Synthesis and Applications of Polymeric Reagent p-Substituted Triphenylamine

Chemical modification of chloromethylstyrene - styrene copolymer throughout reaction of p-substituted carboxylic acid group of bis-(4,4`-dibromo)-4``-triphenylamine carboxylic acid with the chloromethyl group attached to a phenyl group was carried out on soluble copolymer and polymeric cross-linked copolymer. Chemical oxidation of the neutral p-substituted triphenylamine with antimony pentachloride in dichloromethane solvent gives the corresponding cation - radical salt with the counter ion antimony hexachloride (SbCl6-). The isolated deep blue color cation radical salt is soluble or in insoluble (resin) form in the copolymer was used as a thermal cationic initiator for the polymerization of epoxy and vinyl monomers at room temperature. The cation radical resin showed good activity and stability compared to the soluble polymeric cation radical, both can initiate the cationic polymerization of cyclohexene oxide and N-vinylcarbazole in dichloromethane at room temperature.

NMR spectroscopic properties of furo[2′,3′:4,5]pyrrolo[1,2-d][1,2,4]triazine derivatives

The 1H and 13C NMR spectroscopic properties of a series of furo[2′,3′:4,5]pyrrolo[1,2-d][1,2,4]triazin-8(7H)-ones and -thiones were investigated. The influence of various electron donating as well as electron withdrawing substituents at C-5 or N-7 on 1H NMR chemical shifts as well as 13C chemical shifts at C8 were observed. The 5-chloromethyl group had a little influence on the chemical shift of H-7 proton and the 8-thione group causes deshielding of H-7 as well as H-5 protons in comparison with the C-8 carbonyl group.

UNUSUAL WAY OF REACTION OF 3-AMINO-4-(5-CHLOROMETHYL-1,2,4-OXADIAZOLE-3-YL)-FURAZAN WITH HYDRAZINE

The results of our study of the pathways of selective reactivity of 3-amino-4-(5-chloromethyl-1,2,4-oxadiazole-3-yl)furazan versus 5-unsubstituted or 5-methyl and 5-trifluoromethyl substituted 4-(5R-1,2,4-oxadiazole-3-yl)furazans (R = H, Me, CF3) towards the action of hydrazine are discussed. If the reductive opening of 1,2,4-oxadiazole ring in unsubstituted at the С-5 atom (1,2,4-oxadiazol-3-yl)furazan derivatives under the treatment with hydrazine can be used as a method for the preparation of a range of amidrazones of 4-R-furazan-3-carboxylic acid. 3-amino-4-(5-trifluoromethyl-1,2,4-oxadiazol-3-yl)furazan with hydrazine gives amidoxime of 4-aminofurazan-3-carboxylic acid. 3-amino-4-(5-methyl-1,2,4-oxadiazol-3-yl) furazan is inert to the action of hydrazine, on the contrary the reaction of 3-amino-4-(5-chloromethyl-1,2,4-oxadiazole-3-yl)furazan with hydrazine leads to oxidation of chloromethyl group of titled compound to the carbonyl one. In this case the product of reaction of 3-amino-4-(5-chloromethyl-1,2,4-oxadiazole-3-yl)furazan with hydrazine was isolated in a form of corresponding hydrazonomethyl derivative notably as 3-amino-4-(5-hydrazonomethyl-1,2,4-oxadiazole-3-yl)furazan. A possible reaction mechanism for the formation of hydrazonomethyl group by oxidation reaction of chloromethyl group by hydrazine is proposed. 3-Amino-4-(5-hydrazonomethyl-1,2,4-oxadiazol-3-yl)furazan undergoes a transhydrazination reaction with semicarbazide and thiosemicarbazide. But our attempts to its hydrolysis for the purpose to obtain free aldehyde were unsuccessful. Thus, hydrolysis of hydrazonomethyl derivative in acetic acid in the presence of catalytic amount of sulfuric acid results in azine – N,N'-bis(3-(4-aminofurazan-3-yl)-1,2,4-oxadiazol-5-ylmethylyden)hydrazine – precipitation, long-duration boiling in hydrochloric acid leads to Kishner-Wolff reduction of the carbonyl group to 3-amino-4-(5-methyl-1,2,4-oxadiazol-3-yl)furazan, and hydrolysis in alkaline medium leads to 1,2,4-oxadiazole ring opening to amidoxime of 4-aminofurazan-3-carboxylic acid. Synthesis of 3-amino-4-(5-chloromethyl-1,2,4-oxadiazole-3-yl)furazan (R = CH2Cl) was carried out by condensation of amidoxime of 4-aminofurazan-3-carboxylic acid with an excess of chloroacetyl chloride in toluene at elevated temperature. The reaction proceeds through formation of intermediate product – 3-chloromethylamino-4-(5-chloromethyl-1,2,4-oxadiazol-3-yl)furazan. Removing of N-chloroacetyl group in such obtained intermediate was performed by hydrolysis in acidic media. One-pot synthesis without the need for isolation and purification of intermediate is allowed. The structures of obtained compounds were proved by modern methods of physical-chemical analysis (1H, 13C NMR, IR and MS spectroscopy).Forcitation:Stepanova E.V., Stepanov A.I. Unusual way of reaction of 3-amino-4-(5-chloromethyl-1,2,4-oxadiazole-3-yl)furazan with hydrazine. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2017. V. 60. N 4. P. 26-32.

