CS196618B1 - Derivatives of pyridine-4-carboxyhydrazide with potential antitubercular and antitumour actions and method for their preparing - Google Patents

Derivatives of pyridine-4-carboxyhydrazide with potential antitubercular and antitumour actions and method for their preparing Download PDF

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CS196618B1
CS196618B1 CS462676A CS462676A CS196618B1 CS 196618 B1 CS196618 B1 CS 196618B1 CS 462676 A CS462676 A CS 462676A CS 462676 A CS462676 A CS 462676A CS 196618 B1 CS196618 B1 CS 196618B1
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pyridine
derivatives
carboxhydrazide
methoxyphenyl
potential
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CS462676A
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Bohumil Proksa
Jan Fuska
Alzbeta Fuskova
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Bohumil Proksa
Jan Fuska
Alzbeta Fuskova
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Vynález sa týká niektorých nových derivátov pýridín-4-karboxhydrazidu (INH) ako potenciálnych tuberkúlostatík a kancerostatík a spósobu ich přípravy.The present invention relates to certain novel pyridine-4-carboxhydrazide (INH) derivatives as potential tuberculin and cancerostatics, and to a process for their preparation.

Potenciálny protinádorový účinok niektorých derivátov INH sledoval J. P. Matvejčuk (Vopr. eksp. onkol. 3/1968/101) a zistil, že niektoré z nich inhibovali tvorbu tumorov. Pri hodnotení biologických účinkov inej skupiny derivátov INH Μ. I. Colnághi, G. Della Porte á L. Parmí (Tumóri 55/1969/ /309) zistili, že samotný INH nepotláča tvorbú hádorov, žatial’ čo L. D. Jones, D. G. pajrchild a W. C. Morse (Am. Rev, Resp. Dis., 103/1^71/612) potvrdili potenciálny karcinogénny účinpl^blpktorých derivátov INH. F. Lacour, G. Oberling a M. Guerin (Bull. Ass. Franc. Cancer 44/1957/88) zistili,. že antikoagulanciá typu kumarínu inhibovali rast niektorých nádorov u experimentálnych zvierat, pričom tieto látky znižujú tvorbu metastáz v prúcach a v pečeni zvierat, ako to potvrdili vo svojich prácach D. Agostino, E. E. Cliffton, A. Girolamo (Cancer 19/1966/284), M. Lawinski a spol· (Arch. Immunol. Ther. Exp.', 19/1971/532) azvyšujú šúčasné prežívanie pokusných zvierat, ako..udáš vajú vo svojich výsledkách S. Wood, E. D. Holyóke a ί. H. YardJey (Canad.Conf. Cancer 4/1961/223).The potential antitumor effect of some INH derivatives has been studied by J. P. Matvejchuk (Vopr. Eksp. Onkol. 3/1968/101) and found that some of them inhibited tumor formation. In assessing the biological effects of another class of INH derivatives Μ. I. Colnághi, G. Della Porte and L. Parmí (Tumors 55/1969 / / 309) found that INH alone did not suppress the formation of riddles, in particular LD Jones, DG pajrchild and WC Morse (Am. Rev, respectively. Dis. , 103/1 (71/612) confirmed the potential carcinogenic effect of certain INH derivatives. F. Lacour, G. Oberling and M. Guerin (Bull. Ass. Franc. Cancer 44/1957/88) found. that coumarin-type anticoagulants inhibited the growth of certain tumors in experimental animals, which reduce the formation of metastasis in the lungs and liver of animals, as confirmed by D. Agostino, E. Cliffton, A. Girolamo (Cancer 19/1966/284), M. Lawinski et al (Arch. Immunol. Ther. Exp. ', 19/1971/532) and enhance the survival of experimental animals as reported by S. Wood, ED Holyóke and ί. H. YardJey (Canad.Conf. Cancer 4/1961/223).

