DE212782C - - Google Patents
Info
- Publication number
- DE212782C DE212782C DENDAT212782D DE212782DA DE212782C DE 212782 C DE212782 C DE 212782C DE NDAT212782 D DENDAT212782 D DE NDAT212782D DE 212782D A DE212782D A DE 212782DA DE 212782 C DE212782 C DE 212782C
- Authority
- DE
- Germany
- Prior art keywords
- diketodihydro
- water
- derivatives
- thionaphtene
- ketodihydro
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000002378 acidificating Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000003776 cleavage reaction Methods 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 229960000583 Acetic Acid Drugs 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- AJGLCXBDYCEVIE-UHFFFAOYSA-N 5-chloro-3-hydroxy-1H-pyridin-2-one Chemical compound OC1=CC(Cl)=CN=C1O AJGLCXBDYCEVIE-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N Benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000001476 alcoholic Effects 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- VMAQYKGITHDWKL-UHFFFAOYSA-N 5-methylimidazolidine-2,4-dione Chemical compound CC1NC(=O)NC1=O VMAQYKGITHDWKL-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N Martius yellow Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 125000000066 S-methyl group Chemical group [H]C([H])([H])S* 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N Thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- GGISZLOBBISXOZ-UHFFFAOYSA-N acetic acid;chloroform Chemical compound CC(O)=O.ClC(Cl)Cl GGISZLOBBISXOZ-UHFFFAOYSA-N 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
- C07D333/64—Oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Indole Compounds (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
Ig-212782 -/ KLASSE 12 o. GRUPPE Ig-212782 - / CLASS 12 or GROUP
Patentiert im Deutschen Reiche vom 8. November 1906 ab.Patented in the German Empire on November 8, 1906.
Es hat sich gezeigt, daß die Dihalogenverbindungen des 3-Ketodihydro(i)thionaphtens sowie der Homologen und der Derivate dieser Verbindung (cf. französ. Patent 374287) leicht in 2 · 3-Diketodihydro(i)thionaphten oder Derivate desselben verwandelt werden können.It has been shown that the dihalogen compounds of 3-ketodihydro (i) thionaphthene and the homologues and derivatives thereof Compound (cf. French patent 374287) easily in 2 · 3-diketodihydro (i) thionaphtene or derivatives the same can be transformed.
Läßt man auf 2^Dihalogen-3-ketodihydro(i)-thionaphtene alkalische Mittel oder konzentrierte Schwefelsäure oder trockene saure Salze einwirken, so entstehen Thioindigofarbstoffe. Behandelt man dagegen die 2-Dihalogen-3-ketodihydro(i)thionaphtene mit Wasser, oder sauren verseifenden Mitteln, so werden dieselben unter Ersatz der beiden Halogenatome durch Sauerstoff in 2 · 3-Diketodihydro (1)thionaphten bzw. dessen Homologen oder Derivate übergeführt. Sofern hierbei gleichzeitig geringe Mengen von Farbstoff entstehen, kann man letzteren leicht abtrennen, z. B. durch Auflösen des 2 · 3-Diketodihydro (1) thionaphtens in verdünnter Essigsäure und Abfiltrieren. Wenn man auf die genannten Dihalogenketodihydrothionaphtene Körper, welche primäre Aminogruppen enthalten, wie Amine, Hydrazine oder Hydroxylamin usw., einwirken läßt, so entstehen unter Abspaltung von Halogenwasserstoffsäure Derivate von 2 · 3-Diketodihydrothionaphtenen. Dieselben lassen sich durch Behandlung mit verseifenden Mitteln in 2 · 3-Diketodihydrothionaphtene überführen.If one leaves on 2 ^ dihalo-3-ketodihydro (i) -thionaphtene When alkaline agents or concentrated sulfuric acid or dry acidic salts act, thioindigo dyes are formed. If, on the other hand, the 2-dihalo-3-ketodihydro (i) thionaphtenes are treated with water, or with acidic saponifying agents, they are replaced by the two halogen atoms by oxygen in 2 · 3-diketodihydro (1) thionaphtene or its homologues or derivatives converted. Provided that at the same time low Amounts of dye arise, you can easily separate the latter, z. B. by Dissolve the 2x3-diketodihydro (1) thionaphthene in dilute acetic acid and filter off. If you look at the mentioned Dihalogenketodihydrothionaphtene body, which primary Contain amino groups, such as amines, hydrazines or hydroxylamine etc., can act, in this way derivatives of 2 · 3-diketodihydrothionaphthens are formed with the elimination of hydrohalic acid. These can be converted into 2 · 3-diketodihydrothionaphthens by treatment with saponifying agents.
2-Dichlor-3 -ketodihydro (1) thionaphten wird mit Wasser einige Zeit gekocht. Die erhaltene 40 2-dichloro-3-ketodihydro (1) thionaphten is boiled with water for some time. The 40
4545
goldgelbe Lösung wird filtriert und abgekühlt, wobei sich das entstandene 2 · 3-Diketodihydro (1) thionaphten abscheidet. Es bildet orangegelbe Prismen vom Schmelzpunkt ii8°. golden yellow solution is filtered and cooled, the resulting 2 · 3-diketodihydro (1) separates thionaphtene. It forms orange-yellow prisms with a melting point of ii8 °.
2-Dibrom-3-ketodihydro (1) thionaphten wird mit 3oprozentiger Essigsäure bis zum Entstehen einer Lösung gekocht; beim Abkühlen der eventuell filtrierten Lösung scheidet sich das 2 · 3-Diketodihydro (1) thionaphten ab.2-Dibromo-3-ketodihydro (1) thionaphten is treated with 3% acetic acid until it forms boiled a solution; when the possibly filtered solution cools, it separates the 2x3-diketodihydro (1) thionaphtene.
