DE2430207A1 - SCHAEDLINGS KEMPKINKAGEMANS / ITS ACTIVE INGREDIENTS - Google Patents

Description

I FOLLOWED

PATENTANWÄLTE * Vl

DlpL-lng. P. WIRTH ■ Dr. V. SCH MI ED-KOWARZIK DlpWng. G. DANNENBERG Dr. P. WEINHOLD Dr. D. GUDEL

20113- »6 FRANKFURT AM MAIN

TELEPHONE <061 »

287014 GFl. ESCHENHEIMEII STRASSE 38

Ref .: LS B / DLR / 303 94/73
Wd / uin

FISOMS LIMITED

PIson House

9 Grosvenor Street

London

England

Pesticides or their active ingredients

A09883 / U21

The present invention relates to new compounds, their preparation, their use as Pesticides as well as pesticides containing the new compounds.

According to the invention, new carbamates of the formula

, (D

provided, where R is alkyl (preferably with 1 to 6 carbon atoms, such as methyl or ethyl), alkenyl (preferably with 2 to 6 carbon atoms, such as -allyl) or alkynyl (preferably with 2 to 6 carbon atoms, such as propargyl)

2
means; R is hydrogen, alkyl (preferably having 1 to 6 carbon atoms, such as methyl) or carboxylic acyl (e.g. benzoyl or alkanoyl having 2 to 6 carbon atoms, such as acetyl); R and R are the same or different and are each alkyl (preferably with 1 to 6 carbon atoms, such as methyl, ethyl or propyl), alkenyl (preferably with 2 to 6 carbon atoms, such as allyl) or alkynyl (preferably with 2 to 6 carbon atoms

3 4 atoms, such as propargyl) or R and R together form an alkylene chain (for example with 2 to 6, preferably 4 to 6 carbon atoms), which is substituted

409883/1421

may be (e.g. mono- or disubstituted) by alkyl (e.g. having 1 to 6 carbon atoms, such as Methyl); and R, R. and R are the same or different and are each hydrogen, halogen (for example chlorine or Bromine), alkyl (preferably having 1 to 6 carbon atoms such as methyl), carboxylic acyl (e.g. benzoyl or alkanoyl with 2 to 6 carbon atoms, such as acetyl),

OQO O O

-OR, -SR, "SO ₂ R or -SOR, where R is alkyl (preferably with 1 to 6 carbon atoms, such as methyl), aryl (preferably phenyl), which can be substituted (for example mono- or disubstituted) by alkyl (for example with 1 to 4 carbon atoms, such as methyl), or

g in ο IQ Benzyl; -C (OH) R R, where R "and R are identical or different and are each hydrogen or alkyl (preferably having 1 to 6 carbon atoms, such as methyl) -; Nitrile; Nitro; Thiocyanato; Carboxy; Carboxy esters (e.g. alkoxycarbonyl of 2 to 7 carbon atoms such as methoxycarbonyl); Carbamoyl, the nitrogen atom of which can be substituted (for example by alkyl with 1 to 6 carbon atoms,

3 as disubstituted by methyl); or can represent a further -NR R group; or a salt of such Carbamates.

According to the invention, a method for

Preparation of the compounds provided in which R is hydrogen or alkyl, which process consists in that

409883 / U21

a substituted phenol of the formula

(II)

wherein R, R, R, R and R have the same meaning as in Formula (I), or a salt of such substituted one Phenol with a substituted carbamoyl halide of the formula

R ¹ R ² NCOX. , ·

where X is a halogen atom (usually a chlorine atom),

1 '2

R has the same meaning as in formula (I) and R is hydrogen or alkyl.

According to the invention, a process for the preparation of the compound of the formula (I) is also provided which consists in that a chloroformate of the formula

R ³ > N 0
O-Ü-Cl R ⁵

, (HD

wherein R, R, R, R and R have the above meaning. or a salt of such a chloroformate with an amine or

409883/1421

Amide of the formula

R ¹ R ² NH

1 2
is reacted, wherein R and R - have the above meaning.

According to the invention, there is also a method for

Preparation of the compound of formula (I) provided wherein

R denotes hydrogen, which process consists in using a substituted phenol of the formula (II) or a salt of which with an isocyanate of the formula

R ¹ NCO

is reacted, wherein R has the same meaning as in formula (I) has.

In addition, the invention is a method for

Preparation of the compound of formula (I) provided wherein

R carboxyIisches acyl means which process in it

2 consists that a carbamate of formula (I) wherein R is hydrogen means, or a salt thereof is acylated.

With the new connections, pests can be found in which are infected with it or can be infected with it, can be combated by one for pest control sufficient amount of the compound is brought to this location.

Finally, according to the invention, a pesticide is provided which contains the compound, usually in an amount of 0.01 to 80%, and in particular a pesticide which contains the compound together with a surface active agent

09883/1421

fr

contains; solid pesticides contain the compound together with a carrier; liquid Pesticides contain the compound with a liquid carrier, for example a hydrocarbon, with a boiling range from 130 to 270 ° C; the pesticides The compound can also work together with other pesticides or act synergistically Contain substances.

The compounds have high insecticidal activity. This is very surprising since phenyl carbamates are common with a nitro substituent on the phenyl ring have negligible or low insecticidal activity.

The. Carbamates of the formula (I) can be used in the form of the salts in a manner which is customary per se can be produced. The carbamates, which contain both acidic and basic groups on the benzene ring, can are in the form of the internal salts. Acid salts can generally be formed with acids with a pK below 5; they are prepared by reacting a carbamate of the formula (I) with the acid in question. The acid salts are usually salts of the carbamates of the formula (I) with a mineral acid, in particular with hydrochloric acid.

The carbamates can be prepared from the salts by conventional methods, for example by reaction of an acid salt with sodium hydroxide.

