DE2621226B2 - P, p '' - bis-quart.p-terphenylammonium salts and processes for their preparation - Google Patents

Description

description The present invention relates to p, p "-Bis- len new substances not described in the literature.

quartp-terphenylammonium salts and processes for According to the invention, the p, p "-Bis-quartp-ter-

their manufacture. phenylammonium salts by the general formula

The p, p "-to-quart.p-terphenyiammonium salts represent

where R ', R ² , R ^{3 represent} a low molecular weight alkyl radical or the radical C ₆ Hj-SO ₃ -.

stand and R ² and R ³ together with the nitrogen atom The preceding claims explain the invention

can form a pyrrolidinium ring and y for bromine % n dung in detail.

Representatives of these substances are: p, p "-Bis-trimethylammonium-p-terphenyldibenzenesulfonal of the formula

(CH ₃ J _-1 N ρ, ρ '' - bis-diethylmnethylarnmoniurn-p-tert-phenyldibenzenesulfonate of the formula

CM ₁ (C ₂ H ₅ J ₂ N Y_y \ _y VV 'N (C ₁ IIj) ₂ CH., · 2 C ₆ H ₅ SO., Ρ, ρ''- bis-triethylammonium-p-terphynyldibenzenesulfonate of the formula

(C ₂ H ₅ J ₁ N ρ, ρ "- bis-tri-ethylammonium-p-terphenyl dibromide of the formula

^ y N (C ₂ H ₅ ,., · 2 Br ρ, ρ "- bis-dipropylmethylammonium-p-terphenyldibenzenesulfonate of the formula

N (CiH ₇ J ₂ CH., · 2 C ₆ H ₅ SCl,

p, p "-Bis- (N-methylpyrrolidinium) -p-terphenyldibenzoisulfonate of the formula

CH ₂ -CH,

CH ₂ -CH ₂

2C ₆ H ₅ SO,

CHj ₁ CHj

p, p "-Bis- (N-ethyIpyrrolidinium) -p-terphenyldibenzenesulfonate of the formula

C ₂ H ₅

CH ₁ -CH,

-2CH ₅ SO,

CH, -CH,

All substances mentioned are non-depolarizing muscle relaxants of high activity and selectivity and can be used in medicine to block the neuromuscular conduction in surgical interventions be used.

In animal experiments, the neuro-muscle-blocking activity of these substances comes from the activity of the known muscle relaxants of the same type of action - the d-tubokurarine of the formula

HjCO

HO

CH,

CH,

CH,

OCH.,

artificial lung ventilation is non-toxic. Animals tolerate the introduction of dozens and even Hundreds of blocking doses of these substances while

> ~> d-tubocurarine in particular causes the animal to die at a 5 to 10-fold increase in the dose For example, the cats can tolerate the introduction of 200 blocking doses of p, p "-bis-triethylammonium-p-terphenyldibenzenesulfonate and -dibromide and only

one of the three cats died as a result of a sharp drop in arterial pressure and cardiac arrest.

It is known that the muscle relaxants of the not depolarizing effect type compared to the

) -> depolarizing muscle relaxants in the clinic are preferred. First, because it usually succeeds in its blocking effect by the anticholinesterase substances N- (m-dimethyl carbamoyloxyphenyO-trimethyiammoiiium-methylsuI-

4o fat (Proserin) or

N-CH,

- close to or significantly exceeds this.

In contrast to the non-depolarizing muscle relaxant tubokurarine and pyrolaxone (l ^ J-tris / 2- (triethylammonio) ethoxy / -benzene-triiodide) currently used in clinics, none of the substances mentioned do not affect blood pressure because they are histamine do not excrete and do not block the ganglia of the autonomic nervous system. At the same time Pyrolaxone blocks the ganglia of the vagus nerve and therefore triggers tachycardia. By d-tubocurarine-induced muscle relaxation is accompanied by a decrease in arterial blood pressure, which is due to its ability to isolate histamine from tissues in a blocking dose, as well as the Blocking conductivity in sympathetic ganglia. In addition, all substances mentioned, the p, p "-BisquarLp-terphenyiammonium salts, are subject to the conditions

and, secondly, because they differ from the depolarizing muscle relaxants Blood potassium levels do not increase, otherwise serious complications in patients with cardiovascular disease Malfunctions.

