Reaktionen von β-Chlorvinylaldehyden. V [1]. Zur Bildung von 2,2′-Thiopyrylotrimethinfarbsalzen aus 2-(α-Formylalkyliden)-2H-thiopyranen

Reactions of β-Chlorovinylaldehydes. V. The Formation of 2,2′-Thiopyrylocyanine Dyes from 2-(α-Formylalkylidene)-2H-thipyranes Substituted β-chlorocrotonaldehydes react with Na₂S · 9H₂O to form 2-(α-formyl-alkylidene)-2H-thiopyranes 1 . The corresponding thiopyrylium salts 2 which are easily available from 1 and strong acids exist in the enolic form (2-β-hydroxyvinyl-thiopyrylium salts). They are converted at room temperature in methanol solution to dark green compounds, which are identified as 2,2′-thiopyrylotrimethincyanine dyes 3 . The mechanism of formation of compounds 3 is discussed.     

Synthesis and characterization of novel aromatic poly(amide‐imide)s derived from 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl or 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl and various aromatic diamines

New aromatic diimide‐dicarboxylic acids having kinked and cranked structures, 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl (2a) and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl (2b), were synthesized by the reaction of trimellitic anhydride with 2,2′‐bis(4‐aminophenoxy)biphenyl (1a) and 2,2′‐bis(4‐aminophenoxy)‐1,1′‐binaphthyl (1b), respectively. Compounds 2a and 2b were characterized by FT‐IR and NMR spectroscopy and elemental analyses. Then, a series of novel aromatic poly(amide‐imide)s were prepared by the phosphorylation polycondensation of the synthesized monomers with various aromatic diamines. Owing to structural similarity, and a comparison of the characterization data, a model compound was synthesized by the reaction of 2b with aniline. The resulting polymers with inherent viscosities of 0.58–0.97 dl g^?1 were obtained in high yield. The polymers were fully characterized by FT‐IR and NMR spectroscopy. The ultraviolet λ_max values of the poly(amide‐imide)s were also determined. The polymers were readily soluble in polar aprotic solvents. They exhibited excellent thermal stabilities and had 10% weight loss at temperatures above 500 °C under a nitrogen atmosphere. Copyright © 2003 Society of Chemical Industry     

Zur Reduktion von 1,3-Thiaziniumsalzen; Synthese von 6,6′-Bi-1,3-thiazinylen und 6,6′-Bi-1,3-thiazinylidenen

On the Reduction of 1,3-Thiazinium Salts; Synthesis of 6,6′-Bi-1,3-Thiazinyls and 6,6′-Bi-1,3-Thiazinylidenes 1,3-Thiazinium perchlorates 1 are linked together in a reaction with zinc powder or at a cathode forming 6,6′-bi-1,3-thiazinyls 3 . This reaction proceeds via radical intermediates 2 . Evidence of the existence of the very short-lived radicals is given by means of ring-disk-voltammogrammes as well as by electrochemical luminescence excitation. The 6,6′-bi-1,3-thiazinyls 3 undergo the reverse fission at a platinum anode resulting in thiazinium salts 1 , whereas the dehydrogenation by chloranile yields the violet 6,6′-bi-1,3-thiazinylidenes 6 .     

Crystallography and Structure–Property Relationships in 2,2′,2″,2′′′,4,4′,4″,4′′′,6,6′,6″,6′′′‐Dodecanitro‐1,1′ : 3′1″ : 3″,1′′′‐ Quaterphenyl (DODECA)

X‐ray crystallographic study of 2,2′,2″,2′′′,4,4′,4″,4′′′,6,6′,6″,6′′′‐dodecanitro‐1,1′ : 3′1″ : 3″,1′′′‐quaterphenyl (DODECA) has been carried out. Nonbonding interatomic distances of oxygen atoms inside of all the nitro groups are shorter than those corresponding to the intermolecular contact radii for oxygen. By means of the DFT B3LYP/6‐31(d, p) method a difference of 136 kJ mol⁻¹ between the X‐ray and DFT structures of DODECA was found. The bearer of the highest initiation reactivity in its molecule in solid phase should be the nitro group at 4′′′‐position, in contrast to those at 2′‐ or 2″‐positions in its isolated molecule. The most reactive nitro group in the DODECA molecule can be well specified by the relationship between net charges on nitro groups and charges on their nitrogen atoms, both of them for the X‐ray structure. The ¹⁵N chemical shift, corresponding to this nitro group for the initiation by impact and shock, correlates very well with these shifts of the reaction centers of the other six “genuine” polynitro arenes.     

