KR810000411B1 - Derivatives of n-phosphonomethylglycine - Google Patents

Abstract

Title compd. (I; Y = H, lower alkyl or alkali metal; Z = H or alkali metal; R = vinylene, methylvinylene, C2-3 alkylene), having herbicidal activity, was prepd. by the reaction of di (alkali metal) salt of III(N-phosphonomethylglycine) and II in pH 6-10. III was prepd. by treating N-phosphonomethylglycine(16.9g) with 50 % sodium hydroxide in 30 ml H2O. Thus, III and 18.5 g anhydrous phthalic acid were reacted at pH 6 to give N-carboxymethyl-N-(phosphonomethyl)phthalamine.

Description

Method for preparing N-phosphonomethylglycine derivatives.

The present invention relates to a process for preparing the compound of formula (I) which is useful as a post-germination treatment preparation.

In the above structural formula

Y is selected from hydrogen, lower alkyl and alkali metals.

Z is selected from hydrogen and alkali metal, respectively.

R is a vinylene, methylvinylene, a mochloro derivative of alkylene, vinylene and alkylene having 2-3 carbon atoms in between and free carbon atoms, up to 8 carbon atoms, phenylene, carboxyphenylene, 3 -Nitrophenylene, toriene, cyclohexenylene, methylcyclohexenylene cycloalkylene with 4-6 carbon atoms, dicarboxycycloalkylene with 4-6 ring carbon atoms, dicarboxybenzoylphenylene, norbor Nenirene, norbornylidene, N-methylpyrrolilidene, pyridylidene, picorylidene and chienylidene and piconilidene and chienidene. only; Free atoms on the ring should be in the ortho position with respect to the ring carbon atom. As used herein, "lower alkyl" refers to an aliphatic hydrocarbon group that is straight and branched with 1-4 carbon atoms.

Preferred compounds according to the present invention in the above structure is a compound in which R is phenylene, cyclohexerenene or alkylene having 2-3 carbon atoms in between and free carbon atoms up to 5 carbon atoms in total.

의 중심핵이 된다는 것을 이해해야만 한다.As described below, one of the reactants used to prepare these novel compounds is anhydrides of cyclic materials. R in the formula is an anhydride residue

It should be understood that it is the central core of.

Alkyrenic groups represented as R are chained groups obtained from succinic anhydride or glutaric anhydride, these groups being 3,3-dimethylglutaric acid, 2,4-diethylglutaric acid and 2,2-dipropyl stone Substituted chains such as those obtained from sinic acid anhydride.

The groups in the cyclic form represented by R are obtained from anhydrides such as aliphatic, isomeric detrahydrophthalic acid, tri- and hemi-melitinic acid, pyridine-, thiophene- and norbornanedicarboxylic acid, and cycloalkanedicarboxylic acid. I have a group.

,2-토리렌기)로부터 얻은 링을 가진 기들을 포함한다.In a special case where R represents torrene, these groups are isomers of methylphthalan anhydride and homophthalin anhydride (

, 2-torylene group).

The cyclic anhydrides used as reactants herein include some di-anhydrides such as di-anhydrides of benzophenonetetracarboxylic acids and di-anhydrides of alicyclic tetracarboxylic acids. As described in some examples below, the reaction results in the substitution of one of the anhydride groups while the second anhydride group is opened and closed, resulting in a dicarboxy substituent at the ortho position.

The novel compounds according to the invention are prepared by condensation of suitable cyclic anhydrides with di (alkalimetal) salts of N-phosphonomethylglycine or mono (alkalimetal) salts of lower alkylglycinates. The salts are obtained by adding alkali metal hydroxides to N-phosphonomethylglycine or glycinate in a conventional manner, and it can be seen that such adducts attach hydroxyl groups to the phosphors. Although anhydrides and salts are preferably used in excess in order to accelerate the reaction, anhydrides and salts may be used in about equimolar amounts.

This reaction is usually carried out at room temperature and cooled when the exotherm increases. During the reaction, the pH should be in the range of about 6-10, preferably 7-9, which can be easily maintained by periodically adding alkali as necessary.

