DE2600896A1 - BICYCLOHEPTYL AND BICYCLOHEPTENYL POLYAMINES - Google Patents

Description

s patent attorneys: I Ό U \ i υ ο 'j

Dr. ! ng. V /.- Stsr * b! Tz D r. D! 2; "■ r F. a; D rf Dr. Hsrs-A. Browns

MüacliäH S8, Piaozaaauareir. 28 January 12, 1976

15645Y

MERCK & CO., INC. Rahway, New Jersey 07065, V.St.A.

Bicycloheptyl and bicycloheptenyl polyamines

The invention relates to a new class of substituted polyamines which are used as algae inhibitors and microbe control agents, especially against gram-negative and anaerobic bacteria, can be used commercially. The new connections according to the Invention have the general formula

CH-NH-Z (I)

in the

the radicals A can be identical or different and substituted or unsubstituted [3.1.1] - or [2.2.1] -Bicycloheptyl- or -Bicycloheptenyl radicals,

the indices η can be the same or different and have a value of 0 or 1,

the radicals R _{1 can be} identical or different and are C ₁ - to C ^ -alkylene radicals,

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Z denotes a radical -Y-N-Rg, in which

"5

Rc- hydrogen, aminoethyl, aminopropyl, C, - to C »-hydroxyalkyl or C ₂ - to C ^ -dihydroxyalkyl and

R ^ are hydrogen, C ₁ - to C ^ -hydroxyalkyl or C ₂ - to C ^ -dihydroxyalkyl,

Y denotes a radical -Rp-NR ^ - or -R ₂ ", where

»3

Rp denotes the 2-hydroxy-1,3-trimethylene radical or has the same meaning as R ₁ ,

Rz is hydrogen, C ₁ - to C ^ -alkyl, C ₂ - to C ^ -aminoalkyl, C ^ - to C- -hydroxyalkyl or C ₂ - to Cr -dihydroxyalkyl, for example 2,3-dihydroxypropyl or 3,4-dihydroxybutyl and

R ^ denotes the 2-hydroxy-1,3-trimethylene radical or has the same meaning as R ₁ ,

or, when R ^ and R ^ - together form the ethylene radical, R ^ likewise an ethylene radical and Rc aminoethyl, aminopropyl or Mean aminohydroxypropyl.

When A is [2.2.1] -bicycloheptyl or -bicycloheptenyl, has it's the general formula

(II)

in which the radicals R can be identical or different and are C ₁ - to C ^ -alkyl radicals or hydrogen atoms, the radicals R ^{1 can be} identical or different and are hydrogen atoms or C ₁ - to C ^ -alkyl radicals, or two radicals R ¹ to be

609829/08 5 3

adjacent carbon atoms can mean an olefinic double bond.

In general, the sum of the carbon atoms in all of the radicals R and R 'is preferably 10 or less. In particularly preferred embodiments, R ¹ and R, independently of one another, are hydrogen atoms or methyl groups, and less than 5 of all radicals R 'and R are methyl groups. In the very particularly preferred embodiments, each radical A is either a 3,3-dimethylnorborn-2-yl radical or a norborn-2-yl radical and R ^ is an ethylene radical.

If A is [3.1.1] -bicycloheptyl or -bicycloheptenyl,

it has dxe general formula

in which the radicals R can be identical or different and denote hydrogen atoms or Ci- to C ^ -alkyl radicals, while the dashed line means a double bond between positions c and d or between positions d and e, wherein the bicyclo group on (R-j) through the c, d or e position of the ring is bound. Preferred [3.1.1] -bicyclic Groups are those in which R is methyl or hydrogen and no more than 4 R radicals are methyl radicals, such as e.g. 2-, 3- and 4-norpinanyl, 2-, 3- and 4- (2-norpinenyl), 2-, 3- and 4- (6,6-dimethylnorpinanyl), 2- and 4- (3,6 , 6-trimethyl-2-norpinenyl), 3- (2,4,6,6-tetramethyl-2-norpinenyl), 3- and 4-pinanyl, 3- and 4r. (2-pinenyl) and 3- and 4- (3-pinenyl).

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15645Y 2600898

The compounds according to the invention are generally according to the following reaction sequence produced:

A- (R ₁ )

C = O + HN-Z A- (R ₁ J _n

(IV) (V)

(H)

C = N-Z

(Vl)

A- (R ₁ )

^ 0

0-N-Z

(D

(Ia)

HC-N-Z. HX

I.
H

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Here, A, Z and η have the above meanings, HX is a mono- or polybasic organic or inorganic acid, and there is enough HX present to protonate at least one amino group of the polyamine.

The polyamine I is prepared by a simple reaction of the corresponding ketone IV with the corresponding one Amine V to a Schiff base and subsequent hydrogenation of the Schiff * see base VI to the polyamine I.

If the amine V has several primary amino groups, it can be symmetrical or unsymmetrical. An amine V, which is a symmetrical amine, for example when R ₂ and R ^ are the same and R ^ and R ^ are hydrogen atoms, or when Rp and R ^ _{+ form} the ethylene radical, Rp- is an aminoethyl radical and Rg is hydrogen, or when R ^ the trimethylene radical, Rr the 3-aminopropyl radical and Rg hydrogen, forms a single Schiff base VI. This is based on the fact that the same product is always formed, regardless of which terminal primary amino group of the amine V reacts with the ketone IV. However, if the amine V is unsymmetrical, two products can form. One is the Schiff base VI. The other products have, for example, when Rr and Rg are hydrogen atoms, the general formula VI (a)

C = NR ₄ -NR ₂ -NH ₂ (VKa))

or, if, for example, Rj- denotes the aminoethyl or aminopropyl radical, the general formula VI (b)

C = N (CH ₀ ) ₄

² (2, 3) ⁴ I.

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15645Y 2600S96

wherein A, R, g and η have the above meanings. To note is that both products VI (a) and VI (b) fall under the definition for Schiff base VI. When ship's see bases of the general formulas VI and VI (a) or VI (b), they can optionally in a manner known per se, namely by distillation and the like, are separated from each other.

Instead of using an unsymmetrical amine V and a mixture to get from the ship see bases VI and Vl (a) or Vl (b), the implementation can also be carried out in stages. For example, 1,2-diaminoethane can be mixed with 1,5-di- (3,3-dimethylnorborn-2-yl) -3-pentanone Convert into a Schiff base, this catalytically reduce, then selectively cyanoethylate the remaining primary amino nitrogen atom with acrylonitrile and then catalytically hydrogenate to give 1- [1,5-di- (3,3-dimethylnorborn-2-yl) -3-pentyl] -1,4,8-triazaoctane to obtain.

The availability and preparation of the ketones VI is described in detail below. The amines V are known and can be easily prepared. Some particularly preferred manufacturing processes are the condensation of acrylonitrile with ammonia and subsequent hydrogenation to 3.3 ^l -imino-bis-propylamine. You can also react an N-alkylated trimethylenediamine with epichlorohydrin and convert the product with alcoholic ammonia into an N-alkylated N '- (3-amino-2-hydroxypropyl) -trimethylenediamine.

To produce the Schiff base VI, the ketone IV and the amine V is dissolved in a suitable inert solvent, e.g., toluene, and the solution is brought to reflux temperature heated until the reaction is essentially complete, usually 5 to 20 hours for the azeotropic distillation of water are sufficient. Then the solvent is driven off under reduced pressure and the ship

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se VI containing residue in an inert solvent, preferably an alkanol such as ethanol or isopropanol, dissolved.

After dissolving, the Schiff base VI is reduced catalytically or chemically.

If the reduction is catalytic, the carbon will be nitrogen as well bond of Schiff see base VI also reduces all unsaturated carbon-carbon bonds in A. or hydrogenated. In such catalytic reductions, an alkanol solution of the Schiff base VI will be seen with stirring in Presence of conventional hydrogenation catalysts, such as the transition metals or their reducible oxides, with hydrogen saturated. The noble metals and their oxides are particularly effective catalysts. A particularly preferred one The catalyst is platinum oxide. In general, the hydrogenation is carried out in a manner known per se. Small catalyst particles with sizes of, for example, 0.04 to 0.15 mm will see the Schiff base and excess amine in alcohol mixed and placed in a closed vessel under a hydrogen pressure of 3 to 5 atm. When the reaction is complete, the pressure is released and the catalyst is filtered off from the reaction mixture. That the bicycloheptyl polyamine I-containing filtrate is then further purified by conventional methods. Preferably everything is there The solvent is driven off under reduced pressure, the residue is then dissolved in diethyl ether and washed with water and then washed further with saturated aqueous sodium chloride solution. After drying over anhydrous sodium sulfate the diethyl ether is driven off under reduced pressure, and the bicycloheptyl polyamine I is usually obtained in the form of an oil. The Bicycloheptylpolyamine can then again in lower Alkanols, mixtures of lower alkanols and water, diethyl ether or dioxane and then dissolved with an acid, e.g.

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Hydrochloric acid, or it can be neutralized directly with aqueous Acids are neutralized.

Acid addition salts are then optionally isolated by precipitation, evaporation or other conventional methods.

Suitable anions X for the salt I (a) are anions of inorganic ones Acids or organic acids, such as halide, e.g. chloride, bromide or iodide, or sulfate, bisulfate, nitrate, Phosphate, acetate, propionate, maleate, succinate, laurate, oleate, palmitate, stearate, ascorbate, gluconate, citrate, carbonate, Bicarbonate, benzoate, salicylate, pamoate, phthalate, furoate, picolinate, Dodecylbenzenesulfonate, lauryl ether sulfate, nicotinate and like that. If the anion X ~ of the polyamine salt, e.g. the Chlorine ion, which is to be replaced by other anions according to known anion exchange methods, can generally be used use any acid derived anion.

