DE2330242A1 - Propargyl or allyl fluorinated N-phenyl-carbamates - prepd. by reacting propargyl or allyl alcohol with fluorinated phenyl isocyanates - Google Patents

Abstract

Carbamates of formula (I) (where R1 is CF3, CF2Cl, OCF3 OR OCF2Cl; R2 is H, halogen, CH3 or OCH3; R3 is vinyl or ethynyl; and n is 1 or 2) are highly active insecticides and acaricides, and also have fungicidal activity against phytopathogenic fungi. (I) are prepd. by reacting isocyanates of formula (II) (obtainable by reacting corresponding amines with COCl2) with propargyl or allyl alcohol.

Description

Bayer Aktiengesellschaft ^{13 June m}

Central area of patents, trademarks and licenses

^; 509 Leverkusen. Bayerwerk

Rt-Sp Ia

Fluorine-containing N-phenylcarbamates, process for their preparation and their use as insecticides and acaricides

The present invention relates to new fluorine-containing N-phenylcarbamates, which have insecticidal and acaricidal properties and a process for their preparation.

Of the trihalomethylthio compounds belonging to the prior art, compounds with fluorine-containing substituents such as, for example, N ¹ -fluorodichloromethylthio-N ^ -dimethyl-N ¹ -4-tolyl-sulfamide, have achieved great economic importance for the control of phytopathogenic insects and spider mites (cf. German Patent 1 190 723), see also "Bayer" plant protection news; 25123 (1972). However, precisely when combating phosphoric acid ester-resistant spider mites, the action of these known compounds is not always satisfactory.

It has now been found that fluorine-containing N-phenylcarbamates the general formula

(I)

in which

R for trifluoromethyl, difluorochloromethyl, trifluoromethoxy and difluorochloromethoxy,

R ² for hydrogen, halogen, methyl and methoxy Le A 15 089 - 1 -

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R ^ stands for vinyl or ethynyl and η stands for 1 or 2,

have strong acaricidal and insecticidal properties.

It has also been found that the fluorine-containing N-phenylcarbamates can be used of the formula (i) is obtained when substituted phenyl isocyanates of the general formula

(II)

(R ² ) _n

in which

1 p
R, R and η have the meaning given above,

with allyl or propargyl alcohol, if appropriate in the presence of a diluent.

It is extremely surprising that the invention Compounds show a higher insecticidal and acaricidal effect than the previously known carbamates with fluorine-containing Substituents. They thus represent an enrichment of the technology.

The course of the reaction can be carried out using 2-chloro-4-difluorochloromethyl phenyl isocyanate and propargyl alcohol as starting materials using the following equation:

• NCO + HOCH ₂ -C = CH -> CFgC

C 0

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The following isocyanates which serve as starting materials for the preparation of the compounds according to the invention may be mentioned:

2-chloro-4-trifluoromethylphenyl isocyanate, 2,6-dichloro-4-trifluoromethylphenyl isocyanate , 3-chloro-4-difluorochloromethylphenyl isocyanate, 2-chloro-4-difluorochloromethylphenyl isocyanate, 3-chloro-4-difluorochloromethoxyphenyl isocyanate.

These isocyanates which can be used according to the invention can in part be prepared by known processes by the corresponding amines are reacted with phosgene in a known manner.

Insofar as this is necessary, the experimental part also shows the compounds used as starting compounds Phenyl isocyanates described.

Inert organic solvents are used as diluents. These include especially ethers, such as dioxane and Diethyl ethers, ketones such as acetone, hydrocarbons such as Toluene and chlorinated hydrocarbons such as chloroform and chlorobenzene. It is expedient to use an excess of Allyl or propargyl alcohol, the addition of a small amount of a tertiary amine, such as triethylamine, being useful for accelerating the reaction.

The reaction temperatures can be varied within a relatively wide range, in general one works at 0-5O ⁰ C, preferably at 20-40 ⁰ C.

The reaction is generally carried out under normal pressure.

As already mentioned, the active ingredients according to the invention are acaricidal and insecticidal highly effective. You can therefore fight mites, as well as sucking and biting

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Insects, including hygiene and stored product pests will. Their fungicidal activity against phythopathogenic fungi should also be mentioned.

