DE105495C - - Google Patents
Info
- Publication number
- DE105495C DE105495C DENDAT105495D DE105495DA DE105495C DE 105495 C DE105495 C DE 105495C DE NDAT105495 D DENDAT105495 D DE NDAT105495D DE 105495D A DE105495D A DE 105495DA DE 105495 C DE105495 C DE 105495C
- Authority
- DE
- Germany
- Prior art keywords
- carboxylic acid
- sodium
- ester
- esters
- 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
- 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 claims description 8
- -1 indoxyl carboxylic acid esters Chemical class 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- PCKPVGOLPKLUHR-UHFFFAOYSA-N OH-Indolxyl Natural products C1=CC=C2C(O)=CNC2=C1 PCKPVGOLPKLUHR-UHFFFAOYSA-N 0.000 claims description 3
- ZGUNAGUHMKGQNY-UHFFFAOYSA-N alpha-phenylglycine Chemical compound OC(=O)C(N)C1=CC=CC=C1 ZGUNAGUHMKGQNY-UHFFFAOYSA-N 0.000 claims description 2
- PJUXPMVQAZLJEX-UHFFFAOYSA-N 2-(carboxymethylamino)benzoic acid Chemical compound OC(=O)CNC1=CC=CC=C1C(O)=O PJUXPMVQAZLJEX-UHFFFAOYSA-N 0.000 claims 2
- 230000007935 neutral effect Effects 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 235000019439 ethyl acetate Nutrition 0.000 description 4
- 150000003388 sodium compounds Chemical class 0.000 description 3
- 150000007513 acids Chemical group 0.000 description 2
- KVOGJHABINNFCY-UHFFFAOYSA-N 3-(2-nitrophenyl)-2-propynoic acid Chemical compound OC(=O)C#CC1=CC=CC=C1[N+]([O-])=O KVOGJHABINNFCY-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- 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 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000203 mixture 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
- C07D209/30—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
- C07D209/42—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Durch die Einwirkung von metallischem Natrium auf ein Gemenge- von . Benzoesäureester und Essigester entsteht bekanntlich unter Austritt von Alkohol die Natiumverbindung eines Ketonsäureesters, des Benzoylessigesters, aus welcher verdünnte Säuren den Benzoylessigester abscheiden.By the action of metallic sodium on a mixture of. Benzoic acid ester and ethyl acetate is known to form the sodium compound with the escape of alcohol of a ketonic acid ester, the benzoyl acetic ester, from which dilute acids form the benzoyl acetic ester deposit.
Wir haben gefunden, dafs eine ähnliche intermoleculare Bildung stattfindet, wenn man metallisches Natrium auf die Ester der Phenylglycin - ο - carbonsäure einwirken läfst. Die Reaction erfolgt hier im Sinne folgender Gleichung:We have found that a similar intermolecular formation takes place when one metallic sodium has an effect on the esters of phenylglycine - ο - carboxylic acid. the Reaction takes place here in the sense of the following equation:
COORCOOR
A° Na A ° Well
+ Na-H+ Na-H
NH—CH.— COORNH-CH.-COOR
oder die tautomere Formor the tautomeric form
»;R« bedeutet: CH^C2H- etc.";R" means: CH ^ C 2 H- etc.
Verdünnte Säuren scheiden aus dieser Natriumverbindung den freien Ketonsäureester ab, welcher mit Indoxylcarbonsäureester identisch ist.Dilute acids separate from this sodium compound the free ketonic acid ester, which is identical to the indoxyl carboxylic acid ester is.
