DE114839C - - Google Patents
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- Publication number
- DE114839C DE114839C DENDAT114839D DE114839DA DE114839C DE 114839 C DE114839 C DE 114839C DE NDAT114839 D DENDAT114839 D DE NDAT114839D DE 114839D A DE114839D A DE 114839DA DE 114839 C DE114839 C DE 114839C
- Authority
- DE
- Germany
- Prior art keywords
- nitrotoluene
- alkali
- anthranilic acid
- expediently
- act
- 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.)
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- RWZYAGGXGHYGMB-UHFFFAOYSA-N Anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 11
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-Nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- -1 Sulfur ammonium Chemical compound 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000003638 reducing agent Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 230000001476 alcoholic Effects 0.000 description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P Ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 241000272525 Anas platyrhynchos Species 0.000 description 1
- 102100013068 CDCA4 Human genes 0.000 description 1
- 101700022879 CDCA4 Proteins 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L Potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L Potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 239000004285 Potassium sulphite Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N n-pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- IZJVVXCHJIQVOL-UHFFFAOYSA-N nitro(phenyl)methanesulfonic acid Chemical compound OS(=O)(=O)C([N+]([O-])=O)C1=CC=CC=C1 IZJVVXCHJIQVOL-UHFFFAOYSA-N 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 239000001120 potassium sulphate Substances 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Nach den Untersuchungen von Hay duck (Ann. 172, S. 208) wird durch Schmelzen von Amidotoluolsulfosäure mit Aetzkali auffallenderweise nicht nur die Sulfogruppe unter Ersatz durch Wasserstoff eliminirt, sondern aufserdem das Methyl oxydirt, so dafs man Anthranilsäure enthält. Gemäfs der Gleichung:According to the research by Hay duck (Ann. 172, p. 208) is remarkable by melting amidotoluene sulfonic acid with caustic potash not only is the sulfo group eliminated with replacement by hydrogen, but also the methyl oxidizes so that one contains anthranilic acid. According to the equation:
C H3 CH 3
SOBHSO W H
+ 2,KOH = ,COOK+ 2, KOH = ,COOK
+ K2SO1 +6H+ K 2 SO 1 + 6H
werden bei dieser Reaction 6 Wasserstoffatome frei, die in statu nascendi einen Theil des Kaliumsulfats zu Kaliumsulfit reduciren. Es lag nun der Gedanke nahe, sich die freiwerdenden sechs Wasserstoffatome in der Weise dienstbar zu machen, dafs man an Stelle der Amidotoluolsulfosäure die Nitrotoluolsulfosäure in Anwendung bringt, die zur Reduction ihrer Nitrogruppe genau sechs Wasserstoffatome benöthigt. Den Arbeiten von Fischer und Hepp (Berichte XXVI, S. 2233) und Bender und Schulz (Berichte XIX, S. 3235) zufolge findet jedoch bei Anwendung von ρ-Nitrotoluolsulfosäure eine Abspaltung der Sulfogruppe nicht statt, und ebenso schreitet die Oxydation der Methylgruppe nicht bis zum Carboxyl fort.In this reaction 6 hydrogen atoms are released, which in statu nascendi a part of the Reduce potassium sulphate to potassium sulphite. The thought was now obvious, the released six hydrogen atoms in the way to make subservient that nitrotoluenesulfonic acid is used instead of amidotoluenesulfonic acid brings into use, which requires exactly six hydrogen atoms to reduce its nitro group. According to the work of Fischer and Hepp (Reports XXVI, p. 2233) and Bender and Schulz (Reports XIX, p. 3235) however, occurs when ρ-nitrotoluenesulfonic acid is used splitting off of the sulfo group does not take place, and likewise the oxidation of the methyl group does not proceed to Carboxyl on.
Es hat sich nun gezeigt, dafs eine Oxydation der Methylgruppe zur Carboxylgruppe unter gleichzeitiger Reduction der Nitrogruppe eintritt, wenn man o-Nitrotoluol mit Alkali behandelt. Sehr concentrirtes wässeriges oder gar festes Alkali wirkt beim Erhitzen in äufserst stürmischer Weise auf o-Nitrotoluol ein, so dafs dadurch die Bildung unerquicklicher Nebenproducte nicht vermieden werden kann. Sehr verdünntes wässeriges Alkali reagirt nur sehr langsam, so dafs es zweckmäfsig ist, zur Darstellung der Anthranilsäure mit Alkali von mäfsiger Concentration (von etwa 10 bis γορΟ.) zu arbeiten. Bei Verwendung schwacher Alkalilösungen empfiehlt es sich, die Operation unter Anwendung von Druck vorzunehmen.It has now been shown that oxidation of the methyl group to the carboxyl group takes place simultaneous reduction of the nitro group occurs when o-nitrotoluene is treated with alkali. Very concentrated watery or Even solid alkali has an extremely stormy effect on o-nitrotoluene when heated, see above that thereby the formation of unpleasant by-products cannot be avoided. Very dilute aqueous alkali reacts only very slowly, so that it is expedient to use Preparation of anthranilic acid with alkali of moderate concentration (from about 10 to γορΟ.) to work. When using weak alkali solutions, it is recommended to have the operation with the application of pressure.
