DD206318A5 - HERBICIDE COMPOSITION - Google Patents

Abstract

The invention relates to herbalicide compositions for use in agriculture. The aim of the invention is to provide novel compositions for use as herbicides and plant growth regulators. According to the invention, as active ingredient in the novel herbicidal compositions, novel phosphorus salts of N-phosphono-bi-glycine are used with the formula in which R1, R2, R3 and R4 are in each case inactive from the C1-C10-alkyl, phenyl, benzyl, sub-substituted benzyl WHEREAS THE SUBSTITUTES IN QUESTION ARE SELECTED INDEPENDENTLY OF HALOGEN, A LOW ALKOXY GROUP OR A LOWER ALKYL GROUP, PROVIDED THAT AT AT LEAST ONE OF THE RADICALS R1, R2, R3 AND R4, BENZYL, SUBSTITUTED BENZYL OR SUBSTITUTED PHENYL ACT.

Description

The present application is a partial continuation of the co-pending U. S. Serial No. 295,345 patent application registered on Aug. 24, 1981.

The present invention relates to novel chemical compounds and their use as herbicides and plant growth regulators. In particular, the present invention relates to phosphonium salts of N-phosphonoraethylglycine.

Characteristic of the known technical solutions

N-phosphonosine methylglycine is a well-known chemical which can be commercially purchased as a mono-isopropylamine salt for use as a herbicide and in the form of the sodium salt as a growth regulator for sugarcane. Also known are various other salts including substituted ammonium salts, alkali metal salts and alkaline earth metal salts.

Object of the invention

The aim of the invention is to provide novel herbicidal compositions having a broad spectrum of applications as herbicides and plant growth regulators.

31 m

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Explanation of the essence of the invention

The invention is based on the object * to find a new class of N-phosphonomethylglycine with the desired properties »

Erfindungsgeraäß provided a new class of salts of N-phosphonomethylglyzins =, which have efficacy as post-emergence herbicides and plant growth regulators. Whether a herbicidal or wachsturasregulierende effect can be obtained ?, depends on uer culture abs, which the salts are administered; Furthermore, it depends on the method of application, the nature and extent of the weeds present and on the application rate. The determination of suitable cor- basination of such factors is entirely within the competence of the agricultural specialist.

Herbicidal effects range from partial seizure to total killing of weeds or generally undesirable vegetation. "Sometimes, for reasons of cost or in the interest of minimizing damage to crops (depending on the crop stock to be protected), preference is given to partial or total control Plant growth regulating effects are somewhat more varied and also include defoliation and inhibition of vegetative growth.

Defoliation can be used to promote the growth of productive plant parts and to assist in the harvesting process.

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easier. This is particularly useful for flax ·; Cotton and bean plants. Although defoliation kills the leaves of the plant, the rest of the plant is not damaged, so that there is no herbicidal activity. In fact, it is disadvantageous for defoliation. to kill the plant itself? - as the leaves attach much more firmly to a dead plant.

The inhibition of vegetative growth proves to be advantageous in certain cases. In certain plants, it causes a reduction or elimination of the normal apicidal dominance, which in turn leads to shortening of the main stem and increased lateral branch growth. The result is smaller ;, bushier plants with increased resistance to drought and pest infestation · It is also advantageous to delay the vegetative growth of sports field turf in the interest of reducing the vertical wax turn rate> intensified root development and the creation of a dichteren-, firmer turf. The delay at sports field grass also serves to extend the intervals between the individual cut-dates of the courses, golf courses and similar grass areas. For silage crops, potatoes, sugar cane, beets, grapes, melons and fruit trees, the delay in vegetative growth increases the carbohydrate content of the plants and fruits at harvest time. It is believed * that growth inhibition or suppression of the appropriate developmental stage reduces the amount of carbohydrate available for vegetative growth and thus promotes starch and / or sucrose content. The delay

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vegetative growth in fruit trees causes shorter branches and a larger bulk of the tree; Often it also causes a reduced growth in length, These factors facilitate access to the fruit tree and simplify the harvesting process.

According to the present invention, as active ingredients in the novel herbicidal compositions useful for controlling undesired vegetation and regulating the natural growth or development of plants, a novel class of N-phosphonoethylglycine salts are used. These novel salts consist essentially of a substituted phosphonium bi- cation and a glycyl-ethylphosphonate anion. These salts can be represented by the formula

R ^{1 θ} 0 Ο

R ⁴ -P ^S -R ² j; P-CH NHCH _{0 0} COH, HO ^

be represented in which R -, R, R and R are each independently selected from the group consisting of C .... C _1Q alkyl> phenyl, benzyl ·, substituted benzyl and substituted phenyl group ^ wherein said substituents are independently be selected from halogen, a lower alkoxy group or a lower alkyl group - provided that at least one of the radicals R ', R ~, R and R is benzyl, substituted phenyl or substituted benzyl. In addition, these salts have the formula

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^ - ^ ο ο ο

O - r- __

_lx - r-

in which R ", R, R and R are each independently selected from the group consisting of C _{1 to} C ₁ alkyl and phenyl.

Within the scope of the above formula, certain embodiments are preferred, namely those in which R _t R, R and R independently of one another are 0... Cg-Al kyl, phenyl, benzyl, substituted phenyl (wherein the substituent is chlorine ) of a lower alkyl group or a lower alkoxy group and a substituted benzyl (wherein the substituent is chlorine). Most preferred are those embodiments in which R, R, R and R are identical and selected from C ..., C, alkyl and phenyl. However, mixed substituents are also preferred where an activity within the above description is obtained.

