Synthesis and applications of (R)- and (S)-7,7′-dimethoxy-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene

The synthesis of (R)- and (S)-7,7′-dimethoxy-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene 5a and 5b is described. The phosphorus atoms in (S)-(−)-5b are shown to be slightly more basic than the phosphorus atoms in (S)-BINAP by comparing the magnitude of the ¹J (³¹P–⁷⁷Se) coupling constant in their respective diselenide derivatives. (S)-(−)-5b behaved similarly to (S)-BINAP in asymmetric Heck reactions.     

5′-鸟嘌呤核苷三磷酸(5′-GTP)和5′-尿嘧啶核苷三磷酸(5′-UTP)二钠盐的制备

前言核苷三磷酸是含有两个高能磷酸键的高能化合物。除了参与核糖核酸合成外,在生物体内的生命活动中起着重要的作用。ATP 主要用于供给合成细胞的物质所需要的能量,也是被称为“第二信使”的环化AMP(3′5′-cyclicAMP)的前体。而后者已知与多种生化过程有关。CTP 参与重要磷脂类的合成。GTP 在蛋白质合成中是必不可少的。UTP 是肝脏中重要解毒剂尿二磷葡萄糖醛酸(UDPG)的前体,与肝糖元、酸性粘多糖的合成密切相关。根据已知的生理功能有些兄弟研究单位作了一些临床应用试验,还值得进一步探讨。     

1,10-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)癸二酮-(1,10)萃取钪

本文研究了1,10-双(1-苯基-3’-甲基-5’-氧代吡唑-4’-基)癸二酮-〔1,10〕从硝酸溶液中对Sc、Y、La的萃取分离。测定了固态萃合物的溶解性、摩尔电导、热稳定性及UV、IR、~1H NMR谱,讨论了萃合物的可能结构。     

1-(5′-溴-2′-吡啶基)-5-4′-硝基苯基)-3-(2′-呋喃基)甲(月朁)的合成及其与锌显色反应的研究

甲■类试剂是有色金属离子的优良显色剂。它们的各种取代衍生物,有许多作为分析试剂已被研究。近年来,为了改善该类试剂的分析性能,在甲(?)骨架上接上吡啶、噻唑、眯唑及呋喃等杂环基团,合成了一系列不对称型的杂环甲(?)。 本文报导5-Br-PNPFF试剂的合成和提纯方法。研究了它与锌显色反应的条件,用     

3,3′-(1,1′-二苯基-4,4′-二基)-二丙烯酸的合成新方法

通过Heck反应,以4,4′-二碘联苯和丙烯酸为原料,壳聚糖负载钯为催化剂,合成了3,3′-(1,1′-二苯基-4,4′-二基)-二丙烯酸.考察了反应温度、时间、原料配比等因素对产率的影响.结果表明最佳反应条件为:反应温度为100℃,时间为20h,原料配比为1∶3.测试了壳聚糖负载钯催化剂的重复使用性能,并用IR、1 H NMR和MS对产物进行了表征.     

六氟磷酸二(2,2′-联吡啶)(2,2′-联吡啶-4,4′-二羧酸)合钌(Ⅱ)的二维核磁共振谱分析

利用核磁共振氢谱和碳谱研究了电化学探针六氟磷酸二(2,2′-联吡啶)(2,2′-联吡啶-4,4'-二羧酸)合钌(Ⅱ)的立体结构,并通过二维1H-1H同核相关及1H-13C异核相关技术对其氢谱和碳谱进行了归属.     

Transition metal(II) complexes of 1-(α-hydroxynaphthyl)-2-(3′-methyl-5′-mercapto-1′,2′,4′-triazole)-2-aza-ethane

Summary Binuclear metal complexes of the type [M(HMTE)-(H₂O)₂]₂, where HMTE=1-(-hydroxynaphthyl)-2-(3-methyl-5-mercapto-1,2,4-triazolc)2-aza-ethane and M-Cu^II, Co^II, Ni^II and Mn^II have been prepared and characterized. An octahedral geometry around the metals is proposed. The complexes have been screened as possible fungicides.     

