Synthesis and properties of sym-triazine derivatives. 3. alkoxylation of 2-alkyl-4,6-bis(trichloromethyl)-sym-triazines containing higher alkyl radicals

Nucleophilic substitution reactions of trichloromethyl groups in 2-alkyl-4,6-bis-(trichloromethyl)-sym-triazines by alkoxy radicals were studied. It was shown that in the presence of sodium alcoholates, two CCl₃ groups are replaced, and the corresponding 2,4-dialkoxy-6-alkyl-sym-triazines are formed. The products of partial replacement, 2-alkoxy-4-trichloromethyl-6-alkyl-sym-triazines, were synthesized by heating the initial sym-triazines with alcohols in the presence of tertiary amines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1674–1677, December, 1984.     

Reactions of 2-alkoxy-3-alkyl-1,3,2-oxazaphosphinanes with alkyl chloroformates

2-Alkoxy-3-alkyl-1,3,2-oxazaphosphinanes containing a sterically hindered N atom react with alkyl chloroformates according to the Arbuzov mechanism only. The ratio of the open and cyclic reaction products depends on the nature of the alkoxy group in the starting phosphinane. With a less hindered N atom, acylation at the N atom gives acyclic chloridophosphites, in addition to the Arbuzov-type products. The structures of the chloridophosphites were confirmed by their chemical transformations into stable thiophosphates. Oxazaphosphinane analogs of phosphorylformamides and phosphorylformohydrazide were obtained.     

Synthesis of fluorine-containing alkyl 2-cyano-3-oxocarboxylates. Reactions with nucleophiles

Fluorine-containing alkyl 2-cyano-3-oxocarboxylates were synthesized for the first time by the reaction of ethyl cyanoacetate with fluorine-substituted carboxylic acid halides or alkyl carboxylates. The reactions with hydrazine hydrate, phenylhydrazine, ando-phenylenediamine give hydrazinium (ammonium) enolates or products of acid decomposition. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1961–1965, October, 1999.     

Synthesis and properties of novel segmented polyurethanes containing alkyl phosphatidylcholine side groups

In this article, we report the synthesis and properties of novel segmented polyurethanes containing alkyl phosphatidylcholine side groups. Alkyl phosphatidylcholine groups were attached to the hard blocks of the polyurethanes. A novel diol, 9-(2-hydroxy-1-hydroxymethyl-1-methyl-ethylcarbamoyl)-nonyl-phosphatidylcholine (HDEAPC), was synthesized and characterized by FTIR, ¹H-NMR and mass spectroscopy. Two types of polyurethanes, poly(ether urethane)s and poly(carbonate urethane)s, containing alkyl phosphatidylcholine side groups were synthesized using methylenebis(phenylene isocyanate) (MDI), polytetramethyleneoxide (PTMO), poly(1,6-hexyl-1,5-pentylcarbonate) diol (PHPCD), 1,4-butanediol (BDO) and HDEAPC. The obtained phosphatidylcholine polyurethanes had relatively high molecular weights and good mechanical strength, as characterized by GPC and Instron. XPS and contact angle studies revealed that there was enrichment of alkyl phosphatidylcholine side groups near the surface of the polyurethanes. Biocompatibility was evaluated by protein adsorption using conventional polyurethanes as references. The surface of phosphatidylcholine poly(carbonate urethane)s effectively suppressed protein adsorption.     

Synthesis and properties of symm-triazine derivatives. 4. Synthesis of 2,4,6-trisubstituted symm-triazines containing sterically-hindered phenol fragments

2,4,6-Trisubstituted symm-triazines containing sterically-hindered phenol fragments were synthesized by the cyclotrimerization of ethyl iminoesters. 2,4,6-Trimercapto-symm-triazine derivatives containing shielded phenol residues may be formed by the cyclotrimerization of the corresponding thiocyanates in acidic medium.For communication 3, see [1].Translated from Khimiya Geterosiklicheskikh Soedinenii, No. 1, pp. 107–113, January, 1986.     