All of the substances mentioned are non-depolarizing muscle relaxants, the effect of which can easily be eliminated by the cholinesterase inhibitors. In addition, they have a higher specific effect than d-tubokurarine. N- (m-Dimethylcarbamoyloxyphenyl) -trimethylammonium-methylsulfate in the experiments on cats in a dose of O ₁ ] mg / kg intravenously quickly and completely lifts the effect of 5 blocking doses of ρ, ρ '' - bis-triethylammonium-p -terphenyldibenzenesulfonate and -dibromide and only from 3 blocking d-tubokurarin doses.

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

The neuromuscular blocking activity is called the

»■ ten substances compared to d-tubokprarin is in the Table 1 shows, in which BD-block, dose means HDD-Headdrop dose.

N (CH ₃ J ₃

N (C ₂ H ₅ J ₂ CH ₃

N (C ₂ H ₅ ).,

N (C ₂ H ₅ ).,

N (C ₃ H ₇ J ₂ CH ₃

1 ^ H ₂ J ₄ C ₂ H ₅
d-tubocurarine

y Cats
BD in μΜοΙ / kg Effect type Rabbits
HDD in μΜοΙ / kg QH ₅ SO ₃ 0.3 ± 0.04 mixed 0.25 + 0.05 QH ₅ SO ₃ 0.5 ± 0.09 not depolarizing 0.12 ± 0.02 QH ₅ SO ₃ 0.08 ± 0.002 the same 0.022 ± 0.001 Br 0.08 ± 0.002 the same 0.022 ± 0.001 QH ₅ SO ₃ 0.5 ± 0.1 the same 0.1 ± 0.03 QH ₅ SO ₃ 1.0 ± 0.2 the same 0.3 + 0.06 C ₅ H ₅ SO ₃ 0.5 ± 0.08 the same 0.14 i 0.04 0.5 i 0.02 the same 0.18 ± 0.06

As can be seen from the table, have p, p "-Bis-triethylammonium-p-terphenyldibenzene sulfonate and dibromide have the highest blocking activity. These connections exceed 3 'by 6 to 8 times. d-tubocurarine myoparalytic activity.

In contrast to d-tubocurarine, these compounds do not secrete histamine, they block it Ganglia of the autonomic nervous system do not and therefore do not influence blood pressure. In the ■ »< > Versurhen on cats and rabbits is developing only when the dose of these substances is increased tenfold weak and short-lasting depressive effect, while after the introduction of the myoparalytic d-tubokurarin dose a pronounced decrease in the - >> arterial blood pressure is detected.

As already mentioned, these compounds occur under the conditions of artificial pulmonary ventilation non-toxic. They also have a higher specific effect than d-tubokurarine. In particular, d-Tuboku- > o rarin in a dose that blocks the neuromuscular conduction causes the conductivity disorder of the upper neck stanglion in the cat. The p, p "-Bistriethylammonium-p-terphenyldibenzenesulfonat and dibromide call for a weak ganglion-blocking effect until r> in the Do-.is, which exceeds the neuro-muscle-blocking dose tenfold.

The cholinesterase inhibitors remove the blocking effect of these substances more easily than the effect of d-tubocurarine. ho

No potentiation of the effects of these compounds and of halothane on blood pressure was demonstrated in the experiments on decerebral cats, while d-tubokurarine increased the effect of halothane (2-bromo-2-chloro-III-trifluoroethane) on the heart ; therefore, their combined use is considered dangerous because of the possible development of cardiovascular callapses.

The experimental comparison carried out of these compounds with the known, non-depolarizing Muscle relaxant pancuronium (1.1- (3 ".170-diacetoxy-5" -androstan-2 /?. 160-ylene) -bis (l-methylpiperidinium bromide)) also demonstrated some of the advantages of the substances according to the invention.

As already mentioned, the compounds according to the invention affect in a dose that whose myoparalytic dose significantly exceeds arterial blood pressure. The disadvantage of pankuronium consists in its ability to trigger the increase in pulse rate and arterial blood pressure, which can cause increased bleeding during surgery.

