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DE834247C - Process for the preparation of therapeutically effective salts of nicotinic acid - Google Patents

Process for the preparation of therapeutically effective salts of nicotinic acid

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Publication number
DE834247C
DE834247C DEL2882A DEL0002882A DE834247C DE 834247 C DE834247 C DE 834247C DE L2882 A DEL2882 A DE L2882A DE L0002882 A DEL0002882 A DE L0002882A DE 834247 C DE834247 C DE 834247C
Authority
DE
Germany
Prior art keywords
nicotinic acid
salts
preparation
parts
therapeutically effective
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
DEL2882A
Other languages
German (de)
Inventor
Dr Med Alexander Szakall
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aug Luhn & Co GmbH
Original Assignee
Aug Luhn & Co GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aug Luhn & Co GmbH filed Critical Aug Luhn & Co GmbH
Priority to DEL2882A priority Critical patent/DE834247C/en
Application granted granted Critical
Publication of DE834247C publication Critical patent/DE834247C/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D213/00Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79Acids; Esters
    • C07D213/80Acids; Esters in position 3

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

Verfahren zur Herstellung von therapeutisch wirksamen Salzen der Nicotinsäure Salze aus Nicutiiisäurc und stickstoffhaltigen, organischen, basischen Verbindungen, z. B. Piperidin, sind bekannt. Es ist ferner bekannt, daß Nicotinsäure eine erweiternde Wirkung auf die Blutgefälle ausübt. Diese Wirkung ist jedoch sehr vorübergehender Art, da die Nicotinsäure im Körper rasch durch Methylierung oder durch Paarung mit Glykokoll unwirksam gemacht wird. Außerdem führt die cutane Anwendung der Nicotinsäure zii unangenehmen Nebenwirkungen, die sich in Form vom Brennen, Jucken und Rötung ; U ßern. Es wurde nun überraschenderweise gefunden, daß man zu neuen Verbindungen gelangen kann, die die erwähnten unerwünschten Nebenwirkungen der Nikotins:itire nicht oder in nur unerheblichem :Maße besitzen, wenn niair die Nicotinsäure mit antihistaminisch wirksamen, hochmolekularen, organischen, basischen Verbindungen der allgemeinen Formeln worin R, und R2 Aryl- oder Aralkylreste bzw. helerocyclische Reste, R;, und R; Alkyl- oder Cycloalkylreste oder gemeinsam unter Einbeziehung des Stickstoffatoms einen heterocyclischen Rest bedeuten, umsetzt. Ebensogut kann man auch die Salze der Nicotinsäure, z. B. die Alkalisalze, mit den Salzen der erwähnten basischen Verbindungen, z. B. Hydrochloriden, Hydrobromiden oder Sulfaten, zur Umsetzung bringen.Process for the preparation of therapeutically active salts of nicotinic acid Salts from nicutiiic acid and nitrogen-containing, organic, basic compounds, e.g. B. piperidine are known. It is also known that nicotinic acid has a dilating effect on blood gradients. However, this effect is very temporary, as nicotinic acid in the body is quickly rendered ineffective by methylation or by pairing with glycocolla. In addition, the cutaneous application of nicotinic acid leads to unpleasant side effects in the form of burning, itching and reddening ; U uter. It has now been found, surprisingly, that new compounds can be obtained which do not, or only to a negligible extent, have the undesirable side effects of nicotine mentioned, if nicotinic acid is not used with antihistaminic, high molecular weight, organic, basic compounds of the general formulas wherein R, and R2 are aryl or aralkyl radicals or helerocyclic radicals, R ;, and R; Alkyl or cycloalkyl radicals or together with the inclusion of the nitrogen atom mean a heterocyclic radical. The salts of nicotinic acid, e.g. B. the alkali salts, with the salts of the basic compounds mentioned, for. B. hydrochlorides, hydrobromides or sulfates, bring to implementation.

Die Umsetzung selbst kann entweder durch Vereinigen der Komponenten selbst oder aber in geeigneten Lösungsmitteln, z. B. Methanol, Äthanol usw., gegebenenfalls auch in Wasser, durchgeführt werden. '.Ulan erhält die nicotinsauren Salze der erwähnten hochmolekularen, antihistaminisch wirksamen, organischen, basischen Verbindungen häufig in Form öliger oder harziger Produkte, die eine verhältnismäßig geringe Neigung zur Kristallisation aufweisen, insbesondere, solange sie noch SpurenLösungsmittel enthalten. Die kristallisierten Produkte lassen sich durch Umkristallisieren aus geeigneten Lösungsmitteln weiter reinigen.The implementation itself can either be done by combining the components themselves or in suitable solvents, e.g. B. methanol, ethanol, etc., optionally also in water. '.Ulan receives the nicotinic acid salts of the aforementioned high-molecular, antihistaminic, organic, basic compounds often in the form of oily or resinous products that have a relatively low tendency to crystallize, especially as long as they still contain trace solvents contain. The crystallized products can be removed by recrystallization further clean with suitable solvents.

