DE1020346B - Insecticides and processes for their manufacture - Google Patents

Description

GERMAN

It has been found that by further chlorination

by ^ S.öJ.lO ^
trahydrophthalan contains extremely effective insecticides. The chlorination can be carried out by the most varied of processes which cause a substitution in the tetrahydrofuran ring of 4,5,6,7,10,10-hexachloro-4,7-endomethylene-4,7,8,9-tetrahydrophthalane. Chlorination products are obtained as active ingredients, which have an optimal effect when two additional chlorine atoms are absorbed.

The insecticidal compounds obtainable according to the invention can, for. B. by introducing gaseous Chlorine in the solution of 4,5,6,7,10,10-hexachloro-4,7-endomethylene4,7,8,9-tetrahydrophthalane in carbon tetrachloride or other chlorinated hydrocarbons or others customary in chlorination in the liquid phase inert solvents can be obtained. But you can also use such solvents that by chlorination be converted into chlorinated hydrocarbons, in particular benzene, toluene and others. m. on the other hand are Also suitable as chlorinating agents are those compounds from which the chlorine is easily split off can, such as B. Sulfuryl chloride.

However, the reaction can also be carried out without the use of a solvent, the starting material being comes into direct contact with the chlorine or the chlorinating agent. The im general room temperatures. However, it is advantageous to carry out the chlorination, which proceeds as a chain reaction To stimulate heat, light or radical-forming substances and keep them going. The chlorination can be in Carry out glass vessels or enamelled metal vessels discontinuously or continuously. Depending on the Working conditions, with or without a solvent, the chlorine uptake is gravimetric or by ongoing Sampling from the reaction vessel and chlorine determination followed. The reaction can be considered to have ended when the desired degree of halogenation is reached. This is generally a total of 8 g atoms of Cl per mole of starting material, however, are Products with 6.5 to 10 g atoms of Cl per mole are also useful and effective.

When using a solvent, the active substance is separated off by distillation or crystallization. What remains is a white crystalline substance that can be used as a pesticide without prior cleaning can be assembled. When maintaining a degree of chlorination of 8 g atoms of chlorine Musca domestica achieves maximum effectiveness per mole of starting material. In this case it is Chlorination product is a largely uniform substance that can be recrystallized from n-heptane and then has a melting point of 120 to 122 ° (corr.). Apparently it is 1,3,4,5,6,7,10,10-octachlor - 4,7 - endomethylene - 4,7,8,9 - tetrahydrophthalane.

Insecticides and processes
for their manufacture

Applicant:

Ruhrchemie Aktiengesellschaft,
Oberhausen (RhId.) - Holten

Dr. Hans Feicutinger, Duisburg-Beeck,

Dr. Hans Tummes, Duisburg-Meiderich,

and Siegfried Puschhof, Duisburg-Beeck,

have been named as inventors

However, in addition to this compound, especially in the case of chlorination products with less or more than 8 g atoms of chlorine in the molecule, other chlorinated compounds are also present in the reaction product.

The chlorination mixtures obtained with the aid of the process according to the invention or else the pure.

trahydrophthalan can easily be used for commercial packaging be used. It can be used with the usual additives emulsions, Produce suspensions, dusts and grit, sprays, fumigants or aerosols. the Active ingredients can also be formulated as a mixture with other insecticides that do not chemically react with them will.

example 1

100 g of 4,5,6,7,10,10-hexachloro-4,7-endomethylene-4,7,8,9-tetrahydrophthalane were dissolved in 300 ecm of carbon tetrachloride by heating and put into the solution at about 70 ° every hour 1 introduced chlorine under UV irradiation. The solution was stirred vigorously during the chlorination. After 10 minutes the reaction was ended and the solution was evaporated in vacuo. 110 g of a white crystalline substance remained which, on the basis of the elemental _analysis , had _{the composition C 9} H _{6) 4} OCl 6r6.

Example 2

According to Example 1, 100 g of 4,5,6,7,10,10-hexachloro ^^ - endomethylene ^ J.S ^ -tetrahydrophthalane in

709 808/290

300 ecm of carbon tetrachloride dissolved and chlorinated at 70 ° with 25 liters of chlorine per hour for 40 minutes. The white crystalline product (120 g) remaining after the chlorination and evaporation of the solvent had the empirical formula C ₉ H ₃ , ₉ O Cl ₈ , _x . Recrystallized from n-heptane, a substance remained with a melting point of 120 to 122 °. Formula: C ₉ H ₄ OCl ₈ . Molecular Weight: 411.78.

Example 3

As in Example 1, 100 g of 4,5,6,7,10,10-hexachloro-4,7-endomethylene-4,7,8,9-tetrahydrophthalane were dissolved in 300 ecm of chlorocarbon and gassed with 25 liters of chlorine per hour for 2 hours . After evaporation, 130 g of a crystalline product of the empirical formula C ₉ H ₃ OCl _{9 remained} .

