DE2621226A1 - Neuromuscular blocking para-terphenylene-diammonium salts - prepd. by reducing para, para-dinitro-para-terphenyl and alkylating the prod. - Google Patents

Abstract

New bis-quaternary ammonium salts are of formula (I). In the formula, x is +N(R)2R1 or +N (CH2)4.R1; R and R1 are alkyl (pref. lower alkyl); and y is C6H5SO3-or halogen-. (I) are non-depolarising muscle-relaxants with high activity and selectivity. They can be used in medicine for blocking neuromuscular conduction in surgical operations. The neuromuscular blocking activity of (I) approaches or exceeds that of d-tubocurarine. (I) differs from d-tubocurarine and gallamine by not affecting blood pressure, not causing histamine release, and not blocking the ganglia of the vegetative nervous system. (I) are non-toxic under the conditions of artificial lung ventilation, and their action is readily reversed by cholinesterase inhibitors. Specific cpd. (I) include p,p''-dis-trimethylammonia-p-terphenyl dibenzenesulphonate.

Description

P, P "-BIS-QUART. P-TERPHENYLAMMONIUM SALTS AND VER-

DRIVING THEIR PRODUCTION The present invention relates in the field of organic synthesis and in particular on p, p "-Bis-quartz.pterphenylammonium salts and methods of making them.

The p, p15-bis-quart. p-terphenylammonium salts represent new ones in the Substances not described in the literature.

According to the invention, the p, p "-bis-quart.p-terphenylammonium salts are represented by the general formula where x is NR2R¹ x is R and R1 stand for alkyl, in particular lower alkyl, y stands for C6H5S03, halogen, in particular Br. The representatives of these substances are: p, p "-Bis-trimethylammonium-p-terphenyldibenzenesulfonate of the formula p, p "-Bis-diethylmethylammonium-p-terphenyldibenzenesulfonate of the formula p, p "-Bis-triethylammonium-p-terphenyldibenzenesulfonate of the formula p, p "-bis-triethylmethylammonium-p-terphenyldibromide of the formula p, p "-Bis-dipropylmethylammonium-p-terphenyldibenzosulfonate of the formula PSPl -Bis- (N-methylpyrrolidinium) -p-terphenyldibenzenesulfonate of the formula P, P "-Bis- (N-ethylpyrrolidiniwn) -p-terphenyldibenzenesulfonate of the formula All of the substances mentioned are non-depolarizing muscle relaxants of high activity and selectivity and can be used in medicine to block the neurohisicular conduction during surgical interventions.

In animal experiments, the neuro-muscle blocking activity comes from this Substances of the activity of the known muscle relaxant of the same type of action - that d-tubocurarine (from Burroughs Wellcome Co, London) - close to or exceeds this significant.

In contrast to those currently used in the clinic, no depolarizing muscle relaxation-d-tubocurarine and pyrolaxone (gallamine, flaxedil) None of the substances mentioned do not affect blood pressure because they do not have histamine and do not block the ganglia of the autonomic nervous system. To the At the same time, Pyrolaxon blocks the vagus nerve ganglia and therefore loosens them the tachycardia off.

The muscle relaxation caused by d-tubocurarine is through accompanied by a decrease in arterial blood pressure, which is conditioned by its ability is to isolate histamine from tissues in a blocking dose, as well as the conductivity block in sympathetic ganglia. In addition, all substances mentioned are the p, p '-Bis-quart.p-terphenylammonium salts, under the conditions of the artificial Pulmonary ventilation non-toxic. Animals tolerate the introduction of dozens and even Hundreds of blocking doses of these substances while entering d-tubokurarine of the animal already at 5 to 10 times Causes dose increase. In particular, the cats tolerate, for example, the introduction of 200 blocking Doses of p, p "-bis-triethylmethylammonium-p-terphenyldibenzenesulfonate der -dibromide and only when the dose was increased 1000 times did one of the three cats fail a sharp drop in arterial pressure and cardiac arrest.

It is known that the muscle relaxants of the non-depolarizing Effect type compared to the depolarizing muscle relaxants in the clinic are preferred.