The product of this reaction is a tri-salt of the above formula wherein Y and each Z is an alkali metal or glycinatedi-salt where Y is lower alkyl and each Z is an alkali metal. As described later, the product can be used in a form that is not isolated or purified and can be acidified to remove alkali metals.

Acidification of the reaction product can in some cases be done by treatment with hydrochloric acid, but since this process can cause partial or complete reverse reactions, acidification of the salt product via ion exchange chromatography using acidic ion exchange resins. desirable.

The preparation of certain compounds according to the invention is not limited to the following examples.

Example 1

A slurry of 16.9 g (0.10 mol) of N-phosphonomethylglycine in 30 ml of water was simultaneously treated with 16 g (0.20 mol) of 50% aqueous sodium hydroxide solution. The solution is stirred and cooled to 5-15 ° C. to obtain the disodium salt of glycine described above. 18.5 g (0.125 mol) of phthalic anhydride pulverized into fine powder by a motor is added to a salt solution with vigorous stirring at 20-25 ° C. Periodically add 50% aqueous sodium hydroxide solution to maintain about pH 6. After stirring overnight, 2.9 g of phthalic anhydride. After further addition according to sodium hydroxide to maintain about pH8, the reaction mixture is concentrated below 60 ° C and dehydrated to obtain a crumb-like glassy material. 10 g of the product in 40 ml of water are passed through a column of Dow X 50 ion exchange resin in acid form to receive 50 ml each. The second aliquot was dehydrated twice to give N-carboxymethyl-N- (phosphonomethyl) phthalamine as colorless glassy material.

Elemental Analysis, About C ₁₁ H ₁₂ NO ₈ P

Calculated: C; 41.65%, H; 3.81%, P; 9.77%

Found: C; 40.97 H; 4.25% P; 9.34%

Example 2

A disodium salt solution of N-phosphonomethylglycine was prepared as described in Example I, and 11.0 g (0.11 mol) of crushed maleic anhydride was added with stirring. Some sodium hydroxide is added to maintain approximately pH 9 and a small amount of ether is added to promote dissolution of the anhydride. Stirring is continued for several days and then 2.0 or 4.0 g of maleic anhydride is added to ensure that N-phosphonomethyl glycine does not remain in the mixture.

During this time a small amount of sodium hydroxide is added to maintain pH 8. After the reaction is complete the mixture is filtered, washed with water and concentrated and then dehydrated. A product containing disodium malate by-product is obtained as a colorless glassy material. This was confirmed by nmr as a trisodium salt of N-carboxymethyl-N- (phosphonomethyl) maleamic acid.

Example 3

Disodium salt of N-phosphonomethylglycine was prepared by the method described in Example 1 using 8.5 g of glycine and 8.1 g of sodium hydroxide in 15 ml of water. Cool the salt solution and stir with a partial portion of 5.5 g of succinic anhydride over about 2 hours.

Sodium hydroxide is added periodically to maintain the pH in the desired range and stirred overnight. The reaction mixture is passed through an acid-type ion exchange resin column and dehydrated to obtain a colorless sample. This product is dissolved in water and passed through the column again.

Two aliquots of the first 50 ml are dehydrated and dissolved again, followed by dehydration to obtain N-carboxymethyl-N- (phosphonomethyl) succinamic acid (monohydratoform) as a colorless glassy material.

Elemental Analysis, C ₇ H ₁₂ NO ₈ P · H ₂ O

Calculated: C; 29.28%, H; 4.91%, P; 10.79%

Found: C; 29.46 H; 4.57% P; 10.58%

Example 4

Disodium salt of N-phosphonomethylglycine was prepared as described in Example 3. The salt solution is stirred while adding 8.5 g of 3,4,5,6-tetrahydro phthalic anhydride according to sodium hydroxide to maintain the pH above 8.

The reaction mixture is stirred overnight, 1.0 g of anhydride is further added, and the reaction mixture is stirred to complete. The mixture is filtered to give a pink solution containing disodium tetrahydro phthalate as a by-product. The reaction product was identified by nmr as a trisodium salt of N-carboxymethyl-N-phosphonomethyl-3,4,5,6-tetrahydrophthalamine acid.

