Regioselective Deprotection of 1,3-Dibenzyl-5-（N,N-dimethylamino）-6-phenylethyluracil

The deprotection of 1,3-dibenzyl-5-（N,N-dimethylamino）-6-phenyl-ethyluracil I was investigated. A practical, regioselective N3 deprotection of compound I was performed with excellent yield using cyclohexene as a hydrogen donor.     

O-炔丙基-N,N-二(2-氯乙基)-4-氨基苯酚的合成

以对氨基苯酚（1）为原料,经氨基的羟乙基化、酚羟基的苄基保护、氯代、脱保护制得N,N-二 (2-氯乙基) -对氨基苯酚（5）;在碳酸铯作用下,5与溴丙炔经O-烷基化反应合成了新化合物--O-炔丙基-N, N-二(2-氯乙基)-4-氨基苯酚,其结构经¹H NMR, ¹³C NMR和MS表征。     

四方向、六方向醚键型分枝状化合物的合成

本文选用2,4-二羟甲基-1,5-戊二醇和肌醇为四方向及六方向起始核心,通过氧丙基为空间间隔基与带保护基的分支侧链成醚,脱保护后得未端官能团数为原母核两倍的新型有机分子——四方向及六方向醚键型分枝状化合物。     

Synthesis of 3-[2-(1,3-butadienyl)]-1H-indoles en route to murrapanine analogue

A three-step procedure has been developed for the synthesis of 3-[2-(1,3-butadienyl)]-1H-indoles. TBAF was proved to be an effective reagent for dehydrobromination and carbomethoxy deprotection in one step to give 3-[2-(1,3-butadienyl)]-1H-indoles from the corresponding bromo-derivatives. Suitably substituted indolyl-1,3-butadiene has been successfully applied to prepare murrapanine analogue via Diels-Alder reaction.     

Synthesis, Crystal Structure and Fluorescent Properties of 1-（4-（Dimethylamino）benzylidene）- 4-（naphthalen- 1-yl） Thiosemicarbazide

1 INTRODUCTION Recently, for the fluorescent properties, Schiff base has been more and more important and widely studied in density optical memories, nonlinear op- tics (NLO), organic light-emitting diodes (OLED), polymer LED and electrogenerated chemilumines- cence (ECL)[1~5]. Thiosemicarbazones are a kind of Schiff bases with thiourea and good ligands easily chelating with transition metal ions. Although they have been studied extensively for a long time due to their chemical and b…     

2-{[(2'-氰基联苯基-4-基)甲基]氨基}-3-硝基苯甲酸甲酯的合成

以3-硝基-2-氨基苯甲酸甲酯为原料,经三氟乙酰化、N-烷基化和脱保护反应制得坎地沙坦中间体2-{[(2'-氰基联苯基-4-基)甲基]氨基}-3-硝基苯甲酸甲酯,其结构经~1H NMR,~(13)C NMR和MS(ESI)确证。     

Synthesis and Crystal Structure of N,N~′-Bis(p-nitrophenyl)-2,2~′-(p-phenylene-dioxy)diacetamide DMF Monohydrate

1 INTRODUCTION Many crown ethers have been synthesized[1, 2] and widely used[3～5]. The amide-type acyclic poly- ethers with versatile molecular structures offer many advantages over the traditional crown ethers, such as their potential activity for ion-selective electrodes[6] and the extraction of metal ions[7], so they have attracted much scientific attention[8～10]. In an effort to investigate the effect of skeleton of acyclic polyether on the extractability of metal ions, and to find …     

克唑替尼关键中间体(S)-1-(2,6-二氯-3-氟苯基)乙醇的不对称合成

(S)-1-(2,6-二氯-3-氟苯基)乙醇（2）是合成抗癌药物克唑替尼的关键手性前体。本文以1-(2,6-二氯-3-氟苯基)乙酮为起始原料,利用二异松莰基氯化硼［(-)-Ipc₂BCl］不对称还原制得光学纯的2;并将中间体2经Mitsunobu反应、还原、溴代、 Suzuki偶联及脱除Boc保护合成克唑替尼,其结构¹H NMR,¹³C NMR和HR-MS(ESI)确证。对关键中间体2的合成条件进行了优化,并其对反应机理进行了推测。     

