DD218617A1 - PROCESS FOR PREPARING OH-SUBSTITUTED CHINOLINES - Google Patents
PROCESS FOR PREPARING OH-SUBSTITUTED CHINOLINES Download PDFInfo
- Publication number
- DD218617A1 DD218617A1 DD25263583A DD25263583A DD218617A1 DD 218617 A1 DD218617 A1 DD 218617A1 DD 25263583 A DD25263583 A DD 25263583A DD 25263583 A DD25263583 A DD 25263583A DD 218617 A1 DD218617 A1 DD 218617A1
- Authority
- DD
- German Democratic Republic
- Prior art keywords
- preparation
- methyl
- substituted
- acetylacetone
- chinolines
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 10
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940018563 3-aminophenol Drugs 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 239000011541 reaction mixture Substances 0.000 claims abstract description 3
- 229940111121 antirheumatic drug quinolines Drugs 0.000 claims description 4
- 150000003248 quinolines Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000012024 dehydrating agents Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical class C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229940027991 antiseptic and disinfectant quinoline derivative Drugs 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000012458 free base Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- BJMQFQNRVVIERR-UHFFFAOYSA-N 2,4-dimethylquinolin-7-ol Chemical compound C1=CC(O)=CC2=NC(C)=CC(C)=C21 BJMQFQNRVVIERR-UHFFFAOYSA-N 0.000 description 1
- UZSDRHVOBLQYCX-UHFFFAOYSA-N 2-amino-6-hydroxybenzoic acid Chemical compound NC1=CC=CC(O)=C1C(O)=O UZSDRHVOBLQYCX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UNPLRYRWJLTVAE-UHFFFAOYSA-N Cloperastine hydrochloride Chemical compound Cl.C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)OCCN1CCCCC1 UNPLRYRWJLTVAE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Es wird ein einfaches Verfahren zur Herstellung von 7-OH-2-methyl-4-methyl/phenyl-chinolinen beschrieben, indem m-Aminophenol und Acetylaceton bzw. Benzoylaceton, gegebenenfalls in Gegenwart eines indifferenten organischen Loesungsmittels mit konzentrierter Schwefelsaeure in exothermer Reaktion umgesetzt werden und die Base aus dem waessrigen Reaktionsgemisch mit verduenntem NaOH isoliert wird.A simple process for the preparation of 7-OH-2-methyl-4-methyl / phenyl-quinolines is described by reacting m-aminophenol and acetylacetone or benzoylacetone, optionally in the presence of an inert organic solvent, with concentrated sulfuric acid in an exothermic reaction and isolating the base from the aqueous reaction mixture with dilute NaOH.
Description
Verfahren zur Herstellung von OH-substituierten ChinolinenProcess for the preparation of OH-substituted quinolines
Die Erfindung betrifft ein Verfahren zur Herstellung von 7-ÖH-substituierten Chinolinderivaten. Diese können als Zwischenprodukte zur Herstellung von Farbstoffen und für pharmazeutische Verbindungen verwendet werden·The invention relates to a process for the preparation of 7-ÖH-substituted quinoline derivatives. These can be used as intermediates for the preparation of dyes and for pharmaceutical compounds.
