DE2139691A1 - SUBSTITUTED FLUORPHOSPHAZEN - Google Patents

Description

Badische Anilin- & Soda-Fabrik AG

Our reference: O.Z. 27 643 Sws / Wil 67OO Ludwigshafen, August 5th, 1971

Substituted fluorophosphazenes

The present invention relates to new valuable substituted Pluorphosphazene, methods of pest control using these compounds and pesticides containing these compounds contained as active ingredients.

It is known that the compound 2,2,4,4,6,6-hexahydro-2,2,4,4,6,6-hexakis- (l-aziridinyl) -1,3,5,2,4, 6-triazaphosphorine to use in combating insects. Your effect is satisfying However not.

It has been found that substituted fluorophosphazenes of the general formula

W _m < ^N C ^) 2 nm, R ₂

in the

η 3 and m 3 * 4, 5 or η 4 and m 5 »6 or 7 * R, hydrogen or an alkyl or cycloalkyl radical with 2 to

8 carbon atoms (methyl, ethyl, i-propyl), R ₂ an alkyl, alkenyl or cycloalkyl radical with up to 8 carbon atoms (methyl, ethyl, i-propyl)

and R ₁ and R ₂ together represent a heterocycle (e.g. aziridinyl, piperidinyl, pyrrolidinyl, morpholinyl) are well suited for combating pests.

The application takes place in such a way, that the pests with the Active substances or their vapors are sprayed, dusted or brought into contact in any other way.

The active ingredients can be prepared from cyclic phosphorus nitride fluorides and the corresponding amines (R. Schmutzler, Inorg. Synthesis £ p. 75, 0. Glemser, E. Niecke, H. W, Roesky, Chem. Coram. 6 282 (1969), 0. Glemser, E, Niecke, H. Thamm,

Z. Naturforseh. 25 b 754 (1970)).

254/71 309807/1386 -2-

ORiGlWAL! HSPECTED

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In general, one sets to a solution of the phosphorus nitride fluoride in a solvent ^ z. B. ether, tetrahydrofuran, benzene, ToIuOl ₅ xylene, chlorobenzene, alcohol, the calculated amount of amine. In some cases, the amines were also used in excess.

The reaction is generally carried out at temperatures between -20 ° and 100 ⁰ C, preferably in the temperature range of 5 to 6o ° C, it being possible to operate in the presence or absence of suitable acid binding agents. As such, especially tertiary amines or heterocyclic amines, eg. B. pyridine, in question “It is also possible to use a 100% excess of the respective primary or secondary amine as the acid acceptor.

The so produced fluorophosphazene are mostly colorless, solid or liquid compounds, some by distillation or can be purified by recrystallization,

The compounds were identified by analysis, IR and H-NMR spectra.

The implementation of HN (C ₂ Hc) ₂ and Ν, Ρ, Ρ ^ takes place, for example, according to the following equation;

F P F F

In particular, it is possible to implement more basic amines than HN (CH- _{e.g. KN (C 2} Hc) ₂ with Ν ,, Ρ, ΐν, if gentle reaction conditions are chosen.

example 1

Production of. Ν-, Ρ-, Ρ ^ NHCH (CH-,) ₂ isopropylamido-pentafluoro cyclotriphosphazatri © no

309807 / 13S6

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25 parts (parts by weight) of N ₃ P ₃ Fg are dissolved in 100 parts of diethyl ether and 24 parts of H ₂ N (IC ₃ H ₇ ) are added at 5 to 10 ^° C. within 30 minutes. The mixture is then refluxed for 4 hours. After cooling, the hydrofluoride formed is filtered off and the filtrate is concentrated.

There remain 26.9 parts of crude product (93 % of theory, based on N ₃ P ₃ F / -), which is distilled for purification. The purified compound is colorless and has a boiling point ^Kp o, oi = ⁵ °° ^c

Example 2

Preparation of N ₃ P ₃ F ₁ -N (CpHc) ₂ diethylamido-pentafluorocyclotriphosphazatriene

To 25 parts of N ₃ P ₃ F ₆ in 100 parts of diethyl ether, 15 parts of diethylamine at 5 ⁰ C is added within 15 minutes and then stirred for 5 hours at room temperature (20 ⁰ C). Working up is carried out as described in Example 1. After the distillation, YJ parts are obtained (56.3 % of theory, based on

on N-, P, F / r) the compound as a colorless liquid of Kp _1n _ _m "_ _p y ο xu mm rig,

45 to 46 ° C.

