DE1959290A1 - Dinitrophenyl ether for pest control - Google Patents

Description

1359290

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

Case 66ll / E

Germany

Dinitrophenyl ether for pest control. '

The present invention relates to the use certain 2,4-dinitro-o-alkylphenyl ethers are used against various types of plant and animal pests, especially against pests of the order Akarina and against Weeds in crops of useful plants.

These active ingredients are used by the general Formula.

R.
³

comprises, wherein R, for the methyl, isopropyl sec. Butyl, tert-butyl, secondary octyl, cyclohexyl or cyclopentyl radical stands, Rp the meaning of an optionally by halogen substituted alkyl or alkenyl radical with 1-4 carbon atoms or an alkynyl radical with 1-4 carbon atoms or one optionally has phenyl radicals substituted by hydroxyl, halogen or nitro, and R 1 represents hydrogen or the methyl group stands. ''.

These active ingredients are produced by reaction, a compound of the formula R ""

with a second compound of the formula '

Z-CH-R

\ .1

■. ·. ν ■. ■■■ · prepared in which R- ,, R ₂ and R- ,, have the above meaning, R ¹ and R "are hydrogen or a nitro group and in which one of the substituents Y and Z is a halogen atom, especially chlorine or bromine and the other is an OH group _s

- "5 -

which can also be in the form of an alkali or alkaline earth alcoholate, optionally in the presence of a hydrogen halide binding agent, and with further post-nitration of the ether formed in the event that R ¹ and / or R "are solid.

The compounds of the formula I have a surprising breadth of activity in biological terms, which partly expressed in the control of animal and microbial pests, partly in crops of useful plants in addition to the herbicidal effectiveness in the form of beneficial crop plants affects. '

Surprisingly, compounds of the general formula I have a molluscicidal effect, especially in Gastropods, which are schistosome carriers, appear occurs.

The compounds have a good microbicidal activity against bacteria when applied in very small amounts and fungi, especially anti-phytopathogenic fungi Ute gryeiphe aichoraceafum, Alternaria tenuis or Alternaria 'eolftfiit In dert ÖafHir requires »lieheti iCönaentrations are not ! Damage to plants detectable. The compounds of the formula I also have good activity against nematodes, for example: Panagrellus redivivus, Meloidogyne sp. and other.

009828/1955

· ■ ■■■ '- 4 -

Above all, however, the connections are excellent to control pests of the Acarina order, (Ticks, mites, spider mites, etc.) including those who Have resistance properties to phosphoric acid esters. The compounds also act as a chemosterilizer.

The herbicidal action of the compounds according to the invention is selective against weeds in crops of useful plants. It can be used pre-emergence and post-emergence and is mainly used in important large crops such as grain, rice, maize, sugar beet, soy, cotton, Lucerne, alfalfa, potatoes and others observed.

Total herbicidal effect is found at higher application rates before and is always advantageous when the soil is to be prepared for a new planting while still Remnants of a previous culture are present. The ^ bindings can also be used as defoliants and desiccants.

Surprisingly, however, the group of compounds of the formula I also includes representatives that influence growth as well as those that give a crop plant improved fruit set, regulate fruit abscission and an improvement in the resistance to frost and dehydration ("winter hardiness") and an extension of the shelf life of crops-achieve. - ..

009828/1966

1359290

As a particularly biologically active subgroup are to mention those compounds of the formula I in which R denotes the methyl, isopropyl, sec-butyl or tert-butyl radical, R stands for H, the methyl, vinyl, chlorovinyl or ethynyl group and R ^ is H or the methyl group.

The invention also relates to those new compounds of formula II and their stated use,

f ^HR 2 II

for the R, the methyl, isopropyl, sec-butyl, tert-butyl, sec. octyl, cyclohexyl or cyclopentyl radical, Rp an alkyl or alkenyl substituted by halogen; or unsubstituted alkenyl radical with 1-4 carbon atoms or one optionally substituted by hydroxyl, halogen or nitro Represents phenyl radical and R, hydrogen or the methyl group is. The invention also relates to pesticides, which contain these new compounds of formula II, together with one or more of the following additives: Dissolving, diluting, dispersing, emulsifying, wetting, adhesive or thickening agents.

009828/1958

19592Ϊ0 ί

. ■. β · - _r .. ■ -i

■. 'ί.

