DE2751631A1 - O-ARYL-N-PHOSPHONOMETHYLGLYCINNITRILE, METHOD FOR THEIR PRODUCTION AND USE - Google Patents

Description

"O-Aryl-H-phosphoninethylglycinnitrile, method too their manufacture and use "

This invention relates to O-aryl-N-phosphonmethylglycine nitriles, which are suitable as herbicides, as well as processes for their preparation. The invention further relates to herbicidal preparations and herbicidal processes in which O-aryl-N-phosphonmethylglycine nitrile be used.

According to US Pat. No. 3,923,877 , N-phosphonomethylglycine can be prepared by using a dihydrochloride 09-2 .-! 065A 809824/0617

• (W9) 9882 72 »112 73 «8 82 74 913) 10

Mtuerkirchersir 45 8WX1 Munich 8 (1 Tele »mme

BLRÜSTAPI-PATI-NT Munich TtLEX 05 24 SWIBI R (i <1

COPY

Substance phosphite with 1.3.5-tricyanomethyl-hexahydro-i.3.5-triazine in the presence of a catalyst such as hydrogen halide, a Lewis acid, a carboxylic acid halide or a carboxylic acid eanhydr ids and then hydrolyzed the product obtained. The yields from this process are extremely low. In the patent it is stated that the reaction between the Phosphite and the triazine to form an ester intermediate of N-phosphonmethylglycine nitrile. The appropriate ones Esters according to the patent are those with aliphatic groups with 1 to 6 carbon atoms or phenyl-substituted aliphatic groups such as benzyl and preferably alkyl having 1 to 6 carbon atoms. These esters are under Formation of N-phosphonomethylglycine, a post-emergence herbicide, hydrolyzed. It was found that after this procedure produced O.O-diethyl-N-phosphonmethylglycine nitrile no post-emergence herbicidal activity at 4.48 kg / ha and none Has pre-emergence herbicidal effectiveness at 5 * 60 kg / ha.

It has now been found that O.O-diaryl-N-phosphonmethylglycine nitrile can be prepared by a diaryl phosphite with 1.3 · 5-tricyanomethyl-hexahydro-i.3.5-triazine converts without using a catalyst. It was also found that these glycinnitri-Ie prepared in this way, as well as the corresponding monoaryl ester, which by mild Hydrolysis of the diester compounds are produced, pre- and post-emergence herbicidal activity that is complete is unexpected with regard to the inactivity of diethyl-N-phosphonmethylglycine nitrile.

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The N-phosphonomethylglycine nitriles of this invention are compounds the general formula

¹¹ ■ H (Aryl X _a -o) ₂ _ _b - P - CH ₂ - N -GH ₂ - CN _χ (I),

(0H) _b

wherein aryl is phenyl, naphthyl and / or biphenylyl, any substituent X on the aryl group is halogen, alkyl with 1 to 4 carbon atoms, Alkoxy and alkylthio with 1 to 3 carbon atoms, alkoxycarbonyl with 2 to 3 carbon atoms, methylenedioxy, Cyano, trifluoromethyl and / or nitro, Z oxygen or sulfur, a an integer from 0 to 3, b an integer from 0 to 1, R a strong acid which leads to the formation of a Is capable of salt with the amino group, and χ = O or 1, with the proviso that χ = O when b = 1.

According to the condition given above, the salts of strong acids are only formed with a diester «If a strong acid % Vi one? fionoester (see general formula IY below) is added, the only aryl ester group from the molecule can be hydrolyzed.

The N-Phosphonmethylglycinnitrile of the general formula I, wherein χ and b = O are prepared by forms a mixture which is essentially an ester of the phosphorous Acid of the general formula

Z (Aryl X _a -0) ₂ PH (II),

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wherein X ₁ Z and a have the meaning defined above and i ^. ^ - Tricyanomethylhexahydro-IJ ^ -triazine (also denotes N-methylenglycine nitrile trimer) of the formula

CH ₀ CN

Kjttr ^ on _o

I ² (in)

NC-CH ₀ -N N-CH ₀ CN CH ₂

contains and this mixture to a sufficiently elevated temperature heated to initiate the reaction and maintained at that temperature long enough to allow the ester to react the phosphorous acid with the triazine to form N-phosphonmethylglycine nitrile I receive.

Although a solvent is not required in the process of the present invention, it is sometimes desirable to to use a solvent for convenience and to facilitate the reaction. A solvent is also useful for controlling the reaction temperature. A solvent is used in which the triazine is soluble and that 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 no corresponding

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Obtain advantages in because the reaction has essentially to the time at which the temperature reaches 85 ⁰ G.

As can be seen from the previous formulas II and III, for best results the ratio of the Esters of phosphorous acid to triazine 3: 1. Higher or lower ratios can be used, but do not bring corresponding advantages because higher ratios the excess ester of phosphorous acid must be separated off and, in the case of lower ratios of ester to triazine By-product formation is possible.

The reaction is generally for economic reasons carried out at atmospheric pressure. However, higher or lower pressures can be used, however no corresponding advantages can be achieved.

To prepare compounds of general formula I in which b = 1 and x = 0, i.e. compounds of general formula

H
(Aryl X _a -0) - P - CH ₂ - N - CH ₂ - CN (IV),

OH

wherein X, Z and a have the meanings defined above, one simply forms a solution of a compound of the general

formula

Il

(Aryl X _a -0) ₂ - P - CH ₂ - N - CH ₂ - CN (V),

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wherein X, Z iind a have the meaning defined above, in one Solvent that contains at least one mole equivalent of water and keeps this solution at room temperature, at which one the (aryl X -O) groups is hydrolyzed. Acetone is preferred as the solvent for the hydrolysis. -The material you want is isolated using standard methods such as fractional crystallization or vacuum evaporation of the Solvent and other volatile hydrolysis products, with the desired material from a suitable solvent can be crystallized.

For the preparation of the compounds of the general formula I in which b s is 0 and χ β is 1, i.e. compounds of the general formula

H
(Aryl X _a -0) ₂ -P-CH ₂ -N-CH ₂ -CN-R (VI),

in which X, Z and a have the meanings defined above, a compound of the general formula V is dissolved in an anhydrous one Solvent, such as chloroform, and add a strong acid to this solution, either in a solvent or in some cases the acid is added as such, stirring at room temperature long enough to give the compound the general To bring formula V and the acid to react and to prepare the compound of general formula VI. In some The desired product precipitates out of the reaction solution in crystalline form. In other cases, give a 50-50 volume mix Chloroform and diethyl ether to initiate the crystallization of the product or this from the reaction

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to separate the solution as an oil.

The compounds of the general formula VI are salts of the diesters of the general formula V and can also by general formula

Z τ, +

Il ~?

(Aryl X _a -0) ₂ -P-CH ₂ -N-CH ₂ -CN-R "(VII)

are represented, wherein X, Z and a are as defined above and R. is the strong acid anion.

Groups which are substituted on the phenyl, naphthyl or biphenylyl and which are represented by X are, for example Halogen such as chlorine, fluorine or bromine, alkyl such as methyl, ethyl, propyl and butyl, alkoxy such as methoxy, ethoxy and propoxy, Alkylthio such as methylthio, ethylthio and propylthio, as well Methylenedioxy, cyano, trifluoromethyl and nitro. From the formula it follows that the groups represented by X an the same aryl ring can be the same or different.

The strong acids which are suitable for the preparation of the salts of strong acids of the general formula I, VI and VII, are those with a pK in water of 2.5 or less and

3.

they include, for example, p-toluenesulfonic acid, p-chlorobenzenesulfonic acid, Trichloroacetic acid, oxalic acid, fluoroboric acid, hydrogen chloride, hydrogen bromide, hydriodic acid, Trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, trifluoromethanesulfonic acid, nitric acid, sulfuric acid, Phosphoric acid, trichloromethane phosphonic acid, perchloric acid, methane

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thanesulfonic acid and the like.

For the preparation of the salts of strong acids of the general formulas I, VI and VII, it is preferred to use the diester of phosphonic acid and to use the strong acid in equal molar proportions in order to isolate the salt of the strong acid to facilitate. Higher or lower ratios of ester to acid can be used, although isolation of the Product becomes more difficult because of the presence of an excess of one of the reactants.

The hydrolysis of the N-Phosphonmethylglycinnitrile of the general formula I for the formation of N-phosphonomethylglycine can be conveniently and quickly performed in such a manner that the glycinonitrile at moderate temperatures (60-100 ⁰ C) heated to at least -this slight excess in the mixture one molar equivalent (for example 1.01 molar equivalent) of aqueous hydrochloric acid or aqueous hydrobromic acid, which are expediently used with 1, ON and preferably at least 2.0 normal. If concentrated aqueous hydrochloric acid or hydrobromic acid is used, satisfactory hydrolysis to N-phosphonomethylglycine takes place within 24 hours at room temperature.

The compounds represented by the general formula I are useful as herbicides for both pre-emergence and post-emergence use suitable.

The following general procedures show the preferred

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Manufacturing process of the various compounds of these Invention.

The diaryl esters of the general formula V are preferably prepared by one of the following two processes.

(A) An acetonitrile solution (50 ml) of 1.3 · 5-tricyanomethylhexahydro-1.3.5-triazine (3.4 g, 0.0167 mol) and diaryl phosphite (0.050 mol) are mixed in a reaction vessel and heated from 4-5 to 85 ^° C. for 1 to 90 hours until all of the phosphite or triazine is consumed, which is determined by means of CMR analysis. If the CMR spectral analysis shows that there are no impurities, isolate the product using vacuum concentration. If impurities are present, the product is iroliated and purified by crystallization or by chromatography. In some cases it can be difficult to isolate the diester product in highly pure form because hydrolysis occurs during the intended isolation.

(B) A mixture of a Biarylphosphits (0.05 mol) and 1,3,5-Tricyanomethyl-hexahydro-IJ ^ triazine (3,4 g, 0.016? Mol) is added to a reaction vessel and heated from 60 to 10O ⁰ C from 20 minutes to 1 hour until all of the phosphite or triazine is consumed, which is determined by CMR spectral analysis. The products are purified by crystallization or by chromatography.

Wan, the monoaryl ester of li-PhosphonmethylglycInnitril forth characterized in that the diaryl ester in acetone containing a ^ e-

Contains a small amount of water (usually about 2% by weight of water), dissolves and that the reaction mixture is stirred for 18 to 72 hours. The monoesters are usually crystalline and are made up by filtration collected, washed with acetone and air dried.

The strong acid salts of the diaryl esters are preferably prepared by the following general procedure. A solution of the strong acid (or the acid as such) (0.01 mol) is added dropwise to a chloroform solution of Diester at room temperature and lets stand. If crystals form, these are collected by filtering them with Washed a 50% chloroform-ether mixture and turned on air dried. Otherwise a 50 vol. Chloroform-ether mixture is added to bring the salt to crystallize out or to emerge as a solution such as an oil.

