RU2054003C1 - Heterocyclic compounds possessing herbicide activity, herbicide composition and method for control of parasitic flora - Google Patents

Abstract

FIELD: agriculture. SUBSTANCE: product having formula (1)

Description

 The invention relates to new substituted derivatives of benzimidazole and indazole, their use as herbicides and herbicidal compositions containing them.

(I) и их N-оксидные или кватернизованные производные, в которых пунктирные линии указывают на присутствие двух двойных связей, расположенных таким образом, что образуются сконденсированная гетеро-ароматическая кольцевая система;
Ar представляет собой необязательно замещенную арильную или гетероциклическую кольцевую систему;
W представляет О или NR¹, где R¹ Н или низший алкил;
А, В, D независимо выбраны из N, NR², N-E, CR⁶, С-Е или С/R⁶/Е, где Е представляет группу

XR⁵ при условии, что 2 из А, В и D представляют N, NR² или N-E, и по крайней мере один из А, В или D несет группу Е, где R² представляет Н, ОR⁷, CN, COOR⁸, алкил или галоидалкил,
R³ и R⁴ независимо выбраны из Н необязательно замещенного алкила, алкенила или алкинила, галогена, NR⁹R¹⁰, или R³ и R⁴ вместе с углеродом, к которому они присоединены, образуют необязательно замещенную алкенильную или циклоалькильную группу;
R⁵ представляет собой СО₂R¹¹, CN, COR¹¹, CH₂OR¹¹, CH(OH)R¹¹, СН(OR¹¹)R¹², CSNH₂, COSR¹¹, CSOR¹¹, CONHSO₂R¹¹, CONR¹³R¹⁴, CONHNR¹³R¹⁴, CONHN⁺- R¹³R¹⁴R¹⁵ Y^-, СО₂ ^-М⁺ или СООN=CR¹³R¹⁴;
Х представляет собой (CH₂)n, CH= CH, CH(OR¹⁶)CH₂ или СOСH₂, где n представляет 0, 1 или 2;
М⁺ представляет собой сельскохозяйственно приемлемый катион;
Y^- представляет собой сельскохозяйственно приемлемый анион;
R⁶ представляет Н, галоген, CR⁷, CN, COOR⁸, алкил или галоидалкил;
R⁷ и R⁸ представляют независимо Н или низший алкил;
R¹¹, R¹² и R¹⁶ независимо выбраны из Н или необязательно замещенной алкильной, алкенильной, алкинильной или арильной группы и
R⁹, R¹⁰, R¹³, R¹⁴ и R¹⁵ независимо выбраны из Н или необязательно замещенной алкильной, алкенильной, алкинильной или арильной группы, или любые два из R⁹, R¹⁰, R¹³, R¹⁴ и R¹⁵ вместе с атомом, к которому они присоединены, образуют циклоалкильное или гетероциклическое кольцо при условии, что соединение не является 5-/2,4-дихлорфенокси/индазол-1-илуксус-ной кислотой или ее метиловым эфиром.Some derivatives of benzocyclic phenyl ether are known which possess herbicidal activity [1]
Some indazole derivatives are also known [2]
The invention provides compounds of formula (I):
Arw

(I) and their N-oxide or quaternized derivatives, in which the dashed lines indicate the presence of two double bonds arranged in such a way that a condensed heteroaromatic ring system is formed;
Ar is an optionally substituted aryl or heterocyclic ring system;
W represents O or NR ¹ where R ¹ H or lower alkyl;
A, B, D are independently selected from N, NR ² , NE, CR ⁶ , CE, or C / R ⁶ / E, where E represents a group

XR ⁵ provided that 2 of A, B and D represent N, NR ² or NE, and at least one of A, B or D carries group E, where R ² represents H, OR ⁷ , CN, COOR ⁸ , alkyl or haloalkyl,
R ³ and R ^{4 are} independently selected from H optionally substituted alkyl, alkenyl or alkynyl, halogen, NR ⁹ R ¹⁰ , or R ³ and R ⁴ together with the carbon to which they are attached form an optionally substituted alkenyl or cycloalkyl group;
R ⁵ is CO ₂ R ¹¹ , CN, COR ¹¹ , CH ₂ OR ¹¹ , CH (OH) R ¹¹ , CH (OR ¹¹ ) R ¹² , CSNH ₂ , COSR ¹¹ , CSOR ¹¹ , CONHSO ₂ R ¹¹ , CONR ¹³ R ¹⁴ , CONHNR ¹³ R ¹⁴ , CONHN ⁺ - R ¹³ R ¹⁴ R ¹⁵ Y ^- , CO ₂ ^- M ⁺ or COON = CR ¹³ R ¹⁴ ;
X represents (CH ₂ ) n, CH = CH, CH (OR ¹⁶ ) CH ₂ or COCH ₂ , where n represents 0, 1 or 2;
M ⁺ is an agriculturally acceptable cation;
Y ^- represents an agriculturally acceptable anion;
R ⁶ represents H, halogen, CR ⁷ , CN, COOR ⁸ , alkyl or haloalkyl;
R ⁷ and R ⁸ are independently H or lower alkyl;
R ¹¹ , R ¹² and R ^{16 are} independently selected from H or an optionally substituted alkyl, alkenyl, alkynyl or aryl group; and
R ⁹ , R ¹⁰ , R ¹³ , R ¹⁴ and R ^{15 are} independently selected from H or an optionally substituted alkyl, alkenyl, alkynyl or aryl group, or any two of R ⁹ , R ¹⁰ , R ¹³ , R ¹⁴ and R ¹⁵ together with the atom to which they are attached form a cycloalkyl or heterocyclic ring, provided that the compound is not 5- / 2,4-dichlorophenoxy / indazol-1-yl-acetic acid or its methyl ester.

где Ar, W, R², R³, R⁴, R⁵, R⁶ и Х имеют значения, определенные в отношении формулы (1), и У ^- представляет анион, происходящий из кватернизующего агента, такой как тетрафторборат.Quaternized derivatives of compounds of formula (1) are compounds obtained by reacting a compound of formula (1) with a quaternizing agent such as an alkyl halide or trialkyloxonium compounds. It is believed that such quaternized derivatives carry a charge on a single nitrogen atom and this takes place in the molecule of the group NR ² preferably; not group N-E. For example, when A represents NR ² , B represents CR ⁶ and D represents NCR ³ R ⁴ XR ⁵ , it is believed that the quaternized derivative has the formula
Arw

where Ar, W, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and X are as defined in relation to formula (1), and Y ^- represents an anion derived from a quaternizing agent, such as tetrafluoroborate.

 As used herein, the term “alkyl” includes straight or branched chains containing up to 10 carbon atoms, preferably 1-6 carbon atoms. The terms "alkenyl" and "alkynyl" refer to unsaturated straight or branched chains having 2-10 and preferably 2-6 carbon atoms. The term "cycloalkyl" includes rings containing 3-9 carbon atoms, preferably 3-6 carbon atoms. The term “alkoxy” includes straight or branched chains containing up to 10 carbon atoms, preferably 1-6 carbon atoms.

 The term “lower” used with respect to alkyl means that the group contains up to 3 carbon atoms.

 The terms “haloalkyl” and “haloalkoxy” refer to alkyl and alkoxy groups, respectively, substituted with at least one halogen atom such as fluorine, chlorine or bromine. A particular haloalkyl group is trifluoromethyl. The term “aryl” includes phenyl and naphthyl. The term “heterocyclic” includes rings containing up to 10 atoms, preferably up to 6 atoms, up to 3 of which are selected from oxygen, nitrogen or sulfur. The term “halogen” includes fluoro, chloro, bromo and iodo.

 A suitable aryl ring system is phenyl.

 Suitable heterocyclic ring systems for Ar are rings containing up to 10 atoms, up to 3 of which are selected from oxygen, nitrogen or sulfur, preferably aromatic ring systems such as pyridine and pyrazole.

Suitable optional substituents for the aryl or heterocyclic Ar ring systems and for the aryl groups R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ comprise up to 5 substituents, preferably up to 3 members, selected from halogen (fluorine, chlorine, bromine or iodine), lower alkyl, haloalkyl (e.g. trifluoromethyl), haloalkoxy (e.g. trifluoromethoxy), nitro, cyano, lower alkoxy (e.g. methoxy) or S (O) pR ^a , where p represents 0, 1 and or 2, and R ^a represents alkyl (for example, thiomethyl, sulfinylmethyl and sulfonylmethyl).

 Preferred substitutional positions when the aryl ring is a phenyl ring are 2, 4 and 6 positions, especially 2,4,6-tri-substituted rings with a trifluoromethyl group in the 4-position.

Examples of optional substituents for the alkyl, alkenyl, alkynyl groups R ³ , R ⁴ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ include one or more groups selected from a halogen, such like fluorine, chlorine or bromine; nitro, nitrile; aryl such as phenyl; CO ₂ R ¹⁷ , NHCOR ₁₇ or NHCH ₂ CO ₂ R ¹⁷ , where R ¹⁷ represents hydrogen, (1-6) C alkyl or an agriculturally acceptable cation; (1-6) C alkoxy; oxo; S (O) pR ^a , where p is 0, 1 or 2 and R ^a is alkyl (for example thiomethyl, sulfinyl methyl or sulfonyl methyl); amino; mono- or di- (1-6) C alkylamino; CONR ¹⁸ R ¹⁹ , where R ¹⁸ and R ^{19 are} independently selected from hydrogen, (1-6) C alkyl, (2-6) C alkenyl or (2-6) C alkynyl, or R ¹⁸ and R ^{19 are} joined together to form a heterocyclic ring having up to 7 ring atoms, 3 of which can be selected from oxygen, nitrogen or sulfur. An example of a heterocyclic substituent is tetrahydrofuranyl.

Examples of agriculturally acceptable anions for Y ^- are halides, tetrafluoroborate, mesylate and tosylate.

Examples of agriculturally acceptable cations for R ¹⁷ and M ⁺ are sodium, potassium or calcium ions, sulfonium or sulfoxonium ions, for example, formulas S ⁺ (O) qR ⁹ R ¹⁰ R ¹³ , where q represents 0 or 1 and R ⁹ , R ¹⁰ and R ¹³ are as defined herein, or ammonium or tertiary ammonium ions of the formula N ⁺ R ⁹ R ¹⁰ R ¹³ R ¹⁴ , where R ⁹ , R ¹⁰ , R ¹³ and R ¹⁴ are as defined above. Suitable substituents for the alkyl, alkenyl and alkynyl groups in these cations are hydroxy and phenyl. Suitably, when any of R ⁹ , R ¹⁰ , R ¹³ and R ¹⁴ in these cations is substituted alkyl, they contain 1-4 carbon atoms.

Specific examples of R ⁹ , R ¹⁰ , R ¹³ and R ¹⁴ in these cations are hydrogen, ethyl, isopropyl, benzyl and 2-hydroxyethyl.

Suitable halogen groups R ³ , R ⁶ and R ¹⁴ include fluoro, chloro and bromo.

B
(i) являются следующие группы:

N

N-E

N-R²;

N

N

R⁶;
или

E
Предпочтительно группой йод-формулы (i) является группа (a) или (f), как определены выше.Suitable heterocyclic rings formed from two of R ⁹ , R ¹⁰ , R ¹³ , R ¹⁴ and R ¹⁵ and the atom to which they are attached are pyrrolidine, piperidine and morpholine. Suitable groups for the formulas (1):

B
(i) are the following groups:

N

NE

NR ² ;

N

N

R ⁶ ;
or

E
Preferably, the group of iodine formula (i) is a group (a) or (f) as defined above.

Preferably, R ³ is hydrogen.

Preferably R ⁴ is H or (1-3) C alkyl, in particular methyl.

R ⁵ suitably represents CO ₂ R ¹¹ , CONR ¹³ R ¹⁴ , CONHSO ₂ R ¹¹ , COON = CR ¹³ R ¹⁴ , CONHNR ¹³ R ¹⁴ or CONHN ⁺ R ¹³ R ¹⁴ R ¹⁵ Y ^- .

The group R ⁵ preferably represents CO ₂ R ¹¹ .

The R ¹¹ group is suitably (1-6) C alkyl or substituted alkyl, such as alkoxyalkyl or oxo-substituted alkyl.

Preferably R ¹¹ is methyl or ethyl.

где R²⁰ представляет N, CH или CR²²; R²¹ и R²² независимо выбраны из галогена, такого как хлор, или фтор. Предпочтительно R²⁰ представляет CR²² и наиболее предпочтительно один из R²¹ и R²² представляет хлор, а другой фтор.Ar is preferably a group
CF

where R ²⁰ represents N, CH or CR ²² ; R ²¹ and R ^{22 are} independently selected from halogen, such as chlorine, or fluorine. Preferably R ²⁰ is CR ²² and most preferably one of R ²¹ and R ²² is chlorine and the other is fluorine.

 W is preferably oxygen.

Preferably X is (CH ₂ ) _n , where n is zero or 1, especially zero.

When the group of formula (i) is group (a) as defined above, R ⁶ is preferably H or Cl.

When the group under formula (i) is group (f) as defined above, R ^{6 is} preferably H, methyl, trifluoromethyl or CN.

(IА) в которой пунктирные линии указывают на присутствие двух двойных связей, расположенных с образованием сконденсированной гетеро-ароматической кольцевой системы;
Ar, W, X, R³, R⁴ и R⁵ имеют значения, определенные в отношении формулы (I);
V представляет собой Н, галоген, OR⁷, CN, COCR⁸, алкил или галоидалкил при условии, что, когда V представляет галоген, не присоединена к атому азота и при дополнительном условии, что соединение является отличным от 5-(2,4-дихлорфенокси)ндазол-1-илуксусной кислоты или ее метилового эфира.Examples of a subgroup of formula (I) are compounds of formula (IA)
Arw

(IA) in which the dashed lines indicate the presence of two double bonds located with the formation of a condensed heteroaromatic ring system;
Ar, W, X, R ³ , R ⁴ and R ⁵ are as defined with respect to formula (I);
V is H, halogen, OR ⁷ , CN, COCR ⁸ , alkyl or haloalkyl, provided that when V is halogen is not attached to the nitrogen atom and under the additional condition that the compound is other than 5- (2,4- dichlorophenoxy) ndazol-1-yl-acetic acid or its methyl ester.

B′ (IC) или его кватернизованные производные, в которой Ar и W имеют значения, определенные в отношении формулы (I), и
А' представляет собой N, NH или N-низший алкил;
В' представляет собой С-R⁶ или C-Е;
D' представляет N-Е, NH или N-низший алкил при условии, что когда В' представляет С-R⁶, D' не является NH или Н-низшим алкилом;
Е и R⁶ имеют значения, определенные в отношении формулы (I).A further example of a subgroup of formula (I) are compounds of formula (IC)
Arw

B ′ (IC) or its quaternized derivatives, in which Ar and W have the meanings defined in relation to formula (I), and
A 'represents N, NH or N-lower alkyl;
B 'represents CR ⁶ or CE;
D 'is N-E, NH or N-lower alkyl, provided that when B' is C-R ⁶ , D 'is not NH or H-lower alkyl;
E and R ⁶ are as defined in relation to formula (I).

