THE NOVEL MACROCYCLIC AND LINEAR-CHAIN THIOETHERS FROM PERCHLOROBUTADIENE AND DITHIOLES

Compounds 3a–c, 4a, b, 5a–c, and 6a, c were obtained from the reactions of perchlorobutadiene (1) with 1,4-butanedithiol (2a), 1,5-pentanethiol (2b), and 2.2′-(ethlene-dioxyl)diethanethiol (2c) in ethanol in the presence of sodium hydroxide. Compounds 7a, b were obtained from the reactions of thioethers 3a, b with m-chlorperbenzoic acid in CHCl ₃ .     

Untersuchungen über die Bildung von 2-Acylcyclopentanonen aus 1-(1-Äthynyl)-cyclopentenen und Perameisensäure

The reaction of1 a with H₂O₂ in HCOOH yielded 37%4 a and 15%3 a. 1 c reacted under similar conditions to4 c (29%),3 b (12%) and3 c (22%).1 b was less reactive towards H₂O₂ in HCOOH due to its low solubility in HCOOH;4 b was isolated with 6% yield, 69%1 b remained unchanged.Under conditions of epoxide hydrolysis and catalysis of theRupe rearrangement, the epoxides2 a and2 b yielded 37%4 a and 30%4 b, resp.Based upon these experimental results, mechanisms for the observed reactions are proposed.     

Synthesis and Cation-Binding Properties of (1→6)-2,5-Anhydro-D-glucitol with 3,4-Di-O-Pentyl and Decyl Groups by Cyclopolymerization of 1,2:5,6-Dianhydro-D-mannitols

Abstract

The cyclopolymerizations of 1,2:5,6-dianhydro-3,4-di-O-pentyl-D-mannitol (1b) and 1,2:5,6-dianhydro-3,4-di-O-decyl-D-mannitol (1c) were carried out using BF₃OEt₂ and t-BuOK. All the resulting polymers consisted of cyclic constitutional units, i.e., the extent of cyclization was 100%. The polymer structures for the polymerization with t-BuOK were (1→6)-2,5-anhydro-3,4-di-O-pentyl-D-glucitol (2b) and (1→6)-2,5-anhydro-3,4-di-O-decyl-D-glucitol (2c), whereas those with BF₃O-decyl₂ comprised 2,5-anhydro-D-glucitols as major units along with other cyclic ones. These polymers were soluble in n-hexane, CHCl₃, and THF, but insoluble in water, which differs from the amphiphilic solubility of (1→6)-2,5-anhydro-3,4-di-O-methyl-D-glucitol (2a). The cation-binding properties of 2b and 2c were examined using alkali-metal picrates in order to compare them with those of 2a. The extraction yields for each cation decreased in the order of 2c < 2b < 2a. Every polymer exhibited a similar cation-binding selectivity in the order Cs⁺ > Rb⁺ > K⁺ ? Na⁺ > Li⁺. The ratio of K⁺ and Na⁺, K⁺/Na⁺, was 4.6 for 2a, 5.1 for 2b, and 7.1 for 2c in the increasing order 2a < 2b > 2c.     

Ruthenium(II) carbonyl complexes of P,P and P,O donor diphosphine ligands,Ph2P(CH2)nPPh2 and Ph2P(CH2)nP(O)Ph2, n = 2, 3 and their activities in catalytic transfer hydrogenation reactions

The polymeric precursor [RuCl₂(CO)₂]_n reacts with the ligands, P∩P (a, b) and P∩O (c, d), in 1:1 M ratio to generate six-coordinate complexes [RuCl₂(CO)₂(?²-P∩P)] (1a, 1b) and [RuCl₂(CO)₂(?²-P∩O)] (1c, 1d), where P∩P: Ph₂P(CH₂)_nPPh₂, n = 2(a), 3(b); P∩O: Ph₂P(CH₂)_nP(O)Ph₂, n = 2(c), 3(d). The complexes are characterized by elemental analyses, mass spectrometry, thermal studies, IR, and NMR spectroscopy. 1a–1d are active in catalyzed transfer hydrogenation of acetophenone and its derivatives to corresponding alcohols with turnover frequency (TOF) of 75–290 h^?1. The complexes exhibit higher yield of hydrogenation products than catalyzed by RuCl₃ itself. Among 1a–1d, the Ru(II) complexes of bidentate phosphine (1a, 1b) show higher efficiency than their monoxide analogs (1c, 1d). However, the recycling experiments with the catalysts for hydrogenation of 4-nitroacetophenone exhibit a different trend in which the catalytic activities of 1a, 1b, and 1d decrease considerably, while 1c shows similar activity during the second run.     

