DE1668664A1 - 1,1-Disubstituted formaldoxime carbamates and processes for their preparation - Google Patents

Description

PR. ING. F. WUESTHOB ¹ F DIPL ·. ING. G. PULS DR.BVPECIIMANN

PATENT LAWYERS

8 MUNICH 9O SCHWEIOEHSTRASSE 2

on as 0651

TEbSORAMMADRKHSK: HHOTECTPATKNT MCNCHKN

IA-34 174

Description of the patent application

SHELL INTERNATIONAL RESEARCH MIJ.N.V.,

30 Carel van Bylandtlaan, The Hague / NETHERLANDS

concerning:

" l, l-Disubstituted formaldoxime carbamates and process for their preparation"

The invention relates to 1,1-disubstituted formaldoxime carbamates the formula

X.

0 ', N-O-C-N

R ₁

109838/1727

ORIGINAL INSPECTED.:;

wherein R ₁ and R ₂ , which can be identical or different, denote an optionally unsaturated and optionally substituted hydrocarbon radical, R _y and R ₁ ,, which can be identical or different, each denote a hydrogen atom or an optionally substituted alkyl or aryl group and X ,, X ₂ and X-., Which can be identical or different, each represent an oxygen or sulfur atom, as well as their preparation and

Use, in particular as biocides, preferably insecticides and Ijematicides.

Preferred compounds are those in which R ₁ and R 2 each represent a preferably substituted alkyl group, in particular a lower acyclic or alicyclic alkyl group, which are preferably substituted by a halogen atom, a cyano group or a phenyl group, and in particular a methyl, ethyl, Represent isopropyl, cyclohexyl, cyanomethyl or benzyl group or an alkenyl group, in particular an allyl groupj and where R and R ₁ each represent a hydrogen atom, a lower alkyl group, in particular a methyl group, or a phenyl group.

Particularly preferred are the compounds in which X ^ is an oxygen atom; one of the two groups R and R _{1 represent} a hydrogen atom and the other a methyl group and, if at least one of the substituents

- 2 -109838/1727 BADOfWKNAl.

ien X, and X _{2 represent} sulfur, R, and Rp each represent a methyl, ethyl, isopropyl, allyl or benzyl group or, if both X and Xp represent an oxygen atom, each of the groups R ₁ and R _{2 represent} one Represent methyl or ethyl group.

The terms “alkyl”, “aryl” and “alkenyl” are intended in their broadest sense in the following; "Alkyl" to- Λ

closes! «! * aeyl ^ cjLsche (both straight-chain and linked) and cyclic alkyl groups which may optionally be substituted, e.g., by halogen atoms or Cyano or aryl groups, and the term "aryl" embraces carbocyclic aromatic groups, optionally for example, halogen atoms or alkyl groups. The term "lower alkyl groups" is used hereinafter used to denote alkyl groups with a maximum of 8 carbon atoms.

Particularly preferred and for the use according to the invention as biologically active compounds, the following can be mentioned:

l-Allylthio-l-methoxy-formaldoxime-N-methyl-carbamate l-methylthio-l-ethoxy-formaldoxime-N-methyl-carbamate 1-methylthio-1-isopropoxy-formaldoxime-N-methyl-carbainate

10983P / 17 7 7

Another embodiment of the invention relates to new processes for the preparation of the 1,1-disubstituted Formaldoxime carbamates. In all of these processes, a 1,1-disubstituted Pormaldoxime of the formula:

C-N-OH II

and this oxime is then converted into an oxime carbamate converted in the usual way. So can the oxime with phosgene or thiophosgene and the appropriate substituted amine of the formula R-JNHR ^ are implemented or it can be the oxime with an isocyanate or isothiocyanate of the formula R ^ NCX ^ or a carbamoyl chloride the formula:

N-C-Cl

optionally reacted in the presence of a base, preferably an organic base such as a trialkylamine. R _{1 }} R ₂ , R ,, R ₂ ,, X ,, Xg and X-, - in these formulas

. 4 109838/17 27

have the meaning given with regard to formula I. The reaction with isocyanate or carbamoyl chloride is preferably in the presence of a liquid organic reaction medium such as methylene chloride or Benzene carried out, but the reaction can be carried out with phosgene in an aqueous system.

The 1,1-disubstituted formaldoximes of the formula II .., in which both X ₁ and X _{2 are} oxygen atoms, can be prepared in a suitable manner by reacting the corresponding alcohol or an alcohol mixture with chlorine in the presence of a metal cyanide, preferably one
Alkali metal cyanide to form an N-chloro-iminocarbonate
implemented according to the following equation:

R ₁ OH + R ₂ OH + KCN + Cig ^ CN-Cl

/ i

The N-chloro-iminocarbonate is then converted to the corresponding oxime, preferably by reaction with hydroxylamine hydrochloride, and this oxime can then be converted into the corresponding oxime carbamate by means of according to the usual procedures mentioned.

