DE1670817A1 - Process for the production of phosphorus, phosphonic or thionophosphorus (phosphonic) acid esters - Google Patents

Description

The present invention relates to new phosphorus, phosphonic or thionophore- (phosphonic) acid esters des 6-oxychinoxaline with insecticidal and acaricidal properties, and a method for producing these compounds.

In the German patent 927.270 thiophosphoric acid esters of N-methylbenzazimides are already described, which have a good effect against sucking or eating insects, especially against spider mites. The aforementioned Products are therefore used as pesticides.

Furthermore, open-chain and cyclic quinoxalino-2,3-thiophosphoric acid esters are already known from German patent specification 1,115,738. These products are obtained by reaction the corresponding 2,3-dimercaptoquinoxaline with alkyl or Arylphosphoric or -thionophosphoric acid monoeeter-di- or - diester monohalides.

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According to the information in the last cited patent, these compounds are characterized by a good insecticidal and acaricidal effectiveness from; they are particularly effective against resistant spider mites. The manufacture of the aforementioned Active ingredient group is at least on a technical scale but relatively difficult.

It has now been found that in a smooth manner and with very good yields running reaction phosphorus or thionophosphorus (phosphonic) acid-quinoxalyl- (6) -eeter the general constitution

(D

be obtained when 6-hydroxy-quinoxaline of structure (II)

HO-

(II)

with phosphorus, phosphonic or thionophosphorus-CphosphonJ-acid ester halides Formula (III)

R ¹

(III)

implements.

τ »« _Λ roc ο BAD ORIGINAL

109ff1 ² 472l8t

In the above formulas, R and R ¹ stand for lower alkyl radicals with 1 to 4 carbon atoms, R · can also mean a lower alkoxy or phenyl radical, while X represents an oxygen or sulfur atom and Hal a halogen atom.

As has also been found, the products of the process of general structure (I) have strong insecticidal and acaricidal properties Properties on. They have excellent effects against both eating and sucking insects as well excellent effectiveness against spider mites and ticks. In this regard, those which can be made in accordance with the invention are Compounds clearly superior to the 'known products of analogous constitution and the same direction of action; the former thus represent a real asset to technology.

The process according to the invention proceeds as follows Formula schemes (IV):

In the above equation, the symbols R, R ¹ , X and Hai have the meaning given above. Preferably, however, R stands for lower alkyl radicals with 1-3 carbon atoms, such as the methyl, ethyl, n-propyl or isopropyl radicalj R ¹ preferably represents an OR radical or a methyl, ethyl, n- and isopropyl group or the Phenylreet, X represents primarily a sulfur "and Hai a chlorine or bromine atom. " A 10 ^ 108814 / .2Je,

167U817

That for carrying out the method according to the invention 6-hydroxy-quinoxaline required as starting material is from Known literature. It can also be used on an industrial scale without difficulty, for example by condensation of 3,4-diaminophenol with glyoxal or by reducing 6-nitroquinoxaline and diazotizing the corresponding 6-amino compound and boiling it of the diazotization product. For its part, 6-nitroquinoxaline is light by simply nitrating quinoxaline accessible.

The process according to the invention is preferably carried out using suitable solvents or diluents. As such, virtually all inert organic come Solvents or mixtures of the same can be considered, such as hydrocarbons, e.g. gasoline, benzene, toluene, chlorobenzene, xylene, Ither, for example diethyl and dibutyl ethers, dioxane, also Ketones, e.g. acetone, methylethyl, methylleopropyl and methylobutyl ketone. They have proven particularly effective for the aforementioned Purpose, however, low-boiling aliphatic ^ alcohols, for example methanol, ethanol and especially nitriles, e.g. Aceto- and propionitrile, also dimethylformamide.

Furthermore, the reaction according to the process is preferably allowed to proceed in the presence of acid acceptors. For this you can practically all common acid binders can be used. Alkali alcoholates have proven to be particularly suitable and carbonates, such as potassium and sodium methylate or ethylate, Sodium and potassium carbonate, also tertiary aromatic or heterocyclic amines, e.g. triethylamine, dimethylaniline

or pyridine.

