SE440359B - NEW N, N'-METHYLENE BIS (0,0-DIARYL-N-PHOSPHONOMETHYLGYCINON NITRILS) FOR USE AS HERBICIDES, PROCEDURE FOR THEIR PRODUCTION AND USE THEREOF - Google Patents

Description

This mixture is heated to a temperature sufficiently elevated to initiate and maintain the reaction of the phosphoric acid ester with the triazine to form the desired products. Although a solvent is not necessary in the process of the invention, it is sometimes necessary to use a solvent in order for the reaction to be carried out conveniently and easily. A solvent is also useful for controlling the reaction temperature. The solvent used is one in which the triazine is soluble and which does not react with any of the reactants. Such inert solvents include acetonitrile, ethyl acetate, tetrahydrofuran and the like.

It has been found that the reaction temperature can be as low as about 25 ° C to about 110 ° C. Higher temperatures can be used, but this does not bring any corresponding benefits, as the reaction is substantially complete when the temperature reaches about SSOC.

As can be seen from the above formulas for the reactants, the ratio of phosphoric acid ester to triazine should be 3 to 1 for best results.

Higher or lower ratios could be used, but no attendant benefits are thereby obtained, since at higher ratios excess phosphoric acid ester would need to be separated, and at lower ester / triazine ratios by-product formation is possible.

The reaction is usually carried out at atmospheric pressure for economic reasons.

However, higher or lower pressures can be used, even if no corresponding benefits are obtained thereby.

The reaction is allowed to continue until all the phosphoric acid ester and triazine have been consumed according to nuclear magnetic resonance analysis. If such analysis shows the presence of impurities in the form of unreacted excess of starting material or solvent, the reaction mixture may be subjected to vacuum concentration. Thereafter, the desired product is isolated and purified by crystallization or chromatographic procedures. Care should be taken in these latter procedures to avoid hydrolysis of the ester moiety in the molecule.

Using the sequential preparation of the invention, the Op-diaryl-N-phosphonomethylglycinonitrile is first prepared according to the methods described in the above application. This product is then mixed with a hindered phenylazometine and heated under vacuum. An intermediate product consisting of azo adduct is assumed to form, after which the heating is continued until the evolution of the hindered aniline is completed. The reaction mixture is then worked up to isolate the desired methylene by-product.

Inhibited phenylazomethines useful in the practice of the process of the invention are those of formula 7713048-2 N = CH Y where X is lower alkyl and Y is lower alkyl, halogen or lower alkoxy, provided that X and Y may not both be t -butyl. Examples of hindered phenyl groups include 2-methyl-6-ethyl-, 2,6-diethyl-, 2-methyl-6-t-butyl-, 2-chloro-6-t-butyl-, 2-bromo-6-t butyl-, Z-methoxy-Gt-butyl-phenyl, and the like. It has generally been found that without the above hindering groups, the azometine reactant will be trimerized to a hexahydrotriazine.

The glycinonitrile reactants prepared according to the methods described in the above application often contain phenolic impurities which may interfere with the preparation of the desired methylene bis compounds of the invention. It is therefore preferred to first prepare a salt of the glycinonitrile with a strong acid which precipitates to allow easy separation of these impurities.

This salt is then neutralized to give the desired glycinonitrile reactant. Care must be taken during neutralization to avoid hydrolysis of the aryl ester groups. The reaction between the glycinonitrile and the azomethine begins at room temperature based on analysis by nuclear magnetic resonance. Temperatures up to about 125 ° C can be used, although a range of about 60-80 ° C is preferred. Although the reaction proceeds well at atmospheric pressure, the hindered aniline formed can react with the desired product. that you get an unwanted adduct. It is therefore preferred to remove the hindered aniline as it is formed, and this is done efficiently by using reduced pressure, whereby the aniline distills over during the reaction.

The molar ratio of glycinonitrile to azomethine is preferably about 2: 1. Higher or lower ratios can be used, but these reduce the product yields by providing mixtures with unreacted starting materials and said intermediate product consisting of azo adduct. A basic catalyst can be used if so. desired, even if the reaction proceeds to the desired product without it.

