HU202840B - Process for producing pyridine-3-carboxylic acids and theyr acid derivatives - Google Patents
Process for producing pyridine-3-carboxylic acids and theyr acid derivatives Download PDFInfo
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen 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
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen 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
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
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- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
Abstract
Die Erfindung betrifft Verfahren zur Herstellung neuer 6,7-disubstituierter 1-Cyclopropyl-1,4-dihydro-4-oxo-1,8-naphthyridin-3-carbonsaeuren und deren Zwischenprodukte sowie diese Verbindungen enthaltende antibakterielle Mittel und Futterzusatzstoffe. Die Erfindung vermittelt Verfahren zur Herstellung von 6,7-disubstituierten 1-Cyclopropyl-1,4-dihydro-4-oxo-1,8-naphthyridin-3-carbonsaeuren und deren Zwischenprodukte. Diese Verbindungen weisen in den ueblichen Prodrug-Formen eine hohe antibakterielle Wirkung auf und eignen sich daher als Wirkstoffe fuer die Human- und Veterinaermedizin. Erfindungsaufgabe ist die Bereitstellung von Verfahren zur Herstellung neuer Verbindungen, die eine hohe antibakterielle Wirkung besitzen. Erfindungsgemaess wird die Aufgabe dadurch geloest, dass man Verbindungen der allgemeinen Formel I, worin die Substituenten, die in der Beschreibung angegebene Bedeutung besitzen, herstellt, indem man beispielsweise 1-Cyclopropyl-7-halogen-1,4-dihydro-4-oxo-1,8-naphthyridin-3-carbonsaeuren der Formel II, in welchen die Substituenten, die in der Beschreibung angegebene Bedeutung besitzen, gegebenenfalls in die Salze, Ester und andere Prodrug-Formen ueberfuehrt. Formel (I), (II)The invention relates to processes for the preparation of novel 6,7-disubstituted 1-cyclopropyl-1,4-dihydro-4-oxo-1,8-naphthyridine-3-carboxylic acids and their intermediates and antibacterial agents and feed additives containing these compounds. The invention teaches processes for the preparation of 6,7-disubstituted 1-cyclopropyl-1,4-dihydro-4-oxo-1,8-naphthyridine-3-carboxylic acids and their intermediates. These compounds have a high antibacterial activity in the common prodrug forms and are therefore useful as active ingredients for human and veterinary medicine. It is an object of the invention to provide processes for the preparation of novel compounds which have a high antibacterial activity. According to the invention, the object is achieved by preparing compounds of the general formula I in which the substituents which have the meaning given in the description are prepared, for example by reacting 1-cyclopropyl-7-halo-1,4-dihydro-4-oxo 1,8-naphthyridine-3-carboxylic acids of the formula II, in which the substituents which have the meaning given in the description, if necessary, converted into the salts, esters and other prodrug forms. Formula (I), (II)
Description
A találmány tárgya eljárás triszubsztituált piridin-3-karbonsavak és savszármazékaik előállítására.The present invention relates to a process for the preparation of trisubstituted pyridine-3-carboxylic acids and their acid derivatives.
Intermedierként alkalmazható 3-fluor-2,6-dihidroxi-piridin-5-karbonsav-nitril előállítását ismerteti a 82 72 981 számú japán irat, amely nem tér ki azonban a szabad sav vagy alkoxi-karbonil-metil-származékai előállítására. Az ismert eljárás további hátránya, hogy kitermelése nagyon alacsony.The preparation of 3-fluoro-2,6-dihydroxypyridine-5-carboxylic acid nitrile for use as an intermediate is disclosed in Japanese Patent No. 82,72,981, which however does not disclose the preparation of the free acid or its alkoxycarbonylmethyl derivatives. A further disadvantage of the known process is that its yield is very low.