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The mites (Acari) include spider mites in particular
(Tetranychidae) like the bean (Tetranychus telarius =
Tetranychus urticae or Tetranychus Althaeae) and fruit tree red spider mite (Panonychus ulmi Paratetranyohus pilosus =), gall mites, for example the Johannisbeergallmilbe (Eriophyes ribis) and Tarsonemiden example, shoot tip mite
(Hemitarsonemus latus) and cyclamen mite (Tarsonemus pallidus); finally ticks like the leather tick (Ornithodorus moubata).

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The sucking insects mainly include aphids (Aphidae) such as the green peach aphid (Myzus persicae), the black bean (Doralis fabae), oat (Rhopalosiphum padi), pea (Macrosiphum pisi) and potato mouse (Macrosiphum solanifolii), also the currant gall (Cryptomyzus korschelti), floury apple (Sappaphis mali), floury plum (Hyalopterus arundinls) and black cherry aphids (Myzus cerasi), as well as scale and mealybugs (Coccina), e.g. the Ivy shield louse (Aspidiotus hederae) and cup scale louse (Lecanium hesperidum) as well as the mealybug (Pseudococcus maritimus); Bladder feet (Thysanoptera) such as Hercinothrips femoralie and Bed bugs, for example beet (Piesma quadrata), cotton (Dysdercus intermedius), bed (Cimex lectularius), predatory (Rhodnius prolixus) and Chagas bug (Triatoma infestans), as well as cicadas such as Euscelis bilobatus and Nephotettix bipunctatus.

Among the biting insects, butterfly caterpillars should be mentioned above all (Lepidoptera) such as the cabbage moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), gold juicer (Euproctis chrysorrhoea) and ring moth (Malacosoma neustria), furthermore the cabbage (Mamestra brassicae) and the seed owl (Agrotis segetum), the large cabbage white butterfly (Pieris brassicae), small frostworm (Cheimatobia brumata), oak moth (Tortrix viridana), the army (Laphygma frugiperda) and Egyptian Cotton worm (Prodenia litura), also the web (Hyponomeuta padella), flour (Epheatia kühniella) and large ones Wax moth (Galleria mellonella),

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The biting insects also include beetles (Coleoptera) e.g. corn (Sitophilus granarius = Calandra granaria), potato (Leptinotarsa decemlineata), dock (Gastrophysa viridula), horseradish leaf (Phaedon cochleariae), rapeseed (Meligethes aeneus), raspberry (Byturus tomentosus), table beans (Bruchidius = Acanthoscelides obtectus), bacon (Dermestes frischi), khapra (Trogoderma granarium), red-brown rice flour (Tribolium castaneum), corn (Calandra or Sitophilus zeamais), bread beetle (Stegobium paniceum), common flour beetle (Tenebrio molitor) and flat grain beetle (Oryzaephilus surinamensis), but also species living in the ground such. B. wireworms (Agriotes spec.) And white grubs (Melolontha melolontha); Cockroaches like that German (KLatteHa germanica), American (Periplaneta americana), Madeira (Leucophaea or Rhyparobia mader), Oriental (Blatte orientalis), Giant (Blaberus glganteus) and giant black cockroach (Blaberus fuscus) and Henschoutedenia flexivitta; furthermore orthoptera e.g. the cricket (Gryllus domesticus); Termites such as the terrestrial termites (Reticulitermes flavipes) and Hymenoptera such as ants, for example the Meadow ant (Lasius niger).

The Diptera essentially comprise flies like the Tau (Drosophila melanogaster), Mediterranean fruit (Ceratitis capitata), room (Musca domestica), small room (Fannia canicularis), glossy fly (Phormia aegina) and blowfly (Calliphora erythrocephala) as well as the calf trigger (Stomoxys calcitrans); also mosquitoes, e.g. mosquitoes such as the yellow fever (Aedes aegypti), house (Culex pipiens) and malaria mosquito (Anopheles stephensi).

When used against hygiene and stored product pests, especially flies and mosquitoes, the process products are also characterized by an excellent residual effect on wood and clay as well as good alkali stability on limed substrates.