The following experiments serve to further illustrate the invention, 39 in which all parts are by weight unless otherwise expressly indicated.

EXAMPLE 1 An acetonitrile solution (10 ml) of di (3,1L-dimethylphenylphosphite (8.7 g, 0.03 mol) was added to an acetonitrile solution (50 ml) of 1,3,5-tricyanomethyl-hexahydro. (4 L, 3,5-triazine (2.0 μl, 0.0 μ mol), and the mixture was heated at 55 ° C for 90 hours. Filtration of the solid present and evaporation of the solvent gave a chromatography of the oil (8.0 g) over silica gel (450 g) with 50% cyclohexane / 5096 ethyl acetate (60 ml fractions) gave 0,0-di (3,1 + -dimethylphenyl) -N-phosphonomethylgycinonitrile in fractions 30 to 41. Fractions 20 to 25 from the chromatography column gave, after evaporation of the solvent, 1.62 g of an oil, naz = 1, 5387. Crystallization of this oil from carbon tetrachloride isooctane gave a white solid which was identified as N, N'-methylenebis- [0,0- di (3,1-dimethylphenylD-N-phosphonomethylglycinonitrile], m.p. 79-80 ° C.

EXAMPLE 2 An acetonitrile solution (100 ml) of di (m-tolyl) phosphite (10.7 g, 0.04 mol) and 1,3,5-tricyanomethyl-hexahydro-1,3,5-triazine (2.72 g (0.0133 mol) was heated to 50 ° C for 3 days. The solution turned burgundy, and the solvent was evaporated to leave 12.4 g of a red oil (02.096 yield). The oil (9.0 g) was chromatographed on silica gel with 6096 cyclohexane / 4096 ethyl acetate taking 60 ml fractions. Fractions 45-63 were pure 0,0-di (m-tolyD-N-phosphonomethylglycinonitrile. Fractions 28-140 from the chromatograph were evaporated in vacuo to give a solid, m.p. 13-114 ° C and identified as N, N '-methylenebis- [0,0-di (m-tolyD-N-phosphonomethylglycinonitrile] which gave the following analysis.

Calculated: C 62.50, H 5.69, N 8.32 Found: C 62.58, 11 5.72, N 8.23 EXAMPLE 3 Di (p-methylthiophenyl) phosphate (30.1 + g, 0.082 mol) and 1,3,5-tricyanomethylhexahydro-1,3,5-triazine (5.6 g, 0.0275 mol) was heated to 80 ° C for one hour.

The resulting dark reddish brown oil was allowed to cool to room temperature and dissolved in carbon tetrachloride (200 ml). This solution was added to silica gel (30 g), stirred and filtered, and then added again to silica gel (20 g) with stirring and filtration. Half of the resulting solution was attached to silica gel (1.2 g) and chromatographed on silica gel (450 g) eluting with 60% cyclohexane / l 2 O 9 ethyl acetate (60 ml reactions). Fractions 28-39 were combined to give 1.2 g of N, N'-methylenebis-f0,0-di (p-methylthiophenyl) -N-phosphonomethylglycinonitrile, naz = 1,165l. EXAMPLE 4 Diphenylphosphite (230 g, 1, 0 mol) was added to an acetonitrile solution (300 ml) of 1,3,5-tricyanomethyl-hexahydro-1,3,5-triazine (68 g, 0.333 mol) and heated at 75-82 ° C for 3 hours. and concentrated in vacuo to give a black oil which was essentially glycinonitrile A sample of this oil (101 g) was attached to silica gel (which was dissolved in chloroform, more silica gel was added and the solvent was evaporated), and this material was chromatographed on silica gel (1.1 kg) eluting with chloroform (1 liter fractions). Fractions 13-114 were combined, concentrated and recrystallized from dichloromethane-cyclohexane to give 51 g of O-diphenyl-N-phosphonomethylglycinonitrile.

Fractions 11-12 were combined, concentrated to an oil, and the solid removed by filtration. The mother liquor from fractions 11-12 was chromatographed on silica gel (760 g), which was eluted with 60% cyclohexane / 4096 ethyl acetate (100 ml fractions). Fractions 140-09 were combined and recrystallized from cold carbon tetrachloride to give N, N'-methylenebis- (0,0-diphenyl-N-isophonomethylglycinonitrile], m.p. 98 DEG-99 DEG C. The product gave the following analysis.

