CH153379A - Method for the preparation of nitro-B-oxy-a picolin. - Google Patents
Method for the preparation of nitro-B-oxy-a picolin.Info
- Publication number
- CH153379A CH153379A CH153379DA CH153379A CH 153379 A CH153379 A CH 153379A CH 153379D A CH153379D A CH 153379DA CH 153379 A CH153379 A CH 153379A
- Authority
- CH
- Switzerland
- Prior art keywords
- oxy
- nitro
- picolin
- nitration
- preparation
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title claims description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 title 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000006396 nitration reaction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000000802 nitrating effect Effects 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 4
- 229910017604 nitric acid Inorganic materials 0.000 claims 2
- 239000000243 solution Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000974482 Aricia saepiolus Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- -1 nitro- Chemical class 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Darstellung von- Ntro-ss-oxy.a.pfeolin: Gegenstand des Hauptpatentes ist ein Ver fahren zur Darstellung von Nitro-p-oxypyridir), das dadurch gekennzeichnet.- ist, dass man ss Oxypyridin in schwefelsaurer Lösung der Ein wirkung eines Nitriermittels unterwirft.
Es wurde nun gefunden, dass auch ss-Oxy- a-picolin in analoger Weise in Nitro-ss-oxy- a-picolin überführt werden kann. Das Nitro- fl-oxy-a-picolin ist bisher nicht bekannt ge wesen. Es soll zur Herstellung von Farb stoffen und Arzneimitteln Verwendung finden. Es bildet schwach gelbe Kristalle vom Schmelz punkt 107-108 und ist in kochendem Was ser, sowie in warmem Alkohol und Benzol, leicht löslich.
<I>Beispiele:</I> 1. In 700 cm3 konzentrierter Schwefel säure werden unter Kühlung mit einer Kälte mischung 109 gr P-Oxy-a-picolin (= 1 lYIol) bei -5 o eingetragen; darauf lässt man 235 gr 30 /oige Nitriersäure im Laufe einer Stunde bei -5 o zutropfen und rührt dann '/s Stunde bei 0 nach. Es wird dann in Eis gerührt, wobei das Nitro-ss-oxy-a-picolin sich sofort fast völlig in schwach gelben Kristallen ab scheidet.
Ein kleiner Teil kann noch aus der Mutterlauge durch Neutralisieren mit Natron lauge gewonnen werden.
Die Ausbeute ist nahezu quantitativ. Das Nitro-p-oxy-a-picolin ist sehr schwer in kaltem Wasser, leicht in kochendem Was ser löslich mit stark saurer Reaktion; in Sodalösung ist die Substanz kalt leicht lös lich mit rotgelber Farbe. In Alkohol ist die Substanz leiht löslich in der Wärme, sie kristallisiert in der Kälte wieder aus, ebenso ist das Verhalten gegen Benzol. Die Löslich keit in Äther ist gering. Der Schmelzpunkt liegt bei 107-108 Durch Reduktion lässt sich leicht ein schön kristallisierendes Amido-@-oxy-a-picolin vom Festigkeitspunkt 153 gewinnen. Dasselbe ist leicht löslich in Wasser wie Alkohol, ziemlich schwer löslich in Äther, wie in Benzol.
Kochsalz fällt es aus wässeriger Lösung aus. Das Amido-R-oxy-a-picolin kuppelt gut mit Diazolösungen und lässt sich selbst gut diazo- tieren. Die wässerige Lösung reduziert ammoniakalische Silberlösung. Mit Eisenchlo rid entsteht eine grünlichblaue Färbung.
2. Arbeitet man ebenso wie in Beispiel 1, führt aber die Nitrierung bei<B>500</B> durch; so erhält man dasselbe Nitro-19-oxy-a-picolin mit ebenso guter Ausbeute.
Wird die Nitrierung des P-Oxy-a-picolins bei 10"0 0 ausgeführt, so wird dasselbe Nitro- ,Q-oxy-a-picolin in einer Ausbeute von 25 % der Theorie erhalten.