The term lower alkyl group and lower alkoxy group are understood to mean those groups which have 1 to 4 carbon atoms, which may be present in unbranched, branched or cyclic configuration, for example methyl, methoxyethyl, ethoxy, propyl, propoxy, butyl, cyclobutyl, isobutyl ; Butoxy and the like.

The present invention further relates to a

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drive to control unwanted vegetation, consisting in that such a vegetation, a herbicidally effective amount of a compound of the above formula in postemergence Stadiura.appliziert.

Moreover, the present invention relates to a method of regulating the natural growth or development of plants, which comprises administering to said plants a regulatory non-lethal amount of a compound of the above formula *

The term "herbicidally effective amount" refers to any amount of the compounds disclosed herein that can kill or substantially inhibit growth of a plant. "Plants" are understood to mean germinating saplings, budding seedlings, and established vegetation including roots and aerial plant parts.

The term "natural growth or development" refers to the normal life cycle of a plant in accordance with its genetics and environment as well as in the absence of artificial external influences. A preferred utility of the compounds treated herein is to increase the sucrose content of free range cane and sorghum. As used herein, the term "regulating" refers to a teniparous or permanent modification or variation in the normal life cycle of a plant caused by herbal remedies until just prior to its killing.

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Erfindungsgeraäß the weed control is most effective by inserting the compounds immediately after emergence of the weeds. On the other hand, regulation of natural growth or development of crops is achieved by employing the compounds on aerial parts of the crops about A to 10 weeks prior to their harvest. To achieve the latter effect, a growth-regulating amount without herbicidal result is used. As will be understood by those skilled in the art, the effective rates used for this purpose will vary not only with respect to the particular material selected for treatment but also with the regulatory effect to be achieved, depending on the plant species to be treated and its stage of development as well as depending on whether a lasting or only a temporary regulatory effect is intended. Other factors determining the appropriate amount of administration are the nature of the administration of the preparation as well as the weather conditions, for example with respect to temperature and precipitation. The resulting regulation may arise from the effect of the chemical substance regulation on either the physiological processes in the plant or the morphology aer plant or from their combination or succession.

Morphological changes generally manifest by changes in size, shape, color or texture of the treated plant or any of its parts; they also manifest in changes in the quantity of fruits produced by the plant,

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In turn, physiological changes occur within the treated plant and are usually hidden from view. Changes of this type occur most frequently with regard to formation, storage, or use of naturally occurring chemicals in the plant, such as hormones. Such changes can be detected by their accompanying morphological changes; This is possible by various analytical methods known to the person skilled in the art. Regulatory effects occur in a number of different ways, with variations depending on the plant species and the rate of application of the regulatory substance.

The compounds according to the invention can readily be prepared from N-phosphonomethylglycine by reacting it with the suitably substituted phosphonium halide in the presence of propylene oxide. N-phosphonomethylglycine itself can be prepared by the phosphonoraethylation of glycine, the reaction of ethyl glycinate with formaldehyde and diethyl phosphite or the oxidation of N-phosphinoraethylglycine. Such methods are described in U.S. Patent No. 3,799,758 (Franz, Mar. 26, 1974).

On the other hand, the compounds of the present invention are prepared by adding one equivalent of N-phosphonomethyiglycine and one equivalent of the organic salt in methanol and water with stirring. Then in an equivalent amount of silver oxide in small portions

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added over a period of time ", wherein the stirring of the reaction mixture is continued for several hours * The product can be recovered in a conventional manner such as by filtration and the resulting homogeneous solution is concentrated.

Working Example

The invention is explained in more detail below with reference to some examples.

The following embodiments are intended to be merely illustrative, but not limiting, of the preparation of compounds of the invention, and their effectiveness in controlling unwanted vegetation, as well as in regulating plant growth.

Embodiment 1

Preparation of mono-tetra-n-butylphosphoniura salt of N-phosphonofluethylqlycine

A sample amount of the mono-isopropylamine salt of tM-phosphonoraethylglycine was obtained from Monsanto Agricultural Products Co., St. Louis, Missouri, in the form of an aqueous solution containing 41% by mass of the active ingredient. A portion of 51.5 g (0.125 mol) of this solution was diluted with 75 ml of water and treated with 1O, 4 ml of 12 N hydrochloric acid (0.125 mol). The reaction mixture was stirred for one hour, the solid product was filtered off. The

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Product was added sequentially with water; The yield consisted of 15.8 g (75 % of the theoretical amount) of N-phosphonomethylglycine.

A subset of 3r, 4 g (0r, 02Hol) of this substance was found to be 6 ^ 8. g ^(Of; iö2 mol) of tetra-n-butylphosphoniurabromid and 20 ml of propylene oxide in 100 ml of water added together. The mixture was gradually warmed to 50 ° C over 30 minutes, then water and volatiles were stripped off to give a yield of 11.0 g of a clear oil with a refractive index of n_ '= 1.5851. The identity of the product as the mono-tetra-n-butylphosphonium salt of N-Phosphonoraethylglyzin was -karnmagnetischer by C ^J and resonance means I _n frarot spectroscopy confirmed "

Embodiment 2

Preparation of mono-tetramethylphosphoniura salt of N-phosphonofluethylqlyzine -

A 1: 4 g (0.0083 mol) portion of the N-phosphonomethylglycine prepared in Example 1 was combined with 1.8 g (0 °, 0.83 mol) of tetramethylphosphonium iodide in 100 ml of water. The mixture was warmed to 50 C and stirred for one hour. It was then subsequently cooled to 15 C and treated with 6 mL of propylene oxide. Stirring was continued at room temperature for a further 2 hours. The reaction mixture was then extracted with 150 ml of diethyl ether. The aqueous phase was then removed.