C 60.39, H 4.90, N 9.09 C 60.59, H 4.79, N 8.97 EXAMPLE 5 i A mixture of 0,0-diphenyl-N-phosphonomethylglycinonitrile 08.05 g, 0.258 mol ) and Zβ-diethylphenylazomethine (2.1.0 g, 0.129 mol) were placed in a ball tube distillation apparatus with a catalytic amount (about 10 mg) of sodium methoxide.

The mixture was heated at 65-75 ° C under vacuum (0.02-0.07 mm) for about 1 hour. Distillation of 2,6-diethylaniline began almost immediately, and it continued Calculated: Found: for almost 1 hour. The vacuum was removed, and carbon tetrachloride (500 ml) was added until the oil crystallized. The hot solution was filtered and allowed to cool to room temperature. The solid was collected and washed with cold carbon tetrachloride, and the mother liquor was concentrated to give additional solid, which was combined to a total of 72.5 g. The product was identified as N, N * -methylenebis- [0,0-diphenyl-N-phosphonomethylglycinonitrile ], melting point 100-1000, 5 ° C.

EXAMPLE 6 A mixture of 0,0-di (p-methoxyphenyl-N-phosphonomethylglycinonitrile (7.4 g, 0.02 mol) and Zβ-diethylphenylazomethine (1.63 g, 0.01 mol) was prepared, and a small exotherm After about 1/2 hour, the mixture was placed in a tubular distillation apparatus and heated to 60-70 ° C under vacuum (0.1 mm) for about 1/2 hour, while the 2,6-diethylaniline distilled over. The product was cooled, stirred and dissolved in hot carbon tetrachloride, the solution was filtered, then ether was added to the remaining oil and decanted twice, chloroform was added to the oil, and concentration was then given a product identified as N, N'-methylenebis- (0 , 0-di (p-methoxyphenyl D-N-phosphonomethylglycinonitrile] as reddish brown prisms, m.p. 90-92 ° C. This product gave the following analysis. '77130 # S-2 10 -15 20 25 30 35 C 57.07, H 5.20, N 7.61 C 57.06, H 5.22, N 7.63 EXAMPLE 7 A mixture of 0,0-di (le-chloro-B-methylphenyl) -N-phosphonomethylglycinonitrile (2.8 g, 0.007 mol) and Zβ-diethylphenylaz ometin (0.57 g, 0.0035 mol) was prepared, and a slight exotherm occurred. The mixture was placed in a ball tube distillation calculator and heated at 75-80 ° C under vacuum (0.1 mm) for about 1 / Z hour, while the 10-diethylaniline was distilled over. The residual oil was cooled and then crystallized from carbon tetrachloride / methylcyclohexane ether to give a white solid. The product was identified as N, N '-methylenebis- [0,0-di (1 + -chloro-3-methylphenyl-N-phosphonomethylglycinonitrile], m.p. 89.5-90.5 ° C. This product gave the following analysis. Calculated: C 51.87, H 4.23, N 6.91 Found: C 51.55, H 4.25, N 7.01 EXAMPLE 8 The herbicidal activity after emergence of various compounds of the invention is demonstrated as follows. The ingredients are applied in spray form to 14-21 day old specimens of various plant species. The spray, an aqueous solution or an organic solvent-water solution 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 moles of ethylene oxide to 1 mole of tall oil), is applied to the plants in different pot rates in different doses (kg per hectare) of active ingredient, the treated plants are placed in a greenhouse, and the effects are observed and recorded after about 2 weeks or about 4 weeks. are listed in Tables I and II.

