DE1190464B - Process for the preparation of pyridine derivatives - Google Patents
Process for the preparation of pyridine derivativesInfo
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- DE1190464B DE1190464B DEM34126A DEM0034126A DE1190464B DE 1190464 B DE1190464 B DE 1190464B DE M34126 A DEM34126 A DE M34126A DE M0034126 A DEM0034126 A DE M0034126A DE 1190464 B DE1190464 B DE 1190464B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—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
- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—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
- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
- C07D213/85—Nitriles in position 3
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Description
Verfahren zur Herstellung von Pyridinderivaten Die Erfindung betrifft ein neues Verfahren zur Herstellung von Pyridinderivaten, das experimentell leicht zu beherrschen ist und in einer zweistufigen Reaktion- hohe Ausbeuten an Pyridinabkömmlingen mit verschiedensten Substituenten liefert.Process for the preparation of pyridine derivatives The invention relates to a new process for the preparation of pyridine derivatives that is experimentally easy can be controlled and in a two-step reaction - high yields of pyridine derivatives with a wide variety of substituents.
Nach der Erfindung werden a-Carbonyl-acetylen-Verbindungen der allgemeinen Formel R1-CO-C--C worin R1 Wasserstoff oder einen direkt oder über O gebundenen Kohlenwasserstoffrest bedeutet, mit Enaminen der allgemeinen Formel worin R2 eine R300C, R3CO- oder N Gruppe und R3 einen Kohlenwasserstoffrest bedeutet, unterhalb etwa 100"C umgesetzt und die so erhaltenen Additionsverbindungen, gegebenenfalls in Ge- genwart üblicher Dehydratisierungskatalysatoren, auf etwa 110 bis 1600C erhitzt. Hierbei spaltet sich 1 Mol Wasser oder Alkohol unter Ringschluß zu den entsprechenden Pyridinverbindungen ab.According to the invention, α-carbonyl acetylene compounds of the general formula R1-CO-C - C in which R1 is hydrogen or a hydrocarbon radical bonded directly or via O, with enamines of the general formula where R2 is a R300C, R3CO or N group and R3 is a hydrocarbon radical, reacted below about 100.degree. C. and the addition compounds thus obtained, optionally in the presence of conventional dehydration catalysts, are heated to about 110 to 1600C. 1 mol of water or Alcohol with ring closure to the corresponding pyridine compounds.
Der Reaktionsverlauf wird durch die folgende Reaktionsgleichung wiedergegeben:
Der Ringschluß der Additionsverbindung zum Pyridinderivat kann auch in Gegenwart eines üblichen Dehydratisierungskatalysators durchgeführt werden. The ring closure of the addition compound to the pyridine derivative can also be carried out in the presence of a conventional dehydration catalyst.
Nach dem Verfahren der Erfindung können verschiedenartige Pyridinderivate in sehr guten Ausbeuten hergestellt werden, ohne daß dabei Isomerengemische entstehen, die auf umständlichem Wege voneinander getrennt werden müssen. Besonders gut eignet sich das Verfahren zur Herstellung von Derivaten der Nicotinsäureester. Various pyridine derivatives can be prepared according to the method of the invention can be produced in very good yields without the formation of isomer mixtures, the awkward way must be separated from each other. Particularly suitable the process for the preparation of derivatives of nicotinic acid esters.
