DE1901501A1 - Pest repellants - Google Patents

Description

• i. * A λ 9

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

Case 6565 / E

Pesticides

The present invention relates to pesticides containing a compound as an active ingredient the general formula

909835/1499

» '· 111 t » It

(D

wherein X and Y are oxygen or sulfur, R is one optionally substituted by halogen alkyl, alkenyl,

_Ä j alkynyl or alkoxy radical, one 1 or 2 oxygen atoms

alkyl radical contained in the chain, optionally substituted by halogen or the groups -CF-, -CH-, or -OCH Phenyl radical and Rp denotes hydrogen or a lower alkyl radical or R-, and R together with the with them linked nitrogen atom form a heterocyclic ring: and R-. a lower aliphatic radical, which is also found in the Chain can be interrupted by 0 or S (Verb.26) or an unsubstituted or at most triple with halogen, lower alkyl, alkoxy, alkyl mercapto, cyano and / or Trlfluromethy! Group means substituted phenyl radical, as well as optionally at least one of the following additives: carrier, solution, diluent, dispersant, Emulsifiers, wetting agents, adhesives and other pesticides.

One of the particularly important groups comprises compounds of the formula I in which X and Y are oxygen or sulfur, R _{1 is} an alkyl, alkenyl, alkynyl or

909835 / U99

t <t

Alkoxy radical with a maximum of 6 carbon atoms, an alkyl radical containing 1 or 2 oxygen atoms in the chain with a maximum of 6 carbon atoms, a phenyl radical which is unsubstituted or substituted at most three times by halogen, -CF ,, -CH, and / or by -OCH, and Rp denotes hydrogen or the methyl radical or R ₁ and R ₂ together with the nitrogen atom connected to them form a heterocyclic ring with a maximum of 6 carbon atoms and R is a lower alkenyl radical or a lower alkyl radical which is also interrupted in the chain by 0 or S. or a phenyl radical which is unsubstituted or substituted at most three times by halogen, an alkyl, alkoxy or alkyl mercapto group having at most 4 carbon atoms, a cyano and / or trifluoromethyl group.

One of the important groups of these are compounds of the formula I in which X and Y are oxygen or sulfur stand, R, a lower alkyl or alkoxy radical with 1-4 C atoms, Rp is hydrogen or a lower alkyl radical with 1-4 C atoms and R, a lower alkyl radical, which can also be interrupted in the chain by -O-, means.

Of these, herbicidally active substances are particularly selective

Compounds of the formula

S I

NH-C-N

and

OCH,

909835 / U99

«1 · it»

1 · ι. . 11 «

«Ι ■ ■ lit

R '= -CH-., -C ₀ Η ,. or R '= H or CH, ρ j <= ■ D ^ J

-CH ₂ CH ₂ -OC ₂ H ₅

Another group of important active ingredients are those of formula II

II

wherein R, a methyl or methoxy radical, R _{2 is} hydrogen, a methyl or a dihalophenyl radical, R. is a halogen atom, especially chlorine, a methyl, methoxy or methylmercapto group and Ri is hydrogen or a trifluoromethyl group, while X and Y are oxygen or sulfur.

Those of the formula II in which X and Y are oxygen have a favorable spectrum of activity.

The new m-trifluromethylphenylureas of the formula I can be prepared by methods known per se,

by reaction of an aromatic radical A

with a second reactant B, both of which together form the thiourea or urea grouping according to formula I.

909835 / U99

ORIGINAL fNSPECTED

able to form. Therein, X and R have the meaning given for formula I, while one of the substituents A or B the grouping

-N-CYYR '(where -CYYR' means an ester group)

ι
-N-CY halogen

-N-CY-NH ₂ ;

or "-N = C = Y represents (in which Y = O or S) and the other the basic group -NH-, in which the free valencies are linked to g is hydrogen, provided they do not components of a primary or secondary, also cyclic amine are,

in each case with further post-alkylation and / or post-halogenation to obtain special representatives of formula I,

The invention also relates to the new compounds of the formula I.