For the production of bicycloheptenyl polyamines, i.e. the product I in which a double bond is obtained in the ring A remains, one does not use the catalytic but a selective chemical reduction to get the Schiff base VI to reduce the product I.

In this chemical reduction process, the ketone IY, as above, reacted with a suitable amine, but see the Schiff * dissolved in an inert alkanol or ether base VI is reacted with a chemical reducing agent such as sodium borohydride or lithium aluminum hydride.

One can be successful with just 1 equivalent of the chemical Reducing agent work; however, more satisfactory results are obtained with an at least 2 molar and preferably with an at least 2.5 molar excess of the chemical

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see reducing agent. As soon as the initial reaction has subsided, the reaction mixture of Schiff's base VI and reducing agent can be refluxed for 1 or 2 hours
heated, then cooled to room temperature and finally concentrated in vacuo. The residue is then further purified, for example as described above for the bicycloheptyl polyamines I, with mineral acid or an inorganic base, and that
Salt then prepared as described above.

The bicycloheptyl and bicycloheptenyl ketones IV can after
four different methods can be prepared, which are described below under (A) to (D).

(A) The condensation of acids

This manufacturing process proceeds according to the following reaction scheme:

₁ Y _n Fe A

(VII)

C = O + CO ₀ + H ₀ O / 2 2

A- (R ₁ J _n . '

(IV)

The acylating decarboxylation of acids VII is carried out by heating the acid to elevated temperatures with transition metals, preferably iron, transition metal oxides, alkaline earth oxides, polyphosphoric acid or boron trifluoride. The acylating reaction is most conveniently carried out by passing the acid vapors over catalysts, such as heated ones
Thorium Oxide Airgel.

Condensing decarboxylation of an acid is the preferred method of making ketone IV when the A- (R ^) _n -

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Groups are equal to one another, while a product mixture is obtained if several different acids are used for the reaction used. The reaction is preferably carried out by mixing the carboxylic acid VII with reduced iron powder and 1- to Stirring for 6 hours in an inert atmosphere at 195 to 200 C, during which the iron salt is formed.

The carboxylic acid VII and the iron are preferably stirred in for at least 2 hours
Sphere of nitrogen.

at least 2 hours at 195 to 200 ° C in an inert atmosphere

After 2 hours the temperature is increased to 290 to 295 ° C. and stirring is continued for at least a further 3 hours; usually 4 hours are enough. The reaction mixture is allowed to cool, then extracted with a suitable inert solvent, like diethyl ether, and filtered. The solvent extracts are evaporated under reduced pressure. the Liquid remaining as a residue is distilled in vacuo in order to isolate the ketone IV.

The carboxylic acids VII can be prepared by various processes known per se. A particularly valuable one The method is the addition of [2.2.1] -bicycloheptenes, such as camphene, isocamphodiene, ß-fenchen, norbornylene, santen and the like, to an aliphatic acid anhydride.

In this process, a mixture of the bicycloheptene and a catalytic amount, for example 0.2 to 0.3 moles per mole of terpene, of a free radical forming catalyst such as Ditert.butylperoxid, in the course of 3 to 5 hours to a 5- to 15 molar excess of the aliphatic acid anhydride boiling on the reflux condenser was added dropwise. When the addition is complete, the reaction mixture is kept at reflux temperature for 5 to 10 hours, concentrated under reduced pressure and the liquid residue is treated with aqueous sodium hydroxide solution.

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mixes and. Stirred for 2 to 5 hours while heating on the steam bath. After cooling, the alkaline solution is extracted with ether, the ether layer is discarded and the aqueous solution acidified and then extracted well with ether. The United Ether extracts are washed with water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The liquid or solid residue is distilled in vacuo, the corresponding carboxylic acid VII is obtained.

Other carboxylic acids are easily obtained, for example, by the Diels-Alder reaction of cyclopentadiene or alkyl-substituted cyclopentadiene with various unsaturated carboxylic acids, the are described in detail below.

Another suitable process for this synthesis of bicyclo- [2.2.1] -heptyl-substituted alkanoic acid compounds makes use of the addition of methyl or ethyl alkanoates to unsaturated bicyclo- [2.2.1] -heptenes under the influence of free radicals. The catalysis by free radicals takes place, for example, with the help of Ditert.butylperoxid, which mainly splits off a hydrogen atom adjacent to the carbonyl group from the alkanoic acid alkyl ester (see. DJ. Trecker and RS Foote, "Journal of Organic Chemistry ¹¹ , Volume 33, 1968, page 3527 The corresponding esters are obtained by the addition of the free radical that is formed in the process to the olefinic terpene. Conventional saponification processes, for example with dilute aqueous sodium hydroxide solution, set the alcohol free.

(B) Condensation of a Grignard ¹ see reagent with a nitrile

Disubstituted bicycloheptyl or bicycloheptenyl alkanones can also be prepared according to the following reaction scheme:

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Original inspected

A- (R ₁ ) £ - X 3> A- (R ₁ ) _n MgX

A- (R ₁ ) - CN + A- (R ₁ J _n MgX hydrolysis with aqueous acid ^

^A - ( ^R i> iT-Sr < ^R i> ir ^A *

wherein the radicals (R ₁ ) in each reactant can be the same or different.

For the preparation of di- (subst.bicycloheptyl) alkanones, a general procedure involves reacting a Grignard ¹ reagent prepared from a chlorine- or bromine-substituted alkylbicyclo- [2.2.1] -heptane with a cyano-substituted alkylbicyclo- [2.2 .1] -heptane use. The disubstituted iminoalkane salt complex obtained in this way is hydrolyzed with mineral acid to give the corresponding ketone.

The Grignard ¹ see reagent is obtained by reacting the halide with metallic magnesium, usually "in the form of chips or powder, which is catalyzed by very low concentrations of iodine or methyl iodide. Suitable solvents for this are diethyl ether, dibutyl ether, tetrahydrofuran, dioxane and benzene. Usually, gentle heating is sufficient to initiate the reaction and the halide is gradually added to the mixture of metal and solvent. When the addition is complete, the disappearance of virtually all metallic magnesium indicates the end of the reaction. Undercut with a slight excess of metal Exclusion of moisture, working under nitrogen is advantageous. The nitrile is added in 2 to 3 times its volume of solvent over the course of 15 minutes to 1 hour at room temperature to the Grignard * see reagent. The reaction mixture can then be heated to reflux temperature to the completeness to ensure implementation. In space-

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The common practice is to work with a slight excess of Grignard's reagent over the nitrile. 1 to 10 hours Heating on the reflux condenser is sufficient for complete conversion. The imine salt thus obtained is preferably with aqueous mineral acid, such as hydrochloric acid, sulfuric acid or Phosphoric acid, which breaks down to the ketone. The ketones are insoluble in water and can be mixed with water-immiscible solvents extracted. The purification is preferably carried out by fractional distillation under reduced pressure. One can use the crude ketone reaction mixture for the alkylation of polyamines as the reaction byproducts usually Are alcohols or hydrocarbons that do not react with the amines. When the crude product is reactive Contains halides, these should be used prior to the ketone amine alkylation process removed.

In order to ensure good yields in the process, the concentrations of Grignard's reagent and nitrile can be within further limits can be varied.

The halogen, cyano and carboxyl derivatives of bicycloheptanes and bicycloheptenes are commonly available commercially and are derived from bicycloheptanes and bicycloheptenes, such as norcamphan, apocamphan, camphan, oc-fenchan, santan, Camphenilane, Isocamphan, ß-Fenchan, Norbornylen, Apobornylen, Bornylen, cf-Fenchen, Camphenilen, Y-Fenchen, Santen, <£ -Fenchen, norpinan, 2-norpinan, 6,6-dimethylnorpinan, 6,6-dimethyl-2-norpinane, orthodes, homopines, pinane, oc-pinene, ß-pinene and the like.

If these carboxyl, cyano or halogen derivatives are not readily available, they can be synthesized by known methods e.g. by Diels-Alder condensation according to US-PS 3,595,917 and "Newer Methods of Preparative Organic Chemistry" by K. Alder, Interscience Verlag, New York, 1948, Pages 381-456, e.g.

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In the above reaction sequence, D has the meaning R, - (R ₁ J _n -COOH, - (R ₁ J _n -X or - (R ₁ J _n -CN, while R ₁ , R and X have the above meanings D has the meaning R and each radical R is an alkyl radical, the resulting bicycloheptene can be reacted with an aliphatic acid anhydride, as described above.

(C) The reaction of acid halides with malonic acid esters

The third possible method for making the IV ketones is running according to the following reaction scheme:

A- (R ¹ J _n CH (COO-tert. C ₄ H ₉ J ₂

(VIII) A- (R ¹ J _n C "- (COO-tert. C ₄ H ₉ J ₂ + Na ⁺ + H.

(IX)

0 A- (R ¹ J _n C ~ - (COO-tert. C ₄ H ₉ ) _£ Na ⁺ + A- (R ₁ J _n C-Cl

/OO-tert.C^Q
CH _x COOH-H ₀ SO-

A- (R ¹ KC C (Ri) "- A 2 <= _ t_

ⁿ \ ν ' ⁿ

\ Ö

COO-tert. C ₄ H ₉

(IV)

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In the above reaction scheme, A, R ₁ and η have the above meanings, and. R * is a C ^ - to C ^ -alkylene radical. ■■ <:

The bicyclo - ^ - 2'i.2 «-T] -heptyl-substituted malonic acid esters are for example, either from cyclopentadienes and alkenyl-substituted ones Malonic acid esters and then catalytic Hydrogenation of the heptene derivatives to heptanes or by Al-. kylation of malonic acid esters with a halogen-substituted one Bicy & lo - {-. 2 .-. 2 * 1 ··] -heptane, where the halogen is preferred, wise is chlorine, or, bromine, attached directly to the ring or forms part of an alkyl substituent.