Studies on Flavans. III. The Total Synthesis of (±)-7,4′-Dihydroxy-3′-methoxyflavan, (±)-7,3′-Dihydroxy-4′-methoxyflavan,and (±)-7,4′-Dihydroxyflavan

Abstract

The first total synthesis of (±)-7,3′-dihydroxy-4′-methoxyflavan (1) and (±)-7,4′-dihydroxy-3′-methoxyflavan (2), along with the synthesis of (±)-7,4′-dihydroxyflavan (3), three naturally occurring flavans, were described. The key step is the cyclization of 1,3-diaryl-1-propanol by BF₃·Et₂O.     

A Facile Synthesis of an Advanced Glycosylation Endproduct 2-(2′-furoyl)-4(5)-(2′-furanyl)-1H-imidazole

Abstract: A three step synthesis of the advanced glycosylation endproduct 2-(2′-furoyl)-4(5)-(2′-furanyl)-1H-imidazole (4, FFI) has been achieved from 2-acetylfuran. The key step in the synthesis was the rearrangement of the hydrazinium bromide 3 in refluxing methanol.     

Molecular structure of 2,3-(4′-phenylacetyl)- and 2,3-(4′-diphenylacetyl)-benzo-15-crown-5

The conformational state of two benzo-crown ethers with substantially different physiological activity, 2,3-(4-phenylacetyl)- and 2,3-(4-diphenylacetyl)benzo-15-crown-5, was studied in crystals and solutions in CH₃CN and CCl₄ by x-ray crystallographic analysis, IR spectroscopy, and conformational calculations by the method of molecular mechanics. Transition from the crystalline state to solutions was found to be accompanied by a substantial change in the conformation of the macrocyclic ring of all the compounds studied. The nature of the substituent in the benzene ring and the polarity of the solvent have an influence on the conformational state of the macrocyclic ring of the free ligand, which, however, is not the determining factor in the change in the activity of the compounds. The COCCOC fragments of the macrocyclic framework are conformationally labile, readily passing from gauche to trans conformations and the reverse, which is promoted by the negligible energy barriers between the different conformations, determined in the work by a molecular mechanics method.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1819–1825, August, 1991.     

Crystal and molecular structures of (3Z)-(±)-4-(2′-hydroxypropyl)amino-and (3Z)-4-(2′-hydroxyethyl)amino-pent-3-en-2-ones

An X-ray study of (3Z)-(±)-4-(2′-hydroxypropyl)amino-and (3Z)-4-(2′-hydroxyethyl)amino-pent-3-en-2-ones is reported. The bond lengths inside the H ring are equalized due to the classical N-H...O hydrogen bond between the carbonyl oxygen and the amino group. In the 4-(2′-hydroxyethyl)amino-pent-3-en-2-one crystal, due to the classical N-H...O bonds, infinite zigzag chains are formed along the 0b axis and arranged into a layered structure due to the weak C-H...O interactions. In (±)-4-(2′-hydroxypropyl)aminopent-3-en-2-one crystal, however, centrosymmetric dimers are formed, which are then linked by weak C-H...O intermolecular interactions to form a layered structure along the a0b plane.     

Novel 2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-2-yl)methylpyrrolidinyl[60]fullerene-hydroxyoxo(5,10,15,20-tetraphenyl-21H,23H-porphynato) molybdenum(V) dyads

Interaction between hydroxyoxo(5,10,15,20-tetraphenylporphyrinato)molybdenum(V) and 2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-2-yl)methylpyrrolidinyl[60]fullerene in toluene has been studied by means of spectrophotometry. The reaction proceeds via two stages: rapidly established equilibrium between the reactants and their molecular complex 1: 1 [K = (1.97 ± 0.52) × 10⁴ L/mol] followed by slow irreversible displacement of hydroxy group into the second coordination sphere to form cationic outer sphere complex (k = 0.26 L s^?1 mol^?1). The effect of fullerene fragment on pyridine fragments coordination has been considered.     

