DE2707168A1 - AZODIPYRIDINE COMPOUNDS AND THEIR APPLICATION - Google Patents

Description

Dr.-lrg. Waiter Abitz Dr. Dieter F. Mo rf

Dipl .- ::. Ys.fiC ;; i _S chn8der *. ¹⁸ February-1977

8 Münchsn 25, Pienzenauerstr. 28 BA-8164-B

E. I. DU POKT DE MEMOURS AND COMPANY

10th and Market Streets, Wilmington, Delaware I9898, V.St.A.

Azodipyridine compounds and their application

Fungi that infest seeds "do well in all parts of the world often lead to severe crop or yield losses. This is especially true for Helminthosporium species such as H. oryzae, H. teres, H. sativum, H. gramineum and H. avenae, which most of the more important cereal crops and Attack grasses, including barley, wheat, rye,

Oats, sorghum, panicum, rice, maize and cultivated grasses, Helminthosporium species lead to the formation of various Symptoms. In the case of rice, for example, germination can be prevented or seedlings can be killed or deformed by dead ones Entering places at leaves. In barley, lesions appear on the husks that the young shoots hold cover, and plants can die off as a result of stem or basal breakage. On older plants can the formation of immense numbers of spores can result in contaminating or infecting developing seeds and in the Effect of a direct transfer of the fungus from the harvest of one year to that of the next year.

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In the past, various seeds contained quack silver Compounds have been applied to rid them of fungi such as Helminthosporium. More recently have become However, difficulties arise in connection with the use of mercury, and this must no longer be applied to the Market, so that a substitute is needed.

According to the invention, it was surprisingly found that Seed-infesting fungi can be combated by adding an effective amount of 4-, 4 - * - azodipyridine or new acid salts to the seeds the formula

feeds in what

A an acid with an acidic dissociation constant (£ _)

-6
greater than 1 χ 10 and

ρ equals the number of hydrogen atoms attached to the acid A. which have an acidic dissociation constant greater than 1 χ 10 ".

The acid salts of formula I are used for reasons of greater safety that they offer for formulation and application, preferred. The 1,2-benzene dicarboxylate salt is, in turn, of the acid salts preferred.

With the compounds and methods of _t according to the invention can in particular be Helminthcsporium species combat effective as H. oryzae, H. teres, H. sativum, H. gramineum and H. avenae.

The invention also includes valuable agricultural and forestry Compositions of substances for combating fungi

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on or in seeds consisting essentially of a compound according to the invention plus a surface-active agent or a liquid or solid carrier. The statement "from essentially" includes in the sense used here the presence of other active ingredients for pest control or conventional ones Formulation ingredients.

Synthesis of 4,4'-azodipyridine and acid salts

The method of making 4,4 - Az ο dip yri din and the Compounds themselves are described in "J. Chem. Soc." 5316 (1965).

The starting material, 4-aminopyridine, is commercially available.

The azodipyridine is made by reacting 4-aminopyridine with aqueous sodium hypochlorite.

The azodipyridinium salts are prepared by using 4,4 · - Azodipyridine in an appropriate solvent at ambient temperature with an equivalent amount of organic or inorganic acid with an acidic dissociation constant of over 1 χ 10 "".

The illustration method is illustrated by the following examples.

Example 1 4,4 * -azodipyridine

KaOCl

A cold solution (5 ° C) of 50 g (0.5 mol) of 4-aminopyridine in 400 ml of water was added dropwise with 1000 ml (5.25 % \

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0.72 mol) sodium hypochlorite added. The sodium hypochlorite additive took place at such a rate that the reaction temperature was kept below 10 ° C. After complete In addition, the reactants were stirred for an additional 11/2 hours at approximately 10 ° C. When filtering and air drying the resulting suspension left a crude, brown solid. Recrystallization from methylcyclohexane yielded light orange crystals of 4,4'-azodipyridine, m.p. 87 to 89 ° C.

Example 2 4,4'-azodipyridinium 1,2-benzenedicarboxylate

1.66 g (0.01 mol) of 1,2-benzenedicarboxylic acid were added at one time added to a solution of 1.8 g (0.01 mol) of 4,4'-azodipyridine in 25 ml of acetone. The reaction mixture was at Room temperature stirred for 1 hour. When the resulting suspension was filtered, an orange solid remained, its recrystallization from ethanol 2.1 g of 4,4'-azodipyridinium-1,2-benzene dicarboxylate, Mp 171-173 ° C.