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striped to yield 30 g of product; the product was then dissolved and further desorbed with tetrahydrofuran and ether to give 2.3 g of a solid product, which showed decomposition phenomena at 80 ° C. The identity as monotetramethylphosphonium salt of N-phosphonomethylglycine was confirmed by C ¹³ NMR.

Embodiment 3

Preparation of mono-tetraphenylphosphonium salt of N-phosphonoiethylglycine _i

The procedure of Embodiment 2 was repeated using 1.7 g (0.01 mol) of N-phosphonomethylglycine, 4.66 g (0.01 mol) of tetraphenylphosphonium auride, and 3 ml of propylene oxide. The yield consisted of 6.2 g of a liquid product having a refractive index n _n = 1.5768;

13 by C-NMR confirmed ¹ that it was the monotetraphenylphosphonium salt of N-phosphonotethylglycine.

Embodiment 4

Preparation of Mono-tributyl-2-dichlorobenzyl -phosphoniura salt of N-phosphonoethyl-ethylzine

The procedure of Example 2 was repeated using 2.11 g (0.0125 mole) of N-phosphonomethylglycine, 4.97 g (0.0125 mole) of tributyl-2- ⁱ , 4-dichlorobenzylphosphonium chloride and γγ g of propylene oxide. After two days there was no reaction. The phosphono

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methyl glycine was still visible (undissolved). To remove the propylene oxide, approximately 20 ml of the water was removed in vacuo. To the resulting solution was added 0.5 g (0.times.0125 mole) of sodium hydroxide pellets. After the solubilization of the N-phosphonoethylglycine, the solution was refluxed for 1.5 hours. After desorbing, the solution was titrated with methylene chloride / toluene mixture. The solution was desorbed again in vacuo and titrated with 20 ml of toluene. After filtering, a white solid was obtained.

The yield was 1 ^ 6 g at a melting point above 320 ° C. After stripping off the toluene filtrate, the residue (7-3 g) was titrated three times with diethyl ether, each time decanted. After stripping off the solvent, a residue was again collected. The yield at this time was 6 ^ 6 g of a viscous clear oil. The two products were added together. The volatiles were removed in vacuo. In this way 7% 3 g of crude product was recovered. This was redissolved in water to obtain a homogeneous solution. The total amount of aqueous solution was 15.5 g. The solution consisted of 40 % of the product with 4-4 % sodium chloride.

Embodiment 5

Preparation of mono-benzyltriphenylphosphonium salt of N-phosphonoethylglycine

3 ^: > 9 g (gyol mol) of benzyltriphenylphosphoniunichloride were dissolved in 0. ^ 4 g (0f _# 022 mol) of water and methanol; this

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To this was added 1.7 g (0.01 mol) of ethyl N-phosphonomethylglycine. Subsequently, 2.43 g (0.0105 mol) of silver oxide was added in small portions over one hour. After completion of the addition, the mixture was stirred for another two hours. Silver nitrate solution did not indicate any incoming halogen; Similarly, with some drops of supernatant, no other precipitate was seen. The silver chloride and the silver oxide were filtered off, the filter cake was washed with methanol. The filtrate was desorbed at 25 ° C. Were recovered 5 ', 5 g of a white crystalline solid having a melting point at 78 to 82 ⁰ C, which was hygroscopic, but soluble in water or chloroform. The identity was confirmed by C-magnetic nuclear resonance.

Embodiment 6

Preparation of Mono-ethyltriphenylphosphoniuhi salt of N-phosphonomethyl -lycin

The phosphoniura salt, ethyltriphenylphosphonium auride (4 ", 2 g, 0.01 mol) was added with ethyl N-phosphonomethylglycine (1.7 g, 0.01 mol), methanol (150 ml) was added, and the phosphonium salt was dissolved Then, water (0.4 g, 0.022 mol) was added at room temperature, silver oxide was added portionwise over a period of 1 h, the reaction mixture was stirred for 2.5 h at room temperature, the silver iodide and the excess silver oxide were filtered off, and the filtrate was desorbed. in this way, a yield of 4.6 g with a melting point of 59 ... recovered 68 ⁰ C. the

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Identity of the product was determined by nuclear magnetic resonance ^ infrared

confirmed,

13 infrared spectroscopy and C-magnetic nuclear resonance

Embodiment 7

Preparation of the Mono-Raethyitri-p-Tolylphosphonium Salt of N-phosphonomethyl- glycine «_____« _____ »__« _

In a similar procedure as in Example 6, 4.46 g (0.01 mol) of methyltri-p-tolylphosphoniuraiodid were combined with 1.7 g (Oi ₁ mol of oil) N-Phosponomethylglyzin and then treated with methanol and water. Over a period of 40 minutes, silver oxide was added. After completion of the addition, the reaction mixture was stirred for 2 hours at the tin-black temperature. After filtering off the silver oxide and silver iodide, the resulting filtrate was desorbed at 25 C and less than 1 mm Hg pressure. Were obtained 4.8 g of the title compound at a melting point of 75 ... 85 C. The product was hygroscopic. The analysis was done by nuclear magnetic resonance ^

13 C magnetic nuclear resonance and infrared analysis confirmed.

Embodiment 8

Preparation of the mono-methyltri- (4-inethoxyphenyl) phosphonium salt of N-phosphonomethylglycine

In a similar procedure as in Example 6, 5 g (0 ', 1 mole) of methyltri (4-methoxyphenyl) iodide and 1 * 7 g (0 # 0l moles) of N-phosphonomethylglycine were added together. Over a period of 30 to 40 minutes, the SiI

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added oxide. After stirring for 20 minutes at 20 ⁰ C, the silver iodide and the silver oxide were filtered off. The FII was entered in vacuo at 25 ⁰ C and less than 1 mm Hg pressure .. desorbed Recovered were ^5; , 3 g of a white powder melting point 60 ... 68 C -, which was hygroscopic. The structure of the recovered substance was confirmed by nuclear magnetic resonance, C nuclear magnetic resonance and infrared analysis.

