Reaction of trihalo(phenylenedioxy)phosphoranes with acetylenes: X. specific features of the reactions of substituted 2,2,2-trichloro-1,3,2λ5-benzodioxaphospholes with 3-chloro(bromo, iodo)propynes

It was shown for the first time that 3-chloro-, 3-bromo-, and 3-iodopropynes can react with 2,2,2-trichloro-, 2,2,2-trichloro-5-methyl-, and 5,6-dibromo-2,2,2-trichloro-1,3,2λ⁵-benzodioxaphospholes to give derivatives of 4-(halomethyl)-2-chloro-2H-1,2λ⁵-benzoxaphosphinin-2-ones. The reaction involves nonselective chlorination of the phenylene substituent in different positions, and the resulting isomer ratio is temperature-dependent. In the reactions of 3-bromo-and 3-iodopropynes with 2,2,2-trichloro-1,3,2λ⁵-benzo-dioxaphosphole, a side process takes place, viz. nucleophilic substitution of bromine and iodine with chlorine. The structure of some of the prepared 4-(chloromethyl)-1,2-benzoxaphosphinines was studied by means of X-ray diffraction.     

Reactions of Arylenedioxytrihalophosphoranes with Acetylenes: XV.<Superscript>1</Superscript> Reaction of 2,2,2-Tribromo-4,6-di-<Emphasis Type="Italic">tert</Emphasis>-butylbenzo-1,3,2λ<Superscript>5</Superscript>-dioxaphospholedioxaphosphole with Pent-1-yne

2,2,2-Tribromo-4,6-di-tert-butylbenzo-1,3,2λ⁵-dioxaphospholedioxaphosphole reacted with a terminal alkyne, pent-1-yne, to give a mixture of two isomeric 1,2-benzoxaphosphinine derivatives, 6,8- and 5,7-di-tert-butyl-2-bromo-4-propylbenzo-1,2λ⁵-oxaphosphinin-2-oxides, at a ratio of 5.9: 1. The regioselectivity of substitution of oxygen in the dioxaphosphole fragment by carbon differs from that observed previously in the reaction with 4,6-di-tert-butyl-2,2,2-trichlorobenzo-1,3,2λ⁵-dioxaphosphole: the minor isomer was formed as a result of substitution of the oxygen atom in the ortho position with respect to one tert-butyl group of the initial phosphole.     

Formation of cage phosphonate via hydrolysis of 2-(5-methyl-2-phenyl-2<Emphasis Type="Italic">H</Emphasis>-1,2,3-diazaphosphol-4-yl)-1,5-dioxo-4-trifluoromethyl-4-ethoxycarbonylbenzo[<Emphasis Type="Italic">f</Emphasis>]-1,3,2-dioxaphosphepine

A new approach to obtaining of caged bicyclic phosphonate, 4-hydroxy-3-trifluoromethyl-3-ethoxycarbonyl-8-(1-phenylhydrazonoethyl)-5,6-benzo-2,7,1-dioxaphosphabicyclo[3.2.1^1.5]octane, based on hydrolysis of 2,5-dioxobenzo[f]1,3,2-dioxaphosphepine derivative bearing 5-methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl substituent at the phosphorus was developed. The hydrolysis process includes elimination of P(II) atom and intramolecular cyclization involving endocyclic carbonyl group of the phosphepine. Structure of the caged phosphonate was established by NMR and XRD methods.     

Nitropyrazoles: XII. Transformations of the 4-Methyl Group in 1,4-Dimethyl-3,5-dinitropyrazole and Cyclization of the Transformation Products

A preparative procedure for the synthesis of 1,4-dimethyl-3,5-dinitropyrazole by nitration of 1,4-dimethylpyrazole was developed. The reaction of 1,4-dimethyl-3,5-dinitropyrazole with dimethoxymethyl- (dimethyl)amine (N,N-dimethylformamide dimethyl acetal) gave (E)-N,N-dimethyl-2-(1-methyl-3,5-dinitropyrazol- 4-yl)ethenylamine. Acid hydrolysis of the latter afforded (1-methyl-3,5-dinitropyrazol-4-yl)acetaldehyde, and the reaction with sodium nitrite in hydrochloric acid led to formation of 2-hydroxymino-2-(1-methyl- 3,5-dinitropyrazol-4-yl)acetaldehyde. The corresponding O-methyloxime and phenylhydrazone reacted with K₂CO₃ to give 6-methyl-4-nitropyrazolo[4,3-d]isoxazole-3-carbaldehyde O-methyloxime and 1-methyl-3-nitro-4-(2-phenyl-2H-1,2,3-triazol-4-yl)pyrazol-5-ol, respectively. Treatment of (1-methyl-3,5-dinitropyrazol-4-yl)-acetaldehyde with benzenediazonium chloride gave (1-methyl-3,5-dinitropyrazol-4-yl)acetaldehyde phenylhydrazone which underwent intramolecular cyclization with replacement of the 5-nitro group by the action of K₂CO₃ in acetonitrile; in the reaction with K₂CO₃ in ethanol, the 5-nitro group was replaced by ethoxy.     

