DE1567116C3 - Benzofurazan derivatives and their uses - Google Patents

Description

ρ-γ-4- ο

Z ₁₁ ,

wherein R ₁ and R _{2 are} each a C, -C ₄ -AlCyI- or C ₁ -C ₄ -alkoxy group, X and Y are each oxygen or sulfur and Z is the methyl, nitro group, a chlorine or bromine atom where m and / 7 zero or m 1 and η zero or Z denotes the nitro group and η 1 denotes.

2. 4 - Dimethoxyphosphinothioyloxy - 7 - chlorobenzofurazan. . ·

3. 4 - Diethoxyphosphinothioyloxy - 7 - chlorobenzofurazan.

4. Use of the compounds according to claim 1, optionally with customary additives, as an insecticidal agent.

The invention relates to that characterized in the claim Object.

Compounds of the invention can be prepared by a compound of formula

35

R,

Il

P - shark

40

wherein Hai is a halogen atom, preferably a chlorine or Represents bromine atom, reacted with a compound of the formula

/ Vn _x

HO-f O

45

(Z) ₁₁ ,

in the presence of a base, preferably an alkali or Alkaline earth carbonate or a nitrogenous base, e.g. B. pyridine, lutidine or preferably triethylamine.

The reaction is preferably carried out in an inert liquid reaction medium which serves as a solvent for the reaction components and / or the end products. Aliphatic ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone are particularly suitable for this purpose. Other reaction media are e.g. B. benzene, diethyl ether, diisopropyl ether, tetrahydrofuran, chloroform and carbon tetrachloride. The reaction components and the base are used in almost equimolar amounts. The reaction may be at a temperature between O and 15O ^'J C, preferably between 50 and 100 "C is performed.

The reaction mixture can be worked up in a customary manner.

The compounds in which (Z) ,,, is a nitro group can be prepared according to the invention by one compounds of the formula

NO

wherein shark has the above meaning, with a connection the formula

R ₁ X

■ \ ll

P —Y — Me

converts, wherein Mc is an alkali or alkaline earth metal, preferably sodium, potassium or ammonium, represents.

The reaction is preferably carried out in an inert solvent, in particular an aliphatic ketone. B. methyl ethyl ketone, methyl isobutyl ketone or acetone. The reaction is carried out at a temperature between 0 and ^100.degree. C., in particular between 15 and 45.degree. The reaction mixture can be worked up in a customary manner.

The compounds according to the invention are generally used in the form of glicidal agents.

As a carrier z. B. Silicates, plaster of paris, clays, sulfur, soot, resins, waxes and solid fertilizers into consideration.

Suitable liquid carriers are e.g. B. the petroleum spray oils known in horticulture and organic Solvents, e.g. B. alcohols, ketones, liquid hydrocarbons, chlorinated hydrocarbons and Polyalkylene glycol ethers and esters. Suitable gases are, for. B. those in insecticidal aerosols usually used, e.g. B. trichloromonofluoromethane or dichlorofluoromethane.

Examples of suitable surface-active substances are: Condensation products of fatty acids having at least 12 carbon atoms in the molecule with ethylene oxide or propylene oxide; Partial esters of the acids mentioned with glycerine, polyglycerine, sorbitol or mannitol; Alkyl sulfates; Sulfonated castor oil salts; Alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate; Condensation products of alkylphenols, aliphatic Amines or amides of aliphatic carboxylic acids with ethylene oxide or propylene oxide and alkyl amide sulfonates.

The preparations according to the invention can be concentrates which, for. B. 10 to 98 percent by weight contain a compound according to the invention, or it can be dilute preparations, for example 0.00001 to 10%, in particular 0.1 to 0.5 percent by weight, of the active ingredient, calculated on the total weight of the preparation.

The new compounds have a high insecticidal activity against a large number of insects, including related animal organisms that belong to the arthropods, z. B. flies, mosquitoes, caterpillars, grain beetles, aphids, beetles, spiders and mites.

Preferred compounds are of the formula

Cl

removed and the residue dissolved in methylene chloride. The solution was washed with cold water and then dried over sodium sulfate. After the methylene chloride had been distilled off in vacuo, the product was obtained an amber oil that has been purified by silica column chromatography. Yield 95%.

