DE1184759B - Process for the production of new chloromethylthionothiolphosphonic acid esters suitable as pest repellants - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY Internat. Class: C07f

GERMAN

PATENT OFFICE

EDITORIAL

German KL: 12 ο -26/01

Number:
File number:
Registration date:
Display day:

St20283IVb / 12o
February 12, 1963
January 7, 1965

The invention relates to a method of manufacture of new chloromethylthionothiolphosphonic acid esters suitable as pesticides the general formula

Process for the production of als
Pesticide suitable new
Chloromethylthionothiolphosphonic acid esters

ClCH ₂

: p —s — z

in which X is an n-propyloxy or isopropyloxy radical and Z

a) a phenyl radical substituted by halogen or nitro groups or

b) denote the naphthyl radical,

in which one is a compound of the general formula

C1CH ₂ \ Il

, P - halogen

with a compound of the general formula

HS —Z

wherein X and Z have the meaning given, in the presence of a hydrogen halide binding agent By means of and an organic solvent at temperatures between 30 and 65 ° C in itself implemented in a known manner.

The compounds which can be prepared according to the invention are suitable for controlling aphids, mites, Butterflies, fungi and insects and to regulate the activity and growth of Plants, surprisingly, is their pesticidal and herbicidal effects, especially their effects on butterflies, exceptionally high, though they are are relatively little toxic to mammals. The term "pest" refers to the lower forms of life which are usually fought with chemicals, to the exclusion of higher animals.

When carrying out the process according to the invention, for example 3,4-dichlorophenyl-, p-nitrophenyl-, 3,4,5-trichlorophenyl-, o-chloro-p-bromophenyl or o-nitro-p-chlorophenyl mercaptan be used.

Applicant:

Stauffer Chemical Company, New York, N.Y.

(V. St. A.)

Representative:

Dr. W.Beil, A.Hoeppener and Dr. H.-J.Wolff, lawyers, Frankfurt / M., Antoniterstr. 36

Named as inventor:

Ralph B. Fearing, Hammond, Ind .;

Edward N. Walsh, Chicago Heights, JIL;

John Bruce McBain, Campbell, Calif. (V. St. A.)

Claimed priority:

V. St. v. America 13 February 1962 (172 890)

As a hydrogen halide binding agent is suitable, for. B. triethylamine and as an organic solvent Benzene, dioxane, toluene or xylene. The hydrogen halide binding agent serves to to bind the hydrohalic acid which is formed as a by-product during the reaction, and to prevent their reaction with the thionophosphonic acid ester. According to the method according to the invention yields are achieved which correspond to about 85 to 98% of theory.

The following example illustrates the invention.

ecm benzene, 31.2 g chloromethylthionophosphonic acid O-isopropyl ester chloride and 22.0 g of p-chlorophenyl mercaptan were placed in a reaction flask

409 767/398

given, and a solution of 15.4 g of triethylamine in benzene was slowly added while the temperature was kept at 30 ^° C. After the addition of the triethylamine, the contents of the flask were heated to 40 to 42 ° C. for 40 minutes. The product was then washed thoroughly with water to remove triethylamine hydrochloride and with a 10% NaCl solution to remove acidic impurities. The benzene was evaporated in vacuo and the remaining product was filtered through a sintered glass filter. The yield obtained was 42.2 g (89% of the theoretical value) of chloromethylthionophosphonic acid O-isopropyl-Sp-chlorophenyl ester with a refractive index H ² D = 1.5955. The elemental analysis of the product gave 9.9% P, 20.7% S and 22.2% Cl (theoretically calculated values: 9.83% P, 20.35% S and 22.5% Cl.