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The active compounds according to the invention can be used in the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granulates. These are in produced in a known way, e.g. by mixing the active ingredients with extenders, i.e. liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active substances Agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In case of Using water as an extender, organic solvents, for example, can also be used as auxiliary solvents. The main liquid solvents that can be used are: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or Methylene chloride,

aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, Methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; Liquefied gaseous extenders or carriers are liquids that are which are gaseous at normal temperature and under normal pressure, e.g. aerosol propellants such as halogenated hydrocarbons, e.g., freon; as solid carrier materials: natural rock flour, such as kaolins, clays, talc, chalk, quartz, Attapulgite, montmorillonite or diatomaceous earth and synthetic rock flour, such as highly dispersed silica, aluminum oxide and silicates; as emulsifiers and / or foam-generating agents: nonionic and anionic emulsifiers, such as polyoxyethy len fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, Aryl sulfonates and protein hydrolysates; as dispersants: e.g. lignin, sulphite waste liquors and methyl cellulose. The active compounds according to the invention can be present in the formulations as a mixture with other known active compounds.

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The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90 %.

The active ingredients can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use solutions, emulsions, foams, suspensions, powders, pastes, soluble powders, dusts and granules be applied. It is used in the usual way, e.g. by spraying, atomizing, atomizing, dusting, Scattering, smoking, gasifying, pouring, pickling or encrusting.

The active ingredient concentrations in the ready-to-use preparations can be varied over a wide range. In general, they are between 0.0001 and 10 %, preferably between 0.01 and 1 %.

The active ingredients can also be used with good success in the ultra-low-volume process (ULV), where it is possible to apply formulations of up to 95% or even the 100% active ingredient alone.

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Example A.

Tetranychus test (resistant)

Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

Premixed to produce an appropriate active ingredient preparation 1 part by weight of active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilutes the concentrate with water to the desired concentration.

Bean plants (Phaüeoluc vulgaris), which are approximately 10 to 30 cm high, sprayed dripping wet. These bean plants are strong with al'Jori Stages of development of the common spider mite or bean spider mite (Tetranychus urticae).

After the specified times, the effectiveness of the active ingredient preparation is determined by counting the dead animals. The degree of destruction obtained in this way is given in % . 100% means that all spider mites have been killed, 0 % means that none of the spider mites have been killed.

Active ingredients, active ingredient concentrations, evaluation times and The results are shown in the table below:

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Tabel

(plant-damaging mites) Tetranychus test (resistant)

Active ingredients

Active ingredient concentrations. tration in% degree of destruction in % after 2 days

/ ^X \ ii

SO ₂ -N (CH ₃ ) ₂

-SCFC1

(known)

0.1

0.1 0.01

0.1

90 55

100

Cl

CF ₃ -CF ₀ Cl

M-NH-COOCH ₉ -C ^ CH

0.1

0.1

0.1 0.01

0.1 100

100

100 80

100

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Table (continued) (plant-damaging mites) Tetranychus test (resistant)

Active ingredients Active ingredient concentration Degree of destruction occurred in% in % after 2 days

qF ₂ ci

Cl- / Λ NH-COOCH ₂ -C = CH 0.1

C1F ₉ C ~ </ ^) - Nh-COOCH ₂ -CH = CH ₂ 0.1

Cl -ZjViJH-COOCH ₂ -CH = CH ₂ 0.1

₂ -CH = CH ₂

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Example B.
Plutella test

Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

Mixed to produce an appropriate preparation of active ingredients 1 part by weight of active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilutes the concentrate with water to the desired concentration.

Cabbage leaves are sprayed with the active compound preparation (Brassica oleracea) becomes dewy and populates them with caterpillars of the cabbage moth (Plutella maculipennis).

After the specified times, the degree of destruction is determined in % . 100 % means that all of the caterpillars have been killed, while 0 % indicates that no caterpillars have been killed.

Active ingredients, active ingredient concentrations, evaluation times and The results are shown in the table below:

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'Ά-

Tabel

(plant-damaging insects) Plutella test

Active ingredients

Wirkstoffkon- degree of destruction in centration in% after 3 days%

SOp-N (CH,) ,,
/ - \ I

CH ^ Y ^X VN-SCFC1 ₂
(known)

