DE1094256B - Process for the preparation of ethers of 1, 2, 3, 4, 7-pentahalogen-7-hydroxybicyclo - [2, 2, 1] -2, 5-heptadiene - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN // fä9m < PATENT OFFICE

kl. 12 ο 25

INTERNAT. KL. C 07 C

EDITORIAL 1094 256

V16249IVb / 12o

REGISTRATION DATE: MARCH 24, 1959

NOTIFICATION OF THE REGISTRATION AND ISSUE OF THE EDITORIAL:

DECEMBER 8, 1960

The invention relates to the production of ethers of the 1,2,3,4,7 - pentahalogen - 7 - hydroxybicyclo - (2,2,1) - 2,5 heptadiene.

The new compounds obtainable according to the invention can be represented by the following formula:

Therein R denotes an aliphatic, cycloaliphatic or aromatic hydrocarbon radical with up to 14 carbon atoms.

The new compounds are made by reacting l ^ .SAV-Hexachlorbicyclo- ^. LJ- ^ S-heptadiene with so obtained from an alcohol in the presence of alkali.

The products that can be prepared according to the invention are of exceptional value as insecticides and fungicides as well as intermediate products for the production of highly effective insecticides. If the invention available products e.g. B. by Diels-Alder synthesis with a conjugated diene, e.g. B. with furan or cyclopentadiene, are linked, highly active insecticides are formed. The new connections can also z. B. halogenated or epoxidized and thus deliver valuable products.

It was found completely unexpected that the novel ethers obtainable according to the invention by reacting 1,2,3,4,7,7-hexachlorobicyclo- (2,2,1) -2,5 -heptadiene with an alcohol can be prepared in the presence of alkali. This implementation leads to the desired one Replacement of only one of the two chlorine atoms on the bridging carbon atom.

This finding is surprising for a number of reasons. The replaced chlorine atom is a bridging chlorine atom, which is usually pretty persistent. Furthermore, the chlorine atom sits on a carbon atom that is still carries a second chlorine atom, but this second chlorine atom is not attacked. Krynitsky and Bost describe in Journ. At the. Chem. Soc, Vol. 69, 1947, p. 198, the replacement of both chlorine atoms on the methylene carbon atom of hexachlorocyclopentadiene. This is understandable, since both chlorine atoms are attacked, especially since both are in the allyl position to two double bonds. It should be noted that the others, not in the allyl position standing chlorine atoms remain unchanged. In the present case, a chlorine atom that is not allyl is used selectively implemented without attack of the chlorine atom sitting on the same carbon atom.

Process for the preparation of ethers of 1,2,3,4,7-pentahalogen-7-hydrc> xybicyclo- [2.2 _r l] -2,5-heptadiene

Applicant:

Velsicol Chemical Corporation, Chicago, 111. (V. St. A.)

Representative: Dr.-Ing. H. Ruschke, Berlin-Friedenau,

and Dipl.-Ing. K. Grentzenberg, Munich 27, Pienzenauer Str. 2, patent attorneys

Hyman M. Molotsky, Chicago, 111. (V. St. A.), has been named as the inventor

The following list gives some of the alcohols which can be used according to the invention and also those from them available reaction products with 1,2,3,4,7,7-hexachlorobicyclo- (2.2, l) -2,5-heptadiene in the presence of an alkaline substance.

alcohol product Allyl alcohol 1 ^ A ^ -pentachlor ^ -allyloxy-
bicyclo- (2.2.1) -2.5-heptadiene Methyl alcohol l ^ A ^ -Pentachlor ^ -methoxy-
bicyclo- (2.2.1) -2.5-heptadiene Isopropyl alcohol 1,2,3,4,7-PeHtEChIOr ^ -ISOPrOpOXy-
bicyclo- (2.2.1) -2.5-heptadiene n-undecyl alcohol 1 ^ A ^ -pentachlor ^ -undecyl-
oxybicyclo- (2.2.1) -2.5-heptadiene Ethoxyethanol l ^ A ^ -Pentachlor ^ -ethoxy-
ethyloxybicyclo-
(2.2, l) -2.5-heptadiene Propargyl alcohol 1, ^, ^ - Pentachlor ^ -propargyl-
oxybicyclo- (2.2.1) -2.5-heptadiene Butenediol 1,2,3,4,7-pentachloro-7- (4-oxybutene-
2-oxy) -bicyclo- (2.2.1) -2.5-hep-
tadien Butanediol 1,2,3,4,7-pentachloro-7- (4-oxy-
butane-2-oxy) -bicyclo-
(2.2, l) -2.5-heptadiene Cyclohexanol 1, ^, ^ - Pentachlor ^ -cyclohex-
oxybicyclo- (2.2.1) -2.5-heptadieri

