CS236601B1

CS236601B1 - S-nitro-2-ethylfuran meioxyderivative and its preparation

Info

Publication number: CS236601B1
Application number: CS466881A
Authority: CS
Inventors: Daniel Vegh; Jaroslav Kovac
Original assignee: Daniel Vegh; Jaroslav Kovac
Priority date: 1980-11-28
Filing date: 1980-11-28
Publication date: 1985-05-15

Abstract

Vynález rieši spósob přípravy novej látky metoxyderivátu 5-nitro-2-etylfuránu, vzorca I f I ) Tento sa připravuje tak, že na 5-nitro-2- -vinylfurán sa pósobí metylalkoholátom alkalického kovu pri teplote 10 až 120 °C, alebo sa na 5-nitro-2-vl.nylfurán působí metylalkoholom za katalýzy fázovými katalyzátormi v prostředí vody alebo organických rozpúšťadiel v rozmedzí teplůt 10 až 120 °C.The invention provides a method for the preparation of a new methoxy derivative of 5-nitro-2-ethylfuran, formula I f I ) This is prepared by treating 5-nitro-2-vinylfuran with an alkali metal methyl alcoholate at a temperature of 10 to 120 °C, or by treating 5-nitro-2-vinylfuran with methyl alcohol catalyzed by phase catalysts in water or organic solvents in the temperature range of 10 to 120 °C.

Description

Vynález sa týká metoxyderivátu 5-nitro-2etylfuránu a sposobu jeho přípravy.The present invention relates to a 5-nitro-2-ethylfuran methoxy derivative and to a process for its preparation.

Zlúčenina a spósob jej přípravy podl'a vynálezu nie je v literatuře popísaná.The compound and the process for its preparation according to the invention are not described in the literature.

Metoxyderivát-5-nitro-2-etylfurán všeobecného vzorca IThe compound 5-nitro-2-ethylfuran of the formula I

QiN-ZgV-C^-CHjO-CHjQiN-ZgV-C 1 -CH 3 O-CH 3

II i sa podlá vynálezu připravuje sposobom, ktorsho podstata spočívá v tom, že sa 5-nitro-2-vinyifurán [II] reaguje v metylalkohole s metanolátom alkalického kovu, ako sú například sodný, draselný, lítny. Ďalej je možné 5-nitro-2-vinylfurán (lij ponechat reagovat s metylalkoholom za katalýzy fázovými katalyzátormi ako sú například tetrabutylamóniumhydroxid, trimetylbenzylamóniumbromid, tetraetylamóniumhydroxid, benzyltrietylamóniumbromid, tetrabutylfosfóniumbromid, trifenylmetylfosfóniumbromid v prostředí vody a organických rozpúšťadiel ako sú étery ako dietyléter, tetrahydrofurán, dioxán, dimetoxyetán, ketony ako je acetón, metyletylketón, cyklohexanón, aromatické uhlovodíky ako je benzen, toluen, nitrobenzén, estery kyselin ako sú octan etylnatý, octan metylnatý, mravčan etylnatý, alkoholy ako je metylalkohol, etylalkohol, izopropylalkohol, ďalej dimetylsulfoxid, acetonitril alebo ich zmesi s vodou. Obidve reakcie prebiehajú v rozmedzí teplot 10 až 120 °C.According to the invention, the process according to the invention is characterized in that 5-nitro-2-vinyifuran [II] is reacted in methanol with an alkali metal methanolate such as sodium, potassium, lithium. Further, 5-nitro-2-vinylfuran (IIi) can be reacted with methyl alcohol under catalysis by phase catalysts such as tetrabutylammonium hydroxide, trimethylbenzylammonium bromide, tetraethylammonium hydroxide, benzyltriethylammonium bromide, tetrabutylphosphonium bromide, triphenylphosphonium bromide, diphenylphosphonium bromide, dimethoxyethane, ketones such as acetone, methyl ethyl ketone, cyclohexanone, aromatic hydrocarbons such as benzene, toluene, nitrobenzene, acid esters such as ethyl acetate, methyl acetate, ethyl formate, alcohols such as methanol, ethyl alcohol, isopropyl alcohol or mixtures thereof, dimethylsulfoxide, acetonitrile Both reactions are carried out in a temperature range of 10 to 120 ° C.

Reakcia s metylátom prebieha podl'a rovnice:Reaction with methylate proceeds according to the equation:

(II I kde Μ = H, Na, Li, K.(II I where Μ = H, Na, Li, K.

Výhody spósobu přípravy metoxyderivátu 5-nitro-2-etylfuránu podlá vynálezu sú v tom, že sa uskutočňujú z poměrně dostupných zlúčenín, reakcie sú jednostupňové a produkty sa získávajú vo vysokých 60 až 90 percentných výtažkoch a čistotě. Strukturálně zapadá připravená látka do skupiny látok s antibakteriálnymi účinkami.The advantages of the process for preparing the methoxy derivative of 5-nitro-2-ethylfuran according to the invention are that they are carried out from relatively available compounds, the reactions are one-stage and the products are obtained in high 60-90% yields and purity. Structurally the prepared substance fits into the group of substances with antibacterial effects.