A09883 / U21

When the compound in which R is hydrogen is prepared by reaction with the isocyanate, and this is by far the preferred method, the reaction is usually carried out at a temperature of 0 to 150 ° C, for example at room temperature and a pressure of 0 ° C. 5 to 10 atm, preferably 1 to 1.1 atm, in an organic solvent, e.g. acetone, ether, dimethylformamide or a hydrocarbon (e.g. toluene) and preferably in the presence of a catalyst (usually a tertiary amine, e.g. triethylamine or pyridine, or an organotin compound, for example dibutyltin diacetate). When R ^{1 is} methyl, the reaction is usually carried out in a vessel at 1 to 1.1 atm and at a temperature in the range of 0 to 60 ° C taking into account the boiling point of methyl isocyanate.

2 If the connection in which R is another

Has meaning as carboxylic acyl, which is produced by reaction with the carbamoyl halide, the reaction usually at 0 to 150 ° C, preferably with an equimolar Amount of an inorganic or tertiary organic base (e.g. sodium carbonate or preferably potassium carbonate) and preferably also in an inert solvent, e.g., pyridine, which serves as the base and solvent can, or acetone carried out.

When the compound is made by reaction with the amine and amide, the reaction is usually carried out at O

409883 / H21

up to 150 ° C, e.g. in an inert solvent (e.g. hydrocarbon or ether) and preferably in the presence of an equimolar amount of an inorganic base (e.g. sodium carbonate) or organic base (as which an excess of the reacting amine or, for example, a tertiary amine, such as triethylamine, can be used). The chloroformate intermediate is preferably prepared by reacting a substituted phenol of the formula (II) or a salt thereof with phosgene. This reaction is usually carried out at O to 15O ° C, preferably in a hydrocarbon solvent and preferably also in the presence of ¹ equimolar amount of a weak tertiary base (such as dimethylaniline).

2 The compounds of formula (I) in which R is carboxyl

is cal acyl are preferably prepared by

Acylation of the corresponding compound in which R is hydrogen. The intermediate in which R is hydrogen represents is preferably obtained by itself in the above-described way. The acylation is usually carried out at 0 to 150 ° C, carried out for example in an inert solvent. The acylating agent can be a carboxylic acyl halide the formula

R ² X

2
where R is carboxylic acyl and X is halogen (usually chlorine).

409883 / U21

In preparing the novel compounds, it is preferable not to use a salt as the starting material for the reaction used.

Almost all of the substituted phenols of the formula (II) and their salts are new. According to the invention are therefore new substituted phenols of formula (II) or salts thereof provided, with the proviso that when R, R and

R each represent hydrogen, one or both of the

3 4
R and R radicals are different from methyl. Thus, in a particular embodiment, a substituted phenol of the formula (II) is used as a new intermediate in which

3 4
one or both of the radicals R and R are alkyl of at least 2 carbon atoms or alkenyl of at least 2 carbon atoms, or a salt thereof.

The substituted phenols of the formula (II) and their salts can be substituted by dealkylation of a o-alkoxyaniline of the formula

R * ¹

OR

, 11

NO,

R '-R ⁶

(IV)

are obtained, in which R, R, R, R and R have the same meaning

- • 409883/1421

direction as in formula (I) and R are alkyl with 1 to 6 Carbon atoms, preferably methyl, or a salt thereof. Dealkylation is expedient carried out in the presence of a solvent and with or without heating. The dealkylation is preferably carried out by hydrogen bromide acid or by ethanethiolation (e.g. the sodium salt of ethanethiol) and dimethylformamide.

The substituted phenols of formula (II) and their salts can also be prepared by alkylation of a 2-amino-4-nitrophenol of the formula

wherein R, R and R have the same meaning as in formula (I), and this is the method preferably used. The alkylation is expediently carried out in the presence of a base, with heating and with or without a solvent. The alkylation is preferably achieved by means of dialkyl sulfate (e.g. diethyl sulfate) or alkyl halide, e.g. Ethyl iodide in aqueous bicarbonate (usually sodium bicarbonate).

The compounds obtainable according to the invention are

3 4
preferably R and R the same.

409883 / U21

If higher activity is desired, R is

preferably alkyl or carboxylic acyl and not hydrogen. This is surprising insofar as, contrary to the trend for most insecticides, carbamates,

¹ Vi

e.g. in the case of carbaryl (1-naphthylmethylcarbamate).

2
It is particularly favorable when R is alkyl.

If higher activity is desired, it is still

useful when R has a meaning other than nitro.

5 7 It is also preferred that R and R also have a different one Have meaning as nitro. In the case of a special execution

7th
form, R denotes hydrogen and in another embodiment, R, R and R each denote hydrogen. Preferably, R, R and R are identical or different and are each hydrogen, halogen or alkyl. It is particularly preferred that R be hydrogen.

12 3

The hydrocarbon groups of the radicals R, R, R,

R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ can each contain up to 12 carbon atoms, preferably up to 4 carbon atoms.

In the case of a preferred group of compounds:

R ^{1 is} alkyl of 1 to 4 carbon atoms;

2 "

R is hydrogen or alkyl having 1 to 4 carbon atoms; R and R are identical or different and each denotes alkyl with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms or alkynyl with 2 to 4 carbon atoms;

409883 / U21

R and R each represent a hydrogen atom; and R denotes hydrogen, halogen, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms.

In a special embodiment of this preferred

3 4
In this group, R and R are identical or different, each denotes alkyl having 1 to 4 carbon atoms and R denotes hydrogen or halogen.

Specific meanings of the symbols of the compounds of the formula (I) which can be used according to the invention are which are listed in particular below.

Particular compounds obtainable according to the invention

are the carbamates mentioned in the examples and their salts.

