• Bulletin of the Korean Chemical Society
• /
• v.21 no.6
• /
• pp.613-617
• /
• 2000

p-(2-Vinyloxyethoxy)benzylidenemalononitrile (4a), methyl p-(2-vinyloxyethoxy)benzylidenecyanoacetate (4b), 3,5-dimethoxy-4-(2'-vinyloxyethoxy)benzylidenemalononitrile (5a), methyl 3,5-dimethoxy-4-(2'-vinyloxy-ethoxy) benzylidenecyanoacetate (5 b), o-(2 -vinyloxyethoxy)benzylidenemalononitrile (6a), methyl o-(2-viny-Ioxyethoxy) benzylidenecyanoacetate (6b), 1,3-di-(2',2'-dicyanovinyl)-5-methyl-2-(2'-vinyloxyetioxy)benzene (7a), l,3-di-(2'-carbomethoxy-2'-cyanovinyl)-5-methyl-2-(2'-vinyloxyethoxy)benzene (7b), 2,3,4-tri-(2'-viny-Ioxyethoxy) benzylidenemalononitrile (8a), methyl 2,3,4-tri-(2'-vinyloxyethoxy)benzylidenecyanoacetate (8b), 2,4,6-tri-(2'-vinyloxyethoxy)benzylidenemalononitrile (9a), and methyl 2,4,6-tri-(2'-vinyloxyethoxy)benzyl-idenecyanoacetate(9b) were prepared by the condensation of the corresponding benzaldehyde 1-3 with malononitrile or methyl cyanoacetate, respectively. Vinyl ether monomers 4, 6, and 8 polymerized readily with radical initiators to yield crosslinked polymers 10, 12, and 14. However, compounds 5, 7, and 9 were inert to radical initiators due to the steric hindrance. The resulting polymers 10, 12, and 14 were not soluble in common solvents showing a thermal stability up to $300^{\circ}C$.

• Bulletin of the Korean Chemical Society
• /
• v.19 no.8
• /
• pp.851-856
• /
• 1998

2,4-Di-(2-vinyloxyethoxy)benzylidenemalononitrile (2a), methyl 2,4-di-(2-vinyloxyethoxy)benzylidenecyanoacetate (2b), 3,4-di-(2-vinyloxyethoxy)benzylidenemalononitrile (4a), and methyl 3,4-di-(2-vinyloxyethoxy)benzylidenecyanoacetate (4b), 2,5-di-(2-vinyloxyethoxy)benzylidenemalononitrile (6a), and methyl 2,5-di-(2-vinyloxyethoxy)benzylidenecyanoacetate (6b) were prepared by the condensation of 2,4-di-(2-vinyloxyethoxy)benzaldehyde (1), 3,4-di-(2-vinyloxyethoxy)benzaldehyde (3), and 2,5-di-(2-vinyloxyethoxy)benzaldehyde (5) with malononitrile or methyl cyanoacetate, respectively. Trifunctional divinyl ether monomers 2, 4 and 6 were polymerized readily by free radical initiators to give optically transparent swelling poly(vinyl ethers) 7-9. Polymers 7-9 were not soluble in common organic solvents such as acetone and DMSO due to crosslinking. Polymer 7-9 showed a thermal stability up to 300 ℃ in TGA thennograms.

• Bulletin of the Korean Chemical Society
• /
• v.20 no.5
• /
• pp.567-572
• /
• 1999