Predmet vynálezu ilustrujú prieklady prevedenia. Zlúčenina představuje analog známého antibakteriálneho preparátu metyl-5-nitrofuryléteru vzorcaThe invention is illustrated by the examples. The compound represents an analog of the known antibacterial preparation of methyl 5-nitrofuryl ether of formula

Příklad 1Example 1

13,5 g (0,01 mólj 5-nitro-2-vinylfuránu a 0,1 g hydrochinčnu sa rozpustilo v 50 ml metanolu a za intezívneho miešania sa přidalo 5 g metanolátu draselného. Reakčná zmes sa miešala při teplote varu rozpúšťadla 10 hodin. Po oddestilování metylalkoholu za13.5 g (0.01 mol) of 5-nitro-2-vinylfuran and 0.1 g of hydroquinone were dissolved in 50 ml of methanol and 5 g of potassium methoxide were added with vigorous stirring, and the reaction mixture was stirred at the reflux temperature of the solvent for 10 hours. After distilling off the methanol into

0₉N -J >—0 ₉ N -J> -

Á Z. o (I ) vákua sa zvyšok čistil chromatograficky na štipci silikagelu za použitia benzenu ako efluentu. Získalo sa 5 g produktu, čo představuje 30 %-ný výťažok. Teplota topenia látky bola 55 až 60 °C.Under vacuum (I), the residue was purified by silica gel column chromatography using benzene as the effluent. 5 g of product were obtained, which is a 30% yield. The melting point was 55-60 ° C.

P r i e k 1 a d 2 g 5-nitro-2-etylfuránu, 0,1 g hydrochinónu a 0,1 g tetrabutylamóniumhydroxidu sa rozpustilo v 100 ml dimetoxyetánu a k intenzívně miešanému roztoku sa přidalo 7 g metanolátu draselného a 5 ml vody. Po 10 hodinách miešania a zahrievania pri 60 až 70 °C sa rozpúšťadlo oddestilovalo za vákua a zvyšok sa čistil destiláciou za zníženého tlaku pri 1000 až 1500 Pa a 130 až 140 °C. Získalo sa 3,5 g (43 %) produktu.EXAMPLE 2 g of 5-nitro-2-ethylfuran, 0.1 g of hydroquinone and 0.1 g of tetrabutylammonium hydroxide were dissolved in 100 ml of dimethoxyethane and 7 g of potassium methanolate and 5 ml of water were added to the vigorously stirred solution. After stirring and heating at 60-70 ° C for 10 hours, the solvent was distilled off under vacuum and the residue was purified by distillation under reduced pressure at 1000-1,500 Pa and 130-140 ° C. 3.5 g (43%) of the product were obtained.

Metoxyderivát 5-nitro-2-etylfuránu (Ij je zlúčenina vzorca C7H7NO4 — jeho molekulová hmotnost je 175,15.5-Nitro-2-ethylfuran methoxy derivative (Ij is a compound of formula C7H7NO4 - its molecular weight is 175.15).

Vypočítané:Calculated:

49,12 % C, 5,29 % H, 8,18 % N; Stanovená:H, 5.29; N, 8.18; Specified:

49,30 % C, 5,17 O/o H, 8,08 % N.49.30% C, 5.17 O / o H, 8.08% N.

Claims

A 5-nitro-2-ethylfuran methoxy derivative of the formula I

OF THE INVENTION

1, characterized in that 5-nitro-2-vinylfuran of the formula II is used

O _I N Q ^> CH _and CH _and O-CH ₃ (I)

2. A process for the preparation of a compound according to claim 1, characterized in that 5-nitro-2-vinylfuran of formula II is treated in methyl alcohol followed by an added alkali metal methyl alcohol such as sodium, potassium or lithium methyl alcohol in the temperature range 10 to 120 ° C. .

3. A process for the preparation of a compound according to (ID) by methyl alcohol in catalysis with phase catalysts such as tetrabutylammonium hydroxide, trimethylbenzylammonium bromide, tetraethylammonium hydroxide, benzyltriethylammonium bromide, tetrabutylphosphonium bromide, dioxane such as diphenylmethylphosphonium ether such as diphenylmethylphosphonium ether methyl ethyl ketone, cyclohexanone, aromatic hydrocarbons such as benzene, toluene, nitrobenzene, acid esters such as ethyl acetate, methyl acetate, ethyl formate, alcohols such as methanol, ethyl alcohol, isopropyl alcohol, other dimethylsulfoxide, acetonitrile, or mixtures thereof with water in the range 10 to 120 ° C.