First, because it usually succeeds in its blocking effect by removing the anticholinestease substances (Proserin, Nivalin) and, secondly, because, unlike the depolarizing muscle relaxants, they increase the blood potassium level does not increase what would otherwise lead to serious complications in the patient with cardiovascular Malfunctions.

All substances mentioned are non-depolarizing muscle relaxants the effect of which can easily be eliminated by the ChQlinesterase inhibitors. In addition, they have a higher specific effect than d-tubokurarine. So does Proserin in the experiments on cats at a dose of 0.1 mg / kg intravenously quickly and completely the effect of 5 blocking "osen of p, p" -Bis-triäthylammonium-p-terphenyldibenzolsulfoant and dibromide and only 3 blocking d-tubocurarin doses.

The clinical use of the substances mentioned as muscle relaxants can ensure the implementation of a safe and controllable nyorelaxation.

The neuro-muscle-blocking activity of the substances mentioned in comparison for d-tubocurarine is shown in Table 1, in which BD-block.dose HDD-Head-drop dose mean.

Table 1 xy cats effect rabbits BD type HDD inMMol / kg in hMollkg + N (CH3) 3 C6H5S03 0.3 + 0.04 mixed -0.25 + 0.05 + - 0.5j0.09 not depola- 0.12r 0S12 + 0s02 N (C2H5) 3CH3 C6H5S53 0.08 + 0.002 - "- 0.022 + 0.001 N (C2H5) 3 Br 0.08 + 0.002 -ff- 0.022 + 0.001 N (C2H5) 3 Br O.08j0.002 11 0.022 + 0.001 (c3H7) 2cH3 C6H5SU3 0.5 +0.1 ~ ll ~ 0.1 + 0.03 NgCH2) 4CH3 C6H5S53 1.0 +0.2 - "- 0.3 + 0.06 NgCH2) 4C2H5 C6H5S03 0.5 +0.08 11- 0.14+ 0.04 d-tubocurarine 0.5 + 0.02 11 O, 18 + 0.06 As can be seen from the table, p, p "-Bis-triethylammonium-p-terphenyldibenzenesulfonate and -d bromide have the highest blocking activity. These compounds exceed 6 to 8 times the myoparalytic d-tubocurarine activity -Tubokurarin do not excrete these compounds histamine, do not block the ganglia of the autonomic nervous system and therefore do not influence the blood pressure.In the experiments on cats and rabbits, a weak and short-lasting depressive effect develops only after a 10-fold increase in the dose of these substances, while after the introduction of the myoparalytic d-tubokurarin dose, a marked decrease in arterial blood pressure is demonstrated.

As already mentioned, these compounds are subject to the conditions of artificial lung ventilation is non-toxic. They also have a higher specific effect as d-tubocurarine. In particular, d-tubokurarine in a dose releases the blockage the neuromuscular conduction causes the conductivity disorder of the upper cervical ganglion at the cat. The p, p "-bis-triethylammonium-p-terphenyldibenzo isulfonate and -dibromide produce a weak ganglion-blocking effect only in the dose, which exceeds the neuro-muscle blocking dose by 10 times.

The cholinesterase inhibitors eliminate the blocking effect of these Substances lighter than the effects of d-tubokurarine.

No potentiation was found in the experiments on decerebral cats the effect of these compounds and of fluothane on blood pressure has been demonstrated, while d-tubokurarine increases the effects of fluothane (halothane) on the heart; because of this one considers their combined use because of the possible development of the cardiovascular Kallapses considered dangerous.

The experimental comparison of these compounds with the well-known, non-depolarizing muscle relaxant pancuronium (the company Organon Inc. W. Orange N.Y. 07052) also presented some advantages of the substances according to the invention on the day.

As mentioned, the inventive foods affect compounds in a dose which significantly exceeds its myoparalytic dose, the arterial n blood pressure not.

The disadvantage of pancuronium is its ability to die increase Pulse rate and arterial blood pressure trigger what an amplification which can cause bleeding during surgery.

In the experiments on cats, the proerin antagonism was the effect of pancuronium less pronounced than with the action of the compounds according to the invention. at After increasing the dose of pancuronium 4 to 5 times, muscle relaxation began at least 10 minutes after intravenous administration of proserine at a dose of To restore 0.1 mg / kg.

