Trisubstituted 1,3,5-triazines 3. Synthesis of substituted 2,4,6-tris(hydroxyiminomethyl)-1,3,5-triazines

Previously undescribed substituted 2,4,6-tris(hydroxyiminomethyl)-1,3,5-triazines, including 2,4,6-(1,3,5-triazinetriyl)trinitrolic acid, have been synthesized.For Communication 2, see [1].N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 117913. Institute of Chemical Physics in Chernoglovka, Chernoglovka, Moscow Oblast, 142432, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 76–78, January, 1999.     

Isomerism in metal complexes of 1,3,5-diazaphosphorinanes. Synthesis,crystal and molecular structure of conformers ofcis-bis(1,3,5-triphenyl-1,3,5-triazaphosphorinane)dichloroplatinum(II)

The crystal and molecular structures were determined for two individual conformers ofcis-bis(1,3,5-triphenyl-1,3,5-diazaphosphorinane)dichloroplatinum(II) differing in the rotation of the heterocyclic ligand planes around the P-Pt bond and in the orientation of the substituents at the phosphorus atoms in the ligands.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1650–1655, September, 1993.     

Synthesis of 1,3,5-tris-(2-benzoylvinyl)benzene

Conclusions A method was proposed for the synthesis of 1,3,5-tris-(2-benzoylvinyl)benzene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2613–2614, November, 1975.     

Preparation of 16-substituted 3-hydroxyestra-1,3,5(10)-triene-17-ones starting with the bromination of estrone acetate

The bromination of estrone acetate (Ia) leads to a mixture of acetates of 16-bromo-16-bromo-, and 16,16-dibromoestrone (IIa, IIIa, and IVa) in a ratio of 63:28:9. On treatment with an aqueous methanolic solution of potash, depending on the conditions, a mixture of (IIa) and (IIIa) gives 3,16-dihydroxyestra-1,3,5(10)-trien-17-one (V) or 3,17-dihydroxyestra-1,3,5(10)-trien-16-one (VI). When 5 g of (Ia) was brominated with 2.8 g of Br₂ in chloroform and the products were chromatographed on silica gel, 0.36 g of (IVa), C₂₀H₂₂Br₂O₃, mp 165–166°C (from ether) 0.37 g of (IIIa), mp 169–170.5°C, 4.6 g of a mixture of (IIa) and (IIIa), 30 mg of (Ia) and 0.2 g of a mixture of 16- and 16-bromoestrones was obtained. The action of potash on a mixture of (IIa) and (IIIa) in aqueous MeOH at 20°C led to the epimerization of the (IIa) into (IIIa) and then the conversion of the latter into (V) with mp 203.5–206°C; diacetate with mp 172–173°C (acetone-ethanol). Similarly, but with heating (98°C, 3 h), a mixture of (IIa) and (IIIa) was converted into (VI), with mp 234–236°C. Characteristics of the IR and PMR spectra of the compounds obtained are given.S. Ordzhonikidze All-Union Scientific-Research Institute of Pharmaceutical Chemistry, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 465–469, July–August, 1983.     

Influence of a substituent at C3 on the direction of bromination of estra-1,3,5(10)trien-17-ones

The influence of a C₃ substituent on the direction of bromination of estra-1,3,5 (10)-trien-17-one is discussed: Estrone and its methyl ether give mainly derivatives bromine-substituted in ring A, while the bromination of estrone acetate leads to the production of 16-mono- and 16,16,dibromo-substituted estrones.A. Ordzhonikidze All-Union Scientific-Research Institute of Pharmaceutical Chemistry, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 327–330, May–June, 1984.     

Insertion of Ethyl Isocyanate at the Tungsten–Chlorine Bond. Crystal Structure of 1,3,5-Triethyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione

The reaction of tungsten hexachloride with excess ethyl isocyanate in dichloroethane leads to the insertion of three ligand molecules at one of the tungsten–chlorine bonds. The data of elemental analysis and IR spectroscopy confirm that the thermolysis of the reaction mixture affords the WCl₄(L₃Cl) complex (I), where L = –N(Et)C(O)–. The structure of the chain of inserted molecules in I is established on the basis of IR and NMR data, and the results of X-ray diffraction analysis of crystals of an organic product (II) of the hydrolysis of I. According to the latter, compound (II) is a derivative of s-triazine—1,3,5-triethyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.     

