HERBICIDALLY ACTIVE MONOESTERS AND DIESTERS OF N-ALKYL SUBSTITUTED AMINO METHYL PHOSPHONIC ACID AND PROCESS FOR PREPARING SAME

Abstract: Monoesters and diesters of N-alkyl-substituted amino methyl phosphonic acid of the formula wherein a + b = 2 and a is 0 or 1, Z, R and R₁ have various va­ lues, representative compounds being the ethyl, 2-chloroethyl, 2-ethoxyethyl and pentyl esters of N[(1-cyanoethoxy)hydroxy­ phosphinyl]methylglycine, are made by reacting a phosphite of the formula P(OR₁)₃, water and a trisubstituted hexahydro­ 1,3,5-triazine of the formula Compounds of formula I are useful as herbicides.

Description: FIERBICIDALLY ACTIVE MONOESTERS AND DO ESTERS OF N-ALKYL SUBSTITUTED AMINO METHYL PHOSPHONIC ACID AND PROCESS FOR PREPARING SAME This invention relates to monoesters and diesters of N-alkyl substituted amino phosphonic acid which are useful as herbicides. U.S. Patent 4,025,331 issued to Jean-Pierre Leber on May 24, 1977 discloses N-phosphonomethylglycine derivatives of the formula EMI1.1 wherein R of Leber is hydrogen, unsubstituted or substituted hydrocarbon or a cation and M is hydrogen or a cation as well as a two reaction step process for preparing the same. The compounds disclosed in U.S. Patent 4,025,331 supra are said to possess herbicidal and plant growth regulating properties. U.S. Patent 4,008,296 issued to John Edward Duncan Barton on February 15, 1977 discloses a catalyzed process for preparing N-phosphonomethylglycine having the formula EMI1.2 which comprises (a) reacting 1,3,5-tricyanomethylhexa hydro-l,3,4-triazine with an ester of phosphorous acid having the formula EMI2.1 wherein R1 and R2 of Barton are hydrocarbyl or substituted hydrocarbyl radicals, in the presence of a catalyst comprising a hydrogen halide, a Lewis acid, a carboxylic acid halide, or a carboxylic acid anhydride to form an ester of N-phosphonomethylglycinonitrile, and (b) hydrolysing the ester of the N-phosphonomethylglycinonitrile, and recovering N-phosphonomethylglycine. Compounds of the present invention comprise monoesters and diesters of N-alkyl substituted amino methyl phosphonic acid of the formula EMI2.2 wherein a+b=2, a is 0 or 1, and Z is selected from the group consisting of EMI2.3 wherein R2 is lower alkyl, lower alkoxy lower alkyl, halo lower alkyl, or phenyl lower alkyl or Z is lower alkynyl or lower alkyl or NECCH2, R is selected from the group consisting of hydrogen, lower alkyl, lower alkoxy lower alkyl, halo lower alkyl, or phenyl lower alkyl, R1 is independently selected from the group consisting of EMI2.4 wherein n is an integer from 1 to 4, R3 is selected from the group consisting of hydrogen, lower alkyl, lower alkoxy lower alkyl, halo lower alkyl, phenyl lower alkyl and R4 is hydrogen or lower alkyl; ; EMI3.1 wherein R5 is hydrogen, lower alkyl, lower alkoxy carbonyl; and R6 is halogen, lower alkoxy carbonyl, and EMI3.2 wherein L is lower alkyl and nl is an integer from 0 to 3; -(Cn2H2n2)S-X wherein X is lower alkyl or lower alkoxy carbonyl and n2 is an integer from 1 to 4; EMI3.3 wherein T is lower alkyl; and -(Cn3H2n3)-Y, wherein n3 is an integer from 0 to 4 and Y is selected from the group consisting of trihalomethyl, lower alkoxycarbonyl, furanyl, pyrolidinyl, pyranyl, thiopyranyl, EMI3.4 wherein M1 and M are independently lower alkyl; but excluding the compounds of formula (I) wherein n is two and R3 and R4 are both hydrogen and the compounds of formula (I) wherein R1 and R are both ethyl and a is one (or alternatively R1 is ethyl and b is two). Regarding the process of this invention, compounds of formula (I) and including those wherein n is two and R3 and Rq are both hydrogen and wherein R1 and R are both ethyl and a is one (or alternatively wherein R is ethyl and a is zero) and those wherein R1 is independently selected from the same group as R may be prepared by simultaneously reacting a trisubstituted phosphite of the formula P(OR1)3 (11) wherein R1 is defined as recited above with water and with 1,3,5-tri-substituted hexahydro-l, 3, 5-triazine (trimer of the Schiff's base of formaldehyde and a corresponding amine) of the formula EMI4.1 wherein R is as aforedefined to form a crude diester or crude monoester composition containing diester and monoester product. A purified monoester or diester product may be recovered from the crude monoester or diester composition by employing a chromatographic and/or distillation means having sufficient capability and capacity to effect the aforedescribed recovery. The process of this invention does not include the preparation of the compounds of formula (I) wherein R3 and R4 are both hydrogen and n is one or those compounds wherein R1 is EMI5.1 Preparation of those compounds of formula (I) wherein R3 and R4 are both hydrogen when n is one and those compounds of formula (I) wherein R1 is EMI5.2 is illustrated by method of examples 29 and 34 and 35 respectively. The aforedescribed reaction is carried out at a temperature in the range from about 10 to 110 and preferably from about 20 to about 100 C. In preparing monoester and diester compounds of formula (I), the range of reactants is not narrowly critical. Preferably, however for each mole of tri-substituted phosphite employed, one should employ from about 0.5 to about 1.5 mole water, about 1/4 to about 1/2 mole 1,3,5-tri-substituted hexahydro-1,3,5-triazine (which is equivalent to 1 mole of the monomer of a Schiff1s base of formaldehyde and a corresponding amine). As employed throughout the claims and description, the term "lower alkyl" includes alkyl radicals which have up to eight carbon atoms in a straight or branched chain, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl and octyl. As employed throughout the claims and description, the term "lower alkoxy" includes groups of the aforedefined term "lower alkyl" which have one oxygen associated therewith such as methoxy, ethoxy, propoxy and butoxy. Typical examples of the term "lower alkoxy lower alkyl" include groups representing combinations of the aforedefined term "lower alkyl11 and the aforedefined term "lower alkoxy" and include methoxymethyl, ethoxyethyl, propoxymethyl and the like. The term "halo" includes chlorine, bromine; fluorine and iodine. Illustrative groups of the term "phenylloweralkyl" are groups wherein the substituent on the phenyl comprising the aforedefined lower alkyl is in the ortho, meta, or para position, for example, phenylmethyl; phenylethyl, phenylpropyl, phenylbutyl, phenyl t-butyl and the like. While no catalyst is required for the aforedescribed reaction to proceed, a catalyst may be employed if desired. The reaction time is in the range from about 1 to about 72 and is preferably from about 2 to about 50 hours. While the process of this invention can be conducted at atmospheric, sub-atmospheric or superatmospheric pressure, for convenience and economy it is generally preferred to conduct this process at atmospheric pressure. Although a suitable solvent may be employed in the aforedescribed process, it is preferred that the reaction-be carried out in the absence of a solvent. Suitable agitation is provided, preferably by stirring or otherwise agitating the reaction composition. In practicing the aforedescribed process the aforedescribed reactants are admixed together although the reactants may be admixed in any order desired to form a reaction composition. If desired agriculturably acceptable salts may be prepared from the aforedescribed monoesters. While the salt employed may be any agriculturally acceptable salt, preferred salts include those of the alkali metals such as the sodium, potassium, and lithium salts, the alkaline earth metal salts such as magnesium and calcium salts, as well as those salts disclosed in U.S. Patent 3,799,758, issued March 26, 1974, to John E. Franz, the disclosure of which is incorporated herein by reference. Preferred