In general, the. Formulation in liquid or "■ solid form, dry or wet application in the form ¹ of solutions, emulsions, concentrates, Wettable Powders, Stäubemltteln or by gas-phase application These methods' are described in detail in US.P 3 J29 7Q2,.. Or. Brit.P 1 047 '644;. I or Schweizer P. 424 359.. In many cases, the use of granules for the even delivery of active ingredients over a longer period of time is advantageous. ■ The 'blank'. ': By dissolving the active ingredient in an organic solvent.' ■ produce medium, absorption or adsorption of this solution by mineral or organic high polymer, adsorptionsfähiges- '"" Material and removing the Lösungsmitteig'. They can also be prepared in such a way that the active ingredients of the formula I are mixed with polymerizable compounds, whereupon a polymerization is carried out; is, of which the active "substances remain unaffected, and granulation is still carried out during the polymerization.

For the production of dusts and 'grit, such as for combating mites in poultry, can as solid carriers talc, kaolin, benton, calcium carbonate, CaI egg around phosphate, but also coal, cork flour, wood flour and other materials of vegetable origin drawn in.

00 98 2 871968

. ■ ■ - 7 -

The various application standards can be used in the usual By adding substances that improve distribution, adhesion, rain resistance or penetration improve, be provided; These include: fatty acids, resin, glue, casein or alginates.

The agents according to the invention can for themselves

alone or together with common biocides for combating pests, in particular with insecticides, acaricides, Nematocides, bactericides, fungicides, herbicides can be used.

The concentration of the agents used can vary within wide limits depending on the type of application. It is generally 0.01 percent by weight to 20 percent by weight for more dilute agents, but concentrated agents 20 percent by weight to 98 percent by weight of active ingredient. Highly concentrated preparations are used, for example with the so-called ULV technology (ultra-low-volume) with minimal amounts of additives used. The ULV technology is made with ultra-fine atomizing Spray devices applied, preferably with the help of airplanes. . ■. ' :, «. ·. ^, ...

In the production of herbicidally active agents, numerous components can also be combined, of which the most important representatives are mentioned below: .. "· .:.;

009S28 / 18SB _;

ORfGfNAL INSPECTED

N-phenyl-N ¹ , N * -dimethy! -Urea / Np-chlorophenyl-N! , N ¹ -dimethylurea, N-3,4-dichlorophenyl-N ', ν' -dimethylurea, N-3,4-dichlorophenyl-N ¹ -methoxy-N "'- methylurea, N ^ -Bromo- ^ - chlorophenyl- N ¹ -methoxy-N'-methylurea f, trichloroacetic acid, 2,6-Diehlor-benzonitrile, 2,3i6-trichlorobenzoic acid> 2, ¹ ID, 2,4,5-T, MCPB, MCPP, isopropyl-carbanilate ,, Isopropyl-3-chloro-carbanilate, N-3-chloro-ph.enylGarbamic acid- ™ 4 '-GhlDr-but ^ .n-2-yL-1-ester, 2,3 # β-Trlchlorpfaenylesslgsäure and salts, 2- Chlor-diallylacetamide ^ 2-CkIOr - ^,. 6-Ms-äthylamino-E5-triazine,. 2-Methoxy-4,6-his-ethylamine-s-trlazine, 2-Azidp - ^ - methyl-thlo-ö- Isopropylaminotriazine, mono-methylarseniate-di-Na'-salt ^ '■ various ar-senites, Ua-metaborate, sodium chlorate, sulfamic acid »'

When fighting against representatives of the Acarina order Let’s look at the number of known acaricides and especially those use the following for combined use with the active ingredients of formula I:

Dinocap, Binapacryl, 2-sec.butyl-4,6-dinitrophenylcyclopropionate, Dinobuton, chlorine surfactants, fluorosurfactants, Fenson, Ovex, Tetradifon, Tetrasul, 4-chlorophenyl-2,4-5-trichlorophenylazosulfide, 2,4-dichlorophenylbenzenesulfonate, N '- (4-chloro-2-methylphenyl) -N * N-dimethylformamidine, Formetanate, 2-butynyl-p-chlorocarbanilate, Cyclopropanecarboxylic acid-2-nitro-4-chloroanilide, Dicofol,

009823/1855

In the following two preparation examples, parts are parts by weight, and the temperatures are in
Degrees Celsius.

example 1

240 parts of 2,4-dinitro-6-sec-butylphenol are used in 1000
Parts by volume of butanone {2) dissolved and mixed with 180 parts of potassium carbonate and 10 parts of powdered potassium iodide. After one hour, 140 parts of propargyl bromide are added and the mixture is heated under low flow for sixty hours. After dilution with ice water, the reaction product is dissolved in ether
added., which is washed with dilute sodium hydroxide solution and water. After evaporation of the ether, the end product remains, which is made from ethanol with the addition of ligroin
(Bp 110-140 °) is recrystallized; melting point 71-72 ° C.

