1,1,4,4-tetranitrobutane-2,3-diol and its derivatives. 2. Chlorination and bromination of 1,1,4,4-tetranitrobutane-2,3-diol. crystal structure of halogen derivatives of 1,1,4,4-tetranitrobutane-2,3-diol

The bromination of 1,1,4,4-tetranitrobutane-2,3-diol in 60% acetic acid gave 1,4-dibromo-1,1,4,4-tetranitrobutane-2,3-diol in satisfactory yield. The chlorination of 1,1,4,4-tetranitrobutane-2,3-diol under analogous conditions gave 1,4-dichloro-1,1,4,4-tetranitrobutane-2,3-diol as a crystal hydrate. Drying of this latter product in vacuum over phosphorus pentoxide gave 1,4-dichloro-1,1, 4,4-tetranitrobutane-2,3-diol in quantitative yield. The structures of these products were determined by x-ray diffraction structural analysis. The crystal chemical analysis and quantum chemical calculations established an increase in secondary oxygen-halogen interactions in the halodinitromethyl fragment with increasing atomic number of the halogen atom.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2372–2380, October, 1991.     

1,1,4,4-Tetranitrobutane-2,3-diol and its derivatives. 5. Reaction of 1,1,4,4-tetranitrobutane-2,3-diol with formaldehyde; synthesis and crystal structure of 4,4-dinitro-2,3-dihydroxytetrahydrofuran

1,1,4,4-Tetranitrobutane-2,3-diol reacts with formaldehyde, forming 2,2-dinitropropane-1,3-diol or a cyclic ether — 4,4-dinitro-2,3-dihydroxytetrahydrofuran — as a function of the reaction conditions.Institute of Chemical Physics, Chernogolovka, Russian Academy of Sciences, 142432 Chernogolovka. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2755–2759, December, 1992.     

1,1,4,4-Tetranitrobutane-2,3-diol and its derivatives. 1. Reaction of dinitromethane potassium salt with glyoxal. Crystal structure of 1,1,4,4-tetranitrobutane-2,3-diol and its diacetate

The synthesis of 1,1,4,4-tetranitrobutane-2,3-diol has been carried out via the reaction of the dinitromethane potassium salt with glyoxal, at pH values of 7–8 after reagent mixing and 5.5 at the end of the reaction, in the temperature range 35–37°C. X-ray crystal structure analysis has been performed on 1,1,4,4-tetranitrobutane-2,3-diol and its diacetate. The conformations of these molecules are stabilized to a significant extent by O^–...N⁺-type electrostatic interaction, which was confirmed by quantum-mechanical calculations on 2,2-dinitroethanol as a model molecule.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 830–834, April, 1991.     

Development of new methods for the synthesis of 2,3-bis(nitroxymethyl)-2,3-dinitrobutane-1,4-diol dinitrate and its intermediates

Known methods for the synthesis of 2,3-bis(nitroxymethyl)-2,3-dinitrobutane-1,4-diol dinitrate and its intermediates were investigated. New procedures were developed for the preparation of these compounds. 2,3-Bis(nitroxymethyl)-2,3-dinitrobutane-1,4-diol dinitrate was studied by X-ray diffraction.

     

1,1,4,4-Tetranitrobutane-2,3-diol and its derivatives. 3. Synthesis of 1,4-dichloro- and 1,4-dibromo-1,1,4,4-tetranitrobutane-2,3-diol dinitrates and their crystalline structure

1,4-Dichloro- (1) and 1,4-dibromo-1,1,4,4-tetranitrobutane-2,3-diol dinitrates (2) were synthesized by nitration of the corresponding diols with a mixture of trifluoroacetic anhydride and nitric acid. The x-ray diffraction investigations of 1 and 2 that have been carried out showed the influence of the intramolecular interactions of the nitro and nitrate groups on the packing of the molecules in the crystal.Institute of Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 664–671, March, 1992.     

A novel,high-yielding approach to a chiral inducer: (2R,3R)-1,4-dimethoxy-1,1,4,4-tetraphenylbutane-2,3-diol

A new method for preparing (2R,3R)-1,4-dimethoxy-1,1,4,4-tetraphenylbutane-2,3-diol in high yield based on selective 2,3-spiroboration of (2R,3R)-1,1,4,4-tetraphenylbutanetetraol has been developed. It avoids traditional oxidation and reduction steps, and provides a simplified, more straightforward, and high-yielding synthesis of the title compound.     