The herbicidal activity index after emergence used in Tables I and II is as follows: Plant response O-2L196 damage 25-4996 damage 50-7496 damage 75-9996 damage All killed species that were not present at the time of treatment x Index -FWIQI -O In these tables, "WAT" indicates weeks after treatment, and treated plant species are represented by a code letter as follows: 7 A - Thistle (Cirsium arvense) B - Thistle thistle (Xanthium) C - Indian mallow (Císsampelos pareira) D - Flower of the day (Ipomoea) E - Chenopodium album - F - Bitter willow (Polygonum) G - "Nutsedge" (Cyperus) H - Agropyron repens I - Sorghum halepense J - Lobster (Bromus) tectorum) K - Hönshirs (Echinochloa crusgalli) L - Sojaböna M - Sockerbeta N - Vete O - Ris P - Sorghum Q - Vilt bovete (Eriogonum) R - Sesbaníahampa S - Panicum Spp T - Blodhirs (Digitaria) 7713048-2 TABELL k / ha WAT Förenín '77130118-2: dl Nm NN bl Fm: fna HI »am -n- | : nl f-IN or-c w! HN about number f-aoz f-: N to Nu- Ne- QI HN Ha OI fnx fxx 'GW åh Mß r-lr-l LOLÛ u-ln-l NW NW f-í TABLE II Plant species WAT Förenin Bl MI ml bl ul ml ml Gäl cal Oll ml ml OI Zl El l-'ll I-IN 0.28 0.28 N01 7713048-2 10 15 20 25 30 35 77130li8-2 10 From the test results reported in Tables I and II you can see that the herbicidal activity after emergence of the compounds of the invention is for the most part general in nature. In some special cases, however, some selectivity is shown. In this regard, it should be noted that each individual species selected for the above tests is a representative member of a recognized family of plant species.

Herbicidal compositions, including concentrates, which require dilution prior to application to the plants contain from 5 to 95 parts by weight of at least one active ingredient of the invention and from 5 to 95 parts by weight of an adjuvant in liquid or solid form, e.g. from about 0.25 to 25 parts by weight of wetting agent, from about 0.25 to 25 parts by weight of a dispersant and from 4.5 to about 94.5 parts by weight of an inert excipient, e.g. water, all parts being by weight of the total composition. Where required, from about 0.1 to 2.0 parts by weight of the inert liquid excipient may be replaced by a corrosion inhibitor or antifoam, or both. The compositions are prepared by mixing the active ingredient with an adjuvant comprising diluents, excipients, carriers and conditioners to obtain compositions in the form of finely divided particulate solids, pellets, solutions, dispersions or emulsions. Thus, the active ingredient can be used with an adjuvant, such as e.g. a finely divided solid, a liquid of organic origin, water, a wetting agent, a dispersing agent, an emulsifying agent or any suitable combination thereof. When it comes to economy and convenience, water is the preferred diluent.

The herbicidal compositions, in particular liquids and soluble powders, suitably contain as conditioning agent one or more surfactants in sufficient amounts to render a given composition readily dispersible in water or in oil. Incorporating a surfactant into the compositions greatly increases their effectiveness. The term "surfactant" means that wetting agents, dispersants, suspending agents and emulsifying agents are included therein. Anionic, cationic and nonionic agents can be used with the same simplicity.

Preferred wetting agents are alkylbenzene and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isethionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonyls and phenylene phenols nonylphenol) and polyoxyethylene derivatives of mono-higher fatty acid esters of hexitol anhydrides (eg sorbitan). Preferred dispersants are methylcellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalene sulfonate, polymethylene bisnaphthalene sulfonate and sodium N-methyl-N- (long chain acid) - 10 15 20 8 30

Water-dispersible powder compositions may be prepared which contain one or more active ingredients, an inert solid excipient and one or more wetting and dispersing agents. The inert solid excipients are usually of mineral origin, such as natural clays, diatomaceous earth and synthetic minerals derived from silica and the like. Examples of such excipients include kaolinites, attapulgite clay and synthetic magnesium silicate. Water-dispersible powders usually contain from about 5 to about 95 parts by weight of active ingredient, from about 0.25 to 25 parts by weight of wetting agent, from about 0.25 to 25 parts by weight of dispersant and from 4.5 to about 94.5 parts by weight of inert solid excipient. all parts being by weight of the total composition. Where required, from about 0.1 to 2.0 parts by weight of the solid inert excipient may be replaced by a corrosion inhibitor or an antifoam or both.

