DE1110465B - Preparations for influencing, in particular inhibiting, plant growth - Google Patents

Description

Condensation products of phenylhydrazine and acrylonitrile have been proposed as herbicides in US Pat. In addition, the subject of the German patent 1055286, which was not previously published, is weed control agents, the compounds of the general formula
Y

: -R ₁

G Vn- co- N ^

R,

contain, in which X halogen, alkyl, alkoxy and / or nitrile groups, η the number 1, 2 or 3, Y saturated aliphatic radicals with a nitrile group, whereby the carbon chain can also be interrupted by an oxygen or sulfur atom , R ₁ and R ₂ low molecular weight alkyl radicals, e.g. B. methyl, ethyl, propyl or butyl radicals mean.

It has now been found that other not protected by the German patent 1055286 contain cyanoalkyl groups aromatic ureas or thioureas are excellent for combating weeds suitable.

The invention thus relates to means for influencing, in particular inhibiting, plant growth, characterized by a content of aromatic derivatives containing cyanoalkyl groups Urea or thioureas as an active ingredient of the general formula:

Means of influencing, in particular
Inhibition of plant growth

Applicant:
CIBA Aktiengesellschaft, Basel (Switzerland)

Representative: Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse

and Dipl.-Chem. Dr. rer. nat. E. Frhr. v. Pechmann, patent attorneys, Munich 9, Schweigerstr. 2

Claimed priority:
Switzerland from February 10 and December 18, 1959

Dr. Henry Martin, Basel,

and Dr. Hans Aebi, Riehen (Switzerland),

have been named as inventors

p-fluorophenyl, 3-trifluoromethylphenyl, 4-chloro-3-trifluoromethylphenyl, bis-trifluoromethylphenyl, alkoxyphenyl, Nitrophenyl, chloronitrophenyl, alkylphenyl, diphenyl, chlorodiphenyl or alkyldiphenyl.

The substituents R, R ₁ and R ₂ have, as stated, only low molecular weight radicals which advantageously contain 1 to 4 carbon atoms.

The herbicides according to the invention preferably contain compounds of the formula

, R ₃ -CN

Ar —NC-:
RX

R, - <

NH - CON;

(I)

CH _a

(Π)

where Ar is a substituted or unsubstituted phenyl radical, X = O or S, R is hydrogen, a lower alkyl, lower oxyalkyl, lower haloalkyl, lower cyanoalkyl radical, R ₁ and R _{2 are} lower alkyl, lower oxyalkyl, lower alkoxyalkyl , lower haloalkyl, lower cyanoalkyl radicals mean - with the proviso that at least one and only one of the substituents R, R ₁ , R _{2 means} a cyanoalkyl radical - or their salts with acids, with the exception of the compounds protected as weedkillers by German patent 1055286 .

The aromatic radical Ar in the formula (I) is advantageously substituted and, in particular, halogenated. as such residues are z. B. named:

Phenyl, m-chlorophenyl, 3,4-dichlorophenyl, trichlorophenyl, tolyl, xylyl, chlorotolyl, p-bromophenyl, in which R _{3 is} an alkyl radical having 2 to 3 carbon atoms, R ₄ and R _{3 are} hydrogen, a lower alkyl radical, a lower alkoxyl radical or a halogen atom, such as fluorine, chlorine or bromine, or a strongly halogenated side chain, such as a trifluoromethyl group, where at least one of the radicals R ₄ and R _{5 represents} a halogen atom or a strongly halogenated side chain or salts thereof with acids.

The preparation of the cyanoalkylated compounds present as active ingredients in the herbicides according to the invention Urea derivatives can be made using methods known per se.

The urea derivatives can also be used in the form of their salts with acids. There come Salts with common inorganic and organic acids such as hydrochloric acid, nitric acid, sulfuric acid,

109 620/419

3 4

Acetic acid, etc., but especially with halogenated salts, esters and amides, and also certain tertiary or

aliphatic carboxylic acids such as trichloroacetic acid, quaternary amines with herbicidal action, such as. B.