The sodium derivative IX of the malonic acid tert-butyl ester is prepared by adding a small molar excess of sodium hydride to a solution of the malonic acid ester VIII in an inert solvent such as anhydrous benzene added. The reaction is conveniently carried out by heating to 60 bis 80 ° C with stirring until the evolution of hydrogen ceases has, protecting the reaction mixture from atmospheric moisture. A solution of an equimolecular amount of acid halide X in the amount of anhydrous benzene just sufficient to dissolve the acid halide is added and reflux the reaction mixture for about 5 to 20 minutes heated. The mixture is cooled and any excess sodium hydride with anhydrous p-toluenesulfonic acid destroyed. The reaction mixture is filtered and the solvent stripped from the filtrate under reduced pressure. The residue is in glacial acetic acid, which is 0.3 to 0.5 percent by weight Contains anhydrous p-toluenesulfonic acid and about 2 percent by volume acetic anhydride, dissolved. The solution will be Heated to reflux temperature for 1 hour and then cooled to room temperature. The solution is then poured over ice, neutralized with aqueous sodium hydroxide solution and extracted the crude ketone IV with diethyl ether. The ethereal solution is made with water washed, dried over anhydrous magnesium sulfate

- 15 -

ORIGINAL, N ₈ PECT ₆

₆₀

and filtered, whereupon the solvent is driven off.

(D) Condensation of a ketone with a ketone or aldehyde and subsequent reduction .

A fourth method for making the ketone IV starts with the condensation of a ketone with a ketone or aldehyde according to the following reaction scheme:

AC = CC = O + A (R ₁ ) _n C = 0> AC = CC-CH = C (R ₁ J _n A

R * CH ₃ R * O

(XIV) (XV) (XVl) * MR*

. Reduction. ACCC-CH ₀ CIIR (R,) -A (iv)>,, "2 1 η

'R * HO

Here, the radicals A can be identical or different, and A, R ^, R and η have the above meanings, while R * is independent Can mean methyl, ethyl or hydrogen.

To carry out this reaction, the ketone XIV is mixed with stirring and cooling in the presence of catalytic amounts of sodium methylate with a molar equivalent or a slight excess of aldehyde or ketone XV. Now the reaction mixture Maintained at 40 to 55 ° C for 4 to 10 hours and then cooled to room temperature. The reaction mixture is acidified and the residue, after the solvent has been driven off, is extracted with diethyl ether under reduced pressure. The ether extracts are washed with water and dried over magnesium sulfate. Then the solvent is reduced under Pressure driven off.

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ORIGINAL INSPECTED

The residue XVI is dissolved in thiophene-free benzene and under a hydrogen pressure of 3 "to 5 at at 20 to 30 C with a noble metal shaken on carbon as a catalyst. Then the catalyst is filtered off and the solvent removed. The residue is compound IV, which can be further purified using conventional methods »

Once the ketone IV has been obtained, it can be reacted with a suitable polyamine V. Polyamines V, which are exceptionally suitable for the reaction with ketones IV, are diethylenetriamine, triethylenetetramine, 3,3 ^f -imino-bis- (propylamine), 3,3'-methylimino-bis- (propylamine), dipropylenetriamine, N, N '-Bis- (3-aminopropyl) -1,3-trimethylenediamine, N, N'-bis- (2-aminoethyl) -1,3-trimethylenediamine, N, N ¹ -bis- (3-aminopropyl) -piperazine , N- (2-aminoethyl) -1,3-trimethylenediamine, spermidine, spermine, 1,4-bis (2-aminoethyl) piperazine, tris (2-aminoethyl) amine, 1- (2-aryinoethyl) -4- (3-aminopropyl) piperazine. 1 - (3-Amino-2-hydroxypropyl) -4- (2-aminoethyl) piperazine, N- (3-amino-2-hydroxypropyl) -1,3-trimethylenediamine, 1- (2,3-dihydroxypropyl) - 1,5,9-triazanonane, 1- (2-hydroxyethyl) -1,4,7,10-tetraazadecane, 4- (3,4-dihydroxybutyl) -1,4,8-triazaoctane, 1- (2-hydroxypropyl ) -5-hydroxymethyl-1,5,9-triazanonane and tris- (3-aminopropyl) -amine, ethylenediamine, trimethylenediamine and 1 ^ -diamino ^ -hydroxypropane,

The substituted bicycloheptanes obtained by the various synthetic routes described here can be used as exo- and endo isomers exist and are usually mixtures of both configurations. The isomer ratio that forms depends on many factors, such as temperature, solvents, steric effects, equilibrium conditions, the nature of the substituents, etc. The value of the products according to the invention, however, seems to depend on precise control of the Isomeric composition to be independent. The isomer content of a product mixture can be determined by vapor or liquid

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phase chromatography, nuclear magnetic resonance analysis, fractionated Distillation or other methods can be determined. It is also possible to choose the pure isomers to isolate this and other known separation methods.

Example A. Production of 5-norbornene-2-butyric acid

A solution of 120 g (1 mol) of 5-vinyl-2-norbornene and 14.6 g (0.1 mol) of di-tert-butyl peroxide is added dropwise to 1050 g (10 mol) of acetic anhydride boiling on a reflux condenser over the course of 6 hours. When the addition is complete, the mixture is refluxed for 5 hours. After cooling, the reaction mixture is concentrated under reduced pressure, 750 ml of 2 _f 5N sodium hydroxide solution are added to the yellow-orange oil that remains as residue and the mixture is then heated on the steam bath for 1 hour. The cooled solution is extracted once with ether, acidified with concentrated hydrochloric acid and extracted thoroughly with ether. The ether extracts, dried over sodium sulfate, are evaporated under reduced pressure and the residue is distilled in vacuo. 35.5 g of a colorless product are obtained; Yield 20%; ^K P0.2 mm 120-124 ° C.

In a similar way, 3- (2-norbornen-5-yl) propionic acid is obtained from 5-ethylidene-2-norbornene, 1,5,5-trimethylnorborn-3-ylacetic acid from £ -Fenchen, 5,5-dimethylnorborn-2- and -3-ylacetic acid from campheniles, 2,5,5-trimethylnorborn-3-ylacetic acid from r-fenchen, 3- (7,7-dimethylnorborn-2-yl) propionic acid from cc-fenchen, 3- (3,3-dimethylnorborn-2-yl) propionic acid from camphene, 3- (norborn-2-yl) propionic acid from norcamphen, norborn-2-ylacetic acid from norbornylene, 7,7-dimethylnorborn-2-ylacetic acid from apobornylene, 1., 7,7-trimethylnorborn-3-acetic acid from bornylene, 2,3-dimethylnorborn-

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2-ylacetic acid from Santen, 3- (5,5-dimethylnorborn-2-en ~ 6-yl) propionic acid from isocamphodiene, 3- (2,2-dimethylnorborn-5-yl) propionic acid from β-fenchen , 2.7 _f 7-trimethylnorborn-3-ylacetic acid from ^ -Fenchen, 1,2,3-trimethylnorborn-3-ylacetic acid from ^ -Fenchen and 1,2,3,4,5,5,6,6,7 , 7-Decamethylbicyclo- [2.2.1] -heptan-3-ylacetic acid from 1,2,3,4,5,5,6,6,7,7-decamethylbicyclo- [2.2.1] -hept-2-en , which in turn is produced by Diels-Alder condensation from 1,1,2,3,4,5-hexamethylcyclopentadiene and 1,1,2,2-tetramethylethylene.

B is ρ ie 1 B ■. . ■. ■

Bicyclo- [2.2.1] -heptyl-substituted alkanecarboxylic acids

A solution of 15 moles of an alkyl alkanecarboxylate, 1.1 g (0.14 moles) of boron and 3.3 g (2.25 x 10 " ² moles) of di-tert-butyl peroxide is placed in a 3 liter stainless steel autoclave. The autoclave is flushed out with nitrogen and then moved back and forth for 12 hours at 140 ° C. After cooling, unreacted norbornene, unreacted esters and peroxide decomposition products are driven off from the contents of the autoclave. is purified by fractional distillation.

Ethyl acetate and norbornene give ethyl norborn-2-yl acetic acid (KPg, - 62 C) in 64 percent yield, and methyl isobutyrate and norbornene give methyl 2-methyl-2- (norborn-2-yl) propionate (boiling point ^ _{2 m} 84 C) in 55 percent yield. These esters are then hydrolyzed in aqueous hydrochloric acid to (norborn-2-yl) acetic acid or 2-methyl-3- (norborn-2-yl) propionic acid.