B o w d e n und J o n e 5 beschreiben in Journal of the Chemical Society (London), 1946, S. 953 und 954, ein Verfahren zur Herstellung von 2-Phenyl-5-benzoyl-pyridin durch Umsetzung von Benzoylacetylen mit Ammoniumcarbonat in alkoholischer Lösung. Der Reaktionsmechanismus dieses Verfahrens ist nicht bekannt, insbesondere gelingt es nicht, Zwischenprodukte zu isolieren. Ferner ist die Methode auf andere Athinylcarbonylverbindungen bzw. auf Propargylaldehyd oder l-Butin-3-on nicht übertragbar. Das neue Verfahren besitzt ferner gegenüber dem von D o r n o w in Chemische Berichte, Bd. 82, S. 118 bis 217 (1949), beschriebenen Verfahren den Vorteil, daß die Endprodukte in sehr großer Reinheit erhalten werden, da das nach der Erfindung erhaltene Zwischenprodukt leicht gereinigt werden kann. Die von D o rn o w angegebenen Ausbeuten sind ferner nur dann zu erreichen, wenn die als Ausgangsmaterial verwendeten, nur schwierig zugänglichen Acetale in extrem reiner Form verwendet werden. Der Arbeitsaufwand zur Herstellung größerer Mengen an Pyridinderivaten ist nach dem Verfahren der Erfindung wesentlich geringer als nach dem Verfahren von D o r n o w. B o w d e n and J o n e 5 describe in Journal of the Chemical Society (London), 1946, pp. 953 and 954, a process for the preparation of 2-phenyl-5-benzoyl-pyridine by reacting benzoylacetylene with ammonium carbonate in alcoholic solution. The reaction mechanism of this process is not known, but it is particularly successful it doesn't isolate intermediates. Furthermore, the method is based on other ethynyl carbonyl compounds respectively. not transferable to propargylaldehyde or 1-butyn-3-one. The new procedure owns furthermore compared to that of D o r no w in Chemical Reports, Vol. 82, pp. 118 to 217 (1949), the method described has the advantage that the end products in very large Purity can be obtained because the intermediate obtained according to the invention is easy can be cleaned. The yields given by D o rn o w are also only to be achieved when the material used as the starting material is difficult to access Acetals are used in extremely pure form. The labor required to manufacture larger amounts of pyridine derivatives are essential in the process of the invention less than according to the D o r n o w method.
Beispiel 1 129 g ß-Aminocrotonsäureäthylester löst man in 500 ccm absolutem Alkohol und läßt unter Rühren und Kühlen 45 g Propargylaldehyd zutropfen. Dabei hält man die Temperatur zwischen 30 und 40°C. Example 1 129 g of ß-aminocrotonic acid ethyl ester are dissolved in 500 ccm absolute alcohol and 45 g of propargylaldehyde are added dropwise with stirring and cooling. The temperature is kept between 30 and 40 ° C.
Anschließend erwärmt man noch 30 Minuten auf dem Wasserbad und läßt erkalten. Die Hauptmenge der Additionsverbindung kann direkt abgesaugt werden und ist praktisch rein. Eine weitere Menge erhält man nach Einengen der Mutterlauge. Die nach Umkristallisieren aus Methanol erhaltenen farblosen Kristalle schmelzen bei 132°C. Ausbeute 900/0 der Theorie. Ämax = 342, 285 mF (e = 38 400, 10 000) in Methanol. IR-Spektrum: NH 3430; C C - 0 3200, 1640, 1580 cm-1 in Chloroform. Die Additionsverbindung erhitzt man im Vakuum auf 130°C, wobei unter Wasserabspaltung der 2-Methyl-nicotinsäureäthylester übergeht; Kp.o,l 55 bis 60°C. Ausbeute 85010 der Theorie. Pikrat: F. 147°C.Then it is heated on the water bath for a further 30 minutes and left to cool off. The main amount of the addition compound can be sucked off directly and is practically pure. Another amount is obtained after concentrating the mother liquor. The colorless crystals obtained after recrystallization from methanol melt at 132 ° C. Yield 900/0 of theory. Ämax = 342, 285 mF (e = 38,400, 10,000) in Methanol. IR spectrum: NH 3430; C C - 0 3200, 1640, 1580 cm-1 in chloroform. the The addition compound is heated in vacuo to 130 ° C., with elimination of water the 2-methyl-nicotinic acid ethyl ester passes over; Bp. 55 to 60 ° C. Yield 85010 the theory. Picrate: m.p. 147 ° C.
Bei'spiel 2 6,8 g l-Butin-3-on gibt man zu 12,9 g ß-Aminocrotonsäureäthylester in 30 ccm Alkohol. Nach Abklingen der Reaktion erwärmt man noch 15 Minuten auf dem Wasserbad und läßt erkalten. Nach Umkristallisieren aus Methanol erhält man farblose Prismen; F. 135°C. Ausbeute 90°/o der Theorie; Äaz- 346, 290 mµ (e-- 30100, 10700) in Methanol. Example 2 6.8 g of 1-butyn-3-one are added to 12.9 g of ß-aminocrotonic acid ethyl ester in 30 cc alcohol. After the reaction has subsided, the mixture is heated for a further 15 minutes Water bath and let cool. After recrystallization from methanol, colorless ones are obtained Prisms; Mp 135 ° C. Yield 90% of theory; Äaz- 346, 290 mµ (e-- 30100, 10700) in methanol.
