the oxygen atoms cannot be immediately adjacent) and nitrogen and / or at least one carbonyl group; R ² and R ³ may especially, together with the group NS (O) n to which they are attached, be a radical of the group of / O) _n //
NS (O) _n
N-S
N-S
> ( ^O ) n
N-S
NS (O) _n ^ ^O) n
NS (in which the arrow again in each case indicates the connection with G ² ).
R ⁴ and R ⁵ are each independently a radical of the group of C 1 -C 6 alkyl, C 1-C 6 alkoxy, C 2-C 6-alkenyl and C 2-C 6-alkynyl in each case optionally substituted by halogen,
C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6-alkylsulfonyl or C1-C6-haloalkylsulfonyl, C3-C6-C6- cycloalkyl, C3-C6cycloalkyl-C1-C6-alkyl, C3-C6-cycloalkenyl in each case optionally substituted by halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy, in which rings may contain at least one sulfur group heteroatom, oxygen (where the oxygen atoms cannot be immediately adjacent) and nitrogen, aryl, heteroaryl, aryl-C1-C6alkyl, heteroaryl-C1-C6-alkyl, in each if optionally substituted by halogen, cyano (including the alkyl portion), nitro, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6- alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, amino, C1-C6-alkylamino, di (Ci30 C6-alkyl) amino, C1-alkyl -alkylcarbonylamino, C1-C6-alkoxycarbonylami no, C1-C6-alkoxy-C1-C6alkyl, C1-C6-haloalkoxy-C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl-Ci-C6alkyl, Ci-C6- alkylcarbonyl, C1-6 alkoxycarbonyl or aminocarbonyl or NR'R '' where R 'and R' 'are
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9/42 each independently a radical of the hydrogen group, C1-C6-alkyl, C1-C6haloalkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-alkylcarbonyl and C1-C6-alkoxycarbonyl.
R ⁸ is a radical of the hydrogen group, C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl and C2-C6-alkynyl in each case optionally substituted by halogen, C1-C6-alkoxy, C1-C65 haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1C6-alkylsulfonyl or C1-C6-haloalkylsulfonyl, C3-C6-cycloalkyl-C3-cycloalkyl-C3-cycloalkyl-C3-cycloalkyl C6-alkyl, C3C6-cycloalkenyl in each case optionally substituted by halogen, C1-C6-alkyl, C1-C6haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy, in which the rings may contain at least one heteroatom of the group of the group sulfur, oxygen (where the oxygen atoms cannot be immediately adjacent) and nitrogen, aryl, heteroaryl, aryl-C1-C6-alkyl, heteroaryl-C1-C6alkyl, in each case optionally substituted by halogen, cyan, (including the portion alkyl), nitro, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkyl, C1-C6 -alkylsulfinyl, C1-C6-haloalkylsu lfinyl, C1-C6alkylsulfonyl, C1-C6-haloalkylsulfonyl, amino, C1-C6-alkylamino, di (C1-C6-alkyl) amino, C1-C615 alkylcarbonylamino, C1-C6-alkoxycarbonylamino, C1-C6-alkoxy-C1-alkoxy-C1 -alkyl, C1-C6-haloalkoxyC1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl-C1-C6-alkyl, C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl or aminocarbonyl , or NR'R ”where R 'and R” are each independently a radical of the hydrogen group, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6cycloalkyl, C1-C6-alkoxy, C1-C6-alkylcarbonyl and C1-C6-alkoxycarbonyl.
R ² and R ⁴ can also form together with the NC group (X) to which they are attached, a 5- to 7-membered ring saturated or unsaturated and optionally substituted by halogen, C1C6-alkyl, C1-C6-haloalkyl, C1-C6 -alkoxy, C1-C6-haloalkoxy which may contain one or more other heteroatoms of the sulfur group, oxygen (where the oxygen atoms cannot be immediately adjacent) and nitrogen and / or at least one carbonyl group; R ² and R ⁴ may especially, together with the NC group (X) to which they are attached, be a radical of the group of the

z ^ O
XXX (where the arrow again in each case indicates the connection with G ² ).
R ² and R ⁵ can also form together with the NC group (X) to which they are attached, a 5- to 7-membered ring saturated or unsaturated and optionally substituted by halogen, C1C6-alkyl, C1-C6-haloalkyl, C1-C6 -alkoxy, C1-C6-haloalkoxy which may contain one or more other heteroatoms of the sulfur group, oxygen (where the oxygen atoms cannot be immediately adjacent) and nitrogen and / or at least one carbonyl group; R ² and R ⁵ can
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especially, together with the N-C (X) group to which they are attached, be a radical of the group of

X (where the arrow in each case indicates the bond to the sulfur atom in the radical (L)).
R ⁶ is hydrogen or C1-C6-alkyl.
R ² and R ⁶ can also form, together with the nitrogen atom to which they are attached, a 5- to 7-membered ring, saturated or unsaturated and optionally substituted by halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1- C6-alkoxy, C1-C6-haloalkoxy which may contain at least one other heteroatom of the sulfur group, oxygen (where the oxygen atoms cannot be immediately adjacent) and nitrogen and / or at least one carbonyl group; R ² and R ⁶ may especially, together with the group NN to which they are attached, be a radical of the group of ⁽ O!
N-N
SR ' ⁽ O!
N-N
SR ' ⁽ O!
N-N
S-R '
X ⁽ O _ ₇
S — R
N-N
The _z SR ⁷
N-N
(in which the arrow again in each case indicates the connection with G ² ).
R ² and R ⁷ can also form, in the case where G ³ is (E), together with the NS (O) n group to which they are attached, a 5- to 7-membered ring, saturated or unsaturated and optionally substituted by halogen , C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy which may contain one or more other sulfur hetero atoms, oxygen (where the oxygen atoms cannot be immediately adjacent) and nitrogen and / or at least one carbonyl group; R ² and R ⁷ may especially, together with group NS (O) n to which they are attached, be a radical of the group of the
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11/42 'NS ζ' _N _Z 'ν. > ° ' ^η
N-S
N — S ι ° ’S-Z’ ν> ° ’
N-S (where the arrow in each case indicates the link with the group C (X)).
R ⁶ and R ⁷ can also form, in the case where G ³ is (F), together with the NS group (°) n to which they are attached, a 5- to 7-membered ring, saturated or unsaturated and optionally substituted by halogen , C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy which may contain one or more other sulfur hetero atoms, oxygen (where the oxygen atoms cannot be immediately adjacent) and nitrogen and / or at least one carbonyl group; R ⁶ and R ⁷ may especially, together with group NS (°) n to which they are attached, be a radical of the group of
R ²
N ^ ° ’n N-S
R ^{2 N} Z '
N-S
R ²
N ^ ° ’n
N-S
-N Z (° ’
N-S
X Z ’
N-S
R ²
X Z ’
N-S (where the arrow in each case indicates the link with the group C (X)).
R ² and R ⁸ can also form together with the nitrogen atom to which they are attached, a 5- to 7-membered ring, saturated or unsaturated and optionally substituted by halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1- C6-alkoxy, C1-C6-haloalkoxy which may contain one or more other heteroatoms of the sulfur group, oxygen (where the oxygen atoms cannot be immediately adjacent) and nitrogen and / or at least one carbonyl group; R ² and R ⁸ may especially, together with the nitrogen atom to which they are attached, be a radical of the group of tt ° S (in which the arrow in each case indicates the bond with the sulfur atom in the radical (K)) .
L is oxygen or sulfur.
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R ⁹ and R ¹⁰ are each independently a radical of the group of C1-C-alkyl, C2-C6 alkenyl, C2-C6-alkynyl, C1-C-alkoxy, C2-C6-alkynyl, C2-C6-alkenyloxy, C2- C6-alkynyloxy, C3-C6cycloalkyl, Cs-Ce-cycloalkyloxy, Cs-Ce-cycloalkenyloxy, Cs-Ce-cycloalkyl-Ci-Ce-alkoxy, Ci-Cealkylthio, C2-C6-alkenylthio, phenoxy, phenylthio, benzyloxy, benzyl, benzyloxy, benzyl heteroaryloxy, heteroarylthio, heteroaryl-Ci-Ce-alkoxy and heteroaryl-Ci-Ce-alkylthio in each case optionally substituted by halogen.
R ⁹ and R ¹⁰ can also form together with the phosphorus atom to which they are attached, a 5- to 7-membered ring, saturated or unsaturated and optionally substituted by halogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci- Ce-alkoxy, Ci-Ce-haloalkoxy which may contain one or two heteroatoms of the oxygen group (where the oxygen atoms cannot be immediately adjacent) and sulfur; R ⁹ and R ¹⁰ may especially, together with the phosphorus atom to which they are attached, the 0 radical being the
(in which the arrow indicates the bond with 0 nitrogen atom in the radical (G)).
R ¹¹ and R ¹² are each independently a radical of the group of C 1 -C-alkyl, C 2 -C 6 alkenyl and C 2-C 6 -alkynyl, phenyl and phenyl-C 1 -C-alkyl in each case optionally substituted by halogen, C 1 -C -alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy.
Particularly preferred substituents or varieties of the radicals shown in the compounds of formula (I) are elucidated below.
A ¹ is hydrogen, halogen or cyan and A ¹ is especially a radical in the group of hydrogen, fluorine and chlorine.
² is hydrogen.
G ¹ is N or CA ¹ , and G ¹ is especially a radical of the group of N, CH, CF and C-CI. G ² is a radical of the group of
(A) (B)
N-N