Particularly active are:

2- (diethylamino) -4-nitrophenyldimethylcarbamate,

ι
2- (Dipropylamino) -4-nitrophenyldimethylcarbamate,

2- (diethylamino) -4-nitro-5-chlorophenyldimethylcarbamate 2- (diethylamino) ^ -nitro-S-methylphenyldimethylcarbamate, 2- (diallylamino) -4-nitrophenyldimethylcarbamate, 2- (dimethylamine) -4-nitro-S-chlorophenyldimethylcarbamate , 2- (diethylamino) ^ -nitro-S-bromophenyldimethylcarbamate, 2- (diethylamino) ^ -nitro-S-ethylthiophenyldimethylcarbamate

2- (Diethylamino) ^ -nitro-S-methylthiophenyldimethyl carbamate and their salts (e.g. hydrochloride). These compounds are particularly effective against aphidia. Of these connec-

409883 / U21

The first four carbamates and their salts are fertilizers especially preferred.

The new compounds are usually used in the form of mixtures, which you use as the active ingredient contain. Usually these mixtures are first made in the form of concentrates, which contain e.g. 10 to 80% Active ingredient contained, and this then with water or a hydrocarbon, usually with water, before Application diluted, for example so that the concentration of active substances is 0.01 to 0.5%. Parts and percentages mentioned in this description, relate to weight, unless otherwise stated.

The mixtures usually contain a carrier and / or a surfactant. The concentrates usually contain a surfactant that is contained therein is evenly distributed. The surfactant usually makes at least 1%, for example at least 2% of the concentrate.

The carrier can be liquid, e.g. water (e.g. that used to dilute a concentrate for the application used water). When water is used as the carrier in a concentrate, an organic solvent can also be used as the carrier be present, although this cpc is not usually used. A surfactant can be beneficial to be available.

The carrier can be a liquid other than water, for example an organic solvent, usually a

4098 83 / U21

water-immiscible solvent, e.g. a hydrocarbon, which has a boiling range from 130 to 270 ° C., in which the compounds are dissolved or suspended. A concentrate which contains an organic solvent, suitably also contains a surface-active agent, so that the concentrate is effective as a self-emulsifiable oil when mixed with water.

The composition can be in the form of an aerosol composition present, which contains a propellant, as which suitably a polyhalogenated alkane, such as Dichlorodifluoromethane, is used, and it usually also contains a solvent.

The carrier can also be solid and finely divided. Examples of suitable solids are clays, sand, mica, lime, attapulgite, diatomaceous earth, perlite and Sepiolite and synthetic solid carriers such as silicas, silicates, and lignosulfonates.

Wettable powders that are soluble or dispersible in water can be prepared by mixing the compounds with or or the carrier with a surface-active agent and preferably subsequent micronization or powdering getting produced.

A fertilizer can be used as a carrier.

The term "surfactant" is used broadly, including materials should be understood, which are usually emulsifying agents,

409883 / U21

Af

Dispersants and wetting agents can be mentioned. Such means are known.

The surfactants used can be: anionic surface-active agents, for example soaps, fatty sulfate esters such as dodecyl sodium sulfate, octadecyl sodium sulfate and Cety! sodium sulfate, fatty aromatic sulfonates, such as alkylbenzenesulfonates or butylnaphthalene sulfonates, more complex fatty sulfonates such as diamide condensation products of oleic acid and N-methyltaurine or the sodium sulfonate of dioctyl succinate.

Nonionic surfactants can also be used as surface-active agents; Means, for example Condensation products of fatty acids, fatty alcohols or fat-substituted phenols with ethylene oxide or fatty esters and ^ ethers of sugars or polyhydric alcohols, or the products obtained from the latter condensation with ethylene oxide, or the products known as Block copolymers of ethylene oxide and propylene oxide are known.

As the surface active agent, there can also be used cationic surface active agents, for example Cetyltrimethylammonium bromide.

Preferably used surface-active agents are fatty alkyl sulfates, alkyl aryl sulfonates, fatty alkyl ethoxylates, sulfated fatty alkyl ethoxylates, dialkyl sulfosuccinate esters, Lignosulfonate salts, sulfonated naphthalene-formaldehyde condensates and sulfonated urea-formaldehyde condensates.

409883 / U21-

- a »

The pesticides obtainable according to the invention can also be combined with a synergist or others Pesticides are mixed, especially with other insecticides or acaricides.

Synergists with which the new compounds obtainable according to the invention can be mixed for example piperonyl butoxide (butylcarbityl-6-propylpiperonyl ether with a smaller proportion of related compounds), Piprotal (piperonal-bis- (2- / 2-butoxyethoxy / ethyl) acetal), Propylisone (di-n-propyl-ö ^ -methylenedioxy-S-methyl-i, 2,3,4-tetrahydronaphthalene-1,2-dicarboxylate) and sesamin (2,6-bis- (3,4-methylenedioxyphenyl) -3,7-dioxabicyclo / 3,3,0 / octane). Other pesticides with which the new compounds can be mixed are, for example, organophosphorus compounds like dimethoate (0,0-dimethyl-S- (N-methylcarbamoylmethyl) -phosphorodithioate) and malathion (S- / 1,2-di- (ethoxycarbonyl) -ethyl / 0,0-dimethylphosphorodithioate), Carbamate such as carbaryl (1-naphthyl-N-methylcarbamate), bendiocarb (2,2-dimethyl-1,3-benzodioxol-4-yl-N-methylcarbamate), and PropQcvr (2-isopropoxyphenyl-N-methylcarbamate), and chlorinated compounds such as BHC (containing benzene hexachloride the gamma isomer), dicofol (2,2,2-trichloro-1,1-di / chlorophenyl / ethanol) and tetradifon (2,4,4 ', 5-tetrachlorodiphenyl sulfone). The new compounds can be mixed with the pesticide fenazaflor (5,6-dichloro-i-phenoxycarbonyl-2-trifluoromethylbenzimidazole), Tricyclohexyltin hydroxide, formetanate (3-dimethylaminomethyleneiminophenyl-N-

