DE1542659A1 - herbicide - Google Patents

Description

present Brfinäung fesi ^ li'rt ^ v- ' _u r ct% -V sohea Herbicide Gewiiseii , deletes eli Bskso :. >. 1st v. ¹ ^ / *

enthai U _o -

It is known that ihiocyanstverbindimgeii asp sl2-g. Mean Formula MCNS, in which M is an alkali «or E? D ~ Alkali metal or an ammonium group means effective Herbicides are.

It has now been found that 2-halogen ~ 4 »hydroxybenzonitriles and their derivatives, which are also used to regulate undesired plant growth

can be, in the Oemiech with the above-mentioned thio «|

cyanates, surprisingly, a synergistic Bffekt show "that is in a mixture having a greater activity

as each alone.

BATH ORIGINAL

009825/1911

Accordingly, the invention proposes a synergist is a herbicide containing 1 part by weight of an alkali, alkaline earth or avnoniuinthioeyanafcjs, which is characterized in that it is also 0.01 to 10 parts by weight of a 3-halo-4-hydroxybenzonitrile of the formula ^X

NC _ // V. O - R

Shark

contains, where R is a hydrogen atom, a salt-forming Cation, an alkyl group with preferably 1 to 12 carbon atoms, tin alkanoyl group (with preferably 2 to 12 carbon atoms) Carbon atoms) or a sulfonyl group, Hal a halogen atom, and X «mean in hydrogen or halo tone.

The herbicides according to the invention can be used against undesired plant growth, i.e. against for Plants that are harmful to humans or animals and also against other weeds, e.g. against grass on Oartenwege and like that.

Such compounds are referred to as derivatives which enable processing of the relevant compound In herbicidal Oemlsohen enable. For example this is ^ -Halogen-Jl-hydroxybtnsonitril acidic and forms string and other derivatives, which "due to their" larger

009826/1481 _{BAD oi} , _1G , _NAL

ness or other properties can be easy to process ⁹ as the free phenols in the mixture. It is assumed "that these derivatives and especially these salts dissociate to the free phenols and then become herbicidal, so that these derivatives are equivalent to the free phenols",

These derivatives are preferred for agricultural

Use purposes and show no difference compared to ^ the free compounds, for example the free phenols; it only facilitates the method of application of the herbicides, since these compounds have better solubility in carriers such as oil, water, oil / water and water / oil emulsions. In many cases they leave caci. · Ζλ ije ^^^ r -work because they are easier to disperse, adhere better, better

can be distributed or are more weather resistant,

Such suitable salts for agricultural purposes, etc. of the form 3-halo-4 ~ hydroxybenzonitrile can be with ammonia, alkali metals, heavy metals, alkyl and alkanol amines and certain imidazolines of the following formula:

fl £ _R ll

10 η

In which R is a hydrogen atom or an alkyl radical with

8AD ORIGINAL

009825/1981

X up to 8 carbon atoms and R a hydrogen atom or a hydroxyl radical or a 2-aminoethyl radical, 2 «hydroxyethyl radical is * Water-soluble lithium, sodium and potassium salts or sword metal salts of copper and zinc are preferred. The alkyl and alkanolamine salts are preferably with primary secondary or tertiary amines whose hydrocarbon radicals are straight-chain or branched with 1 to 30 carbon atoms. Compounds with a low number of carbon atoms, such as methylamine ethylamine, diethylamine, trimethylamine diethanolamine, tr! Ethanolamine, are water-soluble, while compounds with a larger carbon number such as triootylamine, tridecylamine and commercially available mixtures of primary amines such as branched-chain amino compounds with a molecular formula of C ₁₂ H ₃₅ MH ₂ to C ₁₄ H ₂₉ IIHg and C ₁₈ H ₅₇ NH ₂ to C ₃₂ H ₄₅ HH ₂ , as are the corresponding alkanolamines, which are also soluble. These products are used depending on the intended use.

