# US 2014/0155451 A1 · Aniline Type Compounds

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- Number: US 2014/0155451 A1
- Document ID: US20140155451A1
- Status: Published application
- Kind: A1
- Application number: 14/236,362
- Filed: 2012-08-10
- Published: 2014-06-05
- Earliest claimed: 2011-08-12
- Assignees: BASF SE
- Inventors: Karsten Koerber; Prashant Deshmukh; Florian Kaiser; Michael Rack; Timo Frasetto; Gemma Veitch; Markus Kordes; Marco Naujok
- Web page: https://patentgrep.com/patent/US20140155451A1

## CPC

- A01N 43/56: 1,2-Diazoles; Hydrogenated 1,2-diazoles
- A01N 37/28: containing the group [IMAGE cpc-sch-A01N-0937.gif]; Thio analogues thereof
- A01N 41/12: not containing sulfur-to-oxygen bonds, e.g. polysulfides
- A01N 43/50: 1,3-Diazoles; Hydrogenated 1,3-diazoles
- A01N 43/80: five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
- C07C 381/10: Compounds containing sulfur atoms doubly-bound to nitrogen atoms
- C07D 401/04: directly linked by a ring-member-to-ring-member bond
- C07D 401/14: containing three or more hetero rings
- C07D 409/14: containing three or more hetero rings
- C07D 413/14: containing three or more hetero rings
- C07B 2200/13: Crystalline forms, e.g. polymorphs
- A01N: PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF (preservation of food or foodstuff A23); BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES (preparations for medical, dental or toiletry purposes which kill or prevent the growth or proliferation of unwanted organisms A61K); PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)

## Abstract

The present invention relates to compounds of the formula (I) wherein R1 and R2 independently of one another are hydrogen, C1-C10-alkyl, C1-C10-haloalkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl or together represent an aliphatic chain, or the like; R3 is halogen, cyano, C1-C8-alkyl, C1-C8-haloalkyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C2-C8-alkenyl, C2-C8-haloalkenyl, C1-C8-alkoxy, phenyl, or the like; R4 is hydrogen, C1-C10-alkyl, C1-C10-haloalkyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, phenyl, or the like; t is 0 or 1; p is 0, 1, 2, 3 or 4. The present invention also relates to a process for preparing a compound of the formula (I) which comprises reacting a compound of the formula II with a compound of the formulae III or IV: where t, p, R1 R3, R3 and R4 are as defined in any of claims 1 to 6 and where A− is an equivalent of an anion having a pKB of at least 10 (determined under standard conditions in water).

## Claims

### Claim at position 1

1-20. (canceled)