salts include the ammonium and organic ammonium salts. The organic ammonium salts are those salts prepared from low molecular weight organic amines, i.e., having a molecular weight below about 300. Such organic amines include the alkyl amines such as isopropylamine alkylamines and alkanol amines containing not more than 2 amine groups. Strong acid salts may also be prepared as an agriculturally acceptable salt such as those having a pk of 2.5 or less such as hydrochloric acid, sulfuric, phosphoric acid, trifluoroacetic acid, trichloroacetic and the like. The alkali metal salts maybe prepared by reacting the mono esters with a suitable alkali metal hydroxide or alkale metal carbonate. The alkaline earth metal salts maybe prepared in similar fashion by use of the corresponding hydroxide and carbonate for example. The alkaline earth metal salt will be two parts acid to one part alkaline earth metal. The following examples are presented to define the invention more completely without any intention of being limited thereby. All parts and percentages are by weight, unless otherwise specified. Example 1 A reaction composition comprising 15.8g (0.065 mole) tri-(l-cyanoethyl)phosphite, l.2g (0.q65 mole) water, and 7.5g (0.022 mole) 1,3,5-tri(ethoxycarbony- methyl)hexahydro-1,3,5-triazine was prepared and stirred while maintaining the reaction temperature at about 10 to about 200C with external cooling by an ice-water bath for a time of three hours. After completion of the reaction, -hydroxypropionitrile a reaction alcohol coproduct was removed by employing bulb to bulb distillation at a pressure of 0.05 mm Hg and a temperature of 250C. The desired glycine product was recovered by employing column chromatography of the distillation residue on cellulose (microcrystalline) with ethyl acetate:cyclohexane (1:3). The product, glycine, N-[[bis(l-cyanoethoxy)phosphinyll- methyl],ethyl ester, was obtained as a viscous reddishcolored oil at a yield of 2.0 grams (10.2%) and had the following analysis: Calculated: C, 43.57; H, 5.98; N, 13.86; P, 10.21; Found: C, 44.09; H, 5.90; N, 14.67; P, 10.35. Example 2 A reaction composition comprising 15g (0.053 mole) tri-(l-cyano-l-methylethyl)phosphite, 0.95g (0.053 mole) water, and 6.11g (0.0177 mole) 1,3,5-tri-(ethoxycarbonylmethyl)hexahydro-1,3,5-triazine was agitated at about 250C for 24 hours resulting in the formation of a pale-yellow-colored solution. The pale-yellow-colored solution was heated at about 500C for three hours with agitation. An alcohol coproduct Jazz -hydroxyisobutyronitrile was left in solution. The reaction mixture was purified by employing chromatography on cellulose (microcrystalline) with the eluent ethyl acetate. The product, glycine, N-[bis(1-cyano-1-methyl-ethoxy)phosphinylmethyl], ethyl ester, was obtained as a viscous reddish-brown oil having a yield of 16.6g (94%) and had the following analysis: Calculated: C, 47.13; H, 6.69; N, 12.68; P, 9.35; Found: C, 47.74; H, 6.72; N, 13.41; P, 9.10. Example 3 A mixture of 15.0g (0.0622 mole) of tri-(lcyanoethyl) phosphite, 1.12g (0.0622 mole) of water and 4.17g (0.0207 mole) of 1,3,5-tri-(propynyl)hexahydro 1;3,5-triazine was agitated at about 250C for six hours with a slight exotherm. An alcohol coproduct, 2-hydroxypropionitrile, was removed by bulb to bulb distillation at 250C and 0.1 mm Hg. The distillation residue was chromatographed on microcrystalline cellulose with ethyl acetate as eluent. The compound, phosphonic acid, [(2-propnylamino)methyl]-,bis(1-cyanoethyl)ester was obtained as a viscuous reddish-brown oil in a yield of 87% (13.8g) and had the following analysis: Calculated: C, 47.06; H, 5.53; N, 16.47; P, 12.14; Found: C, 47.16; H, 5.75; N, 16.09; P, 9.62; Rechromatographed Found: C, 47.19; H, 5.70; N, 16.10; P, 9.92. Example 4 A mixture of 15.0g (0.0622 mole) of tri-(lcyanomethyl) phosphite, 1.12g (0.0622 mole) of water and 5.29g (0.0207 mole) of 1,3,5-tri-(tertiary-butyl)hexahydro-1,3,5-triazine was agitated at about 250C for six hours with a slight exotherm. An alcohol coproduct, 2-hydroxy-propionitrile, was removed by bulb to bulb distillation at 250C and 0.1 mm Hg. The distillation residue was chromatographed on microcrystalline cellulose with ethyl acetate as eluent. The compound, (phosphonic acid,[t(l,l-dimethylethyl)aminoRmethyll-,bis(l-cyanoethyl) ester) was obtained as a viscuous orange oil in a yield of 828 (14.0g) and had the following analysis: Calculated: C, 48.35; H, 7.38; N, 15.38; P, 11.34; Found: C, 47.68; H, 7.09; N, 15.10; P, 9.32; Rechromatographed Found: C, 45.95; H; 7.15; N, 14.57; P, 10.68. Example 5 A reaction composition comprising 13.0g (0.05 mole) tri-(l-cyanoethyl)phosphite, 0.97g (0.05 mole) water; and 6.2g (0.02 mole) 1,3,5-tri(ethoxycarbonyl methyl)hexahydro-1;3;5-triazine was agitated at a temperature of about 250C for 5 hours. An alcohol co-product ot-hydroxypropionitrile was removed by employing bulb to bulb distillation at 300C and 0.1 mm Hg. The distillation residue was chromatographed on microcrystalline cellulose employing ethyl acetate as an eluent. A precipitate of the desired product, glycine, (l-cyanoethoxy)hydroxy-phosphinyl]methyl] ethyl ester, was formed in the effluent upon standing at about 250C for 12 hours. The yield was 0.5g (4%). The analysis of the product was: Calculated: C, 38.41; H, 6.04; N, 11.20; P, 12.38; Found: C, 38.35; H, 6.21; N, 11.25; P, 12.11. Example 6 A reaction composition comprising 10.5g (0.04 mole) tri-(l-cyanoethyl)phosphite, 0.8g (0.04 mole) water, and 6. 8g (0.01 mole) 1;3,5-tri(pentoxycarbonylmethyl)- hexahydro-1,3,5-triazine was agitated at a temperature of about 250C for 2 hours. An alcohol co-product ol-hydroxy- propionitrile was removed by employing bulb to bulb distillation at 500C and 0.1 mm Hg. The distillation residue was chromatographed on microcrystalline cellulose employing ethyl acetate/cyclohexane (1/3) as an eluent. A precipitate of the desired product, glycine, N-[[(l-cyanoethoxy)hydroxy-phosphinyl]methyl],pentyl ester, hemihydrate was formed in the effluent upon standing at about 250C for 12 hours. The yield was 2.0g (16%). The analysis of said product was: Calculated: C, 43.85; H, 7.36; N, 9.30; P, 10.28; Found: C, 43.50; H, 7.12; N, 9.57; P, 10.51. Example 7 A reaction composition comprising 11.5g (0.05 mole) tri-(l-cyanoethyl)phosphite, 0.10g (0.06 mole) water, and 7.3g (0.02 mole) l,3,5-tri(2-chloroethoxy- carbonylmethyl)hexahydro-1,3,5-triazine was agitated at a temperature of about 250C for 16 hours. An alcohol co-product i-hydroxypropionitrile was removed by employing bulb to bulb distillation at 500C and 0.02 mm Hg. The distillation residue was chromatographed on microcrystalline cellulose employing ethyl acetate/cyclohexane (1/3) as an eluent. A solid precipitate of the desired product, glycine, N-[[(l-cyanoethoxy)hydroxyphosphinyllmethyl], 2-chloroethyl ester, was formed in the effluent upon standing at about 250C for 12 hours. The yield was 1.6g (11%). The analysis of said product was: Calculated: C, 33.76; H, 4.96; C1, 12.46; N, 9.84; P, 10.88; Found: C, 33.87; H, 4.97; C1, 12.27; N, 9.97; P, 11.05. Example 8 A reaction composition comprising 15.4g (0.05 mole) tri-(l-cyanopropyl)phosphite, 0.9g (0.05 mole) water, and 6.3g (0.02 mole) 1,3,5-tri(ethoxycarbonyl- methyl)hexahydro-1,3,5-triazine was agitated at a temperature of about 250C for 12 hours. An alcohol co-product & hydroxybutyronitrile was removed by employing bulb to bulb distillation at 250C and 0.05 mm Hg. The distillation residue was chromatographed on microcrystalline cellulose employing ethyl acetate/cyclohexane (1/3) as an eluent. A'precipitate of the desired product, glycine, N-C[(1-cyanopropoxy)hydroxy- phosphinyl]methyl],ethyl ester, was formed in the effluent upon standing at about 250C for 72 hours. The yield was lg (7%). The analysis of said product was: Calculated: C, 