DE1668704A1 - Organophosphorus compounds containing nitrogen - Google Patents

Description

DR. JUR. DIPL-CHEM. WALTER BEIL ALFRED HOEPPENER

LAWYERS AND NOTARIES

DR. JUR. DIPL-CHEM. H.-J. WOLFF DR. JUR. HANS CHR. AX

LAWYERS

623 FRANKFURT AM MAIN-HÖCHST

ADELONSTRASSE58

Our Mr. 14 278

2 March 4, 1970

Stauffer Chemical Company Hew York, N.Y., V.St.A.

Organophosphorus compounds containing nitrogen

The present invention relates to a group of new organic compounds containing phosphorus and nitrogen the general formula:

O-

NH ₂ R ¹¹

in which R is a halogen-substituted alkyl group having 1 to 8 carbon atoms or a radical of the general formula

■ a

(0H) _d

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denote in which X is an halogen atom, preferably chlorine, and a, b, c and d are integers from 0 to 5, the sum of which is not greater than 5, R ^{1 is} an II-R " ₂ group, and R" is an alkyl group with 12 to 18 carbon atoms or a hydrogen atom, where only one R "can be a hydrogen atom.

The compounds can be prepared by reacting a phosphonic anhydride with a long chain alkylamine according to the following reaction scheme, in which R and Π "have the above meaning and η a whole Number is over 2.

HO

-PO- .1

+ 2H " ₂ NH

Il

R-P

NO",

0-

They can be obtained by reacting, preferably sammenbringt the phosphonic anhydride slowly at about 0 to 150 ⁰ C for about 50 to 120 ⁰ C, with the desired amine zr. The reaction is exothermic until the PN bond is formed; however, it can be easily regulated by external cooling and vigorous stirring.

The phosphonic anhydride, which is solid at room temperature, is preferably added to the amine in the liquid state so that lower reaction temperatures can be used. For this purpose, the anhydride can be ^{heated to a temperature between 50 and 150 °} C. After the PN bond has been formed, r & j-e.

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16687 (H.

participants can be brought together quickly without that external cooling is required.

after the reactants have been brought together, it is best to maintain the temperature of the reaction mixture another 1 to 2 hours with stirring at about 80 to 150 ° C. to ensure that the reaction is complete is.

In order to prevent the halogen-substituted alkyl group of the phosphonic anhydride from reacting with the alkylamine, the reaction is best carried out in stages. For this purpose, one can first react at a about 50 to 150 ° C a IJoI amine per I.Iol phosphonic anhydride and then bringing the compound obtained at about 0 to 100 ⁰ C in the presence of an inert organic solvent with a further mole of the amine to the reaction .

Although the main product in the reaction is the Alkylammoniumalkylphosphonamiäat receives, there are also smaller! narrow ones of the following by-products:

HHR ¹¹

KHR "

and

R-P

2-

wherein R has the aforementioned meaning or the remainder

or R "iiH {

represents, where η is a whole number from 1 to 8 let and

before-
H "has the meaning mentioned. I> The compounds are by conventional processes, such as crystallization or fractional

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nation, not easy to separate. The impure product ..

However, the mixture has excellent pest killers Properties so that the separation of the reaction components is not required, but even in general for most uses is desired.

The alkyl groups in the salt and amide part of the molecule can be identical or different. If they are different, the connections are made by implementing 1 mol of the appropriate phosphonic anhydride with 1 col of the amine and subsequent conversion of the reaction product obtained with 1 mole of another amine.

Representative compounds included in the scope of the present Invention fall are listed below

Connection 1

O τ,

O | _{/ K} H (CH ₂ ) _lf CH ₃

³ S-

NH ₃ (CH ₂ ) ₁ -J-

link 2

NH (CH ₂ ) ₁₅ -CH ₃ 0-

NH ₃ (CH ₂ ) ₁₅ -

The compounds according to the invention are valuable as pesticides and have, for example, fungicidal and bactericidal activity.

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Un the protective effect of the compounds according to the invention. to examine against fungi that attack the plant foliage, 8 pinto bean plants were carefully sprayed with a concentration of the compound dissolved or suspended in water. The plants are allowed to dry and then inoculated with Uost spores. Three to four weeks after the treatment, the plants are observed and compared with untreated plants which have been inoculated with osteospores. It is found that the product of Example 1 completely destroys the rust fungi at a 1 / o concentration.

The compounds according to the invention are also effective aystemic fungicides. To be effective as a systemic ! • 'ungicidal to test, 60 ecm of the to be tested Compound diluted with distilled water to a concentration of 50 parts / uillion parts, in each of the 4 'L'est flask given. Place a pinto bean plant in each flask brought with a tree plug that holds the plant and prevents it from evaporating. 48 hours later the arrows are inoculated with rust spores. Comparisons between treated and untreated Plants are then pitched periodically and the results are evaluated. It was found that the product of Example 1 in a 0.005-, uigen concentration completely destroyed the rust fungi.

