Chemical and enzymatic synthesis of 2-(2-carbamoylethyl)- and 2-(2-carboxyethyl)aziridines and their conversion into δ-lactams and γ-lactones

Treatment of 1-arylmethyl-2-(2-cyanoethyl)aziridines with a nitrile hydratase afforded the corresponding 2-(2-carbamoylethyl)aziridines, which underwent rearrangement into 5-hydroxypiperidin-2-ones upon heating under microwave irradiation. In addition, treatment of 2-(2-cyanoethyl)aziridines with a nitrilase selectively afforded 5-hydroxypiperidin-2-ones in good yields. On the other hand, chemical hydrolysis of 2-(2-cyanoethyl)aziridines using KOH in EtOH/H(2)O furnished the corresponding potassium 3-(aziridin-2-yl)propanoates, which, upon acidification with acetic acid, smoothly rearranged into 4-(aminomethyl)butyrolactones.     

Synthesis of 2-(hydroxyphenylamino)- and 2-(aminophenylamino)-4-methylquinolines and N,N′-bis(4-methylquinolin-2-yl)benzenediamines

2-(Hydroxyphenylamino)- and 2-(aminophenylamino)-4-methylquinolines and N,N′-bis(4-methylquinolin-2-yl)benzenediamines were synthesized by reactions of 2-chloro-4-methylquinolines with o-, m-, and p-aminophenols and o-, m-, and p-phenylenediamines.     

Synthesis and functionalization oftrans-2-(2′-aminocyclohexyloxy)-andtrans-2-(2′-azidocyclohexyloxy)acetic acid

Summary Synthesis of the hydrochloride oftrans-2-(2-aminocyclohexyloxy)acetic acid (4) fromtrans-2-(2-azidocyclohexyloxy)acetic acid (1) is described.4 was acylated at the amino group to give compounds5–8.1 was converted into acid chloride (9) and amides10–13.

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Synthese und Funktionalisierung dertrans-2-(2-Aminocyclohexyloxy)- undtrans-2-(2-Azidocyclohexyloxy)essigsäure

Zusammenfassung Die Synthese destrans-2-(2-Aminocyclohexyloxy)essigsäurehydrochlorids (4), ausgehend vontrans-2-(2-Azidocyclohexyloxy)essigsäure (1), wird beschrieben.4 wurde durch Acylierung der Aminogruppe in die Verbindungen5–8 übergeführt.1 wurde in das Säurechlorid9 und die Carbonsäureamide10–13 umgewandelt.

     

2-Polyfluoroalkylchromones. 11. Synthesis and structures of 5-hydroxy-3-(2-hydroxyaryl)-5-polyfluoroalkyl-Δ2-pyrazolines and 3(5)-(2-hydroxyaryl)-5(3)-polyfluoroalkylpyrazoles

The reaction of 2-hydroxy-2-polyfluoroalkylchroman-4-ones with hydrazine affords 5-hydroxy-3-(2-hydroxyaryl)-5-polyfluoroalkyl-²-pyrazolines, whereas 2-polyfluoroalkylchromones under similar conditions produce 3(5)-(2-hydroxyaryl)-5(3)-polyfluoroalkylpyrazoles. 5-(2-Hydroxyaryl)-1-methyl-3-polyfluoroalkylpyrazoles were synthesized in the reaction with methylhydrazine, and the reaction with phenylhydrazine afforded regioisomeric 3(5)-(2-hydroxyphenyl)-1-phenyl-5(3)-polyfluoroalkylpyrazoles.     

Synthesis,spectral and RAHB studies on some arylhydrazones of β-diketones: crystal and molecular structures of 2-(2-(3-pyridyl)hydrazono)-5,5-dimethylcyclohexane-1,3-dione and 2-(2-(2-methoxyphenyl)hydrazono)-5,5-dimethylcyclohexane-1,3-dione

The present study describes the synthesis and spectral analysis of a series of arylhydrazones of β-diketones (1–6) along with the single crystal X-ray structural studies of 2-(2-(3-pyridyl)hydrazono)-5,5-dimethylcyclohexane-1,3-dione (3) and 2-(2-(2-methoxyphenyl)hydrazono)-5,5-dimethylcyclohexane-1,3-dione (6). Spectral and structural studies clearly exemplify the effective intramolecular hydrogen bonding and as a result the NH proton signals and carbonyl carbon signals are shifted to higher frequency region in NMR spectra. Structural implications imposed by the formation of pseudo six-membered ring after hydrogen bonding is well observed in XRD analysis. XRD analysis also evidences the envelop conformation of the dimedone ring in both the cases and resonance assisted hydrogen bonding (RAHB) studies were also performed.     

