DE1072616B - Process for the preparation of 0,0-D'ialkylphosphoric acid esters of substituted butenols which are particularly suitable as pesticides - Google Patents

Description

It is known that triesters of phosphoric acids are obtained when dialkoxyphosphoric acid monohalides are used with alcohols or phenols. In the process known from US Pat. No. 2,536,647 for example, the alkali salt of p-nitrophenol is converted to bis-i / S-chloroethyl thiophosphoryl chloride, which is obtained by reacting sulfur with chlorine bis (/ I-chloroethyl / phosphite) act, whereby the bis (chloroethyl) p-nitrophenyl thiophosphate is formed. As alcohols one has for the reaction with phosphoric acid ester halides both saturated, unsaturated, straight-chain or branched chain alcohols as well as thioalcohols are used. For example, you get by repositioning of methallyl alcohol or its alkali salts with phosphoric acid ester halides, e.g. B. with O-Möno- or 0,0-dialkylphosphoric acid halides, the corresponding Methallyl phosphates (see U.S. Patent 2,176,416).

Many of the phosphoric acid triesters that have already been produced in large numbers are of considerable industrial importance and are known as killing agents for insects or rodents or can be used as corrosion inhibitors, flame retardants, flotation agents, Use plasticizers or as additives for high pressure lubricants.

From US Pat. No. 2,394,829 it is known that Phosphoric acid esters of the AHyl type, i.e. compounds of the general formula

O = P ^ -YR ₄ R ₃

¹ OCC = CR ₂ R ₁

in which R ₁ to R _{5 are} hydrogen or an optionally substituted hydrocarbon radical and X and Y are halogen or the radical OR in which R is a cyclic or acyclic, saturated or unsaturated hydrocarbon radical, in particular for the radical

-CC = CR ₂ R ₁

Method of manufacture

of as a pesticide

particularly suitable O, O-dialkyl

pho sphors aur eestern

substituted butenols

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

Dr. Heinz Pohlemann, Dr. Siegfried Winderl,

Ludwigshafen / Rhine,

Dr. Herbert Stummeyer, Mannheim,

and Dr. Heinrich Adolphi, Limburgerhof (Palatinate),

have been named as inventors

It has been found that new O, O-dialkylphosphoric acid esters, particularly those suitable for combating pests, can be obtained substituted butenols of the general formula

RO. .X

RO '0-CH-CH ₂ -Y

CH = CH ₂

where R and R 'are alkyl groups, X is an oxygen or sulfur atom, Z is hydrogen or an optionally substituted alkyl, alkenyl, cycloalkyl or aryl radical and Y is an oxygen or sulfur atom or a sulfone, sulfoxy or imino group , whose hydrogen atom bonded to the nitrogen is optionally substituted by an alkyl, alkenyl or cycloalkyl group, or in which the hydrogen atom is replaced with Z together by a _{radical consisting of four or five CH a} groups, which has one with the N atom nitrogen-containing ring is obtained when 0,0-dialkylphosphoric acid monohalides of the general formula

stands, have plasticizing properties for plastics and as a solvent, intermediates for organic syntheses or for the production of plastics can be used.

RO.

RO '

, X

^v Hal

wherein R and R 'and X have the preceding meaning

909 708/338

and Hal is a halogen atom with a butene- (3) -ol- (2) substituted in the 1-position of the general formula

HO-CH-CH = CH ₂
CH ₉ -YZ

converts, where Y and Z have the meaning given.

Suitable 1-substituted butene- (3) -ol- (2) compounds, those for Y contain an oxygen atom and in which Z is a saturated or unsaturated one, optionally substituted hydrocarbon radical, e.g. B. is an alkyl, alkenyl, cycloalkyl or aryl group are for example l-methoxy-buten- (3) -ol- (2), also the corresponding 1-ethoxy, 1-propoxy, 1-butoxy, 1-pentoxy, 1-heptoxy-, 1-allyloxy-, 1-chlorallyloxy-, 1-phenoxy-, 1-chlorophenoxy, l-dichlorophenoxy, 1-nitrophenoxy, 1-chloronitrophenoxy, 1-alkoxyphenoxy derivatives of Butene- (3) -ols- (2). The derivatives of butene- (3) -ol which have an imino group in the 1-position are also particularly suitable carry, which, as described above, is bound to other radicals and optionally substituted. Examples of such compounds are: 1-methylamino, 1-ethylamino, 1-propylamino, 1-butylamino, 1-pentylamino, 1-hexylamino, 1-allylamino, 1-Cyclohexylamine-, 1-Cyclooctylamino-, 1-Dimethylamino-, 1-diethylamino, 1-dipropylamino, 1-dibutylamino, 1-diallylamino, 1-methylethylamino, 1-ethylenimino, 1-pyrrolidyl, 1-anilino, 1-chloroanilino, 1-nitroanilino, ! - (chloro / methylanilino- and 1- (chlorodimethylanuino) -butene- (3) -ol- (2) as well as much-aminobutene- (3) -ol- (2). Of the butene- (3) -ol- (2) compounds which, in the 1-position, are linked to a saturated or unsaturated aliphatic, contain cycloaliphatic or aromatic hydrocarbon radicals or hydrogen-bonded sulfur atoms, where the sulfur atom can also be oxidized to a sulfoxy or sulfone group, are for example 1-ethylmercapto-, 1-phenylmercapto-, 1-ethylsulfoxy-, 1-phenyl-sulfoxy-, 1-ethylsulfonyl-, 1-phenylsulfonyl-buten- (3) -ol- (2) called.