The hydrolysis of the N-Phosphonmethylglycinnitrile, which by the general formula I are represented, with the formation of N-Phosphonmethylglycine is easily achieved using the general procedure below. The raw or purified Reaction products of a diaryl phosphite with 1.3.5-tricyanomethyl-hexahydro-1.3.5-triazine are hydrolyzed by adding at least a slight excess over a Molecular equivalents (e.g. at least 1.01 mol) aqueous hydrochloric acid or hydrobromic acid are added and the mixture heated to about 100 ° C for several hours under reflux conditions until determined by means of K.M.R.-spectral analysis is that essentially all of the glycine nitrile to N-phosphor

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phonmethylglycine is hydrolyzed. The reaction mixture is then extracted twice with chloroform to remove the phenol formed during the hydrolysis, and the aqueous layers are filtered and evaporated to dryness. The solid residue is dissolved in water and the solution is cooled to ⁰ ° G in order to cause the N-phosphonomethylglycine to crystallize out.

The crude or purified reaction products of a diaryl phosphite with 1.3.5-tricyanomethylhexahydro-i.3 «5-triazine can be hydrolyzed by using a base, namely alkali metal hydroxide or a tetraalkylammonium hydroxide, wherein the alkyl radicals contain 1 to 4 carbon atoms, a mixture of the compound and the base in Water, the mixture is heated to effect complete hydrolysis to a salt of N-phosphonomethylglycine and then converts the salt of N-phosphonomethylglycine, for which purpose an aqueous solution of the salt with a cationic exchange resin is used brings in contact.

The following experiments serve to further explain the Invention, all parts being by weight unless otherwise indicated.

example 1

Di- <p ~ cfalorphenyl) phosphite (25.32 g, 78% purity, 0.06 mol) and i ^ -iJ-tricyanomethyl-hexahydro-IJ ^ -triazine (4.08 g, 0.02 mol) it is mixed in a reaction vessel at room temperature and the mixture is heated to 100 ^° C. for 20 minutes, whereby 0,0-di- (p-chlorophenyl) -N-phosphonmethylglycine nitrile is obtained in 100%

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Yield obtained; 27 g; ηJ '. 1.5747-

Example 2

An acetonitrile solution (10 ml) of di (3,4-dimethylphenyl) phosphite (8.7 g, 0.03 mol) are added to an acetonitrile solution (50 ml) of 1.3.5 — tricyanomethyl — hexahydro — 1.3 · 5 ~ "tri— azine (2.04 g, 0.01 mol) and the mixture heated at 55 ° C for 90 hours. After filtering the solid present and Evaporation of the solvent gives a burgundy-colored oil which, according to K.M.R.analysis, the desired product and the Aminaldehyde in this product contains. By chromatography of the oil (8.0 g) over silica gel (450 g) with 50 # cyclohexane / 5O # Ethyl acetate (60 ml fractions) gives O.O-di- (3.4-dimethylphenyl) -N-phosphonmethylglycine nitrile in fractions 30-41, melting point 61-64 ° C after removal of the solvent. The Solid is crystallized from carbon tetrachloride isooctane around; Melting point 63-66 ° C; 3 * 1 g are obtained (40 # yield).

Example 3

A mixture of 0.02 mol of di (p-methylthiophenyl) phosphite is heated with stirring and 0.0067 moles of 1,3.5-tricyanomethyl-hexahydro-1,3.5-triazine 1 hour at 80 ° C., whereby a dark red-brown oil is obtained. Half of the sample is given in for 8 days the refrigerator and get a semi-solid mass. The sample is then recrystallized from 70 ml of carbon tetrachloride and receives a pink solid. The solid is dissolved in ml of hot carbon tetrachloride and filtered through Celite, the cover with 5.0 g of silica gel. The filtrate is concentrated

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to 50 ml and put in the refrigerator overnight. Filter the suspension to give 1.8 g (45 #) of white solid identified as O, O-di- (p-methylthiophenyl) -N-phosphonomethylglycine nitrile; Melting point 64-65 ⁰ C; Analysis: Calculated: C 51.8, H 4.9, N 7.1 Found: C 51.7, H 4.9, N 7.1 ·

Example 4

A solution of di (o-methoxyphenyl) phosphite (8.05 g, purity, 0.025 mol) and I.3.5-TΓicyanomethyl-hexahydΓo-1.3.5-triazine (1.7 g, 0.0083 mol) is heated at 55 ° C. for 73 hours and then filtered. Concentrate the piltrate to a dark brown one oil (9.6 g). The oil (5.8 g) is attached to 8 g of silica gel and extracted with 80 ml of ethyl acetate. The ethyl acetate solution is concentrated and the oil obtained is attached to <1.0 g of silica gel. This silica gel is extracted with 70 ml of ethyl acetate and the solution is concentrated under vacuum. One obtains a pale

22nd
yellow oil, n _D = 1.5542. The yellow oil was found to be O, O-di- (o-methoxyphenyl) -N-phosphonmethylglycine nitrile, which contains a small amount of o-methoxyphenol.

Example 5

A solution of i ^^ - tricyanomethyl-hejcahydro-i ^^ - triazine (15.6 g, 0.066 mol) and diphenyl phosphite (46.8 g, 0.2 mol) in acetonitrile (100 ml) is heated at 55 ^° C. 48 hours. The CMR of the crude reaction mixture shows the complete conversion to OO-diphenyl-N-phosphonmethylglycine nitrile. The acetonitrile is removed in vacuo and 57 g (94.4 #) viscous are obtained

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black oil. The oil is dissolved in chloroform, 114 g of gel are added and the mixture is evaporated to dryness under vacuum. The product, impregnated in silica gel, is placed in a column containing a slurry of chloroform and silica gel (200 g) and eluted until the product can no longer be detected in the eluent. The chloroform eluents are concentrated, dissolved in methylene chloride and washed twice with cold 5 # KOH (100 ml), then with water. The methylene chloride layer is dried over MgSO ^, filtered and evaporated, and 3? »9 g of light yellow oil is obtained, which solidifies after standing. The solid has a melting point from 64 to 67.5 ⁰ C and is identifiaiert phosphonmethylglycinnitril 0,0-Diphenyl-N-as; 75% yield.

Example 6

line aoetonitrile solution (100 ml) of di- (m-tolyl) -phosphite (10.7 g, 0.04 mol) and i ^^ - tricyanomethyl-hexahydro-ia ^ - triaain (2.72 g, 0.0133 moles) is erhitat at 50 ⁰ C for days. The solution turns wine red, the solvent is evaporated and 12.4 g of red oil are obtained (92.4 $ yield). The oil (9) (0 g) is chromatographed on silica gel while eluting with 609t cyclohexane / 40 pounds of ethyl acetate, with 60 ml fractions being removed . Fractions 43-63 are pure O, O-di- (m- * oijl) -N-phosphonmethylglyonitrile, njp · 1.5467 (1.25 β «Auabeut ·) old of the following analysis * Xr * eefcn« ti 0: 61.81, Ht 5.80, Nt 8.48, Geiundent Ct 61.75, Ht 5.81, Nt 8.41

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Example 7

A solution of di (m-nitrophenyl) phosphite (15.2 g, 83 # purity, 0.0392 mol) and 1.3.5-tricyanomethylhexahydro-1.3.5-triazine (2.66 g, 0.013 mol) in acetonitrile for 20 hours at 5O ⁰ C. The KMR analysis shows complete reaction. The solution is filtered and the solvent is removed under vacuum and 13 g of amber-colored oil is obtained, which is identified as 0,0-di- (m-nitrophenyl) -N-phosphonmethylglycine nitrile with the following analysis:
Calculated: C: 4-5.93, H: 3.34, N: 14.28 Found: Cj 45.80, H: 3.39, N: 14.27

Example 8

Di- (p-methoxyphenyl) phosphite (0.05 mol, 15.63 g, 94 # purity) and 1.3.5-tricyanomethylhexahydro-1.3 «5-triazine (3.4 g, 0.0167 mol) is dissolved in acetonitrile and the solution is refluxed for 1 hour. The solvent is evaporated off under vacuum and receives a dark pink-red oil (19.0 g). This oil (5g) is subjected to high pressure liquid chromatography using a mixture of cyclohexane and ethyl acetate (40/60 vol. #) and receives 4.1 g of 0.0-di- (p-methoxyphenyl) -N-phosphonmethylglycine nitrile as oil j n ^ p - 1.5541, 82 # Lg yield.

B «iapi ·! 9

A mixture of i ^^ - tricyanoraethyl-hexahydro-i ^^ - triazine (2.04 g, 0.01 mol) and di- (p-fluorophenyl) phosphite (8.8 g, 91.6 # purity, 0.03 mol) heated in acetonitrile (50 ml)

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70 hours at 55 ° C. The reaction mixture is then filtered, removes the solvent in vacuo and leaves a brown oil; njp = 1.5270, purity 92 #: O, O-di- (p-fluorophenyl-N-phosphonmethylglycine nitrile.

Example 10

Di (m-chlorophenyl) phosphite (9.93 6, 91.5% purity, 0.03 mol), dissolved in acetonitrile (20 ml), is added to 1.3.5-tricyanomethyl-hexahydro-i ^^ triazine (2.04 g, 0.01 mol) dissolved in acetonitrile (50 ml) and the mixture is heated to 55 ^° C. for 70 hours. The acetonitrile is removed under vacuum and a light pink oil is obtained; njp «= 1.5656 with 92% purity: OO-di- (mchlorophenyl) -N-phosphonmethylglycine nitrile.

The following connections can be made according to the obj ^ n method getting produced: "

0.0-di- (p-cyanophenyl) -N-phosphonmethylglycine nitrile 0.0-Di- (p-biphenylyl) -N-phosphonmethylglycine nitrile

Example 11

The diester (4.0 g, 0.099 mol) prepared in the example is dissolved 10, in 100 ml of 2 # aqueous acetone and stir the solution at room temperature for 6 days, during which time forms a solid. The solid is collected, washed with acetone and dried, giving 1.55 g (60 #) of O-m-chlorophenyl-N-phosphonmethylglycine nitrile as a solid; Melting point 181 182 ° C with the following analysis:

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Calculated: C: 41.5, H: 3.9, N: 10.8 Found: C: 41.5, H: 3.9, N: 10.8

Example 12

The diester prepared in Example 9 (2.38 g, 0.069 mol) is dissolved in 2% aqueous acetone (100 ml) and stirred for 3 days at room temperature. The resulting slurry is filtered, the solids washed with acetone and 0.87 g of a tan solid is obtained; Melting point 258-262 ⁰ C. It is the mother liquor left to stand for 6 weeks, and collecting the resulting solids are combined, washed with acetone and obtained a further 0.8 g of material with the same melting point, identified phosphonmethylglycinnitril Op-fluorophenyl-N-as; 98 # yield; Analysis: Calculated: C: 44.3, H: 4.1, N: 11.5 Found: G: 44.3, H: 4.2, N: 11.5

Example 13

0.0-Diphenyl-N-phosphonniethyl.glyciimitril (1.51 g, Q <, QQ5 mol) is stirred with heating in 50 ml of 2N hydrochloric acid until all of the material has dissolved (2 hours). An amber-colored oil is noticed at the bottom of the flask and it is identified as phenol. The flask is cooled to room temperature, the hydrochloric acid solution is washed twice with methylene chloride (25 ml) to remove any starting material present and the phenol formed in the reaction. The hydrochloric acid solution is then cooled in an ice bath, during which time crystals begin to form. Collect the crystals, wash with cold water and air dry. The crystals can be identified as

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O-phenyl-N-phosphonmethylglycine trile with no definite melting point. You have the following analysis: Calculated: G: 47.79, H: 4.90, N: 12.39 Found: C: 4-7.52, H: 4.93, N: 12.12