Remarkably Efficient and Direct Route to Quinolines and Benzoazepines from the Condensation of Benzoxazinediones with Phosphonium Carbanion Salts

Treatment of 2H‐3,1‐benzoxazine‐2,4(1H)‐dione (1a) with vinyltriphenylphosphonium bromide (2a) gives substituted benzoazepine 8a (48% yield) and indolizinone 12 (27% yield), whereas substituted quinolinone 15 and benzoazepine 8b were isolated from the reaction of N‐methylisatoic anhydride (1b) and 2a. Furthermore, a series of quinoline derivatives was synthesized from the reactions of 1a and 1b with allyl‐(2b), alkyl‐(2c), (2d), and cyanomethyl‐(3) triphenylphosphonium salts.     

1-(2,6-二氯-4-三氟甲基苯基)-3-氰基-5-氨基吡唑及其酰胺、二酰亚胺的合成及晶体结构

2,6-二氯-4-三氟甲基苯胺经重氮化后与2,3-二氰基丙酸酯反应合成了1-(2,6-二氯-4-三氟甲基苯基)-3-氰基-5-氨基吡唑(1), 1与乙酸酐、顺丁烯二酸酐、苯甲酰氯反应得到1的乙酰胺2a、顺丁烯酰亚胺2b和苯甲酰胺2c. 通过元素分析、红外光谱、核磁共振氢谱、核磁共振碳谱、质谱等手段对其结构进行了表征. 用X射线单晶衍射测定了化合物2a, 2b和2c的晶体结构. 2a属于单斜晶系, C2/c空间群, 晶胞参数a＝1.88282(6) nm, b＝0.86541(3) nm, c＝1.90766(6) nm, β＝95.5830(10)°, V＝3.09362 nm³, Z＝8, R＝0.064, wR＝0.170. 2b属于单斜晶系, P2₁/n空间群, 晶胞参数 a＝1.28261(10) nm, b＝0.89942(7) nm, c＝1.46896(12) nm, β＝104.217(1)°, V＝1.6427(2) nm³, Z＝4, R＝0.055, wR＝0.165. 2c属于三斜晶系, P-1空间群, 晶胞参数a＝0.84613(11) nm, b＝0.98923(13) nm, c＝1.14305(15) nm, β＝96.002(2)°, V＝0.9326 nm³, Z＝2, R＝0.0684, wR＝0.1795.     

NEW HETEROAROMATIC π -LIGANDS CONTAINING BORON

The heteroaromatic anions 2-(diisopropylamino)-1,2-thiaborolide(2a), 1-ethyl-2-phenyl-1,2-azaborolide(2b), and 2-(diisopropylamino)-1,2-oxaborolide(2c) have been prepared by a multi-step synthesis using the Grubbs ring-closing metathesis. Reactions of 2a, 2b, and 2c with Cp*ZrCl ₃ afforded the corresponding Zr(IV) complexes 3.     

2-Keto-3-mercaptocinchoninic Acids as Precursors for Novel Thiazino[6,5-c]quinoline-1,5-dione Derivatives

2-Keto-3-mercaptocinchoninic acid derivatives 1a and b react with Schiff's bases 2a–d in toluene at refluxing temperature to give thiazino[6,5-c]quinoline derivatives 4a–h. Also, refluxing of 1a and b with arylazomalononitriles 5a–d in acetic acid afforded the thiazolo[6,5-c]quinoline derivatives 7a–d. The structure of all the newly synthesized products was confirmed based on elemental and spectral data.     

