CS255305B1 - 5-nitro-2-thiophene's halogenacetylenes and method of their preparation - Google Patents
5-nitro-2-thiophene's halogenacetylenes and method of their preparation Download PDFInfo
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Abstract
Riešenie sa týká halagénacetylénov 5-nitro-2-tiofénu vzorca I, kde X je chlór, bróm alebo jód, novej skupiny acetylénojvých derivátov 5-nitro-2-tiofénu, s možným použitím ako antibakteriálnych preparátov a reaktívnych komponentov pře přípravu nových antibiotik. Podstata spósabu přípravy uvedených látok spočívá v tom, že na deriváty 5-nitro- -2-tienylacetylénu vzorca II, kde M je vodík, striebra, meď alebo magnézium,bromid, sa pósobí halogénom v prostředí organických rozpúšťadiel ako sú aromatické kvapalné uhlovodíky, étery, deriváty octovej kyseliny, halogénované rozpúšťadlá vo- vodě a/ /alebo v ich zmesiach s vodou za přítomnosti bázických katalyzátorov typu uhličitanov a hydroxidoví alkalických kovov v rozmedzí teplůt —20 °C až +150 °C.The solution relates to halogen acetylenes of 5-nitro-2-thiophene of formula I, where X is chlorine, bromine or iodine, a new group of acetylene derivatives of 5-nitro-2-thiophene, with possible use as antibacterial preparations and reactive components for the preparation of new antibiotics. The essence of the method for preparing the above substances lies in the fact that the derivatives of 5-nitro-2-thienylacetylene of formula II, where M is hydrogen, silver, copper or magnesium bromide, are treated with halogen in the environment of organic solvents such as aromatic liquid hydrocarbons, ethers, acetic acid derivatives, halogenated solvents in water and/or in their mixtures with water in the presence of basic catalysts of the type of carbonates and hydroxides of alkali metals in the temperature range of -20 °C to +150 °C.
Description
Vynález sa týká halogénacetylénov 5-nitro-2-tiofénu všeobecného vzorca I °č N As>“ C=C-X • (I ) kdeThe invention relates halogénacetylénov 5-nitro-2-thiophene of the formula I ° C with> "C • = CX (I) wherein
X je chlór, bróm, jód a spósobu ich přípravy.X is chlorine, bromine, iodine and a process for their preparation.
Uvedené látky nie sú v literatuře doteraz popísané.These substances are not yet described in the literature.
Podstata sposobu přípravy látok podlá vynálezu spočívá v tom, že na deriváty 5-nitro-2-tienylacetylénu vzorca II N C“ C” M (I!) kdeThe essence of the process for the preparation of the compounds according to the invention consists in that for derivatives of 5-nitro-2-thienylacetylene of the formula II NC " C " M (I) where:
M je vodík, striebro, meď alebo magnézlumbromid, sa posobí halogénom v prostředí organických rozpúšťadiel ako sú aromatické kvapalné uhlovodíky, étery, estery kyselin, ďalej tiofén, sírouhlík, acetonitril, dimetylsulfoxid, dimetylformamid a halogénované rozpúšťadlá vo vodě a/alebo v ich zmesiach s vodou za přítomnosti bázických katalyzátorov typu uhličitanov a hydroxidov alkalických kovov v rozmedzí teplot —20 °C až +150 °C.M is hydrogen, silver, copper or magnesium bromide, halogenated in an organic solvent environment such as aromatic liquid hydrocarbons, ethers, acid esters, thiophene, carbon disulphide, acetonitrile, dimethylsulfoxide, dimethylformamide and halogenated solvents in water and / or mixtures thereof with water in the presence of basic alkali metal carbonates and hydroxides catalysts in the range of -20 ° C to +150 ° C.
Reakcia prebieha podlá nasledujúcej schémy:The reaction proceeds according to the following scheme:
Γ -------> c V- C C - λ + MX pričomΓ - ------> c V - CC - λ + MX where
M a X je hoře uvedené.M and X are listed above.
Výhoda sposobov přípravy halogénacetylénov 5-nitro-2-tiofénu podTa vynálezu spočívá okrem iného v tom, že syntézy sú jednostupňové z poměrně dostupných surovin a získané produkty sú vo vysokých výťažkoch a čistotě. Strukturálně látky podlá vynálezu predstavujú skupinu látok s předpokládanou antibakteriálnou aktivitou.An advantage of the processes for the preparation of 5-nitro-2-thiophene haloacetylenes according to the invention is, inter alia, that the syntheses are one-step from relatively available raw materials and the products obtained are in high yields and purity. Structurally, the compounds of the present invention represent a class of substances with anticipated antibacterial activity.
Predmet vynálezu je poplsaný v nasledujúcich príkladoch bez toho, aby sa iba na tieto příklady obmedzoval.The present invention is described in the following examples without being limited to these examples.