G ³ in which the arrow indicates the connection with the adjacent ring.
R ¹ is hydrogen or C 1 -C 4 -alkyl and R ¹ is especially hydrogen or methyl. B is hydrogen, it is a radical of the group of
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13/42
X (°> n (E) (I) (O) n
N (L) in which the arrow indicates the connection with G ² and the radicals (E) and (L) can be combined with the heterocycles (A), (B), (C) and (D), and the radical (I) with the heterocycle (A).
X is oxygen.
n is 2.
R ² is a radical of the hydrogen group, C1-C4-alkyl and C1-C4-alkoxy-C1-C4-alkyl, C1-C4alkylcarbonyl optionally substituted by halogen, C1-C4-alkoxycarbonyl optionally substituted by halogen, C3-C6- cycloalkylcarbonyl optionally substituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl and cyano, or a cation, for example, a mono or divalent metal ion or an ammonium ion optionally substituted by C1-C4- alkyl, or aryl-C1-C4-alkyl; R ² is especially a radical of the group of hydrogen, methyl, ethyl, CH2OCH3, CH2OCH2CH3, COCH3, COCH2CH3, cyclopropyl, Na +, K + and + NMe4.
R ⁴ is a radical of the group of C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, di-C1-C4alkylamino and heteroaryl-C1-C4-alkyl and R ⁴ is especially a radical of the group of methyl , ethyl, isopropyl, CH2CF3, CH2CF2CH3, cyclopropyl, dimethylamino and CH2- (2-pyrimidyl).
R ⁵ is a radical of the group of C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, di-C1-C4alkylamino and heteroaryl-C1-C4-alkyl and R ⁵ is especially a radical of the group of methyl , ethyl, isopropyl, CH2CF3, CH2CF2CH3, cyclopropyl, dimethylamino and CH2- (2-pyrimidyl).
R ⁷ is a radical of the group of C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, in each case optionally substituted by halogen, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-haloalkylsulfinyl, C1-C4alkylsulfonyl, and C1-C4-haloalkylsulfonyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C4-C4 -cycloalkenyl in each case optionally substituted by halogen, C1-C4alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, in which the rings may contain at least one heteroatom of the sulfur group, oxygen (where oxygen atoms cannot be immediately adjacent) and nitrogen (and especially
O (in which the arrow indicates in each case the bond with the sulfur atom in the radical (E)), aryl, heteroaryl, aryl-C1-C4-alkyl and heteroaryl-C1-C4-alkyl in each case optionally substituted by halogen , cyano, (including alkyl), nitro, C1-C4-alkyl, C1-C4haloalkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4Petition 870170085420 , of 06/11/2017, p. 21/56
14/42 haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-haloalkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4haloalkylsulfonyl, amino, C1-C4-alkylamino, di (C1-C4-alkyl) amino, C1-C4alkylcarbonylamino -C4-alkoxycarbonylamino, C1-C4-alkoxy-C1-C4-alkyl, C1-C4haloalkoxy-C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl-Ci-C4-alkyl ,
C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl or aminocarbonyl, or NR'R '' in which R 'and R''are each independently a radical of the hydrogen group and C1-C4-alkyl, and R ⁷ is especially a radical from the group of methyl, ethyl, i-propyl, CF3, CHF2, CH2f, CH2CF3, cyclopropyl, dimethylamino, diethylamino, phenyl and benzyl.
In the preferred definitions, unless otherwise specified, halogen is selected from the group of fluorine, chlorine, bromine and iodine, preferably, in turn, from the group of fluorine, chlorine and bromine, the aryl group (including as part of a unit greater, for example, arylalkyl) is selected from the group of phenyl, naphthyl, anthryl, phenanthrenyl, and is preferably phenyl, the hetaryl group (including as part of a larger unit, for example hetarylalkyl) 15 is selected furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4 -oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4 - thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl , pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, benzofuryl, benzisofuryl, benzothienyl, benzisothienyl, indolyl, isoindolyl, indazolyl, benzothiazolyl, benzisotol , benzoxazolyl, benz isoxazolyl, benzimidazolyl, 2,1,3-benzoxadiazole, quinolinyl, isoquinolinyl, cinolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, benzotriazinil, purinil, pteridinyl and indolizinil.
In particularly preferred definitions, unless otherwise stated, halogen is selected from the group of fluorine, chlorine, bromine and iodine, preferably, in turn, from the group of fluorine, chlorine and bromine, the aryl group (including as part of a larger unit, for example, arylalkyl) is selected from the group of phenyl, naphthyl, anthryl, phenanthrenyl, and is preferably in turn phenyl, the hetaryl group (including as part of a larger unit, for example hetarylalkyl) is selected from the pyrimidyl, oxadiazolyl, oxazolyl, pyrazinyl, imidazolyl, thiazolyl and furanyl group.
Halogen-substituted radicals, for example, haloalkyl, are mono or polyhalogenated, up to the maximum number of possible substituents. In the case of polyhalogenation, the halogen atoms can be the same or different. In this case, the halogen is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine.
Preference and special preference is given to each of the compounds having the specified and particularly preferred substituents.
Saturated or unsaturated hydrocarbon radicals, such as alkyl or alkenyl, may in each case be straight or branched as much as possible, including in combination
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Optionally substituted radicals can be mono- or poly-substituted, where the substituents, in the case of poly-substitution, can be the same or different.
In the radicals (A), (B), (C) and (D), which G ² can represent, the arrow in each case indicates the connection with the adjacent ring.
The definitions or illustrations of radicals given above in general terms or in areas of preference apply to final products and, correspondingly, to raw materials and intermediate products. These radical definitions can be combined with each other as desired, that is, including combinations between the respective preferred varieties.
Preference is given, according to the invention, for compounds of formula (I) in which the combination of the definitions listed above as being preferred is present.
Particular preference is given, according to the invention, for the compounds of formula (I) in which the combination of the definitions listed above as being particularly preferred is present.
In an emphasized group of compounds of the invention, G ² is the radical (A).
In a more emphasized group of compounds of the invention, G ² is the radical (B). In a more emphasized group of compounds of the invention, G ² is the radical (C). In a more emphasized group of compounds of the invention, G ² is the radical (D). In a more emphasized group of compounds of the invention, X is oxygen.
In a more emphasized group of compounds of the invention, X is sulfur.
In a more emphasized group of compounds of the invention, G ¹ is CH.
In a more emphasized group of compounds of the invention, G ¹ is CF.
In a more emphasized group of compounds of the invention, G ¹ is nitrogen. In a more emphasized group of compounds of the invention, A ¹ is hydrogen. In a more emphasized group of compounds of the invention, A ² is hydrogen. In a more emphasized group of compounds of the invention, n is 2.
In a more emphasized group of compounds of the invention, R ¹ is hydrogen. In a more emphasized group of compounds of the invention, R ¹ is methyl.
In a more emphasized group of compounds of the invention, R ¹ is fluorine.
In a more emphasized group of compounds of the invention, G ³ is the radical (E). In a more emphasized group of compounds of the invention, G ³ is the radical (I). In a more emphasized group of compounds of the invention, G ³ is the radical (L).
The preparation of the compounds of the invention of formula (I) in which G ² is the radical (A) and 35 of the corresponding precursors is elucidated in the following reaction schemes.
Reaction scheme 1
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OH (O) _r (HI _e )
R ²
H-N 1 '
R (HIe-g) n ^ ^S r ⁷ or R ⁶ (lll _F )
L
The compounds of formula (I _E -g) can be prepared, for example, by reacting 5 heterocyclic carboxylic acids of formula (1h) or the corresponding acid chlorides with amine derivatives of formula (IIIe-g).
The acids of formula (lh) in which G ² represents the radicals (A), (B) and (C), which are needed as raw materials, can be prepared in a manner analogous to the methods described in WO 2009/149858.
The acids of formula (lh) in which G ² is the radical (D), which are needed as raw materials, can be prepared in a manner analogous to the methods described for G ¹ = CH and R ¹ = H in the Journal of Heterocyclic Chemistry (Journal of Heterocyclic Chemistry) 1981, 18, 914 and Journal of Organic Chemistry (Journal of Organic Chemistry) 2004, 69, 5578-5587.
The amine derivatives of formula (IIIe-g) needed as raw materials are known or can be prepared by methods, in principle, known.
The acids of the formula (lh) can react, after activation, for example, to produce acid chloride (see, for example, Bioorg & MedChem Letters 15, 4354 (2005)), or by means of activation reagents such as CDI (carbonyl-diimidazole; see, for example, Bioorg & MedChem 9, 1543 (2001)), EDC (1-ethyl-3- [3-dimethylaminopropyl] carbodiimide), in the presence of DMAP (dimethylaminopyridine; see, for example , J. Med. Chem. 50, 3101 (2007)), or DCC (dicyclohexylcarbodiimide) in the presence of HOBT (1-hydroxybenzotriazole; see, for example, J. Med. Chem. 50, 3101 (2007)), with sulfonamides of general formula (II _E ), optionally in the presence of a base such as a metal hydride (especially sodium hydride) or DBU (diazabicycloundecene), to give the compounds of the invention of structural formula (I _E ), wherein X is oxygen.
The additional radicals mentioned for R ¹³ can be prepared from the acids of formula (lh) or their acid chlorides, using methods available in the literature, or in a manner similar to these methods, for example, with compounds of formula (IIIf ) according to Chem. Letters 36, 1370 (2007) or J. Med. Chem. 29, 1299 (1986) to generate the compounds of the invention of general formula (1 _F ) and, for example, with compounds of
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formula (IIIg) according to J. Org. Chem. 72, 465 (2007) or Phosphorus & Sulfur 20, 93 (1984) to generate the compounds of the invention of formula (Ig).
Reaction scheme 2
G ¹ τ,
A ²
A ¹
g! , Oh
Tf
O
G ¹
A ^{2 N}
A ¹
O
NH ₂
R o = s ^z (iiIh) 12 _R 12 12 _R 12 (II1) (| Ih)
Compounds of formula (Ih) can be prepared, for example, by reacting heterocyclic carboxamides of formula (IIh) with sulfoxides of general formula (IIIh) by methods described in the literature or similar methods; see, for example, patent WO 2008/154528.
The carboxamides of formula (IIh) required as raw materials can be prepared from the acids (II1) or their acid chlorides by methods described in the literature or by analogous methods, for example, as described in WO patents
2007/103755 or US 2009/203657.
Reaction scheme 3
HO— ^(| i)
G1
N
A ^{2 N}
G2 (II)
A ¹
G ¹
NH
A ² (ll ₂ ) (O) n ci — s (lllj) (O) n
A ^{2 N} (Ij)
Compounds of formula (Ii) in which X is oxygen can be prepared, for example, by reacting heterocyclic amines of formula (II2) with carboxylic acids of formula (IIIi) or acid chlorides thereof.
The heterocyclic amines of formula (II2), in which G ² is the radical (A), which are necessary as raw materials, can be prepared, for example, in a manner analogous to the methods described in US patents 2006/14700, WO 2004 / 41813 and US 4,528,291.
The heterocyclic amines of formula (II2), in which G ² is the radical (C), which are necessary as raw materials, can be prepared, for example, in a manner analogous to the methods described in Bioorg. & Med. Chem. Let. 1211-1214 (2000), J. Chem. Res. 227249 (1992) and Synth. Comm. 311-342 (1999).
The heterocyclic amines of formula (II2), in which G ² is the radical (D), which are necessary as raw materials, can be prepared, for example, in a similar way
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The carboxylic acids of formula (IIIi) needed as raw materials are known or can be prepared by methods, in principle, known.
The acids of formula (IIIi) can be converted to acid chlorides. Further reaction with amines of formula (II2) in a diluent, for example, dichloromethane or tetrahydrofuran, and in the presence of a base, for example, triethylamine or diisopropylethylamine, leads to the compounds of the invention of formula (Ii) where X is oxygen. The compounds of formula (Ii) can also be prepared directly from the acids of formula (IIIi) by reaction with amines of formula (II2) in the presence of coupling agents, for example, EDC (1-ethyl-3- hydrochloride) [3-dimethylaminopropyl] carbodiimide), DCC (dicyclohexylcarbodiimide) or BoPCl (bis (2-oxo-3-oxazolidinyl) phosphoryl chloride).
Compounds of formula (Ij) can be prepared, for example, by reacting the heterocyclic amines of formula (II2) with sulfonyl chlorides of formula (IIIj) in the presence of a base, for example, pyridine or sodium hydroxide; see, for example, WO 2007/114532 and US 2006/211603.
The chlorosulfinyl or chlorosulfonyl derivatives of formula (IIIj) needed as raw materials are known or can be prepared by methods, in principle, known.
Reaction scheme 4
R ²
R
G ^ XsA, * n a.
A ^{2 N} ( ^I k)
G ¹
A ^{2 N}
R ^G y ^N ( ^O ) n (Il)
Compounds of formula (Ik) can be prepared, for example, by reacting the sulfonyl chlorides of formula (II3) with amines of formula (IIIk), optionally in the presence of a base, for example, pyridine or triethylamine, in a similar way to methods described in US patents 6,265,411, WO 2007/114532 or US 6,673,817.
The heterocyclic sulfonyl chlorides of formula (II2) in which n is 2, and G ² is the radical (A), which are necessary as raw materials, can be prepared, for example, in a manner analogous to the methods described in J. Het. Chem. 1017-1021 (1984), and in US patents 6,555,542 and US 2004/186134.
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The heterocyclic sulfonyl chlorides of formula (II2), in which n is 2 and G ² is the radical (B), which are necessary as raw materials, can be prepared, for example, in a manner analogous to the methods described in J. Chem. Res. 768-769 (2003), Straight. Com. 601606 (2002), Eur. J. Med. Chem. 3340-3344 (2009), Heterocycles 2211-2224 (1983), Boll.
Chim. Pharma. 161-166 (2000).
The heterocyclic sulfonyl chlorides of formula (II2), in which n is 2 and G ² is the radical (C), which are necessary as raw materials, can be prepared, for example, in a manner analogous to the methods described in J. Het. Chem. 1017-1021 (1984).
The heterocyclic sulfonyl chlorides of formula (II2), in which n is 2 and G ² is the radical 10 (D), which are necessary as raw materials, can be prepared, for example, in a manner analogous to the methods described in the patents WO 2009/29439, US 6103708, WO 2005/97162, Bioorg. Med. Chem. 6628-6639 (2006), Heterocycles 1967-1974 (2007), Tet.
Lett. 4026-4028 (2008), Russ. Chem. Bull. 2581-2584 (1996).
The amines of formula (IIIi) required as raw materials are known or can be prepared by methods, in principle, known.
The compounds of formula (Il), where X is oxygen can be prepared, for example, by reacting the sulfonyl chlorides of formula (II3) with amides of formula (IIIl) in the presence of a base, for example, sodium hydride or n-butyl lithium, analogous to the methods described in US2004 / 6143 or Org. Let. 3458-3461 (2009).
The amides of formula (IIIi) required as raw materials are known or can be prepared by methods, in principle, known.
The compounds of formula (Ie-h), (Ii) and (Il) in which X is sulfur can be prepared from the corresponding compounds of formula (Ie-h), (Ii) and (Il), in which X is oxygen by reacting with a thionation reagent. The sulphidating agents (thioning reagents) used are preferably phosphorous reagents, for example, diphosphorus pentasulfide (P2S5), diphosphorus / pyridine pentasulfide (P ₂ S5 / Py), diphosphorus pentasulfide / triethylamine (P ₂ S5 / NEt3), diphosphorus pentasulfide / sodium bicarbonate (P ₂ S5 / NaHCO3 Scheeren's reagent), or more preferably 2,4-bis (4-methoxyphenyl) -2,4-dithioxy-1,3,2,4ditiadiphosphethane Lawesson's reagent (LR), 2,4-bis (4-phenoxyphenyl) -2,4-dithioxo-1,3,2,430 dithiadiphosphethane Belleau's reagent (BR) or 2,4-bis (4-phenylthiophenyl) -2, 4-dithioxo-1,3,2, 4ditiadiphosphethane.
