DE1238904B - Process for the production of thiol or thionothiolphosphorus (- phosphonic) acid esters - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN MJTW> PATENT OFFICE C07f ^c .

EDITORIAL

Int. CL:

German class: 12 ο-23/03

UZl

Number: 1,238 904

File number: F 46711IV b / 12 ο

Filing date: July 24, 1965

Open date: April 20, 1967

PEST

The invention relates to thiol or thionothiol phosphor - (- phosphon-) acid esters of general constitution I.

OR ₁

R - C - O _{- CH 2 --S - CH 2} - S - ^{P X}

R,

(0

which have insecticidal properties and a process for their preparation.

In the above formula, R is a straight or branched QQ-alkyl radical or a cyclohexyl radical, R ₁ is a straight or branched alkyl group, while R _{2 is} a straight or branched alkyl or alkoxy or phenyl radical and X is an oxygen group. or is sulfur atom.

It has been found that thiol or thionothiolphosphorus (- phosphonic) acid esters of the general structure (I) are obtained smoothly and with good yields if Λ-acyloxy- «'• halodimethylthioether of the general formula is used in a known manner Production of thiol or
Thionothiolphosphorus (- phosphonic) acid esters

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Dr. Carl Metzger, Wuppertal-Elberfeld;

Dr. Ingeborg Hammann, Cologne

Salts of the general formula

j!

Me-S -K

OR ₁

(III)

RCO-CH ₂ -S-CH ₂ -HaI

(IT)

with thiol or. thionothiolphosphorus (- phosphonic) acids or with the corresponding free acids in the presence of acid-binding agents.

In the last-mentioned formulas, R, R ₁ , R ₂ and X have the meaning given above, while Hal stands for a halogen atom and Me stands for a monovalent metal equivalent or the ammonium group.

Let the course of the method according to the invention be

verdeuth'cht on the basis of the following reaction scheme:

X
l | , OR ₁

RCO-CH ₂ -S-CH ₈ -HaI + Me- SP

(IV)

-MeHaI il / ^OR i > R-C-O-CH ₂ -S-CH ₂ -S-CH ₂ -SP; '

all symbols have the same meaning as above.

In the above formulas, R stands, for example, for a straight or branched alkyl radical having 1 to 4 carbon atoms, such as the methyl, ethyl, n- and isopropyl, n-, iso- and sec-butyl groups, and also for the cyclohexyl radical; R ₁ preferably denotes n- or iso-alkyl radicals having 1 to 3 carbon atoms and R _{2 is} straight or

branched-chain alkyl or alkoxy groups with 1 to C atoms, while X is preferably a sulfur atom, a chlorine atom or a bromine atom, MBi .Me an alkali metal equivalent, for example a cafium ₇ for sodium ion or the ammonium group. "'J

The starting material! ^, For the implementation the process according to the invention required a-acyloxy - «'- halodimethylthioether are so far in the

. 709 550/368

3 4

Literature not yet described; they can water and dry the organic phase will

however, using known methods, the solvent is also removed by distillation and the

Can be easily prepared on an industrial scale, remaining residue, if possible, in vacuo

by, for example, distilling according to FG Bordwell or by heating to about 100 ^° C.

and B. M. P i 11 ("Journal of the American Chemical 5 reduced pressure of the last volatile

Society ", Vol. 77 [1955], p. 572) freed acylated oxydimethyl fractions and purified in this way

thioether with halogenating agents, for example nigt.

Sulfuryl chloride, reacted in methylene chloride. As already mentioned, the products required as starting materials for this purpose stand out from comparable comparable products (X-Acyloxydimethylthioäther can for their part be obtained in manageable substances through excellent insecticidal properties (see, for example, acaricidal properties. The biocidal Effect H. Böhme, H. Fischer and R. Frank. Sets in quickly and stops for a long time.From this "Liebigs Annalen der Chemie", vol. 563 [1949], p. 54, the basis are the compounds according to the invention L. Horner and E. Jürgens, op. cit., vol. 602 on combating harmful sucking and [1957], p. 135, or L. Horner and P. Kaiser, 15 biting insects, dipteras and mites (Acarina) op. cit., vol. 626 [1959], p. 19). They are also accessible - mainly used in plant protection,
borrowed by a previously unknown method by reacting acid halides with

