DK144334B - N-PHOSPHONOMETHYLGYCLINE DERIVATIVES FOR USE IN HERBICIDES AND PROCEDURES FOR PREPARING THEREOF - Google Patents

Description

144334

This invention relates to novel N-phosphonomethylglycine derivatives for use in herbicides and to a process for their preparation.

Danish Patent Application No. 5116/77 discloses certain mono- and diaryl esters of N-phosphonomethylglycinonitrile and addition salts thereof with strong acids. The present invention relates to certain novel N, N'-methylene bis derivatives of such compounds and it has been found that they have particular utility as herbicidal agents to be used after germination.

The N-phosphonomethylglycine derivatives of the invention are characterized by the features of claim 1.

The preferred alkyl groups do not contain more than two carbon atoms and the preferred halogen is chlorine.

It has been found that the N-phosphonomethylglycine derivatives of the invention can be prepared by a special process which uses as a starting material the 0.0-di-aryl-N-phosphonomethylglycinonitrile described in the aforementioned Application No. 5116 / 77th

According to the process according to the invention, which is characterized by the characterizing part of claim 2, an O, O-diaryl-N-phosphonomethylglycinonitrile is used as starting material, e.g. may be prepared as set forth in the aforementioned Application No. 5116/77, and this product is then mixed with a hindered phenylazomethine and heated under vacuum. It is believed that an intermediate azo adduct is formed, after which heating is continued until the development of the hindered aniline is completed. The reaction mixture is then worked up to isolate the desired methylene bis product.

2 144334

The hindered phenyl-azo-methines useful in the practice of the process of the invention are those in which the phenyl ring contains substituents at both ortho positions. These substituents can both be alkyl except in the case of 2,6-di-t-butyl. In addition, one may use a halogen or a lower alkoxy substituent in one ortho position, the other being the indicated alkyl. Other positions of the ring may also be substituted. Examples of the hindered phenyl groups include 2-methyl-6-ethyl, 2,6-diethyl and 2-methyl-6-t-butyl. It has usually been found that the azomethine reactant will be trimerized to a hexahydro-triazine without the obstacle defined above.

The glycinonitrile reactants prepared as set forth in Application No. 5116/77 will often contain phenolic impurities which may interfere with the production of the desired methylene bis compounds of the invention.

It is therefore preferred to first prepare a salt of a strong acid of the glycinonitrile, which precipitates, to allow easy separation of the impurities. This salt is then neutralized to obtain the desired glycinonitrile reactant. Care should be taken to avoid hydrolysis of the aryl ester groups during neutralization.

The reaction between the glycinonitrile and azomethine begins at room temperature according to analysis with nuclear magnetic resonance. Temperatures up to approx. 125 ° C, although a range of approx.

60-80qC. Since the reaction proceeds well under atmospheric pressure, the hindered aniline formed can then react with the desired product to form an undesirable adduct. It is therefore preferred to remove the hindered aniline when it is produced, and this is done in a very efficient manner by using reduced pressure, whereby the aniline is distilled over during the reaction.

The molar ratio of glycinonitrile to azomethine is preferably ca. 2: 1. Higher or lower ratios can be used, but these can reduce product yields by producing mixtures with unreacted starting materials and the indicated intermediate azo product. If desired, a basic catalyst may be used, although the reaction proceeds to the desired product in the absence thereof.

Using the process of the invention, the desired N-phosphonomethylglycine derivative is obtained in good purity and in good yield.

A particularly preferred embodiment of the method according to the invention is characterized by the characterizing part of claim 3. This results in a high reaction rate.

A particularly preferred embodiment of the method according to the invention is characterized by the characterizing part of claim 4. This achieves that the yield of the reaction product becomes particularly high.

The following examples serve to further illustrate the invention, wherein all parts are by weight unless otherwise expressly stated.

Using the process of the invention, N, N'-methylene-bis- / 0,0-di (3,4-dimethylphenyl) -N-phosphonomethylglycinonitrile 7, m.p. 79-80 ° C, a white solid (compound 1), N, N'-methylene-bis- / S, O-di (m-tolyl) -N-phosphonomethylglycinonitrile 7, m.p.

113-114 ° C (compound 2), N, N'-methylene-bis- / 0,0-di- (p-methylthiophenyl) -N-phosphonomethylglycinonitrile 7, nj 2 = 1.6151 (compound 3) and N, N'- methylene bis- / Q, 0-4 diphenyl-N-phosphonomethylglycinonitrile7, m.p. 98-99 ° C (compound 4).

