CS207497B2 - Herbicide means - Google Patents

Abstract

Substituted bicyclic triazole compounds essentailly as shown in Formula I, agricultural compositions containing them, and the method of use of these compounds as herbicides for the control of undesired vegetation in crops (I).

Description

BACKGROUND OF THE INVENTION The present invention relates to a herbioid composition particularly suitable for combating undesirable vegetation before emergence.

German Offenlegungsschrift (DOS) 1,957,783 discloses amidrazones of formula a

wherein R 1, R a and R 3 are hydrogen, fluoro, chloro, bromo, trifluoromethyl or C 1 -C 3 alkyl, n is 3, 4, or -5, and are said to be useful as antihypertensives .

Belgian patents 802 446 and 802 447 disclose substituted arylamidrazones of the general formula b wherein X can be fluorine, chlorine, bromine or iodine, nitro, methoxy, ethoxy, methylthio, dimethylamino, trifluoromethyl or methylsulfonyl, n can be 3, 4 or 5, as fungicides.

The essence of the herbicidal composition according to the invention is that in combination with a surface-active agent and / or a solid or liquid diluent it contains as active ingredient. a herbicidally effective amount of a bicyclic triazole derivative of the formula I

(if

in which

V represents a hydrogen atom of a fluorine, chlorine or bromine atom, a hydroxyl group, a (C1-C4) alkyl group or an —ORt group in which:

R 1 is alkyl. C 1 -C 6 optionally substituted by C 1 -C 6

207479 to 3 fluorine, chlorine or bromine atoms, a cycloalkyl group having 4 to 6 carbon atoms, a cycloalkylalkyl group having 4 to 7 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, optionally substituted with 1 to 3 fluorine, chlorine or bromine atoms, (C 3 -C 6) alkynyl, -CHR 7 R 8,

in which

R2 represents a hydrogen atom or a methyl group,

R3 represents a hydrogen, chlorine or bromine atom, a methyl group or a methoxy group,

R a is C 1 -C 4 alkyl,

R 5 represents a hydrogen atom, a methyl or methoxy group,

R 6 is C 1 -C 4 alkyl or C 1 -C 4 alkoxy,

R 7 represents a hydrogen atom or a C 1 -C 4 alkyl group,

R 5 represents a group -CO 2 R 9, —CH 2 OR 9,

O —CH2 — O — C — R10,

O

II — CN, · - C — CH3,

O

II —CH = CHCORg or

O R11

II / —C — N

R12 in which

R 9 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

R 10 represents an alkyl group having 1 to 3 carbon atoms,

R 1 represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 3 -C 4 alkenyl group or a C 1 -C 2 alkoxy group and

R 1 is hydrogen or C 1 -C 2 alkyl,

X represents a hydrogen, fluorine, chlorine or bromine atom, a cyano group, a methyl group, a methoxy group or a nitro group,

Y represents a hydrogen, fluorine, chlorine or bromine atom or a methyl group,

Z is hydrogen, fluorine, chlorine or bromine, n is 3, 4 or 5, m is 0, 1 or 2 and

Q represents an oxygen or sulfur atom, with the proviso that

a] if Y is other than hydrogen, then Y is also other than hydrogen,

b] if m is 1, then · n is 4 and Y has a meaning other than hydrogen,

c) when · m is 2, then n is 4, X and Y are each a chlorine atom and Y is an —OR 1 group in which R 1 · is an alkyl group having 1 to 4 carbon atoms,

d) when Q represents a sulfur atom, then m is 0, or the herbicidal composition of the invention comprises agriculturally acceptable salts of said compounds.

Preferred for their high herbicidal activity and / or acceptable cost are those compounds of formula (I) above wherein, independently of each other or in combination with each other. ,

Y represents a hydrogen, fluorine, chlorine or bromine atom, a hydroxyl group, a methyl group or an OR 1 group,

X is fluorine, chlorine, bromine, methyl or nitro,

Y represents a fluorine, chlorine or bromine atom or a methyl group,

Z is hydrogen, fluorine or chlorine, n is 4 or 5 and m is 0.

Even more preferred are those compounds in which

Y represents a hydrogen, chlorine or bromine atom or a group -OR 1, wherein R 1 represents an alkyl group having 1 to 4 carbon atoms,

X represents a fluorine, chlorine or bromine atom;

Z is hydrogen.

Most preferred are those compounds in which n is 4.

The most preferred compounds are those in which the ..

Y represents a hydrogen atom, a chlorine atom or a group -OR 1,

X is chlorine or bromine; and

Y represents a fluorine, chlorine or bromine atom.

2- (2,4-dichloro-5-methoxyphenyl) -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] ^; ) pyridin-3 (2H) -one, mp 1610-163 ° C,

In particular, combinations of said compounds are highly preferred. Particularly preferred are:

2- (2,4-dichloro-5-hydroxyphenyl) -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridin-3 (2H) -one, mp 211 up to 212 ° C,

2- (2,4-dichloro-5-propargyloxyphenyl) -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3a] pyridin-3 (2H) -one, mp 167-169 ° C ,

2- [2,4-dichloro-5- (1-methylethoxy) phenyl] -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3a] pyridin-3 (2H) -one (oil) )

2- (2,4-dichloro-5-ethoxyphenyl) -5,6,7,8-tetrahydro-1,2,4-triazolo {4,3-a] pyridin-3 (2H) -one, mp 130-120 132 ° C

2- [12,4-Dichloro-5- (1-methylethoxy) phenyl] -2,5,6,7,8,9-hexahydro-3H-1,2,4-triazolo [4,3- a] azepin-3-one (oil).

The compounds of the invention may be synthesized as shown in Equations A to G.

Conversion of amidrazones of formula II or their acid salts (e.g. hydrochlorides) to compounds of formula I is carried out either by treatment with phosgene (Q in formula III is an oxygen atom) to give a compound of formula I wherein Q is an oxygen atom. or by treatment with thiophosgene (Q in formula III is sulfur) to give a compound of formula I wherein Q is sulfur.

The treatment is carried out in a suitable inert solvent (organic), for example an aromatic hydrocarbon such as benzene or toluene, a chlorinated alkane such as chloroform or methylene chloride or in an ether type solvent such as tetrahydrofuran. A suitable base, such as a tertiary amine, for example pyridine or triethylamine (with a hydrocarbon solvent such as toluene or xylene, is not required) is used to neutralize the acids liberated during the reaction. Conventional measures are used to eliminate moisture from the reaction. To complete the reaction, it is sometimes necessary to reflux the reaction mixture for one to twenty-four hours.

The product is isolated by pouring the reaction mixture into water and extracting the product with a suitable solvent such as ether or methylene chloride. The organic extract of the product is dried by the addition of a drying agent, for example, anhydrous sodium sulfate, and the solvent is removed by distillation or evaporation under reduced pressure to give the ture product. The crude product is purified by standard techniques, for example, crystallization, chromatography or distillation.

Compounds of formula I wherein Q is O may be readily prepared by the method of Equation B.

(сн ^ (В))

ГСНд) "

Ct-C-O-R) *

The amidrazone salt of formula II with an acid in a suitable solvent, for example anhydrous tetrahydrofuran, is treated with three equivalents of n-butyllithium to give the dianion of the amidrazone of formula IV. Starting from the amidrazone free base, only two equivalents of n-butyllithium are sufficient to obtain the dianion of formula IV. Otherwise, each reaction according to Equation В can be performed under the same conditions. The reaction temperature is maintained between -10 and 10 ° C. When the addition of n-butyllithium is complete, the reaction mixture is stirred for a short time (e.g. between about 5 and 30 minutes) while maintaining the temperature. One equivalent of alkyl chloroformate is then added, where R 1 is an alkyl group having 1 to 3 carbon atoms, for example methyl chloroformate, and the temperature is again maintained between -10 and 10 ° C. The reaction is completed by stirring at room temperature or refluxing for one to twenty-four hours. The product of formula (Ia) can be isolated as described above.

For amidrazones that contain a reactive group on the benzene ring, such as a bromine atom, a cyano group or a nitro group, the butyllithium method may not work well. In this case, the phosgene method described in equation A may be used.

Compounds of the invention of general formula VI (CH? A? Or?)

^ÍCH / ⁿ 1 = 4 У-S tvn where n, pi, О, X, Y and Z mean as is done in the general formula I а V means uveORi, where

R 1 represents an alkyl group having 1 to 6 carbon atoms optionally substituted by 1 to 3 fluorine, chlorine or bromine atoms, a cycloalkyl group having 4 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, optionally substituted with 1 to 3 fluorine, chlorine or bromine atoms, (C 3 -C 6) alkynyl group, -CHR 7 R 8, or

R2 represents a hydrogen atom or a methyl group,

R3 represents a hydrogen, chlorine, bromine atom, a methyl or methoxy group,

R-4 represents an alkyl group having 1 to 4 carbon atoms,

R 5 represents a methyl or methoxylo group,

R 8 is C 1 -C 4 alkyl or C 1 -C 4 alkoxy,

R 7 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

O

II

R11 stands for —CO2R9 —CN, —ССНз, or

O = CH = CHCOR 9a

R 9 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably produced by the process of Equation C.

2D7497 (CHJ

(УП>

SL Z OH

X + X ”Rf + base— * (VIHi

Gu Z OR <

(VI i

To the phenol of formula (VII), the corresponding halide of formula (VIII) is added, wherein R 1 is as described above for compounds of formula (VI), X 'is a halogen atom such as bromine or iodine and an equivalent amount of a suitable base. for example potassium carbonate, sodium hydroxide, sodium hydride, etc., in a solvent such as acetonitrile, acetone, dimethylformamide, etc.

Addition of an alkali metal iodide, e.g. sodium iodide, may facilitate the reaction. The reaction mixture is heated to reflux for several hours, for example 1 to 24 hours. Pouring the reaction mixture into water yields a crude product. The product is extracted with a solvent such as methylene chloride. The product solution is dried with a drying agent, for example anhydrous sodium sulphate, and the solvent is removed by evaporation on a rotary evaporator. The crude product thus obtained can be further purified by standard techniques, for example chromatography or crystallization.

The phenols of formula VII from Equation C (or agriculturally acceptable salts such as sodium, potassium, lithium, triethylammonium, etc.) are novel compounds - and are effective herbicides. The phenols of formula VII are prepared from the corresponding-amidrazones (formula II, where V is a hydroxyl group) as described in Equation A. Other phenols of formula ¹ (Q in the formula is an oxygen atom) can be produced by acid cleavage of the compound of formula (IX) (wherein R 1 is an alkyl group having from 1 to 6 carbon atoms) as shown in Equation D.

(D)

acid hydrolysis (Ο ~ Η hn

O '2 OH ^ (CH 2 I N ~ (oyx (X)

Suitable acids include concentrated sulfuric acid and concentrated hydrobromic acid.