0.1

COOCH ₂ -C = CH

CF ^ .-

.Cl

-COOCH ₂ -C = CH

0.1
0.01

0.1 0.01 0.1
0.01

100 80

100 ■ 95

100 100

ClF ₀ CH / ⁿ > NH-COOCHo-C ^ CH 0.1

^ ^{V 7 2} 0.01

100 100

ClF ₀ CO C 7 NH-COOCH ₀ -C = CH 0.1

^{d x} - ^{/ d} 0.01

100 40

ClF ₂ C 1 -C y -Nh-COOCH ₂ -CH = CH ₂ 0.1

100

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Manufacturing examples

example 1

(D

NHCOCH ₀ -ChCH O

10 g of 3-chloro-4-difluorochloromethyl phenyl isocyanate are dissolved in 50 ml of acetone with the addition of 5 g of propargyl alcohol. To The temperature rises to about 35 ° C. by adding 0.5 g of triethylamine. The mixture is stirred for a while and the reaction solution is concentrated in a vacuum. The residue left behind is 12 g of propargylic N- (3-chloro-4-difluorochloromethylphenyl) carbamic acid with

20 has a refractive index n ^ 1.5492. In a similar way one obtains:

Cl

(2)

CF «Cl

NHCOCHo-CH = CH,

n-

20 1.5352

Example 3?

(3)

CF ₂ Cl

NHCOCH ₀ -C = CH ti ^

720 g of 2-chloro-4-difluorochloromethylphenyl isocyanate and 200 g Propargyl alcohol are dissolved in 500 ml of acetone. After adding 3 g of triethylamine, the temperature rises to boiling of acetone. After concentrating, the oily residue is carried into 500 ml of white spirit. Here, crystallization occurs a. It is filtered off with suction and 804 g of N- (2-chloro-4-difluorochloromethylphenyl) are obtained ) Carbamic acid propargyles have a melting point of 58-60 ° C.

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analogously one obtains:

Cl O
(4) CF, - / _{"Λ-NHC-O-CH2-C} ^ CH mp 58 ⁰ C

(5) ^CF ^ ~ A \ // - ^ HC-O-CH ₂ -C = CH m.p. 117 C.

Example 6:

(6) CF ₂ C10- < _x /) NHCOCH ₂ -CsCH

10 g of 3-chloro-4-difluorochloromethoxyphenyl isocyanate and 5 g of propargyl alcohol are dissolved in 50 ml of acetone. After addition of a few drops of triethylamine, the temperature rises to over 30 ⁰ C. After the reaction has subsided, the solution is concentrated in vacuo. 12 g of the above carbamate are obtained in the form of a yellow oil. n ~ 1.5229

analogously one obtains:

(7) <^ _ J) -NHC0CH ₂ -C = CH Fp 8θ - 8l ⁽

CF,

(8) ^ J) -NHCOCH ₂ -C = CH m.p. 45-46 °

0
CF,

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1.5197

CF ₂ Cl

10 CI- ^ J) -NHcOCH ₂ -C = CH n £ ° 1.5400

c 0

CF ₂ Cl

Cl - ^^ - NHC0CH ₂ -CH = CH ₂ n? ⁰ I.5411

The phenyl isocyanates used as starting compounds are represented as follows:

a) 3-chloro-4-difluorochloromethylphenyl isocyanate

CF ₂ Cl- <v /) NCO

In an iron mixing vessel 650 ml anhydrous hydrofluoric acid are introduced and this at 0 - 5 ⁰ C in 2 hours 1000 g of 3-chloro-4-trichloromethyl-phenyl Kp _16: 173-4 ° C, n | °: 1.6043 (obtained by Chlorination of 3-chloro-4-methylphenyl isocyanate) was added dropwise. This creates a powerful stream of HCl which is discharged via an intensely acting cooler. After the addition is complete, the mixture is slowly heated to room temperature and the reaction is ended after 3 hours regardless of the continuing evolution of HCl. The excess hydrofluoric acid is removed in vacuo, the residue is in 1 1 *. Dissolved chlorobenzene and ^{flushed with nitrogen at 120 °} C. for 2 hours.
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After a forerun (= 3-chloro-4-trifluoromethylphenyl _{isocyanate, boiling point 93 ° / 14 mm n D} 1.5019), 474 g of 3-chloro-4-difluoromethylphenyl isocyanate of 110 ° n £ ° 1.5366 are obtained by distillation.