Dimethyl sulfoxide in the presence of acid-binding agents, example 1
z. B. tertiary bases, especially triethylamine, in inert 20

dry solvents, such as ether, tetrahydro- γ "

furan, benzene, methylene chloride, chloroform, tetra- Il ^ /

chlorocarbon, etc., at temperatures between CH ₃ —C — O — CH ₃ —S — CH ₂ —S — P — OCH ₃

0 and 6O ⁰ C. ^X OCH _S

The reaction according to the method is generally as
carried out in the presence of inert organic solvents or diluents. As such, One come dropwise at 6O ⁰ C 0.1 mole "acetyloxy-a'-chloro virtually all solvents which are in which dimethylthioäther to a solution of 0.1 mole of the above-mentioned tbiol- thionothiolphosphor- or sodium salt of Dissolve 0,0-dimethylthionothiolphosphorus (- phosphonic) acid salts. Particularly proven 30 acid in 250 ml acetonitrile. It is immediately separated from the lower molecular sodium chloride for this purpose. After stirring for 2 hours with aliphatic nitriles such as aceto- and propionitrile. the specified temperature, the mixture is

Instead of using the aforementioned salts, you can cool, pour into 500 ml of ice water and add benzene

the corresponding free acids are also extracted as starting materials. The benzene solution is washed with water,

use materials and these in the presence of 35 dry them over sodium sulfate, filtered, evaporated

acid-binding agents in the sense of the present the filtrate from the solvent and distilled the

Invention with the relevant (x-acyloxy-ix'-halogen residue under reduced pressure. The oc-acetyl-

bring dimethylthioäthem to reaction. As an acid oxy-a'-O.O-dimethylthionothiolphosphoryl-dimethyl-

Alkali carbonates are particularly suitable acceptors, and thioether boils under a pressure of 2 Torr

alcoholates, such as potassium or sodium carbonate, 40 116 to 12O ⁰ C. The product has the refractive

methylate or ethylate, but also tertiary aliphatic «, index ng ¹ = 1.5292 and shows a CO band at

aromatic or heterocyclic amines, e.g. B. Tri- 1755 cm " ¹ .
ethylamine, dimethylaiiilin or pyridine.

Furthermore, the implementation according to the method of Example 2
at a slightly to moderately elevated temperature

taken, with the reaction temperatures in one ° g

larger interval can be varied. In general! ^ '

my work is between 40 and 100 ° C, preferably CH ₃ —CO — CH ₂ —S — CH ₂ —S — P _; - OC ₂ H ₅

at 50 to 70 ^° C. OC ₂ H ₅

To carry out the inventive 5 °
Generally equimolar amounts are used

the reactants reacted, the Λ-Aycl- 0.1 mol Ο, Ο-diethylthionothiolphosphoric acid Na-

oxy-ac'-halo-dimethylthioether in the case of the above an- trium is dissolved in 250 ml of acetonitrile. To this

given temperatures with stirring to the solution solution is added dropwise with stirring 0.1 mol of a-acetyl

of the relevant thiol or thionothiolphosphorus 55 oxy-a'-chloro-dimethylthioether. It immediately falls

(-phosphonic) acid salt in a suitable lotium chloride. After stirring for 2 hours the

solvent is dripped. Mixture at the specified temperature is

In addition, it has proven to be expedient to cool the former down and stir it into 500 ml of ice water, the reaction mixture after combining the starting components, extracting the reaction product to complete the conversion, using benzene, washing the organic phase with water, settling for a long time ( 1 to 3 hours), if necessary, dry over sodium sulfate, filtered and distilled with warming, to stir. The solvent is then removed from the filtrate. The back batch is poured into water and the tx-acetyl-oZ-OP-diethylthionothiolphos precipitated thiol or thionothiolphophoryl dimethylthioether, which remains in oily form, cannot be distilled. Therefore (-phosphonic) acid esters with the help of an inert organic 65 are the volatile components under reduced, niche solvent, for example a. ¹ ; Carbon pressure removed at 120 ° C / 0.2 torr. Thereafter, the hydrogen, such as gasoline, benzene, toluene or xylene, product shows a refractive index of n * S - 1.5257 and extracted. After washing the extract with a CO band at 1755 cm " ¹ .

