US960671A - Process of making indoxyl, &c. - Google Patents

Process of making indoxyl, &c. Download PDF

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Publication number
US960671A
US960671A US54001110A US1910540011A US960671A US 960671 A US960671 A US 960671A US 54001110 A US54001110 A US 54001110A US 1910540011 A US1910540011 A US 1910540011A US 960671 A US960671 A US 960671A
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indoxyl
silicon
parts
weight
derivatives
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US54001110A
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Martin Mugdan
Willy Herrmann
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Consortium fuer Elektrochemische Industrie GmbH
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Consortium fuer Elektrochemische Industrie GmbH
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    • 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
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring

Definitions

  • This invention relates to a process for the production of indoxyl and derivatives thereof from aryl-glycin bodies. It is already known that phenylglycin and its derivatives and homologucs, on being heated with alkali hydroxides can he com-cried into indoxyl, or its derivatives, or homologues, and that indigo may be obtained from the indoxyl thus obtained by oxidation for instance by blowing air into the aqueous solution of the melt. The yield of indigo in this case, however, is very bad.
  • indoxyl and derivatives thereof can be obtained from aryi'glycin bodies by heating these compounds with alloys of silicon and metals of the alkaline earths in the presence of anhydrous caustic alkalics.
  • the process yields good results and is easily carried out, as the alloys of silicon and metals of the alkaline earths are readily and cheaply obtained.
  • Example I Into an anhydrous melt of 280 parts by weight of caustic potash and of 200 parts by weight of caustic soda, are slowly introduced at about 2-50 centigi'ade, 50 parts by weight of pulverized calciumsilicon (containing about 30 )e1' cent. calcium). The calcium-silicon a loy dissolves while a brisk evolution of hydrogen takes place. WVhile the melt is kept well stirred, 50 parts by weight of finely pulverized phenylglycin potassium are introduced at a temperature of 220 ccntigrade. The temperature is then raised to about 250 centigrade and the reaction is interrupted when blowing air through a sample dissolved in water the amount of the dye formed no longer increases.
  • the melt is dissolved in 10000 parts by weight of water at 100 ccnti rade, and the solution thus obtained ⁇ vhici contains the indoxyl, is filtered off from any insoluble substances produced. If it be desired to obtain the indoxyl in the solid state, the solution is evaporated to dryness in the presence of an inert gas such as hydrogen.
  • an inert gas such as hydrogen.
  • the indoxyl is generally prepared for the purpose of obtaining indigo, its isolation may be omitted and the indigo prepared directly by introducing air into the solution. The indigo dye thus obtained is of great purity.
  • Example II Into an anhydrous melt of 300 parts by weight of caustic soda and 500 parts by weight of caustic potash is slowly introduced while stirring, at a temperature of about 220 centigrade, an intimate mixture of 200 parts by weight of phenylglycinpotassium and 130 parts of calcium-silicon (containing about 30 per cent. of calcium). The tcn'iperature is then raised to 250 centigradc and the process carried out as described in Example I.
  • the calcium-silicon can be replaced by alloys of silicon with other metals of the alkaline earths, for instance barium-silicon may be made.
  • phenylglycimpotassium other compounds of l'ihcnylglycin can be used, for instance phenylglycin-sodiuni, phenyiglycinamid or phenylglycin-anilid.
  • I improduuing indnxyl and derivatives thereof by int-rodu'cin a mixture 7 Q5 of an alloy of silicon and u meta of the a1- kaline earths and of an uryllycin body into -mglted anhydrous caustic .a kulies.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Indole Compounds (AREA)

