CH311202A - Process for the preparation of a pyridyl-oxy-methanesulfonic acid. - Google Patents
Process for the preparation of a pyridyl-oxy-methanesulfonic acid.Info
- Publication number
- CH311202A CH311202A CH311202DA CH311202A CH 311202 A CH311202 A CH 311202A CH 311202D A CH311202D A CH 311202DA CH 311202 A CH311202 A CH 311202A
- Authority
- CH
- Switzerland
- Prior art keywords
- pyridine
- oxy
- aldehyde
- acid
- pyridyl
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Substances CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 title description 2
- 229940098779 methanesulfonic acid Drugs 0.000 title description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 11
- BGUWFUQJCDRPTL-UHFFFAOYSA-N pyridine-4-carbaldehyde Chemical compound O=CC1=CC=NC=C1 BGUWFUQJCDRPTL-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- -1 alkaline earth metal bisulfite compound Chemical class 0.000 claims description 6
- ZOJWIGAVBHJWTK-UHFFFAOYSA-N C1=CN=CC=C1OCS(=O)(=O)O Chemical compound C1=CN=CC=C1OCS(=O)(=O)O ZOJWIGAVBHJWTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 2
- 230000001419 dependent effect Effects 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical class [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- TVCJRTUEWOYYHC-UHFFFAOYSA-M sodium;benzaldehyde;hydrogen sulfite Chemical compound [Na+].OS([O-])=O.O=CC1=CC=CC=C1 TVCJRTUEWOYYHC-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
Description
Verfahren zur Herstellung einer Pyridyl-oxy-methansulfonsäure. Natriumbisulfitverbindungen der Alde hyde, hergestellt aus Natriumbisulfit und Al dehy d, sind allgemein bekannt und werden in Wissenschaft und Technik zur Isolierung und Reinigung der Aldehyde verwendet. Mit freier Schwefliger Säure reagieren die aromatischen Aldehyde, z. B. der Benzaldehyd, nicht.
Des gleichen ist die freie Oxysulfomäure des Ben- ;aldehyds, die aus Benzaldehydbisulfitnatrium furch Ansäuern entstehen sollte, unbeständig und deshalb unbekannt.
Es wurde nun gefunden, da.ss im Gegen 3atz hierzu die Pyridinaldehyde mit freier schwefliger Säure Verbindungen - nämlich Sie freien Oxysulfonsäuren - geben. Diese Sind in Wasser schwer löslich und eignen sieh
EMI0001.0021
In dieser Verbindung liegt. der Pyridin-4- aldehyd in einem recht beständigen Derivat vor.
Mit Alkali erhält man die Natriumbisulfit- verbindimg des Pyridin-4-ald-ehyds, die in Wasser leicht löslich und für die üblichen Reaktionen verwendbar ist.
Aus dieser Na- triumbisulfitverbind2mg lässt sich die freie vorzüglich zur Isolierung und Reinigung der Pyridinaldehyde. Aus verdünnten, wässrigen Lösungen, mit etwa 5 % Gehalt an Pyridin- aldehyd, wie sie nach dem Schweizer Patent Nr.304383 anfallen,
lassen sich durch Ein leiten von Schwefeldioxyd die festen Addi tionsverbindungen in sehr guter Ausbeute ge winnen und somit von etwa überschüssigen Pyridinbasen trennen, da die schwefligsauren Pyridinbasen in Wasser leicht löslich sind.
Gegenstand des vorliegenden Patentes ist. ein Verfahren zur Herstellung der 4-Pyridyl- oxy-methansWfonsäure. Diese neue Verbin dung hat die Summenformel C6H704NS und die Strukturformel Oxysulfonsäure durch Zusatz von Mineral säuren oder auch schwachen organischen Säu ren, wie Essig- oder Zitronensäure, wieder fällen.