409883/1421

methyl carbamate), chlordimeform (N _# N-dimethyl-N ^l - (2-methyl-4-chlorophenyl) formamidine), chlorobenzilate (ethyl 4,4'-dichlorobenzilate), quinomethionate (ö-methyl ^ -oxo-i, S-dithiol ^^ - b] - 'quinoxaline, final sulfane (6,7,8,9,10,10-hexachlor-i, 5,5a, 6,9,9a-hexahydro-6,9-methane-2,4, 3-benzodioxathiepin ~ 3-oxide), chlorodecone (Dekachloroctahydro-1,3 ^ -methen- ^ H ^ H-cyclobuta-jjcdJ-pentalen-2 ~ one), bis- (pentachlor-2,4-cyclopentadien-1-yl ),
Chloropropylate (isopropyl 4,4'-dichlorobenzilate), bromopropylate (isopropyl 4,4 ^l -dibromobenzilate), thioquinox (2-thio-1,3-dithiol- £ 4,5-bj-quinoxaline), dinocap (dinitrooctylphenyl crotonate) , Binapacryl (2-sec-butyl-4,6-dinitrophenyl-2-methylcrotonate), dinobutone (2-sec-butyl-4,6-dinitrophenyligopropyl carbonate), naled (1,2-dibromo-2,2-dichloroethyldimethyl phosphate), Monocrotophos (dimethyl-1-methy1-2- (methylcarbamoyl) vinyl phosphate), demetone (diethyl 2- (ethylthio) ethylthiophosphate), phosphorate fO, O-rdiethyl-S- (ethylthiomethyl) phosphorodithioate), oxydemetonmethyl
(0,0-dimethyl-S- (2-ethylsulfinylethyl) phosphorothioate), ethione (tetraethyl-S, S -methylene-bis- (phosphorodithioate)), formothione (S- (N-pormyl-N-methylcarbamoylmethyl) - dimethylphosphorodithioate), ethoatemethyl (S- (N- (1-cyano-1-methylethyl) -carbamoylmethyldiä thy! phosphor thioate), EPN {O-ethyl-Op-nitrophenylphenylphosphonthioatl, carbophenothione (S-C4-chlorophenylthiomethyl) S- (2,3-dihydro-5-methoxy-2-οχο-ί , 3,4-thiadiasol-3-ylmethyl | -dimethylphosphorodithioate), chlorpyrifos' (diethyl-SiSie-trichloro-a-pyridyl-. Phosphorothionate), Diazinon (diethyl-2-isopropyl-6-raethyl-4-pyrimidiny! Phosphorothionate) «azinphosethyl (diethyl-S- (4-oxo-

9883/1421

At

1,2,3-benzotriazin-3-ylmethyl) phosphorodithioate, azinphosmethyl (Dimethyl-S- (4-oxo-1,2, S-benzotriazin-S-ylmethylphosphorodithioate), Fenson (4-chlorophenylbenzene sulfonate), Tetrasul (2,4,4 *, 5-tetrachlorodiphenyl sulfide), chlorine surfactant (4-chlorobenzyl-4-chlorophenyl sulfide), Chlorofensulfide (4-chlorophenyl-2,4,5-trichlorophenylazosulfide), 2- (p-tert-butylphenoxy) -imethylethyl-2-chloroethyl sulfite, 2- (p-tert-butylphenoxy) -cyclohexyl-2-propynyl sulfite, Aldicarb (2-methyl-2- (methylthio) propionaldehyde-0- (methylcarbamoyl) oxime), Methomyl (S-Methy1-N- (methylcarbamoyloxy) thioacetimidate), Methiocarb (4-methylthio-3,5-3ylyl-N-methylcarbamate) , or benomyl (methyl 1- (butylcarbamoyl) benzimidazole-2-carbaraate). The new compounds can also be mixed with the pesticides which are the subject of Dutch patent specification No. 73 00168.

The agents themselves can be formed by mixing the ingredients.

The new compounds have insecticidal and acaricidal activity, especially insecticidal activity. At her Application they are brought into contact with the vermin. The compounds are effective against vermin, in particular Insects, which attack crops, which are animal parasites and which ultimately pose a threat to the general population Represent health. The connections are particularly wIvk » sam against aphidia and related species.

409883/1421

The compounds can be applied to a location that is already infested with the vermin, or also be brought to a-vn place to keep this from vermin to keep clear. The compounds can be on plants, on the ground, on land, on bodies of water, on animals Buildings or surfaces of furniture, such as walls, floors or shelves, and in Areas where food is produced or stored, such as household warehouses, warehouses and ships. The compounds are generally used in an amount of 0.1 to 10 kg of the compound per hectare.

The compounds are preferably used in places on which the respective plants grow or will grow immediately after application, e.g. where Useful or ornamental plants grow or will grow immediately after application. The connections can be in Agriculture and horticulture can be used. For example, the connections can be used to make wingless Bean phidias (Megoura viciae) on bean plants (Viciae fäbae) to fight. To fight vermin on plants, For example, the compounds can be used in an amount of 0.1 to 2 kg of the compound per hectare.

The compounds are also particularly useful against insects that are resistant to organophosphorus compounds are, e.g. against Phorodon humuli on hops, or Myzus Persicae on peaches. Other crops on which.

409883 / U21

the compounds that can be used particularly advantageously are: apples, wine, cotton, citrus fruits, Stone fruits and soft fruits, rice, coffee, vegetables and cereals, sugar beets and potatoes.

The compounds can also be used to control pests that pose a general health hazard represent, e.g. house flies and cockroaches. For these uses, the compounds can be, for example on surfaces in an amount of 100 to 3000 mg

of the compound per m 2 or in the atmosphere in an amount of 0.3 to 30 mg / m.

The compounds have systemic properties in soil and leaves and can protect seeds against crops of the germinating young plants against vermin, e.g. Aphidierv.

