CS264988B1 - Process for preparing the enamphine 5-nitro-2-thiophene and 5-nitro-2-furan series. - Google Patents
Process for preparing the enamphine 5-nitro-2-thiophene and 5-nitro-2-furan series. Download PDFInfo
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Abstract
Riešenie sa týká nového spósobu přípravy enantínov 5-nitro-2-tiofénového a 5-nitro-2-furanového radu obecného vzorca I reakciou 3-bróm-3-/5-nitro-2-tienyl/-resp. 3-bróm-3-/5-nitro-2-furyl/propénových kyselin so sekundárnými amínmi alebo aromatickým primárnými amínmi v prostředí organických rozpúšťadiel pri teplote 40 až 180 °C.The solution concerns a new method of preparing enanthins of the 5-nitro-2-thiophene and 5-nitro-2-furan series of the general formula I by the reaction of 3-bromo-3-/5-nitro-2-thienyl/-resp. 3-bromo-3-/5-nitro-2-furyl/propenoic acids with secondary amines or aromatic primary amines in organic solvents at a temperature of 40 to 180 °C.
Description
Vynález sa týká nového spósobu přípravy enamínov 5-nitro-2-tiofénového a 5-nitro-2-furánového radu.The invention relates to a novel process for preparing enamines of the 5-nitro-2-thiophene and 5-nitro-2-furan series.
Enamíny sú dóležitými východiskovými látkami v organickej syntéze (Cook A. G., Anamines, Synthesis, Structure and Reactions, Dekker, New York-London, 1969). Enamíny 5-nitro-2-tiofénového a 5-nitro-2-furánového radu vykazujú výraznú antibakteriálnu aktivitu a sú predmetom intenzívneho výzkumu (Végh D., Kováč J., Dandárová M. , IvanČo L.: Coli, Czech.Enamines are important starting materials in organic synthesis (Cook A.G., Anamines, Synthesis, Structure and Reactions, Dekker, New York-London, 1969). Enamines of the 5-nitro-2-thiophene and 5-nitro-2-furan series show significant antibacterial activity and are the subject of intensive research (Végh D., Kováč J., Dandárová M., IvanČo L .: Coli, Czech.
Chem. Commun., 45, 155 (1980); Végh D. , šejnkmann A. K., Kováč J., Kondratenko G. P., Geonja N. I.: ZSSR AO 671 254). Ich přípravy vychádzajú z vysoko reaktívnych 5-nitro-2-tienylresp. 5-nitro-2-furylvinylhalogenidov reakciou so sekundárnými amínmi.Chem. Commun., 45, 155 (1980); Végh D., Shejnkmann A.K., Kovac J., Kondratenko G. P., Geonja N.I .: USSR AO 671 254). Their preparations are based on highly reactive 5-nitro-2-thienyl resp. Of 5-nitro-2-furylvinyl halides by reaction with secondary amines.
Pre aplikáciu a výskům sa však vyžadujú vSčšie množstvá a Širšie palety enamínov 5-nitro-2-tiofénového a 5-nitro-2-furánového radu.However, larger amounts and wider palettes of the 5-nitro-2-thiophene and 5-nitro-2-furan series enamines are required for application and elevations.
Uvedené požiadavky v podstatnej miere splňa nový spósob podlá vynálezu, ktorého podstata spočívá v tom, že 3-/5-nitro-2-tienyl/-3-brómpropénová kyselina resp. 3-/5-nitro-2-furyl/-3brómpropénová kyselina reagujú so sekundárnými resp. primárnými aromatickými amínmi v prostředí organických rozpúšťadiel ako v kvapalných aromatických uhlovodíkoch ako v benzéne^, toluéne, xyléne v éteroch ako dietyléteri, 1,2-dimetoxyetáne, dioxáne, tetrahydrofuránepolyetylénglykole 200 až 600, dalej v octane etylovom, acetonitrile, sírouhlíku, dimetylformamide, dimetylsulfoxide, acetone, 2-butanóne resp. v ich zmesiach pri teplote 40 až 180 °C, a poskytujú enamíny 5-nitro-2-tienyl- resp. 5-nitro-2-furánového radu obecného vzorca IThe novel process according to the invention essentially complies with the above-mentioned requirements in that 3- (5-nitro-2-thienyl) -3-bromopropenoic acid, respectively. 3- (5-nitro-2-furyl) -3-bromopropenoic acid reacts with the secondary and / or secondary acids. primary aromatic amines in organic solvent environments such as liquid aromatic hydrocarbons such as benzene, toluene, xylene in ethers such as diethyl ether, 1,2-dimethoxyethane, dioxane, tetrahydrofuranepolyethylene glycol 200-600, further in ethyl acetate, dimethylformamide, acetonitrile, silane, acetonitrile, , acetone, 2-butanone, respectively. in their mixtures at a temperature of 40 to 180 ° C, to give the enamines 5-nitro-2-thienyl- and the like. Of the 5-nitro-2-furan series of formula I
Reakcie prebiehajú podlá nasledujúcej schémy:The reactions follow the following scheme:
(I) kde Z=S,0(I) wherein Z = S, 0
HNR1R2 = HN(CH3)2; HN(CH2CH3)2;HNR 1 R 2 = HN (CH 3 ) 2 ; HN (CH 2 CH 3 ) 2 ;
HN O.HN O.