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Example C Preparation of 1,3-di- (3,3-dimethylnorborn-2-yl) -2-propanone

36.4 g (0.20 mol) of 3,3-dimethylnorborn-2-ylacetic acid and 6.15 g (0.11 mol) of iron which has been reduced with hydrogen are heated to 195 ° C. under nitrogen for 1.5 hours. The temperature is then increased to 290 ° C. and held at this level for 3 hours. After cooling, the reaction mass is extracted well with ether, filtered through kieselguhr, and the ether extracts are concentrated in vacuo. The reddish oil that remains is distilled in vacuo, the product remaining as 21.5 g of a pale yellow liquid; Yield 71 %;

In a similar way, 1,3-di- (norborn-2-yl) -propanone is obtained from 2-norbornane acetic acid, 1,7-di- (5-norbornen-2-yl) -4-heptanone from 4- (5- Norbornen-2-yl) butyric acid, 2,6-di- (5-norbornen 2-yl) -4-heptanone from 3- (5-norborn-2-yl) butyric acid, 1,3-bis- (1 _t 5,5-trimethylnorborn-3-yl) propanone from ί, 5,5-trimethylnorborn-3-ylacetic acid, 1,3-bis- (5,5-dimethylnorborn-2- and -3-yl) -propanone 5,5-dimethylnorborn-2- or -3-ylacetic acid, 1,3-bis- (2,5,5-trimethylnorborn-3-yl) -propanone from 2,5,5-trimethylnorborn-3-ylacetic acid, 1 , 5-bis (7,7-dimethylnorborn-2-yl) pentan-3-one from 3- (7,7-dimethylnorborn-2-yl) propionic acid, 1,5-bis- (3,3- dimethylnorborn-2-yl) pentan-3-one from 3- (3,3-dimethylnorborn-2-yl) propionic acid, 1,5-bis (norborn-2-yl) pentan-3-one from 3 - (Norborn-2-yl) -propionic acid, 1,3-bis- (norborn-2-yl) -propanone from norborn-2-ylacetic acid, 1,3-bis- (7,7-dimethylnorborn-2-yl) propanone from 7,7-dimethylnorborn-2-ylacetic acid, 1,3-bis (1,7,7-trimethylnorborn-2-yl) propanone from 1,7,7-trimethylnorborn-2-yle Acetic acid, 1,3-bis- (2,3-dimethylnorborn-2-yl) -propanone from 2,3-dimethylnorborn-2-ylacetic acid, 1,5-bis- (5,5-dimethylnorborn-2-en-6 -yl) pentan-3-one from 3- (5,5-dimethylnorborn-2-en-6-yl) propionic acid, 1,5-bis- (2,2-dimethylnorborn-5-yl) pentane 3-on from 3- (2,2-di-

- 20 -

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JH

methylnorborn-5-yl) propionic acid, 1,3-bis (2,7,7-trimethylnorborn-3-yl) propanone from 2,7,7-trimethylnorborn-3-ylacetic acid, 1,3-bis ( 1,2,3-trimethylnorborn-3-yl) propanone from 1, Z ^ -trimethylnorborn ^ -yl acetic acid, 1,3-bis- [i, 2,4,5,6,7-hexamethyl-7-propyl- [2.2.1] -hept-5-en-3- ⁱ yl] -acetone from 1,2,4,5,6,7-hexamethyl-7-propyl- [2.2.1] -hep.t-fj- en ^ -yl acetic acid, which in turn is produced by Diels-Alder condensation from 1-methyl-1-propyl-2,3,4,5-tetramethylcyclopentadiene and 4-methylvinyl acetic acid, bis- [1,2,2,3,4 , 5,6, -7,7-nonamethyl-bicyclo- [2.2.1] -hept-5-en-3-yl] -acetone from 1, 2,2,3,4,5,6,7,7 -Nonamethyl-bicyclo- [2.2.1] -hept-5-en-3-ylacetic acid, which in turn is produced by Diels-Alder condensation from 1,1,2,3,4,5-hexamethylcyclopentadiene and 3,4,4- Trimethylvinylacetic acid is produced, 1,3-di- (2,4,6,6-tetramethyl-2-norpinen-3-yl) -2-propanone from 2,4,6,6-tetramethyl-2-norpinen-3- ylacetic acid, 1,3-di- (2-pinene-4-yl) -2-propanone from 2-pinene-4-ylacetic acid, 1,5-bis- (6,6-dimethylnorpinane-4- yl) pentan-3-one from 3- (6,6-dimethylnorpinan-4-yl) propionic acid and 1,5-bis (norpinan-2-yl) pentan-3-one from 3- (norpinan- 2-yl) propionic acid.

Example D

Production of 2- (bicyclo- [2 "2 _e 1] -heptan-2-ylacetyl) -bicyclo- [2.2", 1] -heptane

The sodium derivative of bicyclo- [2.2.1] -heptan-2-ylmalonic acid di-tert-butyl ester is made by adding 0 ^ 36 g of sodium hydride added to a solution of 3.1 g of malonic acid ester in 75 ml of anhydrous benzene. There is a with on the reflux condenser Ascarite-loaded drying tube connected. The reaction is carried out by heating to 80 ° C with stirring until the water st off development ceases (approximately 2 1/2 hours). then a solution of 16 g of bicyclo- [2.2.1] -heptan-2-ylcarboxylic acid chloride is used in 30 ml of anhydrous benzene and carries out the reaction for 10 minutes at reflux temperature. That

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The mixture is cooled to room temperature and the excess sodium hydride is destroyed with 0.9 g of anhydrous p-toluenesulfonic acid. The mixture is filtered and the solvent is driven off from the filtrate under reduced pressure. The residue is in 75 ml of glacial acetic acid, the 0.3 g of anhydrous p-toluenesulfonic acid and contain 2 percent by volume acetic anhydride, solved. The solution is heated to reflux temperature for 1 hour, cooled to room temperature, poured over crushed ice, neutralized with 5 percent sodium hydroxide solution and that Product extracted with diethyl ether. The ether solution is washed with water, dried over anhydrous magnesium sulfate, filtered and freed from solvent by distilling off. The residue consists essentially of pure 2- (bicyclo- [2.2.1] -heptan-2-ylacetyl) -bicyclo- [2.2.1] -heptane.

Under the same reaction conditions, 1- [3-methylbicyclo- [2.2.i] -hept-2-yl] -6- [3,3-dimethylbicyclo. [2.2.1] -hept-2-yl] -hexane 3-one from 3-methylbicyclo- [2.2.1] -hept-2-ylmethylmalonic acid ester and 4- [3,3-dimethylbicyclo- [2.2.1] -hept-2-yl] -butyric acid chloride and 1- [5.6 -Diethylbicyclo- [2.2.1] -hept-2-yl] -4- [i, 7,7-trimethylbicyclo- [2.2.1] -hept-2-yl] -butan-2-one from 5,6- Diethylbicyclo- [2.2.1] -hept-2-ylacetyl chloride and 1 f7, 7-trimethylbicyclo- [2.2.1] -hept-2-ylmethylmalonic acid ester.

Example E.

Preparation of 1- (1,7,7-trimethylbicyclo-r [2.2 _e i] -hept-2-yl) -4- (1,3,3-trimethylbicyclo- [2 "2.1J-hept-2-yl) -butane-2-one

20.6 g (0.1 mole) of 1- (1,3,3-trimethylbicyclo- [2.2.1] -hept-2-yl) -1-buten-3-one and 18.3 g (0.12 mol) of camphor are dissolved in 25 ml of methyl alcohol. Then-you set in the course of 15 minutes with thorough stirring and external cooling, a solution of 3.4 g of potassium hydroxide in 20 ml of methyl alcohol is added. The reaction mixture is kept at 40 to 45 ° C for 6 hours

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It was cooled to 20 ° C., made weakly acidic with dilute hydrochloric acid and, after the solvent had been driven off, the residue was extracted with ether under reduced pressure. The ether solution is washed twice with 1/10 its volume of cold water and dried over anhydrous magnesium sulfate, whereupon the solvent is driven off under reduced pressure. The remaining oil, which is 1- (1,7,7-trimethylbicyclo- [2.2.1] -hept-2-ylidene) -4- (1,3,3-trimethylbicyclo- [2.2.1] -hept- 2-yl) -but-3-en-2-one is dissolved in 100 ml of thiophene-free benzene and the solution under a hydrogen pressure of 3.5 kg / cm ² at 25 ° C with 3 g of 5 percent palladium 'Carbon shaken until a little more than the theoretical amount of hydrogen has been absorbed. The catalyst is then filtered off and the solvent is driven off. The oil which remains as a residue is purified by fractional distillation under reduced pressure. This gives ■ ΐ-Ο _f 7,7-trimethylbicyclo- [2.2.i] -hept-2-yl) -4- (1,3,3-trimethylbicyclo- [2.2.1] -hept-2-yl) -butane-2-one.

The following dialicyclic alkanones are obtained from other aldehyde or ketone derivatives of bicyclo- [2.2.1] -heptane using the same synthetic process:

Aldehyde di- (bicycloheptyl) -

or ketone ketone alkanone

3,3-Dimethylbi- 1- (1,3,3-trimethyl-1-f3,3-dimethylbicyclo- [2.2.1] -heptbicyclo- [2.2.1] -cyclo- [2.2.1] -hept- 2 -ylaldehyd hept-2-yl) -1-buten- 2-ylj-5- (1,3,3-tri-

3-one methylbicyclo-

[2.2.1] _r hept-2 ~ yl) pentan-3-one

2,5-methylene 1- (1,3,3-trimethyl- 1- [bio-cyclo- [2.2.1] -

1,2,5, 6- tetrahydro-bicyclo [2.2.1] - hept-2-yl] -5- (1,3,3-

benzaldehyde hept-2-yl) -1-butene-trimethylbicyclo-

3-on [2.2.1] -hept-2-yl-

pentan-3-one

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15645Y

Aldehyde or ketone

3-methyl-2-norbornanone

2-bornyl n-propyl ketone

3- [1,3,3-Trimethylbicyclo- [2.2.1] -hept-2-yl] -acrolein

Ketone

1- (1,3,3-Trimethylbicyclo- [2,2, i] -hept-2-yl) -1-buten-3-one

2-bornyl-n-propyl ketone

1- (1,3,3-Trimethylbicyclo- [2.2o1] -hept-2-yl) -1-buten-3-one

Di (bicycloheptyl) alkanone

1- [3-methylbicyclo- [2.2.1] -hept-2-yl] -. 4- (1,3 _f 3-trimethylbicyclo- [2,2.1] -hept-2-yl) -butan-2-one

2- [2-Ethyl-3- [1,7,7-trimethylbicyclo- [2.2.1] -hept-2-yl] -hexanoyl] -1,7,7-trimethylbicyclo- [2.2.1] -heptane

methylbicyclo- [2.2.1] -hept-2-yl] -heptan-3-one

Example F

Preparation of 2- (1,7,7-trimethylbicyclo- [2.2.1] -hept-2-ylacetyl) -bicyclo- [2.2.1J-heptane

(a) Preparation of the Grignard ¹ see reagent of bicyclo- [2.2.1] -hept-2-yl-bromide

The reagent is prepared in a dried device under nitrogen by adding 5.0 g (0.029 mol) of the abovementioned bromide in 20 ml of dry ether to 1.0 g (0.041 g-atom) of magnesium under 15 ml of ether contain an iodine crystal. The mixture is refluxed for 1 hour. This Grignard ¹ see reagent can also be prepared by the method of H. Kwart and L. Kaplan, "Journal of the American Chemical Society", Volume 76, 1954, page 1072.