Crystal Structure and Spectra Characters of 2-Benzoly-3-(4-(1,2,4-triazole)-5-anilino-thiophene and 2-(4-Methyl-benzoly)-3-(4- chlrolphenyl)-3-(1,2,4-triazole)-5-anilino-thiophene

Triazole derivatives are widely studied, because they represent the largest group of modern fungicides and are widely used both in human and veterinary therapy and in agriculture. We synthesized the title compound in which the thiophene ring was substituted by a 1,2,4-triazole group, a phenacyl group, a phenylaminol group and a benzene ring.     

Studies on Acylthiosemicarbazides and Related Heterocycles(ⅪⅤ)——Synthesis and Bactericidal Activity of 1-(5-(3-Pyridyl)-2H-Tetrazol-2-ylacetyl) -4-Arylthiosemicarbazides and 3- (5- (3-Pyridyl)-2H-Tetrazol-2-ylmethyl)-4-Aryl-1,2 ,4-Triazole-5-Thiones

Introduction In the preceding paper it was described that various 1-acyl-4-substituted thiosemicarbazides and their derivatives exhibited a broad spectrum of antibacterial activities. Kothari pointed out that some heterocycles linked with tetrazole and 1,2,4-triazole can be used as antiinflammatory agent. We have also demonstrated that both 3-(5-a- naphthyl)-2H-tetrazol-2-ylmethyl)-4-aryl-1,2,4-triazole-5-thiones and 3-(3-pyridyl)-     

Structure and properties of BETS salts: κ-(BETS)8(Cu2Cl6)(CuCl4), θ-(BETS)2(CuCl2) and (BETS)2(CuCl4)

κ-(BETS)₈(Cu₂Cl₆)(CuCl₄) (1), θ-(BETS)₂(CuCl₂) (2), (BETS)₂(CuCl₄) (3) (BETS = bis(ethylenedithio)tetraselenafulvalene) have been prepared by diffusion-electrocrystallisation of BETS and (AsPh₄)₂(Cu₂Cl₆) solutions in chlorobenzene–ethanol. 2 has also been obtained by simple diffusion of BETS and (AsPh₄)₂(Cu₂Cl₆) solutions. 1 and 2 exhibit metal-like behaviour, down to 40 K for 1 and 4 K for 2. 3 behaves as an insulator. The crystal structures of 1, 2, and 3 are determined by X-ray diffraction methods. The structures of 1 (at 140 and 25 K) and 2 are characterised by a strong disorder of their respective anions. The crystal structure of 3 shows an unusual packing of the BETS molecules, consisting of slipped stacked (BETS)₂ dimers, leading to insulating properties. Based on the structures of 1 (at 140 and 25 K), 2 and 3, molecular and band structure calculations are carried out for the interpretation of the physical behaviours of these phases.     

Synthesis and light-emitting properties of 2-(N-phenyl-α-naphthylamino) and 2-dimesitylboron-7-(N-phenyl-α-naphthylamino)-9,9-diethylfluorene

A fluorescent organic triarylamine with a symmetric structure, 2,7-bis(N-α-naphthyl-phenylamino)-9,9- diethylfluorene (NPAEF) was synthesized using two methods, modified Ullmann coupling and modified palladium-catalyzed amination. An activated copper and a combination of Pd(OAc)2/P(t-Bu)3 and Pd(dba)2/P(t-Bu)3 were selected as catalysts to improve yields of reactions. These synthetic procedures were also successfully applied to an asymmetric 2-dimesitylboron-7-(N-phenyl-α-naphthylamino)-9,9-diethylfluorene ...     

Syntheses,spectroscopy, and catalysis of (η 4-cod)Rh(I)-complexes with (R or S)-2-(salicylaldimine)-2-phenylethanol or (rac)-2-(salicylaldimine)-1-phenylethanol

