CS235195B1 - 4-Acetylfuro [3,2-b] pyrrole; - Google Patents

4-Acetylfuro [3,2-b] pyrrole; Download PDF

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CS235195B1
CS235195B1 CS117684A CS117684A CS235195B1 CS 235195 B1 CS235195 B1 CS 235195B1 CS 117684 A CS117684 A CS 117684A CS 117684 A CS117684 A CS 117684A CS 235195 B1 CS235195 B1 CS 235195B1
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Czechoslovakia
Prior art keywords
pyrrole
furo
preparation
acetylfuro
acetic anhydride
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CS117684A
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Czech (cs)
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Alzbeta Krutosikova
Peter Kelemen
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Alzbeta Krutosikova
Peter Kelemen
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Publication of CS235195B1 publication Critical patent/CS235195B1/en

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Abstract

Vynález sa týká odboru organické) syntézy a rieši přípravu novej zlúčeniny 4-acetylfurof 3,2-b Jpyrolu. Podstata sposobu přípravy podía vynálezu spočívá v tom, že sa kyselina 4H-furo[ 3,2-b ]- pyrol-5-karboxylová zahrieva v acetanhydride pri teplotách 100 až 136 °C. Zlúčenina podía vynálezu može nájsť široké uplatnenie v syntéze nových heterocyklických zlúčenín ako sú fůro [ 3,2-b jazepíny, formylované furo- [ 3,2-b jpyroly. 4-Acetylíuro[3,2-bjpyrol podlá vynálezu je charakterizovaný vzorcomThe invention relates to the field of organic synthesis and solves the preparation of a new compound 4-acetylfurof 3,2-b Jpyrrole. The essence of the preparation method according to the invention is that 4H-furo[3,2-b]-pyrrole-5-carboxylic acid is heated in acetic anhydride at temperatures of 100 to 136°C. The compound according to the invention can find wide application in the synthesis of new heterocyclic compounds such as furo[3,2-b jazepines, formylated furo-[3,2-b]pyrroles. 4-Acetyluro[3,2-bjpyrrole according to the invention is characterized by the formula

Description

235195 3 4

Vynález sa týká 4-acetylfuro[ 3,2-b ]-pyro-lu a spůsobu jeho přípravy. Vhodnou metó-dou na jeho přípravu je dekarboxylačná ace-tylácia kyseliny 4H-furo[3,2-b]pyrolkarboxy-lovej.

Dekarboxylácia karboxylových kyselinpředstavuje jednoduchá reakciu, ktorú mož-no uskutočniť niekolkými postupmi. Výběrmetody ovplyvňuje najma struktura a fyzi-kálnochemické vlastnosti východiskovej zlú-čeniny a očakávaného produktu, vačšina de-karboxylačných reakcií sa uskutočňuje v ka-palnej fáze bez katalyzátore, alebo- v přítom-nosti homogenného či heterogenného kata-lyzátoru.

Dusíkové heterocyklické zlúčeniny s NHvazbou, například pyrol, indol alebo karba-zol, sa alkylujú alebo acylujú vo formě ani-ónu generovaného ich reakciou so silnouzásadou, ako například amidom sodným,hydridom litným alebo organokovmi. V lite-ratúre sú opísané alkylácie pyrolu [HeanyH., Ley J.: J. Chem. Soc. Ferkin Trans I 2292(1972), Garner E., Albisser J.: Chemistry andIndustry 110 (1974)]. Acetylácia 2-(4-chlór-fenyl )-5-etoxykarbonylfuro[ 3,2-b Jpyrolu ces-tou N-lítnej soli v náročných reakčnýchpodmienkach bola popísaná v práci Krutoší-ková A., Kováč J., Chudobová M., Ilavský D.:Collection Czechoslov. Ohem. Commun. 45,2949 (1980). Štúdiom literatúry sa zistilo, že 4-acetyl-furo[3,2-b]pyrol nebol doteraz připravený.

Predmetom vynálezu je 4-acetylfuro[ 3,2-b ]-pyrol vzorca I

(I) a spůsob jeho přípravy.