Syntheses of the terpenoid precursors cyclopent-2-enone and cyclohex-2-enone diesters

Summary Two reaction pathways were elaborated for the practical and convenient synthesis of the title compounds. The first route applies a bromination-dehydrobromination sequence to introduce the double bond into 1-alkoxycarbonyl-2-oxocycloalkylacetic and propionic esters (4a–c,7a,b). The application of 2,6-lutidine for dehydrobromination of -bromocycloalkanones diesters (5a–c,8a,b) provides sufficient selectivity to carry out this step without affecting the sensitive ester group. Alternative pathways, involvingMichael reaction of diethyl 2-acetylsuccinate or -glutarate with acrolein and subsequent intramolecular aldol condensation, are presented in the case of cyclohex-2-enone derivatives2a,b.

---

Zusammenfassung Für praktische und bequeme Synthesen der Titelverbindungen werden zwei Reaktionswege präsentiert. Der erste Weg basiert auf einer Bromierungs-Dehydrobromierungs-Sequenz zur Einführung der Doppelbindung in die 1-Alkoxykarbonyl-2-oxocycloalkylessig- und-propionsäureester (4a–c,7a,b). Die Anwendung von 2,6-Lutidin zur Dehydrobromierung der -Bromocycloalkanone-diester (5a–c,8a,b) sichert die ausreichende Selektivität, ohne die empfindlichen Estergruppen anzugreifen. Im Falle der Cyclohex-2-enon-Derivate (2a,b) zeigen wir einen alternativen Weg, der auf derMichael-Reaktion von Diethyl-2-acetyl-succinat bzw. -glutarat mit Acrolein basiert; die anschließende intramolekulare Aldol-Kondensation liefert die Zielprodukte.

     

Synthesis,Spectral Characterization,and Crystal Structure of Two Polymorphs of o,o’-Dichloro Dibenzyl Disulfide

2-Chlorophenyl methanethiol undergoes air oxidation catalyzed by different selenides and yields the corresponding disulfide 1 in two polymorphic forms, 1a and 1b. In the molecular structures of the two new polymorphs of o,o′-dichloro dibenzyl disulfide, the dihedral angles between the dibenzyl groups are 82.0(1)°, (1a), and 73.7(4)°, (1b), respectively [(1a): P-1, a = 8.424(2) Å, b = 8.838(2) Å, c = 10.5823(19) Å, α = 90.122(18)°, β = 112.19(2)°, γ = 95.19(2)°, V = 725.9(3) ų; (1b): P2₁/n, a = 10.5888(10) Å, b = 9.1590(6) Å, c = 15.2489(14) Å, β = 103.072(9)°, V = 1440.6(2) ų]. MOPAC computational studies yield dihedral angles of 89.6(5)° and 71.9(9)°. Crystal packing is stabilized by weak π-ring (C?H···Cg) intermolecular interactions in both 1a and 1b and by additional weak Cg ··· Cg intermolecular interactions in 1b, which influence the bond distances, bond angles, and torsion angles of the dibenzyl groups in each polymorph. Additional characterization of each polymorph has been carried out by TEM, IR, ¹H and ¹³C NMR spectroscopy, microanalysis, and by FAB mass spectrometry. TEM studies of a sample of 1a show that it contains cigar-shaped crystallites.

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.     

苯并(硫)吡喃-4-酮衍生物的合成与表征

以取代或未取代苯并(硫)吡喃-4-酮(1a～1c)为原料, 分别与呋喃甲醛和6-氨基胡椒醛发生缩合反应合成了一系列的取代或未取代苯并(硫)吡喃衍生物2a～2c和3a～3c, 化合物2a～2c和3a～3c的结构经IR, ¹H NMR, MS和元素分析进行鉴定和表征.     

胍基木吡喃糖苷的合成及其抗HIV蛋白酶活性

2,3,4-三-O-乙酰基-b-D-木吡喃糖基异硫氰酸酯1与2-氨基-4/6-取代-苯并噻唑2a～2e反应, 生成糖基硫脲衍生物3a～3e, 再在伯胺存在下经氯化汞脱硫, 得到一系列新的胍基木吡喃糖苷类化合物4a～4e, 5a～5e, 6a～6e, 7a～7e, 所有新化合物的结构均经IR, ¹H NMR, MS谱和元素分析证实, 所得产物均为β-构型. 生物活性测试结果表明, 化合物4c, 5b, 6b～6d, 7b等对HIV-1蛋白酶表现出了较高的抑制活性.     