With the effect of 1.1- (3 <%. 17,9-DiaceUoxy-5a-androstan-2jJ.16 /? - ylene) -bis (l-methyIpiperidinium-bromide) the tests on cats showed the antagonism of N-im- DimethylcarbamoyloxyphenylJ-trimethylammonium methyl sulfate is less pronounced than with the action of the compound according to the invention. In the 4-to 5-fold increase in the dose of 1.1 (3 ".17 / - diacetoxy-5" androstan-2 / ?. 16j -? Ylene) bis ^(l-r methylpipe idinium bromide) began restore muscle relaxation at least 10 minutes after the intravenous introduction of N-im-dimethylcarbamoyloxyphenylJ-trimethylammonium methyl sulfate at a dose of 0.1 mg / kg. Under the same conditions, N-fm-dimethylcarbamoyloxyphenylJ-trimethylammonium methyl sulfate completely eliminated the blocking effect of the substances according to the invention in the same dose after their introduction in an amount which exceeds their myoparalytic dose several times. Even after a 5-fold increase in the dose of these substances, muscle relaxation began to be restored in the range of 5 minutes after the single introduction of N- (m-dimethylcarbamoyloxyphenyi) -trimethylammonium methyl sulfate at a dose of 0.1 mg / kg.

This shows that the clinical application of such preparations compared to the implementation of a safe and controllable muscle relaxation d-tubokurarine and 1.1- (3 ".17 /? - diacetoxy-5" -androstan-20.16 /? - ylene) -bis (1-methylpiperidinium bromide) made possible.

A great advantage of the proposed according to the invention

O ₂ N-

NO,

Genetic substances are their simple synthesis from an accessible cheap raw material using known reagents and solvents that can be easily carried out on an industrial scale. According to the invention, the synthesis of the p, p "-bisquart.-p-terphenylammonium salt is carried out according to the following Scheme realized:

H ₂ N-

NH,

Ur (CH ₂ ) ₄ Br

! ■■ Mi ii; i ₄

(,, HsSO ₁ R ¹

KN K ¹

NK K ¹

NKH ₂ I ₄
K ¹

2 (,, IKSO,

; McI hi I

K-N

K ¹

NK, 2 Ihil ((HI ₄ N K ¹ R ¹

NK "H, I ₄
R ¹

«Elm K and K 'fiii Alk \ I. Mi-. liii Nm. K flour.

The process for the production of the ρ.ρ '' bis-quart.p-Icrphcnylammoniumsal7c closes! the reduction of pp ■ dinitro-p-terphrnyl ? u pp "diaminop-terphenyl. the alkylation of p, p" -diamipo ρ terphenyl to pp -Bis- (terl.amino) ρ tcrphcnylc by alkyl iodide or tetramethylene dibromide. the quaternization of p, p "-Bis (tert.amino) -p-terphenyls with benzenesulfonic acid alkyl esters to p, p" -Bis- (quart.ammonium) -p-lerphenyl-dibenzenesulfonates and, if necessary, halogen salts of p, p "-Bis - To obtain (quart.ammonium) pterphenylene, - the replacement of the benzene sulfonic acid anion in p, p "-bisquart-aiTimonium-p-lerphenyldibenzene sulfonates by the halogen ion by means of an inorganic halogen salt .

The p, p "-Dinitro-p-terphenyl is a well known substance and is obtained by nitrating p-tert-phenyl with fuming nitric acid

The p.p'-dinitrope-tryphenyl reduction can be carried out by various methods, e.g. B. it is possible to subject this to catalytic hydrogenation in the autoclave for 2 to 3 hours.

In addition, the ρ, ρ '' - dinitro-p-terphenyl reduction carried out in the tin dichloride solution in concentrated hydrochloric acid for 3 hours.

However, it is faster and easier to carry out the p, p "-dinitropterphenyl reduction with hydrazine hydrate in the presence of Raney nickel in an inert organic solvent, for example in ethylene glycol with heating. Such a reduction takes a few minutes and is more quantitative Yield of p, p "-diamino-p-terphenyl before it.

The alkylation of ρ, ρ '' - diamino-p-terphenyI can be done with the help of various alkylating agents. In particular, the alkylation goes with the help of Alkyl iodides in the presence of an iodine binding agent in an organic solvent with heating easily in front of you.

The quaternization of p, p "-Bis- {tert.amino) -p-terphenylene is carried out in the solution of alkyl benzenesulfonates with heating.

