DE1013290B - Process for the production of insecticides - Google Patents

Description

GERMAN

By chlorination of 4, 5, 6, 7,10,10-hexachloro-4, 7-methylen-4, 7, 8, 9-tetrahydrophthalan can be used in good yield 1, 3, 4, 5, 6, 7,10, 10-octachlor-4, 7-endomethylene-4, Prepare 7, 8, 9-tetrahydrophthalan, for which the following reaction scheme applies:

Method of manufacture
of insecticides

ClC

ClC

Cl

ClCCl

Tbsp

Cl

H
H"

CL

ClC

ClC

Applicant:

Ruhrdiemie Aktiengesellschaft,
Oberhausen (RhId.) - Holten

Dr. Hans Feichtinger, Duisburg-Beeck,

and Dr. Hans-Werner Linden, Moers,

have been named as inventors

tetrahydrophthalanes obtained according to the following reaction scheme, where X is partly chlorine and partly fluorine means:

Cl

The octachlorinated ether obtained in this way has very good insecticidal properties and is both Undiluted as well as in packaged form, a very good means of combating biting and sucking Insects.

It has been found that this has insecticidal activity not on 1,3, 4, 5, 6, 7,10, 10-octachlor-4, 7-endomethylene-4, 7,8,9-tetrahydrophthalan is limited, but also applies to those halogenated ethers that are im Bicycloheptic part of the molecule contain fluorine and chlorine. These are connections of the general formula

X H. ^ u
X ^ H ^ CC

XC

Cl ₂

XC

in which X is partly chlorine and partly fluorine. These new compounds are used to combat insects and have a high initial effect. Compared with the 1, 3, 4, 5, 6, 7,10,10-octachloro-4, 7-endomethylene-4, 7, 8, 9-tetrahydrophthalan is with the novel compounds, the 100 ° / ₀ cent mortality an insect population considerably reached more easily.

According to the invention, the new compounds are obtained by chlorinating hexahalogenated endomethylene compounds the chlorination, all processes are suitable which require a substitution in the tetrahydrofuran ring of endomethylenetetrahydrophthalane result. By taking up 2 chlorine atoms per molecule of the starting material, chlorination products of optimum effectiveness are obtained. The chlorination takes place in the usual way, for example, by introducing gaseous chlorine into a boiling solution of hexahalogenated phthalane in carbon tetrachloride or other suitable solvents. One can but also work with chlorinating agents from which the chlorine can easily be split off, e.g. with sulfuryl chloride or chlorosuccinimide.

The chlorination can also be carried out without using a solvent. In this case one brings

709 656/346

the hexahalogenphthalan directly with gaseous chlorine or suitable chlorinating agents and optionally with a chlorine transfer agent, for example AlCl ₃ , in contact. The reaction can be carried out at room temperature. However, it is advantageous to stimulate or keep the reaction going by means of heat, light or suitable catalytic additives. The chlorination can be carried out continuously or discontinuously in glass vessels or enamelled metal apparatus

example 1

First, 46.8 g (0.2 mol) of 5, 5-difluoro-l 2, 3 4-tetrachloro-cyclopentadiene (boiling point at 5 mm 46 to 52 °, refractive index »g> = 1.4998) with 28.0 g (0.4 mol) of 5 2,5-dihydrofuran for 15 hours in a closed tube heated to 100 °. The brown reaction product was. rinsed with petroleum ether from the pipe and the over * - distil the schüssige dihydrofuran and the petroleum ether, erti The brownish, oily lead mixed with 15 ecm petroleum ether. Depending on the working conditions, the chlorine residue is revealed after standing in the refrigerator for some time uptake gravimetrically or by taking a sample from a crystal slurry that has been sucked off. After this the reaction vessel and chlorine determination followed. The drying on clay gave 55.2 g (89% of theory ^ The reaction is to be regarded as ended when the desired brownish colored crystals. By Um « Degree of halogenation is reached. This is 2 gram dissolving from petroleum ether with the addition of decolorizing agents 11 || atoms of chlorine per gramol of the starting material, plus 15 needles with a melting point of 58 to 60 ^. borrowed the amount of halogen already present in this. This up to a melting point of 61 to 62 "