A. L. Cetlin a spol, (Tr. Bot. Inst. AN ZSSR 5, No. 16/1972/7) popísali cytotoxický účinok niektorých prírodných derivátov kumarínu na buňky nádorov, R. A.' Finnegan, Κ. E. Merkel a N. Back (J. Pharm. Sci. 61/19/2/1599) účinok syntetických kumarínov na S-180.A. L. Cetlin et al. (Tr. Bot. Inst. AN USSR 5, No. 16/1972/7) described the cytotoxic effect of some natural coumarin derivatives on tumor cells, R. A. ' Finnegan, Κ. E. Merkel and N. Back (J. Pharm. Sci. 61/19/2/1599) the effect of synthetic coumarins on S-180.

Lespagnol A. a spol. (Bull. Soc. Pharm. Lilie 1/1955/30), Η, H. Fox a J. T. Gibas (J. Org. Chem; 18/1953/983), P. P. T. Sah a S. A. Peoples (J. Am. Pharm. Áss,,i 43/1954/513). připravili deriváty, .pyridín-4-karboxhydrazidu so 4-fenyl-3-butén-27onom a mnohými ďalšími karbonylovými zlúčeninami, avšak tieto látky vykazovali v pokusech; iba malý. antituberkulózny efekt.Lespagnol A. et al. (Bull. Soc. Pharm. Lilie 1/1955/30), Fox, H. Fox and JT Gibas (J. Org. Chem; 18/1953/983), PPT Sah and SA Peoples (J. Am. Pharm. Ass. ,, i 43/1954/513). prepared derivatives of pyridine-4-carboxhydrazide with 4-phenyl-3-butene-27one and many other carbonyl compounds, but these have shown in experiments; only small. antituberculous effect.

Deriváty pyri^ín-4-karboxhydrazidu s potenciálnyrr^i antituberkulóznymi a potinádorovýml účinkami obecnéřro vzorca I kdeaR..je -a; .Pyridine-4-carboxhydrazide derivatives having the potential antituberculous and antitumor effects of the general formula I wherein R is -a; .

-R-R

R pričorti Rý znamená metyl alebo fenyl, R2 znamenáR pričorti R y is methyl or phenyl, R 2 is

-CH-GHCH-GH

19661 8 alebo19661 8 or

kde R3 znamená hydroxy alebo metoxy skupinu, alebowherein R 3 represents a hydroxy or methoxy group, or

R,- CH 0 Ί A JlrR, - CH 0 Ί A Jlr

kde R4 znamená hydroxyfenyl, alebo metoxyfenyl, sa pripravujú kondenzáciou pyridín-4-karboxhydrazidu s ketozlůčeninami obecného vzorca II kde Rt a R2 znamená to isté, ako už bolo uvedené, alebo s ketozlůčeninami obecného vzorca IIIwherein R 4 is hydroxyphenyl, or methoxyphenyl, are prepared by condensation of pyridine-4-carboxhydrazide with the ketone compounds of formula II wherein R 1 and R 2 are as previously described or with ketone compounds of formula III

kde R4 znamená hydroxyfenyl alebo metoxyfenyl, v prostředí polárného, alebo semipolárneho rozpúšťadla a výsledný produkt sa izoluje kryštalizáciou.wherein R 4 is hydroxyphenyl or methoxyphenyl, in a polar or semi-polar solvent medium, and the resulting product is isolated by crystallization.

Příklad 1Example 1

Příprava látky č. 1 4-(4-hydroxy-3-metoxyfenyl)-2-pyridín-4-karboxhydrazón-3-buténu j: ¾ ,Preparation of substance no. 1- 4- (4-hydroxy-3-methoxyphenyl) -2-pyridine-4-carboxhydrazone-3-butene j: ¾,