Die Additionsverbindung wird anschließend im Vakuum auf 120 bis 140°C erhitzt, wobei unter Wasserabspaltung der 2,6-Dimethyl-nicotinsäureäthylester überdestilliert; Kp.o,1 60°C. Ausbeute 9001o der Theorie. Pikrat: F. 135°C.The addition compound is then heated to 120 to 140 ° C. in vacuo heated, the ethyl 2,6-dimethyl nicotinate distilling over with elimination of water; B.p. 160 ° C. Yield 9001o of theory. Picrate: m.p. 135 ° C.
Beispiel 3 0,1 Mol Propiolsäureäthylester und 0,1 Mol ß-Aminocrotonsäureäthylester werden in 30 ccm Methanol 1 Stunde auf dem Wasserbad erwärmt. Nach dem Einengen erhält man farblose Kristalle, die aus Äther umkristallisiert bei 111 0C schmelzen. Ausbeute 50°/o der Theorie; Ämaz = 323 mµ (e = 31 000) in Methanol. IR-Spektrum: NH 3435, C-C-O 3250, 1650, 1587, COOR 1680 cm-'. Example 3 0.1 mol of ethyl propiolate and 0.1 mol of ß-aminocrotonic acid ethyl ester are heated in 30 cc of methanol for 1 hour on a water bath. After narrowing colorless crystals are obtained which, recrystallized from ether, melt at 111.degree. Yield 50% of theory; Ämaz = 323 mµ (e = 31,000) in methanol. IR spectrum: NH 3435, C-C-O 3250, 1650, 1587, COOR 1680 cm- '.
Das Addukt löst man in 10 Teilen Toluol und erhitzt unter Zusatz von 5°/o Eisessig 5 Stunden zum Sieden. Nach Verdampfen des Lösungsmittels destilliert man im Vakuum, Kp-0,02 160 bis 180°C. Den erhaltenen 6-Oxy-2-methyl-nicotinsäureester reinigt man über das Natriumsalz; F. 127°C. Das IR-Spek- trum zeigt die für einen Oxypyridincarbonsäureester charakteristischen Banden. The adduct is dissolved in 10 parts of toluene and heated with addition of 5% glacial acetic acid to the boil for 5 hours. Distilled after evaporation of the solvent one in vacuum, bp-0.02 160 to 180 ° C. The 6-oxy-2-methyl-nicotinic acid ester obtained one purifies over the sodium salt; 127 ° C. The IR spec trum shows them for one Oxypyridinecarboxylic acid ester characteristic bands.
Beispiel 4 0,1 Mol Propargylaldehyd gibt man unter Kühlung zu 0,1 Mol 2-Amino-2-penten-4-on in 50ccm absolutem Alkohol. Nach stündigem Stehen können 8001o der Theorie an Additionsverbindung abgesaugt werden. Die farblosen Nadeln schmelzen nach dem Umlösen aus Methanol bei 153°C; #max = 341 mµ 24000). Beim Erhitzen im Vakuum destilliert bei 120°C das 3-Acetyl-2-methylpyridin über. Ausbeute 80% der Theorie. Pikrat: F. 174°C; Dinitrophenylhydrazon: F. 2080C. Example 4 0.1 mol of propargylaldehyde is added to 0.1 with cooling Moles of 2-amino-2-penten-4-one in 50ccm of absolute alcohol. Can after standing for hours 8001o of the theory of addition compound can be sucked off. The colorless needles melt after redissolving from methanol at 153 ° C; #max = 341 mµ 24000). When heated The 3-acetyl-2-methylpyridine distills over at 120 ° C. in vacuo. Yield 80% the theory. Picrate: mp 174 ° C; Dinitrophenylhydrazone: m.p. 2080C.