(b) Reaction of the Grignard's reagent with 1,7,7-trimethyl bicyclo- [2.2.i] -hept-2-yl-acetonitrile

A solution of 3.5 g (0.02 mol) of 2-boronane acetonitrile in 15 ml anhydrous ether is in the course of 15 minutes under good

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JtS

system stirring to see the ^{Grignard 1} reagent prepared according to part (a) added. When the addition is complete, the reaction mixture is stirred for a total of 12 hours and then poured onto a mixture of 50 g of ice and 20 ml of concentrated hydrochloric acid. The ether is driven off under reduced pressure and the residue is heated to reflux temperature for 1 hour. After cooling, the mixture is extracted twice with 50 ml of ether each time,
the organic layer was separated, washed with cold water, dried over anhydrous magnesium sulfate, filtered and the solvent was distilled off. Fractional distillation of the residue in vacuo is obtained
2- (1,7,7-Trimethylbicyclo- [2.2.1] -hept-2-ylacetyl) -bicyclo- [2.2.1] -heptane in the pure state. The product is characterized by its typical carbonyl infrared absorption at 5.8 µ.

If you work under the same conditions and replace the norbornyl bromide with the halides given below and the corresponding Grignard ¹ see reagent with 1,7,7-trimethylbicyclo- [2.2.1] -heptan-2-ylacetonitrile is obtained as intermediates the following ketones:

Halide

Ketone

2- (2-Bromoethyl) -bicyclo- [2.2.1] -heptane

2- (3-bromopropyl) bicyclo [2.2.1] heptane

2- (3-bromopropyl) -5,6-diethyl) -bicyclo- [2.2.1] -heptane

1 .- [1,7,7-Trimethylbicyclo- [2.2.1j-hept-2-yl] -4- (bicyclo- [2.2.i] -heptan-2-yl] -butan-2-one

1- [1,7,7-trimethylbicyclo- '- · ■ * ■ 2-yi] -5-tbi-

-hept-2-yl] -

1 [, 7,7-Trimeyy [2.2.1l-hept-2-yl] -5-ibicyclo- [2.2.1] -l

y [
pentan-2-one

1 '- [1, 7.7-Trimethylbicyclo-.2.2.1j-hept-2-yl] -5- _r (5,6-diethyl) -bicyclo-2.2.1] -hept-2-yl] -pentane 2- on

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15645Y

Halide

2-chloromethyl-1,7,7-trimethylbicyclo- [2.2.1] -heptane

7-bromobicyclo- [2.2.1] -heptane

Ketone

1,3-BiS- [1,7,7-trimethylbicyclo- [2.2.1 J-hept-2-yl] acetone

7- [1,7,7-Trimethylbicyclo- [2.2.1J-hept-2-ylacetyl] -bicyclo- [2.2.1] -heptane

Other examples performed using the same procedure are the following:

Halide

Nitrile ketone

2- (2-Bromoethyl) -bicyclo- [2.2 ~ .1] -heptane

2- (4-bromobutyl) bicyclo [2.2.1] heptane

2- (2-bromopropyl) -

bicyclo- [2.2.1J-

heptane

2- (4-bromobutyl) -5-methylbicyclo- [2.2.1] -heptane

1,7,7-trimethylbicyclo- [2.2.1 J-hept-3-ylacetonitrile

1-methylbicyclo- [2.2.1] -hept-3-ylacetonitrile

1,7,7-Trimethylbicyclo- [2.2.1] -hept-3-ylacetonitrile

3- (3-Cyanopropyl) 1-methylbicyclo- [2.2.1J-heptane 1- [1,7,7-Trimethylbicyclo- [2.2.i] -hept-3-yl] -4- [bicyclo- [2.2.1] -hept-2-yl] -butan-2-one

1- (1-Methylbicyclo- [2.2.1] -hept-3-yl) -6- (bicyclo- [2.2.1] -hept-2-yl) -hexan-2-one

1- (1,7,7-Trimethylbicyclo- [2.2.1] -hept-3-yl] -3-methyl-4- (bicyclo- [2.2.1J-hept-2-yl) -butan-2-one

1- (1-Methylbicyclo- [2.2.1] -hept-3-yD-8- (5-methylbicyclo- [2.2 _e 1-] - hept-2-yD-octan-4-one

example 1

Preparation of 1 - [1,5; -Di- (3,3-dimethylnorborn-2-yl) -3-pentyl] -1,5,9-triazanonane trihydrochloride

6.04 g (0.02 mol) 1,5-di- (3,3-dimethylnorborn-2-yl) -3-pentanone and 13.1 g (0.10 mol) 3,3 ^I -imino-bis -propylamine are in

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150 ml of toluene are heated overnight under a Dean and Stark water separator on a reflux condenser. The cooled solution is concentrated under reduced pressure and the residue is dissolved in ethanol and heated to room temperature with PtO ₉ under a

Hydrogen pressure of 2.8 kg / cm hydrogenated. The platinum catalyst is filtered off and the ethanol is driven off in vacuo. The remaining oil is dissolved in ether and the ethereal solution is washed several times with water in order to remove the excess 3,3'-imino-bis-propylamine. The ether extracts are dried over anhydrous sodium sulfate and evaporated in vacuo to give the polyamine, which is obtained as a colorless oil in a yield of 8.3 g = 100%.

The oil is dissolved in ether and passed into the solution of gaseous hydrogen chloride until no further precipitate separates out. The ether is evaporated off under reduced pressure and the solid residue is digested with hot isopropyl alcohol. The solids are filtered off and dried in vacuo at 70 ° C. to give 10.8 g of a colorless product; Yield 97 %; 260-262 ° C.

In an analogous manner with regard to amounts and reaction conditions, when using 1,5-di- (3,3-dimethylnorborn-2-yl) -3-pentaiion and the amines given below, the following compounds are prepared according to the invention:

Amine polyamine F., ⁰ C.

Triethylenetetramine 1- [1,5-di- (3,3-dimethyl-266-267

norborn-2-yl) -3-pentyl) -1 »4 · f 7 »10-tetraazadecane tetrahydrochloride

N, N'-bis (3-amino- 1- [1,5-di- (3.3'-dimethyl-262-263.5

propyl) -1,3-propanorborn-2-yl) -3-pentyl] diamine '1,5,9,13-tetraazatri-

decane tetrahydrochloride

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ORIGfNAL INSPECTED

15645Y

Amine

Polyamine

N, N ¹ -3is- (2-aminoethyl) -1,3-propanediamine

N, N'-bis (3-aminopropyl) -1,2-athandiarnine

N ₁ N'-bis (3-aminopropyl) piperazine

N, N -Bis- (3-aminopropyl) -N-methyl- amine

Tris - (3 - amino propyl) amine

1- [1,5-di- (3,3-dimethylnorborn-2-yl) -3-pentyl] -1,4,8,11-tetraazaundecane tetrahydrochloride

1- [1,5-Di- (3,3-dimethyl) -norborn-2-yl) -3-pentylJ-1,5 f 8,12-tetraazadodecane

1- (3-aminopropyl) -4- {3- [1,5-di- (3,3-dimethylnorborn-2-yl) -3-pentylaminoJ -propylj-piperazine tetrahydrochloride

1- [1,5-Di- (3,3-dimethylnorborn-2-yl) -3-pentyl] -5-methyl-1,5,9-triazanonane trihydrochloride

1- [1,5-di- (3,3-dimethylnorborn-2-yl) -3-pentyl] -5- (3-aminopropyl) -1,5,9-triazanonane tetrahydrochloride

F., ° C 261-262

263-265

257-259

237-238

255-256

If one works in terms of quantities and reaction conditions in an analogous procedure, but from 1,3-di- (3,3-dimethylnorborn-2-yl) -2-propanone and 3,3'-imino-bis-propylamine or triethylenetetramine the hydrochloride of 1- [1,3-di- (3f3-dimethylnorborn-2-yl) -2-propyl] -1,5,9-triazanonane is obtained and 1- [1,3-di- (3,3-dimethylnorborn-2-yl) -2-propyl] -1,4,7,10-tetraazadecane, respectively.

example

Preparation of 1- [1,5-di- (2-norbornyl) -3-pentyl] -1,5,9-triazanonane trihydrochloride

4.15 g (0.015 mole) 1,5-di- (2-norbornyl) -3-pentanone and 9.8 g (0.075 mol) of 3,3'-imino-bis-propylamine are dissolved in 150 ml of ethanol Heated to reflux temperature for 3 hours. After cooling the solution is at room temperature under a hydrogen

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hydrogenated pressure of 2.8 kg / cm ² to PtO. ₂ The platinum catalyst is filtered off and the ethanol is driven off in vacuo. The remaining oil is dissolved in ether and the ethereal solution is washed several times with water. The ether extracts, dried over anhydrous sodium sulfate, are concentrated in vacuo to give 5.8 g of polyamine in the form of an oil; Yield 99 %.