The compounds can also be used to control vermin on animals, for example to control sheep blow fly (Lucilia sericata) or beef tick (Boophilus microplus). For the treatment of animals, the animals can, for example, in a solution containing 100 to 1000 parts per 1 000 000 of the compounds, immersed or sprayed with it.

The subject matter of the present invention is intended to be illustrated by the following examples, without, however, being restricted thereto. The specified temperatures relate to ⁰ C.

409883 / H21

Example 1: A mixture of 220 parts of N, N-diethyl-2-methoxy-5-nitroaniline and 15,000 parts of concentrated hydrobromic acid was refluxed for 10 hours. The excess of unreacted hydrobromic acid (750 parts) was distilled off and the remaining solution was poured into ice. The solution was made alkaline with sodium hydroxide and extracted with ether. The ethereal solution was extracted with aqueous sodium hydroxide solution and the combined aqueous alkaline extracts acidified to pH 4. This solution was then extracted with ethyl acetate, dried and evaporated to give 91 parts of crude 2- (diethylamino) -4-nitrophenol as a dark oil. (The substituted phenol Fp can be used without further purification in the carbamate be converted, or may be about the hydrochloride, mp. 21O ⁰ C, to a green crystalline solid. 85-86 ° C, are agreed upon.) The ethereal layer was evaporated and yielded 100 parts of unreacted N, N ~ diethyl-2-methoxy-5-nitroaniline, whereupon a net yield of crude product of 81% was calculated.

Example 2i 52 parts of diethyl sulfate were slowly added at t> to 30 ° C. over a period of 1 hour to a stirred mixture of 2-amino-4-nitrophenol (15.4 parts), sodium bicarbonate (22 parts) and water (200 parts) added. The reaction mixture was then ^{heated to 80 °} C. and left at this temperature for 2 hours. The mixture

409883/1421

243O207

was then cooled, made alkaline with sodium hydroxide and washed with ether. The alkaline layer was acidified to pH 4, extracted with ethyl acetate, dried and evaporated to give an oil which solidified. The solid became aqueous Recrystallized ethanol and gave 9 parts of 2-diethylamino-4-nitro-phenol (43% yield), bp. 85 to 86 ° C, identical to the purified product of Example 1. Analysis:

Calculated for C ₁₀ H ₁₄ N ₂ O ₃ : C 57.13, H 6.71, N 13.33%, found: C 57.45, H 6.95, N 13.65%.

• ■ ·

Examples 3 to 22: The following others substituted Phenols were prepared analogously to the method described in Examples 1 and 2; the magnetic The nuclear magnetic resonance spectrum confirmed the assumed one in each case Structure:

2- (Dimethylamine) -4-nitrophenol?
2- (Dipropylamino) -4-nitrophenol?

2- (Diethylamino) -4-nitro-5-broraphenoi, m.p. 103-106 ° Cf 2- (Diethylamino) -4-nitro-5-chlorophenol, mp. Of the crude product 73 to 90 ° C;

2- (Dimethylaraino) -4-nitro-5-chlorophenol, m.p. 166 to 168 ° Cf Analysis:

Calculated for CgH ₉ ClN ₂ O ₃ : C 44.35, H 4.19, Cl 16.37, N 12.93 found: C 44.50, H 4.05, Cl 16.05, N 12.60 «.

A09883 / U21

2- (diethylamino) -4-IiItTo-S- (ethylthio) phenol, m.p. 113 to 115 ° C; £ ~ 0Jläthylamino) -4-nitro-5-methylphenol, m.p. 70 to 72 ° C;

2- (diallylamino) -4-nitrophenol, m.p. of the hydrochloride 165 to 167 ° C;

2- (Dipropargylamino) -4-nitrophenol, mp 131-133 ° C; 2- (Dimethylamine) -a-nltro-S- (ethylthio) -phenol, melting point 136 to 137 ° C;

2- (Dimethylamine) -4-nitro-5- (propylthio) phenol, melting point of the crude product 145 to 155 ° C;

2- (diallylamino) -4-nitro-5- (ethylthio) phenol; 2- (diethylamino) -4-nitro-5- (butylthio) phenol; 2- (diethylamino) -4 * -nitro-5- (methylthio) phenol; 2- (diethylamino) -4-nitro-5- (propylthio) phenol;

2- (Diallylamino) ^ -nitro-S-methylphenol, m.p. of the hydrochloride 173 to 178 ° C;

2- (Dipropargylamino) -4-nitro-5-methylphenol, m.p. 101-103 ° C; 2- (diallylamino) -4-nitro-5-chlorophenol;

2- (Dipropargylamino) -4-HXtTO-S-ChIOrPhCnOl, mp. Of the crude product 105 to 11O ⁰ C and

2- (Diethylamino) -4-nitro-S-methoxyphenol, m.p. of the hydrochloride 200 to 2O5 ° C.

Example 23: A mixture of 4.7 parts of 2- {diethylamino) -4-nitrophenol, 4.7 parts of dimethylcarbamoyl chloride, 3.2 parts of sodium carbonate in 80 parts of acetone were under Heated to reflux with stirring for 12 hours. The mixture was then filtered off and the filtrate evaporated to an oil.

409883 / U21

This was dissolved in ether with ice-cold aqueous sodium hydroxide washed and evaporated to an oil. Purification via the hydrochloride, melting point 70 ° C., gave 3.5 parts of 2- (diethylamino) -4-nitrophenyldimethylcarbamate as orange oil. Analysis:

Calculated for C ₁₃ H ₁₉ N ₃ O ₄ : C 55.50, B 6.81, N 14.94%, found: C 55.80, H 6.95, N 15.15%.

