DE2458689A1 - NEW PHENYLCARBAMATES - Google Patents

Description

CIBA-GEIGY

CLBA-GEIGY AG, CH-4002 Basal

Dr. F. Zumsiein sen. - Dr. E. Assmann Dr. R. Koenigcborger - Dipl. Phys. R. Holzhauer

Dr. f \ Zunisicin jun.

Patent attorneys

8 Mönch * n 2, Bräuhausstraße 4 / III

Case 5-9156 / 1 + 2 / =
GERMANY

New Pheny! Carbamate

The present invention relates to phenyl carbamates, processes for their production and their use in pest control.

The Pheny! Carbamate have the formula

. ⁵ NjhV

O-C-If-!

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wherein R ^ and R ₂ each -hydrogen, C, -C, -alkyl, chlorine or bromine, Rq and R, each methyl or together -CH ₉ -CH ₉ -, • -CH ₂ -CH ₂ -CH ₂ -, -CH-CR ₂ -, -CH - .. CH-,

. CH,
■ 1 CHq CHq CH ₃ CHq CHq • i
CH ₃ I ^T
—C-, -CH ₉ -C-CH ₉ -
² / \ ²
CHq CHq CH ₃ CH ₃ CH ₃ CK ₃ -CH
T CH ₃ -CH-CH ₉ -C-
\ V \
CHq CHq CHq -CH-CH ₉ -CH ₉ -
j ct / m
CH ₃ -CH-CH- or
I. I.
CH ₃ I. I.
CH ₃ I.
CH ₃ mean.

Because of their action, compounds of the formula I are preferred,

where R, hydrogen,

R is hydrogen, chlorine, methyl or tert. Butyl

R ₃ and R / together -CH ₂ -CH ₂ -, -CH -CH-, -CH-CH ₂ -

^ÜU 3 ^Oii 3 ^L 3

or. -CH ₉ -CH ₉ -CH ₀ - mean.

The compounds of the formula I can according to the following known methods can be produced:

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• CH '

O O (II)

.3

(III)

acid "binding agent ".

Tbsp

+ x-

(III)

In formulas II to IV, R _n to R have those for

i. H-

Formula I given meaning and X stands for halogen, in particular ^? £ Ur chlorine and Me for a metal, especially an alkali metal.
Suitable acid-binding agents are: tertiary amines,

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CIBA-GEIGYAG - 4 -

e.g., trialkylatnines, pyridine, dialkylanilines; "inorganic Bases such as hydrides, hydroxides; Carbonates and bicarbonates of alkali and alkaline earth metals. The implementation is it is sometimes necessary to use catalysts such as copper or copper chloride.

The reactions A and B are carried out at atmospheric pressure, at temperatures between -20 to 50 ⁰ C, preferably at 0 to 30 ⁰ C and in Lb'sungs- or diluents. First and foremost, lower ali-. phatic ketones such as acetone, methyl ethyl ketone; Alkanols such as methanol, ethanol, isopropanol; Esters, such as ethyl acetate; Nitriles such as acetonitrile; N-alkylated acid amides; aromatic and halogenated hydrocarbons, such as benzene, toluene, chloroform, methylene chloride; Ethers and ether-like compounds, such as diethyl ether, dioxane, tetrahydrofuran; also water and mixtures of such solvents with one another and with water. Starting materials of the formulas II, III and IV are known and can be prepared analogously to known methods. A process for the production of the starting products II and IV is described, for example, in English patent specification no.

The compounds of the formula I have a broad biocidal action and are therefore suitable for combating various plant and animal pests.

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But they have in particular insecticidal and acaricidal / Properties and can be used against all stages of development such as eggs, larvae, pupae, nymphs and adults are used by insects and representatives of the order Akarina, e.g. against family insects:

Tettigoniidae / Gryllidae, Gryllotalpidae, Blattidae, ■ Reduviidae, Phyrrhocoridae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabacidae, Dermestidae, Coccinellidaej Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Lymatriidae, Pyralidae,

Culcidae, Tripulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae, as well as acarids of the families Ixodidae, Argasidae, Tetranychidae and D.ermanyssidae,

The compounds against Insects of the families Blattidae and Chrysomelidae namely in particular Phyllodromia germanica, Periplaneta americana. and BIatta orientalis and Leptinotarsa decemlineata, respectively. The "insecticidal or acaricidal effect" can be Substantially broaden the addition of other insecticides and / or acaricides and adapt to the given circumstances. Suitable additives are, for example:

organic phosphorus compounds, derivatives of nitrophenols, formamidines, ■

Ureas,

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Carbamates and / or

chlorinated hydrocarbons.