(2R)-2-{(2S,3S)-3-[(1R)-1-叔丁基二甲基硅氧乙基]氮杂环丁-2-酮-4-基}丙酸的合成

从水杨酰胺和环己酮出发,经过亲核反应,丙酰氯取代反应,与4-AA缩合,最后水解合成(2R)-2-[(2S 3S)-3-[(1R)-1-叔丁基二甲基硅氧乙基]氮杂环丁-2-酮-4-基]丙酸,并通过红外,核磁确证其化学结构。该反应条件温和不苛刻,操作简便,适于工业化生产。     

Synthesis,spectral data and extraction of copper by 1-(2′-Hydroxy-5′-alkylphenyl)-1-alkanone Oximes

1-(2′-Hydroxy-5′-alkylphenyl)-1-ethanone oximes with a normal alkyl group containing 2 to 12 carbon atoms and 1-(2′-hydroxy-5′-methylphenyl)-1-alkanone oximes containing 1 to 11 carbon atoms in the hydrocarbon chain were synthesized. Spectral data (u.v., i.r., n.m.r. and ¹³C) of oximes are reported. Four of these oximes were used for copper extraction from acidic solution. The results obtained indicate, that these oximes are better extractants than alkyl derivatives of 2-hydroxybenzophenone oximes.     

Bishydrazinium and Diammonium Salts of 4,4′,5,5′‐Tetranitro‐2,2′‐biimidazolate (TNBI): Synthesis and Properties

The diammonium ( 1 ) and bishydrazinium ( 2 ) salts of 4,4′,5,5′‐tetranitro‐2,2′‐biimidazolate (TNBI) were synthesized and their physical properties as well as predicted explosive performance characteristics are described. These dianionic salts are easily formed in good yields by reaction of TNBI with aqueous solutions of the cationic species. TNBI is synthesized from 2,2′‐biimidazole, which is ultimately synthesized by the condensation of aqueous glyoxal with ammonium acetate. The compounds were characterized by NMR spectroscopy, vibrational (FT‐IR and Raman) spectroscopy, elemental analysis, thermal analysis (DSC, VTS and calorimetry), and small scale safety testing (impact, friction, ESD). The measured densities and heats of formation are reported. The materials show promise for use in IM explosive and propellant formulations due to the combination of their calculated performances, thermal stability and insensitivity to stimuli.     

Synthesis,characterization, and acoustic properties of new soluble polyurethanes based on 2,2′‐[1,4‐phenylenebis(nitrilomethylylidene)diphenol and 2,2′‐[4,4′‐methylene‐di‐2‐methylphenylene‐1,1′‐bis(nitrilomethylylidene)]diphenol

Eight novel polyurethanes based on 2,2′‐[1,4‐phenylenebis(nitrilomethylylidene)]diphenol and 2,2′‐[4,4′‐methylene‐di‐2‐methylphenylene‐1,1′‐bis(nitrilomethylylidene)]diphenol acting as hard segments with two aromatic and two aliphatic diisocyanates (4,4′‐diphenylmethane diisocyanate, toluene 2,4‐diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate) were prepared and characterized with Fourier transform infrared, UV spectrophotometry, fluorescence spectroscopy, ¹H‐NMR and ¹³C‐NMR spectroscopy, thermogravimetric analysis, and differential thermal analysis. All the polyurethanes contained domains of semicrystalline and amorphous structures, as indicated by X‐ray diffraction. The acoustic properties and solubility parameters were calculated with the group contribution method. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

cis/trans-Isomerisierung von 2,2′-Diethyl-5,5′-dimethoxy-4,4′-binaphthyliden-1,1′-dion über eine radikalische Zwischenstufe

cis/trans-Isomerization of 2,2′-Diethyl-5,5′-dimethoxy-4,4′-binaphthylidene-1,1′-dione from a Radical Intermediate The ¹H-NMR spectrum of 2,2′-diethyl-5,5′-dimethoxy-4,4′-binaphthylidene-1,1′-dione ( 1 ) shows flat-topped peaks at room temperature. At higher temperatures sharp peaks are observed while at deep temperatures the spectrum consists of two separated sets of lines. We propose a cis/trans-isomerization with coalescence at room temperature. The rate constants of this isomerization were obtained by dynamic line shape analysis, and an energy barrier of about 74 kJ mol⁻¹ was calculated. The intermediate biradical was proved by ESR spectroscopy.     