40.91; H, 6.49; N, 10.60; P, 11.72; Found: C, 40.84; H, 6.67; N, 10.65; P, 11.71. Example 9 A reaction composition comprising 12.5g (0.05 mole) tri-(l-cyanoethyl)phosphite, 0.9g (0.05 mole) water, and 8.3g (0.02 mole) l,3,5-tri(2-ethoxyethoxycarbonyl- methyl)hexahydro-1,3,5-triazine was agitated at a temperature of about 250C for 14 hours. An alcohol co-product d-hydroxypropionitrile was removed-by employing bulb to bulb distillation at 550C and 0.1 mm Hg. The distillation residue was dissolved in ethyl acetate and agitated at about 250C for 72 hours with formation of the desired product, glycine, N-[[(l-cyanoethoxy)hydroxyphosphinyl]-methyl],2-ethoxyethyl ester as a precipitate. The yield was l.9g (12%). The analysis of said product was: Calculated: C, 40.82; H, 6.51; N, 9.52; P, 10.53; Found: C, 40.44; H, 6.62; N, 9.40; P; 10.30. Example 10 A reaction composition comprising 11.9g (0.05 mole) tri-(l-cyanoethyl)phosphite, 0.9g (0.05 mole) water, and 11.6g (0.02 mole) 1,3,5-tri(phenylmethoxycarbonylmethyl)hexahydro-1,3,5-triazine was agitated at a temperature of about 250C for 48 hours. The reaction mixture was agitated with 100 ml ethyl acetate with formation of the desired product, glycine, N-[F(l-cyano- ethoxy)hydroxyphosphinyl]methyll-,phenylmethyl ester as a precipitate. The yield was 3.6g (24%). The analysis of the product was: Calculated: C, 50.00; H, 5.49; N, 8.97; P, 9.92; Found: C, 50.14; H, 5.49; N, 8.92; P, 9.87. Example 11 A reaction composition comprising 15.0g (0.622 mole) tri-(2-cyanoethyl)phosphite, 1.12g (0.0622 mole) water and 4.22 (0.0207 mole) of 1,3,5-tri(cyanomethyl)- hexahydro-1,3,5-triazine was agitated at about 250C for 12 hours. The resulting product composition was chromatographed on cellulose with ethyl acetate eluent. The product, phosphonic acid, [[(cyanomethyl)amino]methyl],bis 2-(cyanoethyl)ester was isolated as a viscous reddish-brown oil having a yield of 7.2g (45%) and the following analysis: Calculated: C, 42.19; H, 5.11; N, 21.87; P, 12.07; Found: C, 42.89; H, 5.23; N, 21.20; P, 11.21. Example 12 A reaction composition comprising of 5g (0.02 mole) tri-(l-cyanoethyi)phosphite, 0.37g (0.02 mole) water and 1.4g (0.0066 mole) of l,3,5-tri(cyanomethyl)- hexahydro-1,3,5-triazine was agitated at about 150C for 16 hours. A d-hydroxypropionitrile co-product was removed by bulb to bulb distillation at 300C and 0.05 mm Hg. The distillation residue was chromatographed on cellulose (microcrystalline) with eluent of ethyl acetate:cyclohexane (1:3). The collected column concentrates were placed in vacuo at 600C (0.1 mm Hg) for 30 minutes with the residue being the desired product. The product, phosphonic acid, I[(cyanomethyl)aminoI- methyl] ,bis l-cyanoethyl ester was obtained as a viscous reddish-colored oil having a yield of 1.4g (27%) and the following analysis: Calculated: C, 42.19; H, 5.11; N, 21.87; P, 12.09; Found: C, 42.14; H, 5.38; N, 20.45; P, 11.40. Example 13 A reaction composition comprising 15.0g -(0.0441 mole) tri(ethoxycarbonylmethyl)phosphite, 0.79g (0.0441 mole) water and 5.08g (0.0147 mole) 1,3,5-tri-(ethoxycarbonylmethyl) hexahydro-1,3,5-triazine was heated to about 100-1100C for three hours with agitation. An alcohol ethyl glycolate co-product was removed by bulb to bulb distillation of the reaction mixture at 750C and 0.1 mm Hg. The distillation residue was chromatographed on microcrystalline cellulose with an eluent of ethyl acetate. The product, glycine, N-[bis(ethoxycarbonylmethoxy)phosphinylmethyl]-, ethyl ester was obtained as a viscous yellow oil in 62% yield (10.lg) having the following analysis: Calculated: C, 42.28; H, 6.55; N, 3.79; P, 8.39; Found: C, 42.35; H, 6.12; N, 3.90; P, 8.54. Example 14 A reaction composition comprising 19.9g (0.033 mole) tri(l,2-diethoxycarbonylethyl)phosphite, 0.6g (0.033 mole) water and 3.8g (0.011 mole) 1,3,5-tri-(ethoxycarbonylmethyl) hexahydro-1,3,5-triazine was heated to about 100-1100C for 2.5 hours with agitation. An alcohol diethyl malate ( 4-hydroxysuccinate) co-product was removed by bulb to bulb distillation of the reaction mixture at 750C and 0.1 mm Hg. The distillation residue was chromatographed on silica gel with an eluent of ethyl acetate. The product, butanoic acid, 2,2'-[[[(2- ethOxy-2-oXo-ethyl)aminolmethyl]phosphinylidene]bis(oxy)- bis-,tetraethyl ester was obtained as a viscous yellow oil in 13% yield (2.4g) having the following analysis: Calculated: C, 46.58; H, 6.70; N, 2.59; P, 5.72; Found: C, 46.75; H, 6.60; N, 2.85; P, 6.03. Example 15 A reaction cornposition comprising 15.0g (0.0353 mole) butanoic acid, 3,3' ,3",-phosphinidynetris(oxy)- tris-,triethyl ester, 0.64g (0.0353 mole) water and 5.08g (0.0147 mole) 1,3,5-tri-(ethoxycarbonylmethyl) hexahydro-1,3,5-triazine was heated to about 100-1100C for three hours with agitation. An alcohol co-product ethyl B-hydroxybutanoate was removed by bulb to bulb distillation of the reaction mixture at about 800C and 0.1 mm Hg. The distillation residue was chromatographed on microcrystalline cellulose with an eluent of ethyl acetate. The product, butanoic acid, 3,3'-[[[[(2-ethoxy-2-oxoethyl]amino]methyl]phosphinyl- idene]bis-(oxy)]bis-, diethyl ester was obtained as a viscous yellow oil in 61.3% yield (9.2g) having the following analysis: Calculated: C, 48.00; H, 7.58; N, 3.29; P, 7.28; Found: C, 47.03; H, 7.48; N, 3.56; P, 8.07. Example 16 A reaction composition comprising 15.0g (0.039 mole) tri-(l-ethoxycarbonylethyl)phosphite, 0.71g (0.039 mole) water and 4.525g (0.0131 mole) l,3,5-tri-(ethoxy- carbonylmethyl)hexahydro-1,3,5-triazine was heated to about 100-1100C for three hours with agitation. An alcohol coproduct ethyl A-hydroxypropionate was removed by bulb to bulb distillation of the reaction mixture at 250C and 0.1 mm Hg. The distillation residue was chromatographed on microcrystalline cellulose with an eluent of ethyl acetate. The product, propanoic acid, 2,2' - F F (F (2-ethoxy-2-oxoethyl ) amino] methyl] phosphinyl- idenelbis(oxy)]-bis-, diethyl ester was obtained as a viscous yellow oil in 84.5% yield (13.lg) having the following analysis: Calculated: C, 45.34; H, 7.10; N, 3.53; P, 7.80; Found: C, 44.68; H, 6.69; N, 4.v12; P, 8.56. Example 17 A reaction composition comprising 20.0g (0.0742 mole) tri-(2-chloroethyl)phosphite, 1.34g (0.0742 mole) water and 8.53g (0.0247 mole) 1,3,5-tri-(ethoxycarbonylmethyl) hexahydro-1;3,5-triazine was heated to about 100-1100C for three hours with agitation. An alcohol 2-chloroethanol co-product was removed by bulb to bulb distillation of the reaction mixture at 250C and 0.1 mm Hg. The distillation residue was chromatographed on microcrystalline cellulose with an eluent of ethyl acetate. The product, glycine, N-[[bis(2- chloroethoxy)phosphinyl]methyl]-, ethyl ester was obtained as a viscous yellow oil in 96.7% yield (23.lg) having the following analysis: Calculated: C, 33.56; H, 5.63; N, 4.35; P, 9.62; Found: C; 32.94; H, 5.65; N, 4.06; P, 9.51. Example 18 A reaction composition comprising 15.0g (0.0441 mole) tri-(l-methoxycarbonylethyl)phosphite, 0.79g (0.0441 mole) water and 5.08g (0.0147 mole) 1,3;5-tr-(ethoxy- carbonylmethyl)hexahydro-1;3,5-triazine was heated to about 100-1100C for three hours with agitation. An alcohol coproduct methyl drhydroxypropionate co-product was removed by bulb to bulb distillation of the reaction mixture at 750C and 0.1 mm Hg. The distillation residue was chromatographed on microcrystalline cellulose with an eluent of ethyl acetate. The product, propanoic acid, 2,2'-[[(ethoxycarbonylmethyl)aminolmethylphosphinyl- idenedioxy]]bis-, dimethyl ester was obtained as a viscous yellow oil in 73.6% yield (9.2g) having the following analysis: Calculated: C, 42.28; H, 6.55; N, 3.79; P, 8.39; Found: C, 41.92; H, 6.23; N, 3.61; P, 7.74. Example 19 A reaction composition comprising 15.0g (0.031 mole) tri-F [(2-ethoxycarbony1)thio]ethy1]phosphite 