DE1909108A1 - New phosphoric and thiophosphoric ester amides and their use as selective herbicides - Google Patents

Description

CIBA AKTIENGESELLSCHAFT, BASE L (SCHWEI Z)

Case 6405 / E
Germany

New phosphoric and thiophosphoric ester amides and their Use as selective herbicides

Phosphoric acid and thiophosphoric acid ester amides are by the work of EHBlair et al. [J. Agr. Food Chemistry Vol. 14, No. J), 299 (1966).]. Phytotoxicity was observed in connection with the studies of their insecticidal effectiveness.

It has now been found that phosphoric acid and thiophosphoric acid ester amides the general formula

9098U / 1778

< ^I}

Hal

wherein the substituents R independently of one another can denote hydrogen, a C _T -C ^ -alkenyl radical or R, R, denotes a 0, -Ck-alkyl radical, Rp _{denotes a C 1} -Cg -AlkVl or alkenyl radical, R_ an optionally _{represents C 1} -C -alkyl radical bonded to the phosphorus atom via 0 or S, X represents an oxygen-. or sulfur atom and shark stands for a halogen atom, have an extremely selective effect against monocotyledonous weeds such as Panicum, Poa, Digitaria or Alopecurus and protect important, also monocotyledonous crops such as grain, rice, maize, beet, flax, soy, cabbage and others, even show a favorable growth-regulating effect in some crops. Those compounds in which the substituents R independently of one another are hydrogen or a C ₁ -C ₂ -alkyl radical are particularly effective.

The fact of such an extensive range of effects is surprising and has not yet become known to this extent for phosphorus compounds.

The control of weeds in the plant crops can be carried out both in the pre-emergence method (preemergent) as well as in the post-emergence method. Preferred but is the pre-emergence application.

In addition, the compounds of the formula I show a small amount

Application rates good fungicidal effect.

909844/1778

«A · ■ · ι f

r · ■ · * t

Compounds of the formula ## STR3 ## are predominantly selective herbicidally active

Shark

wherein the substituents R independently of one another are hydrogen or a C 1 -C 4 -alkyl radical, PL · optionally one C 1 -C 6 -alkyl radical bonded to the phosphorus atom via O or S represents, X represents an oxygen or sulfur atom and Hal represents a halogen atom.

Among these compounds mentioned, see suitable for this especially that of the formula

Shark

wherein the generally held substituents R, R, Hai and X ™ have the above meaning.

An important group for the selective influence of plants

are compounds of the formula

CH_-G-CH,
^ 3

^X NH-R oo

Shark ο

wherein R ^{1 is} hydrogen or the methyl group, R is hydrogen or a ^{C 1 -C 4 -alkyl radical, R f is} a C -C 4 -alkyl radical, and Hal is a halogen atom.

The compounds of the general formula (i) are new. The invention therefore also relates to these new compounds.

Their production can be carried out by various methods will:

a) A corresponding phenol is used with phosphorus trichloride and sulfur and leaves the resulting

Shark

optionally one after the other with a suitable lower alkanol or a lower alkanethiol and a lower alkylamine under twice HCl elimination react. In the same way, one can also start from phosphorus tribromide.

If, instead of a phosphorus trihalide, phosphorus oxyhalide is used without the addition of sulfur, the corresponding result is obtained

Shark
for further reaction.

b) You can also use O-alkyl dichlorophosphate in a different order or —dichlorothiophosphate or from the alkyldichlorodithiophosphate starting with the corresponding phenol and then reacting with the desired alkylamine. 909844/1778

c) Or you can use the starting phosphorus component PCI, PBr. ,, PXCl ^ react first with the alkylamine and the obtained

Hal X-R

P-N Hal ^ R

with the lower alcohol or mercaptan and the phenol optionally let react in the order.

As mild hydrogen halide binding agents, which can advantageously be added, anhydrous hydrogen carbonates or carbonates, also tertiary amines such as triethylamine, pyridine, picoline, lutidine, quinaldine, diethylaniline, dimethylaniline and others are recommended.

