DE111890C - - Google Patents
Info
- Publication number
- DE111890C DE111890C DENDAT111890D DE111890DA DE111890C DE 111890 C DE111890 C DE 111890C DE NDAT111890 D DENDAT111890 D DE NDAT111890D DE 111890D A DE111890D A DE 111890DA DE 111890 C DE111890 C DE 111890C
- Authority
- DE
- Germany
- Prior art keywords
- acid
- sodium
- parts
- ester
- acid ester
- 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
- -1 indoxyl methyl ketone Chemical compound 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- IFLBCPOGBZTHPU-UHFFFAOYSA-N 2-(2-oxopropylamino)benzoic acid Chemical compound CC(=O)CNC1=CC=CC=C1C(O)=O IFLBCPOGBZTHPU-UHFFFAOYSA-N 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- BULLHNJGPPOUOX-UHFFFAOYSA-N Chloroacetone Chemical compound CC(=O)CCl BULLHNJGPPOUOX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- FVZUNNRWBULVJV-UHFFFAOYSA-N 1-(2,1-benzoxazol-3-yl)propan-2-one Chemical class C1=CC=CC2=C(CC(=O)C)ON=C21 FVZUNNRWBULVJV-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- YEQRASMGLPZYDE-UHFFFAOYSA-N Indoxyl Chemical group C1=CC=C[C]2C(O)=CN=C21 YEQRASMGLPZYDE-UHFFFAOYSA-N 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N Phenylhydrazine Chemical group NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000001476 alcoholic Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- TWLLPUMZVVGILS-UHFFFAOYSA-N ethyl 2-aminobenzoate Chemical compound CCOC(=O)C1=CC=CC=C1N TWLLPUMZVVGILS-UHFFFAOYSA-N 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atoms Chemical group N* 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Description
KAISERLICHES JIMPERIAL J
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
KLASSE 12: Chemische Verfahren und Apparate.CLASS 12: Chemical processes and apparatus.
. Das Patent 105495 betrifft ein Verfahren zur Ueberführung der neutralen Ester der Phenylglycin-o-carbonsäure in Indoxylcarbonsäureester durch Natriumalkoholat oder metallisches Natrium.. The patent 105495 relates to a method to convert the neutral esters of phenylglycine-o-carboxylic acid into indoxylcarboxylic acid esters by sodium alcoholate or metallic sodium.
Es wurde nun weiter gefunden, dafs die Bildung von Indoxylderivaten immer eintritt, wenn Ester aromatischer o-Amidocarbonsäuren, die am Stickstoffatom den Rest — CH2-C O — besitzen, der Einwirkung von Natrium oder Natriumalkoholat unterworfen werden. Solche Verbindungen können erhalten werden durch Umsetzung von o- Amidocarbonsäureester mit Halogenaceton, Halogenacetaldehyd, cu-Halogenacetophenon etc.It has now also been found that the formation of indoxyl derivatives always occurs when esters of aromatic o-amidocarboxylic acids, which have the radical - CH 2 --CO - on the nitrogen atom, are subjected to the action of sodium or sodium alcoholate. Such compounds can be obtained by reacting o-amidocarboxylic acid ester with haloacetone, haloacetaldehyde, cu-haloacetophenone, etc.
Von Wichtigkeit sind allein die Acetonylanthranilester, die leicht zu erhalten sind, -wenn man 1 Mol. Halogenaceton mit 2 Mol. Anthranilsäureester erwärmt. Läfst man beide Körper bei Gegenwart von salzsäurebindenden Mitteln, wie Alkalien, Carbonaten oder Acetaten, auf einander wirken, so ist natürlich das zweite Molecül Anthranilsäureester überflüssig.Only the acetonyl anthranil esters are important, which are easy to obtain, -if one mol. Halogenacetone with 2 mol. Anthranilic acid ester warmed up. If you leave both bodies in the presence of hydrochloric acid binding agents, such as alkalis, carbonates or acetates, act on one another, the second molecule of anthranilic acid ester is of course superfluous.
330 Theile Anthranilsäureäthylester und 92,5 Theile Chloraceton werden bis zum Verschwinden des Chloracetons auf dem Wasserbad erwärmt. Nach Beendigung der Umsetzung setzt man die Lösung von 55 Theilen Soda zu und nimmt das entstandene Gemisch von Acetonylanthranilsäureester und Anthranilsäureester in 1000 Theilen Benzol auf. In die gut getrocknete Lösung trägt man nun 23 Theile fein zertheiltes metallisches Natrium. :ein. Die Reaction kann durch Zusatz von einigen Tropfen Alkohol und durch gelindes Erwärmen unterstützt werden. Der Verlauf wird durch folgende Gleichung veranschaulicht:330 parts of ethyl anthranilate and 92.5 parts of chloroacetone are heated on the water bath until the chloroacetone has disappeared. After completion of the implementation the solution of 55 parts of soda is added, and the resulting mixture of acetonylanthranilic acid ester and anthranilic acid ester is taken up in 1000 parts of benzene. In the A well-dried solution is then used to carry 23 parts of finely divided metallic sodium. :a. the Reaction can be achieved by adding a few drops of alcohol and by gentle warming get supported. The process is illustrated by the following equation:
,OC3H, OC 3 H
ο:% ο: %
+ Na =+ Na =
NH-CH2-CO-CH3 ,ONa ^C-CO-CH3 + C2H11OH + H.NH-CH 2 -CO-CH 3 , ONa ^ C-CO-CH 3 + C 2 H 11 OH + H.