2,2′,6,6′-Tetrabromo-3,3′,5,5′-tetramethyl-4,4′-biphenol (TTB)–flame retardant copolycarbonates and copolyesters

2,2′,6,6′-Tetrabromo-3,3′,5,5′-tetramethyl-4,4′-biphenol (TTB) is a new flame retardant monomer possessing a high degree of chemical and thermal stability. This brominated biphenol can be directly incorporated as a comonomer in condensation polymerizations. An example is the preparation of copolycarbonates of TTB and 2,2-(4-hydroxyphenyl)propane (BPA) via the aqueous caustic phosgenation method. The reaction of TTB with either ethylene oxide or ethylene chlorohydrin affords 4,4′-bis(2-hydroxyethoxy)-2,2′,6,6′-tetrabromo-3,3′,5,5′-tetramethylbiphenyl (TTB-Diol). This diol is melt polymerized into a series of terephthalate copolymers with 1,4 butanediol. The above copolymers possess flame retardancy, thermal stability, and good mechanical properties. These high-bromine-content copolymers are blended with nonhalogen-containing polymers to afford blends with specific degrees of flame resistance.     

Optically active helical vinyl polymers via radical polymerization of (S)‐3‐vinyl‐2,2′‐bisalkoxy‐1,1′‐binaphthyl

(S)‐3‐Vinyl‐2,2′‐bisalkoxy‐1,1′‐binaphthyl ( 3 ) was synthesized via the Wittig reaction. Radical polymerization of all the monomers can take place smoothly in the temperature region tested. These polymers (poly‐ 3 ) showed very large specific optical rotations which were four times as large as those of the corresponding monomers 3 . Poly‐ 3 displayed optical rotations and Cotton effects in the UV?visible absorption region of side groups which were different from the corresponding monomers 3 and the model compounds (S)‐3‐ethyl‐2,2′‐bisalkoxy‐1,1′‐binaphthyl ( 4 ). These facts imply the formation of helicity of the main chain and the helical conformations were quite stable demonstrated by the unchanged pattern of temperature variable circular dichroism spectra. © 2015 Society of Chemical Industry     

(R)-1,1'-联萘-2,2'-二甲酸的合成

研究了(R)-1,1’-联萘-2,2’-二甲酸的合成方法,设计了一条合适的合成路线并进行了优化。以(R)-联二萘酚为起始原料,依次经过羟基的三氟甲基磺酸化反应、甲基化反应、溴代反应、水解反应,最后氧化成(R)-1,1’-联萘-2,2’-二甲酸。在相关文献和专利的基础上,进行了创新,合成路线简单易行,具有应用价值。     

3,1′-Bridged 2-[2′-(4″-dialkylaminophenyl)ethenyl] pyrylium and 1-Benzopyrylium Dyes – Synthesis and Vis/NIR Absorption/Emission Behaviour

A series of new 3,1′-bridged 2-[2′-(4″-dialkylaminophenyl)ethenyl]-4,6-diarylpyrylium perchlorates ( 3 ), 2-[2′-(4″-dialkylaminophenyl)ethenyl]-7-diethylamino-1-benzopyrylium perchlorates 5–8 , 2-[4′-(4″-dialkylaminophenyl)butadien-1′,3″-yl]-, and 2-[2′-(7″-diethylaminocoumar-3″-yl)ethenyl]-7-diethylamino-1-benzopyrylium perchlorates 10–12 were synthesized and characterized by means of elemental analysis, m.p., Vis/NIR, and ¹H NMR spectra. Semiempirical MO calculations were performed to elucidate the essential features of the chromophores. The size of the bridging ring strongly affects the geometry of the chromophores which, in turn, determines the extent of charge transfer of the longest wavelength electronic transition. Increasing deviation from planarity causes the polymethine-like chromophore to become more polyene-like.     

Proton Conducting Membranes Based on Poly(2,2′‐imidazole‐5,5′‐bibenzimidazole)

Poly(2,2′‐imidazole‐5,5′‐bibenzimidazole) (PBI‐imi) was synthesized via the polycondensation between 3,3′,4,4′‐tetraaminobiphenyl and 4,5‐imidazole‐dicarboxylic acid. Effects of the reaction conditions on the intrinsic viscosity of the synthesized polymers were studied. The results show that the molecular weight of the polymers increases with increasing monomer concentration and reaction time, and then levels off. With higher reaction temperature, the molecular weight of the polymer is higher. With the additional imidazole group in the backbone, PBI‐imi shows improved phosphoric acid doping ability, as well as a little higher proton conductivity when compared with widely used poly[2,2′‐(m‐phenylene)‐5,5′‐bibenzimidazole] (PBI‐ph).Whereas, PBI‐imi and PBI‐ph have the similar chemical oxidation stability. PBI‐imi/3.0 H₃PO₄ composite membranes exhibit a proton conductivity as high as 10^–4 S cm^–1 at 150 °C under anhydrous condition. The temperature dependence of proton conductivity of acid doped PBI‐imi can be modeled by an Arrhenius equation.     