Surprisingly, the warm-blooded toxicity of compounds of the formula I is significantly lower than that of similar compounds known from English patent specification No. 1 122 633

The compounds of the formula I can be used alone or together with suitable carriers and / or additives can be used. Suitable.carriers and aggregates can be solid or liquid and correspond to the substances commonly used in formulation technology such as natural ^ or regenerated substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders and / or fertilizers. For application, the compounds of the formula I can be added to dusts, emulsion concentrates, granules, dispersions, Sprays, solutions or slurries in common Formulation used in application technology for General knowledge should be processed.

The agents according to the invention are produced in an known manner by intimate mixing and / or grinding of active ingredients of the formula I with the appropriate ones Carriers, optionally with the addition of opposite dispersants or solvents that are inert to the active ingredients. The active ingredients can be used in the following working-up forms are available and applied;

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Festivals.

Forms of processing: dust, grit,

Granules, coating granules, ■ impregnation granules and

Homogeneous granules Liquids ■
Processing forms:

a) dispersible in water

Active ingredient concentrates: wettable powders

Pastes, emulsions;

b) Solutions

The content of active ingredient in the agents described above is between 0.1 and 95%, it should be mentioned that when applied from the aircraft, or higher concentrations can also be applied by means of other suitable application devices.

The active ingredients of the formula I can, for example, such as can be formulated as follows:

Dust: The following substances are used to produce a) 5% and b) 2% dust:

a) 5 parts of active ingredient
95 parts of talc;

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b) 2 parts of active ingredient

1 part of highly disperse silica, 97 parts of talc

The active ingredients are mixed with the carriers and marry.

Granules: The following substances are used to produce 5% granules:

5 parts of active ingredient

0.25 part of epichlorohydrin, 0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol

91 parts of kaolin (grain size 0.3-0.8 mm). The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol is added and cetyl polyglycol ether added. The solution obtained in this way is sprayed onto kaolin and then the Acetone evaporated in vacuo.

Spray powder: The following ingredients are used to produce a) A0%, b) and c) 25% d) 10% spray powder:
a) 40 parts of active ingredient

5 parts of lignin sulfonic acid, sodium salt, 1 part of dibutylnaphthalenesulfonic acid, sodium salt, 54 parts of silica;

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b) 25 parts of active ingredient

4.5 parts calcium ligin sulfonate,

1.9 parts of champagne chalk / hydroxyethyl cellulose mixture (1: 1),

1.5 parts of sodium dibutyl'-naphthalene sulfonate, 19.5 parts of silica, 19.5 parts of Champagne chalk, 28.1 parts of kaolin;

c) 25 parts of active ingredient

• 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts champagne chalk / hydroxyethyl cellulose

Mixture (1: 1),

8.3 parts of sodium aluminum silicate, 16.5 parts of kieselguhr, 46 parts of kaolin; ■

d) 10 parts of active ingredient

3 parts mixture of the sodium salts of saturated

Fatty alcohol sulfates, 5 parts naphthalenesulfonic acid / formaldehyde condensate

sat,

82 parts of kaolin.

The active ingredients are mixed in suitable mixers with the ingredients intimately mixed and ground on appropriate mills and rollers. You get wettable powder that with water to form suspensions of any desired concentration

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Let the tration dilute.

Emulsifiable concentrates; The following substances are used to produce a) 10% and b) 25% emulsifiable concentrate:

a) IO parts active ingredient

3.4 parts epoxidized vegetable oil,

3.4 parts of a combination emulsifier, consisting of from fatty alcohol polyglycol ether and alkylarylsulfonate calcium salt,

40 parts of dimethylformamide, 43.2 parts of xylene;

b) 25 parts of active ingredient

2.5 parts epoxidized vegetable oil,

10 parts of an alkylarylsulfonate / fatty alcohol poly-

glycol ether mixture, 5 parts of dimethylformamide, 57.5 parts of xylene.