光学活性N-肉桂酰R(S)-4-异丙基四氢噻唑-2-硫酮的合成及其量子化学的研究

用KBH_4,CaCl_2为还原剂使D及L缬氨酸甲酯还原得到光学活性产物R-3-甲基-2-氨基丁醇(2a)及S-3-甲基-2-氨基丁醇(2b)。2a,2b同CS_2在KOH存在下反应得到(R)-4-异丙基四氢噻唑-2-硫酮(3a)及(S)-4-异丙基四氢噻唑-2-硫酮(3b)。肉桂酰氯分别同3a及3b在Et_3N存在下反应得到N-肉桂酰(R)-4-异丙基四氢噻唑-2-硫酮(4a)及N-肉桂酰(S)-4-异丙基四氢噻唑-2-硫酮(4b)。用半经验的量子化学PM3方法研究了反应物和产物的电子结构,得到了产物的最优构型和电荷键序分布以及反应焓变。     

Synthesis, Crystal Structure and Fungicidal Activity of (E)-2-[(4-tert-Butyl-5- (4-methoxybenzyl)thiazol-2-ylimino)methyl]phenol

The title compound(E)-2-(4-tert-butyl-5-(4-methoxybenzyl)thiazol-2-ylimino)me-thylphenol was synthesized by the reaction of 5-(4-methoxybenzyl)-4-tert-butylthiazol-2-amine with salicylaldehyde=and its crystal structure was determined by single-crystal X-ray diffraction.The crystal belongs to the monoclinic system=space group P21/c with a=5.9362(8)=b=11.5070(15)=c=29.460(4)=β=97.326(3)°=V=1995.9(5)3=Z=4=F(000)=808=C22H24N2O2S=Mr=380.49=Dc=1.266 g/cm3=S=1.031=μ=0.181 mm--1=the final R=0.0474 and wR=0.1441 for 4327 observed reflections(I > 2σ(I)).Intramolecular O-H…N hydrogen bond is observed in the crystal.The preliminary bioassay showed that the title compound exhibits 95% inhibition rate against Rhizoctonia solani at the test concentration of 500 mg/L.     

(S)-2-氨基-1,1-二苯基-1-丙醇的合成

以L-丙氨酸为原料,经苄基保护、格氏反应和脱苄基反应合成了(S)-2-氨基-1,1-二苯基-1-丙醇,总收率48.1%,其结构经1H NMR,IR,EI-MS和元素分析表征。     

N-(2-溴乙基)咔唑与N-乙烯基咔唑的气相HeI紫外光电子能谱与电子结构研究

首次报道了N-(2-澳乙基)咔唑和N-乙烯基咏唑的气相Hel紫外光电子能谱(UPS),借助于Gaussian 94采用RHF/6-3lG基组优化几何构型,并用RHF/6-31G基组计算分子轨道及能级.在对咔唑和N-烷基咔唑系列分子UPS电离能变化规律研究的基础上,对这2个分子的UPS谱带给予指认,并讨论其电子结构.结果表明N-(2-溴乙基)咔唑的UPS谱与N-烷基咔唑的不同之处是在10.295,10.540Ve处出现2个Br原子的孤对轨道;N-乙烯基咔唑的UPS谱带与咔唑的相比,电离能变化的特殊性说明乙烯基与咔唑环共平面.     

Syntheses and Crystal Structures of Methyl 2-（4,5-Dibromo- 1-methylpyrrole-2-carbonylamino）-3-phenyl propanoate and 4,5-Dibromo-1-methyl-2-trichloroacetylpyrrole

1 INTRODUCTION Pyrrole and its derivatives have attracted much attention due to their chemical properties as well as biological activities[1]. They have been widely used as the materials to produce pharmaceutical, essences, biochemicals, etc. It has been found that a great deal of pyrrole derivatives present bioactivities, such as antitumor and antiviral activities[2~5]. Thus, due to the interest in exploring the syntheses of potential bioactive materials which contain pyrrole ring andna…     

反-4-羟甲基哌啶-3-醇的合成

以4-羟甲基吡啶为原料,经苄基保护、硼氢化钠的还原、硼氢化氧化和脱苄基保护等四步反应得到新型5-羟色胺受体激动剂的关键中间体反-4-羟甲基哌啶-3-醇。总收率达55. 7%。产物结构经IR、1H NMR和MS分析确证,并对合成工艺进行了优化。     

（—）—莰烷磺内酰胺法合成（S）和（R）切叶蚁警戒信息素

本文以樟脑衍生物(-)-莰烷磺内酰胺(2)为原料,经N-烷酰基莰烷-2,10-磺内酚胺(3)与碘代烷的不对称烷基化反应,用二锂代乙基苯基砜取代磺内酰胺助剂以及铝汞还原性脱硫反应等三步合成(S)和(R)一切叶蚁警戒信息素(1),其光学纯度高达95％e.e以上。     