Stereochemistry and Fate of Hydrogen Atoms in the Diol-Dehydratase-Catalyzed Dehydration of meso-Butane-2,3-diol

The transformation of meso-butane-2,3-diol into butan-2-ol by a strain of Lactobacillus brevis occurs through a diol-dehydratase-catalyzed conversion of the diol into butan-2-one, which is then reduced to the secondary alcohol by dehydrogenases. Experiments performed with deuterated meso-butane-2,3-diols showed that the dehydration reaction brings about an inversion of configuration at the (R)-configured C-atom of meso-butane-2,3-diol as a consequence of the substitution of the OH group by a H-atom; at the same time, the H-atom already bound to the (R) C-atom is retained in the resulting methylene group. The H-atom replacing the OH group was assessed to come from the medium since the H-atom at the (S)-configured C-atom was completely lost. By contrast, in the case of the conversion of (RS)-propane-1,2-diol into propan-1-ol under the same fermentation conditions, an extensive H-transfer (ca. 80%) from the primary-alcohol function to the adjacent C-atom was observed. This fact is taken as an indication of different modes in which the two substrates are processed by the enzyme (despite the same stereochemical outcome). A speculative hypothesis is presented to interpret such a dissimilarity.     

Seven-membered acetals based on cis-2,3-Dichloro-2-butene-1,4-diol

cis-2,3-Dichloro-2-butene-1,4-diol was obtained by reduction of dichloromaleic anhydride with lithium aluminum hydride. Condensation of the diol with carbonyl compounds leads to seven-membered unsaturated acetals, viz., 5,6-dichloro-1,3-dioxa-5-cycloheptenes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 19–21, January, 1980.     

Synthesis of pyrrolidine and other heterocycles from bu tane-1,4-diol and ethane-1,2-diol

The amination reactions of butane-1,4-diol and ethane-1,2-diol on seven different catalysts obtained by modifying a natural alumosilicate — gumbrin — and a natural zeolite — analcite -with iron and chromium salts, and also by activation with sulfuric acid, have been investigated. The maximum yield of pyrrolidine was obtained in the presence of a catalyst containing ferric oxide on gumbrin.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 937–941, July, 1973.     

2,3-Bis(diphenylphosphynyl)-1,3-butadiene via a double [2,3]-sigmatropic rearrangement. A reinvestigation of the reaction of 2-butyne-1,4-diol with chlorodiphenylphosphine

Contrary to previous reports, the reaction of 2-butyne-1,4-diol with chlorodiphenylphosphine yields 2,3-bis(diphenylphosphinyl)-1,3-butadiene 3 instead of the 1,4-isomer. The structure of the product has been elucidated from ¹H, ¹³C and ³¹P-NMR spectroscopic data.     

Resolution of C2-symmetric 2,3-diphenylbutane-1,4-diol and purification of diastereomeric 1,4-diphenylbutane-1,4-diol using (S)-proline and boric acid

Racemic 2,3-diphenylbutane-1,4-diol (±)-1 is resolved to obtain the corresponding (R,R)-isomer in 98% e.e. through reaction with (S)-proline and boric acid. Partially resolved (R,R)-(−)-1 and (S,S)-(+)-1 have been enriched to obtain samples of 95 and 97% e.e. through reaction with (S)-proline and boric acid. Diastereomeric 1,4-diphenylbutane-1,4-diol 2 has been purified to obtain the (R,R)-isomer in 98% e.e. using (S)-proline and boric acid.     

Kinetics of oxidation of butane 2,3-diol by osmium(VIII)

The oxidation of butane 2,3-, propane 1,2-, ethane diol and 2-methoxy ethanol in aqueous alkaline medium by Os(VIII) has been studied. The reaction is base catalyzed and shows first-order kinetics in Os(VIII), whereas the order is less than 1 in butane 2,3-diol [BD]. The rate of oxidation is BD > propane 1,2 > ethane diol ≈ 2-methoxy ethanol. The change in ionic strength has no effect on the rate of reaction. Activation parameters ΔE, PZ, and ΔS* have been evaluated.     

Analysis of products from hydrogenation of 2-butyne-1,4-diol

Conclusions A qualitative and quantitative method has been developed for analysis of a mixture of butane-1,4-diol, cis-2-butene-1,4-diol, trans-2-butene-1,4-diol, and 2-butyne-1,4-diol in the form of their diacetates by gas chromatography.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 942–944, April, 1970.     