These primarily have a selective effect against

Weeds in crops of useful plants. The effect can be in the pre-emergence 'and in the post-emergence process and will mainly observed in important large crops such as grain, rice, maize, soy, cotton, and others. Total herbicidal effect occurs at higher application rates, which is always advantageous if the useful soil for a new planting is to be prepared while remains of a previous culture are still present.

Some of the connections also have Defolians ~ peculiarities

909835 / H99

; _: ; : _;: ; ; _: ^ ORIGfNALfNSPECTED

■ - 6 -

stocks.

The new phenyl ureas have very little Application rates good microbicidal activity against bacteria and fungi such as Asp. Niger, Staph. aureus, Esch. coli or also Rhizoctonia solani, for which in particular the compounds No. 11 and No. 11 listed in Table 1 below. are also suitable against fungi such as Alternaria tenuis or Alternaria solani or against the soil fungus Fusarium, to which Compound no. 20 is particularly suitable for combating.

In addition, Compound No. 9, for example, shows a chemosterilizing effect on insects.

The formulation of the new ureas of the formula I into pesticides in dry or liquid Use as solutions, emulsions, wettable powders, dusts happens in the usual way and is detailed in the

us. P. 3,329,702

or Brit.P. 1,047,644
or Swiss P. 424 359

described. In many cases, the use of granules is recommended over a longer period of time. share active ingredient release beneficial. Leave such granules by dissolving the active ingredient in an organic solvent, absorption of this solution by granulated mineral, e.g. make attapulgite or SiOp and remove the solvent.

909835/1499 ORIGINAL INSPECTED

In the form of one or the other application, such agents can also be applied by distributing them over a large area (Spraying, dusting, etc.) can be carried out with the help of plug tools.

The different forms of application of such funds can in the usual way by adding substances that the distribution, the adhesive strength, the rain resistance and possibly improve the penetration capacity, e.g. fatty acids, resins, wetting agents, glue, casein or alginates, can be adapted more closely to the purposes of use.

Coming in the manufacture of herbicidally active agents also numerous components for combination in question, of which the most important representatives are in the following may be mentioned:

N-phenyl-N ¹ , N'-dimethyl urea, Np-chlorophenyl-N ¹ , N ¹ -dimethylurea, N-3,4-dichlorophenyl-N ^f , N ¹ -dimethylurea, N-3,4-dichlorophenyl- N'-methoxy-N'-methylurea, N-4-bromo-3-chlorophenyl-N ^f -methoxy-N ¹ -methylurea, trichloroacetic acid, 2,6-dichlorobenzonitrile, 2,3,6-trichlorobenzoic acid, 2, 4-D, 2,4,5-T, MCPB, MCPP, isopropyl carbanilate, isopropyl 3-chloro-carbanilate, N-3-chloro-phenylcarbamic acid 4 ^1- chloro-butyn-2-yl-1-ester , 2,3 * 6-trichlorophenylacetic acid and salts, 2-chloro-diallylacetamide, 2-chloro-4,6-bis-ethylamino-s-triazine, 2-methoxy- ¹ ^, 6-bis-ethylamino-s-triazine, 2-Azido - ^ - methyl-thio-ö-isopropylaminotriazine, mono-methylarseniate-di-Na-salt, various arsenites, Na-metaborate,

909835 / U99

ORIGINAL INSPECTED

Na chlorate, sulfamic acid.

The agents according to the invention can also be used in combination be used with insecticides, acaricides, nematocides, bactericides, fungicides or molluscicides.

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

example 1

l) 33 parts of 4-methoxy-3-trifluoromethyl-phenyl isocyanate are dissolved in 50 cm of acetonitrile and, with thorough stirring, '· to a solution of 20 cm of dimethylamine (40 $ aqueous Solution) in 100 cm acetonitrile. The reaction product is precipitated with water and filtered off.

M.p .: 112 ° -115 ° 0

I! . CH
NH- CN ^ ⁵

CH "CF ^

[Compound No. 1]

In the same way, the following compounds were also obtained:

II -NH-C-R

909835 / U99

No.

OH,

-N

₀ -UH-O. Η _Λ 2 4 9

- 9 Table 1

M.p.