0.56g (0.031 mole) water, and 3.59g (0.0104 mole) 1,3,5-tri(ethoxyzarbonylmethyl)hexahydro-1,3,5-triazine was heated at about 100 to about 1l00C for 3 hours with agitation. An alcohol 2-(ethoxycarbonylthio)ethanol co-product was removed by bulb to bulb distillation of the reaction mixture at 750C and 0.05 mm Hg. The distillation residue was chromatographed on silica gel with ethyl acetate eluent. The product, glycine, N-[[bis[2-l(ethoxy- carbonyl)thio]ethoxy]-phosphinyl]methyl]-, ethyl ester was obtained as a viscous yellow oil in 52% yield (7.4g) having the following analysis: Calculated: C, 39.04; H, 6.12; N, 3.04; P, 6.71; Found: C, 38.16; H, 6.16; N, 2.66; P, 6.20. Example 20 A reaction composition comprising 9.6g (0.025 mole) tri-[tetrahydro-2H-thiopyran -3-yl)phosphite, 0.45g (0.025 mole) water, and 2.9g (0.008 mole) 1,3,5-tri(ethoxyzarbonylmethyl)hexahydro-1,3,5-triazine was heated at about 100 to about 1100C for 1-1/2 hours with agitation. An alcohol tetrahydro-2H-thiopyran-3-ol co-product was removed by bulb to bulb distillation of the reaction mixture at 1200C and 0.07 mm Hg. The distillation residue was chromatographed on microcrystalline cellulose with an eluent of ethylacetate/cyclohexane (2:3). The product, glycine, N-t[bis[(tetrahydro-2H-thiopyran-3-yl)-oxy]- phosphinyllmethyll-, ethyl ester was obtained as a viscous yellow oil in 40% yield (4.0g) having the following analysis: Calculated: C, 45.33; H, 7.10; N, 3.52; P, 7.79; S, 16.13; Found: C, 45.49; H, 7.28; N, 3.52; P, 7.60; S, 16.31. Example 21 A reaction composition comprising 15.0g (0.045 mole) tri-(2-furanylmethyl)phosphite, 0.81g (0.045 mole) water, and 5.18g (0.015 mole) 1,3;5-ti(ethoxycarbonyl- methyl)hexahydro-1,3,5-triazine was heated at about 100 to about 1100C for a time of 3 hours. An alcohol 2-furanylmethanol coproduct was removed by employing bulb to bulb distillation of the reaction mixture at 750C and 0.05 mm Hg. The distillation residue was chromatographed on silica gel with an eluent of ethyl acetate. The product, glycine, N-[[bis(2-furanylmethoxy)phosphinyl]methyl]-, ethyl ester was obtained as a viscous yellow oil in 36.6% yield (6.0g) having the following analysis: Calculated: C, 49.31; H, 7.72; N, 3.83; P, 8.48; Found: C, 49.45; H, 8.33; N, 3.38; P, 7.56. Example 22 A reaction composition comprising 15.0g (0.0353 mole) tri-[(2,2-dimethyl-1,3-dioxolan-4-yl)methyl]phosphite; 0.64g (0.0353 mole) water, and 4.07g (0.0118 mole) 1,3,5-tri(ethoxyzarbonylmethyl)hexahydro-1,3,5- triazine was heated at about 100 to about 1100C for a time of 4 hours. An alcohol 2,2-dimethyl-1,3-dioxolan-4-yl methanol coproduct was removed by employing bulb to bulb distillation of the reaction mixture at 800C and 0.1 mm Hg. The distillation residue was chromatographed on silica gel with an eluent of ethyl acetate. The product, glycine, N-F Fbis[(2,2-dimethyl-I,3-dioxolan-4-yl)- methoxy]phosphinyl]methyl]-, ethyl ester was obtained as a viscous yellow oil in 35% yield (5.2g) having the following analysis: Calculated: C, 48.00; H, 7.58; N, 3.29; P, 7.28; Found: C, 48.57; H, 7.60; N, 2.74; P, 6.73. Example 23 A reaction composition comprising 15.0g (0.04 mole) tri-[(tetrahydro-2H-pyran-2-yl]methyl)phosphite, 0.72g (0.04 mole) water, and 4.6g (0.0133 mole) 1,3,5-tri(ethoxycarbonylmethyl)hexahydro-l, 3,5-triazine was heated at about 100 to about 1100C for a time of 3 hours. An alcohol (tetrahydro-2H-pyran-2-yl) methanol byproduct was removed by employing bulb to bulb distillation of the reaction mixture at 750C and 0.1 mm Hg. The distillation residue was chromatographed on silica gel with an eluent of ethyl acetate. The product, glycine, N-[[bis(tetrahydro-2H-pyran-2-yl methoxy)phosphinyl]methyl]-, ethyl ester was obtained as a viscous yellow oil in 57% yield (9.0g) having the following analysis: Calculated: C, 51.90; H, 8.20; N, 3.56; P, 7.87; Found: C, 51.86; H, 8.34; N, 3.37; P, 7.48. Example 24 A reaction composition comprising 15.0g (0.0402 mole) tri-F2-(l-pyrrolidinyl)ethyl]phosphite, 0.72g (0.0402 mole) water, and 4.63g (0.0134 mole) l,3,5-tri(ethoxycarbonylmethyl)hexahydro-l,3, 5-triazine was heated at about 250C for 1 hour and then at about 100 to about 1100C for 3 hours. The reaction mixture was chromatographed on microcrystalline cellulose with an eluent of ethyl acetate. The product, glycine, N-[[bis- [2-(1-pyrrolidinyl)ethoxy]phosphinyl]methylJ-, ethyl ester was obtained as a viscous yellow oil in 41.3% yield (6.5g) having the following analysis: Calculated: C, 52.16; H, 8.75; N, 10.74; P, 7.91; Found: C, 52.62; H, 8.42; N, 10.85; P, 6.43. Example 25 A reaction composition comprising 15.0g (0.0353 mole) butanoic acid, (3,3';3"-phosphinidyne tris(oxy)tris-), triethyl ester, 0.64g (0.0353 mole) water; and 4.08g (0.0118 mole) 1,3,5-tri(ethoxycarbonyl methyl)hexahydro-1,3;5-triazine was heated at about 100 to about 1100C for a time of 3 hours. An alcohol byproduct was removed by employing bulb to bulb distillation of the reaction mixture at about 800C and 0.1 mm Hg. The monoester product was obtained from a solution of ethyl acetate of the distillation residue upon standing at 250C for 48 hours. The product, butanoic acid, 3-F F F F(2-ethoxy-2-oxoethyl)amino]methyl] - hydroxyphosphinyl]oxyl-, ethyl ester was obtained as a white solid in 8% yield (0.9g) having a melting point of 116-1180C and having the following analysis: Calculated: C, 42.44; H, 7.12; N, 4.50; P, 9.95; Found: C, 42.05; H, 7.11; N, 4.31; P, 9.98. Example 26 A reaction composition comprising 15.0g (0.0315 mole) tri-(2,2,2-trichloroethyl)phosphite, 0.57g (0.0315 mole) water; and 3.63g (0.0105 mole) 1,3,5-tritethoxycarbonylmethyl)hexahydro-1,3,5-triazine was heated at about 100 to about 1100C for a time of 3 hours. The reaction mixture was chromatographed on microcrystalline cellulose with an eluent of ethyl acetate. The product was precipitated from ethyl acetate eluent during 12 hours standing at 250C. The product, glycine, N-1(2;2,2-trichloroethoxy)hydroxy- phosphinyl]methyl]- ethyl ester was obtained as a white solid in 14.7% yield (1.6g) having a melting point of 143-1450C and having the following analysis: Calculated: C, 24.26; H, 4.36; N, 4.04; P, 8.94; Found: C, 24.42; H, 3.48; N, 3.66; P, 7.87. Example 27 A reaction composition comprising 15.0g (0.0315 mole) tri-(2,2,2trichloroethyl)phosphite, 0.57g (0.0315 mole) water, and 3.63g (0.0105 mole) 1,3,5-tri(ethoxycarbonylmethyl)hexahydro-1,3,5-triazine was heated at about 100 to about 1100C for a time of 3 hours. The distillation residue was chromatographed on microcrystalline cellulose with an eluent of ethyl acetate. Upon standing for 12 hours at about 250C a hydrated form of the product precipitated. Upon standing the ethyl acetate filtrate after an additional 12 hours at 250C deposited the present product which was collected and dried at 400C and 0.1 mm Hg over P205. The product, glycine, N-[[hydroxy(2,2,2-trichloroethoxy)- phosphinyl]methyl]-, ethyl ester was obtained as a white solid in 10.6% yield (l.lg) having a melting point of 197-1990C and having the following analysis: Calculated: C, 25.59; H, 3.99; N, 4.26; P, 9.43; Found: C, 25.85; H, 3.74; N, 4.44; P, 9.31. If desired a diester compound of formula (I) may be hydrolyzed to a monoester compound of formula (I) by controlled hydrolysis. The temperature is in the range from about 15 to about 50 C and is preferably from about 20 to about 300C. Hydrolysis time is in the range from about 10 to about 60 and preferably from about 20 to about 40 minutes. Example 28 A reaction composition comprising8.0g (0.028 mole) of ethyl NlZbis l-( l-methoxycarbonyl)ethoxy] - phosphinyl]methylglycinate and 0.51g (0.028 mole) water was agitated at about 250C for 30 minutes. The reaction mixture was chromatographed on a cation exchange column with water as eluent. The product, propanoic acid, 2-[[[[(2-ethoxy-2-oxoethyl)amino]methyl]hydroxy- phosphinyl]oxyl-^ methyl ester was isolated as the fourth component determined by a refractive index detector in 41.6% yield (3.30g) having the following analysis: Calculated: C, 36.10; H, 6.67; N; 4.68; P, 10.34; Found: C, 36.18; H, 6.11; N, 4.56; P; 10.38. Example 29 A reaction composition comprising 16.0g (0.1 mole) di-(cyanomethyl)phosphite, and 11.3g (0.0327 mole) 1,3,5-tri(ethoxycarbonylmethyl)hexahydro-1,3,5-triazine was agitated at a temperature of about 50 C for 3 hours. The reaction mixture was chromatographed on microcrystalline cellulose employing ethyl acetate as an eluent. A precipitate of the desired product, glycine, N-[[(cyanomethoxy)hydroxyphosphinyl]-methyl],ethyl ester, exemplifying a compound of formula (I) wherein R3 and R4 are hydrogen when n is one was formed in the effluent upon standing at about 250C for 12 hours. The yield was 7.5g (31.8%). The analysis of said product was: Calculated: C, 40.91; H, 6.49; N; 10.60; P, 11.72; Found: C, 40.84; H, 6.67; N, 10.65; Pt 11.71. Example 30 A reaction composition comprising5.46g (0.0215 mole) di-(2-acetyloxyethyl)phosphite and 2.48g (0.0072 mole) 1,3,5-tri-(ethoxycarbonylmethyl)hexahydro-1,3,5- triazine was heated to about 100-1100C for five hours with agitation. The reaction mixture was diluted with 25 ml of ethyl acetate and the purified compound was obtained by chromatography of this solution on silica gel with an eluent of ethyl acetate. The product, glycine, N-[[bis[2acetyloxyethoxy]phosphinyl]methyl]-, ethyl ester was obtained as a viscous yellow oil in 42.8% yield (3.4g) having the following analysis: Calculated: C, 42.28; H, 6.55; N, 3.79; P, 8.39; Found: C, 42.14; H, 6.70; N, 3.63; P, 7.89. Example 31 A reaction composition comprising 11.7g (0.054 moles) di-(l-cyano-propyl)phosphite and 6.3 g (0.018 mole) 1,3,5-tri(ethoxyzarbonylmethyl)hexahydro-1,3,5-triazine was heated at about 1000C for one hour with suitable agitation. The reaction product was purified by employing chromatography on cellulose (microcrystalline) with an eluent comprising ethyl acetate/cyclohexane (1:3). The product, glycine, N-[[bis(l-cyanopropoxy)phosphinyl]methyl], ethyl ester, was obtained as a viscous reddish-colored oil having a yield of 15.lg (83%) and had the following analysis: Calculated: C, 47.13; H, 6.69; N, 12.68; P, 9.35; Found: C, 47.49; H, 6.81; N, 12.13; P, 9.01. Example 32 A reaction composition comprisingl0.4g (0.04 mole) di-[(2-ethylthioethyl)phosphite, and 4.6g (0.013 mole) l,3,5-tri(ethoxycarbonymethyl)hexahydro-l,3, 5- triazine was heated at about 100 to about 110 C for 45 minutes with agitation. The reaction mixture was dissolved in ethyl acetate with formation of a precipitate upon agitating at about 250C for 12 hours. Solid was collected and filtrate concentrated to about 50 ml. The filtrate was chromatographed on microcrystalline cellulose with an eluent of ethyl acetate/cyclohexane (1:3) to yield 4.8g (32%) of the product, glycine, N-F(FbisF2-(ethyl- thio)ethoxy]phosphinyl]methyll-, ethyl ester having the following analysis: Calculated: C, 41.81; H; 7.56; N, 3.75; P, 8.29; S, 17.17; Found: C, 41.96; H, 7.87; N, 3.93; P, 7.99; S, 16.87. Example 33 A reaction composition comprising 10.4g (0.04 mole) di-[(2-ethylthioethyl)phosphite, and 4.6g (0.013 mole) 1,3,5-tri(ethoxycarbonymethyl)hexahydro-1,3,5- triazine was heated at about 100 to about 1100C for 45 minutes with agitation. The reaction mixture was dissolved in ethyl acetate (100 ml) with formation of a precipitate upon agitating at about 250C for 12 hours. Solid was collected and dried to yield 1.2g (10.5%) of the product glycine, N-t[[2-(ethylthio)ethoxy]hydroxy- phosphiny1]methy1i- ethyl ester having the following analysis: Calculated: C, 37.89; H; 7.07; N; 4.91; P, 10.86; S; 11.24; Found: C; 37.85; H, 7.21; N, 4.87; P, 10.90; S, 11.15. Example 34 A reaction composition comprising 5.0g (0.013 mole) di-[l-(tetrahydro-2-thienyl)ethyl]phosphite-S,S- dioxide and 1.54g (0.005 mole) 1,3,5-tri(ethoxycarbonyl methyl)hexahydro-1,3,5-triazine was heated at about 100 to about 1100C for 1.5 hours with agitation. The reaction mixture was dissolved in 25 ml of ethyl acetate and chromatographed on silica gel with ethyl acetate eluent to yield lg (15.7%) of the product, glycine, N-[[lbis[l- (tetrahydro-2-thienyl)ethoxy]phosphinyl],methyl]-, ethyl ester, S,S,S',S'-tetraoxide having the following analysis: Calculated: C, 41.71; H, 6.59; N, 2.86; P, 6.33; Found: C, 41.82; H, 6.53; N, 2.54; P, 6.02. Example 35 A reaction composition comprising 8.lg (0.018 mole) di-[l-(l-tetrrahydrothien-2-yi)butyl]phosphite-S,S- dioxide and 2.2g (0.006 mole) 1,3,5-tri(ethoxycarbonylmethyl)hexahydro-1,3,5-triazine was heated at about 100 to about 1100C for 2.5 hours with agitation. The reaction mixture was dissolved in 25 ml of ethyl acetate and chromatographed on silica gel with ethyl acetate eluent to yield 0.8g (8%) of the product, glycine, N-[[bis[l (tetrahydro-2-thienyl)butoxy]phosphinyl]methyl-, ethyl ester, S,S,S',S'-tetraoxide having the following analysis: Calculated: C, 46.23; H, 7.39; N, 2.57; P, 5.68; S, 11.75; Found: C, 46.23; H, 7.59; N, 2.19; P, 5.07; S, 11.55. Example 36 A mixture of 20.0g (0.083 mole) of tri-(2cyanoethyl)phosphite, 1.45g (0.081 mole) of water and 9.25g (0.027 mole) of l,3,5-tri-(ethoxycarbonylmethyl)- hexahydro-1,3,5-triazine was heated at about 110-1200C for four hours with agitation. The alcohol coproduct was removed by bulb to bulb distillation of the reaction mixture at 70-800C and 0.05 mm Hg. The distillation residue was dissolved in 100 ml of ethyl acetate and the desired product precipitated. The solid was collected to afford a 39.4% (8.2g) yield. The product glycine,N t(2-cyanoethyl)hydroxyphosphinyllmethyl-, ethyl ester was identified by elemental analysis and nmr. Example 37 A mixture of 10.0g (0.06 mole) of triethylphosphite, 1.08g (0-.06 mole) of water and 6.94g (0.02 mole) of 1,3 ,5-tri-(ethoxycarbonylmethyl )hexahydro- 1,3,5-triazine was heated at 100-1100C for three hours with agitation. The reaction mixture was chromatographed on silica gel with an eluent of ethyl acetate. The compound was obtained as a viscous yellow oil in 80.9% (12.3g) yield. The product, glycine, ethyl ester, N-(diethoxyphosphinylmethyl) had the following elemental analysis: Calculated: Cr 42.70; Hr 7.97; N, 5.53; P, 12.24; Found: C, 43.90; H, 8.36; N, 5.38; P, 11.77. The product had a boiling point of 135-1370C at 0.2 mm Hg pressure and was a colorless oil. Example 38 The post-emergent herbicidal activity of some of the various compounds of this invention was demonstrated by greenhouse testing in the following manner. A good grade of top soil is placed in aluminum pans having holes in the bottom and compacted to a depth of 0.95 to 1.27 cm. from the top of the pan. A predetermined number of seeds of each of several dicotyledonous and monocotyledonous annual plant species and/or vegetative propagules for the perennial plant species were placed on the soil and pressed into the soil surface. The seeds and/or vegetative propagules are covered with soil and leveled. The pans are then placed on a sand bench in the greenhouse and watered from below as needed. After the plants reach the desired age (two to three weeks), each pan except for the control pans is removed individually to a spraying chamber and sprayed by means of an atomizer operating at a 2 positive air pressure of approximately 1.46 kg/cm absolute. The atomizer contains 6 ml. of a solution or suspension of the chemical. In that 6 ml., is an amount of a cyclohexanone emulsifying agent mixture to give a spray solution or suspension which contains about 0.4% by weight of the emulsifier. The spray solution or suspension contains a sufficient amount of the candidate chemical in order to give application rates corresponding to those set forth in the tables. The spray solution is prepared