Aqueous suspensions can 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 the dilution and spray coverage is very homogeneous and usually contains from 5 to about 95 parts by weight of active ingredient, from about 0.25 to 25 parts by weight of dispersant and from about 4.5 to 90.5 parts by weight of water.

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

Emulsifiable oil compositions generally contain from about 5 to 95 parts of active ingredient, about 1 to 50 parts of surfactant and about 1 to 94 parts of solvent, all parts being by weight based on the total weight of emulsifiable oil. Although compositions containing the compounds of the invention may also contain other additives, e.g. fertilizers, phytotoxic substances and plant growth regulators, pesticides and the like used as adjuvants or in combination with some of the above adjuvants, it is preferable to use the compositions separately with treatments in succession with the other phytotoxic substances, fertilizers etc. for maximum effect. Thus, Lex. the field is sprayed with a composition containing a compound of the invention either before or after treatment with fertilizers, other phytotoxic substances and the like. The compositions can also be mixed with the other materials, e.g. fertilizers, other phytotoxic substances, etc., and applied in a single application. Chemicals useful in combination with the active ingredient of the invention either simultaneously or sequentially include, e.g. triazines, ureas, acetamides, acetanilides, uracils, acetic acids, phenols, thiol carbamates, triazoles, benzoic acids, nitriles and the like.

Fertilizers useful in combination with the active ingredients include e.g. ammonium nitrate, urea, potassium carbonate and superphosphate.

In work according to the invention, effective amounts of the glyconitriles are applied to the plants, or to their parts, in any suitable manner.

Application of liquid or particulate solid compositions to plants or soil can be done by conventional methods, e.g. with powder sprayers, boom or hand sprayers and sprayers. The compositions can also be applied from aircraft as a powder or spray due to their effectiveness in low doses.

The application of an effective amount of the compounds of the invention to the plant is important and critical to the practice of the invention. The exact amount of ingredient used depends on the desired response of the plant as well as on other factors such as the plant species and its stage of development, as well as on the amount of precipitation as well as on the particular compound used. In foliar treatment for regulating vegetative growth, the active ingredients are applied in amounts from about 0.25 to about 25.0 or more per kilogram per hectare. An effective amount for phytotoxic or herbicidal control is the amount necessary for total or selective control, ie. a phytotoxic or herbicidal amount. It is believed that those skilled in the art can easily determine the approximate application dose based on what is taught in this specification including the examples. Although the invention has been described with respect to specific modifications, the details thereof are not to be construed as limitations beyond what is set forth in the appended claims.

Claims (7)

7713048-'2 13 PATENT CLAIMS A compound for use as a herbicide, characterized in that it has the formula III (Rmz-P-cz-C112 where R represents phenyl and may contain up to two substituents selected from halogen, lower alkyl, lower alkoxy and lower alkylthio. A compound according to claim 1, wherein R is phenyl, tolyl, methoxyphenyl, xylyl, chlorophenyl, methylthiophenyl or chlorotolyl. A process for the preparation of a compound of formula O II 2 wherein R represents phenyl and may contain up to two substituents selected from halogen, lower alkyl, lower alkoxy and lower alkylthio, characterized in that a mixture of a hindered phenylazomethine of the formula wherein X is lower alkyl and Y is lower alkyl, halogen or lower alkoxy, provided that X and Y may not both be t-butyl, and a compound of formula O (Roi [iš-CH -NH-cn -cN 2 2 10 l5 '77130118-2 14 where R has the same meaning as above, and heats under vacuum until the evolution of the corresponding hindered aniline ceases. 4. A process according to claim 3, characterized in that a catalytic amount of a base is added to the mixture. Process according to Claim 3 or 4, characterized in that the ethyl acetate is present. Use of a compound of formula 2 (H0 QP-cnz-rg: m2 NC-CI-lz 2 where R represents phenyl and may contain up to two substituents selected from halogen, lower alkyl, lower alkoxy and lower alkylthio, as herbicide _ Use according to claim 6, characterized in that in said compound R is phenyl, tolyl, methoxyphenyl, xylyl, chlorophenyl, methylthioienyl or chlorotolyl.