Podstata spQsobu přípravy 4-acetylfuro-

[3,2-b]pyrolu vzorca I spočívá v tom, že sakyselina 4H-furo[3,2-b]pyrol-5-karboxylovávzorca II

zahrieva v acetanhydride pri teplotách 100až 136 °C. Výhody spósobu přípravy zlúčeniny I po-dlá vynálezu spočívajú okrem iného v tom,že sa reakcia dekarboxylácie a súčasnej ace-tylácie uskutočňuje v jednom stupni v nená-ročných podmienkach s dobrým výťažkom,pričom sa získá stabilizovaný 4-acetylfuro-[3,2-b]pyrol. 4-acetylfuro[3,2-b]pyrol může nájsť uplat-něme ako východisková zlúčenina pre novéheterocyklické zlúčeniny ako sú fůro [3,2-b ]-azepíny a formylované fůro [ 3,2b Jpyroly.

Predmet vynálezu ilustrujú, ale neobme-dzujú následovně příklady: Příklad 1

Kyselina 4H-furo [ 3,2-b ] pyrol-5-kárboxylo-vá (3,5 g, 0,025 mol) sa zahrieva pri teplotevaru acetanhydridu (30 ml] počas 4 hod. Pouplynutí reakčnej doby sa acetanhydrid od-destiluje a zvyšok sa destiluje vo vákúu,t. v. 94 °C. Výťažok 1,6 g (35 %) pre C8H7NO2 (149,1)vypočítané 9,39 °/o N, nájdené 9,35 % N, t. t.34 °C.

Struktúra zlúčeniny I sa dokázala spektrál-nými metódami: IR, UV, 1H NMR. IR (CHC13, cm-i) v(C = O) = 1728 UV (metanol, nm) Amax(log ε): 289 (3,30) 1HNMR (DMSO-de): 7,66 (1H, dd, Curii), 7,37 (1H, dd,C(S)-H), 6,84 (1H, dd, C(S)-H, 6,49 (1H, dd, C(ó)-H], J5,6 = 3Hz, J2,3 = 3Hz, J3,6 = 0,8 Hz, J2,5 = 0,6 Hz. Příklad 2

Kyselina 4H-f uro [ 3,2-b ]pyrol-5-karboxylo-vá (35 g, 0,025 mol) sa přidá k acetanhydri-du (30 ml) a mieša sa pri teplote 110 °C po-čas 7 hod. Ďalšie spracovanie ako v příkla-de 1.

Spektrálné merania

Infračervené spektrá sa namerali na spek-trometri SPECORD 71 IR (Carl Zeiss Jena).Elektronové spektrá sa namerali na spektro-metri UV VIS (Carl Zeiss Jena) v oblasti 200až 800 nm pri koncentráciach 2.10-5 mol.l-1.XH NMR spektá boli namerané na 80 MHzspektrofotometri BS 487 C TESLA. Pri meranísa použil vnútorný standard tetrametylsilán.Chemické posuny sa udávajú v ppm.

235195 3 4

The present invention relates to 4-acetylfuro [3,2-b] pyrrole and to a process for its preparation. A suitable method for its preparation is the decarboxylation of acetylation of 4H-furo [3,2-b] pyrrolecarboxylic acid.

Decarboxylation of carboxylic acids is a simple reaction which can be carried out by several procedures. The choice of the method mainly influences the structure and physicochemical properties of the starting compound and the expected product, most of the de-carboxylation reactions are carried out in the catalyst-free liquid phase or in the presence of a homogeneous or heterogeneous catalyst.

The N-linked nitrogen-containing heterocyclic compounds, for example pyrrole, indole or carbazol, are alkylated or acylated in the form of the anion generated by their reaction with a strong base such as sodium amide, lithium hydride or organometallic. Pyrolysis of pyrrole [Heany. L., Ley J .: J. Chem. Soc. Ferkin Trans I 2292 (1972), Garner E., Albisser J .: Chemistry and Industries 110 (1974)]. Acetylation of 2- (4-chloro-phenyl) -5-ethoxycarbonylfuro [3,2-b] pyrrole with N-lithium salt in challenging reaction conditions has been described by Krutošík A., Kováč J., Chudobová M., Ilavský D.:Collection Czechoslov. Ohem. Commun. 45, 2949 (1980). A literature study found that 4-acetyl-furo [3,2-b] pyrrole was not yet prepared.