 Formula (I) is also intended to include tautomeric forms of the depicted structure, as well as physically distinguishable modifications of the compounds, which can occur, for example, in various ways in which the molecules are located in the crystal lattice, or due to the inability of some parts of the molecule to rotate freely with respect to to other parts, or to the results of geometric isomerism, or within the molecular or intermolecular binding of hydrogen, or otherwise.

 Some of the compounds of the invention may exist in enantiomeric forms. The invention encompasses both individual enantiomers and mixtures of the two in all ratios.

 Specific examples of compounds according to the invention are listed in table. 1-5. These characteristics of the compounds are given in table. 6.

O

Соединение 92
CF

O

BF $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$
Cоединение 93
CF

O

Соединение 94
CF

O

Соединение 95
CF

O

Соединение 96
CF

O

Соединение 97
CF

O

Соединение 98
CF

O

Соединение 99
CF

O

Соединения формулы (1) могут быть получены с помощью следующих общих процессов:
а) взаимодействие соединения формулы (2')
Y

B
(2') где А, В и D имеют значения, определенные в отношении формулы (1), и I представляет собой ОН или СF₃СONH с соединением формулы (3)
Ar-Z, (3) где Ar имеет значения, определенные в отношении формулы (1), и представляет собой удаляемую группу, необязательно в присутствии основания; или b) взаимодействие соединения формулы /41/
Ar-W

B″, (41) где Ar и W имеют значения, определенные в отношении формулы (1), и А", B" и D" независимо выбраны из N, NR², NH, CR⁶, CH или CHR⁶ при условии, что два из А", B" и D" представляют собой N, NR² или NH и по крайней мере один из А, В или D несет атом водорода с соединением формулы (7)
R

R⁴, (7) где X, R³, R⁴ и R⁵ имеют значения, определенные в отношении формулы (I) и Z представляет удаляемую группу в органическом растворителе в присутствии основания или
с) циклизация соединений формулы (42):
Ar-W

XR⁵, (42) где Ar, W, R⁴ и R⁵ имеют значения, определенные в отношении формулы (1), и R³⁰ представляет Н или низший алкил в присутствии дегидратирующего агента. Дальнейшие подробности этих общих процессов описаны ниже.The compounds of the invention are as follows:
Compound 56
CF

O

Compound 92
CF

O

Bf $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$
Compound 93
CF

O

Compound 94
CF

O

Compound 95
CF

O

Compound 96
CF

O

Compound 97
CF

O

Compound 98
CF

O

Compound 99
CF

O

Compounds of formula (1) can be prepared using the following general processes:
a) the interaction of the compounds of formula (2 ')
Y

B
(2 ') where A, B, and D are as defined with respect to formula (1), and I is OH or CF ₃ CONH with a compound of formula (3)
Ar-Z, (3) where Ar is as defined in relation to formula (1) and is a leaving group, optionally in the presence of a base; or b) the interaction of the compounds of formula / 41 /
Ar-w

B ″, (41) where Ar and W have the meanings given in relation to formula (1), and A ", B" and D "are independently selected from N, NR ² , NH, CR ⁶ , CH or CHR ⁶ , provided that two of A ", B" and D "are N, NR ² or NH and at least one of A, B or D carries a hydrogen atom with a compound of formula (7)
R

R ⁴ , (7) where X, R ³ , R ⁴ and R ⁵ are as defined in relation to formula (I) and Z represents a leaving group in an organic solvent in the presence of a base or
c) cyclization of compounds of formula (42):
Ar-w

XR ⁵ , (42) where Ar, W, R ⁴ and R ⁵ are as defined in relation to formula (1), and R ³⁰ is H or lower alkyl in the presence of a dehydrating agent. Further details of these general processes are described below.

, (2) где V, X, R³, R⁴ и R⁵ имеют значения, определенные в отношении формулы (IA), с соединением формулы (3):
Ar-Z, (3) где Ar имеет значения, определенные в отношении формулы (I), и представляет собой удаляемую группу необязательно в присутствии основания.Compounds of formula (IA) can be prepared by reacting a compound of formula (2):

, (2) where V, X, R ³ , R ⁴ and R ⁵ are as defined in relation to formula (IA), with a compound of formula (3):
Ar-Z, (3) where Ar is as defined in relation to formula (I), and is a leaving group, optionally in the presence of a base.

 Suitable leaving groups Z include a halide such as fluoride, bromide and chloride, and sulfonates, such as methanesulfonate and n-toluenesulfonate.

 Suitable bases for use in the reaction include bases such as sodium hydride, and alkali metal carbonates, and alkali metal hydroxides.

The reaction is preferably carried out in an organic solvent such as dimethylformamide, dimethyl sulfoxide, lower alkanol or lower ketone. Suitably, the moderate temperatures used, for example 20-120 ° ^C. Conveniently the reaction is carried out at 100-110 ° ^C.

, (4) где V, X, R³, R⁴ и R⁵ имеют значения, определенные в отношении формулы (IA), с помощью диазотирования азотистой кислотой с последующим водно-кислотным гидролизом, например, согласно процедуре, описанной в J.Org.Chem. (1977), 42(12), 2053.Compounds of formula (2) can be prepared from compounds of formula (4)

, (4) where V, X, R ³ , R ⁴ and R ⁵ are as defined in relation to formula (IA) by diazotization with nitrous acid followed by aqueous acid hydrolysis, for example, according to the procedure described in J. Org .Chem. (1977), 42 (12), 2053.

Alternatively, compounds of formula (2) wherein V is other than cyano can be prepared from compounds of formula (4) by reaction with water and sulfuric acid at 150-170 ^{° C} and a pressure of 100-120 lbs. / Sq. inch / 7.03 kg / sq. cm 8.44 kg / sq.cm /; according to the procedure described in I. C. S. (1955) 2412.

 The compounds of formula (2) are new.

Compounds of formula (4) are prepared by reducing the nitro compound of formula (5), where V, X, R ³ , R ⁴ and R ⁵ are as defined with respect to formula (IA).

(5)
Может использоваться широкое множество различных восстанавливающих агентов, и они могут быть выбраны из химической литературы специалистами в данной области. Восстановление может осуществляться, например с помощью использования дитионита натрия или олова и соляной кислоты, железа и соляной кислоты, восстановленного железа с соляной кислотой в изопропаноле или водорода с катализатором палладием на древесном угле. Реакция предпочтительно проводится в органическом растворителе, таком как низший алкиловый спирт, необязательно смешанный с водой, при температуре в интервале 20-90^оС.

(5)
A wide variety of different reducing agents can be used, and they can be selected from the chemical literature by those skilled in the art. Recovery can be carried out, for example, using sodium dithionite or tin and hydrochloric acid, iron and hydrochloric acid, reduced iron with hydrochloric acid in isopropanol or hydrogen with a palladium-charcoal catalyst. The reaction is preferably carried out in an organic solvent such as a lower alkyl alcohol optionally mixed with water at a temperature in the range of 20-90 ° ^C.

 The compounds of formula (4) are new.

(6) с помощью реакции соединений формулы (7):
Z

, (7) где Х, R³, R⁴ и R⁵ имеют значения, определенные в отношении формулы (IA), и Z является удаляемой группой, как определена здесь выше в растворителях, таких как диметилформамид, диметилсульфоксид или низшие алкилкетоны, в присутствии основания такого, как гидрид натрия, карбонаты или гидроокиси щелочных металлов при 20-80^оС.Compounds of formula (5) can be prepared from compounds of formula (6):

(6) using the reaction of compounds of formula (7):
Z

, (7) where X, R ³ , R ⁴ and R ⁵ are as defined in relation to formula (IA), and Z is a leaving group, as defined hereinabove in solvents such as dimethylformamide, dimethyl sulfoxide or lower alkyl ketones, in the presence of a base such as sodium hydride, carbonates or hydroxides of alkali metals at 20-80 ° ^C.

 The compounds of formula (5) are new and form the next aspect of the invention.

 The compounds of formula (3), (6) and (7) are known compounds or they can be obtained from known compounds using known methods.

 Compounds of formula (IA), where Ar-W is attached at positions other than the 6-position of the indazole ring, can be prepared from the corresponding nitro analogue of compounds of formula (6). These analogs can be obtained using methods known in the art.

(8) где Х, R³, R⁴ и R⁵ имеют значения, определенные в отношении формулы (1), с гидридом натрия в диметилформамиде или диметилсульфоксиде и взаимодействия образованного таким образом аниона с соединением формулы (3), как определена выше в диметилформамиде или диметилсульфоксиде при 50-90^оС.Compounds of formula (IA), where W is NH, can be prepared by reacting a compound of formula (3)

(8) where X, R ³ , R ⁴ and R ⁵ are as defined in relation to formula (1) with sodium hydride in dimethylformamide or dimethyl sulfoxide and the interaction of the anion thus formed with the compound of formula (3) as defined above in dimethylformamide or dimethyl sulfoxide at 50-90 ^about C.

 Compounds of formula (8) can be prepared from compounds of formula (4) as defined above by reaction with trifluoroacetic anhydride according to the procedure described in I. Org.Chem. 1965, 30, 1287.

 The compounds of formula (8) are new.

Compounds of formula (IA) obtained by the preceding process can be alkylated using standard techniques to give compounds of formula (IA), where W is NR ¹ .

N (9) где Ar имеет значения, определенные в отношении формулы (IA) с помощью реакции с соединением формулы (7), определенной выше, в растворителях, таких как диметилформамид, диметилсульфоксид, низшие алканолы, низшие алканоны, при температурах в интервале 60-100^оС в присутствии основания, такого как гидрид натрия, карбонаты или гидроокиси щелочных металлов.The compounds of formula (IA), where V is H attached to the carbon atom in the 3 position of indazole and W is oxygen attached to the indazole ring in the 6 position, can be obtained from compounds of formula (9):

N (9) where Ar is as defined with respect to formula (IA) by reaction with a compound of formula (7) as defined above in solvents such as dimethylformamide, dimethyl sulfoxide, lower alkanols, lower alkanones, at temperatures in the range 60- 100 ^° C in the presence of a base such as sodium hydride, carbonates or alkali metal hydroxides.

(10) где R²⁴ представляет собой низший алкил, и Ar имеет значения, определенные в отношении формулы (IA).Compounds of formula (9) are prepared by deacylation of compounds of formula (10)

(10) where R ²⁴ represents lower alkyl, and Ar has the meanings defined in relation to formula (IA).

 The compounds of formula (9) are new.

(11) c помощью реакции Джакобсена (C. Ruchardt and V. Hassman, Synthesis 375, 1972 и F. Trondlin, R. Werner and Ruchardt Ber. 367, 111, 1978) с использованием растворителей, таких как бензол или толуол, при температурах 80-110^оС.Compounds of formula (10) are prepared from compounds of formula (11)

(11) using the Jacobsen reaction (C. Ruchardt and V. Hassman, Synthesis 375, 1972 and F. Trondlin, R. Werner and Ruchardt Ber. 367, 111, 1978) using solvents such as benzene or toluene at temperatures 80-110 ^about C.

 The compounds of formula (10) are new.

 Compounds of formula (11) are prepared by reduction of compounds of formula (12).

(12)
Могут использоваться разнообразные восстанавливающие агенты, и они могут выбираться из химической литературы квалифицированными специалистами в данной области. Восстановление может осуществляться, например с использованием дитионита натрия или олова и соляной кислоты, железа и соляной кислоты, восстановленного железа с соляной кислотой в изопропаноле, или водорода с катализатором палладием на древесном угле. Реакция предпочтительно проводится в органическом растворителе, таком как низший алкиловый спирт, необязательно смешанный с водой, при 20-90^оС.

(12)
A variety of reducing agents can be used, and they can be selected from the chemical literature by qualified specialists in this field. Reduction can be carried out, for example, using sodium dithionite or tin and hydrochloric acid, iron and hydrochloric acid, reduced iron with hydrochloric acid in isopropanol, or hydrogen with a palladium-charcoal catalyst. The reaction is preferably carried out in an organic solvent such as a lower alkyl alcohol optionally mixed with water at 20-90 ° ^C.

 Compounds of formula (11) other than 4- (2,4-dichlorophenoxy) -2-methylaniline are new.

Compounds of formula (7) can be obtained by reacting a compound of formula (3) with the known compound 4-methyl-3-nitrophenol in solvents such as dimethylformamide, dimethylsulphoxide or lower alkanones at 90-120 ^{° C} in the presence of a base such as sodium hydride, carbonates and hydroxides of alkali metals.

 Compounds of formula (7) other than 4- (2,4-dichlorophenoxy) -2-methylnitrobenzene are new.

 The corresponding 5-aryloxy indazoles can be obtained using a similar method using the appropriate starting materials.

_, (IB) где Аr и V имеют значения, определенные в отношении формулы (IA), за исключением того, что V не является галоидалкилом, и R²⁵ представляет собой СН₂СООR¹¹ или СН(СН₃)COOR¹¹, где R¹¹ имеет значения, определенные в отношении формулы (IA), могут быть получены из соединения формулы (2B)

N (2В) с помощью реакции с соединением формулы (3), как описано выше для реакции соединений формулы (2) с соединением формулы (3).Compounds of Formula (IB)

_, (IB) where Ar and V are as defined in relation to formula (IA), except that V is not haloalkyl and R ²⁵ is CH ₂ COOR ¹¹ or CH (CH ₃ ) COOR ¹¹ , where R ¹¹ has the meaning defined in relation to formula (IA), can be obtained from the compounds of formula (2B)

N (2B) by reaction with a compound of formula (3) as described above for the reaction of compounds of formula (2) with a compound of formula (3).

Соединения формулы (2В) могут быть получены с помощью деметилирования соединения формулы (13) с использованием, например, трехбромистого бора при (-70)-(-50)^оС в дихлорметане, необязательно с последующей сложной этерификацией соответствующим R¹¹ спиртом.The compound of formula (2B) is obtained, for example, using the method of Fucher and Tafel Ann. 303, 227, 1885, as shown in the following diagram:

Compounds of formula (2B) may be prepared by demethylation of a compound of formula (13) using for example boron tribromide at (-70) - (- 50) ^{° C} in dichloromethane optionally followed by esterification with the corresponding alcohol R ^11.

A compound of formula (13) may be formed by cyclisation of a compound of formula (14) by reaction with air at 0-20 ^{° C} in aqueous sodium or potassium hydroxide.