Stereochemistry of organophosphorus cyclic compounds—II : Stereospecific synthesis of cis- and trans 2-halogeno-2-oxo-4-methyl-1,3,2-dioxaphosphorinans and their chemical transformations

cis- and trans-2-Chloro-2-oxo-4-methyl-1,3,2-dioxaphosphorinans have been obtained by stereospecific reactions of diastereomerically pure 2-methoxy-4-methyl-1,3,2-dioxaphosphorinans or 2-hydrogen-2-oxo-4-methyl-1,3,2-dioxaphosphorinans with chlorine and sulphuryl chloride, respectively. Similarly, the action of the corresponding brominating agents on isomeric phosphites and phosphonates afforded pure cis- and trans-2-bromo-2-oxo-4-methyl-1,3,2-dioxaphosphorinans. It has been shown that halogenolysis proceeds with retention of configuration at the P atom. On the basis of the ¹H- and ³¹P-NMR spectra conformation of the halogenoanhydrides obtained has been discussed briefly.It has been also found that model nucleophilic substitution reactions occur with inversion of configuration at the P atom in the cyclic halogenoanhydrides.     

Chiral cyclohexene block from <Emphasis Type="Italic">R</Emphasis>-(−)-carvone

The oxidation with SeO₂ of a methyl group linked to an sp²-hybridized carbon in the product of the intramolecular iodoetherification of cis-carveol afforded (1R,5R,7S)-7-iodomethyl-7-methyl-6-oxabicyclo[3.2.1]-oct-3-en-4-carbaldehyde and [(1R,5R,7S)-7-iodomethyl-7-methyl-6-oxabicyclo[3.2.1]oct-3-en-4-yl]methanol that were oxidized to methyl (1R,5R,7S)-7-iodomethyl-7-methyl-6-oxabicyclo[3.2.1]oct-3-en-4-carboxylate. The latter by the Zn-promoted opening of the γ-oxide ring was converted into the target chiral block, methyl (4R,6R)-6-hydroxy-4-(prop-1-en-2-yl)cyclohex-1-encarboxylate.     

Lead tetraacetate assisted formation of bis(acetoxy)acetic acid derivative from carvone

R-Carvone on heating with Pb(OAc)₄ in benzene gives (2RS)-2-hydroxy-2-[(1S)-4-methyl-5-oxocyclohex-3-en-1-yl)]-prop-1-yl bis(acetoxy)acetate. Alkaline hydrolysis of this compound affords the corresponding diol which under acidic catalysis is transformed into bis-hydroxy ether and 1,4-dioxane derivatives.     

Regioselectivity in the reactions of <Emphasis Type="Italic">N</Emphasis>-(polychloroethylidene)-sulfonamides with 1<Emphasis Type="Italic">H</Emphasis>-pyrrole and 1-methyl-1<Emphasis Type="Italic">H</Emphasis>-pyrrole

N-(2,2,2-Trichloroethylidene)arenesulfonamides react with 1H-pyrrole and 1-methyl-1H-pyrrole to give the corresponding N-[2,2,2-trichloro-1-(1H-pyrrol-2-yl)ethyl]arenesulfonamides. The reaction of N-(2,2,2-trichloroethylidene)trifluoromethanesulfonamide with pyrrole leads to a mixture of 2-mono-and 2,5-disubstituted pyrroles, whereas in the reaction with 1-methyl-1H-pyrrole only the 2-substituted compound is formed. N-(2,2-Dichloro-2-phenylethylidene)-4-methylbenzenesulfonamide reacts with 1H-pyrrole to form N-[2,2-dichloro-2-phenyl-1-(1H-pyrrol-2-yl)ethyl]-4-methylbenzenesulfonamide, and its reaction with 1-methyl-1H-pyrrole gives a mixture of 2-and 3-monosubstituted derivatives. The results of quantum-chemical calculations of the initial reactants and products indicate that the process is orbital-controlled. A good agreement is observed between the experimental data and theoretical conclusions concerning the dependence of the reaction regioselectivity on the nature of substituents in the electrophile molecule.     

