Synthesis and structures of pyrimidinophanes containing a nitrogen atom in the bridge

Семенов, В. Э.; Nikolaev, A. E.; Galiullina, L. F.; Лодочникова, О. А.; Литвинов, И. А.; Timosheva, A. P.; Катаев, В. Е.; Efremov, Yu. Ya.; Шарафутдинова, Д. Р.; Чернова, А. В.; Latypov, Shamil K.; Резник, В. С.

doi:10.1007/s11172-006-0292-1

Cited by 6 publications

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“…The structures of other pyrimidocyclophanes incorporating a single thymine have been reported, 46 largely with macrocycle-, 47 aza- [47][48][49] and thio-methylene 47 bridges between points on the pyrimidine base. To the best of our knowledge, 21 is the first such species incorporating cytosine.…”

Section: Synthesis Of Model Siloxanes and Their Compounds With Pendan...mentioning

confidence: 99%

Biomimetic polyorganosiloxanes: model compounds for new materials

et al. 2014

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The chemistry of N-organosilylalkyl-substituted heterocyclic bases (thymine, adenine and cytosine) is described, covering the structures of model compounds, the synthesis of substituted oligo-siloxanes and a preliminary report of the synthesis of a poly(organosiloxane) with pendant N-alkyl(heterocycle) functionalities. N-Alkenylthymines CH2=CH(CH2)(n)T (T = thymine, n = 1 (1), 2 (2), 3 (3)) have been prepared and 2 hydrosilylated to form PhMe2Si(CH2)4T (5). Alternatively, 5 was prepared by reaction of PhMe2Si(CH2)4Br (6) with (O,O-SiMe3)2T, a method which has also been used to prepare PhMe2Si(CH2)4A (7) and PhMe2Si(CH2)4C (8) (A = adenine, C = cytosine). Model di- and tri-siloxanes [Br(CH2)4(Me)2Si]2O (10), Me3SiOSi(Me)2(CH2)4Br (11), PhMe2SiOSi(Me)2(CH2)4Br (12) and (Me3SiO)2(Me)Si(CH2)4Br (13) have been prepared by hydrosilylation of H2C[double bond, length as m-dash]C(H)(CH2)4Br with an appropriate hydrosiloxane and used to prepare Me3SiO(Me)2Si(CH2)4T (14), Me3SiO(Me)2Si(CH2)4A (15) (both from 11), and (Me3SiO)2(Me)Si(CH2)4T (16), (Me3SiO)2(Me)Si(CH2)4A (17) (both from 13). 10 reacts with thymine to give a mixture of the pyrimidocyclophane cyclo-T-N,N-[(CH2)4(Me)2Si]2O (19) and [T(CH2)4Si(Me)2]2O (20), while cytosine reacts similarly to form cyclo-C-N,N-[(CH2)4(Me)2Si]2O (21; as an imine) and [C(CH2)4Si(Me)2]2O (22); adenine only generates [A(CH2)4Si(Me)2]2O (18) in an analogous synthesis. Using a related protocol, polymeric {[MeSi(O)(CH2)4Br]2[Me2SiO]98}n (23) has been converted to {[MeSi(O)(CH2)4T]2[Me2SiO]98}n (24) and {[MeSi(O)(CH2)4A]2[Me2SiO]98}n (25). The structures of 4, 5, 8, 19 and 21, along with a 2 : 1 adduct of 5 with Ni(dithiobiuret)2 (9) are reported.

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Section: Synthesis Of Model Siloxanes and Their Compounds With Pendan...mentioning

confidence: 99%

Biomimetic polyorganosiloxanes: model compounds for new materials

et al. 2014

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“…4,6-Dihydroxy-and 4,6-disulfanylpyrimidine-based crown ethers [40], as well as those including a 2,4-disubstituted pyrimidine fragment [41][42][43][44], were described. Syntheses and properties of macrocycles on the basis of 4-amino-2-sulfanylpyrimidines [45][46][47][48][49][50] were extensively studied; macrocyclic compounds derived from 1,3-disubstituted uracils can DOI: 10.1134/S1070428010080191 1232 X = (CH 2 ) 3 (a), (CH 2 ) 10 also be noted as representatives of the same series [51][52][53]. Some of the synthesized macrocyclic compounds were studied as medicines: they were tested for antitumor [33,34,37] and antiproliferative activity [31,35,36], as well as for the ability to modulate H4 histamine receptor [38].…”

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Amination of 4,6- and 2,4-dichloropyrimidines with polyamines

et al. 2010

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Amination of a double excess of 4,6-dichloropyrimidine with various diamines in the presence of cesium carbonate in boiling dioxane quantitatively afforded the corresponding N, N′-bis(6-chloropyrimidin-4-yl) derivatives, while its reactions with tri-and tetraamines gave N, N′,N″-tris-and N,N′,N″,N′′′-tetrakis(6-chloropyrimidin-4-yl) derivatives. Equimolar amounts of 2,4-dichloro-or 4,6-dichloropyrimidine and diamines reacted in the presence of Pd(0) complexes to form macrocyclic compounds containing pyrimidine fragments. Catalytic reactions of 4 equiv of diamines with 4,6-dichloropyrimidine can lead to the formation of 4,6-bis-(diamino)pyrimidines. Relations between the yield and the nature of diamine and catalytic system were found.Amino-substituted pyrimidines attract interest due to their huge potential as physiologically active substances. 4-Amino-substituted pyrimidines can be obtained by nucleophilic replacement of chlorine in 4-chloropyrimidines. 4-Amino-6-chloropyrimidines are also promising intermediate products, taking into account that the halogen atom therein can be replaced by various functional groups; furthermore, such compounds can be brought into cross coupling reactions. 4-Amino-6-chloropyrimidines are readily available from 4,6-dichloropyrimidines by treatment of the latter with various amines in the absence of a catalyst [1][2][3][4]. Reactions of 4,6-dichloropyrimidines with primary and secondary acyclic and cyclic aliphatic and aromatic amines were reported; either excess amine was used as a base or triethylamine was added; the reactions were carried out in boiling propan-2-ol [5], aqueous tetrahydrofuran [6], or aqueous ethanol [7] at room temperature. Ethyl(diisopropyl)amine was also used as a base [4, 6], and amine immobilized on a solid support was used in [4]. 4-Amino-6-chloropyrimidine was synthesized by reaction of 4,6-dichloropyrimidine with aqueous ammonia at 100°C [8] or with ammonia in ethanol at 100°C [9] or in methanol at 85°C [10].Replacement of the second chlorine atom by amino group required considerably more severe conditions, e.g., heating in boiling butan-1-ol or in N, N-dimethylacetamide [11, 12]; microwave activation was used to improve the yield of diamination products [13,14]. reported on the diamination in ethanol at 80°C. 4,6-Diaminopyrimidine derivatives were studied as inhibitors of protein kinase [16][17][18][19] and other kinases such as CHK1 [20], lymphocytespecific tyrosine kinase [21,22], Janus kinases [23], and VEGFR-2 kinase [8,24], as well as cannabinoid CB1 receptor ligands [25]. 4,6-Diaminopyrimidines were also tested as medicines for prophylactics and treatment of disbolism [26], MCH antagonists for the treatment of disorders of central nervous system [27], and 5-HT7 receptor ligands [28]. 4,6-Bis(imidazolio)-pyrimidine was examined as a receptor for halide ions (Cl -, Br -, and I -) [29].Up to now, some macrocyclic compounds containing a pyrimidine fragment have been reported. Macrocycles based on 4,6-diaminopyrimidine [30-32] and 2,4-diaminopyrimid...

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