^-Methyl^-methyx/phenyl-T-OH-chinoline sind bisher mehrmals beschrieben worden· So berichten BÜLOW, ISSLBR (Ber.dtsch.chem.Ges· 2£» 4-016 (1904)), ferner BÜLOW (Ber.dtsch.ehem.Ges. 2£, 2452 (1903)) über deren Darstellung aus Acetylaceton-mono-3-OH-anil bzw· aus ß-(3-0H-phenylimino)-butyrophenon, die diese durch Einleiten von Chlorwasserstoff bzw. durch Einwirkung von konz. Schwefelsäure in die gewünschten Chinolinderivate überführen. SEKI und YAMADA beschreiben die Darstellung von 2,4-Dimethyl-7-0H-chinolin, indem sie Aminosaiieylsäureamid mit Acetylaceton bei einer Reaktionsdauer von 100 Stunden zur entsprechenden 7-0H-2,4-dimethyl-chinolin-8-carbonsSure umsetzen und diese anschließend decarboxylierten. (Sci.Papaers Inst.Phys. Chem.Res. (Tokyo) 56, No. 1, 101-8 (1962), CA. 58 (1963) 4515 f). Das entsprechende 7-OH-2-methyl-4-phenyl-chinolin stellte Kazutoschi YAMADA dar, indem^ -Methyl-methyx / phenyl-T-OH-quinolines have hitherto been described a number of times. Thus, BÜLOW, ISSLBR (Berdtsch. Chem. Ge. 2, p. 4-016 (1904)), and BÜLOW (Ber. dtsch.ehem.Ges., 2, 2452 (1903)) on the preparation thereof from acetylacetone-mono-3-OH-anil or from ß- (3-0H-phenylimino) -butyrophenone, these by introducing hydrogen chloride or by the action of conc. Convert sulfuric acid into the desired quinoline derivatives. SEKI and YAMADA describe the preparation of 2,4-dimethyl-7-OH-quinoline by reacting amino acid amide with acetylacetone at a reaction time of 100 hours to give the corresponding 7-OH-2,4-dimethyl-quinoline-8-carboxylic acid and these then decarboxylated. (Sci.Papaers Inst.Phys.Chem.Res. (Tokyo) 56, No. 1, 101-8 (1962), CA. 58 (1963) 4515 f). The corresponding 7-OH-2-methyl-4-phenyl-quinoline was presented by Kazutoschi YAMADA by
er des Ammonium« oder Alkylammoniumsalz der 6-Aminosalicylsäure mit Benzoylaceton auf die eben beschriebene Weise umsetzt (ΒΓχρροη, Kagaku Zaschi, 82, 1368-72 (1961)? CA. *&9 3892 a,b (1963))· Diese Verfahren haben Ausgangsprodukte zur Grundlage, die nur sear aufwendig zu synthetisieren sind und bei deren aufwendiger Reaktionsweise nur geringe Ausbeuten erhalten werden*he of the ammonium "or alkylammonium salt of the 6-aminosalicylic acid with benzoylacetone in the manner just described converts (ΒΓχρροη, Zaschi Kagaku, 82, 1368-72 (1961)? CA. * & 9 3892 a, b (1963)) have · This method Starting products based on which only sear are expensive to synthesize and whose complex reaction mode only low yields are obtained *
Ziel ,der. ErfindungGoal of. invention
Ziel der Erfindung ist es, ein technologisch einfaches Verfahren auf der Basis leicht zugängiger Ausgangsstoffe und ohiie erheblichen experimentellen Aufwand für die Herstellung der 7-OH-2-methy 1-4-Hiethyl/phenylehinoline zu schaffen«The aim of the invention is to provide a technologically simple process based on readily available starting materials and ohiie considerable experimental effort for the preparation of 7-OH-2-methy 1-4-Hiethyl / phenylehinoline «
, 4ftr,, 4ft r ,
Der Erfindung liegt die Aufgabe zugrunde, ein technologisch einfaches Verfahren in einer Art "Eintopfverfahren11 für die Herstellung von 7-0H-2-methyl~4-methyl/ pheny!-chinoline zu schaffene The invention has for its object to provide a technologically simple method in a kind of "one-pot process 11 for the preparation of 7-0H-2-methyl ~ 4-methyl / pheny! -Quinolines e
jCqx.jCqx.
. ' R = CH, CHo, 'R = CH, CHo
Erfindungsgemäß wird die Aufgabe dadurch gelöst, daß m-Aminophenol und Acetylaceton bzw· Benzoylaceton, gegebenenfalls in Gegenwart von wenig inertem, mit Schwefelsäure mischbaren Lösungsmittel versetzt, bei normaler Temperatur vereinigt werden und sich in einer exothermen Reaktion zu dem gewünschten Produkt umsetzen* Nach dem Abkühlen wird das Reaktionsprodukt in Wasser \ According to the invention, this object is achieved in that m-aminophenol and acetylacetone or benzoylacetone, if appropriate in the presence of less inert, mixed with sulfuric acid miscible solvent, are combined at normal temperature and react in an exothermic reaction to the desired product * After cooling is the reaction product in water \
gelöst, mit verd· wäßriger HaOH die freie Base ausgefällt und diese gegebenenfalls aus Methanol umkristallisiert. Die Vorteile dieses Verfahrens sind, daß es nicht zeitaufwendig ist, daß es sich durch den Einsatz leicht zugängiger Ausgangsprodukte auszeichnet und die gewünschten Produkte in hoher Ausbeute anfallen· Von besonderem ökonomischen Vorteil ist ferner, daß die Reaktionen ohne Energiezufuhr verlaufen·dissolved, precipitated with dilute aqueous HaOH, the free base and this optionally recrystallized from methanol. The advantages of this process are that it is not time-consuming, that it is characterized by the use of easily accessible starting materials and that the desired products are obtained in high yield. It is also of particular economic advantage that the reactions proceed without energy supply.
