CS256577B1 - 1- (5 (2-nitrophenyl) -2-furyl Jaminocarbonyl Derivatives of Secondary Amines and a Process for their Preparation - Google Patents
1- (5 (2-nitrophenyl) -2-furyl Jaminocarbonyl Derivatives of Secondary Amines and a Process for their Preparation Download PDFInfo
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Abstract
Riešenie sa týká odboru organickej chémie a rieši přípravu nových zlúčenín l-[5- - (2-nitrofenyl) -2-furyl ] amínokarbonyl derivátov sekundárných amínov vzorca I, ktoré svojou štruktúrou patria medzi substituované močoviny. Podstata ich spósobu přípravy spočívá v tom, že sa na azid kyseliny 5-(2-nitrofenyl)-2-furánkarboxylovej pósobí příslušnými sekundárnými amínmi v aromatických uhlovodíkoch pri teplote 80 až 110 °C. Uvedené zlúčeniny možu nájsť uplatnenie ako východiskové látky pre rózne typy heterocyklických zlúčenín.The solution relates to the field of organic chemistry and deals with the preparation of new compounds l-[5--(2-nitrophenyl)-2-furyl] aminocarbonyl derivatives of secondary amines of formula I, which by their structure belong to substituted ureas. The essence of their method of preparation is that the azide of 5-(2-nitrophenyl)-2-furancarboxylic acid is treated with appropriate secondary amines in aromatic hydrocarbons at a temperature of 80 to 110 °C. The mentioned compounds can be used as starting materials for various types of heterocyclic compounds.
Description
25BS77
Vynález sa týká l-[ 5-(2-nitrof enyl)-2-f uryl jaminokarbonyl derivátov sekundárnýchamínov všeobecného vzorca I
/—\ .CO-N X \ vz (i) kde X je CH2, O, alebo
a spQsobu ich přípravy.
Uvedené zlúčeniny, ktoré svojou struktu-rou patria medzi substituované močoviny,neboli doposiať připravené.
Substituované močoviny sa pripravujú a-dičnou reakciou amínov na příslušný izo-kyanát, ktorý vzniká rozkladom příslušného azidu karboxylovej kyseliny, J. H. San-nders, R. Slocombe: Chem. Rev. 43, 203(1948] alebo reakciou amínov s močovinou K. Kurzer, Org. Synth. Coll. Vol. 4, 52(1983).
Mnohé z derivátov močovin sú popísanéako biologicky účinné látky M. Negwer: Or-ganisch-chemische arzneimittel und ihreSyninyma, Akademie-Verlag Berlín (1978). Příprava azidu kyseliny 5-(2-nitrofenyl )--2-furánkarboxylovej je popísaná v čs. AO č.254 049.
Podstata spésobu přípravy l-[5-(2-nitro-f enyl) -2-f uryl ] amínokarbonylderiváto v se-kundárných amínov pódia vynálezu spočí-vá v tom, že sa na azid kyseliny 5-(2-nit-rofenyl)-2-f uránkarboxylovej vzorca II
pósobí sekundárnými amínmi všeobecnéhovzorca III NH XV-/ fíll) kde X‘ je O, CH2, NH v aromatických uhio-vodíkoch pri teplote 80 až 110 °C. Výhody spdsobu přípravy zlúčenín pódiavynálezu spočívajú okrem iného v tom, žesyntéza je jednostupňová, uskutečňuje sa vjednoduchej aparatúre s dobrými výťažka-mi. 1-(5-( 2-nitrof enyl) -2-f uryl ] amínokar-bonylderiváty sekundárných amínov majúpoužitie v organickej syntéze. Reakciou strietylfosfitom poskytujú možnost prikon-denzovania ďalšieho heterocyklického kru-hu.