Using the procedure described in the example, the following compounds were made manufactured:

a)

ClCH ₂ X Il

; p

p -

Chloromethylthionophosphonic acid - O - η - propyl-Sp-chlorophenyl ester; κ !, ⁵ = 1.6000; Yield = 95% of the theoretical amount; Analysis: found 9.6% P, 20.4% S and 21.5% Cl; calculates 9.85% P, 20.3% S and 22.5% Cl.

b)

ClCH ₂
1-C ₃ H ₇ O

P-S

Chloromethylthionophosphonic acid - O - isopropyl-S-3,4-dichlorophenyl ester; raff = 1.6000; Yield = 83% of the theoretical amount; Analysis: found 8.9% P, 17.2% S and 28.3% Cl; calculates 8.8% P, 18.3% S and 30.5% Cl.

c)

ClCH ₂
nC ₃ H ₇ O

Chloromethylthionophosphonic acid - O - η - propyl-Sp-bromophenyl ester; ng = 1.6130; Yield = 95% of the theoretical amount; Analysis: found 8.75% P, 18.1% S and 5.33 m. Ä. Total halogen per gram of product; calculates 8.6% P, 17.8% S and 5.56 m. Ä. total halogen per gram of product.

d)

ClCH ₂ N
iC ₃ H ₇ O ^/

NO ₂

Chloromethylthionophosphonic acid - Q- - isopropyl-Sp-nitrophenyl ester; nf = 1.5930; Yield = 62% of theory; Analysis: found 10.5% P, 20.5% S, 12.2% Cl and 4.8% N; calculates 9.5% P, 19.7% S, 10.9% Cl and 4.3% N.

e)

CLCH _2x JI

nC ₃ H ₇ O ^/

P-S

Chloromethylthionophosphonic acid - O - η - propyl-S-jS-naphthyl ester; n ² i = 1.6425; Yield = 95% of the theoretical amount; Analysis: found 10.5% P, 19.6% S and 10.9% Cl; calculates 9.4% P, 19.4% S and 10.7% Cl.

f)

ClCH

■ 2 \

P-S

nC ₃ H ₇ O ^/

Chloromethylthionophosphonic acid - O - η - propyl-

S-3,4-dichlorophenyl ester; nl ⁵ = 1.6035; Yield = 97% of theory; Analysis: found 8.7% P, 16.4% S and 28.7% Cl; calculates 8.8% P, 18.34% S and 30.5% Cl.

G)

ClCH _2x I.
iC ₃ H ₇ O ^/

Chloromethylthionophosphonic acid - O - isopropyl-Sp-fluorophenyl ester; nS ⁵ = 1.5725; Yield = 100% of theory; Analysis: found 10.1% P, 21.0% S, 13.1% Cl and 6.9% F; calculates 10.30% P, 21.4% S, 11.9% Cl and 6.36% P.

The pest control effectiveness of some of the compounds from the previous examples in comparison with known compounds can be seen from the following table, in which the LD50 values for each group of test animals as a specific one, expressed in micrograms Amount of poison (in the bio-experiment) or as a certain concentration of the poison (in%) in an aqueous one Solution (in the spray test) are specified.

In the table, the different types of pests are identified with the following letters:

HF house fly - Musca domestica (Linn.).

AR American cockroach - Periplaneta americana (Linn.).

GR German cockroach - Blattella germanica (Linn.).

MWB Spotted milkweed bug - Oncopeltus fasciatus (Dallas).

2 SM double-spotted mite - Tetranychus tela-

(P. E.) rius (Linn.) Postembryonic.

SMC saltwater moraine - Estigmene acrea (Drury).

LDo values of compounds produced according to the invention and known for various pests

Type of
link

example

a)

formula

JC ₃ H ₇ C /

₂ V

η - C ₃ H ₇ CK

p -

ClCH

₂ V

i - C ₃ H ₇ CK

Il

p —s

η - C ₃ H ₇ CX

ClCH

_2x

1-C ₃ H

₇ O ⁷

p -

-NO ₂

^CHs )!

H ₅ CX

NO ₂

b)

c)

d)

Comparative substance I

Reference substance II

Comparative substance III

k. W. means: no effect

The comparative experiments show the superiority of the compounds prepared according to the invention compared to the known compounds.

In the spray tests with house fly, cockroach and milkweed bug, ten to twenty-five insects were locked in cardboard tubes (diameter 7.9 cm; length 6.7 cm). The cages were given cellophane bottoms and perforated lids. Food and water were placed in each pod. The test compounds were used to prepare dispersions starting from a solution of ¹ g of the poison in 10 ecm of acetone. This solution was then diluted with water containing 0.015% of a sulfonate wetting agent and 0.005% of methyl cellulose as an emulsifier,

C ₂

CH _3n
η - C ₃ H ₇ O ^/

ClCH:

; p —s-

AR

0.01%

0.1%

0.1%

0.1%

k. W.

