Научная статья на тему 'Investigation of conversion various ilidenmalononitriles'

Investigation of conversion various ilidenmalononitriles Текст научной статьи по специальности «Химические науки»

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ISATILIDENEMALONONITRILE / MALONONITRILE / AMINES / THIOSEMICARBAZIDE / HYDRAZINE / ИЗАТИЛИДЕНМАЛОНОНИТРИЛ / МАЛОНОНИТРИЛ / АМИНЫ / ТИОСЕМИКАРБАЗИД / ГИДРАЗИН

Аннотация научной статьи по химическим наукам, автор научной работы — Maharramov A.M., Naghiyev F.N., Asgarova A.R., Rahimova A.G., Akhundova M.A.

Appropriate derivatives of spiropiridine have first been obtained by means of one-stage condensation of isatilidenmalononitriles, malononitriles and 2-tiophenmethylamine (or fur-furilamine). Besides, by interaction of benzylidenemalononitriles with thiosemicarbazide or 2,4-dinitrophenylhydrazines appropriate Schiff-bases obtained. Structures of synthesized compounds obtained confirmed through 1H and 13C NMR spectroscopy methods.

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Текст научной работы на тему «Investigation of conversion various ilidenmalononitriles»

KiMYA PROBLEML9RÎ № 1 2018 ISSN 2221-8688

69

UOT 547.97+535.37

INVESTIGATION OF CONVERSION VARIOUS ILIDENMALONONITRILES

A.M. Maharramov, F.N. Naghiyev, A.R. Asgarova, A.G. Rahimova, M.A. Akhundova, I.G. Mamedov

Baku State University, Z.Khalilov str. 23, AZ1148 Baku, Azerbaijan e-mail: [email protected]

Appropriate derivatives of spiropiridine have first been obtained by means of one-stage condensation of isatilidenmalononitriles, malononitriles and 2-tiophenmethylamine (or ^fur-furilamine). Besides, by interaction of benzylidenemalononitriles with thiosemicarbazide or 2,4-dinitrophenylhydrazines appropriate Schiff-bases obtained. Structures of synthesized compounds obtained confirmed through 1H and 13C NMR spectroscopy methods. Keywords: isatilidenemalononitrile, malononitrile, amines, thiosemicarbazide, hydrazine

INTRODUCTION

Benzylidenemalononitriles as members of ilidenes class are used as synthones in the synthesis of biologically active compounds, such as 4H-pyrane, substituted pyridines, pyrazoles, imidazopyridine derivatives. It has been widely investigated anticoagulant, anticancer, spasmolitic, anti-anafilactic properties of 4H-pyranes and dihydropiridines

O

O

CN

O + < +

NH

O

CN O

derivatives, which obtained by Michaels addition reactions of benzylidene malononitriles with methylenactive compounds [1-3].

Below-cited is data on effective one-stage synthesis of spirooxindole derivatives by 3-component reaction of isatine, malononitrile and 1,3-dicarbonyl compounds in the aquous media and 10 mol% L-prolin [4].

O-

NH2

10 mol% L-prolin water, 800C

NH

S-Ocn

Note that the simple synthesis has been carried out through the Michaels addition reaction of benzylidenemalononitriles and N,N'-dialkylbarbituric acid in the presence of

molecular bromine and sodium ethylate by 7595% yield, 2-aryl-4,6,8-trioxo-5,7-diazaspiro[2.5] octane- 1,1-dicarbonitriles [5].

R = H, CH3, OCH3, 4-Cl, 4-Br

O

H3C. /CH3

+ N N

O

O

Br2

EtONa/EtOH

NC

NC

OT N O

CH3

Of interest is data on obtaining corresponding malononitriles reaction with primary amines enamines by means of benzylidene [6].

3

RESULTS AND DISCUSSION

Also, the 3-component one-stage furfurilamine) in methanol and room condensation of isatilidenemalononitrile, temperature has first been analyzed. malononitrile and 2-thiophenmethylamine (or

/N

/// N

\ m

C C

II

C=N

c=O +

N H

C=N 2

1

In terms of identical reaction conditions, the rile and thiosemicarbazide (or 2,4-dinitrophe-one-stage 3-component condensation reaction nylhydrazine) has been carried out to reveal between benzylidenemalononitrile, malononit- that malononitrile takes no part in the process.

CN

CN 2

\

A

Sxem 3

NH 8 NH,

/ Y

MeOH, r.t.

-CH=N—NH—C.

S \

nh,

o2n

H2N—NH

rA

O2N

-NO,

=/10

MeOH, r.t.

f \—CH=N—NH—« ^

11

-NO,

9

+

EXPERIMENTAL PART

All reagents were purchased from Merc and Fluca and used without cleaning. The melting points of compounds measured at STUART SPM30. Purity of synthesized compounds was complied with TLC, and

structures confirmed on "Bruker300" NMR apparatus (300 and 75 MHz).

