DE2703363C3 - Phosphorus (phosphonic) or thiophosphorus (thiophosphonic) acid-N-thiazolinyl (thiazolyl) amides, processes for the preparation of these compounds and their use as pesticidal agents - Google Patents

Description

R for d-d-alkyl, halogen-Ci-Gt-alkyl or

Ci - C4 alkoxy group;
R ¹ for Ci -Cj-Alkoxy-, Phenoxy- Halcgenphenoxy-, Ci -CrAlkylamino-, Dialkylamino- or Thiazo-

linyl-2-amino group if

Z = -Ch ₂ -CH ₂ -;
R ^{1 stands} for phenoxy, halophenoxy, Ci-C ₄ -alkylamino, di-alkylamino or thiazolinyl-2-amino group when Z = -CH = CH-, X stands for oxygen or sulfur.

2. O-phenyl-N-thiazolinyl-2-amidomethylphosphonate.

3. O-phenyl-N-thiazolinyl-2-amidomethylthiophosphonate.

4. O ^ .S-Trichlorophenyl-N-thiazolinyl ^ -amidomethylthiophosphonate.

5. CM-Chlorophenyl-N-thiazolinyl ^ -amidomethylthiophosphonate.

6. Process for the preparation of phosphorus (phosphonic) or thiophosphorus (thiophosphonic) acid-N-thiazolinyl (thiazolyl) amides according to claim 1, characterized in that compounds of the formula

10

15th

20th

25th

30th

35

that they are one of the compounds of formula as active ingredient

R N-CH-,

\ Ζ "

P-NH-C

/ Il \

R ¹ XS-CII,

wherein

R for Ci -Cr-alkyl or halogen-C, -Ci-alkyl;

R ¹ for Ci-C ₄ -AIkOXy-, phenoxy, halophenoxy, Ci - Ct-alkylamino, dialkylamino or thiazolinyl-2-amino group;

X stands for oxygen or sulfur,

contains.

9. Composition according to claim 7, characterized in that it is O-phenyl-N-thiazolinyl-2-amidomethylphosphonate as the active ingredient contains.

10. Means according to claim 7, characterized marked !, that they are the active ingredient O-phenyl-N-thiazolinyl-2-amidomethylthiophosphonate contains.

11. Means according to claim 6, characterized in that that they are 0-2,4,5-trichlorophenyl-N-thiazolinyI-2-amidomethylthiophosphonate as active ingredient contains.

12. Composition according to claim 7, characterized in that it is the active ingredient O-4-chlorophenyl-N-thiazolinyl-2-amidomethylthiophosphonate contains.

40

H ₂ N -C

The invention relates to new phosphorus (phosphonic) or thiophosphorus (thiophosphonic) acid-N-thiazolinyl (thiazolyl) amides, Process for the preparation of these compounds and pesticidal and acaricidal agents based on these compounds.

In the literature there are compounds of the formula

wherein Z has the above meaning with phosphoric acid chlorides formula

R X

\ ll

P-Cl
R ¹

R ¹

50

55

P. -N = C C. - N R ³ / Il R ² X S. V \ / ^N

in which R, R ¹ and X have the above meanings, are reacted in an inert organic solvent in the presence of an acceptor for hydrogen chloride.

7. Insecticidal and acaricidal agents, characterized in that they contain as active ingredient one of the compounds according to claim 1, wherein Z is the group -CH ₂ -CH ₂ -, and contains an inert carrier.

8. Means according to claim 7, characterized in that

described in which R ^{1 represents} alkyl, alkoxy or alkylthio group; R ² for alkyl, alkoxy, alkylthio group, chloroalkyl, carbethoxy, alkylthio, chlorophenylthio, nitrobenzyloxy group, phenyl, substituted phenoxy group; R ^{3 represents} alkyl, benzyl, phenyl, alkoxyalkyl, alkenyl, chloralkenyl or 2-propynyl; R ^{4 represents} hydrogen, alkyl, cyclohexyl, vinyl; R ⁵ , R ⁶ and R ^{7 represent} hydrogen or alkyl; X represent oxygen or sulfur (US-PS 76 789 and 38 76 781).

