Synthesis of 1-(2-naphthyl)dihydro- and 1-(2-naphthyl)-2-thiodihydrouracils and their transformations

1-(2-Naphthyl)dihydro- and 1-(2-naphthyl)-2-thiodihydrouracils were obtained from N-(2-naphthyl)--alanine derivatives. The thiodihydrouracil was converted to a dihydrouracil. Bromination of 1-(2-naphthyl)dihydrouracil gave (1-bromonaphthyl)dihydrouracil. 1-(2-Naphthyl)-2-oxo-, 1-(2-naphthyl)-2-thio-. and 1-(1-bromo-2-naphthyl)-2-oxohexahydro-pyrimidines were obtained.Translated from Khimiya Geterotsiklicheskikh Soedinenii. No. 12, pp. 1695–1697, December, 1971.     

Glycidol esters from diethylamido-(4-phenylthiazolyl-2-amido)-ketophosphonates and their chemical modification

Thiazolyl-containing esters of α-ketophosphonic acids (KPE) unknown earlier were synthesized and investigated in Darzens-Claisen reaction. Reactions were demonstrated to proceed by a classic scheme to form the corresponding phosphorylated glycidol esters whose alkaline hydrolysis gave rise to phosphorylated aldehydes of interesting nature.     

Enantioselective synthesis of axially chiral 1-(1-naphthyl)isoquinolines and 2-(1-naphthyl)pyridines through sulfoxide ligand coupling reactions

Racemic 1-(1′-isoquinolinyl)-2-naphthalenemethanol rac-12 was prepared through a ligand coupling reaction of racemic 1-(tert-butylsulfinyl)isoquinoline rac-7 with the 1-naphthyl Grignard reagent 10. Resolution of rac-12 was achieved through chromatographic separation of the Noe-lactol derivatives 14 and 15, providing (R)-(−)-12 of >99% ee and (S)-(+)-12 of 90% ee. The ligand coupling reaction of optically enriched sulfoxide (S)-(−)-7 (62% ee) with Grignard reagent 10 furnished rac-12, with the absence of stereoinduction resulting from competing rapid racemisation of the sulfoxide 7. Reaction of optically enriched (S)-(−)-7 with 2-methoxy-1-naphthylmagnesium bromide was also accompanied by racemisation of the sulfoxide 7, and furnished optically active (+)-1-(2′-methoxy-1′-naphthyl)isoquinoline (+)-3b in low enantiomeric purity (14% ee). The absolute configuration of (+)-3b was assigned as R using circular dichroism spectroscopy, correcting an earlier assignment based on the Bijvoet method, but in the absence of heavy atoms. Optically active 2-pyridyl sulfoxides were found not to undergo racemisation analogous to the 1-isoquinolinyl sulfoxide 7, with the ligand coupling reactions of (R)-(+)- and (S)-(−)-2-[(4′-methylphenyl)sulfinyl]-3-methylpyridines, (R)-(+)-17 and (S)-(−)-17, with 2-methoxy-1-naphthylmagnesium bromide providing (−)- and (+)-2-(2′-methoxy-1′-naphthyl)-3-methylpyridines, (−)-18 and (+)-18, in 53 and 60% ee, respectively. The free energy barriers to internal rotation in 3b and 18 have been determined, and the isoquinoline (R)-(−)-12 examined as a ligand in the enantioselectively catalysed addition of diethylzinc to benzaldehyde; (R)-(−)-12 was also converted to (R)-(−)-N,N-dimethyl-1-(1′-isoquinolinyl)-2-naphthalenemethanamine (R)-(−)-19, and this examined as a ligand in the enantioselective Pd-catalysed allylic substitution of 1,3-diphenylprop-2-enyl acetate with dimethyl malonate.     

Proton sponges-based (2-naphthyl)pyridylmethanol

The action of 2-, 3-, and 4-pyridinecarboxaldehydes on 1,8-bis(dimethylamino)-2-lithium-and 1,8-bis(dimethylamino)-2,7-dilithiumnaphthalenes gave secondary mono-and dicarbinols containing pyridylcarbinol groups at C-2 and C-7 of the proton sponge. Spectral and X-ray diffraction structural data were used to study the molecular structure of these products. Dedicated to Academician B. A. Trofimov, an outstanding organic chemist, who has made a major contribution to the chemistry of acetylenes and nitrogen heterocycles on the occasion of his seventieth jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1409–1417, September, 2008.     

Pyrroles from ketoximes and acetylene. 23. 2-(1-naphthyl)- and 2-(2-naphthyl)pyrroles and their 1-vinyl derivatives

2-(1-Naphthyl)- and 2-(2-naphthyl)pyrroles and their 1-vinyl derivatives were synthesized in 22–64% yields by the reaction of 1- and 2-acetylnaphthalene oximes with acetylene at both atmospheric pressure and elevated pressures in an alkali metal hydroxide-dimethyl sulfoxide system.See [1] for communication 22.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1351–1353, October, 1982.     

烃基磷(膦)酸酯的化学结构及其液相色谱行为

本文研究了各种烷基或芳基磷(膦)酸酯和亚磷(膦)酸酯的化学结构对其在高效液相色谱(HPLC)柱上保留作用的影响. HPLC中容量因子与化合物的类型以及烷基碳原子数有密切关系. 我们讨论了这些化合物的化学结构和它们的容量因子的关系.     

Supramolecular engineering through temperature-induced chemical modification of 2H-tetraphenylporphyrin on Ag(111): flat phenyl conformation and possible dehydrogenation reactions

Scratching the surface: Formation of a monolayer of 2H-tetraphenylporphyrins (2H-TPP) on Ag(111), either by sublimation of a multilayer in the range 525-600?K or by annealing (at the same temperature) a monolayer deposited at room temperature, induces a chemical modification of the molecules. Rotation of the phenyl rings into a flat conformation is observed and tentatively explained, by using DFT calculations, as a peculiar reaction due to molecular dehydrogenation.     