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The 1,1-disubstituted formaldoximes of the formula II, where at least one of the radicals X ₁ and X _{2 is} a sulfur atom, can be prepared by any of the following three new processes, which represent further embodiments of the invention. According to the first process (process A), a hydrocarbon halide of the formula RHaI is combined with an alkali metal xanthate or trithiocarbonate of the formula:

(where M ^{+ represents} an alkali metal cation)

implemented, where the corresponding ester of the formula:

R X C-SR V.

1 1

which is then obtained with hydroxylamine, preferably in the form of the hydrochloride, in the presence an base, preferably an organic base how a trialkylamine is reacted and the resulting thiohydroxamic acid of the formula:

R ₁ X ₁ -C -NHOH VI.

- 6 109838/1727

is then reacted with a hydrocarbon halide of the formula RoHaI.

In the second process according to the invention (process β), the oxime of the formula II, where at least one of the radicals X and Xp is a sulfur atom, is obtained by reacting hydroxylamine, preferably as the hydrochloride, with an alkali metal xanthate or -trithio- μ

carbonate of the formula ^ V in aqueous solution and then Alkylating the resulting thiohydroxamic acid with a hydrocarbon halide of Formula RpHaI prepared in the presence of a base, preferably an organic base such as a trialkylamine. The thiohydroxamic acid is conveniently alkylated in situ by reacting the hydrocarbon halide to the aqueous reaction mixture is added, the reaction between the hydroxylamine and the xanthate or trithiocarbonate. In general, "

preferred, the hydrogen sulfide produced in this process by passing nitrogen through the Solution to remove.

In a third process according to the invention (process C), the oxime of the formula II, where both X and X are ₂ sulfur atoms, by reacting sulfur

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carbon with hydroxylamine, preferably in the form of hydrochloride, produced in alcoholic solution, which contains a base, preferably an organic base such as a trialkylamine, and then Alkylation with a hydrocarbon halide of the formula RpHaI. Generally preferred as alcoholic Use solvent methanol.

It is known that oximes exist in two stereoisomeric forms, known as the syn form and the anti form and the same stereoisomerism occurs with the oxime carbamates according to the invention. Both stereoisomers Forms of the oxime carbamates as well as mixtures of the two forms fall within the scope of the Invention.

The 1,1-disubstituted formaldoxime carbamates according to of the invention are biologically active compounds, which in particular have insecticidal and nematicidal activity demonstrate. The invention accordingly also includes biocidal preparations which contain at least one 1,1-disubstituted Formal'doximcarbamat according to the invention together with a carrier or a surface-active agent or both included.

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By "carrier" is meant a material that is inorganic or organic or synthetic or is of natural origin with which the active compound is mixed or formulated for relief the application to plants, seeds, soil or other objects to be treated, or to improve the Storability, transportability or handling. The carrier can be solid or liquid. Any of the usual Materials used to formulate pesticides can be used as carriers will.

Examples of suitable solid carriers are silicates, clays, e.g. kaolinite, synthetic hydrated silicon oxides, synthetic calcium silicates, elements such as carbon and sulfur, natural and synthetic Resins such as coumarone resins, rosinates, copal, schellac, f

Damar resin, polyvinyl chloride and styrene polymers and copolymers, solid polychlorophenols, bitumen, types of asphalt, Waxes such as beeswax, paraffin wax, montan wax and chlorinated mineral waxes and solid fertilizers such as superphosphates.

Examples of suitable liquid carriers are water, alcohols such as isopropanol, ketones such as acetone,

- 9 109838/1727

Methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, Ethers, aromatic hydrocarbons such as benzene and toluene, petroleum fractions such as kerosene and chlorinated hydrocarbons such as carbon tetrachloride, including liquefied normally vaporized gaseous compounds. Mixtures of different liquids are often suitable.

The surfactant can be a wetting agent, an emulsifier or a dispersing agent; it can be non-ionic or ionic. Any of those commonly used in the formulation of herbicides or insecticides used surfactants can be used. Examples of suitable surfactants are the sodium or calcium salts of polyacrylic acids, the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms contained in the molecule, with ethylene oxide and / or propylene oxide partial esters of the fatty acids mentioned with glycerin, sorbitol, sucrose or pentaerythritol; Condensation products of alkyl phenols, e.g. p-octyl phenol or p-octylcresol with ethylene oxide and / or propylene oxide; Aliphatics or sulphonates of these condensation products; as well as alkali metal salts, preferably sodium salts of sulfuric acid or sulphonic acid esters, the contain at least 10 carbon atoms in the molecule, e.g.

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109838/1727

Sodium lauryl sulphate, sodium secondary alkyl sulphate, Sodium salts of sulphonated castor oil and sodium alkylaryl sulphonates such as sodium dodecylbenzenesulphonate.