5-Nitro-2-(2'-vinyloxyethoxy)benzylidenemalononitrile (2a), methyl 5-nitro-2-(2'-vinyloxyethoxy)benzylidenecyanoacetate (2b), 3-nitro-4-(2'-vinyloxyethoxy)benzylidenemalononitrile (4a), methyl 3-nitro-4-(2'-vinyloxyethoxy)benzylidenecyanoacetate (4b), 2-nitro-5-(2'-vinyloxyethoxy)benzylidenemalononitrile (6a), and methyl 2-nitro-5-(2'-vinyloxyetboxy)benzylidenecyanoacetate (6b) were prepared by the condensation of 5-nitro-2-(2'-vinyloxyethoxy)benzaldehyde (1), 3-nitro-4-(2'-vinyloxyethoxy)benzaldehyde (3), and 2-nitro-5-(2'-vinyloxyethoxy)benzaldehyde (5) with malononitrile or methyl cyanoacetate, respectively. Vinyl ether monomers 2a-b, 4a-b, and 6a-b were polymerized with boron trifluoride etherate as a cationic initiator to yield poly(vinyl ethers) 7-9 having oxynitrobenzylidenemalononitrile and oxynitrobenzylidenecyanoacetate, which is effective chromophore for second-order nonlinear optical applications. Polymers 7-9 were soluble in common organic solvents such as acetone and DMSO. Tg values of the resulting polymers were in the range of 67-83 ℃. Electrooptic coefficient (r33) of the poled polymer films were in the range of 15-27 pm/V at 633 nm. Polymers 7-9 showed a thermal stability up to 300 ℃ in TGA thermograms, which is acceptable for NLO device applications.

• Bulletin of the Korean Chemical Society
• /
• v.26 no.5
• /
• pp.719-728
• /
• 2005

A novel 2-amino-4-(8-quinolinol-5-yl)-1- (p-tolyl)-pyrrole-3-cabonitrile (2) was obtained by the reaction of 2-[2-bromo-1-(8-hydroxyquinolin-5-yl)-ethylidene]-malononitrile (1) with p-toluidene. The new synthon compound (2) could be annelated to the corresponding pyrrolo[2,3-d]pyrimidines (4, 6, 7, 26-28), triazolo[1,5-c]pyrrolo[3,2-e]pyrimidines (10, 29, 30), pyrrolo[2,3-c]pyrazoles (11-15), pyrrolo[1,2-a]pyrrolo[3,2-e] pyrimidine (17) and imidazo[1,2-c]pyrrolo[3,2-e]pyrimidines (18-25) via the reaction with some reagents such as acetic anhydride, formamide, triethyl orthoformate, hydrazine hydrate, hydroxylamine, ethylenediamine, carbon disulfide and phosphorus oxychloride. Chemical and spectroscopic evidences for the structures of these compounds are presented. The antifungal and antibacterial activity of the newly synthesized comounds were evaluated.

• Bulletin of the Korean Chemical Society
• /
• v.19 no.2
• /
• pp.155-159
• /
• 1998

o-(2-Vinyloxyethoxy)benzylidenemalononitrile (4a), methyl o-(2-vinyloxyethoxy)benzylidenecyanoacetate (4b), m-(2-vinyloxyethoxy)benzylidenemalononitrile (5a), methyl m-(2-vinyloxyethoxy)benzylidenecyanoacetate (5b), p-(2-vinyloxyethoxy)benzylidenemalononitrile (6a), and methyl p-(2-vinyloxyethoxy)benzylidenecyanoacetate (6b) were prepared by the condensation of o-(2-vinyloxyethoxy)benzaldehyde (1), m-(2-vinyloxyethoxy)benzaldehyde (2), and p-(2-vinyloxyethoxy)benzaldehyde (3) with malononitrile or methyl cyanoacetate, respectively. Bifunctional vinyl ether monomers 4a-b and 6a-b polymerized readily with cationic initiators to give polymers with the NLO-chromophores o- and p-oxybenzylidenemalononitrile or o- and p-oxybenzylidenecyanoacetate in side chain at -60 ℃, while meta-isomers 5a and 5b gave lower yields of polymers under the same conditions. The resulting polymers 7-9 were soluble in common organic solvents and the inherent viscosities of polymers were in the range of 0.20-0.30 dL/g in acetone. Solution-cast films were clear and brittle, showing Tg values in the range of 40-70 ℃.

