An efficient preparation and some reactions of 2-dimethylaminomethylene-1,3-bis(dimethylimonio)propane diperchlorate

An alternative preparation of 2-dimethylaminomethylene-1,3-bis(dimethylimonio)propane diperchlorate from malonic acid is described along with its application to the synthesis of 2,4,6-trisubstituted phenols and 2-(N-(2,2-diformylethenyl)amino)pyridine.     

A direct synthesis of 1,3-bis(bromomagnesio)propane

Careful addition of 1,3-dibromopropane

to magnesium in Et₂O yields 1,3-bis(bromomagnesio)propane

which is purified via “magnesacyclobutane”

. Reactions of

with H₂O, CO₂, HgBr₂ and Me₃SnCl are reported. MgBr₂ catalyses the decomposition of

to allylmagnesium bromide

.     

New silicon-containing heterocyclic rings derived from 1, 3-bis(methyldichlorosilyl)propane

Reaction of 1,3-bis(methyldichlorosilyl)propane with alcohols gives (methylalkoxychlorosilyl)propanes. Hydrolysis of the latter with the calculated amount of water in the presence of a HCl acceptor gives 2, 6-dimethyl-2,6-dialkoxy-1-oxa-2,6-disilacyclohexanes. Hydrolysis of 1,3-bis(methyl-dichlorosilyl)propane and 1,3-bis(methylalkoxy-chlorosilyl)propane gives a tricyclic carbocyclosiloxane. A study is made of the reactions of 2, 6-dimethyl-2, 6-dialkoxy-1-oxa-2, 6-disilacyclohexane with alcohols, triethylsilanol, triethylchlorosilane, and C₆H₅MgBr.     

Gold(I) chloride adducts of 1,3-bis(di-2-pyridylphosphino)propane: synthesis, structural studies and antitumour activity

The novel water soluble bidentate phosphine ligand 1,3-bis(di-2-pyridylphosphino)propane (d2pypp) has been synthesized by a convenient route involving treatment of 2-pyridyllithium with Cl(2)P(CH(2))(3)PCl(2) and isolation in crystalline form as the hydrochloride salt. The synthesis of the precursor Cl(2)P(CH(2))(3)PCl(2) has been optimized by the use of triphosgene as the chlorinating agent. The 2 : 1 and 1 : 2 AuCl : d2pypp adducts have been synthesized and characterized by NMR spectroscopy and single crystal X-ray studies, and shown to be of the form (AuCl)(2)(mu-d2pypp-P,P') and [Au(d2pypp-P,P')(2)]Cl(.3.75H(2)O), respectively. The latter is more lipophilic than analogous 1 : 2 adducts of gold(I) chloride with the diphosphine ligands 1,2-bis(di-n-pyridylphosphino)ethane (dnpype) for n = 2, 3 and 4, based on measurement of the n-octanol-water partition coefficient (log P = -0.46). A single crystal structure determination of the 1 : 2 Au(I) complex of the 3-pyridyl ethane ligand shows it to be of the form [Au(d3pype-P,P')(2)]Cl.5H(2)O. The in vitro cytotoxic activity of [Au(d2pypp)(2)]Cl was assessed in human normal and cancer breast cells and selective toxicity to the cancer cells found. The significance of these results to the antitumour properties of chelated 1 : 2 Au(I) diphosphine complexes is discussed.     

Syntheses,crystal structures,and DNA-binding of some nickel(II) complexes of 1,3-bis(2-pyridylmethylthio)propane and pseudohalides

A series of neutral octahedral nickel(II) complexes of 1,3-bis(2-pyridylmethylthio)propane (L) and pseudohalide (X), formulated as [Ni^II(L)X₂] (where X?=?azide (1), cyanate (2), and isothiocyanate (3)), was synthesized. The complexes were characterized by physico-chemical and spectroscopic methods, and 1 and 3 also by single-crystal X-ray diffraction analyses. The structural study shows nickel in a distorted octahedral geometry comprised of the tetradentate NSSN ligand with trans pyridines and monocoordinated pseudohalides in cis positions. In dimethylformamide solution, the complexes had quasi-reversible Ni^II/Ni^III redox couples in cyclic voltammograms with E _1/2 values of +0.732, +0.747, and +0.815?V for 1, 2, and 3, respectively. To examine the biological activities of these complexes, interaction of 3 with calf thymus DNA was studied spectroscopically, showing groove-binding interaction.     

An efficient synthesis of 1,3-bis(1,4,7-triazacyclonon-1-yl)-2-hydroxypropane, [1,3-bis(TACN)-2-propanol]

Abstract

An efficient synthesis of 1,3-bis(1,4,7-triazacyclonon-1-yl)-2-hydroxypropane is described. In contrast to earlier procedures, an improved synthetic strategy led to the selection of suitable reagents and conditions that afforded the title compound in excellent overall yield with improved process efficiency and scalability. Moreover, the mildness and synthetic efficiency of the chosen conditions were particularly well-suited for the large-scale synthesis of the title compound, which is in increasing demand for a variety of applications, including the preparation of stationary phases for immobilized metal-ion affinity chromatography of recombinant proteins.     