Trifluoroacetic acid, dichloroacetic acid, chloroacetic acid, the dodecylhexamethyleneimine or its salts, the

Perchlorobutadienecarboxylic acid, ", x-dichloropropion- 1, r-ethylene-2,2'-dipyridilium dibromide or its

acid, trichloropropionic acid, oc-chloroacrylic acid,; x:, /? - di- 5 salts. Also herbicidal carbamates or thiol

chloroacrylic acid, *, i * -dichlorobutyric acid, trichloroacrylic carbamate or dithiocarbamic acid ester or derivative

acid, etc., in question. vate des s-triazine can be added to these agents

The herbicides contain besides the cyanoalkylated ones. Certain herbicidal effects can also be used

Urine derivatives or their salts or carrier heterocycles, such as. B. the 2-chlorobenzothiazole, the

substances that can be solid or liquid. There are io 3-amino-1,2,4-triazole, the maleic hydrazide, the

Carriers which are inert or which are themselves a 3,5-dimethyl-tetrahydro-1,3,5,2,4-thidiazine-2-thione,

exert an effect on plant growth. but also simpler herbicides, such as the penta

For the production of directly sprayable solutions chlorophenol, dinitrocresol, dinitrobutylphenol, the

come z. B. Mineral oil fractions from high to naphthylphthalamic acid or the methylisothio-

medium boiling range, such as diesel oil or kerosene, 15 cyanate, can also be used. After all, that too

also coal tar oils and vegetable oils or the use of insecticidal, fungicidal or nematocidal

animal origin and hydrocarbons, such as dicidally acting compounds, e.g. B. halogenated

alkylated naphthalenes, tetrahydronaphthalene, in hydrocarbons or phosphoric acid esters, possibly

Tracht, optionally borrowed using xylene.

Mixtures, cyclohexanols, ketones, also chlorinated 20 The herbicides according to the invention can be ured hydrocarbons, such as tetrachloroethane, for the selective killing of weeds under cultivated trichlorethylene or tri- and tetrachlorobenzenes. plants as well as used for total kill and VerWerden hydrocarbons as excipients, destruction of unwanted vegetation used as they are to have a boiling point above 100 ⁰ C. will. Among weeds are here too

Aqueous application forms are undesirable from emulsion, i.e. H. previously or nearby Concentrates, pastes or wettable powders understood crop plants. The means defined above prepared by adding water. As emulsifying agents or other inhibitors are also suitable for exercising Dispersants come from nonionic products in influencing plant growth, in particular Consideration, e.g. B. Condensation products from alipha- for defoliation, acceleration of ripening through table top Alcohols, amines or carboxylic acids with 30 times drying out, z. B. of potato plants. the a long-chain hydrocarbon radical of about the agent according to the invention can be used both after 10 to 30 carbon atoms with ethylene oxide, such as pre-emergence and post-emergenceas Condensation product of octadecyl alcohol and process are applied. The cyanoalkylated 25 to 30 moles of ethylene oxide or that of soy urea derivatives are usually quite good fatty acid and 30 moles of ethylene oxide or that of 35 the plant leaves added, which is an advantage too technical oleylamine and 15 moles of ethylene oxide or rate, as this property allows, also in the that of dodecyl mercaptan and 12 moles of ethylene trap of the applications on an already existing one oxide. Among the anion-active emulsifiers, the weed population is a rapid, sometimes selective we uses can be mentioned to achieve the nailing. The derivatives mentioned are in triumsalzdesdodecylalkoholsulfonsäureesterSjdasNa- 40 soil degraded relatively soon, so that the trium salt of dodecylbenzenesulfonic acid, the potassium soil restored a few months after the treatment or triethanolamine salt of oleic acid or abietin can be grown.