009 677/452

alcohol product Cyclopentanol ! ^, S ^ -Pentachlor ^ -cyclopent- oxybicyclo- (2.2.1) -2.5-heptadiene phenol 1 ^, S ^ -pentachlor ^ -phenoxy- bicyclo- (2.2.1) -2.5-heptadiene Chlorophenol l ^ A ^ -Pentachlor ^ -chlor- phenoxybicyclo- (2.2, l) -2.5-heptadiene Benzyl alcohol 1 ^, S ^ J-Pentachlor ^ -benzoxy- bicyclo- (2.2.1) -2.5-heptadiene Furfuryl alcohol !, ^, ^ - PentacWor ^ -furfuroxy- bicyclo- (2.2.1) -2.5-heptadiene Castor Alcohol .. l ^ S ^ J-Pentachlor ^ -ricinoloxy- bicyclo- (2.2.1) -2.5-heptadiene Nonanol 1, 2,3,4,7-pentachlor ~ 7-nonoxy- bicyclo- (2.2.1) -2.5-heptadiene Hesperetin 1,2,3,4,7-pentachloro-7- (2-methoxy- 4-ethylene phenyloxy) -bicyclo- (2.2, l) -2.5-heptadiene 1-borneol l ^ .S / lJ-Pentachlor ^ -bornoxy- bicyclo- (2.2.1) -2.5-heptadiene 1-heptadecanol l ^ .S. ^ - Pentachlor ^ -heptadecyl- oxybieyclo- (2.2.1) -2.5-heptadiene 9-fluorenol l ^ .S ^ J-Pentachlor ^ -fluorenoxy- bicyclo- (2.2.1) -2.5-heptadiene Chrysazine 1,2,3,4,7-pentachloro-7- (8-oxy- anthraquinone) -oxybicyclo- (2.2, l) -2.5-heptadiene Azophenol l ^ .S ^^ - Pentachlor ^ -azophenoxy- bicyclo- (2.2.1) -2.5-heptadiene Tetradecanol l ^ .S ^^ - Pentachlor ^ -tetradecyl- oxybicyclo- (2.2.1) -2.5-heptadiene Heptacosanol ... l ^ .S ^ -Pentachlor ^ -heptacosyl- oxybicyclo- (2.2.1) -2.5-heptadiene Lactic acid 1,2,3,4,7-pentachloro-7- (l-carboxy- ethoxy) bicyclo (2.2, l) -2.5- heptadiene Naphthol l, 2,3A7-pentachloro-7-naphthoxy- bicyclo- (2.2.1) -2.5-heptadiene Silicoheptyl 1, 2,3,4,7-pentachlor-7-silicohept- alcohol oxybicyclo- (2.2.1) -2.5-heptadiene Phytin l, 2,3,4,7-pentachloro-7- (3.7, l 1, 15-tetramethylhexadecenoxy) - bicyclo- (2.2.1) -2.5-heptadiene

35 sation agents can be used. Furthermore, the temperature at which the reaction is carried out is not decisive; temperatures in the range from about 50 to 200 ^° C. are possible. The reaction can be carried out as a single batch or in a continuous process and under reduced, normal or elevated pressure.

The following examples explain the preparation of the new compositions according to the invention. In these examples excess alcohol was used as a solvent.

example 1

! ^, S ^^ - Pentachlor ^ -isopropoxybicyclo- (2.2, l) -2,5-heptadiene

604 g of 1,2,3,4,7,7-HeXaChIoAiCyClo- (2,2,1) -heptadiene (2.02 mol) were placed in a three-necked reaction vessel with stirrer, thermometer, heating mantle and reflux condenser, the 190 g of potassium hydroxide (2.90 mol) and 868.0 g of isopropyl alcohol (14.4 mol). The reaction mixture was heated at reflux at about 90 ⁰ C and held for about 4 hours at the boil.

The unreacted substance was removed by distillation under reduced pressure, and the residue was dissolved in diethyl ether. This ethereal solution was washed with water, dried over anhydrous sodium sulfate and the diethyl ether was removed by distillation under reduced pressure. The desired product was obtained by fractionating the residue from the ether distillation as a fraction boiling from 99 to 105 ° C. at 0.8 mm Hg. This crude product was purified by chromatography. Its boiling point was 105 ⁰ C at 0.8 mm Hg and refractive index "S> = 1.5213.

The analysis of the compound C ₁₀ H ₉ Cl ₅ O showed:

Calculated ... C = 37.24%; H = 2.81 ° / ₀ ; Cl = 54.97%; found .... C = 36.89%; H = 2.85%, - Cl = 55.43%.

Its structural formula is:

40

45

As can be seen from the above list, the surprising implementation according to the invention does not go through influences the structure of the alcohol. Different radicals and substituents can be present in the alcohol be included. Such substituents do not affect the desired conversion.

The process according to the invention can be carried out in the presence or absence of solvents will. It is preferred either no solvent at all or an excess of alcohol as the solvent used. However, other solvents which are inert to the reactants can also be used will.