Embodiment 9

Preparation of the mono-methyltri- (4-chlorophenyl) phosphonium salt of N-phosphonomethylqlyzine

By repeating the procedure of Working Example 6, was added 3 g of 08 (Q ₁ Q mole) of methyltri- (4-chlorophenyl) iodide with i, 7 g (0.01 mol) of N-phosphonomethylglycine zusarumen-

given. Over a 40 minute period, silver oxide was added in portions. After completion of the addition, the reaction mixture was stirred at room temperature for 2.5 hours. The silver oxide and silver iodide were filtered off :, the filtrate was desorbed at 25 ⁰ C and less than 1 MRA Hg pressure. Were obtained 5 *, 5 g of the title compound (hygroscopic, melting point at 85 ... 95 ⁰ C). The structure

13

the substance was confirmed by nuclear magnetic resonance. ', C-nuclear magnetic resonance and by infrared analysis.

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Table A

table the links

R-

R *

O ₀

P-CH ₂ NHCH ₂ COH

Au st. No. 72 9 ¹ »R» R ² 3 4th Physical constant, constant N or melting point 5 rs. -1. HC ₄ H ₉ HC ₄ H ₉ n-0 ₄ H _g "-C ₄ H ₉ ", 5851 2 CH ₃ CH ₃ CH ₃ ^CH 3 80 ° C? IZ £ ³ C 3 phenyl phenyl phenyl phenyl 1'-; 576.8 ⁰ C 4 HC ₄ H ₉ HC ₄ H ₉ HC ₄ H ₉ 2 ^ 4-diCl-benzyl > 320 ^{C 0} C 5 phenyl phenyl phenyl Senzyl 78..82 ⁰ C 6 C ₂ H ₅ phenyl phenyl phenyl 59..68 ⁰ C 7 4-CH ₃ -phenyl 4-CH ₃ -phenyl 4-CH ₃ -phenyl CH ₃ 75..85 ⁰ C 8th 4-CH-0-. phenyl 4-CH ₃ O-phenol 4-CH Q-phenyl. CH ₃ ' 60..68 9 4-Cl-phenyl 4-Cl-phenyl 4-Cl-phenyl CH ₃ 88..85

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Embodiment Herbicidal activity

This embodiment demonstrates the herbicidal after running effect of the hergestell th in the embodiments th compounds.

Flat alurainium planters measuring 15>, 2 χ 22,, 9 χ 8;, 9 cm were filled up to 7 - 6 Tiefe deep with loamy sandy soil containing 50 ppm of the commercial fungicide cis-N (trichlorethylene) ) thio-7'-4-cyclohexene-1 ^; _i 2dikarboxiinide (Captan) and a 17-17-17 ointment (percent NP O ₅ -K ₂ on a mass basis). Seven rows were marked transverse to the width of each shell *; A selection of seeds from both monocotyledonous and dicotyledonous weeds were sown in the rows. The weed species used here are listed below:

Broadleaf weeds:

C.I.

F.I F.2

Iporaoea purpurea Xanthiura sp. Datura stranjomium Sesbania exhalta Abutilon theophrasti Brassica sp. Solanum sp. Convolvulus cassia obtusifolra

weeds:

H. Cyperus esculentus

I. Bromus tectorum

3. Setaria sp.

K. Lolium ruliflorum

L, Echinocloa crusgalli

M. Sorghum bicolor

M.l sorghum bicolor

N, Avena fatua

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The broadleaf species were first sown, and the grasses were planted four days later. Sufficient seeds of every kind were laid out; - depending on the size of the individual plants - to obtain 5 to 50 seedlings per row after emergence.

Ten days after seeding the grasses, the sprouted seedlings of all species were sprayed with aqueous solutions of the test compounds. The solutions were diluted to such an extent that a brewing rate of 750 l / ha gave the desired levels of Q ', 28 ", 4,48 kg / ha for the individual tests Additional planting bowls without any herbicidal treatment were used as standard variants for comparative measurement of Extent of weed control in the treated dishes.

After nineteen days, the test dishes were compared to the standards. The weeds in each row were rated visually for the 3% percent recovery rate, with O % equal to the same level of growth as was present in the standard variant; 100 % control success corresponded to the complete killing of all weeds in the series. All types of plant damage were considered. The results of the observations are listed in Tables I and II:, each of these tables representing an independent series of tests.

f. J

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Table I

Results of the herbicide tests

Call connection

Efficiency © (Ib / A)