 The compound of formula (14) can be obtained by reducing the compound of formula (15) to its corresponding amine, diazotization using sodium nitrite and concentrated hydrochloric acid, followed by additional reduction of the diazonium compound, for example, tin chloride in hydrochloric acid, or sodium sulfite and sulfur dioxide.

A compound of formula (15) may be prepared from compounds of formula (15) by reaction with sodium acetate and acetic anhydride at 150-180 ^C.

 The compound of formula (16) is a known compound.

 As shown, this reaction scheme provides compounds of formula (IB), where V is H. Additional compounds of formula (IB), where V is other than H, can be obtained using standard methods. For example, treating a compound of formula (IB), where V is H, with a lower alkyl halide such as methyl iodide or a lower alkyl sulfate such as dimethyl sulfate or diethyl sulfate, gives compounds where V is lower alkyl.

 Alternatively, treatment with a lower alkyl halide format, such as ethyl chloroformate, provides compounds of formula (IB), wherein is COO-lower alkyl.

As shown, this scheme also provides compounds of formula (IB), wherein R ²⁵ is CH ₂ COOR ¹¹ . Treatment of these compounds with a base such as potassium tert-butylate, bis (trimethylsilyl) idom potassium or lithium, at temperatures of 0-40 ^{° C} in THF with methyl iodide affords the corresponding Formula (IB) compound wherein R ²⁵ is CH (CH ₃₎ SOOR ¹¹ .

 The corresponding 6-aryloxyindazoles can be obtained by a similar process using the appropriate starting materials.

(13)
Соединение формулы (13) может быть получено из соединения формулы (17) с помощью реакции с активированным древесным углем и гидразингидратом в водной гидроокиси натрия при 30-80^оС.An alternative way to obtain compounds of formula (13) is the method of Kariyone and Jagi C.A. 186340, 93, 1980, as shown in the following diagram:
(Xvi)

(thirteen)
A compound of formula (13) can be prepared from a compound of formula (17) by reaction with activated charcoal and hydrazine hydrate in aqueous sodium hydroxide at 30-80 ° ^C.

A compound of formula (17) can be prepared from a compound of formula (16) as defined above, by reaction with malonic acid and ammonium formate in formic acid at 40-95 ° ^C.

R⁶, где Аr и R⁶ имеют значения, определенные в отношении формулы (IC), с соединением формулы (7), определенные выше, в подходящем растворителе, например диметилсульфоксиде, диметилформамиде, ацетонитриле, низшем алкилкетоне, в присутствии соответствующего основания, например гидрида натрия, алкилкарбоната металла, при 50-100^оС.Compounds of formula (IC), where W is oxygen, A is N, B is CR ⁶ , and D is NCR ³ R ⁴ XR ⁵ can be obtained by reacting a compound of formula (18):

R ⁶ , where Ar and R ⁶ are as defined in relation to formula (IC), with a compound of formula (7) as defined above, in a suitable solvent, for example dimethyl sulfoxide, dimethylformamide, acetonitrile, lower alkyl ketone, in the presence of an appropriate base, for example hydride sodium, metal alkyl carbonate, at 50-100 ^about C.

 This reaction gives two regio-isomers that can be easily separated using known techniques (e.g., chromatography or preparative TLC) to give two compounds of formula (IC).

(19) где Аr имеет значения, определенные в отношении формулы (IC), с использованием соответствующей органической, алифатической кислоты при 100-120^оС и с использованием или без водной минеральной кислоты, например соляной кислоты.Compounds of formula (18) can be prepared by cyclization of compounds of formula (19)

(19) wherein Ar is as defined in relation to formula (IC), using an appropriate organic, aliphatic acid at 100-120 ^{° C} and with or without aqueous mineral acid such as hydrochloric acid.

 The compounds of formula (18) are new.

(20)
Могут широко использоваться разнообразные восстанавливающие агенты, и они могут выбираться из химической литературы специалистами в данной области. Восстановление может осуществляться, например с использованием боргидрида натрия с катализатором палладием на древесном угле. Реакция предпочтительно проводится в органическом растворителе, таком, как низший спирт, необязательно смешанном с водой, при (-20)-10^оС.Compounds of formula (19) are prepared by reduction of the corresponding dinitro compound of formula (20)

(20)
A variety of reducing agents can be widely used, and they can be selected from the chemical literature by those skilled in the art. Recovery can be carried out, for example, using sodium borohydride with a palladium-charcoal catalyst. The reaction is preferably carried out in an organic solvent such as a lower alcohol optionally mixed with water at (-20) -10 ^° C

(21) c использованием нитрующего агента, такого как нитрат калия, смешанный с концентрированной серной кислотой. Реакция предпочтительно осуществляется в подходящем растворителе, таком как уксусный ангидрид, метилендихлорид, этилендихлорид или концентрированная серная кислота. Подходящим образом применяются температуры (-20) 25^оС.Compounds of formula (20) can be prepared by nitration of a compound of formula (21)

(21) using a nitrating agent such as potassium nitrate mixed with concentrated sulfuric acid. The reaction is preferably carried out in a suitable solvent, such as acetic anhydride, methylene dichloride, ethylene dichloride or concentrated sulfuric acid. Suitably used temperature (-20) 25 ^° C

Compounds of formula (21) are prepared by reacting m-nitrophenol with a compound of formula (3) as defined above in an organic solvent, for example dimethyl sulfoxide, lower alkyl ketones, such as acetone or butanone, lower glycams, for example MeOCH ₂ CH ₂ OMe, in the presence of a base, for example alkali metal hydroxides (KOH) or alkali metal carbonates (K ₂ CO ₃ ) at 50-120 ^about C.

 If you want to obtain a compound of formula (IC), where Ar W is attached at other positions in the carbocyclic part of the benzimidazole ring, the corresponding dinitro analogue of the compound of formula (20) is usually used. These compounds can be obtained from known starting materials using methods known in the art.

NHCO-низший алкил (22) где Ar имеет значения, определенные в отношении формулы (IC), с помощью нагревания в соответствующей низшей алифатической кислоте при 100-120^оС.Compounds of formula (18) can alternatively be prepared from compounds of formula (22)
Aro

NHCO-lower alkyl (22) wherein Ar is as defined in relation to formula (IC), by heating in a suitable lower aliphatic acid at 100-120 ° ^C.

NHCO-низший алкил, (23) где Ar имеет значения, определенные в отношении формулы (IC), с использованием разнообразных восстанавливающих агентов, которые могут выбираться специалистами в данной области из химической литературы. Восстановление может осуществляться, например, с использованием треххлористого титана в водной соляной кислоте при 0-10^оС.Compounds of formula (22) can be prepared by reducing compounds of formula (23)
Aro

NHCO-lower alkyl, (23) where Ar is as defined with respect to formula (IC) using a variety of reducing agents that may be selected by those skilled in the art from the chemical literature. The reduction may be carried out, for example, using titanium trichloride in aqueous hydrochloric acid at 0-10 ° ^C.

NHCO-низший алкил, (24)
где Ar имеет значения, определенные в отношении формулы (IC), с использованием нитрующего агента такого, как концентрированная азотная кислота, в уксусном ангидриде при (-10)-0^оС.Compounds of formula (23) can be prepared by nitration of compounds of formula (24)
Aro

NHCO lower alkyl, (24)
wherein Ar is as defined in relation to formula (IC), using a nitrating agent such as concentrated nitric acid in acetic anhydride at (-10) -0 ^C.

NHCO-низший алкил (25) c cоединениями формулы (3) в органическом растворителе, таком как ДМСО, ДМФ, низшие алкилкетоны в присутствии основания, например гидроокиси или карбоната щелочного металла, при 50-120^оС.Compounds of formula (24) can be prepared by reacting compounds of formula (25)
HO

NHCO-lower alkyl (25) c of the formula of Compound (3) in an organic solvent such as DMSO, DMF, lower alkyl ketones in the presence of a base such as hydroxide or alkali metal carbonate at 50-120 ° ^C.

 The compounds of formula (25) are known compounds or can be obtained from known compounds using known methods.

NHCO

XR⁵, (26) где Ar, X, R¹, R² и R³ имеют значения, определенные в отношении формулы (IC), в присутствии дегидратирующего агента, такого как пятиокись фосфора, при 120-160^оС.An alternative way to obtain compounds of formula (IC), where W is oxygen, A is N, D is H and B is C-CR ³ R ⁴ XR ⁵ , is to cyclize the compounds of formula (26)
Aro

NHCO

XR ^5, (26) wherein Ar, X, R ^1, R ² and R ³ are as defined in relation to formula (IC), in the presence of a dehydrating agent such as phosphorus pentoxide at 120-160 ° ^C.

, (27) где R³, R⁴, R⁵ и Х имеют значения, определенные в отношении формулы (IC) в растворителе, таком как диэтиловый эфир или дихлорметан, при 10-25^оС в присутствии дициклогексилкарбодиимида.Compounds of formula (26) are prepared from compounds of formula (19) as defined above by reaction with a compound of formula (27)
R

(27) wherein R ^3, R ^4, R ⁵ and X are as defined in relation to formula (IC) in a solvent such as diethyl ether or dichloromethane at 10-25 ^{° C} in the presence of dicyclohexylcarbodiimide.

 The compounds of formula (27) are known or can be obtained from known compounds using known methods.

XR⁵ (28) где Ar, Х, R³, R⁴ и R⁵ имеют значения, определенные в отношении формулы (IС), с использованием процедуры, описанной для получения соединений формулы (IC) из соединений формулы (26).Compounds of formula (IC), wherein A is N, D, is N-lower alkyl, and B — C — CR ³ R ⁴ XR ⁵ can also be prepared from compounds of formula (28)
Ar-o

XR ⁵ (28) where Ar, X, R ³ , R ^4, and R ⁵ are as defined with respect to formula (IC) using the procedure described for preparing compounds of formula (IC) from compounds of formula (26).

, (29) где Ar имеет значения, определенные в отношении формулы (IC), с использованием процедуры, описанной в отношении получения соединений формулы (26) из соединений формулы (19).Compounds of formula (28) are prepared from compounds of formula (29)
Ar-o

, (29) where Ar has the meanings defined for formula (IC) using the procedure described for preparing compounds of formula (26) from compounds of formula (19).

, (30) где Ar имеет значения, указанные в отношении формулы (IC), с использованием широкого разнообразия восстанавливающих агентов, которые могут быть выбраны из химической литературы специалистами в данном области. Восстановление может осуществляться, например, с использованием боргидрида натрия с палладиевым катализатором на древесном угле. Реакция предпочтительно проводится в органическом растворителе, таком как низший спирт, необязательно смешанном с водой, при температурах (-20)-10^оС.Compounds of formula (29) are prepared by reduction of compounds of formula (30)
Ar-o

, (30) where Ar has the meanings indicated in relation to formula (IC), using a wide variety of reducing agents that can be selected from the chemical literature by specialists in this field. Recovery can be carried out, for example, using sodium borohydride with a palladium charcoal catalyst. The reaction is preferably carried out in an organic solvent such as a lower alcohol optionally mixed with water at temperatures of (-20) -10 ^° C

Compounds of formula (30) are obtained from compounds of formula (20) as defined above, at 15-25 ^{° C} in solvents such as dimethylformamide and lower alkanols by reaction with appropriate lower alkylamines in the presence of a suitable base such as triethylamine.

(31) где Х, R³, R⁴ и R⁵ имеют значения, определенные в отношении формулы (IC), с гидридом натрия в ДМФ или ДМСО и взаимодействия полученного при аниона с соединением формулы (7), определенной выше, в ДМФ или ДМСО при 50-90^оС.A further embodiment of the invention is represented by the preparation of compounds of formula (IC) in which W is —NH— by reacting compounds of formula (31):

(31) where X, R ³ , R ^4, and R ⁵ are as defined with respect to formula (IC) with sodium hydride in DMF or DMSO and the reaction of the anion obtained with the compound of formula (7) as defined above in DMF or DMSO at 50-90 ° ^C.

(32) с помощью реакции с трифторуксусным ангидридом согласно процедуре, описанной в I.Org.Chem. 1965, 30, 1287.Compounds of formula (31) can be prepared from compounds of formula (32)

(32) by reaction with trifluoroacetic anhydride according to the procedure described in I. Org. Chem. 1965, 30, 1287.

(33)
Может широко использоваться множество разнообразных восстанавливающих агентов, и они могут быть выбраны из химической литературы специалистами в данной области. Восстановление может осуществляться, например с использованием дитионита натрия или олова и соляной кислоты, железа и соляной кислоты или водорода с палладиевым катализатором на древесном угле. Восстановление предпочтительно проводится в органическом растворителе, таком как низший алкиловый спирт, необязательно смешанном с водой, при 20-90^оС.Compounds of formula (32) are prepared by reduction of the corresponding nitro compound of formula (33)

(33)
A wide variety of reducing agents can be widely used, and they can be selected from the chemical literature by those skilled in the art. Recovery can be carried out, for example, using sodium or tin dithionite and hydrochloric acid, iron and hydrochloric acid or hydrogen with a palladium charcoal catalyst. The reduction is preferably carried out in an organic solvent such as a lower alkyl alcohol optionally mixed with water at 20-90 ° ^C.

(34) с помощью взаимодействия с соединениями формулы (7), определенной выше, в соответствии с процедурой, используемой для получения соединений формулы (IC) из соединения формулы (18).Compounds of formula (33) can be prepared from compounds of formula (34)

(34) by reaction with compounds of formula (7) as defined above, in accordance with the procedure used to prepare compounds of formula (IC) from a compound of formula (18).

 The compound of formula (34) is a known compound.

, (35) где R³, R⁴, R⁵ и Х имеют значения, определенные в отношении формулы (IC), с помощью реакции с соединениями формулы (3), определенной выше, в органическом растворителе, таком как ДМФ, ДМСО, низшие алкилкетоны, в присутствии основания, такого как гидроокиси или карбонаты щелочных металлов при 50-120^оС.The compounds of formula (IC), where A represents N, B represents C-CF ₃ , D represents NCR ³ R ⁴ XR ⁵ and W represents O, can also be obtained from compounds of formula (35)
HO

, (35) where R ³ , R ⁴ , R ⁵ and X are as defined in relation to formula (IC) by reaction with compounds of formula (3) as defined above in an organic solvent such as DMF, DMSO, lower alkyl ketones, in the presence of a base, such as hydroxides or carbonates of alkali metals at 50-120 ^about C.

(36) с помощью деметилирования с использованием трехбромистого бора в органическом растворителе, таком как дихлорметан, при (-70)^оС с последующей сложной этерификацией с использованием спирта, например этанола, и концентрированной серной кислоты при 60-80^оС.Compounds of formula (35) are prepared from compounds of formula (36)
Meo

(36) by demethylation using boron tribromide in an organic solvent, such as dichloromethane, at (-70) ^о С followed by complex esterification using alcohol, for example ethanol, and concentrated sulfuric acid at 60-80 ^о С.