The known compounds have high insecticidal and acaricidal activity, but are only active against certain groups of insects and mites, for example against housefly and common spider mite.

From an article by L. B. Rapp and L D. Procenko, reprinted in report from Chemischer Informationsdient, 1973, pages 153 to 154, report No. 24-323, Formula picture V, d) are compounds of the general formula

R O

p 'CH ₂ CH ₂ Cl XC ₆ H ₁ ON

CH ₂ CH ₂ C! where R is a residue

N CH ₃

(Mehtyl) in the diazole ring or they are attached to the phosphorus via the rest

-HM-

bound.

Furthermore, the prior art does not show that the compounds according to the invention are insecticidal ίο are effective and thus in insecticidal compositions for pest control in agriculture can be used.

The purpose of the present invention was to find new and effective insecticides and acaricides which are a have a broader spectrum of activity and high selectivity against agricultural Qusranta pests, as well as new organophosphorus herbicides.

The stated purpose has been achieved through the development of compounds of formula I.

20th

-HN

25th

^ t> - SO ₂ HN

and X-H, O-CH3O or F are known, which are however, differ significantly from the compounds according to the invention by their structure. In contrast the known compounds always show dichloroethylamino as substituents for the compounds according to the invention. Plus, they either have a substitute

/ Il

R ¹ X

NH-C

wherein R is Ci-C ₄ -alkyl, halogen-C, -d-alkyl or Ci-Q-alkoxy group; R ^{1 represents} Q - Gt-alkoxy, phenoxy, halophenoxy, Ci-Q-alkylamino, dialkylamino or thiazolinyl-2-amino group when Z = -CH ₂ -CH ₂ -; R ^{1 represents} phenoxy, halophenoxy, Ci - Ci-alkylamino, dialkylamino or thiazolinyl-2-amino group when Z = -CH = CH-, X represents oxygen or sulfur.

The compounds of the formula I differ from the previously known compounds by the The mobile proton is present in the molecule and can be used as a mixture of the tautomeric forms A and B.

R N

P -NH-C Z

/ Il \ /

R ¹ XS

R NH

P-N = C Z

/ Il \ /

R ¹ XS

exist.

Typical compounds described by Formula I are as follows:

O- phenyl-methanephosphonic acid-N-thiazolinyl-

2-amide;
O-ethyl-methanephosphonic acid-N-thiazolinyl-

2-amide;
O-butyl-methanephosphonic acid-N-thiazolinyl-2-amide;

O-4-chlorophenyl-methanephosphonic acid-N-thi-

azolinyl-2-amide;
0-2,4-dichlorophenyl methanephosphonic acid

N-thiazolinyl-2-amide;
O-methyl-methanthiophosphoiic acid-N-thi

azolinyl-2-amide;
O-ethyl-methanthiophosphonic acid-N-thiazolinyl-2-amide;

O-butyl-methanthiophosphonic acid-N-thi-

azolinyl-2-amide;
O-phenyl-melhanthiophosphonic acid-N-thi-

azolinyl-2-amide;
O-4-chlorophenyl methanthiophosphonic acid

N-thiazolinyl-2-amide;
0-2,4-dichlorophenyl methanethiophosphonic acid

N-thiazolinyl-2-amide;
0-2,4,5-trichlorophenyl methanethiophosphonic

acid-N-thiazolinyl-2-amide;
0-2,4-dichlorophenyl-chloromethane thiophosphonic

acid-N-thiazolinyl-2-amide;
O-ethyl-chloromethane thiophosphonic acid-N-thi-

azolinyl-2-amide;
O ethyl chloroethanthiophosphonic acid-N-thi-

azolinyl-2-amide;
Methanthiophosphonic acid-NN-diethyl-N'-thi-

azolinyl-2-diamide;