Predmet vynálezu ilustrujú, ale neobme-dzujú následovně příklady: Příklad 1 1-(5-( 2-nitrofenyl) -2-f uryl ] amínokar-bonylpiperidín azid kyseliny 5-(2-nitrofe-nyl )-2-furánkarboxylovej (2,71 g, 0,0105 mo-lu) sa zahrieva v benzéne (200 ml) pri tep-lote varu 4 hodiny. Ku zmesi sa prikvapká-va piperidín (0,89 g, 0,0105 molu) a pokra-čuje sa v zahrievaní 2 hodiny. Rozpúšťadlosa za zníženého tlaku oddestiluje. Zvyžoksa rozpustí v éteri. Éterická vrstva sa pre-mýva zriedenou HC1 a vodou do pH 7. Roz-púšťadlo sa oddestiluje za zníženého tlakua tuhý zvyšok sa krystalizuje z etanolu. Příklad 2 1-(5-( 2-nitrofenyl) -2-f uryl ] amínokar-bonylmorfolín azid kyseliny 5-(2-nitrofe-nyl )-2-furánkarboxylovej (2,71 g, 0,015 mó-lu) sa zahrieva v toluéne (200 ml) pri tep-lote varu 3 hodiny. Ku zmesi sa prikvapkámorfolín (0,91 g, 0,015 molu) a pokračujesa v zahrievaní 2 hodiny. Rozpúšťadlo saza zníženého tlaku oddestiluje a zvyšok sarozpustí v éteri. Éterická vrstva sa premý- 256577 5 va zriedenou HC1 a vodou do pH 7. Rozpúš-ťadlo sa oddestiluje za zníženého tlaku atuhý zvyšok sa krystalizuje. Příklad 3 1,4-bis [ 5 - (2-nitrof enyl) -2-f uryl ] amíno-karbonyl piperazín
Azid kyseliny 5-(2-nitrofenyl)-2-furán-karboxylovej (2,71 g, 0,0105 molu) sa za-hrieva v toluene (200 ml) pri teplote va-ru rozpúšťadla 4 hodiny. Ku zmesi sa při-dá piperazín (0,45 g, 0,00528 molu) a po-kračuje sa v zahrievaní 2 hodiny. Vypadnu-tá zrazenina sa odfiltruje a krystalizuje zozmesi metanol : aceton (1 : 1).
Struktura zlúčenín bola dokázaná ele- 6 mentárnou analýzou (tab. I) a IR, UV (tab.II) a ÍH NMR (tab. III).
Spektrálné merania
Infračervené spektrá sa namerali naspektrořotometri SPECORD 71 IR Carl ZeissJena KBr technikou 1 mg látky na 100 mgKBr. Elektronové spektrá boli namerané naspektrofotometri SPECORD UV VIS CarlZeiss Jena v oblasti 200—800 nm pri labo-ratórnej teplote v etanole. XH NMR spektráboli namerané na 100 MHz spektrometriJEOL FX-100 v hexadeuterodimetylsulfoxi-de za použitia hexametyldisiloxánu ako vnú-torného Standardu.
Tabulka 1 l-[5-(2-nitrofenyl)-2-furyl]amínokarbonyl deriváty sekundárných amínov NO, <->·
L
Ό "NH-CO
N X \_y fl)
Zlúčenina Sum. vzorecMol. hmot. T. t. °C Výťažok [%] % C Elementárna analýzavypočítané/ ná jdené% H % N Ia C16H17N3O4 130—132 60,95 5,43 13,32 X = CH2 315,3 64,2 60,78 5,34 13,54 Ib C15H15N3O5 208—210 56,78 4,77 13,24 X = 0 317,3 62,3 56,59 4,63 13,30 Ic C26H22N6O8 219—221 57,14 4,06 15,38 546,5 70 57,0 3,94 15,50
Tabulka II IR a UV spektrálné údaje zlúčenín Ia-c
Zlúčenina v(C=O) cm'1 v(N—H)cm-1 v(as/NO2) cm-1 »S(NO2) cm-1 Amax nm loge Ia 1605 3 200 1510 1345 218 3,19 308 3,16 Ib 1655 3 220 1505 1340 225 3,03 274 2,75 Ic 1620 3 220 1480 1350 225 3,28 310 3,20
25BS77
The invention relates to 1- [5- (2-nitrophenyl) -2-furyl] aminocarbonyl derivatives of secondary amines of the formula I
CO-N X in (i) wherein X is CH 2, O, or
and how they are prepared.
Said compounds, which by their structure are substituted ureas, have not been prepared.
Substituted ureas are prepared by the appropriate reaction of amines to the appropriate isocyanate formed by the decomposition of the appropriate carboxylic acid azide, JH Sanders, R. Slocombe, Chem. Roar. 43, 203 (1948) or by reaction of amines with urea K. Kurzer, Org. Synth Coll., Vol. 4, 52 (1983).
Many of the urea derivatives are described as biologically active substances of M. Negwer: Organisch-chemische arzneimittel und ihreSyninyma, Akademie-Verlag Berlin (1978). The preparation of 5- (2-nitrophenyl) -2-furanecarboxylic acid azide is described in U.S. Pat. AO No. 254 049.
The process for the preparation of 1- [5- (2-nitro-phenyl) -2-furyl] -amino-carbonylderivative in the secondary amines of the invention is based on the fact that 5- (2-nitrophenyl) acid azide -2-uranecarboxylic acid of formula II
with secondary amines of general formula III NH XV- (f) wherein X 'is O, CH 2, NH in aromatic hydrocarbons at 80-110 ° C. The advantages of the method of preparing the compounds of the invention include, but are not limited to, that the synthesis is a single stage, carried out in a simple apparatus with good yields. Secondary amine 1- (5- (2-nitrophenyl) -2-furyl) aminocarbonylderivatives are used in organic synthesis to provide the possibility of densifying another heterocyclic ring by reaction with striethylphosphite.