The general technique of obtaining spiroindolin-substituted pyridine

derivatives is as follows: mixture of isatilidenemalononitrile (4.3 mmol) and

INVESTIGATION OF CONVERSION VARIOUSA.M. MAHARRAMOV

71

malononitrile (4.4 mmol) dissolved in 30 ml of methanol was stirred up for 5-7 minutes, then 2-thiophenmethylamine (4.4 mmol) (or furfurilamine) added and stirring continued. Reaction progress was tracked by TLC (EtOAc/n-hexane, 2:1) and reaction mixture kept quietly for 48-72 hours. The evaporation of solvent was followed by precipitation of crystals. Also, crystals were separated by filter paper and recrystalliized from ethanol (95%) -water mixture.

2',6'-Diamino-2-oxo-1'-(thiophen-2-ylmethyl)-1'H-spiro[indoline-3,4'-pyridine]-3',5'-dicarbonitrile (5):

1H NMR spektr (DMSO-d6), 5, m.h.: 3.37 s (2H, CH2N), 3.88 s (4H, 2NH2), 6.318.13 m (7H, 4CHarom + 3CH=), 10.55 s (1H, NH). 13C NMR spektr (DMSO-d6), 5, m.h.: 43.24 (CH2N), 54.52 (Ctert), 61.30 (=Ctert), 76.75 (=Ctert), 109.99 (CH^m), 110.20 (CHarom), 116.34 (CN), 116.84 (CN), 122.12 (CHarom), 122.80 (CHarom), 124.16 (Car), 124.67 (Car), 126.57 (CHarom), 130.34 (CHarom), 130.66 (CHarom), 159.60 (=Ctert), 160.23 (=Ctert), 175.10 (=Ctert-S), 177.33 (CONH). Tmp = 2680C.

Found, %: 60.90 C; 3.68 H. C19H14N6OS. Calculated, %: 60.96 C; 3.74 H.

2',6'-Diamino-1'-(furan-2-ylmethyl)-2-oxo-1'H-spiro[indoline-3,4'-pyridine]-3',5'-dicarbonitrile (6):

1H NMR spektr (DMSO-d6), 5, m.h.: 3.36 s (2H, CH2N), 3.78 s (2H, NH2), 6.627.26 m (7H, 4CHarom + 3CH=), 7.69 s (2H, NH2), 10.56 s (1H, NH). 13C NMR spektr (DMSO-d6), 5, m.h.: 54.56 (Ctert), 56.63 (CH2N), 60.71 (=Ctert), 76.85 (=Ctert), 109.96 (CHarom), 110.18 (CHarom), 116.32 (CN), 116.83 (CN), 122.08 (CHarom), 122.63

(CHarom), 124.17 (Car), 124.41 (Car), 126.62 (CHarom), 130.27 (CHarom), 130.65 (CHarom), 159.57 (=Ctert), 160.18 (=Ctert), 175.07 (=Ctert-O), 177.32 (CONH). Tmp = 2460C.

Found, %: 63.63 C; 3.87 H. C19H14N6O2. Calculated, %: 63.69 C; 3.91 H.

General synthesis method of azometin derivatives: Mixture of benzyli-denemalononitriles (5.8 mmol) and malononitrile (5.9 mmol) dissolved in 30 ml of methanol and thiosemicarbazide (5.9 mmol) (or 2,4-dinitrophenylhydrazine) was added and stirred for 14 hours. Reaction progress was tracked by TLC (EtOAc/n-hexane, 2:1). Then reaction mixture was kept quitely for 48-72 hours. After solvent evaporating, crystals perticipated and separated by filter paper. Product was recrystallized in pure form.

2-Benzylidenehydrazine-1-carbothio-amide (9):

*H NMR spektr (DMSO-d6), 5, m.h.: 7.39 t (3H, 3CHarom), 7.78 d (2H, 2CH arom), 8.06 s (2H, NH2), 8.22 s (1H, CH=), 11.45 s (1H, NH). 13C NMR spektr (DMSO-d6), 5, m.h.: 127.76 (2CHarom), 129.12 (2CHarom), 130.31 (CHarom), 134.62 (Car), 142.77 (CH=),

178.44 (C=S). Tmp = 1560C. 1-Benzylidene-2-(2,4-dinitrophenyl)-

hydrazine (11):

1H NMR spektr (DMSO-d6), 5, m.h.: 7.49 t (3H, 3CHarm), 7.80 d (2H, 2CHarm), 8.10 d (1H, CHarm), 8.37 d (1H, CHarm), 8.70 s (1H, CH=), 8.86 s (1H, CHarm), 11.65 (1H, NH). 13C NMR spektr (DMSO-d6), 5, m.h.: 117.32 (CHarom), 123.49 (CHarom), 127.85 (CHarom),

129.45 (CHarom), 129.96 (CHarom), 130.22 (CHarom), 131.03 (Car), 134.28 (Car), 137.47 (Car), 145.05 (tert-C=), 149.88 (CH=N). Tmp = 2410C.

