DE1768662C3 - 1 -Alkoxy- or 1-aryloxy-1-thiono-3halogen- or -3-alkylphospholines, processes for their preparation and their use - Google Patents

Description

or.

CH,
\ "

CH-CH ₂
R.

C = CH

P — O —R '

P —O — R '

CH ₂ - CH ₂

where R is chlorine or methyl, while R 'is C ₁ - to C ₄ -alkyl, allyl, 2-chloroethyl or phenyl, 4 - methylmercaptophenyl, 4 - tertiary - butylphenyl or trichlorophenyl.

2. Process for the preparation of the compounds according to claim 1, characterized in that S
PX

CH-CH,

or.

= CH

Jl

P-X

CH ₂ -CH,

with alcohols or phenols of the formula
HO-R '

preferably reacted in the presence of acid binders, where X is a halogen atom. 3. Use of the compounds according to claim 1 for combating nematodes, insects, Mites and soil-dwelling fungi.

Phosphoric or thiophosphoric acid esters with nema- • odicidal Effects have been known from the literature for a long time. For example, in the USA.-Patent 27 61806 of the Ο, Ο-DiethyI-O - (2,4-dichlorophenyl-Hhionophosphorsäureester • has been described as effective in this respect. Weilerhin the O, O-diithyl-O- (4-methylmercapto-phenyl -) - known from the German laid-open ■ scripts 11 01 406 and 11 56 274 or 0,0-di-ethyl-O-pyrazinyl- (2) -thionophosphoric acid ester through a nematodicidal effectiveness.

On the other hand, have pesticidally effective Phosphorfczw. Thiophosphoric acid esters are known to be mostly one

\ _- rl

P-X + HO —R '

not inconsiderable toxicity to warm-blooded animals. For example, the DL _{50 of} the above-mentioned Ο, Ο - diethyl - O - (2,4 - dichlorophenyl) thionophosphoric acid ester in rats per os 270 mg / kg animal (cf. G. Schrader, "The development of new insecticidal phosphoric acid esters", Verlag Chemie, Weißheim / Bergstrasse, 3rd edition [1963], p. 210).

In contrast, the invention relates to the subject matter characterized in the claims.

The course of the implementation according to the process can be shown by the following equation will:

C CH ₂

\ ^S

CH-CH ₁

P - O - R '

CH CH ₂

C = CH

O— R '

C_ H? "C H5

The fas as starting materials for carrying out process required l-thiono-l, 3-dihalo or -l-halo-3-alkylphospholine one hand and the respective alcohols or phenols are generally uniquely defined by the above formulas, on the other hand.

Phenols can be used for the conversion, for example:

94,5- and 2,4,6-trichlorophenol.

The 1-thiono- ι ο required as starting materials 13-halogen- or -l-halogen-3-alkyl-phospholines are partly already described in the literature and Jonnen can also be produced on an industrial scale using various known methods.

Either one sets the corresponding oxo compounds according to the method of M. J. K. a b a c hnik (Dokl. Akad. Nauk. SSSR, Vol. 110 [1956], 5; 217) according to the following equation with phosphorus pentasulfide around

25th

or leaves 1,1,1-trihalophospholines, as in the DT-AS 11 99 264 described with hydrogen sulfide react:

PX + H ₂ S

P-X + 2HX

According to the information provided by G. M. Bogoljubow et al. (Z. Obs. Chim. [USSR], vol. 33 [1963], pp. 783 and 2419) and DT-AS 11 99 264 are easily accessible.

As can be seen from the above formulas, some migration may occur in the esterification reaction of the double bond of the thionophospholine ring from the 3,4- to the 2,3-position and vice versa. Mixtures of two isomers are therefore obtained in the reaction. Such shifts of double bonds in phospholines are known from the literature (cf. for example »H. Weitkam ρ and A. Körte, Z. analyt. Chem., Vol. 204 [1964], pp. 245 to 263 ", as well as" K. Hasscrodl et al. Tetrahedron, 19, 1563 [1963]). After Weit came ρ and Korte (loc. Cit.) Can do the exact position of the double bond can be determined by nuclear magnetic resonance and ultraviolet spectroscopy. Furthermore, it is easily possible by means of suitable separation methods (e.g. separation columns, preparative gas chromatography or fractional distillation over particularly effective columns) the two isomers 2: u separate. The course of such a separation and the purity of the products obtained can be determined Follow or determine by thin layer chromatography. Also in the production mentioned above the starting products more appropriately by sulphurisation Oxo compounds can already cause a shift in the double bond in the specified Be wise.