Example 4

There were 100 g of 4,5,6,7,10,10-hexachloro-4,7-endomethylene-4,7,8,9-tetrahydrophthalane dissolved in 200 ecm carbon tetrachloride and with 80 g sulfuryl chloride and 0.5 g of benzoyl peroxide heated under the reflux condenser for 8 hours. After the completion of the reaction, the solution became evaporated to dryness in vacuo. A yellowish white residue of the composition remained

30th

Example 5

273 g of hexachlorocyclopentadiene, 100 g of 2,5-dihydrofuran and 50 ecm of benzene were placed in a pressure vessel Heated to 120 ° for 16 hours. The reaction mixture was then evaporated in vacuo freed from benzene and excess dihydrofuran on the water bath and the residue from methanol recrystallized with the addition of decolorizing agents. This gave 310 g of 4,5,6,7,10,10-hexachloro-4,7-methylene-4,7,8,9-tetrahydrophthalane from melting point 225 to 230 °; Partial decomposition of the compound began at the melting point. Formula:

C ₉ H ₆ OCl ₆ . Molecular Weight: 342.88.
Analysis:

substance Relative toxicity
after 24 hours
against 4 days old
Females of
Musca domestica 90%
Mortal
speed 50%
Mortal
speed 10 j / .l ^ .SAS.ö-hexachlorocyclohexane .. 10 3.1 p.p'-dichlorophenyl-trichloroethane .. 0.63 10 1,2,3,4,12,12-hexachloro-1,4,5,8-di-
methylene-LAS.SÄlO-hexahydro-
naphthalene (aldrin) 10 10 '1,4,5,8-dimethylene-1,4,5,6,7,8,9,
10-octahydronaphthalene (dieldrin) 8.6 0.2 Chlordane 1 5 800 3,0-diethyl-thiophosphoric acid-Op-
nitrophenyl ester, 70% (E 605 forte) 150 10 x.yAS.o ^ lO.lO-Octachlor- ^ - methy-
len-1,2,4,7,8,9-hexahydroindene
(Holtan) 10 200 Chlorination product example 1 43 670 Chlorination product example 2 300 25th Chlorination product example 3 10 80 Chlorination product example 4 60

The active substance according to the invention has an extremely good initial effect in an interesting way, as can be seen from the table below, in which the relative values of the 50% supine position after 2 hours are specified.

40 substance

C. H O Cl calculated 31.52%, 1.76%, 4.67 ° _{/ o} , 62.05%; found 31.51%, 1.73%, 4.58%, 62.34%.

45 y.l ^ .SAS.o-hexachlorocyclohexane ρ, ρ'-dichlorodiphenyl trichloroethane

Of the 4,5,6,7,10,10-hexachloro-4,7-methylene-4,7,8,9-tetrahydrophthalane produced 200 g were dissolved in a mixture of 1.5 l of carbon tetrachloride and, after adding 10 g of aluminum chloride, at room temperature gassed with 601 chlorine every hour. After 3 hours 40 minutes the solution was washed with water and the Carbon tetrachloride is distilled off in vacuo after drying with calcined sodium sulfate. It left behind 239 g of crystalline residue which, recrystallized from gasoline, has a melting point of 120 to 122 ° showed. The compound obtained is 1,3,4,5,6,7,10,10-octachloro-4,7-endomethylene-4,7,8,9-tetrahydrophthalane.

The effectiveness of the new insecticides was determined using a modified ^{method described by WM Hoskins and PS Messenger r} Agricultural Control Chemicals, Advances in Chemistry, Series I (1950), pp. 93 to 98] by determining the lethal dose for 50 and 90 respectively % of a strain (LD ₅₀ - respectively. LD ₉₀ values) determined in Musca domestica. 4-day-old females were used for testing. For comparison, the LD ₅₀ and LD ₉₀ values of the pure active substance of some known insecticides were given. ethylene-1,4,5,8,9,10-hexahydronaphthalene (Aldrin)

octahydronaphthalene (dieldrin) ..

Chlordane

0,0-diethyl-thiophosphoric acid-O-p-

nitrophenyl ester, 70% (E 605 forte) x.yASA ^ lO.lO-octachlor- ^ - methylene-1,2,4,7,8,9-hexahydroindene

(Holtan)

Chlorination product example 1

Chlorination product example 2

Chlorination product example 3

Chlorination product example 4

Relative toxicity after 2 hours

against 4 day old females of

Musca domestica

50% supine position

10 1.25

0.36

0.72 0.04

78

0.21 3.1 20.8 1.0 6.3

The effectiveness was shown in a number of other animals, such as Leptinotarsa decemlineata say., Rhizotrogus solstitialis L., Euproctis chrysorrhoea L., Doralis fabae scop. and Oniscus asellus L. tested. In accordance with

Claims (1)

5 6 of the values found on Musca domestica, dusts, grit, sprays, sprays were obtained, and in these cases too, exceptionally good results. Incense or aerosols. 2. Process for the preparation of the active ingredient of the claims: insecticides according to claim 1, characterized in that 1. Insecticides, characterized by a content of 5 that 4,5,6,7,10,10-hexachloro-4,7-endomethylene-4,7,8,9- of chlorination products of 4,5,6,7,10,10-hexa-tetrahydrophthalane per mole up to a content of chloro-4,7-endomethylene-4,7,8,9-tetrahydrophthalans 6.5 to 10 g atoms of chlorine, preferably up to one as an active ingredient in the form of emulsions, suspensions, containing 8 g atoms of chlorine, is chlorinated. ι 709 808/29 »11.57