DE117167C - - Google Patents
Info
- Publication number
- DE117167C DE117167C DENDAT117167D DE117167DA DE117167C DE 117167 C DE117167 C DE 117167C DE NDAT117167 D DENDAT117167 D DE NDAT117167D DE 117167D A DE117167D A DE 117167DA DE 117167 C DE117167 C DE 117167C
- Authority
- DE
- Germany
- Prior art keywords
- dioxyquinoline
- acid
- ber
- mixture
- oxycarbostyril
- 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
- 239000002253 acid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium monoxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N 8-Hydroxyquinoline Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- RWZYAGGXGHYGMB-UHFFFAOYSA-N Anthranilic acid Chemical class NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 1
- VAMXMNNIEUEQDV-UHFFFAOYSA-N Methyl anthranilate Chemical compound COC(=O)C1=CC=CC=C1N VAMXMNNIEUEQDV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium(0) Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- -1 o-nitrobenzoylmalonic acid ester Chemical class 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom 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 ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/22—Oxygen atoms attached in position 2 or 4
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Quinoline Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Das ι -3 -Dioxychinolin (y-Oxycarbostyril) hat bis jetzt keine praktische Verwendung gefunden, und zwar wohl unter Anderem aus dem Grunde, ,weil die seither zu seiner Darstellung benutzten Verfahren von technisch schwer darzustellenden Producten ausgingen oder aber ä'ufserst umständlich waren.The ι -3 -Dioxyquinoline (y-Oxycarbostyril) has so far no practical use has been found, probably for the reason, among other things, , because the methods used since then to represent it are technically difficult to represent Products ran out or were extremely cumbersome.
So verwendeten Baeyer und Blöm (Ber. d. d. ehem. Ges. 15, 2151) o-Amidophenylpropiolsäure, welche sie mittelst concentrirter Schwefelsäure in y-Oxycarbostyril überführten; Friedländer und Weinberg (Ber. 15, 2683) unterwarfen das sogen, α -γ- Brom- (bezw. Chlor-) oxy chinolin der Kalischmelze, während Bischoff (Ber. 22, 387) vom o-Nitrobenzoylmalonsäureester ausging und diesen mit granulirtem Zinn und wässerig-alkoholischer Salzsäure behandelte.Baeyer and Blöm (Ber. Dd. Ges. 15, 2151) used o-amidophenylpropiolic acid, which they converted into γ-oxycarbostyril by means of concentrated sulfuric acid; Friedländer and Weinberg (Ber. 15, 2683) subjected the so-called α-γ- bromine (or chlorine) oxy quinoline to the potash melt, while Bischoff (Ber. 22, 387) started with the o-nitrobenzoylmalonic acid ester and this with granulated tin and aqueous-alcoholic hydrochloric acid.
In neuerer Zeit haben auch Derivate der Anthranilsäure für die Darstellung von 1-3-Dioxychinolin Verwendung gefunden. So ist in der Patentschrift 102894 die Ueberführung von Acetanthranilsäureä'thylester in 1 3 - Dioxychinolin mittelst Natrium in Toluollösung beschrieben worden. Jedoch verläuft eine derartige Condensation nach den Angaben vonMore recently, derivatives of anthranilic acid have also been used for the preparation of 1-3-dioxyquinoline Use found. So is the transfer in patent specification 102894 of ethyl acetanthranilate in 13-dioxyquinoline by means of sodium in toluene solution has been described. However, such a condensation proceeds according to the information from
,H,H
N<co N <co
CH3
\/^COO Me CH 3
\ / ^ COO Me
verläuft.runs.