Example 3

Preparation of .N ^ P ₁₄ F, - (N ^) tri (aziridinyl) -pentaf luor-tetracyclo-phosphazatetraene

66.5 parts of N ^ P ^ Fg are dissolved in 500 ml of diethyl ether and parts of ethyleneimine are added at -5 to 0 ⁰ C within 11/2 hours. The mixture is then stirred for 8 hours at room temperature. For work-up, the undissolved hydrofluoride is filtered off and the filtrate is concentrated in a water-jet vacuum at room temperature.

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61 parts (76 % of theory) of the slightly yellowish, non-distillable substance of the composition N ₄ P ₄ F, - '"remain.

^V NPN

Calc .: C 17.9 H 3.0 F 23.7 N 24.5 P 30.9 mol wt. Found: C 17.8 H 3.2 P 24.4 N 24.0 P 30, 1 "mole wt.

The following compounds were prepared according to Examples 1, 2, 3:

Connection Kp

Torr / ⁰ C

N P _{5 5} F ₅ NHCHgCH ₂ CH ₃ 0.01 / J> 6 to 38 ⁰ C.

N, P, P _C NHCH ₀ CH ' _n " ^y 0.01 / 55 to 57 ° C

s SO έ ^ ~~ Uil ₃

N ₃ P ₃ F ₅ NHCH ₂ CHgCHgCHgCHgCH ₃ 0.01 / 59 to 61 ° C

NPF NH-Hi \ 0.01 / 57 to 59 ° C

N ₃ P ₃ F ₅ NHCHgCH CHg = 0.01 / 35 to 38 ⁰ C.

NPF ₅ N h \ 0.01 / 34 to 36 ⁰ C

0.01 / 32 to 34 ° C

N, P, F (. N 0 0.01 / 30 to 32 ° C

5P ₃ F ₅ K j 0.01 / 41 to Ky

N ₃ P ₃ P ₅ N N-CH ₃ 0.01 / 47 to 50 C

N ₃ P ₃ P ₄ (NHCH ₂ CH ₂ CH ₃ ) ₂ 0.01 / 94 to 95 ° C

, CH) ₂ 0.01 / 103 to 104 ° C

.CH,

N ₃ P ₃ F ₄ (NHCH ₂ CHC ^) ₂ x 0.01 / 110 to 111 ° C

CH-z

N ₃ P ₃ F ₄ (NHCHgCH = CHg) ₂ 0.01 / 100 to 101 ⁰ C

.309807 / 1366 _ ₅ ,

O.ζ. 27 643

Connection ^K P η
Torr / C

N ₃ P ₃ F

N ₄ P ₄ F ₇ NHCH ₂ -CH = CH ₂ N ₄ P ₄ F ₇ NHiC ₃ H ₇

N ₄ P ₄ P ₇ NHnC ₃ H ₇ CH ₂ CH ₃ ) ₂ N ₄ P ₄ F ₇ N (nC ₃ H ₇ ) ₂ 3 N ₄ P ₄ F ₇ N (CH ₂ CH ₂ N ₄ P ₄ F ₇ , Q-OH N ₄ P ₄ P ₇ NHCH ₃

N ₄ P ₄ P ₆ (NHCH ₂ CH = CH ₂ ) ₂ N ₄ P ₄ F ₆ (NH

N ₄ P ₄ P ₆ | n (CH ₂ CH ₂ CH ₂ CH ₃ ) ₂ ] ₂ N ₄ P ₄ F ₆ (NHCH ₃ J ₂

N ₄ P ₄ F ₃ (NHC ₂ H ₅ J ₃ 0.01 / 99 to 0.01 / 87 to 90

0.01 / 105 to IO6 0.01 / 35 to 36

0.01 / 36 to 38 0.01 / 42 to 44 0.01 / 38 to 39 0.01 / 74 to 75

0.01 / 44 to 46 0.01 / 34 to 35 0.01 / 95 to 96 0.01 / 109 to 0.01 / 105 to 0.01 / 88 to 90

0.01 / 76 to 78 not distillable

not distillable cm-1

N ₄ P ₄ F ₅ 0.01 / 120 to 309807/138 6 -6-

- β - O.Z. 27 643

The agents according to the invention can be used as solutions, emulsions, suspensions or dusts. The application forms depend entirely on the intended use; they should ensure a fine distribution of the active substance in each case.

For the production of directly sprayable solutions, hydrocarbons with boiling points higher than 150 ⁰ C, z. B. tetrahydronaphthalene or alkylated naphthalenes, or organic liquids with boiling points higher than 150 ⁰ C and one or more functional groups, z. B. the keto group, the ether group, the ester group or the amide group, this group being a substituent on a hydrocarbon chain or being part of a heterocyclic ring, can be used as spray liquids.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders) by adding Water to be prepared. To produce emulsions, the substances can be used as such or dissolved in a solvent, by means of wetting or dispersing agents, e.g. B. Polyethylene oxide addition products in water or organic solvents be homogenized. However, emulsifiers or dispersants and possibly solvents can also consist of active substances Concentrates are prepared that are suitable for dilution with water.

