DE1212536B - Process for the preparation of 2,4-disubstituted quinoline-3-carboxylic acid alkyl esters - Google Patents

Process for the preparation of 2,4-disubstituted quinoline-3-carboxylic acid alkyl esters

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Publication number
DE1212536B
DE1212536B DEF34308A DEF0034308A DE1212536B DE 1212536 B DE1212536 B DE 1212536B DE F34308 A DEF34308 A DE F34308A DE F0034308 A DEF0034308 A DE F0034308A DE 1212536 B DE1212536 B DE 1212536B
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DE
Germany
Prior art keywords
carboxylic acid
preparation
alkyl esters
water
acid alkyl
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.)
Pending
Application number
DEF34308A
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German (de)
Inventor
Dr Rudolf Gompper
Dr Rolf Kunz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to DEF34308A priority Critical patent/DE1212536B/en
Publication of DE1212536B publication Critical patent/DE1212536B/en
Pending legal-status Critical Current

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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
    • C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C07D215/54—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3
    • C07D215/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3 with oxygen atoms in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C07D221/10—Aza-phenanthrenes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Description

Verfahren zur Herstellung von 2,4-disubstituierten Chinolin-3-carbonsäurealkylestern Es wurde gefunden, daß man 2,4-disubstituierte Chinolin-3-carbonsäurealkylester erhält, wenn man eine Verbindung der allgemeinen Formel worin X ein Sauerstoff- oder Schwefelatom und R einen Alkylrest bedeutet, bei etwa 80 bis 85"C mit in der X und R die oben angegebene Bedeutung besitzen, isoliert.Process for the preparation of 2,4-disubstituted quinoline-3-carboxylic acid alkyl esters It has been found that 2,4-disubstituted quinoline-3-carboxylic acid alkyl esters are obtained when a compound of the general formula is obtained where X is an oxygen or sulfur atom and R is an alkyl radical, at about 80 to 85 "C with in which X and R are as defined above, isolated.

Das Verfahren sei durch nachfolgendes Reaktionsschema erläutert: Die Verfahrensprodukte sollen als Zwischenprodukte für weitere Synthesen, insbesondere für die Herstellung von Farbstoffen, Arzneimitteln und Schädlingsbekämpfungsmitteln verwendet werden.The process is illustrated by the following reaction scheme: The products of the process are to be used as intermediates for further syntheses, in particular for the production of dyes, drugs and pesticides.

Beispiel 1 5 g Dicarbäthoxy-acetanilid, fein pulverisiert, werden mit 30 g Polyphosphorsäure vermischt und das Gemisch 4 Stunden auf 85"C erhitzt (öfteres Um-Polyphosphorsäure behandelt und das entstandene Verfahrensprodukt der allgemeinen Formel schütteln). Die leicht gelbliche Lösung wird über Nacht bei Zimmertemperatur stehengelassen, dann mit Wasser versetzt und der Niederschlag abfiltriert (Auswaschen mit Wasser bis zur neutralen Reaktion des Waschwassers). Schmelzpunkt 205 bis 210°C. Example 1 5 g of dicarbethoxy-acetanilide, finely powdered, are mixed with 30 g of polyphosphoric acid and the mixture heated to 85 ° C. for 4 hours (Frequently treated um-polyphosphoric acid and the resulting process product of shake general formula). The slightly yellowish solution becomes overnight at room temperature left to stand, then mixed with water and the precipitate filtered off (washing out with water until the washing water reacts neutral). Melting point 205 to 210 ° C.

