DE2118872A1 - Substituted pyridazones - Google Patents

Description

Badisciie Anilin- & Soda-Fabrik AG 2118872

Our reference: O.Z. 27 468 Sws / AR 6700 Ludwigshafen, April 15, 1971

Substituted pyridazones

The present invention relates to new and valuable substituted pyridazones _t and containing these herbicides.

It is known, 4- / ~ 1-phenyl-5-chloro-pyridazon- (6) -yl7-oxamic acid ethyl ester to use as a herbicide. However, its effect is not satisfactory.

It has been found that substituted pyridazones of the formula

JH.CO-R ₃

in which R _{1 is} a phenyl or cyclohexyl radical optionally substituted by methyl or trifluoromethyl and R _{2 is} chlorine or bromine, and R is the radical

s 3 CH

-COO-C-CH ₃ , COOCH ^ ³ , -CH ₀ -CHp-COOCH,

Nm ₃

COj ^
-CH ₀ -COOC ₀ H ₁ - or -0-M; \ J means valuable herbicide

effective connections are.

The compounds are strongly herbicidally active against weeds and grasses, in particular against Alopecurus myosuroides, Poa annua, Poa trivialis, Bromus tectorum, Echinod & oa crus-galli. You can therefore used with success in agriculture, in particular in the following crops: Triticum spp., Hordeum spp, Beta spp., Zea meays, Soja hispida, Gossypium hirsutum.

The application rates are about 1 to 6 kg of active ingredient / ha,
β7 / 71 -2-

2098 A4 / 1207

- 2 - O.Z. 27

The connections can be made "for example by Implementation of a 4-amino-pyridazone derivative with a dicarboxylic acid dichloride, hydrolysis of the 4-amic acid chloride obtained and further reaction with alcohols or by reaction with dicarboxylic acid ester chlorides.

The following experimental data explain the preparation of the inventive Links.

example 1

26.6 parts (parts by weight) of 1-phenyl-4-amino-5-bromo-pyridazon- (6) are stirred in 200 parts of dimethylformamide at room temperature. 17 parts of teriv-butyl oxalate are then slowly added. After the mixture has been stirred for a further hour, it is diluted with approximately 5 times the amount of water and the resulting precipitate is filtered off with suction. ^R oxamic acid-ter-fc-butyl ester (Ι), Pp (4 ^ 7136-138 ⁰ G (- are obtained 36 parts of N ^ ~ 1-phenyl-5-bromo-yl pyridazone (6).. Decomposition).

Example 2

22 parts of 1-cyclohexyl-4-amino-5-chloropyridazon- (6) are stirred in 200 parts of dimethylformamide at room temperature. Then are added slowly 15 parts of succinic acid methylester chloride to and heated with mixing for one hour at 130 to 14O ⁰ C. After the cooling, by addition of water, 17 parts of N- _(y / ~ 1-cyclohexyl-5-chloro- pyridazone (6) -yl (4j7- -succinamic acid methyl ester (II) mp .: 105 to 108 ⁰ C (recrystallized from benzene).

Example 3

24.7 parts of 1-phenyl-4-isocyanato-5-chloropyridazon- (6), 200 parts of benzene and 16.3 parts of N-hydroxyphthalamide are heated to the boil for two hours with thorough mixing. After cooling, 29 parts of N- ^ ^- I-phenyl-5-chloro-pyridazon- (6) -yl- (4j / -carbamoyloxy-N'-phthalimide (III), which after recrystallization from acetonitrile and washing with hot water at 188 to 196 C (decomposition) melts.

As the compounds according to the invention, some will be mentioned below Substances listed «,

209844/120? _3_

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- (m-Methylpheny1) -5-chlor-pyrida zon- (6) -yl- (4 ^ 7-oxamic acid tert-butyl ester (IV)

N- _/ £ ~ 1-Phenyl-5-chloro-pyridazon-6- (yl) - (4_) 7-succinamic acid methyl ester (V), pp .: 114 to 117 ° C

N- / ~ 1-Phenyl-5-bromopyridazon-6- (yl) - (4j> 7-malonamic acid ethyl ester (VI), m.p .: 139 Ms HO ⁰ C

N- / ~ 1-phenyl-5- "bromopyridazon-6- (yl) - (4j7-oxamic acid isopropyl ester (VII), pp. 120 to 121 ° C.

The compounds according to the invention can be used as solutions, emulsions, Suspensions or dusts are used. The forms of application depend entirely on the intended use; they should ensure a fine distribution of the active substance in each pail.

