NO141090B - N-PHOSPHONE MATHYLLYCINES FOR USE AS HERBICIDES AND / OR PHYTOTOXIC - Google Patents

Description

The present invention relates to new N-phosphonomethylglycine compounds for use as herbicides and/or phytotoxic agents. Kerbicides containing such compounds are shown in Norwegian patent no. 136,020.

The term "phytotok.sikum" used here means materials such as:

(1) effectively regulates all plants in a particular location, or

(2) selectively regulates the growth of one or more plant species in the presence of other plants. Similarly, the terms "phytotoxic" and "phytotoxicity" are used to identify the total

and selective regulatory activity of the compounds and compositions according to the invention. As used here, the term "regulation" includes activities such as: (1) killing, (2)

inhibition of the growth, new culture or propagation, and (3)

removal, destruction or otherwise reducing the plants' activity, and includes any specified activity or combinations thereof.

The term "plant" as used here means land plants and aquatic plants.

The term "aquatic plant" includes germinating seeds, germinating seeds

plants and bottom vegetation, which includes rats and parts above ground, as well as mature forest plants.

The term "water plant" means algae and higher water plants.

The term "higher water plant" refers to aquatic plants that are botanically taller than algae and include vegetative organisms that grow in the water, whereby the majority of such organisms are normally under water, e.g. rats as for Lemna, leaves as for Vallisneria or whole plants as for Anacharis.

Thus, the term "higher aquatic plant" includes all aquatic plants, whether these are normally free-floating in the surrounding water, such as Salvinia, or submerged species that normally have their roots in sewers, such as Vallisneria, as well as species that appear to grow normally in all respects either free-floating or root-fixed such as Anacharis or Alternanthera.

From US patent no. 3,160,632 it is known:

alkyl, phenyl, alkylphenyl, carboxyalkyl or hydroxyalkyl,

R' can be R, lower alkylene or phenylene NRR' or heterocyclic alkylene NRR', and M means hydrogen or alkaline earth metal ions.

The compounds according to this patent that come closest to those according to the present invention have the following formula

where M is hydrogen, alkali or alkaline earth metal.

From the formula shown, it can be seen that hydrogen can be bonded

to the phosphorus atom, but the compound according to the present invention:

differs from the compound shown above by the fact that R 1 and/or R 2 cannot be hydrogen. N-phosphonomethylglycines according to the invention have the general formula,

wherein R, R<1> and R<2> have the meanings specified in claim 1.

Among the preferred compounds according to the invention are the following

• 12 3

with the above formula, where at least one of R, R and R is OR

6 12

or OR and the remaining substituents R, R and R mean OH or 0R<b>. The most preferred compounds according to the invention are those with the above formula, in which at least one of R,

12 6 12

R and R are OR and the remainder of R, R and R are OH, and wherein R is a salt-forming cation. Particularly preferred compounds according to the invention 1 are those 2 with the formula as indicated above, in which one of R, R and R is OR, and the remaining means OH, and R means ammonium or organic ammonium, whereby the organic ammonium group is selected from the group consisting of monoalkylammonium .

If R, R^ and R<2> mean OH in the above formula, this indicates the known compound N-phosphonomethylglycine which in itself is a very effective phytotoxic or herbicide. Because of. its relative insolubility in water and conventional organic solvents, however, it is not easy to manufacture commercial formulations.

In contrast to N-phosphonmethylglycine, it is therefore more advantageous to use the more easily soluble compounds according to the invention, in which at least one of the hydrogens in the hydroxy groups in N-phosphonmethylglycine has been replaced with an alkali metal or an alkaline earth metal, or has been combined with ammonia or an organic amine. Aminoalkyl esters of N-phosphonomethylglycine are also effective phytotoxic agents. It has surprisingly turned out that these and other compounds according to the above general formula are water-soluble, but nevertheless they show the same high order of magnitude with regard to activity and like N-phosphonomethylglycine.

Moreover, N-phosphonomethylglycine can be easily dehydrated to form linear and cyclic anhydrides, which are also excellent phytotoxic agents or herbicides.

The new compounds can be prepared by phosphonmethylation of

a glycine, preferably with chloromethylphosphonic acids. They can also be prepared by adding phosphite to azomethines. E.g. the reaction of ethyl glycinate with formaldehyde and diethyl phosphite results in the formation of the triethyl ester of N-phosphonomethylglycine. The considered compounds can also be easily obtained by oxidation of corresponding aminophosphine compounds by using mercuric chloride and other oxidizing agents. The N-phosphono-methylglycines are granular or crystalline solids, which are usually soluble in water.