Beispiel 5 0,1 Mol 1 -Butin-3-on gibt man zu 0,1 Mol 2-Amino-2-penten-4-on in 50 ccm Methanol. Nach 1 stündigem Stehen bei 20°C läßt sich in 900/oiger Ausbeute das Addukt absaugen; F. 94°C; #max = 342 ms (E = 23 100). Das Addukt geht beim Erhitzen im Vakuum auf 120 bis 130°C unter Wasserabspaltung in 3-Acetyl-2,6-dimethylpyridin über. Ausbeute 90°/o der Theorie. Pikrat: F. 130°C. Example 5 0.1 mol of 1-butyn-3-one is added to 0.1 mol of 2-amino-2-penten-4-one in 50 cc of methanol. After 1 hour of standing at 20.degree. C., a 900% yield can be obtained suck off the adduct; 94 ° C; #max = 342 ms (E = 23 100). The adduct goes off when heated in vacuo to 120 to 130 ° C with elimination of water in 3-acetyl-2,6-dimethylpyridine above. Yield 90% of theory. Picrate: M.p. 130 ° C.
Beispiel 6 Das wie im Beispiel 2 aus 1-Butin-3-on und ß-Aminocrotonsäureäthylester erhaltene Additionsprodukt wird in 10 Teilen Toluol Eisessig (20: 1) 30 Minuten zum Sieden erwärmt. Nach Verdampfen des Lösungsmittels destilliert man den Rückstand im Vakuum. Ausbeute 950/0 der Theorie 2,6-Dimethylnicotinsäureester. Example 6 The same as in Example 2 from 1-butyn-3-one and ß-aminocrotonic acid ethyl ester The addition product obtained is glacial acetic acid (20: 1) in 10 parts of toluene for 30 minutes heated to the boil. After evaporation of the solvent, the residue is distilled in a vacuum. Yield 950/0 of theory 2,6-dimethylnicotinic acid ester.
Beispiel 7 0,1 Mol l-Butin-3-on gibt man zu 0,1 Mol ß-Aminocrotonsäurenitril in 50 ccm Methanol und erwärmt 30 Minuten auf dem Wasserbad. Nach dem Erkalten wird das bei 207°C schmelzende Addukt in 10 Teilen Eisessig 30 Minuten gekocht. Der Eindampfrückstand wird im Vakuum sublimiert. Das erhaltene 2,6-Dimethyl-nicotinsäurenitril schmilzt bei 82°C; mit einem authentischen Präparat ergibt sich keine Depression des Schmelzpunktes. Ausbeute 90% der Theorie. Example 7 0.1 mol of 1-butyn-3-one is added to 0.1 mol of β-aminocrotononitrile in 50 cc of methanol and heated for 30 minutes on a water bath. After it has cooled down the adduct, which melts at 207 ° C., was boiled in 10 parts of glacial acetic acid for 30 minutes. The evaporation residue is sublimed in a vacuum. The 2,6-dimethyl-nicotinonitrile obtained melts at 82 ° C; with an authentic preparation there is no depression of the melting point. Yield 90% of theory.
Beispiel 8 0,1 Mol Propargylaldehyd gibt man unter Kühlung zu 0,1 Mol ß-Aminocrotonsäurenitril in 50 ccm absolutem Alkohol und isoliert nach einer Stunde das Additionsprodukt, das ohne weitere Reinigung 30 Minuten in 10 Teilen Eisessig gekocht und nach dem Verdampfen des Lösungsmittels im Vakuum destilliert wird. Das 2-Methyl-nicotinsäurenitril schmilzt nach dem Umkristallisieren aus Petroläther bei 56°C. Ausbeute 80°lo der Theorie. Example 8 0.1 mol of propargylaldehyde is added to 0.1 with cooling Mol ß-aminocrotononitrile in 50 ccm of absolute alcohol and isolated after a Hour the addition product, which without further purification 30 minutes in 10 parts Boiled glacial acetic acid and, after evaporation of the solvent, distilled in vacuo will. The 2-methyl-nicotinonitrile melts after recrystallization from petroleum ether at 56 ° C. Yield 80 ° lo of theory.