Ähnlich verhalten sich die Erdalkali- bisulfit-Verbindungen. Aus der freien Oxy- sulfonsäure kann. nach Zugabe von nicht zu verdünnten Mineralsäuren, beispielsweise 30o/oiger Schwefelsäure oder konzentrierter Salzsäure, das Schwefeldioxyd bei gewöhnli chem Druck, besser im Vakuum abgedampft und somit der Pyridinaldehyd wiedergewon nen werden,
während in verdünnten Säuren die Pyridyl-oxy -methansulfonsätire erhalten bleibt. Demgemäss lässt sich auch aiis schwach sauren Lösungen oder aus Lösungen von sau ren Salzen des Pyridin-4-aldehyds durch Be handeln mit schwefliger Säure das neue Pro dukt erhalten. Auch bei Gegenwart von or ga- nischen Lösungsmitteln entsteht die neue Ver bindung nahezu quantitativ, sofern mindestens molare Mengen Wasser, in bezug auf den Aldehyd, vorhanden sind.
Die 4-Pyridyl-oxy-methansulfonsäure ist eine feste, farblose, kristallisierte Substanz, leicht sublimierbar, die im geschlossenen Sehmelzpunktsröhrehen bei etwa 243 C schmilzt. Im Gegensatz zu dem freien Pyridin- 4-a-Idehyd ist die 4-Pyridyl-oxy-methansulfon- säure nicht autoxydabel, also stabil und kann an Stelle des freien Pyrid'in-4-aldehyds zu Synthesen aller Art, insbesondere von phar mazeutischen Produkten,
benutzt werden. Beispiel <I>1:</I> In eine etwa 5 % ige wässrige Lösung des Pyridin-4-a.ldehyds, wie sie bei der Oxydation von y-Picolin nach den Angaben in der Schweiz. Patentschrift Nr. 304383 in guter Ausbeute anfällt, leitet. man Schwefeldioxyd ein. Es fällt die reine 4-Pyridyl-oxy-methan- sulfonsäure aus.
Beispiel <I>2:</I> In eine alkoholische oder benzolische Lö sung des Pyridin-4-aldehyds wird in Gegen wart von molaren Mengen Wasser Schwefel dioxyd eingeleitet. In nahezu quantitativer Ausbeute entsteht die 4-Pyiidyl-oxy-methan- sulfonsäure.
Beispiel <I>3:</I> 14,3g des salzsauren Salzes von Pyridin- 4-aldehyd werden in 35 cm3 Wasser gelöst und unter Kühlung mit Eiswasser wird S02 bis zur Sättigung eingeleitet. Die ausgeschie dene 4-Pyridyl-oxy-metha.nsulfonsäure wird abgesaugt und wiegt nach dem Trocknen 16,2 g.
<I>Beispiel</I> 0,1 Mol 4-pyi-idyl-oxy -methansulfonsaures Natrium oder Kalzium wird in 30 em3 Wasser aufgeschlämmt bzw. gelöst. Durch Zusatz von 20,5 cm3 5n-Salzsäure entsteht, eine klare Lö sung, die nach Schwefeldioxyd und Pyridinal- dehyd riecht. Nach einigen Minuten beginnt die Kristallisation der freien 4-Pyridyl-oxy- metha.nsulfonsäure. Nach etwa 15 Minuten ist die Kristallisation beendet.
Die Ausbeute be- trägt 80-90% der Theorie.
Process for the preparation of a pyridyl-oxy-methanesulfonic acid. Sodium bisulfite compounds of aldehydes, produced from sodium bisulfite and aldehydes, are generally known and are used in science and technology for the isolation and purification of aldehydes. The aromatic aldehydes react with free sulphurous acid, e.g. B. benzaldehyde, not.
Likewise, the free oxysulfomic acid of benaldehyde, which should arise from benzaldehyde bisulfite sodium by acidification, is unstable and therefore unknown.