The strong acids that form salts with N-phosphonomethylglycine are those with a pK of 2.5 or less, e.g. hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, trichloroacetic acid, etc. In certain cases, these acid salts occur in isolation as hemi-salts, i.e. one molecule of the acid is connected to 2 molecules of N-phosphonomethylglycine, and may contain water of hydration.

The acid halides of N-phosphonomethylglycine are prepared as follows

known methods, e.g. the chlorine derivatives can be prepared by reaction of N-phosphonomethylglycine with PC15 or SOCl in an anhydrous solvent, such as ether etc., or another organic solvent.

Amides or esters of N-phosphonomethylglycine can be prepared by reaction of acid halide in a solvent with the corresponding amine or alcohol in the presence of a hydrogen halide acceptor, such as triethylamine, pyridine and the like; or by an ester evolution reaction with the methyl ester of N-phosphonomethylglycine.

The salts of N-phosphonomethylglycine are prepared by partial or

total neutralization of the acid with a corresponding base, basic carbonate, ammonia or organic amine.

According to this invention, it has been found that the growth of germinating seeds/germinating seedlings, growing forest and ground vegetation as well as aquatic plants can be regulated by exposing the germinating seedlings or the above-ground parts of mature and grown vegetation, or aquatic plants to the effect of a effective amount of compounds according to the present invention. The compounds can be used individually, as mixtures of two or more compounds, or in mixture with an auxiliary agent. These compounds are effective as post-acting phytotoxic agents or herbicides, i.e. selectively regulate the growth of one or more dicotyledonous species and/or one or more_tof-rø-bathed species in the presence of other monocotyledonous and/or dicotyledonous species. Furthermore, these compounds are characterized by a broad spectrum of activity, i.e. they regulate the growth of widely different plants, which include but are not limited to ferns, conifers (pine, spruce and the like), aquatic plants, monocotyledons and dicotyledons.

1 the following examples, which shall further explain the

the invention and elsewhere in the description, parts and percentages mean parts by weight and percentages by weight when not stated otherwise.

EXAMPLE 1

A mixture of approx. 50 parts of glycine, 92 parts of chloromethylphosphonic acid, 150 parts of 50% aqueous sodium hydroxide and 100 parts of water were added to a suitable reaction vessel, and kept under reflux temperature while in addition 50 parts of 50% aqueous sodium hydroxide were added. The pH of the reaction mixture was maintained between 10 and 12 by the addition rate of sodium hydroxide. After all the alkaline solution had been added, the reaction mixture was refluxed for a further 20 hours, after which it was cooled to room temperature and filtered.

About. 160 parts of concentrated hydrochloric acid were added, and the mixture filtered to thereby give a clear solution in which N-phosphonomethylglycine was slowly precipitated. This material had an amp. at 230°C during decomposition.

Calculated for C3HgN05P: C, 21.31; H, 4.77; N, 8.28 Found: C, 21.02; H, 5.02; N, 8.05

EXAMPLE 2

N-phosphonmethylglycine was also produced by oxidation of N-phosphinemethylglycine according to the following method: A mixture of approx. 107 parts of phosphinemethylglycine, 625 parts of mercuric chloride and 50 parts of water were added to a suitable reaction vessel, and the mixture was kept at reflux temperature for approx. two hours. The mercuric chloride obtained during the reaction precipitated out and was removed by filtration. The filtrate was saturated with hydrogen sulphide, and the resulting mercury sulphide was removed therefrom by filtration. Thereby a clear filtrate was obtained which was concentrated under reduced pressure, and the residue was diluted with 10 parts of water. The crystalline precipitate was collected and washed with methanol and then with diethyl ether. The product thus obtained was identical to the product from the previous example.

EXAMPLE 3

A mixture of approx. 17 parts of N-phosphonomethylglycine, 100 parts of water and 7 parts of potassium carbonate were mixed in a suitable reaction vessel at room temperature. After the dissolution was complete, which was shown by the reaction mixture becoming clear, the reaction mixture was concentrated on a steam bath under reduced pressure. The residue was washed with hot methanol and then with diethyl ether. The product thus obtained is the monopotassium salt of N-phosphonomethylglycine hemihydrate.