121-124

161 - 166 ¹

128-131

193-197

196-197

OeI

106-109 86-89

909835 / U99

No.

10

14th

16

17th

- 10 -

-NH-CH ₂ -CH = CH ₂

-N

CH

C = CH

-NH-CH

3 OCH.

CH.,

OCH-

-NH-CH ₂ -CH '

OCH-

CH.

/ -1TT Ott rifj

OW ₀ UiI ₀ UW _r ddc.

, nC

, -CH-OCH, 0OH,

O.

M.p. C 129-130 OeI

139 - 140 ° 62 - 65 °

97 -

89-90 ⁰

179-184

909835 / U99

- 11 No. " .
R. M.p. ° C 18th
19th / -ο
-N>
JT 144-148 °
92-96 °

.. as well as the following connections :.

link

"V-NH-C-NHCH, 3

NH-C-N

OH,

CH,

M.p. ⁰ C

135 - 141 143 - 147 ¹

909835 / U99

19015

No.

23

24

!

link

Il -CH,

CP.

CH.

CP

.OH-.

Hr-C ₀ V / χ

0-CH,

NH-CO-N

he..

ο,

M.p. C

124 -

116 -

75-78

66 - 70 '

CP,

X ^CH 3 CH,

108 -

; H CS-CH ₂ CH ₂

H ₂ C = CH-CH ₂ - '

OF

NH-CO-N

65-67

CP. CH.

909835/1 498

• ft · 4

No. -

link

^ -NH-CO-N (CH ₃ ) ₂

Z _- V-HH-CO-H ^- (CH ₃ )

V-O-V V-NH-CO-N (CH ")

CF.

M.p. ⁰ C

111-114

117 - 121

Cl: 204-208

909835 / U99

• a a Ii yes

•. > J ι j jaa j ' J yj

- 14 -

No.

39 40 41

link

HH-CO-N (CH)

3 ^y 2

3 ^; 2

3 ^y 2

L _)> ~ NHCO-N (CH

M.p. ° C

126-130

121-126

ORIGINAL INSPECTED

909835/1

Example 2

It was a wettable powder of the following composition ι manufactured:

an active ingredient listed in Example 1
Bolus alba (kaolin)

finely divided SiOp (under the brand name "Hisil" j commercially available product) ■

3.5 # of a condensation product of 1 mole of dodecyl- f mercaptan with 12 moles of ethylene oxide

• · 1 * 5 $ - a condensation product of p-nonylphenol. ■. ... ..

with 9 moles of ethylene oxide

The finely ground mixture obtained in this way can be

in any way with water to a ready-to-use I.

Dilute the spray liquid.

Example 3

In the greenhouse, clay pots are filled with earth and

sown with several of the following types of seeds: Triticum vulgare, t Hordeum vulgaris, Beta vulgaris, Calendula, Chrysanthemum,
Sinapis arvensis, Lepidium sativum, Digitaria, Poa, Alope- ⁽ curus, Linum, Brassica, Ipomoea, Stellaria, Amaranthus,
Avena, Gossypium, Zea, Oryza, Sorghum, Panicum, Cynodon veg., 'Galium, Soja.

ORIGINAL INSPECTED
909835 / U99

The post-emergent treatment of the plant juices mentioned was carried out with a liquid and 0.06% aqueous solution of one of the compounds described in Example 1 about 10-12 days after sowing, in the 2-3 leaf stage, at an application rate of 2 Kg of active ingredient per hectare.

The evaluation took place about 20 days after the treatment and led to the result shown in Table 2.

The pre-emergent treatment was carried out with the same amount of application before germination, 24 hours after sowing.