Atalálmány tárgya közelebbről eljárás az (I) általános képletű triszubsztituált piridin-3-karbonsavak és savszármazékaik előállítására, a képletbenMore particularly, the present invention relates to a process for the preparation of trisubstituted pyridine-3-carboxylic acids of the formula I and their acid derivatives, wherein
X, X’ és X” jelentése azonos vagy különböző, és lehet halogénatom, előnyösen fluor- vagy klóratom,X, X 'and X' are the same or different and may be halogen, preferably fluorine or chlorine,
R jelentése hidroxilcsoport, halogénatom, előnyösen klóratom, valamint alkoxi-karbonil-metil-csoport, amely alkoxirészében metil- vagy etilcsoportot tartalmaz, oly módon, hogyR represents a hydroxy group, a halogen atom, preferably a chlorine atom, and an alkoxycarbonylmethyl group having a methyl or ethyl group in its alkoxy moiety such that
a) az (I) általános képletű vegyületek közé tartozó(a) a compound of formula (I)
2,6-diklór-5 -fluor-piridin-3-karbonsav előállításához 5-amino-2,6-diklór-3-metil-piridint 2,6-diklór-3-metil-5-(5,3-dimetil-l-triazeno)-piridinné, majd hidrogén-fluoriddal 2,6-diklór-5-fluor-3-metil-piridinné alakítunk, a kapott terméket 2,6-diklór-5-fluor-3-(triklór-metil)-piridinné klórozzuk, és ezt kénsavval elszappanosítjuk, majd a savat kívánt esetben savkloriddá alakítjuk, ezt kívánt esetben dietil- vagy dimetil-etoxi-magnézium-malonáttal reagáltatjuk, elszappanosítjuk, és dekarboxilezzük, vagy5-Amino-2,6-dichloro-3-methylpyridine 2,6-dichloro-3-methyl-5- (5,3-dimethyl-) was used to prepare 2,6-dichloro-5-fluoropyridine-3-carboxylic acid. to 1-triazeno) pyridine followed by hydrogen fluoride to give 2,6-dichloro-5-fluoro-3-methylpyridine to give 2,6-dichloro-5-fluoro-3- (trichloromethyl) pyridine chlorinating and saponifying with sulfuric acid, then converting the acid, if desired, to the acid chloride, optionally reacting with diethyl or dimethylethoxymagnesium malonate, saponifying and decarboxylating, or
b) egy (II) általános képletű vegyület, a képletben X, X’ és X” jelentése a fenti, malonsav-dimetil-észterrel vagy malonsav-dietil-észterrel reagáltatunk, a reakcióterméket parciálisán elszappanosítjuk és dekarboxilezzük.b) reacting a compound of formula II wherein X, X 'and X' are as defined above with dimethyl malonic acid or diethyl ester of malonic acid, partially saponifying the product and decarboxylating the reaction product.
Az eljárás megvalósításához úgy járunk el, hogy a (Π) általános képletű vegyületet malonsav-dimetil-észterrel vagy malonsav-dietil-észterrel oldószerben, így metanolban, etanolban, benzolban, toluolban vagy ezek keverékében nátrium- vagy magnézium-alkoholát, előnyösen -metilát vagy -etilát jelenlétében -20 és+100 ’C közötti, előnyösen -10 és +50 ’C közötti hőmérsékleten, és mintegy 1-100 bar közötti, előnyösen 1-10 bar közötti nyomáson reagáltatjuk, és a reakcióterméket vízben vagy dimetil-szulfoxidban forralva, adott esetben katalizátor, így kénsav, metánszulfonsav, toluolszulfonsav, nátrium-klorid, lítium-klorid vagy lítium-jodid jelenlétében parciálisán elszappanosítjuk, és dekarboxilezzük.The process may be carried out by reacting a compound of formula (Π) with dimethyl malonic acid or diethyl ester of malonic acid in a solvent such as methanol, ethanol, benzene, toluene or a mixture thereof, sodium or magnesium alcoholate, preferably methylate or in the presence of ethylate at a temperature of -20 to + 100 ° C, preferably -10 to + 50 ° C, and a pressure of about 1 to 100 bar, preferably 1 to 10 bar, and the reaction product is boiled in water or dimethylsulfoxide, optionally partial saponification and decarboxylation in the presence of a catalyst such as sulfuric acid, methanesulfonic acid, toluenesulfonic acid, sodium chloride, lithium chloride or lithium iodide.