Analysis for Ci ₀ H ₁₃ N ₂ O ₅ P:

Found ... C 44.2, H 5.1, N 9.6, calcd ... C44.2, H4.8, N 10.3,

(Alkoxy) ₂ = P =

The compounds according to the invention are the 5-hydroxy-piazthio-phosphoric acid esters known from GB-PS 8 86 587 think.

example 1

Manufacture of 5-diethoxyphosphinyloxybenzofurazan

A mixture of 2.72 g of 5-hydroxybenzofurazan (0.002 mol), 2.76 g of anhydrous potassium carbonate (0.002 mol) and 1.35 g of diethyl phosphorochloridate (0.002 mol) in 100 cm ^{3 of} acetone was stirred and refluxed for 2 hours . After filtering off the solvent in vacuo P 11.4%; P 11.4.

Example 2

Using the method described in Example 1, a number of phosphorylated benzofurazans. The corresponding 4- or 5-hydroxybenzofurazan was used in all experiments with an equimolar amount of the corresponding dialkyl phosphorochloridate or Dialkyl phosphorochloridothionate in the presence of an equimolar amount of anhydrous potassium carbonate Boiled under reflux in acetone for 2 hours. In most cases it remained after the ethylene chloride had been distilled off a sufficiently pure product. In one case the crude product was made from petroleum ether recrystallized. The experiments are compiled in the following table.

connection

Reaction components from Fp.
prey

analysis

5-dtethoxyphosphinyloxy
7-methylbenzofurazan Diethyl
phosphorus
chloridal 5-hydrox \ -
7-methylbenzo-
furazan 97 4-diethoxyphosphinyloxy
benzpfurazan the same 4-hydroxybenzo
furazan 95 5-dimethoxyphosphine
thioyloxybenzofurazan Dimethyl
phosphorus
chlorideothionate 5-hydroxybenzo
furazan 90 4-bromo-5-dimethoxy
phosphinthioyloxybenzo-
furazan the same 4-bromo-5-hy-
hydroxybenzo
furazan 95 4-chloro-5-dimethoxy
phosphinlhioyloxybenzo-
furazan the same 4-chloro-5-hy-
droxybenzo-
furazan 94 5-dimethoxyphosphine
thioyloxy-7-methyl-
benzofurazan the same 5-hydroxy
7-methylbenzo-
furazan 95 4-dimethoxyphosphine
thioyloxy-7-methylbenzo-
furazan the same 4-hydroxy
7-methylbenzo-
furazan 90 4-dimethoxyphosphine
thioyloxybenzofurazan the same 4-hydroxybenzo
furazan 90

Oil TUrC ₁₁ H ₁₅ N ₂ O ₅ P:

Found:

C 46.2, H 5.3, P 10.6% calculated:
C 46.2, H 5.3, P 10.8%

Oil WrC ₁₀ H ₁₃ N ₂ O ₅ P:

Found:

C 44.3, H 4.8, N 10.2, P 11.4% calculated:

C 44.0, H 4.8, N 10.3, P 11.0%

47.5-49.0 ⁰ C TUrC ₈ H ₉ N ₂ O ₄ PS:

after Umkri- Found:

install from C 36.5, H 3.8, S 11.9, P 11.8%

Petroleum ether calculated:

C 36.9, H 3.5, S 12.3, P 11.9%

Oil

Oil

Oil

oil

oil

Door C ₈ H ₈ BrN ₂ O ₄ PS: Found:

C 29.2, H 2.7, P 9.5, Br 21.9% calculated:
C 28.4, H 2.4, P 9.2, Br 23.6%

Door QH ₈ ClN ₂ O ₄ PS: Found:

C 33.6, H 3.0 ,. P 9.5, Cl 12.1% calculated:
C 32.6, H 2.7, P 10.6, Cl 12.1%

Door C ₉ H ₁₁ N ₂ O ₄ PS: Found:

C 39.0, H 3.9, S 11.7, P 11.4% calculated:
C 39.4, H 4.0, S 11.7, P 11.3%

TUrC ₉ H ₁₁ N ₂ O ₄ PS: found:

C 39.3, H 3.9% calculated:
C 39.4, H 4.0%

TUrC ₈ H ₉ N ₂ O ₄ PS: found:

C 36.9, H 3.8, S 12.7, P 11.7%. calculated:

C 36.9, H 3.5, S 12.3, P 11.9%

Example 3

Manufacture of 5-dimethylphosphinothioyloxybenzofurazan

2.0 g of triethylamine were added to a solution of 2.7 g of 5-hydroxybenzofurazan and 2.6 g of dimethylthiophosphine chloride in 50 cm ^{3 of dry ether.} The mixture was left to stand at room temperature for 2 hours, then filtered off and the solvent was distilled off. The residue was recrystallized from cyclohexane and gave colorless needles. Yield 90%; Mp 110 to Hl ⁰ C..

Analysis for C ₈ H ₉ N ₂ O ₂ PS:

Found ... C 42.4, H 4.1, S 13.8, P 13.8%;
calculated ... C 42.1, H 4.0, S 14.0, P 13.6%.

Example 6

Preparation of 4-dimethoxyphosphinothioylthio-5 (7) -nitrobenzofuranzan oxide

This compound was obtained from 4-chloro-5 (7) -nitrobenzofurazan oxide by the method described in Example 5 using sodium dimethyldithiophosphate. After recrystallization from a mixture of methylene chloride and hexane: 105.5 to 106 ^° C.

Analysis for C ₈ H ₈ N ₃ O ₆ PS ₂ :

Found ... C 28.9, H 2.8, S 18.5, P 9.4%; calculated ... C 28.5, H 2.4, S 19.0, P 9.2%. 15th

B e i s ρ ie I 4

Preparation of 5-diethylphosphinothioyfoxybenzofurazan

This compound was prepared using diethylthiophosphine chloride according to the method in Example 3 method described. Recrystallization from cyclohexane gave a product from melting point 36.5 to 38.5 ° C; Yield 80%.

Analysis for C ₁₀ H ₁₃ N ₂ O ₂ PS:

Found ... C 46.5, H 5.4, S 12.8, P 12.2%;
calculated ... C46.8, H 5.1, S 12.5, P 12.1%.

Example 7

Preparation of 4-diethoxyphosphinothioylthio-5 (7) -nitrobenzofurazan

12 g of 4-chlorobenzofurazan were dissolved in 100 cm ^{3 of} concentrated sulfuric acid ^{at 0 ° C.} Then 2.5 cm ^{3 of} fuming nitric acid were slowly added over the course of 15 minutes and the mixture was ^{stirred at 0 °} C. for a further 45 minutes. The reaction mixture was poured onto crushed ice, the precipitated product was filtered off and washed with water. After recrystallization from ethanol, 4 - chloro - 5 (7) - nitrobenzofurazan was obtained in 88% yield. Mp. 99 to 100 ° C.

Example 5

Preparation of 4-diethoxyphosphinothioylthio-5 (7) -nitrobenzofurazan oxide

17.0 g (0.1 mol) of 4-chlorobenzofurazan oxide were ^{dissolved in 100 cm 3 of} concentrated sulfuric acid at 0 ° C. ^{4.4 cm 3 of} fuming HNO _{3 were added} dropwise to the solution obtained in the course of 15 minutes at a temperature of 0 ° C. The reaction mixture was allowed to stand for 45 minutes and then poured onto ice. The crude 4-chloro-5 (7) -nitrobenzofurazan oxide was filtered off, washed with water and recrystallized from ethanol. Mp 138-138.5 ° C. Yield 65%.

Analysis for C ₆ H ₂ ClN ₃ O ₄ :

Found ... C 33.0, H 1.0, Cl 16.9%;
calculated ... C 33.4, H 0.9, Cl 16.5%.

A solution of 2.2 g of sodium diethyl dithiophosphate in 50 cm ^{3 of} acetone was added to a solution of 2.15 g of 4 - chloro - 5 - (7) - nitrobenzofurazan oxide in 50 cm ^{3 of} acetone and the mixture was kept at room temperature for 3 hours. After the precipitated product had been filtered off and the aeetone had evaporated, the residue obtained was dissolved in benzene. The solution was purified by chromatography on a silica gel column using benzene as an eluant. After distilling off, 4 - diethoxyphosphinothioylthio - 5 - (7) - nitrobenzofurazan oxide was obtained in 73% yield. Mp. After recrystallization from cyclohexane-benzene 70 to 71 ° C.