Das ι · 3-Dioxychinolin soll als Ausgangs-Mühlstein (»Ueber orthosubstituirte Alkylaniline«, Inaugural-Dissertation zur Erlangung der Doctorwürde der hohen philos. Fakultät der Universität Basel, 189g, S. 31) nichts weniger als glatt, so dafs die Hauptmenge (60 pCt.) des Ausgangsmaterials unverändert zurückerhaltenwird. Schliefslich hat Erdmann (Ber. 32, 3570) die Entstehung des genannten Dioxychinolins bei der Condensation von Anthranilsäuremethylester und Essigester mittelst metallischem Natrium beobachtet, wobei eine intermediäre Bildung von o-Amidobenzoylessigester stattfindet.The ι · 3-Dioxyquinoline is said to be the starting millstone ("About orthosubstituted alkylanilines", Inaugural dissertation to obtain the doctorate of the high philosophical faculty of the University of Basel, 189g, p. 31) nothing less as smooth, so that the majority (60 pCt.) of the starting material is recovered unchanged. Finally, Erdmann (Ber. 32, 3570) has the origin of the aforementioned dioxyquinoline in the condensation of anthranilic acid methyl ester and ethyl acetate by means of metallic substances Sodium observed, with an intermediate formation of o-amidobenzoyl acetic ester takes place.
Es würde nun gefunden, dafs sich mit gröfster Leichtigkeit und unter Erzielung fast quantitativer Ausbeute ι · 3-Dioxychinolin gewinnen läfst, wenn man die trockenen Alkalioder Erdalkalisalze der Acetylanthranilsäure mit möglichst wasserfreiem Alkali oder Erdalkali auf Temperaturen über 1500 erhitzt. Während Alkalien in wässeriger Lösung die Acetanthranilsäure verseifen, bewirken sie unter den oben angegebenen Bedingungen, dafs die Reaction im Sinne der GleichungIt would have found, that with gröfster ease and almost quantitative yield while achieving ι · 3-Dioxychinolin win läfst when heating the dry alkali metal or alkaline earth salts of acetylanthranilic with as anhydrous alkali or alkaline earth metal to temperatures above 150 0th While alkalis saponify the acetanthranilic acid in aqueous solution, under the conditions given above they cause the reaction in the sense of the equation
Λ\ " Λ \ "
C(OHJC (OHJ
I +H2O I + H 2 O
C-HC-H
material zur Darstellung von Farbstoffen etc. Verwendung finden.find material for the representation of dyes etc. use.
I.I.
ι Theil acetanthranilsaures Kalium wird mit 2 Theilen kaustischem Kali innig vermählen. Man erhitzt die Mischung ι Stunde auf 2500, läfst erkalten und neutralisirt dann die Lösung der Schmelze in Wasser. Das Dioxychinolin fällt sofort in reiner Form aus. In seinen Eigenschaften stimmt es mit dem nach dem bekannten Verfahren dargestellten 1 ■ 3-Dioxychinolin überein.Part of potassium acetanthranil is intimately mixed with 2 parts of caustic potash. The mixture was heated to 250 0 ι hour, läfst cool, and the solution is then neutralized the melt in water. The dioxyquinoline precipitates immediately in its pure form. In its properties, it corresponds to the 1 ■ 3-dioxyquinoline prepared according to the known method.
Π.Π.
ι Theil acetanthranilsaures Kalium wird mit ι Theil kaustischem Kali und 2 Theilen gebranntem Kalk innig gemahlen und die Mischung wie im Beispiel I behandelt. Man löst in Wasser, filtrirt und fällt aus dem Filtrat das Dioxychinplin wie vorbesprochen aus.Part of acetanthranilic potassium is combined with part of caustic potash and 2 parts of burnt Lime thoroughly ground and the mixture treated as in Example I. It is dissolved in water, filtered and precipitated from it The dioxyquinpline filtrated out as previously discussed.
III.III.
ι Theil acetanthranilsaures Barium wird mit 2 Theilen Barythydrat und 1 Theil gebranntem Kalk fein vermählen und das Gemisch während 2 Stunden unter Luftabschlufs auf 290 bis 3000 erhitzt. Nach dem Erkalten wird die Schmelze in heifsem Wasser gelöst und aus der Lösung das ι -3-Dioxychinolin durch verdünnte Säuren gefällt.ι part acetanthranilsaures barium is finely ground with 2 parts of barium hydroxide and 1 part of quick lime and the mixture heated for 2 hours under Luftabschlufs at 290-300 0th After cooling, the melt is dissolved in hot water and the ι -3-dioxyquinoline is precipitated from the solution using dilute acids.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE117167C true DE117167C (en) |
Family
ID=386451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT117167D Active DE117167C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE117167C (en) |
-
0
- DE DENDAT117167D patent/DE117167C/de active Active
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