AT8097B - Process for the condensation of aromatic glycines to indoxyl derivatives. - Google Patents
Process for the condensation of aromatic glycines to indoxyl derivatives.Info
- Publication number
- AT8097B AT8097B AT8097DA AT8097B AT 8097 B AT8097 B AT 8097B AT 8097D A AT8097D A AT 8097DA AT 8097 B AT8097 B AT 8097B
- Authority
- AT
- Austria
- Prior art keywords
- glycines
- aromatic
- condensation
- parts
- indoxyl
- Prior art date
Links
- PCKPVGOLPKLUHR-UHFFFAOYSA-N indoxyl Chemical group C1=CC=C2C(O)=CNC2=C1 PCKPVGOLPKLUHR-UHFFFAOYSA-N 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 9
- -1 aromatic glycines Chemical class 0.000 title claims description 7
- 238000009833 condensation Methods 0.000 title claims description 3
- 230000005494 condensation Effects 0.000 title claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 5
- 239000004471 Glycine Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RRTQTOBOLIGMED-UHFFFAOYSA-N 2-(carboxyamino)-2-phenylacetic acid Chemical class OC(=O)NC(C(O)=O)C1=CC=CC=C1 RRTQTOBOLIGMED-UHFFFAOYSA-N 0.000 description 1
- RZVNMMLXLKRPFA-UHFFFAOYSA-N 2-amino-2-phenylacetic acid;sodium Chemical compound [Na].OC(=O)C(N)C1=CC=CC=C1 RZVNMMLXLKRPFA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZGUNAGUHMKGQNY-ZETCQYMHSA-N L-alpha-phenylglycine zwitterion Chemical compound OC(=O)[C@@H](N)C1=CC=CC=C1 ZGUNAGUHMKGQNY-ZETCQYMHSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 239000002253 acid Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
<Desc/Clms Page number 1>
Verfahren zur Condensation aromatischer Glycine zu Indoxyl- derivaten.
EMI1.1
rührt die schlechte ausbeute daher, dass Atzkali das zunächst gebildete Indoxyl wieder /erstiirt, unter Bildung von Anilin, und dass vor allen Dingen (s. a. Biedermann und
EMI1.2
wodurch einer unerwünschten anderweitigen Zersetzung des Glycins infolge zu hoher Temperatur vorgebeugt wird.
EMI1.3
Ctycine lassen sich auch deren Salze und Ester verwenden.
Die Arbeitsweise nach vorliegendem Verfahren kann in der verschiedensten Weise modificiert werden, je nach den Eigens haften dorAusgangsmaterialien : entweder wird das Natriumamid geschmolzen und das Clycin, sei es für sich oder verdünnt, in das geschmolzene Amid eingetragen, oder gemahlenes Amid wird mit Glycin und evontuell
EMI1.4
EMI1.5
EMI1.6
<Desc/Clms Page number 2>
B e i s p i e l e :
1. 3 Theile Natriumamid werden geschmolzen und auf 1800 C. erhitzt und in diese dünne Schmolze wird unter UmrUhron allmäblich ein Theil Phonylglycinnatrium
EMI2.1
geschmolzen und auf 2300 C. gebracht, und in das Gemisch wird allmählich 1 Theil Phenylglycinnatrium eingetragen.
4. In eine Schmelze aus 2 Theilen Natriumamid und 3'5 Theilen Cyankalium worden bei 2300 C. 2 Theile Phenylglycin allmählich unter Umrühren eingetragen.
5. 1 Theil Natriumamid, 4 Theile Ätzkali, 3 Theile Ätznatron worden zusammengeschmolzen und bei etwa 180 bis 2300 C. wird Phonylglycinkalium eingetragen.
6. 1 Theil Natriumamid, 1 Theil Ätzkali, 1 Theil Ätznatron, 1 Then Cyanka1ium worden zusammengeschmolzen und bei 2200 C. 1 Theil Phenylglycinester eingetraen.
7. 1 Theil Natriumamid, 2 Theile Cyankalium werden geschmolzen und 1 Theil p-Tolyl- glycinnatrium bei 2500 C. eingetragen.
8.3 Theile Phenylglycin-o-carbonsaures Natron und 2 Theile Natriumamid werden innig gemischt und successive in ein auf 2500 C. erhitztes Gefäss eingetragen.
Durch die deutsche Patentschrift Nr. 105495 ist ein Verfahren bekannt geworden, nach welchem aus Phenylglycin-o-Carbonsäureester bei gelinder Temperatur Indoxylderivate dargestellt werden. Diesem Verfahren gegenüber besteht der technische Fortschritt des vorliegonden Verfahrens darin, dass man bei Verwendung der Phenylgiycin - 0- Carbonsäure als Ausgangsmaterial nicht darauf angewiesen ist, die umständlich und nicht billig darzustellonden neutralen Ester obiger Säure zu verwenden, sondern dass gerade in diesem Falle von den einfach und billig erhältlichen neutralen Alkalisalzen ausgangen wird.
Auch der Reactionsverlauf ist in dem vorliegenden Falle ein ganz anderer. Während bei dorn Verfahren der deutschen Patentsnchrift Nr. 105495 unter Wasserstoff- und Alkohol-abspaltung Indoxylcarbonsäureester erhalt wird, entsteht nach dem vorliegenden ('ondensationsvorfahron Indoxyl. indem Soda gebildet wird und Ammoniak entweicht. Den
EMI2.2
EMI2.3
<Desc / Clms Page number 1>
Process for the condensation of aromatic glycines to indoxyl derivatives.