Azolyl-substituted 1,2,3-triazoles

Huisgen reaction of (E)-1,5-diarylpent-2-en-4-yn-1-ones and (E)-1,5-diarylpent-1-en-4-yn-3-ones afforded 1-aryl-3-(5-aryl-1H-1,2,3-triazol-4-yl)prop-2-en-1-ones and 3-aryl-1-(5-aryl-1H-1,2,3-triazol-4-yl)-prop-2-en-1-ones, respectively. (E)-1-Aryl-3-(5-phenyl-1H-1,2,3-triazol-4-yl)prop-2-en-1-ones reacted with hydrazine hydrate and phenylhydrazine to give 72–93% of 4-(3-aryl-4,5-dihydro-1H-pyrazol-5-yl)-5-phenyl-1H-1,2,3-triazoles which underwent dehydrogenation on heating in boiling acetic acid with formation of the corresponding pyrazole derivatives. The molecular structures of (E)-3-phenyl-1-(5-phenyl-1H-1,2,3-triazol-4-yl)prop-2-en-1-one and 4-[3-(4-methylphenyl)-1-phenyl-4,5-dihydro-1H-pyrazol-5-yl]-5-phenyl-1H-1,2,3-triazole were studied by X-ray analysis. 4-(3-Aryl-4,5-dihydro-1H-pyrazol-5-yl)-5-phenyl-1H-1,2,3-triazoles showed toxicity against Daphnia magna.     

Synthesis and steric structure of 3,4-dimethyl-2-(3-methyl-1-phenylbuta-1,2-dienyl)-5-phenyl-1,3,2λ<Superscript>5</Superscript>-oxazaphospholane 2-oxide

Allenic 1,3,2-oxazaphospholanes on the basis of d-pseudoephedrine were synthesized. The steric structure of 3,4-dimethyl-2-(3-methyl-1-phenylbuta-1,2-dienyl)-5-phenyl-1,3,2λ⁵-oxazaphospholane 2-oxide was determined by X-ray diffraction.     

Features of Reaction of 2-(5-Methyl-2-phenyl-2<Emphasis Type="Italic">H</Emphasis>-1,2,3-diazaphosphol-4-yl)-4<Emphasis Type="Italic">H</Emphasis>-benzo[<Emphasis Type="Italic">e</Emphasis>]-1,3,2-dioxaphosphorin-4-one with 1,2-Dicarbonyl Compounds

2-(5-Methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl)-4H-benzo[e]-1,3,2-dioxaphosphorin-4-one reacts with perfluorodiacetyl, 3,6-di(tert-butyl)-1,2-benzoquinone and phenanthrenequinone only with the participation of a three-coordinated phosphorus atom to form spirophosphoranes containing acyclic 5-methyl-2- phenyl-2H-1,2,3-diazaphosphol-4-yl substituent, whereas the interaction with tetrachloro-1,2-benzoquinone proceeds via expanding the six-membered heterocycle to the nine-membered one to form 2-(2-phenyl-2H-1,2,3-diazaphosphol-4-yl)-2,9-dioxo-4,5,6,7-tetrachlorodibenzo[d,h]-1,3,8-trioxaphosphonine.     

Stereoselective synthesis of (<Emphasis Type="Italic">Z</Emphasis>,<Emphasis Type="Italic">E</Emphasis>)-bis(2-chloroethenyl)tellanes

A procedure for the stereoselective synthesis of dichloro[(Z)-2-chloro-2-phenylethenyl][(4E)-5- chlorooct-4-en-4-yl]-λ⁴-tellane and [(Z)-2-chloro-2-phenylethenyl][(4E)-5-chlorooct-4-en-4-yl]tellane has been developed on the basis of anti-addition of tellurium tetrachloride–phenylacetylene monoadduct to oct-4-yne.     