Synthesis and Crystal Structure of (1S)-1,1'-Bis{[N-ethyl-N-(1-methylethyl)-amino]-carbonyl}-2-(hydroxydiphenylmethyl)-ferrocene

The title complex, (1S)-1,1'-bis{[N-ethyl-N-(1-methylethyl)-amino]carbonyl}-2- (hydroxyldiphenylmethyl)-ferrocene ([Fe(C24H22NO2)(C11H16NO)]2·H2O, Mr = 1207.13), was synthesized via (-)-Sparteine-mediated enantioselective directed ortho-lithiation of 1,1'-bis{[N- ethyl-N-(1-methylethyl)-amino]carbonyl}-2-(hydroxydiphenylmethyl)-ferrocene. The structure of the title compound was determined by X-ray single-crystal diffraction. The crystal belongs to the orthorhombic system, space group P212121, with a = 10.26...     

Synthesis and Crystal Structure of the First Diaza-spirobifluorene：2-（Spirobifluorene-2-yl）-3,4-diaza-spirobifluorene

The title compound 2-(spirobifluorene-2-yl)-3,4-diaza-spirobifluorene(C48H28N2,Mr = 632.72) has been synthesized and characterized by 1H NMR,13C NMR and single-crystal X-ray diffraction.The crystal crystallizes in the monoclinic system,space group Cc with a = 13.8523(6),b = 29.3297(13),c = 8.6397(4) ,β = 111.8760(10)°,V = 3257.4(3) 3,Z = 4,Dc = 1.290 mg/m3,μ = 0.075 mm-1,F(000) = 1320,the final R = 0.0425 and wR = 0.1110 for 5288 observed reflections(Ⅰ 2σ(Ⅰ)).     

2-[2-(4,6-二甲基)-嘧啶基]-4-苯基-1,2,4-噁二唑烷-3,5-二酮的合成

异氰酸苯醇和N-[2-(4,6-二甲基)-嘧啶基]-羟胺(5)反应生成1-[2-(4,6-二甲基)-嘧啶基]-1-羟基-3-苯基脲(6)。化合物(6)在三乙胺存在下和氯甲酸乙醇反应生成2-[2-(4,6-二甲基)-嘧啶基]-4-苯基-1,2,4-噁二唑烷-3,5-二酮(1)。     

Synthesis and Crystal Structure of Trans-4-[(5-(2,4-Dichlorophenoxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyleneamino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one

The title compound trans-4-[(5-(2,4-dichlorophenoxy)-3-methyl-1-phenyl-1H-pyra-zol-4-yl)methyleneamino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 (C28H23Cl2N5O2, Mr = 532.41) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1 with a = 8.9438(4), b = 11.6065(5), c = 14.2215(6) , α = 112.566(1), β = 92.324(2), γ = 102.91(1)o, V = 1315.65(10) 3, Z = 2, Dc = 1.344 g/cm3, μ(MoKα) = 0.282 mm-1, λ = 0.71073 , F(000) = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections (I > 2σ(I)). X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra-and intermolecular C(12)-H(12)···O(1) and C(28)-H(28)···O(1)#1 hydrogen bonds were observed in the title compound.     

Synthesis,Crystal Structure and Anti-tumor Activity of 2-（2-Chloro-4-nitrophenyl）-4- （4-chlorophenyl）-3a,4-diethoxy-2,3,3a, 4-tetrahydrochromeno[3,4-d] [ 1,2,3]diazaphosphole

The title compound 2-（2-chloro-4-nitrophenyl）-4-（4-chlorophenyl）-3a,4- diethoxy- 2,3,3a, 4-tetrahydrochromeno[3,4-d][1,2,3]diazaphosphole 2 （C29H30Cl2N3O7P, Mr = 633.44） was synthesized and its structure was characterized by IR, MS, ^1H NMR, ^13C NMR, ^31p NMR, elemental analysis and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1^-, a = 9.1549（3）, b = 10.7168（4）, c = 17.6272（6）A, α = 102.9363（12）, β = 90.2713（9）, γ = 117.4265（10）°, V= 1484.41（9）A^3, Z= 2,μ（MoKa） = 0.323, F（000） = 658, Z= 2, De= 1.417 g/cm^3, the final R = 0.0687 and wR = 0.2066 for 4943 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the diazaphospholine ring is almost planar and the two ethoxy groups bonded on the 3a- and 4-positions are in trans configurations. Its antiproliferative activity was also tested in vitro against four human tumor cell lines.