Example 14

0.0-Di- (m-tolyl) -N-phosphonmethylglycine nitrile (4.0 g, 0.012 Mol) is dissolved in acetone (50 ml) containing water (1 ml) and stirred for 60 days at room temperature. Three crops are obtained of crystals. The first two crops of crystals have a melting point of 161 - 166 ° C and are impure. the third crop has a melting point of 179-179.5 ° C and is analytically pure O-m-tolyl-N-phosphonmethylglycine nitrile, which is obtained in 53 # yield: Analysis: Calculated: C: 50.0, H: 5.5, N: 11.7 Found: C: 50.0, H: 5.5, N: 11.7

Example 15

0.0-Di- (m-nitrophenyl) -N-pnosphonmethylglycine nitrile (3.15 g, 0.008 mol) is dissolved in acetone (50 ml) and water (1 ml) and stirred for 16 hours at room temperature. Solids are formed which are collected and washed with acetone; Yield 1.1g (5156). The material is identified as Om-nitrophenyl-N-phosphonmethylglycine nitrile with a melting point of 174-176 ° C with decomposition and the following analysis:
Calculated: C: 40.0, H: 3.4, N: 15.6 Found: C: 40.0, H: 3.4, N: 15.5

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Example 16

An acetonitrile solution (100 ml) of di (m-trifluorotolyl) phosphite (11.64 g, 0.0314 mol) and 1.3.5-tricyanomethyl-hexahydro-1.3.5-triazine (2.15 g, 0.0105 mol) is heated at 50 ° C. overnight. The acetonitrile is evaporated off in vacuo, whereby Solids begin to form. The material residue is dissolved in acetone (50 ml) and water (1 ml), stirred overnight at room temperature, solids form during this time. The solids are collected, washed with acetone and obtained: 3.5 g (39.5 #) white solid; melting point 195-196 ° C; identified as O-m-trifluorotolyl-N-phosphonmethylglycine nitrile; Analysis: Calculated: G: 40.8, H: 3.4, N: 9.5 Found: G: 41.0, H: 3.5, N: 9.7

Example 17

0.0-Di- (p-chlorophenyl) -N-phosphonraethylglycine nitrile (9 * 0 g, 0.024 mol) is dissolved in acetone (50 ml) and water (1 ml) and stirred for two days at room temperature. A solid forms which is collected; Weight 2.35 g · The solid has a melting point of 170 ^° C. with decomposition and is identified as Op-chlorophenyl-N-phosphonmethylglycine nitrile. The mother liquor is left to stand for several weeks and a further 0.85 g is collected. The total yield of product is 3.2 g (51 # yield).

Example 18

Dissolve 21 g of a solution containing 83.8 wt.% Of di (3-methyl-4-nitrophenyl) phosphite (0.05 mol) and 1,3,5-Tricyanomethylhexahydro-1,3,5-triazine (3.4 g 0.0167 mol) in 100 ml

Acetonitrile and heated to 70 ° C for 1 hour. The acetonitrile solvent is removed in vacuo, the residue is dissolved in 50 ml of acetone containing 1 ml of water, and the mixture is stirred at room temperature. The crystals (4.3 g, 30% yield) are identified as O- (3-methyl-4-nitrophenyl) -N-phosphonmethylglycine nitrile; Melting point ^{181-182 0} C. Analysis: Calculated: C: 42.1, H: 4.2, N: 14 ,? Found: C: 42.2, H: 4.3, N: 14.7

Example 19

0.O-Di- (p-methoxyphenyl) -N-phosphonmethylglycine nitrile (3.0 g, 0.0082 mol) is dissolved in acetone (50 ml) and water (1 ml) and stirred for 3 months at room temperature. During this time, solids are formed. The solids are removed by filtration, washed with acetone and dried. The solid material is identified as Op-methoxyphenyl-W-phosphonmethylglycine nitrile; Melting point 185 to 195 ⁰ C with decomposition. Analysis: Calculated: C: 46.9, H: 5.1, N: 11.0 Found: C: 47.1, H: 5.2, N: 10.8

Example 20

Di- (o-chlorophenyl) phosphite (19.5 g, 80% by weight, 0.05 mol) is added to an acetonitrile solution (50 ml) of 1.3.5-tricyanomethylhexahydro-1.3.5-triazine (3 , 4 g, 0.01640 mole) and heated for 2 hours at 70 ⁰ C. A 15 ml portion of the reactant solution was concentrated, dissolved in acetone (50 ml) and water (1 ml) and stirred overnight while during this time Form solids. The solids are collected, washed with acetone and dried to give 3.2 g (82 # yield) of material which can be called

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O-o-chlorophenyl-N-phosphonmethylglycine nitrile identified;

Melting point 170-171 ° C; Analysis: Calculated: C: 41.5, H: 3.9, N: 10.8 Found: C: 41.4, H: 3.9, N: 10.7

Example 21

0.0-Di- (p-fluorophenyl) -N-phosphonmethylglycine nitrile (2.38 g, 0.069 mol) is stirred in a 50% mixture of carbon tetrachloride and methylene chloride, filtered and methanesulfonic acid (0.67 S, 0.069 mol) is added. The solution is allowed to stand overnight, the crystals formed are collected by filtration and washed with carbon tetrachloride to give 2.68 g of white crystalline material which is identified as the methanesulfonate salt of OO-di- (p-fluorophenyl) -N-phosphonmethylglycine nitrile . This salt has a melting point of 132 to 132.5 ⁰ C; Analysis:

Calculated: C: 44.2, H: 4.0, N: 6.5, S: 7.4 Found: G: 44.0, H: 4.0, N: 6.6, S: 7.5

Example 22

p-Toluenesulfonic acid (1.9 g, 0.01 mol) is kept in benzene (100 ml) at reflux and removes the water present azeotropically by means of benzene. This benzene solution is added to a benzene-methylene chloride solution (50/50 vol. #, 100 ml) of O.O-Diphenyl-N-phosphonomethylglycine nitrile (3.02 g, 0.1 mole). The mixture is stirred for 1 minute at room temperature, during which it crystallizes out occurs. The resulting slurry is stirred at room temperature overnight and then filtered. A white solid is obtained, which is called the p-toluenesulfonic acid salt of 0.0-di-

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phenyl-N-phosphonmethylglycine nitrile identified (4.38 g, 92.4 ^ 5 yield); Melting point 152-153 ° C. Analysis: Calculated: C: 55.7, H: 4.9, N: 5.9 Found: C: 55.4, H: 4.9, N: 5.7

Example 23

A chloroform solution of p-chlorobenzenesulfonic acid (1.92 g, 0.01 mol) is added to a chloroform solution of 0.0-diphenyl-N-phosphonmethylglycine nitrile (3.0 g, 0.01 mol). The mixture is stirred and crystallization begins after 10 minutes. The slurry is then stirred overnight, filtered, the contaminants are washed with chloroform to give 4.0 g of white solid (81 #); Melting point 149 to 151 ⁰ C; identified as the p-chlorobenzenesulfonic acid salt of 0.0-diphenyl-N-phosphonmethylglycine nitrile with the following analysis: Calculated: C: 51.0, H: 4.1, N: 5.7 Found: C: 50.7, H: 4, 1, N: 5.7

Example 24

A chloroform solution (20 ml) of trichloroacetic acid (1.63 g, 0.01 mol) is added to a chloroform solution (100 ml) of OO-diphenyl-N-phosphonmethylglycine nitrile (3.0 g, 0.01 mol) and stirred Room temperature overnight. Crystallization could not be initiated and the pests were removed under vacuum to give a light yellow oil, 3.75 g (80 #); nj-5 _m i _i5 4 ₁₀ , identified as the trichloroacetic acid salt of OO-diphenyl-N-phosphonmethylglycine nitrile with the following analysis:

809824/0617

Calculated: C: 43.9, H: 3.5, N: 6.0 Found: C: 43.9, H: 3.5, N: 5.9

Example 25

An acetone solution (25 ml) of oxalic acid dihydrate (1.26 g, 10 mol) is added to an acetone solution of O.O-diphenyl-N-phosphonmethylglycine nitrile (3.02 g, 10 moles). After 10 minutes the salt begins to crystallize out of the solution. One stirs cool the solution overnight and collect the solids (1.9 g and wash with acetone. A second crop is obtained through Concentrate the mother liquor, 0.8 g. The total yield is 2.7 g, 69%, melting point 165 ° C. with decomposition. One identifies the crystals as the oxalic acid salt of 0.0-diphenyl-N-phosphonmethylglycine nitrile; Analysis: Calculated: O: 52.1, H: 4.4, N: 7.1, Found: C: 52.1, H: 4.4, N: 7.1

Example 26

An ether solution of perchloric acid is added to a chloroform-ether solution of OO-diphenyl-N-phosphonmethylglycine nitrile (3.0 g, 10 mol). The perchlorate salt slowly crystallizes out as white prisms. The solids, identified as the perchloric acid salt of OO-diphenyl-N-phosphonmethylglycine nitrile, are collected and washed with ether-chloroform and 0.73 g, 18% yield; Melting point 166 - 168 ⁰ C. This salt has the following analysis:

Calculated: C: 44.7, H: 4.0, N: 7.0 Found: C: 44.8, H: 4.0, N: 7.0

809824/06 17

Example 27

A chloroform-methanol solution of trichloromethanephosphonic acid (1.99 g, 0.01 mol) is added to a chloroform solution of OO-diphenyl-N-phosphonmethylglycine nitrile (3.0 g, 10 mol). After 10 minutes, ether is added, whereby no crystals form. Petroleum ether is then added until just before the cloud point. After 10 minutes, crystals begin to form and the mixture is left to stand for a further 10 minutes. Collect the crystals in two crops, 2.9 g, 58% yield; Melting point 145-146 ° C. The crystals are identified as the trichloromethanephosphonic acid salt of OO-diphenyl-N-phosphonmethylglycine nitrile; Analysis:
Calculated: C: 38.3, H: 3.4, N: 5.6 Found: C: 38.3, H: 3.5, N: 5.6

Example 28

An ethereal solution of fluoroboric acid is added to a chloroform-ether solution of O.O-Diphenyl-N-phosphonmethylglycine nitrile (3.0 g, 10 moles). The solution is stirred overnight, the solids are filtered off, washed with ether-chloroform (50/50) and obtains white crystals, 1.1 g, 28 # yield; M.p. 156-158 ° C; they are identified as the fluoroboric acid salt of O.O-diphenyl-N-phosphonmethylglycine nitrile; Analysis: Calculated: C: 46.2, H: 4.1, N: 7.2 Found: C: 46.0, H: 4.2, N: 7.2

Example 29

Gaseous hydrogen bromide is bubbled into a chloroform solution

809824/0617

of 0.0-diphenyl-N-phosphonmethylglycine nitrile (3.0 ρ; 10 moles). The solution is allowed to stand overhead, with the hydrobromide crystallized out. The crystals are collected and washed with ether. A yield of 3.0 g, 70%, is obtained, which is the hydrogen bromide salt identified by O.O-Diphenyl-H-phosphonmethylglycine nitrile; Analysis:

J ^ r calculates: G: 4-7.0, H: 4.2, N: 7.3 Found: G: 47.1, H: 4.3, N: 7.4

Example 50

A 57 # solution of hydriodic acid (2 ml) is added to a chloroform solution of OO-diphenyl-H-phosphonmethylglycine nitrile (3.0 g, 10 mol). The solution becomes cloudy and turns gold. Since no solids form within two hours, ether is added up to the cloud point and crystallization begins. The solution is stirred for an additional hour, the solids are collected and identified as the hydriodic acid salt of OO-diphenyl-N-phosphonmethylglycine nitrile in the form of pale yellow platelets; Melting point 163 - 164- ⁰ C, 2.4 g, 56 # yield. Analysis:
Calculated: C: 41.9, H: 3.8, J: 29.5 Found: C: 4-1.8, H: 5.8, J: 29.5

Example 31

Trifluoroacetic acid (1.14 g, 10 mol) is added to a chloroform solution of O.O-Diphenyl-N-phosphonmethylglycine nitrile (3.0 g, 10 moles). The solution is stirred overnight and the solvent is evaporated under vacuum and receives a light yellow oil, 4.0 g,

pr

9S # ige yield, η ^ = 1.5172, which is called the Trifluoressip-

^D 809824/0617

acid salt of O.ü-ttiphenyl-N-phosDhonmethylglycinnitril identified.

