Synthesis and thermal decomposition of 3-aroyl-4-aryl-2-pyrazolines

Summary 3-Aroyl-4-aryl-2-pyrazolines (21–40) have been synthesized by the reaction of ,-unsaturated ketones (1–20) with diazomethane. These 2-pyrazolines gave -methyl-,-unsaturated ketones (41–46) on thermal denitrogenation.Dedicated to Prof. Dr.F. Sauter on the occasion of his 65^th birthday     

Zur Kenntnis der gemeinsamen Einwirkung von elementarem Selen und gasförmigem Ammoniak bzw. Ethylenimin auf Ketone

Elemental sulfur reacts with ketones and gaseous ammonia at room temperature yielding thiazoline-3 in excellent yields. Under the same conditions elemental selenium does not react at all. Attempts using the known techniques which have been applied in improving the reactivity of slowly reacting ketones in thiazoline-3-synthesis have been unsuccessful (Exp. No. 1–17). The reaction of -halogenketones with sodiumhydrogenselenide to synthesize -hydroselenoketones gives only the original ketones and selenium in almost quantitative yields (No. 18–23). The same is observed with -haloketones and sodium ore magnesium-diselenides (No. 24–45). The explanation of these unexpected results is the strong reducing power of the hydrogenselenide (No. 46–52). Even -bromoketones with activated bromine (i.g. by phenyl groups) were reduced by sodiumhydrogensulfide giving red undefinite oils. However, -chloroketones give -mercaptoketones in excellent yields (No. 53–61). Hydrogenselenide reduces -mercaptoketones to sulfur and ketones in the presence of triethylamine (No. 62–67). Also the transformation of -selenocyanketones to ,-diketodisenides by alkali or the oxidative hydrolysis of selenium-BUNTE salts does not work and gives elementary selenium only. Studies about the concomitant reaction of elementary selenium and ethylenimine on ketones were continued (No. 68–82).

     

Reaction of 2-methyl-4,5-dihydrofuran with hydrogen chloride

Reaction of 2-methyl-4,5-dihydrofuran with HCl at 0°C yields 5-chloro-2-pentanone (13%) and 1-(2-methyltetrahydrofuryl-2)-5-chloro-2-pentanone (27%) and at 200° 5-chloro-2-pentanone exclusively.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. I. M. Gubkin State Petroleum and Gas Academy, 117917 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 2188–2191, September, 1992.     

Synthesis of new 4,4′-bis(arylethynyl)benzophenones and 4,4′-bis(arylglyoxalyl)benzophenones based on chloral

4,4-Diiodobenzophenone was obtained by a three-stage synthesis from chloral and iodobenzene. 4,4-Bis(arylethynyl)benzophenones were synthesized by cross-coupling of 4,4-diiodobenzophenone with terminal arylethynes in the presence of a complex Pd catalyst; further oxidation of the products obtained in an iodine/DMSO medium afforded new bis(arylglyoxalyl)benzophenones.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 670–672, March, 1996.     

Room temperature phosphorescence optosensing for gadolinium

An optosensing method for gadolinium based on the room-temperature phosphorescence behavior in aqueous solution induced by the transient adsorption of the complex formed by 1,4-bis (1-phenyl-3-methyl-5-pyrazolone-4-)butanedione (1,4) with Gd (III) on the chelating resin Chelex 100 (packed in a flow cell) is proposed. The proposed optosensing is satisfactory for the determination of the gadolinium ion in the range 8 × 10^–7–5 × 10^–5 M with a correlation coefficient of 0.995. The relative standard deviation was 2.0% for determination of 5× 10^–6 M gadolinium ion (n = 10). The response mechanism of the optosensing and the interferences of other lanthanide ions were also investigated. The method has been used to determine gadolinium ion in synthetic sample.     

Formation of asymmetric N-hydroxyaryl-N′-aryl(hetaryl)diazenes in the reaction of N-aryl(hetaryl)-N′-phosphoryldiazene-N-oxides with bases

Aromatic and heterocyclic N-phenoxyphosphoryldiazene N-oxides react with bases to give asymmetric N-hydroxyaryl-N-aryl- and N-hydroxyaryl-N-hetaryldiazenes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 609–610, March, 1993.     

Facile [3,3]-sigmatropic rearrangement in the reaction of α-chloroperfluorostyrene with allyl alcohol

The reaction of -chloroperfluorostyrene (1) with allyl alcohol in the presence of KOH at 45–50°C leads to a mixture of the allyl 2-pentafluorophenyl-2-chloro-4-pentenoate (2) and the product of the addition of the starting reagents (3). Ester2 is formed as the result of a mild [3,3]-sigmatropic rearrangement of the reaction intermediate.A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 630090 Novosibirsk. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1925–1926, August, 1992.     