Die auf diese Weise erhaltenen nicotinsauren Salze der erwähnten organischen, basischen Verbindungen stellen therapeutisch wertvolle Produkte dar, die im Gegensatz zur Nicotinsäure eine lang anhaltende Wirksamkeit besitzen und frei von deren unerwünschten Nebenwirkungen sind.The nicotinic acid salts of the mentioned organic, basic compounds represent therapeutically valuable products, which in contrast to nicotinic acid have a long-lasting effectiveness and free from its undesirable Side effects are.

Insbesondere verursachen sie bei cutaner- Anwendung weder Brennen noch Jucken, und selbst die Rötung der Haut wird erheblich herabgesetzt. Als erwünschte Erscheinung rufen sie ein anhaltendes Wärmegefühl hervor. Beispiele i. In einer Lösung von 22,4 Teilen Phenylbenzylaminoäthylen-N-pyrrolidin in 2o Teilen Äthanol löst man unter leichtem Erwärmen 9,8 Teile Nicotinsäure. Nach Abdampfen des Alkohols im Vakuum erhält man das nicotinsaure Salz als Sirupöse Masse, die nach längerem Stehen oder nach Animpfen kristallisiert. Das Salz löst sich leicht in Methanol, Äthanol und heißem Aceton.In particular, they do not cause any burning sensation when used in cutaneous tissue itching, and even the reddening of the skin is considerably reduced. As desired Appearance they evoke a persistent feeling of warmth. Examples i. In a Solution of 22.4 parts of phenylbenzylaminoethylene-N-pyrrolidine in 20 parts of ethanol 9.8 parts of nicotinic acid are dissolved with gentle heating. After the alcohol has evaporated in a vacuum, the nicotinic acid salt is obtained as a syrupy mass, which after a long time Standing or crystallized after inoculation. The salt easily dissolves in methanol, Ethanol and hot acetone.

Das gleiche Salz erhält man, wenn man die genannten Mengen Phenylbenzylaminoäthylen-N-pyrrolidin und Nicotinsäure im Mörser gründlich verreibt. Das Reaktionsprodukt zeichnet sich in diesem Falle durch eine merklich größere Kristallisationsfreudigkeit aus.The same salt is obtained if the stated amounts of phenylbenzylaminoethylene-N-pyrrolidine are used and nicotinic acid thoroughly rubbed in a mortar. The reaction product stands out in this case by a noticeably greater tendency to crystallize.