A 2,6-diklór-5-fluor-piridin-3-karbonsav előállítása során úgy járunk el, hogy az 5-amino-2,6-diklór-3-metil-piridint vizes sav, például sósav vagy kénsav jelenlétében -20 és +20 ’C közötti, előnyösen -5 és +5 ’C közötti hőmérsékleten és légköri nyomáson diazotáljuk, és dimetil-aminnal 2,6-diklór-3-metil-5-(3,5-dimetil-l-triazeno)-piridinné alakítjuk, ezt hidrogén-fluoriddal 80-160 ’C közötti, előnyösen 110-150 ’C közötti hőmérsékleten autoklávban 2,6-diklór-5-fluor-3-metil-piridinné bontjuk, amelyet mintegy 80-180 ’C közötti hőmérsékleten, előnyösen 1-10 bar közötti nyomásonIn the preparation of 2,6-dichloro-5-fluoro-pyridine-3-carboxylic acid, 5-amino-2,6-dichloro-3-methyl-pyridine is prepared in the presence of an aqueous acid such as hydrochloric acid or sulfuric acid, and It is diazotized at + 20 ° C, preferably -5 to + 5 ° C and at atmospheric pressure, to give 2,6-dichloro-3-methyl-5- (3,5-dimethyl-1-triazeno) pyridine with dimethylamine it is decomposed in an autoclave with hydrogen fluoride at a temperature of 80-160 ° C, preferably 110-150 ° C, to 2,6-dichloro-5-fluoro-3-methylpyridine which is at a temperature of about 80-180 ° C, preferably At a pressure of 1-10 bar
2,6-űiklór-5-fluor-3-triklór-metil-piridinné klórozunk, majd kénsavval 10-110 ’C közötti, előnyösen 25100 ’C közötti hőmérsékleten elszappanosítunk.The 2,6-methylchloro-5-fluoro-3-trichloromethylpyridine is chlorinated and then saponified with sulfuric acid at a temperature of 10-110 ° C, preferably 25100 ° C.
Atalálmány szerinti eljárással előállított (I) általános képletű vegyületek előnyösen alkalmazhatók kiindulási anyagként gyógyászati hatású 4-oxo-l,8-naftiridin- származékok előállítására.The compounds of formula (I) obtained by the process of the present invention are preferably used as starting materials for the preparation of 4-oxo-1,8-naphthyridine compounds having a therapeutic effect.
A találmány szerinti eljárást közelebbről az alábbi példákkal világítjuk meg.The following examples illustrate the invention.
1. példaExample 1
2.6- Diklór-3-metil-5-(3,3-dimetil-l-triazeno)-piridin g (0,24 mól) 5-amino-2,6-diklór-3-metil-piridint (Helv. Chim. Acta 59, 190, 1976) lassan 285 ml 18 tömeg%-os sósavval elegyítünk, majd 0 ‘C hőmérsékletre hűtjük, és 17,2 g (0,25 mól) nátrium-nitrit 70 ml vízben felvett oldatát csepegtetjük hozzá, és 0 ’C hőmérsékleten rövid ideig keverjük. A kapott diazóniumsó oldatot 0-3 ’C hőmérsékleten 90 perc alatt 150 g nátrium-karbonát 400 ml vízben felvett oldatának, és 70 ml 40-50%-os dimetilamin oldatának elegyéhez csepegtetjük, és 0 ’C hőmérsékleten keverjük. A csapadékot leszűrjük, vízzel jól átmossuk, és magas vákuumban 40 ’C hőmérsékleten szárítjuk. így 49,3 g cím szerinti vegyületet kapunk (az elméleti 88%-a), amelynek olvadáspontja 91-95 ’C.2.6-Dichloro-3-methyl-5- (3,3-dimethyl-1-triazeno) -pyridine g (0.24 mol) 5-amino-2,6-dichloro-3-methylpyridine (Helv. Chim. Acta 59, 190, 1976) was slowly added with 285 ml of 18% hydrochloric acid, cooled to 0 ° C, and a solution of 17.2 g (0.25 mol) of sodium nitrite in 70 ml of water was added dropwise and Stir briefly at C. The resulting diazonium salt solution was added dropwise at 0-3 ° C over 90 minutes to a solution of 150 g of sodium carbonate in 400 ml of water and 70 ml of 40-50% dimethylamine solution and stirred at 0 ° C. The precipitate was filtered off, rinsed well with water and dried under high vacuum at 40 ° C. 49.3 g (88% of theory) of the title compound are obtained, m.p. 91-95 ° C.