By using the acid mentioned in the table instead of the phthalic acid of Example 2, the following were obtained as in Example 2 4,4'-Azodipyridinium salts prepared:

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BA- ^c ; i64-3

Sä :: re-Au:; duct reactant

Adipic acid butyric acid oxalic acid hydrochloric acid 1,3-benzene dicarboxylic acid nitric acid sulfuric acid stearic acid Benzoic Acid Salicylic Acid Lactic Acid Citric Acid Cinnamic Acid Phenylacetic Acid 1,4 ~ Benzene Dicarboxylic Acid Acetic acid fumaric acid

Application ;

Melting point of the 4,4'-azodipyridinium salt, ⁰ ° C

197-200

67-67 208-209 ^ 500
24-7-250

195
209-212

81-8 $ 158-140 168-170

70-78 149-150 133-136

65-68> 275

94-97 191-192

The compounds according to the invention - · 4,4'-azodipridine and its acid salts - ability, as described above, to protect seeds from the adverse effects of various fungi, especially from Helminthosporium species. to the seeds which can be protected by using the compounds according to the invention include grain fruit such as Barley, wheat, rye, oats, sorghum, panicum, rice and maize, and cultivated grasses, the compounds according to the Invention can be used in relatively low dosages because of their activity.

Formulation and delivery of the compounds can be in the form of a slurry, a coating of the seed with solid material, an impregnation or a dust on the seed surface. The methods by which the connections

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ORIGINAL INSPECTED

• J.

are added to the seeds, can of course be varied » and the invention encompasses any technique which is intended to be used koa-aan.

The seed should generally weigh about 5 to 1000 g ^ •, V-.vZodipyridine or its salts treated per 100 kg of seeds with a range of about 10 to 500 g / 100 kg preferred and one from about 20 to 250 g / 100 kg especially is preferred.

Formulations

Useful formulations of the compounds according to the invention can be prepared in conventional ways. They include dusts, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these formulations can be applied directly. Sprayable formulations can be used without dilution or can be extended in appropriate media. Highly concentrated compositions are primarily used as intermediate materials for further formulation. In general, the formulations contain about 1 to 99% by weight of active ingredient and at least one material from group a) about 0, ais 20% surface-active agents and b) about 2 to 99 % solid or liquid diluents. Specifically, the formulations will contain these ingredients in the following approximate proportions:

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Active ingredient,
Weight% Dilution
middle,
Weight% Surface
active
Middle,
Weight% Wettable powders 20-90 0-74 1-10 Ül suspension en, Emul
sions, solutions
(including emul-
yawable concentrates) 5-50 40-95 0-15 Aqueous suspensions 10-50 40-84 Dusts 1-25 70-99 0-5 High concentrates 90-99 0-10 0-2

Naturgeaäss can depending on the intended purpose and the physical properties of the compound also present smaller or larger amounts of active ingredient. Sometimes are higher Surface active agent to active agent ratios desirable; they can be reached by presenting them in the formulation or by mixing in the tank.

The compounds according to the invention can also be used in the seed treatment tank Formulate or mix with other seed treatment agents or mix with these on the seed Unite overcoating. The substances to be mixed with the compounds according to the invention can be agents for controlling of pests, to modify growth, for nutritional purposes or to control plant diseases be. Substances for combating plant diseases include benomyl ^ methyl-N- / i-butylcarbamoyl) -2-benzimidazole7-carbamate , Carbendazim / methyl-2-benzimidazole carbamate7 \ Captai / LT- (trichloromethyl thio) -3a, 4,7,7a-tetrahydrophthalmid7, Captafol / [N- (1,1,2,2-tetrachloroethylthio) -3a, 4,7,7a-tetrahydrophthalimide7, Maneb j / Tlanganethylene-1,2-bis-dithiocarbamate7, Mancozeb, Vitavax / 5,6-dihydro-2-methyl-1,4-οχ at hiin-3-carboxanilide7 \ Ethirimol, Oxathiin, Chloroneb / ^, 4-DiChIOr-2,5-dimethoxybenzol7, Thiram / bis (dimethylthiocarbamoyl) -

(S -
disulfide /, Dexon / p-Dimethylaminobenzoldiazonatriumsulfonat7 \ PCNB ^ entachloronitrobenzene /, without this list being exhaustive.

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The compounds according to the invention can also be used with insects Formulated to protect seeds against damage by insects during storage or after ordering protection.