Description

UNITED STATES PATENT OFFICE.
MARTIN MUGDAN AND WILLY HERRMANN, 0F NUREMBERG, GERMANY, ASSIGNORS TO THE FIRM OF CONSORTIUM FUR ELEK'IROCHEMISGHE INDUSTRIE, GESELL- SOHAFT MIT BESCHRKNKTEB HAFTUNG, 0F NUREMBERG, GERMANY.
PROCESS OF MAKING INDOXYL, 850.
No Drawing.
Patented June 7, 1910.
To all whom it may concern:
Be it known that we, MARTIN Muoosn, doctor of philosophy, chemist, and lVmLY Hnnnnsxn, doctor of philosophy, chemist, subjects of the King of Prussia, Gerin nn Emperor, residing at 54 Gugelstrasso, huremberg, Kingdom of Bavaria, German Empire, have jointly invented new and uscfui Improvements in Processes of Manufacturing Indoxvl and Derivatives Thereof, of which the following is a specification.
This invention relates to a process for the production of indoxyl and derivatives thereof from aryl-glycin bodies. It is already known that phenylglycin and its derivatives and homologucs, on being heated with alkali hydroxides can he com-cried into indoxyl, or its derivatives, or homologues, and that indigo may be obtained from the indoxyl thus obtained by oxidation for instance by blowing air into the aqueous solution of the melt. The yield of indigo in this case, however, is very bad. We have found that indoxyl and derivatives thereof can be obtained from aryi'glycin bodies by heating these compounds with alloys of silicon and metals of the alkaline earths in the presence of anhydrous caustic alkalics. The process yields good results and is easily carried out, as the alloys of silicon and metals of the alkaline earths are readily and cheaply obtained.
The following are examples showing how the invention is performed but the invention is not limited to these.
Example I: Into an anhydrous melt of 280 parts by weight of caustic potash and of 200 parts by weight of caustic soda, are slowly introduced at about 2-50 centigi'ade, 50 parts by weight of pulverized calciumsilicon (containing about 30 )e1' cent. calcium). The calcium-silicon a loy dissolves while a brisk evolution of hydrogen takes place. WVhile the melt is kept well stirred, 50 parts by weight of finely pulverized phenylglycin potassium are introduced at a temperature of 220 ccntigrade. The temperature is then raised to about 250 centigrade and the reaction is interrupted when blowing air through a sample dissolved in water the amount of the dye formed no longer increases. The melt is dissolved in 10000 parts by weight of water at 100 ccnti rade, and the solution thus obtained \vhici contains the indoxyl, is filtered off from any insoluble substances produced. If it be desired to obtain the indoxyl in the solid state, the solution is evaporated to dryness in the presence of an inert gas such as hydrogen. As the indoxyl is generally prepared for the purpose of obtaining indigo, its isolation may be omitted and the indigo prepared directly by introducing air into the solution. The indigo dye thus obtained is of great purity.
In carrying out the process the quantitative proportions and temperatures may be varied. I It has been found advantageous to introduce the alloy of silicon and alkaline earth metal intimately mixed with the arylglycin body into the melt. of caustic alkalies.
Example II: Into an anhydrous melt of 300 parts by weight of caustic soda and 500 parts by weight of caustic potash is slowly introduced while stirring, at a temperature of about 220 centigrade, an intimate mixture of 200 parts by weight of phenylglycinpotassium and 130 parts of calcium-silicon (containing about 30 per cent. of calcium). The tcn'iperature is then raised to 250 centigradc and the process carried out as described in Example I.
In the above examples the calcium-silicon can be replaced by alloys of silicon with other metals of the alkaline earths, for instance barium-silicon may be made.
Instead of phenylglycimpotassium other compounds of l'ihcnylglycin can be used, for instance phenylglycin-sodiuni, phenyiglycinamid or phenylglycin-anilid.
If it be desired to produce homologues of indoxyl homologucs of plicuylglycin are used. From tolyl-glychnpotassimu CH,.G l-L NI-I.CI-l COOK methyl indoxyl is obtained.
We claim:
1. A process for producing indoxyl and derivatives thermf by heating an aryl-glycili body with an alloy of silicon and a metal of 100 7 '2. A pmcess dmusicausticz- 'ulkahes.
I improduuing indnxyl and derivatives thereof by int-rodu'cin a mixture 7 Q5 of an alloy of silicon and u meta of the a1- kaline earths and of an uryllycin body into -mglted anhydrous caustic .a kulies.
liqulkaline ngrth in the presence of unhy In testimony whereof we uflix our signatures in presence of two witnesses.
MARTIN MUGDAN. WILLY I'IERRMANN. Witnesses:
ERICK I'IOEFER, ADAM KIBGHEA.
US54001110A 1910-01-25 1910-01-25 Process of making indoxyl, &c. Expired - Lifetime US960671A (en)

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