.

Example 5

Disodium salt of N-phosphomethylglycine was prepared as described in Example III. The solution is stirred and cooled while small amounts of 8.5 g of 1,2,3,6-tetrahydrophthalin anhydride are added in small portions. After stirring overnight, three portions of 0.5 g of anhydride are added periodically with sodium hydroxide to maintain pH 2 or higher. The reaction mixture is concentrated, then dehydrated and dissolved again with water and passed through an acidic ion exchange resin column. 50 ml of the 2nd aliquots are dehydrated and N-carboxymethyl-N-phosphonomethyl- 1,2,3,6- tetrahydro phthalamine acid (monohydrate type) is obtained as a colorless and crumbly glassy substance.

Elemental Analysis for C ₁₁ H ₁₆ NO ₈ P · H ₂ O

Calculation: 38.95%, 5.35%, 9.13%

Found: 40.15%, 5.31%, 8.94%

Example 6

A disodium salt of N-phosphonomethylglycine is prepared as described above for about 0.042 mole solution and 8.67 g (0.045 mole) of 3-nitrophthalic anhydride are added with stirring and cooled. A small amount of 50% aqueous sodium hydroxide solution is added periodically to maintain the pH in the desired range and 2.0 g of anhydride is added to complete the reaction. Dehydrate and apply. The reaction mixture is passed through a column of acid exchange ion exchange resins. 50 ml of the second aliquot was dehydrated twice to give N-carboxymethyl-N-phosphonomethyl- (3- and 6-nitro) phthalamic acid (dihydroform) as a creamy, brittle glassy material. This product reacts at 80 ° C. and decomposes at 165 ° C.

Elemental Analysis for C ₁₁ H ₁₁ N ₂ O ₁₀ P · 2H ₂ O

Calculated: N; 7.03%, P; 7.78%

Found: N; 7.10%, P; 7.59%

Example 7

A disodium salt of N-phosphonomethylglycine was prepared as described in Example 3 and 9.0 g of 5-norbornene-2,3-dicarboxylic anhydride was added with stirring and cooled.

After stirring overnight, 3.0 g of anhydride are added and the last 0.5 g is added after a few hours to complete the reaction. During this time a small amount of sodium hydroxide is added to keep the pH at 7. The reaction mixture is then filtered to afford a product containing the by-product disodium-5-norborne-2,3-dicarboxylate as colorless use. This product was identified by nmr as the trisodium salt of N-carboxymethyl-N-phosphonomethyl-5-norbornene-2,3-dicarboxamine acid.

Example 8

Disodium salt of N-phosphonomethylglycine was prepared as described in Example 3 and 8.1 g of homophthalic anhydride was added with stirring. A small amount of 1.0 or 1.5 g of anhydride is added to complete the reaction, followed by periodic addition of aqueous sodium hydroxide solution to maintain the desired pH range.

The reaction solution is diluted with water, filtered to remove solids, and then passed through an acidic ion exchange resin. Dehydration of the two aliquots at the first 50 ml, dissolution again with water, and re-dehydration resulted in reaction at 80 DEG C. The heat decomposed at 155 DEG C is a yellow, brittle glassy substance, N-carboxymethyl-N- (phosphonomethyl) homophthal. Amino acid is obtained.

Elemental Analysis, C ₁₂ H ₁₄ NO ₈ P

Calculated: C; 43.52%, H; 4.26%, P; 9.35%

Found: C; 43.49%, H; 4.22%, P; 8.77%

Example 9

A disodium salt of N-phosphonomethylglycine was prepared as described in Example 3 and 6.3 g of cyclobutyne-1,2-dicarboxylic acid anhydride were added with stirring. A few drops of aqueous sodium hydroxide solution is added periodically to keep the pH at about 8 and 0.6 g of anhydride is added to complete the reaction. The reaction mixture is dehydrated and redissolved with water and passed through an acidic ion exchange resin column. 50 ml of the second aliquot was dehydrated twice to give a white crumbly N-carboxymethyl-N-phosphonomethyl-2-carboxycyclobutanecarboxamide which was reacted at 87 ° C and decomposed at 172 ° C.