C17H17N3O6 m. v. 311,34 0,18 g (1,3 mM) pyridín-4-karboxhydrazidu (SPOFA, Praha) rozpuštěných v 2 ml 50% vodného etanolu sa přidalo k 0,25 g (1,3 mM) 4-(4-hydroxy-3-metoxyfenyl)-3-butén-2-ónu syntetizovaného z vanilínu a acetonu podl'a Mc Gookin A., Sinclair D. C. J. Chem, Soc., (1928/1170), v 2 ml 50% vodného etanolu. Zmes sa zahriala do varu a nechala krištalizovať. Látka sa prekryštalizovala z 50% vodného etanolu a vákuovo vysušila. Získalo sa 0,20 g (0,6 mM) 4-(4-hydroxy-3-metoxyfenyl)-2-pyridín-4-karboxhydrazón-3-buténu, b. t. 171 až 172,5 °C, UV Amax:C 17 H 17 N 3 O 6 mv 311.34 0.18 g (1.3 mM) pyridine-4-carboxhydrazide (SPOFA, Prague) dissolved in 2 ml of 50% aqueous ethanol was added to 0.25 g (1, 3 mM) 4- (4-hydroxy-3-methoxyphenyl) -3-buten-2-one synthesized from vanillin and acetone according to Mc Gookin A., Sinclair DCJ Chem, Soc., (1928/1170), at 2 ml of 50% aqueous ethanol. The mixture was heated to boiling and allowed to crystallize. The material was recrystallized from 50% aqueous ethanol and dried in vacuo. 0.20 g (0.6 mM) of 4- (4-hydroxy-3-methoxyphenyl) -2-pyridine-4-carboxhydrazone-3-butene was obtained, mp 171-172.5 ° C, UV max :

264 a 204 nm v etanole.264 and 204 nm in ethanol.

Příklad 2Example 2

Priprava látky č. 2 1,3-difenyl-1-(pyridín-4-karboxhydrazón)-2-propénuPreparation of substance no. 2 1,3-Diphenyl-1- (pyridine-4-carboxhydrazone) -2-propene

C21H17N3O m. v. 327,39 K 0,65 g (3,12 mM) 1,3-difenyl-2-propén-1-ónu připraveného z acetofenónu a benzaldehydu podl'a E. P. Kohler, Η. M. Chadwell., Org. Syntheses, Col. Vol, I, (1941/78) v 5 ml 2-propanolu sa přidalo 0,45 g (3,28 mM) pyridín-4-karboxhydrazidu (SPOFA, Praha) a zmes sa zahrievala do rozpustenia tuhých zložiek; na chladnom mieste vykrištalizovaná látka sa rekryštalizovala z 80% vodného etanolu. Získalo sa 0,50 g (1,5mM) 1,3-d ifenyl-1 -(pyridín-4-karboxhydrazón)-2-propénu, b. t. 141 až 142°C, UVAmax: 240 a 204 nm v etanole, IČ: 3400, 3300, 2950, 1680, 1590, 1540, 1490, 1450, 1400, 1360, 1280, 1050, 980, 820 cm'1 v chloroforme.C 21 H 17 N 3 O m v 327.39 To 0.65 g (3.12 mM) of 1,3-diphenyl-2-propen-1-one prepared from acetophenone and benzaldehyde according to EP Kohler, ref. M. Chadwell., Org. Syntheses, Col. Vol, I, (1941/78) in 5 ml of 2-propanol was added 0.45 g (3.28 mM) of pyridine-4-carboxhydrazide (SPOFA, Prague) and the mixture was heated to dissolve the solids; The cold crystallized material was recrystallized from 80% aqueous ethanol. 0.50 g (1.5 mM) of 1,3-diphenyl-1- (pyridine-4-carboxhydrazone) -2-propene was obtained, mp 141-142 ° C, UVA max : 240 and 204 nm in ethanol, IR : 3400, 3300, 2950, 1680, 1590, 1540, 1490, 1450, 1400, 1360, 1280, 1050, 980, 820 cm -1 in chloroform.

