DE2621226C3 - - Google Patents

Description

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

quartp-terphenyianimoniumsalze and process for According to the invention the p, p "-Bis-quartp-ter-

their manufacture. phenylammonium salts by the general formula

The ρ, ρ '' bis-quartp-terphenyammonium salts are

R ¹

wherein R ¹ , R ² , R ^{J stands} for a low molecular weight alkyl radical or ReStCsH ₃ -SO3-

stand and R ² and R ¹ together with the nitrogen atom The preceding claims explain the invention

can form a pyrrolidinium ring and y for bromine 40 training in detail.

Representatives of these substances are:

p.p "-Bis-trimethylammonium-p-terphenyldibenzenesulfonate of the formula

ρ.ρ '' - Bis-diethylmethylammonium-p-lerphenyldibcnzenesulfonate of the formula ^ "SN (C ₂ H ₅ JiCH ₃ · 2 C ₆ H ₅ SO,

CH ₃ IC ₂ Hj) ₂ N ρ.ρ '' - Bis-triithylammonium-p-lerphenyldibcnzenesulfonate of the formula

^^ C _i H _J ) _J ■ 2C ₆ H ₅ SO., Ρ, ρ '' - Bis-triiiihylamTnonium-p-terphenyldibromide of the formula

Κ · _: Η ₅ )., Ν- · / y ■■ ';' / ■ \ / N (C ₂ H,)., · 2 Br p.p'-Uis-dipropylniclhyliiminoniiim-p-terphenyldibcn / olsulfonat of the formcl

CII., (C, II ₇ ) ₂ N

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

CH ₂ -CH ₂ CH ₂ -CH ₂

-2C ₆ H ₅ SO ₃

/ CH ₂ -CH ₂

CH ₂ -CH ₂

CH ₃ CH ₃

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

^ ΓΙ 7 1 ^ Γΐ2 CH ₂ CH ₂ ^ X = ZN = / X = / X CH ₂ -CH ₂ "Χ
ι / CH ₂ -CH ₂

2 C ₆ H ₅ SO ₃

C ₂ H ₅

C ₂ H ₅

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

In animal experiments, the nfcuro 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

H ₃ CO

of the artificial pulmonary ventilation non-toxic. 1 iere tolerate the introduction of dozens and even hundreds of blocking doses of these substances while d-tubocurarine causes the animal to die at a 5 to 10 fold increase in dose in particular For example, the cats can tolerate the introduction of 200 blocking doses of p, p "-bis-triethylammonium-p-terphenyldibenzenesulfonate and -dibromide and only at the 1000 fold increase in dose, one of the three cats walked as a result of a sharp decrease in the arterial blood 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-Dimethyi carbamoyloxyphenylj-trimethylammonium-methylsul- fat (Proserin) or

CH ₃ O

N-CH ₃

HO

- close to or significantly exceeds this.

In contrast to the non-depolarizing muscle relaxant tubokurarine and pyrolaxone (1.2.3-tris / 2- (triäthylammonio) -ethoxy / -benzo! -Triiodide), 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. At the same time, pyrolaxone blocks the vagus nerve ganglia, causing tachycardia. The muscle relaxation caused by d-tubocurarine is accompanied by a decrease in arterial blood pressure, which is due to its ability to isolate histamine from tissues in blocking doses and to block conductivity in sympathetic ganglia. In addition, all substances mentioned, the p, p "-Bisquart.p-terphenylammonium salts, under 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 is easily influenced by the Cholinesterase inhibitors can be eliminated. In addition, they have a higher specific effect than d-tubocurarine. So raised N- (m-dimethylcarbamoyloxyphenyl) -trimethylammonium-methylsulfate in the experiments on cats in a dose of 0.1 mg / kg intravenously

bi quickly and completely blocking the effects of 5 Doses of ρ, ρ '' - bis-triethylammonium-p-terphenyldibenzenesulfonate and -dibromide and only 3 blocking d-tubokurarin doses.