I.
a 27 03
5 5 363
6th 0-2,4-dichlorophenyl-chloromethane thiophosphonic I. O-methyl-O-phenyl-methanthiophosphonic acid Halophenoxy, Ci - d-alkylamino, dialkylamino acid-N-thiazolinyl-2-amide; ψ N-thiazolinyl-2-amide; or thiazolinyl-2-amino group; X for oxygen or 0-2,4-dichlorophenyl methanihiophosphonic acid j. O-butyl-0-phenyl-methanthiophosphonic acid Sulfur; Z represents the group -CH ₂ -CH ₂ -, and N-thiazolyl-2-amide. N-ihiazolinyl-2-amide; contains an inert carrier for this Compounds of Foiniel I can in and of themselves i "' O-methyl-methanephosphonic acid-N-thiazolyl- 10 Particularly active insecticides and acaricides are or used in a mixture with carriers and additives V 2-amide; following connections: will. The carriers can be solid or liquid and O-butyl-methanephosphonic acid-N-thiazolyl- O-phenyl-methanephosphonic acid-N-thiazolinyl- represent conventional ones used for these purposes Ϊ 2-amide; 2-amide; Substances, e.g. solvents, dispersants, ρ O-ethyl-0-phenyl-thiophosphonic acid-N-thi- O-phenyl-meihanthiophosphonic acid-N-thi- Wetting agents, solid carriers, binders, etc. I. azolyl-2-amide; 15th azolinyl-2-amide; Compounds of formula 1 are preferably used I. O-phenyl-methanephosphonic acid-N-thiazolyl- 0-2,4,5-trichlorophenyl methanethiophosphonic wisely in the form of solutions, suspensions, Netzpul I. 2-amide; acid-N-thiazolinyl-2-amide; vern and granules. The concentration of the active ingredient Ί O-4-chlorophenyl-methanephosphonic acid-N-thi- O-4-chlorophenyl methanthiophosphonic acid in the mixtures is 0.01 to 80%. ,1 azolyl-2-amide; N-thiazolinyl-2-amide. The production of the mixtures takes place in conventional I. O ^ -Chlorophenyl-methanthiophosphonic acid- 20th The compounds mentioned exceed in the neller way by mixing and / or grinding the N-thiazolyl-2-amide; Effectiveness against colorado beetles that Substances of the formula I with the carrier. S. O-ethyl-phenylphosphonic acid-N-thiazolyl- 0,0-dimethyl- (1-hydroxy-2Ä2-trichloro- 2-amide; ethyl) phosphonate, I. Methanethiophosphonic acid-N, N'-bis- (thi- 0,0-diethyl-0- (2-isopropyl) -4-methy] pyrimidyl-6) - I. azolinyl-2) diamide; 25th thiophosphate, I. Methane thiophosphonic acid-N-ethyl-N'-thi- N- (4-chloro-2-methyl) -N ', N'-dimethyl- Ί azounyl-2-diamide. formamidine and The inventive method for production 30th Benzophosphate I. of the substances of formula I mentioned consists of are about that against rice beetles I. Implementation of the substances of the formula O, O-Dimethy] - (1-hydroxy-2 ^, 2-trichloroethyl) -
phosphonate
gle ^: ch, surpass in effect against common ones
Spider mite
N- (4-chloro-2-methylene) -N \ N'-dimethylform- 1 N
- / \
H ₂ NC Z amidine and ί \ / O, O-dimethyl-S- (4,6-diamino-1,3,5-tri- I. S. 35 azinyl-2-methyl) dithiophosphate I. The compounds according to the invention can also I. where Z has the above meaning, with phosphorus 40 be used in a herbicidal mixture, which f- (Phosphonic), thiophosphoric and thiophosphonic acid as active ingredient one of the compounds of the formula ψ rechloriden of the formula RN
\ / ■ \
P-NH-C Z t R.
\
P-Cl / Il \ / / Il 45 R ¹ XS ί R ¹ X wherein R is Ci-Q-alkyl, halogen-Ci-C ₄ -alkyl or wherein R, R ¹ and X have the oh ige meaning in Ci-C ₄ -AIkOXVgIUiPPe; R ¹ for Ci-C ₄ -AIkOXy-, Phen an inert organic solvent in the presence oxy-, halophenoxy-, Ci- Gi-alkylamino-, dialkyl- i an acceptor of hydrogen chloride. amino or thiazolinyl-2-amino group; X for Sauer f Alcohols are used as organic solvents, 50 substance or sulfur; Z for the group -CH ₂ -CH ₂ - I. Ketones, chlorinated hydrocarbons, esters and or -CH = CH-, and an inert carrier for I. others in question. As an acceptor for hydrogen chloride contains this. I. preferably serve tertiary amines, for example The following compounds are particularly active herbicides I. Triethylamine, pyridine, collidine and others. gene: ί The components mentioned are taken in stoichiometric 55 metric ratio. The reaction runs under if normal pressure without heating or under heating. I. It has been found that the compounds of the formula A. I have a high level of insecticidal as well as acaricidal and herbicidal ΪΪ Show activity. 60 [ It is according to the invention an insecticidal and acaricidal mixture proposed which as an active ingredient one of the compounds of the formula according to the invention ξ R N 65 I. \. \ I.
I. P-NH-C Z / Il \ /
R ¹ XS I. wherein R is Ci-C ₄ -alkyl, halogen-Ci-C ₄ -alkyl or f Ci -C ₄ alkoxy group; R ¹ for Ci -Gt-alkoxy-, phenoxy, I. ί
i ·
I.

