HYDROBORATION OF UNSATURATED AMINES X. HYDROBORATION-HALOGENATION OF ALLYL PHOSPHORAMIDATES ROUTE TO γ-HALOGENOPROPYL PHOSPHORAMIDATES AND γ-HALOGENATED AMINES

Abstract

This paper describes the synthesis of γ-halogenopropyl phosphoramidates I by hydroboration-halogenation reaction of N-phosphorylated allylamines II (phosphoramidates and phosphoramides). Only the use of allyl phosphoramidates leads to a good regioselectivity of the addition of boron atom on the terminal carbon atom of the allyl structure (compounds III).

The absence of N→B complex formation permits a good reactivity of the trialkylboranes III and IV. The breaking of the P[sbnd]N bond, in acidic medium of the compounds I gives corresponding γ-halogenated amines V.     

SYNTHESIS AND REACTVITY OF N-[N-PHOSPHORAMIDO-1H-BENZIMIDAZOL-2-YL] IMIDATES

N-(-1H-Benzimidazol-2-yl) imidates 1a–c react with chlorophosphoramide to give the N-[-1-N,N,N′,N′-tetramethylphosphoramidoyl-1H-benzimidazol-2-yl]-imidates 2a–c or with dichlorophosphoramide to yield the bis[(N-1-benzimidazol-2-yl)-imidate] phosphoramide derivatives 3a–b. The reaction of compounds 2a–c toward primary amines is studied. The obtained amidine derivatives 4a–b were unambiguously characterized by different spectroscopic techniques (IR, ¹H, ¹³C, and ³¹P NMR, and in some cases MS).     

SYNTHESIS AND CHARACTERISATION OF TIN(IV) AND ORGANOTIN(IV) COMPLEXES OF [N′-2-HYDROXYPHENYL-6-METHYLPYRIDINE-2-CARBALDIMINE. X-RAY CRYSTAL STRUCTURES OF n-BUTYLDICHLORO[N′-2-HYDROXYPHENYL-6-METHYLPYRIDINE-2-CARBALDIMINATO(1-)N,N′,O]TIN(IV) AND DIPHENYLCHLORO [N′-2-HYDROXYPHENYL-6-METHYL-PYRIDINE-2-CARBALDIMINATO(1-) N,N′,O]TIN(IV)

Abstract

The reactions of N′-2-hydroxyphenyl-6-methylpyridine-2-carbaldimine (LH) with tin(IV) chloride and organotin(IV) chlorides result in the formation of the corresponding tin(IV) and organotin(IV) complexes in which LH behaves as a uninegative tridentate ligand coordinating to the central tin atom via an N,N,O donor set. Crystal structure determinations of two of the compounds, n-butyldichloro[N′-2-hydroxyphenyl-6-methylpyridine-2-carbaldiminato(l-)N,N′,O]-tin(IV) (BuSnCl₂.L) and diphenylchloro[N′-2-hydroxyphenyl-6-methylpyridine-2-carbaldiminato(l-)N,N′,O]tin(IV) (Ph₂SnCl.L), have been performed and both structures feature distorted octahedral geometries about the tin centres. Systematic differences in the Sn-ligand separations are rationalised in terms of the reduced Lewis acidity of tin in Ph₂SnCl.L.     

Synthesis and characterization of N′-(11H-indeno[1,2-b]quinoxalin-11-ylidene)benzohydrazonamides as potential antimicrobial agents

Abstract

A series of new N′-(11H-indeno[1,2-b]quinoxalin-11-ylidene)benzohydrazonamides 3a–3j was synthesized in excellent yields from the reaction of N³-substituted benzohydrazonamides 1 and 2-(11H-indeno[1,2-b]quinoxalin-11-ylidene)malononitrile 2 in dichloromethane or with 11H-indeno[1,2-b]quinoxalin-11-one 4 in ethyl acetate at ambient temperature. The new compounds have been characterized and screened for biological activity. Some of them showed significant antibacterial and antifungal activities. In particular, compounds 3c and 3e showed interesting activities as antibacterial agents while compounds 3a 3c, 3e, 3g, and 3i showed high antifungal activities.     