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The real temperature can vary over a wide range

will. In general, between 20 and 120 ^° C. is used

(or the boiling point of the mixture), preferably at 40 to 80 ⁰ C.

The starting materials to be reacted according to the process and the auxiliaries (acid binders) are generally used in stoohiometric amounts. After combining the starting components, it is advantageous to use the To complete the reaction, heat the mixture for a longer time (about 1 to 3 hours), if necessary with stirring. In this procedure, the process products are obtained in excellent yields and in excellent yields Purity.

The phosphorus or. Thionophosphorus (phosphonic) acid esters of s b-üxychinoxalins Partly occur as threadless crystals with a sharp melting point, which, if necessary, recrystallize Can be easily cleaned further from common solvents; however, the products are usually obtained in the form of colorless ones to yellow-colored, viscous, water-insoluble, not undecomposed distillable oils, which, however, by so-called "Incipient distillation", i.e. prolonged heating with reduced The last volatile components can be removed by pressure at moderately elevated temperatures and cleaned in this way. The determination of the refractive index can be used to characterize it more closely.

As already mentioned above, the products of the process are distinguished by their excellent insecticidal and acaricidal effectiveness. They have at the same time only a low level of warm-blooded animals and

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Phytotoxicity. The effect sets in quickly and lasts for a long time. For this reason, can be produced according to the invention Compounds with success in crop protection to control harmful sucking and eating insects and dipteras as well as against mites (acarina).

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The sucking insects mainly include aphids (Aphidae) such as the green peach aphid (Mybus persioae), sohwarse bean (Doralia fabae), oat (Hhopalosiphum padi.), Irbsen (Maorosiphua piei) and potato mouse (Maorosiphum solanifolii), learn the Johann! «beergallen- (Cryptomysus korsohelti), floury apple (Sappaphis mali), floury plum (Hyalopterus arundinis) and black cherry aphid (Mytue cerasi), as well as scale lice and mealybugs (Coccina), e.g. the Efeusohild- (Aepidiotue hederae) and Hapfschildlaus (Lecanium hesperidum) and the mealybug (Pseudococcus maritimus); Blaaenfiifie (Thysanoptera) such as Hercinothrips femo alls and bedbugs for example the beet (Piesma quadrata), cotton (Dysderous internedlus), bed (Cimex lectularius), predatory (Rhodnius prolixus) and . ^ gas bug (Triatoma infestans), also cicadas such as Eusoelis bilowatus and Nephotettix bipunctatue.

Among the biting insects that should be mentioned above all are black caterpillars (Iepidoptera) such as the coal owl (Plutella maculipennisX the Schwamospinnar (I ^ mantria diaper), Goldafter (Euproctie chryeorrhoea) and ring moth (Malacosoma neustria) the cabbage (Mamestra brassicae) and the seed owl (Agrotis segetum), the large cabbage white butterfly (Pieris braeaicae), small frost worms (Cheimatobia brumata), Xichenwiekler (Tortrix Tir ^ dana), the Army (Laphygma frugiperda) and aegyptiache cottonworm (Prodenia litura), as well as the web (Hyponomeuta padella), flour (Ephestia Kuhnieila) and large guard moth (Galleria mellonella).