Reactions of dodecacarbonyltriruthenium with α,β-unsaturated ketones. Crystal and molecular structures of two reaction products

The thermal reactions of Ru₃(CO)₁₂ with RCOCH=CHPh (R=Me, p-MeC₆H₄) in hydrocarbon solvents lead to the formation of a series of complexes, several of which have been isolated as individual compounds by chromatography. The dinuclear complex Ru₂(-H)(CO)₆(-MeCOCH=CPh) and the tetranuclear complex Ru₄(-H)(-CO)(CO)₇(p-MeC ₆H₄ COCH=CPh)(-p-MeC₆H₄COCH=CPh)(₄-p-MeC₆H₃COCH=CHPh) are characterized by an X-ray structural study. The structures of other reaction products are discussed on the basis of spectral data. The reactions are accompanied by reduction of the starting enones to the corresponding unsaturated ketones.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1285–1293, July, 1993.     

Darzens reaction as a convenient method for the synthesis of α-chloroketones, α-chloroepoxides,and symmetrically substituted dioxines

Summary TheDarzens reaction of dichloroacetophenone (DCAP) with substituted benzaldehydes has been studied. The structure of the products was shown to depend on the phenyl group substituents. Reaction of benzaldehyde, 4-bromo-, and 2,4-dichlorobenzaldehydes results in 1-phenyl-3-aryl-3-chloropropane-1,2-diones (2a–c), reaction ofpara- ormeta-nitrobenzaldehydes yields 1-phenyl-2-chloro-3-aryl-2,3-epoxypropane-1-ones (3a, b). Upon the introduction of an alkoxy group into the phenyl ring of benzaldexyde and/or dichloroacetophenone, symmetrically substituted dioxines were obtained (6a–c). The structure of the reaction products has been established by single crystal X-ray investigations.

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Darzens-Reaktion als bequemes Verfahren zur Synthese von -Chloroketonen, -Chloroepoxiden und symmetrisch substituierten Dioxinen

Zusammenfassung DieDarzens-Reaction von Dichloracetophenon (DCAP) mit substituierten Benzaldehyden wurde untersucht. Die Struktur der Produkte ist von den Substituenten an der Phenylgruppe abhängig. Die Umsetzung mit Benzaldehyd, 4-Brom- und 2,4-Dichlorbenzaldehyd liefert 1-Phenyl-3-aryl-3-chloropropan-1,2-dione (2a–c), die Reaktion vonpara- odermeta-Nitrobenzaldehyd 1-Phenyl-2-chloro-3-aryl-2,3-epoxipropan-1-one (3a,b). Durch Einführung einer Alkoxygruppe in den Phenylring des Benzaldehyds und/oder des Dichloracetophenons erhält man symmetrisch substituierte Dioxine (6a–c). Die Struktur der Reaktionsprodukte wurde mittels Röntgenstrukturanalyse bestätigt.

     

Triterpene glycosides ofFatsia japonica. I. Isolation and structure of glycosides fromFatsia japonica seeds

The known triterpene glycosides hederagenin 3-O--L-arabinopyranoside, hederagenin 3-O-\-D-glucopyranoside, oleanolic acid 3-O--sophoroside, hederagenin 3-O--sophoroside, and their 28-O--gentiobiosyl esters, respectively, in addition to the new triterpene glycoside 3-O--sophorosyl-28-O--L-rhamnopyranosyl-(14)-O--gentiobiosyl hederagenin are isolated fromFatsia japonica (Araliaceae) seeds. The structures of these glycosides are established using chemical and spectral methods.Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 131–133, March–April, 2000.     

Aminoamidines

Reactions ofN-aryl- andN-methyl-amidines and -amides of -amino acids with RPCl₂ afford 4-aryl(methyl)imino and 4-oxo-1,3,2-diazaphospholanes. 4-Phenylimino-1,3,2-diazaphosphorinane was obtained in a similar way by the interaction of N(1), N(2)-diphenyl--anilinoisobutyramidine with PhPCl₂.For communication 5 see ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1116–1121, June, 1993.     

3,3′,5,5′-Tetramethylbenzidme for the colorimetric determination of manganese in water

Manganese can be determined by colorimetry with previous oxidation of Mn(II) in a strong basic medium, using 3,3,5,5-tetramethylbenzidine as a chromogenic reagent. The molar absorptivity of the reaction product is 3.4 × 10⁴ mol^–1l cm^–1l, the detection limit 3 ng/ml, the RSD (0.5 mg/l,n = 8) 0.9% and the calibration range (1-cm cells) 0.02–0.8 mg/1 V(V), Cr(VI) and Co(II) are the most significant interferences. The new method was compared with an AAS procedure (air-acetylene flame) with previous solvent extraction and also with a colorimetric method for the determination of manganese in sea and drinking water.     