0.1%

0.1 ο / ο

k. W.

GR

0.003 ° /,

0.050 / ₀

k. W.

k. W.

MWB

0.03%

0.1%

k. W.

0.1%

k. W.

k. W.

k. W.

k. W.

2SM (P.E.)

0.005%

k. W.

0.1%

k. W.

k. W.

k. W.

k. W.

0.1%

SMC

0.0003%

0.003%

0.010 / ₀

O, O5o / o

O, Olo / o

k. W. at 0.003%

0.002%

0.1%

the amount of water being such that the active ingredient is reduced to a concentration of 0.1% or less has been diluted. The test insects were then sprayed with this dispersion. To Live and dead insects were counted for 24 and 72 hours.

Compounds in which many flies died in the spray test were also used in the bio test investigated this species. In this experiment, a certain amount of the toxin was limited in one Brought space. The same cages were used in the bioassay with flies as in the spray tests.-A weighed amount of the toxin was used together with 1 ecm of acetone, that contained light spray oil, in a 6 cm large

Given to petri dish. After the solution air dried it became a twenty-five pod containing female flies placed over the residue. After 24 and 72 hours, the living and dead insects are counted.

In the spray test, which was intended to determine the miticidal effect, were young pinto bean plants in the primary leaf stage are used as host plants for the mites. The bean plants were infected with several hundred mites and then with an aqueous one for so long Test dispersion, prepared as described, sprayed until the dispersion of the leaves dripped down. The sprayed plants were placed in a greenhouse and left there for 14 days. After 7 to 14 days, the effect of the test compounds on the mites was determined.

When evaluating the activity against butterflies, the saltwater moraine caterpillar was used as the test organism used. It is representative of a class to which many are economically significant Include plant pests. The different strength test dispersions were after Process already described prepared by adding the active substance basic solutions from water and added wetting agents. About 12.7 cm long dock leaves were immersed in these dispersions for 10 seconds immersed. Then the leaves were allowed to dry. A round filter paper was inserted into a 1 pound tin can and moistened with 1 ecm of water. The dried dock leaves were put into the container together with five saltwater moor larvae in the third stage. To be easy To be able to observe, the lid of a Petri dish was used. These attempts were 48 hours carried out. After 24 hours, a fresh one, not immersed in the dispersion, became Put the dock leaf in the container. After 24 to 48 hours, the live and dead animals became counted out.

The compounds of the example and compound d) have also been tested for their effect on bedbugs, especially the pea aphid (Macrosiphum pisi) examined, which of both compounds in one Concentration of 0.01% was totally destroyed.

Claims (1)

Claim: Process for the preparation of new chloromethylthionothiolphosphonic acid esters suitable as pesticides of the general formula c ClCH ₂
X P —S —Z in which X is an n-propyloxy or isopropyloxy radical and Z a) a phenyl radical substituted by halogen or nitro groups or b) denotes the naphthyl radical,
characterized in that a compound of the general formula - halogen with a compound of the general formula
HS —Z wherein X and Z have the meaning given, in the presence of a hydrogen halide binding agent and an organic solvent at temperatures between 30 and 65 ⁰ C in a manner known per se. Considered publications:
French patent specification No. 1 266 440, 280,984; U.S. Patents Nos. 2,714,100, 2,841,604, 863,903, 2,900,405, 2,910,402, 2,922,810, 2,927,014, 960,522, 2,988,474, 2,988,565; Reports of the Academy of Sciences of the USSR (Russian) 109, 1956, pp. 555-557 in Chemisches Zentralblatt, 1957, p. 5534; Journal for general chemistry (Russian), 29 (91), 1959, pp. 3954 to 3956, reported in Chemischen Zentralblatt, 1961, p. 10 518; J. is Lab. Denison Univ. 45, 1960, p. 50/51, reported in Chemisches Zentralblatt, 1962, p. 11 159. 409 767/398 12.64 © Bundesdruckerei Berlin