Synthesis of new polydentate tweezers ligands of amido-amine type

A series of new tweezers amido-amine ligands containing pyrrole, bipyrrole, and dipyrrolylmethane fragments were synthesized by reaction of 2-thioxothiazolidin-3-yl derivatives of α-pyrrolecarboxylic acids {5-[1-(5-carboxy-3-methyl-4-phenyl-1H-pyrrol-2-yl)-1-methylethyl]-4-methyl-3-phenyl-1H-pyrrole-2-carboxylic acid, 5-[(5-carboxy-3-methyl-4-phenyl-1H-pyrrol-2-yl)phenylmethyl]-4-methyl-3-phenyl-1H-pyrrole-2-carboxylic acid, 5-(5-carboxy-3-methyl-4-phenyl-1H-pyrrol-2-yl)-4-methyl-3-phenyl-1H-pyrrole-2-carboxylic acid, and 3,4-dimethyl-pyrrole-2,5-dicarboxylic acid} with o-phenylenediamine. All compounds obtained were characterized by elemental analysis, NMR and mass spectra.     

Synthesis of 1,2,4- and 1,3,4-oxadiazoles from 1-aryl-5-methyl-1<Emphasis Type="Italic">H</Emphasis>-1,2,3-triazole-4-carbonyl chlorides

5-Substituted 2-(1-aryl-5-methyl-1H-1,2,3-triazol-4-yl)-1,3,4-oxadiazoles were synthesized by reaction of 1-aryl-5-methyl-1H-1,2,3-triazole-4-carbonyl chlorides with the corresponding 5-substituted 1H-tetrazoles. 5-Methyl-1-phenyl-1H-1,2,3-triazole-4-carbonyl chloride reacted with N′-hydroxybenzimidamides to give 3-aryl-5-(5-methyl-1-phenyl-1H-1,2,3-triazol-4-yl)-1,2,4-oxadiazoles. Reactions of 4-(5-methyl-1H-1,2,3-triazol-1-yl)benzoic acid with N′-hydroxybenzimidamides resulted in the formation of 3-aryl-5-[4-(5-methyl-1H-1,2,3-triazol-1-yl)phenyl]-1,2,4-oxadiazoles.     

Unusual reaction of chloroacetyl chloride with 1,2-dichloroethene. Synthesis and properties of 2-chlorovinyl dichloromethyl ketone

The reaction of chloroacetyl chloride with 1,2-dichloroethene in the presence of AlCl₃ unexpectedly led to the formation of (E)-1,1,4-trichlorobut-3-en-2-one whose structure was proved by ¹H and ¹³C NMR, IR, and mass spectra and independent synthesis. A probable reaction scheme was proposed, which involves transformation of initially formed 1,2,4-trichloro-3-oxobutan-2-yl cation by the action of AlCl₃. The high reactivity of the vinylic halogen atom in (E)-1,1,4-trichlorobut-3-en-2-one was demonstrated by its reactions with nitrogen-centered nucleophiles (triethylamine, aniline, 3,5-dimethyl-1H-pyrazole) and sodium sulfide. These reactions involved only the C-Cl bond in the vinyl fragment and afforded (4,4-dichloro-3-oxobut-2-en-1-yl)triethylammonium chloride, 1,1-dichloro-4-phenylaminobut-3-en-2-one, 1-(4,4-dichloro-3-oxobut-2-en-1-yl)-3,5-dimethyl-1H-pyrazole, and 4,4′-thiobis(1,1-dichlorobut-3-en-2-one), respectively. The reaction of 1,1,4-trichlorobut-3-en-2-one with benzylhydrazine gave a mixture of 1,3- and 1,5-disubstituted pyrazoles.     

Cycloaddition and chlorotropic transformations in reactions of dichloromethylenetrifluoroacetamide with phosphites

Reactions of dichlormethylenetrifluoroacetamide with triphenyl phosphite, diethylchlorophosphite (o-phenylene)diethylamidophosphite, (o-phenylene)chlorphosphite, and 2-fluoro-3-isopropyl-5-tert-butyl-1,3,2-oxazaphospholine proceeded as cheletropic [4+1]-cycloaddition. The formed λ⁵-1,4,2-oxazaphospholines underwent 1,3-migration of the chlorine atom in C=N–C cyclic triad.     

