Yu. G. Trishin

Synthesis of Substituted 4,5,8,7-Tetrafluorobenzo[d]-λ5-phospholes

The reactions of diethyl pentafluorophenylphosphonite and ethyl bis(pentafluorophenyl)phosphinite with activated alkynes proceed as two-stage cycloaddition processes and lead to formation of sufficiently stable heterocyclic fused fluorophosphoranes. Hydrolysis of the latter is accompanied by cleavage of the exocyclic P-O bond and formation of substituted 4,5,6,7-tetrafluorobenzo[d]-λ5-phospholes, previously uknown bicyclic phosphorus-containing compounds.

Formation of substituted pyrazolines in the reaction of C, N-diphenylnitrilimine with a zwitterion derived from triisopropylphosphine and ethyl 2-cyanoacrylate

The reaction of C,N-diphenylnitrilimine with a P-zwitterion derived from Pri3P and H2C=C(CN)CO2Et afforded the first representative of 2-pyrazolines containing the phosphonium group and products of the addition of nitrilimine to Pri3P and H2C=C(CN)CO2Et. The reaction of the P-zwitterion with C-4-nitrophenyl-N-phenylnitrilimine gave rise to a condensation product of one Pri3P molecule and two nitrilimine molecules. The three-dimensional structures of the compounds synthesized were established by X-ray diffraction analysis.

Reaction of Pentafluorophenyl(diphenyl)phosphine with Nitrilimines

Reaction of pentafluorophenyl(diphenyl)phosphine with nitrilimines is a multistep process leading to formation of unstable fused heterocycles with a fluorophosphorane moiety as primary products. Their hydrolysis involves opening of the heteroring and subsequent cleavage of the N-N bond in intermediate phosphorylated hydrazones. The final products are diphenyl(6-arylamino-2,3,4,5-tetrafluorophenyl)phosphine oxides.

Cyclocondensation of ethylenediamine with acetone and methyl ethyl ketone as a synthetic route to 14-membered azamacrocyclic compounds

Abstract14-Membered azamacrocyclic compounds, substituted 1,4,8,11-tetraazacyclotetradeca-4,11-diene and 1,4,8,11-tetraazacyclotetradeca-4,14-diene containing azomethine cycle and amine nitrogen atoms, were obtained as a mixture of trans- and cis-isomers by reacting ethylenediamine with acetone and methyl ethyl ketone. More stable trans-isomers were isolated individually by vacuum distillation.

Addition of trifluoroacetic acid to (R)-(+)-Limonene in the presence of Mo2(OOCCF3)4

Addition of trifluoroacetic acid to alkenes proceeds readily according to the Markovnikovs rule, which allows preparation of the corresponding trifluoroacetates. Thus, the reaction of propylene with trifluoroacetic acid led to the formation of isopropyl trifluoroacetate with a yield of ~100% [1]. Similarly limonene I added trifluoroacetic acid at 20–30°C in toluene or cyclohexane at exocyclic C=C bond to form α-terpinyl trifluoroacetate II [2–4], while the other, endocyclic C=C bond, was not involved into the reaction (Scheme 1). At the same time, in the presence of molybdenum(II) trifluoroacetate dimer, Mo2(OOCCF3)4, the reaction of trifluoroacetic acid with propylene proceeded against the Markovnikov’s rule to afford n-propyl trifluoroacetate with 90–100% selectivity [5]. Accordingly, it is presumable that in the presence of Mo2(OOCCF3)4 the reaction of limonene with trifluoroacetic acid would yield 2-(4-methylcyclohex-3-en-1-yl)propyl trifluoroacetate III, hydrolysis of which would lead to terpene alcohol IV (Scheme 2). DOI: 10.1134/S1070363214120196

Synthesis of azamacrocyclic compounds by cyclocondensation of aliphatic α,ω-diamines with acetone

Cyclocondensation of 1,4-diaminobutane and 1,6-diaminohexane with acetone afforded the corresponding 18- and 22-membered trans-azamacrocyclic Curtis compounds in high yield, which contain two azomethine and amine nitrogen atoms. A complex mixture of the products formed containing less than 25% of 16-membered azamacrocyclic cis- and trans-isomers when reacting 1,3-diaminopropane with acetone.

Synthesis of tricyclic spirophosphoranes via reaction of 2-(4,5-dihydrofuran-3-yl)-N-phenyl-1,3,2-oxazaphospholidine with C,N-diarylnitrile imines

Unique tricyclic compounds with a five-coordinate phosphorus atom shared by three rings, 7-aryl-3′,5-diphenyl-3,5-dihydro-2H-spiro[1,2-oxaphospholo[2,3-d][1,2,4]diazaphosphinine-8,2′-[1,3,2]oxazaphospholidines], have been synthesized for the first time via reaction of 2-(4,5-dihydrofuran-3-yl)-3-phenyl-1,3,2-oxazaphospholidine with C,N-diarylnitrile imines. Presumably, these compounds are formed via a three-step process including generation of P+-C=N-N− dipolar ion, intramolecular N−→C= cyclization with simultaneous opening of the dihydrofuran ring, and closure of oxaphospholane ring.

First example of phosphorylation of macrocyclic azomethine with secondary phosphine oxides

Macrocyclic azomethines are classical host molecules of supramolecular systems [1]. Broad prospects for their use in this capacity have resulted from the development of template-free methods of the synthesis of such compounds [2]. In the last decade, the compounds with different ring sizes, various number of the C=N bonds, structure of hydrocarbon moiety (aliphatic, cycloaliphatic, or aromatic) in the ring have been obtained.

Synthesis and molecular structure of [2,3,4,5-tetrafluoro-6-(p-methoxyphenylamino)phenyl]diphenylphosphine

The reaction of (pentafluorophenyl)diphenylphosphine with C-ethoxycarbonyl-(p-methoxyphenyl) nitrile imine was used to synthesize [2,3,4,5-tetrafluoro-6-(p-methoxyphenylamino)phenyl]diphenylphosphine oxide whose reduction with trichlorosilane gave [2,3,4,5-tetrafluoro-6-(p-methoxyphenylamino)phenyl] diphenylphosphine, the first representative of tertiary ortho-arylamino-substituted arylphosphines. According to X-ray diffraction data, the principal steric characteristics of the phosphine are close to those known for triarylphosphines.

Reactions of 2-(2-chloro-4,5-dihydro-3-furyl)-1,3-diphenyl-1,3-diaza-2λ3-phospholidine with nitrile imines

The multistep reactions of 2-(2-chloro-4,5-dihydro-3-furyl)-1,3-diphenyl-1,3-diaza-2λ3-phospholidine with nitrile imines afforded phosphorus-containing spiro compounds of a new type, viz., 6,8-disubstituted 9-oxo-10-(2-chloroethyl)-1,4-diphenyl-1,4,7,8-tetraaza-5-phosphaspiro[4.5]-deca-6,10-dienes.