The oil is dissolved in absolute methanol and the solution is cooled in an ice water bath. Gaseous hydrogen chloride is passed into the solution, whereupon the methanol is driven off under reduced pressure. What remains is a resinous solid that is recrystallized from isopropyl alcohol. The product obtained is 6.0 g of colorless crystals; Yield 80 %; F. 257-258 ° C.

Using the same procedure, in an analogous manner with regard to the molar amounts and the reaction conditions, 1- [1,3-di- (2-norbornyl) -2-propyl] -1,5,9-triazanonane trihydrochloride from 1,3-di- (2-norbornyl) -2-propanone and 3,3'-imino-bis-propylamine, 1- [1,3-Di- (2-norbornyl) -2-propyl] -1,4,7,10-tetraazadecane tetrahydrochloride from 1,3-di- (2-norbornyl) -2-propanone and triethylenetetramine, 1- [1,7-Di- (2-norbornyl) -4-heptyl] -1,5,9-triazanonane trihydrochloride from 1,7-di- (2-norbornyl) -4-heptanone and 3f3'-imino-bis-propylamine and 1- [2,6-di- (2-norbornyl) -4-heptyl] -1.5, 9-triazanonane trihydrochloride made from 2,6-di- (2-norbornyl) -4-heptanone and 3,3'-imino-bis-propylamine.

Example 3

Preparation of 1- [1,7-di- (5-norbornen-2-yl) -4-heptyl] -1,3,9-triazanonane trihydrochloride

5.96 g (0.02 mol) 1,7-di- (5-norborrien-2-yl) -4-heptanone and 13.1 g (0.10 mol) 3.3 ^l -imino-bis-propylamine are heated to reflux temperature overnight in 150 ml of toluene under a Dean and Stark water separator. Then the toluene

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Stripped off in vacuo, the remaining oil was dissolved in 25 ml of isopropanol and the solution was added dropwise to a suspension of 1.90 g (0.05 mol, excess) of sodium borohydride in 50 ml of isopropanol. After the addition has ended, the reaction mixture is heated on the reflux condenser for a further hour. The isopropanol is driven off under reduced pressure, water is added to the residue and the aqueous mixture is extracted well with ether. The combined ether extracts are washed with water and with saturated sodium chloride solution, dried over anhydrous sodium sulfate and evaporated in vacuo to give the amine, which is obtained in an amount of 7.4 g (yield 90 %) as a clear oil.

The oil is dissolved in ether and the solution is cooled in an ice water bath. Gaseous hydrogen chloride is passed into the solution until no further precipitate separates out. The solid product is filtered off, washed with a little ether and dried in vacuo. The amine trihydrochloride remains as a colorless substance; Yield 96 %.

Example 4

Preparation of 1- [1,5-di- (3,3-dimethylnorborn-2-yl) -3-pentyl] -1,4,8-triazaoctane

A mixture of 9.9 g (0.03 mol) 1,5-di- (3,3-dimethylnorborn-2-yl) -3-pentanone and 12.0 g (0.20 mol) 1,2-diaminoethane is heated to reflux temperature overnight in 250 ml of ethanol. _{After cooling, the reaction mixture is hydrogenated with PtO 2} at room temperature under a hydrogen pressure of 2.8 kg / cm. The platinum catalyst is filtered off and the ethanol is driven off under reduced pressure. The remaining oil is dissolved in ether and the ethereal solution is washed several times with water in order to remove the excess diaminoethane. The ether extracts are dried over anhydrous sodium sulfate and concentrated in vacuo to give 11.2 g of a colorless oil; Yield 100%.

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15645Y "J / 260089G

The oil is dissolved in 20 ml of tert-butanol and the solution is cooled to 0 to 5 ° C in an ice-water bath. 1.75 g (2.2 ml; 0.033 mol) of acrylonitrile are added dropwise over the course of 5 minutes. Man-the reaction mixture is warm to room temperature and heated it overnight at 60 ° C ₀ Then, the tert-butanol is removed under reduced pressure and dissolved behind the residual oil in 150 ml of glacial acetic acid at room temperature under a What-r

hydrogen pressure of 2.8 kg / cm hydrogenated with PtOp. The platinum catalyst is filtered off and the acetic acid is driven off in vacuo. The residue is dissolved in ether and with 10 percent Caustic soda made alkaline. The ether solution is washed with water, dried over anhydrous sodium sulfate and concentrated under reduced pressure to give 12.5 g of a pale yellow oil. The oil is attached to Woelm aluminum oxide (activity III) chromatographed. By eluting with 20 percent Methanol in chloroform gives 4.35 g of analytically pure product; Yield 33%.

Thin layer chromatography on silica gel G under development with a mixture of 4 parts of ethanol and 1 part of ammonium hydroxide gives a spot at R ^ = 0.45.

After the reactions described in the above examples, the others given in the table below are obtained Links. It should be noted, however, that [3.1.1! -Bicycloheptene easily rearrange when trying, as in Example A, under the influence of free radicals To introduce substituents. Therefore [3.1.1] -Bicycloheptylcarbonsäuren preferably prepared by other known methods.

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15645Y A ₁ U ^R 1 2600896 Ethylene Methylene η at
game 2,4,6,6 ~ tetramethyl-2-
norpinen-3-yl Ketone Ethylene 1 5 2,4,6,6-tetramethyl-2-
norpinen-3-yl Ethylene R ₂ 1 6th 2,4,6,6-tetramethyl-2-
norpinen-3-yl Ethylene Ethylene Trimethylene 1 7th 3-pinanyl Methylene Ethylene Tri-
methylene 1 8th 4-pinanyl Tri-
methylene Ethylene Ethy 1 9 2-pinene-3-yl 2-methyl
tri-
methylene Ethylene 1 10 2-pinene ~ 4-yl Methylene Tri
methylene 1 11 3-pinene-3-yl Ethylene 2-methyl
tri-
methylene 1 12th 3-pinene-3-yl Methylene 2-methyl
tri-
methylene 1 13th 2-norpinanyl Ethy Methylene 1 14th 3-norpinanyl Methylene 1 15th 3-norpinanyl 1 16 2-norpinen-2-yl 1 17th 3-norpinen-2-yl Methylene 1 18th 6,6-dimethylnorpinan-
2-yl Ethy 1 19th 6,6-dimethylnorpinan-
2-yl Methylene 1 20th 3,6,6-trimethyl-2-
norpinen-4-yl Ethy 1 21

- Continued on page 33 -

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example

5 6

10

11 12 13

14th

Amine

N, N'-bis (3-aminopropyl) -1,2-ethanediamine

3,3'-imino-bis-propylamine

1- (2-hydroxyethyl) -1,4,7,1O-tetraazadecane

N, N-bis (3-aminopropyl) -1,3-propanediamine

Tris (2-aminoethyl) amine

1-hydroxymethyl-5- (2-hydroxypropyl) -1,5,9- triazanonane

3,3'-imino-bis-propylamine Diethyl triamine

N, N · -Bis- (2-aminoethyl) -1,3-propanediamine

3,3 * -imino-bis-propylamine

Schiff base reduced with

PtOo

NaBH

PtO ₂

PtO,

PtO,

NaBH,

NaBH /

NaBH /

NaBH ₄

PtO,

product

- To be continued see

1- [1,5-di- (2,4,6,6-tetramethylnorpinan-3-yl) -3 -] - 1,5,8,12-tetraazadodecane

1- [1,5-di- (2,4,6,6-tetramethyl-2-norpinen-3-yl) -3-pentyl] -1,5-9-triazanonane '

1- [1,5-di- (2,4,6,6, -tetramethylnorpinan-3-yl) -3-pentyl] -10- (2-hydroxyethyl) -1,4,7,10-tetraazadecane

1- [1,4-Di- (3-pinanyl) -2-butyl] -5- (3-aminopropyl) -1,5,9-triazanonane

1- [1,7-Di- (4-pinanyl) -4-heptyl] 4- (2-aminoethyl) -1,4,7-triazaheptane

1- [2,6-Dimethyl-1,7-di- (2-pinene-3-yl) -4-heptyl] -5- (2-hydroxypropyl) -9-hydroxymethyl-1,5,9-triazanonane

1- [4-methyl-1,5-di- (2-pinene-4-yl) -2-pentyl] -1,5,9-triazanonane

1- [1,4-Di- (3-pinene-3-yl) -2-butyl] -1,4,7-triazaheptane

1- [1,3-Di- (3-pinene-3-yl) -2-propyl] -1,4,8,11-tetraazaundecane

1 ~ [1 »5-di- (2-norpinanyl) -3-pentyl] -1,5,9-triazanonane

CD CD CD OO LO CD

example

15 16

17th

cn I. 18th ο
to -P- 00 I. 19th ro O 00 OI Ia)

20th

21

Amine

Triethylenetetramine

1,4-bis (3-aminopropyl) piperazin

TrIs (3-aminopropyl) amine

.3 »3'-Imino-bis-propylamine

1,4-di (3-aminopropyl) piperidine

5- (2,3 -dihydroxypropyl ) ■ 1 »5» 9-triazanonane

N, N'-bis (2-aminoethyl) 1,3-propanediamine

Schiff base reduced with

PtO ₂ PtO _n

NaBH;

NaBH /

PtO,

PtO,

NaBHy

Product '

1- [1,3-Di- (3-norpinanyl) -2-propyl] -1,4,7,10-tetraazadecane

1- (3-aminopropyl) -4- [3- [1,5-di- (3-norpinanyl) -3-pentylamino] propylj-piperazine

1- [1,4-Di- (2-norpinen-2-yl) -2-butyl] -5- (3-aminopropyl) -1,5,9-triazanonane

1- [1,5-di- (3-norpinen-2-yl) -3-pentyl] -1,5,9-triazanonane

Mixture of 1- (3-aminopropyl) -4- [3- [i, 7-di- (6,6-dimethylnorpinan-2-yl) -4-heptylamino) propyl-piperidine and 1- [3- [1.7-di- (6, D-dimethylnorpinan-2-yl) -4-heptylaminoJ-propyl] -4- (3-aminopropyl) -piperidine

1- [1.5-di- (6,6-dimethylnorpinan-2-yl) -2-pentyl] -5- (2,3-dihydroxypropyl) -1,5,9.-triazanonane

1- [1,5-di- _(t 3 6,6-trimethyl-2-norpinen-4-yl) -3-pentyl] -1,4,8,11-tetraazaunde'can

Each of the ketones IV mentioned in Examples C, D, E and F can be used with each of the individual ones listed in the description Amines can be reacted first according to the method given in Example 1 and then according to Example 3 to cover the entire range of compounds represented by the general formula I.