Of the 0,0-dialkylphosphoric acid monohalides which can be used as the second reaction component of the general formula given are especially the chlorides, bromides and iodides of 0,0-dialkylphosphoric acids and 0,0-dialkylthionophosphoric acids are suitable, • those in the alkyl groups are the lower members of the homologues Contain series of alkyl radicals, in particular alkyl radicals with 1 to 4 carbon atoms. In the following, these monohalides of 0,0-dialkylphosphoric acid or the O.O-Dialkylthionophosphoric acid briefly with O, O-dialkylphosphoric acid monohalides designated. There are readily available known compounds that are known to be for example by reacting phosphorus oxychloride or phosphorothiotrichloride with the calculated amount an aliphatic monohydric alcohol. As representatives for this reaction component are before especially dimethoxyphosphoric acid monochloride, dimethoxyphosphoric acid monobromide and iodide, also the corresponding ones Halides of 0,0-diethyl-, 0,0-dipropyl- and 0,0-dibutylphosphoric acid as well as the chlorides, bromides and iodides of 0,0-dimethylthionophosphoric acid, 0,0-diethylthionophosphoric acid, 0,0-dipropylthionophosphoric acid and 0,0-dibutylthionophosphoric acid.

The reaction is carried out by combining the two reaction components, in general it does not matter which component is presented. The dialkylphosphoric acid monohalide is expediently added to the substituted butenol. The starting materials are used in approximately equivalent amounts. Occasionally, however, it can also be advantageous to use one or the other starting material in a slight excess to use.

Working in the presence of inert diluents can be advantageous. Can be used as a diluent z. B. hydrocarbons such as benzene, toluene, xylene, gasoline, cyclohexane, or chlorinated hydrocarbons, ζ. Β. Methylene chloride, chloroform, ethylene chloride and carbon tetrachloride, to serve.

The implementation already takes place noticeably in the cold, but it is expedient to work at higher temperatures, eg. B. at about 15 to 130 ⁰ C, advantageously at about 40 to 50 ⁰ C, optionally in closed vessels. It is advisable to use hydrogen halide binding agents when carrying out the process, e.g. B. pyridine or other tertiary amines whose boiling points are advantageously above the reaction temperature, e.g. B. triethylamine or tributylamine to be added in order to bind the hydrogen halide released during the reaction. Alkali carbonates or alkali bicarbonates can also be used for this purpose.

The new O, O-dialkyl phosphoric acid esters obtained the substituted butenols are strongly insecticidal and ovicidal and are also characterized by that they are less toxic to warm-blooded animals than other known, insecticidally active phosphoric acid esters.

As the following test shows, the phosphoric esters according to the invention of the substituted Butenols over other phosphoric acid esters suitable for pest control, for example the bis (j # -chorethyl) -p-mtrophenyl thiophosphate known from US Pat. No. 2,536,647 through a systemic effect. Leaf-bearing rungs of Vivia faba are placed on those on the Underside of the leaves of adult, wingless females of Acyrtosiphum onobrychis sitting in Vessels containing an aqueous preparation of the test substances. You then fold it over the test animals perforated plastic bowl that is pressed against the leaf with a clamp. After 24 hours one counts the dead animals.

If the test substances used are those prepared according to the invention according to Example 3 of the description Compound of formula

C ₂ H ₅ -OS

CH = CH ₂

and as a comparative substance the mentioned bis (ß- chloroethyl) p-nitrophenyl thiophosphate (II) known from the USA patent specification 2,536,647 in aqueous preparations containing 0.04% and 0.02% active ingredient, the following results are achieved:

substance Killing of
Acyrtosiphum
onobrychis after
24 hours in% 65
(I) 0.04 ° / ₀ aqueous preparation
(I) 0.02 ° / ₀ aqueous preparation
(II) 0.04 ° / ₀ aqueous preparation
7 ° (II) 0.02% aqueous work-up 93
46

The parts given in the examples are parts by weight.

example 1

56.4 parts of diethoxythionophosphoric acid monochloride are allowed to run slowly into a mixture of 37.7 parts of 1-propylamino-buten- (3) -ol- (2) and 23.7 parts of anhydrous pyridine with vigorous stirring. The temperature rises to 5O ⁰ C. After the addition has ended, the reaction is completed by stirring for a further 4 to 5 hours at 45 to 50 ^° C. The reaction product is cooled to room temperature, 20 parts of water and 100 parts of benzene are added, the mixture is stirred thoroughly and the aqueous layer is separated in a separator from the non-aqueous layer. The latter is dried with sodium sulfate. After the solvent has been distilled off, 72 parts of a non-distillable oil remain.