SYNTHESIS OF 2-THIOXOPYRIDO[2,3-d]PY RIMIDINE-4- ONES AND 1,4-BRIDGED BIS-2-THIOXO-1,2,3,4-TETRAHYDRO-5-PYRIMIDINE CARBOXYLIC ACID ETHYL ESTER DERIVATIVES

Abstract

The synthesis and structural characterization of 2-thioxopyrido[2,3-d]pynmidinethiones 5,9,12 and 4,4′-(1,4-phenylene)-di-(2-thioxo-1,2,3,4-tetrahydropyrimidines) 16-22 are described.     

Über Reaktionen von Alkylbiguaniden mit Benzoin beimpH der Biguanidbasen

Summary Alkylbiguanides2 a–e react with benzoin (1) at thepH of the base in different ways.1 undergoes in presence of2 a, c oxidation to benzoic acid which reacts with the bases2 a, c to yield 4-phenyl-1,3,5-triazinamines3 c, 4 c; in presence of2 b 1 is transformed to benzil, which reacts with2 b under rearrangement to yield 1-(4-oxo-5,5-diphenyl-2-imidazolin-2-yl)-3,3-dimethylguanidine (5 b). However, the cycloalkylbiguanides2 d, e, react in presence of nitrogen as well as oxygen with1 to yield piperidine-1-[N-(4,5-diphenylimidazol-2-yl)-carboxamidine] (7 d), resp. morpholine-4-[N-(4,5-diphenylimidazol-2-yl)-carboxamidine] (7 e). The structure of7 e was established by means of an X-ray structure analysis. All proton- and carbon resonances were assigned on the basis of 2-dimensional NMR data.

     

Über Reaktionen von Arylbiguaniden mit Benzoin beimpH der Biguanidbasen

Summary Arylbiguanides2 a–e react with benzoin (1) at thepH of the base to two different products.1 undergoes in presence of the base2 a–e oxidation to benzil and benzoic acid, which reacts fast with the arylbiguanides2 a–e to yield N-[4-(arylamino)-6-phenyl-1,3,5-triazine-2-yl]benzamides3 a–d. After lowering thepH of the reaction mixture, the bases2 b–e react with benzil to yield 2-[1-aryl-5-oxo-4,4-diphenyl-2-imidazoline-2-yl]guanidine4 b–e. The mechanism of the formation is discussed. The structure of4b was established from a single crystal x-ray structure analysis. The analysis was carried out at 100K: C₂₃H₂₁N₅O,M _r=383.5, monoclinic, C 2/c,a=15.842(6),b=8.419(3),c=30.223(10) Å, =98.44(3)°,V=3 987.3(9) ų,Z=8,d _x=1.277 g/cm³, =0.81 cm^–1,R=5.89%R _w=4.97% (1 537 observations, 233 parameters).

     

2-Ethanethioamide in Heterocyclic Synthesis: Synthesis and Characterization of Several New Pyridine and Fused Azolo- and Azinopyridine Derivatives

Pyridine-2(1H)-thione derivatives 3a,b were synthesized from the reaction of 1-(phenyl-sulfanyl)acetone (1) and cinnnamonitrile derivatives 2a,b. Compounds 3a,b reacted with different halogenated reagents 7a–f to give 2-S-alkylpyridine derivatives 8a–l, which could be, in turn, cyclized into the corresponding thieno[2,3-b]pyridine derivatives 9a–l. Compounds 9d,j reacted with acetic anhydride, formic acid, carbon disulfide, phenyl isothiocyanate, and nitrous acid to yield the corresponding pyrido[3′,2′:4,5]thieno[2,3-d]pyrimidine 12a,b, 15a,b, 17a,b, 20a,b, and pyrido[3′,2′:4,5]thieno[2,3-d][1,2,3]triazinone derivatives 22a,b, respectively.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Thieno[2,3-b]pyridine-2-carbohydrazide in Polyheterocyclic Synthesis: The Synthesis of Pyrido[3′,2′:4,5]thieno[3,2-d]pyrimidine,Pyrido[3′,2′:4,5]thieno[3,2-d][1,2,3]triazine,and Pyrazolyl,Oxadiazolylthieno[2,3-b]pyridine Derivatives