Under the same conditions, Proserin eliminated at the same dose the blocking 3effect of the substances according to the invention completely after their introduction in the amount exceeding their myoparalytic dose a few times. Even at The 5-fold increase in the dose of these substances started muscle relaxation in the area 5 minutes after the single introduction of proserine at a dose of 0.1 mgZkg restore.

This shows that the clinical application of such preparations is the Implementation of a safer and controllable muscle relaxation in comparison to d-tubocurarine and pancuronium.

A great advantage of the substances proposed according to the invention is their simple synthesis from an accessible cheap raw material with utilization of known reagents and solvents that can easily be used on an industrial scale can be carried out.

According to the invention, the synthesis of the p, p "-bis-quart.-p-terphenylammonium salts is carried out according to the following scheme: wherein R and R¹ are alkyl, Me, Na, K is.

The process for making the p, p "bis-quart. P -terphenylammonium salts includes the reduction of p, p "-dinitro-pterphenyl to p, p" -diamino-p-terphenyl, the alkylation of p, p "-diamino-p-terphenyl to p, p '-Bis- (tert. amino) -pterphenyl by alkyl iodides or tetramethylene dibromide, the quaternization of p, p '-Bis (Tert. amino) -p-terphenyls with benzenesulfonic acid alkyl esters to p, p '' -Bis- (quart. ammonium) -pterphenyldibenzenesulfonates and, if necessary, halogen salts of p, p "-Bis- (quart. ammonium) -p-terphenylen, - the replacement of the benzenesulfonic acid anion in p, p '-Bis-quart .ammonium-p-terphenyldibenzoisulfonate by means of the halogen ion an inorganic halogen salt.

The starting material, p, p "- Dinftro-p-terphenyl, is a well known one Substance and is produced by nitrating p-terphenyl using fuming nitric acid obtain.

The p, p '-di-nitro-p-terphenyl reduction can be carried out by various methods carried out, e.g., it is possible to do this in an autoclave for 2 to 3 hours subject to catalytic hydrogenation.

In addition, the p, p "-Dinitro-p-terphenyl reduction in the tin dichloride solution be carried out in concentrated hydrochloric acid for 3 hours.

However, it is faster and easier to perform the p, p "-dinitro-p terphenyl reduction with hydrazine hydrate in the presence of Raney nickel in an inert organic solvent, e.g. in ethylene glycol with heating. Such a reduction goes on during a few minutes and in quantitative yield of p, p "-diamino-p-terphenyl in front of you.

The alkylation of p, p "-diamino-p-terphenyl can be by means of several alkylating agents. In particular, the alkylation takes place with the aid of the alkyl iodides in the presence of an iodine binding agent in an organic solvent Warming up slightly in front of you.

The quaternization of p, p1 -Bis- (tert.amino) -p-terphenylene is carried out in the solution of benzenesulfonic acid alkyl esters with heating.

If necessary, halogen salts of p, p "-bis- (quart.ammonium) -p-terphenylene the latter are obtained by the action of an inorganic halogen salt to the aqueous solution of the corresponding p, p "-Bis- (quart. ammonium) -pterphenyldibenzenesulfonate obtain.

The p, p "-Bis- (quart.

ammonium) p-terphenyldijodide is very slightly soluble in water at room temperature and therefore represent little interest in pharmacological testing.

In practice, the procedure is carried out as follows.

The p, p "-Dinitro-p-terphenyl used is in a reflux condenser, A flask equipped with a thermometer, stirrer and dropping funnel is introduced, and ethylene glycol is used and the hydrogenating catalyst added and heated on the oil bath. When the suspension temperature 1650C is reached, hydrazine hydrate is trickled in with vigorous stirring, whereby excessive foaming is avoided. The reaction takes a few minutes and everything goes in solution, which is still a few minutes with activated charcoal at a temperature of 165 to 1800C is heated.

Then this is filtered. The precipitated after cooling the filtrate Precipitate is filtered off with absolute alcohol washed and dried. The p, p11-diamino-p-terphenyl obtained by this process needs no additional cleaning. Its yield is quantitative.

