DE904534C - Process for the preparation of nicotinic acid ester nitrates - Google Patents
Process for the preparation of nicotinic acid ester nitratesInfo
- Publication number
- DE904534C DE904534C DET4800A DET0004800A DE904534C DE 904534 C DE904534 C DE 904534C DE T4800 A DET4800 A DE T4800A DE T0004800 A DET0004800 A DE T0004800A DE 904534 C DE904534 C DE 904534C
- Authority
- DE
- Germany
- Prior art keywords
- nicotinic acid
- preparation
- nitrates
- acid ester
- nitric acid
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic 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
- C07D213/02—Heterocyclic 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
- C07D213/04—Heterocyclic 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
- C07D213/60—Heterocyclic 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Description
Verfahren zur Herstellung von Nicotinsäureesternitraten Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Nitraten der ß-Pyridincarbonsäureester der allgemeinen Formel in der R ein Alkylrest mit mehr als 3 C-Atomen oder ein Aryl-, Aralkyl- oder Aralkenylrest ist.Process for the preparation of nicotinic acid ester nitrates The invention relates to a process for the preparation of nitrates of the β-pyridine carboxylic acid esters of the general formula in which R is an alkyl radical with more than 3 carbon atoms or an aryl, aralkyl or aralkenyl radical.
In der Literatur ist bisher nur das Nitrat des N icotinsäureäthylesters beschrieben worden (P i c t e t , S u s s -dorff, C. 1898, I, 677).In the literature so far only the nitrate of the ethyl nicotinate has been found (P i c t e t, S u s s -dorff, C. 1898, I, 677).
Es wurde nun gefunden, daB Ester, die von der Nicotinsäure und Alkoholen der Formel H 0 - C H2 - R, wobei R die oben bezeichnete Bedeutung hat, abgeleitet sind, entweder in Substanz oder in ihren Lösungen durch Zugabe der äquivalenten Menge Salpetersäure leicht, rasch und quantitativ in die Nitrate übergeführt werden. Diese Nitrate sind in den meisten organischen Lösungsmitteln und Wasser, im Gegensatz zu den Salzen der übrigen Mineralsäuren, schwer löslich und fallen im allgemeinen in gut kristallisierter Form aus.It has now been found that esters derived from nicotinic acid and alcohols of the formula H 0 - C H2 - R, where R has the meaning given above, either in substance or in their solutions by adding the equivalent amount of nitric acid, quickly and quantitatively converted into the nitrates. In contrast to the salts of the other mineral acids, these nitrates are sparingly soluble in most organic solvents and water and generally precipitate in a well-crystallized form.
Die Überführung in die kristallisierten Nitrate wird mit Vorteil zur Reinigung oder Isolierung von Nicotinsäureestern aus Reaktionsgemischen verwendet. Auf diese Weise lassen sich auch Nicotinsäureester in guter Ausbeute gewinnen, die sich beim Abdestillieren aus dem Veresterungsgemisch teilweise zersetzen, wie z. B. der Benzylester.The conversion into the crystallized nitrates is advantageous for Purification or isolation of nicotinic acid esters from reaction mixtures is used. In this way, nicotinic acid esters can also be obtained in good yield partially decompose when distilling off from the esterification mixture, such as, for. B. the benzyl ester.
Aus den Nitraten lassen sich die Ester durch Behandlung mit Alkalien oder starken organischen Basen wieder in Freiheit setzen. Ferner wurde gefunden, daß die Nitrate die gleichen physiologischen Wirkungen zeigen wie die Ester selbst. Beispiel 1 Zo,o g Nicotinsäurehexylester werden mit 3o cm3 Essigester verdünnt und eisgekühlt. Hierauf werden unter Schütteln 4,86 cm3 Salpetersäure (62,4gewichtsprozentig) hinzugegeben.The esters can be obtained from the nitrates by treatment with alkalis or release strong organic bases again. Further the nitrates were found to have the same physiological effects as the esters themselves. Example 1 10.0 g of hexyl nicotinate are mixed with 30 cm3 of ethyl acetate diluted and chilled. Then 4.86 cm3 of nitric acid (62.4 percent by weight) added.
Nach kurzem Reiben an der Glaswand fallen reinweiße Kristalle von Nicotinsäurehexylester-nitrat aus. F.72°.After a short rubbing on the glass wall, pure white crystals fall off Nicotinic acid hexyl ester nitrate. F. 72 °.
Beispiel 2 15,o g Nicotinsäureoctylester werden mit 45 cm3 Essigester verdünnt und eisgekühlt. Die eisgekühlte Lösung wird unter Schütteln mit 5,69 cm 362,4gewichtsprozentiger Salpetersäure versetzt und durch Reiben mit dem Glasstab zur Kristallisation gebracht. Nach einigen Minuten wird abgesaugt, mit wenig eiskaltem Essigester nachgewaschen und bei etwa 6o° getrocknet.Example 2 15, above-mentioned octyl nicotinate are diluted with 45 cm 3 of ethyl acetate and ice-cooled. The ice-cold solution is mixed with 5.69 cm of 362.4 percent strength by weight nitric acid with shaking and crystallized by rubbing with the glass rod. After a few minutes, it is suctioned off, washed with a little ice-cold ethyl acetate and dried at about 60 °.
