N,N-二乙氧羰基-1,4-二苯氧乙酰胺的合成与结构表征

对苯二酚与氯乙酸乙酯醚化后水解,得到1,4-苯二氧二乙酸(化合物2);将其用二氯亚砜转化为酰氯,再与亚氨基二乙酸二乙酯氨解,获得了新化合物N,N-二乙氧羰基-1,4-苯二氧二乙酰胺(化合物4)。用~1H NMR、~(13)CNMR、IR及MS(MALDI-TOF)表征新化合物结构,并对合成反应进行了讨论。     

Synthesis of some new heterocyclic systems derived from 2-acetylbenzimidazole

The named compound was reacted with thiosemicarbazide and/or semicarbazide to produce the corresponding condensation products II and V respectively. Reaction of II with chloroacetic acid in ethanol containing anhydrous sodium acetate yielded III. Condensation of III with aromatic aldehydes yielded the corresponding arylidene derivatives (IV). Oxidation of the semicarbazone V with selenium dioxide gave 2-(1,2,3-selenadiazole-4-yl)benzimidazole (VIa, b) while with thionyl chloride it gave 2-(1,2,3-thiadiazole-4-yl)benzimidazole (VIIa, b). The chalcones of 2-acetyl and/or 1-methyl-2-acetylbenzimidazole were condensed with hydrazine hydrate, phenylhydrazine and/or hydroxylamine to produce 2-(5-aryl-1(H)-pyrazolin-3-yl)-, 2-(5-aryl-1-phenyl-2-pyrazolin-3-yl)- and 2-(5-aryl-2-isoxazolin-3-yl)benzimidazole (IX, X, XI) respectively.     

Dispersion of FeOOH on Chitosan Matrix for Simultaneous Removal of As(III) and As(V) from Drinking Water

Bio-inorganic chitosan based spherical shaped beads were prepared by dispersing rod-shaped FeOOH nanoparticles into a chitosan matrix for the removal of pure As(III) and As(V) from aqueous media, such as drinking water. A homogeneous mixture of chitosan and ferric nitrate, ferric chloride was prepared respectively with or without oxalic acid. The mixture was added dropwise in to a NaOH bath, where iron salts reacted with NaOH to form FeOOH particles. The scanning electron microscopy (SEM) showed that rod shaped FeOOH particles were distributed homogenously in the chitosan matrix. Diffuse reflective UV-vis (DRUV) spectra revealed that hydrated iron oxide formed a complex with functional groups in chitosan. Adsorption of As(III) and As(V) on different iron salt based bead was found to be pH dependent. The bead prepared from iron nitrate showed better performance for arsenic removal from aqueous solution over the bead that was prepared using iron chloride salt. The bead prepared using chitosan and iron-FeOOH is known as a chitosan-iron oxyhydroxide (CFOH) bead. The CFOH beads were found to be more efficient in removing As(III) from the solution compared to As(V). The adsorption of As(III) and As(V) from aqueous solution on CFOH beads was studied under equilibrium conditions in the concentration range of 1 mg/L to 50 mg/L in the presence of 0.05 M NaNO₃ at pH 6.5 and 298 K temperature. The maximum adsorption capacity of the CFOH bead was found to be 5.4 mg/g for As(V) and 7.2 mg/g for As(III) using the Langmuir equation. The presence of sulphate, phosphate, and silicate in aqueous solution had no effects on adsorption of either As(III) or As(V) on CFOH beads but decreased significantly at pH> 8.     

新型杀菌剂噻氟菌胺的合成研究

以三氟乙酰乙酸乙酯为原料,经氯气氯化得到2-氯-3-三氟乙酰乙酸乙酯,然后与硫代乙酰胺发生环化反应,反应产物水解得到2-甲基-4-三氟甲基-噻唑-5-甲酸.其经酰化后再以甲苯为溶剂,在碱性条件下与2,6-二溴4三氟甲氧基苯胺反应得到噻氟菌胺.总收率55.4％.     