Percent control

Broadleaf weeds B CD E F G 0

Ungräeer 3 K L

M N

Mono-tetra-n-butyl "phosphonium salt

0.5 35 40 35 40 50 30 35 38 50 70 100 98 90 85 65 80

1.0 50 70 60 60 70 70 45 61 70 75 100 100 95 90 70 86

2r, 0 65 70 70 75 80 75 50 69 75 80 100 100 95 95 75 89

3.0 70 75 80 80 90 90 60 78 75 90 100 100 95 98 80 91

4.0 75 80 100 95 100 95 85 90 85 100 100 100 98 100 90 96

Table II

Mono-tetra-n-butylphosphonium salt

0.25 20 40 40 10 30 30

Ο », 5 60 60 50 30 50 50

1.0 65 65 55 50 70 85

2.0 70 75 60 55 80 95

3i, 0 75 80 70 70 100 100

28 O 55 100 65 70 25 20 48

50 40 60 100 75 75 65 60 68

65 45 70 100 90 100 90 70 81

73 55 80 100 100 100 100 80 88

83 65 100 100 100 100 100 90 94

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Table II (continued)

Ercjtebniase of the H-bicide tests

expenditure test compound quantity (lb / A) Mono tatramethyl- 0.25 pho8phonium ~ salt 0.5 1.0 2.0 3.0 Mono ~ ~ tetraphenylspirobifluorene 0.25 ρhosphonium salt 0.5 1.0 2.0 3.0

Percent control

Broad-leaved weeds grass weeds ABCDEFQ 0 HI 3

55 50 25 20 60 50

70 60 40 45 75 80

80 70 50 75 90 90

90 80 75 90 95 100

100 100 100 100 100

10 35 10 10 15 50

35 40 25 20 30 70

50 50 50 45 75 85

65 60 70 70 80 90

75 75 100 80 90 100

42 50 70 100 70 85 80 20 68 62 60 90 100 100 100 100 50 86 76 70 100 100 100 100 100 90 94 88 75 100 100 100 100 100 95 96 100 100 100 100 100 100 100 100 99 22 O 50 , 90 55 70 60 20 49 37 10 60 100 70 75 65 45 61 59 55 75 100 85 90 90 75 81 73 65 95 100 95 100 100 85 91 87 75 100 100 100 100 100 95 96

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Table II (continued). Results of herbicide testing

Call connection

Efficiency θ (lb / A) Percent Control Broad-leaved Weeds Weeds BC DEF G 0 H ΙΟ

MN 0

Mono-tributyl-2,4 1.0 M.I. 35 30 50 ^X 60 50 4o dichlorobenzyl ~ 1.0 F.2 65 65 phosphonium salt 2.0 45 50 100 65 Mono-benzyl ~ trl ~ 0.25 O 0 O ^X 30 30 26 phenyl-phosphorus) 0.25 35 40 SAIZ 0.5 20 35 40 45 45 55 1.0 45 45 65 55 60 65 2.0 60 50 70 75 ^x «Cl a - ^xx β FI b =

35 44 0 20 70 20 20

XX

30 '

25 20 0 25 55 0 0 0 13

10 ^a

35 36 35 40 80 10 20 20 0 29

40 48 45 55 85 40 55 45 25 50

60 63 70 75 90 70 80 85 60 75

Table II (continued) Results of the Herbιiζ1dprüfuπqeη

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test compound

Application rate (lb / A)

Percent control

Broad-leaved weeds grass weeds

ABCD ₁ -FGO HIJ

Mono ethyltriphenylphosphonium salt

0.25 0.5 1.0 2.0 25 16 0 20 45

15 10 20

0 ^X 25 ^b

25 20 10 40 40 40 40 31 0 50

35 35 30 50 50 60 65 46 30 60

50 50 65 60 75 70 80 64 60 75

0 0

10 ^a

65 20 10 20 20 80 55 70 65 40 95 70 80 90 80

Mono-ethyl

tri-p-tolyl-

phοephonium-Saiz

= C.I

F.l

0.25

0.25

0.5

1.0

2i, 0

a »M.I b a F.2

10

30

40

50

20 10 10 35 O 10 10

^XX

O 'lo'

20 30 50 20 20 27 40 10 20 50

40 50 60 40 40 44 50 20 70, 60

70 60 70 50 75 62 55 60 100 75

20 " 0 18 0 30 10 37 20 40 55 74 80 75

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Table II (continued)

Results of the herbicide tests Effort amount 1 B reitblät C Trige Percent control F Ler 0 10 ^XX 20 30 ^XX 20 0 Ung Speeder 3 K L M S Ψ (Lb / A) 2 A G D Unkräui G 20 30 35 30 1 H 1 0 0 0 N 0 0.25 0 O ^0X 0 e 35 50 40 0 0 o ^a 0 test compound - 0.25 0 0 45 10 21 40 20 0 20 13 Monomethyl 0.5 20 35 30 35 39 0 0 50 40 20 30 0 28 tri ~ (4-mathoxphenyl) 1.0 30 55 45 50 20 52 30 20 100 60 80 75 10 73 phosphonium salt 2.0 45 64 60 40 8th 70 60 0 10 0 60 1 0.25 0 0 ^0X 0 55 20 0 o ^a 0 0.25 10 0 21 60 20 0 10 15 Monomethyl 0.5 20 30 30 0 35 30 0 70 50 20 30 0 35 tri- (4-chlorophenyl) - l *, 0 35 40 30 30 45 10 20 phosphonium salt 40 ^x » ΟφΧ a» M. ^xx »FMb» F.

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Embodiment 11 Herbicidal activity

This embodiment demonstrates both the pre-emergence and postemergence efficacy of the same three compounds on a range of grass weeds and broadleaf weeds at a preparation feed rate of 4 x 48 kg / ha. Many of the same weed species have already been used (Table III) the same abbreviations as Tables I and H) V and: the experimental procedures were similar to those of Embodiment 4, except that for the pre-emergence tests, the dishes were sprayed the day after sowing with the chemicals, and the stock rating was thirteen days later took place; for post-emergence testing, the skins were sprayed ten days after sowing and scored thirteen days later. "The results are listed in Table III. It can be clearly seen that the compounds are effective exclusively as post-emergence herbicides.