If there is a need to use halogen salts of p, p "-to-

To obtain (quartammonium) -p-terphenylen, the latter are obtained by the action of an inorganic Halogensalzcs on the aqueous solution of the corresponding p, p "-Bis- (quartammonium) -p-terphenyldibenzenesulfonate obtained.

In practice, the procedure is carried out as follows.

The p, p "-Dinitro-p-terphenyl used is introduced into a flask equipped with a reflux condenser, thermometer, stirrer and dropping funnel, ethylene glycol and the hydrogenating catalyst are added and the mixture is heated on the oil bath. When the suspension temperature reaches 165.degree , hydrazine hydrate the r> reaction with vigorous stirring hinzugeträufelt, whereby strong foaming is avoided. takes a few minutes and everything goes into solution, is heated to a few minutes with activated carbon at a temperature of 165 to 18O ⁰ C. Then it is filtered. The precipitate which separates out after the filtrate has cooled is filtered off, washed with> 0 absolute alcohol and dried. The ρ, ρ "- diamino-p-terphenyl obtained by this process does not need any additional purification. Its yield is quantitative.

The p, p "-diamino-p-terphenyl is introduced into the flask equipped with a reflux condenser and stirrer and adds water, an inert organic solvent, calcium carbonate and alkyl iodide or tetramethylene dibromide. The reaction mixture is stirred v heated for 2 to 4 hours. The p, p "-Bis- (tert.amino) -p-terphenyl begins to precipitate as soon as it is heated and is filtered off after cooling.

The precipitate is crystallized from the organic solvent used. The yield at p, p "-Bis- (tertamino) -p-terphenylene is 70 to 96%. r ·

In the piston or in the glass, the corresponding p, p '-bis (tertamino) -p-terphenyl is heated from a few minutes up to an hour in the Benzolsulfosäurealkylesterlösung at a temperature of 120 to 200 ⁰ C. At the end of the heating condenses the Solution, i <> The cooled hardened mass is treated with absolute diethyl ether or with dry acetone and the resulting precipitate is crystallized from acetone with water. The yield of p, p "-Bis- (quartammonium) -p-terphenyldibenzenesulfonates is 70 to 80% . · »->

To prepare the p, p "-Bis- (quartammonium) -pterphenylhalogenesals is in the with the stirrer P, p "-Bis- (quartammonium) -p-terphenyldibenzenesulfonate is placed in the flask provided with it in water dissolved and the 5-fold excess of the corresponding inorganic halogen salt is under weak Heating partially added. The solution is left to stand overnight at room temperature and then cooled. The deposited precipitate is filtered and crystallized from aqueous acetone. The yield of p, p "-Bis- (quartammoniuni) -p-terphenyl halogen salt is quantitative.

The process according to the invention for the preparation of p, p "-Bis-quartp-terphenylammonium salts consists of three stages, which m> quickly and in high yields verlaufea Well-known, accessible reagents and solvents are used in synthesis, the cleaning of the end product also presents no difficulties. Such a procedure can be used under the Production conditions can be easily realized.

For a better understanding of the present invention, specific examples for the preparation of the listed substances

example 1

Preparation of p, p "-Bis-trimethylammonium-p-terphenyldibenzenesulfonate

a) Reduction of p, p "-Dinitro-p-terphenyl

The suspension of 10 g of p, p "-dinitro-p-terphenyl in 500 ml of ethylene glycol is added to a three-necked flask with a capacity of 1 l, equipped with a reflux condenser, stirrer, thermometer and dropping funnel, 5 ml of freshly prepared Raney nickel are added and then drizzled with stirring and heating (the temperature in the flask is 165 to 170 ^° C.), carefully add 15 ml of 99% strength hydrazine hydrate solution, avoiding excessive foaming.

Everything goes into solution for a few minutes, after which activated charcoal is added. After 10 to 15 The hot solution is filtered off for minutes and the filtrate is cooled.

The deposited precipitate is washed on the filter with alcohol and dried. You get 8.1 g flesh-colored p, p "-diamino-p-terphenyl (the yield is quantitative), the melting point is 240.degree.

p, p

b) alkylation of -Diamino-p-terphenyl with methyl iodide

In one equipped with a reflux condenser and stirrer A 250 ml flask is filled with 1.7 g of p, p "-diamino-p-terphenyl, 2.2 g of calcium carbonate, 75 ml of ethylene glycol, 8 ml of water and 5 ml of methyl iodide.