acid or salts of mixtures of these acids, or The application rates of the herbicides depend on

the sodium salt of a petroleum sulfonic acid. As according to the intended purpose, whether selective or

cation-active dispersants come quaternary 45 total herbicidal effect is to be achieved. In the

Ammonium compounds, such as the cetylpyridinium rule, are used in quantities of 2 to 20 kh / ha of active ingredient

bromide, or the Dioxyäthylbenzyldodecylammonium- needed. The herbicides are useful in

chloride in consideration. concentrated form, so that they are preferentially

For the production of dusts or grit, contain between 20 to 80% active ingredient,

can be used as solid carriers talc, kaolin, bentonite, 50 The to be used in the herbicides according to the invention

Sand, calcium carbonate, calcium phosphate, but also turning active ingredients, their production

Coal, cork flour and wood flour and other materials are not the subject of the present invention,

alien of vegetable origin are used. They can e.g. B. by converting N-alkyl-N-cyanoal-

various application forms can be used in the usual kylaniinen with substituted or unsubstituted

Way with the addition of substances, which the 55 phenyl isocyanates are produced; so you get

division, the adhesive strength, the rain resistance or, for example, a) the N-S-chlorophenyl-N'-methyl-

improve penetration. N '- / S-cyanäthylharnstoff (mp. 88-89 ⁰ C)

Such substances are fatty acids, resins, reaction of N-methyl-N-ß-cyanoethyl with m-chlorine

Glue, casein or z. B. Alginates. Very useful phenyl isocyanate. In an analogous way, the

is also the production of herbicides in granulated 60 thiourea derivatives, z. B. b) the

Shape. N-3-chlorophenyl - N'-methyl - N'-ß- cyanoethylthiourine-

The cyanoalkylated urea derivatives can also material (melting point 83 to 84 ° C) from N-methyl-N - /? - cyano

Fertilizers, e.g. superphosphates ^ Can be added. ethylamine and 3-chloro-phenyl isothiocyanate. Man

The herbicides according to the invention can, in addition to the can in the production of the

cyanoalkylated urea derivatives also other active herbicides to be used

Contain herbicides, e.g. B. halogenated phenoxy bonds also proceed so that one N-alkyl

alkanecarboxylic acids, halogenated benzoic acids or N-cyanoalkylcarbamic acid chloride with an aromatic

Converts phenylacetic acids, halogenated fatty acids or their table amine; so you get z. B. c) the

N-S-trifluoromethylphenyl-N'-methyl-N'-zS-cyanathyl- As another, in the herbicides according to the invention

urea (melting point 70 to 71 ° C) by reacting the methods to be used and described above

N-methyl-ß-cyanoethylcarbamic acid chloride with compounds accessible to 3-tridene are the compounds

fluoromethylaniline. fertilizing called the following formulas:

CH ₂ -CH ₂ -CN

F—; ■ '""' -NH-C-N: '

egg-. Cl CH ₃ O-- CH ₃ - <

NO ₂

Cl-

_/ - NH- CN,

Il ο

, -nh-c-n;

_; - NH-C -N ( O

V-NH- C- n (

Il ο

CH _S

CN -CH

'CH,

/ CH ₂ -CH ₂ -CN

CH ₃

, CH ₂ -CH ₂ -CN ^X CH ₃

CH ₂ -CH ₂ -CN

CH ₃

CH ₂ -CH ₂ -CN

Cl

CH.