Even if the reactions in the following examples are calculated in the presence of potassium hydroxide other alkaline condensate can also be found

Example 2

l ^^^ - Pentachlor ^ -ethoxybicyclo- (2.2, l) -2,5-heptadiene

600gl, 2,3,4,7,7-hexachlorobicyclo- (2.2, l) -2,5-heptadiene (2.0 mol) were placed in a three-necked glass vessel equipped with a stirrer, thermometer, heating mantle and reflux condenser, which contained 204 g of potassium hydroxide (3.6 moles) and 670 g of ethyl alcohol (14.6 moles). The reaction mixture was Heated for 5 hours on the reflux condenser.

After the 5 hours had elapsed, the unreacted alcohol was separated off by distillation under reduced pressure. The distillation residue was poured over with water and extracted with diethyl ether. The ether layer was separated from the aqueous layer and dried over anhydrous sodium sulfate. The desired product was then found to be at 118 ° C at 1.5 mm Hg boiling fraction isolated. It had the refractive index «S ° = 1.5330. Its chlorine content was analyzed:

57.48% Cl;
57.50% Cl.

It has the following structural formula:

Gross yield 57% / ₀ .

Example 3

given from glass with stirrer, thermometer, heating mantle and reflux condenser, the 204 g of potassium hydroxide (3.6 moles) and 336 g of cyclopenten-3-ol (4.0 moles). The reaction mixture is heated under the reflux condenser for 5 hours.

After the reaction time has elapsed, the unreacted substance is distilled off under reduced pressure. The distillation residue is poured over with water and extracted with diethyl ether. The ethereal layer ίο is separated from the aqueous and over anhydrous Dried sodium sulfate. The desired product is then isolated by distillation.

It has the structural formula:

1,2,3,4,7-pentachloro-7-allyloxybicyclo- (2,2,1) -2,5-heptadiene

604 grams of 1,2,3,4,7,7-hexachlorobicyclo- (2,2,1) -2,5-heptadiene (2.02 moles) was placed in a three-necked glass jar given with stirrer, heating mantle, thermometer and reflux condenser, the 190 g of potassium hydroxide (2.90 mol) ao and contained 870 grams of allyl alcohol (15.0 moles). The reaction mixture was refluxed for approximately 4 hours warmed up. The unreacted substances were distilled off under reduced pressure. The product you want was obtained by extracting the residue with diethyl ether, washing with water, drying over anhydrous Sodium sulfate and distilling isolated. It has the following structural formula:

Cl-C-OC ₃ H ₅

Wa

35

40

Cl

Example 4

1,2,3,4,7-pentachloro-7-phenoxybicyclo- (2.2,1) -2,5-heptadiene

600 g 1,2,3,4,7,7 - hexachlorobicyclo - (2,2,1) - 2,5 - heptadiene (2.0 mol) were placed in a three-necked glass vessel equipped with a stirrer, thermometer, heating mantle and reflux condenser given containing 204 g of potassium hydroxide (3.6 moles) and 338.4 g of phenol (3.6 moles). The reaction mixture was refluxed for 4 hours.

After the reaction time has elapsed, the unreacted substance is distilled off under reduced pressure. The distillation residue is poured over with water and extracted with diethyl ether. The ether layer becomes separated and dried over anhydrous sodium sulfate. The desired product will then be through Distilling isolated. Its structural formula is as follows:

55

60

Example 5

1,2,3,4,7-pentachloro-7-cyclopentenoxybicyclo- (2,2,1) -2,5-heptadiene

As already mentioned, those which can be produced according to the invention are Compounds excellent insecticides and fungicides that help combat a variety of harmful Organisms can be made usable. These combined properties allow both one Protection against both insect and fungal attack with a single treatment, saving work and costs and yet the protection is improved.

In addition to their above-described usefulness as fungicides and insecticides, the new ones are according to the invention available substances valuable intermediate products for the production of many highly effective substances. That Diels-Alder adducts that can be prepared according to the invention Compounds with a conjugated diene such as cyclopentadiene is an excellent insecticide and a Another intermediate product for the manufacture of other halogenated products. Furthermore, according to the invention available compounds z. B. be reacted with other olefins, with extremely interesting Products with the PeEtachlorbicyclo- (2.2, l) -heptene ether configuration develop.

Claims (2)

Patent claims: 1. Process for the preparation of ethers of 1,2,3,4,7-pentahalogen-7-hydroxybicyclo- (2,2,1) -2,5-heptadiene the general structural formula in which R is an aliphatic, cycloaliphatic or aromatic radical with up to 14 carbon atoms can be, characterized in that 1,2,3,4,7,7-hexachlorobicyclo- (2.2, l) -2,5-heptadiene is reacted in a known manner with an alcohol in the presence of alkali. 2. The method according to claim 1, characterized in that the alcohol Ätlrylalkohol, isopropyl alcohol, Allyl alcohol, phenol or cyclopenten-3-ol is used. 600 g of 1,2,3,4,7,7-hexachlorobicyclo- (2,2,1) -2,5 -heptadiene (2.0 mol) are placed in a three-necked reaction vessel © 009 677/452 11.60 Considered publications:
U.S. Patent No. 2,562,893.