Carboxylic acids of formula XI wherein n, m, Q, X, Y, Z and R7 are as defined for formula I, produced as described in Equation C, are more readily prepared by acidic or basic hydrolysis of the corresponding esters of formula XII

(Xi)

Q> 7 (CH

Y

H

C-OR,

R * (XII) wherein R 9 represents an alkyl group having 1 to 4 carbon atoms.

When the carboxylic acids of formula XI are treated with thionyl chloride under conditions well known in the literature for converting carboxylic acids to carboxylic acid chlorides, compounds of formula XIII are prepared.

Treatment of a compound of formula XIII with an amine of formula XIV, wherein R 11 and R 12 are as indicated for compounds of formula I, according to Equation E

under conditions well known in the literature for the conversion of acid chlorides to amides leads to carboxylic acid amides of formula XV.

Compounds of the invention of formula XVI

wherein n, m, Q, X, Y, Z and R7 are as defined above in formula I, may be prepared by direct reduction of the carboxylic acid esters of formula XII with suitable reducing agents, for example lithium borohydride in an appropriate solvent, e.g. tetrahydrofuran.

Treatment of the alcohol of formula XVI with the corresponding anhydride of formula XVII results in an ester of formula XVIII according to the invention wherein R 10 is as shown in formula I (equation F).

(CH ₃ ) m (F) НТН-Ц 'Ον': (XVI)

α.

(CH (ch *)

O-CH-CH.OH

xvn (XVIII)

Treatment of phenols of formula VII according to equation G

r with the appropriate isocyanates of formula XIX, wherein R 4 is C 1 -C 4 alkyl, yields a compound of formula XX, wherein R d is as shown in formula I.

The following examples further illustrate the preparation of the compounds of this invention. Unless otherwise stated, all parts are parts by weight and all temperatures are in degrees Celsius (° C).

Example 1

Preparation of 2- (2,4-dichlorophenyl) -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridin-3 (2H) -one

To 9.0 parts of 2,4-dichlorophenylhydrazone hydrochloride 2-piperidone, produced by methods similar to those described in German Disclosure Patents (DOS) 2,235,113 and 2,235,177, 200 parts of dry tetrahydrofuran were added and the mixture was cooled to -10 ° C under a nitrogen atmosphere. To this solution, 37.2 parts of a solution of 1.6 M n-butyllithium (d = 0.68) in hexane was added dropwise while maintaining the temperature of the mixture between -10 and 10 ° C.

After addition of n-butyllithium, the reaction mixture was stirred for about 15 minutes. Then 3.0 parts of methyl chloroformate are added dropwise, maintaining the temperature between -10 and 10 ° C. After addition of the chloroformate, the reaction mixture was allowed to warm to room temperature without cooling. It is then stirred for 30 minutes. The crude reaction mixture was poured into 500 parts of water. The aqueous solution was extracted three times with 200 parts methylene chloride. The crude extracts were combined, dried over anhydrous sodium sulfate and then filtered. The solvent is removed from the filtrate by evaporation on a rotary evaporator under reduced pressure (7 to 40 kPa). The crude product was purified by dry alumina column chromatography. 5.4 parts of product are obtained in the form of an oil which solidifies after three days of standing (m.p. 100-104 ° C).

Using procedures analogous to the example

1S, the following compounds of formula I (where Q is an oxygen atom) can be prepared from the respective amidrazones and methyl chloroformate ["properties" refers to melting point in ° C unless otherwise stated):

n Y X in OF m Physical properties 4 H СНз H н О wax - NMR (CDCl 3) (<S) 2.0 (m, 4H); 2.5 (s. 3H); 2.5 (m, 2H). 3.9 (m. 2H); 7.9 (AABB, 4H) 4 Cl Cl Cl н О oil - NMR (CDCl 3) (? S) 2.1 (m, 4H), 2.9 (m, 2H), 3.9 (m, 4H), 7.95 (s, 1H), _8f 02 (s, 1H) 4 СНз Cl H н О Mp 117-118 ° C 4 F Cl H н О Mp 134-137 ° C 4 H Cl H н О Mp 120-122 ° C 4 H ОСНз H н О Mp 110-113 ° C 4 F F H F О Mp 116-118 ° C 4 Cl СНз H н О Mp 91-92 ° C 4 Cl Cl H С1 О oil - NMR (CDCl 3) (<S) 2.0 (m, 4H); 2.8 (m, 2H). 3.8 (m, 2H). 7.3 (s, 2H). 4 Cl Cl F н О 4 Cl Cl СНз н О 4 Cl Cl СНз н О 4 Cl Cl СНз — сн.2 — OHž— н О 4 Cl Cl —CH— (СНз) 2 н О 4 Cl Cl —СН— (СНз) СНгСНз Η О oil - IR bands: 1725 cm ^{@ 4} , 1600 cm @ ^-1 4 СНз · СНз СНз н О 3 Cl Cl ОСНз н О oil - NMR (CDCl3) (<5) 2.9 (m, 4H), 4.0 (m, 5H); 7.4 (s, 1 H), 7.19 (s, 1H) 3 Cl Cl ОСНгСНз н О Mp 119-120 ° C 3 Cl Cl ОСН (СНз) 2 н О oil - NMR (CDCl3) (δ) 1.4 (d, 6H). 3.0 (m, 4H); (t, 2Ή) 4.6 (m, 1 H), 7.3 (s, 1 H) (s, 1 H) 3 Cl Cl Н н О 76—79 ° C oil - IR bands: 1720 cm ^-1 , 16'20 cm ⁴ , 885 cm ^-1 , 830 cm ⁴ 5 Cl Cl ОСНз н О 100—102%:

m Physical properties

Cl Cl OCH2CH3 Η Cl Cl ОСН (СНз) 2 Η Cl Cl О (СН1) 2СНз Η Cl Cl Η Η Cl Cl Cl Η F Cl Η Η H F Η Η

⁰

Ο oil - IR bands: 1690 cm ^-1 , 1240 cm ^-1 , 1120 cm ^-1 , (NMR (CDCl 3) (<5) 1.0-2.3 (m, 13H),

2.8 (m, 2H).

3.8 (m, 2H).

3.8 (m, 4 H),

7.0 (s, 1 H),

7.4 (s, 1 H)

Mp 123-126 ° C

125-128 ° C

Mp 72-77 ° C

Cl Cl O-CH2-CH (CH3) 2 H

NO. 1 NO. 1 ОСНз н NO. 1 NO. 1 ОСН (С'Нз) 2 н NO. 1 NO. 1 ОСН (ОНз) 1 н NO. 1 NO. 1 OCH2ČH3 н NO. 1 NO. 1 ОСНз н NO. 1 Cl ОСНз н (Ί. Cl Η н NO. 1 Cl ОСН (СНз) 2 н 01 Cl Η н NO. 1 Cl ОСНз н 0.1 Cl 0-СН (СШ) no NO. 1 Cl ОСНз н

oil (NMR (CDCl 3) (δ) 0.8-2.2 (m, 14H),

2.8 (m, 2H).

3.9 (m, 2H); 4.4 (Q, 1H); 7.1 (s, 1H); 7.6 (s, 1H)

5-СНз

5- СНз

6- СНз

6-СНз

6- СНз

7- СНз oil - IR bands:

1680 cm ^-1 , 1515 cm ^-1

7-СНз 98 to 101 ° С

7- СНз

8- СНз oil - IR bands:

1690 cm ^-1 , 1500 cm ¹

8-СНз oil - IR bands: 1700 cm ^-1 , 1570 cm ¹

8-СНз oil - IR bands: 1700 cm ^-1 , 1580 cm ^-1

6- (СНз) 2 oil - IR band:

1710 cm ¹ ,

1580 cm ^-1

Cl Cl ОСН (СНз) 1

H 8- (CH3): oil - IR bands:

1710 cm ^-1 ,

1579 cm ¹

Example d-2

Preparation of 2- (2,4-dichlorophenyl) -5,8,7,8-tetrahydro-1,2,4-triazolo {4,3-a] pyridin-3- (2H) -thlon

To 4.5 parts of piperidone 2,4-dichlorophenylhydrazone hydrochloride was added 100 parts of dry tetrahydrofuran and 4.6 parts of triethylamine. To this mixture was added 2.1 parts of thiophosgene. The reaction mixture was refluxed for 5 hours, then filtered with 5200 parts of alumina activity II (supplied by ICN Liere Science, Clevelan-Ohio, Ohio). The crude product was eluted from alumina with 500 parts of tetrahydrofuran. The filtrate is concentrated under reduced pressure (7-4 kPa) on a rotary evaporator. The crude product obtained is crystallized from benzene-hexane. 1 part of the product is obtained, m.p. - 118-120 ° C.

Using a procedure analogous to Example 2, the following compounds of formula I (wherein Q is sulfur) can be prepared from the appropriate amidrazone and thiophosgene:

n Y X IN of Physical properties 4 Cl Cl H H 118-120 ° C 4 H NO2 H H 4 H Cl H H Mp 171-172 ° C 4 Cl Cl OCH3 H Mp 136-140 ° C 4 Cl Cl OCH2CH3 H 4 Cl Cl OCH (CH3.2 H Oil - IC bands: 1580 cm ^"1, 1240 cm -1, 1120 cm ^_1 4 Cl Br OCH2CH3 H 4 F Cl H H 112-Y116 ° C 5 Cl Cl H H 5 H NO2 H H wax - IC belts: 1605 cm -1, 855 cm -1 5 H Cl. H H oil-IC strips: 1610 cm ^- 1, 1030 cm ~ 1, 800 cm ”1 5 Cl Cl OCH3 H oil - NMR (CDCl 3 (give): 1.9 (m, 6H); 3.0 (m, 2H); 4.0 (s, 3H); 4.4 (m, 2H); 7.3 (s, 1 H), 7.8 (s, 1 H) 5 Cl Cl OCH2CH3 H 5 Cl Cl OCH (CH 3) 2 II oil-NMR (CDCl 3 (δ)): 1.5 (d, 6H); 2.0 (m, 6H); 3.0 (m, 2H); 4.1-5.0 (m, 3H); 7.5 (s, 1 H), 8.0 (s, 1 H) 5 Cl Br OCH3 H

Using a procedure analogous to Example 2, the following compounds of formula I (where Q is an oxygen atom) can be prepared from the respective amidrazone and phosgene:

(cH

η Y ₍ X IN OF m Physical properties 4 F Br Η Η O 4 Cl N02 Η Η O Mp 204-209 ° C 4 H CN Η Η O Mp 164-165 ° C 4 Cl Br Η Η O Mp 136-139 ° C 4 Cl NO2 OCH (CH 3) 2H O M.p. 141-143 ° C 4 Cl Cl OH Βγ O Mp 198-201 ° C 4 Cl Cl OCH3 Br O Mp 152-153 ° C 4 Br Cl Η Η O oltj — NMR (DMSO-d6)

(5)

1.9 (m. 4H),

2.7 (m, 2H).

