Synthesis of poly-3,3-bis(chloromethyl)-oxacyclobutane (penton) derivatives

The derivatives of poly-3,3-bis(chloromethyl)oxacyclobutane were prepared by the reaction of the chloromethyl group with organic alkali salts at 100–130°C. in dimethyl sulfoxide. Various reagents were used, including sodium cyanide, sodium acetate, sodium thiophenolate, sodium phenolate, sodium methoxide, sodium diethyl malonate, and potassium phthalimide. For all the substitution reactions, the infrared spectra and elementary analyses substantiated the structures of the designated products. The intrinsic viscosities of the derivatives decreased with increasing the reaction time. It was found that the ions of these salts are strong nucleophiles in dimethyl sulfoxide.     

Pseudopolymorphism of [2,5-bis(2-pyridyl)­pyrazine]­ferrocenyl(methyl)­boron hexa­fluoro­phosphate

Two pseudopolymorphs of [2,5-bis(2-pyridyl)­pyrazine]­ferrocenyl­(methyl)­boron hexa­fluoro­phosphate have been determined at 173 K, namely the diethyl ether hemisolvate, [Fe(C₅H₅)(C₂₀H₁₇BN₄)]PF₆·0.5C₄H₁₀O, (I), which forms red crystals with Z′ = 1, and the aceto­nitrile hemisolvate, [Fe(C₅H₅)(C₂₀H₁₇BN₄)]PF₆·0.5CH₃CN, (II), which yields green–brown crystals with Z′ = 2. Despite the different crystal packing, the cations in (I) and (II) are similar. The 2,5-bis(2-pyridyl)­pyrazine moiety is almost planar and displays bending along its long axis compared with free 2,5-bis(2-pyridyl)­pyrazine. It is remarkable that both crystals were obtained from the same aceto­nitrile/diethyl ether solution.     

Synthesis of bis(chloromethyl) derivatives of diphenyl sulfide,thianthrene, and dibenzothiophene

Conclusions The chloromethylation of diphenyl sulfide, thianthrene, and dibenzothiophene, respectively, gave 4,4-bis(chloromethyl)diphenyl sulfide, 2,6-bis(chloromethyl)thianthrene, and 2,7-bis(chloromethyl)dibenzothiophene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2799–2801, December, 1976.     

4,5-Bis(chloromethyl)uracil

A one-step synthesis of 4,5-bis(chloromethyl)uracil from readily available starting materials has been accomplished. This substance is a stable, crystalline solid which undergoes facile nucleophilic attack to produce various di-substituted uracil derivatives.     

Polymerization by phase-transfer catalysis 3: Poly(1,4-oxylylene thioethers) synthesis

Poly(1,4-oxylylenethioethers) were synthesized from 2,5-disubstituted-1,4-bis(chloromethyl)-benzenes and sodium sulfide under phase-transfer conditions. The polythioethers were characterized by elemental analysis and infrared spectroscopy. The effect of the catalyst, solvent, and temperature were studied. Their glass transition temperature and thermal decomposition were determined.     

2,6-Bis(porphyrin)-substituted pyrazine: a new class of supramolecular synthon binding to a transition-metal ion and fullerene (C60)

2,6-Disubstituted-3,5-dimethylpyrazines have been synthesized via biased acetal synthesis from symmetric 2,3,5,6-tetrakis(chloromethyl)pyrazine. The pyrazine ligands coordinated to trans-dichloropalladium(II) at the nitrogen whose neighboring carbons were connected to less hindered methyl groups. 2,6-Bis(porphyrin)-substituted pyrazine bound C₆₀ to yield 1:1 inclusion complex. The binding of C₆₀ with the pyrazine ligand and its zinc complex was determined by ESI-MS, NMR, and fluorescence spectroscopic analyses.     

Synthesis and transformations of acyloxy(chloromethyl)phosphonates and acyloxy(chloromethyl)phosphinates

The reactions ofO-phenyl chloromethylphosphonochloridate and bis(chloromethyl)phosphinous chloride with sodium acetate afford the corresponding acyloxyphosphonates and acyloxyphosphinates, which are readily transformed due to disproportionation into pyrophosphonates and pyrophosphinates. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp 2383–2385, November, 1998.     