Transformed steroids

A preparative method for 9a-hydroxylation of ⁵-3-hydroxysteroids using the fungi ofCircinella sp. 10Kh-1220 not capable of modifying theA ring has been developed. It is established that the yields of the main and the side products greatly depend on the transformation conditions, mycelium age, and the structure of the steroid substrate. Under the optimal transformation conditions novel 9-hydroxysubstituted derivatives of androstenolone, pregnenolone, 16-dehydro-16,17-epoxy-, and-16-methoxypregnenolone have been obtained in 36–80 % yields.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 737–743, April, 1994.     

Dimethyl dichloromalonate as a new synthetic equivalent of methyl dichloroacetate in the Darzens condensation

Dimethyl dichloromalonate reacts with aldehydes in the presence of sodium methoxide to form-chloropyruvates,-chloroglycidates, or,-dichlorohydrins, depending on the nature of the aldehyde.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1544–1545, August, 1995.     

The study of the structure of solutions of the H-complexes of diesters of tetracarboxylic acids with diammes by the light scattering method

The process of structurization in solutions of H-complexes of dimethyl 3,3,4,4 -benzophenonetetracarboxylate with 4,4 -diaminodiphenylmethane has been investigated in 90 % aqueous methanol in the concentration range 6 to 0.2 g L^–1. Structural instability of the solutions has been found in the concentration range from 1.2 to 2 g L^–1. The addition of an ionogenic substance stabilizes the solution and results in monotonic changes in the structural parameters as solution is diluted. A tendency toward variation of the extemum in the mean correlation radius of the polarizability fluctuation has been found in the concentration range 0.6-–1 g L^–1, which had been observed previously for polymer systems.For Part 1, see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1219–1221, July, 1994.     

Synthesis of some phosphonocarbonyl compounds via Horner-Emmons reaction of methylenbisphosphonate

Summary The -carbonyl substituted vinylphosphonates6–9 were synthesized from the -dicarbonyl compounds2–5 and the methylenbisphosphonate1 by a Horner-Emmons reaction in different yields.

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Synthese von Phosphonocarbonylverbindungen durch Horner-Emmons-Reaktion von Methylenbisphosphonsäuretetraethylester

Zusammenfassung Es wurden die -carbonylsubstituierten Vinylphosphonate6–9 mittels Horner-Emmons-Reaktion aus den -Dicarbonylverbindungen2–5 und Methylenbisphosphonat1 in verschiedenen Ausbeuten hergestellt.

     

Organomineral sorbents based on clinoptilolite-containing tuffs

The anion-exchange properties of a new organomineral sorbent obtained by modification of clinoptilolite-containing tuffs by polyhexamethyleneguanidine have been studied after different periods of storage (time after synthesis) and numbers of sorption-regeneration cycles. The sorbent can be used as a cation- and an anion-exchanger simultaneously. Selectivity coefficients (exchange constants) for F^–, SO₄ ^2–, and HPO₄ ^2– ionsvs. Cl^– ions on modified clinoptilolite-containing tuffs have been determined. The modification improves the mechanical properties of clinoptilolite tuffs.For part 1, see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1554–1556, September, 1994.     

Zur Reaktion von Permethylcyclosilanen mit Halogenen

The series of ,-diiodopermethylpolysilanes, I(SiMe ₂) _n I, (n=4–6) andX(SiMe ₂)₄ X, (X=Cl, Br) has been prepared by the action of halogen on the corresponding cyclic compounds (SiMe ₂) _n . The mass spectra, NMR-, IR- andRaman-spectra of these compounds have been recorded.

Herrn Prof. Dr.Josef Schurz zum 60. Geburtstag gewidmet.     

2-[2′-(6′-Methyl-benzothiazolyl)azo]-5-dimethylaminobenzoic acid as a new reagent for rapid spectrophotometric determination of copper

2-[2-(6-methyl-benzothiazolyl)azo]-5-dimethylaminobenzoic acid (MBTAMB) has been synthesized and employed as a new reagent for the spectrophotometric determination of copper(II). A blue complex is formed from MBTAMB and Cu(II) in the range of pH 2.0–5.0 in aqueous ethanol. The composition of the complex is Cu(II) MBTAMB=1 1. The maximum absorption of the complex is at 660 nm, its apparent molar absorptivity is 7.0 × 10⁴ 1· mole^–1 · cm^–1. Beer's law is obeyed for copper in the range of 0–0.72 g/ml. The method has been used for the determination of micro amounts of copper in aluminium alloy. The proposed method is simple, rapid and accurate.     

Synthesis of driman-8α,11-diol from sclareol through 8α,12-epoxy-14,15-bisnorlabdan-13-one

A four-step synthesis of driman-8,11-diol from sclareol in 44% total yield is described that includes the intermediates (12R)-8,12-epoxy-14,15-bisnorlabdan-13-one, (12S)-8,12-epoxy-12-acetoxy-13,14,15,16-tetranorlabdane and 8,12-epoxy-13,14,15,16-tetranorlabd-11-ene.Institute of Chemistry, Academy of Sciences of the Republic of Moldova, Kishinev, fax (3732) 73 97 75, Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 124–125, March–April, 2000.