CS226940B1 - 1,2-dihydrofuro (2,3 to 4,5) pyrolo (1,2-d)-1,2,4-triazi-1-ones and method of preparing same - Google Patents

1,2-dihydrofuro (2,3 to 4,5) pyrolo (1,2-d)-1,2,4-triazi-1-ones and method of preparing same Download PDF

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CS226940B1
CS226940B1 CS537482A CS537482A CS226940B1 CS 226940 B1 CS226940 B1 CS 226940B1 CS 537482 A CS537482 A CS 537482A CS 537482 A CS537482 A CS 537482A CS 226940 B1 CS226940 B1 CS 226940B1
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dihydrofuro
pyrrolo
triazin
ones
pyrrole
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CS537482A
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Czech (cs)
Slovak (sk)
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Alzbeta Doc Ing Cs Krutosikova
Jaroslav Prof Ing Drsc Kovac
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Krutosikova Alzbeta
Kovac Jaroslav
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Description

Vynález sa týika l,2-dihydrofuro[2‘,3‘:4,5]pyrolo[l,2-d3-l,2,4-triazín-l-ónov a spůsobu ich přípravy.The present invention relates to 1,2-dihydrofuro [2,3-d: 4,5] pyrrolo [1,2-d3-1,2,4-triazin-1-one and a process for their preparation.

Jednou z metod přípravy zlúčenín s prikondenzovamým 1,2,4-triazínovým jadrom je realkcia dusíkových heterocyklov obsahujúcich v polohe 2 hydrazidoskupinu s octoestermi karboxylových kyselin [Monge Vega A., Aldana I., Rabbani Μ. M., Fernandes-Alvares E.: J. Heterocycl. Chem. 17,77 (1980)]. Z nich niektoré sú popísané ako biologicky účinné látky [Monge Vega A., Aldana I., Fernandes-Alvares E.: Eur. J. Med. Chem. 13, 573 (1978)]. Příprava hydrazídov kyselin fůro [ 3,2-b ] pyrol-5-karboxylových, vhodných medziproduktov na přípravu furo[2‘,3‘:4,5]pyrolo[l,2-d]-l,2,4-triazínov je popísané (autorské osvedčenie č. 226 929).One method of preparing compounds with a condensed 1,2,4-triazine nucleus is by realizing the nitrogen heterocycles containing the 2-position in the 2-position of the hydrazido group with octoesters of carboxylic acids [Monge Vega A., Aldana I., Rabbani Μ. M., Fernandes-Alvares, E .: J. Heterocycl. Chem. 17.77 (1980)]. Some of these are described as biologically active substances [Monge Vega A., Aldana I., Fernandes-Alvares E .: Eur. J. Med. Chem. 13, 573 (1978)]. Preparation of furo [3,2-b] pyrrole-5-carboxylic acid hydrazide acids, suitable intermediates for the preparation of furo [2 ', 3': 4,5] pyrrolo [1,2-d] -1,2,4-triazines are: described (author's certificate No 226 929).

1,2-Dihydrof uro [ 2‘,3‘ :4,5 ] pyrolo [1,2-d]-1,2,4-tríazín-l-Ďny, ktoré můžu slúžiť ako východzie zlúčeniny pre syntézu nových furokondenzováných heterocyklicikých zlúčenín .neboli doposial' připravené.1,2-Dihydrofuran [2 ', 3': 4,5] pyrrolo [1,2-d] -1,2,4-triazine-1-yne, which may serve as starting compounds for the synthesis of novel furocondensated heterocyclic compounds "not ready yet."

Predmetom ‘vynálezu sú 1,2-dihydrofuro- [2‘,3‘:4,5 ]pyrolo[ 1,2-d]-1,2,4-triazín-l-óny všeobecného vzorca IThe present invention provides 1,2-dihydrofuro [2, 3, 3: 4,5] pyrrolo [1,2-d] -1,2,4-triazin-1-ones of formula I

kdewhere

R je H, fenyl, 4-tolyl aR is H, phenyl, 4-tolyl and

R1 je H, CHs a spůsob ich přípravy.R 1 is H, CH 3 and a process for their preparation.

Podstata spůsobu přípravy 1,2-dihydrofurq[ 2*,3‘: 4,5 ] pyrolo [1,2-d ] -1,2,4-triazín-l-ónov vzorca I spočívá v tom, že sa na hydrazidy kyselin fůro [ 3,2-b ] pyrol-5-karboxylových všeobecného vzorca IIThe essence of the process for the preparation of 1,2-dihydrofuran [2 *, 3 ': 4,5] pyrrolo [1,2-d] -1,2,4-triazin-1-ones of the formula I is based on the formation of acid hydrazides furo [3,2-b] pyrrole-5-carboxylic acids of formula II

R %R%

NN

H C^NHNHZ (lil C ^ H NHNH Z (III

R má horeuvedený význam, •posobí trietylesterom kyseliny octomravčej alebo dctooetOvej v dimetylformamide pri teplote 100—153 °C.R is as defined above; it is triturated with triethylester or acetic acid in dimethylformamide at a temperature of 100-153 ° C.