The p, p "-diamino-p-terphenyl is brought into the reflux condenser a flask equipped with a stirrer and add water.

an inert organic solvent, calcium carbonate and alkyl iodide or tetramethylene dibromide. The reaction mixture is stirred while Heated for 2 to 4 hours. The p, p "-Bis- (tert. Amino) -p-terphenyl begins as soon as it is heated precipitate, which is filtered off after cooling.

The precipitate is crystallized from the organic used Solvent. The yield of p, p "-Bis- (tert. Amino) p-terphenylene is 70 to 96%.

The corresponding p, p'1-bis- (tert.

amino) -p-terphenyl from a few minutes to an hour in the Benzenesulfonic acid alkyl ester solution heated at a temperature of 120 to 2000C. At the end of the heating process, the solution condenses. The cooled hardened mass is treated with absolute diethyl ether or with dry acetone and the obtained Precipitate is crystallized from acetone with water. The yield of p, p "-Bis- (quart.ammonium) -p-terphenyldibenzenesulfonates is 70 to 80%.

For the preparation of the p, p "-Bis- (quart. Ammonium) -p-terphenyl halogen salts p, p "-Bis- (quart.ammonium) -p-terphenyldibenzenesulfonate is poured into the flask equipped with a stirrer introduced, it is dissolved in water and the 5-fold excess of the corresponding inorganic halogen salt is partially added with gentle heating. The solution is left to stand at room temperature overnight and then cooled.

The deposited precipitate is filtered and crystallized the end aqueous acetone. The yield of p, p'1-bis (quart.ammonium) -p-terphenyl halogen salt is quantitative.

As can be seen from the description given, there is the inventive Process for the preparation of p, P11-Bisquart. p-terphenylammonium salts of three Steps that proceed quickly and in high yields. Be good at synthesis known, accessible reagents and solvents used to purify the The end product also offers no difficulties. Such a procedure can under the production conditions can be easily realized and is of commercial Interest.

For a better understanding of the present invention, concrete Examples for the production of the substances mentioned are given.

Example 1 Preparation of p, p "-Bis-trimethylammonium-p-terphenyldibenzenesulfonate.

a) Reduction of p, p '1-dinitro-p-terphenyl.

In one with the reflux condenser, stirrer, thermometer and dropping funnel provided three-necked flask of 1 liter content is brought to the suspension of 10 g of p, p "-Dinitro-p-terphenyl in 500 ml of ethylene glycol, add 5 ml of freshly prepared Raney nickel and then add it drizzled while stirring and heating (the temperature in the flask is 165 to 170 ° C) Carefully add 15 ml of 99% hydrazine hydrate solution, causing vigorous foaming is avoided.

For a few minutes everything goes into solution, the activated charcoal is added will. After 10 to 15 minutes, the hot solution is filtered off and the filtrate is cooled.

The deposited precipitate is washed on the filter with alcohol and dried. 8.1 g of p, p "-diaminopterphenyl are obtained (the yield is quantitative) with meat color, the m.p. is 2400C.

b) Alkylation of p, p11-diamino-p-terphenyl with methyl iodide.

Into a 250 ml flask fitted with a reflux condenser and stirrer ml of the contents are added to 1.7 g of p, p "-diamino-p-terphenyl, 2.2 g of calcium carbonate, 75 ml Ethylene glycol, 8 ml water and 5 ml methyl iodide.

While stirring, the suspension is heated to 700C and, during When methyl iodide reacts, the temperature is increased to 100 to 120 ° C. That Heating is continued for 5 hours. The hot solution is filtered and the filtrate is cooled. The precipitate deposited therein in an amount of 2 g of brick red color and decomposition point of @. 250 ° C represents a mixture of p, p "-Bis-dimethylamino-p-terphenyl and p, p" -Bis-trimethylammonium-p-terphenyldiiodomethyl A represent.

c) Quaternization with a benzene sulfonic acid methyl ester.