2. példaExample 2
2.6- Diklór-5 -fluor-3 -metil-piridin2.6-Dichloro-5-fluoro-3-methylpyridine
43,9 g (0,19 mól) 2,6-diklór-3-metil-5-(3,3-dimetil-l-triazeno)-piridint 80 ml hidrogén-fluoridban 125135 C hőmérsékleten autoklávban megbontunk. Desztilláció után gázkromatográfiásán 87%-os tisztaságú cím szerinti terméket kapunk, amely 12% 2- és/vagy 6-helyzetben fluorozott terméket tartalmaz.43.9 g (0.19 mol) of 2,6-dichloro-3-methyl-5- (3,3-dimethyl-1-triazeno) pyridine were decomposed in 80 ml of hydrofluoric acid at 125-135 ° C. After distillation, gas chromatography gives the title product with a purity of 87%, containing 12% of the fluorinated product in the 2- and / or 6-position.
Kitermelés: 19 g, forráspont 81-95 ’C/18 mbar. Olvadáspont 39^11 ’C.Yield: 19 g, boiling point 81-95 'C / 18 mbar. M.p.
3. példaExample 3
2.6- Diklór-5fluor-3-(triklór-metil)-piridin2.6-Dichloro-5-fluoro-3- (trichloromethyl) pyridine
49,4 g (0,27 mól) 2,6-diklór-5-fluor-3-metil-piridint 120 ’C hőmérsékleten összesen 20 (kán keresztül klórozunk, amíg NMR-spektroszkópiásan alifás proton nem mutatható ki. A reakcióelegyet golyós-hűtős desztillációs berendezésben desztilláljuk. így 61,7 g (az elméleti 80,6%-a) cím szerinti terméket kapunk, amelynek forráspontja 130-150 ’C (külső hőmérséklet)/),4 mbar. Tömegspektrum: m/e 281 (M+), 246 (100%, M+-C1),49.4 g (0.27 mole) of 2,6-dichloro-5-fluoro-3-methylpyridine was chlorinated at 120 ° C for a total of 20 [deg.] C. until an aliphatic proton was detected by NMR spectroscopy. distillation in a cooled distillation apparatus afforded 61.7 g (80.6% of theory) of the title product, boiling at 130-150 ° C (external temperature), 4 mbar. Mass Spectrum: m / e 281 (M + ), 246 (100%, M + -Cl),
211(246-C1), 176(211-C1).211 (246-C1), 176 (211-C1).