Br-

CH _a

Cl

Cl

Cl

Cl-

NH-C-]

Il ο

> - NH- CN ^

Il O

> -NH-C-N ^

Il ο

-NH-C-N ^

Il ο

p— NH- C— N '

O> -NH-CO-N '

CH ₃

^ CH ₂ -CH ₂ -CN 'CH ₃ ^ CH ₂ -CH ₂ -CN

^S CH ₃ , CH ₂ -CH ₂ -CN

^S CH ₃

, CH ₂ -CH ₂ -CN CH ₃ , CH ₂ -CH ₂ -CN

CH,

(Mp. 147 to 148 ⁰ C)

(M.p. 107 to 108 ° C)

(M.p. 111 to 112 ⁰ C) (m.p. 104 ° C)

(M.p. 135 to 136 ° C)

(M.p. 76 ° C)

(M.p. 102 ⁰ C)

(M.p. 132 to 133 ° C)

(M.p. 117 ° C)

(M.p. 108 ⁰ C)

NO,

7 8

In the examples below, parts mean Example 6

Parts by weight and percentages percentages by weight. the

Temperatures are given in degrees Celsius. The following weeds and crops are im

Sown outdoors in rows: Agrostis vulgaris,

Example 1 5 Sorghum sudanense, Sinapis alba, Avena sativa,

Zea mays, Glycine hispida, Cannabis sativa, Brassica

80 parts of herbicidal active ingredient of the formula rapa, Sinacia oleracea, Pisum arvense. 15 days after

the sowing is carried out in Examples 4 and 5

.CH ₂ -CH ₂ -CN called urea derivatives each to be aqueous

Q NH - CO - N ¹⁰ dispersions processed and these according to a

'Amount of active ingredient of 5 kg / ha in 10001 of water each

CH ₃ hectares sprayed onto the plants. 14 days after

After the treatment, all plants died.

Also, the extra ones are between the rows

are with 19.5 parts of solid inert carrier, 15 accrued weeds, such as Portula oleracea, Matriz. B. kaolin, and 0.5 g adhesive, e.g. B. Carboxycaria inodora, Rhaphanus raphanistrum, Convolvulus methylcellulose, ground in a suitable ball mill to give arvensis and Sonchus oleracea, also killed, of the greatest fineness. The mixture serves as been.
Dust. Example 7

ZO

Example 2 I ⁿ flower pots are depending on the greenhouse

Seed type 10 to 40 seeds of Avena sativa, Sorghum

5 parts of the active ingredient used in Example 1 sudanense, Dactylis glomeratä, Sinapis alba, Pisum are in 90 parts liquid carriers, i. H. of a sativum, Lepidium sativum and Calendula chrysantha organic solvent, such as xylene, dissolved and sown and lightly covered with earth and poured, with 5 parts of a nonionic emulsifier, e.g. B. On the so pre-worked soil of the individual of the condensation product from 1 mole of tert-octyl flower pots become dispersions on the same day phenol and 8 moles of ethylene oxide, added. The solution to those described above under c), d), f), 1) and m) urea derivatives are sprayed with water in the desired ratio. The application rate and forms a milky emulsion. 30 speaks in any case of 10 kg of active ingredient per hectare.

It was found 4 weeks after the treatment

Example 3 shows that Sinapis alba, Lepidium sativum and

Calendula chrysantha, although first emerged,

10 parts of the active substance used in Example 1 but completely dead at the time of the evaluation are dissolved in 90 parts of spindle oil. The received 35 were. Pisum sativum remained unharmed while Solution can be applied directly. Avena sativa, Sorghum sudanense and Dactylis

glomerata either completely normal or, depending on the example 4 binding, showed slight to moderate damage.

A field which, before the start of the experiment, was completed by all 40 Example 8

growing plants is exempted with the following

Weeds and crops sown: Phalaris In the same experimental arrangement as for example 7

arundinacea, Airacaespitosa, Rhaphanus raphanistrum, flower pots are prepared and sown. To Triticum vulgäre, Beta vulgaris, Setaria italica, takes place on the, depending on the plant species, 2.5 to 14 days Phaseolus vulgaris, Linum usitatissimum, Trifolium 45 35 cm high plants a treatment with the im repens, Spinacia oleracea. Example 7 compounds mentioned in ibid

On the day after sowing, the application rate indicated is N-3-chlorophenyl. The one after 16 days N'-methyl-N'-ß-cyanoethylurea, which gave the following results to an assessment carried out: Wettable powder was processed, according to a In the pot, which with the urea derivatives

Active ingredient quantity of 5 kg / ha in 1000 l of water per 5 ° c), d), f) and m) were treated, became Sinapis Hectares sprayed on the ground. The plants germinate alba, Lepidium sativum and Calendula chrysantha normal, but are completely or completely killed after 3 weeks, while Pisum sativum is whole almost completely dead. remained intact. Avena sativa and Dactylis glomeratä

showed in all cases, even in the pots, with

Example 5 55 the urea derivative 1) were treated only slightly

docile leaf burns.