The polyamines described here are excellent microbicides have a wide spectrum of activity and are particularly effective in aqueous concentrations of 1.0 to 100 ppm against gram-positive and gram-negative bacteria, especially against the troublesome gram-negative bacteria of the genus Pseudomonas. Examples of those sensitive to these agents Microorganisms include Staphylococcus aureus, Streptococcus pyogenes, Bordetella bronchiseptica, Pasteurella multocida, Escherichia coli, Salmonella typhimurium, S. pullorum, Klebsiella pneumoniae, Aerobacter aerogenes, Pseudomonas aeruginosa, Desulfovibrio desulfuricans, Bacillus mycoides, as well as fungi such as Aspergillus niger. and Chaetomium globosum. The compounds can be used in pure or diluted form will. Suitable diluents are inert substances that do not destroy the microbicidal activity; in particular Liquid agents in the form of aqueous dispersions, solutions and emulsions come into consideration. Solid thinners are talc, corn starch, alumina and diatomaceous earth. The microbicides according to the invention can also be applied to fabrics such as natural fibers, including paper, cotton and wool, as well as synthetic fibers, such as Polyamides, polypropylene, and also on inanimate surfaces including hard surfaces such as wood, glass, metal, Bricks, rubber, plastic, as well as on porous surfaces such as concrete, leather and the like, are deposited.

The polyamines according to the invention are particularly suitable for suppressing the growth of aerobic and anaerobic bacteria

- 35 609 829/0853

in liquids used in cutting and grinding operations such as machining metals, as well as in petroleum drilling muds or in water and brine for secondary oil extraction. Anaerobic microorganisms, such as the sulfate-reducing Desulfovibrio desulfuricans, are inhibited by these polyamines in concentrations of 0.1 to 10 ppm. The destruction of these bacteria eliminates hydrogen sulfide evolution and corrosion of equipment, clogging of oil sands, the development of bad smells and other harmful effects. The compounds are also suitable for the preservation of other aqueous systems, such as aqueous emulsions and dispersions, paints or coatings, pigment suspensions, adhesives and the like, against biological degradation, the proliferation of microorganisms leading to the destruction of colloids, changes in pH and the development of bad odors , Formation of corrosive substances, decrease in viscosity and other undesirable effects.

A particularly valuable application of the compounds according to of the invention is the treatment of textile fabrics in order to to give them disinfecting properties. These can be woven or non-woven, washable or disposable trade certain textiles, e.g. diapers, surgical masks, caps, gowns, towels and tissues, Covers can be used for hospital furniture and equipment covers, aseptic facial tissues, napkins, and bathroom tissue. In this application, the compounds of general formula I can be added to the pulp before the extraction or the Strand or thread formation are added, or they can be sprayed onto the finished product. Any method of Deposition is satisfactory provided the fabric only Retains 1 x 10 percent by weight or more of the microbicidal agent. Amounts of more than 0.1 to 1 weight per cent are generally too big and superfluous.

- 36 609829/0853

Furthermore, the compounds can be used alone or in solution or suspension or together with soaps or detergents for cleaning the skin, especially in cleaning agents or agents intended for use before surgical operations to control the growth of Corynebacterium acnes. C. acnes is a strain of bacteria that causes acne, in particular Acne vulgaris; in such cases, 1 to 5 ppm are sufficient to kill the bacteria living in the skin. If desired, higher concentrations, such as 2500 ppm or more, can be used without causing irritation or discomfort is noticed. If the detergents are intended to be diluted with water, they can use the polyamine according to of the invention in concentrations of 0.01 percent by weight and more.

Furthermore, the compounds according to the invention can be used in backwater, such as swimming pools, ponds or industrial water, such as water from paper mills, in concentrations of 0.5 to 5 ppm can be used to suppress the growth of unwanted bacteria, fungi and / or algae.

For the suppression of slime-forming microorganisms and algae in circulating industrial water, especially during cooling processes, especially in water from cooling towers, the polyamine compounds according to the invention are usually on their own used alone; however, they can be added along with other microbicides. To the solubility To increase, the compounds are preferably used in the form of their salts. There are already concentrations in circulating water from 1 χ 10 "" percent by weight for the suppression effective against microbial growth. To be effective, especially against more resistant strains of microorganisms, and Even if fresh water is added to replace evaporation losses, concentrations of

-4 -2
1 × 10 to 5 × 10 percent by weight is most advantageous.

- 37 -

609829/0853

The dosage can be carried out continuously or intermittently as a "shock treatment ¹¹ ", in which case the addition takes place every 4 to 8 hours for a period of 10 to 20 minutes.

An unusually advantageous property of these compounds is their high degree of substantivity for all types of Surfaces. This provides protection against corrosion, and the connections show a kind of depot effect on surfaces through which water in contact with the surfaces is continuously dosed with the compounds will. The same properties are also largely for the above-described effect as a disinfectant for inanimate Surfaces such as walls and ceilings, equipment, animal feathers, hospital supplies, kitchens, Bathroom and the like, responsible.

For the above uses, the compounds can be used together with other microbicides, surfactants, insecticides, Antifoam agents, fragrances or as chelates of metals such as copper, calcium, magnesium and Iron, can be used.

609829/0853

Claims (1)