4. példaExample 4
2,6-Diklór-5 fluor-piridin-3-karbonsav g (0,2 mól) 2,6-diklór-5-fluor-3-(triklór-metil)-piridint 53 ml 92%-os kénsavban oldunk, majd először 45 percen keresztül 25 ’C hőmérsékleten, majd 3 órán keresztül 100 ’C hőmérsékleten keverjük a hidrogén-klorid fejlődés befejeződéséig. A reakcióelegyet 24 g 50%-os kénsavval elegyítjük, és további 6 órán keresztül 100 ’C hőmérsékleten melegítjük. Ezután lehűtjük, jégre öntjük, a csapadékot leszűrjük, vízzel mossuk, és szárítjuk. így 42 g (mintegy az elméleti 100%-a) nyersterméket kapunk, amelynek olvadáspontja 137-149 ’C. Vízből történő átkristályosítás után a termék olvadáspontja 154-161 ’C.2,6-Dichloro-5-fluoropyridine-3-carboxylic acid g (0.2 mole) of 2,6-dichloro-5-fluoro-3- (trichloromethyl) pyridine was dissolved in 53 ml of 92% sulfuric acid and first stirring for 45 minutes at 25 ° C and then for 3 hours at 100 ° C until hydrogen chloride evolution is complete. The reaction mixture was mixed with 24 g of 50% sulfuric acid and heated at 100 ° C for a further 6 hours. The reaction mixture is cooled, poured onto ice, the precipitate is filtered off, washed with water and dried. This gives 42 g (about 100% of theory) of crude product, m.p. 137-149 ° C. After recrystallization from water, the product has a melting point of 154-161 ° C.
Tömegpsektrum: m/e 209 (NT), 192 (M+-0H),Mass Spectrum: m / e 209 (NT), 192 (M + -0H).
164 (192-CO), 129 (164-C1), (129-C1).164 (192-CO), 129 (164-C1), (129-C1).
-2HU 202840 Β-2HU 202840 Β
5. példaExample 5
2,6-Diklór-5-fluor-piridin-3-karbonil-klorid g (0,2 mól) 2,6-diklór-5-fluor-piridin-3-karbonsavat43 g tíonil-klorid, 15 ml dimetil-formamid és 640 ml toluol elegyében 6 (kán keresztül visszafolyatás közben forralunk. A reakcióelegyet bepároljuk, és a maradékot desztilláljuk. így 33,8 g (az elméleti 74%-a) cím szerinti terméket kapunk, amelynek forráspontja 9498 *C/1,3 mbar.2,6-Dichloro-5-fluoro-pyridine-3-carbonyl chloride g (0.2 mol) 2,6-dichloro-5-fluoro-pyridine-3-carboxylic acid43 g thionyl chloride, 15 ml dimethylformamide and 640 ml of toluene was heated to reflux (6 ° C). The reaction mixture was concentrated and the residue was distilled to give 33.8 g (74% of theory) of the title product boiling at 9498 ° C / 1.3 mbar.
Tömegspektrum: m/e 228(M*), 192 (100%, M+-C1), 164 (40%, M+-COC1).Mass spectrum: m / e 228 (M +), 192 (100%, M + -Cl), 164 (40%, M + -COCl).
6. példa (2,6-Dildór-5-fluor-piridin-3-karbonil)-ecetsav-etil-észterExample 6 (2,6-Dildoro-5-fluoropyridine-3-carbonyl) -acetic acid ethyl ester
3,7 g (0,15 mól) magnéziumforgácsot 93 ml etanolban 0,8 g tetraklór-metánnal elegyítünk, és a hidrogénfejlődés megkezdése után cseppenként 23,9 g (0,15 mól) malonsav-dietil-észter, 18,5 ml etanol és 58 ml toluol elegyét adjuk hozzá 50-60 ’C hőmérsékleten. A reakcióelegyet 1 órán keresztül ezen a hőmérsékleten keverjük, majd -5 - -10 ’C közötti hőmérsékletre hűtjűk, és cseppenként lassan 31 g (0,14 mól) 2,6-diklór-5-fluor-piridin-3-kaibonil-klorid 14,5 ml toluolban felvett oldatát adjuk hozzá. Ezután 1 órán keresztül 0 ’C hőmérsékleten keveijük az elegyet, egy éjszakán keresztül szobahőmérsékleten állni hagyjuk, majd 2 órán keresztül 40-50 ’C hőmérsékleten melegítjük. A reakcióelegyhez jeges hűtés közben 60 ml víz és 9 ml koncentrált kénsav elegyét adjuk, és a szerves fázist leválasztjuk. A vizes fázist toluollal extraháljuk, az egyesített