Pyrdine-2(1H)-thione 1 reacted with ethyl chloroacetate 2 to give 2-S-ethoxy-carbonylmethylpyridine derivative 3, which could be cyclized into thieno[2,3-b]-pyridine-2-carbohydrazide derivative 5 by boiling with hydrazine hydrate. The latter compound reacted with cinnamonitrile derivatives 6a, b, triethylorthoformate, formic acid, dimethylformamide-dimethylacetal, and diethyl carbonate to give the corresponding shiff base 7a, b and pyrido[3′,2′;-4,5]thieno[3,2-d]pyrimidine derivatives 10–13 in respective manner. On the other hand, compound 5 also reacted with carbondisulphide and phenyl isothiocyanate to afford the corresponding 2-(1,3,4-oxadiazolo-2-yl)thieno[2,3-b]pyridine derivatives 18 and 22. Finally, compound 5 reacted with some β-dicarbonyl compounds, such as ethyl acetoacetate, acetylacetone and ethyl β-arylazoacetoacetate, to yield the corresponding 2-(pyrazol-1-yl-carbonyl)thieno[2,3-b]pyridine derivatives 24, 25, and 27 respectively.     

One-Pot Synthesis and Methylation of 3-[2-(1H-Benzimidazol-2-yl-Sulfanyl)-Acetyl]-Chromen-2-Ones

Abstract

3-(2-Bromoacetyl)coumarins (I), when treated with 2-mercatobenzimidazole (II) in acetone containing K₂CO₃ (mild base) and tetrabutylammonium bromide (TBAB) as a phase transfer catalyst, at room temperature yielded the title compound 3-[2-(1H-benzimidazole-2-yl-sufanyl)-acetyl]-chromen-2-one (III) in a one-pot synthesis. Alternatively, III could also be prepared by treating dithiocarbonic acid O-ethyl ester, S-[2-oxo-2-(2-oxo-2H-chromen3-yl)-ethyl] ester (V), with o-phenylenediamine (VI). The methylation of the title compound III was performed with dimethyl sulfate (DMS), in acetonitrile containing TBAB and K₂CO₃ at room temperature, resulting in 3-[2-(N-methyl-benzimidazol-2-yl-sulfanyl)]-acetyl-chromen-2-ones (VII). Alternatively, methylation of III could also be performed with DMS in acetonitrile containing K₂CO₃ as base and clay as surface catalyst. All the compounds were synthesized in good yields and their structures were confirmed by spectral and analytical data.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: ¹H NMR of IIIB, VB and VIIB]     

1,3-Bis[tert-butyl(di-tert-butylfluorsilyl)amino]trisulfan – eine Verbindung mit FSiNSSSNSiF-Helix

1,3-Bis[tert-butyl(di-tert-butylfluorosilyl)amino]trisulfane – a Compound with FSiNSSSNSiF Helix The lithium derivative of tert-butyl(di-tert-butylfluorosilyl)-amine ( 1 ) reacts with sulfur or selenium to give the bis[(fluorosilyl)-amino]di- and -trisulfanes 2, 3 and -selane 4 , respectively. The trisulfane 3 crystallizes from n-hexane and exhibits a helical structure (X-ray analysis).     

由MOPIP配体构筑的两种金属配合物的合成、表征及晶体结构(英文)

采用水热法由2种不同金属盐和MOPIP(MOPIP=2-(4-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline)配体合成了2种新型零维配合物[Cd(MOPIP)3(H2O)9]4n(1)和[Mn(MOPIP)3(H2O)6]2n(2),并对其进行了元素分析、红外光谱表征、热失重和X射线单晶衍射测定。结果表明,每个金属中心离子与来自3个不同MOPIP分子上的6个氮原子进行配位,形成畸变的八面体构型。     

Reactivity and Synthetic Utility of 1,3,2λ5-Dioxaphospholanes

Abstract

The kinetics of Lewis acid-mediated decomposition and definitions of the synthetic applicability of 1,3,2λ⁵-dioxaphospholanes for (i) the syntheses of highly-hindered epoxides, and (ii) the stereospecific functionalizations of stereocenters in 1,2-diol arrays are described.     