Beispiel 9 0,1 Mol l-Phenyl-2-propin-1-on gibt man zu 0,1 Mol ß-Aminocrotonsäureester in 50 ccm Methanol und erwärmt 30 Minuten zum Sieden. Nach dem Erkalten wird das ausgefällte Addukt ohne weitere Reinigung im Vakuum auf 160°C erhitzt, wobei der 6- Phenyl - 2 methyl - nicotinsäureester überdestilliert. Example 9 0.1 mol of 1-phenyl-2-propyn-1-one is added to 0.1 mol of β-aminocrotonic acid ester in 50 cc of methanol and heated to boiling for 30 minutes. After cooling, it will precipitated adduct heated in vacuo to 160 ° C without further purification, the 6-phenyl-2-methyl-nicotinic acid ester distilled over.
Die nach dem Umkristallisieren aus verdünntem Methanol erhaltenen Kristalle schmelzen bei 45"C.Those obtained after recrystallization from dilute methanol Crystals melt at 45 "C.
Ausbeute 8001o der Theorie.Yield 8001o of theory.
Beispiel 10 0.1 Mol ß - Aminozimtsäurenitril und 0,1 Mol l-Butin-3-on werden in 50 ccm Alkohol 30 Minuten auf dem Wasserbad erwärmt. Nach dem Erkalten saugt man das Addukt ab und kristallisiert aus Methanol um; F. 155°C; #max = 358 mµ (# = 23 000). Example 10 0.1 mol of β-amino cinnamonitrile and 0.1 mol of 1-butyn-3-one are heated in 50 cc alcohol for 30 minutes on a water bath. After cooling down The adduct is filtered off with suction and recrystallized from methanol; 155 ° C .; #max = 358 mµ (# = 23 000).
Ausbeute 85% der Theorie.Yield 85% of theory.
Das rohe Addukt wird im Vakuum auf 140 bis 150 C erhitzt, wobei das 2-Phenyl-6-methyl-nicotinsäurenitril überdestilliert. Farblose Kristalle aus Petroläther; F. 70°C, #max = 259 mµ (# = 12 200). The crude adduct is heated to 140 to 150 C in vacuo, the 2-phenyl-6-methyl-nicotinic acid nitrile distilled over. Colorless crystals of petroleum ether; F. 70 ° C, #max = 259 mµ (# = 12 200).
Ausbeute 900/0 der Theorie.Yield 900/0 of theory.
Beispiel 11 0,05 Mol - Amino -4 - methyl - zimtsäurenitril in 30 ccm Alkohol werden mit 0,05 Mol l-Butin-3-on versetzt und anschließend 30 Minuten auf dem Wasserbad erwärmt. Die nach dem Erkalten auskristallisierenden Nadeln schmelzen bei 172°C. Example 11 0.05 mol - amino -4 - methyl - cinnamonitrile in 30 ccm of alcohol are mixed with 0.05 mol of 1-butyn-3-one and then for 30 minutes warmed on the water bath. The needles that crystallize out after cooling down melt at 172 ° C.
#max = 361 mµ (# = 25 000); Ausbeute 90% der Theorie. Das Addukt wird im Vakuum auf 140°C erhitzt, wobei das 2-p-Tolyl-3-cyan-6-methyl-pyridin sublimiert. Nach Umkristallisieren aus Petroläther-Äther farblose Kristalle vom F. 102°C; Ausbeute 90% Beispiel 12 0,05 Mol ß - Aminocrotonsäureäthylester in 30 ccm Methanol versetzt man mit 0,05 Mol l-Decin-3-on. Anschließend erwärmt man 15 Minuten auf dem siedenden Wasserbad und saugt nach dem Erkalten die Kristalle ab. Gelbliche Nadeln aus Methanol: F. 105°C. Ausbeute 950/0 der Theorie; #max = 349 mµ (# = 29 000). Das Addukt wird im Vakuum auf 150°C erwärmt, wobei der 2-Methyl-6 - heptyl - nicotinsäureäthylester als leicht bewegliches Öl übergeht; Kp.0,1 125°C. Ausbeute 92% der Theorie.#max = 361 mµ (# = 25,000); Yield 90% of theory. The adduct will heated in vacuo to 140 ° C., the 2-p-tolyl-3-cyano-6-methyl-pyridine subliming. After recrystallization from petroleum ether-ether, colorless crystals with a melting point of 102 ° C .; yield 90% Example 12 0.05 mol of ß-aminocrotonic acid ethyl ester in 30 cc of methanol was added one with 0.05 mol of l-decin-3-one. Then it is heated for 15 minutes on the boiling point Water bath and sucks off the crystals after cooling. Yellowish needles made of methanol: M.p. 105 ° C. Yield 950/0 of theory; #max = 349 mµ (# = 29,000). The adduct will heated in vacuo to 150 ° C, the 2-methyl-6 - heptyl - nicotinic acid ethyl ester passes over as easily moving oil; B.p. 0.1 125 ° C. Yield 92% of theory.