909835/1 499

»· Ft ·

I. Plant species Verb. Verb. Verb. Verb. Verb. Verb. Verb. 1 1 24 24 26th 30th 31 post Pre post Pre post post post

Triticum 2 3 2 2 - 1 2 Hordeum - - 2 - - 2 2 Avena
Zea
Oryza - - - I I OO 2 2
2
3 2
2
2 Digitaria 8th 9 9 9 9 - Sorghum. "-. · - Γ - ■ · ■ · -. -. 9 Pani cum 8th 9 - - 7th - - Poa - - 9 - 8th - " - Alopecurus 7th 8th 8th - - - Cynodon veg. - - - - 9 - - Gossypium - - - 1 - "■ - - Galium ' 6th - - - ψ,
6th _ Calendula 7th 9 9 - - 9 7th Chr y s an the mum - - 9 9 9 9 9 Linum - - 9 - - • 9 - Brassica - - 9 9 9 9 Ipomoea 9 9 9 9 9 9 ON soy - - - - - - 2 Stellaria 9 9 9 - 9 9 9 Amaranthus 9 6th
9098 9
35 / U99- 9 9 9 9

Evaluation: 1 - 3 = plant. Not or hardly affected, 4 - 6 = medium damage, 7 - 8 = 'severe damage,

9 = plant dead,

From the test results it can be seen that Compound 1 and 24 both pre-emergence and post-emergence Recommend as a herbicide in wheat crops. The compounds 30 have a broader spectrum and 31 * the cereals, rice and maize, in the case of connection 31 also tolerate soy, but destroy the weeds that are important for these crops. Connection 24 is available as typical selective herbicide to protect cotton crops in pre-emergence application. As a weed killer Compound 26 is recommended in maize crops, which is particularly advantageous where it has been applied over many years of triazine derivatives for weed killing no longer the has the desired success because once insignificant weed species have now come to the fore, those of these Triazines are hardly attacked.

Example 4.

The following result was obtained in a special field test of compound 1 in Winterweise.

In spring, at the time of tillering, a winter wheat field was treated with 1 kg AS / ha, which was covered by the natural weeds Alopecurus, Poa trivialis, Apera spica-venti ₃

, 909836 / U99 _{0R1G1NAU iNS} PECTED

Geranium, Veronica, Matricaria, Myosotis, Arabidopsis, Stellaria and Sinapis was infested.

The two-time evaluation after 4 and 8 weeks showed that all the weeds listed had been destroyed, the wheat culture, however, remained completely unaffected.

Example 5

The new ureas and thioureas of the formula J (I) show an extremely strong effect against gram-positive bacteria - especially against staphylococci and Streptococci.

The antibacterial activity in the dilution test was determined as follows.
Bacteriostasis

20 mg of active ingredient are dissolved in 10 ml of propylene glycol, 0.25 ml of which is added to 4.75 ml of sterile glucose broth and then further diluted 1:10 in the tube. λ

These solutions are then inoculated with Staphylococcus aureus and incubated for 48 hours at 37 ° C (bacteriostasis). After the specified time, the following concentration in ppm. the bacteriostasis determined:

909835/1 499

ORiGINAL INSPHCTED

190150

Staphylococcus aureus. Connection no. Bacteriostasis 3 ■ Ό, .01 5 0.2 6th 0.1 17th 5 32 0.01

909835/1 499

Claims (5)