New Dibenzocyclooctadiene Lignans from Schisandra sphenanthera and Their Proinflammatory Cytokine Inhibitory Activities

Investigation of the fruits of Schisandra sphenanthera led to the isolation of two new dibenzocyclooctadiene lignans, methylgomisin O (1) and chloromethyl schisantherin B (2), together with twelve known lignans (3 - 14). Their structures were elucidated by using extensive spectroscopic techniques including 1D and 2D NMR spectra. Compound 2 was identified as a cyclooctadiene moiety substituted with a chloromethyl group, which is rarely found in natural products, especially in terrestrial higher plants. Among these isolates, compounds 1 and 7 exhibited considerable inhibitory activity against tumor necrosis factor-α (TNF-α) and interleukin-6 (IL-6) production, and did not display any cellular toxicity against RAW264.7 cells.

Synthesis and Properties of Linear Chloroacetylated Polystyrene

Polystyrene (PS) was synthesized by emulsion polymerization. The linear chloroacetylated PS was prepared high effectively by Friedel-Crafts acetylation of PS using chloroacetyl chloride and anhydrous aluminium chloride as chloroacetylation reagent and catalysts, respectively. The structure of chloroacetyl group is similar to that of chloromethyl group. In this method, carcinogenic compound (chloromethyl ether etc.) was avoided and the reactions of secondary cross link and multi-substitute could be eliminated. The resultant polymers were characterized by Fourier transform infrared spectrometery (FTIR) and thermogravimetric analysis. The effects of reaction conditions on chloroacetylation were studied, and the optimum reaction conditions were obtained. Chloroacetyl group was introduced into benzene ring of PS because of the appearance of the absorption peaks at 1695cm-1 (due to C=O bonds) and 644cm-1 (due to C-Cl bonds) in the FTIR spectrum. The thermal stability of the chloroacetylated PS was decreased with increasing chloroacetyl group. Moreover, there were two decomposing stages. The glass transition temperature of chloroacetylated PS increased with substitution value increasing. The effects of the reaction conditions such as reaction temperature, the solvent amount and the concentration of chloroacetyl chloride and anhydrous aluminium chloride on the chloroacetylation of PS were obvious. The certain loading can be controlled when it is lower than the maximum loading of chloroacetylated PS. The reaction condition is gentle and the operation is safe, simple and economical so that Friedel-Crafts acetylation of PS is an ideal reaction method.

Mass Spectrometric Behaviour of (Z)-2-Chloro-3(Dichloromethyl)-4-Oxobutenoic Acid and (Z)-2-Chloro-3(Chloromethyl)-4-Oxobutenoic Acid (Open Forms of MX and CMCF Respectively) Molecular Ions

Fragmentation pathways of ( Z)-2-chloro-3(dichloromethyl)-4-oxobutenoic acid (MX open form) and ( Z)-2-chloro- 3(chloromethyl)-4-oxobutenoic acid (CMCF open form) are discussed on the basis of recorded metastable ions and high-resolution data. It was found that the presence of the additional chlorine atom in the chloromethyl group affects the fragmentation pathways of MX. The elimination of the dichloromethyl radical was observed for the MX+• ion but elimination of the chloromethyl radical does not occur for the CMCF+• ion. For the latter compound, elimination of a CO molecule was registered. The elimination of an HCl molecule occurs for both ions.