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water will.

Spray: The following ingredients are used to produce a 5% spray:

5 parts of active ingredient, 1 part of epichlorohydrin, 94 parts of gasoline (boiling point 160 - 19O ⁰ C)

G η 00 7 c / ι η Q r \

CIBA-GEIGYAG - 11 - Example 1

Production of N-methyl-Np-chlormercapto-phenyl-O-ClaS- ■ - dioxan-2-yl) phenyl carbamate

To a mixture of 23.7 g of N-methyl-0- (l, 3-dioxan-2-yl) phenyl-carbamate and 50 ml of pyridine under stirring at 5 - 10 ⁰ C. 18 g of ρ-Chlorphenylsulfenylchlorid added dropwise. After stirring for 30 minutes at room temperature, the reaction mixture is poured into a solution of 150 ml of ice water and 40 ml of concentrated hydrochloric acid and stirred for another 30 minutes. The reaction product is extracted with methylene chloride, this is washed with water, dried over sodium sulfate and evaporated. After recrystallization of the solid residue from methanol, the compound of the formula is obtained

0 CH _r

as a white, crystalline powder with a melting point of 108.6 - 109.8 ° C.

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The following compounds of the formula I are also prepared in an analogous manner:

^R l R ₂ R ₃ ^R 4 CH ₃ Physical data P-Cl H -CH ₂ -CH ₂ - CH ₃ M.p. 132.5-134 ° C p-Cl H -CH-CH-
■ ι -CH ₂ -CH ₂ - η ^ ^Ο ° = 1.5927 CH ₃ CH ₃ -CH ₂ -CH ₂ - H H -CH ₂ -CH ₂ - -CH- CH-
• · M.p. 85-87 ° C H H -CH ₂ -CH ₂ -CH ₂ - II
CHq CHo 20 °
n _n - 1.5820
D ' H H I- f
CH ₃ CH ₃ -CH-CH-
1 I.
CH ₃ CH ₃ np °° - 1.5691 H H CH ₃ -C CH-
^ r N ι n ^ ° »1.5703 P-CH ₃ H CH ₃ S ^ \ '
CHq CHq CHq n ^ ° = 1.5672 P-CH ₃ H -C GH
^ \ '
Olio WXlQ L / Hq M.p. 73.2-75.6 ° C o-Cl m-Cl M.p. 65-67 ° C PCH ₃ H 2 Γ 2
^ x Πρ ° β 1.5649 o-Cl m-Cl n ^ ° = 1.5791 p-Cl H Mp 49-52 ° C H H n ^ ° = 1.5567 H •H Mp 80-82 ° C
R «· Λ ^ ** ^ * ** * · & ^ **.

CH

'S

CIBA-GEIGY AG

R ₂ R ₃ CH ₃ Physical data H -CH ₉ -CHq- M.p. 113-1140c P-Cl H -CH ₂ -CH ₂ -
C. CH ₃ CH ₃ M.p. 97-1030c. p-Cl CH ₃ CH ₃ -CH ₂ -CH ₂ -CH ₂ - H -CH-CH-CH-
t II -CHq-CHq-CHq - np ⁰ = 1.5542 P-CH ₃ III
/ "ill /" ¹ TJ C ¹ IJ
OiT-o Vjilo wiTo
3 3 3 ^- CHn "" CHrt "CHq -
£ * £ * £, H -CH-CH-CH-
II! -CH ₂ -CH ₂ - np ⁵⁰ = 1.5677 H 3 3 3 -CH-CH-
II
LH ₃ OH ₃ m-Cl -CH-CH ₀ -CH ₀ -
f LL -C-CH ₂ -CH- M.p. 80-82 ° C o-Cl H CH ₃ (CH ₃ np ⁰ = 1.5818 Hi-CH ₃ H CH ₃ - ι
j) ₂ CH ₃ np ⁰ = 1.5681 0-CH ₃ H np ° = 1.5756 P-CH ₃ H Mp 107-108 ° C 0-CH ₃ m-Cl Mp 115-117 ° C o-Cl H Mp 136-140 ° C ρ-Br H ρ-Br H p-Br