3. Ersetzt man in Beispiel 1 die 235 gr 30 %ige Nitriersäure durch 80 gr 88 %ige Nitriersäure, so wird derselbe Nitrokörper in gleich guter Ausbeute erhalten.
4. In eine Lösung von 27 gr P-Oxy-a- picolin in 200 cms konzentrierter Schwefel säure werden unter Kühlung bei -50 35 gr gepulvertes Kaliumrritrat langsam eingetragen und '/2 Stunde bei 0 0 nachgerührt. Bei glei cher Aufarbeitung wie in Beispiel 1 erhält man 19 gr# Nitro-p-oxy-a-picolin (Fp. 1070) = 50 % der Theorie.
Process for the preparation of- Ntro-ss-oxy.a.pfeolin: The subject of the main patent is a process for the preparation of nitro-p-oxypyridir), which is characterized in that one ss oxypyridine in a sulfuric acid solution has the effect of a Nitrating agent.
It has now been found that ss-oxy-a-picolin can also be converted into nitro-ss-oxy-a-picolin in an analogous manner. The nitro-fl-oxy-a-picoline has not yet been known. It is to be used for the production of dyes and drugs. It forms pale yellow crystals with a melting point of 107-108 and is easily soluble in boiling water as well as in warm alcohol and benzene.
<I> Examples: </I> 1. 109 grams of P-Oxy-a-picoline (= 1 lYIol) at -5 o are added to 700 cm3 of concentrated sulfuric acid while cooling with a cold mixture; 235 g of 30% nitrating acid are then added dropwise over the course of an hour at -5 ° and the mixture is then subsequently stirred at 0 for 1 second. It is then stirred in ice, the nitro-ss-oxy-a-picoline immediately separating out almost completely in pale yellow crystals.
A small part can still be obtained from the mother liquor by neutralizing it with caustic soda.
The yield is almost quantitative. The nitro-p-oxy-a-picoline is very difficult to dissolve in cold water, easily in boiling water with a strongly acidic reaction; In soda solution the substance is easily soluble in cold water with a red-yellow color. In alcohol, the substance is soluble in heat, it crystallizes out again in the cold, and the same is true of benzene. The solubility in ether is low. The melting point is 107-108. A nicely crystallizing amido - @ - oxy-a-picoline with a strength point of 153 can easily be obtained by reduction. It is easily soluble in water, like alcohol, and rather poorly soluble in ether, like benzene.
Table salt precipitates from aqueous solution. The amido-R-oxy-a-picoline couples well with diazo solutions and can be diazo- tated well itself. The aqueous solution reduces ammoniacal silver solution. With iron chloride a greenish-blue color develops.
2. If you work in the same way as in Example 1, but carry out the nitration at <B> 500 </B>; the same nitro-19-oxy-a-picoline is obtained in an equally good yield.
If the nitration of P-oxy-a-picoline is carried out at 10 "0 0, the same nitro-, Q-oxy-a-picoline is obtained in a yield of 25% of theory.
3. If the 235 g 30% nitrating acid is replaced by 80 g 88% nitrating acid in Example 1, the same nitro body is obtained in an equally good yield.
4. 35 g of powdered potassium nitrate are slowly added to a solution of 27 g of P-oxy-apicolin in 200 cms of concentrated sulfuric acid with cooling at -50 and the mixture is subsequently stirred at 0 0 for 1/2 hour. With the same work-up as in Example 1, 19 g # nitro-p-oxy-a-picoline (melting point 1070) = 50% of theory.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE153379X | 1929-11-07 | ||
| CH151323T | 1930-11-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH153379A true CH153379A (en) | 1932-03-15 |
Family
ID=25715781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH153379D CH153379A (en) | 1929-11-07 | 1930-11-04 | Method for the preparation of nitro-B-oxy-a picolin. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH153379A (en) |
-
1930
- 1930-11-04 CH CH153379D patent/CH153379A/en unknown
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