3.6 (m, 2H).

7.6 (m. 2H);

7.9 (m. 1H)

Cl

Cl

Cl

Cl

H Br

Br H glass - NMR (CDCl 3) (δ):

2.0 (m, 4H);

2.8 (m, 2H).

3.8 (m, 2H).

7.9 (s. 1H).

8.1 (s, 1 H),

Cl

Cl

N02

Cl

H OH

138-141 ° C

Mp 218-220 ° C

Example 3

Preparation of 2- (2,4-dichloro-5-hydroxyphenyl) -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridine-3 (2H) -one

To 42.8 parts of 2- [1,2,4-dichloro-5- ( ¹ -methyl-ethoxy) -phenyl] 5,6,7, e-tetrahydro-1,2,4-triazolio [4,3-a] pyridine-3 (2H) 45 g of concentrated hydrobromic acid (48%) was added. The mixture is refluxed for four hours. To the mixture which is refluxed is added 15 parts of concentrated hydrobromic acid. (48%) and heating was continued for an additional 3 hours. The reaction mixture was allowed to cool to room temperature, then poured into a liter of water. The crude product obtained by filtration is then added to 500 parts of water. The pH was adjusted to 12-14 with a 50% aqueous sodium hydroxide solution. The aqueous solution of the product was then extracted three times with 2'50 parts methylene chloride. The organic extracts were removed. The aqueous layer was acidified with concentrated hydrochloric acid (38%) to pH · 2 to 3. The product precipitated and was filtered off. The product was further purified by crystallization from methanol-1-ethyl acetate. Yield: 15.5 parts of product, mp 211-212 ° C.

Example 4

Preparation of 2- [2,4-dichloro-5- (2-chloroethoxy) phenyl] -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridin-3 (2H) -one

3.0 parts of 2- (2,4-dichloro-5-hydroxyphenyl) -1,5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyrimidin-3 (2H) -one, which was produced as described above in Example 3, it is mixed with 1.4 parts of 1-bromo-2-chloroethane, 1.5 parts of anhydrous potassium carbonate and 20 parts of dry acetonitrile and the mixture is refluxed for 6 hours, then stirred at room temperature for 72 hours. The mixture was poured into 200 parts water, the aqueous suspension was extracted three times with 200 parts methylene chloride, and the organic extracts were dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure on a rotary evaporator. 2 parts light brown solid, mp 14'8-150 ° C.

Using a procedure analogous to Example 4, the following compounds of formula I can be prepared from the corresponding phenol of formula VII and the halide of formula VIII:

К см

Physical properties

ООО

AS AS AS from (v) from:

ООО \ r-t

I o

Д5> f-4 гИ ω

I p

СЭ ·· Q >> co сл to 'WH rH> O i

Ф Co O rH

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ТМ rt <Tf <

м <Mi -Ф

Tt <’Ф

X

Physical properties ~ E

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AND

CD rH rH

O o

bx CD rH

CD cnE

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I2® I —K to * ^K

Q3E 0 cm

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e ас а

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Physical properties

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CH2CH2CH2CH5

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Physical properties *

Q со

”'Cd р ΐλ O e o í t <

ω

Ο >> - I 'ώ >>

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as s

WHAT ГГ what and PS X Ol X it ÍE нЦ O 9 and £ o | p AND O O AND it \ p it X Ol x \ ^χ / Ol X · X o OF and o | O O AND O | O AND O 1 = Q AND I o = o AND o = ° AND I o = O | o == 0 O AND 1 = U AND 1 O I o AND O AND O I O AND O

O O 5 5 ω 5 O O 5 O O 5 ω 3 O

Physical properties

TI co

cm

CM IS

CM

WHAT

> í Д4 JsJ 5řH 4 »H \ <- M \ rH Я Я > rM ^ 5 7/5 7/5 7/5 w 7/5 ω сю 7/5 >> > 4 >> >> >> > 4 > S >> O O O O O O O O O

НН НИ НИ НМ ни кН кН кН НН нм

O = U

Д Д Д Дмя ЯД '·

I0 of о

I to z

OF o ^.-_- o 1 O-4 ¹ Q | OF 0 I CM it 1 at it я 1 OF OF OF of CN LC 1 z u I at —0 1 0 1 O O —0 1 1 1 0 O 0 0 0

Ю я

no

O

I = о

I from U

II z u

AND

CM

Z о

I о

tQ я о <N • Ό

К ω ____

О о о о О δ δ ббйййй

ΙΌ я о

I.

CH — CH2OCH3. H O-oxygen

CH 2 - CH 2 - OCH 2 CH 3 H O (oxygen oil - IR love):

1700 'cm' ¹ , 1590 cm '

чф чф чф чф

Чф чф Чф

Ю Tt <тф -ф чф чф ”Ф

X тй

Physical properties of it

Q -

7 «л«

XCM со «д« Й, *> СО СО S. “LG

- 6 Е ® _CÁ

X LO v4

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SK

u ω oo CO CO ю CV r r ^{-I -} 1 1 • CM LO CO OJ RH RH 44 4tí 4tí \ Ř — 1 \ rH > —I TO to it £ ·> 4 4 4 o o O X X X

oxygen

сэ

сэ

t Φ f ΐη. LO ю

το ιο to το

Physical properties

ω

О о

IQ

СО

д ω

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Д О еч «д о О

ιη ιη

> г— * >>

6.5 - 6.7 (1Η), 7.1 (s, 1Ή),

7.5 (s, 1H) hr hr ¹ 'т *' т * Т ⁴

Μ-1 М-4 М-1 Μ-1 М-1

Tt <

СМ ω ω

II

Physical properties

и и 1 СМ £ Д ω о Т 1 СМ 1 ем * -τ < 5 G 1 Ί CM it Д и 1 Д ω- AND '° Ϊ' _4 1 Ρ Ρ д ω II o — ω ω II Д 1 Д Ρ о д 1 Д, О о 1 II 1 Ρ СМ д о 1 1 ω 1 ο

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Example. 5. . г ...

Preparation of 2- [2,4-dichloro-5- (1-ethoxycarbonylethoxy) phenyl] -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridine3 (2H) -onu

20.1 parts of 2- (2,4-dichloro-5-hydroxyphenyl) -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridin-3 (2H) -one, prepared as described in Example 3, 12.1 parts of ethyl 2-bromopropionate, 9.3 parts of anhydrous potassium carbonate and 100 parts of dry acetonitrile were refluxed for 5 hours. The aqueous product suspension was extracted three times with 2-5 parts (0 parts methylene chloride), then the solution was dried over anhydrous sodium sulfate, and the solvent was distilled off on a rotary evaporator under reduced pressure. m.p. 1316-138 ° C.

Using a procedure analogous to Example 5, the following compounds of formula I can be prepared from the phenol of formula VII and the corresponding haloester of formula VIII.

η Y X V Z m Q Physical properties

4 Cl Cl 0 II О — СНг — С — ОСНз н О oxygen M.p. 172-174 ° C СНз О 1 II О — СН — С — ОСНз СНз О 1 II О — СН — С — OCH2GH2CH3 СНз О 1 II —ОСН — С — О (СНг) зСНз СНз О 1 II О — СН — С — ОСНз 4 Cl Cl н О oxygen 4 Cl Cl н О oxygen 4 Cl Cl н О oxygen 5 Cl Cl no О oxygen oil (NMR) (CDCl 3) (5), 1.8 (m, 9H); 2.8 (m, 2H). 3.8 (m, 5H); 4.8 (Q, 1H); 7.0 (s, 1H, 7.5 (s, 1H) 5 Cl Cl О — ОН — С — ООН2СН3 1 II СНз О СНгСНз О 1 z н О oxygen 4 Cl Cl О — ОН — с \ ОСНз (СNг) гСНз О н О oxygen 4 Cl Cl О — СН — с \ н О oxygen

ОСНз η Υ X V

Z m Q Physical properties (СНг) з — СНз

О

Cl Cl о — сн — с \ ООНз

Example 6

Preparation 2 [2,4-dichloro-5- (1-carboxyethoxy) phenyl] -5 / 6,7,8-tetrahydro-1,2,4-trlazolo [4,3a] pyridine-3 (2H) - onu

10.8 parts of 2 - ['2,4-dichloro] ^- 5- (1-ethoxycarbonylethoxy) -4-phenyl] -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3a] pyridin-Э (2H) -one was added to 20.6 parts of concentrated hydrochloric acid (38%) and 175 parts dioxane, and the mixture is heated at 80 ° C for 30 hours, after cooling, the solution is poured into 760 parts water, adding solid sodium bicarbonate to raise the pH of the solution to 8-9.

The aqueous product solution was then extracted three times with 250 parts of methylene chloride. The organic extracts were removed. The aqueous product solution was then acidified by the addition of concentrated hydrochloric acid (38%) to pH 1. The aqueous product solution was extracted three times with 250 parts methylene chloride. The product solution was dried over anhydrous sodium sulfate. The solvent was distilled off on a rotary evaporator under reduced pressure. The glassy residue was triturated with ether. 4.4 parts of a white solid are obtained, m.p. 183-185 ° C.

Using a procedure analogous to Example 6, the following compound of formula I can be prepared from the corresponding ester of formula XII.

11 Y X in 4 Cl Cl O — CH2 — COOH СНз 4 Cl Br | O — CH — COOH СНз 4 F Cl O — OH — COOH СНз AND 5 Cl Cl 1 O — CH — COOH

of m Q Physical properties H O oxygen oil - IR bands: 3400—2200 cm ^-1 (br), 1750—1600 cm ^-1 (br), 1560 cm ^-1 H O oxygen H 0 oxygen H 0 oxygen

Example 7

Preparation of 2- [2,4-dichloro-5- (1-N-methoxy-N-methyl-1-carboamoylethoxy) phenyl] 45,6,7,8-tetrahydro-1,2,4-triazolo [4, 3-a] pyridin-3 (2H) -one

a) Preparation of 2- [2,4-dichloro-5- (1-carbonylethoxy) phenyl] -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridine-3 - (2H) -one

To 3.7 parts of 2- [2,4-dichloro-5- (1-carboxyethoxy) -phenyl] - [eta] &lt; 6 &gt; -Etetrahydro-1H-triazolo [eta] &lt; 5 &gt; -alpyridin-B &apos; and 1.2 parts of thionyl chloride and the mixture was refluxed for 3 hours. The reaction mixture was stirred for an additional 12 hours at room temperature. The solvent and excess thionyl chloride were removed from the product by evaporation on a rotary evaporator under reduced pressure. 4.0 parts of crude product are obtained and used in the next step without further purification.

b) Preparation of 2 - [: 2,4-dichloro-5- (1H-methoxy-N-methylcarbamoyl-ethoxy) -phenyl] -6,6,7,8-tetrahydro-1,2,4-triazolo [14] 3-a] pyridin-3 (2 H) -one parts of the crude acid chloride of Example 7a were dissolved in 50 parts of tuluene containing 2.2 parts of triethylamine and 1.3 parts of N-methoxy-N-methylamine.