Příklad 3Example 3

Priprava látky č. 3 1,3-difenyl-1-(pyridín-4-karboxhydrazón)-3-(4-hydroxykumarin-3-yl)-propánuPreparation of substance no. 1,3-Diphenyl-1- (pyridine-4-carboxhydrazone) -3- (4-hydroxycoumarin-3-yl) -propane

C30H23N3O4 m. v. 441,54 0,9 g (2,42 mM) 1,3-difenyl-1-(4-hydroxykumarin-3-yl)-propán-3-ónu (získaný reakciou 4-hydroxykumarínu s 1,3-difenyl-2-propén-1-ónu, Ikawa M., a spol., J. Am. Chem. Soc., 66 (1944/902) v 5 ml 2-propanolu sa zmiešalo s 0,34 g (2,5 mM) pyridín-4-karboxhydrazidu (SPOFA, Praha) a zahriala sa do rozpustenia tuhých častíc. Zmes sa nechala kryštalizovať a vylúčené kryštály (0,11 g) nezreagovaného pyridín-4-karboxhydrazidu sa odsáli. Z matečného luhu sa vákuovo oddestilovalo rozpúšťadlo a zbytok sa trikrát rekryštalizoval z 94% etanolu. Po vysušení sa získalo 0,62 g (1,40 mM) 1,3-difenyl-1-(pyridín-4-karboxhydrazón)-3-(4-hydroxykumarin-3-yl)-propánu, b. t. 139 až 141 °C, UVAmax 303, 289, 239, 207 nm v etanole, IČ: 3700. 3300, 2990, 1690, 1610, 1550, 1480, 1450, 1400, 1370, 1310, 1250, 1190, 1060, 920 cm1 v chloroforme.C 30 H 23 N 3 O 4 mv 441.54 0.9 g (2.42 mM) 1,3-diphenyl-1- (4-hydroxycoumarin-3-yl) -propan-3-one (obtained by reaction of 4- hydroxycoumarin with 1,3-diphenyl-2-propen-1-one, Ikawa M., et al., J. Am. Chem. Soc., 66 (1944/902) in 5 ml of 2-propanol was mixed with 0, 34 g (2.5 mM) of pyridine-4-carboxhydrazide (SPOFA, Prague) was heated to dissolve the solids, the mixture was allowed to crystallize and the precipitated crystals (0.11 g) of unreacted pyridine-4-carboxhydrazide were filtered off with suction. The solvent was distilled off in vacuo and the residue was recrystallized three times from 94% ethanol to give 0.62 g (1.40 mM) of 1,3-diphenyl-1- (pyridine-4-carboxhydrazone) -3- (4- hydroxycoumarin-3-yl) -propane, mp 139-141 ° C, UVA max 303, 289, 239, 207 nm in ethanol, IR: 3700, 3300, 2990, 1690, 1610, 1550, 1480, 1450, 1400, 1370 , 1310, 1250, 1190, 1060, 920 cm -1 in chloroform.

Příklad 4Example 4

Priprava Jatky č. 4 1-(4-hydroxy-3-metoxyfenyl)-1- (4 -hyplroxykumarin-3-yl) -3- (pyridín-4-karboxhydrazónj-butánuPreparations Slaughterhouses no. 4- 1- (4-Hydroxy-3-methoxyphenyl) -1- (4-hydroxycoumarin-3-yl) -3- (pyridine-4-carboxhydrazone) butane

C26H23N3O6 m. v. 473,48 , 2,0 g (6i,4 mM) 3-Jl-^-hydřoxy-S-metoxyfenyO-S-oxobutylJ-4-hydroxykumarínu (získaný reakciou 1(-4-hydroxy-3-metoxyfenyl)-3-oxobuténu-1 s 4-hydroxykumarínu, Ikawa M., a spol., J. Am. Chem. Soc., 66 (1944/902) a 0,88 g (6,4 mM) pyridín-4-karboxhydrazidu (SPOFA, Praha) sa zahrievalo v 15 ml dioxánu do úplného rozpustenia. Po vychladnutí z roztoku vypadávajú kryštály, ktoré po 2násobnej rekryštalizácii z 2-propanolu poskytliC 2 6H 23 N 3 O 6 mv 473.48, 2.0 g (6i, 4 mM) of 3-β-hydroxy-5-methoxyphenyl-5-oxobutyl-4-hydroxycoumarin (obtained by reaction 1 (-4- hydroxy-3-methoxyphenyl) -3-oxobutene-1 with 4-hydroxycoumarin, Ikawa M., et al., J. Am. Chem. Soc., 66 (1944/902) and 0.88 g (6.4 mM ) of pyridine-4-carboxhydrazide (SPOFA, Prague) was heated in 15 ml of dioxane until complete dissolution.After cooling, crystals precipitated from the solution, which after recrystallization from 2-propanol twice gave