For the preparation of directly sprayable solutions hydrocarbons may be higher than 150 ⁰ C, for example, tetrahydronaphthalene or alkylated naphthalenes having boiling points, or organic liquids having boiling points higher than 15O ⁰ C and one or more functional groups, for example, the keto group, the ether group, the Estergruppe or Amide group, this group being a substituent on a hydrocarbon chain or being part of a heterocyclic ring, can be used as spray liquids.

Aqueous application forms can be obtained from emulsion concentrates, pastes or wettable powders (wettable powders) can be prepared by adding water. The substances can be used to produce emulsions as such or dissolved in a solvent, by means of wetting or dispersing agents, e.g. polyethylene oxide addition products be homogenized in water or organic solvents. Ss can also consist of active substances, emulsifying agents or concentrates consisting of dispersants and possibly solvents are prepared for dilution with water are suitable. Oils of various types can be added to the finished spray liquors.

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Dusts can be produced by mixing or grinding together of the active substances with a solid carrier, e.g. kieselguhr, talc, clay or fertilizer.

The following examples show the application of the invention Middle.

Example 4

The plants Zea mays, Triticum aestivum, Echinocloa crus-galli, Poa annua, Stellaria media and Sinapis arvensis at a height of 2 to 17 cm with 2 kg / ha active ingredient N- ^ fI-Pheny1-5-brom-pyridaζon- (6) -yl- (4 ^ 7-oxamic acid tert.- butyl ester (I) and for comparison * with 2 kg / ha active ingredient N- / ~ 1-phenyl-5-brcm ^> yridazon- (6) -yl- (4j7-oxamic acid ethyl ester (VIII), each dispersed in 500 liters of water per hectare. This showed up after 3 to 4 weeks following result:

Active ingredient VIII I. Crops 0 Zea mays 0 10 Triticum aestivum 0 Unwanted plants 70 Echinodioa crus-galli 95 85 Poa annua 100 90 Stellaria media 100 85 Sinapis arvensis 100

0 = without damage
100 = total damage

Example 5

In the greenhouse, test pots were filled with loamy sandy soil and the seeds of Triticum aestivum, Zea mays, Beta vulgaris, Stellaria media, Sinapis arvensis, Matricaria chamomilla, Poa annua and Echincchloa crus-galli were sown. Thereafter, the soil with 2 kg / ha active ingredient N- ^ ~ 1-phenyl-5-bromopyridazon- (6) -yl- (4jy ^r -oxamic acid tert-butyl ester (I) and for comparison with

209844/1207 " ⁵ ~

O.Z. 27 468

2 kg / ha active ingredient N- / ~ "i-phenyl-5-bromo-pyridazon- (6) -yl- (4,) 7-oxamic acid ethyl ester (YIII), each dispersed in 500 liters of water per hectare. This showed up after 4 to 5 weeks following result:

■ Active ingredient
I.

VIII

Crops

Triticum aestivum 0 0 Zea mays 0 0 Beta vulgaris 0 0 Unwanted plants

Stellaria media 90 80

Sinapis arvensis 90 75

Matricaria chamomilla 80 80

Poa annua 80 75

Echinoclioa crus-galli 80 55

0 = without damage
100 = total damage

Example 6

In the greenhouse, loamy sandy soil was filled into test pots and the seeds of Triticum aestivum, Beta vulgaris, Zea mays, Sinapis arvensis, Stellaria media, Poa annua, Poa trivialis and Echinodioa crus-galli were sown. The soil was then treated with 2 kg / ha active ingredient N- / ~ i-0yclohexyl-5-chloro-pyridazon- (6) -yl- (4 ^ 7-succinamic acid methyl ester (II)) and, for comparison, with 2 kg / ha active ingredient 1-Phenyl-4-amino-5 ^ chloropyridazon- (6) (IX), each dispersed in 500 liters of water per hectare. After 4 to 5 weeks, II compared to IX showed an equally good tolerance to crop plants and a stronger herbicidal effect The result can be seen from the following table;

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O. Z. 27,468

Active ingredient IX I. Crops 20th Triticum aestivum 10 0 Beta vulgaris 5 10 Zea mays 0 Unwanted plants 70 Sinapia arvensis 100 70 Stellaria media 100 70 Poa annua 95 65 Poa tricialis 100 60 Echinccltoa orus-galli 95

0 = without damage
100 = total damage

As effective as II are?

ester (Y)

a'- £ ¹ "i-Phe
ester (Ti)