The preparations according to the invention can be used as wettable Powders, dust preparations, granulates, solutions, encapsulated materials, emulsifiable concentrates, 4I

Emulsions and pastes can be pre-formulated. Wettable powders are usually adjusted to a content of 25, 50 or 75 % of the active ingredient and usually contain, in addition to the solid carrier, 3 to 10 % of a dispersing agent and, if necessary, 0 to 10% of one or more stabilizers and / or other additives, such as penetration enhancers or adhesives. Dust supplements are usually formulated as a dust concentrate, similar in composition to a wettable powder, but with a dispersing agent, and when applied in the field are diluted with another solid carrier to form a formulation that usually contains 1/2 to 10 % active ingredient . Granules are usually made to be between 10 and 100 meshes of the British standard sieve (1.68 to 0.152 mm sieve mesh size), and they

109838/1727

nt

can be produced by agglomeration or impregnation according to known processes. In general, granules will contain 1/2 to 25 % active ingredient and 0 to 25 % additives such as stabilizers, modifying agents for slow release of active ingredient, binders and the like. Emulsifiable concentrates usually contain, in addition to the solvent and, when necessary, co-solvent, 10 to 50 wt -.% Per volume active ingredient, 2 to 20 wt .- ^ per volume emulsifiers and 0 to 20% of suitable additives such as stabilizers, agents for promoting penetration and anti-corrosion agents. Pastes are mixed so that they are a stable, flowable product and usually contain 10 to 60 % active ingredient, 2 to 20 % suitable additives and, as a carrier, water or an organic liquid in which the active ingredient is essentially insoluble.

The preparations according to the invention can contain other ingredients, e.g. protective colloids such as gelatin, glue, Contain casein, gum and polyvinyl alcohol. They can also contain sodium polyphosphates, cellulose ethers, stabilizers such as ethylenedlamine tetraacetic acid and other herbicides or pesticides and adhesives, e.g. contain non-volatile oils.

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109838/1727

Aqueous dispersions and emulsions, e.g. mixtures, by diluting a wettable powder or thin emulsifiable concentrate according to the invention with Water obtained are also within the scope of the invention. The emulsions can be water-in-oil emulsions or oil-in-water emulsions and can have a thick consistency similar to mayonnaise.

In a further embodiment of the invention, the compounds for controlling insects and / or Nematodes used, being on the insects or nematodes or their breeding sites a biologically effective amount of the 1,1-disubstituted according to the invention Oxime carbamate or a biocidal preparation that contains a contains such a compound is applied.

The new connections, the new processes for their f

Preparation and biological activity of the compounds are described in the following examples, wherein parts by weight and parts by volume in a ratio of kg: available l and all temperatures are in ⁰ C.

Example 1

Production of 1-isopropoxy-l-allylthio-formaldoxime N-methyl-carbamate according to method A.

3 109838/1727

(a) Preparation of methyl isopropyl xanthate

Potassium isopropyl xanthate (95 parts by weight) was dissolved in methanol (500 parts by volume) suspended and brought into solution by heating and stirring. The stirred solution was then chilled in ice, 35 parts by volume of methyl iodide dropwise added over a period of 45 minutes and the mixture then stirred for a further 2 hours. To 400 parts by volume of ether were added to the removal of the methanol by distillation, and the mixture with water (2 χ 150 parts by volume) washed. After drying over anhydrous sodium sulphate, the ether solution became evaporated and an oil obtained which, after distillation, methylisopropylxanthate from K.p. 68 to 69 ° / 10 mm Hg.

(b) Preparation of l-isopropoxy-l-allylthio-formaldoxime

7.7 parts by weight of hydroxylamine hydrochloride were dissolved in warm methanol (50 parts by volume), the solution was stirred and cooled in ice and 13.8 parts by volume of triethylamine and then 15 parts by weight of the methyl isopropylxanthate prepared as above were added. The mixture was cooled in ice and stirred for 2 hours and then evaporated to dryness under reduced pressure at around ⁰

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The residue was shaken with 200 parts by volume of ether the triethylamine hydrochloride removed by filtration and 13 * 8 parts by volume of triethylamine and 9 parts by volume of allyl bromide were added to the ice-cold solution in ether with stirring. The mixture was Stirred overnight at 2 ° C, washed with water (2 χ parts by volume) and after drying over anhydrous Sodium sulphate, the ether solution was evaporated to dryness and the crude oxime obtained as an oil.

The crude material was purified by column chromatography (column of 53 χ 3.2 cm) using silica gel of ether / light petroleum (K.ρ. 40 to 60 ° C) in the volume ratio Purified 1: 1 as a solvent system.

analysis

NO ₂ SC ₇ H ₁₅ Calculated: C 48, Oi H 7.4; N 8.0; S 18.3 % Found: C 47.8; H 7 * 4; N 8.5; S 18.0 %

(c) Preparation of 1-isopropoxy-1-allylthioformaldoxime-N-methyl-carbamate

The oxime obtained in (b) (10.1 parts by weight) was dissolved in dichloromethane (20 parts by volume) and 3.7 parts by weight Methyl isoeyanate and 1 drop of triethylamine were added.

