DE168292C - - Google Patents
Info
- Publication number
- DE168292C DE168292C DENDAT168292D DE168292DA DE168292C DE 168292 C DE168292 C DE 168292C DE NDAT168292 D DENDAT168292 D DE NDAT168292D DE 168292D A DE168292D A DE 168292DA DE 168292 C DE168292 C DE 168292C
- Authority
- DE
- Germany
- Prior art keywords
- acid
- indoxyl
- cooh
- isatin
- phenylglycine
- 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.)
- Active
Links
- 239000002253 acid Substances 0.000 claims description 8
- YEQRASMGLPZYDE-UHFFFAOYSA-N Indoxyl Chemical group C1=CC=C[C]2C(O)=CN=C21 YEQRASMGLPZYDE-UHFFFAOYSA-N 0.000 claims description 7
- XSCYATGDVRPMHG-UHFFFAOYSA-N acetic acid;1H-indole-2,3-dione Chemical compound CC(O)=O.C1=CC=C2C(=O)C(=O)NC2=C1 XSCYATGDVRPMHG-UHFFFAOYSA-N 0.000 claims description 5
- RRTQTOBOLIGMED-UHFFFAOYSA-N 2-(carboxyamino)-2-phenylacetic acid Chemical compound OC(=O)NC(C(O)=O)C1=CC=CC=C1 RRTQTOBOLIGMED-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000003518 caustics Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 9
- 239000000155 melt Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 229940097275 Indigo Drugs 0.000 description 3
- 241001062009 Indigofera Species 0.000 description 3
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 230000001264 neutralization Effects 0.000 description 3
- -1 phenylglycine carboxylic acid Chemical class 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JXDYKVIHCLTXOP-UHFFFAOYSA-N Isatin Natural products C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 2
- HKOOXMFOFWEVGF-UHFFFAOYSA-N Phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 2
- VZJVWSHVAAUDKD-UHFFFAOYSA-N Potassium permanganate Chemical compound [K+].[O-][Mn](=O)(=O)=O VZJVWSHVAAUDKD-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229940067157 phenylhydrazine Drugs 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229960000583 Acetic Acid Drugs 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000015450 Tilia cordata Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
- C07D209/32—Oxygen atoms
- C07D209/36—Oxygen atoms in position 3, e.g. adrenochrome
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
Description
ι. S ι. S.
KAISERLICHESIMPERIAL
PATENTAMT,PATENT OFFICE,
PATENTSCHRIFTPATENT LETTERING
- M 168292 KLASSE Mp. - M 168292 CLASS Mp.
Verfahren zur Darstellung von Indoxyl. Patentiert im Deutschen Reiche vom 14. April 1904 ab.Process for the preparation of indoxyl. Patented in the German Empire on April 14, 1904 .
Es wurde gefunden, daß sich die Anthranilodiessigsäure in technisch vorteilhafter Weise in Indoxyl und sonach auch in Indigo überführen läßt, wenn man sie zunächst nach dem Verfahren des Patentes 128955 der Kl. 22 e in Indigodiessigsäure umwandelt und diese dann entweder in wässerig alkalischer Lösung mit Luftsauerstoff oxydiert oder mit anderen oxydierenden Agentien, wie Bleisuperoxyd, Kaliumpermanganat, Chlorlauge usw.,It has been found that anthranilodiacetic acid is technically advantageous can be converted into indoxyl and thus also into indigo if they are first traced the process of patent 128955 of cl. 22 e converts into indigodiacetic acid and this is then either oxidized in an aqueous alkaline solution with atmospheric oxygen or with other oxidizing agents such as lead peroxide, potassium permanganate, chlorine lye, etc.,
COOHCOOH
^N(CH2COOH)2 ^ N (CH 2 COOH) 2
coco
ceHi\ /C ■ c c e H i \ / C ■ c
coco
CH2COOH CH2COOHCH 2 COOH CH 2 COOH
CO CRH( )C0CO C R H () C0
behandelt. Es bildet sich hierbei zunächst die Isatinessigsäure, welche leicht schon beim Eindampfen ihrer alkalischen Lösungen unter Abspaltung der C O- Gruppe und Bildung von Ameisensäure in die Phenylglycin - ocarbonsäure übergeht. Letztere läßt sich dann in bekannter Weise in Indoxyl überführen. Die Reaktion vollzieht sich nach folgenden Gleichungen:treated. Isatin acetic acid is initially formed, which is easily converted into phenylglycine carboxylic acid when its alkaline solutions are evaporated, with the C O group being split off and formic acid being formed. The latter can then be converted into indoxyl in a known manner. The reaction takes place according to the following equations:
COCO
C :C:
COCO
/4 = Indigodiessigsäure. / 4 = indigodiacetic acid.
CH2COOH CH2COOHCH 2 COOH CH 2 COOH
coco
2O — = Isatinessigsäure. 2O - = isatin acetic acid.
- CH2-COOH+ 2H2O = C6H - CH 2 -COOH + 2H 2 O = C 6 H
yy
N. CH2CO OHN. CH 2 CO OH
COOHCOOH
NH-CH2COOH+ COOH.NH-CH 2 COOH + COOH.
Anstatt entsprechend der Gleichung 3 die Isatinverbindung zunächst in ' die Phenylglycin-o-carbonsäure und letztere in Indoxyl überzuführen, kann man auch die neutralen Salze der Isatinessigsäure unmittelbar mit Ätzalkalien eventuell unter Zusatz von Oxyden der Erdalkalimetalle behandeln.Instead of first converting the isatin compound into the phenylglycine-o-carboxylic acid according to equation 3 and to convert the latter into indoxyl, one can also use the neutral salts of isatin acetic acid directly Treat caustic alkalis with the addition of oxides of the alkaline earth metals.