REFERENCE

1. Bonsignore L., Loy G., Secci D., Calig-nano A. Synthesis and pharmacological activity of 2-oxo-(2H) 1-benzopyran-3-carboxamide derivatives. European Journal of Medicinal Chemistry. 1993, vol. 28, no.6, pp. 517-520.

2. Muharrem Kaya, Ersin Demir & Hatice Bekci. Synthesis, characterization and antimicrobial activity of novel xanthene

sulfonamide and carboxamide derivatives. Journal of Enzyme Inhibition and Medicinal Chemistry. 2013, vol. 28, no. 5, pp.885-893.

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3. Ulloora, Ramakrishna Shabaraya, Rajesh Ranganathan, Airody Vasudeva Adhikari. Synthesis, anticonvulsant and antiinflammatory studies of new 1,4-dihydropyridin-4-yl-phenoxyacetohydra-

zones. European Journal of Medicinal Chemistry. 2013, vol. 70, pp. 341-349.

4. Yuling Li, Hui Chen, Chunling Shi, Daqing Shi, and Shunjun Ji. Efficient One-Pot Synthesis of Spirooxindole Derivatives Catalyzed by L-Proline in Aqueous Medium. J.Comb.Chem. 2010, vol. 12, no. 2, pp. 231-237.

5. Michail N. Elinson, Anatolii N.Vereshcha-gin, Nikita O.Stepanov, Tatiana A.Zaimovskaya, Valentina M. Merkulova, Gennady I. Nikishin. The first example of the cascade assembly of a spirocyc-lopropane structure: direct transformation

of benzylidenemalononitriles and N,N'-di-alkylbarbituric acids into substituted 2-aryl-4,6,8 -trioxo-5,7-diazaspiro[2.5] octane-1,1-dicarbonitriles. Tetrahedron Letters. 2010, vol. 51, no. 2, pp. 428-431.

6. Liqi Shi, Yanyan Fu, Chao He, Defeng Zhu, Yixun Gao, Yuerong Wang, Qingguo He, Huimin Cao and Jiangong Cheng. A mild and catalyst-free conversion of solid phase benzylidenemalononitrile/benzylidene-malonate to N-benzylidene-amine and its application for fluorescence detection of primary alkyl amine vapor. Chem. Commun. 2014, v.50, no. 7. pp. 872-874.

BOZiiLiDENMALONONiTRiLLdRiN ÇEVRiLMd REAKSiYASININ TdDQiQi

A.M. Mshsrrsmov, F.N. Nagiyev, A.R. dsgsrova, A.Q. Rshimova, M.д. Axundova, i.Q. M9mmadov

Baki Dövldt Universiteti AZ1148 Baki, Z.Xdlilov Mç., 23; e-mail: [email protected]

ilk ddfd olaraq izatilidenmalononitrilldrin malononitril vd 2-tiofenmetilamin (yaxud furfurilamin) ild bir-mdrhdldli щ-komponentli reaksiyasi aparilmiç vd reaksiyadan uygun spiropiridin tördmdldri alinmiçdir. Hdmçinin benzilidenmalononitrilldrin tiosemikarbazid vd ya 2,4-dinitrofenilhidrazin ild qarqihqli tdsir reaksiyasindan uygun §iff dsasinin alindigi mü§ahidd edilmi§dir. Aninan birld§mdldrin qurulu§u 1H vd 13C NMR spektroskopiyasinin kömdyild tdsdiq olunmuçdur.

Açar sözfor: izatilidenmalononitril, malononitril, aminldr, tiosemikarbazid, hidrazin

ИССЛЕДОВАНИЕ ПРЕВРАЩЕНИЯ НЕКОТОРЫХ ИЛИДЕНМАЛОНОНИТРИЛОВ

А.М. Магеррамов, Ф.Н. Нагиев, А.Р. Аскерова, А.Г. Рагимова, М.А. Ахундова, И.Г. Мамедов

Бакинский государственный университет AZ1148 Баку, ул. З.Халилова, 23; e-mail:[email protected]

Впервые путем трехкомпонентной одностадийной конденсации изатилиденмалононитрилов, малононитрила и 2-тиофенметиламина (или фурфуриламина) получены соответствующие производные спиропиридина. Кроме того, взаимодействием бензилиденмалононитрилов с тиосемикар-базидом или 2,4-динитрофенилгидразином получаются соответствующие Шиффовы основания. Структуры полученных соединений подтверждены методами 1Н и 13С ЯМР спектроскопии. Ключевые слова: изатилиденмалононитрил, малононитрил, амины, тиосемикарбазид, гидразин.

Received 21.02.2018.

KiMYA PROBLEML9RÎ № 1 2018

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