A field whose soil was heavily covered with weed seeds Sorghum sudanense only in those with the

is contaminated, is cleaned of all growing plant urea derivatives 1) and m) treated pots parts and then completely destroyed with a spray. In the other pots, powder of N-4-chlorophenyl-N'-methyl-N '- / S-cyanoethyl-60 of this grass showed either no or only slight leaf urea, corresponding to an amount of active ingredient of damage.
5 kg / ha, sprayed in 10001 water per hectare. In example 9

Compared to the untreated plot, the weeds mentioned below are prevented from emerging. In the greenhouse, only the leaves of or destroyed shortly after emergence: Cirsium 65 bean plants (Phaseolus vulgaris), which were the first arvense, Agropyron repens, Sinapis arvensis, Callium have two leaves completely unfolded, with Disperaparine, Mercurialis annua, Ranunculus repens, sions, each of which is 0.6% of the Chenopodium used in Example 5 album. deten urea derivative (= A) or 0.6% of the im

Example 4 used urea derivative (= B) or 0.6% of the N-p-chlorophenyl-N'-N'-dimethylurea (= C) contained, sprayed. After 6 days, the damage to the plants is determined according to the following scheme rated:

0 = undamaged.

1 to 9 = increasing degree of damage.
10 = completely dead.

link Degree of damage on beans A.
B.
C. 6th
7th
1

IO

15 Example 10

Tomato plants are grown in small clay pots in the greenhouse. When the plants have formed five leaves, only the soil is made with dispersions, which contain 0.6% of the active ingredient below mentioned compounds contain splashed. Urea derivative a) (= A), urea derivative k) (= B), urea derivative i) (= C), N- p -chlorophenyl-N'.N'-dimethylurea (= D). The effect is rated after 7 days according to the scheme mentioned in Example 9.

link

A.
B.
C.
D.

Degree of damage on tomatoes

10
10
10

Claims (2)

PATENT CLAIMS: 35 1. Agents for influencing, in particular inhibiting, plant growth, characterized by a content of cyanoalkyl groups Derivatives of aromatic ureas or thioureas as active ingredients of the general formula , R ₁ Ar - N - C - ■ I Il R X wherein Ar is a substituted or unsubstituted phenyl radical, X = O or S, R is hydrogen, a lower alkyl, lower oxyalkyl, lower haloalkyl, lower cyanoalkyl radical, R ₁ and R _{2 are} lower alkyl, lower oxyalkyl, lower alkoxyalkyl , lower haloalkyl, lower cyanoalkyl radicals mean - with the proviso that at least one and only one of the substituents R, R ₁ , R _{2 means} a cyanoalkyl radical - or their salts with acids, with the exception of the compounds protected as weedkillers by German patent 1055286 . 2. Agent according to claim 1, characterized by a content of compounds of the formula R., - NH-CON; . R, - CN CH _S wherein R _{3 is} an alkyl radical having 2 to 3 carbon atoms, R ₄ and R _{5 are} hydrogen, a lower alkyl radical, a lower alkoxy radical, a halogen atom such as fluorine, chlorine or bromine, or a strongly halogenated side chain such as a trifluoromethyl group, where at least one of the radicals R ₄ and R _{5 represents} a halogen atom or a strongly halogenated side chain or their salts with acids. Legacy Patents Considered:
German Patent No. 1,055,286. © 109 620/419 6.61