Example 32

Trifluoromethanesulfonic acid (1.50 g, 10 mol, fuming) is added to a chloroform solution of O.O-diphenyl-N-phosphonmethylglycine nitrile (3.0 g, 10 moles). The reaction mixture is stirred for 2 hours at room temperature and ether is added up to the cloud point to. A product crystallizes out. After an hour Let stand collect the solids and wash with chloroform-ether ($ 50) to give 3.8 g, 84% yield; Melting point 119 - 120 ° C, which is called the trifluoromethanesulfonic acid salt identified by 0.0-diphenyl-N-phosphonmethylglycine nitrile; Analysis:

Calculated: C: 42.5, H: 3.6, N: 6.2 Found: C: 42.7, H: 3.6 "N: 6.2

Example 33

To a chloroform solution of O.O-diphenyl-N-phosphonmethylglycine nitrile (15.1 g, 0.05 mol) are added methanesulfonic acid (5.0 g, 0.051 mol) and the solution is stirred for two hours at room temperature.

The precipitated pest is collected, washed with ether and dried. The pesticide weighs 15.90 g and is identified as the methanesulfonic acid salt of OO-diphenyl-N-phosphonmethylglycine nitrile; Melting point ^{147-15O 0} Cj yield of salt

82.1 #. Analysis:

Calculated: C: 44.2, H: 4.0, N: 6.5, S: 7.4 Found: C: 44.0, H: 4.0, N: 6.6, S: 7.5

809824/0617

3 *

Example 34

An ether solution (10 ml) of nitric acid (70 wt. 0.01 Hol). There is no clouding. Additional ethyl ether and then isooctane (20 ml) are added, at which point solids begin to crystallize out of the solution. The mixture is stirred for 1 hour at room temperature, the crystals are collected, washed with chloroform and air-dried. 2.66 g of crystals are obtained which are identified as the nitric acid salt of OO-diphenyl-N-phosphonmethylglycine nitrile; Melting point 116 to 116.5 ⁰ C; Yield 72ίυ of the theoretical Μβηίξβ. Analysis:

Calculated: C: 49.32, R: 4.42, N: 11.5 Found: C: 49.2, H: 4.42, N: 11.6

Example 5 5

An ether solution of 98% sulfuric acid (1.01 g, 0.01 mol) is added to a solution of OO-diphenyl-N-phosphonmethylglycine nitrile (3.0 g, 0.01 mol) in chloroform (100 ml). Additional chloroform is added and the mixture is stirred for two hours. The solids are removed by filtration, washed with chloroform, then with ether, dried to obtain 3.9 g of material identified as the sulfuric acid salt of OO-diphenyl-N-phosphonmethylglycine nitrile; Melting point 151 to 151.5 ⁰ C; Yield 1C0>j; Analysis:
Calculate L: G: v ,, u,, ·. · 4.23, S: -5.01

Example 36

An ethereal solution of phosphoric acid (0.01 mol) is added a chloroform solution of O.O-diphenyl-N-phosphonmethylglycine nitrile (3.0 g, 0.01 mol) at room temperature with stirring. The solution immediately becomes cloudy. An oil is obtained on the bottom of the piston. After cooling, the solvent is decanted off, evaporated to dryness and dried over anhydrous magnesium sulfate. The solid is identified as the phosphoric acid salt of O.O-diphenyl-N-phosphonmethylglycine nitrile; Melting point 74.5-78.5 ° C. The salt is obtained in a yield of 25; Analysis:

Calculated: C: 45.0, H: 4.5, N: 7.0 Found: C: 44.8, H: 4.6, N: 7.1

Example 37

A heterogeneous solution of OO-Oiphenyl-N-phosphonmethylglycinnitril (60.4 g, 0.2 mol) in ethanol (500 ml) is cooled in an ice bath and dry HCl bubbled through. The solution is allowed to stand, ethyl ether is added and the white solid is collected by suction filtration. Another white solid is obtained after bubbling dry HCl through the ethanol-ether mother liquor at about ⁰ ° C., which is collected and washed with ether. The yield is 62.7 g (93 #) of the hydrochloride salt of OO-diphenyl-N-phosphonmethylglycine nitrile; Melting point 112 - 123 ° C Analysis:

Calculated: C: 53.19, H: 4.79 »N: 8.27 Found: C: 53.51, H: 4.78, N: 8.30

- ifO

example ^x > ij

Di (2.4.6-trimethylphenyl) phosphite (17.8 g, 0.05 mol) is added to an acetonitrile solution (50 ml) of 1.3.5-tricyanomethylhexahydro-i.3.5-triazine (3.4 g , 0.0164 mol) and the mixture is heated for 18 hours at RO ⁰ '.'. :. »The black / .e reading that forms is filtered off and concentrated to a Cl. Part (7 g) is chromatographed on silica gel (450 pe) with 70% cyclohexane / 30% ethyl acetate (60 ml fractions) and 1.0 g (14 #) 0.0-di- (2.4.6-trimethylphenyl) -N is obtained -phosphonmethylglycine nitrile; , In the fractions 28 120 ⁰ C - - 40, which crystallize upon standing Melting point 118th Analysis:

Calculated: C: 65.27, H: 7.04, N: 7.25 Found: C: 65.38, H: 7.07, N: 7.18

Example 39

A solution of the diester from Example 3 (0.025 mol) in moist acetone (50 ml) is refluxed for 2 hours and then left to stand at room temperature for 5 days. The suspension was filtered to give an impure pink solid (0.9 g). The filtrate was placed in a sealed flask and allowed to stand at room temperature for an additional 30 days. The resulting suspension is filtered and the solid is washed with acetone (50 ml). 4.5 g (66 #) Op-methylthio-N-phosphonmethylglycine nitrile are obtained as a white solid; Melting point 250 253 ⁰ C (disintegration). The product has the following analysis: Calculated: C: 44.12, H: 4.81, N: 10.29 Found: C: 44.26, H: 4.86, N: 10.22

809824/0617

Example 40

Diphenylthiophosphite (8.2 g, 0.0246 mol) and 1.3.5-tricyanomethylhexahydro-1.3.5-triazine (1.68 r, 0.00823 mol) are dissolved in acetonitrile (50 ml) and the solution 2 is heated hours at 60 The resulting 01 to 65 ⁰ C. is chromatographed over SiIikagel (450 g), eluting with cyclohexane 6OjIi / 4O # ethyl acetate (60 ml fractions) to give to give 1.6 g (20 #) 0.0-

25 Diphenyl-N-thiophosphonmethylglycine nitrile, n ^ = 1.5847, in Fraction 30. The product has the following analysis: Calculated: 0: 56.60, H: 4.75, N: 8.80, S: 10.07 Found: C: 56.40, H: 4.80, N: 8.73, S: 10.26

At ST) iel 41

An acetonitrile solution (100 ml) of di- (ß-naphthyl) phosphite (33.5 g, 0.1 mol) and i ^^ - ^ ricyancmethyl-hexahydro-1.3.5-triazine (20.4 g, 0.1 mol) at reflux for one hour and then concentrated to a red-brown oil. A 10 g sample is purified by high pressure liquid chromatography over silica gel, eluting with 60% cyclohexane / 40% ethyl acetate (20 ml fractions). Fractions 45-64 are combined and concentrated to give an oil which crystallizes out from carbon tetrachloride with the formation of 1.1 g of OO-di- (β-naphthyl) -N-phosphonmethylglycine nitrile as a brown colored solid; Melting point 104-105 ⁰ C. The product has the following analysis: Calculated: C: 68.65, H: 4.76, N: 6.96 Found: C: 68.58, H: 4.79, H: 6, 92

Example 42

ivirie .bösunp; of üi- (3.4-; nethylenedioxyphenyi) -phosphite (0.0 '; mol)

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and 1.3.5-tricyanomethyl-hexahydro-i.3.5-triazine (0.016 mol) in acetonitrile (75 ml) is heated to 75 ° O for 3 hours and then left to stand at room temperature overnight. The received The solution is concentrated to an amber oil. To a Chloroform solution; (100 ml) of the oil (7.6 ^, 0.02 mol) are added Add methanesulfonic acid (1.92 g, 0.02 mol) dropwise. After 15 After stirring for minutes, ether (200 ml) is added and a white precipitate is dropped Solid off. The solid is crystallized twice from acetone and receives 4.6 g (47 #) methanesulfonic acid salt of - (3.4- methylenedioxyphenyl) -N-phosphonmethylklycine nitrile;

Melting point 135-136.5 ° C. The product has the following analysis :

Calculated: G: 44.45, H: 3.94, N: 5.76

Found: G: 44.26, H: 3.94, N: 5.71

Beis pie l_4J

A solution of 0.01 mol of the amber-biped oil of Example 42 in wet acetone (70 ml) is refluxed for 4 days. The amber-colored solution is then left to stand for one day at room temperature. The suspension obtained is filtered and 1.7 g of 0- (3,4-MethyLendioxyphenyl) -N-phosphonmethylglyeinnitril are obtained as a white pesticide; Melting point 160 - 161 ⁰ C.

Example 44

A solution of Di-C 3.4-d i J ornheny L) -phosphi t (0.04 mol) and 1.3.5-Tric.yanometh.yL-hexahvdro-i. ^. ^ - triazine (0.013 mol) in acntnnitr ^: I (40 niL) is heated to BO ⁰ G with stirring and this temperature is maintained for 18 hours. The received [.ösunr

809824/06 1 7

Concentrate to an oil, add wet acetone (80 ml) and reflux the mixture for 80 hours. The suspension obtained filter to give a white solid which is washed with acetone (50 ml) to give 6.3 pr ($ 53) 0- (3.4-Dichlorophenyl) -N-phosphonmethyl (5lycinnitrile) melting point Ί69 - 170 ° C.

Example 45

Diphenyl phosphite (234 g, 1.0 mol) is added to an acetonitrile solution (300 ml) of 1.3.5-tricyanomethylhexahydro-'1.3 '? - triazine (68 g, 0.333 mol) and the mixture is heated at 75-82 for 3 hours ° C. The solution is cooled and concentrated under vacuum, thereby obtaining _v mainly containing a black oil the product of Example 5. FIG. A sample of this oil (10 g) is attached to silica gel (which has been dissolved in chloroform, additional silica gel is added and the solvent is evaporated) and this material is chromatographed on silica gel (1.1 kg), 1 fractions being obtained with chloroform ^ eluted. Fractions 13-14 are mixed, concentrated and recrystallized from dichloromethane-cyclohexane and 51 g of OO-diphenyl-N-phosphonmethylglycine nitrile are obtained.