EMI1.1
The poor yield is due to the fact that Atzkali re-suppresses the initially formed indoxyl, with the formation of aniline, and that above all (see also Biedermann and
EMI1.2
which prevents undesired other decomposition of the glycine as a result of excessively high temperatures.
EMI1.3
Ctycins can also be used with their salts and esters.
The procedure according to the present process can be modified in the most varied of ways, depending on the properties of the starting materials: either the sodium amide is melted and the glycine, be it alone or diluted, is added to the melted amide, or ground amide is mixed with glycine and possibly
EMI1.4
EMI1.5
EMI1.6
<Desc / Clms Page number 2>
EXAMPLE:
1. 3 parts of sodium amide are melted and heated to 1,800 ° C., and a part of phonylglycine sodium is gradually added to this thin melt with stirring
EMI2.1
melted and brought to 2300 ° C., and 1 part of phenylglycine sodium is gradually added to the mixture.
4. Two parts of phenylglycine were gradually introduced into a melt of 2 parts of sodium amide and 3'5 parts of potassium cyanide at 2300 ° C., with stirring.
5. 1 part of sodium amide, 4 parts of caustic potash, 3 parts of caustic soda are melted together, and at about 180 to 2300 ° C., potassium phonylglycine is introduced.
6. 1 part of sodium amide, 1 part of caustic potash, 1 part of caustic soda, 1 part of cyanka1ium were melted together, and 1 part of phenylglycine ester was allowed to enter at 2200 C.
7. 1 part of sodium amide, 2 parts of potassium cyanide are melted, and 1 part of p-tolylglycine sodium is added at 2500 ° C.
8.3 Parts of phenylglycine-o-carboxylic acid sodium and 2 parts of sodium amide are intimately mixed and successively introduced into a vessel heated to 2500 ° C.
The German patent specification No. 105495 discloses a process according to which indoxyl derivatives are prepared from phenylglycine-o-carboxylic acid esters at a low temperature. Compared to this process, the technical progress of the present process consists in the fact that when using the phenylgycin-0-carboxylic acid as the starting material, one does not have to rely on using the inconvenient and not cheap to present neutral ester of the above acid, but that in this case, of the neutral alkali salts that are easily and cheaply available.
The course of the reaction is also quite different in the present case. While in the process of the German patent specification No. 105495 indoxyl carboxylic acid ester is obtained with elimination of hydrogen and alcohol, according to the present (ondensationsvorfahron indoxyl. By the formation of soda and ammonia escaping
EMI2.2
EMI2.3
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT8097T | 1901-08-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AT8097B true AT8097B (en) | 1902-06-25 |
Family
ID=3500207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AT8097D AT8097B (en) | 1901-08-17 | 1901-08-17 | Process for the condensation of aromatic glycines to indoxyl derivatives. |
Country Status (1)
| Country | Link |
|---|---|
| AT (1) | AT8097B (en) |
-
1901
- 1901-08-17 AT AT8097D patent/AT8097B/en active
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1087609B (en) | Process for the preparation of 3,5-diaminopyrazine-2,6-dicarboxylic acid amides | |
| AT8097B (en) | Process for the condensation of aromatic glycines to indoxyl derivatives. | |
| DE954596C (en) | Process for the production of fungicides and insect repellants of the crotonic acid amide and ª ‰ -Methylcrotonic acid amide series | |
| DE527237C (en) | Process for the preparation of guanidine or guanidine salts, in particular of guanidine phosphate | |
| DE954597C (en) | Process for the production of fungicides and insect repellants of the ª ‰ -Methylcrotonic acid amide series | |
| DE137955C (en) | ||
| DE710129C (en) | Process for the preparation of fluorinated aliphatic hydrocarbons | |
| DE1670923B2 (en) | Process for the preparation of N-substituted maleimides from the corresponding monoammonfum salts of maleic acid | |
| DE530052C (en) | Process for the production of urea phosphate fertilizers | |
| DE523034C (en) | Process for the preparation of alkali and ammonium salts of the mono- or disubstitution products of dithiocarbamic acid | |
| DE855398C (en) | Process for the preparation of p-aminobenzenesulfonylguanidine | |
| DE911493C (en) | Process for the preparation of 2- (1, 4-diamino-2-anthraquinonyl) -1, 3, 4-oxydiazoles | |
| DE930688C (en) | Process for the preparation of 4-amino-2-oxybenzoic acid acetylamide | |
| DE2048913B2 (en) | Process for the preparation of 1-aminoalkane-1,1-diphosphonic acids | |
| DE2714255A1 (en) | METHOD FOR PRODUCING M-AMINOPHENOLS AND THEIR USE | |
| DE282226C (en) | ||
| DE555489C (en) | Process for the preparation of cyano compounds | |
| DE2503049B2 (en) | METHOD OF PREPARING N-BROMINE-N'-CHLORINE-5,5-DIMETHYLHYDANTOIN | |
| DE942027C (en) | Process for the preparation of substituted 2-iminothiazolidines | |
| AT214421B (en) | Process for the preparation of methylalkyl maleic anhydrides | |
| AT236382B (en) | Process for the preparation of new derivatives of sulfanilamide | |
| DE807686C (en) | Process for the manufacture of nitrogenous sulphonation products | |
| DE733514C (en) | Process for the preparation of aromatic sulfonic acid amides | |
| AT132713B (en) | Process for the preparation of acetic anhydride. | |
| DE1019310B (en) | Process for the production of diguanamines |