- aar -

Table III - Results of the herbicide tests - Pre and post run up to 4 ^ 48 kg / ha.

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test compound application Breitblätt. A D O 80 Weeds E G O 95 H Weedgrass α L N Mono-tetra-n-butyl-phosphonium salt Pre-emergence post-emergence 0 70 O 100 O 95 O 100 O 75 O 100 O 100 O 75 Morio-tetramethylphosphonium salt Pre-emergence post-emergence O 85 O 85 O 100 O 90 O 85 O 100 O 100 O 100 Mono-tetra- phenylphosphonium salt Pre-emergence post-emergence O 98 O 100 O 65 O 100 O 95 O 90

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Embodiment 12 Efficacy as Pflanzenwachsturasrequlator

This embodiment demonstrates the effectiveness of the mono-tetra-n-butylphosphonium salt as well as the mono-tetraraethylphosphonium salt of N-phosphonoraethylglycine in the regulation of sweet sorghum (Sorghum vulgare) growth.

The following experimental procedure was chosen:

A series of fibrous vessels of 12.7 cm diameter and 12.7 Era depth was filled with sandy loam soil, which was screened and treated with sufficient 17-17-17 Oanger wan ^ura a concentration of 150 ppm PO _n . And KpO A single row of sorghum seeds was laid out and the vessels were placed in a greenhouse: in which the temperature throughout the day was 27 ⁰ C and during the night 21 ° G. After the aa Vessels isolated, aerial roots and lateral shoots were removed at the time of their appearance until the time of treatment of the plants, and the vessels were periodically fed with 17-17-17 oats.

Nine weeks and four days after sowing, the stem length was measured to the ligula of the uppermost visible leaf, and the plants were sprayed with a solution of the test compound dissolved in water, adding to the water an additional 0-5% by mass of a surfactant ( Polyoxyethylene sorbitan monolaurate) were added. The spray

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The device was pressurized by means of carbon dioxide and grown on a two-wheeled type apparatus. The test solution was applied at an application rate of 234 l / ha, the concentration of the active ingredient had been predicted so that amounts of 0.56... 4.48 kg / ha of active substance could be applied at this infusion rate.

Ten days later, the plants were harvested by cutting the stems at ground level, and all leaves and leaf sheaths were removed. Again the length of the stems was measured up to the level of the ligules of the uppermost visible leaf. These measurements as well as the data obtained at the application date were included in the formula below for the determination of the "percent stem extension".

Percentage) _{Length 2Uj} .

_{Length 2Uj harvest}

Stem Ver {= - 1,0 χ 100

renewal Γ " ^Län S ^{8 zura} spraying date

The stem length from soil level to the topmost node was then measured and reported as "stem length". The peduncle and peduncle ( the stem portion projecting beyond the topmost node and reaching the base of the seedling) was then removed and the "fresh mass" of the remaining stem was determined. Oeder stems were now cut into pieces about 3.8 cm in length and in a Carver press at a pressure of

10 340 N / cm pressed. The quantity "of the pressed juice of

24 187 2 p

AP A Ol N / 241 872 61 109 12/37

- 28 -

each stem was recorded as well as its content of "total dissolved solids" "after it had been determined by means of a hand juice refractometer in mass%. The crushed stems were then dried in a drying oven and then weighed to determine their dry mass.

The results obtained, including average measurements of three untreated control plants for comparison, are shown in Table IV. The data indicate a reduction in stem elongation, fresh mass and dry matter, as well as an increase in the percentage of total dissolved solids in the PreSsaft - all due to the administration of the test compounds,

Mono ~ tetra-n- l ', 0 4i8 110 10.0 l ', 22 7 .0 1.8 butyl-phospho- 2 ^, 0 3.4 105 10.9 1.23 7- , 6 3.0 nium salt 4.0 51.3 160 16.3 l * i80 3 » , 5 7 *; 4 Mono-tetra 0.5 5.4 185 24.4 3.52 12 , 4 6.6 m e thyl-phosph o- 1.0 2.3 255 26;, 2 2.75 7 \ 7i ', 6 nium salt • 2, 0 4.5 245 23 *, 9 2.19 7 , 4 8.6

"F. W." = Frl8chma8se

"D. W." ^ Dry matter

"T.D.S." ^ Total dissolved solids

Table IV

AP A 01 N / 241 872 109 12/37

_t the P ₁ Jp ₁ Uf " , ng , hipsiojitlich ZuGkeranrelGheruna, in sweet sorghum

Effort Percent Stem

r-Mfv / ArMnHiinn " ^ΙΘη 9 ^β Stem length

call connection _{(lfa / A)} . _(mm)

g of juice

" ^ΙΘη 9 ^β stem length F, W, DWTDS quantity

_{(lfa /) lä () () () (%) (rnl)}

control

62r, 3

265

42.1

3.36

9.0

Average of three repetitions

AP A Ol N / 241,872

24187 2 5 ... * "" ^w

Method of application

For outdoor use, the compounds of the invention are generally housed in suitable formulations which contain additional ingredients and diluents to aid spreading. Examples of such constituents or carriers are water-soluble organic solvents, dusts, granules, surface-active substances, dispersion aids and emulsifiers. Overall, the formulations are in the form of stauberv solutions, emulsifiable concentrates or dispersion spraying agents.