Reactions of 3-oxo-2,3-dihydrobenzofuran with alkyl 2-cyano-3-alkoxypropenoate and alkyl 2-alkoxycarbonyl-3-alkoxypropenoate. Synthesis of pyran derivatives

3-Oxo-2,3-dihydrobenzofuran reacted with ethyl 2-cyano-3-ethoxypropenoate, methyl 2-cyano-3-methoxy-propenoate affording compounds 3 (2-(2-cyano-2-alkoxycarbonylvinyl)-3-hydroxybenzofuran) obtained as a mixture of Z + E isomers. Methyl 2-methoxycarbonyl-3-methoxypropenoate gave compound 4 . Malonic compounds added on 2-dimethylaminomethylene-3-oxo-2,3-dihydrobenzofuran 6 for giving compound 3 or 2-oxo-3-methoxycarbonyl-2H-pyrano[3,2-b]benzofuran 8 . Compound 8 was also obtained by heating compound 4 in xylene.     

Reactions of pyranylidenemethylpyrylium salts with ammonia and amines

Pyranylidenemethylpyrylium salts (1) react with ammonia to give pyranylidenepyridines as a result of the replacement of one of the oxygen atoms of 1 by nitrogen. Aliphatic primary amines react with 1 by replacing both of the oxygen atoms by nitrogens. Aniline and 1 give the monoreplacement product. Pyranylidenemethylthiopyrylium salts have only the oxygen atom replaced by reaction with primary aliphatic amines.     

Reactions of the carbonate radical with aliphatic amines

Carbonate radicals react with aliphatic amines by a dual mechanism, viz. (i) hydrogen abstraction and (ii) electron transfer. The former is more probable with primary amines. Tertiary amines react via electron transfer. Both mechanisms may operate in secondary amines. Cyclic tertiary amines react with different rates and their relative reactivities are explained on the basis of the concept of Hoffmann's ‘through bond’ interaction.     

Synthesis of new imines and amines containing organosilicon groups

The Peterson olefination reaction of terephthalaldehyde with tris(trimethylsilyl)methyl lithium, (Me₃Si)₃CLi, in THF at 0 °C gives 4-[2,2-bis(trimethylsilyl)ethenyl]benzaldehyde (1) and 4,4-bis[2,2-bis(trimethylsilyl)ethenyl]benzene (2). The new aldehyde (1) reacts with variety of amines in ethanol to afford the corresponding imines (3) containing vinylbis(trimethylsilyl) group. The newly synthesized imines (3) can be completely converted into amines containing vinylbis(trimethylsilyl) group with an excess amount of NaBH₄. In the case of N-[4-(2,2-bis(trimethylsilyl)ethenyl)benzyl]-2,6-dimethylaniline LiAlH₄ was used as a reducing agent in THF.     

Synthesis and properties of derivatives of sym-triazines. 11. Synthesis of 2-amino-sym-triazines containing alkyl radicals

2-Amino-4,6-dialkyl-sym-triazenes were synthesized by the condensation of aliphatic nitriles with guanidine. 2-Amino-4-alkyl-6-substituted sym-triazines were prepared by the reaction of N-acylguanidines with nitriles or imino esters. Aminotriazines of this type are also formed in the condensation of N-imidoylguanidines with esters.For Communication 10, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1271–1276, September, 1993.     

Reactions of tetracyanocyclopropyl ketones with ammonia and primary amines

Reactions of aliphatic 2,2,3,3-tetracyanocyclopropyl ketones with aqueous ammonia afforded 4-alkyl- 4-amino-2-oxo-3-azabicyclo[3.1.0]hexane-1,6,6-tricarbonitriles with conservation of the three-membered ring. Reactions of the same compounds with primary amines were accompanied by opening of the cyclopropane ring, and they led to the formation of 5-amino-6,6a-dimethyl-2-oxo-1,2,6,6a-tetrahydropyrrolo[2,3-b]-pyrrole-3,4-dicarbonitriles as a result of successive heterocyclizations.     