Claims 1. Pesticides containing at least one compound of the general formula as active ingredient wherein X and Y are oxygen or sulfur, R, an alkyl, alkenyl, alkynyl or alkoxy radical which is optionally substituted by halogen, an alkyl radical containing 1 or 2 oxygen atoms in the chain, an alkyl radical which is optionally substituted by halogen or the -CF groups means. ,, CH., or OCH., substituted phenyl group and R _p is hydrogen or a lower alkyl radical or R, and R p together with the nitrogen atom linked to them a 'heterocyclic ring and B.-, a similar lower aliphatic radical , which can also be interrupted in the chain by 0 or S, or a phenyl radical which is unsubstituted or substituted at most three times by halogen, lower alkyl, alkoxy, alkyl mercapto, cyano and / or trifluromethyl groups, and optionally at least one of the following Additives: Carriers, solvents, 909835 / U99 Diluents, dispersants, emulsifiers, wetting agents, adhesives, as well as other pesticides. 2. A pesticide according to claim 1, containing as active ingredient at least one compound of the formula wherein X and Y are oxygen or sulfur, R is an alkyl, alkenyl, alkynyl or alkoxy radical with at most 6 carbon atoms, an alkyl radical containing 1 or 2 oxygen atoms in the chain with a maximum of 6 carbon atoms, an unsubstituted one or at most three times with halogen, -CF ^, -CH, and / or with -OCH-, substituted phenyl radical and R Means hydrogen or the methyl radical, or R, and R ~ together with the nitrogen atom connected to them form a heterocyclic ring with a maximum of 6 carbon atoms and R ^ a lower alkyl radical or a lower alkyl radical, which can also be interrupted in the chain by 0 or S, or an unsubstituted or at most threefold by halogen, an alkyl, alkoxy containing at most 4 carbon atoms or alkyl mercapto group, a cyano and / or trifluoromethyl group substituted phenyl radical. 909835 / U99 3. Pesticides according to claims 1 and 2, containing as active ingredient at least one compound of Y
formula wherein X and Y are oxygen or sulfur, R _{1 is} a lower alkyl or alkoxy radical having 1-4 C atoms, R _{2 is} hydrogen or a lower alkyl radical having 1-4 C atoms and R is a lower alkyl or alkoxy radical 1-4 C atoms, Rp is hydrogen or a lower alkyl radical with 1-4 C atoms and R is a lower alkyl radical which can also be interrupted in the chain by -0-. 4. Pesticides according to claim 1, 2 and 3 * containing at least one compound of the as active ingredient Formula w «_n ^ _ _w /} . CH, NH-CO-N wherein Rp 'and R,' represent a methyl or ethyl group. 5. A pesticide according to claims 1 to 4 containing the compound of the formula as Witetoff 909835/1 499 ORIGINAL INSPECTED NH-CO-N CH, OCH, 6. Pesticide according to claim 1, 2 and 3, containing as active ingredient at least one compound of the formula ^ CH " NH-CS-N R ¹ wherein R 'is hydrogen or methyl. 7. Pesticides according to claim 1 to 3> containing as active ingredient the "compound of the formula 8. A pesticide according to claims 1 and 2, containing at least one compound of the formula as active ingredient 909835 / U99 where R is a methyl or methoxy radical, R _{2 is} hydrogen, a methyl or a dihalophenyl radical, R ₂ ^ is a halogen atom, especially chlorine, a methyl, methoxy or methylmercapto group and R ₁ - is hydrogen or a trifluoromethyl group, while X and Y oxygen or sulfur are pesticides according to claims 1, 2 and 8, containing at least one compound of the formula as active ingredient where R- ,, R _? i R ₁ . and R ₁ . have the meaning given in claim 7. 10. Pesticides according to claims 1, 2, 8 and 9j containing at least one of the compounds as active ingredient the formula wherein R '^ is hydrogen or chlorine 909835 / 1A99 11. Use of the active compounds mentioned in claims 1 to 10 for combating weeds in crops of useful plants such as cereals, rice, maize, soy, cotton Pre-emergence or post-emergence method. 12. Use of the active compounds mentioned in claims 1 to 10 for combating bacteria and fungi. 13. Procedure for the production of m-trifluoromethylphenyl ureas of the general formula in which R., Rp, R ^, X and Y the meaning given in claim 1 to have, by reaction of an aromatic radical A with a second reactant B, both of which together form the thiourea or urea according to the final formula able, wherein X and R-, have the meaning mentioned, while one of the substituents A or B represents the grouping -N-CYYR ' -N-CY halogen -N-CY-NH ₂ 90P835 / U99 oer represents -N = C = Y, with Y = O or S and R ^{f stands} for any C-containing and easily cleavable radical, and the other substituent denotes the basic group -NH, in which the free valences are bonded to hydrogen, unless they are components of a primary or secondary, including cyclic amine, in each case with, if appropriate, further post-alkylation and / or post-halogenation. 14. The active compounds mentioned in claim 1. ' ä 15. The active compounds mentioned in claim 2. 16. The active compounds mentioned in claim 3. 17. The active compounds mentioned in claim 4. 18. The active compounds mentioned in claim 5. 19 · The active compounds mentioned in claim 6. 20. The active compound mentioned in claim 7. 21. The active compounds mentioned in claim 8. 22. The active compounds mentioned in claim 9. 23 · The active compounds mentioned in claim 10. 909835/1499