 The compounds of formula (35) are new.

Compounds of formula (36) can be prepared from 6-methoxy-2-trifluoromethylbenzimidazole by reaction with compounds of formula (7) in an organic solvent such as acetonitrile, DMF, lower alkyl ketones, in the presence of a base such as alkali metal hydroxides or carbonates , at 50-120 ^about C.

6-methoxy-2-triftormetilbenzimida-sol can be prepared from the known compound 4-methoxy-1,2-phenylenediamine hydrochloride by reaction with trifluoroacetic anhydride in trifluoroacetic acid at 70-80 ^C according to the general method described in Organic Synthesis Coll. Volume 11, p. 65.

 Compounds of formula (36) are new.

CN, (37) где Ar имеет значения, определенные в отношении формулы (IC), с помощью реакции с соединением формулы (7) в подходящем растворителе, например ацетонитриле, диметилсульфоксиде, диметил- формамиде или низшем алкилкетоне, в присутствии соответствующего основания, например карбоната или гидрида щелочного металла, при 70-100^оС. Данная реакция дает два регио-изомера, которые могут легко разделяться с помощью известных приемов (например, хроматографии или препаративной ТСХ), давая два соединения формулы (IC).Compounds of formula (IC) wherein B is CR ⁶ , W is O, and R ⁶ is CN, may be prepared from compounds of formula (37)

CN, (37) where Ar is as defined in relation to formula (IC) by reaction with a compound of formula (7) in a suitable solvent, for example acetonitrile, dimethyl sulfoxide, dimethyl formamide or lower alkyl ketone, in the presence of an appropriate base, for example carbonate or an alkali metal hydride at 70-100 ° ^C. This reaction produces two regio-isomers, which can easily be separated by known techniques (e.g. chromatography or preparative tlc) to give two compounds of formula (IC).

CN,
(38) где Ar имеет значения, определенные в отношении формулы (IC) согласно способу S. Takahashi и H. Kano, Chem. Phasm. Bull. (Токио), 1219, 14, 1966.Compounds of formula (37) can be prepared from compounds of formula (38)

CN
(38) where Ar is as defined in relation to formula (IC) according to the method of S. Takahashi and H. Kano, Chem. Phasm. Bull. (Tokyo), 1219, 14, 1966.

 Compounds of formula (37) are new.

NHCH₂CN
(39) где Ar имеет значения, определенные в отношении формулы (IC), согласно способу D.I.Moody и др. I.C.S. Perkin I, 1988, 681.Compounds of formula (38) can be prepared by cyclization of compounds of formula (39)
Ar-o

NHCH ₂ CN
(39) where Ar is as defined in relation to formula (IC) according to the method of DIMoody et al. ICS Perkin I, 1988, 681.

 Compounds of formula (38) are new.

NH₂
(40) где Ar имеет значения, определенные в отношении формулы (IC), по способу D.I. Moody и др. I.C.S. Perkin I, 1988, 681.Compounds of formula (39) can be prepared from compounds of formula (40)
Ar-o

NH ₂
(40) where Ar is as defined in relation to formula (IC) according to the method of DI Moody et al. ICS Perkin I, 1988, 681.

 The compounds of formula (39) are new.

Compounds of formula (40) may be prepared from compounds of formula (23) as defined above, by hydrolysis, for example aqueous hydrochloric acid or sulfuric acid in a lower alcohol, for example ethanol, at 60-100 ° ^C.

If necessary, one or more of the following steps may be carried out:
when R ⁵ is alkoxycarbonyl, hydrolysis to the corresponding acid;
when R ⁵ is COOH, complex esterification or formation of a salt, amide, sulfonamide, hydrazide or hydrazinium derivative;
when R ⁵ is alkoxycarbonyl, reduction to the corresponding alcohol;
when R ⁵ is an amide, dehydration to the corresponding nitrile;
when A is N, the formation of a quaternary ammonium salt;
when R ⁵ is alkoxycarbonyl, alkylation with a base into an appropriate substituted ester.

 The compounds of formula (1) are active as herbicides, and therefore the invention provides a method for severely damaging or killing unwanted plants, which comprises applying to plants or a plant growth medium an effective amount of a compound of formula (1) as defined above.

 The compounds of formula (1) are active against a wide range of weed species, including monocotyledonous and dicotyledonous species. They may exhibit some selectivity with respect to certain species and be used as selective herbicides in crops of cotton, soy, corn, rice, and wheat.

 The compounds of formula (1) can be applied directly to plants (post-emergence application) or in relation to the soil before emergence of plants (pre-emergence application). They are especially useful when applied after emergence.

 The compounds of formula (1) can be used alone to inhibit the growth, severe damage or destruction of plants, but they are preferably used in the form of a composition comprising a compound of the invention in admixture with a carrier comprising a solid or liquid diluent.

 Therefore, according to yet another aspect, the invention provides compositions for inhibiting plant growth, damaging plants, or killing plants, comprising a compound of formula (1) as defined hereinabove and an inert carrier or diluent.

Compositions containing compounds of formula (1) include both diluted compositions that are ready for immediate use and concentrated compositions that require dilution before use, usually with water. Preferably, the compositions comprise 0.01-90% by weight of the active ingredient. Diluted compositions ready for use preferably contain 0.01-2% of the active ingredient, while concentrated compositions may contain 20-90% of the active ingredient, although 20-70% are usually preferred
The solid compositions may be in the form of granules or powdered powders in which the active ingredient is mixed with a finely divided solid diluent, for example kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, fuller earth and gypsum. They may also be in the form of dispersible powders or granules comprising a wetting agent to facilitate dispersion of the powder or granules in a liquid. A solid composition in the form of a powder can be used in the form of dusts for foliage.

 Liquid compositions may include a solution or dispersion of the active ingredient in water, optionally containing a surface-active agent, or may include a solution or dispersion of the active ingredient in a water-immiscible organic solvent that disperses in the form of droplets in water.

 Surfactants may be of the cationic, anionic or nonionic type, or of a mixed type. Cationic agents, for example, are quaternary ammonium compounds (e.g. cetyltrimethylammonium bromide). Suitable anionic agents are soaps, salts of aliphatic sulfuric acid monoesters, for example sodium lauryl sulfate and salts of sulfonated aromatic compounds, for example sodium dodecylbenzenesulfonate, sodium, calcium and ammonium lignosulfonate, butylnaphthalene sulfonate and mixtures of diisopropyl trisulfonic acid and sodium salts. Suitable nonionic agents are the condensation products of ethylene oxide with fatty alcohols, such as oleyl alcohol and cetyl alcohol, or with alkyl phenols, such as octyl or ionyl phenol (e.g. Agral 90) or octyl cresol. Other non-ionic agents are partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitan monolaurate; condensation products of a partial ester with ethylene oxide; and lecithins; silicone surfactants (water soluble surface active agents having a skeleton that includes a siloxane chain, for example Silvet L 77). A suitable mixture in mineral oil is Atlus 411F.

 Aqueous solutions or dispersions can be prepared by dissolving the active ingredient in water or an organic solvent, optionally containing a wetting or dispersing agent (s), and when using organic solvents, by adding the mixture thus obtained to water, optionally containing a wetting or dispersing agent (s). Suitable organic solvents include, for example, ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes and trichlorethylene.

 Compositions for use in the form of aqueous solutions or dispersions are usually supplied in the form of a concentrate containing a large amount of the active ingredient, and the concentrate is then diluted with water before use. The concentrates are required to withstand storage for extended periods of time and that after such storage they are able to be diluted with water to form aqueous preparations that remain homogeneous for a sufficient time to enable them to be used with conventional spray equipment. Concentrates conveniently contain 20-90%, preferably 20-70%, by weight of the active ingredient (s). Diluted preparations, ready for use, may contain varying amounts of active ingredient (s) depending on the intended purpose; amounts of 0.01-10.0% and preferably 0.1% -2% by weight of the active ingredient (s) are usually used.

 A preferred form of the concentrated composition comprises an active ingredient that is finely divided and which is dispersed in water in the presence of a surface-active agent and a suspending agent. Suitable suspending agents are hydrophilic colloids, and they include, for example, polyvinylpyrrolidone and sodium carboxymethyl cellulose, and vegetable gums or resins, for example acacia gum and tragacanth. Preferred suspending agents are agents that impart thixotropic properties and increase the viscosity of the concentrate. Examples of preferred suspending agents include hydrated colloidal mineral silicates such as montmorillonite, beidellite, nontronite, hectorite, saponite and suacorite. Bentonite is particularly preferred. Other suspending agents include cellulose derivatives and polyvinyl alcohol.

 The degree of use of the compounds of the invention depends on a number of factors, including, for example, the compound selected for use, the identity of the plants whose growth they want to inhibit, the form of the finished product selected for use, and whether the compound is used for foliage treatment or is it intended to be absorbed by the roots. However, as a rule, or in the form of a general guide, a degree of application of 0.01-20 kg per 1 ha is appropriate, with application rates of 0.025-10 kg per 1 ha being preferred.

 The compositions of the invention may include, in addition to one or more compounds of the invention, one or more compounds not related to the invention, but which have biological activity, for example a herbicide, fungicide, insecticide (optionally with an insecticidal synergist) or plant growth regulator. Accordingly, according to yet another aspect, the invention provides a herbicidal composition comprising a mixture of at least one herbicidal compound of formula (1) with at least one other herbicide.

 Another herbicide can be any herbicide that is not related to formula (1) (i.e., a different formula). It is usually and mainly a herbicide indicating a complementary action in a particular application.

Examples of useful complementary herbicides include
And benzo-2,1,3-thiadiazin-4-one-2,2-dioxides, such as bentazone;
To hormone herbicides, especially phenoxyalkanoic acids, such as MCPA, MCPA-thioethyl, dichloroprop, 2,4,5-T, MCPB, 2,4-D, 2,4-DV, mecoprop, trichlopyr, clopyralide and their derivatives (e.g. , salts, esters and amides);
C 1,3-dimethylpyrazole derivatives such as pyrazoxifene, pyrazolate and benzophenap;
D dinitrophenols and their derivatives (e.g. acetates), such as dinoterb, dinoseb and its ester dinoseb acetate;
E dinitroaniline herbicides such as dinitramine, trifluralin, etalflurolin, pendimethalin, oryzaline;
F arylurea herbicides such as diuron, flumeturon, methoxuron, neburon, isoproturon, chlorotoluron, chloroxuron, linuron, monolinuron, chlorobromururon, daimuron, metabenzothiazuron;
G phenylcarbamoyloxyphenylcarbamates such as phenmedipham and desmedipham;
H 2-phenylpyridazin-3-ones such as chloridazone and norflurazone;
I uracil herbicides such as lenacil, bromacil and terbacil;
triazine herbicides such as atrazine, simazine, aziprotrin, cyanazine, promethrin, dimetamethrin, simetrin and terbutrin;
K phosphorothioate herbicides such as piperophos, benzulide and butamiphos;
L thiol carbamate herbicides such as cycloate, vernolate, molinate, thiobenocarb, butylate *, EPTC *, tri-allate, di-allate, esprocarb, thiocarbazyl, pyridate and dimepiperate;
M 1,2,4-triazin-5-one herbicides such as metamitron and metribucin;
N benzoic acid herbicides such as 2,3,6-TBA, dicamba and chloramben;
O anilide herbicides such as tretylachlor, butachlor, alachlor, propachlor, propanyl, metazachlor, metolachlor, acetochlor and dimethachlor;
P dihalobenzonitrile herbicides such as dichlobenil, bromoxynil and ioxynil;
Q haloalkane herbicides such as dalapon, TCA and their salts;
R diphenyl ether herbicides such as lactophen, fluroglycofen or their salts or esters, nitrofen, biphenox, aciflurofen and its salts and esters, oxyfluorfen, fomesafen, chloronitrophen and chlomethoxifene;
S phenoxyphenoxypropionate herbicides such as diclofop and its esters such as methyl ester, fluazifop and its esters, haloxifop and its esters, chisalofop and its esters and fenoxaprop and its esters such as ethyl ether;
T cyclohexanedione herbicides, such as alloxydim and its salts, sethoxydim, cycloxydim, tralkoxydim and celodime;
U sulfonylurea herbicides such as chlorosulfuron, sulfomethuron, metsulfuron and its esters, benzosulfuron and its esters such as DRX-M6313, chlorimuron and its esters such as ethyl ether, pyrimisulfuron and its esters such as methyl ether, 2- [3- (4-methoxy-6-methyl-1,3,5-triazin-yl] -3-methylureidosulfonyl (benzoic acid esters), such as methyl ether (DRX-LS 300) and pyrazonsulfuron;
V imidazolidinone herbicides such as imazahine, imazamethabenz, imazapyr and its isopropylammonium salts, imazetopyr;
W aryl anilide herbicides such as flamprop and its esters, benzoylpro-ethyl, diflufenican;
X amino acid herbicides such as glyphosate and glyphosinate and their salts and esters, sulfosate and bialaphos;
Y arsenic-organic herbicides such as monosodium arsenate (M S MA);
Z herbicidal amide derivatives such as napropamide, propisamide, carbetamide, tebutam, bromobutide, isoxaben, naproanilide and naptalam;
AA mixed herbicides, including etofumezate, cinmethylin, diphenzquat and its salts, such as methyl sulphate salt, clomazone, oxadiazone, bromofenoxime, barban, tridifan, flurochloride, quinchlorac, dithiopyr and mefanacet;
BB Examples of useful contact herbicides include:
bipyridylium herbicides, such as those in which the active part is paraquat, and those herbicides in which the active principle is diquat;
* These compounds are preferably used in combination with a safety agent (antidote) such as dichloromide.

 PRI me R 1. Obtaining compound I (table. 1).

 Stage A.

6-nitroindazole (10 g) was dissolved in dry DMF (200 cm ³ ) and 50% sodium hydride (2.94 g) was added portionwise with stirring. After 20 minutes, ethyl 2-bromopropionate (8 cm ³ ) was added, and the mixture was stirred at room temperature for 4 hours, poured into water (1 L) and extracted four times with ethyl acetate. The combined organic extracts were washed with water, dried (magnesium sulfate), filtered, and the filtrate was concentrated in vacuo. The residue was purified by chromatography (silica, hesan: tert-butyl methyl ether; 7: 3) to give ethyl 2- (6-nitroindazol-1-yl) propionate (1.3 g), mp. 99.7-100.1 ^about C, M ⁺ = 263;
NMR (CDCl ₃ ): 1.21 (triplet) 3H, 2.0 (d), 3H, 4.2 (q) 2H, 5.41 (q) 1H, 7.25 (s) 1H, 7.85 (d) 1H, 8.05 (d. .) 1H, 8.19 (s.) 1H, 8.4 (s.) 1H.