The compounds of the general formula (i) according to the invention are used alone or in conjunction with additives in the form of herbicidal agents. On the one hand, known herbicides whose action supplements that of the M compounds according to the invention, such as 2-methyl-4-chlorophenoxyacetic acid, 2-methyl-4-chlorophenoxybutyric acid and / or a- [2-methyl-4- chlorophenoxy] propionic acid, on the other hand also growth hormones.

These agents are also the subject of the invention.

Carriers, solvents, thinners, ^

Dispersing, emulsifying, thickening, adhesive and / or fertilizing

agents and possibly other pesticides ^

from the same or from other application areas in question. co

The administration of these funds is directed exclusively ⁰ ^ finally the intended use. They can be applied in various forms, e.g. in the form of emulsions,

Dust powders, dispersions, granulates, etc.

Mineral oil fractions, for example, are used to prepare directly sprayable solutions of the compounds of the general formula (i) of high Ms medium boiling range, such as diesel oil or kerosene, coal tar oil and vegetable or animal oils Origin, as well as hydrocarbons, such as alkylated naphthalenes, tetrahydronaphthalene, into consideration given-φ if using xyiol mixtures, cyclohexanols, Ketones, also chlorinated hydrocarbons, such as trichloroethane and tetrachloroethane, trichlorethylene or tri- and Tetrachlorobenzenes. Organic solvents are advantageous used, the boiling point of which is above 100 C.

Aqueous application forms are particularly useful from emulsion concentrates, pastes or wettable wettable powders by adding water. As an emulsifier or dispersants, non-ionic products come into consideration, e.g. condensation products of aliphatic alcohols, amines or carboxylic acids with a long-chain hydrocarbon radical of about 10 to 20 carbon atoms with ethylene oxide, such as that Condensation product of octadecyl alcohol and 25 to 30 mol Ethylene oxide, or that of technical oleylamine and 15 mol ° ethylene oxide or that of dodecyl mercaptan and 12 moles of ethylene oxide. Among the anion-active emulsifiers, the "available -" * can be mentioned: the sodium salt of dodecylal

jj koholsehwefelsaureesters _s the sodium salt of Dodecylbenzolsul- ^Ä sulfonic acid, the potassium or triethanolamine salt of oleic acid or abietic acid or of mixtures of these acids, or

Sodium salt of a petroleum sulfonic acid. As a cation-active Dispersants are quaternary ammonium compounds, such as cetylpyridinium bromide or dioxyethylbenzyldodecylammonium chloride into consideration.

For the production of dust and grit, talc, kaolin, bentonite, calcium carbonate, but also coal, cork flour, wood flour and other mateii of vegetable origin can be used. very is also useful, especially for use in rice pudding, ™ the manufacture of the preparations in granulated form. The various application forms can be added in the usual way of substances that improve the distribution, the adhesive strength, the rain resistance or the penetration capacity, be provided j as such substances are mentioned: fatty acids, resin, glue, casein or alginates »

In the following, parts are parts by weight, temperatures are given in degrees Celsius.

9098 ^ / 1778

example 1

36.5 parts of 2-bromo-5-t-butylphenylthioGichlorphosphat (bp _no 118-120 °), prepared in the usual way by reacting 2-bromo-5-t-butylphenyl with phosphorus trichloride and sulfur, are in 50 parts by volume of methylene chloride with 6 ₅ 4 parts of methanol kept at the boil for 16 hours under reflux. After the volatile parts have been evaporated off in vacuo at a bath temperature of 50 °, 35 parts of O-methyl-2-bromo-5-t-butylphenyl thiochlorophosphate are obtained «

34 parts of this compound are in 150 parts by volume

Dissolved methylene chloride, and 11.2 parts of isopropylamine were added dropwise over the course of 30 minutes at 15-25. The mixture is stirred overnight at room temperature Naeh _s are 100 parts of water and separated the organic layer. These are washed successively with 30 parts of water, twice with 20 parts of dilute sodium hydroxide solution each time and dried over sodium sulfate. After removing the solvent in vacuo at a bath temperature, 33 parts of the compound of the formula are obtained