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Furthermore «ahleη su den. biting insect beetle (Coleoptera) s.B grain (SitοphiIue granarius * Calandra granaria), Potato (Leptinotarsa decemlineata), Aapfer- (Gastropbysa Tiridula), horseradish leaf (Phaedon cochleariae), Hapsgl & ns- (Meligethee aeneue), Hiebeer- (Byturas toaentosus), white bean (Bruohidiu »· Acanthoeoelidee obtectue), Speok- (Deraeetee frisohi), khapra (Trogoderma granariua), red-brown rice (Tribolium oaetaneua), Maie- (Calandra or Sitophilua seacais), Bread (Stegobiua panioeua), common flour (Tenebrio aolitor) and tadpole beetles (Oxysaephilue surinaaensis), but auoh ia soil living species s.B. urahtwüraer (Agriotee epee.) and White grubs (Melolontha melolontha); Cockroaches like Deuteohe (Blatella geraanica), Anerikanieohe (Periplan · ta aaericana), Madeira- (Laucophaea or Hhyparobia aadeirae), Orientaliaohe (Blatta orientali ·), Hieeen- (Blaberue giganteue) and echwarse Eieeeneohabe (Blaberua fueoue) and Heneohoutedenia flexivitta; also Orthopteren s.B. the Heiaohen (Gryllue doaeetioue); Teraites like the Erdteraite (Retiouliteraee f IaYi pe β) and Hyaenoptera - ie ants, for example the meadow ant (Laeiue niger).

The Diptera uafaesen ia essential flies like the dew (Droeophila aelanogaeter), Mittelaeerfrucht- (ceratitis capitata), Room (Musoadoaestioa), small room (fannia oanicularis), Qlans fly (Phoraia aegina) and Sohaei fly (Calliphora erythrooephala) and the upper calf (Stoaozys oalcitrans);

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i »n» f Jftükeu, tB, mosquito »« ie die üeibi'ieber «(A®d« s m «eypti), house mosquito (Culex pipiena) and malaria mosquito (Anophelee Stephens!)»

Among the mites (Aoari) are the spider mites in particular Cfe-fcranyefeida ·} «ie the bean (fetranychue teiariu« * fetranyohus althaeae or Tetranychus urticae) and the ObetbauBspinosil ^ e (Paratetranyohue pilosus »Panonyohus ulai), Gall mites i.3. the currant mite (Sriophyes ribis) and Tareonemide «for example the shoot tip mite (H «« l-taxecnea'is latus) and cyclamen mite (Tarsoneaus pallidivi); stthlie-Slioh Zec & en «ie die Lederxeoke (Ornithodorus moubata).

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Depending on their purpose of application, the new effects can be

be converted into the usual formulations, never

Iarolsianes, suspensions, powders, pastes and granulates.

«Earth produced in a known manner, e.g. by

a «r active ingredients with extender! *, i.e. liquid solvents and / or solid carriers, optionally using of surface-active agents, i.e. emulsifying and / or dis ^ ergiaj aitteIn »where z * S, in the case of using water as a stretch medium, if necessary, organic solvents as auxiliary solutions

medium can be used. As liquid * xommejt essentially in question: aromatics (e.g. xylene,

chlorinated aromatics (e.g. chloroboxols), paraffins (see-l * petroleum

Fractions) "alcohols (x.B. methanol ^ butanes!}" Strongly polar Solvent actttel such as dimethylformamide and dimethylsulioxide as well

barrels; as solid sawing materials: natural GeeteinsEishl "

e.g. kaolins, clays, talc, chalk} and aesthetic leeteinemehle (e.g. highly dispersed Kj «c & elaic acid, silicates); as Emulsifiers: nonionic and anionic emulsifiers such as Polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates and Aryl sulfonates) as dispersants e.g. lignin, sulfite tablets and Ms thy! cellulose.

The active ingredients according to the invention can be used in the formulations present in a mixture with other known active ingredients.

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The formulations generally contain between

0.1 and 95 percent by weight active ingredient, preferably between

0.5 and 90 Ji.

Me & Wirkstoffkonsentr functions Koenen be varied within a relatively wide range, in general, from ₅ concentrations of D OOOOI i »to 20 #, preferably from 0.01 i» to 5 £ ♦

The active ingredients can be used as such, in the form of their formulations or the application forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, suspensions, wettable powders, fast, soluble powders, dusts and granules. They are used in the customary manner, for example by painting, spraying, atomizing, smoking, scattering, dusting, gasifying.