109838/1727

/ Τ »

The mixture was refluxed for 4 hours and then evaporated to dryness. Crystallization began on trituration with light petroleum one (b.p. 40 to 6O ⁰ C) and the crude · Mater al was recrystallized from ether / light petroleum (K.ρ. 40 to 60 ° C) and N-methyl carbamate, melting at 61 to 62 ⁰ C obtained.

analysis

C ₉ H ₁₆ N ₂ O ₅ S Calculated: C 46.55ί H 6.9; N 12.1; S 15.8 % Found: C 46.8} H 7.1; N 12.3; S 14.0 %

Example 2

Production of 1-ethoxy-l-methylthio-formaldoxime-N-methyl-carbamate according to process j5 «

W (a) Preparation of 1-ethoxy-l-methylthio-formaldoxime

A solution of 7 parts by weight of hydroxylamine hydrochloride in 15 parts by volume of water was added to a stirred solution of potassium ethoxanthate (16 parts by weight) in water
(25 parts by volume) are added and the mixture is JO minutes
stirred at 20 ^{° C.} It was nitrogen through for JO minutes
the mixture passed, then the solution in ice

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109838/1727

cools and 28 parts by volume of triethylamine and then 15 parts by volume of methyl iodide are added. The mixture was stirred for 60 minutes, 0 χ 100 parts by volume) extracted with ether and evaporated after drying over anhydrous sodium sulphate the ether extract to dryness. The residue was crystallized from ether and the oxime with a melting point of 73 to 74 ^° C. was obtained.

Analysis:

C 1 H NO ₂ S Calculated: C 25.6; H 6.7; N 10.4; S 25.7 tf Found: C 35 Al H 6.61 N 10.6; S 25.9 %

(b) Preparation of 1-ethoxy-1-methylthio-formaldoxime-N-methyl-carbamate

To a solution of the oxime obtained according to (a) (4.2 parts by weight) in dichloromethane (50 parts by volume) were 2.5 parts by volume of methyl isocyanate and 1 drop of triethylamine were added. The solution was taking 16 hours Heated to reflux and then evaporated to dryness. By crystallization of the residue from ether it was made the N-methyl carbamate obtained from 60 to 61 °.

Analysis:

C ₆ H ₁₂ N ₂ OS Calculated: C, 57.5; H 6.3; N 14.6; S $ 16.7 Found: C 37.7; H 6.4; N 15.0; S 16.5 %

1 0 9 8 3 8 / Ί Ψ2 7

example J>

Production of 1,1 -dirnethylthio-formadoxime-N-methyl-carbamate according to process C

(a) Production of 1,1-dimethylthio-formaldoxire

^ There were 1 ^ * 9 parts by weight of hydroxylamine hydrochloride

dissolved in 100 parts by volume of methanol, the solution was stirred and ^{cooled to 0} ° C. and 40.4 parts by weight of triethylamine and then 12 parts by volume of carbon disulfide were added. The solution was stirred 1 hour at 0 ⁰ C, and then 20.2 parts by weight of triethylamine and 56.8 wt. Parts of methyl iodide was added. The mixture was allowed to warm to room temperature over a period of 4 hours and then evaporated to dryness. The residue was extracted with ether (5 × 100 parts by volume) and the ether solution was evaporated to dryness. The residue was purified by chromatography on a column of silica gel using ether / light petroleum

(Bp 40 to 6O ⁰ C) in the volume ratio 1: 1 as solvent system, and the eluted product is crystallized from ether to give the oxime was obtained, melting at 73 to y4 ° C.

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1098 38/1727

Analysis:

C ₃ H ₇ NOS ₂ Calculated: C 26.3; H 5.1; N 10.2; S 46.7 Found: C 26.4; H 5.3 * N 9 * 8; S 46.7

(b) Preparation of 1,1-dimethylthio-formaldoxime-N-methyl-carbamate

To a solution of the oxime obtained in (a) (1.37 _

Parts by weight) in 20 parts by volume of dichloromethane were 0.65 parts by weight of methyl isocyanate and 1 drop of triethylamine admitted. The solution was refluxed for 5 hours and then evaporated to dryness. The N-methyl carbamate with a melting point of 57 to 59 ° C. was obtained by crystallizing the residue from ether.

Analysis:

CH ₁₀ N ₂ O ₂ S ₂ Calculated: C, 30.9; H 5.2; N 14.4; S 33.0 %

Found: C 31 * 1; H 5 * 3J N 14.2; S 32.8 % {

Example 4

Further 1,1-disubstituted formaldoximes were produced in accordance with the procedures described in Examples 1 to 3 synthesized and in a corresponding manner into the corresponding 1,1-disubstituted formaldoxime-N-methylcarbamate transferred, the properties of which are given in Table I below.