N-oxides can be obtained, for example, by reacting compounds of formula (I) with mCPBA (meta-chloroperbenzoic acid). The salts of the compounds of formula (I) are obtainable by the reaction of compounds of formula (I) with compounds of formula RX in which
X is, for example, a halogen such as chlorine or bromine and R is, for example, an alkyl, alkenyl or alkynyl radical in each case optionally substituted.
The active principles of the invention, given good plant tolerance, favorable toxicity
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20/42 to homeotherms and good compatibility with the environment, they are suitable for the protection of plants and plant organs, to increase the yield of the harvest, to improve the quality of the harvested material and for the control of animal pests, especially insects, arachnids , helminths, nematodes and molluscs, which are found in agriculture, horticulture, animal husbandry, forests, gardens and leisure spaces, in the protection of stored products and materials, and in the hygiene sector. They can preferably be used in the form of crop protection compositions. They are active against normal and resistant sensitive species and against all or some stages of development. The aforementioned pests include:
Of the order Anoplura (Phthiraptera - lice), for example, Damalinia spp.,
Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.
Of the class of Arachnida (arachnids), for example, Acarus siro, Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae , Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Ornithchospp. Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici.
From the Bivalvia class, for example, Dreissena spp.
Of the order of Chilopoda (kilopods), for example, Geophilus spp., Scutigera spp. From the order of the Coleoptera (beetles), for example, Acanthoscelides obtectus,
Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apogonia spp., Atomaria spp.,
Attagenus spp., Bruchidius obtectus, Bruchus spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zealandica, Curculio spp., Cryptorhynchus lapathi, Dermestes spp., Diabrotica spp., Epbrilica spp. , Gibbium psylloides, heteronychus arator, Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Lachnosterna consanguinea, Leptinotarsa decemlineata, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp., Meltus spp., Meltus spp. , Naupactus xanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Otiorrhynchus sulcatus, Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp., Popillia japonica, Premnotrypes spp., Spil.
Sphenophorus spp., Sternechus spp., Symphyletes spp., Tenebrio molitor, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp.
From the Collembola order, for example, Onychiurus armatus.
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Of the order of the Dermaptera, for example, Forficula auricularia.
From the order of the Diplopoda (diplopods), for example, Blaniulus guttulatus.
Of the order of Diptera (diptera), for example, Aedes spp., Anopheles spp., Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata, Chrysomyia spp., Cochliomyia spp., 5 Cordylobia anthropophaga, Culex spp., Cuterebra spea. Dac , Dermatobia hominis,
Drosophila spp., Fannia spp., Gastrophilus spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liriomyza spp., Lucilia spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Stomoxys spp., Tabanus spp., Tannia spp., Tipula paludosa, Wohlfahrtia spp.
Of the Gastropoda (gastropod) class, for example, Arion spp., Biomphalaria spp.,
Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.
Of the helminth class, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubicoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchispp., Clonorchis Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Sphere, sp. ., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp., Strongyloides fuelleborni,
Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Native trichinella, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancr.
Control of protozoa, such as Eimeria, is also possible.
Of the order Heteroptera (heteropterans), for example, Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Dichocopsis, Diconocorisetti spp., Euschistus spp., Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Nezara spp., Oebalus spp., Pentomidae, Pies , Psallus seriatus, Pseudacysta persea,
Rhodnius spp., Sahlbergella singularis, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.
From the order of Homoptera (homopterans), for example, Acyrthosipon spp., Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui, Aonidiella spp. Aphostigma ., Arboridia apicalis,
Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Carneocephala fulgida, Ceratovacuna lanigera, Fr.
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Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp., Dyspis spp., Dorpis spp. spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus,
Geococcus coffeae, Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes Spp. dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga,
Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp. spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp., Scaphoides titanus,
Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurpodes spp. vitifolii.
From the order of Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp.,
Monomorium pharaonis and Vespa spp.
Of the order of the Isopods (isopods or isopods), for example, Armadillidium vulgare,
Oniscus asellus and Porcellio scaber.
Of the order of the Isoptera (termites and termites), for example, Reticulitermes spp. and Odontotermes spp.
Of the order of Lepidoptera (lepidoptera), for example, Acronicta major, Aedia leucomelas, Agrotis spp., Alabama argillacea, Anticarsia spp., Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius, Cacoecia podana, Capua reticulana, Carpocapsa pomonella, spp., Choristoneura fumiferana, Clysia ambiguella, Cnaphalocerus spp., Earias insulana, Ephestia kuehniella, Euproctis chrysorrhoea, Euxoa spp., Feltia spp., Galleria mellonella, Helicoverpa spp., Heliothis spp., Hommann Laphygma spp., Lithocolletis blancardella, Lithophane antennata, Loxagrotis albicosta, Lymantria spp., Malacosoma neustria, Mamestra brassicae, Mocis repanda, Mythimna separata, Oria spp., Oulema oryzae, Panolis flammea, Pectinophora spocn. xylostella, Prodenia spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, Spodoptera spp., Thermesia gemmatalis, Tinea p ellionella, Tineola bisselliella, Tortrix viridana, Trichoplusia spp.
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From the order of Orthoptera, for example, Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., American periplaneta, Schistocerca gregaria.
Of the order of Siphonaptera (fleas), for example, Ceratophyllus spp. and Xenopsylla 5 cheopis.
Of the order of the Symphyla (symphiles), for example, Scutigerella immaculata.
Of the order of Thysanoptera (thrips or lacerdinhas), for example, Baliothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothríps cruentatus, Scirtothothips spp.
Of the order of the Thysanura, for example, Lepisma saccharina.
Phytoparasitic nematodes include, for example, Anguina spp., Aphelenchoides spp., Belonoaimus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp., Heliocotylenchus spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Meloidogyne spp. , Radopholus similis, Rotylenchus spp., Trichodorus spp., Tylenchorhynchus spp.,
Tylenchulus spp., Tylenchulus semipenetrans and Xiphinema spp.
The compounds of the invention can also, at certain concentrations or rates of application, be used as herbicides, protective agents against phytotoxicity (safeners), growth regulators or agents to improve plant properties, or as microbicides, for example, as fungicides , antimycotics, bactericides, virucides (including agents against viroids) or as agents against MLO (organisms similar to mycoplasmas) and RLO (organisms similar to rickettsia (a genus of bacteria)). They can also be used as intermediates or precursors for the synthesis of other active ingredients.
The active ingredients can be converted into the usual formulations, such as solutions, emulsions, wettable powders, water and oil based suspensions, powders, dust, pastes, post-soluble, soluble granules, dispersion granules, suspension / emulsion concentrates , natural substances impregnated with the active ingredient, synthetic substances impregnated with the active ingredient, fertilizers and microencapsulations in polymeric substances.
These formulations are prepared in a known manner, for example, by mixing the active ingredients with diluents, that is, liquid solvents and / or solid vehicles, optionally with the use of surfactants, that is, emulsifiers and / or dispersants, and / or agents foam makers. The formulations are produced either in appropriate plants or before or during application.
The auxiliaries used can be those substances that are appropriate to give particular properties to the composition itself and / or to the preparations derived therefrom (for example, spray liquors, prepared for seed treatment), as
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24/42 certain technical properties and / or also particular biological properties. Typical auxiliaries include: thinners, solvents and vehicles.
Suitable diluents are, for example, water, polar and non-polar organic chemical liquids, for example, from the classes of aromatic and non-aromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes and chlorobenzenes), of alcohols and polyols (which, optionally, can substituted, etherified and / or esterified), ketones (such as acetone, cyclohexanone), esters (including fats and oils) and (poly) ethers, unsubstituted and substituted amines, amides, lactams (such as N-alkylpyrrolidones ) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide).
If the diluent used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Useful liquid solvents essentially include: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example, oil fractions, oils minerals and vegetables, alcohols such as butanol or glycol, as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone (butanone), methyl isobutyl ketone or cyclohexanone, highly polar solvents such as dimethyl sulfoxide, and water. Useful solid vehicles include:
for example, ammonium salts and flours of natural rocks, such as kaolin, clays, talc, chalk, quartz, atapulgite, montmorillonite or diatomaceous earth, and flours of synthetic rocks, such as finely divided silica, alumina and silicates; solid vehicles useful for granules include: for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic flours, and granules of organic material such as paper, sawdust , coconut shells, corn cobs and tobacco stalks; Useful emulsifiers and / or foaming agents include: for example, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example, polyalkyl glycyl alkyl ethers, alkyl sulfonates, alkyl, aryl sulfonates and also protein hydrolysates; Suitable dispersants are ionic and / or non-ionic substances, for example, from the POE and / or POP alcohol ethers class, POP and POE esters and / or acids, POP and POE and / or alkylaryl ethers, addition of fat and / or POP and POE, derivatives of POP and / or POE polyols, addition products of POE- and / or POP sorbitan or sugar, alkyl or aryl sulfates, alkyl or aryl sulfonates and alkyl phosphates or aryl or the corresponding PO ether addition products. In addition, oligomers or polymers, for example, those derived from vinyl monomers, from acrylic acid, from ethylene oxide and / or propylene oxide alone or in combination with, for example, (poly) alcohols are suitable or (poly) amines. It is also possible to
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25/42 use of lignin and its derivatives of sulfonic acid, modified and unmodified celluloses, aromatic and / or aliphatic sulfonic acids, as well as their addition products with formaldehyde.
In formulations, it is possible to use adhesion promoters such as 5 carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latex, such as arabic gum, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids, such as cephalins and lecithins and synthetic phospholipids.
It is possible to use dyes such as inorganic pigments, for example, iron oxide, titanium oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and metallic phthalocyanine dyes, and micro nutrients such as iron salts, manganese, boron, copper, cobalt, molybdenum and zinc.
Other additives can be perfumes, mineral or vegetable oils, optionally modified, waxes and nutrients (including micro nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Additional components can be stabilizers, such as cold stabilizers, preservatives, antioxidants, light stabilizers, or other agents that improve chemical and / or physical stability.
If applicable, the formulations and forms of use derived from it may also comprise additional auxiliaries. Examples of such additives include protective colloids, binding agents, adhesives, thickeners, thixotropic agents, penetrating agents, retention promoters, sequestrants, complexing agents, humectants, spreaders. In general, the active ingredients can be combined with any solid or liquid additive commonly used for formulation purposes.
Useful retention promoters include all those substances that reduce dynamic surface tension, for example, dioctyl sulfosuccinate, or increase viscoelasticity, for example, hydroxypropyl guar polymers.
Penetrating agents useful in the present context are all substances that are normally used to improve the penetration of the active agrochemicals in plants. In this context, penetrating agents are defined by their ability to penetrate, from the application liquor (usually aqueous) and / or from the spray layer, into the cuticle of the plant and, thus, increase the mobility of the principles active in the cuticle. The method described in the literature (Baur et al., 1997, Pesticide Science 51, 131-152) can be used to determine this property. Examples include alcohol alkoxylates, such as coconut fatty ethoxylate (10) or isotridecyl ethoxylate (12), fatty acid esters, for example, rapeseed oil methyl ester or soy oil methyl ester, fatty amine alkoxylates, for example, tallow amine ethoxylate (15), or ammonium and / or phosphonium salts, for example, ammonium sulphate or diPetition hydrogen phosphate 870170085420, from 11/06/2017, p. 33/56
26/42 diamonium.
The formulations generally contain between 0.01 and 98% by weight of the active ingredient, preferably between 0.5 and 90%.
The active principle of the invention can be present in its commercially available formulations and in its forms of use, prepared from these formulations, as a mixture with other active principles, such as insecticides, attractants, sterilizers, bactericides, acaricides, nematicides, fungicides , growth regulators, herbicides, phytotoxicity protection agents (safeners), fertilizers or semi-chemicals.
Mixing with other known active ingredients, such as herbicides, fertilizers, 10 growth regulators, phytotoxicity protection agents (safeners), semi-chemicals, or with agents to improve plant properties, is also possible.
When used as insecticides, the active ingredients of the invention can also be present in their commercially available formulations and in their forms of use, prepared from these formulations, as a mixture with synergistic agents. Synergistic agents are compounds that increase the action of the active ingredients, without any need for the added synergist to be active.
When used as insecticides, the active ingredients of the invention can also be present in their commercially available formulations and in their forms of use, prepared from these formulations, as a mixture with inhibitors that reduce the degradation of the active principle after its use in the environment of the plant, on the surface of parts of plants or in plant tissues.