Typical solid diluents for use in formulating compounds according to the invention are described in Watkins et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, NJ, V.St.A. The more absorbent diluents are preferred for wettable powders and the more dense ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide", 2nd Ed., Interscience, New York, 1950. A solubility of less than 0.1% is preferred for suspension concentrates; Solution concentrates are preferably resistant to phase separation at 0 ° C. Surfactants and recommendations for use can be found in the "i'IcCutcheon ^1's Detergents and Emulsifiers Annual", MC Publ. Corp., Kidgewood, New Jersey, as well as in Sisely and Wood, "Encyclopedia of Surface Active Agents," Chemical Publ. Co ., Inc., New York, 1964 ·. All formulations can also contain additives to reduce foaming, caking, corrosion or microbiological growth, to reduce dusting, to improve adhesion to the seed, to give treated seeds a color, to improve the flow of the seed, etc.

The methods of making such compositions are familiar. Solutions are made by simply mixing the ingredients obtain. Fine solid compositions are obtained by mixing, and usually also, as on one Hammer or jet mill, grinds. To produce suspensions, wet milling is used (cf., for example, US Pat. No. 3,060,084). In In this context, reference is also made to J. E. Browning, "Agglomeration," Chemical Engineering, Dec. 4, 19671 Pp. 147ff., And "Perry's Chemical Engineer's Handbook", 4th Ed., McGraw-Hill, N.Y., 1963, pp. 8-59ff.

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For further information on formulation technology, reference is made to, for example

U.S. Patent 3,576,834, column 5, line 36 through column 7, line 70,

and Examples 1 to 4, 17, 106 and 123 to 140,

U.S. Patent 3,560,616, column 3, line 48 through column 7, line 26,

and Examples 3 to 9 and 11 to 18,

E. Somers, "Formulation," Chapter 6, in Torgeson, "Fungicides," Vol. I, Academic Press, New York, 1967.

The following examples serve to further illustrate the invention.

Example 3 Seed dust cover

4,4'-A * odipyridine 75 %

"Permanent Red 2B", Ca-SaIs,

on barium sulfate extended 5 %

Diatomaceous earth 20 %

The ingredients were mixed, roughly hammer-painted and passed through a jet mill to obtain active substance particles, all of which were less than 10 microns in diameter. The product was remixed before packaging.

Example 4 Seed suspension about »ug

4,4'-axodipyridine 65 %

Calcium lignosulfonate 4 % Trimethylnonyl polyethylene glycol

ether .4 %

Rhodanine B Λ%

"Permanent Hed 2B ^N , Ca. Salt, extended to barium sulfate 1 %

Kieselguhr 25 %

BA-816-4-B

The liquid surfactant was sprayed onto the kieselguhr, followed by the addition of the other ingredients and thoroughly mixed together on an efficient mixer. The mixture was then roughly hammer milled and passed through a jet mill to obtain active ingredient particles, all of which are less than or equal in diameter 10 microns. The product was remixed before packaging.

Example 5 Seed solution about zuK

^ ■, V-Azodipyridinium-1,2-benzenedicarboxylate 20%

Dimethylformamide 1 ^, 1%

fihodamine B 0.3%

The materials were combined and stirred until a solution was obtained. The solution was applied directly to the seeds.

Example 6 Seed solution sub ore Uf ^

4, V-azodipyridine 20 %

Dimethylformamide 79.7%

Ehodamine B 0.3 %

The materials were combined and stirred until a solution was obtained. The solution was applied directly to the seeds.

Example 7

This example explains a formulation in which connec-

fertilize according to the invention with another seed treatment agent be mixed.

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Seed solution coating

* t-

4, V-azodipyridine 35 %

Carbendazim 35 %

"Permanent Red 2B", Ca-SaIz,

on barium sulfate extended 10%

Diatomaceous earth 20 %

For the seed dust treatment, the ingredients were mixed and then processed as in Example 3.

The following examples illustrate the ability of the compounds according to the invention to attack by a fungus To rid the seeds of the fungus.

Example 8

Barley and rice seeds naturally grown by one Fungus - Helminthosporium sativum or H. oryzae - attacked Was in glass bottles of 237 car capacity entered. Each bottle contained 10 g rice and 15 g barley seeds. Samples were with the compound according to of the invention, 4-, V-azodipyridine, in various dosages treated. Me chemical was applied to the seeds in a solution in 9: 1 acetone / dimethylformamide, while this was being circulated. The treated seeds were placed in sterile soil and in the greenhouse on a Given bank. The treated seeds were 14 to 18 days grown and observed for diseased tissue. According to the formula

Number of healthy plants in the treatment "_ Number of seeds introduced per treatment

the healthy percentage was calculated.