REAKTIONEN VON THIOXOHETEROCYCLEN MIT N-CHLORAMIDEN 111.1 2- ODER 4-THIOPYRIDONE OHNE SUBSTITUENTEN AM STICKSTOFF UND NATRIUM-N-CHLORBENZOLSULFONAMIDE

Abstract

2- and 4-pyridinethiones (A) react with sodium N-chlorobenzenesulfonamides (1) in alcoholic solvents to N- (pyridy1thio)benzenesulfonamides (C), sodium N, N′-bis(phenylsulfonyl)-S-pyridylsulfodiimidates (D) and S-alkoxy-N-phenylsulfonyl-S-pyridylsulfimides (E). Constitution proofs for the new compounds D, E are reactions and ¹H-, ¹³C-, ¹⁵N-nmr data.

2- und 4-Thiopyridone (A) reagieren mit Natrium-N-chlorbenzolsulfonamiden (1) in alkoholhaltigen Lösungsmitteln zu N- (Pyridylthio)benzolsulfonamiden (C), Natrium-N, N′-bis(phenylsulfony1)-S-pyridylsulfodiimidaten (D) und S-Alkoxy-N-phenylsulfonyl-S-pyridylsulfimiden (E). Konstitutionsbeweise für die neuen Verbindungen D, E sind Reaktionen sowie ¹H-, ¹³C- und ¹⁵N-NMR-Daten.     

One-Pot Green Synthesis of 3'-(2-Aminobenzimidazolyl)-2-Phenyl Spiro[4H-Benzopyran-4,2'-Thiazolidin]-4-Ones and Acylation Using Trifluoroacetic Anhydride

Abstract

An expeditious one-pot synthesis of a novel heterocyclic system, 3′-(2-aminobenzimidazolyl)-2-phenyl spiro[4H-benzopyran-4,2′-thiazolidin]-4-ones, has been accomplished by condensing substituted hydrazinobenzimidazole, flavanone, and mercaptoacetic acid by conventional heating in ethanol or toluene, and in an ionic liquid, viz., 1-butyl-3-methyl-imidazolium hexafluorophosphate. Excellent yields (85%–90%) and higher purity are obtained in the ionic-liquid-mediated synthesis as compared with the conventional procedure (55%–60%). Further, these compounds were acylated with trifluoroacetic anhydride. The structures of the compounds were confirmed by IR, ¹H NMR, ¹³C NMR, mass spectral data, and elemental analysis. The compounds, upon evaluation for their antibacterial, antifungal, and insecticidal activities, exhibited excellent results.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Table S1, S2, and S3]

GRAPHICAL ABSTRACT      

Reactions of trimethinecyanines of the 1,3-dioxenium series with nucleophiles. The structures of the parent carbocation and of a product of its reaction with methanol

The chemistry and the regioselectivity of alcoholysis, aminolysis, and hydrolysis of symmetrical trimethinecyanine carbenium ions in 4-[3-(2,2-diorganyl-6-phenyl-4H-1,3-dioxen-4-ylidene) prop-1-enyl]-2,2-diorganyl-6-phenyl-1,3-dioxenium perchlorates (4a,b) were investigated. The structures of trimethinecyanine 4,5:4′,5′-bisannelated at the methine chain (3) and of a product of the reaction of nonannelated trimethinecyanine with the methoxide anion were established by X-ray diffraction analysis,¹H NMR spectroscopy, and quantum-chemical calculations (PM3). The nucleophile attacks the mesomeric π-conjugated system of the trimethinecyanine cation selectivily at the C(6) atom of one of the dioxenium fragrments, the second dioxenium ring being deactivated. Alcoholysis affords products of addition of the methoxy group to trimethinecyamines. In the course of aminolysis and hydrolysis, the dioxenium ring that is subjected to the attack eliminates acetone to form 1,3-dioxenylidenepropenylic derivatives of 1,3-enaminoketones and 1,3-ketoenols, respectively. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 521–529, March. 1999.     