Example 46

Diphenyl phosphite (33.43 ß, 0.1 mol (70 # purity) is stirred and 1.3.5-Tricyanomethyl-hexahydro-1.3.5-triazine (6.73 g, 0.033 mol) in a flask and heated to 100 ° C (using an oil bath). The reaction has ended after 40 minutes (K.M.R. analysis). The reaction mixture is hydrolyzed by adding

809824/0617

of 150 ml of PN hydrochloric acid and refluxes it for 16 hours. The material obtained is extracted twice with chloroform (to remove the phenol), the aqueous layers filtered and evaporated to dryness to give a browned orange solid which is dissolved in 60 ml of water and cooled to ^{0 ° C.} The crystals obtained are collected and air-dried, and 10.7 g of N-phosphonomethylglycine are obtained. Analysis 95 + ^ purity. Further yields are isolated by evaporation and the addition of ethanol, all of these materials containing varying amounts of ammonium chloride and aminomethylphosphonic acid. The mother liquors from the above crystallizations mainly contain phosphorous acid (4.4 g).

Example 47

Di- (p.-methoxyphenyl) phosphite (50.82 g, 0.1 mol, 95% purity) and 1.3.5-tricyanomethylhexahydro-3.5-triazine are mixed (6.81 g, 0.0333 mol), stir and heat to 100 ° C. After 15 minutes all of the hexahydrotriazine has been in the Dissolved phosphite. A sample shows that the reaction has proceeded to about $ 50. The mixture is heated for a further 15 minutes, hydrolyzed and then processed as described in Example 46. Analysis of the first crop (10.1 g dry) gives pure N-phosphonomethylglycine. No other yields can be obtained in pure form. The K.M.R. analysis the mother liquor shows a complex mixture.

Example 48

Mix di-p-chlorophenyl phosphite (19.6 g, 0.05 mol, 78%

809824/061 7

Purity) and 1.3.5-tricyanomethyl-hexahydro-1. $.!? - triazine (3 »41 6» 0.0167 mol) at room temperature (not exothermic). Heating the slurry 20 minutes 100 ⁰ C (KMR sample shows that the reaction is complete). After processing and hydrolysis procedures as described in Example 46, 4.8 g of N-phosphonomethylglycine is isolated (initial yield $ 56). The second crop, 0.44 g, is NH ^ Cl. The CMR analysis of the mother liquors is very difficult and shows that the hydrolysis conditions were too harsh to achieve optimal results.

Example 49

The tetramethylammonium hydroxide salt of N-phosphonomethylglycine is prepared by dissolving 6 g (0.02 mol) of OO-diphenyl-N-phosphonmethylglycine nitrile in 30 ml of water containing 14.5 g (0.08 mol) of tetramethylammonium hydroxide and then the mixture was heated for 16 hours at 10O ⁰ C until the KMRAnalyse shows that the entire glycine nitrile is converted to the Tetramethylammoniumhydroxidsalz N-phosphonomethylglycine. The solution is cooled, extracted with methylene chloride in order to remove the phenol, then concentrated under vacuum and a mixture of tetramethylammonium salts is obtained. The salt product obtained is dissolved in 20 ml of water and placed in an ion exchange column packed with a commercially available cation exchange resin ("Dowex 50") and eluted with water at room temperature. The eluate is concentrated and 2.4 g of beige colored crystalline solid are obtained (71% yield). The crystalline solid was found to be essentially pure N-phosphonomethylglycine by KMR analysis.

809824/0617

Example 50

The disodium salt of N-phosphonomethylglycine is prepared by mixing 6.04 g (0.02 mol) of OO-diphenyl-N-phosphonomethylglycine nitrile with 50 ml of water containing 3.2 g (0.06 mol) of sodium hydroxide and then the mixture is ^{heated at 70 °} C. for one hour while stirring continuously, at which point the KMH analysis of the reaction mixture shows that about 1/3 of the reaction mixture has been converted into the disodium salt. The reaction is continued for a further 4 hours at 70 ° C. and a 40% conversion to the disodium salt is determined by means of CMR analysis. By heating for a further 15 hours at 70 ^° C., an 80 to 90 degree conversion to the disodium salt is obtained. The reaction product is concentrated and a dark amber-colored glassy solid is obtained. N-phosphonomethylglycine is prepared by dissolving the solid in water and feeding the solution to an ion exchange column which is packed with a commercially available cation exchange resin ("Dowex 50"). The column is eluted with water at room temperature. The eluate is concentrated and 2.7 g (80% yield) of light-colored solid are obtained and it is determined by means of CMR spectral analysis that it is essentially pure W-phosphonomethylglycine.

The finding that O-aryl-N-phosphonmethylglycine nitrile in high yields from the reaction of a diaryl phosphite with i ^ - ^ - tricyanomethyl-hexahydro-i ^^ - triazine without a catalyst can be prepared is completely unexpected in view of the disclosures of TT.S. Patent 3,923,877. Es

809824/06 1 7

the use of an acidic catalyst, such as a hydrogen halide, a Lewis acid, a carboxylic acid anhydride or an acid halide is required there. According to the only example in this regard, a calculated yield of only 6.12% diethyl ester of N-phosphonmethylprlycinnitrile is obtained by reacting a solution of diethyl phosphite and 1 x 3 x 5-tricyanomethyl-hexahydro-i ^. ^ - triazine saturated with hydrogen chloride obtain. In contrast to such low yields, yields of diaryl esters of N-phosphonomethylglycine nitrile of about 45 to 10,056 can be obtained by the process disclosed here. Surprisingly, if the example of US Pat. No. 3,923,877 is carried out with stoichiometric amounts of the reactants and without the hydrogen chloride catalyst, no reaction can be found when the process is carried out at 40 ^° C. or even after a reaction time of 100 ^° C. for 24 hours duroh leads. The same negative result is obtained if the example is carried out as above (without acid catalyst), if acetonitrile is used as the solvent for the reactants and the reaction is carried out ^{at 100 ° C. for 24 hours.} In a further experiment, corresponding to the experimental example given above, but using chloroform as the solvent for the reactants, no reaction at 40 ^° C. or at 100 ^° C. can be detected either.

When using an acid catalyst of the type described in U.S. Patent 3,923,877 in the reaction of a diaryl phosphite, i.e. Diphenylphosphb.it, with 1.3.5-tricyanomethyl-hexahydro-1.3.5-triazine in the presence of hydrogen chloride after

809824/0617

In the process described in the Bezufsbeispiel used, one obtains only a yield of 15 $ of the desired diester compared to the yield of 75% obtained in Example 5 Diaryl phosphites with 1 ^^
triazine.

Example 51

The post-emergence herbicidal effectiveness of the various compounds this invention is demonstrated below. The active ingredients are sprayed onto 14 to 21 day old plantings applied to the different plant species. The brewing agent, a water or organic solvent-water solution, which contains the active ingredient and a surfactant (35 parts butylamine salt of dodecylbenzenesulfonic acid and 65 parts of tall oil condensed with ethylene oxide in a ratio of 11 moles of ethylene oxide to 1 mole tall oil) is placed on the plants in different sowing pans with different application ratios (kg per ha) of active ingredient applied. The treated plants are placed in a greenhouse and the effects are observed and arrested after about 2 or about 4 weeks. The values are given in Tables I and II.

809824/0617

In Tables I and II, the following index is used for post-emergence herbicidal effectiveness:

Addressing the plants index 0-24 # damage 0 25-4-9 # damage 1 5O-74 # damage 2 75-99 # damage 3 All killed

Species absent

at the time of treatment

In the tables, WnB gives the number of weeks after treatment and the treated plant species is specified according to the following key:

A - Thistle B - Burdock

C - Cissampelos pareira D - Morning glory E - White goose foot F - water pepper G - Cyperus H - common couch grass I - Sorghum halepse J - Bronus tectorum

K - chicken millet L - soybeans

M - sugar beet N - wheat

0 - R _e is

P - sorghum

Q - Bindweed knotweed R - "Hemp Sesbania" (Canabis) S - Panicum Spp T - blood millet

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Table I. Connection WnB kg / ha

4th 11.2 4th 5.6 4th 11.2 4th 5.6 4th 11.2 4th 5.6 4th 11.2 4th 5.6 4th 11.2 4th 4.48 4th 11.2 4th 5.6 4th 11.2 4th 5.6

Planter species

A. B. C. D. E. F. G H I. J K 3 4th 4th 1 4th 4 · 3 2 3 3 3 3 3 4th 2 4th 4th 2 1 1 2 3 4th 4th 3 2 4th 3 3 2 2 3 4th 3 3 3 2 4th 4th 2 1 1 4th 3 3 3 3 3 4th 4th 2 3 3 2 3 3 4th 1 2 4th 4th 2 2 2 1 2 4th 4th 3 4th 4th 4th 2 2 2 4th 3 4th 3 3 2 3 4th 2 1 1 3 4th 2 4th 3 4th 4th 3 2 2 3 3 4th 3 4th 3 3 4th 4th 2 1 2 1 3 3 4th 4th 3 4th 4th 1 2 2 2 3 2 4th 1 3 4th 4th 1 1 3 1 3 2 3 2 1 4th 3 2 1 4th 2 2 3 2 2 1 3 3 1 1 4th 1 3

Table I (continued)

OD O CO QO KJ

VMB kK / ha Ά B. C. D. Plant species F. G H I. J K link 4th 11.2 2 4th 2 1 E. 4th 2 3 4th 1 3 8th 4th 5.6 3 3 3 2 4th 4th 2 1 4th 1 3 4th 11.2 4th 4th 4th 3 4th 4th 1 3 2 3 4th 9 4th 5.6 4th 4th 4th 2 4th 4th 1 3 2 3 4th 4th 11.2 4th 4th 3 3 4th 4th 2 3 3 4th 4th 10 4th 5.6 3 3 3 2 4th 4th 1 2 1 3 4th 4th 11.2 4th 4th 4th 4th 4th 4th 3 3 2 3 4th 11 4th 5.6 4th 4th 4th 2 4th 4th 2 3 1 3 4th 4th 11.2 4th 4th 3 2 4th 4th 2 3 4th 2 4th 12th 4th 5.6 4th 4th 3 2 4th 4th 3 3 3 1 4th 4th 11.2 2 * 4th 4th 4th 3 3 3 4th 3 4th 13th 4th 4.48 3 * 3 3 4th 2 3 3 3 3 3 4th 11.2 4th 4th 4th 3 4th 4th 4th 2 2 3 4th 14th 4th 5.6 3 3 3 2 4th 4th 1 1 2 3 4th 4th 11.2 4th 4th 4th 2 4th 4th 4th 3 3 4th 4th 15th 4th 5.6 3 4th 0 1 4th 4th 2 2 4th 3 3 3