1, 8-二氮杂双环(5, 4, 0)-7-十一烯的合成工艺及其应用开发

以ε-己内酰胺和丙烯腈为原料,反应合成1, 8-二氮杂双环（5, 4, 0）-7-十一烯（DBU,Ⅰc）,再以DBU分别和5种取代基氯苄经两步法合成5种新型取代苄基脒类光产碱剂,产品及中间产物经1HNMR、LC-MS和HPLC进行结构表征和含量测试。结果表明：以ε-己内酰胺和丙烯腈为原料,氢氧化钾为催化剂,在70 ℃下,反应24 h,产物Ⅰa收率98.1%,纯度97.8%;以镍加氢方法,在85～90℃下,反应5 h将Ⅰa还原得产物Ⅰb,收率91.1%,纯度98.0%;以对甲基苯磺酸为催化剂,Ⅰb经环合反应7.5 h得Ⅰc,收率97.3%,纯度大于95.0%;以DBU（Ⅰc）和氯化苄为原料,在90 ℃下反应成盐,再以0.7当量的氢化铝锂还原得Ⅱa,收率达到76.7%,纯度93.2%;以先成盐再还原方法可成功合成4种取代苄基DBU类光产碱剂,收率均达到70%以上,说明此方法普遍适用此类光产碱剂的合成,提高了DBU的应用价值,也为进一步的研究奠定理论基础。     

水杨醛席夫碱功能化荧光素化合物的合成

以对氨基苯甲酸甲酯和水合肼为原料,经酰胺化反应制得对氨基苯甲酸甲酰胺与水杨醛还原氨化反应生成水杨醛类席夫碱1,化合物1在丙酮溶剂中与三聚氯氰亲核取代得到一缩产物对氨基苯甲酰水杨醛肼腙三嗪产物2,然后以荧光素和水合肼的合成产物荧光素酰肼3与化合物2在四氢呋喃溶液中45~50℃反应得到目标产物二缩产物荧光素酰肼三嗪水杨醛席夫碱4,并通过IR与~1H NMR对其结构进行表征。     

松果腺素的合成

以四氢呋喃、4 甲氧基苯胺为主要原料 ,经五步合成了松果腺素。四氢呋喃和氯化氢气体在 1 0 5℃下反应 0 5h ,得到 4 氯丁醇 (Ⅰ) ,产率为 6 8 6 % ;(Ⅰ)用氯铬酸吡啶盐氧化得 4 氯丁醛 (Ⅱ) ,产率为6 0 7% ;4 甲氧基苯胺经重氮化和还原反应得 4 甲氧基苯肼 (Ⅲ) ,产率为 6 0 9% ;(Ⅱ) +(Ⅲ)经环化得 5 甲氧基色胺 (Ⅳ) ,产率为 47 6 % ;(Ⅳ)经乙酰化得松果腺素 (Ⅴ) ,产率为 83 5 %。     

N-硝基-N-(2,6-二硝基-4-三氟甲基苯基)脲衍生物的合成及除草活性

以2,6-二硝基-4-三氟甲基氯苯为起始原料,与氨水反应生成2,6-二硝基-4-三氟甲基苯胺;该苯胺与乙酰硝酸酯反应生成N-硝基-2,6-二硝基-4-三氟甲基苯胺;以三乙胺为缚酸剂,N-硝基-2,6-二硝基-4-三氟甲基苯胺与固体光气在二氯甲烷中反应,生成酰氯中间体;酰氯中间体再与取代苯胺反应得到了7种含N-硝基的不对称脲类化合物。产物经IR1、HNMR、质谱、元素分析表征。对目标化合物进行了除草生物活性测试,初步测试结果表明:当其水溶液质量浓度为500 mg/L时,脲基另一端的苯环为2-氯苯基、4-氯苯基、2-甲基苯基、4-甲基苯基时,这些化合物对稗草的校正根长抑制率和校正茎长抑制率都大于40%;但这些化合物对苋菜作用不明显,对苋菜的校正根长抑制率和校正茎长抑制率小于20%。     

2,2-二甲基环丙烷甲酸的合成与拆分

S-( )-2,2-二甲基环丙烷甲酸是合成西司他丁(一种肾脱氢二肽酶抑制剂)的关键中间体,今设计了一条新的2,2-二甲基环丙烷甲酸合成路线并改进了拆分工艺,它是以异戊烯酸为原料,经酸的酯化、烯键的环丙烷化、酯水解制得2,2-二甲基环丙烷甲酸,收率为44．1％。其中,环丙烷化反应用锌粉／氯化亚铜-乙酰氯作为催化剂,二溴甲烷作为环丙烷化试剂,这样可以在温和的条件下进行反应,降低成本。此外用L-肉碱草酸盐作为手性拆分试剂,经酰化、成盐、部分结晶、水解得到S-( )-2,2-二甲基环丙烷甲酸．收率为16．7％,手性纯度大于95％．此路线工艺简单、环境友好、成本较低,易于工业化。     