The active ingredient content of application forms prepared from commercially available formulations can vary within a wide range. The active ingredient concentration of the application forms can be comprised between 0.00000001% to 95% by weight of the active principle, preferably between 0.00001% and 1% by weight.
The compounds are applied in the usual manner appropriate to the forms of use.
All plants and plant parts can be treated according to the invention. Plants are understood here to be all plants and plant populations, such as desired and unwanted wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants that can be obtained by conventional breeding and optimization methods, or by biotechnological and genetic engineering methods, or combinations of these methods, including transgenic plants and including the varieties of plants that are protected and not protected by rights of plant breeders. Plant parts are understood to mean all plant parts and organs located above and below ground, such as bud, leaf, flower and root, examples including leaves, stems, stems, trunks, flowers, flesh of fruits, fruits and
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The treatment of plants and parts of plants with the active ingredients of the invention is carried out directly or by their action in the environment surrounding the plants, habitat or storage area, by the usual treatment methods, for example, by immersion, spraying , evaporation, nebulization, spreading, coating, injection and, in the case of propagating material, in particular in the case of seeds, by the application of one or more layers of coating.
As already mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred configuration, species of wild plants and plant cultivars, or those obtained by conventional methods of biological reproduction, such as crossing or fusing protoplasts, as well as their respective parts, are treated. In another preferred configuration, transgenic plants and plant cultivars obtained by genetic engineering, if appropriate in combination with conventional methods (Genetically Modified Organisms) and their parts, are treated. The terms parts or parts of plants have already been explained above.
More preferably, plants of plant cultivars that are each commercially available or in use are treated according to the invention. Plant cultivars are understood to be those plants with new properties (characteristics) and which were obtained by conventional methods of reproduction, by mutagenesis or by recombinant DNA techniques. They can be cultivars, biotypes and genotypes.
Depending on the species of plants or plant cultivars, and their location and growing conditions (soils, climate, vegetation period, diet), the treatment of the invention can also result in superadditive (synergistic) effects. For example, possibilities include lower application rates and / or broadening of the activity spectrum and / or an increase in the activity of compounds and compositions usable according to the invention, better plant growth, greater tolerance to high or low temperatures , greater tolerance to drought or water levels or soil salinity, better flowering performance, easier harvesting, accelerated ripening, higher yields, higher quality and / or greater nutritional value of harvested products, increased storage time and / or the processing capacity of the harvested products, which exceed the effects normally expected.
Transgenic plants or plant cultivars (those obtained by genetic engineering) that are to be treated preferentially according to the invention include all plants that, through genetic modification, received genetic material that
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28/42 imparts particular advantageous useful properties (characteristics) to these plants. Examples of such properties are: better plant growth, greater tolerance to high or low temperatures, greater tolerance to drought or to water or soil salinity levels, better flowering performance, easier harvesting, accelerated maturation, higher yields, higher quality and / or greater nutritional value of the harvested products, better storage time and / or processing capacity of the harvested products. Other particularly emphasized examples of such properties are a better defense of plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or viruses, and also increased tolerance of plants to certain principles with herbicidal activity. Examples of transgenic plants include important crop plants, such as cereals (wheat, rice), corn, soybeans, potatoes, sugar beet, tomatoes, peas and other types of vegetables, cotton, tobacco, rapeseed, and also fruit plants (with the fruits of apples, pears, citrus fruits and grapes), with special emphasis on corn, soybeans, potatoes, cotton, tobacco and rapeseed. Characteristics that are particularly emphasized are: a better defense capacity of plants against insects, arachnids, nematodes, slugs and snails by toxins formed in plants, especially those formed in plants by the genetic material of Bacillus thuringiensis (for example, by the CryIA genes (the ), CrylA (b), CrylA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF, and also combinations thereof) (hereinafter referred to as plants
Bt). Characteristics that are also particularly emphasized are: a better defense of plants against fungi, bacteria and viruses by acquired systemic resistance (SAR), system, phytoalexins, elicitors and also the resistance genes and the corresponding proteins and expressed toxins. In addition, characteristics that are particularly emphasized are: a greater tolerance of plants to certain active herbicidal principles, for example, imidazolinones, sulfonylureas, glyphosate or phosphinothricin (for example, the PAT gene). The genes that confer the desired characteristics in question may also be present in combination with each other in transgenic plants. Examples of Bt plants include maize varieties, cotton varieties, soy varieties and potato varieties that are sold under the trade names YIELD GARD® (for example, corn, cotton, soy), KnockOut® (for example, corn) , StarLink® (for example, corn), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide tolerant plants include maize varieties, cotton varieties and soy varieties that are sold under the trade names Roundup Ready® (glyphosate tolerance, eg maize, cotton, soy), Liberty Link® (tolerance phosphinothricin, for example, rapeseed), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulfonylureas, for example corn). Plants with resistance to herbicides (plants grown in a conventional way to have tolerance to herbicides) that can be mentioned include the varieties
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29/42 marketed under the name Clearfield® (for example, maize). Of course, these statements also apply to plant cultivars that have these genetic characteristics or genetic characteristics that are yet to be developed and that will be developed and / or commercialized in the future.
The listed plants can be treated according to the invention in a particularly advantageous manner with the compounds of general formula (I) and / or with the mixtures of active ingredients according to the invention. The preferred ranges indicated above for the active ingredients or mixtures also apply to the treatment of these plants. Special emphasis is placed on the treatment of plants with the compounds or mixtures specifically mentioned in this text.
The active principles of the invention act not only against plant pests, hygiene conditions and stored products, but also in the veterinary medicine sector against animal parasites (ecto and endoparasites), such as hard ticks, soft ticks, scabies mites , mites, flies (biting / sucking and licking), larvae of parasitic flies, lice, hair lice, feather lice and fleas. These parasites include:
Of the order of Anoplura, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.
From the order of Mallophaga and suborders Amblycera and Ischnocera, for example, 20 Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp.
Of the order of Diptera and subordens Nematocera and Brachycera, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp.,
Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp. ., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.
Of the order of the Siphonaptera, for example, Pulex spp., Ctenocephalides spp.
(Ctenocephalides canis, Ctenocephalides felis), Xenopsylla spp. and Ceratophyllus spp.
Of the order of Heteroptera, for example, Cimex spp., Triatoma spp., Rhodnius spp. and
Panstrongylus spp.
From the Blattaria order, for example, Blatta orientalis, American Periplaneta, Blattella germanica and Supella spp.
From the subclass of Acari (Acarina) in and orders from Meta and Mesostigmata, for example,
Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus
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Of the order of Actinedida (Prostigmata) and Acaridida (Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp. ., Tyrophagus spp., Caloglyphus spp.,
Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.
The active principles of the invention of formula (I) are also suitable for the control of arthropods that attack domestic animals in agriculture, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, honey bees, other domestic animals such as, for example, dogs, cats, cage birds, aquarium fish, as well as experimental animals, for example, hamsters, guinea pigs (guinea pigs), rats and mice. The control of these arthropods is intended to reduce cases of death and reduced productivity (of meat, milk, wool, leather, eggs, honey, etc.), and thus the creation of animals in a more economical and easier way is possible through the use of the active ingredients of the invention.
The active principles of the invention are used in the veterinary sector and in animal husbandry in a known manner, by enteral administration in the form of, for example, tablets, capsules, potions, liquids, granules, pastes, cakes, through the feeding process and through suppositories, for parenteral administration, such as, for example, by injection (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal administration, through the skin in the form of, for example, immersion or bath, spray, pouring over or by topical use, washing and spraying, and also with the aid of molded objects containing the active principle, such as collars, ear tags, tail tags, bandages / bandages for limbs, halters, marking devices and the like .
When used in livestock, livestock, poultry, domestic animals and the like, the active ingredients of formula (I) can be used as formulations (for example, powders, emulsions, dispersible compositions) comprising the active ingredients in an amount from 1 to 80 % by weight, either directly, or after 100 to 10,000 times dilution, or they can be used as a chemical bath.
It has also been found that the compounds of the invention have an intense insecticidal action against insects that destroy industrial materials.
Preferred, but not limiting, examples include the following insects:
beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,
Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Specyl.
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Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec., Dinoderus minutus;
dermoptera, such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur;
termites (termites), such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus;
moths, such as Lepisma saccarina.
Industrial materials in the present context are understood to be those 10 inert materials such as, preferably, plastics, adhesives, glues, papers and cards, leather, wood, processed wood products and coating compositions.
Ready-to-use compositions can optionally also comprise other insecticides and, optionally, one or more fungicides.
With regard to possible additional mixing partners, reference is made to the insecticides and fungicides mentioned above.
At the same time, the compounds of the invention can be used to protect objects that come into contact with salt water or brackish water, especially hulls, screens, nets, buildings, anchorages and signaling systems, against fouling.
In addition, the compounds of the invention can be used as antifouling compositions, alone or in combinations with other active ingredients.
The active ingredients are also suitable for pest control in domestic animals, in the hygiene sector and in the protection of stored products, especially insects, arachnids and mites, which are found in enclosed spaces, for example, houses, factory corridors , offices, offices, vehicle cabins and the like. They can be used to control these pests, alone or in combination with other active and auxiliary ingredients in household insecticide products. They are effective against sensitive and resistant species, as well as against all stages of development. These pests include:
From the order of Scorpionidae, for example, Buthus occitanus.
From the order of the Acarina, for example, Argas persicus, Argas reflexus, Bryobia spp.,
Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae.
Of the order of Araneae, for example, Aviculariidae, Araneidae.
From the order of the Opiliones (harvestman), for example, Pseudoscorpiones chelifer,
Pseudoscorpiones cheiridium, Opiliones phalangium.
From the order of the Isopods (isopods), for example, Oniscus asellus, Porcellio scaber.
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Of the order of the Diplopoda (diplópoda), for example, Blaniulus guttulatus, Polydesmus spp.
Of the order of the Chilopoda (kilopods or centipedes), for example, Geophilus spp.
From the order of the Zygentoma, for example, Ctenolepisma spp., Lepisma saccharina, 5 Lepismodes inquilinus.
Of the order of Blattaria (cockroaches), for example, Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, American periplaneta, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.
From the order of the Saltatoria, for example, Acheta domesticus.
Of the order of the Dermaptera (dermápteros), for example, Forficula auricularia.
Of the order of the Isoptera (termites and termites), for example, Kalotermes spp., Reticulitermes spp.
From the order of Psocoptera, for example, Lepinatus spp., Liposcelis spp.
Of the order of Coleoptera (beetles), for example, Anthrenus spp., Attagenus spp.,
Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.
Of the order of the Diptera, for example, Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicular Sarcophaga carnaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa.
Of the order of Lepidoptera (lepidoptera), for example, Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
Of the order of the Siphonaptera (fleas), for example, Ctenocephalides canis,
Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
From the order of Hymenoptera (wasps, bees and ants), for example, Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
Of the order of Anoplura (lice), for example, Pediculus humanus capitis, Pediculus humanus corporis, Pemphigus spp., Phylloera vastatrix, Phthirus pubis.
Of the order of Heteroptera (bedbugs), for example, Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.
In the field of household insecticides, they are used alone or in combination with other suitable active ingredients, such as phosphoric esters, carbamates, pyrethroids, neonicotinoids, growth regulators or active ingredients of other known classes of insecticides.
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They are used in aerosols, non-pressurized spray products, for example, pump sprays or atomizers, automatic vaporization systems, nebulizers, foams, gels, evaporator products with evaporator tablets made of cellulose or plastic, liquid evaporators, evaporators gel and membrane, propeller-powered evaporators, passive or energy-free evaporation systems, paper, bags and gels (moth catch / fly catch) for moths / moths, such as granules or powders, in bait to spread or in traps.
Examples of Preparations
Example A: 3,3,3-Trifluoro-N- [4-methyl-2- (pyridin-3-yl) -1,3-thiazol-5-yl] propanamide
Phase 1: 4-Methyl-2- (pyridin-3-yl) -1,3-thiazol-5-amine