109838 / 1112-7

TABEL

N-methyl carbamate of the formula; 3

R ₂ SOH

C = N-O-C-N

RjX * CH ₃

- * R- X- R ₀ P. C analysis

ο ^{x 1} ^

CO

OO '

CO

⁰⁰ CH, O CH,

73-74 Ber. for N ₃ SO ₃ C ₅ H ₁₀ : C, 33.7; H 5.65; N 15.7; S 18.0 %

Found: C, 34.0; H 5.9; N 15.6; S 18.0 %

C ₂ H ₅ 86-88 calc. for N ₂ SO ₃ CgH ₁₂ : C 37.5; H 6.3; N 14.6; S 16.7 %

Found: C, 37.6; H 6.2; N 14.8; S 16.8 % ^

CH ₃ O CH ₂ = CH-CH ₂ 44-46 calc. for N ₂ SO ₃ C ₇ H ₁₂ : C, 41.2; H 5.9; N 13.7; S 15.7 % _OT

Found: C 4l.0; H 5.8; N 13.6; S 15.5 % co

TABLE I continued;

P. ⁰ C analysis

CH

CN-CH ₂ 131-133 calc. for N ₃ SO ₃ CgH ₉ : C, 35.4; H 4.4; S 15.8 %

Found

: C, 35.7; H 4.5; S 15.9 %

- * C ₂ H ₅

C ₂ H ₅

64-66 Ber. for N ₂ SO ₃ C ₇ H ₁₄ CC 40.7; H 6.84; N 13.6 % Found: C 40.9; H 6.7; N 13.5 %

C ₂ H ₅

CH ₂ = CH-CH ₂ 79-80 calc. for Found

rC 44.0; H 6.46; N 12.8; S 14.6: C 43.8; H 6.3; N 12.4; S 14.6

C ₃ H ₅

CN-CH ₂ 136-137 calc. for N ₃ SO ₃ C ₇ H ₁₁ IC 38.7; H 5.1; N 19.4; S 14.7

Found

: C, 39.0; H 4.9; N 19.0; S l4.7 %

(CH,) «CE

CH

87-89 Ber. for N ₂ SO ₃ C ₇ H ₁₄ : C 40.8; H 6.8; N 13.6; S 15.5 Found: C 40.8; H 6.8; N 13.7; S 15.6

co co co

TABLE I continued;

P. ⁰ C

analysis

(CH " ₃ ) ₂ CH 0 benzyl

78-80

Ber. for Found

: C, 55.3; H 6.4; N 9.9; S 11.3 % : C 55.5; H 6.4; N 9.9; S 11.2 %

0OCH ₀ = CH-CH,

to ^ά <

CH

64-66 Ber. for N _o S0-.C "H.,: C 41, 2; H 5.9; N 13.7; S 15.7 % Found: C 4l, l; H 6.0; N 13.7; S 15.9 %

CH ₂ = CH-CH ₂

C ₂ H ₅

Ber. for Found

: C, 44.0; H 6.5; N 12.8 % : C 44.3; H 6.2; N 13.4 %

CH ₂ = CH-CH ₂

CH ₂ = CH-CH ₂

67-69 Ber. for N ₂ SO ₃ C ₉ H ₁₄ : C, 46.9; H 6.1; N 13.9; S 12.2 % Found: C 47.1; H 6.1; N 14.2; S 12.2 %

TABLE I continued;

F. ⁰ C

analysis

Benzyl 0 CH ₂ = CH-CH ₂ 72-73 calc. for

Found C 55.7; H 5.7; N 10.0; S 11.4 % C 56.0; H 5.6; N 9.8; S 11.3 %

^CH

74-75 Ber. for N ₃ SO ₃ C ₁₀ H ₁₈ : C, 48.8; H 7.3; N 11.4; S 13.1 % Found: C 49.3; H 7.5; N 11.8; S 13.3 %

CH ₂ SCH-CH ₂

65-66 Ber. for N ₃ SO ₃ C ₁₂ H ₂₀ : C, 52.9; H 7.4; N 10.3; S 11.8 %

Found: C, 53.5; H 7.4; N 10.4; S 12.0 %

(CH ₃ ) ₂ CH S

CH ₂ = CH-CH ₂

56-58

Ber. for Found: C, 43.5; H 6.5; N 11.3; S 25.8 % : C 43.5; H 6.4; N ll, 4; S 25.6 %

CH ₂ = CH-CH ₂ S

CH ₂ = CH-CH ₂

45-46

Ber. for Found: C, 43.9; H 5.7; N 11.4; S 26.0 % : C 43.9; H 5.9; N 11.2; S 25.9 %

Example 5

Preparation of 1,1-diethoxy-formaldoxime-N-methyl-carbamate

(a) Production of N-chloro-diethyl-iminocarbonate

100 parts by volume of ethanol were added to a solution of 40 parts by weight of sodium hydroxide and 40 parts by weight of potassium cyanide in 300 parts by volume of water. The mixture was stirred, cooled to -10 ⁰ C and 71 parts by weight of chlorine was passed at a rate to keep the temperature below ⁰ ° C. The mixture was allowed to warm to room temperature and extracted with ether (3 x 100 parts by volume). The solvent was drawn off from the extract dried with sodium sulphate and the residue was distilled under reduced pressure and the iminocarbonate with a boiling point of 80 to 81 ° / 10 mm was obtained.