009828/1965

Example 2

Preparation of the compound of the formula NO,

0 - CH ₀ - CH = 2

2 [verb. No. 4]

To 130 parts of 2-chloro-3,5-dinitrotoluene in parts Allylalkohol.tropft it at 50 ⁰ C with stirring, a mixture consisting of 45 parts of 85 $ strength potassium hydroxide, 30 parts of water and 100 parts of allyl alcohol. After two hours, it is poured onto ice water, filtered and the end product is recrystallized from ethanol; Melting point: 51-52 k In the same way as in one of Examples 1 or

2 described, the following compounds of the formula II manufacture;

II

y- 0 - CH ₀ - R ₉

/ C. d.

00S828 / 19S5

- li -

Connection no. Λ H ' Physical
Characterization ft ι — ί CH, CH,. Mp. 68-69 ⁰ C 2 CH, ; ^c a ^H 5; Mp. 49-50 ⁰ C 3 CH,
CH, -CHSCH. Mp. 34-35 ⁰ C
M.p. 51-52 C 5 CH, -C = Xi-CH,
3 M.p. 105.5-106 ° C 6th CH, ■
3 H M.p. 112-114 ° C ^^ 7th sec-butyl CH, pf \
OeI, ng = ■ 1.5 ^ 80 8th sec-butyl -CH = CHp OeI, n ^ ° = 1.5393 9 sec-butyl -C = CH OeI, n ^ ° = 1.5 ^ 75 10 sec-butyl - ° 2 ^H 5 Mp. 71-72 ⁰ C 11th sec.ButyΓ -C (Cl) = CH ■ - -
OeI, n _D = * l> 534 * l 12th sec-butyl -C ₃ H ₇ OeI 13th sec *. Butyl H OeI, n ^ ° = 1.5299 14th tert-butyl ■ - (™ 2> 10- ^CH 3 M.p. 81-82 ° C 15th sec-butyl -C ₆ H ₄ C1 (4) OeI, n ^ ° = 1.5051 16 sec-butyl -C ₆ H ₄ CK ₃ ) M.p. 77-79 ° C 17th sec-butyl -C ₆ Ci ₅ Snip. 69-7O ⁰ C 18th Isopropyl Mp. 163-165 ⁰ C.

009828/1966

Verb.
No. ^R l R ₂ ' Physically
characterization 19th Isopropyl -C ₃ H ₇ OeI, n ^ ° - 1.5328 20th
21 Isopropyl
Isopropyl Br Br
-CII-CH ₀
et Mp. 85-86 ⁰ C
Snip. 71-72 ^O C 22nd Isopropyl -C ₆ H ₄ ClW Smp.130-131 ⁰ C 23 Isopropyl -C H Cl (3.4) M.p. UO-141 ° C. 24 Isopropyl -CgH ₃ Cl ₂ (2.4) M.p. 147-1 ^ 8 ° C 25th Cyclohexyl H M.p. 64-65 ° C 26th Cyclohexyl -CH ₃ Mp. 92-93 ⁰ O 27 Cyclohexyl -CH = CH ₂ Mp. 64-65 ⁰ C 28 sec-butyl -C ₆ H ₄ Cl (2) Mp. 96-97 ⁰ C 29 sec-butyl -C ₆ H ₄ NO ₂ (4) M.p. 112-113 ° C 30th sec-butyl -CgH ₄ N0 ₂ (2) M.p. 76-77 ° E 31 CH, -CgH ₄ -N0 ₂ (4) M.p. 144-1H 5 ° C 32 sec-butyl -C ₆ H ₃ Cl ₂ 0.4) M.p. 117-II8 C 33 sec-butyl -GgH ₃ Cl ₂ (2.4) M.p. 108-109 ° C 34 Cyclohexyl -CgH ₄ Cl (4) Snip. 102-103 ⁰ C 35 Cyclohexyl -C ₆ H ₃ CLp. 4) M.p. "l43-l4 ^ ^o C 36 CH, -CH = CHCl OeI, rip ⁰ = 1.5637 37 Isopropyl H M.p. 54-55 ° C