However, since both isomers are practically equally effective, the products can be used as a pesticide Pesticides do not require the separation of the mixture. The strong biocide, in particular nematicidal activity of the 1-alkyl or l-aryl-l-thiono-3-halogen according to the invention or -3-alkylphospholine could not in any way be foreseen once the products have proven to be almost non-toxic to warm-blooded animals, on the other hand, compounds of analogous constitution neither have an insecticidal effect nor a special one biological effect was even known. Provide the new substances according to the present invention thus a real enrichment of the technology.

The implementation according to the process is preferably carried out in the presence of a solvent or diluent performed. As such, an excess of the alcohol to be converted can be used, if the latter is liquid under the conditions of the reaction. Otherwise there are also inert ones organic solvents such as ketones (e.g. acetone, methyl ether, methyl isopropyl or methyl isobutyl ketone), Ethers (for example diethyl ether, di-n-butyl ether, dioxane or tetrahydrofuran), and optionally chlorinated aliphatic or aromatic hydrocarbons, for example methylene chloride, Di-, tri- and tetrachloroethane. Chloroform, carbon tetrachloride, benzene. Chlorobenzene, toluene or Xylene into consideration.

The products according to the invention are preferably produced in the presence of acid binders accomplished. Alkali alcoholates, hydroxides and carbonates are particularly suitable for this purpose such as potassium or sodium methylate, ethylate, hydroxide or carbonate, also aliphatic, aromatic and heterocyclic bases e.g. B. triethylamine, diethylaniline, Ben2: yldimethylamine or pyridine.

The reaction temperature can be varied within a relatively wide range for esterification. Preferably 20 and + 80 ^c C, at +10 to + 50'C - in general carried out between.

To prepare the compounds according to the invention, per mole of l-thiono-l, 3-dihalogen- or -1-halogen-3-alkylphospholine expediently 2 to ΙΟ mol of the alcohol to be esterified is used. In the case of reactions using phenols, on the other hand, stoichiometric ones are used Amounts or only a slight excess of the latter (about 10%). Finally, the acid binder is used in equimolar amounts.

The reaction mixture is worked up in a generally known manner by adding it with water, extraction of the crude product using a suitable solvent (e.g. ether or chlorinated hydrocarbon). Drying the organic phase, stripping off the solvent under reduced pressure and, if appropriate, distillation or recrystallization of the residue. Provided the products can be obtained in the form of viscous, non-crystallizing or distillable oils it by so-called "distilling," d. H. short-term heating in a vacuum to weak to moderate elevated temperatures freed from the last residues of solvent and other volatile compounds and be purified in this way.

The products according to the invention are characterized by only low toxicity to warm-blooded animals and phytotoxicity

by an excellent, fast onset nematodicidal effectiveness and also have another good insecticidal, akari.äde and soil fungicidal side effect.

Depending on their intended use, the new active ingredients can be converted into the customary formulations like solutions, emulsions. Suspensions, powders, pastes and granulates. These will produced in a known manner, e.g. B. by mixing the active ingredients with extenders, d. H. liquid Solvents and / or carriers, optionally using surface-active substances So means emulsifying and / or dispersing agents, where z. B. in the case of using water as Extenders, optionally organic solvents, can be used as auxiliary solvents. The main liquid solvents are: aromatics (e.g. XyJoI, benzene), chlorinated Aromatics (e.g. chlorobenzenes), paraffins (e.g. earthen fractions), Alcohols (eg methanol, butanol), »strongly polar solvents such as dimethylformamide tend dimethyl sulfoxide and water; as solid carriers • natural rock flour (e.g. kaolins, clays, Talc, chalk) and synthetic rock powder (e.g. highly dispersed silica, silicates); as Emulsifiers: non-ionogenic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol -Ether, e.g. B. Alkyiaryl polyglycol ether. Alkyl sulfonates and aryl sulfonates; as a dispersant: e.g. lignin, sulphite waste liquor! and Methyl cellulose.

The active ingredients according to the invention can be used in the

Formulations mixed with other known

Active ingredients are present. The formulations contain

generally between 0.1 and 95 percent by weight

Active ingredient, preferably between 0.5 and 90%.