Ausführungsbeispiele Beispiel 1Exemplary embodiments Example 1
In einem 2-Halskolben mit Rührer und Rückflußkühler werden 0,2 mol 3-Aminophenol und 0,2 mol Acetylaceton vermischt· Unter starkem Rühren werden langsam 0,4 mol ' konz· H„SO^ hinzugefügt· Die Reaktion verläuft stark exotherm, nach wenigen Minuten ist eine trockene, kristalline Masse entstanden, die das Salz des 2,4-Di«· methyl-chinolin-7-ol darstellt. Zur Abscheidung der Base wird das Rohprodukt in wenig Wasser gelöst, die wäßrige Lösung mit verdünnter wäßriger Natronlauge schwach alkalisch gemacht· Die in 85%iger Ausbeute ausgefallene Bas« wird aus wenig Methanol umkristallisiert, die anfallenden Kristalle haben einen Schmelzpunkt von 217,5 - 218 0C.In a 2-necked flask equipped with a stirrer and reflux condenser, 0.2 mol of 3-aminophenol and 0.2 mol of acetylacetone are mixed. Under vigorous stirring, 0.4 mol of conc.H "SO.sub.4 are added slowly. The reaction proceeds strongly exothermically A few minutes later, a dry, crystalline mass has formed, which is the salt of 2,4-dimethyl-quinolin-7-ol. For separation of the base, the crude product is dissolved in a little water, the aqueous solution made weakly alkaline with dilute aqueous sodium hydroxide solution. The base precipitated in 85% yield is recrystallised from a little methanol and the resulting crystals have a melting point of 217.5-218 0 C.
7-Hydro3cy-2-me thy 1-4-Phen.vl-chino lin7-Hydro3cy-2-methyl-1-4-phen-vinylquinoline
In einem mit Rührer und Rückflußkühler ausgestatteten Kolben werden 0,2 mol m-Aminophenol und 0,20 mol Benzoyl· aceton in wenig Tetrachlorkohlenstoff gelöst· Unter starkem Rühren werden 0,4 mol konz· Schwefelsäure zugetropft· Das Reaktionsgemisch erwärmt sich sehrIn a flask equipped with a stirrer and reflux condenser, 0.2 mol of m-aminophenol and 0.20 mol of benzoyl acetone are dissolved in a little carbon tetrachloride. With vigorous stirring, 0.4 mol of concentrated sulfuric acid are added dropwise. The reaction mixture heats up very much
stark und erstarrt zu einem Kristallbrei· Aus dem angefallenen Kristallbrei wird im Vakuum das organische Lösungsmittel abgezogen, die freie Base mit verdünnter, wäßriger HaOH ausgefällt und aus Methanol umkristallisiertestrong and solidifies into a crystal pulp · The organic solvent is stripped off from the resulting crystal pulp in vacuo, the free base is precipitated with dilute, aqueous HaOH and recrystallized from methanol
Das Ghinolin fällt in orangefarbenen Nadeln vom Schmelzpunkt 262 0C in 80%iger Ausbeute an*The Ghinolin precipitated in orange needles of melting point 262 0 C in 80% yield *
Claims (2)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD25263583A DD218617A1 (en) | 1983-07-01 | 1983-07-01 | PROCESS FOR PREPARING OH-SUBSTITUTED CHINOLINES |
| CS838057A CS240772B1 (en) | 1983-07-01 | 1983-11-01 | Method of 7-hydroxyquinoline derivatives production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD25263583A DD218617A1 (en) | 1983-07-01 | 1983-07-01 | PROCESS FOR PREPARING OH-SUBSTITUTED CHINOLINES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DD218617A1 true DD218617A1 (en) | 1985-02-13 |
