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KiMYA PROBLEML9RÎ № 1 2018 ISSN 2221-8688
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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: farid.orgchemist@gmail.com
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
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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: farid.orgchemist@gmail.com
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:farid.orgchemist@gmail.com
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