2. In einer siedenden Lösung von 14,3 Teilen Natriumnicotinat in 35o Teildn Methanol löst man 31,6 Teile Phenyibenzylaminoäthylen-N-pyrroliditihydrochlorid. Man engt auf etwa % ein und filtriert vom ausgeschiedenen Natriumchlorid ab. Aus der Restlösung erhält man durch weiteres Eindampfen das nicotinsaure Salz der erwähnten organischen, basischen Verbindung. 3. In eine Suspension von 13,5 Teilen Nicotinsäure in Zoo Teilen Äthanol trägt man 28,5 Teile Benzyl-a- pyridylaminoäthylendimctliylamin ein. Unter Grün- färbung erfolgt rasche Lösung, die man durch leichtes Erwärmen fördert. Nach Abdampfen des Äthyl- alkohols erhält man das nic@)tinsatirc Salz des Benzyl- a-pyridvlaminoäthvlendimethvIatnins als blaßgrün- liches öl, das nur eine geringe 1"ristallisations- freudigkeit besitzt. 4. Zu 25 Teilen I)imettivlaminc>ätliylbenzhvdry#1- äther gibt man 12,1 Teile Nicotinsäure und erhitzt auf dem Wasserbad bis zur völligen Auflösung der Nicotinsäure. Das derart erhaltene nicotinsaure Salz stellt ein gelbliche: Ö1 dar, dns auch nach Abkühlung in einer Eis-Kochsalz-Mischung nur langsam kristalli- siert. 5. In gleichartiger Weise, wie in Beispiel 4 be- schrieben, stellt man aus 23 Teilen i-Plieriyl-i-a-pyri- dyl-3-dimethylaminopropan und 11,8 Teilen Nicotin- säure das i-Phenvl-i-<c-lwridvl-3-dimetiiv1aminoprt@- pannicotinat dar. Diese ölige -Stihstanz erstarrt nach Abkühlen in einem Eis-hochsa lz-Geinisch oder nach Animpfen allmählich kristallin. - 2. 31.6 parts of phenyibenzylaminoethylene-N-pyrrolidite hydrochloride are dissolved in a boiling solution of 14.3 parts of sodium nicotinate in 35o parts of methanol. It is concentrated to about% and the sodium chloride which has separated out is filtered off. The nicotinic acid salt of the organic, basic compound mentioned is obtained from the residual solution by further evaporation. 3. In a suspension of 13.5 parts of nicotinic acid in zoo parts of ethanol one carries 28.5 parts of benzyl-a- pyridylaminoäthylendimctliylamin a. Under green staining takes place quickly dissolving, which can be achieved by light Warming promotes. After evaporation of the ethyl alcohol you get the nic @) tinsatirc salt of the benzyl a-pyridvlaminoäthvlendimethvIatnins as pale green- lich oil that has only a slight 1 "crystallization owns joy. 4. To 25 parts I) imettivlaminc> ätliylbenzhvdry # 1- ether is added to 12.1 parts of nicotinic acid and heated on the water bath until the complete dissolution of the Nicotinic acid. The nicotinic acid salt thus obtained represents a yellowish: Ö1, even after cooling in an ice-salt mixture only slowly crystallizes sated. 5. In the same way as in Example 4 wrote, one makes from 23 parts i-Plieriyl-ia-pyri- dyl-3-dimethylaminopropane and 11.8 parts of nicotine acid das i-Phenvl-i- <c-lwridvl-3-dimetiiv1aminoprt @ - pannicotinate. This oily -Stihstanz solidifies afterwards Cool down in an ice cream dish or after Inoculation gradually crystalline. -

Claims (1)

PATESTANSPRI-C;I1: Verfahren zur Her:tellting von therapeutisch wertvollen Salzen der \ic@>tinsäure durch Um- setzen der letzteren mit stickstoffhaltigen, orga- nischen Basen, dadurch gekennzeichnet, daß man Nicotinsäure oder deren Salze mit antihistaminisch wirksamen, hochmolekularen, stickstoffhaltigen, organischen Basen der allgemeinen Formeln
worin R1 und R2 Aryl- oder Aralkylreste bzw. heterocyclische Reste, R.3 lind R, Alkyl- oder Cycloalkylreste oder geneinsam unter Einbe- ziehung des Stickstoffatoms einen lieterocvclicclien Rest bedeuten, oder mit deren Salzen umsetzt.
Angezogene Druckschriften: Chem. Zentralbl. 1898, I, 678.
PATEST APPLICATION-C; I1: Process for the manufacture of therapeutic valuable salts of \ ic @> tinic acid through conversion put the latter with nitrogen-containing, organic niche bases, characterized in that one Nicotinic acid or its salts with antihistamine effective, high molecular weight, nitrogenous, organic bases of the general formulas
wherein R1 and R2 are aryl or aralkyl radicals or heterocyclic radicals, R.3 and R, alkyl or Cycloalkyl radicals or together, including drawing of the nitrogen atom a lieterocvclien Mean remainder, or reacts with their salts.
Cited publications: Chem. Zentralbl. 1898, I, 678.
DEL2882A 1950-06-29 1950-06-29 Process for the preparation of therapeutically effective salts of nicotinic acid Expired DE834247C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEL2882A DE834247C (en) 1950-06-29 1950-06-29 Process for the preparation of therapeutically effective salts of nicotinic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEL2882A DE834247C (en) 1950-06-29 1950-06-29 Process for the preparation of therapeutically effective salts of nicotinic acid

Publications (1)

Publication Number Publication Date
DE834247C true DE834247C (en) 1952-03-17

Family

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Family Applications (1)

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DEL2882A Expired DE834247C (en) 1950-06-29 1950-06-29 Process for the preparation of therapeutically effective salts of nicotinic acid

Country Status (1)

Country Link
DE (1) DE834247C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1227459B (en) * 1962-12-14 1966-10-27 Biochemie Gmbh Process for the preparation of a new salt of nicotinic acid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1227459B (en) * 1962-12-14 1966-10-27 Biochemie Gmbh Process for the preparation of a new salt of nicotinic acid

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