H _? (iso)

alfc viscous oil, i ^ ²⁵ I, 54l8 [compound no "1]

The following thiophosphoric ester amides are produced in an analogous manner the formula

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L ⁰ V

ο — ρ

Hal

shown:

Verb. Hal V R. Refractive index J 2 Br methyl methyl n _D ²³ 1.5516 3 Br methyl Ethyl n _D ²³ 1.5463 4th Br methyl n-propyl n _D ²³ 1.5425 5 Br methyl n-butyl n _D ²³ 1.5373 6th Br Ethyl Isopropyl ⁿ D ^ ^X '5333 7th Br Ethyl Ethyl • n _D ° 1.5462 8th Br Propyl methyl 9 Br Propyl Isopropyl 10 Cl methyl Isopropyl ⁿ D l _f 5320 11th Cl methyl methyl n _D ²³ 1 ^ 5428 12th Cl methyl Ethyl • n _D ²³ 1.5425 13th Cl methyl n-propyl n _D ²³ 1.5332 14th J methyl methyl n _D 23 1.5554 15th J methyl Ethyl n _D ² 3 1.5552 16 J methyl n-propyl 17th J methyl Isopropyl Xi ^ 1.5443

as following connections formula (CH ₃ ) ₃ C * D f
fr \ j ₂ -ch = ch ₂ : Refractive index Verb. No. Br / "\ /" ΊΤΤ
■ ι v * WXX * - »
P.
^X N (CH n ^ ²⁵ 1.5368 18th n _D ²³ 1.5476
2 19th

"'909844/1778

Connection no. formula Refractive index 20th CH ₅ -CMH ₃ Z
> β _γ ^ NHC ₃ H ₇ (XSo) njj ²⁵ 1.5458 21 (CH ₃ J ₃ C ^ OCSH ₃
Br N ^{7 3}
^ CH ₂ -C = CH ₂
Cl njj ²⁵ 1.5518 22nd ^(C VA t ^C 2 ^H 5
<^ - 0 - P
Br ^X »HC ₃ H7 ^(iS0) njj ²² 1.5470

Example 2

34.6 parts of 2-bromo - ^ - 6 ^ butylphenyldichlorophosphate (bp 115 °), produced in the usual way by reacting 2-bromo-5-t-butylphenol with fMffhrtrlUUi ' ^, are in 200 parts by volume of carbon tetrachloride at 20-30 ° 6 parts of ethanol reacted and, after the removal of the hydrogen chloride gas by nitrogen, reacted with 16 parts of isopropylamine. After the usual work-up, 30 parts of a compound of the formula are obtained

Melting point: 92 ° C

[Compound No.23]

909844/1778

• »· C

Formulation examples

Dust

Equal parts of an active ingredient according to the invention and precipitated silica are finely ground. When mixed with kaolin or talc, it can be used to produce dusts with an active ingredient content of preferably 1-6 $. Wettable powder

20 parts of Hisil 50 parts of active substance according to the present invention (highly adsorptive silicic acid) 25 parts of bolus alba (kaolin): The following constituents for preparing a spray powder beispiels- \ example mixed and finely ground

3.5 parts of reaction product from p-tert. Octylphenol and ethylene oxide

1.5 parts (1-benzyl-2-stearyl-benzimidazole-6,3'-disulfosaures Sodium).

Emulsion concentrate

Highly soluble active ingredients can also be used as emulsion concentrates ™ occurred to be formulated according to the following rule: 20 parts of active ingredient 70 parts of xylene

10 parts of a mixture of a reaction product of an alkylphenol with ethylene oxide and calcium dodecylbenzenesulfonate

are mixed. When diluting with water to the desired Concentration creates a sprayable emulsion.

909844/1778

Granules

7.5 g of one of the active ingredients of formula 1 are dissolved in 100 ecm of acetone and the acetone solution obtained in this way on 92 g granulated attapulgite (Mesh size: 24/48 = mesh / inch). The whole thing is mixed well and the solvent is drawn off in a rotary evaporator. One receives a Granules with an active ingredient content of $ 7.5.