It has now been found that, in contrast to this, the pyridine aldehydes give compounds with free sulphurous acid - namely they give free oxysulphonic acids. These are sparingly soluble in water and see
EMI0001.0021
In this connection lies. the pyridine-4-aldehyde in a fairly stable derivative.
With alkali, the sodium bisulfite compound of pyridine-4-aldehyde is obtained, which is easily soluble in water and can be used for the usual reactions.
From this sodium bisulfite compound, the free one can be used for the isolation and purification of pyridine aldehydes. From dilute, aqueous solutions with about 5% pyridine aldehyde content, as accrued according to Swiss Patent No.304383,
the solid addition compounds can be obtained in very good yield by introducing sulfur dioxide and thus separated from any excess pyridine bases, since the sulfurous pyridine bases are easily soluble in water.
The subject of the present patent is. a process for the preparation of 4-pyridyl oxy-methanesulfonic acid. This new compound has the empirical formula C6H704NS and the structural formula oxysulfonic acid by adding mineral acids or weak organic acids such as acetic or citric acid.
The alkaline earth bisulfite compounds behave similarly. From the free oxysulfonic acid can. After adding mineral acids that are not too dilute, for example 30% sulfuric acid or concentrated hydrochloric acid, the sulfur dioxide can be evaporated at normal pressure, better in a vacuum and thus the pyridine aldehyde can be recovered,
while in dilute acids the pyridyl-oxy-methanesulfonate is retained. Accordingly, the new product can also be obtained from weakly acidic solutions or from solutions of acidic salts of pyridine-4-aldehyde by treating with sulphurous acid. Even in the presence of organic solvents, the new compound is formed almost quantitatively, provided that at least molar amounts of water are present in relation to the aldehyde.
The 4-pyridyl-oxy-methanesulphonic acid is a solid, colorless, crystallized substance, easily sublimable, which melts at about 243 C in a closed Sehmelpfelzenröhen. In contrast to the free pyridine-4-a-idehyde, 4-pyridyl-oxy-methanesulphonic acid is not autoxidizable, i.e. stable, and can be used in place of the free pyridine-4-aldehyde in all kinds of syntheses, especially pharmaceuticals Products,
to be used. Example <I> 1: </I> In an approximately 5% aqueous solution of pyridine-4-aldehyde, as used in the oxidation of γ-picoline according to the information in Switzerland. No. 304383 is obtained in good yield. one sulfur dioxide. The pure 4-pyridyl-oxy-methanesulfonic acid precipitates out.
Example <I> 2: </I> In the presence of molar amounts of water, sulfur dioxide is introduced into an alcoholic or benzene solution of the pyridine-4-aldehyde. 4-Pyiidyl-oxy-methanesulphonic acid is produced in almost quantitative yield.
Example <I> 3: </I> 14.3 g of the hydrochloric acid salt of pyridine-4-aldehyde are dissolved in 35 cm3 of water and, while cooling with ice water, SO2 is passed in until it is saturated. The excreted 4-pyridyl-oxy-metha.nsulfonic acid is filtered off with suction and weighs 16.2 g after drying.
<I> Example </I> 0.1 mol of 4-pyi-idyl-oxy-methanesulphonic acid sodium or calcium is suspended or dissolved in 30 cubic meters of water. The addition of 20.5 cm3 of 5N hydrochloric acid creates a clear solution that smells of sulfur dioxide and pyridine aldehyde. After a few minutes, the free 4-pyridyl-oxy-metha.nsulfonic acid begins to crystallize. The crystallization is complete after about 15 minutes.
The yield is 80-90% of theory.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE311202X | 1951-03-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH311202A true CH311202A (en) | 1955-11-30 |
Family
ID=6128399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH311202D CH311202A (en) | 1951-03-12 | 1952-01-26 | Process for the preparation of a pyridyl-oxy-methanesulfonic acid. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH311202A (en) |
-
1952
- 1952-01-26 CH CH311202D patent/CH311202A/en unknown
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