DE1002341B - Process for the preparation of halogenated bicyclo- [2,2,1] -heptene- (2) - Google Patents

Description

Process for the preparation of halogenated bicyclo- [2, 2, l] -heptene- (2) Through the Diels-Alder synthesis, a number of new derivatives of bicyclo [2, 2, l] -heptens- (2) have become easily accessible, their synthesis in other ways is not possible or only possible with great difficulty. It was also found that diene syntheses can be carried out with highly chlorinated cyclopentadienes.

So z. B. in British Patent 614 931 the Diels-Alder synthesis of hexahalogencyclopentadienes with various eienophilic compounds such as Butadiene, isoprene, styrene and maleic anhydride are described. The ones available after that Compounds are derivatives of hexahalogen bicyclo- [2,2,1] -heptens- (2).

In J. Am. Chem. Soc., Vol. 67, 1945, p. 728; Vol. 76, 1954, p. 2709 and 2710; Z. Naturf., Vol. 9b, 1954, p. 684, especially table, is also the Accumulation of z. B. halogenated unsaturated hydrocarbons in hexachlorocyclopentadiene described. The usefulness of hexachlorocyclopentadiene for diene synthesis can but cannot be regarded as generally valid, as several cases are known according to which hexachlorocyclopentadiene with unsaturated compounds such as vinylidene chloride, Tetrafluoroethylene, asymmetric dichlorodifluorethylene or 2,3-dichloropropene, not reacted.

It is known that such unsaturated compounds that do not contain activating groups, e.g. B. a carbonyl or carboxyl group, have themselves with very reactive diene components poorly or not at all according to Diels-Alder react. This is particularly true for chlorinated unsaturated compounds too, for example for dichloroethylene or vinylidene chloride.

It has now been found that, surprisingly, however, cis-1,4-dihalobutenes- (2), in particular cis-1,4-dichlorobutene- (2), can be added to halogenated cyclopentadienes in a smooth manner at elevated temperature and optionally under elevated pressure . The reaction is not restricted to the known hexachlorocyclopentadiene, but can also be carried out with tetra- and pentahalocyclopentadienes. Compounds of the general formula are obtained in which X = H or halogen, but at least 4 halogen atoms, and Y is halogen, which are eminently suitable as active ingredients for the production of pesticides.

A particular advantage of the process products is their low toxicity for warm-blooded animals, which is lower than that of the known highly chlorinated insecticides the hydrocarbon series. Thus show those which can be produced according to the present process Products have an LD50 of over 10CO mg, while the LD ,, for dichlorodiphenyltrichloromethylmethane (»DDT«) is about 200 mg and for [γ-hexachlorocyclohexane] 125 mg. For the off cis-1, 4-dichlorobutane (2) and hexachlorocyclopentadiene preparable compound with the melting point 104 to 106 ° results in an LD ,, of over 15,000 mg.

For other comparable insecticides on the market is the LD50 50 to 60 mg. The present process products also have opposite comparable compounds have the advantage of a longer lasting permanent effect, such as is explained below with reference to the table.

The new compounds can be used on their own or in combination with others known pesticides applied in the usual compositions will.

From 30 ° / 0 5, 6-bis (chloromethyl) -1, 2, 3, 4, 7, 7-hexachlorbicyclo- [2, 2, 1] -hepten- (2), 50% dioxane as solvent and 20% oxyethylated nonylphenol As an emulsifier, an emulsifiable spray can be produced, which z. B. on Gold afer caterpillars (Euproctis chrysorrhoea) in a concentration of 0.4% (= 0.12% active ingredient) applied in water has a strong insecticidal effect. The agent of the composition mentioned moves such caterpillars in a few hours into a state of paralysis, so that they are damaging to their plants task can no longer exercise and die soon after.-An appropriately applied Agent from 5-chloromethylhexachlorobicyclo- [2, 2, 1] -hepten- (2) shows an essential less effect, namely only one effect at the above concentration of 20% compared to 100% in the case of the aforementioned means, which according to the invention 5, 6-bis- (chloromethyl (-1, 2, 3, 4, 7, 7-hexachlorbicyclo- [2, 2, 1] -hepten- (2) contains.

A dust containing 1 ° / o of the said compound as effective Contains substance in addition to talc as a base, is sufficient in a mixture with cereal seeds in a ratio of 1: 1000 to prevent storage pests, e.g. B. Corn beetle (Calandra granaria), that are in the grain, migrate or hatch, kill in 1 to 2 days or render it harmless through irreversible damage.