2 g of the above are placed in a 100 ml flask Mixture of p, p "-Bis-dimethylamino-p-terphenyl and p, p" -Bis-trimethylammonium-p-terphenyldiiodide and heated for 2 hours with 30 ml of methyl benzenesulfonate, first at 100 ° C, then at 120 ° C. The resulting solution condenses at the end of the Heating. After cooling, the hard mass is treated with absolute diethyl ether and filtered off.

The precipitate in the amount of 2.5 g of beige color (the yield is 80%) is crystallized from 50 ml of water with activated charcoal.

The obtained p, p "-Bis-trimethylammonium-p-terphenyldibenzenesulfonate of thorough color does not melt up to 300 ° C. It is dried under vacuum and kept in a dark place.

Found in%: C 65.50, 65.57; H 6.49, 6.41; s 9.68, 9.61. C36H40N206S2.

Calculated in: C 65.43, H 6.10, s 9.68.

Example 2 Preparation of p, p "-Diethylmethylammonium-p-terphenyldi benzenesulfonate.

a) The reduction of p, p'1-dinitro-p-terphenyl is analogous to the example 1 carried out.

b) Alkylation of p, p "-diamino-p-terphenyl with ethyl iodide.

Into a 250 ml flask fitted with a reflux condenser and stirrer To the ml contents, add 8 g of p, p1'-diamino-p-terphenyl, 10 g of calcium carbonate, 100 ml Dimethylformamide, 10 ml of water and 23 ml of ethyl iodide and heated at a bath temperature from 120 to 1300C. Within a few minutes everything goes into solution and begins immediately the formation of the precipitate. The boiling is for 2 hours under vigorous Stirring is continued, after which the slurry is cooled.

The filtered precipitate is crystallized from 100 ml of dimethylformamide and receives 7.65 g (the yield is 70%) of p, p "-Bis-diethylamino-p-terphenyl from light beige color with a melting point of 198 ° C.

Found in%: C 83.30, 83.42; H 8.68, 8.61; N 7.63, 7.61.

C26H32N2 -Calculated in: C 83.82, H 8.65, N 7.52.

c) Quaternization of p, p "-Bis-diethylamino-p-terphenyl with the benzenesulfonic acid methyl ester.

1 g of p, p11-bis-diethylamino-p-terphenyl is placed in a 50 ml flask and heated with 5 ml of benzenesulfonic acid methyl ester at a bath temperature of 1200C for 1 hour.

The solution obtained thickens and crystallizes after cooling the end. The hard mass is treated with absolute diethyl ether and filtered off.

The light beige precipitate is obtained from 30 ml of aqueous acetone (Acetone: water 10: 1) crystallized with activated charcoal.

1.5 g (80%) of p, p "-Bis-diethylmethylammonium-p-ter phenyldibenzenesulfonate are obtained white in color that turns a little green in the air. The decomposition point is 270.5 ° C. The product is dried under vacuum and stored in a dark place.

Found in%: C 67.35, 67.10; H 6.68, 7.05; S 9.16, 9.15; N 3.78, 3.77. C40H48N2O6S2.

Calculated in ': C, 67.02; H 6.75; S 8.92; N 3.90.

Example z Preparation of p, p p "-bis-triethylammonium-p-terphenyldibenzenesulfonate.

a) The reduction of p, p "-Dinitro-p-terphenyl is analogous to the example 1 carried out.

b) The alkylation of p, p "-diamino-p-terphenyl with ethyl iodide is carried out analogously to Example 2.

c) Quaternization of p, p "-Bis-diethylamino-p-terphenyl with the ethyl benzosulfate.

7.5 g of p, p "-Bisdiäthylamino-p-terphenyl are placed in a flask with a capacity of 100 ml and heated with 20 ml of ethyl benzenesulfate at a bath temperature of 140 ° C for one hour. The solution formed during the first 30 minutes crystallizes out at the end of heating. After cooling, the reaction mass becomes treated with absolute diethyl ether and filtered.

The precipitate of light beige color is obtained from 100 ml of aqueous Acetone (10: 1) crystallized with activated charcoal. 10 g of (70, ') p, p "-Bis-triethylammonium-p-terphenyldibenzenesulfonate are obtained white in color that turns a little green in the air. The decomposition point is 228 to 229 0C. The product is dried under vacuum and stored in a dark place.