Výhody spQjsoibu přípravy zlúčenín padla vynálezu spočívajú akrem iného, že sa reakcia uskutočnuje v jednom stupni v jednoduchej aparatúre s dobrými výťažkami.The advantages of the preparation of the compounds according to the invention are, besides others, that the reaction is carried out in one step in a simple apparatus with good yields.

1,2-Dihydrofuro[ 2‘,3‘: 4,5 ] pyr olo [ 1,2-d ] -1,2,4-triázín-l-óny majú široké použitie ako ireakčné komponenty v organickej syntéze, napr. reagujú s pentasulfidom fosforečným na korešpondujúce tióny, s trichlorldotm fosforečným na chlórderiváty a poskytujú možnost prifkondenzovania dalšieho heterocyklického kruhu.1,2-Dihydrofuro [2 ‘, 3‘: 4,5] pyrrolo [1,2-d] -1,2,4-triazin-1-ones are widely used as irrational components in organic synthesis, e.g. they react with phosphorus pentasulfide to the corresponding thions, with phosphorus trichlorodotrate to the chloro derivatives and provide the possibility of condensing another heterocyclic ring.

Predmet vynálezu ilustrujú, ale neobmedzujú následovně příklady:The invention is illustrated but not limited by the following examples:

Příklad 1Example 1

1,2-Dihýdrof uro [ 2‘, 3 ‘ :4,5 ] pyroloj 1,2-d ] -1,2,4-triazín-l-ón (la kde R = R1 = H)1,2-Dihdrofuran [2 ', 3': 4,5] pyrrole 1,2-d] -1,2,4-triazin-1-one (1a where R = R 1 = H)

Hydrazid kyseliny 4H-furo[3,2-b]pyrol-5-karhoxylovej (1,82 g, 0,011 mol) a trietylester kyseliny ortomravčej (2 g, 0,014 mol) v dímetylformajnide (10 ml) sa zahrieva pri teplote varu ipo dobu 2,5 h. Rozpúšťadlo sa vákuovo oddestiluje a zvyšok sa prekryštalizuje z dimetylformamidu.4H-Furo [3,2-b] pyrrole-5-carboxylic acid hydrazide (1.82 g, 0.011 mol) and triethyl orthoformate (2 g, 0.014 mol) in dimethylformajnide (10 ml) are heated at boiling point for a period of time. 2,5 h. The solvent was distilled off in vacuo and the residue was recrystallized from dimethylformamide.

Podobné sa z hydrazidů kyseliny 2-fenyl-4H-furo [ 3,2-b ] pyrol-5-karboxylovej připraví 7-fenyl-l,2-dihydrofuro[2‘,3‘:4,5]pyrolo[1,2-d]-1,2,4-triazín-l-ón (Ih kde R je fenyl, R1 = H) a z hydrazidů kyseliny 2-(4-tolyl)-4H-furo[ 3,2-b ]pyrol-5-karboxylovej sa připraví 7-(4-tolyl )-l,2-dihydrof uro [2‘,;3‘:4,5jpyrolof 1,2-d]-1,2,4-triazín-l-ón (Ic kde R je 4-tolyl, R1 = H).Similarly prepared from 2-phenyl-4H-furo [3,2-b] pyrrole-5-carboxylic acid hydrazides 7-phenyl-1,2-dihydrofuro [2 ', 3': 4,5] pyrrolo [1,2] d] -1,2,4-triazin-l-one (Ih wherein R is phenyl, R 1 = H) from the hydrazide of 2- (4-tolyl) -4H-furo [3,2-b] pyrrole 5- (4-tolyl) -1,2-dihydrofuran [2 ', 5-carboxylic acid ; 3 ': 4,5'-pyrrolof 1,2-d] -1,2,4-triazin-1-one (Ic wherein R is 4-tolyl, R 1 = H).

