DE1667964A1 - herbicide - Google Patents

Description

The present invention relates to herbicides, and in particular synerglstlsohe Herblzldgemlsohe, which a Benzonitrllderlv & t contain.

It is known that phenylalkoxyoarboxylic acids of the general formula

VV-O- (CHpV COOH (I)

in which the phenyl ring optionally by one or more Halogen atoms, alkyl or alkoxy radicals with 1 to 4 carbon atoms or nitro groups is substituted and η in 4 is one Number between 1 and 9 is «and their derivatives and their quaternary ammonium salts show herbicidal effectiveness.

It was found that halogen-4-hydroxybene-nitrile and their derivatives, which can also be used to regulate undesired plant growth, in a mixture with the The above-mentioned pheny compounds of the formula I surprisingly show an eynergietic effect, i.e. in the Oemisch

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have greater activity than either alone.

The subject of the invention is therefore a synsrgiatisches Herbal medicine containing 1 part by weight of the above Phenylalkoxycarboxylic acid, which is characterized by the fact that £ it also 0.01 to 10 weight points of a J-halo-4-hydroxybenzonitrile of the general formula

NC - # X ^ -O-R (II)

contains, in which R is a hydrogen atom, a salt-forming Cation, an alkyl group with preferably 1 to 12 carbon atoms, an alkanoyl group with preferably 2 to 12 carbon atoms or a sulfonyl group, Hal a halogen atom, and X Hydrogen or halogen atom.

So the erfindungßgeraäßen herbicides can be used against undesirable plant growth, ie ge-xen kang fllr Mens Chan: 'r animals damaging crops and g £ gen other weeds, for example against Oras on garden paths and the like.

BATH OPiQINAL

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In addition to the free benzonyltriles, there are also their derivatives suitable, provided that processing of the compound in question to form herbicidal mixtures is possible. For example JoHalogen-'J-hydroxytenzonitrile is acidic and forms salts and other derivatives which, owing to their greater solubility or other properties, are more easily distinguished than the free ones Let phenols work in the mixture. It can be assumed that these derivatives, especially the base, belong to the free Phenols dissociate and then become herbicidal so that so these derivatives are equivalent to the free phenols.

These derivatives are preferred for agricultural use use and show no difference compared to the free compounds, for example the free phenols; it will only the application of herbicides is made easier because these compounds are in carriers such as oil. Water, oil / water y ^ water / oil emulsions have better solubility. In many cases they can also be processed better because they are more easily dispersible, adhere better, or can be distributed better are more weather resistant.

Such salts of 5-halo-4-hydroxybenzonitriles which are suitable for agricultural purposes can be mixed with ammonia, Alkali metals, heavy metals, alkyl and alkanolamines and certain 'imldazolines of the following formula:

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BAD OBiGiNAL

(Uli

in which H is a hydrogen atom or alkyl radical kit 1 to 8 ^ carbon atoms and R is a hydrogen atom, a hydroxyl, a 2-aminoethyl or a 2-hydroxyethyl radical. Preferred
are water-soluble lithium, sodium and potassium salts or heavy metal salts of copper and zinc. The alkyl and
Alkanolamine salts are preferably formed with primary, secondary or tertiary amines, their hydrocarbons
straight or branched chain with 1 to 50 carbon atoms
are. Salts of the compounds with a low number of carbon atoms, such as methylamine, ethylamine, diethanolamine, triethanolamine, diethanolamine, and triethanolamine, for example, are water-soluble, while the P salts of the compounds with a larger carbon number
such as trioctylamine, tridecylamine and commercially available
Available mixtures of primary amines such as branched-chain amino compounds with a molecular formula _{of C 12} Hp ₁ -NH ₂ to ^{C 14 H} 29 ^NH 2 ^{and C} 18 ^H 37 ^NH 2 ^{to σ} 22 ^Η 45 ^ΝΚ 2 * ^{as well as the} corresponding alkanolamines are oil-soluble. These products are depending on
Purpose used.

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“AD

The ^ halo-4-hydroxybenzonitriles can also be used as ethers or esters, in particular as alkyl ethers and esters, where again numerous derivatives can be formed. In general, Xther with 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 sulfonyl esters, can also be used. Particularly suitable Xther are methyl and ethyl ethers and the esters are methyl, ethyl, hexyl, isooetyl and isononyi esters .