szerves fázisokat telített nátrium-klorid oldattal mossuk, vízmentes nátrium-szulfáton szárítjuk, és az oldószert leszívásuk. így 50,1 g (2,6-diklór-5-fluor-piridin-3-karbonil)-malonsav-dietil-észtert kapunk nyers termékként Ezt 50 ml víz és 0,1 g 4-toluolszulfonsav hozzáadása után 10 órán keresztül visszafolyatás közben forraljuk, majd a reakcióelegyet diklór-metánnal extraháljuk, az extraktumot nátrium-szulfáton szárítjuk, bepároljuk, és a maradékot kevés éterben elkeverjük, és a kristályokat izoláljuk. így 14,3 g cím szerinti terméket kapunk (az elméleti 34%-a), amelynek olvadáspontja 69-72 ’C.Magnesium turnings (3.7 g, 0.15 mol) in ethanol (93 ml) were mixed with tetrachloromethane (0.8 g) and, after the evolution of hydrogen, 23.9 g (0.15 mol) of diethyl malonic acid, 18.5 ml of ethanol were added dropwise. and 58 ml of toluene at 50-60 ° C. After stirring at this temperature for 1 hour, the reaction mixture was cooled to -5 to -10 ° C and 31 g (0.14 mol) of 2,6-dichloro-5-fluoropyridine-3-carbonyl chloride was slowly added dropwise. A solution of 14.5 ml of toluene is added. The mixture is stirred at 0 ° C for 1 hour, allowed to stand at room temperature overnight and then heated at 40-50 ° C for 2 hours. Under ice-cooling, a mixture of water (60 mL) and concentrated sulfuric acid (9 mL) was added and the organic layer was separated. The aqueous phase is extracted with toluene, the combined organic phases are washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate and the solvent is removed by suction. This gives 50.1 g of (2,6-dichloro-5-fluoropyridine-3-carbonyl) -malonic acid diethyl ester as a crude product. After adding 50 ml of water and 0.1 g of 4-toluenesulfonic acid, it is refluxed for 10 hours. After boiling, the reaction mixture is extracted with dichloromethane, the extract is dried over sodium sulfate, concentrated and the residue is stirred in a little ether and the crystals are isolated. 14.3 g (34% of theory) of the title compound are obtained, m.p. 69-72 ° C.
Tömegspektrum: m/e 279 (M+), 244 (60%, M+-C1),Mass Spectrum: m / e 279 (M + ), 244 (60%, M + -Cl).
216 (74%, 244-28), 192 (100%, C6HC12FNO), 164,29.216 (74%, 244-28), 192 (100%, C 6 HCl 2 FNO), 164.29.
NMR-spektrum (CDC13) alapján a vegyület gyakorlatilag teljesen enol formában található.By NMR (CDCl 3 ), the compound is substantially completely in enol form.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3500562 | 1985-01-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| HU202840B true HU202840B (en) | 1991-04-29 |
Family
ID=6259522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| HU871847A HU202840B (en) | 1985-01-10 | 1986-01-09 | Process for producing pyridine-3-carboxylic acids and theyr acid derivatives |
Country Status (3)
| Country | Link |
|---|---|
| DD (3) | DD257428A5 (en) |
| HU (1) | HU202840B (en) |
| ZA (1) | ZA86163B (en) |
-
1986
- 1986-01-08 DD DD86296483A patent/DD257428A5/en unknown
- 1986-01-08 DD DD86286039A patent/DD241258A5/en unknown
- 1986-01-08 DD DD86296482A patent/DD257427A5/en unknown
- 1986-01-09 HU HU871847A patent/HU202840B/en unknown
- 1986-01-09 ZA ZA86163A patent/ZA86163B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DD241258A5 (en) | 1986-12-03 |
| ZA86163B (en) | 1986-09-24 |
| DD257428A5 (en) | 1988-06-15 |
| DD257427A5 (en) | 1988-06-15 |
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