• Bulletin of the Korean Chemical Society
• /
• v.22 no.9
• /
• pp.999-1004
• /
• 2001

(1-Chloro-2,2-dicyanovinyl)benzene or 1,4-bis(1-chloro-2,2-dicyanovinyl)benzene was reacted with 2-amino-phenol to give the model compound, hydroxy enaminonitrile, which was found to undergo thermal cyclization reaction to form the corresponding benzoxazole. This intramolecular cyclization reaction is expected to occur through nucleophilic attack to electropositive enamine carbon by ortho-hydroxy group on the phenyl ring, which is accompanied by the release of neutral malononitrile through rearrangement. From each bifunctional monomer, o-hydroxy substituted polyenaminonitrile was prepared and characterized as a new precursor polymer for well-known aromatic polybenzoxazole. Also the unusual macrocyclic dimer formation from the 1,4-bis(1-chloro-2,2-dicyanovinyl)benzene and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane polymerization reaction system was discussed. The thermal cyclization reactions and the properties of polymers were investigated using FT-IR and thermal analysis (DSC & TGA).

• Archives of Pharmacal Research
• /
• v.13 no.2
• /
• pp.142-146
• /
• 1990

Reaction of ethyl 4-chloro-2-phenylpyrimidine-4-carboxylate (4) with 5-chloro-2-methylthiophenol or 3-aryl-4-phenyl-1, 2, 4-triazole-5 thiol yielded the corresponding thioethers (5) and (8a, b), respectively. Careful alkaline hydrolysis of (5) yielded the corresponding carboxylic acid (6). Reaction of (4) with p-aminoacetophenone yielded compound (10) which was reacted with certain aromatic aldehyde to afford the$\alpha,\beta$-unsaturated ketones (11a-d). Condensation of (11a-d) with malononitrile or phenylhydrazine yielded the 2-amino-3-cyanopyridines (12a-f) or the 2-pyrazolines (13a, b) respectively. Seven representative compounds were tested for their in vitro antimicrobial activity against some pathogenic micro-organisms, some of them were proved to be active.

• Journal of the Korean Applied Science and Technology
• /
• v.4 no.1
• /
• pp.61-66
• /
• 1987

2,4,6-Triamino-5-nitrosopyrimidine was prepared using malononitrile and guanidine carbonate, and acetylated refluxing in acetic acid with acetic anhydride in order to activate the nitroso group for nucleophilic attack. Nucleophilic attack of phenylpyrimidium bromide on the nitroso group of 2,4,6-triacetamido-5-nitrosopyrimidine gave the intermediate, which lost pyrdidine to give the nitrone derivative. Addition of the methanethiol anion to nitrone gave 2,4-diacetamido-7-phenyl-6-methylthiopteridine which was hydrolyzed to give 2,4-diamino-7-phenyl-6-methylthiopteridine. Spectral data (IR, M.S, NMR) were provided to identify the reaction products during synthesis.

• Archives of Pharmacal Research
• /
• v.13 no.1
• /
• pp.24-27
• /
• 1990

Reaction of 2-formyl-4H-thieno [2, 3-b] benzothiopyran-4-one (1) with different heterocyclic amines afforded the corresponding Schiff's bases (2-4). Diethyl malonate, ethyl cyanoacetate and malononitrile were reached with 1 to afford compounds 5, 7 and 8, respectively. Compound 5 was cyclized to the pyrazolidin-3, 4-dione (6) by the action of hydrazine hydrate, whereas compound 7 was utilized for the synthesis of the thiazolin-4 one derivatives (9-13).

• Journal of the Korean Chemical Society
• /
• v.56 no.3
• /
• pp.328-333
• /
• 2012

A simple, convenient and practical green synthetic protocol for sodium bisulfite catalyzed multicomponent reaction of ethyl acetoacetate, hydrazine hydrate, malononitrile, and various aldehydes for the synthesis of 6-amino-4-phenyl-3-methyl-2,4-ihydropyrano[2,3-c]pyrazole-5-carbonitriles using ultrasound irradiations in solvent free condition. This method provides the advantage of operational simplicity, shorter reaction time and excellent yields making the protocol environment friendly and economically lucrative.