Elemental Analysis, About C ₉ H ₁₄ NO ₈ P

Calculated: C; 36.62%, H; 4.78%, P; 10.49%

Found: C; 35.64%, H; 4.96%, P; 10.07%

Example 10

Disodium salt of N-phosphonomethylglycine was prepared as described in Example 3 and 6.0 g of methylsuccinic anhydride was added with stirring. The mixture is cooled and the pH is maintained at about 8 by adding 50% aqueous sodium hydroxide solution.

Two portions of 1.0 g of the anhydride described above are added according to the alkali to complete the reaction. The pH is then lowered to 8 or less, the reaction mixture is diluted with water and passed through an acidic ion exchange resin column. Dehydrate the 50 ml of the second aliquot twice,

N-carboxymethyl-N-phosphonomethyl 2-succinic acid (monohydrate type) is obtained.

Elemental Analysis, C ₈ H ₁₄ NO ₈ P · H ₂ O

Calculated: C; 32.77%, H; 5.10%, N; 8.33%, P; 9.97%

C; 31.90%, H; 5.35%, N; 8.38%, P; 10.29%

Example 11

Sodium salt of N-phosphonomethylglycine was prepared as described in Example 3 and 8.5 g of cyclohexane-1,2-dicarboxylic anhydride were added with stirring. This anhydride is slowly dissolved and the sodium hydroxide is added in small portions periodically to maintain a pH of about 8. Add 1.0 gDMF of anhydride as described above to complete the reaction. The reaction mixture is filtered to give the product as a colorless solution containing disodium cyclohexane-1,2-dicarboxylate as a by-product. The above-mentioned product was identified by nmr as a trisodium salt of N-carboxymethyl-N-phosphonomethyl-2-carboxycyclohexane carboxyamine acid.

Example 12

Disodium salt of N-phosphonomethylglycine was prepared as described in Example 3 and 7.8 g of 2,3-pyridine dicarboxylic anhydride were added with stirring. Two portions of 20 g of the anhydride described above were added to complete the reaction, and a small amount of 50% aqueous sodium hydroxide solution was added periodically to maintain the desired pH range.

The reaction mixture is passed through an acidic ion exchange resin to dehydrate the first few fractions twice to give N-carboxymethyl-N- (phosphonomethyl) quinolinamic acid (monohydrate form) as a brittle white solid.

Elemental Analysis, C ₁₀ H ₁₁ N ₂ O ₈ P · H ₂ O

Calculated: C; 35.73%, H; 3.90%, P; 9.21%

Found: C; 36.23%, H; 5.89%, P; 9.24%

Example 13

A disodium salt solution of N-phosphonomethylglycine was prepared as described in Example 1 except using 0.03 mol of glycine and 0.06 mol of hydroxide. 6.4 g of trimellitic anhydride is added to the solution with stirring, and a small amount of 50% aqueous sodium hydroxide solution is added periodically to maintain pH 7-9.

1.0 and 2.0 g of the anhydride described above is added to complete the reaction.

The reaction mixture is passed through an ion exchange resin column in acid form to recombine several aliquots and then become slightly alkaline. Depending on the alkali, 1.0 g of anhydride is added and added to the resulting solution, concentrated and passed through another ion exchange column. Dehydration of the two aliquots twice in the first 20 ml yields N-carboxymethyl-N-phosphonomethyl-2,4-dicarboxybenzamide (monohydrate form) as a colorless, brittle glassy material.