Dusts can be produced by mixing or grinding the active substances with a solid carrier, e.g. B. kieselguhr, talc, clay or fertilizers can be produced.

Example k

90 parts by weight of the compound I are mixed with 10 parts by weight of N-methyl-o \ -pyrrolidone and a solution is obtained which leads to the application in the form of the smallest drops is suitable.

309807/1366 ~ ⁷ '

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2133691

Example 5

20 parts by weight of compound II are dissolved in a mixture, that of 80 parts by weight of xylene, 10 parts by weight of the Addition product of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt Dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which Contains 0.02 percent by weight of the active ingredient.

Example 6

20 parts by weight of compound III are dissolved in a mixture that of 40 parts by weight of cyclohexanone, JO parts by weight Isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of the Addition product of 40 moles of ethylene oxide and 1 mole of castor oil consists. By pouring the solution into and finely distributing it 100,000 parts by weight of water give an aqueous dispersion which contains 0.02 percent by weight of the active ingredient.

Example 7

20 parts by weight of compound I are dissolved in a mixture those from 25 parts by weight of cyclohexanol, 65 parts by weight a mineral oil fraction with a boiling point of 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide consists of 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives a · aqueous dispersion containing 0.02 percent by weight of the active ingredient.

Example 8

20 parts by weight of the active ingredient II are 3 parts by weight of the sodium salt of diisobutylnaphthalene-or-sulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a

309807/1366

-0-

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Sulphite waste liquor and 60 parts by weight of powdered silica gel mixed well and ground in a hammer mill. Obtained by finely distributing the mixture in 20,000 parts by weight of water a spray mixture containing 0.1 percent by weight of the active ingredient.

Example 9

3 parts by weight of compound III are 97 parts by weight finely divided kaolin intimately mixed. One gets in this way a dust containing 3 percent by weight of the active ingredient.

Example 10

30 parts by weight of compound I are mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil, which is applied to the surface of this silica gel was sprayed, intimately mixed. In this way, a preparation of the active ingredient with good adhesion is obtained.

The well-known active ingredient became purely for the biological tests

and the following compounds of the invention

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used.

Example 11 Effect on caterpillars of the cabbage moth (Plutella tnaoulipennis)

Young cabbage leaves are immersed in the aqueous emulsion of the test Samples immersed and, after drying, populated with larvae of the cabbage moth. The effect (mortality of the cockroaches) will determined after 48 hours.

Result; Active substance concentration mortality

of the active ingredient

A 0.1 % ineffective

1 0.02 %. 100 % 0.01 % 80 %

2 0.025 % 100 % 0.02 % 90 % 0.01 % 75 %

Example 12 Effect on aphids (Aphis fabae) on beans

Bean plants infested by the black louse (Aphis fabae) are sprayed to runoff with the test emulsions. The effect (Aphid mortality) is determined after 24 hours.

Result; Active substance concentration mortality

of the active ingredient

A 0.1 % ineffective

1 0.04 % 100 % • 0.02 % ■ 80 %

2 x 0.05 % 90 %

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Example IJ,

Effect on mosquito larvae

Larvae of the mosquito Aedes aegypti ( ^{1 year} larval stage) are brought into contact with boiled tap water and the samples in 1 liter glasses. The effect (mortality of the larvae) after 24 hours is recorded.

Result: active substance concentration mortality

of the active ingredient

A 5.0 ppm ineffective

1 1.0 ppm 100 % 0.5 ppm 80 %

2 1.0 ppm 90 % 0.5 ppm 80 %.

.309807 / 1366 _u_

Claims (5)

- 11 - O "Ζ. 27 claims 1. ) Substituted fluorophosphazenes of the general formula VA, ⁽ⁱ <^ 2 nm, in which η 5 and m 3, 4, 5 or η 4 and m 5, 6 or 7, R _{1 is} hydrogen or an alkyl or cycloalkyl radical 2 to 8 carbon atoms, R _{2 is} an alkyl, alkenyl or cycloalkyl radical with up to 8 carbon atoms and R, and Rp together form a heterocycle radical mean. 2. Pesticides, characterized by a content of a substituted fluorophosphazene according to claim J). Use of a substituted fluorophosphazene according to claim 1 as a pesticide. 4. Ethylamido-pentafluoro-cyelotriphosphazatriene. 5. Isopropylamido-pentafluoro-cyclotriphosphazatriene. Aniline & Soda Factory in Baden 309807/1366