Examples 24-25: The following other dimethyl carbamates were analogous to the procedure described in Example 22 by reacting between the corresponding phenol and dimethylcarbamoyl chloride hcrgedbellt:

2- (Dimethylamino) -4-nitrophenyldimethylcarbamate, red oil, Analysis:

Calculated for C ₁₁ H ₁₅ N ₃ O ₄ : C 52.17, H 5.97, N 16.59%,

found: C 51.85, H 5.80, N 16.25%.

2- (diethylamino) - ^ - nitro-S-bromophenyldimethylcarbamate, M.p. 60 to 62 ° C.

Analysis:

Calculated for C ₁₃ H ₁₈ BrN ₃ O ₄ : C 43.34, H 5.04, Br 22.19, N 11.67%,

found: C 43.30, H 5.00, Br 21.90, N 11.70%.

2- (Dipropylamino) -4-nitrophenyldimethylcarbainate, orange oil, analysis:

Calculated for ^c i5 ^H ₂ 3 ^N 3 ° 4 ^{! c} 58.23, H 7.49, N 13.58%,

found: C 58.50, H 7.20, N 13.60%.

409883 / H21

2A3O207

■ if

2- (diethylamino) ^ - nitro-S-chlorophenyl-dimethylcarbamate,

red oil, "

Analysis:

Calculated for C ₁₃ H ₁₈ ClN ₃ O ₄ : C 49.45, H 5.75, Cl 11.23, N 13.31%,

Found: C 49.85, H 6.25, Cl 10.80, N 13.55%.

2- (Dimethylamino) - ^ - nitro-S-chlorophenyldimethylcarbamate,

M.p. 95 to 97 ° C,.

Analysis:

Calculated for C ₁₁ H ₁₄ ClN ₃ O ₄ : C 45.92, H 4.91, Cl 12.32, N 14.61%,

Found: C 46.35, H 5.15, Cl 11.95, N 15.00%.

2- (diallylamino) -4-nitrophenyldiraethylcarbamate, m.p. 57 to 59 ° C; 2- (Dipropargylamino) .- 4-nitrophenyldiraethylcarbamate, m.p. 107 bis

2- (Dimethylamine) -4,5-dinitrophenyldimethylcarbamate, m.p. 151 up to 153 ° C;

. 2- (diethylamino) -4, 5 ^ dinitrophenyldimethylcarbamat, m.p. 108 to 110 ⁰ C;

2- (diethylamino) -4-nitro-5-methylphenyldimethylcarbamate, liquid; 2HDimethylandno) ^ -nitro-S-ethylthiophenyldimethylcarbamate,

Mp 100-101 ° Cj. ·

2- {diethylamino) -4-nitiro-5-8thylthiophenyldimethylcarbamate, mp 72 ° C, mp of the hydrochloride 125 to 128 ° C; 2- (Dimethylamino) -4-nitro-5-propylthiophenyldimethylcarbamate, m.p. 82 ° C, ·

2- (diethylamino) -i-nitro-S-methylthiophenyldimethylcarbamate, Mp 57 to 59 ° C;

2- (diallylamino) - ^ - nitro-S-ethylthiophenyldimethylcarbamate,

40 * 9883/1421

Mp 56 to 58 ° C;

2- (diethylamino) - ^ - nitro-S-butylthiophenyldimethylcarbamate, Mp 47 to 49 ° C;

2- {diethylamino) ^ - nitro-S-propylthiophenyldimethylcarbamate, fluid;

2- (Diällylamino) • M-nitro-S-methylphenyldimethylcarbamate, M.p. 41 to 42 ° Cj

2- (Dipropargylamino) -M-nitro-S-methylphenyldimethylcarbamate, M.p. 99 to 1O1 ° Cj

2- (Diällylamino) - ^ - nitro-S-chlorophenyldimethylcarbamate,

Mp. 52 to 53 ° Cj '' '

2- (Dipropargylamino) ^ - nitro-S-chlorophenyldimethylcarbamate, Mp 71 to 73 ° C; and

2- (diethylamino) - ^ - nitro-S-methoxyphenyldimethylcarbamate, M.p. 74 ° C.

Example 46; A solution of 36 parts of 2- (diethylamino) -4-nitrophenol in 300 parts of ether was treated with an excess of methyl isocyanate and a small amount of diethylamine. The mixture was left to stand for 16 hours and then evaporated to dryness. The surviving solid was recrystallized from a mixture of ether and petroleum ether (bp. 60 to 80 ⁰ C) to give 27 parts of 2- (diethylamino) ~ 4-nitrophenylmethylcarbamat (59% yield) as orange needles, mp. 98 to 100 ⁰ C.

409883 / U21

Analysis:

Calculated for C ₁₂ H ₁₇ N ₃ O ₄ : C 53.92, H 6.41, N 15.72%,

Found: C 54.20, H 6.45, N 16.00%.

Examples 47-50: The following others Methyl carbamates were analogous to that described in Example 46 Process prepared by reaction between the corresponding phenol and methyl isocyanate:

2- (Dimethylamino) -4-nitrophenylmethyl carbamate, m.p. 112-114 ° C Analysis:

Calculated for C ₁₀ H ₁₃ N ₃ O ₄ : C 50.20, H 5.48, N 17.57%,

Found: C 50.40, H 5.48, N 17.57%.

2- (Diethylamino) -4-nitro-5-bromophenylmethylcarbamate, m.p. 114 bis

Analysis:

Calculated for C ₁₃ H ₁₆ BrN ₃ O ₄ : C 41.63, H 4.66, Br 23.08, N 12.14%,

found: C 41.95, H 4.40, Br 22.90, N 12.50%. ·

2- (Dipropylamino) -4-nitrophenylinethylcarbamate, m.p. 66 to 68 ^° C.