Found in ': C 67.97, 68.22; H 7.76, 7.66; S 8.75, 8.55; N 3.801 3.90. C42H52N206S2.

Calculated in: C, 67.72; H 7.04; S 8.59; N 3.76.

Example 4 Preparation of p, p "-Bis-triethylammonium-p-terphenyl.

a) The reduction of p, p "-Dinitro-p-terphenyl is analogous to the example 1 carried out.

b) The alkylation of p, p "-diamino-p-terphenyl with ethyl iodide is carried out analogously to Example 2.

c) The quaternization of p, p "-Bis-diethylamino-p-terphenyl with the Benzolsulfosäureäthy1ster is carried out analogously to Example 3.

d) Preparation of p, p "-Bis-triäthylammonium-p-terphenyldibromide from p, p "-triethylammonium p-terphenyl dibenzenesulfonate.

Place in a 250 ml flask fitted with a stirrer 5 g of p, p "-Bis-triethylammonium-p-terphenyldibenzenesulfonate are dissolved in 50 ml Water with gentle heating and add 7 g of sodium bromide with stirring. the The solution is left to stand for 12 hours at room temperature, after which it is cooled.

The deposited precipitate is filtered off and extracted from 100 ml of acetone crystallized with water 10: 1.

4.2 g of p, p ″ -Bis-triethylammonium-p-terphenyl dibromide are obtained (95, ') White in color, which turns a little green in the air.

The decomposition point is 195 to 1,970C. The product is under Vacuum dried and stored in a dark place.

Found in%: C 54.25, 54.63; H 7.60, 7.70; Br 23.90, 24.20; N 4.29, 4.16. C30H42Br2N2. 4H2O.

Calculated in: C, 54.38; H 7.60; Br 24.12, N 4.23.

Example 5 Preparation of p, p '-Bis-dipropylmethylammonium-p-terphenyl dibenzenesulfonate.

a) The reduction of p, p "-Dinitro-p-terphenyl is analogous to the example 1 carried out.

b) Alkylation of p, p "-diamino-p-terphenyl with propyl3odide.

Into a 50% flask equipped with a reflux condenser and stirrer ml of contents are added to 2.1 g of p, p "-diamino-p-terphenyl, 2 g of calcium carbonate, 25 ml Dimethylformamide, 2.5 ml water and 7 ml of propyl iodide and heated for 2 hours at a bath temperature of 100 to 1200C, then it is cooled. The deposited precipitate is filtered off and extracted from 30 ml of dimethylformamide with Water (5: 1) crystallized with activated charcoal.

2.45 g (70%) of p, p "-Bis-dipropylamino-p-terphenyl vonweiß are obtained Color, from m.p. 115 to 116 ° C.

Found in ': C 84.03, 84.49 g, H 9.71, 9.57; N 7.03, 6.98.

C30H40N2.

Calculated in: C 84.06; H 9.40; N 6.53.

c) Quaternization of p, p "-Bis-dipropylamino-p-terphenyl ait Benzolsulfos acid methyl ster.

1 g of p, p "-Bis-dipropylamino-p-terphenyl is placed in a flask with a capacity of 50 ml a, heated for 15 minutes with 3 ml of methyl benzosulfate at a bath temperature from 1200C. 7 minutes after the start of heating, the solution crystallizes out. The cooled suspension is treated with dry acetone, the precipitate filtered off and crystallized from 30 ml of acetone with water (10: 1) with activated charcoal.

1.45 g (80%) of p, p "-Bis-dipropylmethylammonium-pterphenyldibentzo sulfonate are obtained white in color that turns a little green in the air. The decomposition point is 245 ° C. The product is dried under vacuum and stored in a dark place.

Found in%: C 66.39, 66.37; H 7.19, 7.43; N 3.59, 3.33; S 8.24, 8.19. $ C44H56N2O6S2 # H2O.

Calculated in%: C 66.81; H 7.39; N 3.54; S 8.28.

