DE1593389C3 - Process for the preparation of 4,5,6,7,8,8-heptachloro-4,7-methano-3a, 4,7,7a-tetrahydroindane - Google Patents

Description

4,7-methano-3a, 4,7,7a-tetrahydroindane changes significantly.

example 1

40 g of 4,5,6,7,8,8-hexachloro-4,7-methano-3a, 4,7,7a introduced -tetrahydroinden and 1.6 g of iron (IIl) chloride (anhydrous) and 120 g 1,2-dichloroethane and heated to 30 ⁰ C. Hydrogen chloride gas washed over concentrated sulfuric acid was introduced into the mixture in such an amount that as little as possible escaped through the reflux condenser. The excess HCl was passed into sodium hydroxide solution. After 90 minutes the HCl-STRCM was turned off, the reaction mixture cooled to 10 ⁰ C and the crystallizing / S-Dihydroheptachlor filtered off. Yield 17.8g. A further 40 g of 4,5,6,7, 8,8-hexachloro-4,7-methano-3a, 4,7,7a-tetrahydroindene and 0.4 g of iron (III) chloride were added to the mother liquor brought the reactor back and introduced HCl ^{again at 30 ° C.} After 90 minutes, the HCl STRCM was again interrupted, cooled to 10 ⁰ C and collected another 40 g / 3 DihydroheptachIor. The process was repeated three more times and gave a total of 163.3 g / 8-dihydroheptachlor (73.5% of theory) of 99% purity.

The mother liquor that remained last still contained 13.7 g (6% of theory) β-dihydroheptachlor, 2 g (1% of theory) γ-dihydroheptachlor and 36.6 g (16% of theory) 4,5,6,7 , 8,8-hexachloro-4,7-methano-3a, 4,7,7a-tetrahydroindene. The / J-dihydroheptachlor contained 0.318% iron, corresponding to 0.93% FeCl ₃ . After washing twice with 11% strength hydrochloric acid each time for 30 minutes, the product contained less than 0.01% iron, corresponding to less than 0.03% FeCl ₃ .

dry hydrogen chloride gas introduced. After 200 minutes, the reaction was stopped and done Cooling that / 5-dihydroheptachlor crystallizes out and filtered off. The mother liquor was examined for impurities by gas chromatography. There were Apart from 0.9% ferric chloride, no other substances were detected. The conversion, based on the amount used, was thus 4,5,6,7,8,8-hexachloro-4,7, methano-3a, 4,7,7atetrahydroindene, 100%. The yield was 99% the theory.

When the iron (III) chloride was replaced by aluminum chloride under otherwise identical conditions, the conversion, based on 4,5,6,7,8,8-hexachloro-4,7-methano-3a, was 4,7,7a-tetrahydroindene , 95%. The yS-dihydroheptachlor yield was 81% of theory. In addition, 8% α-dihydroheptachlor and 6% γ-dihydroheptachlor were found in the mother liquor. CrCl ₃ , ZnCl ₂ and BF ₃ ether did not produce any conversion when they were used as a catalyst _{instead of FeCl 3 under otherwise identical conditions.}

Example 3

Example 2 was repeated using FeCl ₃ as a catalyst and in each case 240 g of chloroform, dichloromethane, benzene and monochlorobenzene in place of 1,2-dichloroethane as solvent. The reaction was terminated after 1.5, 3.5 or 5 hours in each case and the products formed were identified.

The results are shown in the following table:

Example 2

40

80 g of 4,5,6,7,8,8-hexachloro-4,7-methano-3a, 4,7,7a-tetrahydroindene were placed in a 500 ecm three-necked flask equipped with a stirrer, contact thermometer, gas supply and reflux condenser , 240 g of 1,2-dichloroethane and 3.6 g of iron (III) chloride introduced. The temperature was kept at 20 ⁰ C and

solvent each = 1.5
χ = 3.5 Composition of
mix after χ hours in 53
92 Reaction
/ 0 each = 1.5
each = 5.0 Chlorden / J-Dihydro-
heptachlor 34
92 y-dihydro
heptachlor CHCl ₃ each = 1.5
each = 3.5 OJ Ul 53
90 2
4th CH2CI2 each = 1.5
each = 5.0 66
2 VO OJ
OJ VO 1 benzene 47
2 1 Mono
chlorine
benzene 60
1

Claims (1)