### Claim 21

A compound of the formula (I)
in which
t is 0 or 1;
p is 0, 1, 2, 3 or 4;
R1 and R2 are selected, independently of one another, from the group consisting of hydrogen, C1-C10-alkyl, C1-C10-haloalkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, and C2-C10-haloalkynyl, wherein the eight last radicals may optionally be substituted by one or more radicals Ra,
or R1 and R2 together represent a C2-C9-alkylene, C2-C9-alkenylene or C6-C9-alkynylene chain forming together with the sulfur atom to which they are attached a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or fully unsaturated ring, wherein 1 to 4 of the CH2 groups in the C2-C9-alkylene chain or 1 to 4 of any of the CH2 or CH groups in the
C2-C9-alkenylene chain or 1 to 4 of any of the CH2 groups in the C6-C9-alkynylene chain may be replaced by 1 to 4 groups independently selected from the group consisting of C═O, C═S, O, S, N, NO, SO, SO2 and NRy, and wherein the carbon atoms in the C2-C9-alkylene, C2-C9-alkenylene or C6-C9-alkynylene chain may be substituted with 1 to 5 identical or different substituents Rx, and wherein the sulfur and nitrogen atoms in the C2-C9-alkylene, C2-C9-alkenylene or C6-C9-alkynylene chain, independently of one another, may be oxidized;
R3 if present, are independently selected from the group consisting of halogen, cyano, azido, nitro, —SCN, SF5, C1-C8-alkyl, C1-C8-haloalkyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C2-C8-alkenyl, C2-C8-haloalkenyl, C2-C8-alkynyl, C2-C8-haloalkynyl, wherein the eight last radicals may optionally be substituted by one or more radicals Ra,
—ORb, SRb, —S(O)mRb, —S(O)nN(R)Rd, —N(R)Rd, —Si(Rf)2Rg, —N(Rc)C(═O)Rb, —C(═NRc)Rb, —C(═O)N(Rc)Rd, —C(═S)N(Rc)Rd,
phenyl which may be substituted by 1, 2, 3, 4 or 5 radicals Re, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1, 2 or 3 heteroatoms or heteroatom groups selected from the group consisting of N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals Re,
for p>1 it being possible that R3 are identical or different,
or two radicals R3 bound on adjacent carbon atoms may be together a group selected from the group consisting of —CH2CH2CH2CH2—, —CH═CH—CH═CH—, —N═CH—CH═CH—, —CH═N—CH═CH—, —N═CH—N═CH—, —OCH2CH2CH2—, —OCH═CHCH2—, —CH2OCH2CH2—, —OCH2CH2O—, —OCH2OCH2—, —CH2CH2CH2—, —CH═CHCH2—, —CH2CH2O—, —CH═CHO—, —CH2OCH2—, —CH2C(═O)O—, —C(═O)OCH2—, —O(CH2)O—, —SCH2CH2CH2—, —SCH═CHCH2—, —CH2SCH2CH2—, —SCH2CH2S—, —SCH2SCH2—, —CH2CH2S—, —CH═CHS—, —CH2SCH2—, —CH2C(═S)S—, —C(═S)SCH2—, —S(CH2)S—, —CH2CH2NRy—, —CH2CH═N—, —CH═CH—NRy—, —CH═N—NRy—, —OCH═N— and —SCH═N—, thus forming, together with the carbon atoms to which they are bound, a 5- or 6-membered ring, where the hydrogen atoms of the above groups may be replaced by one or more substituents selected from the group consisting of halogen, methyl, halomethyl, hydroxyl, methoxy and halomethoxy or one or more CH2 groups of the above groups may be replaced by a C═O group;
R4 is selected from the group consisting of hydrogen, C1-C10-alkyl, C1-C10-haloalkyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C2-C10-haloalkynyl, wherein the eight last radicals may optionally be substituted by one or more radicals Ra,
phenyl which may be substituted by 1, 2, 3, 4 or 5 radicals Re; and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1, 2 or 3 heteroatoms or heteroatom groups selected from the group consisting of N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals Re;
Ra is selected from the group consisting of cyano, azido, nitro, —SCN, SF5, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy-C1-C6-alkyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, —Si(Rf)2Rg, —ORb, —SRb, —S(O)mRb, —S(O)nN(Rc)Rd, —N(R)Rd, —C(═O)Rb, C(═O)ORb, C(═O)N(Rc)Rd,
phenyl which may be substituted by 1, 2, 3, 4 or 5 radicals Re, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or completely unsaturated heterocyclic ring containing 1, 2 or 3 heteroatoms or heteroatom groups selected from the group consisting of N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals Re;
or two geminally bound radicals Ra together form a group selected from ═CRhRk, ═NRc, ═NORb and ═NNRc;
or two radicals Ra, together with the carbon atoms to which they are bound, form a 3-, 4-, 5-, 6-, 7- or 8-membered saturated or partially unsaturated carbocyclic ring or a 3-, 4-, 5-, 6-, 7- or 8-membered saturated or partially unsaturated heterocyclic ring containing 1, 2 or 3 heteroatoms or heteroatom groups selected from the group consisting of N, O, S, NO, SO and SO2, as ring members;
wherein, in the case of more than one Ra, Ra can be identical or different;
Rb is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, where the five last mentioned radicals may be unsubstituted, partially or fully halogenated and/or wherein one or two CH2 groups may be replaced by a CO group; and/or may carry 1-2 radicals selected from C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, C1-C6-alkoxycarbonyl, —Si(Rf)2Rg, phenyl, benzyl, pyridyl and phenoxy,
it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1, 2 or 3 substituents selected from the group consisting of C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6 haloalkoxy and C1-C6-alkoxycarbonyl;
wherein, in the case of more than one Rb, Rb can be identical or different;
Rc, Rd are, independently from one another, selected from the group consisting of hydrogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, where the five last mentioned radicals may be unsubstituted, partially or fully halogenated and/or wherein one or two CH2 groups may be replaced by a CO group; and/or may carry 1 or 2 radicals selected from C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylthio, C1-C6-alkoxycarbonyl, —Si(Rf)2Rg, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1, 2 or 3 substituents selected from the group consisting of C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6 haloalkoxy and C1-C6-alkoxycarbonyl;
or Rc and Rd, together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6- or 7-membered saturated, partly unsaturated or completely unsaturated N-heterocyclic ring which may contain 1 or 2 further heteroatoms selected from the group consisting of N, O and S as ring members, where the heterocyclic ring may carry 1, 2, 3 or 4 substituents selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy;
Re is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and C3-C8-cycloalkyl, where the four last-mentioned radicals may be unsubstituted, partially or fully halogenated and/or wherein one or two CH2 groups may be replaced by a CO group, and/or may carry 1-2 radicals selected from C1-C4-alkoxy, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, C1-C6-alkoxycarbonyl, —Si(Rf)2Rg, phenyl, benzyl, pyridyl and phenoxy,
it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1, 2 or 3 substituents selected from the group consisting of C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6haloalkoxy and C1-C6-alkoxycarbonyl;
wherein, in the case of more than one Re, Re can be identical or different;
Rf, Rg are, independently of each other and independently of each occurrence, selected from the group consisting of C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy-C1-C4-alkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl and benzyl;
Rh, Rk are, independently from one another, selected from the group consisting of hydrogen, halogen, cyano, azido, nitro, —SCN, SF5, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and C3-C8-cycloalkyl, where the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or oxgenated, and/or may carry 1 or 2 radicals selected from C1-C4-alkyl; C1-C4-haloalkyl; C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylthio, —Si(Rf)2Rg, —OH, —SH, phenyl, benzyl, pyridyl and phenoxy, it being possible for phenyl, benzyl, pyridyl and phenoxy to be unsubstituted, partially or fully halogenated and/or to carry 1, 2 or 3 substituents selected from the group consisting of C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6haloalkoxy; (C1-C6-alkoxy)carbonyl, (C1-C6-alkyl)amino, and di-(C1-C6-alkyl)amino;
or Rh and Rk together form a group ═C(C1-C4-alkyl)2, ═N(C1-C6-alkyl), ═NO(C1-C6-alkyl), or ═O;
Rx is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl, said substituents Rx being identical or different from one another if more than one substituent Rx is present;
Ry is selected from the group consisting of hydrogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl and C3-C8-cycloalkyl-C1-C4-alkyl;
m is 1 or 2, wherein, in the case of several occurrences, m may be identical or different.
n is 0, 1 or 2; wherein, in the case of several occurrences, n may be identical or different;
or a salt thereof.