Extraction—spectrophotometric determination of boron with naphthalene-2,3-diol and crystal violet

Boron reacts with naphthalene-2,3-diol to form a complex anion extractable into benzene with crystal violet and is determined indirectly by measuring the absorbance of the crystal violet in the extract at 610 nm. The calibration graph is linear for boron over the range 8.0 × 10^-7–8.0 × 10^-8 mol l^-1; the apparent molar absorptivity is 8.8 × 10⁴ l mol^-1 cm^-1. The method is applied to the determination of boron in natural waters.     

Chiral crystallization of cis-2,3-dichloro-buth-2-ene-1,4-diol

The X-ray diffraction study of cis-2,3-dichlorobuth-2-ene-1,4-diol (3) obtained by the reduction of 3,4-dichloro-5-ethoxy- and 5-isopropoxi-2(5H)-furanones with lithium aluminum hydride is performed. The crystals of compound 3 are trigonal: a = b = 15.746(9) Å, c = 6.848(4) Å; V = 1470.5(15) ų, space group P3₁, Z = 9 (three independent molecules). Independent molecules have identical planar conformation, and hydroxyl groups are located on different sides of the multiple bond plane. The supramolecular motif of the crystal is spirals about the threefold screw axes; the neighboring spirals are linked by OH…O hydrogen bonds.     

合成(E)-2,3-二卤-2-丁烯-1,4-二醇及其衍生物的新方法

采用乙醇 /苯为反应溶剂 ,以α -炔醇为反应原料 ,氯化铜为卤化剂 ,立体专一性合成 (E) - 2 ,3-二卤 - 2 -丁烯 - 1 ,4-二醇及其衍生物。分离产率为 1 0 0 % ,粗产品纯度即可达 98% (GC)     

2,3-Di(phenylsulfinyl)-1,3-butadiene via a double [2,3]-sigmatropic rearrangement of the bis-sulfenate ester of 2-butyne-1,4-diol.

a one-step conversion of butyne-1,4-diol (1) to 2,3-di(phenylsulfinyl)-1,3-butadiene (4) and the conversion of this bis-sulfoxide to the sulfoxide-sulfone 6 and the bis-sulfone 5 are reported.     

Stereoselective synthesis of cis-p-menth-8-ene-1,7-diol, cis-p-menthane-1,7-diol, and cis-p-menthane-1,7,8-triol

The natural products cis-p-menthane-1,7-diol (cis-IV), cis-p-menth-8-ene-1,7-diol (cis-I) and cis-p-menthane-1,7,8-triol (cis-II) are obtained starting from the corresponding cis-cyanohydrins, cis-2 and cis-7, respectively, by chemical transformation of the cyano into the hydroxymethyl group. The key step of the synthesis is the very high cis-selectivity (> or = 96 %) of the MeHNL-catalyzed HCN addition to 4-alkylcyclohexanones. From 4-isopropylcyclohexanone (1) the cyanohydrin cis-2 and from 4-(1-methylvinyl)cyclohexanone (6) the cyanohydrin cis-7 result almost quantitatively. Regioselective hydroxylation of cis-I affords the triol cis-II. X-ray crystal structure determinations of the final products confirm their cis-configuration.     

Electrolytic reduction of 2-butyne-1,4-diol as a route to trans-2-butene-1,4-diol

The effect of the cathode material on the electrochemical transformations of 2-butyne-1,4-diol at atmospheric pressure was studied by chromatographic analysis. The optimal parameters of the selective synthesis of trans-2-butene-1,4-diol were determined.     

Synthesis and study of organic nitrates of heterofunctional series. 5. Synthesis of 3,3-bis(hydroxymethyl)oxetane mono- and dinitrates and 2,2-bis(hydroxymethyl)propane-1,3-diol (pentaerythritol) mono- and dinitrates

New procedures were developed for the synthesis of 3,3-bis(hydroxymethyl)oxetane dinitrate (1) by O-nitration of the corresponding glycol (3) or its mononitrate (6), which were prepared by the reactions of 2,2-bis(hydroxymethyl)propane-1,3-diol (pentaerythritol) (2) mono- (4) and dinitrates (5), respectively, with alkali. A new method was devised for the synthesis of compounds 4 and 5 by the reaction of tetraol 2 with concentrated HNO₃ in dichloroethane. The structures of compounds 1 and 6 were established by X-ray diffraction analysis.