Synthesis and reactions of some 6-(2-hydroxy-1-naphthyl)-1,2,4-triazines

4,5-Benzocoumaran-2,3-dione condenses with semicarbazide and thiosemicarbazide at the 3-position and the products obtained were converted to the corresponding 6-(2-hydroxy-1-naphthyl)-1,2,4-triazines. Reactions of these triazines with some reagents are described.     

1-benzoyl-2-(2-naphthyl)-selenourea

During our synthesis of N-benzoyl-N'-aryl selenourea derivatives, we isolated the title compound. One of them was selected optically for the diffraction study. The crystal belongs to the Monoclinic space group P21/n, Mr = 353.27, a = 11.073(1)A, b = 5.745(1) A, c = 24.356(5) A, β= 92.10 (1) °, V= 1548.3 (4) A3, Z = 4, Dx=1.515 Mg/m3, λ (Mo Kα )=0.71073 A, θ = 1.67-25, μ= 2.428 mm-1 , T = 296 (2) K.View of the molecule showing the labeling of the non-H atoms are described as:The selenourea and thiourea have analogous structure, a few literatures have reported the crystal of N-benzoyl-N'-aryl thiourea derivative1,2. In the reported crystal structure of N-benzoyl-N'-aryl thiourea derivative, there is a intermolecular hydrogen bond between the carbonyl O and H atom on N', in each -C(O)-NH-N'H- moiety, forming a planar six-membered ring. In this title compound,[2.654(2)A], C (8), N (1) and C (7)l.In the crystal structure of N-benzoy-N'-aryl thiourea derivative, there have a two dimensional With the intramolecular hydrogen bond [2.654(2)A] they form the planar four-membered ring between every molecular. The atom of Se dose not link the moleculars like the S atom of N-benzoyl-N'-aryl thiourea derivative, and it is only out of six-membered ring, which forms by N (2)H…O, C (8), N (1) and C (7).     

Preparation of 2-deoxy-2-C-p-tolylsulfonyl-beta-D-glucopyranosyl p-tolylsulfones having non-chair conformation and their elimination reactions

When the title sulfones, which have non-chair conformations, were stirred with silica gel, elimination of sulfinic acid occurred to give a 1-enitol derivative, if the hydroxyl group at C-6 was protected, whereas such an elimination did not proceed if the hydroxy group was free.     

Acetylation of 2-(1-naphthyl)thiophene

Acetylation of 2-(1-naphthyl) thiophene with acetyl chloride in the presence of SnCl₄, or with acetic anhydride in the presence of H₃PO₄ gives 5-aceto-2-(1-naphthyl) thiophene. 5-Ethyl-2-[1-(3, 4-dihydronaphthyl)] thiophene, 5-ethyl-2-(1-naphthyl) thiophene and 3, 4-diacetoxymercuri-5-ethyl-2-(1-naphthyl) thiophene are now synthesized and characterized.     

Kinetics of the reactions of OH radicals with selected acetates and other esters under simulated atmospheric conditions

The relative hydroxyl radical reaction rate constants from the simulated atmospheric oxidation of selected acetates and other esters have been measured. Reactions were carried out at 297 ± 2 K in 100-liter FEP Teflon®-film bags. The OH radicals were generated from the photolysis of methyl nitrite in pure air. Using a rate constant of 2.63 × 10^?11 cm³ molecule^?1 s^?1 for the reaction of OH radicals with propene, the principal reference organic compound, the rate constants (×10¹² cm³ molecule^?1 s^?1) obtained for the acetates and esters used in this study are:

Gas-liquid chromatography of digitoxigenin and digoxigenin as acetates of their epoxygeninic acid methyl esters

Gas chromatographic analysis of ditigoxigenin and digoxigenin, the genins of the cardenolide glycosides digitoxin and digoxin, cannot be done without derivatization. However, during the derivatization, side-reactions often present serious problems. A procedure has been found for transforming digitoxigenin and digoxigenin into the corresponding acetates of their epoxygeninic acid methyl esters, which are stable compounds and suitable for gas chromatographic analysis.     

Nitro derivatives of 2-(1-naphthyl) thiophene

2-[1-(3, 4-Dihydronaphythyl)]thiophene, 2-(1-naphthyl)thiophene, 3, 4, 5-triacetoxymercuri-, 3, 4-diacetoxymercuri-5-nitro-, 4, 5-diacetoxymercuri-3-nitro-2-(1-naphthyl)thiophenes and 3, 3, 4-triacetoxymercuri-2[1-(4-nitronaphthyl)]thiophene are synthesized and characterized. Nitration of 2-(1-naphthyl)thiophene with copper nitrate in acetic anhydride leads to formation of two isomeric mono-nitro derivatives, 4-nitro- and 5-nitro-2-(1-naphthyl)thiophene.     

Methods for the synthesis of 2-aminothiophenes and their reactions (review)

2-Aminothiophenes are readily formed as a result of various cyclization reactions. The method of preparation of derivatives of 2-aminothiophene-3-carboxylic acids and 2-amino-3-acylthiophenes from carbonyl compounds, nitriles that have an active methylene group, and sulfur is particularly simple and rich in possibilities. The aminothiophenes can be converted to other thiophene derivatives and used primarily for the preparation of condensed thiophenes such as thionaphthenes, thienopyrroles, thienothiazoles, thienoisothiazoles, thienopyrimidines, thienopyridines, and thienodiazepines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1299–1315, October, 1976.