эа

The reaction mixture was stirred at room temperature for three hours. To the mixture was added 50 parts of water and the reaction was stirred for an additional 10 minutes. The organic phase was separated, washed twice with 25 parts of saturated sodium bicarbonate and once with 25 parts of water. The organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off on a rotary evaporator under reduced pressure. 1.4 parts of a glassy solid are obtained, which has the following NMR spectrum:

CDCl 3 (δ) 1.7 (d, 3H), 2.0 (m, 4H),

2.7 (m, 2H); 3.2 (s. 3H);

3.7 (m, 5H), 5.2 (q, 1 H),

7.1 (s, 1 H), 7.5 (s, 1 H)

Using a procedure analogous to Example 7b, the following compounds of formula I can be prepared from the corresponding acid chloride of formula XIII, which is prepared as described in Example 7a, and from the corresponding amine of formula XIV:

n Y X V '..... Z m 0 Physical properties 4 Cl Cl 0 II ОСНг — C — NH2 Η 0 oxygen 205-207 ° C 4 Cl Cl СНз 0 ОСН — C — NHCH 3 Η 0 oxygen 4 Cl Cl СНз О СНз 1 II FROM ОСН — С — N Η 0 oxygen 4 Cl Cl \ СНз СНз О СНз 1 II Z О — СН — С — N Η 0 oxygen 4 Cl Cl \ СНзСНз СНз О СНгСНз 1 II z ОСН — С — N Η 0 oxygen 4 Cl Cl \ (СНз) 2СНз СНз О СНз 1 II / ОСН — С — N Η 0 oxygen 5 Cl Cl \ (СNг) зСНз СНз О СНз 1 II z ОСН — С — N Η 0 oxygen 5 Cl Cl \ ОСНзСНз СНз О СНз О — СН — С — ν '/ СНз СНз О СНз 1 II z O-CH-C-N Η 0 oxygen 5 Cl Cl Η 0 oxygen \

ОСНз за η ^? · Υ ') ”Χ V ----------- —Ζ · - rti-qr Physical properties

СНз О

5 Cl Cl O-CH-C-NH-CH2-CH2 = CH2 H О oxygen СНз О СНз 5 Cl Cl Ί 1 O — CH — C — NH — CH — СН = СНгН О oxygen СНз О 5 Cl Cl O — CH — C — NH2 Η О oxygen 4 Cl Cl СНз О СНз О — CH — С — Ν ^ Н О sulfur

\

СНз

Example 8

Preparation of 2- (2,4-dichloro-5-hydroxyphenyl) -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridin-3- (2H) -one methylcarbamate

A mixture of 25 parts methylene chloride, 1.1 parts methyl isocyanate, 3.0 parts 2- (2,4-dichloro-5-hydroxyphenyl) -5,6,7,8-tetrahydro-1,2,4-triazolo [4, 3-a] pyridin-3 (2H) -one and 0.05 part 1.4

-diazobicyclo [2.2.2] octane was refluxed for 4 hours. The solvent was distilled off on a rotary evaporator under reduced pressure. The crude product obtained by crystallization from acetonitrile gives 2.5 parts of solid product 1.1. Mp 167-170 ° C.

Using a procedure analogous to Example 8, the following compounds of formula I can be prepared from the phenol of formula VII and the corresponding isocyanate:

η Y X V

4 Cl Cl O — CNHCH2CH3 II 0 4 Cl Cl O-C-NH (CH 2) 2 CH 3 II O 5 Cl Cl O - C - NH (CH 2) 3 CH 3 II 0 5 Cl Cl O — C — NHCH3 0

of m Q H O oxygen H 0 sulfur

H O oxygen

H O oxygen

Example 9

Preparation of 2- [2,4-dichloro-5- (1-hydroxymethyl-ethoxy) -phenyl] -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridine-3 ( 2H) -one

4.0 parts of 2- [2,4-dichloro-5- (1-ethoxy-carbonyl-ethoxy) -phenyl] -5,6,7,8-tetrahydro-1,2,4-triazolof4,3- a] pyridin-3- (2H) -one, which was prepared as described in Example 5, was treated with 75 parts of sodium borohydride and 0.3 parts of lithium chloride in 75 parts of tetrahydrofuran. The reaction mixture was heated at 40 ° C for 6 hours. After this time, 0.6 parts of sodium borohydride and 0.5 parts of lithium chloride were added and the reaction mixture was stirred at room temperature for 12 hours. The reaction was heated to reflux and an additional 3.0 parts of sodium borohydride and 2.8 parts of lithium chloride were added in small portions over 48 hours. The mixture was cooled and slowly added to 100 parts water while foaming the mixture. The product was extracted three times with 200 parts ether. The ether was then extracted twice with 100 parts water. The ether layer was dried over sodium sulfate. The ether was distilled off on a rotary evaporator under reduced pressure. The residue is triturated with methylene chloride to give 0.35 parts of a tan solid, m.p. of formula (XI) may be prepared by the following method analogous to that of formula (I):

n Y X in of m Q Physical properties 4 Cl Cl OCH2CH2OH H O oxygen oil - NMR (CDCl3) (5): 2.0 (m, 4 H), 2.8 (m, 3H); 4.5 (m, 6H), 7.4 (s, 1H), 7.8 (s, 1H) . СНз 5 Cl Cl O — CH — CH2OH H 0 oxygen Mp 54-57 ° C 5 Cl Cl O-CH 2 CH 2 OH H 0 oxygen

Example 10

Preparation of 2 - {[5- (2-acetyloxy) ethoxy] -2,4-dichlorophenyl} -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridine-3 ( 2H) -one

3,8 parts of 2- [2,4-dichloro-5- (2-hydroxyethoxy) -phenyl] -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridine The -3 (3H) -one, which was produced in a manner analogous to Example 9, was combined with 2.2 parts of anhydrous sodium acetate and 2.8 parts of acetic anhydride in 15 parts of toluene. The reaction mixture was heated at 80 ° C for 3 hours and then cooled to room temperature. The reaction mixture was poured into water. The organic phase is extracted with 209 parts of methylene chloride and dried over anhydrous sodium sulfate. The solvent was distilled off on a rotary evaporator under reduced pressure. 3.0 parts of oil are obtained,

NMR-CDCl3 (δ):

1.8-2.4 (m, 7H), 2.8 (m, 2H), 3.9 (m, 2H), 4.3-4.8 (m, 4H),

7.4 (s, 1 H), 7.9 (s, 1 H).

Using a procedure analogous to Example 10, the following compounds of formula I can be prepared from the corresponding alcohol of formula XVI

Z m Q Physical properties

СНз O

4 Cl Cl O — CH — CH2 — О — С — СНз H 0 oxygen 0 5 Cl Cl 0- -CH 2 - CH 2 - O - S 1 CH 2 - CH 3 H 0 0 oxygen 4 Cl Cl Cl · -CH 2 CH 2 O - C - (CH 2) 2 CH 3 n H 0 oxygen 4 Cl Cl 0- II -CH2CH2—0 — С — СНз Ы 0 oxygen oil - NMR

(CDCl 3) (δ) 1.8-2.3 (m, 9H),

2.8 (m, 2H).

3.9 (m, 2H); 4.2-4.8 (m, 4H); 7.4 (s, 1H);

7.8 (s, 1H)

Resources

Useful compositions of the compounds of Formula I include powders, granules, tablets, solutions, suspensions, wettable powders, emulsifiable concentrates and the like. Many of these compositions can be applied directly. Compositions capable of forming a spray can be diluted with a suitable medium, and the spray can be used in a volume of several liters to several hundred liters per hectare. High-performance formulations are primarily used to produce more dilute formulations for use in the field. The compositions, broadly, consist essentially of about 0.05 to 99% by weight of the active ingredient (s), and about 0.1 to 20% surfactant (s) and / or about 1 to 99.95% solid or liquid diluent (s). More specifically, they usually consist of these components in the following approximate ratios:

% By weight active ingredient diluent (s) surfactant (s) wettable powders 5-90 1-94 1-HO oil suspensions, emulsions, solutions (including emulsifiable)

concentrates) 5—60 40—95 0—15 aqueous suspensions 5—50 40—94 1-20 pills 0,05—25 70—99,95 O — 5 granules and pills 0,05—95 1—99.95 0—15 means high efficiency 90-99 0-10 0—2

Any of the compounds of Formula I may be used in these compositions.

However, depending on the intended use and the physical properties of the compound, less or more active ingredient may be present. Sometimes higher ratios of surfactant to the active ingredient are desired, this is achieved by mixing in the composition or mixing in a tank.

Typical solid diluents are described by Watkinsonei and ispol .: Handbook on Insecticide Duet Diluents and Carriers, Second Edition, Borland Books, Caldwell, NJ. , kaolinity, limestone, mica, montmorillonites, phosphates, pyrophyllites, sulfur, sand, talc, tripolites, vermiculite and synthetic materials such as precipitated hydrated silica, precipitated hydrated calcium silicate, precipitated calcium carbonate, and synthetic organic materials. More absorbent diluents are preferred for wettable powders, denser diluents are preferred for powders. Typical liquid diluents and solvents are described by Marsden: Solvents Guide, Second Edition, Intersclence, New York, 1950. For suspension concentrates, solubility below 0.1% solution concentrates are preferably stable against phase separation at 0 ° C. .

For a list of surfactants and their recommended uses, see "McCutcheon's Detergents and Emulsifiers 1975 Annual", MC Publ. Gorp., Ridgewood, New Jersey, as well as Sisely and Wood: Encyc lopedia of Surface Active Agents, Chemical Publ. Col., New York, 1964.

All compositions may contain minor amounts of ingredients that reduce foaming, caking, corrosion, microbiological growth, etc., or visibly indicate the area that has been treated.

Solutions are made simply by mixing the ingredients. The finely divided solid formulations are prepared by mixing and usually grinding in different kinds of mills. Suspensions are made by wet grinding (see, for example, Littler, US Pat. 3,060,084).

The granules can be produced in several ways. For example, the active ingredient may be sprayed onto preformed granular carriers. Suitable preformed granular carriers include those listed previously, having a particle size in the range of 74 nanometers (USS No. 2G10) to 2000 nanometers (USS No. 10). A preferred particle size is from 105 nanometers (USS No. 140) to 840 nanometers (USS No. 20).