009828 / 1QSS

Verb.
No. ^R l R ₂ : Physlkal
characterization 38 Isopropyl -CH M.p. 44-45 ° C 39 CH -GAL
6 5 Mp. 99-10O ⁰ C 40 CH C ₆ H ₄ Cl (2) M.p. 111-112 ° C 41 CII c ₆ H ₃ ci ₂ (3.4) M.p. 153-154 ^O C 42 Cyclohexyl -CHBr-CH ₂ Br Snip. 87 to 88.5 ⁰ C 43 CH, -C ₆ H ₃ Cl ₂ (2-4) M.p. 149-15O ° C 44 sec-butyl 65 • Smp. 57-58 ^o C CH- ₅ 6 5 M.p. 214-215 ° C 46 tert-butyl C ₆ H ₄ Cl (4) M.p. 142-145 ° C * 7 Isopropyl "'-CH = CH ₂ M.p. 45-46 ° C 48 Isopropyl • -CHsCH Mp. 79-8O ⁰ C 49 Isopropyl -C (Cl) = CH ₂ M.p. 63-64 ° C

as well as the connections

GlL, . ■ 5

O - CH - CH, CE,

CII - CII.

CIL

CH ₂ - CII

- CH - CH -CII., - CiL. ^J

OeI, n ^? _n ° - 1.54:

OeI, n ^f ^ l, b'f) km

Formulation examples "-

Dust :

Equal parts of an active ingredient according to the invention and precipitated silica are finely ground. By mixing with kaolin or talc, dusts with preferably 1-6% active ingredient content can be produced from them. Wettable powder

™ To produce a wettable powder, for example the following components mixed and finely ground: 50 parts of active ingredient according to the present invention 20 parts of Hisil (highly adsorptive silica). 25 parts Bolus alba (kaolin)

• 3.5 parts of reaction product from p-tert-octylphenol and ethylene oxide

1.5 parts (.1 -Benzyl ^ -stearyl-benzimidazole-ö ^ '-disulfosaures Sodium). ■

fc, emulsion concentrate

Easily soluble active ingredients can also be formulated as an emulsion concentrate according to the following rule: 20 parts active ingredient
70 parts of xylene ■ ___.

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

been mixed. For dilution with water to the desired level Konzonlral-.i on ent r.tclit an applicable emulsion.

Ü09828719B5

Granules

7.5 g of one of the active ingredients of the formula I are dissolved in 100 ml of acetone and the acetone solution thus obtained is poured onto 92 g of granulated attapulgite (mesh size: 24/48 masses / inch). The whole thing is mixed well and the solvent is drawn off in a rotary evaporator. Granules with a 7.5 % active ingredient content are obtained.

009828/1965

Example 3:

Ä) 'Effect; against airborne mites. ,.

Bush bean plants (Phaseolüs vülgaris) 'are in the two-leaf stage 12 hours before the active ingredient treatment with spinning. . mites through application of infected leaf pieces from a cultivation

infected., so that after this time a population is found on the plant in all stages of development. With the help of a chromatography nebulizer v; erdeii äi &. Plants then: sprayed with the ernulgiertcn .Wirkstoff ,, until a _^DC:

: massive drip coating develops on the leaf surface. After 2 and 7 days, the following is evaluated: The plant parts are used under a stereo microscope to "calculate the ...

-A ^ killing percent inspected. The effect on liier is'

^:) ·. ■ ■ ■ ''. '■■■■■■'. ■■■

With this test arrangement, after 2 days, the average hatching time is still not possible; ^; this

»'■ ■. ■■■■■■■■' - ■; . ■. ■ '^; - "■ ■ '■.' ■ ■■ '''; ■ -: ■ · ■; ■■ ·. · ■> ■ ■. ■'. - ^L ■■, ■ ■. '■■ ' ■ Time not yet, exactly ^ known... ■■■ .. ·..,

-En-the following "table are-the atetot-ungSiprozente \ '

normalsensibien 'species Tetranycteus. -for ^ ti-cae Ko'Ch ^ and -die ;.

der; pliosphorus
^ chus ^ telarius iL. specified.

Compound .Wr, 9 · serves as the Kiirfestof f.

BATH ORIGINAL

~ 17 -

a) Action against Te br. urticae

Mortification

Conc. after
[ppm] larvae 2 days.
Adults Eggs after 7
Larvae Days
Adults 800 $ 100 $ 100 $ 100 .100 $ $ 100 400 $ 100 $ 100 $ 60 $ 60 $ 100 200 $ 100 $ 100 $ 0 $ 0 $ 100 100 $ 80 $ 80 '0 $ $ 0 $ 100

Effect against tetr. telarius

[ppm] after
Larvae Mortification Eggs after 7
Larvae Days
Adults Kon z. $ 100 2 days,
Adults' $ 100 $ 100 $ 100 8OO $ 100 ■ $ 100 $ 60 $ 60 $ 100 400 $ 100