1 2 Tar formation that occurs during pressure reactions Patent claim: avoided. Iron (III) chloride is preferably used as the catalyst used and a temperature of about Process for the production of 2-exo-4,5,6,7,8,8-30 ⁰ C kept as constant as possible, if necessary under heptachlor ^ J-methano-Sa.VJa-tetrahydroindane 5 cooling, since the reaction is exothermic. In (/ S-dihydroheptachlor) by reaction of temperatures above 50 ° C it has been found that 4 ₎ 5,6,7,8,8-hexachloro-4,7-methano-3a, 4,7,7a-tetra- the yield drops very quickly and is ^{only hydroindenes in the presence of a Lewis acid at 70 0} C than 14% / 9-dihydroheptachlor with a 4,5,6,7, catalyst and a solvent with chlorine SS-Hexachlor ^ - methano-Sa ^ JJa-tetrahydroinden hydrogen gas, marked by this conversion of 18%. net that the reaction is carried out at atmospheres as solvents are, for example, chloro- pressure within a temperature range of 20 form, dichloromethane, 1,2-dichloroethane, benzene, chlorine up to 50 ⁰ C using iron (III) chloride benzene good, while the solvency of tetra or aluminum chloride as a catalyst and a chlorocarbon, heptane, 1, 2,3-Trichloropropane or optionally trichlorethylene with one or more chlorine atoms 15 for the smooth running of the reaction of substituted hydrocarbons which one solution is not sufficient. One can, however, readily a capacity of at least 0.02 g-mol Chlorwasser- mixture of solvents useful with Westoff per 1000 g (at 20 ⁰ C and 760 mm pressure) niger readily dissolving use, provided that the solubility possesses performs as a solvent. "the mixture for HCl is 0.02 g-mol HCl Exceeds 20 per 1000 g of solvent. Of course, the solvent or the Solvent mixture also dissolve the other reactants and not to complex or Give rise to the formation of disruptive secondary products. The invention relates to a process for the preparation. The amount of solvent used should be that of the insecticide dihydroheptachlor. It is from chemical solubility ratios of the reactants demixing reports, Volume 99 (1966), pp. 405 to 415, discuss. For the 1,2-dichloro-4,5,6,7,8,8-hexachlor-4,7-methano-3a, 4,7, 7a - tetraethane, an optimal 4,5,6,7,8,8-hexachloro-4,7-mehydroindene in the presence of a Lewis acid under 30 thano-Sa ^^^ a-tetrahydroindene solvent ratio pressure of over 10 at and at an elevated temperature of 1: 3 or greater. A smaller ratio of 50 to 250 ⁰ C to produce a mixture which, because of the viscosity of the solution, leads to technical 91% of the theory 2-exo-4,5,6,7,8,8-heptachloro-4,7-me - Difficulties in working up, thano - 3a, 4,7,7a - tetrahydroindane (ß - dihydrohepta- The catalyst is used in amounts of about 5 chior) in addition to the isomers, which the seventh chlorine weight percent uses. About 1 percent by weight of the atom in the 1-exo position (oc-dihydroheptachlor) and in the catalyst is found in the end product, so-2-endo-position (y-dihydroheptachlor), so that in a batch production of the β-ΌΊ - holds. Hydroheptachlor is the preferred Lewis acid and the mother liquor is used every time iron (III) chloride, for example, can be used again as a solvent, but about 1 percent by weight carbon tetrachloride or heptane if you do not have to add new catalyst. Iron (III) chloride prefers solvent-free work. The / S-Di- is preferred as a catalyst, hydroheptachlor has as an insecticide above all the- For the process according to the invention is preferably of great importance because it is an unusually low warm pentadiene free of hexachlorocyclopentadiene and dicyclo hydrocarbon for a chlorinated starting material used because it has blood toxicity. Whereas with oral administration, substances have a disruptive influence, which is expressed in richness as the dose required to kill half of the high catalyst consumption and low conversions of test animals (LD ₅₀ ) in mice. than 9000 mg / kg of body weight, this amount is that according to the method according to the invention in dogs more than 5000 mg / kg, in chickens more than / S- (dihydroheptachlor can be reduced from it to -2000 mg / kg. In a few days, the main amount of 50 adhering catalyst residue (with FeCl ₃ about 1 weight in the animal body is already broken down and excreted - percent) with water or dilute hydrochloric far left, are exempt outgoing A disturbing influence of it has now been found that / S Dihydrohepta- catalyst residues becomes apparent after Ί also emperaturen chlcr produced at atmospheric pressure may, over 90 ⁰ C after. noticeable for a longer time, with a slight regression of 4,5,6,7,8,8-hexachloro-4,7-methano- 3a, 4,7,7a-tetrahydroindene within chloro-4,7-methano-3a, 4,7,7a-tetrahydroindene and HCl half enters a temperature range of 20 to 50 ⁰ C in. Since the / 5-Dihydroheptachlor slightly crystalline - Presence of aluminum chloride or iron (III) - sated, it can act as a catalyst and in the pure state directly from the chloride be crystallized from an optionally reaction mixture. The iso is carried out by one or more chlorine atoms substituted 60 mers and unconverted 4,5,6,7,8,8-hexachlorohydrocarbon as a solvent. The 4,7-methano-3a, 4,7,7a-tetrahydroindene remain in the solvent must have a solvent power of little mother liquor. Under the reaction conditions least 0.02 mole of hydrogen chloride per g 1000 g (in the case occurs to a certain extent a Ismorisierung on, so 20 ⁰ C and 760 mm pressure) have. the mother liquor with fresh 4,5,6,7,8,8-hexa-j This procedure results in a much shorter 65 chloro-4,7-methano-3a, 4,7,7a-tetrahydroinden and after j time easily reproducible Yields with high supplementation of the spent catalyst can again be used for selectivity towards the formation of the desired further batches without the isomer of the / S-dihydroheptachlor and the ratio of the isomeric heptachloro formed