The 3-halo-lt-hydroxybenzonitriles can also be used as ethers or esters, in particular as alkyl ethers and esters, in which case numerous derivatives can again be formed. In general, ethers and lower alkyl radicals with 1 to 12 carbon atoms, in particular 1 to 6 carbon atoms, and lower alkanoyl esters with 2 to 12 and preferably 2 to 6 carbon atoms are used. Other esters, such as SuIfpnyletter, can also be used. As an ether, methyl-ufid can be queried with ethyl ether and as a setter, methyl, ethyl, hexyl, Ieooctyl- and leononyl-Bater can be requested.

BATHROOM ORIGINAL

009825/1981

Particularly preferred 3-halo-4-hydroxybenzonitriles and their Derivatives are the following compounds:

^ -Chlor - ^ - hydroxybenzoriitril, 3, S-Diehlor - ^ - hydroxybenzonitrile, 3-bromo-4-hydroxybenzonitrile; 3, S-dibromo - ^ - hydroxybenzonitrile, 3-fluorine-4-hydroxybenzonyltrile, 3,5-difluoro-4-hydroxybenzonitrile, 3-iodo-4-hydroxybenzonitrile, 3,5-diiodo-4-hydroxybenzonitrile,

3-bromo-4-hydroxybenzonitrile acetate, ^

3,5-diiodo-4-hydroxybenzonitrile acetate, 3-chloro-4-hydroxybenzonitrile propionate, 3-fluorine-4-hydroxybenzonitri 1-propionate, 3,5-dibromo- ⁱ l - hydroxybenzonitrile butyrate, 3,5-dichloro-4-hydroxybenzonitrile butyrate, 3-chloro- ⁱ ^ -raethoxybenzonitrile, 3,5-diiodo-4-methoxybenzonitrile, 3-bromo-4-ethoxybenzonitrile, 3,5-difluoro-4-ethoxybenzonitrile, 3-BΓΌm- ⁱ ^ -propoxybenzonitΓil, 3,5-dibromo-4-isopropoxybenzonitrile;

the sodium or lithium salt of 3,5-diiodo-4-hydroxybenzc- f

nitriles; the sodium saia of IJ-bromine - ^ - hydroxybenzonibrils; the potassium salt of 3-Jo <i-4-hydroxybenzonitrile; the ammonium salt of 3-fluorine-4-hydroxybenzonitrile; the trimethylamine salt of 3,5-dibrora-4-hydroxybenzonitrile. The monomethylamine salt of 3-bromo-4-hydroxybenzonitrile; the diethylamine salt of 3-iodo-4-hydroxybenzonitrile; the propylamine of 3,5-dichloro-4-hydroxybenzonitrile; the diethanolamine salt of 3,5-diiodo-4-hydroxybenzonitrile; the diiaopropanolamine salt of 3-chloro- ⁱⁱ f-hydroxybenzonitrilej the t-butylamine _{salt of 3 #} 5-diiodo-4-hydroxybenzonitrile; delayed / elgtkettlge octylarainalze des 3,5-dibrora-4-hydroxybtnzonitril ·; branched chain nonylamine salt of the 3-chloro-4-hydroxybenzonitrile triootylamine salt of the JH ^ S-Dliodo - ^ - hydrosiybenzonitrile.

009826/1981 bad originai

Amine salts made from branched-chain amines with a molecular formula ^C J2 ^H 25 ^NH 2 ^{to c} l4 ^ 2 ^^ 2 ^{and the} formula C ^ gHy ^ NHg ^ * ^C 22 ^ 4 ⁽ "^ ¹ S * S-Ethylinsidazoline salt de« 5.5 ~ Dibromo-4-hydroxyb $ n3onIfcx .Usj 2-0ctylimidazo.liii "sala des 3-Jod" .4 "hydrojcybenzonit.X '! I8i 2-i-PiOpy.ll ->{2' ^ üü äthyij-iinidazolinaalz des 5 , 5-Dijad-4-hydiH> xybeazonit Iraidazoline salt dee ^ -Chlor- ^ - hydrojqrbenzonitrilsj and the ^ 2-ethyl-1- (2'hydroxyeth3rl) -im.tdfln; olir?, Salt of 3-chloro-4-hydroxy -benzonitrlls.