by taking an aliquot of a 1.0% by weight stock solution or suspension of the candidate chemical in an organic solvent such as acetone or tetrahydrofuran or in water. The emulsifying agent employed is a mixture comprising 35 weight percent butylamine dodecylbenzene sulfonate and 65 weight percent of a tall oil ethylene oxide condensate having about 11 moles of ethylene oxide per mole of tall oil. The pans are returned to the greenhouse and watered as before and the injury to the plants as compared to the control is observed at approximately two and four weeks as indicated in the tables under WAT and the results recorded. In some instances, the two-week observations are omitted. The post-emergent herbicidal activity index used in Tables I and II is as follows: Plant Response Index 0 - 24% control 0 25 - 49% control 1 50 - 74% control 2 75 - 99% control 3 100% control 4 The plant species utilized in these tests are identified by letter in accordance with the following legend: A - Canada Thistle* K - Barnyardgrass B - Cocklebur L - Soybean C - Velvetleaf M - Sugar Beet D - Morningglory N - Wheat E - Lambsquarters O - Rice F - Smartweed P - Sorghum G - Yellow Nutsedge* Q - Wild Buckwheat H - Quackgrass* R - Hemp Sesbania I - Johnsongrass* S - Panicum Spp J - Downy Brome T - Crabgrass * -- Established from vegetative propagules. Table I Plant Species Compound of Example No. WAT kg/h A B C D E F G H I J K 1 4 11.2 3 3 3 3 1 4 3 2 4 2 4 4 5.6 4 3 4 3 3 3 2 3 3 3 4 2 4 56.0 4 1 0 1 1 1 0 0 0 0 0 4 11.2 - 0 0 0 0 0 0 0 0 0 1 2 5.6 - 0 0 0 0 0 0 0 0 0 0 3 2 11.2 0 0 0 0 0 1 0 0 0 0 2 4 2 11.2 0 0 0 0 1 1 0 0 0 0 1 5 4 11.2 2 3 4 4 4 4 3 4 3 3 4 4 11.2 4 4 4 4 4 4 2 4 4 4 4 4 5.6 2 4 4 3 2 4 3 3 4 2 4 4 5.6 3 3 3 3 4 4 3 4 3 3 4 6 4 11.2 4 3 3 2 4 4 4 3 2 3 3 4 5.6 4 3 3 3 2 4 2 2 1 1 3 7 4 11.2 2 3 3 2 3 '4 3 0 0 2 2 4 5.6 2 4 3 2 4 4 - 2 1 2 3 8 4 11.2 4 4 4 3 4 4 4 4 4 4 4 4 5.6 4 3 3 2 4 4 3 4 3 3 3 9 4 11.2 - 4 4 3 4 3 3 4 4 3 3 4 5.6 - 3 3 2 4 2 1 4 4 2 3 Table I (Cont'd) Plant Species Compound of Example No. WAT kg/h A B C D E F G H I J K 10 4 11.2 2 2 3 2 3 4 1 2 1 1 3 4 5.6 1 2 3 2 3 - 1 2 0 2 2 11 4 11.2 2 1 0 2 1 1 1 1 0 0 1 2 5.6 0 0 0 0 1 0 0 0 0 0 0 12 4 11.2 2 2 2 2 2 4 3 2 3 1 3 4 5.6 2 2 2 2 3 4 3 1 4 2 2 13 2 11.2 0 0 0 1 0 0 0 0 0 0 0 2 5.6 0 0 0 0 - 0 0 1 0 0 0 14 2 11.2 0 0 0 0 0 0 0 0 0 0 0 2 5.6 0 0 0 0 0 0 0 0 0 0 0 4 56.0 4 4 4 3 4 4 4 4 3 3 4 2 56.0 1 4 3 2 4 3 1 3 3 2 3 15 4 11.2 0 1 0 1 0 0 1 1 0 0 3 2 5.6 0 0 0 0 0 0 0 0 0 0 0 16 4 11.2 0 1 0 1 0 0 1 0 0 1 1 2 S.6 0 0 0 1 0 0 0 0 0 0 0 17 4 11.2 0 0 1 1 1 1 0 0 0 0 1 2 5.6 0 0 0 0 0 0 0 0 0 0 0 18 4 11.2 0 0 0 1 0 0 2 3 1 2 2 4 5.6 0 0 0 I 0 0 1 0 0 0 1 * Sprayed in 935 liters per hectare tetrahydrofuran immediately after formulation. Table I (Cont'd) Plant Species Compound of Example No. WAT kg/h A B C D E F G H I J K 19 4 11.2 2 2 0 2 0 1 1 1 2 0 2 4 5.6 1 0 0 2 0 0 0 0 1 0 1 20 4 11.2 0 0 1 1 1 0 0 1 0 0 1 2 5.6 0 0 0 0 0 0 0 0 0 0 0 21 4 56.0 3 2 1 2 1 1 1 0 0 1 2 4 11.2 0 0 0 1 0 0 0 0 0 0 0 22 4 56.0 2 2 3 2 3 3 2 2 1 2 3 4 11.2 0 0 0 1 0 0 0 0 0 0 3 23 4 11.2 0 0 0 1 0 1 0 0 - 0 1 2 5.6 0 0 0 0 0 0 0 0 0 0 0 24 4 11.2 1 2 1 2 1 2 1 2 2 1 3 4 5.6 1 1 1 1 3 2 2 1 1 0 2 25 4 11.2 1 2 1 2 0 0 2 1 2 0 2 4 5.6 0 0 0 1 0 0 0 0 1 0 1 26 4 11.2 0 1 0 0 1 0 0 0 0 0 1 4 56.0 0 1 0 1 1 1 1 0 0 0 1 27 4 11.2 2 2 2 2 3 2 2 1 0 0 3 4 5.6 1 2 1 2 3 2 0 1 2 0 3 28 4 11.2 1 2 2 3 3 3 3 2 3 1 2 4 5.6 1 1 0 1 0 0 1 0 2 1 2 Table I (Cont'd) Plant Species Compound of Example No. WAT kg/h A B C D E F G H I J R 29 4 11.2 4 4 4 4 4 4 3 4 4 4 4 4 5.6 4 4 4 4 4 4 3 4 4 3 4 30 4 11.2 1 - 1 - 1 0 2 2 2 1 3 4 5.6 0 - 0 - 1 0 1 1 2 1 2 31 4 11.2 4 3 2 2 3 4 3 2 3 3 4 4 5.6 3 3 1 2 1 4 3 3 3 1 3 32 4 11.2 1 1 0 1 0 0 1 1 3 0 2 4 5.6 1 1 0 1 0 0 1 0 0 0 2 33 4 11.2 4 4 3 3 3 4 0 3 4 2 4 4 5.6 2 2 4 2 0 3 1 3 4 2 4 34 2 11.2 0 0 0 0 0 0 0 0 0 0 0 2 56.0 0 1 0 1 1 1 0 0 0 0 0 4 56.0 0 1 0 1 0 1 0 0 1 0 0 35 2 11.2 0 0 0 0 0 1 0 0 1 0 0 2 5.6 0 0 0 0 0 0 0 0 1 0 0 **Applied in 935 liters per hectare tetrahydrofuran immediately after formulation. *** Weighed and formulated just prior to treatment. - Indicates species of plant absent during test. Table II Plant Species Compound of Example No. WAT kg/h L MN O P B Q D R E F C J S K T 1 4 5.6 4 4 4 4 4 3 4 3 2 3 4 4 4 4 4 4 4 1.12 2 4 2 1 3 2 2 2 - 3 3 2 2 4 3 3 4 0.28 0 2 1 0 1 1 0 1 0 0 0 0 0 2 2 1 5 4 5.6 4 4 4 4 4 4 4 4 3 4 4 4 3 4 4 4 4 1.12 2 2 3 2 3 2 2 2 2 4 4 2 2 4 3 4 4 0.28 1 1 1 0 3 2 0 2 1 2 2 1 1 3 3 3 6 4 5.6 4 4 4 4 4 3 4 3 4 4 3 3 4 4 3 4 4 1.12 2 4 2 2 3 2 2 2 2 3 3 2 3 4 3 3 4 0.28 1 2 2 1 1 2 2 2 1 1 1 1 3 4 2 3 7 4 5.6 3 4 4 3 3 3 2 2 4 2 4 3 3 3 3 - 4 1.12 2 3 3 3 2 2 2 2 2 2 3 2 2 4 3 - 4 0.28 1 4 3 1 2 2 2 1 3 4 4 2 2 3 2 - 8 4 5.6 4 4 4 4 4 4 4 3 4 4 4 3 3 4 4 - 4 1.12 3 4 4 3 4 3 3 3 2 3 3 3 3 4 4 4 0.28 <RTI ID=33.10> 1 1 2 0 2 2 1 2 1 1 1 0 2 3 3 - 2** 0.056 0 0 1 0 0 0 0 0 0 0 0 0 0 0 1 9 4 5.6 4 4 3 3 3 4 3 2 1 4 1 3 4 4 3 - 4 1.12 3 2 3 2 1 1 0 2 1 4 2 3 1 4 3 - 4 0.28 1 3 2 1 2 1 1 2 1 4 2 1 2 4 2 - 10 4 5.6 3 3 2 2 3 3 3 2 1 3 4 1 2 4 3 4 4 1.12 1 2 2 1 2 2 2 2 1 3 4 1 2 4 2 4 4 0.28 1 3 1 0 2 1 1 2 - 2 4 1 1 3 2 4 2 0.056 1 0 0 0 0 0 0 0 0 1 0 0 0 0 0 1 2 0.011 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Table II (cont'd) Plant Species Compound of Example No. WAT kq/h L M N O P B Q D R E F C J S K T 12 4 5.6 1 1 2 2 4 3 0 - 0 4 2 2 3 1 3 2 4 1.12 1 0 0 0 3 1 1 1 0 2 0 1 0 0 1 2 2 0.28 0 0 0 0 1 0 0 0 0 1 0 o 0 0 0 0 13 2 5.6 1 0 2 0 1 1 0 1 - - 1 1 0 0 1 3 2 1.12 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 2 0.28 0 0 0 0 0 0 0 0 0 - 0 0 0 0 0 0 15 4 5.6 1 0 1 0 0 0 0 1 0 1 0 0 0 1 0 2 2 1.12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 22 4 5.6 0 0 1 0 1 0 2 1 - 0 - 1 0 3 2 2 2 1.12 0 0 0 0 0 - 0 0 2 1 - 0 0 0 1 1 24 4 5.6 2 1 2 2 2 3 1 2 - 3 2 2 2 4 3 4 4 1.12 0 0 0 0 0 0 0 1 1 1 2 0 0 1 1 2 27 4 5.6 3 3 4 4 3 3 3 2 3 3 3 2 3 4 3 4 4 1.12 2 2 2 3 2 2 2 2 2 2 2 1 3 4 3 3 4 0.28 2 2 3 3 2 2 2 2 1 1 3 1 3 3 3 2 0.56 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0.02 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 - 28 4 5.6 1 0 1 2 2 2 0 2 3 1 1 0 0 2 3 3 2 1.12 1 0 0 0 0 0 0 1 0 0 0 0 0 0 1 2 2 0.28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 29 4 5.6 4 4 4 4 4 3 4 4 4 4 4 4 4 4 4 4 4 1.12 3 4 4 4 4 3 4 3 3 4 4 3 4 4 3 4 4 0.28 1 3 3 3 3 2 1 2 2 3 4 2 3 4 3 4 0.056 0 0 1 0 2 0 0 2 0 0 1 1 1 3 2 3 0.011 0 0 0 0 0 0 0 1 - 0 0 0 0 0 0 2 30 4 5.6 1 - 3 2 2 0 4 2 3 1 1 1 1 3 2 3 4 1.12 1 0 1 1 1 1 0 1 Il 0 0 0 2 2 3 2 0.28 0 0 0 0 0 0 - 1 0 0 0 0 0 0 0 0 31 4 5.6 2 4 4 3 4 4 3 4 4 4 4 4 3 4 4 4 1.2 2 3 2 3 3 3 1 2 3 2 3 2 1 4 3 3 4 0.28 1 0 2 2 2 1 1 2 2 1 1 1 2 3 3 3 2 0.06 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 2 2 0.01 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 33 4 5.6 3 - 4 3 4 4 3 4 4 4 4 4 4 4 3 3 4 1.12 1 4 1 1 3 3' 2 2 4 1 4 1 3 4 2 2 4 0.28 0 1 0 1 1 0 1 0 2 3 0 0 0 2 1 2 - Species of plant absent during test. ** Formulated immediately prior to treatment. +** Sprayed in 935 liters per hectare immediately after formulation. From the test results presented in Tables I and II, it can be seen that the post-emergent herbicidal activity of the compounds of this invention is, for the most part, general in nature. In certain specific instances, however, some selectivity is demonstrated. In this regard it should be recognized that each individual species selected for the above tests is a representative member of a recognized family of plant species. From Table III, it can be seen that the pre-emergent herbicidal activity demonstrated some selectivity. The herbicidal compositions, including concentrates which require dilution prior to application to the plants, of this invention contain from 5 to 95 parts by weight of at least one compound of this invention and from 5 to 95 parts by weight of an adjuvant in liquid or solid form, for example, from about 0.25 to 25 