Calculated for C3H7N05PK.1/2H2O: C, 16.65; H, 3.70; N, 6.46 Found: C, 16.67; H, 3.85; N, 6.32

By increasing the amount of potassium carbonate used, the corresponding dipotassium and tripotassium salts of N-phosphonomethylglycine can be produced. Corresponding ammonium salts and salts of other alkali metal and alkaline earth metal salts, as well as copper, zinc, manganese and nickel salts can be easily prepared in essentially the same way.

By using the above-mentioned method, the following salts of N-phosphonomethylglycine can be obtained as white powder: Mono-, di- and trisodium salts;

mono-, di- and trilithium salts.

EXAMPLE 4

About. 170 parts of N-phosphonomethylglycine were added to a solution of 45 parts of dimethylamine dissolved in 10 parts of water, whereby the whole was in a suitable reaction vessel. The reaction mixture became clear in a short time when the mixture was subjected to agitation. The resulting solution was then concentrated by heating to 100°C under reduced pressure. The residue was a viscous oil from which a crystalline solid was obtained. The product was identified as the mono-dimethylamine salt of N-phosphonomethylglycine, m.p. 150°C during decomposition.

Calculated for C5H15<N>2<0>5<P>: C, 28.04; H, 7.06; N, 13.08;

P, 14.66

Found C, 27.88; H, 6.92; N, 12.88;

P, 14.22

By using the method described above, other amine salts of N-phosphonomethylglycine can be prepared, e.g. pyridine salts (monosalt - white solid), diethylamine salts, morpholine salts, piperidine salts, ethanolamine salt (flowable powder to viscous liquid), ammonium salt (white powder).

EXAMPLE 5

Chlorine hydrogen gas was passed through a suspension of 6 g (0.0355

mol) N-phosphonomethylglycine in an excess of methyl alcohol until a clear solution was obtained. The solution was concentrated under reduced pressure, and the residue mixed with a solution of methanol containing at least one equivalent of triethylamine. The solvent was removed under reduced pressure and the residue extracted with ether until a granular substance was obtained. The solid grains were finally extracted with methanol to remove triethylamine hydrochloride. The insoluble product, namely methyl-N-phosphono-methylglycine, was prepared in high yield. After recrystallization in dilute methanol, the product melted during cleavage at 208.5°C.

Calculated for C4H10N05P: C, 26.24; H, 5.50

Found: C, 26.15; H, 5.43

The following esters were prepared using the above method (all compounds melted during cleavage at the indicated temperatures):

EXAMPLE 6

A mixture of 10 g (0.055 mol) of methyl N-phosphonomethylglycinate and an excess of concentrated aqueous ammonium hydroxide was heated for two hours at reflux temperature. The solution was then concentrated under reduced pressure, the residue washed with ether and methanol, and the granular product was stirred with a mixture consisting of excess glacial acetic acid in methanol. The precipitated solid was collected, washed with methanol and crystallized in dilute ethanol. The yield of N-phosphonomethylglycinamide was 8 g, i.e. 87% of the theoretical amount, and m.p.

22 7°C during cleavage.

Calculated for C3HgN2O4P: C, 21.44; H, 5.40

Found: C, 21.26; H, 5.39

EXAMPLE 7

A solution of 16.9 g (0.10 mol) N-phosphonomethylglycine i

300 ml of hot water was heated at reflux temperature with 5.6 g (0.10 mol) of calcium oxide. After approx. 10 minutes, the mixture was cooled and filtered. The residue was washed with methanol and ether. After air drying, the yield of calcium salt of N-phosphono-methylglycine hydrate was 17.5 g or 84% of the theoretical yield: Calculated for C3H6N05PCa.2 1/2 H2O: C, 13.73; H, 4.05;

Approximately, 15.76

Found: C, 13.75; . H. 4.20;

Approximately, 15.28

EXAMPLE 8

A mixture of 17 g (0.10 mol) N-phosphonomethylglycine and 2 g

(0.05 mol) magnesium oxide in 300 ml of water was heated for 10 minutes at reflux temperature. The solution was cooled to room temperature and filtered to remove small amounts of precipitate. The clear filtrate was then concentrated under reduced pressure, and the granular residue washed with methanol and ether.

An excellent yield of magnesium bis-N-phosphonomethylglycinate hydrate was obtained.