Photochemical formation of [4.4.4](1,3,5)cyclophanes from 1,3,5-tris(3-phenylpropenoyl)benzenes

Irradiation of 1,3,5-tris(3-phenylpropenoyl)benzene (1a) yields in solution a dimer 2a by a threefold head-to-head/anti [2π+2π]cycloaddition. The stereochemistry of this [4.4.4](1,3,5)cyclophane was determined by ¹H and ¹³C NMR studies including NOE measurements and a calculation of the AA′MM′ spin pattern of the methine protons. In contrast to the solution photochemistry, which is presumably controlled by the arrangement of an excimer, the irradiation in the crystalline state leads by a topochemical control to a dimer 3a, which contains a single four-membered ring.     

Trisubstituted 1,3,5-triazines. 4. Synthesis of 2-nitroamino-4,6-bis(trinitromethyl)-1,3,5-triazine

The nitration, at the amino group, of 2-amino-4,6-bis(trinitromethyl)-1,3,5-triazine and its derivatives has been studied.For Communication 3, see [1].n. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 117913. Institute of Chemical Physics in Chernoglovka, Chernoglovka, Moscow Oblast, 142432, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 79–81, January, 1999.     

Complexes of 1,3,5-triphenyl-1,3,5-diazaphosphorinane with Pt(II), Co(II), Ni(II), AND Cu(I) salts

1,3,5-Triphenyl-1,3,5-diazaphosphorinanes form 21 complexes with Pt(II), Co(II), Ni(II), and Cu(I).³¹P NMR spectroscopy indicated that Pt, Co, and Ni are coordinated at the phosphorus atoms, while Cu(I) is coordinated at the nitrogen atoms.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 209–211, January, 1991.     

Synthesis of 18,19-bisnor-δ1,3,5(10),13(17)-pregnapentaen-3-ol-20-one methyl ethek

Conclusions A method was developed for the synthesis of S-methoxy-^{1,3,5(10),13(17)}-D-homoestrapentaen-Ha-one, from which it was possible to obtain 3-methoxy-18,19-bisnor-_{1,3,5(10),13(17)}-pregnapentaen-20-one, a key compound in the total synthesis of 18-cyanosteroids.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1844–1848, August, 1973.     

Geometric structure of molecule of 1,3,5-trinitro-1,3,5-triazacyclohexane in the gas phase

M. V. Lomonosov Moscow State University. Translated from Zhurmal Strukturnoi Khimii, Vol. 33, No. 1, pp. 41–45, January–February, 1992.     

(1,3,5-C3P3H3)M与(1,3,5-C3P3H3)2M (M=Ti,V, Cr)配合物的结构与芳香性

运用密度泛函理论研究了(1,3,5-C3P3H3)M和(1,3,5-C3P3H3)2M (M=Ti,V,Cr)的结构、键合能以及芳香性.结果表明:低自旋的(1,3,5-C3P3H3)M和(1,3,5-C3P3H3)2M基态结构分别具有C3v和D3h对称性.金属与配体间为共价作用,二者之间存在σ、π和σ三种成键方式.V的三明治配合物的解离方式与Ti和Cr的三明治配合物不同,前者为分步解离,后两者则为一步解离.其中(1,3,5-C3P3H3)2Cr(D3h)的第一解离能最大,配合物最稳定.这些三明治和半三明治配合物都具有中心芳香性、内芳香性和外芳香性,且中心芳香性均大于自由配体(1,3,5-C3P3H3)的中心芳香性,芳香性主要贡献来源于π键和金属原子的孤对电子.内芳香性按照Ti、V、Cr的顺序依次增大,且内芳香性明显要大于外芳香性.高自旋的半三明治(1,3,5-C3P3H3)Ti(C3,5A1)与单重态(1,3,5-C3P3H3)Ti (C3v,1A1)相比,配体的变形性增大,稳定性增加,且C平面中心芳香性和内芳香性均增大,但P平面的中心芳香性却降低.     