Synthesis and physiochemical studies on binuclear Cu(II) complexes derived from 2,6-[(N-phenylpiperazin-1-yl)methyl]-4-substituted phenols

Preparation of the ligands HL¹ = 2,6-[(N-phenylpiperazin-1-yl)methyl]-p-ethylphenol; HL² = 2,6-[(N-phenylpiperazin-1-yl)methyl]-p-methoxyphenol and HL³ = 2,6-[(N-phenylpiperazin-1-yl)methyl]-p-nitrophenol are described together with their Cu(II) complexes with different bridging units. The exogenous bridges incorporated into the complexes are: hydroxo [Cu₂L(OH)(H₂O)₂](ClO₄)₂.H₂O (L¹=1a, L² =1b, L³ =1c), acetato [Cu₂L(OAc)₂]ClO₄.H₂O (L¹ =2a, L² =2b, L³ =2c) and nitrito [Cu₂L¹(NO₂)₂(H₂O)₂]ClO₄.H₂O (L¹=3a, L² =3b, L³ =3c). Complexes1a,1b,1c and2a,2b,2c contain bridging exogenous groups, while3a,3b,3c possess only open μ-phenolate structures. Both the ligands and complexes were characterized by spectral studies. Cyclic voltammetric investigation of these complexes revealed that the reaction process involves two successive quasireversible one-electron steps at different potentials. The first reduction potential is sensitive to electronic effects of the substituents at the aromatic ring of the ligand system, shifting to positive potentials when the substituents are replaced by more electrophilic groups. EPR studies indicate very weak interaction between the two copper atoms. Various covalency parameters have been calculated.     

Reactions of 3-alkylsulfanyl-2-arylazo-3-(1-azacycloalk-1-yl)acrylonitriles with maleimide

Reactions of 2-arylazo-3-(1-azacycloalk-1-yl)-3-methylsulfanylacrylonitriles with male-imide in benzene gave octahydropyrrolo[3,4-a]pyrrolizines 2a–c, decahydro-2,7a-diaza-cyclopenta[a]indene 2e, and decahydro-5-oxa-2,7a-diazacyclopenta[a]indene 2f as a result of 1,3-dipolar cycloaddition. In a similar reaction with 3-allylsulfanyl-2-arylazo-3-(1-azacycloalk-1-yl)acrylonitriles 3, dipolar cycloaddition and intramolecular cyclization competed to give a mixture of compounds 2 (major products) and 1,4,6,7,8,8a-hexahydropyrrolo[2,1-c]-1,2,4-triazines 4b–d, 1,6,7,8,9,9a-hexahydro-4H-pyrido[2,1-c]-1,2,4-triazine 4e, and 1,4,6,7,9,9a-hexahydro-1,4-oxazino[3,4-c]-1,2,4-triazine 4f (minor products).     

CONDENSATION OF TETRAKIS(HYDROXYMETHYL)PHOSPHONIUM SULFATES AND SULFONATES WITH 1,3-DIMETHYLUREA

Abstract

An unexpected displacement of one of the phosphorus groups occurred when the chloride 1a was replaced by the sulfate 1b in its reactions with 1,3-dimethylurea. The products, 2c and 5c, were bisulfates rather than sulfates. In contrast, no displacement occurred when 1a was replaced by the sulfonates 1e or 1f. A method was developed for preparing the sulfonates 1d-h, all new compounds, by metathesis of the sulfate 1b with the appropriate barium sulfonate. The sulfates 2b and 5b, prepared from the chlorides 2a and 5a by ion exchange, yielded the bisulfates 2c and 5c upon treatment with sulfuric acid. The significance of the findings is discussed.     

Synthesis and Antiviral Evaluation of Some 5‐N‐Arylaminomethyl‐2‐glycosylsulphanyl‐1,3,4‐oxadiazoles and Their Analogs against Hepatitis A and Herpes Simplex Viruses

N‐Arylaminomethyl‐3H‐1,3,4‐oxadiazole‐2‐thiones 2a,b were prepared from the corresponding N‐arylglycinoylhydrazides. A number of their thioglycoside derivatives 4–7a–c and S‐functionalized analogs 8–11a,b were synthesized by the reaction with different acetobromosugars and acyclic hydroxyalkylating agents. The antiviral activity of a number of the synthesized compounds against herpes simplex virus type 1 (HSV‐1) and hepatitis A virus (HAV) was evaluated. Compounds 5a and 5b showed promising results against HAV.     