parts by weight ofbwetting 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 inert liquid extender, e.g., water, acetone, tetrahydrofuran, all parts being by weight of the total composition. Preferably, the compositions of this invention contain from 5 to 75 parts by weight of at least one compound of this invention, together with the adjuvants. Where required, from about 0.1 to 2.0 parts by weight of the inert liquid extender can be replaced by a corrosion inhibitor such as ethanol mercaptan, sodium thiosulfate, dodecylmono or dimercaptan or anti-foaming agent such as a dimethylpolysiloxane, or both. The compositions are prepared by admixing the active ingredient with an adjuvant including diluents, extenders, carriers and conditioning agents to provide 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 a finely-divided solid, a liquid of organic origin, water, a wetting agent, a dispersing agent, an emulsifying agent or any suitable combination of these. The herbicidal compositions of this invention, particularly liquids and soluble powders, preferably contain as a conditioning agent one or more surface-active agents in amounts sufficient to render a given composition readily dispersible in water or in oil. The incorporation of a surface-active agent into the compositions greatly enhances their efficacy. By the term "surface-active agent", it is understood that wetting agents, dispersing agents, suspending agents and emulsifying agents are included therein. Anionic, cationic and nonionic agents can be used with equal facility. Preferred wetting agents are alkyl benzene and alkyl naphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfates or sulfonated fatty acid esters petroleum sulfonates, sulfonated vegetable oils, polyoxyethylene derivatives of phenols and alkylphenols (particularly isooctylphenol and nonylphenol) and polyoxyethylene derivatives of the mono-higher fatty acid esters of hexitol anhydrides (e.g., sorbitan). Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium ligninr sulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalene sulfonate; polymethylene bisnaphthalenesulfonate and sodium N-methyl-N-(long chain acid) taurates. When operating in accordance with the present invention, effective amounts of the compounds or compositions of this invention are applied to the plants, or to soil containing the plants, or are incorporated into aquatic media in any convenient fashion. The application of liquid and particulate solid compositions to plants or soil can be carried out by conventional methods, e.g., power dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray because of their effectiveness at low dosages. The application of herbicidal compositions to aquatic plants is usually carried out by adding the compositions to the aquatic media in the area where control of the aquatic plants is desired. The application of an effective amount of the compounds or compositions of this invention to the plant is essential and critical for the practice of the present invention. The exact amount of active ingredient to be employed is dependent upon the response desired in the plant as well as such other factors as the plant species and stage of development thereof, and the amount of rainfall as well as the specific glycine employed. In foliar treatment for the control of vegetative growth, the active ingredients are applied in amounts from about 0.112 to about 56.0 or more kilograms per hectare. In pre-emergent treatments, the rate of application can be from about 0.56 to about 22.4 or more kilograms per hectare. In applications for the control of aquatic plants, the active ingredients are applied in amounts of from about 0.01 parts per million to about 1000 parts per million, based on the aquatic medium. An effective amount for phytotoxic or herbicidal control is that amount necessary for overall or selective control, i.e., a phytotoxic or herbicidal amount. It is believed that one skilled in the art can readily determine from the teachings of this specification, including examples, the approximate application rate. There are several methods for applying liquid compositions of this invention to emerged plants. Such methods include the use of wiper systems whereby the plant to be treated is contacted with an absorbent material containing the particular liquid composition, a portion of which is thereby released onto the plant upon contact therewith. Such wiper systems typically comprise a reservoir of the liquid composition into which a portion of the absorbent material is placed and is fed therethrough. Generally, substances employable as absorbent material include substances of any shape or form capable of absorbing the liquid composition and releasing a portion of the same upon contact with the plant. Typical absorbent materials include felt, foam rubber, cellulose, nylon, sponges, hemp, cotton, burlap, polyester over acrylic, combinations thereof and the like. Forms of absorbent material include rope, twine, string, cloths, carpets, combinations thereof and the like. These forms may be assembled in any manner desired including a pipe rope wick, a wedge rope wick, a multi-rope wick and the like. In another application method, liquid compositions may be selectively applied to weeds by the use of recirculating sprayer systems wherein the recirculating spray unit is mounted on a tractor or high clearance mobile equipment and the spray is directed horizonially onto the weeds growing over a crop. Spray not intercepted by the weeds is collected in a recovery chamber before contacting the crop and is reused. Roller applications may also be employed to apply liquid compositions to weeds growing over a crop. In yet another application method, shielded applicators may be employed to direct the liquid composition in the form of a spray onto the weeds while effectively shielding the crops from the spray. These and other application methods for selectively applying liquid compositions to weeds are discussed in detail in Innovative Methods of Post-Emergence Weed Control, McWhorter C.G, Southern Weed Science Society, 33rd Annual Meeting Proceedings, Jan. 15-17, 1980; Auburn University Printing Service, Auburn, Alabama U.S.A., the teachings of which are incorporated herein by reference in their entirety. Another method of applying liquid compositions of this invention to plants includes controlled droplet application which is also known as the ultra low-volume chemical application. Controlled droplet application involves the production of uniform or nearly uniform spray drops of a predetermined size and the conveyance of these drops with negligible evaporation to a spray target. In particular, this method comprises feeding spray solutions to a rotary atomizer comprising a small disk with serrated edges that disperses liquid into droplets as the disk spins. Different droplet sizes are produced by changing solution flow rates to the spinning disk or changing the speed of rotation of the disk. The aforementioned and other methods for applying liquid compositions to plants are discussed in detail in "Rope Wick Applicator - Tool With A Future", Dale, James E., pp. 3-4, "The Recirculating Sprayer and RoundupS Herbicide", Derting, Claude W., pp. 5-7, and "C.D.A. Herbicide Application", McGarvey, Frank X., Weeds Today, Volume 11, Number 2, pp. 8-9, Late Spring, 1980, 309 W. Clark St., Champaign, Illinois, the teachings of which are incorporated herein by reference in their entirety. Although this invention has been described with respect to specific modifications, the details thereof are not to be construed as limitations, for it will be apparent that various equivalents, changes and modifications may be resorted to without departing from the spirit and scope thereof and it is understood that such equivalent embodiments are intended to be included herein.