5 g Anthranilodiessigsäure werden mit 25 kg Natronlauge von 400Be. ungefähr 12 Stunden unter Rückfluß erhitzt und das Reaktionsgemisch alsdann mit so viel heißem Wasser verdünnt, daß eine Lösung von 6 bis 8° Be. entsteht. In diese wird unter Erwärmen so5 g Anthranilodiessigsäure are mixed with 25 kg of sodium hydroxide of 40 0 Be. Heated under reflux for about 12 hours and the reaction mixture is then diluted with so much hot water that a solution of 6 to 8 ° Be. arises. In this one becomes so under warming
lange Luft eingeleitet, bis die zunächst entstehende grüne Farbe der Indigodiessigsäure in die gelbrote der Isatinverbindung übergegangen ist. Nach beendeter Oxydation färbt sich eine Probe der Lösung beim Ansäuern nicht mehr grünlich.long air is introduced until the green color of the indigodiacetic acid is initially formed has passed into the yellow-red of the isatin compound. After the oxidation has ended a sample of the solution no longer turns green when acidified.
Die fertig oxydierte Lösung isatinessigsauren Natrons wird zur Umwandlung des letzteren in das phenylglycin-o-carbonsaureThe finished oxidized solution isatinessigsauren sodium is used to convert the the latter into phenylglycine-o-carboxylic acid
ίο Salz auf 40 bis 42 ° Be. eingedampft und das auskristallisierte neutrale Salz der Phenylglycin-o-carbonsäure nach dem Erkalten abgesaugt und gepreßt.ίο Salt to 40 to 42 ° Be. evaporated and that crystallized neutral salt of phenylglycine-o-carboxylic acid filtered off with suction after cooling and pressed.
Der erhaltene alkalihaltige Preßkuchen kann unmittelbar, z. B. durch Verschmelzen im Vakuum, auf Indoxyl bezw. Indigo verarbeitet werden.The resulting alkaline press cake can be used directly, for. B. by merging in Vacuum, on indoxyl respectively. Indigo are processed.
Beispiel II.Example II.
15 kg der nach Beispiel III des Patents 128955 erhältlichen Schmelze werden in etwa 2001 heißem Wasser gelöst und die gelbgrüne Lösung wie im vorhergehenden Beispiel durch Einblasen von Luft oxydiert.15 kg of the melt obtainable according to Example III of patent 128955 are approximately 2001 dissolved in hot water and the yellow-green solution as in the previous example oxidized by blowing air.
Aus der gelbroten Lösung fällt beim Ansäuern mit Mineralsäuren die Isatinessigsäure in zarten gelben Kristallnadeln aus, die zwischen 198 und 1990 schmelzen. Sie ist leicht löslich in Eisessig und Alkohol, schwer löslieh in Wasser oder Äther. Mit Phenylhydrazin bildet sie ein bei 242 ° schmelzendes Phenylhy drazon.When acidifying with mineral acids, the isatin acetic acid precipitates from the yellow-red solution in delicate yellow crystal needles that melt between 198 and 199 0. It is easily soluble in glacial acetic acid and alcohol, poorly soluble in water or ether. With phenylhydrazine, it forms a phenylhydrazine that melts at 242 °.
In einem Rührkessel werden bei etwa 2OO° in 200 Gewichtsteile einer molekularen Mischung von Ätzkali und Ätznatron 100 Gewichtsteile von isatinessigsaurem Kalium langsam eingetragen. Wenn das Eintragen beendet ist, wird unter Umrühren bei Luftabschluß noch eine Stunde auf 250° erhitzt. Nach dem Erkalten wird die erhaltene Schmelze in üblicher Weise auf Indigo verarbeitet. In a stirred tank at about 2OO ° in 200 parts by weight of a molecular Mixture of caustic potash and caustic soda 100 parts by weight of potassium isatinetic acid slowly registered. When the feeding is finished, stir with exclusion of air heated to 250 ° for another hour. After cooling down, the Melt processed in the usual way on indigo.
Beispiel III.Example III.
10 kg neutrales isatinessigsaures Natrium werden mit 17,5 kg Ätznatron und 7,5 kg gebranntem Kalk in der Kugelmühle zu einem feinen Pulver vermählen und dieses sodann zweckmäßig in dünner Schicht unter Luftabschluß 2 Stunden auf 260° erhitzt.10 kg of neutral sodium isatinetic acid are mixed with 17.5 kg of caustic soda and 7.5 kg of burnt Grind the lime in the ball mill to a fine powder and then this expediently heated in a thin layer with the exclusion of air at 260 ° for 2 hours.
Die weitere Verarbeitung der Schmelze erfolgt in bekannter Weise.The further processing of the melt takes place in a known manner.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE168292C true DE168292C (en) |
Family
ID=433530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT168292D Active DE168292C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE168292C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5790993A (en) * | 1997-09-08 | 1998-08-11 | Otis Bed Manufacturing Company, Inc. | Automatic futon frame |
-
0
- DE DENDAT168292D patent/DE168292C/de active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5790993A (en) * | 1997-09-08 | 1998-08-11 | Otis Bed Manufacturing Company, Inc. | Automatic futon frame |
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