 Stage B.

Ethyl 2- (6-nitroindazol-1-yl) propionate (1 g), water (3.7 cm ³ ) and reduced iron (2.3 g) were mixed in isopropanol (17 cm ³ ) at room temperature. Concentrated hydrochloric acid (0.14 cm ³ ) was added, and the mixture was stirred and heated at reflux for 20 minutes. The mixture was filtered through hyphlo while being hot, and the filter medium was washed with ethanol. The combined filtrate was concentrated in vacuo, and the residue was purified by chromatography (silica, chloroform ether, 3: 1) to give ethyl 2- (6-aminoindazol-1-yl) propionate (0.64 g). M ⁺ = 233.

NMR (CDCl ₃ ): 1.19 (t) 3H, 1.88 (d) 3H, 3.88 (s) 2H, 4.16 (q) 2H, 5.18 (q) 1H, 6.52 (s) 1H, 6.58 ( dd.) 1H, 7.49 (d) 1H, 7.97 (s) 1H.

 Stage C.

Ethyl 2- (6-aminoindazol-1-yl) propionate (0.49 g) was mixed with hot 35% sulfuric acid (2.12 cm ³ ), ice, (2.12 g) was added, and the mixture was cooled in a bath of ice / salt mixtures. Dropwise at ⁰ ° C was added sodium nitrite (0.187 g) in water (2 cm ^3). The mixture was stirred 5 min at ⁰ ° C and a few crystals of urea were added. Then added hydrated copper nitrate (II) (8 g) in water (74 cm ³⁾ followed by the addition of copper oxide (I) (0,3 g) and the mixture was stirred 15 min at ⁰ ° C and for 1.5 h at room temperature. The reaction mixture was extracted four times with ethyl acetate, the combined organic extracts were washed with water, dried (magnesium sulfate), filtered, and the filtrate was concentrated in vacuo. The residue was purified by chromatography (silica, diethyl ether, then hexanediyl ether, 35:65) to give ethyl 2- (6-hydroxyindazol-1-yl) propionate (30 mg).

NMR (CDCl ₃ ): 1.16 (t) 3H, 1.88 (d) 3H, 4.14 (q) 2H, 5.20 (q) 1H, 6.67 (s) 1H, 6.76 (m) 2H, 7.55 ( d.) 1H, 7.95 (s.) 1H.

 Stage D.

Ethyl 2- (6-hydroxyindazol-1-yl) propionate (30 mg) was dissolved in (0.72 cm ³ ) a mixture of dry methyl isobutyl ketone (6 cm ³ ) and 1 drop of dry DMF, 3-chloro-4,5-difluorobenzotrifluoride was added (42 mg) and dry potassium carbonate (27 mg). The mixture was stirred and heated at reflux for 7 hours, after which additional dry potassium carbonate was added after 3 hours. After cooling, the solvents were removed in vacuo and diethyl ether was added to the residue, the mixture was filtered, and the inorganic part was washed thoroughly with diethyl ether. The combined ether filtrate was concentrated in vacuo and the residue was purified by chromatography (silica, 4: 1 hexane-tert-butyl methyl ether) to give compound I, ethyl 2- [6- (2-chloro-4-trifluoromethyl-6- fluorophenoxy) indazol-1-yl] propionate (29 mg). M ⁺ = 430.

 PRI me R 2. This example illustrates the preparation of compound 1 in the table. 1 and compounds 33 in the table. 2.

 Stage A.

3-chloro-4,5-difluorobenzotrifluoride (99 g) was dissolved in dry MVIK (100 cm ³ ), and 25 drops of dry DMF and dry potassium carbonate (48 g) were added. The mixture was stirred and refluxed, while a solution of 4-methyl-3-nitrophenol (35 g) in dry MIBK (methyl isobutyl ketone) (70 cm ³ ) was added over 1 h. When the addition was complete, stirring and refluxing continued for 2 hours. The solvent was removed from the reaction mixture under vacuum, and the residue was triturated with water (500 cm ³ ). The resulting solid was filtered off, washed with water and dried in air. The crude solid was recrystallized from ethanol to give 4- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) -2-nitrotoluene (73.5 g) as an off-white solid, mp. 112.8-115.4 ^about S.

 Stage B.

4- (2-Chloro-6-fluoro-4-trifluoromethylphenoxy) -2-nitrotoluene (5.57 g) and reduced iron powder (9.7 g) were suspended in isopropanol (73 cm ³ ) and water was added ( 16 cm ³ ) and concentrated hydrochloric acid (0.83 cm ³ ). The mixture was stirred at reflux for 7 h, then it cooled down and filtered through Hyflo. The filter medium was washed with hot ethanol. The combined filtrate was evaporated to dryness, dissolved in ethyl acetate and washed with brine. The organic phase was dried (magnesium sulfate), filtered, and the filtrate was evaporated to dryness, giving a brown oil, which was purified by flash phromatography (CHCl ₃ ), giving 4- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) -2-aminoto- luol (4 g) as a pale brown oil. M ⁺ = 320.

NMR (CDCl ₃ ): δ2.1 (s) 3H, 3.55-3.70 (s) 2H, 6.28 (dd) 1H, 6.21 (d) 1H, 6.93 (d) 1H, 7.36 (dd) 1H, 7.56 (s.) 1H.

 Stage C.

4- (2-Chloro-6-fluoro-4-trifluoromethylphenoxy) -2-aminotoluene (3.66 g) was dissolved in toluene (34 cm ³ ), and anhydrous potassium acetate (1.14 g) and acetic anhydride were added. (3.54 g). The mixture was stirred and heated under reflux for 30 minutes. Heating was reduced and added dropwise over 20 min at 90 ° ^C was added isoamyl nitrite (2.04 g). After the addition was completed, stirring and heating continued for another 3 hours, then the mixture was cooled and shaken with water (100 cm ³ ) in a separatory funnel. The organic phase was separated, and the aqueous phase was extracted twice with ethyl acetate. The combined organic phase was washed with water, dried (magnesium sulfate) was filtered, and the filtrate was evaporated under reduced pressure to give a brown oil, which was purified by flash chromatography (CHCl ₃ : hexane, 9: 1) to give 1-acetyl-6- (2 -chloro-6-fluoro-4-trifluoromethylphenoxy) indazole (2.32 g) as a light brown oil. M ⁺ = 372.

NMR (CDCl ₃ ): δ2.74 (s) 3H, 7.09 (dd) 1H, 7.42 (dd) 1H, 7.61 (s) 1H, 7.7 (d) 1H, 7.85 (s) 1H, 8.09 (p.) 1H.

 Stage D.

1-Acetyl-6- (2-chloro-6-fluoro-4-trifluoro-methylphenoxy) indazole (2.05 g) was stirred and heated under reflux with methanol (10 cm ³ ) and concentrated hydrochloric acid (6 cm ³ ) in for 2 hours, and then left to stand at room temperature for 48 hours. The solvent was removed in vacuo and the residue was partitioned between ethyl acetate and saturated sodium bicarbonate. The organic phase was washed with water, dried (magnesium sulfate), filtered, and the solvent was removed from the filtrate in vacuo. The residue, a brown oil, was purified by flash chromatography (CHCl ₃ ethyl acetate, 85:15) to give 6- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) indazole (1.3 g) as a straw-colored oil which hardened upon standing. Mp 133.9-143.1 ^about C M ⁺ = 330.

NMR (CDCl ₃ ): δ6.82 (s) 1H, 6.93 (dd) 1H, 7.42 (dd) 1H, 7.61 (s) 1H, 7.71 (d) 1H, 8.04 (s) 1H, 10.1-10.4 (s.) 1H.

 Stage E.

6- (2-Chloro-6-fluoro-4-trifluoromethylphenoxy) indazole (0.7 g) was dissolved in dry DMF (1.5 cm ³ ) and cooled in a water bath, while 50% sodium hydride was added (0 , 1 g) in portions with stirring. The mixture was stirred for 10 minutes and ethyl 2-bromo-propionate (0.42 g) was added. The mixture was stirred with cooling for 5 minutes and then at room temperature for 8.5 hours. The reaction mixture was poured into water (15 cm ³ ) containing 2M hydrochloric acid (1 cm ³ ) and the mixture was extracted three times with ethyl acetate. The organic phase was combined, washed with water, dried (magnesium sulfate), filtered, and the solvent was removed from the filtrate in vacuo. The residue was purified by flash chromatography (hexane: TBME, 7: 3) to give compound I, ethyl 2- [6- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) indazol-1-yl] propionate (0.51 d) as a colorless oil, and compound 33 ethyl 2- [6- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) indazol-2-yl] propionate (0.154 g) as an oil.

 Compounds NN 2, 10, 11, 12, 34, 35 and 36 were obtained using a similar method using the appropriate reagents.

PRI me R 3. This example illustrates the preparation of compound 3 in the table. 1. Ethyl 2 [6- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) indazol-1-yl] propionate obtained as described in Example 2 (30 mg) was dissolved in THF (0 , 1 cm ³ ) and isopropanol (0.28 cm ³ ). 1.7 M sodium hydroxide (0.04 cm ³ ) was added and the mixture was stirred at room temperature for 8 hours and allowed to stand overnight. The solvent was removed in vacuo, and the residue was dissolved in water (2 cm ³ ). 2M hydrochloric acid (0.035 cm ³ ) was added dropwise with stirring. After 1.5 hours, the solid was filtered off, washed with water and dried with air to give 2- (6- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) indazol-1-yl) propionic acid (11 mg) as a white solid substances. Compound 4 was prepared using a similar process using the appropriate reagents.

 PRI me R 4. This example illustrates the preparation of compound 5 in the table. 1.

6- (2-Chloro-6-fluoro-4-trifluoromethylphenoxy) indazol-1-yl-acetic acid, prepared as described in Example 3 (0.319 g), was suspended in dry dichloromethane (6 cm ³ ) and methanol was added (0.04 cm ³ ) and DMAR (10 mg). Dicyclohexylcarbodiimide (0.169 g) was added and the mixture was stirred at room temperature for 2 hours and allowed to stand overnight. The mixture was filtered and the solvent was removed from the filtrate in vacuo. The residue was purified by flash chromatography (hexane: TMBE, 3: 2) to give methyl 2- [6- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) indazol-1-yl] acetate (0.28 g) in the form of oil that hardens upon standing.

 Compounds NN 51 and 52 were obtained in a similar manner using the appropriate reagents.

 PRI me R 5. This example illustrates the preparation of compound 9 in the table. 1.

 Stage A.

Following the RR Davies methodology (ICS 2412, (1955)), ethyl 2- (6-aminoindazol-1-yl) propionate, prepared as described in Step B of Example 1 (8 g), was added to water (34 cm ³ ) and concentrated sulfuric acid (3.4 g) contained in an autoclave. The mixture was heated at 170 ° ^C and 110 pounds / square inch (7.73 kg / cm ²⁾ 11 h. After cooling, the contents were decanted and the autoclave rinsed with water. The crude product was dissolved in 2M sodium hydroxide, and the solution was acidified again to pH 6. The precipitated solid (2.25 g) was removed by filtration, washed with water and dried with air. The aqueous filtrate was extracted with ethyl acetate three times, the combined organic phase was dried (magnesium sulfate), filtered, and the solvent was removed from the filtrate in vacuo to give a dark yellow solid (2.32 g).

The aqueous residue from the extraction was evaporated and azeotropically distilled (ethanol) to dryness, giving a dark brown solid. Each solid fraction was treated with ethanol (50 cm ³ ) saturated with hydrogen chloride for 2 hours. TLC (CHCl ₃ : diethyl ether, 3: 1) showed that each fraction gave the same product. The three reaction products were combined and the solvent was removed in vacuo. The residue was partitioned between ethyl acetate and water, and the organic phase was washed with water, dried with magnesium sulfate, filtered, and the solvent was removed in vacuo to give a black gum; which was purified by flash chromatography (CHCl ₃ : diethyl ether, 3: 1) to give ethyl 2- (6-hydroxyindazol-1-yl) propionate (4.61 g) as a brown oil M ⁺ = 234.

NMR (CDCl ₃ ): δ1.16 (t), 3H, 1.88 (d) 3H, 4.14 (q) 2H, 5.21 (q) 1H, 6.18 (s) 1H, 6.74 (m) 2H 7.55 (d) 1H, 7.94 (s) 1H.

 Stage B.

3-Chloro-4-fluorobenzotrifluoride (0.64 g) and ethyl 2- (6-hydroxyindazol-1-yl) propionate (0.5 g) were dissolved in dry DMSO (5 cm ³ ) and dry potassium carbonate (0 44 g). The mixture was stirred and heated at ¹⁰⁰ ° C for 4 hours. The solvent was removed in vacuo, the residue dissolved in ethyl acetate and water, the organic phase was separated and washed with brine. The organic phase was dried with magnesium sulfate, filtered, and the solvent was removed from the filtrate in vacuo. The residue was purified by flash chromatography (hexane TBME, 7: 3) to give ethyl 2- [6- (2-chloro-4-trifluoromethylphenoxy) indazol-1-yl] propionate (0.425 g) as a colorless oil.

 Compounds NN 6, 14, 15, 16, 17, 21, 22, 23 and 38 were obtained in a similar manner using the appropriate reagents.

 PRI me R 6. Obtaining connection 37.

2-Fluoro-3-chloro-5-trifluoromethylpyridine (0.64 g) and ethyl 2- (6-hydroxyindazol-1-yl) propionate, obtained as described in example 1, step C (0.5 g) were dissolved in dry methyl isobutyl ketone (12 cm ³ ) and dry potassium carbonate (0.44 g) and 2 drops of dry DMF were added. The mixture was stirred and heated at ¹⁰⁰ ° C for 6 hours. The solvent was removed under vacuum and the residue dissolved in chloroform and water. The organic phase was separated, dried (phase-separation paper), and the solvent was removed from the filtrate in vacuo. The residue was purified by flash chromatography (hexane: TBME, 7: 3) to give ethyl 2- [6- (3-chloro-5-trifluoromethylpyrid-2-yloxy) indazol-1-yl] propionate (0.58 g) in a colorless oil.

 Compounds NN 7 and 8 were obtained using a similar process using the appropriate reagents.

 PRI me R 7. Obtaining compound 31 in the table. 1.

 Stage A.