The thiazolinyl (thiazolyl) amides of phosphoric acid of the formula I can be used alone or as a mixture used with other pesticides.

The invention is illustrated by the following examples, of which Examples 1-15 illustrate the process for the preparation of the substances, example 16 the preparation of the mixture, examples 17 to 18 the Illustrate pesticidal properties.

example 1
O-phenyl-methanephosphonic acid-N-thiazolinyl-2-amide

To 3.4 g of O-Phenylmnethanphosphonsäurechlorid in A solution of 1.8 g of 2-aminothiazoline and 2.5 ml of diethylamine in benzene is added dropwise to benzene while cooling with ice. The mixture is left to stand overnight. Then the triethylamine hydrochloride is filtered off and the solvent is distilled off in vacuo. Water is added to the precipitate and the crystals are filtered off off, washed with ether and recrystallized twice from acetone. O-phenyl-methanephosphonic acid-N-thiazolinyl-2-amide is obtained, Yield 76%, melting point 137 to 138 ° C.

Found in %:

N 10,78,10,80; P 12.07.11.85;

S 12.75,12,55.

C ₁₀ H ₁₃ N ₂ O ₂ PS
Calculated in%:

N 10.93; P 12.09; P. 12.51.

Example 2

O-phenyl-methanthiophosphonic acid-N-thiazolinyl-2-amide

Analogously to Example 1, O-phenyl-methanthiophosphonic acid-N-thiazolinyl-2-amide is obtained from 2.6 g of O-phenylmethantiophosphonic acid chloride, 1.3 g of 2-aminothiazoline and 2 ml of triethyiamine, yield 28.8%, melting point 130 to 130 , 5 ⁰ C.

Found in %:

N 10,24,10,25; P 10.75,10.89.

C ₁₀ H ₁₃ N ₂ OPS ₂
Calculated in%:

N 10.29; P 11.37.

Example 4

0-2,4-dichlorophenyl-methanthiophosphonic acid-N-thiazolinyl-2-amide

Analogously to Example 1, 6.8 g of 0-2,4-dichlorophenyl methanethiophosphonic acid chloride are obtained from 2.5 g of 2-aminothiazoline and 3.5 ml of triethyiamine 0,2,4-dichlorophenyl-methanthiophosphonic acid-N-thiazolinyl-2-amide, Yield 55%, melting point 117 to 118 ° C.

Found in %:

N 8.29.8.25; S 18.28.19.07.
C ₁₀ H ₁₁ Cl ₂ N ₂ OPS
\% Calculated in%:

N 8.21; S 18.79.