Analysis:

Calculated for C ₁₄ H ₃₁ N ₃ O ₄ : C 56.93, H 7.17, N 14.23%,

found: C 56.90, H 7.35, N 14.45%; and

2- (diethylamino) -4,5-dinitrophenylmethyl carbamate, m.p. 128 bis

Examples 51 to 76: Aqueous acetone solutions containing 1000, 300, 100 and 10 ppm of those given below

409883 / 1.421

■ ι *

Compounds together with 500 ppm nonylphenol / ethylene oxide condensate as wetting agents were applied to young bean plants, Viciae fabae, which were then treated with wingless bean aphidia, Megoura viciae, who in turn were infected beforehand with the same concentrations of the text solutions had been sprayed.

The treated plants and insects were together with controls treated with wetting agent alone for 24 hours under plastic cylinders with the above Gaas were sealed, kept at 20 ° C.

The percent mortality of the insects was determined, the results are given below: Compound Percent Mortality

2- (Dimethylamine) -4-nitrophenyldimethylcarbamate

2- (diethyiamino) -4-nitrophenyl dimethyl carbamate

2- (diethyiamino) -4-nitrophenyldimethylcarbamate hydro- chloride

2- (Dipropylamino) -4-nitrophenyl dimethyl carbamate

2- (diethyiamino) -4-nitro-5-bromophenylmethyl carbamate

2- (diethyiamino) -4-nitro-5-bromophenyldimethyl- carbamate

2- (diallylamino) -4-nitrophenyl dimethyl carbamate

2- (Dipropargylamino) -A- nitrophenyldirnethyl-

carbamate 100 100 100

409883/1421

1000 ppm 300 ppm 100 ppm 10 ppm 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 1OO 100 loo 100 100 100 100 100

- Hf -

2- (diethylamino) -4-nitro-5-methylphenyldimethyl carbamate

2- (Dimethylamino) -4-nitro-5-ethylthiophenyldimethylcarbamate

2- (diethylamino) -4-nitro-5-ethylthiophenyldimethyl carbamate

2- (diethylamino) -4-nitro-S-ethylthiophenyldimethyl- carbamate hydrochloride

2- (Dimethylamino) ^^ - 4-5-propylthiophen.yldimethyl- carbamate

2- (diethylamino) -4-nitro-5-methylthiophenyldimethyl- carbamate

2- (diallylamino) -4-nitro-5-ethylthiophenyldimethyl- carbamate

2- (diethylamino) -4-nitro-5-butylthiophenyldimethyl- carbamate

2- (Diethylamino) -4-nitro-5-propylthiophenyldimethyl · ^ carbamate

2- (Dipropargylamino) -4-nitro-u 5-methylphenyldimethylcarbamate

2- (diallylamino) -4-nitro-5-chlorophenyldimethyl carbamate

2- (Dipropargylamino) -4-nitro-5-chlorophenyldimethylcarbamate

2- (diethylamino) -4-nitro-5-methoxyphenyldimethyl- carbamate

2- (Dimethylamino) -4-nitrophenylmethyl carbamate 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100

100

100

100

100

50

100 100

100 100

100 100

100 100

100

100

100

A09883 / H21

2- (Diethylaraino) -4-nitro- • phenylmethylcarbamate 50

2- (dimethylamino) -4-nitro-

5-chlorophenyl dimethyl carbamate 100 100 100 100

2- (diethylamino) -4-nitro-

5-chlorophenyl carbamate 100 100 100 100

Examples 77 to 91: 1 ml of portions of acetone solutions containing the compounds given below 1000, 300, 100 and 30 ppm were on dental cotton wool rolls Applied with dimensions of 1 cm in diameter and 2 cm in length. After drying, these were placed in glass vials given that had theάτβι diameter of 2 cm and 5 cm in length and were closed with a cotton plug.

The treated cotton rolls were then impregnated with 1 ml of sheep serum with larvae of the sheep blow fly Lucilia seriatica of the first manifestation was infected and then kept at 25 ° C for 24 hours.

The percent mortality of the insects was then determined and is reported as follows: Compound Percent Mortality

2- (dimethylamino) -4-nitrophenyl dimethyl carbamate

2- (diethylamino} -4-nitrophenyl dimethyl carbamate

2- (diethylamino) -4-nitromethyl carbamate

2- (dimethylamino) -4-nitrophenylmethyl carbamate

409883 / U21

1000 ppm 300 ppm 100 ppm 3 O ppm 100 80 100 100 100 100 100 20th 100 100

2- (diethylamino) -4-nitrophenyldimethylcarbamate-

hydrochloride 100, 100

2- (Dipropylamino) -4-nitrophenyl dimethyl carbamate 100 lOO

2- (diallylamino) -4-nitrophenyl dimethyl carbamate 100 100

2- (Dimethylamine ») -4-nitro-5-chlorophenyldimethylcarbamate 100 100

2- (diethylamino) -4-nitro-5-chlorophenyl dimethyl carbamate 100 100

2- (diethylamino) -4-nitro-5-bromophenyldimethylcarbamate 100 100

2- (diethylamino) -4-nitro-5-methylphenyldiniethyl-

carbamate 100 100

2- (diallylamino) -4-nitro-5-yne thy Ip he ny dimethyl carbamate 100 100

2- (Dipropargylamino) -4-nitro-5-methylphenyldimethylcarbamate 100 100

2- (diallylamino) -4-nitro-5-chlorophenyl dimethyl carbamate 100 100

2- (Dipropargylamino) -4-nitro ^ -5-chloro phenyl dimethyl carbamate 100 100

A09883 / U21

Claims (13)