NH ₂
10.1 g (45.6 mmol) of 3- (4-methyl-5-nitro-1,3-thiazol-2-yl) pyridine (for preparation see DE 2221647) were dissolved in 100 ml of hydrochloric acid 10 % together with 10 ml of concentrated hydrochloric acid, and 25 g of tin (II) chloride dissolved in 10% hydrochloric acid were added in portions, and the mixture was stirred for 1 h (hour), during which heating occurred. The mixture was poured over ice / sodium hydroxide solution, and methyl-t-butyl ether, ethyl acetate and saturated sodium chloride solution were added. The mixture was extracted 4 times at pH = 10 with ethyl acetate, the combined organic phases were dried over MgSO4 and the mixture was concentrated. The residue was recrystallized from benzotrifluoride.
Yield: 7.27 g (79% of theory).
¹ H NMR (D6-DMSO): 2.2 (s, 3H), 5.4 (s, 2H), 7.45 (dd, 1H), 7.95 (d, 1H), 8.55 (m , 1H), 8.85 (s, 1H)
Phase 2: 3,3,3-Trifluoro-N- [4-methyl-2- (pyridin-3-yl) -1,3-thiazol-5-yl] propanamide
N
NH
Cl
N
Ή ' _S ^ NH ^S Á-F
F
286 mg (1.49 mmol) of 4-methyl-2- (pyridin-3-yl) -1,3-thiazol-5-amine were dissolved in THF, 0.52 ml of triethylamine were added, and 263 mg of trifluoropropionyl chloride was added at the same time as the mixture was cooled with an ice bath. The mixture was stirred at room temperature overnight and then concentrated. Ethyl acetate, saturated sodium chloride solution and an aqueous phosphate buffer pH = 7 were
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Yield: 308 mg (68% of theory), logP (HCOOH) 1.47 ¹ H NMR (CD3CN): 2.4 (s, 3H), 3.45 (q, 2H), 7.4 (dd, 1H ), 8.15 (d, 1H), 8.55 (m, 1H), 8.9 (br, 1H), 9.05 (s, 1H)
Example B: N- [4-Methyl-2- (pyridin-3-yl) -1,3-thiazol-5-yl] -2- (pyrimidin-2-yl) acetamide
N z
HO
250 mg (1.81 mmol) of 2-pyrimidyl acetic acid, 3.04 g (23.5 mmol) of di10 isopropylethylamine and 254.5 mg (2.17 mmol) of Bop chloride were stirred in 5 ml of acetonitrile at room temperature for 20 min, then 553 mg (2.17 mmol) of the aminothiazole were added and the mixture was stirred for an additional 12 h.
For processing, the reaction mixture was concentrated to 2-3 ml and purified on a silica gel chromatography column (eluent: dichloromethane).
Yield: 10 mg (2% of theory), logP ¹ ) (HCOOH) 0.74 ¹ H NMR ((CD3) 2SO): 2.45 (s, 3H), 4.14 (s, 2H), 7, 35-9.05 (m, 7H) ppm.
N
O + KN + ^α Μ> ₀
N
II s'
N
-S ^{= O}
O
112.8 mg (0.55 mmol) of 3-pyridyl boronic ester, 120.4 mg (0.50 mmol) of chlorothiazole and 18.3 mg (0.02 mmol) of 1,1'-bis chloride (diphenylphosphine) ferrocenepaladium (II) was initially loaded in 10 ml of dimethoxyethane in an argon atmosphere, 0.75 ml of 2 M potassium carbonate solution was added and the mixture was stirred at 80 ° C for 16 h.
For processing, the mixture was separated between water and ethyl acetate, and the organic phase was dried, concentrated and purified by means of column chromatography on silica gel (eluent: dichloromethane).
Yield: 60 mg (40% of theory), logP ¹ ) (HCOOH) 1.86 ¹ H NMR ((CD3) 2SO): 2.67 (s, 3H), 2.81 (s, 6H), 7, 55 (m, 1H), 8.32 (m, 1H), 8.72 (m, 1H), 9.05 (m, 1H) ppm.
Example D: N- (Dimethylsulfamoyl) -1- (pyridin-3-yl) -1H-pyrazol-4-carboxamide
Stage 1: Ethyl 1- (pyridin-3-yl) -1H-pyrazol-4-carboxylate
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Br hn
^The N
0.412 ml (4.28 mmol) of 3-bromopyridine was dissolved in 2 ml of dimethylformamide. Subsequently, 1.035 g (7.49 mmol) of potassium carbonate, 0.034 g (0.017 mmol) of copper iodide, 0.081 g (0.71 mmol) of trans-N, N'-dimethyl-1,2-cyclohexanediamine and 0.500 g (5.371 mmol) of ethyl pyrazole-4-ethyl carboxylate was added. The mixture was heated to 110 ° C for 24 hours and then cooled to room temperature. Water was added and the precipitate formed was filtered off.
Yield: 600 mg (77% of theory), logP ¹ ) (HCOOH) 1.55 ¹ H NMR ((CD3) 2SO): 1.31 (t, 3H), 4.29 (q, 2H), 7, 57-7.60 (m, 1H), 8.20 (s, 1H), 8.3110
8.34 (m, 1H), 8.61 (bs, 1H), 9.19 (bs, 2H) ppm Stage 2: 1- (Pyridin-3-yl) -1H-pyrazole-4-carboxylic acid