Example 3

The active ingredients of the formula (i) according to the invention showed in the preemergent process excellent action against grass-like weeds with sparing of grain, rice and maize crops as well as crops of dicotyledonous plants.

The treatment was carried out with application rates of 5 kg / ha and 2.5 kg / ha active ingredient on the day after sowing. The evaluation took place after 20 days. Results were obtained that are similar to those in are shown in Table 1 below. Legend: 1-2 = plant not damaged, 3-4 = temporary impairment 5-7 = major damage

8-9 = total inhibition of plant development or plant dead.

909844/1778

Table 1

Plant species verb
1 5 kg /
Verb.
2 'AS / ha
Verb.
3 Verb.
17th Verb.
20th 2.5
Verb.
1 kg A
Verb.
2 S / ha
Verb.
3 Verb.
4th Verb.
17th Triticum 1 1 1 1 1 1 1 1 1 1 Hordeum 1 1 1 1 1 1 1 1 1 1 Avena 1 - - - 1 1 - - 1 - Zea 1 1 1 1 1 1 1 1 1 1 Oryza 1 1 1 1 1 1 1 1 1 1 Dlgitaria 9 9 9 9 9 8th 9 9 7th 8th Sorghum 2 - - - 1 1 - - 1 - Pan! Cum 7th 9 9 . 9 8th 4th 8th 6th 1 8th Poa 9 9 - 8th 8th 9 7th 9 6th 6th Alopecurus 9 8th 9 6th 9 7th 4th 7th 2 1 Cyperus veg. 1 - - - 2 1 - - 1 - beta 1 1 1 1 1 1 1 1 1 1 Gallum ■ 1 - - - 1 1 - - 1 - Calendula 1 - - 1 1 - - 1 - Chrysanthemum 1 - - - 1 1 - - 1 - Linum 1 - - - 1 1 - - 1 - Brassica 1 - - - 1 1 - - 1 - Gossypium 1 1 1 1 1 1 1 1 1 1 Daucus 1 - - - 1 1 - - - - soy
L_. 1 1 1 1 1 1 1 1 1 1

9098A4 / 1 778

example Experiments in rice culture

In containers made of asbestos cement (6Ox6Ox4o cm) with The seeds of the weed Panicum crus galli are filled with mixed soil and covered with water to a height of 2 cm. Then it became Pre-soaked rice seeds, on the one hand of the Caloro variety, on the other of the Hatsunisiki variety, sprinkled one of the active ingredients into the water together with the above-mentioned granules. The application rates were between 1 kg AS / ha and 6 kg AS / ha.

The results shown in Table 2 were achieved 14 days after application (see evaluation scheme Example 3).

These experiments show a high specific selectivity of the compounds according to the invention, even in the case of large Application rates of 4 kg AS / ha and 6 kg AS / ha are available. A rice plant damage occurs even with accidental local Do not overdose with the majority of the substances listed.

909844/1778

Tabel

ο «ο co

Verb. 7th Application rate Rice variety Hatsunisxki • - Echinochloa No.- [kgAS / ha] Caloro 1 · 2 1 1 3 r-i 8th 2 3 1 9 10 1 «Η 1 - 7th 2 ι · - 8th 4th 1 - 1 9 6th 1 r-i 9 1 * 1 - - 1 11th 2 1 8th 4th 1 1 9 6th 1· 9 1 1 - 6th 12th 2 1 1 9 4th 1 1 9 6th 1 - 9 1 ^ - 4th 14th 2 1 - 8th 4th 1 1
1 8th · 6th 1 - 9 1 1 4th 15th 2 1 8th 4th 1 9 6th 1 '9 17th 1 1 6th 2 1 8th 4th 1 9 6th 1 9 1 1 1 2
4th 1
1 6th
8th 6th 1 8th

ι -ι π

Example 4
Growth regulation

The compounds of general formula I have growth-regulating properties in plant crops. They produce in different plants characterized dwarfism _s that the stretchiness resp. internode growth is inhibited. The plants modified in this way do not experience any yellowing or other damage and remain photosynthetically active. As a result of the treatment with the compounds mentioned, a darker green coloration of the leaves can often be observed. The compounds mentioned or their agents also have other growth-regulating properties such as triggering increased formation of side shoots in various plants.