The reaction product purified by chlorination of 10, 10-difluoro-4, 5, 6, 7-tetra- (corrected) possessed emejn chlorine - 4, 7 - endomethylene - 4, 7, 8, 9 - tetrahydrophthalan pleasant, camphor-like odor and was in deto. For example, 10,10-difluoro-1,3, 4, 5, 6, 7-hexa- most common organic solvents are very good chlorine - 4, 7 - endomethylene - 4, 7, 8, 9 - tetrahydrophthalan 20 soluble. It was practically pure 10, lOnDär according to the following reaction equation in a yield of fluoro-4, 5, 6, 7-tetrachloro-4, 7-endomethylene-4, 7 8, 9-

tetrahydrophthalan.

31.0 g (0.1 mol) of 10,10-difluoro-4, 5, 6, 7-tetrachloro-4, 7-endomethylene-4, 7, 8, 9-tetra-I hydrophthalan (F. = 61 to 62 °) dissolved in 150 ecm of carbon tetrachloride and in the boiling heat under irradiation with UV light (80 W lamp at a distance of 5 to 6 cm from the reaction vessel) within 4 ^χ / ₂ hours with 5, 41 Chlorine fumigated. The solvent was distilled off and (WrI colorless, oily residue was stirred with a little petroleum ether. ”Almost immediately, the separation of a white,

85% of the theory received:
Cl

.H

ClC

ClC

FCF

Cl

ClC

ClC

Cl

FCF

Cl

Xl

H
"C"

H H'

: c

Cl

It was found that in this chlorination reaction there was no exchange of the with the bicycloheptic moiety of the phthalan molecule linked fluorine occurs against chlorine.

The reaction products obtainable according to the invention are white, crystallized compounds. The 10,10-difluoro-l, 3, 4, 5, 6, 7-hexachlor-4, 7-endometlrylen-4, 7, 8, 9-tetrahydrophthalane has a melting point of

Crystal mass, which has a melting point of 73 ° (beg and a halogen content of 10.3% fluorine and 55.7% Exhibited chlorine.

The chlorination mixture obtained was redissolved in petroleum ether, 32.5 g of 10,10-difluoro-1,3, 4,% 6, 7-hexachlor-4, 7-endomethylene-4, 7, 8, 9-tetrahydropJrtha> lan were obtained with a melting point of 86 to 88 °; Pet I corrected melting point of the analytically pure compound was 91 °.

- The yield was 85% of the theoretical amount.

Example 2

fraud. 4.5 g of 10,10-difluoro-1,3, 4, 5, 6, 7-hexaeKkw ^ l separated from the chlorination mixture for a short time 4, 7-endomethylene-4, 7, 8, 9-tetrahydrophthalan.

I .:

Example 3

In the manner evident from Example 1, S0.3 g (0.033 mol) of 10, 10-difluoro-4, 5, 6, 7-tetrachlor-4, 7-endo ^ methylene-4, 7, 8, 9-tetrahydrophthalane, dissolved in .3Qi.xKaiO (carbon tetrachloride, gassed with 2.71 chlorine. Na (MIdBm ₁₁

91 ° (corrected). A reaction product was obtained in the customary organic 50 distilling off, solvents readily soluble, for example in alcohols, ethers, the halogen content of which is 9.7% fluorine and 57.0% hI
Ketones, esters or hydrocarbons. In water
the connection is practically insoluble. In the air
this is also in accordance with the invention in contact with water
available chlorination product resistant. 55

For making the new connections you can
all hexahalogenated endomethylenetetrahydrophthalanes serve as starting materials, which in their bicyclo- According to Example 1 were 18.6 g (0.6 mol)