Example 6 Preparation of p, p "-Bis- (N-methylpyrrolidinium) -p-terphenyldibenzenesulfonate.

a) The reduction of p, p "-Dinitro-p-terphenyl is analogous to the example 1 carried out b) alkylation of p, p "-diamino-p-terphenyl with tetramethylene dibromide.

Into a 250 ml flask fitted with a reflux condenser and stirrer ml of contents are added to 52 g of p, p "-diamino-p-terphenyl, 4.5 g of calcium carbonate, 50 ml Dimethylformamide, 5 ml of water and 8.6 g of tetramethylene dibromide and heated during 4 hours at a bath temperature of 110 to 125 ° C. The cooled suspension it is filtered off and 7.1 g (96%) precipitate of sand paint are obtained. The precipitate can and will be very little soluble in organic solvents therefore not cleaned additionally; the melting point is approx. 3100C.

For analysis, p, p "-Bis (N-pyrrolidinyl) -p-terphenyl is taken from a large Amount of dimethylformamide crystallized.

Found in%: o C 84.47> 84.61; H 7.42, 7.59; N 7.34, 7.20.

C26H28N2.

Calculated in C to be 84.74; H 7.66; N 796Oc c) Quaternization of p, p "-Bis (N-pyrrolidinyl) -p-terphenyl with BenzolsulfosSuremeth ~ ylestere 1 g p, p "-Bis (N-pyrrolidinyl) -p-terphenyl, heated for 15 minutes with 10 ml of benzenesulfonic acid methyl ester at a bath temperature of 200 ° C and cools immediately away. The reaction mixture is treated with absolute ether and the precipitate is filtered off and crystallized from 30 ml of acetone with water (10: 1) with activated charcoal.

1.45 g of (76, ') p, p "-Bis- (N-methylpyrrolidinium) -pterphenyldibenzenesulfonate are obtained of white color which turns green when exposed to the air. The decomposition point is 273 to 2740C. The product is dried under vacuum and stored in a dark place.

Found in%: C 64.74, 64.45; H 6.91, 6.66; N 3.94, 3.77; S 8.89, 9.03; C40H44N2O6S2. H2O.

Calculated in%: C 64.15; H 6.46; N 3.74; S 8.55.

Example 7 Preparation of p, p "-Bis- (N-ethylpyrrolidinium) -p-terphenyldibenzenesulfonate.

a) The reduction of p, p "-Dinitro-p-terphenyl is analogous to the example 1 carried out.

b) The alkylation of p, p "-diamino-p-terphenyl with tetramethylene dibromide is carried out analogously to Example 6.

c) Quaternization of p, p "-Bis- (N-pyrrolidinyl) -p-terphenyl with ethyl benzenesulfonate.

1 g of p, p "-Bis- (N-pyrrolidinyl) -p-terphenyl is placed in a 50 ml flask amine, heated for 10 minutes with 6 ml of ethyl benzenesulfonate at a Bath temperature of 2000C. The cooled reaction mass is washed with dry acetone treated, the precipitate is filtered off and from 30 ml acetone crystallized with water (10: 1) with activated charcoal. 1.6 g (80%) of p, p "-Bis- (N-ethylpyrrolidinium) -p-terphenyldibenzenesulfonate are obtained white in color which turns a little green in the air; the decomposition point is 277 ° C. The product is dried under vacuum and stored in a dark place.

Found in%: C 66.50, 66.55; H 6.85, 6.70; N 3.33, 3.65; S 8.43, 8.49 C42H48N20682. H2O.

Calculated in ': C, 66.47; H 6.64; N 3.69; S 8.43.

