One-pot synthesis of 3-substituted-2-[(3-methyl-1H-pyrazol-5-yl)imino]-5,6-diphenyl-1,3-thiazin-4-ones

New classes of 3N-substituted-2-[(3-methyl-1H-pyrazole-5-yl)-imino]-5,6-diphenyl-2H-1,3-thiazin-4(3H)-ones have been synthesized, via one pot reactions between pyrazolylthioureas, 2,3-diphenylcyclopropenone and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. The structures of the products have been confirmed by different spectroscopic analyses. A rationale for the formation of the products is presented.     

A Simple Route to 4-aryl and 4-hetaryl substituted 6-methyl-2,2-difluoro-1,3,2-(2H)-dioxaborines

4-(Het)aryl-2,2-difluoro-6-methyl-1,3,2-(2H)-dioxaborines 3a-3i, 6a-6c, 8 were prepared in a one-pot reaction from donor substituted arenes and hetarenes 2a-2i, 5a-5c, 7 , resp., by a boron trifluoride mediated acetoacetylation. With resorcinol dimethylether ( 11 ), diphenyl ether ( 13a ), and 1,3-phenoxy-propane ( 13b ) this acetoacetylation gives rise to the formation of bis-1,3,2-(2H)-dioxaborines 12, 14a , and 14b , respectively. From triphenylamine ( 9 ) a tris-1,3,2-(2H)-dioxaborine 10 has been obtained. Phloroglucinol trimethylether ( 15a ) is demethylated as well as acetylated and acetoacetylated at once to give a bis-1,3,2-(2H)-dioxaborine derivative 17 .     

4-(1-Methyl-2-sulfamoylvinyl)pyrazoles by Ring Transformation of 1,1-dioxo-2H-1,2-thiazine-4-carbaldehydes with hydrazines

As masked 1,3-dicarbonyl compounds, 1,1-dioxo-2H-1,2-thiazine-4-carbaldehydes ( 2a–e, 7 ) undergo ring transformations with nucleophilic hydrazines to produce 4-[1-methyl-2-(arylsulfamoyl)vinyl]pyrazoles ( 9a–i ). For 9h , an X-ray structural analysis is reported. With less nucleophilic semicarbazide and p-nitrophenylhydrazine the hydrazones ( 11a, b ) were isolated. The carbaldehydes 2a–e , 7 and 8a, b were synthesized by formylation of the 1,1-dioxo-2H-1,2-thiazines 1a–e, 5 and 6a, b with dichloromethyl methyl ether/TiCl₄. In the case of 1a–e mixtures of 4- and 6-carbaldehydes ( 2a–e/3a–e ) were obtained, which, however, could be used for the synthesis of pyrazoles.     

Synthesis and characterization of new polyamides derived from 1,3-bis[4-(4-aminophenoxy)phenyl]adamantane

Several new polyamides were synthesized by direct polycondensation of the 1,3-bis[4-(4-aminophenoxy)phenyl]adamantane ( I ) with various dicarboxylic acids. The polyamides had inherent viscosities and number-average molecular weights (M_n) of 0.46–0.96 dL/g and 28,000–109,000, respectively. All polyamides III had good solubilities and were soluble in N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and pyridine. Polyamides had tensile strengths of up to 72.3 MPa, elongation to breakage values of up to 10.2%, and initial modulus of up to 2.1 GPa. Their glass transition temperatures were found to be 228–269°C and 252–307°C using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA), respectively. The melting temperature of III_f was observed at 318°C using DSC. The temperatures of polyamides III at a 5% weight loss ranged from 395 to 435°C in air and from 400 to 450°C in a N₂ atmosphere. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:315–321, 1998     

