Calix[4]resorcinols functionalized with amino acid residues

By the Mannich reaction in ternary systems calix[4]resorcinol-amino acid (amino acid ester, amino acid ester hydrochloride)-formaldehyde calix[4]resorcinols were obtained functionalized on the upper molecule rim by amino acid residues.     

Synthesis and basic properties of bisporphyrinocalix[4]arene

A bisporphyrinocalix[4]arene was prepared, and its basicity was examined spectrophotometrically. The protonation of tetrapyrrole fragments of the porphyrinocalixarene conjugate in the ethanol-sulfuric acid system occurs in two steps and is described by the Hammett equation. The ionization constants and the concentration intervals of the formation of the mono-and dicationic forms of the bisporphyrinocalixarene were determined.     

Synthesis and GCP II inhibitory activity of 4[4-(3-bromobenzyl)-5-hydroxyisoxazol-3-yl]benzoic acid heterocyclic analogs

A method for the synthesis of analogs of glutamate carboxypeptidase II inhibitor 4-[4-(3-bromobenzyl)-5-hydroxyisoxazol-3-yl]benzoic acid-4-[4-(3-bromobenzyl-5-hydroxypyrazol-3-yl]-benzoic acid and 4-[4-(3-bromobenzyl)-3-hydroxyisoxazol-5-yl]benzoic acid from 4-(2-ethoxycarbonylacetyl)benzoic acid was developed. The GCP II inhibitory activity of all the compounds synthesized was determined. Substitution of the 5-hydroxyisoxazole group by the 5-hydroxypyrazole group led toa complete loss of activity, while replacement with the 3-hydroxyylisoxazole gave the compound with slightly less inhibitoer activity comparing with the initial compound. __________ Translated from Khimiya Geteritsiklicheskikh Soedinenii, No. 11, 1693–1697, November, 2007.     

Synthesis and properties of analogs of 5(4)-aminoimidazole-4(5)-carboxamide and purines. 15. Ring opening in imidazo[4,5-d]-1,2,3-triazines

It has been shown that 4-methylthio-, ethoxy-, and methoxyimidazotriazines and imidazotriazin-4-ones, unlike benzo-1,2,3-triazines, do not display cryptodiazonium behavior. A novel type of fission of the triazine ring to give esters and thioesters of 5-aminoimidazole-4-carboxylic acid is described.For Communication 14, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1248–1250, September, 1989.     

Diazabicycloalkanes with nitrogen atoms in bridgehead positions. 16. Synthesis and properties of benzo[b]-1,4-diazabicyclo[2.2.2]octene and dibenzo[b,e]-1,4-diazabicyclo[2.2.2]octadiene,containing primary aromatic amino acids

4-Aminobenzo[1,2-b]-1,4-diazabicyclo[2.2.2]octene and 4-aminodibenzo[1,2-b, e]-1,4-diazabicyclo[2.2.2]octadiene have been prepared by cyclization reactions of N--chloroethyl derivatives of 1,2,4-triaminobenzene and aminophenazine, and subsequent catalytic hydrogenation of the corresponding 4-nitrobenzo[1,2-b]-1,4-diazabicyclo[2.2.2]octene and 4-benzylaminodibenzo[1,2-b,e]-1,4-diazabicyclo[2.2.2]-octadiene. Using the conversion of these compounds to azides as an example, we have demonstrated the feasibility of applying these primary aromatic amines for the synthesis of derivatives of these heterocycles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 831–837, June, 1988.     

Synthesis of pyrido[1,2-a]pyrimido[4,5-d]pyrimidin-5-ones. Cyclization reaction of 4-[(3-hydroxy-2-pyridyl)amino]-2-phenyl-5-pyrimidinecarboxylic acid with acetic anhydride

Treatment of 4-[(3-hydroxy-2-pyridyl)amino]-2-phenyl-5-pyrimidinecarboxylic acid (X) with acetic anhydride under refluxing conditions afforded 10-hydroxy-2-phenyl-5H-pyrido[1,2-a]-pyrimido[4,5-d]pyrimidin-5-one acetate (IX). The intermediate X was prepared from 4-chloro-2-phenyl-5-pyrimidinecarboxylic acid ethyl ester (V). The reaction of V with the sodium salt of 2-amino-3-hydroxypyridine at room temperature gave 4-(2-amino-3-pyridyloxy)-2-phenyl-5-pyrimidinecarboxylic acid ethyl ester (VI). Treatment of VI with a hot aqueous sodium hydroxide solution and subsequent acidification gave X. Involvement of 4-[(3-hydroxy-2-pyridyl)amino]-2-phenyl-5-pyrimidinecaroboxylic acid ethyl ester (VIII) (Smiles rearrangement product) as an intermediate in the above alkaline hydrolysis reaction of VI to X was demonstrated by the isolation of VIII and its subsequent conversion into X under alkaline hydrolysis conditions. Acetylation of VIII with acetic anhydride in pyridine solution gave 4-[(3-hydroxy-2-pyridyl)amino]-2-phenyl-5-pyrimidinecarboxylic acid ethyl ester acetate (XI), which afforded IX on fusion at 220°. This alternative synthesis of IX from XI supported the structural assignment of IX. Fusion of VI gave 10-hydroxy-2-phenyl-5H-pyrido[1,2-a]pyrimido]4,5-d]pyrimidin-5-one (VII). The latter was also obtained when VIII was fused at 210°. Acetylation of VII with acetic anhydride afforded IX.     