1,3-Disubstitutedpyrazole-4-caboxaldehyde in Heterocyclic Synthesis: A Novel Synthesis of Pyridine-2(1H)-thione and Fused Nitrogen and/or Sulfur Heterocyclic Derivatives

Pyridine-2(1H)-thione 5 was synthesized from the reaction of 3-[3-(4-chlorophenyl)-1-phenyl-1H-pyrazol-4-yl]-1-phenylpropenone (3) and cynothioacetamide (4). Compound 5 reacted with halogented compounds 6a–e to give 2-S-alkylpyridine derivatives 7a–e, which could be in turn cyclized into the corresponding thieno[2,3-b]-pyridine derivatives 8a–e. Compound 8a reacted with hydrazine hydrate to give 9. The latter compound reacted with acetic anhydride (10a), formic acid (10b), acetic acid, ethyl acetoacetate, and pentane-2,4-dione to give the corresponding pyrido[3′,2′:4,5]thieno-[3,2-d]pyrimidine 13a,b, pyrazolo[3′,4′:4,5]thieno[3,2-d]pyridine 14 and thieno[2,3-b]-pyridine derivatives 18 and 20, respectively. Alternatively, 8c reacted with 10a,b and nitrous acid to afford the corresponding pyrido[3′,2′:4,5]thieno[3,2-d]pyrimidine 24a,b and pyrido[3′,2′:4,5]thieno[3,2-d][1,2,3]triazine 26 derivatives, respectively. Finally compound 5 reacted with methyl iodide to give 2-methylthiopyridine derivative 27, which could be reacted with hydrazine hydrate to yield the corresponding pyrazolo[3,4-b]-pyridine derivative 29.     

SYNTHESIS OF 2,2-DISUBSTITUTED-1,3-PROPANE-DITHIOLS

Abstract

A method for the preparation of 2,2-disubstituted-1,3-propanedithiols from the corresponding diols is described. The success of the synthesis is governed by the solvent in which the nucleofilic substitution, dimesylate to dirhodanide, is performed. The proposed reaction sequence is tested out for several diols and the overall yields are very good with respect to the strongly hindered[sbnd]sterically ‐neopentyl-structure. All compounds are identified by ¹H-nmr.     

Lanthanide Recognition: Development of an Asymetric Gadolinium Microsensor Based on N-(2-pyridyl)-N′-(4-nitrophenyl)thiourea

Abstract

The first asymmetric potentiometric Gd(III) microsensor is reported here. N-(2-Pyridyl)-N′-(4-nitrophenyl)thiourea (PyTu₄NO₂) was found to have a very selective and sensitive behavior toward Gd(III) ions, in comparison to other lanthanide ions as well as inner transition and representative metal ions and hence was used as a sensing material in the construction of a Gd(III) microelectrode. The Gd(III) sensor exhibits a Nernstian slope of 17.46 ± 0.3 mV per decade over the concentration range of 1.0 × 10^?8 to 1.0 × 10^?3 M and a detection limit of 3.0 × 10^?9 M of Gd(III) ions. The potentiometric response of the sensor is independent of the solution pH in the range of 4.0–9.0. It manifests advantages of low detection limit and fast response time (10–15 s).     

Facile Preparation and Molecular Structure of a Novel Metacyclophane

Abstract

A novel 1,1,10,10,19,19-hexamethyl-5,14,23-trimethoxy[3.3.3]metacyclophane (2) was prepared in 25% yield by Friedel–Crafts cyclization of 4-(2-methoxyphenyl)-2-methylbutan-2-ol (1) at ? 78 °C using TiCl₄ as Lewis acid catalyst in anhydrous dichloromethane. The structure of cyclophane 2 was determined by single-crystal X-ray diffraction, and the impact of substrate concentration on the yield of macrocycle 2 was also examined. The study on the effect of substituents at the phenyl ring showed that the methoxy group in 1 is crucial for its trimerization to give the hexamethyl[3.3.3]metacyclophane derivative. Demethylation of 2 with BBr₃ gave 1,1,10,10,19,19-hexamethyl-5,14,23-trihydroxy[3.3.3]metacyclophane (4) in 96% yield, and its three hydroxyl groups provide the possible modification sites for further construction of supramolecular assemblies.