A) dusts

Dusts are dense powder compositions consisting of the active compounds and a dense, free-flowing solid carrier. They are designed for dry application and are designed for rapid settling, thus avoiding wind-borne spreading on surfaces where the presence of these preparations is undesirable.

The carrier may be of mineral or vegetable origin; preferably it is an organic or inorganic powder of high bulk density, low specific surface area and low liquid absorbency. Suitable carriers include mica, pyrophyllite, heavy kaolin clays, tobacco dust and ground calcium phosphate rock.

AP A Ol N / 241 872 61 109 12/37

241872 5

The suitability of a dust is sometimes supported by the inclusion of a liquid or solid Netzraittels of ionic, anionic or nonionic character. Preferred wetting agents are alkylbenzene and alkylnaphthalenesulfonates, sulfated fatty alcohols, amines or acid amides, long-chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils and ditertiary acetylenic glycols. Dispersing agents are also advantageously used in the same dust compositions , Typical dispersants are methyl cellulose, polyvinyl alcohol, lignin sulfonates, polymeric acyl naphthalene sulfonates, sodium metaphthalene sulfonate, polymethylene bis naphthalene sulfonate and sodium N-methyl-N- (long-chain acid) -7aurate.

In addition, reaction-promoting absorptive grinding aids are often included in the dust compositions to aid the processability of the dust. Suitable Verraahlungshiifsraittel are attapulgite clay, diatomaceous silica, synthetic Feinsilikatinaterial and synthetic calcium and magnesium silicates.

In typical dust composition compositions, the vehicles are usually present in concentrations of about 30-90% by weight of the total dusts compositions. The Verraahlungshilfe will usually constitute about 5 ... 5O mass% of se- _'# can make during the wetting agent up to about 1.0% by mass. Dispersion aids, if present, are present in proportions of up to about 0.5 mass%;

AP A Ol N / 241 872 61 109 12/37

lh 187 2 5 _ ₃₂ _

likewise, minor amounts of anti-caking agents and antistatic additives may appear in the composition. The particle size of the total composition is usually about 30 ... 50 microns,

B) Solutions

Aqueous solutions of the active compounds are formulated to provide the required amount of active ingredient at about 9 to about 1875 l / ha. To improve the wettability of the solution and thus improve its distribution over the plant surface, a small amount of a non-phytotoxic surfactant is typically included in the solution in a proportion of typically between 0.05 and 0.5 mass% . In this regard, both anionic cationic, nonionic, arapholytic and zwitterionic surfactants are useful.

Suitable anionic or surfactants include alkali metal, ammonium and amine salts of fatty alcohol sulfates containing 8, 18 carbon atoms in the fatty chain as well as sodium salts of alkyl benzene sulfonates of 9 to 15 carbon atoms in the alkyl chain. Suitable cationic surfactants include alkyl chain dialkyl quaternary ammonium halides of 8, 18 carbon atoms. Suitable nonionic surfactants include polyoxyethylene adducts of fatty alcohols having 10 to 18 carbon atoms, polyethylene oxide condansate of alkylphenols having alkyl chains of

AP A Ol N / 241 872 61 109 12/37

241872 5

- 33 -

5. * 12 carbon atoms, wherein 5 to 25 moles of ethylene oxide are fused to each mole of alkylphenol. Finally, this includes Polyethyienoxid condensates of sorbitan esters> wherein each mol of sorbitan ester 10 to 40 moles of ethylene oxide are fused. Suitable aphytolytic surfactants include secondary and tertiary aliphatic amine particles wherein one aliphatic substituent contains from 8 to 18 carbon atoms, and wherein another substituent contains an anionic water solubilizing group such as a sulfate or a sulfonate. Examples of these are sodium 3-dodezylaminopropionate and Natriura-3-dodezylaminopropansulfonat. Suitable zwitterionic surfactants include derivatives of aliphatic quaternary ammonium compounds of which one aliphatic substituent contains 8-18 carbon atoms and another substituent contains an anionic water-solubilizing group. Examples of these are 3- {N, N-ethyl-N-hexadezylammonio) propane-i-sulfonate and 3- (N, N-ethyl-N-hexadezylamraonio) -2-hydroxypropane-1-sulfonate

C ) Emulsifiable concentrates

The emulsifiable concentrates are solutions in which the active ingredients and an emulsifying agent are dissolved in a non-water-miscible solvent. Prior to use, the concentrate is diluted with water to form a suspended emulsion of solvent droplets.

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24 187 2 5

- 34 -

typical solvents for use in enteric concentrates are weed oils ^; ; chlorinated hydrocarbons and water immiscible ethene, esters and ketones.

Typical emulsifying substances are anionic or nonionic surfactants or mixtures thereof. Examples include long-chain mercaptan polyethoxy alcohols "; Alkylaryl Polyethoxy Alcohols> Sorbitan Fatty Acid Esteri Polyoxyethylene Ether with Sorbitan Fatty Acid Esters ·; Polyoxyethylene glycol esters with fatty acids or resin acids, fatty alcohol amide condensates; Calcium and amine salts of fatty alcohol sulfate oil-soluble petroleum sulfonates or preferably mixtures of these emulsifying agents. Such effluents usually account for about 1 to about 1% by mass of the total composition.

Typical emulsifiable concentrates contain about 15, 50% by weight active ingredient, about 40 to 82% by weight solvent, and about 1 to 10% by weight emulsifier. In addition, other additives such as wetting agents or adhesives may also be included.