A) The following 11 plants were sown and 10 days after Casserole sprayed with active ingredient quantities of 2.5 kg / ha: Beta, Calendula chrysantha, Chrysanthemum segetum, Linum usitatissimum, Brassica rapa, Ipomoea purpurea, Gostypium hirsutum. Soy max., Galium aparine, Gtellaria media.

The evaluation took place after 20 days. The one from this representative number of plants determined average growth inhibition for the individual active ingredient of the invention:

909844/1778

Verb. No. grade Connection no. grade 2 3.7 10 3.9 3 3.6 11th 2.9 4 - 3.0 12th . 3.6 5 2.1 13 · 2.5 6th 3.2 14th 3.7 7th 4.1 15th 4.0 8th 2.1 16 2.5 17th 2.9

The growth inhibition notes are graded from 1 to 5. 1 = no inhibition,

5 = strong growth inhibition.

B) In the same way as described under A), the special growth inhibition was applied for two important useful crops determined (Lin = Linum usitatissimum, Gos = Gossypium hirsutum):

Connection no. Lin. Goss. Connection no. Lin. Goss. 2 5 2 11th VJl 3 3 5 3 12th 4th 3 4th 4th 3 13th 2 3 VJl 1 4th 14th 4th 3 6th 5 2 15th 5 '3 7th 5 3 16 2 8th 2 2 17th 4th 3 10 6th 3

9 0 9 8 4 4/1778

ιδ -

C) Chrysanthemum plants of various varieties . 7 weeks after sowing, the leaves with a solution of 1000 ppm of the active ingredient no. 3 sprayed. When these plants came to bloom after a further 7 weeks, their height was significantly reduced compared to corresponding untreated chrysanthemums.

The following heights were measured:

Average length of the main shoots in percent (main shoot length of corresponding untreated plants = $ 100)

Chrysanthemum segetum: 41 % ■

Chrysanthemum parthenium: 47 %

Chrysanthemum coronarium: 71 %

Chrysanthemum carinatum: 79 %

Chrysanthemum indicum: 58 %

Phytotoxic phenomena were not observed in any case, i.e. the plants all had a healthy appearance with dark green Leaves and a good set of flowers.

D) Wheat seeds were germinated in distilled water for about 42 hours in the dark. The 1 to 1.5 cm high wheat seedlings were then transferred to culture vessels with active ingredient solution or distilled water (= controls) and exposed to light. The active ingredient solution contained 100 ppm of active substance of the formulated preparation no. 3 i * ¹ distilled

Water.

ο After 4 days, the active ingredient solution was completely

* ° valuable nutrient solution with the same active ingredient content (100 ppm AS of ■ ^ Verb. 3) and during the controls accordingly the "J replaced distilled water with inactive nutrient solution. The evaluation was carried out after a further 10 days

Measurement of the growth in length of wheat plants?

It was found here that, in the case of plants treated with active ingredient, the length of the 2nd stem internodal was reduced by an average of 33 · 1% compared with the controls. The length of the stem from the base to the 2nd ligula was reduced by an average of 36.3% compared to the controls in plants treated with active ingredient.