While stirring, the slurry is heated at 70 ⁰ C and, while methyl iodide occurs in the reaction, the temperature is increased to 100 to 120 ° C. Heating is continued for 5 hours. The hot solution is filtered and the filtrate is cooled. The precipitated precipitate therein in an amount of 2 g of brick-red color and decomposition point of about 250 ⁰ C is a mixture of p, p '-bis-dimethylamino-p-terphenyl and p, p' -bis-trimethylammonium pterphenyldijodmethylat represents.

c) Quaternization with a 4-> Benzoisulfonic acid methyl ester

2 g of the above-mentioned mixture of ρ, ρ "- bis-dimethylamino-terphenyl and ρ, ρ" - bis-trimethylammonium-p-ter vt phenyldiiodide are placed in a flask with a capacity of 100 ml and heated for 2 hours at 30 ml Benzoisulfosäuremethylester, first at 100 ° C, then at 120 ⁰ C. the resulting solution is condensed to the end of 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 ρ, ρ '' - bis-trimethylammonium-p-terbo phenyidibenzolsulfonat of greenish color melts not up to 300 ° C. It is dried under vacuum and stored in a dark place

Found in %:

C 65.50.65 ^ 7; H 6,49,6,41; S 9.68,9.61.

C ₃₆ H ₄₀ N ₂ O ₆ S ₂ . Calculated in%:

C 65.43, H 6.10, S 9.68.

Example 2

Production of p, p "-diethylmethyl ammonium p-terphenyl dibenzenesulfonate

a) The reduction of p, p "-Dinitro-p-terphenyl is carried out analogously to Example 1.

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

Into a flask equipped with a reflux condenser and a stirrer, 250 ml flask contents are brought 8 gp, p "-Diaminop-terphenyl, 10 g calcium carbonate, 100 ml of dimethylformamide, 10 ml of water and 23 ml of ethyl iodide and heated at a bath temperature of 120 to 130 ⁰ C. For a few minutes everything goes into solution and the precipitate begins to form immediately. Heating is continued for 2 hours with vigorous stirring, after which the slurry is cooled.

The filtered precipitate is crystallized from 100 ml of dimethylformamide and 7.65 g (the Yield is 70%) ρ, ρ '' - bis-diethyIamino-p-terphenyl and light beige color with a melting point of 198 ° C.

Found in %:

C 8330.83.42; H 8.68.8.61; N 7.63, 7.61.

C ₂₆ H ₃₂ N ₂ . Calculated in%: C 83.82, H 8.65, N-7.52.

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

In a flask of 50 ml to 1 g brings ρ, ρ '' - Bis-diethylamino-p-terphenyl and heated with 5 ml Benzolsulfosäuremethylester at a bath temperature of 120 ⁰ C for 1 hour.

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

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

1.5 g (80%) ρ, ρ ″ - bis-diethylmethylammonium-p-terphenyldibenzenesulfonate are obtained which are white in color and turn a little green in air. The decomposition point is 270.5 ⁰ C. The product is stored under vacuum and dried in a dark place.

Found in %:

C 6735.67.10; H 6.68, 7.05;

S 9.16.9.15; N 3.78.3.77.

CoH ₄₈ N ₂ O ₆ S ₂ . Calculated in%:

C 67.02; H 6.75; S 8.92; N 3.90.

Example 3

Production of p, p "-Bis-triethylammonium p-terphenyldibenzenesulfonate

a) The reduction of p, p "-Dinitro-p-terphenyl is carried out analogously to the example!" _ b) The alkylation of ρ, ρ '' - diamino-p-terphenyl with Ethyl iodide is carried out analogously to Example 2

c) Quaternization of p, p "-Bis-di8thyiamino-p-terphenyl with the ethyl benzoisulfate.

73 g are placed in a 100 ml flask ρ, ρ '' - bis-diethyIamino-p-terphenyI and heated with

20 ml of benzene sulfo! (Acid ethyl ester at a bath temperature of 140 ° C. for one hour of the first 30 Mkuitcn formed solution crystallizes at the end of the heating. After cooling down, the ■> Reaction mass treated with obsolete diethyl ether and filtered.