Das 2,4-Dihydroxy-3-carbäthoxy-chinolin wird aus Aceton und anschließend noch zweimal ausAthanol-Wasser umkristallisiert. Schmelzpunkt 205 bis 210°C (Zersetzung). Ausbeute 3,9 g an Rohprodukt (930/0 der Theorie). OH W PolvnhosDhorsåure C6HsNHCOCH(COOR)2 ) %/ uN/> OH N -§^ (bzw. tautomere Formen) Beispiel 2 7,7 g Dicarbäthoxy-thioacetanilid (hergestellt aus Phenylsenföl und Malonester nach D. E. W o r r a 11, J. Am. Chem. Soc., 50, S. 1456 [1928]; 46, S. 2834 [1924]) werden mit 45 g Polyphosphorsäure innig vermischt und das Gemisch 4 Stunden auf 84°C erhitzt. Die homogene gelbe Lösung wird nach Erkalten mit Wasser versetzt, der Niederschlag ab- filtriert, zweimal mit Wasser aufgekocht und anschließend auf dem Filter noch gründlich mit Wasser ausgewaschen. Ausbeute an 4-Hydroxy-2-mercapto-3-carbäthoxy-chinolin 5,9 g (920in der Theorie).The 2,4-dihydroxy-3-carbethoxy-quinoline is recrystallized from acetone and then twice more from ethanol-water. Melting point 205 to 210 ° C (decomposition). Yield 3.9 g of crude product (930/0 of theory). OH W. PolvnhosDhorsåure C6HsNHCOCH (COOR) 2)% / uN /> OH N -§ ^ (or tautomeric forms) Example 2 7.7 g of dicarbethoxy-thioacetanilide (prepared from phenyl mustard oil and malonic ester according to DE W orra 11, J. Am. Chem. Soc., 50, p. 1456 [1928]; 46, p. 2834 [1924]) are added 45 g of polyphosphoric acid are intimately mixed and the mixture is heated to 84 ° C. for 4 hours. After cooling, the homogeneous yellow solution is mixed with water, the precipitate is filtered off, boiled twice with water and then thoroughly washed out with water on the filter. Yield of 4-hydroxy-2-mercapto-3-carbethoxy-quinoline 5.9 g (920 in theory).

Umkristallisiert aus Wasser-Äthanol, Schmelzpunkt 159 bis 160"C. Ausbeute 4,6 g (780/0 der Theorie). Recrystallized from water-ethanol, melting point 159 to 160 "C. Yield 4.6 g (780/0 of theory).

Durch mehrfaches Umkristallisieren kann der Schmelzpunkt auf 161,5"C gebracht werden. OH C6H57 NH - CS - CC(COOC2H5)1 Polyphosphorsäure > t COOC2Hs (bzw. tautomere Formen) Beispiel 3 24 g 1-Naphthylisocyanat werden langsam zu einer ätherischen Suspension von 25,5 g Na-Malonsäurediäthylester (etwa 300 ccm Äther) getropft und anschließend noch 5 Stunden unter Rückfluß zum Sieden erhitzt. Nach Stehenlassen über Nacht wird der Niederschlag abfiltriert (47,5 g), in Eisessig gelöst und das Dicarbäthoxy - essigsäure -1- naphthylamid durch Zugabe von Wasser ausgefällt. Ausbeute (als Na-Salz) 960/0 der Theorie. Umkristallisiert aus Methanol.The melting point can be brought to 161.5 ° C. by repeated recrystallization. OH C6H57 NH - CS - CC (COOC2H5) 1 Polyphosphoric acid> t COOC2Hs (or tautomeric forms) Example 3 24 g of 1-naphthyl isocyanate are slowly added dropwise to an ethereal suspension of 25.5 g of sodium malonic acid diethyl ester (about 300 cc of ether) and then refluxed for a further 5 hours. After standing overnight, the precipitate is filtered off (47.5 g), dissolved in glacial acetic acid and the dicarbethoxy-acetic acid -1-naphthylamide is precipitated by adding water. Yield (as Na salt) 960/0 of theory. Recrystallized from methanol.

3 g Dicarbäthoxy-essigsäure-1-naphthylamid und 20 g Polyphosphorsäure werden 3 Stunden auf 80"C erhitzt, nach Abkühlen in Wasser eingerührt und die wäßrige Suspension über Nacht stehengelassen. 3 g of dicarbethoxy-acetic acid-1-naphthylamide and 20 g of polyphosphoric acid are heated to 80 "C for 3 hours, stirred into water after cooling and the aqueous Suspension left to stand overnight.