EXAMPLE 1

A mixture of 0.0-diphenyl-N-phosphonomethylglycino nitrile (78.5 g, 0.258 mole) and 2,6-diethylphenylazomethine (21.6 g, 0.129 mole) was introduced into a "kugelrohr" distillation apparatus with a catalytic converter. amount (about 10 mg) of sodium methoxide. The mixture was heated to 65-75 ° C under vacuum (0.02-0.07 mm) for approx. 1 hour. Distillation of 2,6-diethylaniline began almost immediately and continued for almost 1 hour. The vacuum was released and carbon tetrachloride (500 ml) was added until the oil crystallized. The hot solution was filtered and allowed to cool to room temperature. Dry and washed solids with cold carbon tetrachloride were collected and the mother liquors were concentrated to form additional solids which were combined to a total amount of 72.5 g. The product was identified as NIjN'-methylene bis-ZD₂O. -diphenyl-N-phosphonomethyl-glycinonitrile /, m.p. 100-100.5 ° C (compound 5).

EXAMPLE 2

A mixture of 0.0-di (p-methoxyphenyl) -N-phosphonomethylglycinonitrile (7.4 g, 0.02 mole) and 2,6-diethylphenylazomethine (1.65 g, 0.01 mole) was prepared, and a reaction with a small exothermic reaction tint appeared.

After about 1/2 hour, the mixture was introduced into a "Kugel-Rohr" distillation apparatus and heated to 60-70 ° C under vacuum (0.1 mm) for approx. 1/2 hour while 2,6-diethylaniline distilled over. The residual product was cooled, stirred and dissolved in hot carbon tetrachloride. The solution was filtered, then ether was added to the residual oil and decanted twice. Chloroform was added to the oil and upon concentration a product was identified as N, N'-methylene-bis- [O, O-di (p-methoxyphenyl) -N-phosphonomethylglycinonitri17 as reddish brown prisms, m.p. . 90-92 ° C (compound 6). This product showed the following analysis:

Calculated: C, 57.07; H, 5.20; N, 7.61. Found: C, 57.06; H, 5.22; N, 7.63.

EXAMPLE 3

A mixture of O, O-di (4-chloro-3-methyl-phenyl) -N-phosphonomethylglycinonitrile (2.8 g, 0.007 mol) and 2,6-diethylphenylazomethine (0.57 g, 0.0035 mol) was prepared. ), and a slight exothermic reaction occurred. The mixture was introduced into a "Kugelrohr" distillation apparatus and heated to 75-80 ° C under vacuum (0.1 mm) for approx. 1/2 hour while 2,6-diethylaniline distilled over. The residual oil was cooled and then crystallized from carbon tetrachloride / methylcyclohexyl ether to give a white solid. The product is identified as N, N'-methylene-bis- / 0,0-di (4-chloro-3-methylphenyl) -N-phosphonomethylglycinonitrile /, m.p. 89.5-90.5 ° C (compound 7). This product showed the following analysis:

Calculated: C, 51.87; H, 4.23; N, 6.91. Found: C, 51.77; H, 4.25; N, 7.01.

EXAMPLE 4

The herbicidal activity after germination of the various compounds of the invention is demonstrated as follows. The active ingredients are applied in the form of a spray of 14-21 days old samples of various plant species. The spray liquid which is a solution in water or organic solvent and water containing active ingredient and a surfactant (35 parts butylamine salt of dodecylbenzenesulfonic acid and 65 parts tall oil condensed with ethylene oxide in the ratio of 11 moles of ethylene oxide to 1 molar oil) is applied. on the plants in different sets of bowls with different application intensities (kg / ha) of active ingredient. The treated plants are introduced into a greenhouse and the effects are observed and recorded after approx. 2 weeks or after approx. 4 weeks. The relevant data are given in Tables I and II.

The herbicidal activity index after germination used in Tables I and II is as follows: 7 144334

Plant Response Index - 0-24% Damage 0 25-49% Damage 50-74% Damage 2 75-99% Damage 3

Everything killed 4

Species not present at time of treatment $ In these tables, WAT means weeks after treatment, and the treated plant species are represented separately by a code letter as follows: A - Agertidsel F - "Smartweed" K - Hanespore P - Sorghum B - Bread Seed G - " Nutsedge "1 - Soybean Q - Wild buckwheat C - Velvet leaf H - Mercury M - Sugar beet E - Sesbania hemp D - Ipomoea I - Durra N - Wheat S - Panicum spp.