Example 5

0-2,4-dichlorophenyl methanephosphonic acid

N-thiazolinyl-2-amide

Analogously to Example 1, 7.6 g of 0-2,4-dichlorophenylmethylphosphonic acid chloride are obtained from 3 g of 2-aminothiazoline and 4.1 ml of triethyiamine O-2,4-dichlorophenyl-methanephosphonic acid-N-thiazolinyl-2-amide, Yield 18%, melting point 112-113 ° C.

Found in %:
N 8.15.8.20; S 10.16.9.83.

C ₁₀ H ₁₁ Cl ₂ N ₂ O ₂ PS
Calculated in%:

N 8.62 S 9.86.

Examples

0-2,4,5-Trichlorophenyl-methanethiophosphonic acid-N-thiazolinyl-2-amide

Analogously to Example 1, 7.6 g of O-2,4,5-trichlorophenylmethanthiophosphonic acid chloride are obtained, 2.5 g of 2-aminothiazoline and 3.5 ml of triethyiamine O-2,4,5-trichlorophenylmethanthiophosphonic acid-N-thiazolinyl-2- amide, yield 31.4%, melting point 124-124.5 ° C.

45

50 Found in%:

N 7.30,7,31; P 8.04.7.99;

S 16,73,16,54.

C ₁ OH ₁₀ Cl ₃ N ₂ OPS ₂
Calculated in%:

N7.46; P8.25; S17.07.

Example 3

O-4-chlorophenyl methanephosphonic acid

N-thiazolinyl-2-amide

Analogously to Example 1, from 5.3 g of O-4-chlorophenylmethanephosphonic acid chloride, 2.88 g of 2-aminothiazoline and 3.8 ml of triethyiamine, O-4-chlorophenylmethanephosphonic acid-N-thiazolinyl-2-amide, yield _b0 71%, melting point 122 to 123.5 ° C.

Found in %:

N 93.930; P 10,86,10,62;

S 11.06.11.26.

Ci ₀ H ₁₂ CIN ₂ O ₂ PS
Calculated in%:

N9.64; P10.65; S 11.03.

Example 7

0-2,4-dichlorophenyl-chloromethane thiophosphonic acid-N-thiazolinyl-2-amide

Analogously to Example 1, 7.7 g of 0-2,4-dichlorophenylchlonnethanthiophosphonic acid are obtained from

chloride, 2.5 g of 2-aminothiazoline and 3.5 ml of triethyiamine O ^^ - dichlorophenyl-chloromethanthiophosphonic acid-N-thiazolinyl-2-amide, Yield 32.2%, melting point 145 to 146 ° C.

Found in %:

N 7.19.7.06; P 8,11,8,12.

Ci ₀ H ₁ OCl ₃ N ₂ OPS ₂
Calculated in%:

N 7.46; P 8.25.

Example 8

O-ethyl-methanthiophosphonic acid-N-thiazolinyl-2-amide

Analogously to Example 1, 4.7 g of O-ethyl methanethiophosphonic acid chloride are obtained, 3 g of 2-aminothiazoline and 4.1 ml of triethylamine O-ethyl-methanthiophosphonic acid-N-thiazolinyl-2-amide, Yield 68%, melting point 104 to 105 ° C.

Found in %:

P 14,10,13.95; S 28,18,28,39.

C ₆ H ₁₃ N ₂ OPS ₂
Calculated in%:

P 13.81; S 28.59.

10

15th

Example 11

O-phenyl-methanephosphonic acid-N-thiazolyl-2-amide

Analogously to Example 10, from 2.0 g of 2-aminothiazole, 3.81 g of O-phenylmethanephosphonic acid chloride are obtained and 2.02 g of triethylamine O-phenyl-methanephosphonic acid-N-thiazolyI-2-amide, Yield 38%, melting point 83 to 85 ° C.

Found in %:

N 9.58.9.63; P 10,31,10,40;

S 10.66, 10.95.

C ₁ OH ₁₀ ClN ₂ O ₂ PS
Calculated in%:

N9.70; P10.73; S11, ll.