Cyclization of 3-methoxy-Δ1,3,5,(10)-8,14-secoestratriene-14,17-dione

Conclusions Depending on the conditions, 3-methoxy-^1,3,5(10)-8,14-secoestratriene-14,17-dione (III) under the influence of acid agents is cyclized to estradiol, equilenol, 18-norequilenane, and cyclopentanophenanthrene derivatives. As a result, the spatial factor determines the course of the reaction even if the ⁹⁽¹¹⁾-double bond, which activates the H atoms at C₇, is absent.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1628–1632, July, 1973.     

Synthesis of acylated (2′-hydroxyethyl)amino- and (2′-aminoethyl)amino-1,3,5-triazines

The acylation of (2-hydroxyethyl)amino-1,3,5-triazines with chloroacetyl chloride with subsequent reaction of the resulting (2-chloroacetoxyethyl)aminotriazines with potassium thiocyanate is described. Acylated derivatives of substituted (2-aminoethyl)aminotriazines were obtained by the reaction of the chlorotriazines with monoacylethylenediamines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 260–263, February, 1982.     

Synthesis of 1,3,5-triazine derivatives on the basis of carboxylic acid imino esters (review)

Data on methods for the synthesis of 1,3,5-triazine derivatives by cyclotrimerization and cyclocondensation reactions with the participation of carboxylic acid imino esters are systematized in the review.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No.12, pp. 1587–1605, December 1992.     

Crystal Structures and Packing of 2,4,6-tris(4-Fluorophenoxy)-1,3,5-triazine and 2,4,6-tris(3,4-Dimethylphenoxy)-1,3,5-triazine. New Materials for Octupolar Nonlinear Optics

The crystal structures and packing of 2,4,6-tris(4-fluorophenoxy)-1,3,5-triazine and 2,4,6-tris(3,4-dimethylphenoxy)-1,3,5-triazine are discussed. These structures have been determined as a continuation of a series of octupolar NLO materials we have been investigating. The crystal structures are characterized by C–H...F and C–H... hydrogen bonds, respectively. A characteristic of these triazine structures is the presence of dimeric Piedfort Units (PU) that are extended into more elaborate two-dimensional (2-D) networks. The structure of the fluoro derivative is compared with that of the corresponding unsubstituted and chloro/bromo-substituted derivatives. The structure of the dimethyl triazine is compared with that of the corresponding 4-methyl derivative. The noncentrosymmetric nature of the dimethyl derivative was confirmed by a powder SHG signal at 1.064 m of the order of 0.5 × KDP. Interestingly, the dimethyl derivative studied here is isostructural with the corresponding 4-methyl triazine. This H/Me isostructurality is shown to be an uncommon phenomenon by an analysis with the CSD.     

Three copper(II) complexes constructed from a new 1,3,5-triazine derivative ligand

Three new complexes {[Cu(dpdapt)(Hhbd)] · 6H₂O}_n (1) (dpdapt = N,N′-di(2-pyridyl)-2,4-diamino-6-phenyl-1,3,5-triazine, Hhbd = 2-hydroxybutanedioicate dianion), [Cu(dpdapt)(SO₄)] · 2H₂O (2) and [Cu(dpdapt)(oxa)] · H₂O (3) (oxa = oxalate dianion) have been synthesized and structurally characterized. The non-covalent interactions of π–π stacking and hydrogen bonding extend complexes 1–3 into supramolecular architectures, where 1 self-assembles into a 1D polymeric chain by dicarboxylate bridges and exhibits a 3D framework with 1D open channels, while complexes 2 and 3 display 2D wavelike networks. Interestingly, in 1, the host framework encapsulates hexameric water clusters that are connected into 1D arrays by supramolecular association along the 1D open channels. The UV/vis, IR spectra, fluorescence and TG analysis for complexes 1, 2 and 3 are also discussed.     

1,3,5-Trimethyl- und 1,3,5-Tri[methyl(d3)]borazinderivate

Zusammenfassung Es wurden mehrere neue N-Trimethyl- und N-Tris(trideuteromethyl)borazinverbindungen dargestellt und mit bereits bekannten Derivaten verglichen. Die IR-Spektren werden ausführlich diskutiert.

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Several new N-trimethyl- and N-tris(trideuteromethyl)borazines have been prepared and their properties studied together with those of known compounds in this class. A detailed discussion of the IR-spectra is given.

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