The present invention provides 4-acetylfuro [3,2-b] pyrrole of formula I

(I) and the method of its preparation.

The principle of the preparation of 4-acetyl

The [3,2-b] pyrrole of formula (I) is characterized in that the 4H-furo [3,2-b] pyrrole-5-carboxylic acid acid (II) is

heated in acetic anhydride at 100-136 ° C. The advantages of the process for the preparation of Compound I of the invention include, but are not limited to, that the decarboxylation and simultaneous acetylation reaction is carried out in one step under non-annealing conditions in good yield to obtain a stabilized 4-acetylfuro [3,2- b] pyrrole. 4-Acetylfuro [3,2-b] pyrrole can be used as a starting compound for new heterocyclic compounds such as furo [3,2-b] azepines and formyl furo [3,2b] pyrrole.

The invention is illustrated but not limited by the following examples: Example 1

4H-furo [3,2-b] pyrrole-5-carboxylic acid (3.5 g, 0.025 mol) was heated at reflux of acetic anhydride (30 mL) for 4 h. After the reaction time, acetic anhydride was distilled off and the remainder distilled in vacuo, mp 94 ° C Yield 1.6 g (35%) for C 8 H 7 NO 2 (149.1) calculated 9.39 ° N, found 9.35% N, mp 34 ° C.

The structure of compound I was demonstrated by spectral methods: IR, UV, 1H NMR. IR (CHCl 3, cm -1) v (C = O) = 1728 UV (methanol, nm) λ max (log ε): 289 (3.30) 1 HNMR (DMSO-d 6): 7.66 (1H, dd, Curii) 7.37 (1H, dd, C (S) -H), 6.84 (1H, dd, C (S) -H, 6.49 (1H, dd, C (6) -H), J5 Δ = 3Hz, J2.3 = 3Hz, J3.6 = 0.8 Hz, J2.5 = 0.6 Hz

4H-Fluoro [3,2-b] pyrrole-5-carboxylic acid (35 g, 0.025 mol) was added to acetic anhydride (30 mL) and stirred at 110 ° C for 7 h. Further processing as in Example 1.

Spectral measurements

Infrared spectra were measured on a SPECORD 71 IR spectrometer (Carl Zeiss Jena). Electron spectra were measured on a UV VIS spectrophotometer (Carl Zeiss Jena) in the range of 200 to 800 nm at concentrations of 2.10-5 mol.l-1.XH NMR spectra were measured at 80 MHzspectrophotometer BS 487 C TESLA. The tetramethylsilane internal standard was used for the meran. Chemical shifts are reported in ppm.

Claims (2)

235195 5 6 PREDMET VYNÁLEZU 4-Acetylfuro[3,2-b]pyrol vzorca I že sa kyselina furo[3,2-b]pyrol-5-karboxylo vá vzorca II coch5 H 1 1-7 A I 1 py-coow ΪΓ l 0' (1 ) (II)235195 5 6 SUBJECT OF THE INVENTION 4-Acetylfuro [3,2-b] pyrrole of formula I that furo [3,2-b] pyrrole-5-carboxylic acid II coch 5 H 1 1-7 Al 1 pyrazole 0 '(2) (II) 2. Sposob přípravy 4-acetylfuro[3,2-b]py-rolu pódia bodu 1 vzorca I, vyznačený tým, zahrieva v acetanhydride pri teplotách 100až 136 °C.2. The process for the preparation of 4-acetylfuro [3,2-b] pyrrole according to step 1 of the formula I, characterized in that it is heated in acetic anhydride at temperatures of 100 to 136 ° C.
CS117684A 1984-02-20 1984-02-20 4-Acetylfuro [3,2-b] pyrrole; CS235195B1 (en)

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