The thiocyanates are preferably ammonium thiocyanates and alkali thiocyanates, especially sodium, potassium » and lithium thiocyanates.

The particularly preferred herbicide oils according to the invention contain ala benzonitrile compound, "5-chloro- or 5-ßrom- or 3 * 5-diiodine or 5,5-dibromo- or 3,5- ™ Dichloro-4-hydroxybenzonitrile, while as a thiooyanate Sodium, lithium or ammonium thiocyanate is used

The weight ratio of the individual components depends on the type of vegetation to be controlled and on the particular compounds used, but preferably 1 part by weight of benzonitrile and not more than about 70% by weight of the second component are used.

009825/1981

1 to 50, in particular 1 to, are particularly preferred 20 parts by weight of thiooyanate per part by weight of benzonitrile used. The most favorable ratio in each case can be can be easily determined by means of suitable tests. A preferred proportion is, for example, 0.12-2 Parts by weight of benzonitrile per 0.125 to 2 parts by weight Thiooyanate.

The invention is to be explained in more detail below with the aid of examples. In experiments A to G, 5,5-diiodo-4-hydroxybenzonitrile (ioxynil) were used, in experiment H 3,5-di-chloro-4-hydroxybenzonitrile (chloroxynil) and in experiment I 5 * 5-dibromine »4 “Hydroxybenzonitrile (bromoxynil) was examined as a benzonitrile component alone and in combination with thiocyanates. DJIe various mixtures were used in the amount indicated; the results are rated on a scale from 0 to XO, where 0 corresponds to no measurable effect, the value 1 to a 10%, the value 2 to a 20% and finally the value 10 to a 100% plant destruction. At pieI P, the plants were 4 weeks old and the results were noted two weeks after spraying.

BATH ORIGINAL

009825/1981

Table I.

CO CD

CD

example herbicide Dose / 4000 m in g Abution spp. I. 3.5
0 effectiveness «Β κβη A. a) Ioxynll
b) NH ₄ 3CN
a + b 0
2 ° cotton Soybeans • B a) ioxynil
b) NaSCN
a · ♦ · b 28
225
28 ^ 22 | 1.0
0
7.0 0.5
0
7.0 C. a) loxynll
b) LiSCN
a + b 56
225
56/225 2.5
0
6.5 D. a) loxynil
b) LlSCN
a + b ^] : 28
225
28 ^ 225 1
0
7th 0.5
0
7th 56
225
... S§ ^ 22§ “ _H 2.5
0
-§A5 -

00 I.

3Y O

cn

-ΕΚ) CD

cn co

Table I continued

example Herbicide Doeis / 4000b ² ing 112
^ 500 Effectiveness against epp. Rumex orispus 4.5
0
10 5
h ⁹ Eruoa sativa Tagetes (Dotterbl 3
9 ι
VO
I. Atriplex b) NaSGN
a + b 56
56A5 Stellaria media, Abutilon Ruraex criapue Abutilon ssp. 1
0
7th 2
5 3
0
5 F. a) Xo3cynil
b) ioxamil + 1 508
1016
508/1016 0
3 Abutilon scp 0 a) Chloroxyni
b) KSCN
a + b 3
0
8th 0
0
5 O a) Bromoaynil
b) NaSCH
y a + b 56
1016
56/1016 Kochia H 0
0
5 J

15A2659

If the active ingredients are soluble in water, such as "B" Alkali metal, ammonium * or low molecular weight amino salts, water is conveniently used as the liquid * possibly with the addition of sequestering agents. Organic solvents, Emulsifiers, agents to improve wetting and / or dispersants can also be added.