Are rows of Petri dish bottoms with 3 ° 10igen, dust-like preparations of 5-chloromethyl-1, 2, 3, 4, 7, 7-hexachlorbicyclo- [2, 2, l] -hepten- (2) or 5, 6-bis - (Chloromethyl) -l, 2, 3, 4, 7, 7-hexachlorbicyclo- [2, 2, 1] -hepten- (2) dusted in a density of 20 kg per hectare, open and airy and one row each populated with grain beetles (Calandra granaria) at certain intervals, it is clear that the dust coating that contains the 5, 6-bis- (chloromethyl) -1, 2, 3, 4, 7, 7-hexachlorbicyclo- [2, 2 , l] -hepten- (2) contains, compared to which the 5-chloromethyl-1, 2, 3, 4, 7, 7-hexachlorobicyclo- [2, 2, l] -hepten- (2) contains, is significantly longer effective remain. Busy with grain beetles after link immediately 2 days 4 days 6 days 7 days 5-chloromethyl-1, 2, 3, 4, 7, 7-hexachlorobicyclo- [2, 2, 1] -hepten- 100 0 4 0 0 5, 6-bis (chloromethyl) -1, 2, 3, 4, 7, 7-hexachlorbicyclo- [2, 2, 1] -hepten- 100 100 100 98 32 Numbers = lying on your back in percent.

With an emulsion, the 0.1 ° lo a solution of 60 ° / o of the above Compound and contains 40% of oxyethylated nonylphenol as an emulsifier, you can Kill bed bugs (Cimex lectularius) by e.g. B. the document on which the Insects run, moistened with it.

The insecticidal effect of 5, 6-bis (chloromethyl) -1, 2, 3, 4, 7, 7-hexachlorbicyclo- [2, 2, 1] -heptens- (2) as well as the one important for precautionary use The durability of pointed coatings can easily be found in the well-known Petri dish experiment prove. Are Petri dishes each with 1 ccm of an acetone solution of the substance each half a bowl poured out and after the solvent has evaporated with houseflies (Musca domestica) occupied, these flies show both on the first day of the experiment as well as after prolonged exposure of the treated bowls, signs of paralysis in a short time, that lead to death.

If you use z. B. a 0, 4% acctonic solution of 5, 6-bis (chloromethyl) -1, 2, 3, 4, 7, 7-hexachlorbicyclo- [2, 2, l] -heptens- (2), one still achieves after For 4 days, all flies were constantly lying on their backs within 4 hours, on the other hand when using 5-chloromethyl-1, 2, 3, 4, 7, 7-hexachlorobicyclo- [2, 2, 1] -hepten- (2) practically no effect after an observation time of 6 hours.

If heavily lousy green plants with a preparation that is 30 ° l0 des 5, 6-bis (chloromethyl) -1, 2, 3, 4, 7, 7-hexachlorbicyclo- [2, 2, 1] -heptens- (2) in emulsifiable Contains form, sprinkled in 0, 2 to 0, figy aqueous emulsion all lice are killed after 1 to 2 days.

To combat beetles that are harmful to plants, e.g. B. the Rübenderbrüßler (Bothnoderes punctiventris), a preparation of 5 ° / 0 5, 6-bis (chloromethyl) -1, 2, 3, 4, 7, 7-hexachlorbicyclo- [2, 2, 1] -hepten- (2) and 95% talc, which is used as a dusting agent is distributed to the infected plants in a known manner.

A pig infected with lice (Haematopinus suis) is rubbed with it such a dust, the lice are killed within a few hours.

Other parasites, e.g. B. the plague flea (Xenopsylla cheopis), can be destroyed by this means, both on the host animal and outside it.

The effectiveness of 5, 6-bis (chloromethyl) -1, 2, 3, 4, 7, 7-hexachlorbicyclo- [2, 2, 1] -hepten- (2) for ectoparasites can also be tested exactly in the laboratory, by placing filter paper of a certain area with acetone solutions of the substance soaks so that the content of active ingredient per unit area is known.

A killing of ticks residing thereon, z. B.