The clinical application of the substances mentioned as Muscle reiaxantia can ensure the implementation of a safe and controllable myorelaxation, The neuromuscular blocking activity of the

Table 1

The ten substances in comparison with d-tubocurarine are shown in Table 1, in which BD-block, dose HDD-HeaU-drop dose mean.

X y Cats
BD in μΜοΙ / kg Effect type Rabbits
HDD in μΜοΙ / kg N (CH ₃ J ₃ C ₆ H ₅ SO ₃ 0.3 ± 0.04 mixed 0.25 ± 0.05 N (C ₂ H ₅ J ₂ CH ₃ C ₆ H ₅ SO ₃ 0.5 ± 0.09 not depolarizing 0.12 ± 0.02 N (C ₂ H ₅ J ₃ C ₆ H ₅ SO ₃ 0.08 ± 0.002 the same 0.022 ± 0.001 N (C ₂ H ₅ J ₃ Br 0.08 ± 0.002 the same 0.022 ± 0.001 N (C ₃ H ₇ J ₂ CH ₃ C ₆ H ₅ SO ₃ 0.5 ± 0.1 the same 0.1 ± 0.03 N (Jh ₂ J ₄ CH ₃
^ H ₂ J ₄ QH ₅ C ₆ H ₅ SO ₃
C ₆ H ₅ SO ₃ 1.0 ± 0.2
0.5 ± 0.08 the same
the same 0.3 ± 0.06
0.14 ± 0.04 d-tubocurarine 0.5 ± 0.02 the same 0.18 ± 0.06

As can be seen from the table, ρ, ρ '' - have bis-triethyiammonium-p-terphenyldibenzenesulfonate and dibromide have the highest blocking activity These compounds exceed d-tubocurarine myoparalytic activity 6 to 8 times

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 the blood pressure Experiments: on cats and rabbits develops only when these substances are increased tenfold weak and short-lasting depressive effect, while after the introduction of the myoparalytic d-tubokurarin dose shows a marked decrease in arterial blood pressure.

As already mentioned, these compounds are under the conditions of artificial lung ventilation non-toxic. They also have a higher specific effect than d-tubokurarine. In particular, d-tubocurarine dissolves in a dose that will block the neuromuscular conduction causes the conduction disorder of the upper neck gonjlion in the cat. The p, p "-Bistriethylammonium-p-terphenyldibenzolsu! Fonat and dibromide produce a weak ganglion-blocking effect only in the dose that is 10 times that neuro-muscle blocking dose exceeds

The cholinesterase inhibitors eliminate the blocking Action of these substances lighter than the action of d-tubokurarine.

In the experiments on decerebred cats, the effect of these compounds was not potentiated and demonstrated by halothane on blood pressure, while d-tubokurarine has the effect of halothane (2-bromo-2-chloro-l.l.l-trifluoroethane) strengthened on the heart; therefore one considers their combined application annually 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.l- (3 ".17 /? - diacetoxy-5" -androstane-2 /?. 16 /? - yIen) -bis (l-methyIpiperidinium 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 pancuronium 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.l- (3 ".17 / S-diacetoxy-5" -androstane-2 / J.l 6jJ-ylen) -bis (1-methylpiperidinium bromide) was the antagonism of the experiments on cats N- (m-Dimethylcarbamoyloxyphenyl) trimethylammonium methyl sulfate less pronounced than with the action of the compound according to the invention. At the 4-bis 5-fold increase in the dose of 1.l- (3 «.17 /? - diacetoxy-5« -androstan-2 / S.16j3-ylene) -bis (l-methylpiperidinium bromide) muscle relaxation began at least 10 minutes after intravenous administration of N-tm-dimethylcarbamoyloxyphenylI-triethylaminemonium methyl sulfate restore at a dose of 0.1 mg / kg. Eliminated under the same conditions N- (m-Dimethylcarbamoyloxyphenyl) -trimethy! - ammonium methyl sulfate in the same dose as the blocking Effect of the substances according to the invention completely after their introduction in the amount that their myoparalytic Dose exceeds a few times. Muscle relaxation began even with a 5-fold increase in the dose of these substances in the range of 5 minutes after N- (m-dimethylcarbamoyloxyphenyl) trimethylammonium methyl sulfate has been stirred in once restore at a dose of 0.1 mg / kg.