Beispiel 13 0,1 Mol p - Methoxy - phenyl - äthinylketon in 20 ccm Alkohol gibt man zu einer Lösung von 0,1 Mol A-Aminocrotonsäureäthylester in 20 ccm Alkohol und erhitzt 1 Stunde zum Sieden. Der nach dem Erkalten anfallende Niederschlag wird aus Methanol umkristallisiert; F. 159°C. Ausbeute 90% der Theorie; AmaZ = 385 mµ. Das Addukt löst man in 30 ccm Toluol unter Zusatz von 10% Eisessig und erhitzt 30 Minuten zum Sieden. Nach Verdampfen des Lösungsmittels wird der kristalline Rückstand aus Methanol umkristallisiert; F. 70"C. Example 13 0.1 mol of p-methoxyphenyl-ethinyl ketone in 20 cc Alcohol is added to a solution of 0.1 mol of A-aminocrotonic acid ethyl ester in 20 cc of alcohol and heated to boiling for 1 hour. The precipitate that occurs after cooling is recrystallized from methanol; 159 ° C. yield 90% of theory; AmaZ = 385 mµ. The adduct is dissolved in 30 cc of toluene with the addition of 10% glacial acetic acid and heated 30 minutes to simmer. After evaporation of the solvent, the crystalline residue becomes recrystallized from methanol; F. 70 "C.
Ausbeute 8001o der Theorie an 2-Methyl-6-(p-methoxy-phenyl)-nicotinsäureäthylester.Yield 80010 of theory of ethyl 2-methyl-6- (p-methoxyphenyl) nicotinate.
Beispiel 14 0,1 Mol p - Methoxyphenyl - äthinyl - keton in 20 ccm Alkohol gibt man zu 0,1 Mol ß-Aminoy-äthyl-crotonsäureäthylester in 20 ccm Alkohol und erhitzt 1 Stunde zum Sieden. Das rohe Additionsprodukt wird in Toluol-Eisessig (10: 1) 1, Stunde gekocht und der Eindampfrückstand aus äthern Petroläther umkristallisiert; F. 84°C. Ausbeute 8001o der Theorie an 2-n-Propyl-6-(p-methoxy-phenyl)-nicotinsäureäthylester; #max = 305 mµ (E = 28 300). Example 14 0.1 mol of p-methoxyphenyl-ethinyl-ketone in 20 ccm Alcohol is added to 0.1 mol of ß-aminoy-ethyl-crotonic acid ethyl ester in 20 cc of alcohol and heated to boiling for 1 hour. The crude addition product is dissolved in toluene-glacial acetic acid (10: 1) boiled for 1 hour and the evaporation residue recrystallized from ether petroleum ether; M.p. 84 ° C. Yield 80010 of theory of 2-n-propyl-6- (p-methoxyphenyl) nicotinic acid ethyl ester; #max = 305 mµ (E = 28 300).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEM34126A DE1190464B (en) | 1957-05-09 | 1957-05-09 | Process for the preparation of pyridine derivatives |
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| Application Number | Priority Date | Filing Date | Title |
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| DEM34126A DE1190464B (en) | 1957-05-09 | 1957-05-09 | Process for the preparation of pyridine derivatives |
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| DE1190464B true DE1190464B (en) | 1965-04-08 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4684220A (en) * | 1984-07-12 | 1987-08-04 | Seiko Epson Kabushiki Kaisha | 2-phenylpyridine derivatives and liquid crystal compositions including same |
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1957
- 1957-05-09 DE DEM34126A patent/DE1190464B/en active Pending
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4684220A (en) * | 1984-07-12 | 1987-08-04 | Seiko Epson Kabushiki Kaisha | 2-phenylpyridine derivatives and liquid crystal compositions including same |
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