3-Chloro-6-nitroindazole (20 g) was dissolved in dry DMF (180 ^cm3) and the solution cooled to 5 ^° C was added portionwise 50% sodium hydride (4.86 g) under stirring and cooling between 5 and 10 ^about With, and then for an additional 15 minutes Was added slowly ethyl bromoacetate (16.91 g) at 5 ^{° C,} the reaction mixture was warmed to 30 ^C. The reaction mixture was then stirred ^at 20 ° C for 4 hours. Water (1 L), and the mixture was acidified with dilute hydrochloric acid, shaken with ethyl acetate and filtered through Hyflo. The organic phase was separated from the filtrate, and the aqueous phase was extracted twice with ethyl acetate. The combined organic phase was washed with water, dried with magnesium sulfate, filtered and the solvent was removed from the filtrate in vacuo. The residue was purified by flash chromatography (silica), a mixture of gesan and TBME, 7: 3, and then a mixture of chloroform: ethyl acetate 95: 5), giving ethyl 3-chloro-6-nitroindazole-1-yl acetate (16.25 g) in the form of a pale yellow solid, mp 109.1-110.3 ^about C.

NMR (CDCl ₃ ): δ1.29 (t) 3H, 4.26 (q) 2H, 5.18 (s) 2H, 7.84 (d) 1H, 8.10 (dd) 1H, 8.30 (s) 1H.

 Stage B.

Ethyl 3-chloro-6-nitroindazole-1-yl acetate (16.25 g) was dissolved in hot isopropanol (260 cm ³ ), stirred and reduced iron powder was added (35.4 g) followed by water (57 cm ³ ) and concentrated hydrochloric acid (2.1 cm ³ ). The mixture was stirred and heated at reflux for 30 minutes, and then filtered, while hot, through Hyflo. The solvent was removed from the filtrate in vacuo, and the residue was partitioned between soda and chloroform. The organic phase was filtered through phase separation paper, and the solvent was removed from the filtrate in vacuo to give a pale yellow solid (12.6 g). The crude solid was recrystallized from hexane / ethyl acetate to give ethyl 6-amino-3-chloroindazole-1-yl acetate (7.42 g) as a dark yellow (buffalo color) crystal, m.p. 151.7-152.2 ^about C.

NMR (CDCl ₃ ) δ1.24 (t) 3H, 3.94 (s) 2H, 4.20 (q) 2H, 4.91 (s) 2H, 6.38 (s) 1H, 6.60 (d) 1H 7.42 (d) 1H.

 Stage C.

Ethyl 6-amino-3-chloroindazole-1-yl acetate (11.5 g) was heated with 35% sulfuric acid to obtain a solution. Ice (54 g) was added and the solution was cooled to (-5) ^° C in an ice and salt bath. A solution of sodium nitrite (4 g) in water (43 cm ³⁾ was added slowly with stirring and cooling at 0 ° ^C. When the addition was complete, the mixture was stirred 15 min at ⁰ C. A precooled solution (5 ° ^C) of copper nitrate ( 173 g) in water (1.6 l) with stirring and cooling at ⁵ ° C. a copper oxide (I) (6,5 g) and the mixture was stirred at ⁰ ° C for 0.5 hours, after which it was allowed to warm to room temperature for 4.5 hours. The reaction mixture was extracted with ethyl acetate (4 times), and the combined organic phase was washed with water, dried with magnesium sulfate, filtered and the solvent removed from the filtrate under vacuum. The residue was mixed with ethanol (400 cm ³ ), saturated with hydrogen chloride overnight, evaporated in vacuo, and then partitioned between water and ethyl acetate. The organic phase was washed with water, dried with magnesium sulfate, filtered and the solvent was removed from the filtrate in vacuo. The residue was purified by flash chromatography (silica, chloroform) ether, 3: 2) to give ethyl 3-chloro-6-hydroxyindazol-1-yl acetate (4.34 g) as a brown solid, recrystallized from toluene, pl. 138-142 ^about S.

NMR (CDCl ₃ ) δ1.25 (t) 3H, 4.19 (q) 2H, 4.95 (s) 2H, 6.05 (s) 1H, 6.62 (s) 1H, 6.76 (dd) 1H, 7.49 (d.) 1H.

 Stage D.

Ethyl 3-chloro-6-hydroxyindazole-1-yl acetate (1.615 g), 3-chloro-4,5-difluorobenzotrifluoride (2.1 g), anhydrous potassium carbonate (1.31 g) were mixed and heated under reflux 3.5 h in MIWK (35 cm ³ ) containing dry DMF (9 drops). After cooling, the solvent was removed from the reaction mixture under vacuum and the residue was triturated with ether (70 cm ³ ), filtered, and the solvent was removed from the filtrate under vacuum. The residue was purified by flash chromatography (silica, hexane: TBME, 4: 1) to give compound N 31 ethyl 3-chloro-6- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) indazol-1-yl acetate (1.5 g) as a colorless oil.

 Compounds NN 13, 24, 25, 26, 27, 28, 29, 30, 39, 40, 42, 43, 44, 45, 46, 47, 48, 49, 53, 54 and 55 were obtained using similar processes using appropriate reagents.

 PRI me R 8. Obtaining compound 32 (table. 1).

2- [6- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) indazol-1-yl] propionic acid (0.44 g) (prepared as described in Example 3), dicyclohexylcarbodiimide (0.23 g ) and 1,1 (dimethylhydrazine) (0.066 g) were stirred at room temperature in dry dichloromethane (5 cm ³ ) for 4.5 hours. The mixture was filtered and the solvent was removed from the filtrate in vacuo. The residue was purified by flash chromatography (silica, ethyl acetate: hexane, 4: 1 followed by ethyl acetate) to give compound 32 2- [6- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) indazol-1-yl] propionyl -N, N-dimethyl hydrazide (0.36 g), mp 173.5-174.9 ^about C M ⁺ = 444.

 PRI me R 9. Obtaining compound 20 (table. 1).

2- [6- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) indazol-1-yl] propionyl-N, N-dimethylhydrazide (0.36 g) (obtained as in Example 8) was dissolved in methanol (14 cm ³ ), and methyl iodide (1.16 cm ³ ) was added with stirring. The mixture was allowed to stand in a sealed flask for 18 days at room temperature. The solvent was removed in vacuo and the residue was triturated with ether to give 20, 2- [6-2-chloro-4-trifluoromethyl-6-fluorophenoxy) indazol-1-yl] propionyltrimethylhydrazinium iodide (0.369 g) as a pale yellow solid, mp 166.8-167.5 ^about S.

 PRI me R 10. Obtaining compound 19 (table. 1).

Ethyl 2- [6- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) indazol-1-yl] propionate (0.41 g) (obtained as described in Example 1) was dissolved in methanol (25 cm ³ ), 880 ammonia (15 cm ³ ) was added and the mixture was stirred at room temperature for 18 hours. A white precipitate was collected by filtration and the solvent was removed from the filtrate in vacuo. The residue was purified by flash chromatography (silica, ethyl acetate) to give compound 19, 2- [6- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) indazol-1-yl] propionamide as a white solid; total yield 250 mg, mp 171-172.5 ^about S.

 PRI me R 11. Obtaining compound N 56.

2- [6- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) indazol-1-yl] propionic acid (0.45 g) was suspended in dry 1,2-dichloroethane (5 cm ³ ) and added thionyl chloride (0.1322 g) together with 1,2-dichloroethane (3 cm ³ ). The mixture was stirred and heated under reflux for 3 hours, cooled, and the solvent was removed in vacuo. Dry 1,2-dichloroethane (5 cm ³ ) was added to the residue, the solution was stirred and cooled in ice water, and DMAP (0.136 g) was added, followed by methanesulfonamide (0.106 g). The mixture was stirred at room temperature overnight, and the solvent was removed in vacuo. The residue was purified by flash chromatography (silica, chloroform: acetone: glacial acetic acid, 900: 67: 33) to give 2- [6- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) indazol-1-yl] -N- (methylsulfonyl) propi (0.39 g) as a white solid, mp. 175-177 ^about S.

 PRI me R 12. Obtaining compound 61 in the table. 4 and compound 75 in the table. 5.

Stage A. 4- (2-Chloro-4-trifluoromethyl-6-fluorophenoxy) -1,2-diaminobenzene (5.65 g) was stirred overnight at room temperature with a mixture of trifluoroacetic acid (9.6 cm ³ ) and trifluoroacetic anhydride (2.6 cm ³ ). The mixture was then heated under reflux for 2 hours, cooled and added to ice water (100 cm ³ ). With stirring, 2M sodium hydroxide (71 cm ³ ) was added and the mixture was shaken with ethyl acetate. Additional small amounts of 2M sodium hydroxide were added until the mixture changed color from dark blue to pink. The aqueous phase was separated and the organic extract was washed with water. The organic phase was dried with magnesium sulfate, filtered, and the solvent was removed from the filtrate in vacuo. The residue was triturated with hexane to give a solid (6.26 g), mp. 170.2-171.9 ° C. A portion ^{of the} material was purified by flash chromatography (silica, CHCl ₃ : diethyl ether, 96: 4) to give 2-trifluoromethyl-6- (2-chloro-4-trifluoromethyl-6- fluorophenoxy) benzimidazole. M ⁺ = 398.

 Stage B.

2-Trifluoromethyl-6- (2-chloro-4-trifluoro-methyl-6-fluorophenoxy) benzimidazole (2 g) was dissolved in dry acetonitrile (10 cm ³ ), and ethyl 2-bromopropionate (0.93 g) and dry potassium carbonate (1.04 g). The mixture was stirred and heated under reflux for 2 hours, cooled and filtered. The filtrate was concentrated in vacuo to give a dark brown oil. The oil was purified by chromatography (silica, CHCl ₃ and then CHCl ₃ : diethyl ether, 95: 5) to give ethyl 2- [2-trifluoromethyl-5- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) benzimidazole - 1-yl] propionate, (0.76 g) (compound 61) as a faster component and ethyl 2- [2-trifluoromethyl-6- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) benzimidazol-1- sludge] propionate, (compound 75) (0.62 g) as a slower component.

 PRI me R 13. Obtaining compound 93.

Ethyl 2- [2-trifluoromethyl-6- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) benzimide-zol-1-yl] propionate, (0.43 g), was dissolved in dry dichloromethane (1.4 cm ³ ), and a 1M solution of triethyloxonium tetrafluoroborate (0.86 cm ³ ) was added with stirring. The reaction mixture was allowed to stir at room temperature for 7 days, then the solvent was removed in vacuo. The residue was triturated with ether and a solid collected, which was washed with ether and dried to give ethyl 2- [6- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) -3-ethyl-2-trifluoromethylbenzimide-zol-1-yl ] propionate tetrafluoroborate compound 93 (0.227 g), mp. 135-136.1 ^about S.

 Compound 92 in the table. 4 was obtained in a similar manner using the appropriate reagents.

 PRI me R 14. Obtaining compound 95.

 Stage A.

4- (2-Chloro-4-trifluoroethyl-6-fluorophenoxy) -1,2-diaminobenzene (1.04 g), monomethyl 2-methylmalonate (473 mg) and DMAP (20 mg) were dissolved in stirred, ice-cold dry dichloromethane (20 cm ³ ) and dicyclohexylcarbodiimide (690 mg) was added. The mixture was stirred at room temperature for 24 hours, filtered, and the filtrate was concentrated in vacuo. The residue was purified by column chromatography (silica, hexane: ethyl acetate, 3: 2) to give ethyl 2- [2-amino-4- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) phenylcarbamoyl] propionate, (0.58 g) M ⁺ = 448.

NMR (CDL ₃ ): δ1.3 (t) 3H, 1.55 (d) 3H, 3.48 (q) 1H, 3.9 (br.s) 1H, 4.25 (q) 2H, 6.25 (dd) 1H 6.32 (d) 1H, 7.1 (d) 1H, 7.93 (dd) 1H, 7.58 (s) 1H, 8.12 (br.s) 1H.

Stage B. Ethyl- [2-amino-4- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) phenylcarbamoyl] propionate (0.4 g) and phosphorus pentoxide (0.5 g) were heated at 140-160 ° C. ^for 2 hours. After cooling, water was added followed by sodium carbonate to adjust the pH to 4-5. A beige precipitate was collected, air dried, dissolved in methanol and treated with decolorizing charcoal. The filtrate was concentrated in vacuo to give ethyl 2- [6- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) benzimide-zol-2-yl] propionate, compound 95 (0.33 g) as a pale brown glass.

 PRI me R 15. Obtaining connection 94.

Stage A
Triethylamine (1.64 cm ³ ) in DMF (4 cm ³ ) was added to a stirred solution of 4- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) - 1,2-dinitrobenzene (2.24 g) and methylamine hydrochloride ( 0.45 g) in dry DMF (6 cm ³ ) at room temperature. Stirring was continued for 2.5 days. The mixture was added to saline, acidified and extracted with ethyl acetate. The organic extract was washed with brine, dried over magnesium sulfate, filtered, and the filtrate was concentrated in vacuo to give 2.3 g of a bright yellow oil. The oil was purified using column chromatography (silica, hexane: diethyl ether, 9: 1) to give 4- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) -2-methylamine-1-nitrobenzene (0, 71 g) M ⁺ = 364.

NMR (SDL ₃ ): δ2.88 (d) 3H, 6.0 (dd) 1H, 6.24 (d) 1H, 7.38 (dd) 1H, 7.54 (s) 1H, 8.1 (d + br. s.) 2H.

 Stage B.

5% palladium on charcoal (0.12 g) was added to stirred ice-cooled methanol (15 cm ³ ) while blowing nitrogen, while sodium borohydride (0.25 g) in water (7 cm ³ ) was added dropwise. At 2-5 ^{° C} dropwise over 20 minutes added 4- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) -2-methylamino-1-nitrobenzene sol (0.81 g) in methanol (80 cm ³ ), the mixture was then stirred at room temperature for 2 hours. The mixture was filtered (hyphlo) and the filtrate was evaporated in vacuo. Water was added to the residue, and the aqueous mixture was extracted with chloroform. The combined chloroform extracts were filtered (phase separation paper) and the filtrate was evaporated in vacuo. The crude product was purified by column chromatography (silica, hexane: ethyl acetate, 3: 2) to give 4- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) -2-methylaminoaniline (0.48 g) kind of oil.

NMR (CDCl ₃ ): δ2.84 (s) 3H, 6.0 (dd) 1H, 6.39 (d) 1H, 6.6 (d) 1H, 7.37 (dd) 1H, 7.58 (s) 1H.

 Stage C.

4- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) -2-methylaminoaniline (0.48 g), monoethyl 2-methylmalonate (0.38 g), DMAP (20 mg) were dissolved in stirred dry dichloromethane ( 5 cm ³ ). The mixture was cooled with cold water, dicyclohexylcarbodiimide (0.34 g) was added, and the ses was allowed to stand overnight at room temperature. The mixture was filtered (hyphlo) and the filtrate was concentrated in vacuo. The residue was purified using preparative plates (silica, CH ₂ Cl ₂ : diethyl ether, 9: 1) to give ethyl 2- [2-methylamino-4- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) phenylcarbamoyl] propionate (0.38 g) as a white solid.