Condensation of salicyldehyde with (R or S)-2-amino-2-phenylethanol or rac-2-amino-1-phenylethanol gives enantiopure (R or S)-2-(salicylaldimine)-2-phenylethanol (R- or S-H₂L1) or (rac)-2-(salicylaldimine)-1-phenylethanol (rac-H₂L2). The Schiff bases coordinate to [Rh(η ⁴-cod)(μ-O₂CCH₃)]₂ to afford mononuclear [Rh(η ⁴-cod){(R or S)-2-(salicylaldiminato)-2-phenylethanol-κ ² N,O}], [Rh(η ⁴-cod)(R- or S-HL1)] (1 or 2), or [Rh(η ⁴-cod){(rac)-2-(salicylaldiminato)-1-phenylethanol-κ ² N,O}], [Rh(η ⁴-cod)(rac-HL2)] (3). The Schiff base and complexes are characterized by IR-, UV/Vis-, ¹H/¹³C-NMR-, mass-spectroscopy, circular dichroism (CD), and polarimetry. The synthetic and spectroscopic results suggest that deprotonated Schiff base coordinates to [Rh(η ⁴-cod)] as a six-membered N,O-chelate with distorted square planar geometry at rhodium. CD and polarimetry measurements show the enantiopurity of the Schiff bases as well as the complexes in solution. The in situ system composed of [Rh(η ⁴-cod)Cl]₂ and S-H₂L1 has been used as a catalyst for the reduction of acetophenone into rac-1-phenylethanol with 85% conversion in diphenylsilane at 0–5°C.     

Crystal and molecular structures of (3Z)-(±)-4-(2′-hydroxypropyl)amino-and (3Z)-4-(2′-hydroxyethyl)amino-pent-3-en-2-ones

An X-ray study of (3Z)-(±)-4-(2′-hydroxypropyl)amino-and (3Z)-4-(2′-hydroxyethyl)amino-pent-3-en-2-ones is reported. The bond lengths inside the H ring are equalized due to the classical N-H...O hydrogen bond between the carbonyl oxygen and the amino group. In the 4-(2′-hydroxyethyl)amino-pent-3-en-2-one crystal, due to the classical N-H...O bonds, infinite zigzag chains are formed along the 0b axis and arranged into a layered structure due to the weak C-H...O interactions. In (±)-4-(2′-hydroxypropyl)aminopent-3-en-2-one crystal, however, centrosymmetric dimers are formed, which are then linked by weak C-H...O intermolecular interactions to form a layered structure along the a0b plane.     

Synthesis and spectroscopic characterization of new heteroleptic ruthenium(II) complexes incorporating 2-(2′-pyridyl)quinoxaline and 4-carboxy-2-(2′-pyridyl)quinoline

Starting from cis-[Ru(dcbpyH₂)₂Cl₂] (1), two new heteroleptic ruthenium(II) complexes, [Ru(dcbpyH₂)₂(L¹)](NO₃)₂ (L^1?=?2-(2′-pyridyl)quinoxaline (2), and [Ru(dcbpyH₂)₂(L²)](NO₃)₂ (L^2?=?4-carboxy-2-(2′-pyridyl)quinoline (4); dcbpyH_2?=?2,2′-bipyridine-4,4′-dicarboxylic acid), were synthesized and spectroscopically characterized. During the preparation of 2 and 4, the homoleptic [Ru(dcbpyH₂)₃]Cl₂ complex (3) was isolated as a side product. Characterization includes IR and Raman spectroscopy, UV-Vis, multinuclear NMR spectroscopy, elemental, and ESI-mass spectrometric analyses.     

Study of cis–trans stereochemistry of 2-(2-chlorobenzylideneamino)phenol and 2-(2-chlorophenyl imino)methyl)phenol (Schiff bases) by GC and GC-MS spectrometry

Cis–trans stereochemistry of 2-(2-chlorobenzylideneamino)phenol (1) and 2-(2-chlorophenyl imino)methyl)phenol (2) (Schiff bases) was studied by GC-MS spectrometry, and cis–trans conversion of the two compounds in solution was investigated by GC. Thus, 2 exists as a sole trans configuration and its conversion to cis was unsuccessful in any circumstance, while compound 1 exists as a mixture of two configurations in solution, occurrence of which were dependent on the temperature, heating time, solvent, and acid catalyst. X-ray crystallography of solid 1 presented a sole trans configuration.     

Synthesis and Crystal Structure of Rctt-1-(2-benzoxazolyl)-2-(4-chlorophenyl)-4-phenyl-3-(4-pyridinyl)cyclobutane

1INTRODUCTIONThephotodimerizationof1,2-bisarylethenederivativesisaconvenientwayforsynthesizingtetraarylsubstitutedcyclobutane.Forthisreason,thephotochemistryofstilbeneandstyrylpyridinederivativeshasbeenextensivelystudied[1,2].UpontheirradiationwithUVlight(?=300～400nm),thesemonomersareconvertedtohead-to-tailphotodimersinpolarsolventwithperfectyields.Inrecentyears,ourgrouphasbeenstudyingthephotodimerizationreactionsofheteroarylethenescontainingbenzoxazolyl[3]andphenyloxazolyl[4]groups.Itw…     

A Convenient Synthesis of (S)-2-Methyl and (2S)-2,3-Dimethyl Butyl Phenylsulfones from (S)-(-)-3-Methyl-γ-butyrolactone

Suitably functionalized alkylphenylsulfones have been used as building blocks for the synthesis of several modified side-chains steroids¹. We describe here the synthesis of (S)-2-methyl and (2S)-2,3-dimethyl butyl phenylsulfones (4a) and (6), which can be used for the construction of the side chain of a few marine sterols² or brassinosteroids³ as well.     