5 6

Example 3 cannot be distilled. The volatile components are therefore

Q under a pressure of 0.01 to 0.05 Torr at 100 ^° C

IS removed. The index of refraction of the compound is

CH ₃ CH ₂ -C -O -CH ₂ S CH ₁ -S-Pt-OCH. ₅ "* ^{= 1} ^ ^{dne 0} ^ *" ¹ * * " ^ ¹⁷⁵⁵ ^ " * '

OCH ₃ example 6

0.1 mol of the sodium salt of O, O-Di- ° is dissolved

methylthkmothiolphosphoric acid in acetonitrile and ³ \ ι! /,

added dropwise at 50 ° C. with stirring to this solution io 'CH-CH ₂ -CO CH ₂ S CH ₈ -S-PQ-OCH ₈

0.1 mole of propionyl-cx'-chloro-dimethylthioether. It £ jr y OCH

Sodium chloride is formed immediately. One stirs the ^s "

Mix for 2 hours at the specified temperature,

The reaction mixture is then cooled, in a solution of 0.1 mol of the sodium salt of

500 ml of ice water, the organic phase with 15 O, O-Dimethylthionothiolphosphorsäurein250mlAce benzene-extracted, this benzene solution with tonitril at 50 ⁰ C was added dropwise with stirring, washed water, dried over sodium sulfate, with 0.1 mol ct-iso-valeryl oxy-a'-chloro-dimethylthiofiltriert and the solvent is displaced from the filtrate from ether. Sodium chloride precipitates out immediately. distilled. The surviving "-propionyl a'-OO-di- After stirring for 2 hours at the indicated methylthionothiolphosphoryl-ao dimethylthioäther boiling temperature cools raan from the mixture and poured under a pressure of 0.6 torr at 105 to 106 ⁰ C. 500 ml of ice water. The organic phase is ^{extracted with benzene, the compound has the refractive index wS 0} = 1.5250, the benzene solution is washed with water and shows a CO band at 1755 cm " ^1. , Dried over sodium sulfate, filtered and

the solvent is distilled off from the filtrate. Of the

Example ^{4 a} 5 "-iso-valeryl-a'-OO-dimethylthionothiolphosphoryl-

dimethylthioether can also be used under greatly reduced

Do not distill under pressure. The volatile components

l ^! / Therefore be removed at 0.01 Torr and 10O ⁰ C. That

CH ₃ -CHs-CO-CH ₂ -S-CH ₂ -SP- ^ OC ₂ H ₈ product has the refractive index / i | ' ^s = 1.5180

OC ₂ H ₅ 30 and a CO band at 1755 cm " ¹ .

Example 7

To a solution of 0.1 mol of the sodium salt _

of O.O-diethylthionothiolphosphoric acid in 250 ml 1 g

Acetonitrü added dropwise at 6O ⁰ C with stirring, 0.1 mole 35 / ~ '~ \ ^/;

«-Propionyl-oxy-Ä'-chloro-dimethylthioether. It differs- \ H / -CO-CH ₂ -S-CH ₂ -S- P- 'OCH _; , immediately detects sodium chloride. After 2 hours ^ OCH

Stir the mixture at the specified temperature

the former is cooled, poured into 500 ml of ice water, 0.1 mol of Ο, Ο-dimethylthionothiol-

the organic phase extracted with benzene, the 40% phosphoric acid sodium in 250 ml acetonitrile with benzene solution washed with water, ^{dried over 50 0} C with stirring 0.1 mol «-hexahydrobenzoyl-oxy-sodium sulfate, filtered, from the filtrate jc'-chlorine -dimethylthioether. Immediately separates Nadas solvent evaporated and the residue trium chloride. After stirring for 2 hours the distilled under reduced pressure. The Λ-propionyl reaction mixture at 50 "C is cooled, a! - O, O - diethylthionothiolphosphoryl - dimethylthio 45 poured into 500 ml of ice water, the organic phase is ether at 121 to 125 ° C / 0.5 Torr; it has been extracted with benzene, the benzene solution has been washed with water with the refractive index η ™ = 1.5052 and a CO band, and the organic layer is washed over sodium sulfate

at 1755 cm- ¹ . dried, filtered and from the filtrate the solution

_R. . . medium distilled off. The «-hexahydrobenzoyl-

For example 5 ₅₀ ^ '- OO-dimethylthionothiolphosphoryl-dimethylthio-

O ether cannot be distilled. The volatile components

, S are therefore distilled under a pressure of

CH ₃ CH ₈ - CH ₂ C- O- CH ₂ -S-CH ₂ -SP ^ OCH ₄ J ^{7 T} _u ^orr *** ¹⁰⁰ ° £ ^εη ^ ™ * · ^Da f ^ ^ 1

\ Refractive index n% ~ 1.4982 and a CO band at

° CH ₃ 55 1755 cm- ¹ .