Elemental Analysis for C ₁₂ H ₁₂ NO ₁₀ P · H ₂ O

Calculated: C; 38.00%, H; 3.72%, N; 3.69%, P; 8.16%

Found: C; 38.30%, H; 3.26%, N; 3.82%, P; 8.15%

Example 14

A solution of disodium salt of N-phosphonomethylglycine was prepared as described in Example 13 and 4.7 g of 3,3-dimethylglutaric anhydride was added with stirring. The 50% aqueous sodium hydroxide solution is periodically maintained at pH 8-9 and the anhydrides 1.5 and 1.0 described above are added to complete the reaction. The reaction mixture was then passed through an ion exchange resin column in acid form to dehydrate the three aliquots of the first 20 ml to give N-carboxymethyl-TT-phosphonomethyl-3,3-dimethylglutamic acid as a colorless glassy material. .

Elemental Analysis, C ₁₀ H ₁₈ NO ₈ · P

Calculated: C; 38.59%, H; 5.83%, N; 4.50%, P; 9.95%

Found: C; 39.18%, H; 60.6%, N; 3.84%, P; 8.38%

Example 15

A disodium solution of N-phosphonomethylglycine was prepared as described in the examples, and 4.7 g of 2,2-dimethyl glutaric anhydride was added with stirring. A small amount of sodium hydroxide is added periodically to maintain pH 8-9 and the reaction is completed by adding 2.0 and 1.5 g of the anhydride described above.

The reaction mixture is then passed through an ion exchange resin column in acid form. 20 ml of the 2nd and 3rd aliquots were mixed and dehydrated to obtain an amber glassy substance.

N-carboxymethyl-N-phosphonomethyl-2,2-dimethylglutamic acid is obtained.

Elemental Analysis, About C ₁₀ H ₁₈ NO ₈ P

Calculated: C; 38.59%, H; 5.83%, N; 4.50%, P; 9.95%

Found: C; 38.81%, H; 5.91%, N; 4.06%, P; 8.92%

Example 16

Fill a suitable reaction vessel with 3.94 g (0.02 mol) of ethyl N-phosphonomethyl glycinate in 15 ml of water. While cooling to below about 15 ° C. in an ice batch, 50% aqueous sodium hydroxide solution is added to bring the pH to about 8. Next 2.51 g (0.02 mol) of methylsuccinic acid anhydride are added with stirring and cooling is continued. Two parts of 1.0 g of the anhydride described above are added to complete the reaction, and alkali is added to maintain pH. The reaction mixture is diluted with water and passed through an acid exchange ion exchange resin column.

20 ml aliquots of the first seventh are mixed with 20 ml of water and 1.2 g of the anhydride described above is added. The resulting reaction mixture is passed through a column, 20 ml aliquots of the first to fourth mixture are mixed and dehydrated. The product is cooled in dry ice to give N-carbetoxymethyl-N- (phosphonomethyl) -2-methyl-succinic acid (monohydrate type) as a transparent glassy gum.

Elemental Analysis, C ₁₀ H ₁₈ No ₈ P · H ₂ O

Calculated: N; 4.25%, P; 9.40%

Found: N; 4.01%, P; 9.13%

Example 17

Ethyl N-phosphonomethylglycinate in water is cooled and treated with sodium hydroxide as described in Example 16. Then 3.0 g of 2,3-pyridine dicarboxylic anhydride are added with stirring. Two portions of 1.0 g of the anhydride described above are added to complete the reaction and alkaline is added to maintain pH. The reaction mixture is diluted with water and passed through an acid exchange ion column. Each 20 ml aliquot of the first sixth mixture is mixed and dehydrated to obtain N-carbetoxymethyl-N- (phosphonomethyl) quinolinamine acid as a fragile glassy material.

Elemental Analysis, C ₁₂ H ₁₅ N ₂₈ O ₈ P

Calculated: N; 8.09%, P; 8.95%

Found: N; 7.94%, P; 8.93%

Example 18

5.47 g of ethyl N-hydroxy (phenoxy) phosphonomethyl glycinate in 50 ml of water is added to a suitable reaction vessel, and 50% aqueous sodium hydroxide solution is added and cooled to maintain a pH of 8 or less. 3.3 (0.022 mol) of phthalic anhydride in flake form is added and a small amount of alkali is added periodically to maintain pH until the reaction is complete. The reaction mixture is diluted with water and passed through an acid exchange ion exchange resin column.