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^R l R ₂ R ₃ R ₄ Physical data 77-79 ° C p-Cl H Π PU PU
(CH ₃ ) ₂ CH ₃ = 1.5600 0-CH ₃ . H -CH ₂ -CH ₂ - Fp. 80-82OC 0-CH ₃ H -C -CH-
(CH ₃ ) ₂ CH ₃ 20th = 1.5769 p-Cl H -C C-
> I.
(VjJIo / o vVJflo Jn
JZ J Δ , Fp. H H ρττ _PTJ_PTJ
- ΟΓΧο wll "wfln ™
J 3 20th - 1.5721 η-Π U -PTT -ΓΗ-ΓΗ YY Vy Y-
P-CH ₃ η
H Kj [Ln Oil VjIIo
-CH ₂ -CH-CH ₃ 20th
ⁿ D. o-Cl m-Cl —CHo —CH-CHo 80 - 83 ° c o-Cl m-Cl CH ₃ -CH- (S.
(CH ₃ ) ₂ Fp. = 1.5644 PIC ₄ H ₉ H -CHp-CHp - 20th
ⁿ D 77 - 80 ° C PIC ₄ H ₉ H -CHp-CHp-CHp - Fp.

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CIBA-GEIGYAG - Example 2

To test for their action against various pests of the Blattidae and Chrysomelidae families, 2 g of the Compounds according to Example 1 are mixed with 38 g of talc and the whole is finely ground. So you get a very effective one Dust powder with which the areas affected by the pests were treated. Dust powder containing one of the Compounds according to the example showed a good action against Phyllodromia germanica, Periplaneta americana and Blatta orientalis or Leptinotarsa decemlineata.

Example 3

A) Insecticidal feed poison effect

Cotton plants and potato plants were with a 0.05% aqueous active substance emulsion (obtained from a lO7oigen emulsifiable concentrate) sprayed.

After the covering had dried on, the cotton plants became each with Spodoptera littoralis or Heliothis virescens larvae Lo and the potato plants with Colorado potato beetle larvae (Leptinotarsa decemlineata) occupied. The experiment was carried out at 24 ° C. and 60% relative humidity.

Compounds according to Example 1 showed insecticides in the above test Food poison effect against Spodoptera, Heliothis and Leptinotarsa decemlineata larvae.

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CIBA-GEIGY AG - Example 4 Effect against Chilo suppressalis

6 rice plants of the Caloro variety were placed in plastic pots, which had an upper diameter of 17 cm, transplanted and raised to a height of approx. 60 cm. The infestation with Chilo suppressalis larvae (L,; 3-4 mm long) took place 2 days after the addition of the active ingredient in granulate form (application rate 8 kg of active substance per hectare) in the paddy water. the Evaluation for insecticidal action takes place 10 days after the addition of the granules.

Compounds according to Example 1 counteracted in the above test Chilo suppressalis.

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CiBA-GEIGYAG < - hf - Example 5 Effect against soil insects

Sterilized compost soil is mixed homogeneously with a wettable powder containing 25% active ingredient, so that a concentration from 16 ppm resp. of 8, 4, 2, 1 ppm arises. Young courgette and cabbage plants are planted in the soil treated in this way and immediately with 5 larvae of Aulacophora fentoralis (Age: 15 d / 25 ° C) resp. 15 eggs of Chortophila brassicae (cabbage flies) infected; a third corresponding earth pattern is provided with apple carving as food and planted with 5 larvae of Pachnoda savignyi (20 d / 25 ° C). 10 days mortality is rated after application and infestation. The screening test with groundworms (Agrotis Y-L ~) proceeds analogously, with the difference that the concentrations 40, 20, 10 ppm. Mallow leaves are used as food.

Compounds according to Example 1 showed in the above tests Action against Aulacophora femoralis-, Ghortophila brassicae-, Pachnoda savignyi and Agrotis larvae.