The oc-acyloxy required as starting materials

0.1 mole (Xn-butyryl-ix'-chloro-dimethylthioäther or "acyloxy oc'-halo-dimethylthioäther can be obtained at 5O ⁰ C with stirring to 0.1 mole of O, O-di- example, as follows are: sodium methylthionothiolphosphoric acid, dissolved in "" , .. ,,.,

250 ml of acetonitrile, added dropwise. 60 1 · «-Acetyl-oxy-dimethylthioather is formed immediately

Sodium chloride. After stirring for 2 hours, the MI CH ₃ -COO-CH ₂ -S-CH ₃

Schung at 50 ⁰ C this is cooled and poured into

500 ml ice water. Then the organic 1 mole of acetyl chloride is in 100 ml dry

Phase extracted with benzene, the benzene solution dissolved with benzene. To this solution is added dropwise, washed with water, dried over sodium sulfate, 65 stirring at 2O ⁰ C was slowly added a mixture of each filtered and from the filtrate the solvent off 1 mol of dimethyl sulfoxide and triethylamine in 100 ml distilled. The remaining "-n-butyryl-a'-CO-di- dry benzene. After stirring the methylthionothiolphosphoryl - dimethylthioether is reaction mixture, the triethylammonium is

Sucked off hydrochloride, the solvent was distilled off from the filtrate at normal pressure and the residue fractionated over a column in vacuo. The Λ-acetyl-oxy-dimethylthioether boils under a pressure of 10 Torr at 47 ° C. The product has the refractive index η "= 1.4551.

2. "-Hexahydrobenzoyi-oxy-dirnethylthioether

H V-COO-CH ₂ -S-CHs

A solution of 1 mol of <x-propionyl-oxy-dimethylthioether in 300 ml of dry methylene chloride is added at room temperature and under vigorous Stir slowly dropwise with 1 mole of sulfuryl chloride. After the evolution of gas has ceased, the solvent is distilled off and the residue fractionated on a column. The «-propionyl-oxy- «.'- chloro-dimethylthioether goes under a pressure from 17 torr at 36 to 39 ° C above.

15th

1 mol of hexahydrobenzoyl ^{chloride is slowly added dropwise at 20 °} C. to a mixture of 1 mol each of dimethyl sulfoxide and triethylamine in 400 ml of dry ether. The reaction mixture is then refluxed for 3 hours, cooled, the precipitated triethylammonium hydrochloride is filtered off with suction, the solvent is distilled off from the filtrate and the residue is fractionated on a column, the α-hexahydrobenzoyl-oxy-dimethylthioether under a pressure of 2.5 torr 90 to 91 ⁰ C passes. The product has the refractive index nf = 1.4830.

3. Ä-Acetyl-oxy - ^ '- chloro-dimethylthioether
CH ₃ -COO-CH ₂ -S-CH ₂ -Cl

1 mol of acetyl-oxy-dimethylthioether is dissolved in 300 ml of dry methylene chloride, and 1 mol of sulfuryl chloride is slowly added dropwise to this solution at room temperature and with vigorous stirring. After the evolution of gas has ceased, the solvent is removed by distillation and the residue is fractionated over a column under reduced pressure. The (x-Acetyl-oxy-a'-chloro-dJmethylthioäther boils at 32 to 35 ^e C / 22 Torr.

35

4. a-Propionyl-oxy-a'-chloro-dimethylthioether
CH _S - CH ₂ - COO - CH ₂ - S - CH ₂ - Cl

Claims (1)

Claim: Process for the production of Tluol- resp. Thionothiolphosphoric (phosphonic) acid esters, thereby marked that one in on known way «-Acyl oxy- * '-halogen -dimethylthioätber of the general formula R - C - O - CH ₂ - S - CH ₈ - Hai with thiol- or tbionothiolphosphor - (- phosphon-) acid salts of the general formula Me — SP ( OR ₁ or with the corresponding free acids in the presence of acid-binding agents, where R is a QQ-alkyl radical or the cyclohexyl radical, R _{1 is} an alkyl group, R _{2 is} an alkyl or alkoxy or phenyl radical, X is an oxygen or Sulfur, Hal represents a halogen atom and Me represents a monovalent metal equivalent or the ammonium group. A test report was displayed when the registration was announced. 709 550/368 4.67 0 Bundesdruckerei Berlin