E - White flour J - Tag heron 0 - Rice T - Fingerak's goose foot

TABLE I

plant species

Past n- WAT kg

part Ea ABCDEFGHIJK

1 2 11.2 11112111112 4 11.2 12124222223 2 5.6 11112100112 4 5 ^ 6 12114221112 2 2 11.2 11011100100 4 11.2 11014211101 2 5.6 01001000000 4 5.6 01001100001 3 2 11.2 22114321113 4 11 , 2 2311442211 3 2 5.6 12114311112 4 5.6 12114322213 4 2 11.2 2314443343 3 4 11.2 34144444434 2 5.6 12113422402 4 5.6 33034433413 6 2 11.2 11113100002 2 5.6 -1111 * 10 0 001 7 2 11.2 21114100101 2 5.6 1111311120 3 8 144334

B HfO HCM Η rO <h HCM O -t-d- HPJ H

! j4 HH HH O CMCM OH O CM ΙΟ H CM H

CO Η Η. Η Η H -d "-d * HH H CM to HC \ I O

H CMCM HH O CM-d „HH O H C \ J OH O

O OH HH O HtO OO O CM ro HH O

fo H CM HH H -d "-d" -d "-d" H tO-d- CM CM O

t m H CM H CM H <| - <f CM fO H <(<(· CM fO H

CO

CD

-μ

S Bi H tO OH O HH OH O HCM HH O

H CO

Η H

J 'Q HHHHHCMCMHCMOCMCMHHH

H

9

Eh O HH HH O -d - d- OO O HH HO O

PQ HCM HH Η ΓΟΓΟ CM CM H tOtO HH H

(¾ CM IO H H H ro-d- CM ΙΟ H TO <f H CM H

O Η Η Η H O CO-d- OH O CM CM H O O

S CM CM HH O CM CM OO O CMCM HH O

S HH HH H • the-d «HH O HH OO O

H HCM HH H CMCM HH O CMCM HH H

CMCM 00 CMCM 00 CMCM 00

COCO HH CM CDVO HH CM ΌΌ HH CM

b (1 k «s ·» *> »k« v * v · «» v »ti \« k, ylc | IfklTV HH O LO to HH O min HH o <$ CM-d- CM-d- cm cM -d "cM-d- cm CM-d · cM-d- cm &

PI

• H 0) fii M

Ur4 H tO

fo Ό 9 144334

From the experimental results shown in Tables I and II, does it appear? that the herbicidal activity after germination of the compounds of the invention is mostly of a general nature. In this regard, it should be borne in mind that each individual species selected for the above trials is representative of a recognized family or plant species.

The herbicidal compositions containing the compounds of the invention, including concentrates requiring dilution prior to application to the plants, contain between 5 and 95 parts by weight of at least one active ingredient and between 5 and 95 parts by weight of an adjuvant in liquid or solid form, e.g. from approx. 0.25 to 25 parts by weight of wetting agent, from ca. 0.25 to 25 parts by weight of a dispersant, and from 4.5 to approx. 94.5 parts by weight of inert liquid extender, e.g. water, whereby all parts are by weight of the total mixture. When required, from approx. 0.1 to 2.0 parts by weight of the inert liquid extender is replaced by a corrosion inhibitor or anti-foaming agent or both. The mixtures are prepared by admixing the active ingredient to an adjuvant comprising diluents, extenders, carriers and conditioning agents to provide mixtures in the form of finely divided, particulate solids, tablets, solutions, dispersions or emulsions. Thus, the active ingredient can be used with an adjuvant such as a finely divided solid, an organic liquid, water, a wetting agent, a dispersant, an emulsifier or any suitable combination thereof. From an economic and expedient point of view, water is the preferred diluent.

The herbicidal compositions containing the compounds of the invention, especially liquids and soluble powders, preferably contain as a conditioning agent one or more surfactants in amounts sufficient to make a given mixture readily dispersible in water or in oil. The incorporation of a. surfactant in the mixture greatly increases their efficiency. The term "surfactant" includes wetting agents, dispersing agents, suspending agents, and emulsifying agents. Anionic, cationic and nonionic agents can be used with equal ease.

