DE1249859B - Process for the preparation of 2 ammo 1 4 5 6 7 7 hexachlorobicyclo- [2 2 l] -heptene (5) optionally substituted with alkyl in the 3 position - Google Patents

Description

'CH; -Äs'

* FEDERAL REPUBLIC OF GERMANY

PATENT OFFICE

GERMAN

EDITORIAL

Int. CL:

C07c 2-

German class: 12 ο-25

Number: 1 249 859

File number: B 60341IV b / 12 ο

Filing date: December 3, 1960

Opened on September 14, 1967

It has been found that 2-amino-1,4,5,6,7,7-hexachlorobicyclo- [2,2,1] -hepten- (5) which is optionally alkyl-substituted in the 3-position is obtained in an advantageous manner and in good yields if 2-carbamido-1,4,5,6,7,7-hexachlorobicyclo- [2.2, l] -heptene- (5) which is optionally alkyl-substituted treated with a hypochlorite and an alkali hydroxide according to known methods.

The reaction can be carried out when using the unsubstituted 2-carbamido-1,4,5,6,7,7-hexachlorobicyclo- [2.2, l] -hepten- (5) formulate as follows:

4OH "

- + 2HoO

The amines corresponding to the starting materials are obtained in yields of around 80% of theory.

The conversion of carboxylic acids into amines through the action of hypohalites and bases is known under the name "Hofmannscher Abbau". The preparation of 2-amino-1,4,5,6,7,7-hexachlorobicyclo- [2.2, l] -heptenen- (5) however, Hofmann's degradation of the corresponding carboxamides did not appear to be promising from the outset. the The starting materials are namely y, <5-unsaturated acid amides, and it is known that such acid amides only with poor yields in the corresponding Amines can be converted (Organic Reactions, III [1949], p. 276). After the said In the literature reference, the amines are only obtained in yields of 15 to a maximum of 40%. Surprisingly the process according to the invention provides the amines in yields of 80%.

The 2-carbamido-1,4,5,6,7,7-hexachlorobicyclo- [2,2,1] -heptene- (5) optionally substituted in the 3-position are easy and in good yields by processes for the preparation of possibly
2-aminol substituted by alkyl in the 3-position, 4,5,6,7,7-hexachlorobicyclo- [2.2, l] -heptene- (5)

Applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, Ludwigshafen / Rhein

Named as inventor:

Dr. Günter Scheuerer, Ludwigshafen / Rhine

Diene addition of hexachlorocyclopentadiene to «, ^ - unsaturated Acids such as acrylic acid, crotonic acid and heptene (2) carboxylic acid (l), and conversion of the Diene adducts available in the usual way in the acid amides. You can also use hexachlorocyclopentadiene react directly with acrylic acid amide or the corresponding alkyl-substituted acrylic acid amides, but this reaction is generally less successful. Preferred starting materials are the unsubstituted ones 2-carbamido-1,4,5,6,7,7-hexachlorobicyclo- [2,2,1] -hepten- (5), i.e. the diene addition product of acrylic acid amide and hexachlorocyclopentadiene, and its 3-position by lower alkyl radicals with 1 to 4 carbon atoms substituted derivatives.

To prepare a suitable solution for the reaction, which contains both the hypochlorite and the alkali metal hydroxide, you can, for. B. proceed so that one dissolves per mole of acid amide 4.4 to 8 moles, expediently about 6 moles of sodium hydroxide or potassium hydroxide in water to form a 2.5 to 3 molar solution. 1.05 to 1.5 mol, advantageously about 1.2 mol of chlorine are then passed into the solution, expediently at temperatures around 0 ^{° C.} The 2-carbamido-1,4,5, oJJ-hexachloro-bicyclo-P ^ ll-tS-heptenes) dissolve at 50 to 60 ° C in such a Hypochloritlauge clear and at 60 to 100 ⁰ C, preferably 65 to 70 ⁰ C, implemented quickly. To separate the amines formed from impurities, the reaction mixture is expediently acidified and the substances which do not go into solution are removed, for example by filtration. The amines can then be set free from the filtrate by adding bases, for example sodium hydroxide and potassium hydroxide solution. In many cases they can be used directly, but also by sublimation in a vacuum

709 647/577

further cleaned. Another possibility for purification is the crystallization of salts of the 2 - amino -1,4,5,6,7,7 - hexachlor - bicyclo - [2,2,1] - heptene ^). So z. B. the hydrochloride of acetone and petroleum ether of the unsubstituted in the 3-position 2-Amino-1,4,5,6,7,7-hexachlorobicyclo- [2,2,1] -heptens- (5) fall over or recrystallize from water.