b) 2-chloro-4-difluoromethyl-phenyl isocyanate CF ₂ Cl ^ 3) ^NC0

Is obtained from 2-chloro-4-trichloromethylphenyl isocyanate (b.p. _10: 153-5 ° C, n ^ °: 1.5958) by fluorinating with hydrogen fluoride acid 2-chloro-4-difluorchlormethylphenyl isocyanate as a liquid, bp _12: 105 ⁰ C, n ^ °: 1.5272

c) 2-chloro-4-trifluoromethylphenyl isocyanate

Cl
CF, - {' \\ - NCO

585 g of 4-trifluoromethylphenyl isocyanate (prepared according to DAS 1 138 391) are passed at 30 ^° C. to

a hydrogen chloride to saturation, adds 6 g of iodine and then passes in gas-free chlorine until

20th

Refractive index of approx. N _D : 1.4950 is reached. Reaction time 2 hours. Distillation gives 513 g of 2-chloro-4-trifluoromethylphenyl, bp ^ _0: 84-6 ° C, ng ^u: 1.4931.

d) 2,6-dichloro-4-trifluoromethylphenyl isocyanate

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200 g of 2-chloro-4-trifluoromethylphenyl isocyanate are mixed with 2 g of FeCl, (sublimed) and treated with gaseous chlorine at 10 ° C. until the refractive index has risen to about 1.5150. It is then filtered and distilled. After an approximately 30% strength flow is obtained 121 g of 2,6-dichloro-4-trifluoromethyl-phenyl isocyanate of boiling point _10: 97 - 98 ° C, ^τξ Ό: 1.5138 F: 18-19 ⁰ C

e) 3-chloro-4-difluorochloromethoxyphenyl isocyanate

From 135 g of difluorochloromethoxybenzene (obtained analogously to the process known from German Auslegeschrift 1 000 393 as a liquid with bp: 144 ⁰ C, n ^ °: 1.4479) at -10 ° C with a nitration mixture of H ₂ S0 ^ / HN0 ^ / H nitrated in a weight ratio of 56/28/16 and the 14O g of 4-difluorochloromethoxy-nitrobenzene obtained from bp ^,: 118 ⁰ C,

NJ5 °: 1.4995 chlorinated under addition of 1% FeCl ₃ at 100 to 120 ⁰ C in the core.

To yield the 3-chloro-4-difluorochloromethoxy-nitrobenzene as a liquid, bp _14: 131 -32 ⁰ C, ^ ° n: 1.5182.

This is reduced in 20% strength tetrahydrofuran solution with Raney nickel as a catalyst at 40 ° C. and 50 atmospheric H _2. The 3-chloro-4-difluorochloromethoxyaniline Kp ,, _o ° ^u

135 -37 ° C, ng ^u : 1.5238.

This amine is phosgenated in 15% chlorobenzene solution with excess COCl ₂ by the known method of base phosgenation. The 3-chloro-4-difluorochloromethoxyphenyl isocyanate obtained boils at boiling point ₁₀ : 115 -17 ° C and

on ' * -

has a refractive index of n ^: 1.5090. Le A 15 089 - 19 -

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Claims (6)

Patent claims: 1) Fluorine-containing N-phenylcarbamates of the general formula (I) R ¹ for trifluoromethyl, difluorochloromethyl, trifluoro- in which for Trij methoxy and difluorochloromethoxy, R ^{2 represents} hydrogen, halogen, methyl and methoxy, Rp represents vinyl or ethynyl and η represents 1 or 2. 2) Process for the preparation of fluorine-containing N-phenylcarbamates, characterized in that isocyanates of the formula R ¹ (R ² ) _n (II) in which R ¹ , R ² and reacts with propargyl or allyl alcohol 1 2 R, R and η have the above meaning 3) insecticides und.akarizlde smocks, characterized by a content of at least one fluorine-containing N-phenyl carbamate according to claim 4) A method for combating insects and mites, characterized in that fluorine-containing N-phenylcarbamates according to claim 1 to insects and / or mites or their Lets living space act. Le A 15 089 - 20 - 409882/1172 5) Use of fluorine-containing N-phenylcarbamates according to Claim 1 for combating insects and / or mites. 6) Process for the preparation of an insecticidal or acaricidal agent, characterized in that fluorine-containing N-phenyl carbamates according to claim 1 mixed with extenders and / or surface-active agents. Le A 15 089 - 21 - 409882/1172