Claims (1)

Claims 1. p, p "-bis-quart. P-terphenylammonium salts of the general formula where x is NR2R¹ x is R and R1 represent alkyl, in particular lower alkyl, y represents C6H5SO3 halogen. 2. p, p "-Bis-trimethylammonium-p-terphenyldibenzenesulfonate according to claim 1, 3. p, p "-bis-diethylmethylammonium-p-terphenyldibenzosulfonat according to claim 1, 4. p, pS '-Bis-triethylammonium-p-terphenyldibenzenesulfonate according to claim 1, 5. p, p "-Bis-triäthylammonium-p-terphenyldibromide according to claim 1, 6.p, p "-Bis-dipropylmethylammonium-p-terphenyldibenzolfulformate according to claim 1, 7. p, p "-Bis- (N-methylpyrrolidinium) -p-terphenyldibenzolaulfonate according to claim 1, 8. p, p "-Bis- (N-ethylpyrrolidinium) -p-terphenyl-dibenzenesulfonate according to claim 1, 9. A process for the preparation of p, p "-Bis-quart. P-terphenylammonium salts according to claim 1 to 4 and 6 to 8, characterized in that it is the reduction of p, p '-dinitro-p-terphenyl to p, p "-Diamino-p-terphenyl, the alkylation of p, p" - diamino-p-terphenyl to p, p "- bis (tert .amino) -p-terphenylene by means of alkylodides or tetramethylene dibromide, the quaternization of p, p '' - bis (tert. amino) -p-terphenylene with benzenesulfonic acid alkyl esters to p, p '-Bis- Includes (quart. ammonium) pterphenyldibenzenesulfonates in a known manner. 10. The method according to claim 9, d a d u r c h g e k e n n -z e i c h n e t that for the production of the substances mentioned in the form of halogen salts p, p "-Bis-quart. ammonium-p-terphenyldibenzenesulfonate treated with an inorganic halogen salt will. 11. The method according to claim 9, d a d u r c h g e k e n n -z e i c h n e t that the reduction with hydrazine hydrate in the presence of a hydrogenating catalyst is carried out in the medium of an inert organic solvent with heating. 12. The method according to claim 11, d a d u r c h g e k e n n -z e i c n e t that the reduction in the ethylene glycol solution at a temperature of 165 to 1800C. 13. The method according to claim Ii, d a d u r c h g e k e n n -z e i c Not that the reduction is carried out in the presence of the Raney nickel. 14. The method according to claim 9, d a d u r c h g e k e n n -z e i c h n e t that the alkylation of p, p "-diamino-pterphenyl with alkyl iodides im MEdium of an inert organic solvent is carried out with heating. 15. The method according to claim 9, d a du r c h g e k e n n -z e i c h n e t that the alkylation of p, p "-diaminopterphenyl in the presence of a halogen forming agent is carried out. 16. The method according to claim 9, d a d u r c h g e k e n n -z e i c hn e t that the alkylation in an inert organic solvent with addition is carried out by water. 17. The method according to claim 14, d a d u r c h g e k e n n -z e i c h n e t that the alkylation with methyl iodide in methanol with water at a temperature from 70 to 1200C is carried out. 18. The method according to claim 14, d a d u r c h g e k e n n -z e i c h n e t that the alkylation with ethyl iodide in dimethylformamide with water a temperature of 120 to 130 0C is carried out. 19. The method according to claim 14, d a d u r to o h g e k e n n -z e i c h n e t that the alkylation with propyl iodide in dimethylformamide with water is carried out at a temperature of 100 to 1200C. 20. The method according to claim 9, d a d u r c h g e k e n n -z e i c h n e t that the alkylation with tetramethylene dibromide in dimethylformamide with Water is carried out at a temperature of 110 to 1250C. 21. The method according to claim 9, d a d u r c h g e k e n n -z e i c Note that the alkylation is carried out with heating for 2 to 5 hours will. 22. The method according to claim 9, d a d u r c h g e k e n n -z e i c h n e t that the quaternization of p, p "-Bis- (tert. amino> -p-terphenylene with benzenesulfonic acid alkyl ester with heating is carried out. 23. The method according to claim 22, d a d u r c h g e k e n n -2 e i c h n e t that the quaternization in the benzenesulfonic acid methyl ester solution at a Temperature from 120 to 2000C is carried out. 24. The method according to claim 22, d a d u r c h g e k e n n -z e i c Not that the quaternization occurs in the solution of ethyl benzenesulfonate a temperature of 140 to 2000C is carried out. 25. The method according to claim 22, d a d u r c h g e k e n n -z e i c Not that the quaternization is carried out with heating for 10 minutes to 2 hours will.