The 4-hydroxybenzonitriles themselves and their salts with amines of higher molecular weight, including the xisidazoline salts, and their esters and ethers, in particular the lower alkyl esters and ethers, are practically insoluble in water. Accordingly, it has proven to be desirable to bring compositions containing these compounds into a form which can be used for herbicides by means of inert extenders and diluents. These inert ingredients may liquids such as organic solvents or oils used in agriculture, emulsifiers ,, wetting "- and w dispersant and the finely divided Feststoffβ above seinο

The concentration of active herbicide in the listed compositions can generally be from 0.1% by weight up to £ 95 qew. The exact concentration will depend on the particular composition and nature of the ingredients. Preferably about 0.5 to 93 percent of the compositions are used taken, which is a practically water-insoluble Benzonltrile contain. Aqueous · Herbicide solutions are preferably used with

BATH ORIGINAL

009825/1901

«11 -

a content of up to 36Q g of active ingredients per liter of solution. To facilitate transport and handling, it is also advantageous to produce a concentrate with at least 25% and advantageously less than about 90% by weight of the herbicide # the specified herbicide mixture is mixed with a suitable carrier. Furthermore, the invention also extends to a process for the preparation of said herbicidal mixtures and compositions, which are characterized in that the different components are brought together with each other _β Conveniently, the ingredients are mixed together.

The typical examples of herbicide mixtures according to the invention listed below are intended to provide a more detailed explanation to serve.

In the following examples, "parts" means "parts by weight" of the relevant component.

BATH ORIGINAL

0 0 9825/1981

Example I parts

3,5-Diiodo-4 »hydroxybenzonitrll 1

Sodium or potassium thiocyanate 2 Methylated naphthalene 2 Polyoxyethylene sorbitol oil condensate 0.5

The mixture according to Example I can be used in all proportions are diluted with water to form stable oil = in = Water emulsions suitable for spraying.

Example II parts

3,5-dichloro-Riethoxybenzon-III 75

Sodium «or potassium thlosyanate 150

Kieselguhr 20 mixed polymethylene esters

Fatty and resin acids 5

The wettable mixture of Example II can be prepared by mixing the ingredients and can be calibrated with water for use on a large or small scale as a spray.

While it's important that's weeds with the active mixture | su wet «However, the herbicidal for the desired Effect The dose to be applied depends on many factors, e.g. the type of soil in the area concerned « the average amount of rain and the age of the un- * krauts, as well as the mixture used in each case · The dose to be used will therefore vary considerably · doqh must them for the corresponding surface as well as for wetting or Pollination of the weeds is sufficient. Generally will

009826/1981

BAD ORlGlNAt

to achieve a corresponding herbicidal »effect a dose of less than about 2250 g or even only 225 g or possibly 675 to about 900 g per 4000 m It has been found that the herbicides according to the invention in mixtures and compositions are sufficient are particularly active against unwanted plant growth by representatives of botanical classes who are against> -? & lied » Hydroxybenzonitrile and its derivatives alone are resistant are «, therefore the specified mixtures are particularly valuable» full to containment and in many cases to destruction of the plants enumerated in Examples A to P. However, the present blends and compositions are compatible genes generally applicable and allow a good to iier » excellent weed control of practically all types of weeds in grain fields.

ugsssch.

BATH ORIGINAL

009825/1981

Claims (1)

Amchem Products, Inc. (31 * 9) Ambler, Pa. / V, St.A. Hamburg, the ^f >. November * 1969 (P 15 ^ 2 659.2) Claim Synergistic herbicide mixture containing 1 part by weight of an alkali, alkaline earth or ammonium thloeyariafcs, characterized in that it also contains 0.01 to 10 parts by weight of a 3-part 4-hydroxybenonitrile of the formula NC / \ 0 - R contains, where R is a hydrogen atom, a salt-forming cation, an alkyl group with preferably 1 to 12 Carbon atoms, an alkanoyl group (preferably with 2 to 12 Carbon atoms) or a sulfonyl group, Hai a halogen atom, and X represents a hydrogen or halogen atom. 009825M9B1 New documents ««, ·. «. *« «-» - »——" ^4A