(b) Preparation of 1,1-diethoxy-formaldoxime

27.4 parts by weight of hydroxylamine hydrochloride were dissolved in 20 parts by volume of hot water, the solution was stirred, chilled in ice and a solution of anhydrous

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Potassium carbonate (14 parts by weight) in water (15 parts by volume) was added. The solution was cooled to below 5 ° C and a solution of N-chloro-diethyl-iminocarbonate (10 parts by weight) in ether (50 parts by volume) added dropwise over 30 minutes with vigorous stirring. That Stirring was continued for an additional 2 hours, ice added to the mixture to bring the temperature below 5 ° C hold, the ether layer separated and the aqueous layer extracted with ether (6 100 parts by volume). The combined and dried over sodium sulphate ether extracts were evaporated to dryness and the The residue is distilled under reduced pressure and 1,1-diethoxy-formaldoxime, K.p. 103 to 106 ° / 12 mm obtain.

(c) Preparation of 1,1-diethoxy-formaldoxime-N-methyl-carbamate

There were 4.7 parts by weight of 1,1-diethoxy-formaldoxime in a solution of 1.4 parts by weight of sodium hydroxide dissolved in 20 parts by volume of water and the mixture added dropwise over 30 minutes to a stirred, ice-cold Solution of 4.2 parts by weight of phosgene in 80 Parts by volume given dichloromethane. The mixture was stirred for a further 30 minutes, the dichloromethane layer

OWeiN «. « ^IsreCtSD 109838/1727

separated and added dropwise over 1 hour to a 25 # strength aqueous methylamine solution (25 parts by volume). The dichloromethane layer was separated aqueous layer extracted with dichloromethane (2 χ parts by volume) and the combined over sodium sulphate evaporated dried extracts to dryness. When the residue was rubbed with ice-cold ether obtained a white substance which was recrystallized from benzene / light petroleum (K.ρ. 40 to 60 °) and gave the N-methyl carbamate from P. II7 to 118 ° C.

Analysis:

Calculated for N ₂ O ₂₁ C ₇ H ₁ ^: C, 44.2; H 7.4; N 14.7 %

Found: C, 44.2; H 7.3; N 14.9 %

Example 6

Production of 1,1-dimethoxy-formaldoxime-N-methylcarbamate

Following the procedure of Example 1, but using methanol instead of the ethanol found in of step (a) was used 1,1-dirnethoxy-formaldoxime-N-methyl-carbamate with a melting point (after recrystallization from benzene / ether) of 75 to 77 ° G. received.

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Analysis:

Calculated for N ₂ O 1 -C ₅ H ₁₀ : C, 57.0; H 6.2; N 17.5 %

Found: C, 56.5; H 6.0; N 17.1 %

Example 7

Production of 1-A * thoxy-1-methylthioformaldoxime » N-phenylthionoc arbamate

A solution of 1-ethoxy-l-methylthioformaldoxime (0.95 parts by weight) in water (20 parts by volume) containing sodium hydroxide (0.28 parts by weight) was dropwise to a stirred ice-cold solution of thiophosgene (0.8 parts by weight) in benzene (70 parts by volume) given. The mixture was stirred for a further 50 minutes, separated the benzene phase and dried over sodium sulphate. .

The benzene solution was added dropwise into a stirred ice-cold solution of 0.7 part by weight of aniline and 0.8 parts by weight of triethylamine in 40 parts by volume of benzene are added, and the solution is stirred for a further 2 hours with water washed (2 50 parts by volume) and over sodium sulphate dried. Evaporation of the solution gave an oil which crystallized on standing and emerged from ether

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was recrystallized, the N-phenylthionocarbamate from the mp 93 to 94 ° C was obtained.

Example 8 Insecticidal effects of oximcarbamates

P The insecticidal effect of the according to the preceding Compounds obtained in the examples were tested as follows:

I. A solution of the compound in a concentration of 1 wt -.% In acetone was prepared and mounted in a micrometer syringe. 2 to 3 day old adult female house flies (Musca domestica) were anesthetized with carbon dioxide and 1 ul of the test solution was brushed onto the abdomen of the abdomen of each fly, treating 20 flies. The treated flies were kept for 24 hours in glass containers which contained some granulated sugar as fly food and the percentage of dead and moribund flies was then recorded.

II. An amount of 0.1 ml of a 1 percent by weight Solution of the compound in acetone was in each case in

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mixed in a beaker with 100 ml of water. Twenty 5 to 6 day old mosquito larvae (Aedes aegypti) added and the beakers kept for 24 hours · Then the percentage of dead and recorded moribund larvae.