NMR (CDL ₃ ): δ 1.3 (t), 1.55 (d), 2.82 (s) 3H, 3.48 (q) 1H, 4.25 (q + br s) 3H, 6.05 (dd) 1H 7.08 (d) 1H, 7.39 (dd) 1H, 7.58 (s) 1H, 7.86 (s) 1H.

 Stage D.

Ethyl 2- [2-methylamino-4- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) -fenilkarbamoil] propionate (0.36 g) and phosphorus pentoxide (0.5g) were heated together at 140-160 ^C. within 2 hours. After cooling, water was added followed by sodium carbonate to adjust the pH to 5-6. A saline solution was added and the aqueous mixture was extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulfate, filtered, and the filtrate was concentrated in vacuo. The residue was purified by preparative plate chromatography (silica, methylene dichloride: diethyl ether, 85:15) to give ethyl 2- [1-methyl-6- (2-chloro-4-trifluoromethyl-6-fluoro-phenoxy) benzimidazole- 2-yl] propionate, compound 94, (0.19 g) as a pale yellow solid, mp. 123.2-128.6 ^about S.

 PRI me R 16. Obtaining compound 69 in the table. 4 and compounds 84 in table. 5.

 Stage A.

4-Methoxy-1,2-phenylenediamine hydrochloride (35 g) was dissolved in trifluoroacetic acid (100 s ³ ), and trifluoroacetic anhydride (28 cm ³ ) was slowly added to the stirred solution. The mixture was heated under reflux for 2 hours, cooled to room temperature overnight, and made basic with 6 M sodium hydroxide while cooling with ice. The aqueous mixture was extracted three times with ethyl acetate, and the combined organic phase was washed with brine, then with water, treated with decolorizing activated carbon, and dried with magnesium sulfate. After filtration, evaporation under reduced pressure gave an orange-brown solid (14.4 g), which was triturated with petrol (gasoline), filtered and air dried to give 6-methoxy-2-trifluoromethylbenzimidazole (14.02 g) as a solid buffalo colored substance.

NMR (CDL ₃ ): δ3.85 (s) 3H, 7.05 (dd) 1H, 7.1 (dd) 1H, 7.6 (d) 1H.

 Stage B.

6-Methoxy-2-trifluoromethylbenzimidazole (14 g) and ethyl bromoacetate (11.94 g) were dissolved in dry acetonitrile (200 cm ³ ). Anhydrous potassium carbonate (15 g) was added, and the mixture was stirred and heated under reflux for 2.5 hours and allowed to cool to room temperature overnight. The reaction mixture was filtered and the solvent was removed from the filtrate under reduced pressure to give a mixture of ethyl 5- and 6-methoxy-2-trifluoromethylbenzimidazol-yl acetate (19.9 g) as a thick orange-brown oil, which solidified upon standing.

NMR (CDL ₃ ): δ1.25 (m) 6H, (2xCH ₃ ), 3.88 (d) 6H, (2xOCH ₃ ), 4.25 (m) 4H (2xCH ₂ ), 5.5 (d) 4H ( 2xCH ₂ ), 6.72 (d) 1H, 7.02 (dd) 1H, 7.1 (dd) 1H, 7.25 (d) 1H, 7.32 (d) 1H, 7.7 (d) 1H.

 Stage C.

A mixture of ethyl 5- and 6-methoxy-2-trifluoromethylbenzimidazole-I-yl-acetate (6g from step 2) was dissolved in dry dichloromethane (100 m ³⁾ under a nitrogen atmosphere and cooled to (-70) ^° C dropwise with stirring at (-70) ^{° C} was added boron tribromide (25 g) in dry dichloromethane (10 cm ³⁾ to give a bright brown precipitate. After the addition was complete, the mixture was stirred at room temperature for 3 hours. It was then cooled at ⁰ C and was added dropwise ethanol (45 cm ³⁾ whilst maintaining the temperature below 5 ° ^C. After the addition was complete, the mixture was stirred at room temperature for overnight, and then the solvents were removed in vacuo. Ethanol (100 cm ³ ) was added to the residue, followed by concentrated sulfuric acid, and the solution was heated under reflux for 1.5 hours, cooled, and the solvent was removed in vacuo. Water (100 cm ³ ) was added and the mixture was made basic with an ammonia solution and extracted three times with ethyl acetate. The combined organic phase was washed with water, dried with magnesium sulfate, filtered, and the solvent was removed from the filtrate in vacuo to give a mixture of ethyl 5- and 6-hydroxy-2-trifluoromethylbenzimidazol-1-yl acetate (4.25 g) as a tan solid substances.

NMR (CDCl ₃ ): δ1.25 (m) 6H, (2xCH ₃ ), 4.2 (m) 2H 2xCH ₂ 4.9 (s) 2H, 5.0 (s) 2H, 6.75 (d) 1H, 6.9 (dd.) 1H, 7.02 (dd.) 1H, 7.2 (m.) 2H, 7.6 (d.) 1H, 7.9-8.6 (wide) 1H.

 Stage D.

A mixture of ethyl 5- and 6-hydroxy-2-trifluoromethyl-benzimidazol-1-yl acetate (4.25 g from step C), 3-chloro-4,5-difluorobenzotrifluoride (3.57 g) and anhydrous potassium carbonate (8 d) were mixed and heated at 100 ^about C for 4 hours in DMF (200 cm ³ ). The reaction mixture was cooled and poured into water, acidified with dilute hydrochloric acid, and extracted with ethyl acetate. The combined organic phase was washed with water, dried with magnesium sulfate, filtered, and the solvent was removed from the filtrate in vacuo to give an orange-brown oil (7.24 g), which partially solidified upon standing. A portion of this substance (5.26 g) was purified by preparative plate chromatography (silica, methylene dichloride) to give ethyl 5- (2-chloro-6-fluoro-4-trifluoromethyl-phenoxy) -2-trifluoromethylbenzimidazol-1-yl -acetate (1.7 g), mp 77.2-79.2 ^о С as a faster component, and ethyl 6- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) -2-trifluoromethylbenzimidazol-1-yl acetate (2.83 g, t. pl. 112.2-113.2) as a slower component.

 Compounds NN 64, 65, 66, 67, 68, 70, 71, 79, 80, 81, 82, 83, 85, 86, 86, 97, 98, 99, 108 and 109 were obtained in a similar manner using the appropriate reagents.

 PRI me R 17. Obtaining compound 87 (table. 5).

Ethyl 6- (2-chloro-6-fluoro-4-trifluoromethyl-phenoxy) -2-trifluoromethylbenzimidazol-1-yl acetate (1 g), obtained as described in Example 16, was dissolved in isopropanol (50 cm ³ ). Sodium hydroxide (0.15 g) in water (5 cm ³ ) was added and the mixture was stirred at room temperature for 1 hour. The mixture was poured into water, acidified with dilute hydrochloric acid, and extracted with ethyl acetate (3 times). The combined organic phase was washed with water, dried with magnesium sulfate, filtered, and the solvent was removed from the filtrate under reduced pressure to give a buff solid (0.87 g), from which 400 mg was recrystallized from a mixture of ether and hexane, giving 6- (2 -chloro-6-fluoro-4-trifluoromethylphenoxy) - 2-trifluoroethylbenzimidazole-1-acetic acid (290 mg).

 Compounds NN 72 and 76 were obtained in a similar manner and using the appropriate reagents.

 PRI me R 18. Obtaining compound 88 in the table. 5.

6- (2-Chloro-6-fluoro-4-trifluoromethylphenoxy) -2-trifluoromethylbenzimidazol-1-yl-acetic acid (0.47 g) was heated under reflux in thionyl chloride (20 cm ³ ) for 45 minutes, cooled to room temperature, and the excess thionyl chloride was evaporated under reduced pressure. Dry toluene (20 cm ³ ) was added and evaporated under reduced pressure. The resulting residue was dissolved in a minimum volume of dry toluene and added with vigorous stirring to 880 ammonia (20 cm ³ ), giving a thick cream suspension. Stirring was continued for 0.5 hours. Water (50 cm ³ ) was added and the mixture was extracted three times with ethyl acetate. The combined extracts were washed in water, dried over magnesium sulfate, filtered, and the solvent was removed from the filtrate under reduced pressure to give a creamy solid (350 mg). Recrystallization from dichloromethane afforded 6- (2-chloro-6-fluoro-4-trifluoro-methylphenoxy) -2-trifluoromethylbenzimidazol-1-yl acetamide (195 mg) as an off-white solid.

 Compounds NN 73, 74, 89, 90 and 91 were obtained in a similar manner using the appropriate reagents.

 PRI me R 19. Obtaining compound 62 in the table. 4 and compounds 77 in the table. 5.

 Stage A.

3-Chloro-4,5-diftorbenzotriftorid (10 g), 4-atsetamido-phenol (7 g) and anhydrous potassium carbonate (12 g) were stirred and heated at ¹⁰⁰ ° C for 3 hours in dimethylsulphoxide (70 ^cm3). After cooling, the mixture was poured into water, extracted with ethyl acetate three times, and the combined organic extracts were washed with water. The extract was dried with magnesium sulfate, filtered, and the solvent was removed in vacuo to give an off-white solid (17.3 g), which was triturated with hexane and filtered to give 4- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) acetanilide (13.95 g) as an off-white solid.

NMR (CDCl ₃ ): δ2.15 (s) 3H, 6.85 (d) 2H, 7.3-7.5 (dd) 2H and (m) 2H, 7.6 (s) 1H.

 Stage B.

4- (2-Chloro-6-fluoro-4-triftormetilfeno- xi) acetanilide (6 g) was suspended in acetic anhydride (40 cm ³⁾ was stirred and cooled to ^(-10 ° C). Was added dropwise a mixture of concentrated nitric acid (1.63 ^cm3) in acetic anhydride (6.6 cm ^3), and the resulting yellow slurry was stirred at (-10) ^{° C} for 45 min before it was allowed to warm to room temperature and stand overnight. The reaction mixture was cooled to (-5) ^° C and concentrated, nitric acid (0.81 cm ³ ) in acetic anhydride (3.3 cm ³ ) was added. The mixture was left at room temperature for 4 days, and then poured into water and extracted with diethyl ether (three times). The combined ether extracts were washed with water, dried with magnesium sulfate, filtered, and the solvent was removed in vacuo to give a bright yellow suspension. The suspension was poured into water, re-extracted with ether, dried with magnesium sulfate and evaporated to give a yellow solid, which was triturated with ether / hexane and filtered to give 2-nitro-4- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) acetanilide (3.13 g) as a bright yellow solid, M ⁺ = 392.

 Stage C.

2-Nitro-4- (2-chloro-6-fluoro-4-trifluoromethyl tilfenoksi) acetanilide (2.9 g) was dissolved in acetone (60 ^cm3) and the solution was stirred at ⁵ ° C in an ice bath. Dropwise over 30 minutes was added 40 cm ³ of a 30% solution of titanium trichloride in hydrochloric acid and the reaction mixture was stirred at ⁵ ° C for an additional 45 min before it was warmed up over night to room temperature. The reaction mixture was poured into water and extracted with diethyl ether three times. The combined ether extracts were washed with water, dried over magnesium sulfate, filtered, and the filtrate was evaporated under reduced pressure to give a pale yellow solid (1.7 g). This material was triturated with a 1: 1 mixture of gasoline / ether and filtered to give 2-amino-4- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) acetanilide (1.2 g) as a cream solid.

NMR (CDCl ₃ ): δ2.2 (s) 3H, 4.2-3.6 (broad) 1H, 6.225 (dd) 1H, 6.3 (d) 1H, 7.025 (d) 1H, 7.225 (br.s. ) 1H, 7.35 (dd.) 1H, 7.55 (s.) 1H.

 Stage D.

2-Amino-4- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) acetanilide (1.2 g) was dissolved in glacial acetic acid (5 cm ³⁾ and heated at ¹⁰⁰ ° C for 1 hour. After cooling, the solution poured into water, and the mixture was basified with 2M sodium hydroxide. The precipitate was filtered off, washed with water and dried in air. The solid was purified by preparative plate chromatography (silica, ethyl acetate + 5% HOAc) to give 2-methyl-6- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) benzimidazole (0.5 g) in as a pale brown oil.

NMR (CDCl ₃ ): δ2.1 (s) 3H, 2.45 (s) 3H, 6.85 (dd) 1H, 6.9 (d) 1H, 7.4 (m) 2H, 7.6 (s) 1H.

 Stage E.

2-Methyl-6- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) benzimidazole (0.66 g), ethyl 2-bromopropionate (0.28 cm ³ ) and anhydrous potassium carbonate (1 g) were mixed and heated under reflux in methyl ethyl ketone (MEK) overnight. The reaction mixture was cooled, poured into water and extracted with ethyl acetate three times. The combined organic phase was washed with water, dried with magnesium sulfate, filtered, and the solvent was removed from the filtrate in vacuo to give a brown oil (0.76 g). The oil was purified using preparative plate chromatography (silica, ethyl acetate) to give ethyl 2- [2-methyl-6- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) benzimidazol-1-yl] propion at ( compound 77) (110 mg) as a slower component and ethyl 2- [2-methyl-5- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) benzimidazol-1-yl] propionate (compound 62) (220) d) in the form of a faster component.

 Compounds NN 63 and 78 were obtained in a similar manner using the appropriate reagents.

 PRI me R 20. Obtaining compounds 100 in the table. 1 and compounds 101 in the table. 5.

 Stage A.

4- (2-Chloro-4-trifluoromethyl-6-fluorophenoxy) -2-nitroacetanilide (4.8 g) was heated under reflux for 2 hours in ethanol (200 cm ³ ) and concentrated hydrochloric acid (4 cm ³ ). The solution was cooled and the solvent was removed in vacuo to give an orange solid, which was dissolved in ethyl acetate, washed in water, dried with magnesium sulfate and filtered. Evaporation of the filtrate in vacuo afforded 4- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) -2-nitro-aniline (4.05 g) as an orange solid.

NMR (CDCl ₃ ): β7.6 (s) 1H, 7.5 (d) 1H, 7.4 (dd) 1H, 7.2 (dd) 1H, 6.85 (d) 1H, 6.0 (br.s) 2H.

 Stage B.

Glacial acetic acid (40 cm ³ ) containing concentrated sulfuric acid (3 drops) was added to a stirred mixture of 4- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) -2-nitroaniline (1 g) paraformaldehyde (0.26 g ), anhydrous zinc chloride (1.43 g) and potassium cyanide (0.56 g). The resulting slurry was heated at 50-55 ^{° C} for 7.5 hours and allowed to stand at room temperature overnight. The mixture was poured into water and extracted with ethyl acetate twice. The combined organic phase was washed with water, dried with magnesium sulfate and filtered. The solvent was removed from the filtrate in vacuo to give 4- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) -2-nitro-N-cyanomethylaniline (0.82 g) as an orange solid. M ⁺ = 389.