One-pot synthesis of 1,3-bis(cytisinyl)propan-2-ol

Russian Journal of Organic Chemistry -     

2D-layered structure of coordination polymer,zinc trifluoroacetate-1,3-bis(4-pyridyl)propane

Compound [Zn(CF₃CO₂)₂(Bpp)₂], where Bpp is 1,3-bis(4-pyridyl)propane, was synthesized and its structure and luminescent properties were determined. Crystals are monoclinic, space group C2/c, a = 21.261(1) Å, b = 17.642(1) Å, c = 18.632(1) Å, β = 115.85(1)°, V = 6289.3(6) ų, ρ_calcd = 1.453 g/cm³, Z = 8. The structure comprises 2D neutral layers of conjugated multiunit rings composed of four Zn²⁺ ions united by four bridging Bpp ligands. Each of two crystallographically nonequivalent Zn atoms is coordinated at the octahedra apices to four nitrogen atoms of two Bpp ligands and two O(CF₃CO₂) atoms. Trifluoroacetate anions are coordinated to Zn²⁺ ions in monodentate manner. The compound exhibits photoluminescence in solid state.     

1,3-bis(4-pyndyl)propane complexes of divalent metal halides and pseudohalides

Summary Coordination compounds formed by the interaction of 1,3-bis(4-pyridyl)propane (DPP) with some divalent metal halides and pseudohalides have been prepared and characterized by magnetic susceptibilities, electronic and i.r. spectral measurements down to 200 cm^–1 in the solid state. The i.r. spectra indicate that DPP acts mostly as a bidentate bridging ligand in these complexes. Moreover, the two pyridyl rings which are nonplanar in uncoordinated DPP become coplanar upon coordination. Tentative stereo chemistries of the complexes have been suggested in the solid state. The ligand field parameters Dq, B, , and ₂/₁ have been calculated for the cobalt(II) and nickel(II) complexes and are consistent with the proposed stereo chemistries.     

天然产物1,3-二-(2-羟基-4-甲氧基苯基)丙烷和1,3-二-(2,4-二羟基苯基)丙烷的合成

1,3-二-(2-羟基-4-甲氧基苯基)丙烷(1)和1,3-二-(2,4-二羟基苯基)丙烷(2)是从菊叶薯蓣(Dioscorea composita Hemsl.)分离出来的天然产物, 以间苯二酚为起始原料, 分别经甲酰化和乙酰化得到2,4-二羟基苯甲醛和2,4-二羟基苯乙酮, 然后经选择性地甲基化、甲氧甲基化、羟醛缩合、还原、脱保护等步骤完成了上述两种天然产物的首次全合成. 产物通过¹H NMR, IR, MS进行了结构确证.     

Utilization of cyanoacetohydrazide and 2-(1,3-dioxoisoindolin-2-yl) acetyl chloride in the synthesis of some novel anti-proliferative heterocyclic compounds

Abstract

Owing to its high reactivity and commercial availability, 2-cyanoacetohydrazide can be utilized as a versatile and appropriate intermediate for synthesis of a broad variety of heterocyclic compounds. Thus, 2-cyanoacetohydrazide and 2-(1,3-dioxoisoindolin-2-yl) acetyl chloride were used as starting materials for construction of new heterocyclic compounds bearing 1,3-dioxoisoindoline moiety. The newly synthesized compounds were recognized by elemental analyses and spectral data (IR, ¹H-NMR, and ¹³C-NMR spectra). The synthesized compounds were screened for their anti-proliferative activity against two human epithelial cell lines; breast (MCF-7) and liver (HepG2) as well as to normal fibroblasts (WI-38). The data showed distinctly that compounds 1 and 12 presented promising in-vitro anti-proliferative activity against two cell lines (MCF-7 and HepG2) without harming normal fibroblasts.     

1,3-双(氯硅烷基)丙烷与活泼金属作用的偶联环化产物的研究

1,3-双(烃基氯硅烷基)丙烷Cl_(3-m)R_mSi(CH_2)_3SiR’_nCl_(3-n)的合成及其与水、氨(胺)、硫化氢的反应已有较详尽的报道,但与活泼金属作用的偶联环化反应则涉及较少。我们分别以钾-钠合金、金属锂对1,3-双(二烃基氯硅烷基)丙烷进行偶联环化,合成了五个新的非对称1,1,2-三甲基-2-烃基-1,2-二硅杂环戊烷类化合物(1a～     

Three Mn(II) complexes with 1,3-bis(4-pyridyl)propane and their supramolecular nets

Three complexes, [Mn(bpp)₄(H₂O)₂](ClO₄)₂?·?1.5H₂O (1), [Mn(bpp)₃Br₂]?·?2H₂O (2), and [Mn(bpp)₂(H₂O)₂](ClO₄)?·?I?·?H₂O?·?bpp (3) (bpp?=?1,3-bis(4-pyridyl)propane), were synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 is mononuclear where M(II) is coordinated to a monodentate TT-bpp, three monodentate TG-bpp, and two water molecules. Complex 2 possesses a single-stranded helical chain formed from MnN₄Br₂ octahedra by a single TT-bpp, with pendant monodentate TG-bpp ligands. Complex 3 consists of a ribbon-type double-stranded chain formed from MnN₄O₂ octahedra by double TG-bpp ligands. 2-D supramolecular architectures of 1–3 are formed by hydrogen bonds. The fluorescence of the three complexes comes from the π*–π transition of the ligand.