Example 9

20th

O-4-Chlorophenyl-methanethiophosphonic acid-N-thiazolinyl-2-amide

Analogously to Example 1, 6.2 g of O-4-chlorophenylmethanthiophosphonic acid chloride are obtained, 2.8 g of 2-aminothiazoline and 3.8 ml of triethylamine O-4-chlorophenylmethanthiophosphonic acid-N-thiazolinyl-2-amide, Yield 34%, melting point 130 to 131 ° C.

Found in %:

P 9.62; S 20.85.

C ₁₀ Hi ₂ ClN ₂ OPS ₂
Calculated in%:

P10.09; S20.91.

Example 10

O-4-chlorophenyl-melhanthiophosphonic acid-N-thiazolyI-2-amide

35

40 Example 12

O-ethyl-methanephosphonic acid-N-thiazolinyl-2-amide

Analogously to Example 1, from 4.08 g of 2-aminothiazoline, 5.70 g of O-ethylmethanephosphonic acid chloride are obtained and 4.04 g of triethylamine O-ethyl-methanephosphonic acid-N-thiazolinyl-2-amide in quantitative yield from melting point 114 to 115 ° C.

Found in %:

N 12.45.12.48; S 13,98,14,14;

C ₈ H ₁₅ N ₂ O ₃ PS.
Calculated in%:

N 12.38; S 14.17.

A solution of 1.9 g of 2-aminothiazole and 3 ml of triethylamine in 200 ml of benzene is added dropwise at a Temperature from 10 to 15 ° C 4.5 g of O-4-chlorophenyl methanethiophosphonic acid chloride to. The mixture is boiled for 5 hours and the precipitate is filtered off. The filtrate is evaporated in vacuo. The oil chromatographs one on a column with silica gel. With a mixture of acetone with hexane in a ratio of 1:20 First, N, N'-bis- (4-chlorophenoxymethylthiophosphinyl) -iminothiazoline is washed off, yield 6.3%, melting point 133-134 ° C

Found in %:

Cl 13.74, 13.73; N 5.32.5.23;

P 12.35.11.77.

C ₁₇ H ₁₆ Cl ₂ N ₂ O ₂ P ₂ S ₃
Calculated in%:

C113.91, N5.50, P12.16.

Example 13

O-methyl-O-phenyl-thiophosphoric acid-N-thiazolinyl-2-amide

Analogously to Example 1, from 3.06 g of 2-aminothiazoline, 6.7 g of O-methyl-O-phenylchlorothiophosphate are obtained and 3.03 g of triethylamine O-methyl-O-phenylthiophosphoric acid-N-thiazolinyl-2-amide, Yield 5%, melting point 164 to 165 ° C.

Found in %:

N 9,70,9,60; P 10,67,10,87;

P. 22 38 22 49

C ₁₀ H ^ N ₂ O ₂ PS ₂
Calculated in%:

N 9.72; P 10.74; S 22.24.

Then, O-4-ChlorphenyI-methanthiophos- e> o washes phonsäure-N-thiazolyl-2-amide from, yield 34.6%, melting point 105 to 106 ⁰ C.

Found in %:

N 9,11,9,13; S 20.82.20.88.

C ₁₀ H ₁ OCIN ₂ OPs ₂
Calculated in%:

N 9.19; S 21.04.

Example 14

Methanephosphonic acid-N, N-diethyl-N'-thiazolinyl-2-diamide

Analogously to Example 1, 3.06 g of 2-aminothiazoline, 5.10 g of Ν, Ν-diethylamidomethanephosphonic acid chloride are obtained and 3.03 g of triethylamine-methanephosphonic acid-N, N-diethyl-N'-thiazolinyl-2-diamide in the form of oil in a yield of 74%. When treating the oil with aloholic solution of

Picric acid forms the picrate of methanephosphonic acid-N, N-diethyl-N-thiazolinyl-2-diamide from the

Melting point 102 ⁰ C.

Found in %:

N 17.90.17.80; S 7.04.

C ₈ Hi ₈ N ₃ OPS
Calculated in%:

N 18.10; S 6.90.