20 ml each of the fourth and fifth aliquots are mixed, dehydrated and remixed. The dumped product is N-carbetoxymethyl-N- (phosphonomethyl) phthalamine acid as wet glassy material.

Elemental Analysis, C ₁₃ H ₁₆ NO ₈ P

Calculated: C; 43.25%, H; 4.84%, P; 9.29%

Found: C; 43.72%, H; 4.76%, P; 9.20%

Example 19

To 28.6 g (0.03 mol) of disodium salt of N-phosphonomethyl glycine prepared according to the method of the above-described embodiments, 4.2 g (0.015 mol) of cyclobutyne-1,2,3,4-tetracarboxylic acid dianhydride was added. Add. Alkaline is added periodically to maintain the pH at about 8 and 4.2 g and 1.0 g of the anhydrides described above are added to complete the reaction. The reaction mixture is diluted with water and passed through an acid exchange ion exchange resin column. 20 ml of the second to fourth aliquots were collected and dehydrated to give N-carboxymethyl-N-phosphonomethyl-2,3,4-tricarboxycyclobutane carboxamide (mono) as a creamy, crumbly foamy substance. Hydrate type).

Elemental Analysis for C ₁₁ H ₁₄ NO ₁₂ P · H ₂ O

Calculated: C; 32.93%, H; 4.02%, N; 3.49%, P; 7.72%

Found: C; 33.38%, H; 3.94%, N; 3.27%, P; 7.31%

Example 20

3.2 g (0.01 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride is added to 0.02 mol of disodium salt of N-phosphonomethylglycine prepared according to the method of the above-described embodiments. .

Alkaline is added periodically to maintain the pH at about 8, and 3.2 g and 1.0 g of the anhydride described above are added to complete the reaction. The reaction mixture is diluted with water and passed through an acidic ion exchange resin column. 20 ml of the second and third aliquots were mixed and dehydrated to give 4- (3 ', 4-dicarboxybenzoyl) -N-carboxymethyl-N- (phosphonomethyl) phthalamine acid (monohydrate type) as a yellowish brown glassy substance. Get

Elemental Analysis for C ₂₀ H ₁₆ NO ₁₃ PH ₂ O

Calculated: C; 45.55%, H; 3.44%, N; 2.16%, P; 5.87%

Found: C; 44.18%, H; 3.47%, N; 2.77%, P; 6.12%

Post-germination treatment herbicidal effects of various compounds according to the present invention can be explained as follows. The active ingredient is sprayed on various plant species 14-21.

A sparse aqueous solution containing the active ingredient and surfactant (35 parts of dodecylbenzenesulfonic acid and 11 moles of ethylene oxide: 65 parts of tall oil condensed with ethylene oxide at a ratio of 1 mole of tall oil) was used in several ratios (kg / ha) was used for plants in several sets of pans. The treated plants are placed in a greenhouse and recorded after approximately 2 or 4 weeks of observation.

Data is shown in Table 1 and Table 2.

In each table, WAT means the number of days after treatment, and the species of the treated plants are represented by the following abbreviations.

TABLE 1

TABLE 2

The last four rows of data for compound 4 and the last four rows of data for compound 7 in Table 1 show the test results in which the active ingredient was sprayed with an aqueous solution without the surfactant used at all other time points.

From the data presented in the tables it can be seen that the example compounds according to the invention are effective post-germination treatment herbicides. However, these data show that the compounds have selectivity with respect to the various plant species used in the test process.

Since each of the plant species described above was chosen as a sample of several plant families (eg wild buckwheat-perennial grass; Ramsquater-middle subfamily), the specialists in this distribution found that the selectivity of crops and weeds was very good. have.

A potent composition according to the present invention, including concentrates that require dilution before use in plants, contains at least one active ingredient and auxiliary in liquid or solid form. The composition is prepared in the form of a crushed solid, pellet, solution dispersant or emulsion in admixture with an adjuvant containing an extender, co-agent, carrier and modulator in the active ingredient. As such, the active ingredient may be used in combination with adjuvants such as crushed solids, organic stocks, water, humectants, dispersants, emulsions or mixtures thereof. In terms of cost and convenience, water is a preferred extender, especially when the active ingredient is dissolved in water.