Claims: CLAIMS 1. A process for the preparation of phosphonate compounds useful as herbicides of the formula EMI40.1 wherein a+b=2, and a is O or 1, Z is EMI40.2 wherein R2 is C18 alkyl, (C18 alkoxy) C1-8 alkyl, halo C1-8 alkyl, phenyl C1-8 alkyl or Z is C2-8 alkynyl, C18 alkyl, or N#CCH2, R is selected from hydrogen, C1-8 alkyl , (C1-8 alkoxy) C18 alkyl, halo C18 alkyl, or phenyl C1-8 alkyl and R1 is independently selected from R or EMI40.3 wherein n is an integer from 1 to 4, R3 is selected from hydrogen, C18 alkyl, (C18 alkoxy) C1-8 alkyl, halo C1- 8 alkyl, phenyl C1-8 alkyl and R4 is hydrogen or C1-8 alkyl; excepting that R3 and R4 cannot both be hydrogen when n is one and b is I or 2; EMI40.4 wherein R5 is hydrogen, C1-8 alkyl, (C1-8 alkoxy) carbonyl; and R6 is halogen, (C1-8 alkoxy) carbonyl or EMI41.1 wherein L is C1-8 alkyl and n1 is 0 or an integer from 1 to 3; -(Cn2H2n2)S-X,wherein X is C18 alkyl or (C1-8 alkoxy) carbonyl and n2 is an integer from 1 to 4; or 0n H2n )-Y, wherein n3 is 0 or an integer from 1 to 4 anA Y is selected from trihalomethyl, (C1-8 alkoxy)carbonyl, furanyl, pyrolidinyl, pyranyl, thiopyranyl, EMI41.2 wherein M1 and M are independently C1-8 alkyl, said process comprising : (a) reacting (i) a trisubstituted phosphite of the formula P(OR1)3 wherein R1 is as defined above, with (ii) water, and (iii) a compound of the formula EMI41.3 wherein Z is as aforedefined to prepare a crude phosphonate composition containing said phosphonate compound, and (b) thereafter recovering said phosphonate compound from said crude phosphonate composition. 2. A process of Claim 1, wherein said process is conducted in the absence of a solvent. 3. A process of either of Claims 1 and 2 wherein said process is conducted in the absence of a catalyst. 4. A process of any of Claims 1 to 3 wherein the reaction is carried out at a temperature in the range from about 10 to about 110 C. 5. A process of Claim 4 wheretn the temperature is in the range from about 20 to about 100 C. 6. A process of any of Claims 1 to 5 wherein a + b = 2, a isO or 1, and Z is selected from EMI42.1 wherein R2 is (C1-8 alkoxy) C18 alkyl, halo C18 alkyl or phenyl Cl-8-alkyl, or N # CCH2; R is hydrogen, R1 is independently selected from R or EMI42.2 wherein n is an integer from 1 to 4, R3 is selected from C18 alkyl, (C1-8 alkoxy) C1 -8 alkyl, and R4 is hydrogen or C1 8 alkyl; or R1 is (Cn H2n )¯Y wherein n3 is O or an integer from 1 to 4 and Y is trihlomthyl. 7. A process of Claim 6 wherein said compound is glycine, N-[[(1-cyanoethoxy)hydroxy-phosphinyl] methyl] ,-pentyl ester; glycine, N-(l-cyanoethoxy)hydroxyphosphinyl7methyl ,2-ch?oro-ethyl ester; glycine, N-W (1-cyanopropoxy)hydroxyphosphinyl] methyl, ethyl ester; glycine, N-[[ (1-cyanoethoxy)hydroxyphosphinyl] methyl] , 2-ethoxyethyl ester; glycine, N-[[(1-cyanoethoxy)hydroxyphosphinyl] methyl, phenylmethyl ester; glycine, N- [[hydroxy(2,2,2-trichloroethoxy) phosphinyl]-methyl 2 ethyl ester; glycine, N- [[(cyanomethoxy)hydroxy- phosphinylamethyl], ethyl ester; or glycine, N- [[bis(1-cyanopropoxy) phosphinyl]methyl3, ethyl ester. 8. A compound of the formula EMI43.1 wherein a + b = 2, and a is 0 or 1, Z is EMI43.2 wherein R2 is C1-8 alkyl, (C1 8 alkoxy) C18 alkyl, halo C18 alkyl, phenyl C1-8 alkyl or Z is C2-8 alkynyl, C18 alkyl, or N#CCH2, R is selected from hydrogen, C1-8 alkyl, (C1-8 alkoxy) C1-8 alkyl, halo C1-8 alkyl, or phenyl C1-8 alkyl and R1 is independently selected from EMI43.3 wherein n is an integer from 1 to 4, R3 is selected from hydrogen, C1-8 alkyl, (C1-8 alkoxy) C1-8 alkyl, halo C1-8 alkyl, phenyl C1-8 alkyl and R4 is hydrogen or C1-8 alkyl; EMI44.1 wherein R5 is hydrogen, C1-8 alkyl, (C1 8 alkoxy) carbonyl; and R6 is halogen, (C18 alkoxy) carbonyl, and EMI44.2 wherein L is C1-8 alkyl and nl is 0 or an integer from 1 to 3; (Cn H2n )S-X wherein X is (C1-8 alkyl) or (C1 8 alkoxy) carbonyl and n2 is an integer from 1 to 4; EMI44.3 wherein T is C1-8 alkyl; and -(Cn3H2n3)-Y, wherein n3 is 0 or an integer from 1 to 4 and Y is selected from trihalomethyl, (C1-8 alkoxy)carbonyl, furanyl, pyrolidinyl, pyranyl, thiopyranyl and EMI44.4 wherein M1 and M are independently C1-8 alkyl, or an agriculturally acceptable salt thereof, but excluding the compounds wherein n is two and R3 and R4 are both hydrogen and the compounds wherein R1 and R are both ethyl (or alternatively R1 is ethyl and b is two) and n is one. 9. A compound of Claim 8 wherein a + b = 2, a is 0 or 1 and Z is EMI45.1 wherein R2 is C1-8 alkyl, halo C18 alkyl, (C1- 8 alkoxy) C1-8 alkyl, phenyl C1-8 alkyl, or Z is NCCH2; R1 is independently selected from EMI45.2 wherein n is 1 or (Cn H2n )-Y wherein n3 is 1 and Y is trihalomethyl; R3 R3 is C18 alkyl and 4 is hydrogen, or an agriculturally acceptable salt thereof. 10. A compound of Claim 9 wherein said compound is glycine, N- [[(1-cyanoetoxy)hydroxy-phosphinyl]methyl],-pentyl ester or an agriculturally acceptable salt thereof. 11. A compound of Claim 9 wherein said compound is glycine, N- 1 cyanoethoxy)hydroxyphosphinyllmethyl], 2-chloroethyl ester or an agriculturally acceptable salt thereof. 12. A compound of Claim 9 wherein said compound is glycine, N- [[(1-cyanopropoxy)hydroxyphosphinyl]methyl], ethyl ester or an agriculturally acceptable salt thereof. 13. A compound of Claim 9 wherein said compound is glycine, N-[[(1-cyanoethoxy)hydroxyphosphinyl]methyl], 2-ethoxyethyl ester or an agriculturally acceptable salt thereof. 14. A compound of Claim 9 wherein said compound is glycine, N- pr(l-cyanoethoxy)hydroxyphosphinyl]methyl|, phenylmethyl ester or an agriculturally acceptable salt thereof 15. A compound of Claim 9 wherein said compound is glycine; N- hydroxy(2,2,2-trichloroethoxy)phosphinyl methylzethyl ester or an agriculturally acceptable salt thereof. 16. A compound of Claim 9 wherein said compound is glycine, N- [[(cyanomethoxy)hydroxyphosphinyl]methyl], ethyl ester or an agriculturally acceptable salt thereof. 17. A compound of Claim 9 wherein said compound is glycine, N-[[bis(1-cyanopropoxy)phosphinyl]methyl], ethyl ester or an agriculturally acceptable salt thereof. 18. A herbicidal method which comprises applying to the plants a herbicidally effective amount of a compound of Claim 8. 19. A herbicidal method which comprises applying to the plants a herbicidally effective amount of a compound of Claim 9 or an agriculturally acceptable salt thereof. 20. A herbicidal method which comprises applying to the plants a herbicidally effective amount of a compound of any of Claims 10 to 17 or an agriculturally acceptable salt thereof. 21. A herbicidal composition comprising a herbicidally effective amount of a compound of either of Claims 8 and 9 and a herbicidally inert diluent. 22. A herbicidal composition comprising a herbicidally effective amount of a compound of Claim 10 or an agriculturally acceptable salt thereof and a herbicidally inert diluent. 23, A herbicidal composition comprising a herbicidally effective amount of a compound of Claim 11 or an agriculturally acceptable salt thereof and a herbicidally inert diluent. 24. A herbicidal composition comprlstng a herbicidally effective amount of a compound of Claim 12 or an agriculturally acceptable salt thereof and a herbicidally inert diluent. 25. A herbicidal composition comprising a herbicidally effective amount of a compound of Claim 13 or an agriculturally acceptable salt thereof and a herbicidally inert diluent. 26. A herbicidal composition comprising a herbicidally effective amount of a compound of Claim 14 or an agriculturally acceptable salt thereof and a herbicidally inert diluent. 27. A herbicidal composition comprising a herbicidally effective amount of a compound of Claim 15 or an agriculturally acceptable salt thereof and a herbicidally inert diluent, 28. A herbicidal composition comprising a herbicidally effective amount of a compound of Claim 16 or an agriculturally acceptable salt thereof and a herbicidally inert diluent. 29. A herbicidal composition comprising a herbicidally effective amount of a compound of Claim 17 or an agriculturally acceptable salt thereof and a herbicidally inert diluent.

Inventors: PURDUM, WILLIAM RONALD
Applicants: MONSANTO COMPANY
Application year: 1982
Main classification: C07F9
IPC codes: A01N57, C07F9