Statt des metallischen Natriums kann auch Natriumalkoholat angewendet werden. Zweckmäfsig bedient man sich einer alkoholischen Lösung, wie man sie für vorliegendes Beispiel durch Auflösen von 23 Theilen Natrium in 300 Theilen absolutem Alkohol bei mäfsiger Wärme erhält. Nach beendeter Reaction läfst man erkalten und schüttelt zur Zersetzung der Natriumverbindung mit verdünnter Säure durch.Instead of the metallic sodium, sodium alcoholate can also be used. Appropriate one uses an alcoholic solution like one used for this example by dissolving 23 parts of sodium in 300 parts of absolute alcohol with a moderate amount Receives warmth. After the reaction has ended, it is allowed to cool and shaken to decompose the Sodium compound with dilute acid.
Der Benzolschicht, die aufser dem Indoxylmethylketon noch Anthranilsäureester enthält, kann ersteres durch verdünnte Alkalilauge entzogen werden. Aus der alkalischen Lösung wird das Keton durch Kohlensäure nur theilweise ausgefällt, vollständig erst durch Essigsäure oder verdünnte Mineralsäuren. Es ist ein schwach gelblicher Körper vom Schmp. 1330, leicht löslich in Aether, Alkohol und Benzol," schwer löslich in Chloroform. Beim Erhitzen· mit Aetzalkali. entsteht eine gelbeThe benzene layer, which, in addition to the indoxyl methyl ketone, also contains anthranilic acid ester, can be removed by using dilute alkali. The ketone is only partially precipitated from the alkaline solution by carbonic acid, and completely only by acetic acid or dilute mineral acids. It is a pale yellowish body of mp. 133 0, slightly soluble in ether, alcohol and benzene, "sparingly soluble · When heated with caustic. Originates in chloroform. A yellow
Schmelze, deren wässerige Lösung an der Luft Indigo ausscheidet. In cone. Schwefelsäure löst sich das Indoxylmethylkelon mit gelber Farbe, die beim Erwärmen unter Indigobildung in Blau übergeht. Als Keton ist der Körper dadurch charakterisirt, dafs er mit Phenylhydrazin ein Hydrazon bildet und beim Erwärmen mit alkalischer Hypochlorillösung Chloroform abspaltet.Melt, the aqueous solution of which exudes indigo in the air. In cone. sulfuric acid the indoxylmethylkelon dissolves with a yellow color, which when heated under indigo formation turns blue. The body is characterized as a ketone by the fact that it has Phenylhydrazine forms a hydrazone and when heated with alkaline hypochlorous solution Splits off chloroform.
In diesem Beispiel kann ohne Aenderung des Resultates der Anthranilsöureäthylester durch einen beliebigen anderen Anthranilsäureester ersetzt werden, z. B. durch den Methyl ester oder den Isoamylester.In this example, the ethyl anthranil ester can be used without changing the result be replaced by any other anthranilic acid ester, e.g. B. by the methyl ester or the isoamyl ester.
Das Indoxylmcthylketon ist wegen seiner leichten Ueberführbarkeit in Indigo ftlr die Darstellung dieses Farbstoffes von Wichtigkeit.The indoxyl methyl ketone is because of its easy convertibility into indigo for the Representation of this dye is of importance.
Claims (2)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE111890C true DE111890C (en) |
Family
ID=381596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT111890D Active DE111890C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE111890C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4611064A (en) * | 1984-10-18 | 1986-09-09 | Basf Aktiengesellschaft | Preparation of indole derivatives |
| US7718690B2 (en) | 2002-11-28 | 2010-05-18 | Venkata Satya Nirogi Ramakrishna | N-arylsulfonyl-3-aminoalkoxyindoles |
-
0
- DE DENDAT111890D patent/DE111890C/de active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4611064A (en) * | 1984-10-18 | 1986-09-09 | Basf Aktiengesellschaft | Preparation of indole derivatives |
| US7718690B2 (en) | 2002-11-28 | 2010-05-18 | Venkata Satya Nirogi Ramakrishna | N-arylsulfonyl-3-aminoalkoxyindoles |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE111890C (en) | ||
| DE44002C (en) | Process for the preparation of dyes from the group of the metaam dophenol-phthalein | |
| DE3732169A1 (en) | METHOD FOR PRODUCING TRIAZOLES CONDENSED WITH AROMATIC SYSTEMS | |
| DE415318C (en) | Process for the preparation of 4-arylamino-1-arylimino-2-naphthoquinones | |
| DE109663C (en) | ||
| DE224953C (en) | ||
| DE365367C (en) | Process for the preparation of 2-oxy-1-arylaminonaphthalenes | |
| DE286151C (en) | ||
| DE217477C (en) | ||
| DE113240C (en) | ||
| DE153861C (en) | ||
| DE42726C (en) | Process for the preparation of diphenylpyrazolone and diphenylmethylpyrazolone from benzoylacetate and phenylhydrazine | |
| DE212205C (en) | ||
| DE202398C (en) | ||
| DE859617C (en) | Process for the preparation of tetracyclic derivatives of the sterol series | |
| DE286668C (en) | ||
| DE103578C (en) | ||
| DE499745C (en) | Process for the preparation of phthaloyl-23-thionaphthene and its derivatives | |
| DE495789C (en) | Process for the preparation of concentrated solutions of Trimercuri-diacetone hydrate | |
| DE537767C (en) | Production of acridyl-9-carbamic acid esters | |
| DE502042C (en) | Process for the preparation of new condensation products of the benzanthrone series | |
| DE507638C (en) | Process for the preparation of 6-oxybenzylamine-3-arsinic acids and their acyl derivatives | |
| DE702064C (en) | Process for the preparation of aminoalkyl sulfones | |
| DE720160C (en) | Process for the preparation of 6-aminodihydrocinchonine and -dihydrocinchonidine | |
| DE589971C (en) | Process for the preparation of 4, 8-dioxy-1, 2, 5, 6-dibenzophenazines |