Analysis for C ₁₀ Hj ₂ Ni ₂ N ₃ O ₆ PS ₂ :

Found ... C 33.0, H 3.5, S 17.8, P 8.7%;
calculated ... C 32.9, H 3.3, S 17.6, P 8.5%. Analysis for C ₆ H ₂ ClN ₃ O ₃ :

Found ... C 36.4, H 1.0, Cl 17.9%; calculated ... C 36.1, H 1.0, Cl 17.8%.

A solution of 2.2 g of sodium diethyldithiophosphate in 20 cm ^{3 of} acetone was added to a solution of 2 g of 4-chloro-5 (7) -nitrobenzofurazan in 30 cm ^{3 of} acetone. The mixture was left to stand for 4 hours at room temperature, and then the precipitated sodium chloride was filtered off. The solvent was distilled off and the remaining oil was taken up in methylene chloride. The resulting solution was washed with water and dried, and the solvent was distilled off. The residue was purified by chromatography on a silica gel column and gave a pale amber oil. Yield 90%.

Analysis for C ₁₀ H ₁₂ N ₃ O ₅ PS ₂ :

.50 Found ... C 34.4, H 3.6, S 18.2, P 9.3%. calculated ... C 34.4, H 3.4, S 18.4, P 8.9%.

Example 8

Preparation of 4-dimethoxyphosphinothioylthio-5 (7) -nitrobenzofurazan

This compound was made from 4-chloro-5 (7) -nitrobenzofurazan using sodium dimethyldithiophosphate obtained by the method described in Example 7. Received a pure product by recrystallization from a mixture of benzene and hexane. Yield 70%; Mp. 106-107 ° C.

Analysis for QH ₈ N ₃ O ₅ PS ₂ :

Found ... C 30.4, H 2.7, S 20.2, P 9.6%; calculated ... C 29.9, H 2.5, S 20.0, P 9.7%.

Example 9

Preparation of 4-dimethoxyphosphinothioyloxy-7-chlorobenzofurazan

In this and the following example 10, the parts by weight (w) are related to parts by volume (ν) as Kilograms to liters.

To a solution of 4-hydroxy-7-chlorobenzofurazan (2.55 w, 0.015 mol) in methyl isobutyl ketone (50 v), dimethylphosphorochlorochlorothionate (2.4 w, 0.015 mol) was added. The mixture was stirred and ^{heated to 110 °} C. for 3 hours. The inorganic material was filtered off and the filtrate was evaporated under reduced pressure. The residue was dissolved in methylene chloride, washed with ice water and finally passed through a short silica gel column. A light brown oil (4.2 w) was obtained. Yield 95%.

Analysis for C ₈ H ₈ N ₂ O ₄ PSCl:

Found ... C 32.6, H 3.0, Cl 11.1, P 10.4%;
calculated ... C 32.7, H 2.7, Cl 11.1, P 10.6%.

Example 10

Preparation of 4-diethoxyphosphinothioyloxy-7-chlorobenzofurazan

In a solution of 4-hydroxy-7-chlorobenzofurazan (2.55 w, 0.015 mol) in methyl isobutyl ketone (50 v) were ethyl phosphorochloridothionate (2.83 w,

ίο 0.015MoI) and anhydrous potassium carbonate (2.1 w, 0.015MoI) given. The mixture was stirred and heated for 3 hours at 11O ⁰ C. The inorganic material was filtered off and the filtrate was evaporated under reduced pressure. The residue was dissolved in methylene chloride, washed with ice water and finally passed through a short silica gel column. A slightly brown oil (4.6 w) was obtained. Yield 95%.

Analysis for C ₁₀ H ₁₂ N ₂ O ₄ PSCl:

Found ... C 37.4, H 3.8, P 9.6, Cl 11.3%;
calculated ... C 37.2, H 3.7, P 9.6, Cl 11.0%.

509 522/369

Claims (1)

Patent claims: 1. Benzofurazan phosphorus compounds
formula the R ₁ X R, (O) _n