Part of the heptin contains fluorine and chlorine. The compounds required for the preparation of 10,10-difluoro-4, 5, 6, 7-tetrachlor-4, 7-endomethylene of the chlorination products according to the invention 60 4, 7, 8, 9-tetrahydrophthalane in 50 ecm tetrachloride oil | DietD, h as starting material , ie substance dissolved and gassed with 12.21 chlorine. After the ih
the 10, lO-difluoro-4, 5, 6, 7-tetrachlor-4, 7-endomethy work-up resulted in 24.5 g of a colorless ''
len-4, 7, 8, 9-tetrahydrophthalan and the 4, 5,10,10- the fluorine content of 9.2% and a g ^)

Tetrafluoro-6, 7-dichloro-4,7-endomethylene ~ 4, 7,8,9-tetra- of -59.6%. The oil could in the Hochva% »p! I hydrophthalan, are new compounds. These starting 65 are distilled and passed at a boiling point (äjisäaata substances can, for example, by Diels-Alder reaction from Hg) of 112 to 122 °. The distillate has
2, 5-dihydrofuran and hexahalogenated cyclopenta refractive index «" = 1.5492 and yielded according to ijS
serve to be obtained in a known manner. Her chromatographic analysis is another step
Position of these starting materials is not considered to be about 10% of 10,10-difluoro-l, 3, 4, 5, 6, 7-hexai | i
claimed. 70 4, 7-methylene-4, 7, 8, 9-tetrahydrophthalane.

Example 4

There were 31.0 g (0.1 mol) of 10, 10-difluoro-4, 5, 6, 7-tetrachlor-4, 7-endomethylene-4, 7, 8, 9-tetrahydrophthalane, 32.5 g (0.22 moles) sulfuryl chloride and 50 ecm carbon tetrachloride heated under reflux for 10 hours with the addition of 0.3 g of benzoyl peroxide **. After evaporation the residue was taken up in ether in vacuo, once each with bicarbonate solution and Washed with water and the ethereal layer finally dried over calcined sodium sulfate. After this Distilling off the ether gave 35 g (92% of theory) of a yellow to brown crystal mass which after cleaning with petroleum ether and decolorizing agents showed a melting point of 85 to 88 °.

The present invention available, fluorine and chlorine Endomethylentetrahydrophthalane containing compounds are valuable insecticides against the only chlorine-containing phthalans same constitution have the advantage that, to achieve a 100% mortality (eg Musca domestica) much lower loading ^ao legungsdichten are required.

To prove this fact, 20 houseflies (Musca domestica L.) at the age of four days were used, and only female animals because they have an ^a 5 increased resistance compared to male individuals. The test flies were caught from their cages in a round-bottomed flask and the females were selected after being lightly anesthetized with gaseous carbonic acid. 20 female animals each were transferred into a test tube, which consisted of cylindrical glass tubes with an inner surface of 73 ecm. The insecticidal substances were applied to the inner surface of these tubes in various concentrations from a petroleum ether dilution and the occupancy density was converted into y / qcm. After a residence time of 30 minutes, the flies were transferred to recovery cages in which they found water and sugar. All manipulations were carried out at a room temperature of 20 ° ± 1 ° and at 60 to 75% relative humidity.

The flies were observed, and after 60, 90, 120, 150 and 180 minutes, the number of animals was the were in an irreversible supine position, related to the total number of flies used. To eliminate small sensitivity fluctuations among the flies, ten consecutive Test approaches mean values formed.

In the table below is one of the new chlorination products that mainly consists of 10,10-difhior-l, 3, 4, 5, 6, 7-hexachlor-4, 7-endomethylene-4, 7, 8, 9-tetrahydrophthalan consists of 1, 3, 4, 5, 6, depending on the time and the occupancy density 7,10, 10-octachlor-4, 7-endomethylene-4, 7, 8, 9-tetrahydrophthalane juxtaposed.