Calculated for c6H14N2<0>io<P>2<Mg>'2 X// 2 H2°:C' 17- 795 Hi 4-575

Mg, 5.56

Found C, 17.80; H, 4.69;

Mg, 6.OO

EXAMPLE 9

A mixture of 20 g (0.11 mol) methyl-N-phosphonomethylglycinate

and approx. 23 g (0.33 mol) of pyrrolidine were heated on a steam bath for 2 hours. Excess amine was then removed by reduction

pressure, and the residue washed with ether and tetrahydrofuran. The gum product was stirred with a mixture of excess glacial acetic acid in methanol, and the crystalline precipitate was collected by filtration. After washing with methanol and ether, 12 g of tetramethylene-N-phosphonomethylglycinamide were obtained, i.e. 49% of the theoretical amount, with m.p. 243°c during decomposition. The product was recrystallized in dilute ethanol for analysis.

Calculated for C7H15N0 P: C, 37.84; H, 6.81

Found: C, 37.82; H, 6.96

EXAMPLE IO

N-phosphonomethylglycine (10 g) was added to a small beaker and covered with concentrated hydrochloric acid (ca. 5 ml). After the exothermic reaction had ended, the mixture was allowed to stand for approx.

IO to 15 minutes. The crystallized solid was washed with tetrahydrofuran, then air dried to give a substantial yield of N-phosphonomethylglycine hemihydrochloride hemihydrate (m.p. greater than 300°C).

Other compounds according to the present invention which can be manufactured according to the preceding methods include: 1) Monosodium salt of N-phosphono-methylglycine m.p. 220°C with cleavage. 2) Disodium salt of N-phosphono-methylglycine m.p. 150-155°C with cleavage. 3) Trisodium salt of N-phosphono-methylglycine m.p.>300°C. 4) Monolithium salt of N-phosphone->methylglycine m.p. 5) Dilithium salt of N-phosphono-methylglycine m.p.> 300°C. 6) Trilithium salt of N-phosphono-methylglycine m.p.> 300°C.

7) Monoammonium salt of N-phosphono-methylglycine.

m.p. 208-210°C with cleavage.

8) Monomethylamine salt of N-phosphono-methylglycine m.p. 83°C 9) (Dimethylamine) salt of N-phosphono-methylglycine m.p. 150-160°C with cleavage.

10) Diethylamine salt of N-phosphono-methylglycine

m.p. 153-155°C with decomposition.

11) Triethylamine salt of N-phosphono-methylglycine m.p. 83°C. 12) Diisopropylenamine salt of N-phosphono-methylglycine m.p. 95°C. 13) Monoisopropylamine salt of N-phosphono-methylglycine m.p. 95°C. 14) Monoisobutylamine salt of N-phosphono-methylglycine m.p. 89°C. 15) Mono-secbutylamine salt of N-phosphono-methylglycine m.p. 91-95°C. 16) Monoethylamine salt of N-phosphono-methylgycine m.p. 82°C. 17) Monoethylenediamine salt of N-phosphono-methylglycine m.p. 95°C. 18) Monoaniline salt of N-phosphono-methylglycine m.p. 210°C with decomposition. 19) Monopiperidine salt of N-phosphono-methylglycine m.p. 125°C. 20) Monopropargyl salt of N-phosphono-methylglycine m.p. 25°C. 21) M noethanolamine salt of N-phosphon-methylglycine m.p. <( 25°C. 22) Mono(diethanolamine) salt of N-phosphono-methylglycine m.p. < 25°C. 23) Copper salt of N-phosphon-.methylglycine m.p. 216°C with decomposition. 24) Zinc salt of N-phosphono-methylglycine m.p. > 300°C. 25) Monotallow ammonium salt of N-phosphono-methylglycine m.p. 125°C. 26) Isopropylamine salt of N-phosphono-methylglycinamide m.p. 175-177°C with cleavage. 27) Sodium salt of N-phosphono-methylglycinemethylamide m.p. 203-205°C with cleavage. 28) Dipotassium salt of N-phosphono-methylglycinooctylamide m.p. 200°C with cleavage. 29) Monosodium salt of ethyl N-phosphono-methylglycinate m.p. 155°C with decomposition. 30) Monoisopropylamine salt of phenoxyethyl N-phosphono-methylglycinate m.p. 90°C. 31) Disodium salt of hexyl-N-phosphono-methylglycinate m.p. >300°C. 32) Calcium salt of N-phosphine-imethylglycine m.p. 3 50°C. 33) Monodiisopropylamine salt of N-phosphono-methylglycine m.p. 172-175°C with cleavage. 34) Hemmagnesium salt of N-phosphono-methylglycine m.p. 150°C with decomposition. 35) Monopyridine salt of N-phosphono-methylglycine m.p. 215°C with decomposition. 36) Magnesium salt of N-phosphono-methylglycine at m.p. 350°C.