The drug concentrations can be in a ίο larger area can be varied. Generally used one has concentrations of 0.00001 to 20%, preferably from 0.01 to 5%.

The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrals, emulsions, suspensions, Wettable powders, pastes, soluble powders, dusts and granules can be applied.

When used against nematodes, the preparations are applied in amounts of 5 to 50 kg of active ingredient Evenly spread per hectare and then worked into the soil.

Surprisingly, those according to the invention stand out Products compared to the active ingredients with the same direction of action known from the literature through a much better effective wedge with significantly lower warm-blooded toxicity out.

example

Cl

C CH, S

CH-CH ₂ OCHj

or.

C == CH S

CH ₂ -CH ₂ OCH,

62 g (0.33 moles) of 1-thiono-1-4 dichlorophospholine (Kp.3 99 to 103 "C) are presented in 150 ml of benzene.

To this mixture is added dropwise with vigorous stirring at 10 to 15 ⁰ C 76 ml of a methanolic sodium methoxide solution containing 0.33 mole Natriummelhylat, then the reaction mixture stirred for a further 2 hours at 40 ° C after pouring the latter then in ice water , absorbs the mixture in ether, dries the ethereal solution over sodium sulfate and removes the solvent. the residue will

then distilled under reduced pressure; the 1 - methoxy -1 - thiono - 3 - chlorophospholine boils at 96 to 98 ° C / 2 Torr.
The yield is 50 g (83% of theory).

Analysis for C ₅ H ₈ ClOPS (molecular weight 182.5):

Calculated ... P 16.99, S 17.53, Cl 19.44%;
found .... P 17.18, S 17.70, Cl 19.11%.

The DL _{50 of} the compound in the rat per os is above 1000 mg / kg.

Example 2 Cl

C CH ₂ S

/ \ CH — CH ₂ OCH ₃

The isomer mixture obtained according to Example 1 The purity of the preparation and its identity

becomes clearer the situation by column chromatography on silica gel at 65 with the given formula

Room temperature separated, whereby a mixture of the double bonds can be caused by nuclear magnetic resonance,

determined from benzene and petroleum ether in the volume ratio infrared and ultraviolet spectroscopy

1: 1 serves as a flow agent. will.

Example 3

Cl

C == CH S

\ 'f
P.

CH ₂ -CH ₂ 0-CH ₃

10 at 93 to 95 ° C / 2 Torr (a separation into the isomers is - as described above - possible).

The yield is 52 g (79% of theory).

Analysis door C ₆ H ₁₀ ClOPS (molecular weight 196.5):

Calculated ... P 15.78, S 16.28, Cl 18.04%; found .... P 15.72, S 16.27, Cl 17.96%.

Example 5 Cl

The compound of the above formula is prepared from the mixture prepared according to Example 1 according to the in Example 2 given procedure obtained and identified.

Example 4

or.

Cl

I. c-

CH ₂

C CH ₂ S

\ f

CH -CH ₂ 0-C ₃ H ₇ ,,,

Cl

C = CH S

CH-CH ₂ QC ₂ H ₅

Cl

= CH

POC ₂ H ₅

CH ₇ -CH ₂

To a mixture of 62 g (0.33 mol) of 1-thiono-1,3-dichlorophospholine and 150 ml of benzene are added dropwise at 10 to 15 ° C with vigorous stirring 145 ml of a ethanolic solution containing 0.33 mol of sodium ethylate. Then the reaction mixture Stirred for a further 2 hours at room temperature and then poured into ice water. The work-up mixing takes place as indicated in Example 1.

The l-ethoxy-l-thiono-3-chloT-phospholine boils / \
CH ₂ -CH ₂ Ο -C ₃ H ₇₁₅₀

62 g (0.33 mol) of 1-thiono-1,3-dichlorophospholine are added at 40 ^° C. within 10 minutes with 50 ml of isopropanol, then 27 g (0.33 mol) of pyridine are added dropwise to the mixture with stirring and heated the latter for a further 2 hours to 40 to 50 ^° C. The reaction mixture is then poured into ice water, the product is extracted with carbon tetrachloride and the extraction solution is dried over sodium sulfate. Finally, the solvent is stripped off under reduced pressure and the residue is distilled.

The 1 - isopropoxy -1 - thiono - 3 - chlorophospholine boils at 99-101 ° C / 2 torr.

The yield is 50 g (72% of theory).