Depending on the nature of the carrier, the active ingredient may remain on the surface of the carrier or may be absorbed into the carrier. When the active ingredient remains on the surface of the carrier, a binding agent is typically used to maintain the active ingredient on the surface. The binding agent should bind the active ingredient to the surface so well that not more than 10% of the active ingredient is removed during normal shipping and handling. Suitable binders include materials which are at least partially soluble in any liquid used in the manufacture of the granules and which adhere to the surface of the granules. Preferred are those water-soluble binding agents. Suitable binders include, but are not limited to, water-soluble polymers such as polyvinyl alcohols, polyvinylpyrrolidines and oxethylene polyes. Other binding agents include lignin sulphonates, starches, sugars and certain surfactants listed in "McCutcheons Detergents and Emulsifieris 1975 Annual", MC Publ. Corp., Ridgewood, New Jersey.

The active ingredient may be sprayed onto the granules as a solution in a suitable solvent, which may or may not be removed from the composition. If the active ingredient is a liquid, it may be sprayed on or mixed directly with the carrier. If the active ingredient is a solid, it can be melted and applied directly as a liquid. If very low potency granules are desired, the active ingredient may be sprayed onto the carrier.

Granules can also be produced by agglomeration techniques. For example, the active ingredient and the finely divided solid diluent may be mixed and agglomerated by techniques well known in the art, such as by spraying with a liquid in a fluidizing nest or a wheel granulator. The active ingredient and diluent may also be mixed with the other ingredients of the formulation and tableted. The tablets may be comminuted into granules of the desired size. Tablets may be prepared by agglomeration techniques. See J. E. Browning: Agglomeration, Chemical Engineering, December 4, 1957, pages 147 et seq. And &quot; Perry &apos; s Chemical Engineers Handbook, fourth edition, McGraw-Hill, N.Y., 19163, pages 8-59 et seq.

For more information on resources, see for example: Η. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16 through Col. 7, line 19, and Examples 10-41. R. W. Luckenbaugh, US Pat. 3'309 192, March 14, 1967, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166 —167, 169—182. Gysin and E. Knusli, US Pat. No. 2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Ex. 1—4. Klingman, G. C.: Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pages 81-96. J. D. Fryer and S. A. Evans: Weed Control Handbook, Fifth Edition, Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

Example 11

Wettable powder

2- (2,4-dichloro-5-ethoxyphenyl) -4,6,6,8,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridin-3 (2H) -one 25% ligninsuliphonane sodium 2% alkylnaphthalenesulfonate sodium 2% synthetic amorphous silica 3% kaolinite 68%

The ingredients are mixed together, ground in an air mill to give particles below 15 nanometers in diameter, mixed again and sieved through US No. 50 sieve (0.3 mm apertures) prior to packaging.

Example 12

Solution

2- [2,4-dichloro-5- (1-methylethoxy) -phenyl] -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridin-3 (2H) -on 20% dimethylformamide 80%

The components are combined and mixed to produce a solution that can be used for low c-bjcmu applications.

Example 13

Compressed tablets

- (2,4 - dichlorophenyl or 1 -5 - eth о x у _{phenyl-5,6,7,8-tetrahydro-2,} 4-triazolo [4,3-a] pyridin-3 (2H) - on 1% anhydrous sodium sulphate 10 ° / o crude calcium ligninsulphonate 5% sodium alkylnaphthalenesulphonate 1% polyoxyethylene (average molecular weight 4.10 ⁶ ) 1% calcium / magnesium bentonite 82%

The ingredients are mixed, ground in a hammer mill, and then moistened with about 12% water. The mixture is compressed in the form of a roller with a diameter of about 3 mm, which, by cutting, gives tablets of a length of 3 mm. These can be used directly after drying or the dried tablets can be crushed enough to pass through a USS No. 29 mesh (0.84 mm aperture). The granules remaining on USS No. 40 (0.42 mm holes) can be packaged for use, finer particles being recycled.

Example 14

Emulsified concentrate

2- [2,4-dichloro-5- (1-methoxyethoxy) -phenyl] -2,5,6,7,8,9-hexahydro-3H-2,4-triazolo [4,3-a] azepine- 3-one 25% mixture of oil-soluble sulfonates and polyoxyethylene ethers xylene

4%%

The ingredients are combined and mixed until complete dissolution. A fine mesh filter is included in the packaging operation to remove any foreign undissolved material from the product.

Example 15

Aqueous suspension

2- (2,4-dichloro-5-ethoxyphenyl) -5,6,7,8-tetrahydro-1,2,4-trlazolo [4,3-a] pyridin-3 (2H) -one 50.0% polyacrylic acid, hardener 0.3% polyethylene glycol ether dodecylphenol 0.5% sodium hydrogen phosphate 1.0% sodium dihydrogenphosphate 0.5 ° / o polyvinyl alcohol 1.0 ° / o pentachlorophenol 0.4% water 46.3%

The components are ground together in a sand mill to give particles having substantially all sizes less than 5 nanometers.

Example 1 G

Wettable powder

2- (2,4-dichloro-5-methoxyphenyl) -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridin-3 [2H] -one 50% sodium alkylnaphthalenesulfonate 2% sodium ligninsulfonate 2% synthetic amorphous silica 3 ° / o kaolinite 4'3%

The components are mixed together, ground in an air mill to give particles of average size below 15 nanometers, mixed again, and sieved prior to packaging through USS No. 50 sieve (0.3 mm apertures).

Example 17 The active ingredient in a blender and sieved prior to packaging was screened with USS # 40 (0.42 mm apertures). For use in the field, the concentrate may be further treated.

Example 18

Granules of low efficiency

2- [2,4-dichloro-5- (1-methoxyethoxy] -phenyl] -2,5,6,7,8,9-hexahydro-3H-1,2,4-triazolof4,3-a] Azepln-3-one 0.5% Atapulgite granules (low volatile material, size 0.59-0.25 mm, ie USS 30-00 meish) 99.5% grams of solution containing 2.5% 2- [2 4-dichloro-5- (1-methyloxy) phenyl] -2,56,7,8,9-hexahydro-3H-1,2,4-triazolo [4,3-a] azepin-3-one dissolved in methanol, is slowly sprayed in a fluidising nest with atapulgite granules (199 g) After spraying, the fluidization of the granules is continued until all of the methanol from the granules has evaporated, and the granules are packaged for use.

Example 19

Limbane teblets

2- (2,4-dichloro-5-methoxyphenyl) -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridin-3 (2H) -one 2> 5% anhydrous sodium sulfate 10 '% crude calcium ligninsulfonate 5% sodium alkylnaphthalenesulfonate 1% magnesium / calcium bentonite 5-9%

The ingredients are mixed, ground in a hammer mill and moistened with about 10-12% water. The ae palk mixture is compressed into a cylinder having a diameter of about 3 mm, which is cut into pieces of about 3 mm in length. These tablets may be used directly after drying or the dried tablets may be crushed to pass through a USS No. 20 sieve (0.84 mm aperture). Tablets retained by USS No. 40 screen (0.42 millimeter openings) can be packaged for use, finer recycled.

Example 20

High efficiency concentrate

Granules of low efficiency

2- (2,4-Dichloro-5-methoxyphenyl) - -6,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridin-3 (2H) -one 99% 2- (2,4-Dichloro-5-ethoxyphenyl-5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridin-3 (2H) -one) 0.2% trimethylnonylether anhydrous sodium sulphate 10% polyethylene glycol 1% crude calcium ligninsulfonate 5%

Surfactant is sprayed onto sodium alkylnaphthalenesulfonate 1% finely powdered attapulgite clay 83.8%

The ingredients are mixed, ground in a hammer mill and placed in a fluidized bed granulator. Water is allowed to soak into the fluidized bed with powder until small granules are formed. The water soaking is then terminated, but the fluldization is continued to dry the formed granules. The granules are removed from the granulator and sieved through USS No. 20 sieve (0.84 mm apertures). The granules retained on USS No. 40 sieve (0.42 mm apertures) are packaged for use. Granules larger than 0.84 mm are ground and recycled. Particles smaller than 0.42 mm are also recycled.

Example 2 1

Compressed tablets

2- (2,4-dichloro-'5-methoxyphenyl) -5,6,7, ^l 8-tetrahydro-2,4-triazolo [4,3-a] pyridint3 (2H) -one 0,1% anhydrous sodium sulphate Ю% crude. calcium ligninsulphonate 5% sodium alkylnaphthalenesulphonate 1% polyoxyethylene (average molecular weight

4.10P) 1% calcium / magnesium bentonite 82.9%

The ingredients are mixed, ground in a hammer mill, and then moistened with about 12% water. The wetted mixture is compressed in the form of a roller having a diameter of about 1 mm and a length of about 2 mm. These small tablets are dried and packaged. They are used directly.

Example 22

Granules of low efficiency

2- [2,4-dichloro-5- (1-methylethoxy) -phenyl-5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridin-3 (2H) - on 0,05 ·% dimethylformamide 5% attapulgite granules (low volatile material, size 0,59–0,25 mm, ie USS No. 30–60 mesh) 94,95 ·%

One-tenth of a gram of 2- [2,4-dichloro-5- (1-methylethoxy) phenyl] -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridin-3 ( 2H -one was dissolved in 9.9 g of dimethylformamide. This solution is sprayed very slowly into a rapidly inverting nest with 190.1 g of atapulgite granules. After the application of the active ingredient, the composition is mixed for a further few minutes. Dimethylformamide is not removed from the composition. The granules are packaged for use.

Example 23

Emulsified concentrate

2- [2,4-Dichloro-5- (1-nitro-1H) -ethoxy] -phenyl] -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3- a] pyridin-3 (2H) -one 10% mixture of an oily-soluble sulfonate with a polyoxyethylene ether 6% aromatic hydrocarbon solvent having a flash point in a Tag closed crucible between 43.3 and 46.1 ° C 84%

The ingredients are mixed and mixed until all are dissolved. Prior to packaging, the solution is filtered through a fine mesh filter to remove any foreign undissolved material.

Example 24

Granules -o · low efficiency

2- (2,4-dichloro-5- (1-methylethoxy) -phenyl) -2,5,6,7,8,9-hexahydro-3H-1,2,4-triazolo [4,3-a] azepine -3-on 0.1% sodium lignin sulphonate pre-made sand granules having a particle size ranging from 150 nanometers (USS screen # 140) to 297 nanometers (USS screen 30) 94 , 9%

0.5 grams of 2- [2,4-dichloro-5- (1-methylethoxy) -phenyl] -2,5,6,7,8,9-hexahydro-3H-1,2,4-triazolo [4, 3-α] azepin-3-one and 25 g of sodium ligninsulfonate are dissolved in 50 g of water. This solution is sprayed slowly into an inverting nest with sand granules (474.5 g). When spraying is complete, the inverted granules are heated to remove water. The obtained granules are packaged before use.