Particularly preferred 3-halo-4-hydroxybenzeiiitriles and their derivatives are the following compounds: 3-chloro-4-hydroxybenzonitrile 11,
3 »5-dichloro-4-hydroxybenzonitr11,

3 $ 5-dibromo-4-hydroxybenaonitrile,

5,5-Dlfluoro-4-hydroxybenxonitr11 , 3-iodo-4-hydroxybβnzonitrll, 3,5-Dl iodine-4-hydro3cybens5onitrile, 3-Bro «-4-hydro3 (ybenaonitrll-aoetat, 3,5-di iodine-4-hydroxybene nitrate 11-aoetat, 3-σhloΓ-4.-hydroxybentonltril-proplonate _i

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> -Fluoro ~ 4-hydroxybenzonitrile ~ propionate,

3 ~ chloro ~ 4-methoxybenzonyltrile, 3,5diiodo-4-raethoxybenzonitrll, > -Brom-4-Stho: xybenzoni tr 11, 3,5-DIfluoro »4 ~ & thoxybenzonitrile, 3-bread ~ 4-propoxybenzonitr 11, 2.5 Dilbrora = 4 »isopropoxybenzonitrile;

the N & ferium or Lithl ^ snsalz de3 nitrilsi that natural salt of J.

BSUz ύ & Β > Fluor-4-hydi ^t oxybenzonitrllsj aas ^ rim das ^ iS-ßibrcm - ^ - Iiyöroxy'Densonitrils, Sas Mon ^: ^ sals des 3-Broffl »4-hydro3rybanzonltrili3j« ias Dain: ^f .ät.hylaralz das 3 -J © &"4" hydrcxybenzc * itrllsj the propylamine salt of 3 "5"i> iohlor-4 * i ^ aroxybenKontrllsi the disthariolamine salt of 3 _> 5 "J> i ^ or" 4-hydroxybenzanti ^ ils5 the isopropanolahiinsalz des ^ -chlor - ^ - hydroxybenzonitrilsi the v-Butylarainalz des ^, S-Dldod ^ -hydroxybenzontrilsj branched octyl amine salts of 3,5-dibromo-4 "hydroxyb'2n:!;ontrils; branched-chain nonylamine salts of the 3" chloro-4-hydroxybenzontrilsjalze 3.5 "Dijocl-4-'hydroxybenzor3trils,

109833/1 ^ 99 bad original

Missed amine salts from branched-chain amines with a molecular formula ⁰ Ia ¹ W * ¹ ^ ^{to 0} IA ¹ W ¹³ ? and of the formula C ₁₈ H ₅₇ NH ₂ to C ₂₂ NH ^ ₅ NH ₂ I 2-Ethyliaidazolinsal2 des 3,5-Dibro «-4-hydroxybenzonitrile; 2-octyl midazoline salt of 3-iodine-4-hydroxybenzonitrile; 2-i-propyl-1- (2-assilnoilthyl) -imidaaol in salt des] 5,5-diiodo-4-hydroxybenzontril6; Iaiciazolinsala des J-chloro - ^ - hydroxybeniontolles and the 2-.äthyl-2- (2-bydroxyäthyl} -inidazollnsalz des J-chloro - ^ - hydroxy-benzoni 'j

Particularly preferred compounds of formula I are those "whose alkyl chain has a methylene-oöer methyl-raethylsii radical, or products" in which the substituents in the phenyl ring are either a chlorine or bromine atom or a methyl radical. These include 2-kethrl- ^ -chlor-phenoxypropionic acids, 3nsb36 «» idere oj-propionic acid {"MCPP") i 2, ^ -Dichlorphanoxyprcpionsa ^ ren, especially ύΤ ~ propionic acid ("2,4-DP ¹¹ )? 2-methyl-4-chlorophenoxyessiijshure (" MCPA ¹¹ ) 5 2,4-dichlorophenoxyacetic acid ("2,4-D"); 2,4-dichlorophenoxybutyric acids, in particular / -butyric acid ( ⁿ 2,4-DB ⁿ ) j 2,4,5-triehlorphenoxyproplonic acids, in particular ^ -propionic acid ( ⁿ 2,4,5-TP ⁿ ); and 2,4,5-Trlohlophenoxyesslgsäure ("2,4,5-T"),

The particularly preferred herbicidal mixtures according to the invention contain J-chlorine or 5-bromine or 3,5-DiJod- or JjS-E'ibrora- or 3,5-I> lchlor-4-hydroxy-

btnzonltril.