5-烷基-2-(4-氰基苯基)-1,3-二噁烷的合成

对 5 烷基 2 (4 氰基苯基 ) 1,3 二 口恶烷的合成进行了研究 ,以 5 戊基 2 (4 氰基苯基 ) 1,3 二口恶烷的合成为例 ,论述了以溴代烷和丙二酸二乙酯为初始原料 ,采用相转移催化烃基化反应合成了 2 戊基丙二酸二乙酯 ,收率 91 7% ;进而以四氢铝锂和硼氢化钠为还原剂于 0～ 2 0℃在四氢呋喃溶剂中合成了 2 戊基丙二醇 ,收率≥ 80 % ;再与对氰基苯甲醛在催化剂氯化钙存在下反应合成了 5 戊基 2 (4 氰基苯基 ) 1,3 二 口恶烷 ,收率≥ 90 %。并通过核磁共振氢谱和红外光谱证实了其结构     

Synthesis and Structural Analysis of Structured Triacylglycerols with CLA Isomers in the <Emphasis Type="Italic">sn</Emphasis>-2- Position

The present research deals with the chemical esterification of the sn-2- position of sn-1,3-diacylglycerol (sn-1,3-DAG) with 9cis,11trans (c9,t11) and 10trans,12cis (t10,c12) conjugated linoleic acid (CLA) isomers to obtain structured triacylglycerols (TAG); the sn-1,3-DAG substrates were produced from extra virgin olive oil by means of enzymatic reactions while CLA isomers were obtained using a three-step procedure based on alkaline hydrolysis of sunflower oil, urea purification of linoleic acid (LA) and alkaline isomerization of LA. The results showed good levels of CLA incorporation in structured TAG at the tested temperatures: 37.5% at 4 °C and 39.1% at 14 °C. To evaluate the incorporation of CLA isomers in sn-2- position of sn-1,3-DAG structural analysis of the newly synthesized TAG was carried out using an enzymatic and a chemical method. The results of the structural analysis also showed up the occurrence of acyl migration. The pancreatic lipase method allowed the direct determination of the fatty acid composition of TAG sn-2- position but this enzymatic method showed different results (p < 0.05) in respect to the chemical one; this occurrence could be due to an acylic specificity of the lipase. High incorporation of CLA isomers in sn-2- position of TAG was observed, 77.0% at 4 °C and 81.5% at 14 °C, considering the results of the chemical procedure.     

A hydrocarbon-soluble difunctional orgaolithium anionic initiator. Synthesis of 2,2-bis[3-(1-lithio-2,3-dimethylpentyl)-4-methoxyphenyl]propane

The reaction of stoichiometric amounts of sec-butyllithium with 2,2-bis[3-(1-propenyl)-4-methoxyphenyl]propane ( 4 ) produces a new difunctional organolithium initiator, 2,2-bis[3-(1-lithio-2,3-dimethylpentyl)-4-methoxyphenyl] propane, which is soluble in hydrocarbon solvent in the absence of any polar additive. Following isolation and purification by gas liquid chromatography, the structures of ( 4 ) and the methanolysis product of the difunctional initiator were characterized by ¹H NMR, FTIR and mass spectroscopy and elemental analysis. The dilithium initiator is effective for the polymerization of 1,3-butadiene and allows the preparation of polybutadienes with predictable molecular weights, narrow, monomodal molecular weight distribution and low 1,2-diene microstructure.     

Enzymatic Synthesis of Structured Triacylglycerols Containing CLA Isomers Starting from <Emphasis Type="Italic">sn</Emphasis>-1,3-Diacylglycerols