Zum Zwecke der praktischen Ausführung des Verfahrens kann man z. B. in folgender Weise vorgehen:For the purpose of practical execution of the process can be done, for. B. proceed as follows:
In eine Lösung von 25 ThI. Phenylglycino-carbonsä'urediäthyläther (Schmp. 72 bis 730) in 100 ThI. kochendem Benzol werden 2,5 ThI. granulirtes (oder in anderer Form fein zerkleinertes) Natrium eingetragen und zur Einleitung der Reaction einige Tropfen Alkohol hinzugefügt. Es beginnt alsbald eine Wasserstoffentwicklung, die bei gelinder Wärme immer lebhafter wird. Durch Abscheidung der ent-ROH + In a solution of 25 ThI. Phenylglycino-carbonsä'urediäthyläther (mp. 72-73 0) in 100 ThI. boiling benzene are 2.5 ThI. granulated (or in some other form finely divided) sodium was introduced, and a few drops of alcohol were added to initiate the reaction. The evolution of hydrogen immediately begins, which becomes more and more lively with mild warmth. By separating the ent- ROH +
.C- ONa.C- ONa
-C-COOR-C-COOR
C-COORC-COOR
NHNH
NHNH
stehenden Natriumverbindung des Indoxylsäureäthylesters erstarrt die Flüssigkeit allmälig zu einem weifsen Brei. Nachdem alles Natrium verschwunden ist, wird die Reactionsmasse mit einer verdünnten Säure durchgeschüttelt, die Benzolschicht abgehoben und das Benzol abdestillirt. Es hinterbleibt hierbei ein OeI, welches schnell krystallinisch erstarrt. Nach einmaligem Umkrystallisiren aus heifsem Alkohol ist der Körper völlig rein und zeigt sich beim Vergleiche mit dem nach A. Baey er (Ber. XIV, 1744) aus o-Nitrophenylpropiolsäure durch Reduction erhaltenen Indoxylsä'ureester mit diesem identisch.standing sodium compound of ethyl indoxylate the liquid gradually solidifies to a white pulp. After all the sodium has disappeared, the reaction mass becomes with shaken with a dilute acid, lifted off the benzene layer, and distilled off the benzene. What remains is an OeI which quickly solidifies in a crystalline manner. After a one-off Crystallization from hot alcohol makes the body completely pure and shows itself in the process Compare with that according to A. Baeyer (Ber. XIV, 1744) from o-nitrophenylpropiolic acid by reduction obtained indoxylic acid ester identical to this.
Genau ebenso verläuft die eben geschilderte Reaction, wenn man an Stelle des genannten Aethylesters der Phenylglyein - o- carbonsäureThe reaction just described proceeds in exactly the same way if one takes the place of the one mentioned Ethyl ester of phenylglyein - o-carboxylic acid
die äquivalenten Mengen anderer Ester derselben Säure, z. B. den Methylester, nimmt.the equivalent amounts of other esters of the same acid, e.g. B. the methyl ester takes.
Wie' bei der Herstellung von Acetessigester, Benzoylessigester u. s. w. kann man auch bei unserem Verfahren an Stelle des metallischen Natriums die äquivalente Menge eines Natiumalkoholates nehmen. Der Verlauf der Reaction bleibt derselbe, nur dafs an Stelle des im obigen Beispiel enstehenden Wasserstoffatoms hier ι Mol. Alkohol gebildet wird.As with the production of acetoacetic ester, benzoyl acetic ester and so on, one can also use In our process, instead of the metallic sodium, the equivalent amount of a sodium alcoholate to take. The course of the reaction remains the same, only in place of the im above example resulting hydrogen atom here ι mol. Alcohol is formed.
Die Indoxylcarbonsäureester dienen zur Darstellung von Indigo nach den bekannten Methoden von A. Bae)>-er.The indoxyl carboxylic acid esters are used to prepare indigo by the known methods by A. Bae)> - er.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE105495C true DE105495C (en) |
Family
ID=375784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT105495D Active DE105495C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE105495C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0071935A3 (en) * | 1981-08-08 | 1983-08-17 | Kali-Chemie Pharma Gmbh | 1-phenyl-2-aminocarbonylindole compounds, process and intermediates for their preparation and medicines containing them |
-
0
- DE DENDAT105495D patent/DE105495C/de active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0071935A3 (en) * | 1981-08-08 | 1983-08-17 | Kali-Chemie Pharma Gmbh | 1-phenyl-2-aminocarbonylindole compounds, process and intermediates for their preparation and medicines containing them |
| US4803198A (en) * | 1981-08-08 | 1989-02-07 | Kali-Chemie Pharma Gmbh | 1-Phenyl-2-aminocarbonylindole compounds, preparation thereof and pharmaceutical compositions containing them |
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