Synthesis of 1,3,4-oxadiazol-2-ones with aliphatic groups at N-3

A series of 3-substituted-5-methoxy-1,3,4-oxadiazol-2-ones were prepared from aldehydes, ketones, phenylacetic acids, and 1,2- and 1,3-diketones. Conditions for the formation of these oxadiazolones from the precursor N-carbamoyl chlorides depended on the structure, and varied from spontaneous ring closure to those requiring bases. Variation in the N-3 substituents sometimes produced mixtures of isomers which were separated and identified. These molecules were prepared in order to study the effect of the N-3 substituent variation on the biological properties of oxadiazolones.     

N-Lithium derivatives of aliphatic amines in the synthesis of 1-alkyl-2-phenyldiazene 2-oxides

Magnesium derivatives of aliphatic amines containing -hydrogen atoms, in contrast to t-BuNHMgBr, do not form phenylaliphatic diazene oxides upon reaction with nitrobenzene, but rather reduce it to azobenzene and azoxybenzene. Asymmetric diazene oxides are formed when the magnesium derivatives are replaced by lithium derivatives. The reaction of t-BuNHLi with dimethylnitramine gives 1,3,5-trimethyl-1,3,5-triazacyclohexane.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1452–1454, June, 1991.     

Extraction of nickel in the presence of ammonia with β-diketones containing phenyl and alkyl groups

The extraction of nickel chelates with β-diketones containing either alkyl or phenyl groups was examined in the absence and in the presence of ammonia in the aqueous solution, in order to define the effect of substituents and the coordinating effect of ammonia on the extraction. In the extraction of nickel chelates in the presence of ammonia, the extracted species were identified to be [NiA₂(NH₃)₂] (A: β-diketone anion) and ammonia acts both as adduct-forming in the organic phase and as a masking reagent in the aqueous phase.     

Reactions of diols and epoxides Communication 10. Synthesis of 3-alkyl- and 3-aryl-oxetanes

Conclusions New synthesis of 3-methyl-, 3-ethyl-, 3-propyl-, 3-isopropyl-, 3-butyl-, 3-t-butyl-, 3-cyclohexyl-, 3-phenyl-, and 3-benzyl-oxetanes are described, and their more important physical constants are given. These cyclic ethers can be prepared in fairly good yields (40–60%) from the corresponding chloro acetates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1241–1244, July, 1966.     

Reactions of 4-amino-1,3,5-dithiazine with ammonia and amines

It is shown that selective replacement of the sulfur atom in the 3 position by a nitrogen atom, which leads to 2,6-dimethyl-4-amino-3H-2,6-dihydro-1,3,5-thiadiazine, occurs when 2H,6H-2,6-dimethyl-4-amino-1,3,5-dithiazine is treated with ammonium hydroxide. Under the same conditions, amines cause profound destruction of 2H,6H-2,6-dimethyl-4-amino-1,3,5-dithiazine with the production of thiourea.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 652–655, May, 1982.     

Synthesis and mesomorphism of new aliphatic polycarbonates containing side cholesteryl groups

New cholesterol side-functionalised polycarbonate polymers were synthesised by the ring-opening homo- and copolymerisation reaction of the cyclic monomer cholesteryl 5-methyl-2-oxo-1,3-dioxane-5-carboxylate and d,l-lactide using Sn(Oct)₂ as a catalyst. The chemical structures and average molecular weights of the cyclic monomer, homopolymer and block copolymers obtained in this study were characterised using FT-IR, ¹H NMR and gel permeation chromatographic measurement. The mesomorphism and mesophase structure were investigated with polarising optical microscopy, differential scanning calorimetry and X-ray diffraction measurement. As a result, the homopolymer and block copolymers showed an enantiotropic smectic A (SmA) phase. With the concentration of the lactide segment increasing, the glass transition temperature and isotropic temperature of the corresponding block copolymer all decreased. In addition, XRD suggested that the homopolymer and two block copolymers showed the SmA double-layer packing of side chains.     

Synthesis and properties of aliphatic oligoamides containing methionine fragment

Oligoamides were prepared from dimerized fatty acid, hexamethylenediamine, and an amino acid (methionine). The effect of methionine on the course of polycondensation and properties of the reaction products was examined. New thermoplastic adhesive compounds based on these products were developed.