Merck & Co., Inc. Jan. 12, 1976 15645Y Claims 1. Compound characterized by the general formula CH-NH-Z in the the radicals A can be identical or different and are a [2.2.1j-bicyclic group of the general formula R ¹ or a [3.1.ij-bicyclic group of the general formula b) mean, where the radicals R can be the same or different and are hydrogen atoms or C ₁ - to C ^ -alkyl radicals - 39 - 609829/0853 mean, the radicals R ^{1 can be the} same or different. and hydrogen atoms or C, - to C ^ -alkyl radicals, or two radicals R ¹ on adjacent carbon atoms together can mean an olefinic double bond and the dashed line means a double bond between the positions c and d or between the positions d and e, the radicals R * can be the same or different and are Cp to C ^ alkylene radicals, the indices η can be the same or different and have the value O or 1, Z denotes a radical -Y-N-R / - in which ι ^D Rc hydrogen, aminoethyl, aminopropyl, C ^ - to C ^ - hydroxyalkyl or C ₂ - to C ^ -D! Hydroxyalkyl and Rg hydrogen, C -.- to C λ-hydroxyalkyl or Cp- to C ^ - Mean dihydroxyalkyl, Y denotes a radical -R ₉ -NR /.- or -R ₉ -, where R ₂ denotes the 2-hydroxy-1,3-trimethylene radical or has the same meaning as R ^, Rz hydrogen, Cp to C ^ -alkyl, Cp to C ^ -aminoalkyl, Cp to C ^ -hydroxyalkyl or C ₂ - to C ^ -dihydroxyalkyl, R ^ denotes the 2-hydroxy-1,3-trimethylene radical or the has the same meaning as R ^, or, when R- * and Rg together form the ethylene radical, R ^ also an ethylene radical and R, - aminoethyl, aminopropyl or Aminohydroxypropyl, as well as acid addition salts thereof. - - 40 - 609829/0853 2. Compound according to claim 1, characterized in that R ¹ and R are hydrogen atoms or methyl groups. 3. A compound according to claim 1, characterized in that Rr and Rr represent hydrogen atoms. 4. A compound according to claim 1, characterized in that Rc- the aminoethyl radical, Rp the ethylene radical and Rg a hydrogen atom mean. 5. A compound according to claim 1, characterized in that Rc is the aminopropyl radical, Rp is the trimethylene radical and Rg is a hydrogen atom. 6 ·. Compound according to claim 1, characterized in that R ^ denotes the ethylene radical and R-, and Rg together one Form ethylene residue. 7. A compound according to claim 1, characterized in that R 1 denotes the aminoethyl radical. 8. A compound according to claim 1, characterized in that R 1 denotes the methyl radical. 9. A compound according to claim 1, characterized in that R-2 denotes the 2-hydroxyethyl radical. 10. A compound according to claim 1, characterized in that R ^ is a hydrogen atom. 11. A compound according to claim 1, characterized in that the radicals A are [3.1.1] -bicyclic groups. 12. A compound according to claim 11, characterized in that η has the value 1. - 41 - 609829/0853 13. A compound according to claim 11, characterized in that R- the ethylene residue, R ^ a hydrogen atom, R ^ the ethylene residue, Rc denotes the aminoethyl radical and R ^ denotes a hydrogen atom. 14. A compound according to claim 11, characterized in that Rp "and R ^ form a trimethylene radical and R ^, R, - and Rg Mean hydrogen atoms. 15. Compound characterized by the general formula CH-NH-Z A- (R) 1 η $ in which the radicals A can be identical or different and [2.2.1] -bicyclic groups of the general formula R ¹ mean, in which the radicals R can be identical or different and represent hydrogen atoms or C ^ - to C ^ -alkyl radicals, the radicals R * can be identical or different and represent hydrogen atoms or C ^ - to C ^ -alkyl radicals, or two radicals R ¹ on adjacent carbon atoms together can denote an olefinic double bond, the radicals R ^ can be identical or different and C -, - to Mean Cr-alkylene radicals, the indices η can be the same or different and have the value O or 1, - 42 609829/0853 Z denotes a radical -Y-N-Rg, in which * "'Rc hydrogen, aminoethyl, aminopropyl, Cy to C ^ - hydroxyalkyl or C ₂ - to C ^ -dihydroxyalkyl and Rg is hydrogen, Cy to C ^ -hydroxyalkyl or C ₂ - to C ^ - dihydroxyalkyl, Y, a ReSt-R ₂ -NR ^ - or -R ₂ -, where · ■ '■■ ί, R ₂ denotes the 2-hydroxy-1,3-trimethylene radical or has the same meaning as R ,, R ₅ hydrogen, C ₁ - to C ^ -alkyl, Cy to C ^ -aminoalkyl, Zy to CjTj-hydroxyalkyl or C ₂ - to C ^ -dihydroxy ^ - alkyl, R. denotes the 2-hydroxy-i, 3-trimethylene radical or the has the same meaning as R-j, or, when R, and Rg together form the ethylene radical, R. also represents an ethylene radical and R ₁ - aminoethyl, aminopropyl or aminohydroxypropyl, as well as acid addition salts thereof. 16. A compound according to claim 15, characterized in that R and R ^{f are} hydrogen atoms or methyl radicals and less than five of the radicals R and R ^{f are} methyl radicals. 17. A compound according to claim 15, characterized in that A is a [2.2.1] -Bicycloheptenylrest, two of the radicals R * on adjacent carbon atoms are an olefinic double bond and the remaining radicals R ¹ and R can be identical or different and hydrogen atoms or Mean methyl radicals. - 43 - 609829/0853 18. A compound according to claim 16, characterized in that η has the value 1. 19. A compound according to claim 17, characterized in that η has the fourth one. 20. A compound according to claim 15, characterized in that A is the 3,3-dimethylnorborn-2-yl radical. 21. A compound according to claim 15, characterized in that A denotes the norborn-2-yl radical. 22. A compound according to claim 15, characterized in that Y a radical -RpN-R ^ -, Rp the ethylene radical, R ^ water- . * 3 substance, R ^ the ethylene residue, R, - an aminoethyl residue and
R ^ mean hydrogen. 23. A compound according to claim 15, characterized in that Y means a radical -Rp-N-R ^ -, Rp and R ^ a tri- R ₃ Form a methylene radical and R- *, R ₁ - and Rg are hydrogen atoms. 24. A compound according to claim 22, characterized in that the radicals A are 3,3-dimethylnorborn-2-yl radicals. 25. A compound according to claim 23, characterized in that the radicals A are 3i3-dimethylnorborn-2-yl radicals. 26. A compound according to claim 24, characterized in that R ^ means the ethylene radical. - 44 - 6 0 9829/0853 27. A compound according to claim 25, characterized in that R ^ denotes the ethylene radical. 28. A compound according to claim 24, characterized in that R ₁ denotes the methylene radical. 29. A compound according to claim 25, characterized in that R ^ denotes the methylene radical. 30. 1- [1,5-Di- (3,3-dimethylnorborn-2-yl) -3-pentyl] -1,5,9-triazanonane trihydrochloride. 31. 1- [1,5-Di- (3,3-dimethylnorborn-2-yl) -3-pentyl] -1,4,7,10-tetraazadecane tetrahydrochloride. 32. 1- [1,7-Di- (5-norbornen-2-yl) -4-heptyl] -1,5,9-triazanonane trihydrochloride. 33. Process for the preparation of compounds of the general formula A- (R ₁ ) _n ^ CH-NH-Z characterized in that one has a compound of the general formula A- (R ₁ )
ι η CH = NH-Z reduced, whereby the radicals A can be identical or different and one - 45 609829/0853 [2.2.1] -bicyclic group of the general formula a) or a [3.1.1J-bicyclic group of the general formula b) mean, where the radicals R can be the same or different and mean hydrogen atoms or Cj- to C ^ -alkyl radicals, the radicals R * can be identical or different and denote hydrogen atoms or Cj- to C ^ -alkyl radicals, or two radicals R * on adjacent carbon atoms together can denote an olefinic double bond and which dashed line means a double bond between positions c and d or between positions d and e, the residues R-. can be the same or different and C.-bis Mean C ^ alkylene radicals, the indices η can be the same or different and have the value 0 or 1, Z denotes a radical -Y-N-R / - in which I ° ^R 5 Rc is hydrogen, aminoethyl, aminopropyl, Cj- to C ^ - hydroxyalkyl or C ₂ - to C ^ -dihydroxyalkyl and Rg hydrogen, Cj- to C »-hydroxyalkyl or Cp- to C ^ - - 46 - 609829/0853 15645Y W 2600396 Mean dihydroxyalkyl,
Y denotes a radical -Rp-NR ^ - or -R ₂ ", where Rp denotes the 2-hydroxy-1,3-trimethylene radical or has the same meaning as R ₁ , Rz is hydrogen, C ₁ to C ^ alkyl, C ₁ to C ^ aminoalkyl, C ₁ to C ^ hydroxyalkyl or C ₂ to C ^ dihydroxyalkyl, R, denotes the 2-hydroxy-1,3-triraethylene radical or has the same meaning as R ₁ , or, when R, and Rg together form the ethylene radical, R. also an ethylene radical and Rj-aminoethyl, aminopropyl or aminohydroxypropyl. 34 »A method for combating the growth of microorganisms and algae, characterized in that the microorganisms or algae with an effective amount of a compound of the general formula CH-NH-Z A- (R ₁ ) _n in the the radicals A can be identical or different and are a [2.2.1] -bicyclic group of the general formula a) -47 - 609829/0853 or a [3.1.1] -bicyclic group of the general formula b) where the radicals R can be identical or different and are hydrogen atoms or C ₁ - to C ^ -alkyl radicals, the radicals R ^{1 can be} identical or different and are hydrogen atoms or C ₁ - to C ^ -alkyl radicals, or two radicals R * on adjacent carbon atoms together can denote an olefinic double bond and the dashed line denotes a double bond between positions c and d or between positions d and e, the radicals R _{1 can be} identical or different and are C _{1 to} C ^ alkylene radicals, the indices η can be the same or different and the Have value 0 or 1, Z denotes a radical -Y-N-Rg, in which R ^ hydrogen, aminoethyl, aminopropyl, C ₁ - to C ^ ₊ - hydroxyalkyl or C ₂ - to C ^ -dihydroxyalkyl and Rg is hydrogen, C ₁ - to C ^ -hydroxyalkyl or C ₂ - to C ^ - dihy.droxyalkyl, Y is a radical -R ₂ -NR ^ - or -R ₂ -, where R ₂ denotes the 2-hydroxy-1,3-trimethylene radical or has the same meaning as R ₁ , R ^ hydrogen, C ₁ - to C ^ -alkyl, C ₁ - to C ^ -aminoalkyl, C ₁ - to C ^ -hydroxyalkyl or C ₂ - to C ^ -dihydroxyalkyl, - 48 609829/0853 15645Ύ R- denotes the 2-hydroxy-1,3-trimethylene radical or the has the same meaning as R ^, or, when R ^ and Rg together form the ethylene radical, R, also an ethylene radical and R, - mean aminoethyl, aminopropyl or aminohydroxypropyl, or an acid addition salt of such a compound. 35. A method for combating microorganisms and algae in backwater, characterized in that the backwater 0.0001 to 0.05 percent by weight of a compound of the general formula A- (R ₁ ) CH-NH-Z in the the radicals A can be identical or different and are a [2.2.1] -bicyclic group of the general formula a) R ¹ or [3.1.1J-bicyclic group of the general For ^mel b) 609829/0853 where the radicals R can be identical or different and are hydrogen atoms or C ₁ - to C ^ -alkyl radicals, the radicals R ^{f can be} identical or different and are hydrogen atoms or C, - to C ^ -alkyl radicals, or two radicals R * on adjacent carbon atoms together can denote an olefinic double bond and the dashed line denotes a double bond between positions c and d or between positions d and e, the radicals R _{1 can be} identical or different and are C _{1 to} C ^ alkylene radicals, the indices η can be the same or different and have the value 0 or 1, Z denotes a radical -Y-N-Rg, in which "s Rc hydrogen, aminoethyl, aminopropyl, C, - to C ^ - hydroxyalkyl or C ^ - ^bl3 C ^ -dihydroxyalkyl and Rg is hydrogen, C ₁ - to C ^ -hydroxyalkyl or C ₂ - to C ₁₊ - dihydroxyalkyl, Y is a radical -Rp-N-R ^ - or -Rp ", where Rp denotes the 2-hydroxy-1 _f 3-trimethylene radical or has the same meaning as R ₁ , R, hydrogen, C ₁ - to C ^ -alkyl, C ₁ - to C ^ - aminoalkyl, C ₁ - to C ^ -hydroxyalkyl or Cp- to C ^ -dihydroxyalkyl, R ^ denotes the 2-hydroxy-1,3-trimethylene radical or has the same meaning as R ₁ , or if R- * and Rg together form the ethylene radical, R- is also an ethylene radical and R _{5 is} aminoethyl, aminopropyl or aminohydroxypropyl, or an acid addition salt of such a compound clogs. 609829/0853