Example 15

Methanthiophosphonic acid N.N'-bis (thiazolinyl-2) -diamide

3.7 g of methanethiophosphonic acid chloride are added to 5.5 g of 2-aminothiazoline and 7.5 ml of triethylamine. The mixture is stirred for 30 minutes and 100 ml of chloroform are added. Falling out of solution when standing Crystals of methanethiophosphonic acid-N.N-bis-thiazolinyl-2) diamide off, yield 28%, melting point 152 to 154 ° C.

Found in %:

N 21.06; P 11.55; S 23,20,23,13.

C ₇ H ₁₃ N ₄ OPS ₂
Calculated in%:

N 21.20; P 11.71; S 24.26.

solutions

b) Action against rice beetles
(Calandra oryzae L.)

Rice beetles were sprayed with aqueous or aqueous-alcoholic solutions of the compounds of the formula I. The liquid consumption was 35 ml / m ² . The dead beetles were counted after 48 hours.

10

c) Action against graphosomal bugs
(Graphosoma semipunetatum F.)

Drops of de ·· solutions of the Compounds of formula 1 in acetone in a volume of 1.1 ml. The count of the living or dead bedbugs occurred after 24 hours.

Example 16
Mesh powder

25 parts by weight of the compound of formula 1.10 parts by weight of a mixture of polyethylene glycol alkylaryl ether, 5 parts by weight of alcoholic sulphite waste liquor and 60 parts by weight of kaolin are mixed up to to achieve a homogeneous mixture that is used in the form of an aqueous suspension.

Granualt

10 parts by weight of the compound of formula 1 are dissolved in acetone, and 90 parts by weight of silicon oxide are added to, mixes and removes the acetone.

50

60

Example 17
Insecticidal and acaricidal effects

a) Effect against house flies
(Musca domestica L)

Solutions of the compound of Foi mel I in acetone (0.5 Ml) was applied locally to the front backs of house flies. The count of those who died Insects occurred after 24 hours.

20th

d) Action against colorado beetles
(Leptinotarsa decemlineata Say)

Drops of the solutions of the compounds of formula 1 in acetone in a volume of 3.3 ml were brought on the vetral surface of the beetle. The dead beetles were counted 24 hours after Treatment.

JO

1 to 20 weights ^; The compounds of the formula I are dissolved in 99 to 80 parts by weight of a suitable solvent (water, acetone, alcohol, etc.), after which the solution is ready for use.

e) Action against mosquito larvae
(Culex pipiens molestus F.)

B ^ i the determination of the toxicity one brought the Mosquito larvae for 24 hours in the solutions to be tested, which contain a certain amount of the Compounds of formula I contained. The living and dead larvae were counted after 24 Hours.

f) Action against common spider mites
(Tetranychus urticae Koch)

Bean leaves infected with common spider mite were immersed in the solutions of the Compound of formula 1 in acetone (to determine the contact effect) or the upper one is wetted Leaf area (to determine depth).

Tables 1 and 2 show the LC ₅₀ values of the compounds of the formula I tested

Example 18

Systemic effect of the
O-phenyl-methanephosphonic acid-N-thiazolinylamide

against alfalfa
(Aphis medicaginis cook).

Ten percent of the granules were placed in the ground Preparations (Example 16) at an application rate of 1.2 to 3 kg / ha.

The experiments showed that the preparation had systemic effects against aphids that damage cotton, has, protects it for 10 days and is more effective than Dimethoat®

13 14

Table 1

Comparative toxicity (LC ₅₀ ,%) of the compounds of the formula I for harmful insects and mites

link

Grapho- housefly rice beetle

somawanze

L = W Colorado mosquito beetle (Lai ven)