BATH ORIGINAL

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The Oewichteverhältniß the individual Koinponeafcsn depends ζγ: ατ the bekXmpfenden to vegetation and on the particular compounds used on the kind, but preferably 1 weight adjusting benzonitrile and not "be ore than about 70 Ge ?? icb.t site uses the second component. Generally Benzonitrll used in deficiency.

Oute Herblzide obtained "if the compounds of allget & a formula I IMD preferably their derivatives in! Singeing 1 to 10 and iriSbeaciröars 1 to 8 Oewiohtstellen S @ Gewiefcijsfceil Benzont £ *? L ei £> .sets ^, Bie exact amount to be IHST It can easily be determined by suitable experiments. Further preferred corner ratios result from the following list:

Weight parts Benzonitrll Oewiohtstelle the second component

a) 0.5 - 1 0.75 - 1 * 5 phenoxyacetic acid (I), where

the alkylene group is a methyler »· rest is

b) 0.25-0.5 2-3 plienoxypropionic acid (I), where

the alkylene group is a methylwethylene radical.

The following compositions were used on different surfaces against weeds of the species Matrloaria and PolygcnuM perelcaria, Chenopodium album, Stellaria, media, Ciriiium arvensa and Spergula arvensis used in wheat, oat or barley fields (quantities in kg / ha).

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a) 0 * 75 g 3,5-miodo-4-hydroxy-benzonitrile (loxynil)

b) 2.25 g of NCPP

0) 2.5Og 2,4-DP d) 1.25 g MCPA ·) 1.0 g of 2,4-D

f) 0.25 g loxynil ■ ♦ 1.25 g MCPP

β) 0.25 g ioxynil + 1.25 g 2,4-PP |

h) 0.25 g loxynil + 0.75 g MCPA

1) 0.25 g ioxynil + 0.5 g 2,4-D

No damage to the grain occurred in any of trials f through i, and all four compositions allowed adequate child tmraing of all weed species, being the agents in the indicated dosage were just as effective as the compositions a to g when using the listed, considerably higher quantities.

The invention is to be explained in more detail below with the aid of further examples. In experiments A to II, the benzene oil component and the other component were each examined alone and in combination with one another. The various mixtures were used in the amounts indicated. The results are listed on a scale from 0 to 10, with 0 corresponding to no measurable effect, the value 1 to 10%, the value 2 to 20% plant destruction, and so on, the value 10 corresponding to 100% destruction.

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Tabel ο example Herbiaid Dose (kg / ha) 0.38 Effectiveness against co 1.12 Matricaria lnodora, Aspera etc. CD
LO
oa A. a) ioxynil 0.28 0.25 / 0.5 7 9 b) MCPA 1.12 4.9 (D
CD c) a + b 0.28 / 1.12 0.58 8.8 40 d) 2,4-D? 2.8 1.12 6.4 • 0.38 / 0.38 Effectiveness against Amalnckia B. a) Bramoxynil 0.25 / 0.5 7.5 b) NCPA 2.0 e) a + b 0.4 8.0 0.56 Effective against Amsinokia C. a) BPQMKjfnll 0.4 / 0.56 7.5 b) 2,4.DP 2.0 e) a + b 8.0 <t) a + b 10.0 WlrfceaalceJLt against thistle I » a) BroMCdgrnil 7.0 b) 2,4-D 9.0 e) a + b 10.0

Example j herbicide ■ a) bromoxynil
(Na-SaIa) Dose (kg / ha) Effectiveness against Polygonuni convulvulus,
Matricarla Inodora, Poa annua, Polygonua
avioulare, Chenopodium album,
Stellaria media 0 b) 2,4-DB 7 ^ 25 2.3 S. c) a + b 0.24 6.5 3.0 1.6 10 4.0 a) KCPA 0.24 / 2.0 Effectiveness against
Broadleaf grasses 1.7 b) broaoxynil
butyr & fc 0 2.3 O
co P. c) a + b 0.25 7.5 3.3 838 d) chloraxynil
ootanoat 0.25 9.2 ·> » e) a + d 0.25 / 0.25 6.7 cn
co f) chloroxynil
butyrate 0.5 8.7 s) * + f 0.5 / 0.5 5.7 0.25 7.0 0.25 / 0.25