Pyrrolidine salt of N-(phosphonomethyl)-glycine

Dipropanolamine salt of N-(phosphonomethyl)glycine

Chloroethylamine salt of N-(phosphonomethyl)glycine

Phenoxyethylamine salt of N-(phosphonomethyl)glycine

N,N-diethylaminoethyl-N-(phosphonomethyl)glycinate

EXAMPLE 11

To show the phytotoxic activity of the compounds

according to the invention against aquatic plants, Alternanthere philoperoirides was sprayed with an aqueous solution of N-phosphono-methylglycine in a ratio of 140 g/hectare. The plants were kept under greenhouse conditions for four weeks, and the plants' reaction was observed. By the end of the four-week period, all the plants were dead. The control plants were normal after 4 weeks.

EXAMPLE 12

The subsequent herbicidal activity of various compounds according to the invention will be shown in the following.

The active ingredients are applied in spray form to 14 or 21 old samples (as indicated) of different plant species. the spray,

water or organic solvent-aqueous solution containing the active ingredient and a surface-active agent (35

parts butylamine salt of dodecylbenzenesulfonic acid and 65 parts tallow oil, condensed with ethylene oxide in a ratio of 11 mol ethylene oxide to 1 mol tallow oil), is fed to the plants in different bowls and with different quantity ratios (kg per hectare) actively

medium. The treated plants are placed in a greenhouse and the effects are observed and noted after approx. 2 weeks and after approx. 4 weeks and appears from the last column in table I.

The resulting herbicidal activity index, which is used in table I, is as follows:

The plant species used in the experiments are indicated by means of letters in accordance with the following legend:

The following are compounds that are referred to by Roman numerals in the table:

Although the invention is described with regard to particular embodiments, the previously described shall not limit the invention.

Claims (10)

1. Compound for use as herbicide and/or phytotoxic agent, characterized in that it has the general formula where R and R1 mean -OH, OR3, -NR4R5 or -OR6 and R2 means -OH or -OR6, in which R 4 and R 5 are independently hydrogen, alkyl and hydroxyalkyl with 1-4 carbon atoms, alkenyl with 2-4 carbon atoms, or R 4 and R 5 together with the nitrogen atom to which they are attached form a heterocyclic ring, R<3 > is alkyl, alkenyl, alkoxyalkyl, alkoxy-alkoxyalkyl with up to 18 carbon atoms or phenyl, cycloalkyl or phenoxyethyl, in which the alkyl and alkoxyalkyl group may be substituted with 1-3 halogen atoms, 4 5 in which n is 1-4 and R and R have the meanings given above, and R<6> is a salt-forming cation, such as a cation of alkali metals, alkaline earth metals, copper, zinc, manganese, nickel, ammonium or organic ammonium, where the ammonium salt is a primary amine salt, when the organic group is aryl, as well as mixtures of such salts, 12 6 provided that no more than two of R, R and R mean OH or -OR or R <6> is an ammonium cation or an organic ammonium cation. 2. Compound according to claim 1, characterized in that it is the mono(methylamine) salt of N-phosphonomethylglycine. 3. Compound according to claim 1, characterized in that it is the mono(butylamine) salt of N-phosphonomethylglycine. in 4. Compound according to claim 1, characterized in that it is the mono-ethanolamine salt of N-phosphonomethylglycine. 5. Compound according to claim 1, characterized in that it is the mono-dimethylamine salt of N-phosphonomethylgylcine. 6. Compound according to claim 1, characterized in that it is the mono-ammonium salt of N-phosphonomethylglycine. 7. Compound according to claim 1, characterized in that it is the monosodium salt of n-phosphonomethylglycine. 8. Compound according to claim 1, characterized in that it is the disodium salt. of N-phosph onmethylglycine. 9. Compound according to claim 1, characterized in that it is the trisodium salt of N-phosphonomethylglycine. 10. Compound according to claim 1, characterized in that it is the mono(isopropylamine) salt of N-phosphonomethylglycine.