NH2;NH 2 ;
Predmet vynálezu ilustrujú ale neobmedzujú nasledujúce příklady:The following examples illustrate the invention but do not limit it:
Přikladl.EXAMPLE.
V 500 ml benzénu sa zmieša 27,8 g 3-/5-nitro-2-tienyl/-3-brómpropénovej kyseliny a 30 g morfolinu a po 1 h miešania pri teplote laboratória reakčná zmes sa zahřeje k varu.27.8 g of 3- (5-nitro-2-thienyl) -3-bromopropenoic acid and 30 g of morpholine are mixed in 500 ml of benzene and, after stirring at room temperature for 1 hour, the reaction mixture is heated to boiling.
Po 4 h zahrievania k varu intenzívně červený roztok po ochladeni na teplotu laboratória sa přečisti chromatografiou na silikageli. Získá sa 17 g l-/5-nitro-2-tienyl/-2-morfolínoeténu o t. t. 167 až 168 °C.After heating to boiling for 4 h, the vigorously red solution, after cooling to room temperature, was purified by silica gel chromatography. 17 g of 1- (5-nitro-2-thienyl) -2-morpholinoethene of m.p. t. Mp 167-168 ° C.
Přiklad 2Example 2
Pri 5 °C k intenzívně miešanej zmesi 27,8 g 3-/5-nitro-2-tienyl-3-brómpropenovej kyseliny a 200 ml 2,2-dimetoxyetánu sa přidá 20 g dimetylamínu. Po 2 h miešania pri teplote laborátoria reakčná zmes sa uvedie do varu na 5 h. Po oddestilování rozpúšťadla zvyšok sa čistí chromatografiou na silikageli (eluent octanetylový-eter). Získá sa 14 g l-/5-nitro-2-tienyl/-2-N,N-dimetylaminoeténu o t. t. 125 až 127 °C.At 5 ° C, 20 g of dimethylamine are added to a vigorously stirred mixture of 27.8 g of 3- [5-nitro-2-thienyl-3-bromopropenoic acid and 200 ml of 2,2-dimethoxyethane. After stirring at room temperature for 2 h, the reaction mixture is boiled for 5 h. After distilling off the solvent, the residue was purified by silica gel chromatography (eluent: ethyl acetate-ether). 14 g of 1- (5-nitro-2-thienyl) -2-N, N-dimethylaminoethene of m.p. t. Mp 125-127 ° C.
Příklad 3 g 3-/5-nitro-2-furyl/-3-brómpropénovej kyseliny sa zmieša s 30 g piperidínu v 50 ml benzénu a 250 ml 2-butanónu. Po 3 h miešania a zahrievania k varu, vylúčená amóniová sol sa odfiltruje a zvyšok sa čisti kryštalyzáciou. Získá sa 16 g l-/5-nitro-2-furyl/-2-N-piperidinoeténu o t. t. 78 až 79 °C.Example 3 g of 3- (5-nitro-2-furyl) -3-bromopropenoic acid are mixed with 30 g of piperidine in 50 ml of benzene and 250 ml of 2-butanone. After stirring and boiling for 3 h, the precipitated ammonium salt is filtered off and the residue is purified by crystallization. 16 g of 1- (5-nitro-2-furyl) -2-N-piperidinoethene of m.p. t. 78-79 ° C.
Příklad 4Example 4
Postupuje sa ako v příklade 3 za použitia polyetylénglykol 400 pri 140 °C. Získá sa 8 g l-/5-nitro-2-furyl/2-N-piperidinoeténu o t. t. 79 °C.The procedure was as in Example 3 using polyethylene glycol 400 at 140 ° C. 8 g of 1- (5-nitro-2-furyl) -2-N-piperidinoethene of m.p. t. 79 ° C.
Příklad 5Example 5
260 g 3-/5-nitro-2-furyl/-3-brómpropénovej kyseliny sa suspenduje v 500 ml toluénu a pri teplote laboratória sa přidal naraz 200 g anilínu. Po 2 h miešania pri teplote laboratória a 5 h zahrievania k varu rozpúšťadla sa získá 100 g 1-/5-nitro-2-furyl/-2-N-fenyletěnu o t. t. 90 až 92 °C.260 g of 3- (5-nitro-2-furyl) -3-bromopropenoic acid are suspended in 500 ml of toluene and 200 g of aniline are added at the same time at room temperature. After stirring at room temperature for 2 h and heating to reflux for 5 h, 100 g of 1- (5-nitro-2-furyl) -2-N-phenylethylene of m.p. t. Mp 90-92 ° C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS88341A CS264988B1 (en) | 1988-01-19 | 1988-01-19 | Process for preparing the enamphine 5-nitro-2-thiophene and 5-nitro-2-furan series. |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS88341A CS264988B1 (en) | 1988-01-19 | 1988-01-19 | Process for preparing the enamphine 5-nitro-2-thiophene and 5-nitro-2-furan series. |
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| Publication Number | Publication Date |
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| CS34188A1 CS34188A1 (en) | 1988-12-15 |
| CS264988B1 true CS264988B1 (en) | 1989-09-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CS88341A CS264988B1 (en) | 1988-01-19 | 1988-01-19 | Process for preparing the enamphine 5-nitro-2-thiophene and 5-nitro-2-furan series. |
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