Strukturelle Abwandlungen an partiell silylierten Kohlenhydraten mittels Triphenylphosphan-Azodicarbonsäureester, 5. Mitt.: Transformationen an Glykonolactonen

Reaction ofD-glucono-1,5-lactone1 with two equivalents oft-butyldimethylchlorosilane yields via a ringcontraction 2,6-bis-O-(t-BDMSi)-D-glucono-1,4-lactone2a as main product and a small amount of 5,6-bis-O-(t-BDMSi)-D-glucono-1,4-lactone2c. Under the same conditionsL-mannono-1,4-lactone3 is transformed to the derivatives 2,6-bis-O-(t-BDMSi)-L-mannono-1,4-lactone3a and 3,6-bis-O-(t-BDMSi)-L-mannono-1,4-lactone3c as the minor product. 2,6-bis-O-(t-BDMSi)-D-galactono-1,4-lactone4a and 2,6-bis-O-(t-BDMSi)-D-gulono-1,4-lactone5a are also prepared from the corresponding glyconolactones4 and5. Whereas the compounds2a, 2c, 4a and5a withAc ₂O-pyridine give the bisacetylderivatives2b, 2d, 4b and5b, 3c is converted by an accompanying migration of one silylgroup to the 5,6-bis-O-(t-BDMSi)-2,3-bis-O-acetyl-L-mannono-1,4-lactone3d. The gluconolactone derivative2a reacts easily withTPP/DEAD/HX to the 5-X-L-idono-1,4-lactone derivatives6a (X=N₃),6b (X=p-NO₂-C₆H₄COO) and6c (3-O-acetylderivative of6a). Treating6b with a second equivalentTPP/DEAD/HX leads to the unsaturated sugarlacton7b. Without an external nucleophile2a affords withTPP the mixture of 2,6-bis-O-(t-BDMSi)-3,5-carbonato-D-glucono-1,4-lactone2c, 3,5-anhydro-L-idono-1,4-lactone8 and 3,6-anhydro-D-glucono-1,4-lactone9. Analogous procedures applied to4a yield theL-altronolactonoderivatives10a, 10b and10c, the unsaturated sugarlactone11b on the one and the 3,5-carbonatogalactonolactone4c and the 2,6-bis-O-(t-BDMSi)-3-desoxy-5-ethoxycarbonyl-D-threo-hex-2-en-1,4-lactone12 on the other hand.Whereas the bis-silyletherderivative3a is transformed by the title system exclusively by an elimination process to13, the derivative5a affords withTPP/DEAD without any elimination the 3,6-anhydrosugar14. Partial desilylation of14 followed by acetylation gives the derivatives14a and14b.Structural elucidations were achieved by¹H-NMR-analysis. In some cases also CD-measurements allowed suitable correlations.

Mark, E., Zbiral, E., Brandstetter, H. H., 4. Mitt., Mh. Chem.111, 289 (1980).     

Syntheses,structures, and spectroscopic properties of copper(II) and cobalt(III) complexes containing 1,4,7-tribenzyl-1,4,7-triazacyclononane ligand

Three new complexes [CuL(N₃)₂] (1), [CuL(SCN)₂] (2), and [CoL(SCN)₃] (3) (L?=?1,4,7-tribenzyl-1,4,7-triazacyclononane) have been synthesized and structurally characterized. Complex 1 crystallizes in monoclinic space group P2(1)/n with unit cell parameters a?=?14.105(7), b?=?8.999(5), c?=?21.603(11)?Å, β?=?100.470(7)°. While 2 crystallizes in triclinic space group P-1 with unit cell parameters a?=?9.6380(16), b?=?10.6993(18), c?=?15.798(3)?Å, α?=?106.636(3), γ?=?116.478(3)°. Complex 3 crystallizes in trigonal space group P–3c1 with unit cell parameters a?=?14.744(3), b?=?14.744(3), c?=?16.098(4)?Å, γ?=?120°. Elemental analysis, IR, UV-vis spectra of complexes 1–3 and ESR spectra of complexes 1–2 were also determined.