杂环有机锡化合物的谱学表征

合成了八个杂环芳基正丁基有机锡化合物,它们的通式是RnSnBu_(4-n)(R=2-呋喃基或2-噻吩基,n=l,2,3;R=2-(N-甲基)吡咯基或2-吡啶基,n=l)。其中二正丁基-二(2-呋喃基)锡、正丁基-三(2-呋喃基)锡、二正丁基-二(2-噻吩基)锡和正丁基-三(2-噻吩基)锡是新化合物。这些化合物都经过了元素分析和¹H、¹³C和¹¹⁹Sn NMR及IR谱表征,文中重点讨论了它们的谱学特征。     

2,2-二甲基-3-(2,2-二氯乙烯基)环丙烷羧酸乙(甲)酯及其合成中间体的结构测定

由异戊烯醇-原乙酸三乙(甲)酯法相继合成了拟除虫菊酯类农药中间体3,3-二甲基-4-戊烯酸乙(甲)酯,4,6,6,6-四氯-3,3-二甲基己酸乙(甲)酯和2,2-二甲基-3-(2,2-二氯乙烯基)环丙烷羧酸乙(甲)酯等化合物,对这些化合物进行了元素分析、红外光谱、¹H NMR等测定,与文献结果相符,为了进一步明确结构,测定了未见报道的¹³C NMR,给出了波谱数据归属.     

海洋真菌Penicillium sp.中的环二肽类化合物

从南海采集的海泥中分离得到的海洋真菌Penicillium sp.中分离得到3种环二肽类化合物。通过理化性质和波谱数据分析鉴定了3种化合物的结构。它们分别是3-异丁基-6-异丙基哌嗪-2,5-二酮(1)、3-另丁基-6-异丁基哌嗪-2,5-二酮(2)、3-另丁基-6-异丙基哌嗪-2,5-二酮(3)。     

两种杂二齿螯合物的合成

研究两种具有光学活性的杂二齿螯合物(1S,2S)-2-{甲基[(R)-3甲基-2-丁基]氨基)-1-苯基-1-丙醇和(1R,2R)-2-氨基-1-苯基-1-丙醇的合成方法。分别以麻黄碱和苯甲醛为原料通过成环、还原等方法得到光学活性单一的目标化合物,其结构通过~1H NMR确认。设计的合成路线有收率高、反应条件相对温和、生成物光学活性单一等特点。     

单甲基酯亚磺酸帕珠沙星盐的波谱学研究

帕珠沙星(Pazufloxacin), (S)-7-(1′-氨基环丙基)[N,8-缩-(2″-甲基)乙氧基]-3-羧酸-6-氟-喹啉-[4]酮-(S)-7-(1′-Aminocyclopropy1)-[N,8-de]-(2″-methy1)-epoxyethane-3-Carbony1ic acid-6-fluoro-quino1-[4]-one,及其单甲基酯亚磺酸盐是一种可望用于抗革兰氏阳性菌和阴性菌的防治药物. 本文采用¹H NMR、¹³C NMR、DEPT及二维谱¹H-¹H COSY、HMQC、HMBC和IR、MS推证了单甲基酯亚磺酸帕珠沙星盐分子结构的正确性,并进行了¹H、¹³C NMR谱峰的全归属. 对其IR、MS各主要峰也进行了归属.     

2,2-二甲基-3-(2,2-二氯乙烯基)环丙烷羧酸乙(甲)酯及其合成中间体的结构测定

由异戊烯醇-原乙酸三乙（甲）酯法相继合成了拟除虫菊酯类农药中间体3，3-二甲基-4-戊烯酸乙（甲）酯，4，6，6，6-四氯-3，3-二甲基己酸乙（甲）酯和2，2-二甲基-3－（2，2-二氯乙烯基）环丙烷羧酸乙（甲）酯等化合物，对这些化合物进行了元素分析、红外光谱、1HNMR等测定，与文献结果相符，为了进一步明确结构，测定了未见报道的13CNMR，给出了波谱数据归属．     