The precipitate of light beige color is made from 100 ml of aqueous acetone (10: 1) with activated charcoal crystallized. 10 g (70%) ρ, ρ '' - bis-triäthylam-Ki monium-p-terphenyldibenzenesulfonate of white color are obtained, that turns a little green in the air. The decomposition point is 228 to 229 ° C. The product is under vacuum dried and stored in a dark place.

Found in %:

'' C 67.97, 68.22; H 7.76, 7.66; S 8.75, 8.55; N 3.80, 3.90. C ₄₂ H ₅₂ N ₂ O ₆ S ₂ . Calculated in%: C 67.72; H 7.04; S 8.59; N 3.76.

Example 4

Production of p, p "-bis-triethyl-, ammonium-p-terphenyl bromide

a) The reduction of p, p "-Dinitro-p-terphenyl is carried out analogously to Example 1.

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

ι »c) The quaternization of ρ, ρ '' - bis-diethylamino-pterphenyl with the ethyl benzoisulfate is carried out analogously to Example 3.

d) Production of ρ, ρ '' - bis-triethylammonium-p-terphenyldibromide from ρ, ρ '' - triethylammonium-p-terpher> nyldibenzenesulfonate

Into a flask equipped with the stirrer flask of 250 ml content was 5 g brings ρ, ρ '' - bis-triethylammonium-p-terphenyldibenzolsulfonat one, dissolved in 50 ml of water under gentle heating and stirring are under w 7 g of sodium bromide added. The solution is left to stand for 12 hours at room temperature, after which it is cooled

The deposited precipitate is filtered off and crystallized from 100 ml of acetone with water 10: 1. ■ »"> One receives 4.2 g ρ, ρ "- bis-triethylammonium-p-terphenyldibromide (95%) of white color, which at the Air turns a little green. The decomposition point is 195 up to 197 ° C. The product is dried under vacuum and kept in a dark place.

Found in%: C 54.25,54.63; H 7.60, 7.70; Br 2330,24.20; N 43.4.16. C ₃₀ H ₄₂ Br ₂ N ₂ ^ H ₂ O. «Calculated in%:

C 5438; H 7.60; Br 24.12, N 4.23.

Example 5

Production of ρ, ρ '' - bis-dipropylmethylammonium-p-terphenyldibenzenesulfonate

a) The reduction of p, p "-Dinitro-p-terphenyI will carried out analogously to Example 1

b) Alkylation of p, p "-diamino-p-terphenyi with W Pfopyljodäd.

In one equipped with a reflux condenser and stirrer Flask of 50 ml capacity brings 2.1 g of p, p "-Diaminop-terphenyl, 2 g of calcium carbonate 25 ml of dimethylform-

imid, 2.5 ml of water and 7 ml of propyl iodide and heated for 2 hours at a bath temperature of 100 to 120 ° C, then it is cooled. The precipitate formed is filtered off and crystallized from 30 ml of dimethylformamide with water (5: 1) with activated charcoal

This gives 2.45 g (70%) ρ, ρ '' - bis-dipropylamino-pterphenyl of white color, a melting point of 115-116 ⁰ C..

Found in %:

C 84.03,84.49; H 9.71.9.57; N 7.03.6.98.

C} oH ₄ oN ₂ .

Calculated in%:

C 84.06; H 9.40; N 6.53.

c) Quaternization of ρ, ρ '' - bis-dipropylamino-p-ter phenyl with methyl benzenesulfate.

1 g of p, p "-Bis-dipropylamino-p-terpheny! Is placed in a flask with a capacity of 50 ml, while the mixture is heated 15 minutes with 3 m! Benzenesulfonic acid methyl ester Found in%:

C 84.47, 84.61; H 7.42. 7.59; N 7.34, 7.20.

C ₂₆ H ₂₈ N ₂ .
Calculated in%:

C 84.74; H 7.66; N 7.60.

c) Quaternization of p, p "bis- (N-pyrrolidinyl) -pterphenyl with benzenesulfonic acid methylene ester.