Preparation of new poly(amide–imide)s with chiral architectures via direct polyamidation reaction

N‐trimellitylimido‐L ‐methionine ( 3 ) was prepared by reaction of trimellitic anhydride ( 1 ) with ‐L ‐methionine ( 2 ) in acetic acid solution at refluxing temperature. This diacid was reacted with thionyl chloride, and N‐trimellitylimido‐L ‐methionine diacid chloride ( 4 ) was obtained in quantitative yield. The resulting diacid chloride was reacted with p‐aminobenzoic acid in dry acetone and bis(p‐aminobenzoic acid)‐N‐trimellitylimido‐L ‐methionine ( 5 ) was obtained as a novel optically active amide–imide diacid monomer in high yield. The direct polycondensation of amide–imide diacid monomer 5 with several aromatic diamines was carried out with tosyl chloride (TsCl)/pyridine (Py)/dimetheylformamide (DMF) system. The resulting thermally stable poly(amide–imide)s (PAIs) were obtained in good yields and inherent viscosities ranging between 0.24 and 0.46 dL g^?1 and were characterized with FTIR, ¹H NMR, CHN, and TGA techniques. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1248–1254, 2007     

富马海松酸三酰基异氰酸酯的制备及表征

以富马海松酸为原料制备了中间产物富马海松酸三酰胺,再与草酰氯反应制备了标题化合物,中间产物和目标产物结构经IR、1 HNMR、13CNMR和MS等表征.标题化合物在国内外属首次合成,可用于硬质聚氨酯泡沫塑料的制备中.     

Crystalline oligomeric stereocomplex as an intermediate compound in racemic poly(DL-lactic acid) degradation

Hydrolytic degradation of intrinsically amorphous poly(DL -lactic acid) was re-examined in pH 7.4 isoosmolar phosphate buffer at 37°C. Size-exclusion chromatogarphy, X-ray scattering and differential scanning calorimetry were used to monitor molecular weight and morphology changes up to the ultimate degradation stage. It was found that heterogeneous degradation of poly(DL -lactic acid) yielded a crystalline residual material of low molecular weight. Comparison with a stereocomplex made of equimolar poly(L -lactic acid) and poly(D -lactic acid) showed that the poly(DL -lactic acid) degradation residue was actually an oligomeric stereocomplex. The formation of stereoregular oligomeric enantiomers agreed well with the predominantly isotactic structure of poly(DL -lactic acid) obtained by ring-opening polymerization of DL -lactide and argued in favour of the stereodependence of main chain ester bond cleavage.     

负电荷区Glu224-Glu225-Asp226对精氨酸激酶结构和功能的影响

精氨酸激酶224-226氨基酸残基是高度保守的负电荷区域,其在激酶家族的地位一直是学术界关注的问题之一.将刀额新对虾精氨酸激酶高度保守的负电荷密集区氨基酸残基Glu224-Glu225-Asp226突变为Gly224-Gly225-Gly226,消除负电荷性质.突变体在Rosetta中实现了可溶性表达,用His-tag亲和层析纯化了蛋白.采用酶括力测定及光谱学分析等手段的研究结果表明,该“负电荷区”对酶的结构与功能有着重要的影响.     

不对称金属络合染料C.I.酸性棕355的合成

6-硝基-1,2-重氮氧基萘-4-磺酸与乙萘酚偶合,得偶合物I;2-氨基-4-硝基苯酚-6-磺酸重氮化与1-苯基-3-甲基-5-吡唑啉酮偶合,得到偶合物II;偶合物I与铬明矾在水杨酸存在下络合,得到单络合物III;络合物III再与偶合物II在碱性条件下络合,得到不对称金属络合染料C.I.酸性棕355。     

R-二苯基脯氨醇的合成

以L脯氨酸为原料、(2R,3R)酒石酸为拆分剂,采用不对称转换的方法将L-脯氨酸转换成D-脯氨酸。再以D-脯氨酸为原料,先后与乙酰氯、三乙胺和(BOC)2O反应,最后与苯基溴化镁反应,经乙酸乙酯萃取制得目标产物R-二苯基脯氨醇。总产率为46%。     