(S)-1-苄基-3-羟基吡咯烷的合成及红外光谱研究

从L-苹果酸出发,经过与苄胺缩合反应得到(S)-1-苄基-3-羟基吡咯烷-2,5-二酮,再通过硼氢化钠-碘体系还原制得重要的医药中间体(S)-1-苄基-3-羟基吡咯烷。采用红外光谱法对原料、中间体及产物进行了测试并对硼氢化钠-碘体系还原酰亚胺的机理进行了研究。通过比较原料、中间体及产物相应特征吸收峰的消失或是出现,可知所得的产物为(S)-1-苄基-3-羟基吡咯烷;还原机理研究表明,硼氢化钠在碘催化下生成的硼烷与酰亚胺中的羰基形成四元环状过渡态,同时另外一分子硼烷与酰亚胺中的氮原子形成N-BH3复合物,然后羰基还原完全,得到(S)-1-苄基-3-羟基吡咯烷-硼烷复合物,最后在甲醇作用下脱去硼烷得到最终产物。     

(6aR,11aR)-3-羟基-4,9-二甲氧基紫檀烷分子的晶体结构

从多刺锦鸡儿 (豆科 )中分离得到一个紫檀烷型化合物— (6aR ,11aR) 3 羟基 4,9 二甲氧基紫檀烷 ,通过红外光谱、质谱、核磁共振氢谱、核磁共振碳谱、氢核 氢核相关谱、异核多量子相干谱和异核多键相干谱进行结构鉴定 .其单晶经X射线衍射测试表明 ,该化合物晶体属单斜晶系 ,空间群为P2 1 ,化学式为C1 7H1 6 O5,Mr =3 0 0 .3 0 .晶胞参数为 :a =6.4778(13 ) ,b =12 .63 1(3 ) ,c=8.83 68(18) ,β =95 .80 (3 ) o,V =719.3 (3 ) 3,Z =2 ,Dc=1.3 86Mg/m3,F(0 0 0 ) =3 16,μ =0 .10 2mm- 1 .结构由直接法解出 ,用全矩阵最小二乘法修正 ,最终偏离因子R =0 .0 3 3 2 ,wR =0 .0 862 .该分子由一个苯并吡喃环和苯并呋喃环组成 ,X射线衍射测试表明其绝对构型为顺式紫檀烷型     

核磁共振氢谱中二苯基乙二胺衍生物手性识别其结构类似物(英文)

本文通过手性二苯基乙二胺与异氰酸酯的衍生化反应,合成了一种C_2对称的手性主体1.该主体可以手性识别其结构类似物:α-苯乙胺(客体2)、α-对甲氧基苯乙胺(客体9)以及它们的衍生物(客体3～8和10～13).高分辨核磁共振氢谱(~1H NMR)显示了对映体识别中主客体间的氢键作用.结果表明,除含2个NO_2的客体7和12外,主体1可以较易识别含有两个伯胺的脲和酰胺衍生物.研究还发现,主体1对脲衍生物2、9比对酰胺衍生物有更强的氢键作用,此外主体1对(R)和(S)-脲衍生物中的CHCH_3基团也有更高的辨识能力.     

新型荧光试剂1-(8-喹啉)-3-(3,5-二溴吡啶)-三氮烯的合成及其分析应用

将具有荧光特性的8-氨基喹啉与吡啶类试剂结合,首次合成了标题化合物1-(8-喹啉)-3-(3,5-二溴吡啶)-三氮烯(QBPyT).其结构经过元素分析、红外光谱、核磁共振谱证实.研究表明,在碱性介质中,该试剂在λex/λem=248nm/496nm处产生强荧光,并且能被Sb(Ⅲ)荧光增强.基于此,建立了QBPyT测定S...     

13C cross-polarization MAS NMR study of some steroidal sapogenins

Cross-polarization (CP) magic angle spinning (MAS) solid-state 13C NMR spectra of five steroidal sapogenins: tigogenin ((25R)-5alpha-spirostan-3beta-ol), hecogenin (3beta-hydroxy-(25R)-5alpha-spirostan-12-one), diosgenin ((delta5-(25R)-5alpha-spirosten-3beta-ol), sarsasapogenin ((25S)-55beta-spirostan-3beta-ol), and smilagenin ((25R)-5beta-spirostan-3beta-ol) were recorded. The solid-state chemical shifts are almost the same as for solution, which indicate that confirmations of sapogenins are similar in both phases. The doubling of some resonances in the spectra of solid diosgenin shows that there are two molecules in the crystallographic asymmetric unit. The cross-polarization time constants T(CP) and relaxation times in the rotating frame T(1rho)H were obtained from the variable-contact cross-polarization experiments for tigogenin and diosgenin. The values of T(CH) for methyl carbons indicate fast rotation of methyl groups and are close (0.30-0.35 ms), suggesting that the interaction with their intramolecular neighbors is similar. The values of T(1rho)H for carbons of tigogenin are longer than of diosgenin. Very efficient cross-polarization dynamics results in short time required for obtaining a spectrum of sapogenin of remarkably good quality.     