NMR-spektroskopische Untersuchungen zum Konformations-verhalten von 2′- und 3′-halogensubstituierten Pyrimidinnucleosiden

N.M.R. Spectroscopical Investigations on the Conformational Behaviour of Some 2′ - and 3′-Halogen-substituted Pyrimidine Nucleosides A series of 2′- and 3′-halogenated pyrimidine nucleosides has been synthesized and investigated by ¹H, ¹³C and ¹⁹F n.m.r. spectroscopy. The ¹H and ¹³C chemical shifts for the positions 2′ and 3′ depend linearly but oppositely on the substituent electronegativities X_R. The conformational equilibrium N ⇌ S of the nucleosides in solution is determined. An approximately linear correlation between the prefered gauche-gauche interaction of the exocyclic CH₂OH groups and the ribose N conformation has been found.     

Synthesis and Energetic Properties of 4,4′,5,5′‐Tetranitro‐2,2′‐biimidazolate(N4BIM) Salts

This paper describes the synthesis and characterization of several salts of 4,4′,5,5′‐tetranitro‐2,2′‐biimidazolate (N4BIM). Each of the salts were characterized chemically, thermally, morphologically, as well as with respect to destructive stimuli (impact, electrostatic discharge, friction, thermal). These salts show promise as propellant ingredient additives, and in particular, the bis‐triaminoguanidinium salt of N4BIM displays excellent burn rate and combustion behavior. Our combustion studies have shown that TAGN4BIM displays a fast burning rate and has the lowest pressure dependence exponent yet measured for a triaminoguanidinium salt.     

(1S,2S,5R)-1-苯基薄荷醇的合成

L-薄荷醇经Jones试剂氧化制得L-薄荷酮(1),将L-薄荷酮与苯基锂试剂反应制得产物(1S,2S,5R)-1-苯基薄荷醇(2),其结构经1HNMR,13CNMR,IR以及元素分析进行了表征。分析了影响反应的因素和分离纯化方法,研究结果表明,以投料比n(L-薄荷酮)∶n(苯基锂)∶n(无水乙醚)=0.08∶0.10∶0.76,在-40℃、氮气保护机械搅拌下反应8h,高收率(65%)合成了目标产物2。     

Combustion Properties of Amino‐Substituted Guanidinium 4,4′,5,5′‐Tetranitro‐2,2′‐biimidazolate(N4BIM) Salts

This paper describes the combustion properties of the amino‐substituted guanidinium 4,4′,5,5′‐tetranitro‐2,2′‐biimidazolate (N4BIM) series, including the bis‐mono, di and triaminoguanidinium salts. These salts are of interest as propellant ingredient additives, and in particular, the bis‐triaminoguanidinium salt of N4BIM displays excellent burn rate and combustion behavior. Our combustion studies have shown that TAGN4‐BIM displays a fast burning rate and has the lowest pressure dependence exponent yet measured for a triaminoguanidinium salt.     

The STOBBE condensation. X. The cyclisation of (E)-3-methoxycarbonyl-4-(5′-methyl-2′-furyl)-but-3-enoic acid,and (E)−3-methoxycarbonyl-4-(2′-furyl)-pent-3-enoic acid,to Benzofuran Derivatives

The condensation of 5-methyl-furan-2-aldehyde and 2-furyl-methyl ketone with dimethyl succinate using either potassium t-butoxide or sodium hydride as condensing agents, gives predominantly (E)-3-methoxycarbonyl-4-(5′-methyl-2′-furyl)-but-3-enoic acid 1a and (E)-3-methoxy-carbonyl-4-(2′furyl)-pent-3-enoic acid 5 respectively. Their configurations are inferred by cyclisation with sodium acetate in acetic anhydride to the corresponding benzofuran derivatives 2,6 . Alcoholysis of (E)-3-carboxy-4-(5′-methyl-2′-furyl)-but-3-enoic anhydride 3 gives the half-ester 1c which is isomeric with the half-ester 1a . A competing side reaction also gives the self-condensation product of the succinic ester 4 .     

新手性试剂(1R,2S)-2-氨基醇的合成

采用格氏试剂C6H13MgBr和C10H2MgBr对光学活性O-TMS保护的(R)-氰醇的氰基加成,随之用NaBH4对亚胺化合物立体诱导还原氢化,以98%的de值合成了两个新的手性试剂(1R,2S)-2-氨基醇,产率分别达到59%和62%.并通过X射线单晶结构分析法测定了分子结构和晶体结构.