### Claim 22 (depends on 21)

The compound as claimed in claim 21, where t is 0.

### Claim 23 (depends on 21)

The compound as claimed in claim 21, where R1 and R2, independently of each other, are selected from the group consisting of C1-C6-alkyl, C3-C7-cycloalkyl and C3-C8-cycloalkyl-C1-C4-alkyl or
R1 and R2 together represent a C3-C7-alkylene or C3-C7-alkenylene forming together with the sulfur atom to which they are attached a 4-, 5-, 6-, 7- or 8-membered saturated or partially unsaturated ring, wherein 1 or 2 of the CH2 groups in the C3-C7-alkylene chain or 1 or 2 of any of the CH2 or CH groups in the C3-C7-alkenylene chain may be replaced may be replaced by 1 or 2 groups independently selected from the group consisting of O, S and NRy, and wherein the carbon atoms in the C3-C7-alkylene or C3-C7-alkenylene chain may be substituted with 1 to 5 identical or different substituents Rx.

### Claim 24 (depends on 21)

The compound as claimed in claim 21, where p is 0, 1 or 2.

### Claim 25 (depends on 21)

The compound as claimed in claim 21, where R3 is selected from the group consisting of halogen, methyl, cyano and halomethyl, for p>1 it being possible that R3 are identical or different.

### Claim 26 (depends on 21)

The compound as claimed in claim 21, where R4 is hydrogen.

### Claim 27 (depends on 21)

The compound as claimed in claim 21, which is represented by the following formula IIa:

### Claim 28 (depends on 27)

The compound as claimed in claim 27, where R3a is selected from the group consisting of hydrogen, halogen, methyl and halomethyl and where R3b is selected from the group consisting of hydrogen, halogen, methyl, cyano and halomethyl.

### Claim 29 (depends on 21)

A process for preparing a compound of the formula I according to claim 21, which comprises reacting a compound of the formula II with a compound of the formulae III or IV:
where A− is an equivalent of an anion having a pKB of at least 10 (determined under standard conditions in water).