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CIBÄ-GEIGY AG Example 7 Comparison of when blood toxicity

The warm-blooded toxicity of the following inventions Connection is significantly lower than that of the connection known from English patent specification No. 1 122 633 as can be seen from the following results. (DL rat p.o. acute):

according to the invention 1100 mg / kg

■ known from the English patent sciirift

Mr. 1 122-635

~ 6® mg / kg

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Claims (1)

CIBA-GEIGY AG - ■ Claims ! Phenylcarbamates of the formula 0 CH,
l ⁵ R ₄ O wherein R, and R _{2 are} each hydrogen, CL -C, -alkyl, chlorine or bromine, Ro and R, each methyl or together -CH ₂ -CH ₂ -, -CH ₉ -CH ₉ -CH ₉ -, -CH-CH ₉ -, ^ CH- ~ GH-, * ■ ^{Δ Δ} j * ι ι CH ₃ ^CH 3 ^CH 3 -C-CH ₉ -, -CH-CH ₉ -CH ₀ -, -C C-) • / \ ^ι I ^{2 2} / \ / Y CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CK ₃ CHo . ■ · I, -CH ο- -CH ₉ -C-CH ₉ -, -CH ~ r — CH CH- or ■ ι ι / \ ι "ι ι CH ₃ CH ₃ . CH ₃ CH ₃ CH ₃ ■ CH ₃ CH -CH-CH ₀ -C- mean. ι ² / \ CH ₃ CH ₃ CH ₃ 509825/1090 CIBA-GEIGYAG - 20 - 2. Compounds of formula (I) according to claim 1, wherein R * is hydrogen, R _{2 is} hydrogen, chlorine, methyl or tert. Butyl and R, together -CH ₂ -CH ₂ -, -CH-CH-, -CH, ,- mean. 3. Compound according to claim 2 of the formula O CH. CH-CH ₂ 4. A compound according to claim 2 of the formula O CH ^ CH 5. A compound according to claim 2 of the formula O CH, 509825/1090 CIBA-GEIGY AG 6. A compound according to claim 2 of the formula 0 CE, CH ₂ —CH 7. A compound according to claim 2 of the formula O CH, CH N) A compound according to claim 2 of the formula 0 CH ^ N-S- ^> ~ CH, CH (Z- N) I CH2-CH OH, 50 9 8 25/1090 CIBA-GEIGY AG 9. A compound according to claim 2 of the formula 0 CH, Cl CH c / N> CH. 10. A compound according to claim 2 of the formula 0 CH " Il ■ C-K - S- Cl CH CMr-CH ² I. ^CH 3 11. A compound according to claim 2 of the formula 0 CH <k ^> - OCK ¹ -S- <v> -CH, CH CH CH I I CH "CH, 3 3 5098 25/1090 CIBA-GEIGY AG - ZX- 12. A compound according to claim 2 of the formula O CH Cl Ii I ■> CH Cl CH - CH I. J CH ₃ CH ₃ A compound according to claim 1 of the formula 0 CH ₇ - CH CH ₃ CH ₃ 14. A compound according to claim 2 of the formula O CH 3 • N-S- <k CH N; o CH ₀ ^CH 2 509825/1090 15. A compound according to claim 1 of the formula O CH, O-CHff-S- ^> -Cl 1C ₃ H ₇ 1C ₃ H ₇ 16. A compound according to claim 1 of the formula O CH Eq CH Cl 17. Process for the preparation of a compound according to claims 1 to 16, characterized in that one a compound of the formula with a compound of the formula Ίι -O-C-NH CH 509825/1090 CiBA-GEiGYAG - 25 - in the presence of an acid-binding agent or with a Compound of formula CH N) converts, in which R 1 to R 1 has the meaning given in claim 1 and X stands for halogen and Me for a metal. 18. Pesticides, which as the active component a compound according to claims 1 to and contains suitable carriers and / or other additives. 19. Use of compounds according to claims 1 to 16 for combating various types of animal and plant-borne pests. 20. Use according to claim 19 for combating Insects and representatives of the order Akarina. 21. Use according to claim 19 for combating insects of the Blattidae and Chrysomelidae families. 509825/1090