Diazabicycloalkanes with nitrogen atoms in the nodal positions. 6. Synthesis and some properties of benzo[f]-1,5-diazabicyclo[3.2.2]nonene and benzo[g]-1,6-diazabicyclo[4.2.2]decene

The reaction of N-acetyl derivatives of N,N-trimethylene- and N,N-tetramethylene-o-phenylenediamines with ethylene oxide gave the corresponding N-(-hydroxyethyl)-N-acetyl derivatives, the cyclization of which in refluxing hydrobromic acid leads to benzo[f]-1,5-diazabicyclo[3.2.2]nonene and benzo[g]-1,6-diazabicyclo[4.2.2.]decene.See [1] for Communication 5.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1538–1542, November, 1981.     

Synthesis of analogs of 5(4)-aminoimidazole-4(5)-carboxamide and purines. 7. 7-(β-d-ribofuranosyl)-4-methylthioimidazo[4,5-d]-1,2,3-triazine

The synthesis of 7-(-D-ribofuranosyl)-4-methylthioimidazo[4,5-d]-1,2,3-triazine, 7-methyl-4-methylthioimidazo[4,5-d]-1,2,3-triazine, and 5-methyl-4-methylthioimidazo [4,5-d]-1,2,3-triazine is described. The structures of the synthesized compounds were confirmed by ¹³C NMR spectroscopy.See [1] for communication 6.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 836–838, June, 1979.     

Synthesis of the penta-glutamyl derivative of N-[4-[N-[3-(2,4-diamino-1,6-dihydro-6-oxo-5-pyrimidinyl)-propyl]amino]benzoyl]-L-glutamic acid (5-DACTHF). An acyclic analogue of tetrahydrofolic acid

The penta-glutamyl derivative of N-[4-[N-[3-(2,4-diamino-1,6-dihydro-6-oxo-5-pyrimidinyl)propyl]amino]-benzoyl)-L-glutamic acid (1, 5-DACTHF, 543U76) was synthesized by a convergent route. L-γ-Glutamyl-L-γ-glutamyl-L-γ-glutamyl-L-γ-glutamyl-L-γ-glutamyl-L-glutamic acid heptakis t-butyl ester ( 20 ) was prepared in ten steps from L-glutamic acid di-t-butyl ester and N-(benzyloxycarbonyl)-L-glutamic acid α-t-butyl ester. 4-[N-[3-(2,4-Diamino-1,6-dihydro-6-oxo-5-pyrimidinyl)propyl]trifluoroacetamido]benzoic acid ( 6 ), which was synthesized from pyrimidinylpropionaldehyde 3 in three steps, was condensed with 20 , followed by deprotection to provide N-[4-[N-[3-(2,4-diamino-1,6-dihydro-6-oxo-5-pyrimidinyl)propyl]amino]benzoyl]-L-γ-glutamyl-L-γ-glutamyl-L-γ-glutamyl-L-γ-glutamyl-L-γ-glutamyl-L-glutamic acid ( 2 ). Hexaglutamate 2 is a potent inhibitor of glycinamide ribonucleotide transformylase.     

新型杯[4]芳烃衍生物的合成及其氨基酸萃取性能

杯[4]-1,3-二乙酸乙酯衍生物(1)与水合肼反应生成杯[4]芳烃酰肼衍生物(2),化合物(2)与异硫氰酸苯酯反应得到含酰胺和硫脲单元的新型杯[4]芳烃衍生物(3).总产率达70%.系列氨基酸萃取实验表明化合物(3)对异亮氨酸有较好的选择性萃取能力.     

Synthesis and aggregation properties of novel amino acetals with the calix[4]resorcinol platform

Reactions of calixarenes with methylaminoacetaldehyde dimethyl acetal and formalin gave Mannich bases with the calixarene platform. It was found by dielcometric titration that calix[4]resorcinols with acetal groups in the aminomethyl fragment form head-to-head supra-molecular aggregates in chloroform at low concentrations. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 888–891, May, 2006.     

Synthesis of chalcone analogs -4- and 5-nitropyrrole derivatives

Nitropyrrole analogs of chalcone have been synthesized by aldol condensation in basic medium from 5-nitropyrrole-2-carboxaldehyde, 4- and 5-nitro-2-acetylpyrrole, and the corresponding aromatic aldehydes and methyl ketones; their 2, 4-dinitrophenylhydrazones have been obtained. Some considerations are expressed concerning the reactivity of pyrrole-2-carboxaldehyde, 2-acetylpyrrole, and their nitro derivatives.     