Table I (continued) Plant species

O CO OO

link WOB kg / ha A. B. C. D. E. F. G H I. J K 16 4th 11.2 4th 4th 3 1 4th 4th 3 4th 4th 2 4th 4th 5.6 4th 4th 2 1 4th 4th 2 3 4th 0 3 17th 4th 11.2 4th 4th 4th 3 4th 4th 3 3 4th 3 4th 4th 5.6 3 4th 4th 3 4th 4th 2 2 4th 3 4th 18th 4th 11.2 3 3 3 2 4th 4th 2 2 3 2 3 4th 5.6 4th 3 2 2 4th 4th 2 1 3 1 3 19th 4th 11.2 4th 4th 4th 2 2 2 3 1 3 '0 2 4th 5.6 2 4th 1 1 2 2 3 1 1 0 2 20th 4th 11.2 3 4th 2 2 3 4th 2 3 3 2 3 4th 5.6 3 3 1 2 4th 4th 2 1 3 2 3 21 4th 11.2 4th 4th 3 2 4th 4th 2 3 4th 3 3 4th 5.6 2 3 3 2 4th 4th 2 2 2 3 3 22nd 4th 11.2 4th 4th 4th 3 4th 4th 4th 4th 4th 4th 4th 4th 5.6 3 3 4th 2 4th 4th 3 3 3 2 4th 23 4th 11.2 4th 4th 4th 4th 4th 4th 4th 4th 2 4th 4th

- iar-

N -P Φ m • ρ U ο tu

(O Φ • Η

(0 β Φ

σ) γΗ «Μ

• η »·» «Η

rH CM f »t-l

ρ * η η t-i! -ι cn

«Ν f-4

«Μ C>

• Η O

<Ν «Η

Ι »> Ol P *

(M

cn M

τ ^ r * <w

cn ^ *

ro cn

ΓΜ VO

in rH in

m f-i m r-t in

t4 ti

• rl

in VO Ι 00 ο « O N (M Ο » (N Γ4 «Η

809824/0617

Table I (continued)

Plant Oezies

O CO OO

Connection WnB kg / ha

31

32

33

35

36

37

38

4th 11.2 4th 5.6 4th 11.2 4th 5.6 4th 11.2 4th 5.6 4th 11.2 4th 5.6 4th 11.2 4th 5.6 4th 11.2 4th 5.6 4th 11.2 4th 5.6 2 11.2 2 5.6

A. B. C. D. E. F. G H I. J X 2 4th 3 4th 4th 4th 1 2 2 2 3 2 3 2 2 3 3 1 O 4th 1 2 4th 4th 4th 4th 4th 4th 2 2 4th 4th 4th 2 4th 4th 4th 4th 4 · 2 2 2 4th 4th 4th 4th 4th 4th 4th 3 4th 4th 3 4th 4th * 4th 2 4th 4th 3 3 4th 3 4th 4th 4th "4 4th 4th 4th 2 3 3 3 4th 2 3 4th 2 4th 3 2 3 3 3 3 4th 4th 3 3 4th 4th 2 3 "3 3 4th 4th 3 4th 2 4th 4th 2 3 3 3 3 3 4th 4th 3 4th 4th 3 3 4th 4th 4th 4th 4th 2 3 4th 3 2 3 4th 2 3 4th 4th 4th 3 4th 4th 3 3 4th 4th 4th 4th 4th 4th 3 4th 4th 3 3 3 3 4th O 1 1 O O O O O 3 O O O 1 O O O O O O 1 O O

Table I (continued)

WnB kg / ha λ B. C. D. Plant species F. G H I. J K link 4th 11.2 2 4th 3 1 E. 4th 3 3 4th 2 3 39 4th 5.6 2 3 2 1 4th 2 3 2 4th 2 3 4th 11.2 1 2 1 1 2 1 1 1 2 0 2 40 4th 11.2 4th 4th 4th 4th 4th 3 3 4th 4th 3 4th 42 4th 5.6 4th 3 2 3 4th 4th 3 2 4th 1 4th 4th

a> ο co OO NJ

O CJ)

₁
V

K> cn σ>

CJ

S <; | rorOrHrO (Moro (MrHfO

(Ol (M (M rH ^ O «if CO ΓΟ

CM rH O «Ό

O fO (M rH

O Π Cl ii O

rt O

UlM (MrHfO (M O "* (M O

ro rH

Π O

ω .ω
co

CO α> • Η N O) P ω β Q) IS) C CD rH

i-t

rH O ro rH O (M O «1 · (M O

Oil

O (M rH rH (M rH rH

rH O "ί-

WIfO (MrHfO (MrHrO (M Ptl CO (M rH ro rH ι

OJ ro r4 1-4 η rt ι (M (M

Γ0 (M i-H

fO (MrH> * (M (M

ro (M rH ro ro

O <* t -rHO

O ΓΜ

SI (MrHrHfOi-HOfOrHO

«* Ro ro

ro i-l

O fO rH O

CM rH <*

CD

PQl

CMOO (MOO (MOO (MOOOO (MOI VDrH (MVDrH (MVDrH (NVDrHrM ^ rH (M

IA rt IT) rt ID rl ΙΛι-Η f ii

* ■ «r

«* CM ^ in

809824/0617

Table II (continued)

Plant species

Connection WnB kg / ha

O (O OO

7 8 9

10

13th

4th 1.12 4th .28 4th .056 4th 1.12 4th 1.12 4th 5.6 4th 1.12 4th .28 4th 5.6 4th 1.12 4th .28 4th 4.48 4th 1.12 4th .224

L 2 1 1 O 1 4 2 1 3 2 1 3 1 1

1 1 O O 1 3 2 1 3 3 1 3 2 O

1 1 O O 1 2 2 1 2 2 1 3 1 O

O 3 1 O O 1 3 3 1 4 3 1 3 2 2

P 4 3 1 1 2 3 3 2 4 3 1 3 2 2

Ä
ι

1
O
O
1
3
1
1
4th
2
2
3
2
1

D.
2

1
4th

1
*

2
2
4th

3
1
3
2

R.
4th

1
O
O
4th
4th
2
4th
2
1
3
2
1

E.
4th
2
O
O
2
4th
4th
2
4th
4th
4th
4th
3
3

P.
4th

1
O
3
4th
4th
2
4th
4th
2
3
1
1

C.
4th

O
O
2
4th
4th
2
4th
2
2
4th
1
1

J 4

1 O O 1 3 2 1 4 2 O 3 2 1

S 4 3 1 O O 4 4 2 4 4 2 4 4 4

K 4 2

1 O 1 4 3 2 4 3 1 3 3 2

T 4 3 2 O 4 4 4 2 4 4 2 4 3 3

HI

η ro ΓΜ ο

ro f-l οι

(Al τ »cm

CM CM

CMiHfOCNIOrHi-l «*** CMr-lrOCM '^ COr-l'irM

ο ο η

CO r-l O CO ΓΜ

St.

η «s γμ

ω cd

• Η Cs! ω P ω

C co

Kl «* ^ r 0 cm

Ql ΓΜ ΓΜ ι-Ι CN Ol Ή O O ιΗ

«Η ΓΜ ΓΜ Ο

ΓΜ ΓΜ ι-Ι CM

ΓΟ

ΓΜ

O ΓΜ

O f-l

O ΓΜ r-l (N

Ol ΓΟ ΓΜ O CM

Zl η W ο H

SI M CM O r-l

Pl ΓΟ ΓΜ r-l ΓΜ

ΓΜ «Η ΓΜ ΓΜ

ro r-l ν ΓΜ

• Η O

• Η r-l ΓΟ

O rH O f-l ΓΜ

ο η

rH O ΓΜ ■ -!

r-l ΓΜ ΓΜ

ΓΜ rH

CO

Λ!

3 τί CS ■ Η

ΓΜΓΜ ΓΜΟΟ CMOO ΓΜ CMOD CM

IfI r-t r ~ l IfI r-l ΙΛ r-l ΙΛ r-l LT) r-l 1/1 ιΗ

CO CTl

CM

809824/061 7

-J?

ro rH «» ro cm

CM rH ¹ W CM rH ro

οι * »» η cm

col

Ul

rorHororHOrorHO

■ »CMrHrOCMrH ^ iMrHxrrO

O «Ο

co ■ ρ U ο

oil

Ol rH O rH

Ol fl H «

CM CM V CM _M

CM rH ^ CM CM

rH O CM rH, _ |

^ • CMrH «* CMrHrOCMrHrOCM CM

^ i ro r ^ ^ * l * cm ^ i * ro cm ^ J ¹ ro cm mcMo ^ rorHTroo ^ ro-i

CM r-4

O (M rHO

CM rH i-t rO

StrHCMrOrHOCMrH

CM rH ro rH rH ro CM CM

O (M rH O 4

O ro rH O ro

CM rH Γ0

«* CM ^

CM CM

VO rH VO rH

CO CM C0 CM CO

(MtOrHCMtOrH (MVD

CM OO CM <o

rH CM VO rH CM

in rH (Π IT! rH

Λ rH

in

in

ti • rl X>

(-I

Ο)

rH CM

O"

CM

ro CM (M

in

CM

VD (M

809824/0617

Table II (continued)

link t 28 WnB kg / ha 27 4th 5.6 4th 1.12 29 4th .28 4th 5.6 30th 4th 1.12 4th .28 4th 5.5 31 4th 1.12 4th .28 4th 5.6 4th 1.12 4th .28 4th 5.6 4th 1.12 4th .28

Plant species

LMNOPBQDREFC 4
2
2
3
2
1
4th
2
1
4th
1
1
3
2
1

4th
1
O
4th
1
O
4th
2
O
4th
1
1
3
3
O

1
O
3
1
1
4th
1
1
2
1
1
2
1
O

4th
1
O
3
2
1
3
2
1
4th
1
1
2
1
1

4th
3
2
4th
3
2
3
3
2
4th
2
2
3
4th
2

2
1
3
2
2
4th
2
1
4th
1
1
3
4th
1

2
2

1
2

1
1
1
1
1
4th
1
1
1
2
1

4 2 1 4 2 1 4 2 1 4 2 1 3 2 1

3 2 1 3 2 2 3 2 2 4 2 2 3 2 1

4 3 2 4 3 2 4 4 2 4 4 2 4 4 3

4 3 2 4 3 2 4 4 2 4 4 2 4 4 2

4 2

2 4 2 2 4 2 1 4 4 2 4 4 1

4 2

1 4 2 1 4 2 O 4 1 O 4 3 1

4 4 2 4 4 2 4 3 2 4 2 2 4 3 1

4 3 2 4 3 2 4 3 2 4 2 2 4 3 1

4 4 2 4 3 2 4 4 2 4 4 2 4 3 2

Table II (continued)

O CO CO

link WnB 5.6 32 4th 1.12 » 4th .28 4th 5.6 33 4th 1.12 4th .28 4th 5.6 34 4th 1.12 4th .28 4th 5.6 35 4th 1.12 4th .28 2 5.6 36 4th 1.12 4th .28 4th

M. N O Plant species 3 Q D. R. E. F. C. J S. K T ι L. 4th 3 4th P. 4th 2 3 4th 4th 4th 4th 4th 4th 4th 4th 4th 1 1 1 4th 3 1 1 4th 3 2 3 1 2 3 3 2 1 O 1 2 1 O O • 1 1 1 1 O 1 2 2 1 3 2 4th 1 3 1 2 1 4th 4th 3 4th 4th 4th 3 2 2 1 1 4th 2 1 1 O 2 1 1 1 1 1 2 O 1 O O 4th 1 O 1 O 1 1 O O O O 2 1 3 3 4th 2 4th 2 2 2 4th 2 1 3 4th 4th 4th to 3 1
* 1
Λ O 4th 3 1 1 1 4th 2 1
Λ 2
Λ 2
τ 2 2 • ο
cn 2
1 2 U
1 4th 4th 3 2 2 2 4th 4th U
2 U
2 χ
4th JL
3 1
4th σ>
CO χ
2 2 1 1 4th 2 1 1 1 3 2 1 1 2 2 2 1 O O O 2 O O O O O O O O 1 O O 1 2 3 3 1 3 3 2 2 3 4th 3 3 3 3 4th 3 1 1 1 4th 2 1 2 1 2 1 1 1 1 2 2 1 O O 1 2 1 O 1 1 1 O O 1 O O 1 1 1

rH ρ

tsl -P Q) ω -ρ Jh ο

Q) rH H

Q) • Η N Q)

0)

co

«Η Ρ4

rH T CM rH

O Ti rH rH

r-l · ») · ΓΛ i-H

r-l f) C) rH

O T rH

rH CM rH

O · «* rH ο

PQ

6d

•H

rQ

Q)

CM 00 CM 00 CM.