Analysis for C ₇ H _n ClOPS (molecular weight 210.5):

Calculated ... P 14.71, S 15.20%; found .... P 14.85, S 15.05%.

Cl

Example 6 Cl

CH,

\ f

CH CH ₂ O — C ₄ H ₉ -,

or = CH S

\ S

CH ₂ -CH ₂ 0-C ₄ H _9. ,

The compound is obtained in a manner analogous to that in the preceding example with a yield of 80% of theory. The in-butoxy-1-thiono-S-chlorophospholine boils under a pressure of 3 torr

at 124 to 127 ° C

Example 7

Cl

Cl C-

CH-

-CH ₂

\ P.

or.

Q-CH ₂ -CH ₂ -Cl CH

CH ₂ - CH ₂ 0-CH ₂ -CH ₂ -Q

Production ¹ is carried out analogously to the information in the example. The Hp-Chloräthoxyyi-thiqno-S-chlornhosnholin is obtained with 50% igec yield and boils at 133 ° C / 3 Torr. : ■.

Cl
C-

Example 8

CH,

CH CH ₂ Ο — CH ₂ -CH = CH,

Cl
C =

CH

Example 9

CH ₃

CH ₂

CH CH ₂ Ο-CH ₃

CH ₃

Vjri2 CH2 O "

10

obtained according to Example 1. The yield is 68% of theory. The 1-methoxy-1 -thiono-methylphospholin 3-boiling under a pressure of 2 Torr at 104 to 108 ⁰ C.

Example 10

Cl

ρ _

CH

CH ₂ S

CH

egg
γ

₂ 0- ^ V-Cl

CH ₂ -CH ₂ 0-CH ₂ -CH = CH ₂

In a manner analogous to that described in Example 5, l-allyloxy-l-thiono-3-chlorophospholine is obtained with a yield of 81% of theory. The compound boils at 101 to 103 ° C / 2 torr. or.

The product is made from 1-thiono-1-chloro-3-methyl-

phospholine (melting point 49 to 51 ° C.) and a solution of ι - ^, «+, j - ι ncniorphenyloxy) -1 - thionc Sodium methylate in methanol according to the information 50 phospholine is about 80% of theory

A slurry of 49 grams (0.25 moles) of 2,4,5-trichlorophenol (Mp. 64 to 67 ° C) in 250 ml of Benzol wire

mixed with 50 ml of a solution containing 0.25 mol of sodium methylate Contains dissolved in methanol. Methanol is then distilled with vigorous stirring and benzene and the residue is taken up in 250 ml of methyl ethyl ketone. After that, the

Mixture dropwise at 20 ° C with stirring mil 47 g (0.25 mol) of l-thiono-1,3-dichlorophospholine were added and the mixture was heated to 45 to 50 ° C. for a further 3 hours The reaction mixture is then poured into cold water and the organic phase is diluted with ether

separates the ethereal layer and dries it over Sodium sulfate. After the solvent has been distilled off, a red-brown, water-insoluble nichi becomes Obtain distillable oil. The yield ar 1 - (2 ', 4', 5 '- Trichlorphehyloxy) -1 - thiono - 3 - chloro-

example

or Cl
C =

CH S

CH ₂ -CH ₂ oS \

C (CH ₃ J ₃

The compound is obtained analogously to Example O from 4 ~ tert- 6 ₅ phospholine TJa * 1 (ά. ' T / rt η ,, ΐνΐηΉρ sodium butylphenolate »with l-TOono-U ^ icMc» - S Αικ ^^ ΤκΤΑ'οη " . ^

11th

12th

CH CH ₂ O

2 pp

P or

Example 12 Cl

C == CH S \ / P

SCH ₃

CH ₂ -CH ₂ Ο- / V-SCH ₃

The production takes place in the above-described lin. The l- (4'-methylmercaptophenyloxy) -l-thiono-

Way, starting from 4-methylmercapto-phenol and 3-chlorophospholine is a water-insoluble, nich

Sodium methylate and conversion of the corresponding distillable oil.

the sodium salt with l-thiono-l ^ -dichlorophospho- 15 The yield is 90% of theory.

Claims (1)

Ii one in a known manner 1-thiono-1,3-di- halogen- or l-thiono-l-halogen-3-alkylphosphorus 1.1- alkoxy- or 1-aryloxy-1-thiono-3-halogen- or -3-alkylphospholines of the formula Patent claims: pholine the formula
R. C - CH ₂