U) i OO

example herbicide Dose (kg / ha) Effectiveness against
Breitblatt Grüser G
t
Ή
I.
I. a) Broaioxynil
b) 2,4-D / Araln
d.) a * b
a) Chloroxynll
b) 2,4-DP
o) a + b 0.4
0.4
0.28 / 0.28
0.72
2
0.24 / 1.5 4.5 5.4
3 · 0 5.5
7.0 7.0
Effectiveness against
I II III IV V VI VII 10 6 4 10 2 5 10
10 7 8 10 10 10 10
10 10 10 10 2 5 10

cn 1 Cireiu »arvense CO XX Polygonum spp CD XXX fionohue arvensis XV Sinapis arvensis V Viol * arvensia VI ScleranthuB annus VII Chenopodlue album

Chloroxynil Broffloxynll

Ioxynil

3,5-dichloro-4-hydroxybenzonitrile, 3,5-dibrora-4-hydroxybenzonitrile , 3,5-diiodo-4-hydroxybenzonitrile

While the herbicide mixtures of this invention can be found in pure form can be used against unintentional plant growth, but it is generally more beneficial to use them in Mixture with a suitable carrier substance to be used. For example, they can be added to a solid such as talc, clay, diatomaceous earth, vermiculite, walnut shell flour, and also potassium carbonate or a dissolving or non-dissolving liquid.

When the active ingredients are water soluble, e.g. Alkali metal, ammonium or low molecular weight Amino salts, water is more conveniently used as a 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 anines higher molecular weight including the imidazoline salts and their esters and ethers, especially the lower allyl esters and ethers, are practically insoluble in water. Accordingly, it has proven to be desirable to add compositions containing these compounds by inert Extenders and thinners In a form useful for herbicides bring to. The inert component can be liquid substance, used like organic solvents or in agriculture · oil ·. Emulsifiers »Wetting · and dispersing agents as well as dl finely divided solids described above be *

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The concentration of active herbicide in the compositions listed can generally be from 0.1% by weight to 95% by weight. The exact concentration will depend on the particular composition and the nature of the constituents. Preferably about 0.5 to 95 parts by weight of the composition are taken which contain a practically water-insoluble benzonitrile. Aqueous herbicide solutions are preferably made up with a content of up to 150 g of active ingredients per liter of solution. For ease of transport and handling, it 1st furthermore convenient to prepare a concentrate with at least 25 wt.%, And advantageously less than about 90 wt. £ of the herbicide.

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It is indeed important to wet the weeds with the active mixture. However, the dose to be used in each case for the desired herbicidal effect will depend on many factors, for example the type of soil in the area in question, the average amount of rain and the age of the weeds, as well as the mixture used in each case. The dose to be used will therefore vary considerably, but it must be suitable for the corresponding PIA, before and for wetting or dusting the weeds ^

sufficient. In general, to achieve a corresponding Herbal effects a dose of less than about 5.6 kg / ha

γ 2

or even as little as 0.56 kg / ha or possibly 0.84 to about 1.12 kg / ha are sufficient. It has been found that the herbicides according to the invention are particularly useful in mixtures and compositions are active against undesired plant growth of representatives of botanical classes that are active against> -halogen-4-hydroxybenzonitrile and their derivatives alone are resistant. Therefore, the given mixtures bind particularly valuable for containment and in many Pills to destroy the I listed in the examples

Plants. However, the present mixtures and compositions are generally applicable and allow good to excellent weed control of virtually all weed species in Grain fields.

Ugstbb

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Claims (1)

(Appl. 3 - 52 * 9) taehe «iroduets. »„. 1667964 Ambler, Pa., V.St.A. Hamburg, January 9, 1968 Claim Synergistic herbicide containing a weight part a phenylalkoxyearbic acid of the general formula - 0 - (CH ₂ ) J ₁ COCH in which the phenyl ring is optionally replaced by one or more Halogen atoms, alkyl or alkoxy radicals with ϊ to 4 carbon atoms or nitro groups and in which η is a number between 1 and 9, or a part by weight thereof Derivatives or their quaternized ammonium salts, thereby characterized in that there are also 0.01 to 10 parts by weight of a 3-halogen ~ 4-hydroxybenzontrils of the general formula MC - ^ y ~ 0 ~ R (II) Shark includes, in the R atom is hydrogen, a salt forming cation, an alkyl group preferably having 1 to 12 carbon atoms, an alkanoyl "group old preferably 2 to 12 carbon atoms or a SuIfony! group, Hal is a Haiogenatom 'nd X is a Hydrogen or halogenated means » ugejbb 109838/1599 • AD