The debilitating compositions according to the invention, in particular liquids, are dissolved in water or oil by adding at least one surfactant as a modifier. Incorporation of surfactants in the composition increases the efficacy even more. "Surfactant" means a humectant, a dispersant, a suspending agent and an emulsifier. Cationic, anionic and nonionic surfactants can be used in the same function.

Preferred humectants include alkylbenzenes, alkylnaphthalene sulfonates, sulfonated fatty alcohols, amines or acid amides, long chain acid esters of sodium isocionate, esters of sodium sulfosuccinate, sulfated or sulfonated Fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, polyoxyethylene derivatives of alkylphenols (particularly isooctylphenol and nonylphenol), and polyoxyethylene derivatives of monohigh fatty acid esters of hexitol anhydrides such as sorbitan. Preferred dispersants are methylcellulose, polyvinyl alcohol, sodium lignin sulfonate, alkyl naphthalenesulfonate as polymer, sodium naphthalenesulfonate, polymethylenebisnaphthalenesulfonate and sodium N-methyl-N (long chain acid) tauray Etc.

Hydrating compositions are made of one or more active ingredients, inert solids, and one or more wetting agents, dispersants.

Such a fluorinable solid extender uses minerals synthesized from such materials as fumed clay and diatomaceous earth silica. Also, kaolin, attapulgite clay, synthetic magnesium silicate and the like are used.

This hydrating agent consists of 5-95 parts by weight of active ingredient, 0.25-25 parts by weight of a humectant, 0.25-25 parts by weight of dispersant, 4.5-94.5 parts by weight of inert solid extender, and the like. If necessary, about 0.1-2.0 parts of the inert solid extender may be replaced with an anticorrosive or antifoaming agent.

The aqueous suspension is mixed with a slurry of insoluble active ingredient in water in the presence of a dispersant and ground to form a fine particle concentrate. Because this concentrated water suspension is very fine particles, the coating surface is very uniform when diluted or sprayed and usually consists of 5-95 parts of active ingredient, 0.25-25 parts of dispersant and 4.5-94.5 parts of water.

Emulsions are mixed with a surfactant solution of the active ingredient in a solvent that is not mixed or partially mixed with fire. Suitable solvents for the active ingredient include ethers, esters or ketones which are incompatible with hydrocarbons and water. The emulsion composition generally consists of about 5-95 parts of active ingredient, about 1-50 parts of surfactant and about 4-94 parts of solvent.

The composition of the present invention may contain fertilizers, plant poisons and plant growth regulators, insecticides or similar auxiliaries, or the like as mentioned above, but in order to achieve the maximum effect, only the composition of the present invention may be used alone. Subsequently, plant poisons, fertilizers, and the like are preferably used. For example, the composition of the present invention may be sprayed onto the ground area before or after treatment with fertilizers or other plant poisons. In addition, it may be sprayed by mixing with a plant poison or a fertilizer, or may be sprayed alone of the composition of the present invention.

Examples of materials that can be used with the composition of the present invention include triazines, urea, carbamates, acetamides, acetanilides, uracils, acetic acids, phenols, thiol carbamates, triazoles, and benzoin Acid nitriles and the like are listed below.