The excellent insecticidal and acaricidal effectiveness of the process products can be seen from the following application examples:

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Example A.
Phaedon larvae teat

"» 670817

Solvent: 3 parts by weight of acetone

Emulsifier: 1 part by weight »alkylaryl polyglycol

ether

To produce a suitable active compound preparation, 1 part by weight of the active compound in question is mixed
Substance with the specified amount of the respective solvent, which contains the above-mentioned amount of emulsifier, and dilute the concentrate obtained with water to the desired concentration.

This active ingredient preparation is used to make cabbage leaves
(Brassica oleracea) sprayed to runoff and then with mustard beetle larvae (Phaedon
cochleariae) occupied.

After the times given in the table below, the degree of destruction of the pests is determined and expressed in # 100 means that all and 0 # means that no larvae of beetles were killed.

Tested active ingredients, applied active ingredient concentrations, evaluation times and obtained test results go from the following table 1:

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(p £ läüze: iöch * di§end # insects)

Active substance consensus Degree of destruction in active substance (constitution) in $ after 3 days

O η

0.1

G, 01
0.001

100

too

100

0.1
0.0 \

100 100

^ ₂ U ₅ "

C ₂ H ₅ O

S.
a

P-O-

0.1

0.01

0.001

100 100 100

P-O-

0.1
0.01

100 100

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For example B.

Myzus test (contact effect) Solvent: 3 parts by weight of acetone

Emulsifier: 1 part by weight * alkylery polyglycol ether

For the production of an appropriate preparation of the active substance
1 part by weight of active ingredient is mixed with the stated amount of solvent which contains the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea), which are strongly dependent on the peach aphid (Myzus
persicae) are infected, sprayed dripping wet.

The degree of destruction is determined in% after the specified periods. 100 % means that all aphids have been bagged off, 0 % means that none of the aphids have been killed.

Active ingredients, active ingredient concentrations, evaluation times and Results are shown in Table 2 below;

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ORIGINAL

Table 2ϊ (insects that are harmful to plants)

itfirkstoffkon- active ingredient (constitution) concentration in degree of destruction in after 24 days

0.1 0.01

known comparative preparation) 100 40

O η

0.1 0.01 100 70

S η

0.1 100 0.01 100 0.001. 99

O ₂ H ₅ B ^N po-,

0.1 100 0.01 100 0.001 100

C ₂ H ₅ O

Vo

0.1 0.61 100 90

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Example c Tetranychus test

Solvent: 3 parts by weight acetone Emulsifier: 1% by weight alkylaryl polyglycol ether

For the production of an appropriate preparation of the active substance 1 part weight of active ingredient is mixed with the specified Amount of solvent that contains the specified amount of emulsifier and dilute the concentrate with water to the desired Concentration.

Bean plants (Phaseolus vulgaria), which are approximately 10 - 30 cm high, sprayed dripping wet. These bean plants are strong with all stages of development of the bean spider mite (Tetranychus telarlus) infested.

After the times given, the effectiveness of the active compound preparation is determined by counting the dead animals. The degree of destruction obtained in this way is given in % . 100 % means that all spider mites have been killed, 0 % means that none of the spider mites have been killed.

Active ingredients »Active ingredient concentrations, evaluation times and Results are shown in Table 3 below:

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Table 3; (plant-damaging mites)

Active ingredient (constitution) active ingredient concentration
tration in $>

Degree of destruction in 48 hours

Il

0.1
0.01

(known comparator preparation)

100 0

It

(G ₂ H ₅ O) ₂ PO

0.1
0.01

100 40

C ₂ H ₅ O '

0.1
0.01

100 99

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BATH ORIGINAL

Example 1:

C ₂ H ₅ O

C ₂ H ₅ O ^^ N

36.5 g (0.25 mol) of 6-hydroxyquinoxaline, 35 g of finely powdered potassium carbonate and 4-00 ml of acetonitrile is stirred for 30 minutes at 75 ⁰ C. Then added dropwise 47 g of 0,0-Diäthylthionophosphorsäureesterchlorid to the reaction mixture and stirred for one hour at the latter 75 to 80 ⁰ C. After cooling the mixture, it is poured into water, taken up with benzene, the benzene solution first with water, then treated with 2- normal potassium hydroxide solution, finally several times with water until the reaction is neutral, dried over triue-sulphate charcoal and evaporated, black and white under a pressure of 0.01 gate at 60 to 70 ° C. The Auebeutt of 0,0-Diätbyl-thionophoephoreäure-0 -. / ^ Quinoxalyl (6Ji7 eBter-loading contributes 78 g (87% of theory), the refractive index of the product is n £ ⁸ - 1,5669- Ana l ysis ;

χ O

Calculated for C ₁₂ H ₁₅ N ₂ O ₅ PS (molecular weight 298.3): 10.30 #; 10.75 #>', Found: 10.48 56; 11.26 56.

Example 2:

Cp ^H 5 ° »

PO

In the same way as described in Example 1, 36.5 g (0.25 mol) of 6-hydroxyquinoxaline are reacted with 43 g (0.25 mol) of 0,0-diethylphosphoric acid ester chloride and 35 g of potassium carbonate in aueto nitrile and 53 g ( 63 t of theory) 0.0 diethyl

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phosphoric acid O-zquinoxalyl Ce ^ ester roi * ^detn refractive index n £ ¹ = 1.5380.

Analysis; _N ρ

Calculated for C ₁₂ H ₁₅ N ₃ O ₄ P (molecular weight 282.2): 9.92 #; 10.97 #; Found: 9.82 #; 11.29 #

example 3 '

C ₂ H ₅ O?

* ■ J X

Analogously to Example 1 and 2, by reacting 44 g (0.3 mol) of 6-hydroxyquinoxaline and 52 g (0.3 mol) of ethylthionophosphonic acid O-ethyl ester chloride, 62 g (72 % of theory) of ethylthionophosphonic acid-0-ethyl are obtained -0- / quinoxalyl- (6_) 7-ester with the Bre

21
ching index n ^ = 1.5850.

Analysis: _{p g}

Calculated for C ₁₂ H 'N ₃ O ₂ PS (molecular weight 282.3): 10.97 96; 11.36 #; Found: 12.0 # ;. 12.10%.

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The following process products can be obtained in an analogous manner:

Constitution Yield Refractive sum formula / ($ of theory) index Molecular weight Elementary analysis calculated ($) found

G ₂ H ₅ OS FS /

P-O-

78

= 1.6290

N 8th, 48 N 8th, 01 P. Q 37 P. 9, 98 S. Q 71 S. 10 , 01

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Claims (5)

Patent claims: 1) Process for the production of phosphorus, phosphonic or. Thionophosphorus (phosphonic) acid esters, characterized in that 6-hydroxy-quinoxaline with phosphorus, phosphonic or thionophosphorus (Pho8phon) acid ester halides of the formula P-HaI R ¹ reacted, where in the aforementioned formula R and R ¹ stand for lower alkyl radicals having 1 to 4 carbon atoms, R ¹ also stands for a lower alkoxy group or a phenyl radical, while X is an oxygen or sulfur and Hal is a halogen atom. 2) Phosphorus, phosphonic or thionophosphorus-Cphosphonic acid esters the general formula RO J ^N P-0-, in which R, R ¹ and X have the meaning given in claim 1. Le A 10 585 - 21 - 109814/2181 1B70817 3) Insecticidal and acaricidal agents, characterized by a content of phosphorus, phosphonic or thionophosphorus - (- phosphonic) acid esters according to claim 2. 4) Method of combating insects and mites, thereby characterized in that one phosphorus, phosphonic or thionophosphorus - (- phosphonic -) - acid esters according to claim 2 can act on insects and / or mites or their habitat. 5) Process for the preparation of insecticides and acaricidal agents, characterized in that one phosphorus, phosphonic or thionophosphorus (phosphonic) acid esters according to claim mixed with extenders and / or surface-active agents - Le A 10 585 - 22 - 109814/2181