Příklad 1Example 1
K intenzívně miešanej suspenzii 2,6 g strieboruej soli 5-nitro-2-tienylacetylénu sa přidá pri teplote 0 °C po kvapkách 0,8 g chlóru v 20 ml éteru. Po 1 hodině sa roztok odfiltruje od nerozpustného zvyšku a po oddestilovaní sa získá 1,5 g l-chlór-2(5-nitro-2-tienyl}acetylénu o t. t. 73 až 75 °C.To a vigorously stirred suspension of 2.6 g of 5-nitro-2-thienylacetylene silver salt was added dropwise 0.8 g of chlorine in 20 ml of ether at 0 ° C. After 1 hour, the solution is filtered off from the insoluble residue and, after distillation, 1.5 g of 1-chloro-2- (5-nitro-2-thienyl) acetylene is obtained, m.p. 73-75 ° C.
Hmotnostně spektrum (na spektrometrii AEI MS 920—Sj:Mass spectrum (on AEI MS 920-Sj spectrometry):
+ (M ) 187 (100 %), ++ (M) + 187 (100%);
(M . + 2) 189 (47 °/o).(M + 2) 189 (47 ° / o).
Příklad 2Example 2
K intenzívně miešanej suspenzii 11 g meďnej soli 5-nitro-2-tienylacetylénu v 20 ml dichlóretáne sa přidá pri teplote —10 °C 8 g brómu v 50 ml dichlórmetáne. Po 1 hodině sa roztok odfiltruje od nerozpustného zvyšku a po oddestilovaní rozpúšťadla zvyšok sa čistí na štipci silikagélu (100 — 150 μηι, eluent benzen ). Získá sa 10,2 g l-bróm-2-(5-nitro-2-tienyl]acetylénu o t. t. 103 až 105 °C. Molekulová hmotnost na základe hmotnostně j spektrometrie) 231 — 233 (100 %). Příklad 3To a vigorously stirred suspension of 11 g of the copper (I) salt of 5-nitro-2-thienylacetylene in 20 ml of dichloroethane was added at -10 ° C 8 g of bromine in 50 ml of dichloromethane. After 1 hour, the solution is filtered off from the insoluble residue and, after distilling off the solvent, the residue is purified on a column of silica gel (100-150 μηι, eluent benzene). 10.2 g of 1-bromo-2- (5-nitro-2-thienyl) acetylene of m.p. Example 3
K suspenzii 26 g acetylidu striebra v 50 ml tetrahydrofuráne za intenzívneho miešania sa přidává v malých porciácb 25,4 g jódu. Každá porcia jódu sa přidala až po odfarbeni roztoku. Po přidaní sa 1 h zahrievala k varu a po oddestilovaní rozpúšťadla za vakua sa získá 23 g l-jód-2(5-nitro-2-tienyl)acetylénu o t. t. 121 — 124 °C.To a suspension of 26 g of silver acetylide in 50 ml of tetrahydrofuran under vigorous stirring, 25.4 g of iodine are added in small portions. Each portion of iodine was added after the solution was decolorized. After the addition, it was heated to boiling for 1 h and after distilling off the solvent in vacuo, 23 g of 1-iodo-2- (5-nitro-2-thienyl) acetylene of m.p. 121-124 ° C were obtained.
Hmotnostně spektrum (na spektrometrii AEI MS 920—S):Mass spectrum (AEI MS 920-S):
(M. j 279 (100 °/o).(M. j 279 (100%).
253305253305
Příklad 4Example 4
15,2 g 5-nitroi-2-tienylacetylénu sa rozpustilo v 100 ml sírouhlíku a za intenzívneho miešania pri —20 °C přidalo 10 g NažCO3 a 16 g brómu. Po 2 hodinách miešania sa rozpúšťadlo oddestilovalo za vakua a po pridaní 50 ml dimetylformamidu sa zahrievalo na 130 — 140 °C 1 h. Po oddestilování rozpúšťadla sa zvyšok čistil chromatograficky ako v příklade 2. Získalo sa 15 g l-bróm-2-(5-nitro-2-tienylJacetylénu o t. t. 103 až 104 stupňov Celzia.15.2 g of 5-nitro-2-thienylacetylene was dissolved in 100 ml of carbon disulphide and 10 g of Na 2 CO 3 and 16 g of bromine were added with vigorous stirring at -20 ° C. After stirring for 2 hours, the solvent was distilled off under vacuum and, after addition of 50 ml of dimethylformamide, heated to 130-140 ° C for 1 h. After distilling off the solvent, the residue was purified by chromatography as in Example 2. -nitro-2-thienyl-acetylene having a mp of 103-104 degrees Celsius.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS858212A CS255305B1 (en) | 1985-11-14 | 1985-11-14 | 5-nitro-2-thiophene's halogenacetylenes and method of their preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS858212A CS255305B1 (en) | 1985-11-14 | 1985-11-14 | 5-nitro-2-thiophene's halogenacetylenes and method of their preparation |
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| Publication Number | Publication Date |
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| CS821285A1 CS821285A1 (en) | 1987-07-16 |
| CS255305B1 true CS255305B1 (en) | 1988-03-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CS858212A CS255305B1 (en) | 1985-11-14 | 1985-11-14 | 5-nitro-2-thiophene's halogenacetylenes and method of their preparation |
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1985
- 1985-11-14 CS CS858212A patent/CS255305B1/en unknown
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| CS821285A1 (en) | 1987-07-16 |
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