Příklad 2Example 2

4-Metyl-l,2-dihydrof uro [ 2‘,3‘:4,5 ] pyrolo[l,2-d-]-l,2,4-triazín-l-ón (Id kde R =' H, R1 = CH3)4-Methyl-1,2-dihydrofuran [2 ', 3': 4,5] pyrrolo [1,2-d] -1,2,4-triazin-1-one (Id where R = 'H, R 1 = CH 3)

Hydrazid kyseliny 4H-f uro [3,2-b ]pyrol-5karhoxylovej (1,82 g, 0,011 mol] a trietylester kyseliny ortoctovej (2 g, 0,012 mol) v dimetylformamide (10 ml) sa zahrieva pri teplote varu po dobu 2,5 h. Rozpúšťadlo sa •vákuovo oddestiluje a zvyšok sa prekryštaíizuje z dimetylformamidu. Podobné sa z hydrazidu kyseliny 2-feny l-4H-furo[ 3,2-b] pyrol-5-karboxylovej připraví 7-fenyl-4-metyl-l,2-dihydro [ 2*,3‘:4,5 ] pyrolo[ 1,2-d ] -1,2,4-triazín-l-ón (Ie kde R = fenyl, R1 = CH3) a z hydrazidů kyseliny 2-(4-tolyl)-4H-furo[3,2-b]pyrol-5-karboxylovej sa připraví 4-metyl-7- (4-tolyl) -1,2-dihy dro [ 2 ‘, 3 ‘: 4,5 ] pyrolo[ 1,2-d]-1,2,4-triazín-l-ón (If kde R =' 4-tolyl, R1 =' CH3). Štruktúra zlúčenín bola dokázaná elementárnou analýzou (tab. I) a IR, UV a 1H NMR spektraimi (tab. II a III). Spektrálné merania4H-Fluoro [3,2-b] pyrrole-5-carboxylic acid hydrazide (1.82 g, 0.011 mol) and triethyl orthoacetate (2 g, 0.012 mol) in dimethylformamide (10 ml) are heated at boiling point for 2 hours. The solvent was distilled off in vacuo and the residue was recrystallized from dimethylformamide and similarly prepared from 2-phenyl-4H-furo [3,2-b] pyrrole-5-carboxylic acid hydrazide 7-phenyl-4-methyl-. l, 2-dihydro- [2 *, 3 ': 4,5] pyrrolo [1,2-d] -1,2,4-triazin-l-one (Ie wherein R = phenyl, R 1 = CH 3) and hydrazides 2- (4-tolyl) -4H-furo [3,2-b] pyrrole-5-carboxylic acid prepared by 4-methyl-7- (4-tolyl) -1,2-dihydro [2 ', 3' : 4,5] pyrrolo [1,2-d] -1,2,4-triazin-l-one (If which R '4-tolyl, R1 =' CH 3). The structure of the compounds was shown by elemental analysis (Table I) and IR, UV and 1 H NMR spectra (Tables II and III)

Infračervené spektra sa namerali na spektrofotametri [SPECORD 71 IR (Carl Zeiss Jena)]. Elelktrónové spektrá sa namerali na spektrofotometr! [UV VIS (Carl Zeiss Jena)] v oblasti 200—800 nm pri koncentráciach 2 . ΙΟ-5—105 mol . I-1. XH NMR spektrá holi namerané na 80 MHz spektrometri [BS 487 C Tesla] v hexadeuterodimetylsulfoxide za použitia vnútorného štandardu hexametyldisiloxánu.Infrared spectra were recorded on a spectrophotometer [SPECORD 71 IR (Carl Zeiss Jena)]. The electron spectra were measured on a spectrophotometer! [UV VIS (Carl Zeiss Jena)] at 200-800 nm at concentrations of 2. ΙΟ- 5 —10 5 mol. I -1 . X H-NMR spectra obtained on stick 80 MHz spectrometer [Tesla BS 487 C] in hexadeuterodimethylsulfoxide using an internal standard of hexamethyldisiloxane.

Tabulka ITable I

1,2-Dihydrofuro[2‘,3‘:4,5]pyrolo( 1,2-d]-1,2,4-triazín-l-óny1,2-Dihydrofuro [2 ‘, 3‘: 4,5] pyrrolo (1,2-d) -1,2,4-triazin-1-one

Zlúčenina Sumář, vzorec M. h. Compound Summary, Formula M. h. T. t. °C Výťaž. % T. t. ° C Yield. % Elementárna analýza vypočítané/nájdené % C % Η % N Elemental analysis calculated / found % C% Η% N Ia ia C8H5N3O2 C8H5N3O2 285 285 54,87 54.87 2,88 2.88 23,98 23.98 175,1 175.1 72 72 54,76 54,76 2,78 2.78 24,16 24.16 lb lb C14H9N3O2 C14H9N3O2 312 312 66,93 66.93 3,61 3.61 16,72 16.72 251,2 251.2 76 76 66,88 66.88 3,59 3.59 16,71 16.71 íc o u C15H11N3O2 C15H11N3O2 347 347 71,71 71.71 4,18 4.18 15,84 15.84 265,3 265.3 78 78 71,80 71.80 4,18 4.18 15,49 15.49 Id Id C9H7N3O21 C9H7N3O21 258 258 57,16 57,16 3,73 3.73 22,21 22.21 189,2 189.2 75 75 57,08 57.08 3,52 3.52 22,27 22.27 Ie Ie C15H11N3O2Í C15H11N3O2Í 318 318 67,90 67.90 4,18 4.18 15,84 15.84 265,3 265.3 79 79 67,82 67.82 4,20 4.20 15,48 15.48 If If C16H131N3O2 C16H131N3O2 348 348 68,80 68.80 4,69 4.69 15,04 15.04 279,30 279.30 80 80 68,76 68.76 .4,59 .4,59 15,18 15.18