### Claim 30 (depends on 29)

The process as claimed in claim 29, where the reaction of the compound of the formula II with the compound of the formulae III or IV is performed in the presence of a base.

### Claim 31 (depends on 30)

The process as claimed in claim 30, where the base is selected from the group consisting of alkalimetal alkanolates and tertiary amines.

### Claim 32 (depends on 21)

A process for preparing a compound of the formula V
comprising the steps of
i) providing a compound of claim 21, and;
ii) reacting the compound of the formula I with a compound of the formula VI:
where
r is 0, 1, 2, 3 or 4;
X is a leaving group;
Q is N or CH;
R5 is hydrogen, halogen, cyano, azido, nitro, —SCN, —SF5, C1-C8-alkyl, C1-C8-haloalkyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C2-C8-alkenyl, C2-C8-haloalkenyl, C2-C8-alkynyl, C2-C8-haloalkynyl, wherein the eight last radicals may optionally be substituted by one or more radicals Ra,
—Si(Rf)2Rg, —ORb, —OS(O)nRb, SRb, —S(O)mRb, —S(O)nN(Rc)Rd, —N(Rc)Rd, —N(Rc)C(═O)Rb, —C(═O)Rb, —C(═O)ORb, —C(═S)Rb, —C(═S)ORb, —C(═NRc)Rb, —C(═O)N(Rc)Rd, —C(═S)N(R)Rd, phenyl which may be substituted by 1, 2, 3, 4 or 5 radicals Re, or a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1, 2 or 3 heteroatoms or heteroatom groups selected from the group consisting of N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals Re;
R6 is selected from the group consisting of halogen, cyano, azido, nitro, —SCN, SF5, C1-C8-alkyl, C1-C8-haloalkyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C2-C8-alkenyl, C2-C8-haloalkenyl, C2-C8-alkynyl, C2-C8-haloalkynyl, wherein the eight last radicals may optionally be substituted by one or more radicals Ra, —Si(Rf)2Rg, —ORb, —OS(O)nRb, SRb, —S(O)mRb, —S(O)nN(Rc)Rd, —N(Rc)Rd, —N(R)C(═)Rb, —C(═O)Rb, —C(═O)ORb, —C(═S)Rb, —C(═S)ORb, C(═NRc)Rb, phenyl which may be substituted by 1, 2, 3, 4 or 5 radicals Re, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1, 2 or 3 heteroatoms or heteroatom groups selected from the group consisting of N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals Re,
for r>1 it being possible that R6 are identical or different.

### Claim 33 (depends on 32)

The process according to claim 32, wherein R5 in formulae V and VI is selected from the group consisting of halogen, C1-C4-fluoroalkyl, CBrF2, C1-C4-alkoxy and C1-C4-fluoroalkoxyalkyl, and in particular selected from the group consisting of halogen, CF3, CHF2, CBrF2 and methoxy.

### Claim 34 (depends on 33)

The process according to claim 33, wherein R5 in formulae V and VI is selected from the group consisting of halogen, CF3, CHF2, CBrF2 and methoxy.

### Claim 35 (depends on 32)

The process according to claim 32, where in formulae V and VI
r is 1, and
R6 is located in the ortho position with regard to the point of attachment of the pyrazole nitrogen.

### Claim 36 (depends on 32)

The process according to claim 32, wherein R6 in formulae V and VI is selected from the group consisting of halogen and CF3.

### Claim 37 (depends on 21)

A method for controlling invertebrate pest, which method comprises contacting the invertebrate pest or their food supply, habitat, breeding grounds or their locus with a compound of claim 21 in a pesticidally effective amount.

### Claim 38

A crystalline form of 2-(3-chloro-2-pyridyl)-N-[2-methyl-4-chloro-6-[(diethyl-λ4-sulfanylidene)carbamoyl]phenyl]-5-(trifluoromethyl)pyrazole-3-carboxamide which, in an X-ray powder diffractogram at 25° C. and Cu-Kα radiation, shows at least four of the ten following reflexes, given as 2θ values: 9.31, 11.22, 15.50, 15.79, 17.16, 18.38, 18.74, 18.98, 26.23, 26.58.

### Claim 39 (depends on 38)

A method for controlling invertebrate pest, which method comprises contacting the invertebrate pest or their food supply, habitat, breeding grounds or their locus with a pesticidally effective amount of the crystalline form of claim 38.