Preferred wetting agents are alkylbenzene and alkyl naphthalene sulphonates, sulphated fatty alcohols, amines or acid amides, long chain acidic esters of sodium isethionate, esters of sodium sulphosuccinate, sulphated or sulphonated fatty acid esters, petroleum sulphonated, sulphonated, sulphonated, sulphonated and alkyl phenols (especially isooctylphenol and nonylphenol) and polyoxyethylene derivatives of the mono-higher fatty acid esters of hexitol anhydrides (e.g. sorbitan). Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalene sulfonates, polymethylene bis-naphthalene sulfonates, and sodium N-methyl-N- (long chain acid) taurates.

Water dispersible powder mixtures containing one or more active ingredients, an extender, inert, solids and one or more wetting and dispersing agents can be prepared.

The inert solid solvents are usually of mineral origin, such as the natural clays, diatomaceous earth and synthetic minerals derived from silica and the like. Examples of such extenders include kaolinites, attapulgitles and synthetic magnesium silicate. The water-dispersible powders usually contain from ca. 5 to approx.

95 parts by weight of active ingredient, from approx. 0.25 to 25 parts by weight of wetting agent, from approx. 0.25 to 25 parts by weight of dispersant and from 4.5 to approx. 94.5 parts by weight of inert solid extender, all parts being by weight of the total mixture. If necessary, from approx. 0.1 to 2.0 parts by weight of the solid, inert extender is replaced by a corrosion inhibitor or anti-foaming agent or both.

Aqueous suspensions may be prepared by mixing and grinding an aqueous slurry of water-insoluble active ingredient in the presence of dispersants to obtain a concentrated slurry of very finely divided particles. The resulting concentrated aqueous suspension is characterized by its extremely small particle size, so that, after dilution and spraying, the coverage is very uniform and usually contains between about 5 and about 5 minutes. 95 parts by weight of active ingredient, from approx. 0.25 to 25 parts by weight of dispersant, and from ca. 4.5 to 94.5 parts by weight of water.

Emulsifiable oils are usually solutions of active ingredient in water immiscible or partially water immiscible solvents together with a surfactant. Suitable solvents for the active ingredient of the invention include hydrocarbons and water-immiscible ethers, esters or ketones.

The emulsifiable oil mixtures generally contain from about 5 to 95 parts of active ingredient, approx. 1 to 50 parts of surfactant and approx. 4 to 94 parts of solvent, all parts being by weight based on the total weight of emulsifiable oil.

Although mixtures containing the compounds of the invention may also contain other additives, e.g. fertilizers, phytotoxic agents and plant growth regulators, pesticides and the like used as adjuvants or in combination with any of the above adjuvants, it is preferred to use mixtures containing the compounds of the invention alone with sequence treatments together with the other phytotoxic agents, fertilizers and the like. in order to achieve the maximum effect. For example, the field may be sprayed with a mixture containing the compounds of the invention either before or after it has been treated with fertilizers, other phytotoxic agents and the like. The mixture containing the compounds of the invention may also be mixed with the other materials, e.g. fertilizers or other phytotoxic agents and applied in the form of a single application. As examples of chemicals useful in combination with the active ingredients of the invention, either simultaneously or in the form of a sequential treatment, are to be mentioned triazines, ureas, carbamates, octamides, acetanilides, uracils, acetic acids, phenols, thiol carbamates, triazoles, benzoic acids and nitriles.

Examples of fertilizers which are useful in combination with the active ingredients must be mentioned ammonium nitrate, urea, potash and superphosphate.

When working with the compounds of the present invention, effective amounts of the glycinonitriles are applied to the plants or parts thereof in any convenient manner. The application of liquid and particulate solid mixture to plants or soils can be carried out using conventional methods, for example, powders powered by an energy source, boom and manual sprayers, and sprayers. The mixtures can also be applied from airplanes such as a powder or spray mist due to their effectiveness at low doses.

The application of an effective amount of the compounds of the invention to the plant is essential and critical to the practice of the invention. The exact amount of active ingredient to be used depends on the desired plant response as well as on such other factors as the plant species and the stage of plant development. In foliar treatment to control vegetative growth, the active ingredients are applied in amounts between ca. 0.25 and approx.

25.0 kg / ha or more. An effective amount for phytotoxic or herbicide control is the amount needed for total or selective control, namely a phytotoxic or herbicide amount. It is believed that one skilled in the art can readily determine the approximate application intensity on the basis of the indications in this specification.