1,8 g (3,6 mM) 1-(4-hydroxy-3-metoxyfenyl)-1-(4-hydroxykumarin-3-yl) - 3 - (pyridin - 4 -karboxhydrazón)-butánu, b. t.. 208 až 209 °C, UVAmax 345, 250 a 204 nm v metanole, IČ: 3700, 3550, 3000, 1680, 1660, 1630, 1595, 1500, 1410, 1360, 1250, 950 cm1 v chloroforme.1.8 g (3.6 mM) of 1- (4-hydroxy-3-methoxyphenyl) -1- (4-hydroxycoumarin-3-yl) -3- (pyridine-4-carboxhydrazone) butane, m.p. 208 DEG-209 DEG C., UVA max 345, 250 and 204 nm in methanol, IR: 3700, 3550, 3000, 1680, 1660, 1630, 1595, 1500, 1410, 1360, 1250, 950 cm @ -1 in chloroform.

966 1 8965 1 8

P r í k I a d 5EXAMPLE 5

Příprava látky č. 5 3-(2-hydroxybenzal)-4-(pyridín-4-karboxhydrazón)-2-oxochromanuPreparation of substance no. 5 3- (2-Hydroxybenzal) -4- (pyridine-4-carboxhydrazone) -2-oxochroman

C22H15N3O4 m. v. 385,39 Zmes 0,50 g (1,8 mM) 3-(2-hydroxybenzal)-2,4-diketochromanu (syntetizovaný z 4-hydroxykumarínu a salicylaldehydu, Sullivan W. R., a spol., J. Am. Chem. Soc., 65 (1943/2288) a 0,25 g (1,8 mM) pyridín-4-karboxhydrazidu sa zahrievalo v 6 ml 2-propanolu do rozpustenia zložiek. Na chladnom mieste vykríštalizovala látka, ktorá po trojnásobnej rekryštalizácii z 2-propanolu poskytla 0,22 g (0,5 mM) 3-(2-hydroxybenzal)-4-pyrldín-4-karboxhydrazón-2-oxochromanu, b. t. 243 až 245 °C, UVAma'x: 334, 296, 288, 238, 214 nm v metanole. Potenciálny protinádorový účinok bol hodnotený na základe inhibície značkovaných prekurzorov do buniek Ehrlichov ascitový karcinom a Leukémia P-388 in vitro metodou, ktorú popísali J. Fuška a spol. (Neoplasma 18/1971/631), antituberkulózny účinok bol hodnotený na dva kmene TBC: Myobacterium tuberculosis BCG a Mycobacterium fortuitum.C22H15N3O4 mv 385.39 A mixture of 0.50 g (1.8 mM) of 3- (2-hydroxybenzal) -2,4-diketochroman (synthesized from 4-hydroxycoumarin and salicylaldehyde, Sullivan WR, et al., J. Am. Chem. Soc., 65 (1943/2288) and 0.25 g (1.8 mM) of pyridine-4-carboxhydrazide were heated in 6 ml of 2-propanol to dissolve the components. propanol afforded 0.22 g (0.5 mM) of 3- (2-hydroxybenzyl) -4--pyridine-4-karboxhydrazón-2-oxochromanu, mp 243-245 DEG C., UVA has "x: 334, 296, 288 The potential antitumor effect was assessed by inhibiting the labeled precursors into Ehrlich's ascites carcinoma cells and Leukemia P-388 in vitro by the method described by J. Fuška et al (Neoplasma 18/1971/631), antituberculous the effect was evaluated on two strains of TB: Myobacterium tuberculosis BCG and Mycobacterium fortuitum.