Weiße Kristalle von Nicotinsäureoctylester-nitrat. F. 82°.White crystals of octyl nicotinate nitrate. F. 82 °.
Beispiel 3 lo,o g Nicotinsäurebenzylester werden in 3o cm3 Essigester gelöst und unter Kühlen und Schütteln mit 3,4 cm3 62,4prozentiger Salpetersäure versetzt. Das ausgeschiedene Kristallisat wird abgesaugt, mit wenig eisgekühltem Essigester gewaschen und bei etwa 8o° getrocknet.Example 3 Lo, o g of benzyl nicotinate are dissolved in 3o cm3 of ethyl acetate dissolved and while cooling and shaking with 3.4 cm3 of 62.4 percent nitric acid offset. The precipitated crystals are filtered off with suction, with a little ice-cold Washed ethyl acetate and dried at about 8o °.
Weiße Blättchen von Nicotinsäurebenzylester-nitrat. F. 122 bis 123°.White flakes of benzyl nicotinate nitrate. 122 to 123 °.
Beispiel 4 lo,o g Nicotinsäurebenzylester werden unter Rühren in eine abgekühlte Lösung von 3,4 cm3 62,4prozentiger Salpetersäure in 15 cm3 Wasser gegossen. Hierbei fallen bald Kristalle aus, die sich zu einem Brei verdichten. Nach Absaugen und Waschen mit kaltem Wasser wird am besten im Vakuum getrocknet.Example 4 lo, o g nicotinic acid benzyl ester are stirred into a The cooled solution of 3.4 cm3 of 62.4 percent nitric acid is poured into 15 cm3 of water. Crystals soon precipitate and condense into a paste. After suction and washing with cold water is best dried in a vacuum.
Nicotinsäurebenzylester-nitrat. F. 122 bis 123°. Beispiel 5 5,oo g Nicotinsäure ß-phenäthylester werden in 15 cm3 Essigester gelöst und unter Umschütteln und Eiskühlung mit 1,30 cm3 Salpetersäure (62,4gewichtsprozentig) versetzt. Es fallen sofort schöne weiße Kristalle aus, die abgesaugt und mit etwas Essigester gewaschen werden.Benzyl nicotinate nitrate. 122 to 123 °. EXAMPLE 5 5, oo g of β-phenethyl nicotinate are dissolved in 15 cm 3 of ethyl acetate and 1.30 cm 3 of nitric acid (62.4 percent by weight) are added while shaking and cooling with ice. Beautiful white crystals immediately precipitate, which are filtered off with suction and washed with a little ethyl acetate.
Nicotinsäure-ß-phenäthylester-nitrat. F. Z37°. Beispiel 6 6,Z7 g Nicotinsäurecinnamylester werden in 2o cm3 Äther gelöst, und unter Umschütteln und Eiskühlung werden 1,74 cm3 Salpetersäure (62,4gewichtsprozentig) zugegeben. Nach einigen Minuten wird abgesaugt, mit Äther nachgewaschen und bei 5o bis 6o" getrocknet.Nicotinic acid-ß-phenethyl ester nitrate. F. Z37 °. Example 6 6, Z7 g of cinnamyl nicotinate are dissolved in 20 cm3 of ether, and while shaking and cooling with ice they become 1.74 cm3 of nitric acid (62.4 percent by weight) was added. After a few minutes the suction is performed, washed with ether and dried at 5o to 6o ".
Kristalle von Nicotinsäurecinnamylester-nitrat. F.117° (Zers.).Crystals of cinnamyl nicotinate nitrate. 117 ° (dec.).
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DET4800A DE904534C (en) | 1951-09-04 | 1951-09-04 | Process for the preparation of nicotinic acid ester nitrates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DET4800A DE904534C (en) | 1951-09-04 | 1951-09-04 | Process for the preparation of nicotinic acid ester nitrates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE904534C true DE904534C (en) | 1954-02-18 |
Family
ID=7544778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DET4800A Expired DE904534C (en) | 1951-09-04 | 1951-09-04 | Process for the preparation of nicotinic acid ester nitrates |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE904534C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3092634A (en) * | 1959-08-24 | 1963-06-04 | Synergistics Inc | Novel [nitric acid ester] derivatives of nicotinic acid |
| US3168438A (en) * | 1962-08-09 | 1965-02-02 | Synergistics Inc | Vasodilation by nitric acid ester derivatives of nicotinic acid |
-
1951
- 1951-09-04 DE DET4800A patent/DE904534C/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3092634A (en) * | 1959-08-24 | 1963-06-04 | Synergistics Inc | Novel [nitric acid ester] derivatives of nicotinic acid |
| US3168438A (en) * | 1962-08-09 | 1965-02-02 | Synergistics Inc | Vasodilation by nitric acid ester derivatives of nicotinic acid |
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