Reaction Of Compound 1a Research Articles

The directing effect of mono primary and secondary amine group substituted cyclotriphosphazenes on the reactions of the disodium salt of tetraethylene glycol

This study examines how the mono primary and mono secondary amine groups on the cyclotriphosphazene ring will direct the tetraethylene glycol (a flexible diol) and which of the five active P-Cl bonds in the structure will be preferred in detail. Isopropylaminopentachlorocyclotriphosphazene (1a) and dimethylaminopentachloro-cyclotriphosphazene (1b) were reacted with the disodium salt of tetraethylene glycol in THF solution at 1:1 mole ratio. Four new cyclotriphosphazene derivatives; 1,3-mono ansa (2a), mono spiro (3b), trans 3,5-mono ansa (4b) and cis 3,5-mono ansa (5b) were isolated. The structures of these compounds were characterized by elemental analysis, mass spectrometry (MALDI-TOF), 1H and 31P NMR spectroscopy. Additionally, the structure of compounds 2a, 4b and 5b were illuminated by single crystal X-Ray diffraction technique. In the reaction of compound 1a with the disodium salt of tetraethylene glycol, it was determined that the ONa+ group was primarily replaced the chlorine atom of the PCl(NHR) group (via proton abstraction/chloride elimination), whereas compound 1b gave a nucleophilic substitution reaction with chlorine atoms on other phosphorus atoms (via SN2 and SN1 reaction mechanisms, respectively).

Synthesis and reactivity of germyl complex of Ruthenium(II)

Reaction of [RuCl(η5-C5Me5)L] and [RuCl(η5-C9H7)L] (L = 1,2-[bis(diphenyl) phosphanyloxy]-1,2-diphenylethane) with an excess of GeCl2·dioxane afforded the half-sandwich trichlorogermyl complexes [Ru(GeCl3)(η5-C5Me5)L] (1a) and [Ru(GeCl3)(η5-C9H7)L] (1b). Trihydridogermyl derivatives [Ru(GeH3)(Cp′)L] [Cp′ = η5-C5Me5 (2a), η5-C9H7 (2b)] were obtained by treating 1a and 1b with LiAlH4. Reaction of compound 1a with MeMgBr gave the monomethyl derivative [Ru(GeMeCl2)(η5-C5Me5)L] (3a) while the reaction between the complex 1b and MeMgBr yielded the trimethylgermyl derivative [Ru(GeMe3)(η5-C9H7)L] (3b). All the complexes present optical activity. The complexes were characterized spectroscopically and the X-ray crystal structure of [Ru(GeCl3)(η5-C5Me5)L] (1a) was determined.

Synthesis, antibacterial activity, and fluorescence properties of a novel series from [2,4-dioxochromen-3(4H)methyl]amino acid

A new solvent-free method for synthesis of starting compounds 2,4-dioxochromen-3(4H)methyl amino acetic acid derivatives 1a–e via a green approach is reported. Also, the behavior of compound 1a towards various nitrogen nucleophiles such as primary amines, hydrazine hydrate, and hydroxylamine hydrochloride to give corresponding compounds 2–4 was studied. Furthermore, chlorination of compound 1a using a mixture of PCl5/POCl3 to yield acid chloride derivative 5 and the reaction of the latter compound 5 with various amino acids to obtain dipeptide compounds 6a–e are described. Moreover, cyclization of compound 1a in alkaline medium to afford dihydrochromeno[3,4-c]pyrrole-1-carboxylic acid 7 and cyclization of 6b in acidic medium, namely Ac2O, to yield piperazine derivative 8 are reported. Also, reaction of compound 1a with maleic anhydride in dioxane to afford Diels–Alder adduct 9, which posteriorly reacted with hydrazine hydrate to give 10, was investigated. Most of the newly synthesized compounds were screened against Gram-positive and Gram-negative bacteria, with compound 5 exhibiting the maximum inhibition zone towards all four types of bacteria. In addition, the absorption and fluorescence emission of some of the substituted coumarins were studied in dioxane, revealing that the substituents altered both the absorption and fluorescence emission maxima.

