US960671A - Process of making indoxyl, &c. - Google Patents
Process of making indoxyl, &c. Download PDFInfo
- 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
- Authority
- US
- United States
- Prior art keywords
- indoxyl
- silicon
- parts
- weight
- derivatives
- 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.)
- Expired - Lifetime
Links
- PCKPVGOLPKLUHR-UHFFFAOYSA-N indoxyl Chemical group C1=CC=C2C(O)=CNC2=C1 PCKPVGOLPKLUHR-UHFFFAOYSA-N 0.000 title description 23
- 238000000034 method Methods 0.000 title description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910000676 Si alloy Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 5
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 4
- 229940097275 indigo Drugs 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HCLZWWBOYHLGME-UHFFFAOYSA-N 2-amino-n,2-diphenylacetamide Chemical compound C=1C=CC=CC=1C(N)C(=O)NC1=CC=CC=C1 HCLZWWBOYHLGME-UHFFFAOYSA-N 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N Adamantane Natural products C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 description 1
- IPSFAGOTHDYEJB-UHFFFAOYSA-N [K].OC(=O)C(N)C1=CC=CC=C1 Chemical compound [K].OC(=O)C(N)C1=CC=CC=C1 IPSFAGOTHDYEJB-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides 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
- 239000007864 aqueous solution Substances 0.000 description 1
- OOJQNBIDYDPHHE-UHFFFAOYSA-N barium silicon Chemical compound [Si].[Ba] OOJQNBIDYDPHHE-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- COHYTHOBJLSHDF-BUHFOSPRSA-N indigo dye Chemical compound N\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-BUHFOSPRSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 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
- C07D209/08—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.
Landscapes
- 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US54001110A US960671A (en) | 1910-01-25 | 1910-01-25 | Process of making indoxyl, &c. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US54001110A US960671A (en) | 1910-01-25 | 1910-01-25 | Process of making indoxyl, &c. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US960671A true US960671A (en) | 1910-06-07 |
Family
ID=3029069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US54001110A Expired - Lifetime US960671A (en) | 1910-01-25 | 1910-01-25 | Process of making indoxyl, &c. |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US960671A (en) |
-
1910
- 1910-01-25 US US54001110A patent/US960671A/en not_active Expired - Lifetime
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