This shows that the clinical application of such preparations is safe and adjustable muscle relaxation compared to d-tubocurarine and 1.l- (3 <%. 17 /? - diacetoxy-5 «-androstan-2 / 3.16 /? - ylene) -bis (1-methylpiperidinium bromide) enables.

A great advantage of the proposed according to the invention

O, N-

NO,

[H]

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 salts realized according to the following scheme:

H ₂ N

NH,

R.

Br (CH ₂ UBr

INK,

(Cn ₂ I ₄ N

Γ "

C _n H ₅ SO ₃ R ¹

R, N

2 C ₆ H ₅ SO ₃

2 CH, SO,

McHaI

R, N

NR, 2HaI (CH ₂ I ₄ N R ¹ R ¹

where R and R ¹ door alkyl, Me. door Na. K stands.

The process for the preparation of the p, p "-bis-quart.p-terphenylammonium salts includes the reduction of 5 <p, p "-Dinitro-p-terpheny | to p, p" -Diamino-p-terphenyl, the alkylation of p, p "-diamino-p-terphenyl to p, p" -Bis- (tertamino) -p-terphenyIe by alkyl iodides or tetramethylene dibromide, the quaternization of p, p "-bis (tertamino) -p-terphenyIe with benzenesulfonic acid alkyl esters to p, p "-Bis- (quartammonium) -p-terphenyldibenzenesulfonates and, if necessary, to obtain halogen salts of p, p "-Bis- (quartammonium) -p-terphenylene, The replacement of the benzenesulfonic acid anion in p, p "-bisquaitammonium-p-terphenyldibenzenesulfonates by t> o the halogen ion by means of an inorganic halogen salt a.

The p, p "-dinitro-p-terphenyl is a well known one Substance and is obtained by nitrating p-terphenyl using fuming nitric acid.

The p, p "-dinitro-p-terphenyreduction can be carried out by various methods, e.g. 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 do the p, p "-Dinitropterphenylreduction with hydrazine hydrate in the presence of Raney nickel in an inert organic Solvents, e.g. B. to carry out 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-terphenyI can be carried out with the aid of various alkylating agents. In particular, the alkylation takes place with the aid of the alkyl iodides in the presence of an iodine-binding agent an organic solvent with heating.

The quaternization of p, p "-Bis- (tertamino) -p-terphenylene is carried out in the solution of alkyl benzenesulfonates with warming

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

(quart.ammoriium) -p-terphenylen, the latter are obtained by the action of an inorganic Halogen salt to the aqueous solution of the corresponding p, p "-Bis- (quart.ammonium) -p-terphenyldibenzenesulfonate obtain.

In practice, the procedure is carried out as follows.

The p, p "-Dinitro-p-terphenyl used is in a: with the reflux condenser, thermometer, stirrer and a dropping funnel is placed in the flask, and ethylene glycol and the hydrogenating catalyst are added added and warmed on the oil bath. When the suspension temperature reaches 165 ° C, will hydrazine hydrate was added dropwise with vigorous stirring, avoiding excessive foaming. the Reaction takes a few minutes and everything goes into solution, which is still a few minutes with activated charcoal a temperature of 165 to 180 ° C is heated. Then this is filtered. After the

10

example 1

Production of p, p "-bis-trimethyl
ammonium p-terphenyl dibenzenesulfonate

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

In a three-necked flask from I I equipped with a reflux condenser, stirrer, thermometer and dropping funnel Contents are brought into suspension of 10 g of p, p "-Dinitro-p-terphenyl in 500 ml of ethylene glycol,

in 5 ml of freshly prepared Raney-Nickel are added and then it trickles under stirring and heating (the temperature in the flask is 165 to 17O ⁰ C) 15 ml 99% hydrazine hydrate solution cautiously added, whereby strong foaming is avoided.