Synthesis, Structure of Zinc Complexes Containing Sulfonylated Binaphtholate Ligands and Their Catalytic Activities towards Ring‐Opening Polymerization of Lactide and ε‐Caprolactone

AbstractReaction of sulfonylated binaphthol [2‐hydroxy‐2′‐tosyloxy‐1,1‐binaphthyl (1a, Ts‐Binol) or 2‐hydroxy‐2′‐(phenylsulfonyloxy)‐1,1‐binaphthyl (1b, Ps‐Binol)] with 1 equiv. of ZnEt2 afforded zinc complexes [(Ts‐Binol)ZnEt]2 (2a) and [(Ps‐Binol)ZnEt]2 (2b). Further reaction of zinc complexes 2a and 2b with benzyl alcohol (BnOH) gave the zinc benzyloxide [(Ts‐Binol)2Zn2(OBn)2]2 (3a) and [(Ps‐Binol)2Zn2(OBn)2]2 (3b). Alternatively, the zinc benzyloxides 3a and 3b could also be obtained by reaction of compound 1a or 1b with Zn(OBn)2 (in situ reaction of ZnEt2 and BnOH). The complexes were fully characterized by elemental analyses and spectroscopic analyses, and complexes 2a, 2b and 3a were further characterized by single‐crystal X‐ray analyses. The catalytic activities of these zinc complexes towards ring‐opening polymerization of ε‐caprolactone and D,L‐lactide were studied.

Utility of α-Oxoketene and α-Cyanoketene Thioacetals in Heterocyclic Syntheses: Synthesis of Some New Benzothiazepine Derivatives

Benzo[b][1,5]thiazepines 1a or 1b were prepared via reaction of o-aminothiophenol with 3-(bis(methylthio)methylene)-pentane-2,4-dione or 2-(bis(methylthio)methylene)-3-carbonitrile, respectively. Reaction of compound 1a with malononitrile afforded pyrano[4,3-b]benzothiazepine 2a, which underwent cyclization into pyrido[4,3-b][1,5]benzothiazepine 2b. Also, reaction of compound 1a with ethyl cyanoacetate afforded pyrano[4,3-b][1,5]benzothiazepin-3-one 3. Reaction of compound 1a with hydrazine, phenylhydrazine, or hydroxylamine afforded the corresponding azolobenzothiazepines, 4–6, respectively. Reaction of compound 1a with ethylenediamine afforded 1,5-benzothiazepin-ethanone 7, which underwent cyclization to [1,4]diazepino[5,6-b][1,5]benzothiazepine 8. Also, compound 1b was reacted with acetylacetone or ethyl acetoacetate to afford pyrano[4,3-b][1,5]benzothiazepines 9a or 9b, which reacted with ammonium acetate to give pyrano[4,3-b][1,5]-benzothiazepine 10a or pyrido[4,3-b][1,5]-benzothiazepine 10b, respectively. Compound 1b was allowed to react with hydrazine, phenylhydrazine, or hydroxyl amine to afford pyrazolo or isoxazolo[3,4-b][1,5]benzothiazepines 11, 12, or 13, respectively.

Reactions of 3-[N-chloroacetylamino-N-(4-nitrophenyl)]-2-formylindole with alkylamines

The reactions of 3-[N-chloracetylamino-N-(4-nitrophenyl)]-2-formylindole (1a) with 2-(N, N-dialkylamino)ethylamines afford complex condensation products 7b,c consisting of two similar but not identical diazepinoindole fragments. For the reaction of compound 1a with 3-(N,N-diethylamino)propylamine, the process occurs in a different manner, and the predominant product is 4-ethylaminopropyl-1-(4-nitrophenyl)-2-oxo-1,2,3,4,5,6-hexahydro[1,4]diazepino[6,5-b]indole hydrocloride (14). Two routes of these unexpected transformations were proposed. The structures of the synthesized products were proved by the 1sH and 13C NMR, HMBC, and HSQC (direct proton-carbon correlation) spectra.