Family
ID=5548717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DD25263583A DD218617A1 (en) | 1983-07-01 | 1983-07-01 | PROCESS FOR PREPARING OH-SUBSTITUTED CHINOLINES |
Country Status (2)
| Country | Link |
|---|---|
| CS (1) | CS240772B1 (en) |
| DD (1) | DD218617A1 (en) |
-
1983
- 1983-07-01 DD DD25263583A patent/DD218617A1/en not_active IP Right Cessation
- 1983-11-01 CS CS838057A patent/CS240772B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS805783A1 (en) | 1985-07-16 |
| CS240772B1 (en) | 1986-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1795808C2 (en) | Process for the preparation of 2,2,6,6-tetramethyl-4-oxopiperidine | |
| DE2206366C3 (en) | Process for the preparation of substituted diaminocarbonyl derivatives | |
| DE1518934A1 (en) | Process for the preparation of compounds containing silyl groups | |
| DE2237632A1 (en) | METHOD FOR PREPARING 1- (4-METHYL-6-METHOXY-2-PYRIMIDINYL) -3-METHYL-5METHOXYPYRAZOLE | |
| DD218617A1 (en) | PROCESS FOR PREPARING OH-SUBSTITUTED CHINOLINES | |
| DE2536950A1 (en) | CYAN CONNECTIONS | |
| DE2527157C2 (en) | Process for the preparation of 2-formylquinoxaline-N → 1 →, N → 4 → -dioxide dimethylacetal | |
| DE2065698C3 (en) | Process for the preparation of 2-isopropyl-6-methyl-4 (3H) -pyrimidone | |
| DE908613C (en) | Process for the preparation of fatty acids substituted in the ª-position by guanidine | |
| DE1063598B (en) | Process for the preparation of water-soluble derivatives of the tetracyclines | |
| DE1909577A1 (en) | Process for accelerating the anionic polymerization of lactams | |
| DE2008874A1 (en) | Pyrimidine derivs from urea and beta-keto - esters | |
| DE3500029A1 (en) | Anthracycline esters | |
| DE1294371B (en) | Process for the preparation of 1-aminoadamantane and its N-alkyl or N-cyclohexyl derivatives | |
| AT214440B (en) | Process for the preparation of 3-iminoisoindolin-1-ones | |
| DE3223913C1 (en) | Process for the preparation of pyridine 2-,3- or 4-aldoximes or their derivatives which are alkyl-substituted on the pyridine ring | |
| AT276641B (en) | Process for the preparation of new hydraziyohimbanes | |
| DE2344608C3 (en) | Process for the preparation of D-lysergic acid amides | |
| EP0071018A1 (en) | Process for preparing 2,4-dihydroxypyrimidine (Uracil) | |
| DE1050348B (en) | Process for the production of amebicidally active dichloroacet - 4 - oxy-N-methylanilide | |
| DE2300549A1 (en) | Phosphorous mono-and di-amides prepn - from phosphorous oxide and amines | |
| DE1809121A1 (en) | Magnesium monoaspartate hydrobromide useful - as a sectative or tranquilliser | |
| DD296801A7 (en) | PROCESS FOR PREPARING 4-DICYANOMETHYLENE-2-MEHYL-6-P-DIALKYLAMINOSTYRYL-4H-PYRANEES | |
| DD201025A1 (en) | METHOD OF PREPARING N- (2'-DIAETHYLAMINOETHYL) -2-METHOXY-4-AMINO-5-CHLORO BENZAMIDE HYDROCHLORIDE MONOHYDRATE | |
| DD257829A1 (en) | PROCESS FOR THE PREPARATION OF 7-AMINO-6-AMINOALKYL-5-METHYL-S-TRIAZOLO (1,5-A) PYRIMIDINES |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| ENJ | Ceased due to non-payment of renewal fee |