Claims; wherein R is alkyl, alkenyl or alkynyl; R is hydrogen, alkyl or carboxy-acyl; 4th
R and R are identical or different and are each alkyl, 3 4 are alkenyl or alkynyl or R and R together form an alkylene chain which is substituted by alkyl can be;
and
R, R and R are the same or different and are each hydrogen; Halogen; Alkyl; carboxylic acyl; -OR ⁸ , -SR ⁸ , -SO ₂ R ⁸ or -SOR ⁸ where R ⁸ Alkyl, aryl which may be substituted by alkyl q in Q represents m or benzyl; -C (OH) RR, where R and R are identical or different and are each hydrogen or alkyl; Nitri.1; Nitro; Thiocyanate; Carboxy; A0 9883 / U21 ■ * ■ .- « Carboxy ester; Carbamoyl, the nitrogen atom of which is substituted 3 4 can be tuated; or another -NR R group mean, dantellen,
or a salt of this carbamate. 2. A compound according to claim i, characterized in that R ^{1 is} alkyl having 1 to 6 carbon atoms / alkenyl with 2 to 6 carbon atoms or alkynyl with 2 to 6 carbon means material atoms; R is hydrogen, alkyl with 1 to 6 Carbon atoms> Benzoyl or alkanoyl with 2 to 6 carbon atoms means; R and R are identical or different and are each alkyl with 1 to 6 carbon atoms, Alkenyl with 2 to 6 carbon atoms or Akinyl with 2 to Represent 6 carbon atoms or R and R together form an alkylene chain with 2 to 6 carbon atoms, through. Alkyl with 1 to 6 carbon atoms can be substituted? and R, R and R are the same or different and are each Hydrogen; Halogen; Alkyl of 1 to 6 carbon atoms; Benzoyl; Alkanoyl of 2 to 6 carbon atoms; -OR, -SO ⁸ , -SO ₂ R ⁸ or -SOR ⁸ , in which R ^{8 is} alkyl having 1 to 6 carbon atoms, phenyl, which can be substituted by alkyl having 1 to 4 carbon atoms, or benzyl 9 10 9 10 means; -C (OH) R R, where R and R are identical or different and are each hydrogen or alkyl of 1 to 6 carbon atoms; Nitrile; Nitro; Thiocyanato; Carboxy; Alkoxycarbonyl of 2 to 7 carbon atoms; Carbamoyl, whose 40.98 83 / U21 243Q207 - VK Nitrogen atom by alkyl or with 1 to 6 carbon 3 4 atoms may be substituted; or another -NR R group mean, represent. 3. A compound according to claim 1, characterized in that R ^{1 is} alkyl having 1 to 4 carbon atoms; R ^{2 represents} hydrogen or alkyl of 1 to 4 carbon atoms; R and R are identical or different and each represent alkyl having 1 to 4 carbon atoms, alkenyl having 2 to 4 carbon atoms or alkynyl having 2 to 4 carbon atoms; R. 1 (\ and R each represent a hydrogen atom; and R Hydrogen, halogen, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms or alkyl with 1 to Means 4 carbon atoms. 4. 2 -. (Diethylamino) -4-nitrophenyldimethylcarbamate, 2- (dipropylamino) -4-nitrophenyldimethylcarbamate, 2- (diallylamino) -4-nitrophenyldimethylcarbamate, 2- (dimethylamine) ^ -nitro-S-chlorophenyldimethylcarbamate, 2- (diethylamino ) ^ - nitro-S-chlorophenyldimethylcarbamate, 2- (diethylamino) ^ -nitro-S-bromophenyldimethylcarbamate, 2- (diethylamino) -4-nitro-5-methylphenyldimethylcarbamate, 2- (diethylamino) -4-nitro-5-ethylthiophenyldimethylcarbamate, 2- (diethylamino) ^ -nitro-B-methylthiophenyldimethyl carbamate, or a salt of these compounds. 409883/1421 5. Method of making a compound of general formula (I), wherein R is hydrogen or alkyl, characterized in that a substituted Phenol of the "formula , (II) wherein R, R, R, R and R are those given in claim 1 Have meaning, or a salt of this substituted phenol with a substituted carbamoyl halide the formula R ¹ R ² NCOX, wherein X is a halogen atom, R is that in claim 1 2
has given meaning and R 'is hydrogen or alkyl, is implemented. 6. A process for the preparation of a compound of the general formula (I), characterized in that a chloroformate of the formula 409883/1421 NO, , (III) wherein R, R, R, R and R are those given in claim 1 Have meaning or a salt of this chloroformate with an amine or an amide of the formula R ¹ R ² NH, 1 2
wherein R and R have the meaning given in claim 1, is reacted. 7. Method of making a compound of 2 general formula (I), in which R is hydrogen, characterized in that a substituted phenol of the general formula (II), wherein R, R, R, R and R the have the meaning given in claim 1, or a salt of this phenol with an isocyanate of the formula R ¹ NCO, wherein R has the meaning given in claim 1, is reacted. 8. Process for the preparation of a compound of general formula (I), in which R is carboxyIic acyl, characterized in that a connection of the general 2 Formula (I), in which R is hydrogen, is acylated. 409883 / U21 9. Pesticides, characterized in that it is a compound according to one or more of the Claims 1 to 4 contains. ", Methods of combating vermin in a location in which it is or may be infected with it, characterized in that the pests on this place controlling amount of a compound according to one or more of claims 1 to 4 or an agent according to claim 9 applied will. 11. ' A compound characterized by being a is, ο λ c. c substituted phenol of the formula (II) / in which R, R, ΈΓ, R and R have the meaning given in claim 1, with the proviso that when R, R and R are each hydrogen, one or both of the radicals R and. R are different from methyl, or a salt of this substituted phenol. 12. A process for the preparation of a substituted phenol according to claim 11 or a salt thereof, characterized in this characterized in that a substituted o-alkoxyaniline of formula , (IV) A09883 / U21 wherein R, R, R, R and R are those given in claim 11 Have meaning and R denotes alkyl having 1 to 6 carbon atoms, or a salt thereof is dealkylated. 13. A process for the preparation of a substituted phenol according to claim 11 or a salt thereof, characterized in that a 2-amino-4-nitrophenol of the formula wherein R _r R and R have the meaning given in claim 11, is alkylated. 409883/1421