Ii for a few minutes everything goes into solution, after which activated carbon is added. After 10 to 15 minutes, the hot solution is filtered off, the filtrate cooled down.

The deposited precipitate is on the filter

iVicuci SCiiiäg Wifu dLHim'fcfi, ιΓιίΐ 2Ct i'i'lii ΛΜΐίυιιυι gcw'äSCiicfi tiiiu gctrOCKnct. ιτιΰΰ 5Γ

washed in absolute alcohol and dried. The p, p "-diamino-p-terphenyl obtained by this process does not need any additional cleaning. Its yield is quantitative.

The p, p "-diamino-p-terphenyl is introduced into the flask equipped with the reflux condenser and stirrer and gives water, an inert organic solvent, calcium carbonate and alkyl iodide or tetramethylene dibromide added. The reaction mixture is heated with stirring for 2 to 4 hours. Already at When heated, the p, p "-Bis- (tert.amino) -p-terpheny! Begins to precipitate, which 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%.

In the flask or in the glass, the corresponding p, p "-Bis- (tert.amino) -p-terphenyl is heated from a few minutes to an hour in the benzene sulphate alkyl ester solution at a temperature of 120 to 200 ° C. At the end of the heating process, it is compressed The solution is cooled. The hardened mass is treated with absolute diethyl ether or with dry acetone and Hpr prhaltpnp Niprfprcrhlajr is crystallized from acetone with water . The yield of p, p "-Bis- (quartammonium) -p-terphenyldibenzenesulfonates is 70 to 80% .

For the preparation of the p, p "- bis (quartammonium) pterphenyl halogen salts p, p "-Bis- (quarummonium) -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 will be Left to stand overnight at room temperature and then cooled. The precipitate it is filtered and crystallized from aqueous acetone. The yield of p, p "-bis (quartammonium) -p-terphenyl halogen salt is quantitative.

The process according to the invention for the production of ρ, ρ "- bis-quartp-terphenylammonium salts consists from three stages that proceed quickly and in high yields. In the synthesis, well-known accessible reagents and solvents are used, the cleaning of the end product does not offer any Trouble. Such a method can be easily realized under the production conditions.

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

8.1 g of flesh-colored p, p "-diamino-p-terphenyl (the yield is quantitative), the melting point is 240 ° C.

p, p

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

1.7 g of p, p "-Diami-

w no-p-terphenyl, 2.2 g calcium carbonate, 75 ml ethylene glycol, 8 ml water and 5 ml methyl iodide.

The suspension is heated to 70 ° C while stirring and, while methyl iodide reacts, the temperature is increased to 100 to 120 ° C. That

J5 heating continues 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 a decomposition point of approx. 250 ° C is a mixture of p, p "-Bis-dimethylamino-p-terphenyl and ρ, ρ "- bis-trimethylammonium-pterphenyldiiodomethylate represent.

c) Quaternization with a
4) methyl benzene sulfate

Put 2 g of des into a 100 ml flask Above-mentioned mixture of p, p "-Bis-dimethylamino-terphenyl and ρ, ρ" -bis-trimethylammonium-p-terphenyldiiodide and heated for 2 hours with 30 ml of methyl benzene sulfate, first at 100 ° C, then at 120 ° C. The resulting solution condenses End of lirheating. After cooling, the hard mass is treated with absolute diethyl ether and filtered off

The precipitate in an 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-ter-

M phenyldibeinzolsulfonate of greenish color melts not up to 300 ° C. It is dried under vacuum and stored in a dark place.

Found in %:

C 65,50,65,57; 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 "-Diethylmet: hyl
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 one equipped with a Rüi-Kfluss condenser and stirrer A 250 ml flask is filled with 8 g of p, p "-diaminopterphenyl, 10 g of 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 ° C. Everything goes into solution for a few minutes and the precipitate begins to form immediately. That Heating is continued for 2 hours with vigorous stirring, after which the suspension is cooled.