III. The compounds were formulated as solutions or suspensions in water containing 20 wt .- ^ acetone and 0.05 wt -% Triton X 100 containing as a wetting agent.. The formulations contained 0.7% by weight of the compound to be investigated. Beet plants and broad bean plants trimmed to one leaf were sprayed with the formulations on the underside of the leaf. Spraying was carried out using a device delivering 72.6 l / ha (40 gallons per acre) with the plants moving under the spray on a conveyor belt. There were ten 8 days old diamond back moth larvae (Plutella maculipennis), ten wingless 6 days old Wicke mites (Megoura viciae) and ten adults 1 to 2 weeks old mustard beetle (Phaedon cochleariae) respectively placed on the sprayed leaves and placed each plant in a glass cylinder, the was closed at one end with a muslin sleeve. The morning

- 29 109838/1727

tality was counted after * 24 hours.

IV. In experiments with red spider mites (Tetranychus

telarius) in the greenhouse, leaf disks cut from French beans were sprayed as under III. One hour after spraying, the disks were populated with ten adult mites. The mortality was counted after 24 hours.

V. In experiments with larvae of the large cabbage white butterfly (Pieris brassicae), cabbage leaves were as shown below III splashed. Ten 8 to 10 day old larvae were placed on disks which were sprayed from the Leaves were cut out and placed in petrol dishes. Mortality was Counted 24 hours after the occupation.

The results of these tests are given in Table II below, A denoting 100 % killing, B partial killing and C denoting no killing of the test insects.

- TABLE II -

- JO -

109838/1727

TABLE II N-methyl carbamate of the formula

R ₂ X ₂

C = N-C-N

R ₁ X ₁

CH,

link X ₂ M.d. A.a insecticides evaluation P.b. M.v. T.t. ^R l X ₁ R ₂ S. A. C. P.c. P.m. A. A. B. CH ₃ O CH, S. A. A. B. A. A. A. A (r * OH ₃ 0 CH ₂ = CH-CH ₂ S. A. A. A. A. - A. A. OH ₃ 0 CN-CHg S. A. C. B. B. A. A. A. O ₂ H ₅ 0 CH, A. B.

cn cn co σι cn

TABLE II continued;

^R l link X ₂ M.d. Insecticidal evaluation A.a. P.c. P.m. P.b. M.v. T.t. C ₂ H ₅ X ₁ R ₂ S. C. B. A. B. A. A. B. C ₂ H ₅ O CHg = CH-CH ₂ S. B. A. C. C. B. A. C. 109838 (CH ₃ ) ₂ CH O CN-CHg S. A. A. A. A. A. A. A fjj / 1727 CCH ₃ ) gCH O CH ₃ S. B. B. A. B. A. A. A. O CHg = OH-CHg S. A. B. A. B. A. A. B.
t ig O CH ₃

CHg = CH-CHg O CHg = CH-CHg S

cn CO CD <X

Part setting TABLE II:

QO U) CD

link R ₂ ^X 2 M.d. Insecticidal evaluation P.m. P.b. M.v. T.t. ^X l OH ₃ S. A. A.a. P.c. B. A. A. B. 3 S. = CH-CH ₂ S. A. B B B. A. A. A. CH ₂ = CH-CH ₂ S CHj CH ₃ O A. B C C. B. A. C. CH, O C C

Example 9

Nematicidal effects of oxime carbamates

The in vitro action of the compounds according to the invention was determined by mixing an aqueous solution of the respective oxime carbamate with a suspension of larvae of the root nodule nematode (Meloidogyne incognita) in a watch glass. The watch glass was covered and ^{incubated in the dark at 23 °} C. for 24 hours. After incubation, the watch glass was illuminated and the nematodes observed for mobility under a microscope. The experiments were carried out twice and the results are listed in Table III below, the dose values LD and LD being determined.

50 90

- TABLE III -

109838/1727

TABLE III

N-methyl carbamates of the formula :

R ₂ S

C = N-O-C-N

R ₁ X ₁

CH,

-J ho -J

link • ^R i ^X l ^R 2 Mortification the nematode 16686 CH ₃ O CH ₂ = CH-CH ₂ LD ₉₀ PPm CD C ₂ H ₅ O CH ₃ 40 500 C ₂ H ₅ O C ₂ H ₅ 500 C ₂ H ₅ O CH ₂ = CH-CH ₂ 420 > 500 500 "500

Continued TABLE III;

CD Ca)

link ^R l H ^R 2 Mortification the nematode CHg = CH-CHg 0 CH, LD ₅₀ ppm LD ₉₀ PPm CHg = CH-CH g 0 CHg = CH-CHg 26O 460 CH ₃ S. OH, 280 460 (CEL) ₂ CH S. CHg = CJH-CHg 225 500 CHg = CH-CHg S. CHg = CH-CHg 65 120 35 85

CD OO CD CD

Claims (1)