Relapsing fever tick (Ornithodorus moubata), is achieved with 0, 0006 mg / qcm.-of 5-chloromethyl-1, 2, 3, 4, 7, 7-hexachlorbicyclo- [2, 2, 1] -hepten- (2) is To achieve the same effect, four times the amount is necessary, as can be seen from the following test result: % in a permanent supine position, after days mg / 100 sq cm 1 2 3 4 5 5, 6-bis (chloromethyl) -1, 2, 3, 4, 7, 7-hexachloro- 0.24 0 20 80 100 - bicyclo- [2, 2, 1] -hepten- (2) ................. 0.12 0 20 60 90 100 0.06 0 10 90 100 - 5-chloromethyl-1, 2, 3, 4, 7, 7-hexachlorobicyclo- 0.24 0 50 80 100 - [2, 2, 1] -hepten- (2) ......................... 0.12 0 10 20 50 80 0.06 0 0 0 10 40 The superiority over 5-chloromethyl-1, 2, 3, 4, 7, 7-hexachlorobicyclo- [2, 2, 1] -hepten- (2) on bed bugs (Cimex lectularius) can also be shown in a somewhat modified manner. Concentrated emulsions are used which consist of 60 "/ o of the active substance and 40% oxethylated nonylphenol as emulsifier. If aqueous emulsions with 0.1 and 0.05% of the concentrated emulsions are prepared, 1 ccm each Spread the emulsion on a round filter with a diameter of 9 cm and place it on the still moist filter bed bug imagines, the result is the following effect: active ingredient% in permanent supine position, after days % 1 2 3 5 5, 6-bis (chloromethyl) -1, 2, 3, 4, 7, 7-hexachloro- 0.06 0 85 100 - bicyclo- [2,2,1] -hepten- (2) 0.03 0 50 80 100 5-chloromethyl-1, 2, 3, 4, 7, 7-hexachlorobicyclo-0, 06 0 90 90 90 [2, 2, 1] -hepten- (2) 0.03 0 5 10 10 Example 1 25 g (0.2 mol) of 1,4-dichlorobutene- (2), which is obtained by chlorination of predominantly cis-butene- (2) -diol- (1,4), are mixed with 70 g of hexachlorocyclopentadiene for 48 hours heated in the shooting tube to 180 to 200 °, and then the tube contents are distilled in vacuo.

After a forerun, which boils at bp 3 ~ 4 = 40 to 110 °, distilled the main amount of the reaction product at bp 2 = 172 to 176 °. The distillate is a viscous oil that partially solidifies after standing for a while. After detaching the crystals, which melt at a temperature of 104 to 106 °, leave an oily residue, which apparently represents a mixture of isomers. The appearance of steric isomers is to be expected due to the molecular structure. CgHsCl8.

Calculated: Cl = 71.350 / OX found: Cl = 71.04 ° / 0.

Example 2 25 g (0.2 mol) of pure cis-1,4-dichlorobutene are mixed with 70 g of hexachlorocyclopentadiene heated to 150 to 160 ° for about 30 hours with stirring. The unreacted hexachlorocyclopentadiene is then distilled off in vacuo and the crystalline reaction product by recrystallization from methanol or Purified ethanol.

The substance obtained melts at 104 to 106 °.

The following can be prepared in a corresponding manner: 5, 6-bis- (chloromethyl) -l, 2, 3, 4, 7-pentachlorobicyclo- [2, 2, l] -hepten- (2), bp 0.8-1 = 147 to 150 °; 5, 6-bis- (chloromethyl) -tetrachlorobicyclo- [2, 2, 1] -hepten- (2), bp 2 = 148 to 150 °; 5, 6-bis (bromomethyl) -1, 2, 3, 4, 7, 7-hexachlorobicyclo- [2, 2, 1] -heptene- (2), b.p. o, i-o, 141 to 145 °; 5, 6-bis (bromomethyl) -1, 2, 3, 4, 7-pentachlorobicyclo- [2, 2, l] -heptene- (2); 5, 6-bis (bromomethyl) -tetrachlorobicyclo- [2, 2, 1] -hepten- (2).

PATENT CLAIMS 1. Process for the preparation of halogenated bicyclo- [2, 2, 1] -heptene- (2) of the general formula in which X = H or halogen, but at least 4 halogen atoms, and Y is halogen, characterized in that the corresponding cis-1,4-dihalobutenes (2) in a conventional manner at elevated temperature, optionally under elevated pressure, with halogenated cyclopentadienes.

Claims (1)

2. The method according to claim 1, characterized in that as Starting material hexachlorocyclopentadiene and cis-1,4-dichlorobutene- (2) used. References considered: J. Am. Chem. Soc., Vol. 67, 1945, p. 728; Vol. 76, 1954, pp. 2709 and 2710; Z. Naturf., Vol. 9b, 1954, p. 684 ; British Patent No. 699,373; Chimie & Ind., Vol. 64, 1950, p. 695 to 698; German Health Service, Vol. 3, 1948, p. 718; News sheet f. The German Plant Protection Service, Vol. 8, 1954, pp. 181 to 183; Indian patent specification No. 37 910.