d-dimensional black hole entropy spectrum from quasinormal modes

Starting from recent observations about quasinormal modes, we use semiclassical arguments to derive the Bekenstein-Hawking entropy spectrum for d-dimensional spherically symmetric black holes. We find that, as first suggested by Bekenstein, the entropy spectrum is equally spaced: S(BH)=kln((m(0))n, where m(0) is a fixed integer that must be derived from the microscopic theory. As shown in O. Dreyer, gr-qc/0211076, 4D loop quantum gravity yields precisely such a spectrum with m(0)=3 providing the Immirzi parameter is chosen appropriately. For d-dimensional black holes of radius R(H)(M), our analysis predicts the existence of a unique quasinormal mode frequency in the large damping limit omega((d))(M)=alpha((d))c/R(H)(M) with coefficient [formula: see text], where m(0) is an integer.     

电场催陈米酒核磁共振分析

以自行研制的设备对新产广东玉冰烧米酒进行催陈 (处理条件 :4 0kV·m- 1 的电场强度处理 180min ,5 0Hz) ;然后采用1 HNMR对新酒、电场催陈酒及成品酒进行了分析 ,研究发现新酒中甲基和亚甲基峰出现了 4个杂峰而其他样品没有 ,说明新酒中单分子与各种状态的缔合结构共存 ,其他各主要有机物质亦参与成峰 ;而关于羟基质子峰 ,新酒为平头峰 ,推断出溶液中有 2种羟基质子存在 ,一种参与形成缔合 ,另一种未参与缔合 ;成品酒为单一峰 ,说明溶液中形成了单一稳定的大分子缔合结构 ;电场处理酒样为不规则峰 ,反映出多种缔合状态共存 ,其主要缔合结构接近成品酒缔合结构     

三乙烯四胺基双(二硫代甲酸钠)及其重金属配合物的光谱研究

采用红外光谱、紫外光谱、原子吸收光谱及元素分析研究了三乙烯四胺基双(二硫代甲酸钠)(DTC-TETA)的结构及其重金属配合物的配位行为。在DTC-TETA的红外光谱图中,在1 461～1 388 cm-1处和1 174～996 cm-1处分别出现含有部分双键性质的CN键和CS键的特征吸收峰;在紫外光谱图中,分别在265和290 nm处出现两个最大吸收峰,分别对应于N…C…S基团的π—π*跃迁和S…C…S基团中硫原子上非键电子向共轭体系的n—π*跃迁;元素分析结果表明该化合物中碳、氢、氮、硫的摩尔比近似为2∶4∶1∶1。在Cu(Ⅱ), Cd(Ⅱ), Zn(Ⅱ), Ni(Ⅱ)配合物的紫外光谱图中分别在紫外区的321, 310, 311, 325 nm处出现新的最大吸收峰。流动注射与火焰原子吸收联用分析结果表明DTC-TETA对铜、镉、镍、锌等重金属离子的络合能力强于二乙基二硫代氨基甲酸钠(DDTC)。     

Study of CP violating effects in time dependent B0(B0)-->D(*)-/+pi+/- decays

We report measurements of time dependent decay rates for B0(B(0))-->D((*)-/+)pi(+/-) decays and extraction of CP violation parameters containing phi(3). Using fully reconstructed D((*))pi events from a 140 fb(-1) data sample collected at the Upsilon(4S) resonance, we obtain the CP violation parameters for D(*)pi and Dpi decays, 2R(D((*))pi)sin((2phi(1)+phi(3)+/-delta(D((*))pi)), where R(D((*))pi) is the ratio of the magnitudes of the doubly Cabibbo-suppressed and Cabibbo-favored amplitudes, and delta(D((*))pi) is the strong phase difference between them. Under the assumption of delta(D((*))pi) being close to either 0 degrees or 180 degrees, we obtain |2R(D(*)pi)sin((2phi(1)+phi(3))|=0.060+/-0.040(stat)+/-0.019(syst) and |2R(Dpi)sin((2phi(1)+phi(3))|=0.061+/-0.037(stat)+/-0.018(syst).     