The invention is illustrated, but not limited to, examples: EXAMPLE 1 5- (2-Nitrophenyl) -2-furancarboxylic acid 1- (5- (2-nitrophenyl) -2-furyl] aminocarbonylpiperidine azide (2, 71 g (0.0105 mol) was heated in benzene (200 ml) at reflux temperature for 4 hours, and piperidine (0.89 g, 0.0105 mol) was added dropwise to the mixture. The solvent was distilled off under reduced pressure and the residue was dissolved in ether, the ether layer washed with dilute HCl and water to pH 7. The solvent was distilled off under reduced pressure, and the solid residue was crystallized from ethanol. 5- (2-nitrophenyl) -2-furanecarboxylic acid (2-nitrophenyl) -2-furyl] aminocarbonylmorpholine azide (2.71 g, 0.015 mol) was heated in toluene (200 ml) at After boiling for 3 hours, morpholine (0.91 g, 0.015 mol) was added dropwise and the heating was continued for 2 hours, the solvent was distilled off and the residue was dissolved in ether. The ether layer was washed with 256577 5 in dilute HCl and water to pH 7. The solvent was distilled off under reduced pressure and the solid residue crystallized. Example 3 1,4-bis [5- (2-nitrophenyl) -2-furyl] amino-carbonyl piperazine
5- (2-Nitrophenyl) -2-furanecarboxylic acid azide (2.71 g, 0.0105 mol) was heated in toluene (200 mL) at rt for 4 h. Piperazine (0.45 g, 0.00528 mol) was added and heating continued for 2 hours. The precipitate formed is filtered off and crystallized from a 1: 1 mixture of methanol: acetone.
The structure of the compounds was demonstrated by mental analysis (Table I) and IR, UV (Table II) and 1 H NMR (Table III).
Spectral measurements
Infrared spectra were measured on a SPECORD 71 IR Carl ZeissJena KBr spectrometer using 1 mg of substance per 100 mgKBr. The electron spectra were measured on a SPECORD UV VIS spectrophotometer CarlZeiss Jena at 200-800 nm at room temperature in ethanol. 1 H NMR spectra were measured on a 100 MHz FX-100 spectrometry in hexadeuterodimethylsulfoxide using hexamethyldisiloxane as an internal Standard.
Table 1 1- [5- (2-Nitrophenyl) -2-furyl] aminocarbonyl derivatives of secondary amines NO, <-> ·
L
Ό "NH-CO
NX \ _y fl)
Compound Sum. vzorecMol. wt. Mp ° C Yield [%]% C Elemental analysis calculated / calculated% H% N 1a C 16 H 17 N 3 O 4 130-132 60.95 5.43 13.32 X = CH 2 315.3 64.2 60.78 5.34 13.54 Ib C15H15N3O5 208-210 56.78 4.77 13.24 X = 0 317.3 62.3 56.59 4.63 13.30 Ic C26H22N6O8 219-221 57.14 4.06 15.38 546 , 5 70 57.0 3.94 15.50
Table II IR and UV spectral data for compounds Ia-c
Compound v (C = O) cm -1 in (N-H) cm -1 in (as / NO 2) cm -1 »S (NO 2) cm -1 Amax nm loge Ia 1605 3 200 1510 1345 218 3.19 308 3.16 Ib 1655 3 220 1505 1340 225 3.03 274 2.75 Ic 1620 3 220 1480 1350 225 3.28 310 3.20
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS866477A CS256577B1 (en) | 1986-09-08 | 1986-09-08 | 1- (5 (2-nitrophenyl) -2-furyl Jaminocarbonyl Derivatives of Secondary Amines and a Process for their Preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS866477A CS256577B1 (en) | 1986-09-08 | 1986-09-08 | 1- (5 (2-nitrophenyl) -2-furyl Jaminocarbonyl Derivatives of Secondary Amines and a Process for their Preparation |
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| Publication Number | Publication Date |
|---|---|
| CS647786A1 CS647786A1 (en) | 1987-08-13 |
| CS256577B1 true CS256577B1 (en) | 1988-04-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CS866477A CS256577B1 (en) | 1986-09-08 | 1986-09-08 | 1- (5 (2-nitrophenyl) -2-furyl Jaminocarbonyl Derivatives of Secondary Amines and a Process for their Preparation |
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1986
- 1986-09-08 CS CS866477A patent/CS256577B1/en unknown
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| CS647786A1 (en) | 1987-08-13 |
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