N · / OH
O
9.10 g (41.8 mmol) of ethyl 1- (pyridin-3-yl) -1H-pyrazol-4-carboxylate were dissolved in 170 ml of dioxane and 17 ml of water and 8.94 g of a solution of 45% aqueous sodium hydroxide were added. The mixture was heated to reflux for 5 h. The solution was cooled to room temperature and the dioxane was removed under reduced pressure. A little cold water was added to the residue. The aqueous phase was adjusted to pH 3 with concentrated hydrochloric acid. The HCl and the precipitate formed were separated by filtration.
Yield: 7.54 g (95% of theory), logP ¹ ) (HCOOH) 0.50 ¹ H NMR ((CD3) ₂ SO): 7.55 (m, 1H), 8.08 (s, 1H) , 8.28 (m, 1H), 8.57 (m, 1H), 8.98 (s, 1H), 9.13 (m, 1H) ppm
Yield: 7.54 g (95% of theory), logP ¹ ) (HCOOH) 0.50
Stage 3: N- (Dimethylsulfamoyl) -1- (pyridin-3-yl) -1 H-pyrazol-4-carboxamide
OH
O / + H2N-S-N
O
N
O /
N — s — N
H \
O
0.250 g (1.32 mmol) of 1- (pyridin-3-yl) -1 H-pyrazol-4-carboxylic acid were initially loaded in 5 ml of tetrahydrofuran, and 0.43 ml (1.98 mmol) was added of N, N'carbonildiimidazole. The mixture was heated to reflux for 1 h. 0.246 g (1.98 mmol) of N, N-dimethylsulfonamide were dissolved in 3 ml of tetrahydrofuran and added dropwise,
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36/42 at room temperature, with the first solution. The mixture was stirred at room temperature for 10 min. After adding 0.30 ml (1.98 mmol) of 1,8-diazabicyclo (5.4.0) undec-7-ene, the mixture was stirred at room temperature for 12 h. The solvent was removed on a rotary evaporator and water was added to the residue. The aqueous phase was extracted with dichloromethane. The organic phase was discarded and the aqueous phase was acidified with concentrated HCl. The formed precipitate was filtered off with suction.
Yield: 0.120 g (30% of theory), logP ¹ ) (HCOOH) 1.03 ¹ H NMR ((CD3) 2SO): 2.89 (s, 6H), 7.58-7.62 (m, 1H ), 8.24-8.27 (m, 1H), 8.38 (s, 1H), 8.60-8.62 (m, 1H), 9.10-9.11 (m, 1H), 9.22 (s, 1H) ppm.
Example E: 1,1-DifluorO-N- [1- (pyridin-3-yl) -1H-pyrazol-4-yl] methanesulfonamide
Stage 1: 3- (4-Nitro-1H-pyrazol-1-yl) pyridine
Br +
HN
N = /
N ^ =
N; f ^NO
NO ₂
N
A flask that was dried with vacuum heat (baked-out) and filled with argon, was initially loaded with 8.3 g (56.6 mmol) of copper oxide, 31.9 g (228 mmol) of salicylaldoxima, 200 g (1.71 mol) of 4-nitro-1H-pyrazole and 597 g (1.83 mol) of cesium carbonate. The flask was repeatedly emptied and filled with argon. 218 g (800 mmol) of 3-bromopyridine and 1 l of DMF that had been degassed on a rotary evaporator were added. The reaction mixture was stirred at 130 ° C overnight, cooled and filtered, and the DMF was removed on a rotary evaporator. The substance was dissolved in 1 l of ethyl acetate and extracted with 2 l of H ₂ O. The aqueous phase was extracted twice with 500 ml of ethyl acetate. Filtration of the aqueous phase generated a green solid. Then 1 liter of ethyl acetate and 100 ml of DMF were added, and the mixture was heated to 50 ° C. Cooling was followed by filtration with Hyflo and washing with 500 ml of ethyl acetate. The filtrate was washed with 300 ml of water and 300 ml of saturated NaCl solution, dried over Na ₂ SO4, filtered and concentrated. The solid was suspended in 100 ml of ethyl acetate, filtered and washed with ethyl acetate and methyl tert-butyl ether, and the beige solid (45 g) was dried on a rotary evaporator.
The combined organic phases were washed twice with 500 ml of NaHCO3 solution (5%), with 500 ml of water and with 300 ml of saturated NaCl solution. The organic phase was then dried over Na ₂ SO4, filtered and concentrated to a thick paste. Then 500 ml of ethyl acetate, 630 ml of hydrochloric acid (2 M) and 500 ml of water were added thereto. After filtration, the aqueous phase was washed twice with 250 ml of ethyl acetate, adjusted to pH 10-11 with 1 M sodium hydroxide and left to stand overnight. The solid was filtered off, washed to neutrality with water and coevaporated twice with dioxane on a rotary evaporator. A brown solid (59 g) was obtained.
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Yield: 104 g (40% of theory) ¹ H NMR ((CD3) 2SO): 7.65 (m, 1H), 8.38 (m, 1H), 8.63 (s, 1H), 8.66 (m, 1H), 9.20 (s, 1H), 9.79 (s, 1H) ppm.
Stage 2: 1- (Pyridin-3-yl) -1H-pyrazol-4-amine
Q '^N>'
98.9 g (520 mmol) of 3- (4-nitro-1H-pyrazol-1-yl) pyridine were dissolved in 1.3 l of hot dioxane, and twice emptied and filled with argon. 500 ml of ammonia in methanol (~ 7 mol / l) was added and the air was again removed twice from the mixture (vacuum) and it was filled with argon. 27.5 g of Raney nickel (wet paste with water) were added and the mixture was subjected to vacuum twice and filled with argon, and another three times vacuum and filled with hydrogen. The suspension was stirred in an atmosphere of hydrogen overnight. Another 32 g of Raney nickel was added and the mixture was stirred in a hydrogen atmosphere for an additional 24 hours. The hydrogen atmosphere was replaced with argon, and the reaction mixture was filtered with Hyflo and washed with 500 ml of dioxane. The filtrate was concentrated on a rotary evaporator and dried in a high vacuum. The brown oil obtained crystallized in a refrigerator. The crude product was dissolved in 750 ml of ethyl acetate, 20 g of activated carbon were added and the mixture was stirred at 50 ° C for 30 minutes. After filtration, activated carbon was added again and the mixture was again stirred at 50 ° C for 30 minutes. Filtration with Hyflo was followed by concentration to approx. 250 g. 350 ml of diisopropyl ether were added and the mixture was stirred at room temperature. The solid was filtered off and washed with diisopropyl ether and heptane. Drying on a rotary evaporator gave a beige solid.
Yield: 54.7 g (66% of theory) ¹ H NMR ((CD3) 2SO): 4.24 (s, 2H), 7.36 (s, 1H), 7.43 (m, 1H), 7 , 79 (m, 1H), 8.06 (m, 1H), 8.40 (m, 1H), 8.96 ppm (s, 1H) ppm.
Stage 3: 1,1-Difluoro-N- [1- (pyridin-3-yl) -1H-pyrazol-4-yl] methanesulfonamide
NH ₂
Cr
O / O \ // / F
250 mg (1.56 mmol) of 1- (pyridin-3-yl) -1H-pyrazol-4-amine were initially loaded in 4 ml of dichloromethane, 343 pl (3.12 mmol) of N-methylmorpholine was added and the mixture was cooled to -78 ° C. Then, 235 mg (1.56 mmol) of difluoromethanesulfonyl chloride were added and the reaction mixture was allowed to cool until
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38/42 room temperature overnight. Then, an additional 235 mg (1.56 mmol) of difluoromethanesulfonyl chloride was added and the reaction mixture was stirred at room temperature for 6 hours. The reaction mixture was filtered over silica gel and then washed with dichloromethane and ethyl acetate. After verification by TLC, the ethyl acetate phase was concentrated and purified by chromatography on silica gel.
Yield: 124 mg (29% of theory), logP ¹ ) (HCOOH) 1.01 ¹ H NMR ((CD3) 2SO): 7.14 (t, 1H), 7.54 (m, 1H), 7, 74 (s, 1H), 8.23 (m, 1H), 8.54 (m,
1H), 8.59 (s, 1H), 9.09 (m, 1H), 10.78 (br. S, 1H) ppm
Number of
Structures
LogP compound ¹⁾
NMR data (HCOOH) (Example A)
¹ H NMR (CD3CN): 2.4 (s, 3H), 3.45 (q, 2H), 1.47 7.4 (dd, 1H), 8.15 (d, 1H), 8.55 ( m, 1H),
8.9 (br, 1H), 9.05 (s, 1H) ppm (Example B)
ch ₃ ¹ H NMR ((CD3) 2SO): 2.45 (s, 3H),
0.74
4.14 (s, 2H), 7.35-9.05 (m, 7H) ppm (Example C)
¹ H NMR ((CD3) 2SO): 2.67 (s, 3H),
1.86 2.81 (s, 6H), 7.55 (m, 1H), 8.32 (m, 1H),
8.72 (m, 1H), 9.05 (m, 1H) ppm,
(Example E)
¹ H NMR ((CD3) 2SO): 2.89 (s, 6H), 7,587.62 (m, 1H), 8.24-8.27 (m, 1H),
1.03
8.38 (s, 1H), 8.60-8.62 (m, 1H), 9,109.11 (m, 1H), 9.22 (s, 1H) ppm ¹ H NMR ((CD3) 2SO): 7.14 (t, 1H), 7.54 (m, 1H), 7.74 (s, 1H), 8.23 (m, 1H),
1.01
8.54 (m, 1H), 8.59 (s, 1H), 9.09 (m, 1H), 10.78 (br, s, 1H) ppm ¹ H NMR ((CD3) 2SO): 2, 34 (s, 3H), 7,577.72 (m, 4H), 7.98-8.00 (m, 2H), 8,131.71 8.17 (m, 1H), 8.56-8.58 (m , 1H), 9,009.01 (m, 1H), 9.14 (s, 1H), 12.1 (s, 1H)
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Number of
Structures
LogP compound ¹⁾
NMR data (HCOOH)
N ^{// O z} r ^s ' õ ¹ H NMR ((CD3) 2SO): 2.88 (s, 6H), 8,268.30 (m, 1H), 8.40 (s, 1H), 8,631.42 8.64 (m, 1H), 9.03 (s, 1H), 9.26 (s, 1H),
11.72 (s, 1H)
F
^s
O
O
1.28 ¹ H NMR ((CD3) 2SO): 1.09-1.19 (m, 4H), 3.08-3.14 (m, 1H), 8.28-8.31 (m, 1H ), 8.41 (s, 1H), 8.64-8.65 (m, 1H), 9,049.05 (m, 1H), 9.28-9.29 (m, 1H), 12.02 ( s, 1H)
H // ^O
O ¹ H NMR ((CD3) zSO): 7.54-7.66 (m, 4H), 7.95-7.97 (m, 2H), 8.20-8.24 (m, 2H), 8.561.39 8.58 (m, 1H), 9.04 (s, 1H), 9.079.08 (m, 1H)
O
S — NH
O
1.35
0.83
0.54 ^ = S-NH