Danach wird das 2,4-Dihydroxy-3 -carbäthoxy-benzo(h)chinolin abfiltriert und gut mit Wasser ausgewaschen. Umkristallisiert aus Eisessig und wenig Wasser. Zersetzungspunkt etwa 240"C. OH COOC21l, NHCO - CH(COOC2H5)2 N OH -.Polyphosphorsäure . OH Beispiel 4 15 g w,w - Dicarbäthoxy- thioacet- a - naphthylamid werden mit 70 g Polyphosphorsäure innig gemischt und das Gemisch 41/2 Stunden auf 84"C erhitzt.Then the 2,4-dihydroxy-3-carbethoxy-benzo (h) quinoline is filtered off and washed well with water. Recrystallized from glacial acetic acid and a little water. Decomposition point about 240 "C. OH COOC21l, NHCO - CH (COOC2H5) 2 N OH -.Polyphosphoric acid. OH Example 4 15 gw, w - dicarbethoxy thioacet a - naphthylamide are intimately mixed with 70 g of polyphosphoric acid and the mixture is heated to 84 ° C. for 41/2 hours.

Die homogene Lösung wird nach dem Erkalten mit Wasser versetzt, der Niederschlag abfiltriert und auf dem Filter gründlich mit Wasser ausgewaschen.The homogeneous solution becomes after cooling mixed with water, the The precipitate is filtered off and washed thoroughly with water on the filter.

Ausbeute 11,0 g 4-Hydroxy-2-mercapto-benzo(h)chinolin-carbonsäure-(3)-äthylester (840/0 der Theorie).Yield 11.0 g of 4-hydroxy-2-mercapto-benzo (h) quinoline-carboxylic acid (3) ethyl ester (840/0 of theory).

Umkristallisiert aus Dimethylformamid-Wasser, Schmelzpunkt 252 bis 253"C. SH HCS .- CH(COOC2H5)2 SOCHOC2Hs Polyphosphorsäure. X Recrystallized from dimethylformamide-water, melting point 252 to 253 "C. SH HCS .- CH (COOC2H5) 2 SOCHOC2Hs Polyphosphoric acid. X

Claims (1)

Patentanspruch: Verfahren zur Herstellung von 2,4-disubstituierten Chinolin-3-carbonsäurealkylestern, d a -durch gekennzeichnet, daß man eine Verbindung der allgemeinen Formel worin X ein Sauerstoff- oder Schwefelatom und R einen Alkylrest bedeutet, bei etwa 80 bis 85"C mit Polyphosphorsäure behandelt und das ent- standene Verfahrensprodukt der allgemeinen Formel in der X und R die oben angegebene Bedeutung besitzen, isoliert.Claim: Process for the preparation of 2,4-disubstituted quinoline-3-carboxylic acid alkyl esters, characterized in that a compound of the general formula is used where X denotes an oxygen or sulfur atom and R denotes an alkyl radical, treated with polyphosphoric acid at about 80 to 85 ° C. and the resulting process product of the general formula in which X and R are as defined above, isolated. In Betracht gezogene Druckschriften: J. Sci. Ind. Research India, 18 B (1959), Nr. 9, S. 391/392; 19 B (1960), Nr. 5, S. 176, und 19 B (1960), wNr. 11, S. 436 bis 438. References considered: J. Sci. Ind. Research India, 18 B (1959), No. 9, pp. 391/392; 19 B (1960), No. 5, p. 176, and 19 B (1960), wNr. 11, pp. 436 to 438.
DEF34308A 1961-06-30 1961-06-30 Process for the preparation of 2,4-disubstituted quinoline-3-carboxylic acid alkyl esters Pending DE1212536B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEF34308A DE1212536B (en) 1961-06-30 1961-06-30 Process for the preparation of 2,4-disubstituted quinoline-3-carboxylic acid alkyl esters

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF34308A DE1212536B (en) 1961-06-30 1961-06-30 Process for the preparation of 2,4-disubstituted quinoline-3-carboxylic acid alkyl esters

Publications (1)

Publication Number Publication Date
DE1212536B true DE1212536B (en) 1966-03-17

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Application Number Title Priority Date Filing Date
DEF34308A Pending DE1212536B (en) 1961-06-30 1961-06-30 Process for the preparation of 2,4-disubstituted quinoline-3-carboxylic acid alkyl esters

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DE (1) DE1212536B (en)

Non-Patent Citations (1)

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