Ueber die Einwirkung alkoholischen Alkalis auf o-Nitrotoluol war seither nur bekannt, dafs sie zu o-Azotoluol führt (vergl. Journal of the Chemical Society 37, S. 554, und Berichte XIII, 1875). Aber auch hier wird, wie die Versuche ergeben haben, zugleich Anthranilsäure nebst den zugehörigen Azo- und Azoxybenzoesäuren gebildet. Die Quantität der entstehenden Anthranilsäure ist bei Verwendung einer verdünnten alkoholischen Alkalilösung gering, nimmt aber mit wachsender Concentration der letzteren zu und kann durch nachherige Behandlung des Säuregemisches mit Reductionsmitteln (z. B. mit Schwefelammonium) noch weiter gesteigert werden.Since then only that has been known of the action of alcoholic alkali on o-nitrotoluene it leads to o-azotoluene (see Journal of the Chemical Society 37, p. 554 and Reports XIII, 1875). But here too, like the trials have shown, at the same time anthranilic acid together with the associated azo and azoxybenzoic acids educated. The quantity of the resulting anthranilic acid is when using a dilute alcoholic alkali solution, but it increases with the concentration of the latter and can be changed by subsequent treatment of the acid mixture can be increased even further with reducing agents (e.g. with ammonium sulphide).
137 kg o-Nitrotoluol werden mit 120 kg Aetznatron und 500 kg Alkohol am Rückflufskühler so lange gekocht, bis der Geruch nach o-Nitrotoluol verschwunden ist. Hierauf wird die Reactionsflüssigkeit mit Ammoniak und Schwefelwasserstoff gesättigt und wiederum mehrere Stunden gekocht behufs vollkommener137 kg of o-nitrotoluene weigh 120 kg Caustic soda and 500 kg of alcohol are boiled on the reflux condenser until the smell persists o-nitrotoluene has disappeared. Then the reaction liquid with ammonia and Saturated hydrogen sulfide and boiled again for several hours to make it more perfect
Reduction zu Anthranilsäure. Durch Verdampfen zur Trockne wird das überschüssige Schwefelammonium sowie der Alkohol verjagt ; das Reactionsproduct wird sodann mit Wasser aufgenommen, die. Lösung nöthigenfalls filtrirt und die Anthranilsäure daraus in bekannter Weise abgeschieden.Reduction to anthranilic acid. Evaporation to dryness will remove the excess Sulfur ammonium as well as alcohol drives away; the reaction product is then with Water absorbed that. Solution if necessary filtered and the anthranilic acid separated from it in a known manner.
An Stelle von Aethylalkohol können im vorstehenden Beispiel auch andere Lösungs- und Verdünnungsmittel,' z. B. Amylalkohol angewendet werden.Instead of ethyl alcohol, other solvents and solvents can also be used in the above example Diluents, 'e.g. B. amyl alcohol can be used.
ι oo Theile Natronlauge von 400B. werden in einem geschlossenen, mit Sicherheitsventil versehenen Rührcylinder auf ca. 1500 G. erhitzt. Dann läfst man unter gutem Umrühren und unter Aufrechterhaltung der gleichen Temperatur nach und nach 100 Theile o-Nitrotoluol einfliefsen und erhitzt und rührt so lange (ca. 12 Stunden), bis eine Probe zeigt, dafs der gröfste Theil des Nitrotoluols verschwunden ist. Alsdann treibt man das OeI mit Wasserdampf über und scheidet aus der rückständigen wässerigen Lösung die Anthranilsäure in bekannter Weise ab.ι oo parts of sodium hydroxide solution of 40 0 B. be heated in a closed and provided with safety valve Rührcylinder to about 150 0 G.. Then, while stirring well and maintaining the same temperature, gradually flow in 100 parts of o-nitrotoluene, and heat and stir until a sample shows that most of the nitrotoluene has disappeared. The oil is then driven over with steam and the anthranilic acid is separated from the residual aqueous solution in a known manner.
Die auch bei Verwendung von wässerigem Alkali neben Anthranilsäure, wenn auch in geringerer Menge entstehenden Azoxy- und Azosäuren können im Bedarfsfalle in der in Beispiel I beschriebenen Weise ebenfalls in Anthranilsäure übergeführt werden.This also applies when using aqueous alkali in addition to anthranilic acid, albeit in a lower amount Amount of resulting azoxy and azo acids can, if necessary, in the example I described manner can also be converted into anthranilic acid.
Als Alkalien können aufser Aetznatron auch Aetzkali, sowie alkalische Erden verwendet werden.Besides caustic soda, caustic potash and alkaline earths can also be used as alkalis will.
Claims (3)
Publications (1)
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DE114839C true DE114839C (en) |
Family
ID=384308
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