Synthesis and properties of novel poly(N-oxyimide)s

Novel poly(N-oxyimide)s (PNOI) were synthesized by the room temperature polycondensation of N,N′-dihydroxypyromellitimide (I) with dichloro compounds in N,N-dimethylformamide (DMF) in the presence of triethylamine both as base as well as catalyst. The dichloro compounds used were 1,4-bis(chloromethyl)-2,5-dimethylbenzene (II), 1,5-bis(chloromethyl)-2,4-dimethylbenzene (III), 1,4-bis(chloromethyl)-2,5-dimethoxybenzene (IV) and 1,4-dichlorobut-2-yne (V). Polymer synthesis, characterization, and properties such as density, viscosity, solubility, crystallinity, and thermal stability were described. Two model compounds, viz. (i) MNOI-1 from N-hydroxyphthalimide and a dichloro compound (III), (ii) MNOI-2 from I and benzyl chloride were also synthesized to confirm the formation of polymers. The polymers thus obtained had high intrinsic viscosities in the range 1.09–1.18 dl/g. The thermal decomposition of the polymers started around 260°C with 20–25% decomposition and about 50% weight loss was observed at 400°C.     

Synthesis, structure, spectroscopic properties, and photochemistry of homo- and heteropolynuclear copper(I) complexes bridged by the 2,5-bis(2-pyridyl)pyrazine ligand

Cu(I)-Cu(I) and Cu(I)-Ru(II) dinuclear complexes bridged by the 2,5-bppz (2,5-bis(2-pyridyl)pyrazine) ligand have been prepared and characterized including the X-ray crystallographic study of the dinuclear [{CuI(PPh3)2}2(mu-2,5-bppz)](PF6)2)2CH3Cl complex: a = 13.974(2), b = 13.993(2), c = 13.537(2) A; alpha = 101.98(1), beta = 103.22(1), gamma = 113.90(1) degrees ; triclinic, P, Z = 1. The trinuclear [{(bpy)2RuII(mu-2,5-bppz)}2CuI](PF6)5 complex was also prepared, and the structure of the complex in solution was studied by spectrometric titration. The dinuclear Cu(I) complex and [(bpy)2RuII(mu-2,5-bppz)CuI(PPh3)2](PF6)5 show photoluminescence in the solid state, which should arise from MLCT states. Photochemical oxidation of the trinuclear RuII2CuI complex occurs in the presence of oxygen to give a RuII2CuII complex. The MLCT states and the redox reaction in the excited state are discussed.     

Reaction ofN,N-bis(chloromethyl)amides withN,N′-diacylated alkene(arylene)diamines

Reactions ofN,N-bis(chloromethyl)amides withN,N′-diacyl derivatives of ethylenediamine (oro-phenylenediamine) result in formation of the corresponding 1,3,5-triacylated perhydro-1,3,5-triazepines (or their benzoanalogs) or 1,3-diacylated imidazolidines (or their benzoanalogs). Reactions ofN,N-bis(chloromethyl)amides withN,N′-ditosylated trimethylenediamine occur in a similar way. The direction of the reactions depends on the type of the acyl substituents and the strength of the bases. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2270–2273, November, 1998.     

Molecular structure of (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide. Synthesis of (3,5-diallylisocyanuratomethyl)phosphine sulfides

X-Ray study of the (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide showed that the phosphorylmethyl group is bonded to the nitrogen atom of the cycle. Reaction of the tris(chloromethyl)phosphine sulfide with sodium diallylisocyanurate gave (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide, and treatment of the tris(3,5-diallylisocyanuratomethyl)phosphine oxide with phosphorus pentasulfide gave a tris(3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1446–1448, August, 1993.     

Synthesis and structures of 1,4-bis(chloromethyl)-and 1,4-bis(bromomethyl)cubanes

1,4-Bis(chloromethyl)-and 1,4-bis(bromomethyl)cubanes were synthesized by the reactions of triphenylphosphine with CCl4 and NBS, respectively. The structures of the compounds were studied by X-ray diffraction analysis. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1399–1401, August, 2006.     

Hedrit-Strukturen des Poly-3,3-bis(chloromethyl)-oxirans

Zusammenfassung Bei der Kristallisation des Poly-3,3-bis(chloromethyl)-oxirans entstehen quadratische Strukturen, die wir in Analogie zu Kristallstrukturen des Polyoxymethylens als Hedrite bezeichnen. In der Mitte der Hedrite befindet sich eine als Krater ausgebildete Schraubenversetzung, um die sich die Lamellenkristalle herumlagern. Die Hedrite bilden eine morphologische Zwischenform zwischen Einkristallen und Sphärolithen.

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Summary Poly-3,3-bis(chloromethyl)oxacyclobutane crystallizes in the form of square structures, which we called hedrites analogous to the morphological structures of polyoxymethylene. In the centre of the hedrites there is a screw dislocation in the form of a crater, which is surrounded by the lamellas. The hedrites are a morphological structure between single crystals and spherulites.

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Herrn Professor Dr.K.- H. Hellwege danke ich für die Anregung zu dieser Arbeit und für fördernde Diskussionen.     