D) Effect on ticks. About 10-20 tick larvae of Bpophiluss mlcroplus are placed in a glass tube and immersed for 1-2 minutes in 2 ml of an aqueous emulsion from a dilution series of 100, 10, ¹ J and 1 ppm testubutance, whereupon the VerjuchHlörjung ontfornt and the vessel is closed with a cotton ball. According to ^ 'Tai ^ on , at the following limit concentrations .100 $ killing foi; tgai; tellt: Vci'b.Hr. 9 5 ppm

'■ Verb. No ... 7 10 ppm Verb, No ₁ 8 10 ρρπι

BATH ORIGINAL

0 0 98 28 - / 19-B-

Example 4

Herbicidal effect. The following plants became

Sown in clay pots in the greenhouse: Triticum, Hordeunv Beta, DactyliSj Calendula / Linum., Brassica, Daucus, Cj Soy, Oryza., Panicura, Poa, Digitaria.

In a series of tests, the compounds No. 50j 2 and 1 were in each case in application rates of 5 kg / ha before the emergence of the Plants (Pro) applied. In a second series of tests, the same compounds were used at an application rate of 5 kg / ha applied after emergence of the plants (post). The evaluation was carried out every 3 weeks. Results:

Connection no. 50 pre post pre 2 post pre 1 post plant 1 ' 2 1 3 1 1 Triticum 1 1 1 5 " 1 3 Hordeum - - .9 - • - - beta - - 8th - - - Dactylis - - 1 . 9 1 6th Calendula - 5 9 1 9 Linum 9 - 9; 3 9 1 9 Brassica - - 2 - - Daucus 8th 1 9 1 Cyperus

Ü09820 / 19SS

Connection no. pre post 2 pre post 1 pre post plant - - · 2 - - - soy - - 1 - - - Oryza 9 1 ν 8th 9 4th 8th Pani cum 9 1 7th 7th 6th 8th Poa - - 9 -. - ■ - Dissitar! A

Valuation:

1-2 = no damage

3-6 = medium damage

7-8 = severe damage

9 "- plant dead

009828/1956

BAD OBiGiNAL

Claims (1)

Claims 1. Use of compounds of the formula where R, for the methyl, isopropyl, sec-butyl, tert-butyl, sec.Octyl, cyclohexyl or Cy.clopentylrest, R the Meaning of an alkyl or alkenyl radical with 1-4 carbon atoms which is optionally substituted by halogen or an alkynyl radical with 1-4 carbon atoms or a phenyl radical which is optionally substituted by hydroxyl, halogen or nitro has, and R ^ for .hydrogen or the methyl group stands, ■ for combating pests of the Acarina order and weeds. 2. Use according to claim 1 of compounds of Formula" GH "3 viorin.R, the methyl, isopropyl, oek.Butyl, tert.Butyl, sekiQet-yl, cyclohexyl, or cyclopentyl radical means, R ' BAD OF [JGlNAL represents a halogen-substituted alkyl or alkenyl radical or unsubstituted alkenyl radical having 1-4 C atoms or a phenyl radical optionally substituted by hydroxyl, halogen or nitro and R-, hydrogen or the methyl group . -,. ^: .: ■ '".; ■■ .- ·. ''; _ ■■■ .". ■ '■ ·; -. 3 · Use according to claim 1 of compounds of ■. formula H. where R den-methyl, isopropyl, sec-butyl or tert. Butyl radical means, R for H, the methyl, vinyl, chlorovinyl or ethynyl group and R ·, H or the methyl group. -.- .. '■■■: Λ. Use according to claim 1 of the compound of the formula O - CH ₂ - GH = CH " ^N CH - CH ₀ - CIL 5. Öciiädlingnbekärnpfimgsm'ittel, which as active ingredients 'compound fertilize the formula .' M. '■■: ·;, ■ ;. .; ^; . ^4th 009823 / 19IS 1959295 - 22 .- ^v ■ -. ■ contain., where R, the methyl, isopropyl, sec-butyl, tert-butyl, secondary octyl, cyclohexyl or cyclopentyl radical. means, R ^ is an alkyl or substituted by halogen ^ Alkenyl radical or unsubstituted alkenyl radical with 1-4 C atoms or a phenyl radical optionally substituted by hydroxyl, halogen or nitro and R-, hydrogen or is the methyl group, together with one or more of the following additives: solvent, diluent., dispersant, Emulsifying agents, wetting agents, adhesives or thickening agents or others Insecticides, acaricides, nematocides, bactericides, fungicides, herbicides. ^ 6. Pesticides according to claim 5 j the as active ingredient the compound of the formula O - CH ₀ - CH = CPL - CH - contain. . J) The compounds mentioned in claim 5, 8. The compound mentioned in claim 6. QG9828 / 18Sf