909844/1778

Claims (1)

Attachment for submission to da & Deui & qlie patent office dated May 20, 1969 File number: £ '19 09 Ί08.8 - CIBAAG, Basel 1909108 US. Sign: 21 456-BR / ro - Case: 6405 / E Claims l. ^ compounds of the general formula J Hal wherein the substituents R are independently hydrogen, a C - ^ - C ^ -alkenyl radical or R ₁ , R _{1 is} a Ci-CVr alkyl radical, R is a C -C ^ -alkyl or alkenyl radical, R is optionally above 0 or S is C ..- C _t - -alkyl radical bonded to the phosphorus atom, X is an oxygen or sulfur atom and Hai is a halogen atom.
2. Compounds according to claim 1, of the formula Shark wherein the substituents R independently of one another are hydrogen or R _{1 ;} R _{1 is} a C 1 -C 4 -alkyl radical, R _{2 is} a 9098 ^^ / 1778 C ₁ -C / - alkyl or alkenyl radical, PU is a C 1 -C alkyl radical optionally bonded to the phosphorus atom via O or S, X is an oxygen or sulfur atom and Hal stands for a halogen atom. 3- Compounds according to claim 1 of the formula Shark wherein the substituents R independently of one another are hydrogen or a C 1 -C 4 -alkyl radical R-, optionally one is C, -C -alkyl radical bonded to the phosphorus atom via 0 or S, X is an oxygen or sulfur atom and " Hai stands for a halogen atom. 4. Compounds according to claim 1 of the formula wherein R «R- *, Hal and X have the meaning given in claim 3 to have. 909844/1 778 Compounds according to claim 1 of the formula Hal NH-R where R ^{T is} hydrogen or the methyl group, R is hydrogen or a C ₁ -C ₁ -alky Ire st, R 'is a C, -C ^ -alkyl radical and Hal is a halogen atom. 6. Compounds according to claim 1 of the formula (CH ₅₁ ) JS Hal wherein R is a methyl, ethyl, n-propyl or isopropyl group means and Hai stands for a chlorine, bromine or iodine atom. 7- The compound according to claim 1 of the formula (CH,), C. 9098 4 kl 177 8 • ff * The compound according to claim 1 of the formula CH -GH-CH, NH-XSoC ₃ H ₇ The compound according to claim 1 of the formula The compound according to claim 1 of the formula NH-CH, 11. Selective herbicidal compositions containing as active ingredient the compounds mentioned in Am3 claim 1 together with one or more of the following additives: carriers, solvents, diluents, dispersants, emulsifiers, thickeners, 9098 ^ / 1778 Adhesive and / or fertilizers and other pesticides. 12. Composition according to claim 11 containing as active ingredient the compounds mentioned in claim 2. 13. A composition according to claim 11 containing the compounds mentioned in claim 3 as active ingredient. 14. Means according to claim 11 containing the compounds mentioned in claim 4 as active ingredient. 15. Means according to claim 11 containing the compounds mentioned in claim 5 as active ingredient. 16. A composition according to claim 11 containing the compounds mentioned in claim 6 as active ingredient. 17. A composition according to claim 11 containing the compound mentioned in claim 7 as active ingredient. . 18. Composition according to claim 11 containing as active ingredient the compound mentioned in claim 8. 19. Composition according to claim 11 containing as active ingredient the compound mentioned in claim 9. 20. A composition according to claim 11 containing the compound mentioned in claim 10 as active ingredient. 21. A composition according to any one of claims 11 to 20 containing 2-methyl-4-chlorophenoxyacetic acid as additional active ingredients, 2-methyl-4-chlorophenoxybutyric acid and / or α- [2-methyl-4-chlorophenoxy] propionic acid. 90984Λ / 1778 22. Use of those mentioned in claims 1 to 10 Compounds for weed control in crops of useful plants. 23. Use of the compounds mentioned in claims 1 to 10 for combating grasses in cereals, rice, maize,
Soy, cotton, cabbage and beets. 24. Use of the compounds mentioned in claims 5 to 10 for combating grasses such as Echinochloa and Poa in grain or rice crops. 25 · Use of the compounds mentioned in claims 1 to 10 for combating monocotyledon weeds in the Pre-emergence method. 26. Use of those mentioned in claims 1 to 10 Compounds as growth regulators. 27 · Use of the compounds mentioned in claims 1 to 10 for regulating growth in crops of useful plants like flax, wheat, chrysanthemum? Cotton and other crops. 909844/1778