The compounds of formula I may also be combined with other herbicides and are particularly useful in combination with symtriazines such as atrazine [2-chloro-4- (ethylamino) -6- (isopropylamino) -symtriazine], linuron [ 3- (3,4-dichlorophenyl) -1-methoxy-1-methylurea], alachlor [2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) acetanilide], bromoacil [3- (sec butyl) -5-bro ^; m-6-methyluracil], diuron [3- (sec-butyl) -5-bromo-6-methyl-uracil],

3- cyclohexyl-l-methyl-6-dimethylamino-s-triazine-'2,4 (1H, 3H) -dione, paraquat [l, l'-dimethyl-4,4 ^{<-bipyridiniový} ion], m- [ 3,3-Dimethyl-tert-butylcarbamate, β-methyl-α-chlorophenoxyacetic acid, its salts or esters,

4-amino-S-tert-butyl-3-methylthioasyme-

-triazin-5 (4H-1-one, aryl-4-nitrophenyl ethers such as 2,4,6-trichlorophenyl-4-mtrophenyl ether and 2,4-dichlorophenyl-4-nitrophenyl ether, methyl-m-hydroxycarbanilate-m-methylcarbanilate,

5- (2,3,6-E1-E1-E1-E1-diisopropyl) thiocarbamate,

S- (2,3-Dichloro-Orallyl) diisopropylthiocarbamate,

3-cyclohexyl-5,6,6-methylenuracil, S-ethyl-N-ethylthiocyclohexanecarbamate, 5-amino-4-chloro-2-phenyl-3 (2H) -pyridazinone,

4-amino-3-methyl 6-phenyl-1,2,4-thiazolin-S (4H) -one, for controlling a wide range of weeds.

The compounds of formula (I) are useful for selective pre-emergence control of undesirable vegetation in crops such as corn, diabetes and wheat. The compounds of the invention can be used in the form of a direct action for pre-emergence (post-emergence) or post-emergence (after emergence) weed control in various crops including corn and cotton.

The exact amount of compounds of formula I to be used in a given situation varies according to the desired end result, the method of use, the type of crop and weeds, the type of soil, the composition used, the method of application, according to the prevailing weather conditions, the number of leaves and the like. Since so many influences play a role, it is not possible to specify the ratio of the application - suitable for all situations. Roughly said compounds of the invention are used in ratios of about 0.015 to about 15 kilograms per hectare, preferably about 0.03 to about 10 kilograms per hectare. Lower ratios from this range are generally used in lighter soils, in soils with low organic material content, for selective weed control in crops or in situations where maximum stability is not required.

The herbicidal activities of these compounds have been discovered in many greenhouse tests. The test procedure is as follows:

Example 25

Seeds of the cudweed (Digitaria sp.), Hedgehogs (Echinochloa crusgalli), deaf oats (Avena 'fatua), cassia' (Cassia torah), barley (IpomOea sp.), Beet (Xanthiumsp.) Sorghum (Sorghumsp.), corn, soybean, rice, wheat and tubers are grown in nutrient media and then treated preemergently with chemicals that have been 'dissolved' in a non-phytotoxic solvent. By the time cotton had five leaves (including uterine), broad bean third unfolding, three-leafed dew, two-leafed dew, hedgehog corns 'foot' two leaves, oat deaf one leaf, cassia three leaves (incl. uterine), four leaf leaves (including uterine), sorghum three leaves, maize three leaves, soybean two uterine leaves, two rice leaves, one leaf 'wheat and three to five leaf leaves,' were sprayed. The treated and control plants are kept in the greenhouse for 16 days, then all are compared to control and the processing response is evaluated visually. The rating is given 'on a numerical scale ranging from 0' = no effect to 10 · (or a,) - complete destruction. Other descriptive symbols have the following meanings: B = burnt, G = growth inhibition, C = chlorose or necrosis, D = de ^; foliation, E = key inhibition, 1 H = formative effects. Pre- and post-emergence evaluations of compounds tested in this manner are shown in Table I.

The data illustrates the herbicidal potency of the compounds of the invention.

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These data show good control of a wide range of weeds at low application rates and selectivity to crops such as corn, sugar beet and wheat.

Table II

Preemergence on Fallsington sedimentary sandy loam soil

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The test demonstrating the utility of the compounds of the invention for selective pre-emergence weed control in maize is carried out as follows: a 25 cm diameter plastic cup is filled with Flanagan sedimentary sandy loam soil (prairie soil containing approximately 5.5% organic material) · and either planted with Funk G 4646 maize seeds, planted to a depth of 3.7 cm, or with different weed seeds, which are evenly mixed with the upper two-and-a-half centimeter layer of soil. The following weeds were used: field mustard, parsnip, durman, dew, hedgehog and leg.

Immediately after planting, test chemicals dissolved in non-phytotoxic solvents are applied to the bare soil surface. Each treatment was duplicated · (Experiment I, Experiment II}, · Processed seedlings are left in the greenhouse where they are watered as needed. is the same as described above.

Table III

Effect of 2- [2,4-dichloro-5-1-methylethoxy) phenyl] -5,6,7,8-tetrahydro-1,2,4-triazolo [4,3-a] pyridin-3 ( 2H) -one for selective pre-emergence weed control in maize

Greenhouse. test .....

Assessment of weed damage Assessment of broadleaf ¹ grassy2 corn ³

Application rate kg / ha attempt · I experiment · II pokus I pokus II attempt · I try 0/06 6C 80 · - 7'C 70 .. 0.12 7C 80 80 70 10 . 10 0,25-: 9C 9C ·. 9C.  9G 4C 20 May 0.50 « 40  3C 0.75 < ec 7C - 0 0 0 O O 0

¹ mustard. field, undercover, durman dew, hedgehog corns leg

Funk G · 4646

Example 28

In another test, soybeans are planted in plastic cups filled with Fallsdington sedimentary sandy loam soil. cotton, alfalfa (Medicago sativa), corn, rice, wheat, sorghum, Abutilon theophrasti, Sesbania exaltata, cassia (Cassia tora), bitterwort · · (Ipomoea sp.), durman (Datura stramonium), beet (Xanthium) pennsylvanicum), dew (Digiiarl-a sp.), flathead (Cyperua rotundus), hedgehog (Echinochloa · crusgaUl), shear (Setaria faberi) and deaf oats (Avenua fatua),

Fifteen days after planting, the young plants and soil around them are sprayed with test chemicals dissolved in a non-phytotoxic solvent. Fourteen days after processing, the samples are compared with unprocessed control samples. The processing response is evaluated visually. The evaluation is again carried out on a numerical scale ranging from 0 = no damage to 10 = complete destruction. The accompanying "descriptive symbols" have the following meanings:

B = burned · ·· ·

C = chlorose / necrosis

H = formative effects. The evaluation of compounds tested in this manner is shown in Table IV.

Table IV

Ground / leaf surface treatment

XOflo

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Bisisq щедвхе ¹ viupqsas qjUQaurqspod qoq AAofos eq / 8q jguiod

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CM Q rH iD CM O rH ID CM O rHiň o O cq. ςα © cq

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Tf 'f' - ©

X CQ in ID

03 / X CQ WHAT O O rH t — 1 03 / CQ X tF in LD 04 / E _CQ E pq tx tn cD tn O řH 03 / CQ 03 / CM what tx

03 / CQ 03 / what 00 © rH_ 03 / CQ 03 / tx CD © rH 03 / CQ x E CM What tx in X CQ 03 / WHAT what

§ O tH CQ O rH CQ CQ CQ CD O O t-H CQ CQ X CD .tx ¹ OH · CQ CQ CQ O O Φ tH TH. tH F CQ CQ 1 LĎ OH CQ CQ X what CD O. tH CQ CQ CQ O C5 O tH rH tH CQ CQ CQ c0 00 CD

© © cm cm rH iD O O

EXAMPLE 1-a d '2 9 [4,3-a] azepin-3-one. The data below are grown in the field of sugar beet either to lustrate the usefulness of the chemical for combating pre-emergence or post-emergence -with 2-weeds. in this plant.

- [2,4-dichloro-5- (1-methylethoxy) phenyl] -

Preemergence Ratio Grassy Shirolists Diabetes kg / ha ° / o destroy ¹ % Kill ¹ ° / damage to ^one crop 0.125 20 May 20 May 0 0.25 35 30 0 0.5 80 550 0 1.0 · · · 95 90 10

Evaluated 6 weeks after processing.

Postemergence

Ratio kg / ha Grassy% destruction2 Widespread% destruction ² Diabetes % damage! crop 0.125 40 70 • 30 0.25 50 65 30 0.50 • 76 95 30 1.0 93 99 90

Rated 3-1 / 2 weeks after processing.

Example -3 0

Spring wheat, grown in sedimentary sandy loam soil, is treated preemergently with 2- [2,4-dichloro-5- (1-methyl-ethoxy) phenyl] -5,6,7,8 * tetrahydro-1-ol. 2,4-triazolo [4,3-a] pyridin-3 (2H) -one. The weed control data presented below is obtained 10 weeks after treatment and shows that the material is effective in controlling weeds.

Ratio kg / ha% grass weed destruction - broadleaf% wheat damage

Wheat yield in% relative to control

0.06 557 80 0 120 0.125 92 93 0 131 0.25 98 96 10 128 0.50 98 99 57 88

In the second test, the compound damages - good - as shown. -data that will get 6 nicely somewhat more, but the combat -levelly is weeks after processing.

Ratio kg / ha weed destruction % damage to wheat grassy broadleaf 0.06 20 May 73 0 0.125 50 90 20 May 0.25 80 94 50 0.60 92 99 80

Example 31

The primary activity of the other compounds of the invention was tested by the procedure of Example 25. The results are shown in Table V. The meanings of the rating evaluation symbols used are shown in Example 25.