Vor-ICMvorHCMVorHCM IArH UIr-I in - <

CM

80982Λ / 0617

Example 52

The pre-emergence herbicidal effectiveness of the various compounds this invention is demonstrated below. Good quality planting soil is placed in aluminum pans and placed on top a depth of 9.5 to 12.7 mm, each pan compacted. A predetermined number of seeds or reproductive shoots each of the different plant species is placed on top of the bottom of each pan and then pressed in. The herbicidal preparations are made using the active ingredients of this invention (as described in Example 51) used to mix them with the top layer of the soil or to bring them into the top layer of the soil.

In this procedure, the soil is used to cover the seedlings or the shoot is required, weighed and with a herbicidal preparation that contains the »known amount of active ingredient, mixed. The pans are then filled with the mixture and leveled. Water is supplied in such a way that the Soil in the pans Moisture through openings in the bottom of the Pans open. The pans containing seeds and shoots are placed on a wet sand bath and held for about two weeks kept under the ordinary conditions of sunlight and watering. After this time the number of emerged plants of each species and compared with an untreated control.

Used for the representation of the pre-emergence herbicidal effectiveness the following index, which indicates the average percentage of control of the species achieved.

809824/0617

° / o control index

0-25 # 0

26 - 50 % 1

51 - 75 % 2

76 - 100% 5

Plant species are in Table III with the same Prepare letters as in example 51.

809824/0617

Table III

link kg / ha 1 11.2 2 11.2 3 11.2 4th 11.2 5 11.2 6th 11.2 7th 11.2 8th 11.2 9 11.2 10 11.2 11 11.2 12th 11.2 13th 11.2 14th 11.2 15th 11.2 16 11.2

B. C. D. E. Plant species G H I. J K A. O O O O F. O O O O O 3 O O O O O f-l O 3 O O 2 O O O 1 O 1 1 O O O 3 O O O O O O O O O O 2 O 3 O 1 O O 1 2 1 O 3 O O O O O O O O O O 1 O O O O O O O O O O 1 O O O O O O O O O 1 O O O O O 1 1 O O O 3 O O O O O O O O O O 3 O O O O O O O O O O 3 O O O O O O O O O O r-l O O 3 3 O O O 1 O O 2 O O O 3 O O O 1 O 1 3 O O O O O O O O O O O O O O O O O O O O O O O

$ 6

frSloooooooooooooooo t-jloooooooooooooooo

φ P

MloOOOOOOOOOOOOrHOO

οοοοΟιΗΟίΗοσοοο

OloOOOOtHOOOOrHOOOOO

CU

«T-4 P-

foloOOOOOf-IOOOOOOOOO

WloooooomooooooGoo QloOOOOOOOOOi-IOO

O O

oloooooooooooooooo (Qloooooooooooooooo

(0

Hi

X)

• Η

fMrMrMfMfMrMCN fM · ΓΜ CN ro

809824/0617

Table ITI ( Continued)

link kp; / ha 33 11.2 34 11.2 35 11.2 36 11.2 37 11.2 38 11.2 39 11.2 40 11.2 42 11.2

B. C. D. Plant Oez F. G ies I_ J K A. 0 0 0 E. 0 0 H 1 0 0 3 0 0 1 0 0 0 0 1 0 0 3 0 0 0 0 0 2 0 3 0 0 3 0 0 0 0 0 1 2 0 0 0 3 0 0 0 0 0 0 1 0 0 0 3 0 0 0 1 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 1 0 0 0 3 0 0

6 *

From the test results presented in Tables T and TT It can be seen that the Hachauflauf herbicidal effectiveness of the compounds of this invention are for the most part more general Nature is. However, there is some selectivity in certain specific cases. On the other hand, the research results show the casserole herbicidal activity clearly shows the selective action against field thistle and few others Species. In this regard it should be pointed out that each individual species of oxy-gen investigations is a typical one Belongs to a known family of plant species.

The herbicidal preparations, including concentrates, that require dilution before application to the plants Make this invention contain 5 to 95 parts by weight at least an active ingredient and 5 to 95 parts by weight of adjuvant in liquid or solid form, for example about 0.25 to 25 parts by weight of hardening agent, about 0.25 to 25 parts by weight of dispersant and 4.5 to about 9.5 parts by weight inert liquid extender, for example water, all parts being based on the weight of the total preparation. If necessary, can about 0.1 to 2.0 parts by weight of inert liquid extender can be replaced by a corrosion inhibitor or an antifoam agent or both. The preparations are produced by combining the active ingredient with an adjuvant, including diluents, extenders, carriers and conditioning agents mixes to form preparations to form finely divided particulate solids, pellets, solutions, dispersions or emulsions. The effective

809824/0617

ORIGINAL INSPECTED

substance with an adjuvant such as a finely divided solid, a liquid of organic origin, water, a wetting agent, a dispersing agent, an emulsifying agent or any combination of these possibilities can be used. From the point of view of economy and practicality water is the preferred diluent.

The herbicidal preparations of this invention, in particular the liquids and soluble powders, preferably contain as a conditioning agent one or more surface-active agents in sufficient quantities to make a given preparation to make them easily dispersible in water or in oil. The incorporation of a surfactant into the preparations significantly increases their efficiency. Included in the term "surfactant" as used herein wetting agents, dispersants, suspending agents and emulsifying agents are included. It can be anionic, cationic and non-ionic agents can be used without difficulty.

Preferred wetting agents are alkylbenzene and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long-chain acid esters of sodium isothionate, esters of sodium sulf osuccinate, sulfated or sulfonated fatty acid esters of petroleum sulfonates, sulfonated vegetable oils, polyoxyethylene derivatives of phenols and alkylphenols (in particular isooctylphenol and nonylphenol) and polyoxyethylene derivatives of mono-higher fatty acid esters of hexitol anhydrides (for example sorbitan). Preferred dispersants are methyl cellulose, Polyvinyl alcohol, sodium lignin, sulfonates, polymers

809824/0617

Alkyl naphthalene sulfonates, sodium naphthalene sulfonate, polymethyl enbisnaphthalene sulfonate and; sodium-N-methyl-N- (long-chain Acid) taurate.

Water-dispersible powder preparations can be produced in that they contain one or more active ingredients, an inert solid extender and one or more wetting and / or dispersing agents. The inert solid extenders are usually of mineral origin such as natural clays, diatomaceous earth and synthetic minerals of silica and the like. Examples of such extenders include kaolinites, attapulgite clay, and synthetic magnesium silicate. The water-dispersible powders of this invention usually contain about 5 to about 95 parts by weight of active ingredient, about 0.25 to 25 parts by weight of wetting agent, about 0.25 to 25 parts by weight of dispersant, and 4.5 to about 9.5 parts by weight .Parts of inert solid extender, all parts being based on the weight of the total preparation. If necessary 0.1 to 2.0 pbw _e ile solid inert extender can be replaced by a corrosion inhibitor or antifoaming agent or both approximately.

Aqueous suspensions can be prepared by an aqueous slurry of water-insoluble active ingredient in the presence of dispersants and mixed together for grinding brings to this a concentrated slurry of finely divided particles. The concentrated aqueous suspension obtained is characterized by an extremely small particle size marked so that after dilution and spraying

809824/06 17

the cover is very uniform and contains the suspension usually 5 to about 95 parts by weight of active ingredient, about 0.25 to 25 parts by weight of dispersant and about 4.5 to 9.5 parts by weight Water.

Emulsifiable oils are usually solutions of the active ingredient in water-immiscible or partially water-immiscible Solvents together with a surface active agent. Suitable solvents for the active ingredient of this invention include hydrocarbons and water immiscible Ethers, esters or ketones. The emulsifiable oil preparations usually contain about 5 to 95 parts by weight of active ingredient, about 1 to 50 parts of surfactant and about 4 to 9 parts Solvent, all parts being parts by weight and relating to the total weight of the emulsifiable oil.

Although the preparations of this invention also contain other additives, for example fertilizers, phytotoxic agents and plant growth regulators, pesticides and the like may contain as adjuvants or together with any of the adjuvants described above, it is preferred to use the preparations of this invention alone, optionally with subsequent treatments with others to use phytotoxic agents, fertilizers and the like to achieve maximum effect. For example can field a preparation of this invention either before or after fertilizing with artificial fertilizers Application of other phytotoxic agents and the like. The preparations of this invention can also

809824/0617

mixed with other materials, for example with Fertilizers, other phytotoxic agents, etc. and they can be used in a single application. About the chemical compounds that work together with the active ingredients suitable for this invention either simultaneously or in succession include, for example, triazines, ureas, carbamates, Acetamides, acetanilides, uracils, acetic acids, phenols, thiocarbamates, triazoles, benzoic acids, nitriles and the like.

Fertilizers that are suitable together with the active ingredients include, for example, ammonium nitrate, urea and potash and superphosphate.

When operating in accordance with the present invention, effective amounts of the glycine nitriles are on or on the plants applied to the soil containing the plants or in aquatic media in any suitable manner. The application of liquid and particulate solid preparations Planting or soil can be done using suitable methods, for example with powder dusters, tree and hand sprayers and spray atomizers. The preparations can also be taken from airplanes as dust or as spray because of them Efficacy can be drained at low dosages. The use of herbicidal preparations over aquatic Planting is usually carried out in such a way that adding the preparations to aquatic media in the area where control of the aquatic plants is desired.

809824/06 1 7

The application of an effective amount of the preparations of this invention to the plants is essential and critical for practicing the present invention. The exact amount of active ingredient intended for use depends on the response of the desired plant, as well as other factors such as the plant species and its stage of development, the amount of rainfall, as well as the specifically used glycine. When treating the leaves to control vegetative growth the active ingredients are used in amounts of about 0.112 to about 22.4 or more kg / ha. Can be used for pre-emergence treatments the application rate in the range from about 0.56 to about 22, more stupidly more kg / ha. For the purpose of controlling aquatic Plants can contain the active ingredients in amounts of about 0.01 parts (ppm) to about 1000 ppm, based on the aquatic Medium can be used. An effective amount for phytotoxic or herbicidal control is that amount that is required for total or selective control, i.e. a phytotoxic or herbicidal amount. It is believed that those skilled in the art from the teachings of this specification, including the examples, the appropriate ratios of use can be readily derived can.

Although the invention is in light of specific modifications has been described, the details given here are not intended to limit the scope of the invention.