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Treatment active ingredient, g / 100 kg Gesund-Proζent Seed set

4,4'-azodipyridine

barley rice 500 100 98 250 92 96 125 94 96 63 96 90 31 96 86 16 82 70 untreated 30th 26th solution treated 98 24

Example 9

Rice seed naturally infected by De Pile Helminthosport in the oryzae was placed in glass vials with a capacity of 20 ca *, each vial containing 3 g of rice seed. The samples were treated with compounds according to the invention in various dosages. The chemical was applied in a solution in 9: 1 acetone / dimethylformamide while the seeds were circulated. The treated seeds were placed on a pad made of absorbent paper, which was moistened and given a humidity chamber for 1% days. The incidental plants obtained were assessed visually on the percentage of control on the basis of a scale from 0 to 100, where 0 means disease control equal to 0 % and 100 means disease control rate of 100%.

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4,4 '~ 4sodipyridlit- active ingredient, g, Käapfunge-

Acid than per 100 kg of seed percentage (rice)

Adipat 250 80

125 SO

63 80

n-butyrate 250 80

125 80

63 80

Oxalate 250 50

125 50

63 30

Chloride 250 50

125 O

63 O

1,2-benzene dicarboxylate 250 90

125 90

63 90

1,3-benzene dicarboxylate 250 50

125 50

63 O

Hitrat 250 50

125 50

63 50

Bisulfate 250 50

125 50

63 0

Fumarate 250 70

125 80

63 100

Benzoate 250 70

125 70

63 60

Salicylate 250 60

125 50

63 50

Lactate 250 50

125 60

63 50

Citrate 250 50

125 50

63 40

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4-, 4'-azodipyridine active ingredient, g, anti-acid salt per 100 kg of seed percentage (rice)

Cinnamat 230-60

125 60

63 50

Phenyl acetate 250 70

125 50

63 30

1,4-benzene dicarboxylate 250 60

125 60

63 30

Acetate 250 60

125 60

63 30

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Claims (11)

Patent claims 1.Methods for controlling seed-infesting fungi, characterized in that the seeds are given a fungicidally effective amount of a compound from the group of 4,4'-azodipyridine and 4-, V-azodipyridinium acid salts of the formula • 2A P supplies, wherein A is an acid with an acidic dissociation constant greater than 1 χ 10 "and ρ is equal to the number of hydrogen atoms attached to the acid A, which is an acidic dissociation constant greater than 1 χ 10 ". 2. The method according to claim 1, characterized in that the compound used is 4,4'-azodipyridine. 3 · The method according to claim 1, characterized in that the compound is a ^ -, V-azodipyridiniunic acid salt used. 4. The method according to claim 3 »characterized in that the acid salt used is 4.4 ^l -azodipyridinium-1,2-benzenedicarboxylate. 5. The method according to claim 1, characterized in that one grain seeds 10 to 500 g of the compound per kg of seeds to combat Helminthosporium supplies. 6. Felt control agent consisting essentially of a compound selected from the group consisting of 4,4'-diazopyridine and 4,4'-diazopyridinium acid salts the formula ' - 15 - 709835/0801 ORIGINAL INSPECTED O) -N-N- where A is an acid with an acidic dissociation constant greater than 1 χ 1O ~ and ρ is equal to the number of hydrogen atoms attached to the acid A, which is an acidic dissociation constant larger than. Have 1 χ 10, and at least one substance from the group of surfactants and solid or liquid diluent. 7- means according to claim 6, characterized in that the Compound is 4,4'-diazopyridine. 8. Means according to claim 6, characterized in that the Compound is a 4,4 · '-diazopyridinium acid salt. 9- means according to claim 8, characterized in that the Compound 4,4 -'-diazopyridinium-1,2-benzenedicarboxylate is. 10- compound of formula 2A P wherein A is an acid with an acidic dissociation constant greater than 1 χ 10 "and ρ equals the number of hydrogen atoms attached to the acid A. which have an acidic dissociation constant greater than 1 χ 10 ". 709835/0801 BA-8164-B? 707 1 R8 11. A compound according to claim 10, characterized in that it is ^^ '- diazopyridinium-i ^ -benzenedicarboxylate. - 17- 709835/0801