Účinok niektorých látok na jednotlivé modely je uvedený v tabuTke 1.The effect of some substances on each model is shown in Table 1.

9661896618

Inhibícia rastu Growth inhibition M. tuberculosis .... ... gCQ M. fortuitum M. tuberculosis .... gCQ of M. fortuitum σι 3. σι Third 25 25 o about 40 40 m m m m Inhibícia využitia ”C prekurzoru (%) Inhibition of the use of ”C precursor (%) P-388 P-388 A V AND IN O) o o ABOUT) about about 6,0 6.0 59,3 59.3 42,0 42.0 OJ OJ 32,0 32.0 30,0 30.0 EAC EAC A V AND IN 4,0 4.0 24,0 24.0 49,6 49.6 13,0 13.0 20,0 20.0 47,8 47.8 Testovaná látka Test substance 1 X S ° X o n X Λ O 5-i B Ť X z 1 o o é z* » 1 X N ° X o n X Λ 5-i B X X of 1 o o z I z 1 o o . i z I from 1 o o. and from O X / \ CH ° ®4 1 X z 1 o o έ z ABOUT X / \ CH ° ®4 1 X from 1 about about έ from Číslo látky Number substances - - OJ OJ co what

Claims (2)

PREDMET VYNÁLEZUOBJECT OF THE INVENTION 1. Deriváty pyridín-4-karboxhydrazidu s potenciálnymi antituberkulóznymi a protinádorovými účinkami obecného vzorca I1. Pyridine-4-carboxhydrazide derivatives having potential antituberculous and antitumor effects of the general formula I 2. Spósob přípravy derivátov pyridín-4-karboxhydrazidu podfa bodu 1, vyznačujúci sa tým, že sa kondenzuje pyridín-4-karboxhydrazid s ketozlúčeninami obecného vzorca II.2. A process for the preparation of pyridine-4-carboxhydrazide derivatives according to claim 1, characterized in that the pyridine-4-carboxhydrazide is condensed with the ketone compounds of the general formula II. kde R je pričom Ri znamená metyl alebo fenyl, R2 znamenáwherein R is wherein R 1 is methyl or phenyl, R 2 is CH=»CH alebo o—cCH = CH or o-c Ř«Ø « II kde R1 znamená metyl alebo fenyl, R2 znamená _CH=«GH alebo kde R3 znamená hydroxy alebo metoxy skupinu, ale s ketozlúčeninami obecného vzorca III kde R3 znamená hydroxy alebo metoxy skupinu, alebo rm- ch .oWherein R 1 is methyl or phenyl, R 2 is -CH = GH or wherein R 3 is hydroxy or methoxy, but with keto compounds of the general formula III wherein R 3 is hydroxy or methoxy, or r m -ch. III kde R4 znamená hydroxyfenyl, alebo meťóxyfenyl. \ kde R4 znamená hydroxyfenyl, alebo metoxyfenyl, v prostředí polárného alebo semipolárnehoErozpúšťadla a výsledný produkt sa izoluje kfyštalizáciou.III wherein R 4 is hydroxyphenyl or methoxyphenyl. wherein R 4 is hydroxyphenyl, or methoxyphenyl, in a polar or semi-polar E-solvent, and the resulting product is isolated by crystallization.
CS462676A 1976-07-13 1976-07-13 Derivatives of pyridine-4-carboxyhydrazide with potential antitubercular and antitumour actions and method for their preparing CS196618B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103601711B (en) * 2013-11-04 2016-09-07 广东中烟工业有限责任公司 A kind of coumarin derivative and its preparation method and application

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103601711B (en) * 2013-11-04 2016-09-07 广东中烟工业有限责任公司 A kind of coumarin derivative and its preparation method and application

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