0.81
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1) Description of the method for determining logP values (formic acid method)
The logP values shown in the table were determined in accordance with EEC Directives 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography - High
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Performance Liquid Chromatography (HPLC) using a reverse phase column (C18). Temperature: 55 ° C.
Eluents for the determination in acid medium (pH 3.4):
Eluent A: acetonitrile + 1 ml formic acid / liter. Eluent B: water + 0.9 ml of formic acid / liter.
Gradient: from 10% eluent A / 90% eluent B to 95% eluent A / 5% eluent B in 4.25 min.
Calibration was performed with unbranched alkan-2-ones (containing 3 to 16 carbon atoms) with known logP values (logP values determined based on retention times, by linear interpolation between two successive alkanones). The maximum lambda values were determined at the maximum of the chromatographic signals using the UV spectra from 200 nm to 400 nm.
2) Measurement of NMR spectra
NMR spectra were
a) determined with a Bruker Avance 400 equipped with a flow probe (volume of 60 pl). The solvent used was CD3CN or d6-DMSO, with tetramethylsilane (0.00 ppm), used as a reference.
b) determined with a Bruker Avance 600 II. The solvent used was CD3CN or d6-DMSO, with tetramethylsilane (0.00 ppm), used as a reference.
The separation of the signals was described as follows: s (singlet), d (doublet), t (triplet), q (quartet), quin (quintet), m (multiplet).
Test with Boophilus microplus test (injection)
Solvent: dimethyl sulfoxide
To prepare an appropriate active ingredient formulation, 10 mg of active ingredient are mixed with 0.5 ml of solvent and the concentrate is diluted with solvent to the desired concentration. The active ingredient solution is injected into the abdomen (Boophilus microplus), and the animals are transferred to plates and stored in a temperature-controlled room. Activity is assessed by laying fertile eggs.
After 7 days, the effectiveness in% is determined. 100% means that none of the ticks laid any fertile eggs.
In this test, for example, the following compound of the example preparations demonstrated 100% efficacy at an application rate of 20 pg / animal: 1.
Myzus test (spray treatment)
Solvent: 78 parts by weight of acetone
1.5 parts by weight of dimethylformamide
Emulsifier: 0.5 parts by weight of alkylaryl polyglycol ether
To prepare an appropriate preparation of the active ingredient, 1 part by weight of the
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42/42 active principle is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water containing emulsifier to the desired concentration. Chinese cabbage discs (Brassica pekinensis) infested by all stages of the green peach aphid (Myzus persicae), are sprayed with a preparation of the active ingredient in the desired concentration.
After 6 days, the effectiveness in% is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.
In this test, for example, the following compounds of the example preparations showed 100% efficiency at an application rate of 500 g / ha: 7, 6, 3, 2.
In this test, for example, the following compounds of the example preparations showed an efficiency of 90% at an application rate of 500 g / ha: 4, 8.
In this test, for example, the following compound of the example preparations showed an efficiency of 80% at an application rate of 500 g / ha: 1.
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1/4