Example 7

_{The plants Zsa mays9 Beta irulgaris, 'Triticum aestivum 9} Sinapis ar' / ensis ₉ Ohenopodiuai albuE _s Poa annug ₉ Bromus tectorum and Echinochloa crus-gaili were grown on a lan & v / iz-t schaft usable area at a height of 3 to 15 cm with 2 kg / ha active ingredient H- ₍ / ~ 1-Pheiiyl ~ 5-chloro "-pyridazon- (6) -yl- (4 _> ) 7'-oarTDamoyloxy-U'-phthalimid (III) and in comparison with 2 kg / ha active ingredient 1-phenyl-4 = ainino-5-chloro-pyridazon- (6) (IX), each dispersed in 500 liters of water per ha _c "treated for 3 to 4 weeks it was found that III compared to IX showed an equally good crop plant tolerance and a stronger herbicidal effect. The result can be seen from the following table:

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209844/1207

Active ingredient IX III Crops 10 Zea mays 0 0 Beta vulgaris 0 20th Triticum aestivum 0 Unwanted plants 80 Sinapis arvensis 90 80 Chenopodium album 90 50 Poa annua 85 '40 Bromus tectorum 80 40 Echinochloa crus-galli 80

O.Z. 27 468

0 = without damage
100 = total damage

As effective as III are:

N- / ~ 1-Phenyl-5-chloro-pyridazon-6- (yl) - (4j7-succinamic acid methyl ester (V)

N- / ~ 1-Phenyl-5- "bromopyridazon-6- {yl) - (4j7-malonamic acid ethyl ester (VI).

Example 8

80 parts by weight of compound I are mixed with 20 parts by weight of N-methyl-J £ -pyrrolidone and a solution is obtained which is suitable for use in the form of the smallest drops is suitable.

Example 9

20 parts by weight of compound II are dissolved in a mixture consisting of 80 parts by weight of xylene * 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40
Mol of ethylene oxide consists of 1 mole of castor oil. By pouring out
and finely distributing the solution in 100,000 parts by weight of water gives an aqueous dispersion which contains 0.02 percent by weight of the active ingredient.

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Example 10

2C parts by weight of compound III are dissolved in a mixture those from 40 parts by weight of cyclohexanone, 30 parts by weight T. isobutanol, 20 parts by weight of the adduct of 7 mol Ethylene oxide in 1 mole of isooctylphenol and 10 parts by weight of the Addition product of 40 moles of ethylene oxide and 1 mole of castor oil consists. By pouring the solution into 100,000 parts by weight of water and finely distributing it there is obtained an aqueous dispersion, which contains 0.02 percent by weight of the active ingredient.

Example 11

20 G-ewichtsteile of the compound IV are dissolved in a mixture Ge- "consisting of 25 G-ewichtsteilen cyclohexanol, 65 G-ewichtsteilen of a mineral oil fraction of boiling point 210 ° to 280 ⁰ C and 10 G-ewichtsteilen of the adduct of 40 mol of ethylene oxide with 1 By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02 percent by weight of the active ingredient.

Example 12

20 parts by weight of the active ingredient V with 3 parts by weight of the sodium salt of diisobutylnaphthalene - ^ - sulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a Sulphite waste liquor and 60 parts by weight of powder! Silica gel mixed well and ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives it a spray mixture containing 0.1 percent by weight of the active ingredient.

• Example 13

3 parts by weight of compound II are 97 parts by weight finely divided kaolin intimately mixed. In this way a dust is obtained which contains 3 percent by weight of the active ingredient «

-9-

209844/1207

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Example 14

30 parts by weight of the compound I are with a mixture from 92 parts by weight of powdered silica gel and 8 parts by weight Paraffin oil, which has been sprayed onto the surface of this silica gel, is intimately mixed. One receives on this Way, a preparation of the active ingredient with good adhesion.

. . ■ ■ ·.-.- ■■■ .-- -10 *

2008U /> 40 7

Claims (5)

- 10 - O.Z. 27 ^ 68 Claims Λ) · Substituted pyridazones of the formula HH.CO-R ₃ ^E 1 in which R is a phenyl or cyclohexyl radical optionally substituted by methyl or trifluoromethyl and R _? Chlorine or bromine, R, the rest -COO-C-CH ₃ , COOCH _x ^J , -CH ₂ -CH ₂ -COOCH ₃ , -CH ₂ -COOC ₂ H ₅ ^ ^CH 3 or -O-N ^ P J means. 2. Herbicide containing a solid or liquid carrier and a compound as characterized in claim 1 as Active ingredient. 3. Use of a compound according to claim 1 as a herbicide. 4. N- / ~ 1-Phenyl-5-bromo-pyridazon- (6) -yl- (4j7 ° xamic acid tert-butyl ester. 5. N- / ~ 1-Cyclohexyl-5-chloro-pyridazon- (6) -yl- (4 ^ 7-succinamic acid methyl ester. 6, N- / ~ "i-Phenyl-5-chloro-pyridazon- () -ylphthalimide. Badische Anilin- & Soda-Fabrik AG