PATENT CLAIMS: in which R ₁ and R _{2 are} identical or different and each represent an optionally unsaturated, optionally substituted hydrocarbon group, Rz and Rw are identical or different and each represent a hydrogen atom or an optionally substituted alkyl or aryl group and X ₁ , X «and X , are identical or different and each represent an oxygen or sulfur atom * 109838 ^p / ¹ 1727 2. Formaldoximcarbamate according to claim 1, wherein R ₁ and PU each a preferably substituted alkyl or alkenyl group and R-, and R ₁ . each represent a hydrogen atom, a lower alkyl group or a phenyl group. J), formaldoxime carbamates according to claim 2, wherein R, and Rp each represent an acyclic or alicyclic lower alkyl group which is optionally substituted by a halogen atom, a cyano group or a phenyl group or alkenyl group. 4. Formaldoximcarbamate according to claim 3, wherein R ₁ and R _{2 in} each case a methyl, cyanomethyl, ethyl, isopropyl, cyclohexyl, benzyl or allyl group and R, and Ru in each case a hydrogen atom or a methyl «- or phenyl group . 5. Formaldoxime carbamates according to claim 4, wherein at least one of the radicals X ₁ and Xp is a sulfur atom, Χ-, an oxygen atom, one of the radicals R, and R ^ is a hydrogen atom and the other is a methyl group and R ₁ and R _{2 are} each methyl -, ethyl, isopropyl, allyl or benzy! Group. - 2 - 109838/1727 6. Formaldoximcarbamate according to claim 4, wherein both X ₁ as Xg and X, an oxygen atom, one of the radicals R-, and R ₂ , a hydrogen atom and the other are each a methyl group and R ₁ and R _{2 are} each a methyl or ethyl group. γ. 1-Allylthio-1-methoxy-formaldoxime-N-methylcarbamate. 8. 1-Methylthio-1-ethoxy-formaldoxime-N-methyΙο arbamat. 9. 1-methylthio-1-isopropoxy-formaldoxime-N-methyΙο arbamat. 10. Process for the preparation of 1,1-disubstituted ten formaldoxime carbamates according to claim 1, characterized characterized in that one is a 1,1-disubstituted Oxime of the formula: R ₂ X ₂ C = N-OH II R ₁ X ₁ 109838/1727 with 1) phosgene or thiophosgene and a corresponding substituted amine of the formula: or with 2) an isocyanate or isothiocyanate of the formula: R ₃ NCX ₃ or with 3) a carbamoyl chloride of the formula: \ I ³ ■ ^N NC-C1 III reacted, where in the formulas R ^, Rp, R ₃ , R ₂ ,, X-, X "W and X-, have the meaning mentioned. 11. The method according to claim 10, characterized in that that the reaction is carried out in the presence of a base. 12. The method according to claim 11, characterized in that 10 9838/1727 that the base is a trialkylamine. Ij5 method according to claim 10, 11 or 12, characterized in that when the oxime is reacted with an isocyanate, isothiocyanate or carbamoyl chloride the reaction is carried out in the presence of a liquid organic reaction medium. 14. The method according to claim 1; 5, characterized in that that methylene chloride or benzene is used as the liquid organic reaction medium. 15. The method according to claim 10, 11 or 12, characterized in that in the implementation of the Oxime with phosgene or thiophosgene, the reaction is carried out in an aqueous system. 16. The method according to claim 10 to I5, characterized in that if at least one of the residues X, and Xp is sulfur, the oxime of formula II by Reacting a hydrocarbon halide of the formula RHaI with an alkali metal xanthate or trithiocarbonate the formula: RX -CS ⁰ M * IV 1 1 109838 ^ / 1727 and converting the obtained ester of the B'ormel: with hydroxylamine in the presence of a base and reacting the obtained thiohydroxamic acid of the formula: R ₁ X ₁ -C-NHOH VI with a hydrocarbon halide of the formula RgHaI, where R ₁ , R ₂ and X ₁ are as defined, M® is an alkali metal cation and Hal is a halogen atom. 17. The method according to claim 10 to I5, characterized in that if at least one of the radicals X ₁ and Xp is sulfur, the oxime of the formula II by reacting hydroxylamine with an alkali metal xanthate or trithiocarbonate of B'ormel IV in aqueous solution and subsequent alkylation of the resulting thiohydroxamic acid of B'ormel VI with a hydrocarbon halide of B'ormel RoHaI in the presence of a base. 109838/1727 18. The method according to claim 10 to 15, characterized in that when both X ₁ and Xp are sulfur, the oxime of the formula II by reacting carbon disulfide with hydroxylamine in alcoholic solution in the presence of a base and subsequent alkylation with a hydrocarbon halide of the formula RgHaI will be produced. 19. The method according to claim 16, I7 or 18, ^ j characterized in that the hydroxylamine in Form of the hydrochloride is used. 20. The method according to claim 16 to I9, characterized in that the base used is a gfrennzelehnet Trialkylamine is. 21. The method according to claim 18, 19 or 22, characterized in that the alcoholic solvent Is methanol. 22. Use of the 1,1-disubstituted Formaldoxime carbamates according to Claims 1 to 9 in combination with a carrier or a surface active agent or both as pesticides. 109838/1727 23 «Use according to claim 22 in the form of wettable Powders, dust preparations, granulates, solutions, encapsulated substances, emulsifiable concentrates, Emulsions or pastes.