The compound has the formula:

C ₂ H ₅ O,

C ₂ H ₅ '

; pf

■ OCH - CH ₂ - NH - C ₃ H ₇

Cxi = ^{= z} CJEl ₂

Thorough stirring, slowly run in 37.6 parts of diethoxythionophosphoric acid monochloride. The reaction temperature rises to 45 ° C. After completion of addition, stirring to 50 ⁰ C and worked up as in Example 1 for 5 hours at 55th After the solvent has been distilled off, 60 parts of the compound of the following formula are obtained as a non-distillable oil:

C ₂ H ₅ OS

C ₂ H ₅ O "

'OCH-CH ₂ -HN-

CH = CH ₂

Example 5

42.4 parts of 1-phenylsulfonyl-buten- (3) -ol- (2) and 15.8 parts of pyridine are mixed and 37.6 parts of diethoxythionophosphoric acid chloride are run in with thorough stirring. The mixture is subsequently stirred at 50 to 60 ^° C. for 5 hours, worked up as indicated in Example 1, and parts of the new phosphoric acid ester are obtained as a non-distillable oil of the formula:

C ₂ H ₅ O, .S

Example 2

56.4 parts of diethoxythionophosphoric acid monochloride are allowed to run into the mixture of 42.9 parts of diethylaminobutene- (3) -ol- (2) and 23.7 parts of pyridine. After completion of the addition the mixture is stirred for a further 5 hours at about 6O ⁰ C and worked up as in Example. 1 After the solvent has been distilled off, 68 parts of an oil which cannot be distilled remain as residue.

The compound has the following formula:

C ₂ H ₅ O _x , S.

40

C ₂ H ₅ O "

■ och — ch ₉ —n:

C ₂ H ₅ O ⁷ ^ OCH-CH ₂ -SO ₂ -CH = CH ₂

Claims (2)

PATENT VISIONS: 1. Process for the preparation of 0,0-dialkylphosphoric acid esters which are particularly suitable as pesticides substituted butenols of the general formula RO, , X CH = CH, Example 3 45 56.4 parts of diethoxythionophosphoric acid monochloride are added to 39.6 parts of 1-ethylmercapto-buten- (3) -ol- (2) and 23.7 parts of anhydrous pyridine with thorough stirring. The mixture is then stirred for 5 hours at 40 to 45 ° C. The reaction mixture is cooled to room temperature, about 20 parts of water and 100 parts of benzene are added, the mixture is stirred thoroughly and the layers are separated. The benzene solution is then washed with dilute hydrochloric acid and with water and dried over sodium sulfate. The solvent is distilled off, the residue can be distilled with partial decomposition. . At ₀ bp, 5 = 130 to 135 ° C 74Teile is obtained the compound of the following formula: C ₂ H ₅ O, .S : p. C ₂ H ₅ O ' SC ₂ H ₅ 60 ^x OCH —CH ₂ CH = CH ₂ ^b5 Example 4 In a mixture of 32.6 parts of 1-anilino-buten- (3) -ol- (2) and 15.8 parts of anhydrous pyridine is added R'O OCH-CH = CH, CH ₂ -YZ where R and R 'are alkyl groups, X is an oxygen or sulfur atom, Z is hydrogen or an optionally substituted alkyl, alkenyl, cycloalkyl or aryl radical and Y is an oxygen or sulfur atom or a sulfone, sulfoxy or imino group whose hydrogen atom bonded to the nitrogen is optionally substituted by an alkyl, alkenyl or cycloalkyl group, or in which the hydrogen atom with Z is replaced by a _{radical consisting of 4 or 5 CH 2} groups which is connected to the N atom forms a nitrogen-containing ring, characterized in that 0,0-dialkylphosphoric acid monohalides of the general formula RO, R'O ' , X ¹ shark wherein R and R 'as well as X have the above meaning and Hal is a halogen atom, with an in 1-position substituted butene- (3) -ol- (2) of the general 7 8 my formula 2. Method according to claim 1, characterized λττ records that one is the implementation in the presence Carries out hydrogen halide binding agents. CH ₂ -Y reacting, in which Y and Z are as defined I ⁿ contemplated publications: to have. U.S. Patent No. 2,394,829, 2,536,647. © 309 708/338 12.59