The synthesis of structured triacylglycerols (TAG) by the enzymatic reaction between sn-1,3-diacylglycerols (sn-1,3-DAG) and conjugated linoleic acid (CLA) isomers was studied. Both the substrates of the reaction were produced from vegetable oils, the sn-1,3-DAG from extra virgin olive oil and the CLA isomers from sunflower oil. The enzymatic reactions between these substrates were catalyzed for 96 h by an immobilized lipase from Rhizomucor miehei (Lipozyme IM) and the reactions carried out in solvent were monitored every 24 h by using high-performance liquid chromatography-evaporative light scattering detector (HPLC-ELSD). The enzymatic reactions were carried out in different reaction media (hexane, isooctane and solvent free) and with different CLA/sn-1,3-DAG ratios. Total % acidic composition and structural analysis data were evaluated to verify the presence of CLA isomers in sn-2- position of synthesized TAG. The results showed good levels of CLA incorporation in sn-1,3-DAG, from 19.2% of TAG synthesized in solvent free conditions with a 0.5:1 substrate ratio, to 47.5% of TAG synthesized in isooctane with a 2:1 substrate ratio. It was observed that for all the reaction media, the best sn-2- acylic specificity was obtained with a 0.5:1 substrate ratio.     

Design,synthesis, antibacterial and antifungal activity of novel spiro-isoxazolyl bis-[5,5′]thiazolidin-4-ones and spiro-isoxazolyl thiazolidin-4-one-[5,5′]-1,2-4 oxdiazolines

The synthesis of novel isoxazolyl 1,6-dithia-4,9-diazaspiro[4.4]nonane-3,8-diones (4a–h) and isoxazolyl 1-oxa-6-thia-2,4,9-triazaspiro[4.4]non-2-ene-8-ones (5a–h) analogs is described. Reaction of N-1-\{3-methyl-5-[(E)-2-aryl-1-ethenyl]-4-isoxazolyl}-2-chloroacetamide (2) with aryl isothiocyanates yielded 3,3-methyl-5-[(E)-2-aryl-1-ethenyl]-4-isoxazolyl-2-(arylimino)-1,3-thiazolan-4-ones (3). Cyclocondensation of 3 with mercaptoacetic acid furnished novel isoxazolyl-1,6-dithia-4,9-diazaspiro[4.4]nonane-3,8-diones (4a–h). Cycloaddition of 3 with benzonitrile oxides afforded novel isoxazolyl 1-oxa-6-thia-2,4,9-triazaspiro[4.4]non-2-ene-8-ones (5a–h). Compounds 4a–h and 5a–h showed significant biological activity against all the standard strains.     

Transition metal complexes in organic synthesis. Part 46. Synthesis of 5-arylmethyl-substituted tricarbonyl(1-4-η-cyclohexa-1,3-diene)iron complexes

The reaction of tricarbonyl(η⁵-cyclohexadienylium) iron tetrafluoroborate 3 with the methyl arylacetate 6 , the dimethyl arylmalonate 12 , and the di-tert-butyl arylmalonate 14 provides regio- and stereoselectively the tricarbonyliron-complexed 5-arylmethylcyclohexa-1,3-dienes 7, 13 and 15 .     

Thermal polymerization and reactive blending of 2-(4-hydroxyphenyl)-1,3-oxazoline

Summary Upon heating above its melting temperature at 195°C, 2-(4-hydroxyphenyl)-1,3-oxazoline (HPO) was polymerized thermally in melt phase within a few minutes to produce a polymer with etheramide and N-4-hydroxybenzoyl-ethyleneimine repeat units. Polymerization in solution afforded only oligomers with 93% etheramide structure after several hours. Reactive blending, combining 2-phenyl-1,3-oxazoline (PO) grafting with in-situ HPO thermal polymerization in poly(ethene-co-methacrylic acid), was the key to novel self-reinforced multiphase ethene copolymer blends containing spherical dispersed poly(HPO) microphases. Poly(HPO) microstructures, blend morphologies, thermal and mechanical properties were investigated.     