The filtered precipitate is crystallized out

I: -ι cc _ / _i: _

r \: * u..ir

LVI! Lll »lllJlllH

: j ι i_ui *

IIICIllllU UIIU CIIIClIl

Yield is 70%) ρ, ρ '' - Bis-diethylamino-p-terphenyl and a light beige color, mp 198 ⁰ C..

Found in %:

C 83.30, 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 ρ, ρ '' - bis-diethylaminop-terphenyl with the methyl benzenesulfonate

1 g of p, p "-Bis-diethylamino-p-terphenyl is placed in a 50 ml flask and heated with it 5 ml of benzenesulfonic acid methyl ester at a bath temperature of 120 ° 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 obtained from 30 ml aqueous acetone (acetone: water 10: 1) crystallized with activated charcoal.

This gives 1.5 e (80%) pp "Bis-Diäthylmethylammonium-p-terpheny! Dibenzoisulfonat of white color, which is somewhat green in air. The decomposition point is 270.5 ⁰ C. The product is dried under vacuum and in a dark place kept.

Found in %:

C 6735, 67.10; H 6.68, 7.05;

S 9.16.9.15; N 3.78, 3.77.

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

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

Example 3

Production of ρ, ρ '' - bis-triäthyIammoniump-terphenyldibenzenesulfonat

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

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

c) Quaternization of ρ, ρ '' - bis-diethyIamino-p-terphenyl with the ethyl benzene sulfate.

In a flask of 100 ml are brought gp 7.5, p '-bis-diethylamino-p-terphenyl and heated with 20 ml Benzolsulfosäureäthylester at a bath temperature of 140 ⁰ C for one hour. The is formed during the first 30 minutes The solution crystallizes out at the end of the heating process

> Reaction mass treated with absolute diethyl ether and filtered.

The precipitate of light beige color is made from 100 ml of aqueous acetone (10: 1) with activated charcoal crystallized. 10g (70%) of p, p "-Bis-triäthylam- are obtained

in monium-p-terphenyldibenzenesulfonate which is white in color and turns slightly green in air. The decomposition point is 228 to 229 ^° C. The product is dried under vacuum and stored in a dark place.

Found in %:
^Π C 67.97, 68.22; 117,76,7,66;

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 S 59 • N 3 76

Example 4

Preparation of p, p "-bis-triethylammonium-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.

jo c) The quaternization of ρ, ρ '' - bis-diethylamino-pterphenyl Example 3 is carried out with the ethyl benzenesulfate.

d) Production of ρ, ρ '' - bis-tnäthylammonium-p-terphenyldibromid from ρ, ρ '' - triethylammonium-p-terphe-

3t nyldibenzenesulfonate.

5 g of ρ, ρ '' - bis-triethylammonium-p-terphenyldibenzenesulfonate are placed in a 250 ml flask equipped with a stirrer one, dissolves in 50 ml of water with gentle warming and is under

4% stirring, 7 g of sodium bromide are added. The solution is for Left to stand for 12 hours at room temperature, then cooled.

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

4.2 g of ρ, ρ "- bis-triethylammonium-p-terphenyldibromide (95%) are obtained which are white in color and turn a little green in air. The decomposition point is 195 to 197 ^° C. The product is dried under vacuum and stored in a dark place.

Found in %:

C 54.25, 54.63; H 7.60, 7.70;
Br 23 ^ 0.24.20; 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

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

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

b) Alkylation of ρ, ρ '' - diamino-p-terphenyl with propyl iodide.

It: one equipped with a reflux condenser and stirrer Flask with a capacity of 50 ml, add 2.1 g ρ, ρ '' - diaminopterphenyl, 2 g calcium carbonate, 25 ml dimethylform-

atfiid, 2.5 ml of water and 7 ml of propyl iodide and heated for 2 hours at a bath temperature of 100 to 120 ⁰ C, then cooled. The deposited precipitate is filtered off and crystallized from 30 ml of dimethylformamide with water (5: 1) with activated charcoal.