Synthesis and Crystal Structure of 1-(o-methylphenyl)-2-(p-methoxyphenyl)-1,3,2-diazaphospholidin-4-thione-2-sulfide

11NTRODUCTIoNThederivativesofdiazaphospholidinoneorthecorrespondingthionesareknowntopossessinterestingbiologicalproperties,suchasherbicidalactivity"'2i.Inrecentyears,itwasreportedthatthel,4,2-diazaphospholindine-5-thione-2havegoodselectiveherbicidalactivity"'41.Tolookformoreeffectiveherbicideswithlowtoxicity,aseriesofnovel1-(o-methylphenyl)-2-(p-methoxyphenyl)-phospholidin-4-thione-sulfideshavebeensynthesizedandtheirmolecularstructuresstudied.PreliminarybioassaysshowthatthesecomPoundshaveg…     

Long-term γ-radiolysis kinetics of NO3(-) and NO2(-) solutions

Radiolysis kinetics in NO(3)(-) and NO(2)(-) solutions during γ-irradiation were studied at an absorbed dose rate of 2.1 Gy·s(-1) at room temperature. Air- or argon-saturated nitrate or nitrite solutions at pH 6.0 and 10.6 were irradiated, and the aqueous concentrations of molecular water decomposition products, H(2) and H(2)O(2), and the variation in the concentrations of NO(3)(-) and NO(2)(-) were measured as a function of irradiation time. The experimental data were compared with computer simulations using a comprehensive radiolysis kinetic model to aid in interpretation of the experimental results. The effect of nitrate and nitrite, present at concentrations below 10(-3) M, on water radiolysis processes occurs through reactions with the radical species generated by water radiolysis, (?)e(aq)(-), (?)O(2)(-), and (?)OH. The changes in H(2) and H(2)O(2) concentrations observed in the presence of nitrate and nitrite under a variety of conditions can be explained by a reduction in the radical concentrations. The kinetic analysis shows that the main loss pathway for H(2) is the reaction with (?)OH and the main loss pathways for H(2)O(2) are reactions with (?)e(aq)(-) and (?)OH. Nitrate and nitrite compete for the radicals leading to an increase in the concentrations of H(2) and H(2)O(2). Post-irradiation measurements of H(2), H(2)O(2), NO(2)(-) and NO(3)(-) concentrations can be used to calculate the radical concentrations and provide information on the redox conditions of the irradiated aqueous solutions.     

Reactions of 1,3-bis(ω-bromoalkyl)-6-methyluracils with 2-(dialkylamino)ethylphosphonates and 2-(dialkylamino)ethyl phosphates

1,3-Bis(4-bromobutyl)-6-methyluracil reacts with diethyl 2-(dimethylamino)ethylphosphonate to form a bisquaternary ammonium salt, whereas the reaction of 1,3-bis-(6-bromohexyl)-6-methyluracil with diethyl 2-(diethylamino)ethyl phosphate gives 1,3-bis-[(6-diethoxyphosphoryloxy)hexyl]-6-methyluracil and 1,1,4,4-tetraethylpiperazinium dibromide. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1130–1132, June, 2000.     

Indole derivatives. 138. Synthesis of α-(5-indolyl)ethylamine and 5-(2-aminoethoxy)- and 5-(aminoethylthio)tryptamines

The reaction of 5-acetylindole with hydroxylamine with subsequent reduction of the resulting oxime gave -(5-indolyl)ethylamine. Coupling of 4-(2-phthalimidoethoxy)- and 4-(2-phthalimidoethylthio)phenyldiazonium chlorides with ethyl -acetyl--phthalimidovalerate, subsequent cyclization of the resulting hydrazones, hydrolysis, decarboxylation, and removal of the phthalyl protecting group led to the formation of 5-(2-aminoethoxy)- and 5-(2-aminoethylthio)tryptamines, respectively.For Communication 137, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 46–48, January, 1992.