228940228940

Tabulka IITable II

IČ a UV spektra zlúčenín Ia—If υ cm-1 λ—nmIR and UV spectra of Ia-If υ cm -1 λ-nm

Zlúčenina compound υ (C = O) (C = O) λ max λ max log ε log ε λ max λ max log ε log ε Ia ia 1647 1647 321 321 3,50 3.50 295 295 3,31 3.31 Ib ib 1656 1656 333 333 3,64 3.64 279 279 3,23 3.23 Ic ic 1657 1657 335 335 3,60 3.60 277 277 3,27 3.27 Id Id 1639 1639 294 294 3,32 3.32 238 238 3,50 3.50 Ie Ie 1646 1646 333 333 3,74 3.74 279 279 3,24 3.24 If If 1641 1641 335 335 3,61 3.61 277 277 3,27 3.27

XH NMR spektra zlúčenín Ia—If ffi X H NMR spectra of the compounds Ia-If ffi

Oí ee tí • I—<Oe ee t • I— <

>o <3 i-SM> o <3 i-SM

N cmN cm

CM~ wCM ~ w

ls cols co

CMCM

C/3 C/3 C/3 CM 00 CO CO CO^ CM* CM CM as aC / 3 C / 3 C / 3 CM 00 CO CO

ts. 1>. ts. 1>. s with tx- TX- co what 7 1 7 1 ! *7 ! * 7 ί Ό ί Ό 1 1 1 1 in [>. in [>. in and CM CM CM CM CM~ CM ~ ts ts

xJDHB

CMCM

CM lsCM ls

Xll

CDCD

CO tsCO ts

XJ το Ό *d *3 T3 Xji r4 tS T-t O CM rd tJI CO rd IO.CO ts K ts C< ls lsXJ το d * d * 3 T3 Xj r4 tS T-t O CM rd tJI CO rd IO.CO ts K ts C <ls ls

Td xj T3 X3 XJ X$ XÍ XJ oco^iňoo Ή rd O rd rd O ists ls ls ls s tn w w irt rH co Cs ř^in co oo co o x o ·£ o o ta xj o Ό ω <wTd xj T3 X3 XJ X $ XÍ XJ oco ^ ň Ή rd O rd rd O ists ls ls ls s tn w w irt rH what Cs ^ ^ in what oo what about x o · £ o ta xj o Ό ω <w

M A Μ Μ Μ HM A Μ Μ Μ H

Claims (2)

1. 1,2-Dihydroí uro[ 2‘,3‘:4,5 ]pyrolo[ 1,2-d ] -1,2,4-triazín-l-óny všeobecného vzorca I1. 1,2-Dihydro-uro [2 ‘, 3‘: 4,5] pyrrolo [1,2-d] -1,2,4-triazin-1-one of formula I VYNALEZUWe claim: -ónov podlá bodu 1 vyznačený tým, že sa na hyd-razidy kyselin furo[3,2-b]pyrol-5-karboxylových všeobecného vzorca II kde-one according to claim 1, characterized in that the furo [3,2-b] pyrrole-5-carboxylic acid hydrazides of the formula II are: R je H, fenyl, 4-tolyl a R1 je H, CH3.R is H, phenyl, 4-tolyl and R 1 is H, CH 3. 2. Sposob přípravy 1,2-dihydrofuro[ 2‘,3‘:4,5 ]pyrolo[ 1,2-d] -triazín-1kde2. Preparation of 1,2-dihydrofuro [2 2, 3 ‘: 4,5] pyrrolo [1,2-d] triazine-1-anywhere R má už uvedený význam, posobí trietylesterimi kyseliny ortomravčej alebo ortooctovej v dimetylformamide pri teplote 100—153 °C.R is as hereinbefore defined, it triethyl orthoformate or orthoacetic acid in dimethylformamide at a temperature of 100-153 ° C.
CS537482A 1982-07-14 1982-07-14 1,2-dihydrofuro (2,3 to 4,5) pyrolo (1,2-d)-1,2,4-triazi-1-ones and method of preparing same CS226940B1 (en)

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