2.45 g (70%) ρ, ρ ″ - bis-dipropylamino-pterphenyl are obtained white in color, from m.p. 115 to 116 ° C.

Found in %:

C 84.03, 84.49; H 9.71, 9.57; N 7.03, 6.98.

C ₃₀ H ₄₀ N ₂ .
Calculated in%:

C 84.06; H 9.40; N 6.53.

c) Quaternization of ρ, ρ '' - bis-dipropylamino-p-terphenyl with methyl benzene sulfate.

1 g of p, p "-Bis-dipropylamino-p-terphenyl is placed in a flask with a capacity of 50 ml, while the mixture is heated 15 minutes with 3 ml of benzenesulfonic acid methyl ester at a bath temperature of 12 ° C./minutes 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 of 245 ⁰ C. The product is stored under vacuum and dried in a dark Sielle.

Found in %:

C 6639, 6637; H 7.19, 7.43;

N 3.59, 333; S 8,24,8,19.

C ₄₄ H ₅₆ N 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

The »DorlnLllnn

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%:

0 84.74; H 7.66; N 7.60.

c) Quaternization of p, p "-Gis- (N-pyrrolidiny!) - pterphenyl with methyl benzenesulfate.

1 g of p, p "-Bis- (N-pyrrolidinyl) -p-terphenyl is placed in a flask with a capacity of 50 ml, while the mixture is heated 15 minutes with 10 ml of benzenesulfonic acid methyl ester at a bath temperature of 200 ° C. and cools down immediately. The reaction mixture is treated with absolute ether, the precipitate is filtered off and extracted from 30 ml Acetone with water (10: 1) crystallized with activated charcoal.

1.45 g (76%) of p, p "-Bis- (N-methylpyrrolidinium) -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 dried and stored on a dark slope.

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

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

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

1 g is placed in a 50 ml flask

nn r> n "rVnU-." _ "U"".. I. , ..- A

u \

carried out analogously to Example 1.

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

52 g of p, p "-diamino-p-terphenyl, 4.5 g calcium carbonate, 50 ml dimethylformamide, 5 ml water and 8.6 g 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-pyrrolidinyl) -p-terphenyl crystallized from a large amount of dimethylformamide.

rend 10 minutes 6 ml Benzolsulfosäur 'ethyl ester at a bath temperature of 200 ⁰ C. The cooled reaction mass is treated with dry acetone, the precipitate is filtered and recrystallized from 30 ml of acetone with water (10: 1) was crystallized with charcoal. 1.6 g (80%) of p, p "-Bis- (N-ethylpyrrolidinium) -pterphenyldibenzenesulfonate are obtained which are white in color and turn somewhat green in 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.

C ₂ H ₄₈ N ₂ O ₆ S ₂ . H ₂ O.
Calculated in%:

C 66.47; H 6.64: N 3.69; S 8.43.

Claims (2)

Patent claims: 1. p, p "-bis-quartp-terphenylammonium salts of general formula R ¹ R ² - v_ ^ \ s vih »:. IO 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 CeH ₃ —SO ₃ - 2. Method of making the connection according to Claim 1, characterized in that one initially p, p "-Dinitro-p-terphenyI with hydrazine hydrate in the presence of Raney nickel in a Ethylene glycol solution at temperatures from 165 to 180 ° C, then the p, p "-diaminop-terphenyl obtained with alkyiodides or tetramethylene dibromide in an inert organic solvent with heating for 2 to 5 hours in the presence of a halogen acceptor with addition alkylated by water and the resulting p, p "-Bis- (tertamino) -p-terphenylene in an alkyl benzenesulfonate solution with heating at temperatures of 120 to 200 ° C for 10 minutes to 2 Quaternized hours and optionally treated the p, p "-Bis- (quartammonium) -p-terphenyldibenzenesulfonate obtained with an inorganic bromine & ek