Es ist nicht erforderlich, von isolierter Dihalogenverbindung auszugehen, vielmehr kann man z. B. die bei der Darstellung der Dihalogenderivate erhaltenen Reaktionsmassen (vgl. z. B. Beispiel 3 der französ. Patentschrift 374287) direkt weiter auf 2·3-Diketodihydro(1)-thionaphten verarbeiten, indem man mit heißem Wasser verdünnt und kocht.It is not required of isolated dihalogen compound go out, rather you can z. B. those in the representation of the dihalogen derivatives reaction masses obtained (cf., for example, Example 3 of French Patent 374287) directly further to 2 · 3-diketodihydro (1) -thionaphthene process by diluting with hot water and boiling.
Wird in obigen Beispielen an Stelle der dort genannten 2-Dihalogen-3-ketodihydrothiqnaphtene s-Methyl^-dibrom-s-ketodihydrothionäphten oder 5 - Chlor - 2 - dibrom - 3 - ketodihydrothionaphten usw. verwendet, so erhält man 5-Methyl- bzw. 5-Chlor-2 · 3-diketodihydro(i)-thionaphten von ganz ähnlichen Eigenschaften wie das 2 · 3-Diketodihydrothionaphten,Is used in the above examples instead of the 2-dihalo-3-ketodihydrothiqnaphtene mentioned there s-methyl ^ -dibromo-s-ketodihydrothionäphten or 5 - chloro - 2 - dibromo - 3 - ketodihydrothionaphthene etc. are used, one obtains 5-methyl- or 5-chloro-2 · 3-diketodihydro (i) -thionaphthene of very similar properties to the 2 3-diketodihydrothionaphthene,
Das 5-Methyl-2 · 3-diketodihydro(i) thionaphten ist in ganz reinem Zustand, mit Wasserdampf destilliert, orangegelb; aus Alkohol umkristallisiert bildet es braune · Tafeln vom Schmelzpunkt 143 bis 144 °; Chloroform und Eisessig lösen es sehr leicht, Petroläther fast nicht.The 5-methyl-2 · 3-diketodihydro (i) thionaphten is in a completely pure state, with water vapor distilled, orange-yellow; Recrystallized from alcohol, it forms brown tablets from Melting point 143 to 144 °; Chloroform and Glacial acetic acid dissolves it very easily, petroleum ether almost not.
Das 5-Chlor-2 · 3-diketodihydro(i)thionaph-The 5-chloro-2 3-diketodihydro (i) thionaph-
ten kristallisiert aus Benzol, worin es heü3 sehr leicht, kalt mäßig löslich ist, in roten Platten, die, nach nochmaligem Umkristallisiereix aus Alkohol bei 148 bis 149 ° schmelzen.Ten crystallizes from benzene, in which it is very easily soluble in hot water and moderately soluble in cold water, in red Plates which, after repeated recrystallization, melt from alcohol at 148 to 149 °.
Beispiel III.Example III.
Zu einer heißen Lösung von 30,8 Teilen 2-Dibrom-3-ketodihydrothionaphten in AlkoholTo a hot solution of 30.8 parts of 2-dibromo-3-ketodihydrothionaphthene in alcohol
ίο fügt man eine heiße alkoholische Lösung von 30 Teilen kristallisiertem Natriumacetat und 9,3 Teilen Anilin hinzu und erwärmt etwa 1/2 Stunde auf dem Wasserbad. Hierauf wird die Flüssigkeit in das zehnfache Volum kalten , 15 angesäuerten Wassers eingegossen, das in braunen Flocken abgeschiedene Reaktionsprodukt abgesaugt, mit Wasser gewaschen und getrocknet. Es ist in organischen Mitteln leicht mit gelbbrauner Farbe löslich; aus der Lösung in Äther läßt es sich durch Ligroin in hellbraunen, mikrokristallinischen Flocken ausfällen.ίο one adds a hot alcoholic solution of 30 parts of crystallized sodium acetate and 9.3 parts of aniline and warms about 1/2 hour on the water bath. The liquid is then poured into ten times its volume of cold , acidified water, and the reaction product, which has separated out in brown flakes, is suctioned off, washed with water and dried. It is easily soluble in organic means with a yellow-brown color; from the solution in ether it can be precipitated by ligroin in light brown, microcrystalline flakes.
Man kann auch so verfahren, daß man die alkoholische Lösung einige Zeit bei gewöhnlicher Temperatur unter öfterem Umschütteln stellen läßt," wobei die Reaktionsmasse zu einem Brei brauner Flocken erstarrt. Mit verdünnter Essigsäure unter Zusatz einiger Tropfen Mineralsäure- gekocht, zerfällt die Verbindung in Anilin und 2 · 3-Diketodihydrothionaphten. Erwärmt man die.trockene Substanz einige Zeit auf dem Wasserbad, so gelingt die Verseifung nicht mehr glatt.One can also proceed in such a way that one uses the alcoholic solution for some time with ordinary Temperature can be set with frequent shaking, "whereby the reaction mass solidifies to a paste of brown flakes. With When boiled with dilute acetic acid with the addition of a few drops of mineral acid, the compound breaks down in aniline and 2x3-diketodihydrothionaphthene. The dry substance is heated for a while on the water bath, the saponification no longer works smoothly.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE212782C true DE212782C (en) |
Family
ID=474496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT212782D Active DE212782C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE212782C (en) |
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