First-order distributed feedback dye laser effect in reflection pumping geometry

Tunable distributed feedback lasing output based on reflection grating configuration instead of the traditional transmission one was realized from rhodamine 6G (R6G)-doped ethanol and 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl)-4H-pyran-(DCM)-doped methanol. Pure gain coupling and additional index coupling were obtained in R6G-doped ethanol and DCM-doped methanol, respectively. The tuning, which was found to be independent of the refractive index of the lasing media, went through the entire stimulated emission band for the two cases. Dual-peak lasing emission indicative of the existence of an index grating was observed in DCM-doped methanol. The interval between the two peaks increased with pump energy.     

含R2dtc配体和V=O基的金属簇红外光谱研究

本文报道两类含Ｒ２ｄｔｃ配体的金属簇的红外光谱特点及某些规律,含Ｒ２ｄｔｃ的立方簇合物在４００－５００ｃｍ＾－１有较宽而弱的吸收,可归结于Ｍ－μ３Ｓ振动。Ｍ－Ｓｄｔｃ在３３０－３８０ｃｍ＾－１,Ｃ－Ｎ振动在１４７０－１５１０ｃｍ＾－１。二甲基ｄｔｃ配体立方的ｖ（Ｃ－Ｎ）与ｖ（Ｃ＝Ｓ）比值他二烷基ｄｔｃ立方烷的相应振动分别蓝移和红移,可归结于甲基超共轭效应所致。「Ｖ２Ｃｕ２Ｓ４（Ｒ２ｄｔｃ）２（ＰｈＳ）２」＾２－和「ＶＣｕ４Ｓ４（Ｒ２ｄｔｃ）ｎ（ＰｈＳ）４－ｎ」＾３－（ｎ＝０,１,２）的Ｍ－μ３Ｓ振动分别出现在４８０和４６５ｃｍ＾－１,可作为区别两类化合物的一个指标。另一类含（Ｒ２ｄｔｃ）２Ｖ２Ｏ２（μ－Ｓ）２单元的金属簇中,Ｖ－Ｏ伸缩频率在８４４－９７０ｃｍ＾－１范围内,（Ｅｔ４Ｎ）「Ｖ２Ｓ２Ｏ３（Ｅｔ２ｄｔｃ     

β-苄基苯乙酮吸收与发射光谱的密度泛函研究

β-苯基羰基化合物的光化学特征历来受到重视,是n,π*羰基三线态猝灭机理的典型代表。研究了气相和甲醇中β-苄基苯乙酮的基态结构和激发态结构,模拟了其吸收和发射光谱,并从分子轨道角度阐明了其发光机制。研究发现:(1)在甲醇中,β-苄基苯乙酮的基态结构与气相结构非常接近,只是在羰基官能团附近键长有差别;(2)在甲醇中,β-苄基苯乙酮的S1态无法维持平面构型,且αC—C键显著拉长;(3)在气相中,β-苄基苯乙酮的吸收光谱很弱,而在甲醇中很强;(4)气相中,β-苄基苯乙酮的荧光光谱的发光机制与甲醇中不同;(5)在气相中,β-苄基苯乙酮荧光光谱的最大发射峰蓝移到228.67nm处,发射强度(f=0.306 1)比吸收光谱大幅增加;(6)从分子轨道角度看,荧光光谱是吸收光谱的逆过程;(7)在气相中,β-苄基苯乙酮的磷光光谱在252.58和246.04nm处有两个较强的发射峰,而甲醇中只在258.88nm处有一个很强的发射峰。     

Raman spectroscopic and optical absorption study of the high pressure behaviour and polymorphism in KO2

Abstract

Raman scattering, visible absorption, and optical observation studies have been made on polycrystalline potassium superoxide (KO₂) in a diamond anvil cell as a function of pressure and temperature. Three new phases are observed. With increasing pressure at 298 K, KO₂ transforms from the well known modified CaC₂ structure (Phase II), to two new phases (VII, and VIII). The transformation from III to VII occurs at about 3.2GPa. Phase VII transforms to phase VIII at about 4.4GPa. However, in some samples phase VII does not occur and phase II transforms directly into phase VIII at about 4.2 GPa. These structural transformations are indicated by marked changes in the Raman spectrum. The transitions out of phase II are also marked by a discontinuous red shift in the optical absorption edge. From optical observations we have also determined the pressure and temperature dependence of the transitions from phase II to the high temperature cubic (B1) phase I as well as from the high pressure phases VII and VIII to a new nonbirefringent phase IX. This new phase IX has the cubic B2 (CsCl) structure as is shown by our recent X-ray synchrotron experiments.