The bacteriostatic and fungicidal activity of the compounds according to the invention in vitro is determined by the following searches. The ^c in distilled water in a concentration of 0.005 p dissolved active compound is placed in a 28.5 g (1 ounce) flask, which is already filled with 10 cc of malt broth or partially. The containers are then covered with aluminum

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covered umfolie and sterilized, and there will be a solution of the compound to be tested by means of a syringe through the film into the broth gSspritzt ^e. Aqueous suspensions of typical fungi such as Aspergillus niger and Penizillium sp. and bacteria such as Escherichia coli are injected into the broth and the flasks are sealed and left off for a week. Then the growth is determined. It has been found that the product of Example 1 at the concentration of 0.005 /> leads to a complete destruction of the fungi and bacteria.

In addition to the methods described above, the compounds according to the invention can also be used for combating of microorganisms can be applied by numerous methods known in the art. For example, can a solution of the compound in an organic solvent is applied directly to the soil as a spray will. Dispersions of the compound in an aqueous medium can also be used with advantage. in the in the latter case the use of various surfactants or soaps may be desirable. As surface active agents, anionic, cationic or nonionic agents including sulfonated animal ones can be used and vegetable oils, sulfonated petroleum oils, sodium lauryl sulfonate, Ethylene oxide condensation products, for example by reacting octylphenol with Ethylene oxide can be obtained and higher alkylpyridinium halides, for example laurylpyridinium bromide. In a3.1 common Extremely satisfactory results are obtained when the surfactant is about 1 to 15/5 the composition.

It should be noted that the compounds are non-toxic to mammals, making them very versatile can be used without the livestock

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there was danger. The toxicity to mammals is determined using albino mice, and the Results are expressed as mg of the toxic agent per kg of body weight that was responsible for causing a 50 # fatal Effect required for intraperitoneal injection are indicated. It was found that the product of the example 1 has a 50 $ lethal dose of 390 mg / kg.

The following examples are intended to explain the present invention in more detail:

example 1
Manufacture of

In a 500 cc three-necked flask equipped with a separating funnel, stirrer and thermometer, 119 »4g (1.06 moles) was added solid Chlormethylphosphonsäui'eanhydrid. The Peststoff was heated to about 150 ⁰ C to a molten state, and the melt was added with # 63 »Og (2.13 mol) frisch'destilliertem laurylamine. The reaction mixture was stirred vigorously during the addition of the outside ge and cools, so that the temperature of the reaction mixture was maintained between about 110 and 120 ⁰ C. After all the amine has been added, ie after 40 minutes, the viscous mass obtained was kept at a temperature between 80 and 90 ° C. for about 2 hours. The mixture was then allowed to cool to room temperature and the product was recovered directly.

example 2

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37 S (0.2 mol) of distilled laurylamine was placed in a 500 ecm three-necked flask equipped with a stirrer, thermometer and separating funnel. 14 g (0.1 mol) of phenylphosphonic anhydride were added through the separating funnel with stirring while the temperature of the reaction mixture was kept below 56 ° C. The mixture was then kept for about 1.5 hours with further stirring within a temperature range of 90-100 ° C. The mixture was then allowed to cool to room temperature, whereupon it solidified to a semi-solid. and won the product straight away.

Example 3

amidate

113 g (0.42 mol) of stearylamine were placed in a 500 ecm three-necked flask equipped with a stirrer, thermometer and separating funnel. The amine was within a temperature range of 70 - 80 ⁰ C and kept mixed with 163 g (0.78 mol) Phenylphosphonsäureanhydrid. W After complete addition, the mixture was heated to 10O ⁰ C. At this point, a red transparent liquid was observed. The mixture was then allowed to cool to room temperature where it solidified into a semi-solid material. The product was obtained directly.

Example 4

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119 »4g (1.06 mol) of chloromethylphosphonic anhydride were added to a 500 ecm three-necked flask equipped with a separating funnel, stirrer and thermometer. The solid was heated to about 150 ⁰ O to a molten state, and the melt was mixed with 182.5 g (1 »O6 Hol) freshly distilled laurylamine. During the Ziigabe the reaction mixture was stirred vigorously and cooled from the outside, so that the temperature of ßeaktionsgemischs was maintained between about 110 and 120 ⁰ C. After the addition of the amine, and after the subsequent exothermic reaction had ended completely, a further equivalent of the amine, dissolved in 100 ecm of toluene, was added. The reaction was carried out at room temperature and the resulting viscous material was recovered directly.

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Claims (4)

- ίο - claims 1. Nitrogen-containing organophosphorus compounds, consisting from the reaction product of a) a primary or secondary long-chain alkylamine with 12 to 18 carbon atoms in the alleyl group and b) a phosphonic anhydride of the general formula Il -0 - P - OH where η is an integer greater than 2 and II is a halogen-substituted alkyl group having 1 to 8 carbon atoms or a remainder of the general formula (cn), (OH), mean in which X is an Ilalogenatom and a, b, c and d represent integers from 0 to 5, the sum of which is not greater than 5. 2. Compounds according to claim 1, characterized in that the amine component is laurylamine or stearylamine. 3. Compounds according to claim 1, characterized in that the phosphonic anhydride component is chloromethylphosphonic anhydride or phenylphosphonic anhydride. 109838 / ^ * 28 BUILDING 4. A compound according to claim 1, characterized in that the amine component is laurylamine and the phosphonic anhydride component Is chloromethylphosphonic anhydride. Pure Stauffer Chemical Company Kew York, Ii.Y., V.St.A. (Dr. ΗΪ J. Wolff) Legal attorney BATH ORIGINAL 109838/1728