权利要求:
Claims (5)
[1]
1. Compounds, characterized by presenting the formula (I) in which
A ¹ and A ² are each independently hydrogen, halogen, cyano, nitro, C1-C6alkyl, C3-C6-cycloalkyl or C1-C6-alkoxy,
G ¹ is N or CA ¹ and
G ² is a radical of the group of
R * (A) in which the arrow indicates the connection with the adjacent ring,
R ¹ is hydrogen, halogen, cyano, C1-C6-alkyl, C1-C6-alkoxy or C1-C6-haloalkyl, B is hydrogen, halogen, cyano, nitro, C1-C6-alkyl, C1-C6-haloalkyl C1- C6alkoxy or C3-C6-cycloalkyl,
G ³ is where the arrow indicates the connection with G ² ,
X is oxygen or sulfur, n is 1 or 2,
R ² is a radical of the hydrogen group, C1-C6-alkyl, C1-C6-haloalkyl, cyano-C1-alkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C2-C6-alkenyl, C1-C6- alkoxy-C1-C6-alkyl, C1-C6alkylcarbonyl optionally substituted by halogen, C1-C6-alkoxycarbonyl optionally substituted by halogen, C3-C6-cycloalkylcarbonyl optionally substituted by halogen, C1-C6-alkyl-, Ci-C6-alkoxy-, C1-C6-haloalkyl- and cyano-, or a cation,
^R7 is a radical group which in each case -C6 -alkyl, C2 -C6 -alkenyl, C2 -C6alquinila optionally substituted by Halogen - , Ci-C6-alkoxy-, C 6 -C haloalcóxi- C1 -C6alkylthio-, C1-C6-haloalkylthio-, C1-C6-alkylsulfinyl-, C1-C6-haloalkylsulfinyl-, C1-C6-alkylsulfonyl C1-C6-haloalkylsulfonyl-, in each case C3-C6-cycloalkyl, C3-C6- cycloalkenyl optionally substituted by halogen-, C1-C6-alkyl-, C1-C6-haloalkyl-, C1-C6-alkoxy- or C1-C6-haloalkoxy-, in which the rings may contain at least one heteroatom of the group of
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[2]
2/4 sulfur, oxygen (where the oxygen atoms should not be immediately adjacent) and nitrogen, in each case aryl, heteroaryl, aryl-C1-C6-alkyl and heteroaryl-C1-C6-alkyl, optionally substituted by halogen-, cyano- (included in the alkyl portion), nitro-, C1-C6alkyl-, C1-C6-haloalkyl-, C3-C6-cycloalkyl-, C1-C6-alkoxy-, C1-C6-haloalkoxy-, C1-C6alkylthio-, C1-C6-haloalkylthio-, C1-C6-alkylsulfinyl-, C1-C6-haloalkylsulfinyl-, C1-C6alkylsulfonyl-, C1-C6-haloalkylsulfonyl-, amino-, C1-C6-alkylamino-, di (C1-C6-alkyl) ) amino-, C1-C6-alkylcarbonylamino-, C1-C6-alkoxycarbonylamino-, C1-C6-alkoxy-C1-C6-alkyl-, C1-C6haloalkoxy-C1-C6-alkyl-, C2-C6-alkenyl-, C2 -C6-alkynyl-, C3-C6-cycloalkyl-C1-C6-alkyl-, C1-C6-alkylcarbonyl-, C1-C6-alkoxycarbonyl- or aminocarbonyl-, or NR'R '' where R 'and R are each a independently a radical of the hydrogen group, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-alkylcarbonyl and C1-C6-alk oxycarbonyl;
R ² and R ⁷ can also form together with the NS (O) n group to which they are attached, a saturated or unsaturated 5- to 7-membered ring that may contain one or more additional sulfur heteroatoms, oxygen (where the oxygen atoms must not be immediately adjacent) and nitrogen and / or at least one carbonyl group and optionally substituted by halogen-, Ci-C6-alkyl-, Ci-C6-haloalkyl-, Ci-C6-alkoxy-, Ci-C6 -haloalkoxy-;
and in which halogen is selected from the group of fluorine, chlorine, bromine and iodine;
aryl (including as part of a larger unit, for example arylalkyl) is selected from the group of phenyl, naphthyl, anthryl, phenanthrenyl, and heteraryl (including as part of a larger unit, eg hetarylalkyl) is selected from the group of furila, thienyl , pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl,
1.3.4- oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl,
1.2.5- thiadiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl,
1.3.5- triazinyl, benzofuryl, benzisofuryl, benzothienyl, benzisothienyl, indolyl, isoindolyl, indazolyl, benzothiazolyl, benzisothiazolyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, 2,1,3-benzoxadiazol, quinolinyl, quinolinyl, quinoline, quinolinyl naphthyridinyl, benzotriazinyl, purinyl, pteridinyl and indolizinyl.
2. Compounds of formula (I) according to claim 1, characterized by the fact that
A ¹ is hydrogen, halogen or cyan,
A ² is hydrogen,
G ¹ is N or CA ¹ ,
G ² is a radical of the group of
Petition 870170085420, of 11/06/2017, p. 52/56
[3]
3/4 in which the arrow marks the bond to the adjacent ring, R ¹ is hydrogen or C 1 -C 4 -alkyl,
B is hydrogen, in which the arrow marks the connection to G ² ,
X is oxygen,
N is 2,
R ² is a radical of the group of hydrogen, C1-C4-alkyl and C1-C4-alkoxy-C1-C4alkyl, C1-C4-alkylcarbonyl optionally substituted by halogen-, C1-C4-alkoxycarbonyl optionally substituted by halogen-, C3 -C6-cycloalkylcarbonyl optionally substituted by halogen-, C1-C4-alkyl-, C1-C4-alkoxy-, C1-C4-haloalkyl- and cyano-, or a cation;
R ⁷ is a radical of the group of which in each case C1-C4-alkyl, C2-C4-alkenyl, C2-C4alkynyl optionally substituted by halogen-, C1-C4-alkoxy-, C1-C4-haloalkoxy-, C1-C4alkylthio -, C1-C4-haloalkylthio-, C1-C4-alkylsulfinyl-, C1-C4-haloalkylsulfinyl-, C1-C4alkylsulfonyl- and C1-C4-haloalkylsulfonyl, in each case C3-C6-cycloalkyl, C3-C6-cycloalkylCi-cycloalkyl -alkyl and C3-C4-cycloalkenyl optionally substituted by halogen-, Ci-C4-alkyl, Ci-C4-haloalkyl-, Ci-C4-alkoxy-, Ci-C4-haloalkoxy-, in which the rings may contain at least one heteroatom of the sulfur group, oxygen (where the oxygen atoms should not be immediately adjacent) and nitrogen, in each case aryl, heteroaryl, aryl-C1-C4-alkyl and heteroaryl-C1-C4-alkyl, optionally substituted by halogen- , cyano- (including in the alkyl portion), nitro-, C1-C4alkyl-, C1-C4-haloalkyl-, C3-C6-cycloalkyl-, C1-C4-alkoxy-, Ci-C4-haloalkoxy-, C1-C4alkylthio- , C1-C4-haloalkylthio-, C1-C4-alkylsulfin ila-, C1-C4-haloalkylsulfinyl-, C1-C4alkylsulfonyl-, C1-C4-haloalkylsulfonyl-, amino-, C1-C4-alkylamino-, di (C1-C4-alkyl) amino-, Ci-C4-alkylcarbonylamino-, C1-C4-alkoxycarbonylamino-, C1-C4-alkoxy-C1-C4-alkyl-, C1-C4haloalkoxy-C1-C4-alkyl-, C2-C4-alkenyl-, C2-C4-alkynyl-, C3-C6-cycloalkyl -Ci-C4-alkyl-, C1-C4-alkylcarbonyl-, C1-C4-alkoxycarbonyl- or aminocarbonyl, or NR'R where R 'and R are each independently a radical of the hydrogen group and C1-C4-alkyl;
and in what
Petition 870170085420, of 11/06/2017, p. 53/56
[4]
4/4 halogen is selected from the group of fluorine, chlorine, bromine and iodine;
aryl (including as part of a larger unit, for example arylalkyl) is selected from the group of phenyl, naphthyl, anthryl, phenanthrenyl, and heteraryl (including as part of a larger unit, for example hetarylalkyl) is
[5]
5 selected from the group of pyrimidyl, oxadiazolyl, oxazolyl, pyrazinyl, imidazolyl, thiazolyl and furanyl.
3. Composition, characterized in that it comprises a content of at least one compound of formula (I) as defined in claim 1 or 2 and usual diluents and / or surfactants.
4. Pest control method, characterized in that a compound of formula (I) 10 as defined in claim 1 or 2 or a composition as defined in claim 3 is left to act on the pests and / or their habitat.
Use of compounds of formula (I) as defined in claim 1 or 2 or of composition as defined in claim 3, characterized by being for pest control.
Petition 870170085420, of 11/06/2017, p. 54/56
1/1

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CN103119034B|2016-08-03|

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法律状态:
2016-05-31| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2017-08-08| B07A| Technical examination (opinion): publication of technical examination (opinion)|

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2018-02-14| B15K| Others concerning applications: alteration of classification|Ipc: C07D 401/04 (2006.01), C07D 417/04 (2006.01), C07D |

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2018-02-27| B09A| Decision: intention to grant|

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2018-03-20| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/04/2011, OBSERVADAS AS CONDICOES LEGAIS. |

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2020-02-04| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 9A ANUIDADE. |

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2020-08-11| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: MANUTENCAO DA EXTINCAO - ART. 78 INCISO IV DA LPI |

优先权:

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申请号 | 申请日 | 专利标题

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US32509410P| true| 2010-04-16|2010-04-16|

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US61/325,094|2010-04-16|

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EP10160189|2010-04-16|

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EP10160189.6|2010-04-16|

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PCT/EP2011/055645|WO2011128304A2|2010-04-16|2011-04-11|Novel heterocyclic compounds as pest control agents|

---