I. R. Golding

Reactions of distabilized β-dicarbonyl sulfonium and iodonium ylides with isocyanates

The reactions of tosyl isocyanate with diethyl diphenylsulfuranylidenemalonate, 2-dimethylsulfuranylidenedimedone, and 2-dimethylsulfuranylideneindane-1,3-dione afforded 1,3-ditosyl-5,5-diethoxycarbonylimidazolidine-2,4-dione and tosylimination products at the keto groups, respectively. Phenyliodonium ylides derived from diethyl malonate and ethyl acetate react with 3,4-dichlorophenyl isocyanate to form substituted oxazolin-2-ones.

Molecular and crystal structure of 2-cyano-(2E)-pentadien-2,4-oic acid and ethyl-2-cyano-(2E)-pentadien-2,4-oate

X-ray study of 2-cyano-(2E)-pentadien-2,4-oic acid (1) and its ethyl ester (2) showed that the molecules of1 and2 in the crystalline phase form stacks by translating along the shortest crystallographic axis. The nature of the intermolecular interactions favoring the formation of such β-structures was analyzed within the framework of the Bader topological theory. Possible routes of topochemical reactions of compounds1 and2 are considered.

Reactions of isocyanates with compounds containing active methylene groups in the presence of triethylamine

Compounds containing active methylene groups react with isocyanates of different structures in the presence of triethylamine to form functionally substituted amides.

N-substituted amides of 2-cyanopenta-2E,4-dienoic acid

N-Substituted amides of 2-cyanopenta-2E,4-dienoic acid were synthesized by condensation ofN-substituted cyanoacetamides with acrolein in a dioxane-DMSO solution in the presence of Zn(OAc)2·2H2O as a condensing agent. X-ray diffraction study of 3-methylanilide of 2-cyanopenta-2E,4-dienoic acid (2d) demonstrated that the crystal structure of this compound is similar to that of 2-cyanopenta-2E,4-dienoic acid studied previously. However, the presence of themeta-tolyl substituent in molecule2d apparently results in the fact that the β-structure, which is typical of 2-cyanopenta-2E,4-dienoic acid, does not exist in the crystalline phase of2d.

Complexes of copper(I) halides with bis (trimethylsilyl) acetylene

Conclusions1.The authors have synthesized 1∶1 complexes of bis (trimethylsilyl) acetylene with copper(I) chloride and bromide, and investigated their vibrational spectra.2.Using x-ray diffraction analysis they have determined the dimer structure of the complex [(Me3SiC≡CSiMe3)·CuCl]2.

Reactivity of esters of 2-cyanoacrylic acid toward some free radicals

The rate constants for the addition of ·CH(Ph)CH2CCl3, ·CH2Ph, ·CH2Prn, and ·CCl3 radicals to the ethyl 2-cyanoacrylate molecule were determined by ESR spectroscopy using the spin trapping technique.

2-cyanopenta-(2E,4)-dienoic acid and its amide

Knoevenagel condensation of acrolein with NCCH2COOK or NCCH2CONH2 in 1M aqueous solutions of K and Na phosphates gave 2-cyanopenta-(2E,4)-dienoic acid and its amide, respectively.

Synthesis and X-ray structural investigation of 1,3,5-tris[4-(2-propynyloxy)phenyl]benzene

Synthesis and X-ray structural investigation of 1,3,5-tris[4-(2-propynyloxy)phenyl]benzene (1) were carried out. Compound1 is a trifunctional monomer for the synthesis of cross-linked polymers and a model of a section of polymeric network of this kind. In a crystal, the molecule of1 is located on the threefold symmetry axis and has a propeller-like conformation (the dihedral angle between the central and peripheral benzene rings is ∼35°). An essential feature of the crystal structure of1 is the proximity of the ethynyl groups of the neighboring molecules, which may be favorable to cyclotrimerization in the crystal. The spatial prerequisite to this process is the simultaneous rotation of the neighboring molecules1 about their symmetry axes by ∼10°. The displacements of the atoms in the reacting groups should amount to ∼1.6–1.8 Å.

Complexes of cuprous phenylacetylenide with phosphorous acid amides

Complexes of cuprous phenylacetylenide (CPA) were obtained with various amides of phosphorous acid, which are cubane-like tetramers (PhC=CCuL)4. Copper is coordinated at the phosphorus atom in these complexes. The coordination shift of the ligands in the31P NMR spectra are directly dependent on the electronegativity of the heteroatoms at phosphorus.

Crystal Structure of N-Propargylcarbazole and N-(3-lodopropargyl)carbazole

Abstract An X-ray study of N-propargylcarbazole (I) and N-(3-iodopropargyl)carbazole (II) has been carried out. In the crystal II acetylenic groups form zigzag ladder-like infinite motives extended along the b axis. The motives are characterized by alternation of more close (and capable, in principle, of topochemical dimerization in crystal) and more distant pairs of acetylenic groups. A hypothetical possibility of topochemical polymerization in crystal II under uniaxial compression with formation of the ordered trans-polyacetylene is considered.