NMR (CDCl ₃ ): δ8.0 (broad) 1H, 7.7 (d) 1H, 7.6 (s) 1H, 7.4 (dd) 2H, 7.0 (d) 1H, 4.3 (d) 2H.

 Stage C.

4- (2-Chloro-4-trifluoromethyl-6-fluorophenoxy) -2-nitro-N-cyanomethylaniline (1 g) was suspended in hot ethanol (50 cm ³ ) and anhydrous potassium carbonate (0.18 g) was added. . The mixture was then stirred under reflux for 4 hours and left at room temperature overnight. The solvent was evaporated from the mixture in vacuo, and the residue was dissolved in water (75 cm ³ ), filtered, and acidified with 2M hydrochloric acid. A yellow precipitate was collected and washed with water, then hexane and dried in air, giving 2-cyano-5- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) -1H-benzimidazole-3-oxide (0.8 g) . M ⁺ = 370.

Stage D. 2-Cyano-5- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) -1H-benzimidazole-3-oxide (0.8 g) was suspended in chloroform (5 cm ³ ), stirred and cooled to 5 ^o C in an ice bath. Phosphorus trichloride, (0.25 cm ³ ) was added dropwise and, when the addition was completed, the mixture was heated under reflux for 5 minutes. The resulting solution was cooled, water (10 cm ³ ) was slowly added, and the mixture was made basic with aqueous ammonia. The organic layer was separated, and the aqueous layer was extracted twice with chloroform. The combined organic phase was washed with water, dried with magnesium sulfate, filtered, and the filtrate was evaporated in vacuo. A portion of the residue was purified by preparative plate chromatography (silica, ether) to give 2-cyano-5- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) benzimidazole as a pale yellow solid, recrystallized from ether. / hexane M (positive FAB) MH ⁺ = 356.

 NMR: δ7.8-7.6 (br) 1H, 7.6 (s) 1H, 7.4 (dd) 1H, 7.2-6.8 (br m) 2H, 13.8-13.1 (br.s) 1H.

 Stage E.

2-Cyano-5- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) benzimidazole (0.325 g), ethyl 2-bromopropionate (0.13 cm ³ ) and anhydrous potassium carbonate (1 g) were heated under reflux in acetonitrile (30 cm ³ ) for 2 hours and left at room temperature overnight. The mixture was filtered and the solvent was removed from the filtrate in vacuo. The residue was purified using preparative plate chromatography (silica, hexane: ether 1: 1) to give ethyl 2- [2-cyano-6- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) benzimidazol-1-yl] propion t (0.14 g) as the faster component (compound 101) and ethyl 2- [2-cyano-5- (2-chloro-4-trifluoromethyl-6-fluorophenoxy) benzimidazol-1-yl] propionate (0, 15 g) as a slower component (compound 100).

 Compounds NN 102, 103, 104, 105, 106 and 107 were obtained in a similar manner using the appropriate reagents.

 Biological data are as follows.

 The herbicidal activity of the compounds was tested as follows.

Each chemical compound was converted into the finished form of the drug (or the finished formulation) by dissolving it in the appropriate amount depending on the final volume of spraying or spraying, a surfactant solvent mixture, which includes 78.2 g / l Tween 1 20 and 21 , 8 g / l Span 80, adjusted to 1 l using methylcyclohexanone. Tween 20 is a trademark of a surfactant, including condensate 20 molar proportions of ethylene oxide and sorbitan laurate. Span 80 is a trademark of a surface active agent including sorbitan monolaurate. If the chemical did not dissolve, the volume was adjusted to 5 cm ³ with water, glass beads were added, and the mixture was then shaken to dissolve or suspend the chemical agent, after which the balls were removed. In all cases, the mixture was then diluted with water to the required spray volume. If spraying was carried out independently, pre-emergence and after-emergence tests required 25 cm ³ and 30 cm ³ , respectively; if sprayed together, 45 cm ^{3 was} required. An aqueous emulsion for spraying or spraying contains 4% of the initial mixture of solvent and surfactant, and the test chemical in an appropriate concentration.

 Compositions for spraying, prepared in this way, were sprayed onto young plants in pots (post-emergence test) at a flow rate equivalent to 1000 liters per 1 ha. Damage to plants was evaluated 13 days after spraying compared to untreated plants on a scale of 0-9, where 0 represents 0% damage, 1 1-5% damage, 2 6-15% damage, 3 16-25% damage, 4 26- 35% 5 36-59% damage, 6 60-69% 7 70-79% 8 80-89 and 9 90-100% damage.

 In a test to determine pre-emergence herbicidal activity, crop seeds were sown to a depth of 2 cm (i.e., Sb, Ct, Rp, Ww, Mz, Ro, Sy), and weed seeds to a depth of 1 cm in compost soil and sprayed with compositions at a flow rate of 1000 liters per 1 ha. 20 days after spraying, the seedlings in the sprayed plastic trays (trays) were compared with the seedlings in the unsprayed control trays, and the damage was evaluated on the same scale 0-9.

 The test results are given in table. 7.

 In the table. 8 shows the results of post-emergence studies, determined on the 6th day after treatment, and in table. 9 results of a post-emergence study performed using the methods and score system specified in biological data.

O

Соединения B, C, D, E (изобретение)
Y

O

Cоединения Х Y Z B H Cl H C H CF₃ H D Cl CF₃ H E H CF₃ Cl
Примеры препаративных форм
П р и м е р 1. Иллюстрация композиции эмульгируемого концентрата, которую можно легко превратить при помощи разбавления водой в жидкую препарацию, пригодную для опрыскивания.The following are test plants:
Sb Sugar beet (sugar beet)
Rp Rape (rapeseed)
Ct Cotton
Sy Soybean (Soybeans)
Mz Maize (corn)
Ww Winter wheat (winter wheat)
Rc Rice (rice)
Bd bidens pilosa
Ip Ipomoea lacunosa (pre-emergence)
Ipomoea hederacea (post-emergence)
Am amaranthus retroflexus
Pi Polygonum aviculare
Ca Chenopodium album
Ga galium aparine
Xa Xanthium spinosum
Xs Xanthium strumarium
Ab abutilon theophrasti
Eh euphorbia heterophylla
Av avena fatua
Dg Digitaria sanquinalis
Al alopecurus myosuroides
St setaria viridis
Ec Echinochloa crus-galli
Sh sorghum halepense
Ag agropyron repens
Ce cyperus esculentes
The following compounds are given as a comparison:
Compound A (prototype)
Cl

O

Compounds B, C, D, E (invention)
Y

O

Compounds X YZBH Cl HCH CF ₃ HD Cl CF ₃ HEH CF ₃ Cl
Formulation Examples
PRI me R 1. Illustration of the composition of an emulsifiable concentrate, which can be easily converted by dilution with water into a liquid preparation suitable for spraying.

Mas. Compound of formula (I) 10 Sinperonic HIPP (nonylphenol ethylene oxide condensate, Sinperonic is a registered trademark) 2.5 Calcium dodecylbenzenesulfonate 2.5 Aromazole U (alkylbenzene solvent up to 100
Aramazole is the dawn
registered trademark).

 PRI me R 2. Illustration of the composition of an emulsifiable concentrate, which is easily converted by dilution with water into a liquid preparation suitable for spraying.

Mas. Compounds of formula (I) 1.0 Synperonic OP10 (octyl phenol ethylene oxide condensate, synperonic is a registered trademark) 3.0 Calcium dodecylbenzenesulfonate 2.0
Aromazole V (alkylbenzo-
Aromatazole is a registered trademark) 94.0
PRI me R 3. Illustration of a wettable powder or composition of water dispersible granules, which are easily converted by dilution with water into a liquid preparation suitable for spraying.

Mas. Compound of formula (I) 25.0 Silicon dioxide 10.0 Sodium lignosulfonate 5.0 Sodium lauryl sulfate 2.0 Kaolinite Up to 100
PRI me R 4. Illustration of a wettable powder or dispersible composition in the form of granules, which are easily converted by dilution with water into a liquid preparation suitable for spraying.

Mas. The compound of formula (I) 1.0 Sodium lignosulfonate 5.0 Sodium lauryl sulfate 2.0 Kaolinite 92.0
PRI me R 5. Illustration of a wettable powder or composition of water dispersible granules, which are easily converted by dilution with water into a liquid preparation suitable for spraying.

Mas. The compound of formula (I) 40.0 Silicon dioxide 20.0 Calcium lignosulfonate 5.0 Sodium lauryl sulfate 2.0 Kaolinite up to 100
PRI me R 6. Illustration of a suspension concentrate in a capsule, which is easily converted by dilution with water to form a preparation suitable for use in the form of a water jet.

Mas. Compound of formula (I) 1.0 Alkylbenzene solvent (e.g. Aromazole x) 10.0 Toluene diisocyanate 3.0 Ethylene diamine 2.0 Polyvinyl alcohol 2.0 Bentonite 1.5 Polysaccharide (e.g. Keltrol, Keltrol is a registered trademark) 0.1 Water 80.4
PRI me R 7. Illustration of the composition of the concentrate of an aqueous suspension, which is easily converted by dilution with water into a liquid preparation suitable for spraying.

Mas. Compounds of formula (I) 20.0 Sinperonic NPE1800 (alkoxylated alkyl phenol, sperononic is a registered trademark) 2.0 Propylene glycol 10.0 Bentonite 2.0 Polysaccharide (e.g., Celtrol, Celtrol is a registered trademark) 0.1 Bactericide (e.g. , proxel, proxel is a registered trademark) 0.1 Water Up to 100
PRI me R 8. This example illustrates the composition of an aqueous suspension concentrate, which is easily converted by dilution with water into a liquid preparation suitable for spraying.

Mas. Compounds of formula (I) 20.0 Morvet D425 (condensate-alkyl naphthalene sulfonate, Morvet is a registered trademark) 2.0 Propylene glycol 10.0 Bentonite 2.0 Polysaccharide (e.g. celtrol, celtrol is a registered trademark) 0, 1 Bactericide (e.g., proxel, proxel is a registered trademark) 0.1 Water Up to 100
Example 9. This example illustrates a composition of water dispersible granules, which are easily converted by dilution with water into a liquid preparation suitable for spraying.

 Mas. Compound of formula (I) 50.0 Morvet D425 (condensate-alkyl naphthalene sulfonate, Morvet is a registered trademark) 10.0 Kaolinite Up to 100

Claims (7)

1. Heterocyclic compounds of the general formula

where the dashed lines indicate the presence of two double bonds arranged so that they form a condensed heteroaromatic ring system;
Ar is

or

where R ^y is hydrogen, halogen, nitro, cyano;
R ^z is halogen, nitro, cyano;
W is oxygen;
A, B and D independently - CR ₆ , N, NC ₂ H ₅ , N - E, where E -

with the proviso that two of A, B and D are N, NC ₂ H ₅ or NE and at least one of A, B or D carries a group E, R ₄ is hydrogen, methyl, R ₅ —CO ₂ R _{1 1} , CONR _{1 3} R _{1 4} , CONHN ⁺ (CH ₃ ) ₃ J ^- , COON = C (CH ₃ ) ₂ , CONHSO ₂ CH ₃ , COONa, R _{1 1} - hydrogen, lower alkyl, R _{1 3} and R _{1 4} independently hydrogen or ethyl, R ⁶ hydrogen, chloro, trifluoromethyl, cyano or its tetrafluoro boriate,
possessing herbicidal activity. 2. The compound according to claim 1, in which the ring system

represents

where E and R ₆ have the indicated meanings. 3. The compound according to claim 1, in which the ring system

represents

where E and R ₆ have the indicated meanings. 4. The compound of claim 2, wherein the compound of general formula I is a compound of general formula 1E

where E, R ₆ and Ar have the indicated meanings. 5. The compound of claim 3, wherein the compound of general formula I is a compound of general formula 1G

where E, R ₆ and Ar have the indicated meanings. 6. The compound according to any one of claims 1 to 5, in which E represents

where R ₄ and R _{1 1} have the indicated meanings. 7. A herbicidal composition comprising an active ingredient and targeted additives, characterized in that, in order to enhance the herbicidal activity, it contains as a active ingredient a compound of the general formula

where the dashed lines indicate the presence of two double bonds arranged so that they form a condensed heteroaromatic ring system;
Ar is

or

where R ^y is hydrogen, halogen, nitro, cyano;
R ^z is halogen, nitro, cyano;
W is oxygen;
A, B and D independently - CR ₆ , N, NC ₂ H ₅ , NE, where E -

with the proviso that two of A, B and D represent N, NC ₂ H ₅ or NE and at least one of A, B or D carries group E;
R ₄ is hydrogen, methyl;
R ₅ -CO ₂ R _{1 1} , CONR _{1 3} R _{1 4} , CONHN ⁺ (CH ₃ ) ₃ J ^- , COON = C (CH ₃ ) ₂ , CONHSO ₂ CH ₃ , COONa;
R _{1 1} is hydrogen, lower alkyl;
R _{1 3} and R _{1 4} independently are hydrogen or ethyl;
R ₆ is hydrogen, chlorine, trifluoromethyl, methyl, cyano or its tetrafluoroboriate,
with the following ingredients, wt.%:
Active ingredient - 1 - 50
Targeted Supplements - Else
8. A method of controlling the growth of undesirable vegetation by treating plants or their distribution sites with active ingredients, characterized in that, in order to enhance the herbicidal activity, a compound of the general formula is used as an active ingredient

where the dashed lines indicate the presence of two double bonds arranged so that they form a condensed heteroaromatic ring system;
Ar is

or

where R ^Y is hydrogen, halogen, nitro, cyano;
R ^z is halogen, nitro, cyano;
W is oxygen;
A, B and D independently - CR ₆ , N, NC ₂ H ₅ , N -E, where E - represents

with the proviso that two of A, B and D are N, NC ₂ H ₅ or NE and at least one of A, B or D carries a group E;
R ₄ is hydrogen, methyl;
R ₅ -CO ₂ R _{1 1} , CONR _{1 3} R _{1 4} , CONHN ⁺ (CH ₃ ) ₃ J ^- , COON = C (CH ₃ ) ₂ , CONHSO ₂ CH ₃ , COONa;
R _{1 1} is hydrogen, lower alkyl;
R _{1 3} and R _{1 4} independently are hydrogen or ethyl;
R ₆ is hydrogen, chlorine, trifluoromethyl, methyl, cyano or its tetrafluoroboriate,
in the amount of 0.01 - 1 kg / ha.

Images