One can clearly see the superior initial effect of the new active ingredient containing fluorine and chlorine compared to the compound containing only chlorine and having the same carbon structure. While at an occupancy density of 1.37 y / sq cm or 6.85 y / sq cm within 120 minutes for the latter compound 80 or 87% of the population were killed, you could with the active ingredient according to the invention among the same Conditions achieve 100% kill. This success was not only with flies, but also with Calandra granaria, Calandra orycea and other harmful insects.

It is particularly advantageous if the chlorination is carried out so far that reaction products are formed which contain an average of approximately 1.7 to 2.5 chlorine atoms in the tetrahydrofuran ring of endomethylene phthalan. These chlorine contents arise because some of the endomethylene phthalan molecules during the chlorination inevitably takes up more or less than 2 chlorine atoms in the tetrahydrofuran ring.

Table I.

Irreversible damaged animals 1.37 0.685 when applying from 1.37 ! 0.685 7 't' 1, 3, 4, 5, 6, 7, 10,10-octachlor-4, 7-endo- 48% 37% 93% Minutes methylene-4, 7, 8, 9-tetrahydrophthalan in
an occupancy density of y / qcm 67% 46% 96% 6.85 80% 52% 100% 60 61% 81% 55% Chlorination mixture according to Example 1
with an occupancy density of y / qcm 100% 90 72% 81% 58% 6.85 100% 120 87% 98% 87% 150 89% 99% 90% 180 90% 100% 92% 100% 95% 100% 98%

Example 5

There were 21 g of tetrafluorodichlorocyclopentadiene without prior purification by distillation with 15 g of 2,5-dihydrofuran heated in a bomb tube for 16 hours at 120 to 125 °. The resulting, brown colored reaction product was fractionated in vacuo. Here received 14.6 g of a slightly yellowish liquid boiling between 90 and 110 ° under 1 mm Hg pressure, whose Halogen content of the 4, 5,10, 10-tetrafluoro-6, 7-dichloro-4, 7 - endomethylene - 4, 7, 8, 9 - tetrahydrophthalan corresponded.

13.8 g of this distillate were treated with 2.31 g of chlorine gas in the manner indicated in Example 1. After removal of the solvent, 17.2 g of a pale, viscous residue were obtained as the reaction product.

Vacuum distillation of the chlorination mixture gave a main fraction, which under a pressure of 0.1 mm Hg boiled at 98 to 109 ° and from 4, 5,10,10-tetrafluoro-1, 3, 6, 7-tetrachloro-4, 7-endomethylene-4, 7, 8, 9-tetrahydrophthalan consisted of.

This compound had the insecticidal properties shown in the table below Musca domestica, Calandra granaria, Calandra orycea and similar insects.

60 Time Irreversible Table II Occupancy density of y / qcm 1.37 in a in 6.85 33% Minu 'Damaged animals when using the 62% 35% 0.685 th Chlorination mixture according to Example 5 65% 37% 20% 60 69% 37% 23% 90 13.7 73% 43% 25% 120 78% 74% 27% 150 88% 27% 70 180 94% 100% 100%

Claims (2)

PATENT KITCHEN: 1. A process for the preparation of insecticides, characterized in that compounds of the general formula XC XC X tbsp
XCX
X ET "H in which X is partly chlorine and partly fluorine, by treatment with chlorinating agents to in 1, 3-control chlorinated 4, 5, 6, 7,10,10-hexa- (fluor and chlorine) -4, 7-endomethylene-4, 7, 8, 9-tetrahydrophthalanes of the general formula X H Cl Γ -η Γ XC I ^ ^C \ 'I XCX Ι ο xc ^: _c χ ή. " ^ a ■ f ^; implemented. , ;;, 2. The method according to claim 1, characterized in that the chlorination of the fluorine and: ChJp | ·. ■ [. containing endomethylene phthalane is passed through so far that the reaction products have an average of approximately 1.7 to 2.5 chlorine atoms; . ^ h containing the tetrahydrofuran ring of the molecule. © 709 656S «7.57