New 1,2,4‐Triazine‐Containing Podands: Synthesis and Properties.

AbstractFor Abstract see ChemInform Abstract in Full Text.

New 1,2,4-triazine-containing podands: synthesis and properties

A method of one-step C-C coupling of 1,5-bis(2,6-dimethylphenoxy)-3-oxapentane (1a) and 1,8-bis(2,6-dimethylphenoxy)-3,6-dioxaoctane (1b) with 3-methylthio- (2) and 3-amino-1,2,4-triazine (3) and 3-aryl-1,2,4-triazin-5-one (6-8) has been described. The reaction of compounds 1a,b with compounds 2 and 3 in the presence of trifluoroacetic acid results in the addition of the dimethylphenoxy group to the unsubstituted C(5) carbon atom of the triazine ring. The reactions of triazinones 6-8 with compounds 1a,b in a mixture of trifluoroacetic acid and organic anhydrides are accompanied by the acylation of the nitrogen atom adjacent to the reaction center and affords bis[(3-R-1-acyl-5-oxo-1,4,5,6-tetrahydro-1,2,4-triazin-6-yl)-2,6-dimethylphenoxy]-3-oxapentane or -3,6-dioxaoctane. The obtained adducts can smoothly be oxidized under mild conditions to form more stable products of nucleophilic hydrogen substitution in the triazine ring. The extraction and transport of Ca2+ and Mg2+ cations through an organic membrane by the compounds synthesized are discussed.

Thiazoline and thiazoloxazole in synthesis of novel meso-substituted mono-, tri-, and hepta-methine cyanine dyes

2-Cyanomethylene (2-ethoxy carbonylmethylene)-4,5-dihydrothiazolin-4-one 1a,b and 2-cyanomethylene (2-ethoxy carbonylmethylene)-4,5-dihydrothiazolo [3,2-a]oxazole 3a, b were synthesized as starting material. Reaction of both compounds 2a, b and 3a, b with N-methylheterocyclic quaternary salts afforded meso-substituted monomethine cyanine dyes 4a– d and 9a– d, respectively. Reaction of compounds 1a, b and 8a, b with ethyl orthoformate gave the intermediate compounds 5a, b and 10a, b, followed by the reaction with 1,2-dimethyl quinolinium iodide resulted in meso-substituted trimethine cyanine dyes 6a, b and 11a, b, respectively. Also, reaction of both 2a, b and 3a, b with 2-chlorocyclohexane-1,3-dicarboxaldehyde followed by the reaction with 1,2-dimethyl quinolinium iodide afforded the asymmetrical heptamethine dyes 8a, b and 13a, b. The new compounds were characterized by elemental analysis, visible absorption, 1H NMR, IR Spectroscopy and Ms spectral data. Relation between the constitution and the UV/Vis spectroscopic properties of these dyes has been studied.

Synthesis of New Fused and Spiro 1,5‐Benzodiazepines

Abstract[1,3‐Dihydro‐4‐phenyl(1,5)benzodiazepin‐2‐ylidene]malononitrile 1a was treated with formaline and some different primary amines to give the corresponding pyrimido(1,5)benzodiazepines 2a–d. Treatment of compound 1a with halo reagents yielded the corresponding pyrrolobenzodiazepines 3a,b. The reaction of compound 1a with active methylenes, bidentates, S,S‐ and N,S‐acetals afforded the corresponding spiro(1,5)‐benzodiazepines 4a‐c–8a,b, respectively.