(R)-2-芳基-4-羟甲基-1,3-(噁)唑啉类化合物的合成

以L-丝氨酸甲酯盐酸盐和芳基甲腈类化合物为原料,经亚胺化、环合、还原3步反应合成了标题化合物。产物结构经IR、MS和1HNMR确证。实验结果表明,在乙醇溶剂中,NaBH4能把(S)-2-芳基-4-甲酯基-1,3-噁唑啉类化合物中的酯基有效地还原为羟甲基。     

Preparation and properties of 2-Dialkylamino-5-haloacetyl-thiazoles and 4-(2-Dialkylamino-5-thiazolyl)-thiazoles

By the reaction of N-acylthioureas 7 with 1,3-dichloroacetone 9 2-dialkylamino-5-chloroacetyl-thiazoles 11 are available. These compounds react with thioureas or arylthioamides under heterocyclisation to give bis-(2-dialkylamino-5-thiazolyl)-ketones 13 , 2-aryl-4-(2-dialkylamino-5-thiazolyl)-thiazoles 14 , or 2-dialkylamino-4-(2-dialkylamino-5-thiazolyl)-thiazoles 15 , resp., from which the last-mentioned compound exhibit a high reactivity towards several electrophilic reagents. Thus, deeply colored cyanovinyl, arylazo, and arylmethine substituted bisthiazole dyes 17, 18 , and 19 , resp., have been formed.     

Layered zinc 4-phosphonoisophthalates pillared by flexible bis(imidazole) Co-ligands

This paper reports two zinc phosphonates based on 4-phosphonoisophthalic acid (4-piH₄) and bis(imidazole) co-ligands, namely, [Zn₂(4-pi)(1,2-bix)] (1) and [Zn₂(4-pi)(1,3-bix)] (2) (1,2-bix = 1,2-bis(imidazol-1-ylmethyl)benzene, 1,3-bix = 1,3-bis(imidazol-1-ylmethyl)benzene). Both show layer structures in which the inorganic tetranuclear cores of Zn₄P₂O₆ are connected by 4-pi⁴⁻ligands. The 1,2-bix or 1,3-bix ligand binds to the Zn atoms within the tetranuclear unit or between the neighboring tetranuclear units in a cis-coordination mode, and fill in the interlayer spaces in both cases. The luminescent properties are investigated.     

固载杂多酸催化合成2-甲基-2-(4-甲基-3-戊烯基)-1,3-二氧六环

以离子交换树脂固载磷钨酸为催化剂合成了 2 -甲基 - 2 - (4-甲基 - 3 -戊烯基 ) - 1 ,3 -二氧六环。考察了影响收率的因素。其最优条件为 :6 -甲基 - 5 -庚烯 - 2 -酮∶ 1 ,3 -丙二醇∶催化剂∶带水剂为 1mol∶ 1 .5 mol∶ 1 2 g∶ 2 0 0 m L,反应在回流温度下进行 ,反应时间 3 .0 h。收率可达 89.6 %,催化剂可重复使用。     

Internal hydrogen bonding,rotational isomerism and differentiation of 1,2- and 1,3-diglycerides by near infrared spectroscopy

The OH stretching modes of 1,2- and 1,3-diglycerides in dilute carbon tetrachloride solution have been investigated in the fundamental and first overtone region with a spectral resolution of about 1 cm⁻¹. The spectra of both position isomers can be interpreted in terms of three predominant configurations: one internally H-bonded and two involving no H-bonds. The fraction of H-bonded molecules appears to be relatively low. The data suggest that the H-bonded form of 1,3-diglycerides has atrans, gauche configuration around the glyceride CC bonds, while the non-H-bonded forms probably have atrans, trans configuration around the glyceride backbone, OH being eithertrans orgauche with respect to the nearest C-H group. In 1,2-diglycerides H-bonds seem to be predominantly formed between groups attached to the α, γ carbons of the glyceride residue, the configuration around the backbone beingtrans, trans; two stretching band of non-H-bonded OH groups are associated with rotational isomerism around the alcoholic CO bond. The usefulness of OH stretching modes for analyzing mixtures of 1,2- and 1,3-diglycerides is discussed. Presented in part at the AOCS meeting in Toronto, Canada, 1962. E. Utiliz. Res. & Dev. Div., ARS, U.S.D.A.     