2,3- and 3,4-Bis(diethoxyphosphorylmethyl)-5-tert-butylfurans

Reduction of 2-, 4-acetoxymethyl derivatives of 5-tert-butylfuran-3-carboxylic acid leads to the corresponding bis(hydroxymethyl)furans. Bis(chloromethyl)furans prepared from the latter were involvedin reaction with sodium diethyl phosphite. In the presence of two equivalents of a phosphorus-containing nucleophile, bis(phosphonomethyl)furans are formed. One equivalent of sodium diethyl phosphite reacts with 3,4-bis(chloromethyl)furan to give a mixture of 3-and 4-phosphorylated products in a 4.5:1 ratio in a low yield. The revealed difference in reactivity between the 3- and 4-chloromethyl groups demonstrates the importance of shielding of the chloromethyl group by the neighboring tert-butyl substituent. Examination of the ¹H NMR spectra of 3,4-bis(hydroxymethyl)-, 3,4-bis(chloromethyl)-, 3,4-bis(diethoxyphosphorylmethyl)-5-tert-butylfurans, and also specially prepared 5-tert-butyl-3-(diethoxyphosphorylmethyl)-4-(ethoxymethyl)-2-methylfuran established that the signal of the substituent neighboring to the tert-butyl group is always shifted downfield.     

An unexpected synthesis and application of ethyl 2,4-bis(chloromethyl)-6-iodoquinoline-3-carboxylate

Research on Chemical Intermediates - An unexpected and direct synthesis of ethyl 2,4-bis(chloromethyl)-6-iodoquinoline-3-carboxylate (3) from the chlorotrimethylsilane (TMSCl)-promoted...     

A new type of photodegradable polymer having a pyrazine moiety in the chain

Photooxidative degradation of poly-2,5-distyrylpyrazine (poly-DSP) has been studied in detail. Both amorphous poly-DSP film and poly-DSP solution were photooxygenated and degraded by irradiation by sunlight in the air. The nitrile group was formed, together with carbonyl groups and hydroxyl group. The photodegradation of a pyrazine derivative to a nitrile derivative is a new reaction. Next, photodegradation behavior of polymers having a cyclobutane moiety in the main chain, poly-1,4-bis[2-(2-pyridyl)-vinyl]benzene (poly-P2VB) and polydiethyl p-phenylenediacrylate (poly-p-PDA Et), was studied. The photodegradability of these polymers decreases in the order: poly-DSP > poly-P2VB ? poly-p-PDA Et. Further, the photodegradation behavior of various vinyl polymers containing a vinylpyrazine or vinylpyridine component and polyamides having pyrazine or pyridine ring in the main chain, was investigated. Of these, polyvinylpyrazine has the largest photodegradability.     

Reactions of alkoxy(chloromethyl)methylsilanes with sodium diethyl phosphate and with sodium dimethylphosphinate

Summary The reactions of alkoxy(chloromethyl)methylsilanes with sodium diethyl phosphate and with sodium dimethylphosphinate provide a method for the preparation of some silicon-phosphorus organic compounds containing an Si-C-O-P linkage and functional groups attached to the silicon atom.     

Investigation of 2,6-dichlorojulolidines and 1-aryl-2,5-di(chloromethyl)pyrrolidines

9-Substituted 2,6-dichlorojulolidines and 1-aryl-2,5-di(chloromethyl)pyrrolidines-alkylating compounds with alkylating centers in fixed positions — were synthesized, and their basicities and rates of hydrolysis were determined. The relationship between the structure, basicity, and rate of hydrolysis of these compounds is discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 41–44, January, 1972.     

A new approach to A,B-difunctionalisation of cyclodextrins using bulky 1,3-bis[bis(aryl)chloromethyl]benzenes as capping reagents

1,3-Bis[bis(4-tert-butylphenyl)chloromethyl]benzene and 1,3-bis[bis(4-anisyl)chloromethyl]benzene were employed as regioselective capping reagents for the preparation of C-6A,C-6B-bridged, permethylated alpha- and beta-CD derivatives; isolated yields up to 55% of proximally capped, methylated CDs were obtained, thus opening the way to the straightforward preparation of a wide range of A,B-functionalised CDs. As revealed by a single crystal X-ray diffraction study, the benzene-1,3-bis[bis(4-tert-butylphenyl)methyl] spacer is perfectly suited for A,B-capping of beta-cyclodextrin.     

New Morpholine Derivatives

A study was carried out on the reaction of morpholine with 2,5-di(chloromethyl)-p-xylene, 4,6-di(chloromethyl)-m-xylene, 4,5-di(chloromethyl)-o-xylene, 4,4′-bis(chloromethyl)diphenyl, 4,4′-bis-(chloromethyl)diphenyl ketone, and 4,4′-bis(chloromethyl)diphenyl sulfide. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1691–1692, November, 2005.