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 estersInfo
- 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
- Authority
- 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
Links
- 238000000034 method Methods 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title claims description 3
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- -1 3 Chemical compound 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BDQNKCYCTYYMAA-UHFFFAOYSA-N 1-isocyanatonaphthalene Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1 BDQNKCYCTYYMAA-UHFFFAOYSA-N 0.000 description 1
- OAXSBIJZTFSWRG-UHFFFAOYSA-N 2-(2-sulfanylidenepyrrolidin-1-yl)acetamide Chemical compound NC(=O)CN1CCCC1=S OAXSBIJZTFSWRG-UHFFFAOYSA-N 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- UCPROKAMDJHLMK-UHFFFAOYSA-N diethyl 2-(phenylcarbamothioyl)propanedioate Chemical compound CCOC(=O)C(C(=O)OCC)C(=S)NC1=CC=CC=C1 UCPROKAMDJHLMK-UHFFFAOYSA-N 0.000 description 1
- UQFFIFUYIQXSPD-UHFFFAOYSA-N diethyl 2-(phenylcarbamoyl)propanedioate Chemical compound CCOC(=O)C(C(=O)OCC)C(=O)NC1=CC=CC=C1 UQFFIFUYIQXSPD-UHFFFAOYSA-N 0.000 description 1
- PDQYDAMNFMHSJS-UHFFFAOYSA-N diethyl propanedioate;sodium Chemical compound [Na].CCOC(=O)CC(=O)OCC PDQYDAMNFMHSJS-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- LGLPFJDOUVCBNP-UHFFFAOYSA-N ethyl 4-hydroxy-2-oxo-1h-quinoline-3-carboxylate Chemical compound C1=CC=C2NC(=O)C(C(=O)OCC)=C(O)C2=C1 LGLPFJDOUVCBNP-UHFFFAOYSA-N 0.000 description 1
- HDWHOZFOEFXPBD-UHFFFAOYSA-N ethyl 4-hydroxy-2-sulfanylidene-1H-quinoline-3-carboxylate Chemical compound C1=CC=C2C(=O)C(C(=O)OCC)=C(S)NC2=C1 HDWHOZFOEFXPBD-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- QKFJKGMPGYROCL-UHFFFAOYSA-N phenyl isothiocyanate Chemical compound S=C=NC1=CC=CC=C1 QKFJKGMPGYROCL-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C07D215/48—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
Landscapes
- 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).
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.
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.
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.
Claims (1)
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 |
Family
ID=7095495
Family Applications (1)
| 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 |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1212536B (en) |
-
1961
- 1961-06-30 DE DEF34308A patent/DE1212536B/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| None * |
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