(E)-1-氯-6,6-二甲基-2-庚烯-4-炔的立体选择性合成

(E)-1-氯-6,6-二甲基-2-庚烯-4-炔是合成盐酸特比萘芬的关键中间体,N-氯代二异丙胺/三苯基膦与6,6-二甲基-1-庚烯-4-炔-3-醇反应,可以立体选择性地得到反式的该化合物,其反式/顺式异构体的比例达9/1,为特比萘芬提供了可工业放大生产的立体选择性合成方法。     

4-Aminopyridine Adducts of Cu(II) 2-Chloro- and 2,6-Dichlorobenzoate

Reaction products of Cu(II) 2-chlorobenzoate and 4-aminopyridine (1), and of Cu(II) 2,6-dichlorobenzoate and 4-aminopyridine (2) formulated as CuL′₂(4-apy)₂ and CuL″₂(4-apy)₂((L′ =C₇H₄ClO^? ₂,L″ =C₇H₃Cl₂O^? ₂, 4-apy = 4-aminopyridine), were prepared and characterized by structural and spectroscopic measurements, thermochemical properties and magnetic susceptibilities. Compound (1) crystallizes in the orthorhombic space group Pbca, a = 8.875(2), b = 13.236(4), c = 21.603(3) Å, V = 2537.7(10) ų, Z = 4, and the Compound (2) crystallizes in the monoclinic space group P2₁/c, a = 11.516(2), b = 8.749(2), c = 13.469(3) Å, β = 103.36(3)°, V = 1320.3(5) ų, Z = 2. Complexes (1) and (2) decomposes to gaseous products at 473 and 513 K, respectively.     

Third-order nonlinear optical properties and structures of (E)-N-(4-nitrobenzylidene)-2,6-dimethylaniline and (E)-N-(4-nitrobenzylidene)-2,3-dimethylaniline

(E)-N-(4-Nitrobenzylidene)-2,6-dimethylaniline (1) and (E)-N-(4-nitrobenzylidene)-2,3-dimethylaniline (2) have been synthesized. The crystal structures of both compounds have been defined by X-ray diffraction analysis. The maximum one-photon absorption (OPA) wavelengths recorded by quantum mechanical computations using a configuration interaction (CI) method are estimated in the UV region to be shorter than 450 nm, showing good optical transparency to the visible light. To provide an insight into the microscopic third-order nonlinear optical (NLO) properties of the investigated molecules, both dispersion-free (static) and also frequency-dependent (dynamic) linear polarizabilities (α) and second hyperpolarizabilities (γ) at λ = 825–1125 nm and 1050–1600 nm wavelength areas have been computed using time-dependent Hartree–Fock (TDHF) method. According to the ab initio calculation results, the title molecules exhibit second hyperpolarizabilities with non-zero values, implying microscopic third-order NLO behavior.     

Chemical Transformations of 4-(4-Aminophenyl)-2,6-diphenylpyrimidine

Russian Journal of Organic Chemistry - 4-(4-Aminophenyl)-2,6-diphenylpyrimidine was synthesized by reaction of (E)-1-(4-aminophenyl)-3-phenylprop-2-en-1-one with benzamidine and was involved in a...