1,2-Nucleophilic addition on 2-phenyl-3H-indol-3-one and 2-phenyl-3-phenylimino-3H-indole and their corresponding 1-oxides. An attempt to synthesize water-soluble aminoxyls. Crystal structure of 3-ethoxycarbonyl-2,3,3a,4-tetrahydro-2,4-dioxo-3a-phenylisoxazolo[2,3-a]indole

3-Indolinonic (1a) and 3-phenyliminoindolinonic (1b) 1-oxides react at carbon 2 with diethyl malonate and ethyl acetoacetate anions, yielding intermediate anions which undergo cyclization in the reaction medium to form an isoxazolidine ring. The cyclization occurs through the interaction of the oxygen of the primitive N-oxide function with a carbonyl group of the reagents. The same substrates react with dilithium phenylacetate anion, leading to the formation of stable and water-soluble carboxylated aminoxyls. The indolenin-3-one 2a and its corresponding 3-phenylimino derivative 2b also react with the above-mentioned nucleophiles to form carboxylated 3-indoxyls without cyclization; oxidation with m-chloroperbenzoic acid does not yield carboxylated aminoxyls in appreciable amount. The structure of the product of cycloaddition obtained from the reaction of compound 1a with diethyl malonate was determined by X-ray analysis.

Synthesis and reactivity of bis(ethylene)-phosphite complexes of molybdenum(0)

The compounds trans-Mo(C 2H 4) 2{P(OR) 3&} 4 (R = Me, 1a:Et, 1b) were prepared by the direct reduction of MoCl 4(THF) 2 with NaHg, under ethylene, in the presence of the appropriate phosphite. Reaction of 1 with CO yields trans,trans-Mo(C 2H 4) 2(CO) 2 [P(OR) 3] 4 (R = Me, 2a: Et, 2b), while the interaction of 1a with CN 1Pr affords the comples trans,trans-Mo(C 2H 4) 2(CN 1Pr) 2{P(OMe) 3&} 2 ( 3). The reaction of compounds 1a and 1b with CO 2 provides hybrido acrylate derivatives of composition MoH(OOCCHCH 2){P(OR) 3&} 4 (R  Me, 4a: Et, 4b), which are formed through a coupling of the ethylene ligand and carbon dioxide at the molybdenum center. The analogous reaction of 1b with CS 2 produces instead Mo(C 2S 4)(C 2H 4){P(Et) 3&} 3 ( 5) containing a head-to-tail carbon disulfide metallacycle dimer.

Isolation, structure and reaction of selenobenzophenones. X-Ray molecular structure of 4,4′-dimethoxyselenobenzophenone and of 4,4-biphenyl-2,3-diselenabicyclo[3.3.0]oct-7-ene

4,4′-Dimethoxy-1a and 4,4′-dimethyl-selenobenzophenone 1b could be isolated in moderate yields by the reaction of the corresponding ylides 3 with elemental selenium in benzene at 80 °C. Their spectral data are described. Attempted isolation of unsubstituted selenobenzophenone afforded only its dimer 5. Compound 1a crystallizes in space group P21/n with unit-cell parameters a= 7.191(3), b= 7.505(4), c= 24.856(4)A, β= 90.32(1)°, Z= 4, R= 0.055. The oxidation and thiation of 4,4′-dimethoxyselenobenzophenone 1a afforded the corresponding benzophenone and thiobenzophenone in good yields. The reaction of compound 1 with cyclopentadiene afforded the corresponding cycloadducts 7(3,3-diaryl-2-selenabicyclo[2.2.1] hept-5-enes), whereas bicyclic diselenides 8(4,4-diaryl-2, 3-diselenabicyclo[3.3.0]oct-7-enes) were obtained by using an excess of selenium and a higher temperature. Oxidation of compound 8c gave the corresponding diol 12, aldehyde 13, and diphenylfulvene 11. The reaction of compound 1a with benzenediazonium carboxylate afforded 2,2- bis-(4-methoxyphenyl)-4H-3,1 -benzooxaselenin -4-one 17.