4,4’-氧代双苯磺酰肼的合成研究

研究了４,４’ 氧代双苯磺酰肼的合成条件。当硫酸与二苯醚的摩尔比在１２～１３之间时,磺化反应温度控制在１１５～１３０℃之间时反应产率可达５１％,产物开始分解的温度在１３０℃左右,剧烈分解温度在１５０～１７０℃。     

修饰β-环糊精与非瑟酮包合物的制备及其抗氧化活性研究

水溶液法合成β-CD顺丁烯二酸单酯,再与氯化亚砜和N,N′-二(3-氨丙基)乙二胺反应,从而制得N,N′-二(3-氨丙基)乙二胺修饰β-CD(主体).通过饱和水溶液法制备主体与非瑟酮(客体)的包合物.采用UV、IR等表征并测定主体与客体的结合稳定常数,通过DPPH法测定包合物的抗氧化活性.结果表明,主体与客体的结合稳定...     

Preparation and characterization of new photoactive polyamides containing 4‐(4‐dimethylaminophenyl)urazole units

4‐(4‐dimethylaminophenyl)‐1,2,4‐triazolidine‐3,5‐dione ( DAPTD ) was prepared from 4‐dimethylaminobenzoic acid in five steps. The compound DAPTD was reacted with excess acetyl chloride in N,N‐dimethylacetamide (DMAc) solution and gave 1,2‐bisacetyl‐4‐[4‐(dimethylaminophenyl)]‐1,2,4‐triazolidine‐3,5‐dione as a model compound. Solution polycondensation reactions of monomer with succinyl chloride (SucC), suberoyl chloride (SubC), and sebacoyl chloride (SebC) were performed under conventional solution polymerization techniques in the presence of triethylamine and pyridine as a catalyst in N‐methylpyrrolidone (NMP) and led to the formation of novel aliphatic polyamides. These novel polyamides have inherent viscosities in the range of 0.09–0.21 dL/g in N,N‐dimethylformamide (DMF) at 25°C. Fluorimetric studies of the model compound as well as polymers were performed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 947–954, 2007     

聚吡咯涂覆型导电纸导电性能的进一步改善

在纸浆纤维悬浮液体系中通过原位聚合法制备了聚吡咯涂覆型导电纸,对其导电性进行了进一步的研究。将三氯化铁与磺基水杨酸以物质的量之比1:1的比例络合生成磺基水杨酸合铁,代替三氯化铁作氧化剂制得的导电纸的导电性及环境稳定性都有所提高。此时,磺基水杨酸不仅与铁离子络合,也起到掺杂的作用,且无需再加对甲苯磺酸为掺杂剂就能获得良好导电性的纸张。电镜及电镜能谱分析结果表明,不同氧化剂和掺杂剂制备的试样图像亮度及掺杂水平有明显差异。由于对甲苯磺酸铁的氧化能力较弱,故使用这一络合物作氧化剂兼掺杂剂并不能得到导电性能优异的纸张。此外,模拟纸浆贮存这一生产过程,将反应后的浆料贮存不同时间,发现水对导电纸的导电性能并无显著负面影响。     

Synthesis and antibacterial activity of some new diarylsulphides and diarylsulphones containing azetidin-2-one and/or diazetidin-2-onyl moities

Cyclonucleophilic addition of N-phthaloylaminoacid chlorides (II on 4-(N-ary-lideneamino)-4′-nitrodiphenyl sulphides (I) in dioxane and triethylamine afforded 4-(4″-aryl-3″-phthalylamino-2″-oxo-azetidin-1″-yl)-4′-nitro-diphenyl sulphides (III). Hydrazinolysis of III yielded 4-(4″-aryl-3″-amino-2″-oxo-azetidin-1″-yl)-4′-nitro-diphenyl sulphide hydrochlorides (IV). Condensation of IV with anisaldehyde using ethanol and piperidine as a basic catalyst gave 4-(4″-aryl-3″-anisylidine amino-2″-oxoazetidin-1″-yl)-4′-nitrodiphenylsulphides (V) in good yields. Interaction of V with chloroacetyl chloride in dioxane and triethylamine produced 4-(4″-aryl-3″-substituted β-lactamyl-2″-oxo-azetidin-1″-yi)-4′-nitrodiphenyl sulphides VI. Oxidation of IV, V and VI using hydrogen peroxide/glacial acetic acid mixtures gave the corresponding sulphones (VII), (VIII) and (IX). Sulphones of the type IX were obtained by unequivocal synthesis through interaction of sulphone-anils VIII with chloroacetyl chloride. The antibacterial activities of some of these compounds were determined.