Low-dielectric-constant aromatic homopolyimide and copolyimide derived from pyromellitic dianhydride, 4,4′-oxydianiline, 2,2-bis[4-(4-aminephenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)benzene,or 1,3-bis(4-aminophenoxy)benzene

Low-dielectric-constant aromatics, homopolyimide and copolyimide, were introduced. Homopolyimides were prepared by pyromellitic dianhydride (PMDA) as an anhydride monomer and 4,4′-oxydianiline (ODA), 2,2-bis[4-(4-aminephenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)benzene, or 1,3-bis(4-aminophenoxy)benzene as an amine monomer. The copolyimides were prepared with PMDA as an anhydride monomer, ODA as an amine monomer with the addition of 2,2-bis[4-(4-aminephenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)benzene, or 1,3-bis(4-aminophenoxy)benzene as another amine monomer. The polyimides were well characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, thermomechanical analysis, dielectric measurements, and tensile testing. The homopolyimide and copolyimides showed lower dielectric constants than the homopolyimide formed by ODA and PMDA. The results also indicate that the interchain distance, the quantities of phenyl ether, and the position of the substitute are factors that not only affected the thermal performance of polyimide by improving the molecular flexibility but also reduced the dielectric constant of polyimide by increasing the free volume of the molecular chain and decreasing the polarization points per unit volume. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47405.     

Separation of γ- and α-linolenic acid containing triacylglycerols by capillary supercritical fluid chromatography

The separation of γ- and α-linolenic acid containing triacylglycerols with an identical acyl carbon number and degree of unsaturation was obtained on capillary supercritical fluid chromatography using a 25% cyanopropyl−75% methylpolysiloxane stationary phase. The resolution of 1,3-dioleoyl-2-γ-linolenoyl-sn-glycerol and 1,3-dioleoyl-2α-linolenoyl-sn-glycerol was 1.35 on a 10 m×50 μm i.d. column, whereas the resolution was enhanced to 1.66 by combining two 10-meter columns in series. The difference in the position of double bonds in one linolenic acid residue of triacylglycerols resulted in two series of peaks in the separation of alpine currant (Ribes alpinum) and black currant (R. nigrum) seed oils. The use of the 10-meter column was found to be appropriate for the screening of the triacylglycerol profile in both seed oils studied.     

1,3-双(二甲基羟基硅基)-2,2,4,4-四甲基环二硅氮烷的合成

通过1,3-双（二甲基氯硅基）-2,2,4,4-四甲基环二硅氮烷的水解反应合成了1,3-双（二甲基羟基硅基）-2,2,4,4-四甲基环二硅氮烷。初步探讨了反应的条件。产物收率达到92％。并经红外光谱和X射线衍射表征产物结构。     

Synthesis and derivatization of angular 3-chloro-3-chlorosulfenyl naphtho[1,2-b]pyran(4H)-4-ones with evaluation of antiviral activity

Angular 2,3-dihydronaphtho[1,2-b]pyran(4H)-4-ones 1a,b react with an excess of thionyl chloride to give the α-chlorosulfenyl chlorides 2a,b, which are reduced by iodide ion to give the corresponding 1,3,4-oxadithiino derivatives 3a,b. However, the aducts 4a,b and 5a,b were obtained by reduced 2a,b with iodide ion in the presence of 2,3-dimethyl-1,3-butadiene and 1,3-cyclohexadiene, respectively. Direct oxidation of 2a,b afford 3,3-dichloronaphthopyran-4-ones 6a,b, whilst conversion to the sulfenamides 7a,b prior to oxidation provides 3-chloronaphthopyranones 8a,b. While α-chloro β-oxo sulfenyl chlorides 2a,b undergo straight forward substitution with 1-methylpiperazine and with potassium cyanide to give 9a,b and 10a,b, respectively. Some of the prepared products were selected and tested for their antiviral activity against herpes simplex virus type-1 (HSV-1). Plaque reduction infectivity assay was used to determine virus count reduction as a result of treatment with test compounds. Compound 5a showed moderate effect against HSV-1.