Common spider mite

Conclusion effect

Deep effect

0.05

CH ₃ P

NH-C

S ^J

S OCf ₁ H ₃ Cl, -2.4 CH ₃ P N-,

0.10

N Η — Ο

S- ¹

O ^ -Dimethyl-S-l ^ -di- -

(carba thoxy) ethyl dithiophosphate

0,0-dimethyl- (1-hydroxy-2,2,2-trichloroethyl) phosphonate

O, O-dimethyl-O- (4-methyl- - thio-3-methylphenyl) thiophosphate

O, O-diethyl-O- (2-isopropyl) - 0.1 4-methylpyrimidyl-6) thiophosphate

O.O-dimethyl-O ^ -chloro-0.12

1 - (2,4,5-trichlorophenyl vinyl phosphate

Ο, Ο-diethylphosphoryl-0.04

O- (2-cyanobenzaldoxime)

N- (4-chloro-2-methyl) -N ', N'-di

methylformamidine

O, O-dimethyl-O- (3-methyl- - 4-nitrophenyl) thiophosphate

0,0-diethyl-S- (6-chloro- -

benzoxazolinon-2-yl-3-methyl) dithiophosphate

2,4,5,4-tetrachlorodiphenyl- '- sulfone

O, O-Dimethyl-S- (4,6-diamino- - 1,3,5-triazinyl-2-methyl) dithiophosphate

^ ChlorphenyW-chlorobenzene- - sulfonate

0.01 0.06

0.25 0.23

0.20

0.04 0.07

0.02

0.07

0.04 KtO ⁵ 0.002 0.02

0.10 2.10 " ⁷ 0.23 0.10

3.10 "

0.08 5.10 " ²

8.1Q- ²

9.10 "

0.25 7.10 "

0.005 0.4

2 10 0.02 0.003 10

15 16

Table 2

Comparative toxicity of the compound of the formula I for harmful insects

links

LC ₅₀ %

Grapho- colorado beetle mosquitoes

soma bug (larvae)

3 4

S OC ₆ H, C1 ₃ - (2,4,5) 0.1

P Ν _Ί

CH ₃ NH-C

S OC ₆ H ₃ CI -, - (2.4) -

PN _n

ClCH ₂ NH-C

S OC ₆ H ₃ Cl ₂ - (2.4)

P Ν-,

CH ₃ NH-C

C_

N-i

CH ₃ NH-C

O OC ₆ H ₄ CI- (4)

P N-i

CH ₃ NH-C

S ^J

S OC ₆ H ₄ Cl- (4)

P Ν-,

CH ₃ NH-C

O OC ₂ H ₅

PN ₁

CH ₃ NH-C

S ^J

0.05

0.1 0.014
(0.01-0.02)

0.027
(0.020-0.039)

0.1

0.056

3.2.10 ~ ⁷ (2.7.1Q- ⁷ -3.8.10 " ⁷ )

8,1.1 (T ⁶ (6.S.10 " ⁶ - 9.6.10 ~ ⁶ )

2,5.10 ^"7 (2,1.10 ^-7 -2,9.1 (T ⁷⁾

6.5.10 " ⁵ (3.8.10 ~ ⁵ -8.0.10 ~ ⁵ )

1.10

-5

1.4.10- ⁶ (!,! ΙΟ ^"6 -1.6.10- ⁶⁾

1.10

-5

continuation

links

LC ₅₀₁ V.

Grapho- colorado beetle soma bug

2 mosquitoes (larvae)

OQH ₃ Cl ₂ - (2.4)

CH ₃ NH-C

Nn

S-

2,4,5,6,7,8,8-heptachlor-4,7-endo

methylenebicyclo (4,3,0) -nanen-5

O, O-dimethyl- (1-hydroxy-2,2,2-trichloroethyl) phosphonate

Ο, Ο-diethylphosphoryl-0- (2-cyanobenzaldoxime)

0.025

0.022 (0.017-0.029)

0.14 (0.11-0.17)! .ΙΟ

" ⁵

2,5.10- ⁶ (2, ⁶ LlO- -2,9.10 ^"6)

4,2.10 ~ ^{7 (3.3.10- 7 -5.2.10- 7)}

Claims (1)

Patent claims: 1. Phosphorus (phosphorus) or thiophosphorus (ThiGphosphonic) acid thiazolinyl (thiazolyl) amides the formula R N P-NH-C Z / Il \ / R ¹ XS