Synthesis and photochromic properties of 4-[2-(anthracen-9-yl)-5-methyloxazolyl] fulgide

New photochromic fulgide, viz., 4-{1-[2-(anthracen-9-yl)-5-methyloxazol-4-yl]ethylidene}-3-isopropylidenetetrahydrofuran-2,5-dione, with fluorescent properties was synthesized. Studies by electronic, IR, and ¹H NMR spectroscopy and X-ray diffraction demonstrated that this fulgide exists in the Z form. Light irradiation of its solutions at a wavelength of 365 nm causes Z/E isomerization giving rise to the thermally stable cyclic form. The latter is transformed into the starting E isomer under light irradiation at λ = 436 nm. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 97–101, January, 2006.     

Cyclazines and their analogs. 4. Synthesis of triazolopyrido[1,2-c]pyrimidines

Alkylation of isomeric 2-mercapto-6- and 4-mercapto-2-methylpyrimidines by ethyl -bromoacetoacetate yields the corresponding S-substituted pyrimidines. Formylation of these intermediates by the Vilsmeier reagent gives diformyl derivatives of a new cyclazine series, namely, thiazolopyridopyrimidines. These cyclazine dialdehydes react with nucleophilic reagents used for the synthesis of polymethine dyes to give highly colored biscyanines. The interrelationship between the color and structure of these heterocyclic products and derived dyes was analyzed.For Communication 3, see [1].Institute of Organic Chemistry, National Academy of Sciences of Ukraine, 252660 Kiev, Ukraine. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 392–395, March, 1998.     

3-[N-(4-甲基苯基)氨基羰基]-5-[4-(4-甲酸基苯甲氧基)苯亚甲基]-2,4-噻唑烷二酮的合成

以对甲苯胺和对甲基苯甲酸甲酯为起始原料,经NBS溴化、亲核取代、酸水解和Knoevenagel缩合等6步反应合成了抗细菌生物膜化合物—3-[N-(4-甲基苯基)氨基羰基]-5-[4-(4-甲酸基苯甲氧基)苯亚甲基]-2,4-噻唑烷二酮,总收率57.3％,其结构经1H NMR,ESI-MS和元素分析确证.     

Synthesis of 1- and 4-substituted-5H-benzo[a]phenoxazin-5-ones

The 1- and 4-substituted-5H-benzo[a]phenoxazin-5-ones (substitutents: nitro, amino and acetylamino) were prepared by the condensation of o-aminophenol with 5-substituted-2,3-dichloro-1,4-naphthoquinones. The resulting compounds were subjected to reduction, acetylation and dehalogenation.     

Synthesis and amino acid extraction abilities of chiral calix[4]arene triamides containing amino alcohol units

Herein the synthesis and extraction abilities of new d-/l-phenylalaninol substituted p-tert-butylcalix[4]arene triamide derivatives (3 and 4) towards amino acids are reported. These compounds (3 and 4) have been easily synthesized via aminolysis of p-tert-butylcalix[4]arene trimethylester (2) with d-/l-phenylalaninol in methanol-toluen solvent system at one step. The extraction properties of the prepared chiral calix[4]arene triamide derivatives (3 and 4) towards some selected amino acid methylesters are studied by liquid–liquid extraction. Results show that these chiral calix[4]arene triamide derivatives (3 and 4) exhibited a good affinity towards all amino acid species without any remarkably discrimination.     

N-丁基-4-[乙基-(3-甲基苯基)氨基]丁酰胺的合成

以γ-丁内酯为起始原料,经开环氯化和酰化反应制得N-丁基-4-氯丁酰胺(2);2与N-乙基间甲苯胺经N-烷基化反应合成了N-丁基-4-[乙基-(3-甲基苯基)氨基]丁酰胺,总收率74.6%,纯度97.6%,其结构经1H NMR和MS(ESI)确证。     

Synthesis and characterization of poly[4-(4-hydroxyphenoxy) benzoic acid]

Poly[4-(4-hydroxyphenoxy) benzoic acid] was prepared by the bulk polycondensation of 4-(4-acetoxyphenoxy) benzoic acid. Polycondensation was conducted at 350°C for 3 h under a reduced pressure of 0.1 mmHg and gave a polymer with X?n of 255. The polymer was characterized by elemental analysis, IR spectroscopy, differential scanning calorimetry, and wide-angle X-ray measurement. The crystal/nematic and nematic/isotropic phase transition temperatures of polymer, which depend on the molecular weight, were observed at about 300°C and 410°C, respectively. The polymers with low molecular weights showed nematic textures above 300°C. This nematic/isotropic phase transition temperature is lower than that of poly (4-hydroxybenzoic acid). This thermal behavior of polymer comes from ether units, which increase the flexibility (the rotation or torsion of skeletal bonds) of the polymer chain. © 1994 John Wiley & Sons, Inc.