Ar kg / ha

Table V

0.4 0.4

O

OC ~ NHCH ₃ post-allergenic

bean 9B 8B 9B cotton 9B 9B 9B povijnice WB WB WB beet 9B 9B 9B kasia 7B 5B 4B šáchor 5B 2B 4B rosička 8B 9B 9B hedgehog corns the leg 9B 9B WB oat deaf 8B 7B WB wheat 8B 5B 8B 9H maize 8B 4B 5B 9-H soya 8B 7B 9B rice 9B 7B WB sorghum 6B 7B 9B preemergently povijnice WC 9G 9H beet 10C 6G WC kasia 1C 9G 8H šáchor 8C 5C 4C rosička WC WC WC hedgehog corns the leg WC WC . WC oat deaf 10C WC WC wheat WC 9C 9C maize 2C 2C 5C 9H soya 2C 1C 3C 9H rice 8C 8C 9C sorghum WC 9C WC

Ar

ОСН> СН = СНСО ^ СН ^

Cl о И

Br OH

Cl

kg / ha; 0.4 0.4 0.4 postemergence bean - general 1OB 9B 7B cotton 9B 1OB 9B povijnice 1OB 1OB 1OB beet 9B 9B 1OB kasia— .......’........................ ............- 9B .......... ' ___________________________ 1OB ........... _______.___ .........- -1B šáchor 5B 5B 5B rosička 1OB 9B 5B hedgehog corns the leg 1OB 9B 1OB oat deaf 9B 8B 3B wheat 1OB 8B 5B maize 9B 7B 7B soya 9B 9B 8B rice 1OB 8B 7B sorghum 9B 8B 9B preemergently povijnice 1OC 9C 90 beet 40 9C 50 kasia 5C 1OC 10 šáchor 9C 9C 10 rosička 1OC 10C 0 hedgehog corns the leg 1DC 10C 0 oat deaf 90 10C 0 wheat 1OC 90 0 corn. 2C- 9H 20 9H 3G soya 1C 4H 20 8H 1G rice 90 90 30 sorghum 9C 90 10 7G

Ar

kg / ha 0.4 0.4 0.4 postemergence bean 5B 4B 9B cotton 9B 9B 1OB povijnice 10B 10B 9B beet 5b 9B 9B kasia 3B 1B 9B šáchor 3B 4B ЮВ rosička ЗВ 5H 9B НОВ hedgehog corns the leg 9B 1OB 10B oat deaf 3B 5B 10B wheat 3B 9B 9B maize 3B 8B 7B soya 9B 8B 9B rice 2B 4B 9B sorghum 5B 9B 10B preemergently povijnice 9G 10C 10C beet 1C 4H 50 50 kasia • = ~ 0 10C šáchor 80 10C 90 hedgehog corns the leg 10C юс 10C rosička ЮС 10C 10C oat deaf 9C 40 10C wheat 9C 90 10C maize ЗС 9H 2G 9H soya 9H 0 10E rice 90 90 10C sorghum 10C 1OC WC

Ar

kg / ha 0.4 0.4 0.4 postemergence bean WB WB WB cotton WB 9B 9B povijnice WB WB WB beet WB 5B 9B kasia WB 9B 9B šáchor 9B 4B 7B rosička WB 8B WB hedgehog corns the leg WB 9B WB oat deaf WB 5B 9B wheat 10B 5B 9B maize 9B 213 7B soya WB 7B 9B rice WB 1B 9B sorghum WB 4B 9B preemergently povijnice WC 2C 9H WC beet WC 1C 8G WC kasia 10C 9C WC šáchor WC 5C 9C rosička WC WC WC hedgehog corns the leg WC WC 10C oat deaf 10C 9C 9C wheat WC 9C 9C maize 9H 9H 90 soya WC 9H 9H rice WC 8C 9C sorghum WC 9C WC

Ar

kg / ha 0.4 0.4 0.4 postemergence bean ЭВ 8B 8B cotton 1OB 9B 9B povijnice 10B 10B 10B beet 5B 1B 4B kasia 4B 4B 2B šáchor 6B ΘΒ 3B rosička 8B 10B 4B 9H hedgehog corns the leg 10B LOB 9B oat deaf 8B 8B 8B wheat 7B 7B 5B maize 4B 7B 3B soya 7B 5B 2B rice 9B 7B 5B sorghum 9B 9B 7B preemergentně povijnice 2C 6G 20 May beet 50 - - kasia 40 8G 30 šáchor 20 May 20 May 10 rosička 10 8G 8G 8H hedgehog corns the leg 90 90 90 oat deaf 90 90 90 wheat 90 90 90 maize 30 9H 40 8H 30 9H soya 20 7.G 20 9G 30 rice 90 90 90 sorghum WC 10H WC

Ar cw ₃ о-сн-со, н

Whose

kg / ha 0.4 O; 4 0.4 poste mergentě bean 7B 9B WB cotton 9B WB 9B povijnice WB WB WB beet ав 9B WB kasia 2B 9B WB šáchor 5B 7B 7B rosička 8B WB WB hedgehog corns the leg WB WB • WB oat deaf 5B 9B 9B wheat - 7B WB maize SB 9B 9B soya 8B 9B 9B rice 4B 9B 9B sorghum 9B 9B 9B preemergently povijnice 1C 7G WE WC beet 1C 3H WC caste 0 10C WC šáchor BC 9C 9C rosička 9H WC WC hedgehog corns the leg WC WC WC oat deaf 6C WC WC wheat 8C 9C WC maize Ό 2C 9H 9H soya 2G 9H 9H rice 9.C 9C WC sorghum 9C WC WC

Ar kg / ha

postemergence bean 10B 8B 9B cotton 9B 9B 10B poVijnice 1OB 10B 10B beet 9B 0 5B kasia 8B 1B 9B šáchor 7B 1B 6B rosička 1OB 5B 9B hedgehog corns the leg 10B 8B 9B oat deaf 8B 3B 9B wheat 8B 3B 7B maize 7B 2B 5G 6B soya 9B 1B 5G 9B rice 8B 1B 7B sorghum 9B 6B 8B preemergently povijnice 1OC 2G 9H beet 70 - [0100] 2H kasia 2C 3H 9H šáchor 9C 0 90 rosička 1OC 3G 10C hedgehog corns the leg 10C 0 10C oat deaf 90 0 10C wheat 9C 0 100 ALIGN! maize 9H [0100] 2H 9H soya 9H 0 9H rice 90 0 90 sorghum 100 ALIGN! 3G 9H

kg / ha 0.4 0.4 0.4 postemergence bean 9B WB 9B cotton 1OB 1OB 9B povijnice WB WB WB beet WB 9B 9B kasia WB 10B 6B šáchor 8B 8B 9B rosička WB 1OB WB hedgehog corns the leg WB 10B 1OB oat deaf 9B 7B 9B wheat 9B 0B 9B maize 8B 5B 6B 6H soya 9B 9B 9B rice 9B 1OB 1OB sorghum 1ЮВ 8B 9B preemergently povijnice WE 2C 9H WC beet 2C 8H WC 5H kasia WC 7IC 9C šáchor 9C 7C ac rosička WC WE WC hedgehog corns the leg WC WC WC oat deaf WC 9G WC wheat 9C 9C 5C 9H maize 2C 9H 1C 8H 9H soya 9H 9H 9H rice 10C 9C 9C sorghum WC 9C WH

297497

Ar

kg / ha 0.4 0.4 0.4 postemergence bean 8B 9B WB cotton 9B WB WB povijnice WB WB WD beet 9B 9B WB kasia 5B 9B WB šáchor 7B 4B 9B rosička WB WB WB hedgehog corns the leg WB 9B 1OB oat deaf WB 8B WB wheat 9B 9B 9B maize 7B ав 9B soya 9B 9B 9B rice WB 9B WB sorghum 9B WB WB preeimeřgentně povijnice 9H 10C WC beet 9H 9C 2C 8H kasia WC 1OC WC šáchor 9C 9C 9C rosička night WC WC hedgehog corns the leg WC WC WC oat deaf WC WC WC wheat 9H WC WC maize 9H 9H 9H soya 9H 9H WH rice 9C WC 9C sorghum WH 9H юн

Аг

kg / ha 0.4 0.4 0.4 postemergence bean l0B 4B 7B cotton 9B 5'B 9B povijnice .. l0B IB 9B beet 9B 3B OB kasia 7B IB IB 5G šáchor 9B IB 7B rosička IOB 5B 9B hedgehog corns the leg 9B 6B 8B oat deaf 9B 5B 8B wheat 9B IB 9B maize; 5B 9H IB 8B soya 9B 2B 9B rice. IOB 3B 9B sorghum. 9B IB 4B preemergently povijnice I0C IH 20 8H beet 9H 0 I0 ’5H kasia 10C 0 7C šáchor 90 0 90 rosička I0E 5H I0E hedgehog corns. leg 10E 20 8H IOE oat . deaf 90 30 9H I0C wheat 9C 30 8H I0C maize; 50 9H 2C 9H soya - -..... 9H IH 9H rice I0C 0 9C sorghum 90 0 9H

20749I

Cl ·

kg / ha 0.4 0.4 0.4 postemergence bean 7B 7B 10B cotton 8B 9B 9B povijnice 9B 10B 10B beet 5B 5B 7B kasia 2B 2B - šáchor 5B 4B 4B 90 rosička 5B 4B 5B 9H hedgehog corns the leg 8B 3B 9B oat deaf 4B 3B 7D wheat 4B 3B 6B maize 4B 5B 4B soya 5B 5B 5B rice 6B 4B 9B sorghum 3B 3B 6B preemergently povijnice 2H-9G 2G 10C beet 0 0 10 4H kasia 0 0 100 ALIGN! šáchor 80 1C 5G 90 rosička 9H 5G 10E hedgehog corns the leg 10C 1OC 10E oat deaf 90 > 20 7H 100 ALIGN! wheat 90 2C 9G 90 maize 9H 20 - βΗ 9H soya 1C '8G [0100] 2H 20 -9G rice 90 90 90 sorghum 9H 9H 10E

A.r

AND

ОСН, С W = CW-C-OC

сн.о

I ³ II о-сн-с-осн (*)

kg / ha 0.4 0.4 0.4 postemergence bean 5B 9B - baolník 8B · 9B 9B povijnice 5B 10B 4B beet - 7B 9B kasia 2B 6B 1B Páchor 2B * 5B 1B rosička 3B 7B 1B 2H hedgehog corns - foot 5B 5B · 9B ooes deaf 2B OB - 3B wheat 2JB 4B 5B maize 2B 5B 4B soya 4B 5B 8B rice 4B 8B 8B sorghum 5B , 7B 8B preemergently povijnice 0 10 7H 80 beet 0 2C 3C kasia 0 90 0 Páchor 0 8C - 10 rosička 2G 9H [0100] 2H hedgehog corns the leg [0100] 2H 1QC 10 .5H ooes deaf 0 100 ALIGN! 20 May wheat 0 90 80 maize 0 9H 0 soya 0 4G 5G rice . 0 90 · 70 sorghum 0 1OH 80

kg / ha 0.4 0.4 0.4 postemergence bean 2B 8B 6B cotton 2B 7B 8D ΘΒ povijnice 6B 1OB 1B beet 5B 5B 2B kasia 1B 5B 1B šáchor 0 4B 1B rosička 2B 1OB 2B hedgehog corns the leg 5B 7H 1OB 1OB oat deaf 1B 6B 1B wheat 2B 6B 1B maize 1B 3B 2B soya 1B 8B 2B rice 2B 5B 2B sorghum 3B 7B 3B preemergentně povijnice 0 1C 5G 0 beet 0 2C - kasia 0 2C 0 šáchor 0 8C 0 rosička 0 10C 0 hedgehog corns the leg 1C 10C 7C oat deaf 0 10C 2C wheat 0 100 ALIGN! 2G maize 0 3C 9H 4G soya 0 1C 8G 0 rice 0 9C 0 sorghum 0 10C 0

kg / ha postemergence broadleaf cotton bean 'beetroot cassia broadleaf hedgehog corns leg oats deaf wheat maize soy rice sorghum preemergence bittersweet caste castor. dew hedgehog corns leg oats deaf wheat corn soy rice sorghum

3B

2iB

4B

2B

1B

1B

1B

2B

1B

1B

1B

1B

1B

2B '0 o 0 0 o o Q 0 o o o O

Example 32

The secondary pre-marketing herbicidal activity of compound A (according to the invention) was compared to that of two known herbicidal compounds, namely the compound B known as the commercial herbicide lenacil and compound C known as the herbicide diuron.