Halocyclization of 3-{[2-methyl(bromo)prop-2-en-1-yl]-sulfanyl}-5<Emphasis Type="Italic">H</Emphasis>-[1,2,4]triazino[5,6-<Emphasis Type="Italic">b</Emphasis>]indoles

Reactions of 3-[(2-bromoprop-2-en-1-yl)sulfanyl]-5H-[1,2,4]triazino[5,6-b]indole with bromine and of 3-[(2-methylprop-2-en-1-yl)sulfanyl]-5H-[1,2,4]triazino[5,6-b]indole with iodine and bromine afforded 3-halomethyl-10H-[1,3]thiazolo[3′,2′: 2,3][1,2,4]triazino[5,6-b]indol-4-ium halides whose structures were determined by ¹H NMR and X-ray analysis.     

Synthesis and Reactivity of Fusion Product of 2-Methylthiazole Fragment to 2-(Furan-2-yl)benzimidazole

Reaction of 1,2-diamino-4-nitrobenzene with furan-2-carbaldehyde in the presence of copper sulfate afforded 2-(furan-2-yl)-5(6)-nitro-1H-benzimidazole. Its N-methylation provided 1-methyl-5(6)-nitro isomers. After reduction of isomers with tin in conc. HCl a pure 3-methyl-2-(furan-2-yl)benzimidazol-5-amine was obtained. The condensation of this amine with acetic anhydride led to the formation of N-[3-methyl-2-(furan-2-yl)benzimidazol-5-yl]acetamide whose treatment with excess P₂S₅ in anhydrous pyridine resulted in the corresponding thioamide. The latter was oxidized with K₃[Fe(CN)₆] in alkaline environment to obtain 2,8-dimethyl-7-(furan-2-yl)-8H-imidazo[4,5-g][1,3]benzothiazole. Its reactions of electrophilic substitution were studied: nitration, bromination, sulfonation, formylation, acylation. The substituent is introduced exclusively in the position 5 of the furan ring.     

Reaction of N-methylsulfonyl-and N-(p-tolylsulfonyl)-2-(cyclopent-1-en-1-yl)anilines with bromine in the presence of potassium thiocyanate and in methanol

The reactions of N-methylsulfonyl-and N-(p-tolylsulfonyl)-2-(cyclopent-1-en-1-yl)-6-methylaniline with molecular bromine in the presence of potassium thiocyanate gave N-methylsulfonyl-and N-(ptolylsulfonyl)-2-(5-isothiocyanatocyclopent-1-en-1-yl)-6-methylanilines. N-Methylsulfonyl-2-(cyclopent-1-en-1-yl)-6-methylaniline reacted with bromine in methanol in the presence of NaHCO₃ or with CuBr₂ in MeOH to afford N-methylsulfonyl-2-(5-methoxycyclopent-1-en-1-yl)-6-methylaniline. The reaction of N-methylsulfonyl-2-(5-isothiocyanatocyclopent-1-en-1-yl)-6-methylaniline with diethylamine led to the formation of N-methylsulfonyl-2-{5-[diethylamino(thioxo)methyl]aminocyclopent-1-en-1-yl}-6-methylaniline which was converted into 5-methyl-4-methylsulfonyl-2,3,3a,4-tetrahydrocyclopenta[b]indole by heating with potassium hydroxide.     

Reaction of (phenylenedioxy)trihalophosphoranes with arylacetylenes: VI. Regiochemistry of the reaction of 2,2,2-trihalo-5-methylbenzo[<Emphasis Type="Italic">d</Emphasis>][1,3,2]dioxaphospholes with arylacetylenes

NMR and IR spectroscopy and X-ray diffraction were used to show that the reaction of 2,2,2-trichloro- and 2,2,2-tribromo-5-methylbenzo[d][1,3,2]dioxaphospholes with para-substituted arylacetylenes proceeds with regioselective formation of 4-aryl-2-halo-7-methyl-2-oxobenzo[e][1,2]oxaphosphorines. With the trichlorophosphole, selective chlorination of the phenylene fragment in the para position to the endocyclic oxygen atom occurs. With the tribromophosphole, 6-bromo- and unsubstituted benzo[e][1,2]oxaphosphorines are formed as major products. The molecular and supramolecular structure of some of the obtained oxaphosphorines was studied by X-ray diffraction.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 12, 2004, pp. 1953–1972.Original Russian Text Copyright © 2004 by Mironov, Shtyrlina, Varaksina, Gubaidullin, Azancheev, Dobrynin, Litvinov, Musin, Konovalov.For communication V, see [1].This revised version was published online in April 2005 with a corrected cover date.