D ) suspension spray

Suspension spray compositions are water-dispersible compositions containing the active ingredient, a non-reactive solid stretch agent, and one or more surfactants to ensure rapid wetting and to avoid flocculation when suspended in water. Suitable solid stretch agents

AP A Ol N / 241 872 61 109 12/37

241872 5

- 35 -

Tel are both natural minerals and synthetically derived from such minerals materials. Examples include kaolinites, attapulgite clay = ^{Monttnorillonit-tone,} synthetic silicas, synthetic magnesium silicate and calcium sulfate dihydrate.

The suitable surface-active substances may belong to both the nonionic and the anionic type, they act as wetting agents and dispersion auxiliaries. Usually one of these substances is included. Preferred wetting agents are alkylbenzene and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long-chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfurs onate, sulfonated vegetable oils and ditertiary acetylenic glycols. Preferred dispersants are methylcellulose ", polyvinyl alcohol, lignosulfonates *, polymeric Alkylnaphthalensulf onate, Natriunnaphthalensulfonat, polymethylene bis-naphthalensulfonat and sodium N-ethyl-N (long-chain acid) taurate.

Typical wettable powders contain 25, 90% active ingredient, 0.5 ... 2.0% of wetting agent, 0.25 ... ^5:.., 0% dispersant and 9.25 ... 74.25% by mass of non-reactive stretch fabric. Frequently, 0.1 to 1.0 % of the extender is replaced by a corrosion inhibitor and / or an antifoam agent.

AP A Ol N / 241 872 61 109 12/37

241872 5 _ ₃₆ _

E) General

In general, all conventional application methods can be used, using the usual dusts or spraying devices. The amount of active ingredient required to achieve the desired result, be it an anti-weed or plant growth regulative effect, depends on the nature of the plant species to be treated and on the prevailing conditions. Herbicidal effects are commonly found in Of; 1 × 10 5 Ib. Active substance per acre, preferably Ι., ΙΟ Ib, / A -, whereas plant growth regulating activity is usually 0.1 .mu.l, 20 Ib / A, preferably O.sub.2. 5. ,, 5 Ib./A - is reached. It will be readily apparent to a person skilled in the art ¹ that compounds of low effectiveness require higher application rates:; than this is the case with more strongly acting compounds in order to achieve the same treatment success.

Claims (10)

¹ , R, R ^ and R independently of one another under C. to C. * ¹ 0 0. 0 > - R ² in which R, R, R and R are each independently selected from the group consisting of C 1 to C 6 alkyl, phenyl, benzyl, substituted benzyl and substituted phenyl wherein the phenyl and benzyl substituents are independently from each other under halogen, a lower alkoxy group or a lower one 241872 5 -38- 15.9.1983 AP A 01 N / 241 872 61 109/12/37 Alkyl group, with the proviso that at least one of R, R, R ^ or R is benzyl, substituted benzyl or substituted phenyl; and further characterized by containing an inert diluent or carrier. 1. A herbicidal composition, characterized in that it consists of a herbicidally active amount of a substantially substituted phosphonium cation and a Glyzylmethylphosphonat anion-containing compound and an inert diluent and carrier _β 2β A method for controlling undesired vegetation, characterized by a Sachauflaufbehandlung.der vegetation with a herbicidal composition, which consists of a herbicidal. effective amount of a substantially substituted phosphonium cation and a glyzylmethylphosphonat-a-ion-containing compound and a non-reactive diluent and carrier material is » 2-34
R, K ^ and R were independently selected from C. to Gg-AIkyl and phenyl « 187 -40- 15.9.1983 AP A 01 1/241 372 61 109/12/37 3. A herbicidal composition according to item 1, characterized in that it consists of a berbicidally effective amount of a compound of formula 4. Composition according to point 3> characterized in that 12 3 R, R and R 1 are independently selected from the group consisting of G to C 1-4 -alkyl and phenyl, and R is benzyl, substituted benzyl or substituted phenyl.  The herbicidal composition according to item 1, characterized in that it contains a herbicidally effective amount of a compound of the formula R ⁴ -PWR 1 -P-CH ₂ IiHGH ₂ COH wherein R, R, R 1 and R 'are independently selected from C 1 to C 4 alkyl and phenyl and contain an inert diluent or carrier. 6. A method for controlling unwanted vegetation according to item 2, characterized by a liachauflaufbehandlung the vegetation with a herbicidal composition which consists of a herbicidally active amount of a compound of formula k 1 87 2 5 -39- 15.9.1-983 AP A 01 Ιί / 241 872 61 109/12/37 0. 0 0 P-CHJuHCH ₀ COH HO · ^ And R .jeweils independently selected from the group consisting of C, -C _Q alkyl, phenyl selected group _consisting% benzyl, substituted benzyl and substituted phenyl, wherein the phenyl and benzyl substituents independently selected from halogen, a lower alkoxy With the proviso that at least one of R ', R, R- * or R ^{4 is} benzyl, substituted benzyl or substituted phenyl, and is an inert diluent, or a lower alkyl group. Carrier is present, 7. The method according to item 6, characterized in that 12 3 R, R and R are independently selected from C. to C 1-4 -alkyl and phenyl, and that R 1 is benzyl, substituted benzyl or substituted phenyl 8, method according to item 6, characterized in that R ¹ , R, R ^ and R are independently selected from alkyl and phenyl. 9. The method according to item 8, characterized in that R, 10 * Method according to point S, characterized in that R, R, R ^ and R are identical a ι
and phenyl were selected. E ', R ^ and R are identical and under G. to G. alkyl