Compound A ienacil (col. B)

NCNP

diuron (col. C)

The experiments were carried out in sandy soil. The data presented in Table VI below shows that although the doses of Compound A of the invention are only in doses of Compounds B and C, Compound A at these low doses is much more effective than Compounds B and C as a herbicide. for Halle sorghum, paspal and Kentucky bluegrass.

Claims (24)

SUBJECT OF THE INVENTION A herbicidal composition, characterized in that, in combination with a surfactant and / or a solid or liquid diluent, it contains, as an active ingredient, a herbicidally effective amount of a bicyclic triazole derivative of the formula I X (l) wherein V represents a hydrogen, fluorine, chlorine or bromine atom, a hydroxyl group, a (C1-C4) alkyl group or a group -ORi in which: R 1 represents an alkyl group having 1 to 6 carbon atoms optionally substituted by 1 to 3 fluorine, chlorine or bromine atoms, a cycloalkyl group having 4 to 6 carbon atoms, a cycloalkylalkyl group having 4 to 7 carbon atoms, an alkenyl group (C 3 -C 6) optionally substituted by (1 to 3) fluorine, chlorine or bromine, (C 3 -C 6) alkynyl, -CHR 7 R 8 R2 represents a hydrogen atom or a methyl group, R3 represents a hydrogen, chlorine or bromine atom, a methyl-group or a methoxy group, R4 represents an alkyl group having from 1 to 4 carbon atoms, R5 represents a hydrogen atom, a methyl or methoxy group, R e represents a (C 1 -C 4) alkyl or (C 1 -C 4) alkoxy group, R2 represents a hydrogen atom or a (C1 -C4) alkyl group, R 5 represents a group -CO 2 R 9, —CH 2 OR 9, II — OH2 — O — C — R10, O II- -. . —CN, —C — СНз, —CH = CHCOR9 or O Rii II / —C — N, \ R12 in which R 9 represents an atom, a hydrogen or a C 1 -C 4 alkyl group, R 10 represents an alkyl-group having 1 to 3 carbon atoms, R 11 represents a hydrogen atom, a C 1 -C 4 alkyl group, a C 3 -C 4 alkenyl group or a C 1 -C 2 alkoxy group; and R12 represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms, X represents a hydrogen, fluorine, chlorine or bromine atom, a cyano group, a methyl group, a -methoxy group or a nitro group, Y represents a hydrogen, fluorine, chlorine or bromine atom or a methyl group, Z denotes hydrogen, fluorine, chlorine or bromine, n is 3, 4 or 5, m is 0, 1 or 2 -a Q is an oxygen or sulfur atom, with the proviso that (a) if V has a meaning other than -hydrogen, then Y also has a meaning other than hydrogen, b) if m is 1, then -n is-4 and Y has a meaning other than hydrogen, c) when m - is -2, - then n is 4, X and Y are each a chlorine atom and V is a group --OR 1, in which - R 1 is an alkyl group having 1 to 4 carbon atoms, d) if Q is a sulfur atom, then -m is -O, or an agriculturally acceptable salt thereof. 2. A herbicidal composition as claimed in claim 1, wherein the active ingredient is a bicyclic triazole derivative of the formula I, wherein: Y represents a hydrogen, fluorine, chlorine or bromine atom, a hydroxyl group, a methyl group or an —OR 1 group in which R 1 is as defined in point 1, and X, Y, Z, n, m and Q are as defined in point 1. 3. A herbicidal composition as claimed in claim 1, wherein the active ingredient is a bicyclic triazole derivative as defined in claim 1, wherein: X is hydrogen, fluorine, chlorine or bromine, methyl or nitro, and V, Y, Z, n, m- and Q are as defined in 1. 4. A herbicidal composition as claimed in claim 1, wherein the active ingredient is a bicyclic-triazole derivative of the formula I, wherein: Y represents a fluorine, chlorine or bromine atom or a methyl group; V, X, Z n, m - and - Q have the meaning given in point 1. 5. A herbicidal composition as claimed in claim 1, wherein the active ingredient is a bicyclic triazole derivative of the formula I, wherein: Z represents hydrogen atom, net chlorine atom and V, X, Y, n, -m and -Q are as defined in point 1. 6. The herbicidal composition of claim 1, wherein the active ingredient is a bicyclic-triazole derivative as defined in claim 1 wherein n is 4 or 5; V, X, Y, Z, -m and -Q have the meanings given at -1. 7. A herbicidal composition as claimed in claim 1, wherein the active ingredient is a bicyclic triazole derivative of the formula I wherein m is 0 and V, X, Y, Z n and Q are as defined in 1. 8. A herbicidal composition as claimed in claim 1, wherein the active ingredient is a bicyclic-triazole derivative of the formula I, wherein: V is hydrogen, chlorine or bromine, or -OR 1, wherein R 1 is C 1 -C 4 alkyl; X represents an atom of fluorine, chlorine or bromine, Y is - fluorine, - chlorine, bromine or methyl, Z is hydrogen, n is 4 or - 5 and m - and Q - have the meanings given in 1. 9. A herbicidal composition as claimed in claim 1, wherein the active ingredient comprises a bicyclic triazole derivative of the above general formula (I) wherein n is 4; V, X, Y, - - Z, - m - and Q are as defined in -1. 10. A herbicidal composition as claimed in claim 1, wherein the active ingredient is a bicyclic-triazole derivative of the formula I, wherein: V represents a hydrogen or chlorine atom or a group -OR 1 in which R 1 is as defined in point 1, X represents a chlorine or bromine atom, Y represents a fluorine, chlorine or bromine atom; Z, n, - m and Q are as defined in point 1. 11. A herbicidal composition as claimed in claim 1, wherein the active ingredient is 2- [2,4-dichloro-5- (1-methylethoxyphenyl) -5,6,7,0-tetrahydrohydrof1,4,4-triazole [4, 3-a] pyridin-3 (2H-om 12. The herbicidal composition of claim 1, wherein the active ingredient is 2- (2,4-dichloro-5-methoxyphenyl) -5,6,7,8-ietrahydro-1,2,4-riazolo [4]. 3-α] pyridin-3 (2 H) -one. · ’ 13. A herbicidal composition as claimed in claim 1, wherein the active ingredient is 2- (2,4-dichloro ([eta] &lt; 5 &gt; -ethoxyphenyl) -5,6,7,8-tetrahydro-1,2-a); 4-triazolo [4,3-a] pyridin-3 (2H) -one. 14. The herbicidal composition of claim 1, wherein the active ingredient is 2- [2,4- (1,3-chloro-5- (1-methylethoxy) phenyl) -2,5,6,7,8. 9-hexahydro-3H-1,2,4-triazolo [4,3-a] -zepin-3-one. 15. The herbicidal composition of claim 1, wherein the active ingredient is 2- (2,4-dichloro-5-hydroayphenyl) -5,6,7,8-tetrahydro-2H-2H-rthiazole-4,3- a] pyridin-α (2H) -one. 16th herbicidal composition according to claim 1, characterized in that it contains as active ingredient 2- (2,4-dichloro-5-propargyloayfenyl ·) _f -5 _{6,7,8-tetrahydro-l>} 2,4-1triazólo [ 4- _> 3-al] pyridin-3 (2H) -oin. 17. The herbicidal composition according to claim 1, wherein, in association with the surfactant, and / or the solid or liquid diluent, the herbicidally effective amount of a bicyclic triazine derivative of the formula Ia is contained as an active ingredient. X in which V represents a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, a -methyl group or a group -OR 1 in which R 1 represents an alkyl group having from 1 to 4 carbon atoms optionally substituted by 1 to 3 fluorine, chlorine or bromine atoms, X represents a hydrogen, fluorine, chlorine or -bromine, cyano, methyl, imethoayl or nitro group, V is hydrogen, chloro, fluoro, or bromo or methyl, n is 3, 4 or 5; and Q represents an oxygen or sulfur atom. 18. A herbicidal composition as claimed in claim 17, wherein the active ingredient is a bicyclic triazole derivative as defined in claim ¹ , wherein: V represents a hydrogen, fluorine, chlorine or bromine atom, a methyl group or an —OR 1 group in which R 1 is as defined in point 17, and X, Y, n and Q are as defined in point 17. 19. The herbicidal composition of claim 17, wherein the active ingredient is a bicyclic triazole derivative of formula (Ia) above, wherein: X represents a hydrogen, fluorine, chlorine or bromine atom, a cyano group, a methyl group or a nitro group, and V, Y, n and Q have the meaning given in point 17. 20. The herbicidal composition according to claim 17, wherein the active ingredient is a bicyclic triazole derivative of the above formula (Ia), wherein: Y represents a fluorine, chlorine or bromine atom or a -methyl -a group V, X, n and Q have the meaning given in point 17. 21. A herbicidal composition according to claim 17, wherein the active ingredient is a bicyclic triazole derivative of formula (Ia) wherein n is -4 or 5; V, X, Y and Q are as defined in point 17. 22. A herbicidal composition as claimed in claim 17, wherein the active ingredient is a bicyclic triazole derivative of formula (Ia), wherein: Y represents a hydrogen atom, a chlorine or a bromine atom, or a group - OR 1 in which R 1 represents an alkyl group of - 1 - to 4 carbon atoms, X represents a fluorine, chlorine or bromine atom, Y represents a fluorine, chlorine or bromine atom or a methyl group, n is 4 or -5 and Q is as defined in point 17. 23. The herbicidal composition of claim 17, wherein the active ingredient is a bicyclic triazole derivative of formula (Ia) wherein n is 4; V, X, Y- and - Q are as defined in point 17. 24. The herbicidal composition of claim 17, wherein the active ingredient is a bicyclic triazole derivative of formula (Ia), wherein: Y represents a hydrogen or chlorine atom or an ORi group in which R 1 is the same as in point 17, X is -atom-chlorine or bromine, Y represents a fluorine, chlorine or bromine atom and n - and Q - have the meanings given in -17. Savarografía, *. я * »xivod 7, Most