-Patent claims- 809824/0617

Claims (1)

Patent claims: (Aryl X -O) ₀ , - P - Ch ₀ - N - CH- - CN R (I), 31 ^ "" D ι c c Λ wherein aryl is phenyl, naphthobyl and / or biphenylyl, leather substituent X on the aryl group halogen, alkyl with 1 to 4 carbon atoms, alkoxy and alkylthio with 1 to 3 carbon atoms, alkoxycarbonyl with 2 to 3 carbon atoms, methylenedioxy, cyano, trifluoromethyl and / or nitro, Z oxygen or sulfur, a an integer from O to 3 _? b is an integer from 0 to 1. R is a strong acid that forms a salt with the amino group can, and χ = O ode "" 1, with the proviso that χ = O be must if b = 1. 2. Compound according to claim 1, characterized in that a = O. 3. A compound according to claim 1, characterized in that χ = Λ and b = O. 4. A compound according to claim 1, characterized in that x = 0 and b = 1. 5. A compound according to claim 1, characterized that b and χ = 0. 809824/0817 original inspected 6. A compound according to claim 1, characterized in that the strong acid has a pKa-V / ert in water of 2.5 or less. 7. A compound according to claim 1, characterized in that the aryl group is phenyl and Z is oxygen
is. 8. A compound according to claim 7, characterized that χ = 1 and b = O. 9. A compound according to claim 7, characterized in that x = 0 and b = 1. 10. A compound according to claim 7, characterized in that b and χ = 0. 11. A compound according to claim 1, characterized in that it is OO-diphenyl-N-phosphonmethylglycine nitrile, 0,0-di- (p-methoxyphenyl) -N-phosphonmethylglycinnitrile, 0,0-di- (p-fluorophenyl) -N -phosphonmethylglycine nitrile, O-phenyl-N-phosphonmethylglycine nitrile, om-nitrophenyl-N-phosphonmethylglycine nitrile, Oo-chlorophenyl-N-phosphonmethylglycine nitrile, the hydrogen bromide salt of 0.0-diphenyl-N-phosphonomethylglycine nitrile
of OO-diphenyl-N-phosphonmethylglycine nitrile or methanesulphonic acid salt of OO-diphenyl-N-phosphonmethylglycine nitrile
is. 809824/061 7 1?. I erbicidal preparation, characterized in that they contain a herbicidally effective amount of a compound according to claim 1 and an inert extender or diluent contains. 13. Herbicidal preparation, characterized in that it contains a herbicidally effective amount of a A compound according to claim 2 and an inert extender or diluent contains. 14. Herbicidal preparation, characterized that they contain a herbicidally effective amount of a compound according to claim 3 and an inert extender or diluent contains. 15 · Herbicidal preparation, characterized that they are a herbicidally effective lienge of a compound according to claim 4 and an inert extender or diluent contains. Ib. Herbicidal preparation, characterized in that it contains a herbicidally effective amount of a A compound according to claim 5 and an inert extender or diluent contains. 17. Herbicidal preparation, characterized in that it contains a herbicidally effective amount of a A compound as claimed in claim 6 and an inert extender or diluent contains. 809824/0617 - «τ- 275Ί63Ϊ 1ο. Herbicidal preparation, characterized in that it contains a herbicidally effective HeN ^ e a connector ~ em according to claim 7 and an inert stretch or Vercrir rpm ^r "G ⁿⁱ " ttol. 1Q. herbicide Zubereitunn, characterized <~ Eke η η z ei levels that Rie a herbicidally effective Henre a connecting ··· ^ e measured to claim 8 and ttel contains an inert stretching or VerprT ^. 20. herbicidal preparation, thereby r eke η η - ζ ρ ; ': c ^] · η ο t, that never contains a herbicidally effective Γ'en re a Vc ^ h- ⁵ ndunr- ^r pin according to claim 9 and an inert extender or diluent. 21. herbicide Zubered.tunr, thereby r-ekennzei chnet that they are a herbicidally effective Henpre one Compound according to claim 10 and an inert stretching or Ver thinunxrs-ni.i ttel contains. 22. l.orbicidp preparation, characterized in re that they are a herbicidally effective menu A compound according to claim 11 and an inert extender or diluent contains. 2 ?. herbicidal process, characterized by r- e k e η η, that one is a plant or a plant growth medium with a herbicidally active ingredient a? · connection Claim 1 in account!: T brings. 80982Λ / 06 1 7 ORlGiNAL INSPECTED COPY 24. Herbicides demonstrations, characterized by. ^ E k e η π, that one can grow a plant or a plant medium with an effective amount of a compound according to Brings claim 2 in contact. 25. Herbicides method, characterized that one is a plant or a plant growth medium with a herbicidally effective l-ienge of a compound ~ according to claim 3 brings in contact. 26. Herbicides method, characterized that one is a plant or a plant growth medium with a herbicidally effective amount of a compound brings according to claim 4 in Kentakt. 27. Herbicides process, characterized in that one is a plant or a plant growth medium with a herbicidally effective amount of a compound according to claim S in contact. 28. Herbicides method, characterized that a plant or a plant growth medium with a herbicidally effective amount of a compound according to claim 6 brings into contact. 29. Herbicidal process, characterized in that a plant or a plant growth medium is brought into contact with a herbicidally effective amount of a compound according to claim 7. _Ληον 80982Α / 06Ϊ7 ^C0PY 30. Herbicidal method, which draws r e k e η η that one is a plant or a plant growth medium with a herbicidally effective amount of a compound according to claim 5 in contact. 31. Herbicides method, characterized in that one is a plant or a plant growth medium with a herbicidally effective amount of a compound according to claim ° in contact. 32. Herbicides method, characterized that you can a plant or a plant growth medium with a herbicid. effective amount of a compound according to claim 10 brings into contact. 33 · Herbicides method, characterized that a plant or a plant growth medium with a herbicidally effective amount of a compound according to claim 11 brings into contact. 34. Process for the preparation of a diester of the general formula Aryl XO. ZH ^a \ "' Aryl X -0 cL wherein aryl is phenyl, naphthyl and / or biphenylyl, any substituent X on the aryl group halogen, alkyl with 1 to 4 carbon 809824/0617 lenstoffntomen, alkoxy and alkylthio with 1 to 3 carbon atoms, alkorvcarbonyl with ? until J is carbon atoms, methylenedioxy, cyano, trifluoromethyl and / or nitro, Z is oxygen or sulfur and a is an additional number from 0 to 3, in that one can denote a diaryl>hosr> hit the general formula Il (Aryl X ₃ -O) ₂ - P-II where X, Z and a have the meaning defined above and 1.3 · S-tricyanomethyl-hexahydro-1.3 · 5-triazine without an i-iän ^ e- katalyea'cor implements. 35 · The method r ^ ^ emäli claim 3 »characterized in that one carries out the reaction at a temperature from 25 to 110 ⁰ C. 36. The method according to claim 35 »characterized that the diaryl phosphite and the triazine are reacted together in the presence of an inert solvent. 37. The method according to claim 34, characterized that the diaryl phosphite is diphenyl phosphite, di- (m-chlorophenyl) phosphite, di- (p-methoxyphenyl) -nhosDhit, Di- (3.4 ~ dimethylphenyl) -phosphite or Dj- (p-fluorophenyl) -phosphite begins. 809824/0617 3ü. Process for the preparation of a salt of the general formula Z H It I (Aryl XO) ₀ - P-CH ₀ - Ν®- CH ₀ - CN OL C- C- ι £ 1 wherein aryl, X, a and Z have the same meanings as in claim 5 * f and R- is the anion of a strong acid, characterized in that a diester of the general formula Z H Il I (Aryl X _a -O) ₂ - P - CH ₂ - N - CH ₂ - CN, wherein aryl, X, a and Z have the meanings defined above, in an anhydrous solvent which has a strong acid one pK. -Value in water of 2.5 or less and which is a salt can form with the amino group, dissolves. 39 · Method according to claim 38, characterized that the reaction is carried out with substantially equal molar ratios of strong acid and diester. 40. Process for the preparation of a monoester of the general formula Z K Il I Aryl XOP- Ch ₀ - H - CH ₀ - CN, 3 ι egg el. OH 80982 ^ / 0617 275Ί631 wherein aryl, X, a and Z have the same meanings as in claim 34, characterized in that that one has a diester of the general formula Z H Il I (Aryl X -O) ₀ - P - CH _p - N - CH _p - CN, wherein aryl, X, a and Z have the meanings defined above, dissolved in an inert solvent containing an equivalent amount of water _{to effect the hydrolysis of an (aryl X 0} -O) group. 41. Process for the preparation of a salt of N-phosphonomethylglycine or the thio analogue thereof, characterized in that a mixture in water of a glycine nitrile of the general formula Z H Il I (Aryl X ₀ -O) ₀ . - P - CH ₀ - N - CK ₀ - CN, a £. - D 1 cc (0H) _b wherein aryl is phenyl, naphthyl and / or biphenylyl, any substituent X on the aryl group is halogen, alkyl with 1 to 4 carbon atoms, alkoxy and alkylthio with 1 to 3 carbon atoms, Alkoxycarbonyl with 2 to 3 carbon atoms, methylenedioxy, Cyano, trifluoromethyl and / or nitro, Z is oxygen or sulfur, a is an integer from 0 to 3 and b = 0 or 1, with a base, namely alkali metal hydroxides and / or tetraalkylammonium hydroxide, wherein the alkyl radicals contain 1 to 4 carbon atoms and forms the mixture for the preparation of the salt 809824/0617 heated. 42. Process for the preparation of N-Phosphonmethylglycine or its thioanalors from a basic SnIz of glycine, where the base alkali metal hydroxide and / or a tetraalkylanimonium hydroxide, wherein the alkyl radicals have 1 to 4 carbon atoms is contained, characterized in that an aqueous solution of d-es salt with a cation exchange resin brings the resin into contact, eluted with water, and then concentrated the solvent to form N-phosphonomethylglycine or its thio analogs. 43. Process for the preparation of N-Phosphonmethylglycine or its thioanalogues, characterized in that that one is a mixture of glycine nitrile of the general formula Z H Il I (Aryl \ -0) ₂ _ _b - P - CH ₂ - N - CH ₂ - CN, (OH) _b wherein aryl is phenyl, naphthyl and / or biphenylyl, each substituent X on the aryl group is halogen, alkyl with 1 to 4 carbon atoms, alkoxy and alkylthio with 1 to 3 carbon atoms, alkoxycarbonyl with 2 to 3 carbon atoms, methylenedioxy, cyano, trifluoromethyl and / or nitro, Z is oxygen or sulfur, a = is an integer from 0 to 3 and b is 0 or 1, with wenirstens a slight excess over einerr MoI aauivalent wäßri ve hydrochloric acid or aqueous hydrobromic acid 809824/0617 copy mix and heat the mixture until essentially all Glycinnitrj] to N-Phosphonmethylglycine or its thioanalotrene hydrolyzed. 44. The method according to claim 40, characterized in that the diester 0.0-di- (phenyl) -N-phosphonmethylglycine nitrile, O.O-Di- (m-nitrophenyl) -N-phosphonmethylglycine nitrile or 0.0-di- (o-chlorophenyl) -N-phosphonmethyl plycine nitrile begins. 45. The method according to claim 30, characterized that the diester O.O-Diphenyl-K-phosphonmethylplycinnitril and the strong acid used is hydrobromic acid, trifluoroacetic acid or methanesulfonic acid. 809824/0617 _C0PY