3-Amino-2,5-dichlorobenzoic acid

3-amino-1,2,4-triazole

-트리아진2-methoxy-4-ethylamino-6-isopropylamino-

Triazine

-트리아진2-Chloro-4-ethylamino-6-isopropylamino-

Triazine

2-chloro-N, N-diarylacetamide

2-chloroaryldiethyldithiocarbamate

W '-(4-Chlorophenoxy) phenyl-N, N-dimethylurea

1,1'-dimethyl-4,4'-bipyridinium dichloride

-(3-클로로페닐) 카바마이트Isopropyl

-(3-chlorophenyl) carbamite

2,2-dichloropropionic acid

S-2,3-dichloroallyl N, N-diisopropylthiocarbamate

2-methoxy-3,6-dichlorobenzoic acid

2,6-dichlorobenzonitrile

N, N-dimethyl-2,2-diphenylacetamide

6,7-dihydrodipyrido (1,2-a: 2 ', 1'-C) -pyrazidiinium salt

3- (3,4-dichlorophenyl) -1,1-dimethylurea

4,6-Dinitro-0-2-butylphenol

2-methyl-4,6-dinitrophenol

Ethyl N, N-dipropylthiolcarbamate

2,3,6-trichlorophenylacetinic acid

5-bromo-3-isopropyl-6-methyluracil

3- (3,4-dichlorophenyl) -1-methoxy-1-methylurea

2-Methyl-4-chlorooxyacetinic acid

3- (P-chlorophenyl) -1,1-dimethylurea

1-butyl-3- (3,4-dichlorophenyl) -1-methylurea

N-1-naphthylphthalamine acid

1,1'-dimethyl-4,4'-bipyridinium salt

- 트리아진2-chloro-4,6-bis (isopropylamino)-

-Triazine

- 트리아진2-chloro-4,6-bis (ethylamino)-

-Triazine

2,4-dichlorophenyl-4-nitrophenyl ether

,

,

-트리플루오로-2,6-디니트로-N,N-디프로필-P-톨루이딘

,

,

-Trifluoro-2,6-dinitro-N, N-dipropyl-P-toluidine

-프로필 디프로필티올카바메이트

-Propyl dipropyl thiol carbamate

2,4-dichlorophenoxycedinic acid

N-isopropyl-2-chloroacetanilide

2 ', 6'-diethyl-N-methoxymethyl-2-chloroacetanilide

Monosodium acid metanersonate

Disodium metanerate

N- (1,1-dimethylpropynyl) -3,5-dichlorobenzamide

Fertilizers that can be used with the active ingredient include ammonium nitrate, urea, kali and superphosphate.

When the medicament of the present invention is used in a target area, an effective amount of glycine is sprayed on the plant on the ground. When spraying the herbaceous composition which is a liquid and a particulate solid to the above-ground plant, it can carry out by a conventional method, for example, a powder mill, a boom manual sprayer, etc. It is also effective at low doses, so it can be sprayed by air. Application to myelin sheaths can be effected by application of the composition to myelin sheath plants in the subject area, which usually requires control of the implant.

When using the composition of the present invention, it is important to apply an appropriate amount. The appropriate amount of active ingredient applied depends on the species of the plant and its growth stage, rainfall, the type of glycine applied or the degree of reaction desired for the plant.

In the case of foliar treatment, the active ingredient should be 0.25-0.24 or more per hectare.

To control myelin sheath plants, use about 0.01-1000 parts of active ingredient per million parts of water.

Although specific details have been described with respect to the present invention, the details thereof are not limited to the following claims.

Claims (1)

The di (alkalimetal) salt of N-phosphonomethylglycine or the mono (alkalimetal) salt of lower alkyl N-phosphonomethylglycinate is reacted with anhydride of the following formula (II) and the pH of the reaction mixture is about 6-10. A process for preparing a compound of formula (I) characterized by reacting while maintaining the range.

In the above formula Y is hydrogen, lower alkyl or alkali metal, Z is hydrogen or an alkali metal, respectively, R is binylene, methyl beanene, alkylene having 2 to 3 carbon atoms which may be substituted by alkyl, in which total carbon atoms are up to 8, such vinylene and alkylene Monochloro derivatives, phenylene, carboxyphenylene, 3-nitrophenylene, toriene, cyclohexelene, methylcyclohexelene, cycloalkylene having 4 to 6 carbon atoms, having 4 to 6 ring carbon atoms Dicarboxycycloalkylene, N-metalpyrrolilidene, picorylidene, thienylidene, dicarboxybenzoylphenylene, norbornerirene, norbornyrilene, pyridylidene. Provided that the cyclic moiety is at the ortho position of two adjacent carbonyls.