The new 2-amino-1,4,5,6,7,7-hexachlorobicyclo- [2,2,1] -heptene- (5) are solid substances that are insoluble in water, in all common organic solvents however, are soluble. They can be used as intermediates in the manufacture of insecticides, fungicides and herbicides can be used.

The parts mentioned in the following examples are parts by weight.

example 1

8.4 parts of chlorine are passed at 0 to 5 ° C. into a solution of 24 parts of caustic soda in 200 parts of water. In this alkaline Hypochloritlauge then transmits at room temperature 35 parts of 2-CarbamidolAS ^ JJ-hexachloro-bicyclo-ß ^ lJ-hepten ^) and brings it within 30 minutes at a temperature of 55 to 60 ⁰ C in solution. The temperature of the clarified solution is then increased to 65 to 7O ⁰ C. The mixture is stirred at this temperature until the amine precipitates, which takes about 50 to 60 minutes.

After the mixture has been stirred for a further 30 minutes at 65 to 70 ^° C., 1200 parts of water and so much concentrated hydrochloric acid are added that the reaction against Congo red is clearly acidic. At a temperature of 60 ⁰ C the hydrochloride of 2-amino-l, 4,5,6,7,7-hexachloro-bicyclo- [2,2, l] -heptens- (5) remains in solution, so that the impurities can be removed by filtration. To the filtrate were then added at 30 to 40 ⁰ C so much caustic soda such that the pH value is 10 degrees. The precipitated amine is filtered off with suction and dissolved in 500 parts of benzene. To remove chlorine, the solution is shaken with an alkaline sodium dithionite solution, then washed with water and then dried with sodium sulfate. The benzene is distilled off and the residue is sublimed at 0.01 torr and a bath temperature of ^{12O 0 C.} 25 parts of pure 2-aminol, 4,5,6,7,7-hexachlorobicyclo- [2.2.1] -heptene- (5) melting point 147 to 148 ° C. are obtained.

Analysis: C ₇ H ₅ NCl ₆ (molecular weight 315.88) Calculated ... C 26.61, H 1.60, N 4.43, Cl 67.36; Found ... C 26.59, H 2.04, N 4.46, Cl 67.2.

The hydrochloride of the compound is hardly soluble in cold water, crystallized from water with ίο »1 mol of water of crystallization and melting above 300 ⁰ C.

Analysis: C ₇ H ₅ NCl ₆ ■ HCl · H ₂ O (molecular weight 370.36) Calculated ... C 22.70, H 2.18, N 3.78, Cl 67.02; Found ... C 23.15, H 2.45, N 3.99, Cl 66.8.

Example 2

In the manner described in Example 1, 2-carbamido-3-methyl-1,4,5,6,7,7-hexachlorobicyclo- [2,2,1] -hepten- (5) is obtained from 36 parts and a solution of parts of caustic soda and 8.4 parts of chlorine in 200 parts of water 25 parts of 2-amino-3-methyl-l, 4,5,6,7,7-hexachlorobicyclo- [2.2, l] -heptene - (5) with a melting point of 92 ° C.

Analysis: C ₈ H ₇ NCl ₆ (molecular weight 329.91)

Calculated ... C 29.12, H 2.14, N 4.25, Cl 64.49; Found ... C 29.0, H 1.8, N 4.4, Cl 65.0.

Claims (1)

Claim: Process for the preparation of 2-amino-1, 4,5,6, optionally substituted in the 3-position alkyl 7.7 - hexachlor - bicyclo - [2.2, I] - hepte η - (5), d a through characterized in that 2-carbamido which is optionally alkyl-substituted in the 3-position -1,4,5,6,7,7 - hexachlor - bicyclo - [2,2,1] - hepten- (5) with a hypochlorite and an alkyl hydroxide treated according to known methods. Considered publications: Deutsche Auslegeschrift R 13195 IVb / 12 o; U.S. Patent No. 2,758,918; Journal of the American Chemical Society, Vol. 82 (I960), pp. 2021 to 2025; Organic Reactions, Vol. Ill (1949), p. 276.