A. L. Rusanov

New aryloxy-substituted condensation polymers

Abstract Large family of new aromatic diamines containing aryloxy side groups was developed. All the diamines were obtained on the basis of 2,4,6-trinitrotoluene (TNT) — very cheap and available explosive material. TNT was converted into 1,3,5-trinitrobenzene (TNB); subsequent aromatic nucleophilic nitro-displacement reactions led to mono- and diaryloxy-substituted mono- and dinitrobenzenes which were converted into the final aryloxy-substituted diamines. Interaction of the diamines obtained with aromatic dicarboxylic acids chlorides and aromatic tetracarboxylic acids dianhydrides led to the formation of new aryloxy-substituted polyimides and polyimides combining high thermal properties with solubility in organic solvents.

Synthesis of unsaturated 7,8- and 7,9-di(hydroxymethyl)decahydro-7,8- and-7,9-dicarba-nido-undecaborate(1−) diethers

Dicarba-nido-undecaborate(1−) anions were obtained by treatment of 1,2-di(hydroxymethyl)-1,2-dicarba-closo-dodecaborane(12) diallyl ether, 1,2-di(hydroxymethyl)-1,2-dicarba-closo-dodecaborane (12), and 1,7-di(hydroxymethyl)-1,7-dicarba-closo-dodecaborane(12) with ethanolic solutions of KOH and subsequent reaction of the products with cesium and tetramethylammonium chlorides.

Formation of diamond from carbyne

Highly disperse diamond (HDD) was obtained by heating amorphous carbyne in the presence of small amounts of HDD.

Replacement of the nitro groups in 1,3,5-trinitrobenzene through the action of phenols; a general method for preparation of 3,5-dinitrophenyl aryl ethers and 5-nitroresorcinol diaryl ethers

3,5-Dinitrophenyl aryl ethers (3,5-DNPAE) and 5-nitroresorcinol diaryl ethers inaccessible yet. At the same time, these compounds may be considered, for example, to be potential pesticides 1,2 and also as the starting compounds for preparing novel monomers for polycondensation. We found a method for preparing 3,5-DNPAE based on nucleophilic substitution of a nitro group in 1,3,5trinitrobenzene (TNB) through the action of phenols containing both electron-donating and electron-withdrawing substituents in an amide type dipolar aprotic solvent* (DMF, N-methylpyrrolidone, tetramethylurea, etc.). The reaction occurs in the presence of bases (K2CO 3 is the most efficient) at 80--90 ~ over a period of 4--8 h. Using 2-naphthol and 3-pyridinol as examples we showed that not only phenols, but also other aromatic hydroxy compounds can be used. Phenols incorporating two hydroxy groups (hydroquinone, 2,2-bis(4-hydroxyphenyl)propane) can be involved in this reaction (TNB : Ar(OH)2 2 : 1). The reaction yields the corresponding bis-3,5-dinitrophenyl ethers.

Benz[4,5]Isoquino[1,2- b ]Quinazoline-7,9-Dione and a Rearrangement Product of its Hydrolysis, 2-(1,8-Naphthalenedicarboximido)benzamide

Benz[4,5]isoquino[1,2-b]quinazoline-7,9-dione, (1), C 19 H 10 N 2 O 2 , was isolated as a product of the reaction between naphthalic anhydride and anthranylamide after crystallization from dimethylformamide. Recrystallization from concentrated (95%) formic acid resulted in 2-(1,8-naphthalenedicarboximido)benzamide, (2), C 19 H 12 N 2 O 3 , as a rearrangement product of hydrolysis [alternative systematic name: 2-(1,3-dioxo-2,3-dihydro-1H-benz[de]isoquinol-2-yl)benzamide]. The two crystallographically independent molecules of (1) [(1a) and (1b)] are substantially non-planar as a result of strong intramolecular steric repulsion between their cis-arranged carbonyl groups [the O...O distances are 2.584(3) and 2.664(3)A, and the dihedral angles between the naphthalene and benzene nuclei are 8.75 (7) and 14.46 (7)°, respectively]. Molecule (2) is also sterically hindered with an approximately orthogonal orientation of the naphthalenedicarboximide and o-phenylene groups [dihedral angle 87.05 (4)°] and absence of π-conjugation between the o-phenylene and amide groups [dihedral angle 40.02 (6)°].

Synthesis and crystal structure of 1,3,5-tris [4-(phenylethynyl)phenyl]benzene

The crystal structure of 1,3,5-tris[4-(phenylethynyl)phenyl]benzene (1) has been investigated. Compound1 represents a model of the repeating unit of the most typical polyphenylene, which contains 1,3,5-trisubstituted benzene rings (chain centers) and acetylenic groups (complex-forming and cross-linking centers) in the main chain. The acetylene groups of neighboring molecules have a tendency to close mutual arrangement, which is favorable for their topochemical interaction. However, the relative conformational rigidity of molecules1 restricts not only the possibility of the optimal adjustment of the reactive sites of neighboring molecules to one another, but also hampers the close packing of molecules in the crystal, which contains channels filled by the solvent molecules (chloroform).

Selective cross-coupling of 1-ethynyl-4-iodobenzenes with activated arylacetylenes

Conditions were found for selective cross-coupling of 1-ethynyl-2,5-dihexyl-4-iodobenzene with arylethynyl-activated arylacetylenes. The reaction is not accompanied by homo-condensation of 1-ethynyl-2,5-dihexyl-4-iodobenzene.

New bis-tetraarylcyclopentadienones

Reactions of new bis(α-diketones) with 1,3-diphenylacetone resulted in new bis(tetraarylcyclopentadienones).

Novel aromatic tetracarboxylic acid dianhydrides

The Diels-Alder reactions of 4,4′-bis(2,4,5-triphenylcyclopentadienon-3-yl)benzophenone with carboxylic anhydrides containing multiple carbon-carbon bonds afforded novel tetracarboxylic dianhydrides.

Improved synthesis of bis[p-(phenylethynyl)phenyl]hetarylenes

Bis[p-(phenylethynyl)phenyl]hetarylenes were synthesized in high yields by an improved method using cross-coupling between phenylacetylene and 4,4′-dibromobenzil followed by condensation of the 4,4′-di(phenylethynyl)benzil obtained with eithero-phenylenediamine and 3,4-diaminobenzoic acid or with benzaldehyde andp-nitrobenzaldehyde in the presence of ammonium acetate.