In a flask of 50 ml is placed 1 gp, p "bis (N-pyrrolidinyl) -p-terphenyl a heated for 15 minutes with 10 ml Benzolsulfosäuremethylester at a bath temperature of 200 ⁰ C and cooled immediately. The reaction mixture is treated with absolute ether, the precipitate is filtered off and crystallized from 30 ml of acetone with water (10: 1) with activated charcoal.

1.45 g (76%) of p, p "-Bis- (N-methyIpyrrolidinium) -p-terphenyldibenzenesulfonate are obtained white in color which turns green in the air. The decomposition point is 273 to 274 ° C. The product is under vacuum

at the beginning of the heating the solution crystallizes out. The cooled suspension is mixed with dry Treated acetone, the precipitate filtered off and 30 ml of acetone with water (10: 1) with activated charcoal crystallized.

1.45 g (80%) ρ, ρ ″ - bis-dipropylmethylammonium-p-terphenyldibenzenesulfonate are obtained which are white in color and turn 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.

C ₄₄ HwN ₂ O ₆ S ₂ -H ₂ O.
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 carried out analogously to Example 1.

b) Alkylation of p, p "-diamino-p-terphenyl with tetra-ethylene dibromide.

52 g of p, p "-diaminopterphenyl are placed in a 250 ml flask equipped with a reflux condenser and stirrer. 4.5 g calcium carbonate, 50 ml dimethylformamide. 5 ml of water and 8.6 g of tetramethylene dibromide and heated for 4 hours at a bath temperature of 110 to 125 "C. The cooled The suspension is filtered off and 7.1 g (96%) precipitate of sand paint is obtained. Of the Precipitate can be dissolved very little in organic solvents and is therefore also not cleaned: the melting point is approx. 310 ° C.

For analysis, p, p "-Bis- (N-pyrrolidinyI) -p-terphenyl crystallized from a large amount of dimethylformamide.

rrn * * -r> n \ r nnf tt η Λ nn

Found in %:

C 64.74, 64.45; H 6.91, 6.66;

N 3.94, 3.77; S 8.89, 9.03;

C ₄₀ H ₄₄ N ₂ Oe ₁ S ₂ Jl ₂ O.
Calculated in%:

C 64.15; 116.46; 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 carried out analogously to Example 1.

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

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

1 gp, p "-Bis- (N-pyrrolidinyl) -p-terphenyl is placed in a 50 ml flask and heated for 10 minutes with 6 ml Bcnzenesulfosäureäthylestei at a bath temperature of 200" C. The cooled reaction mass is treated with dry acetone, the precipitate is filtered off and crystallized from 30 ml of acetone with water (10: 1) with activated charcoal. This gives 1.6 g (80%) of p, p '-bis (N-äthylpyrrolidinium) -p-ι terphenyldibenzolsulfonal of white color, which is somewhat green in the air, the amount Zersetzungspunkl: 277 ^C C. The product is Vacuum dried and stored in a dark place

Found in %:
⁵ C 66.50, 66.55; H 6.85,6.70;
N 3.33, 3.65; S 8.43, 8.49.
C ₄₂ H ₄₈ N ₂ O ₁ S ₂ -H ₂ O.
Calculated in%:
"C 66.47: H 6.64: N 3.69: S 8.43.

Claims (2)

Patent claims: 1. ρ, ρ '' - bis-quartp-terphenylammonium salts of general formula R ³ 10 where R ¹ , R ² , R ³ stand for a low molecular weight alkyl radical and R ² and R ³ together with the nitrogen atom can form a pyrrolidinium ring and y stands for bromine or the radical C ₆ H ₃ —SO ₃ - 2. Process for the preparation of the compound according to claim 1, characterized in that one first reduced p, p "-Dinitro-p-terphenyl with hydrazine hydrate in the presence of Raney nickel in an ethylene glycol solution at temperatures of 165 to 180 ° C, then the resulting p, p" -Diaminop-terphenyl with alkyl iodides or tetramethylene dibromide in an inert organic solvent is alkylated with heating for 2 to 5 hours in the presence of a halogen acceptor with addition of water and the resulting p, p "-Bis- (tertamino) -p-terphenylene in an alkyl benzenesulfonate solution with heating at temperatures of 120 to 200 ⁰ C for 10 Quaternized minutes to 2 hours and optionally treated the p, p "-Bis- (quartammonium) -p-terphe-iyldibenzenesulfonate obtained with an inorganic bromine salt