铽(Ⅲ)-1,4-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)丁二酮-[1,4]体系荧光性质的研究及应用

本文研究了Tb(Ⅲ)-1,4-双(′-苯基-3′-甲基-5′-氧代吡唑-4′-基)丁二酮-[1,4](BPMPBD)-溴化十六烷基三甲胺(CTMAB)体系的荧光性质,探讨了响影体系荧光性质的诸因素,确定了最佳实验条件。该体系中Tb(Ⅲ)浓度以2.0×10~(-5)～1.0×10~(-10)mol/L范围内与其荧光强度呈线性关系,检测限可达到5.0×10~(-11)mol/L。应用于合成样品中微量Tb(Ⅲ)的分析,结果令人满意。     

Synthesis and functionalization oftrans-2-(2′-aminocyclohexyloxy)-andtrans-2-(2′-azidocyclohexyloxy)acetic acid

Summary Synthesis of the hydrochloride oftrans-2-(2-aminocyclohexyloxy)acetic acid (4) fromtrans-2-(2-azidocyclohexyloxy)acetic acid (1) is described.4 was acylated at the amino group to give compounds5–8.1 was converted into acid chloride (9) and amides10–13.

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Synthese und Funktionalisierung dertrans-2-(2-Aminocyclohexyloxy)- undtrans-2-(2-Azidocyclohexyloxy)essigsäure

Zusammenfassung Die Synthese destrans-2-(2-Aminocyclohexyloxy)essigsäurehydrochlorids (4), ausgehend vontrans-2-(2-Azidocyclohexyloxy)essigsäure (1), wird beschrieben.4 wurde durch Acylierung der Aminogruppe in die Verbindungen5–8 übergeführt.1 wurde in das Säurechlorid9 und die Carbonsäureamide10–13 umgewandelt.

     

1,4-双[5′-(2′-苯基(口恶)唑基)]苯及其双2′-(4″-取代苯基)衍生物的研究

本文用p-α,α＇-二氨基二乙酰基苯盐酸盐(1)与芳基甲酰氯,合成了1,4-双[5＇-(2＇-苯基(口恶)唑基)]苯(4a)和双2′-(4″-取代苯基)衍生物(?)(4b-1)。新化合物(4b-1)的结构经质谱和元素分析鉴定。并且发现,化合物(4a-g)是一类激光转换效率高,溶解性能好的激光染料(和POPOP比)。     

一锅法合成O-(3-薯蓣甙元) -O′-[5′-(3′-叠氮-3′-脱氧胸苷)]-氢亚磷酸酯

3′-叠氮-3′-脱氧胸苷(1)(AZT结构见Scheme 1)是FDA批准的第一个用于治疗HIV感染的双脱氧核苷类药物, 已在临床上得到了广泛的使用[1]. 但作为一种有效的逆转录酶抑制剂, 该药物在临床使用过程中面临许多亟待解决的问题. 例如, 长期使用会引起核苷第一步磷酰化所需胸苷激酶的活性降低, 从而引起病毒对药物的耐受性, 降低治疗效果. 另外, 长期使用该药物会产生脊髓抑制的副作用, 如贫血和中性粒细胞减少, 因而使治疗不能持续[2,3].     

Photochemical Synthesis of 5-Ethynyl-5′-(1-Propynyl)-2.2′-Bithiophene

The synthesis of the title compound is described. The key-step is the photochemical coupling between 5-iodo-2-thienylcarbaldehyde and 2-bromothio-phene to give 5-bromo-2,2′-bithienyl-5′-carbaldehyde.     

Stereoselective Synthesis and Characterization of (Z)-(−)-4-(1′-Alkoxyl-1′-alkyloxycarbonyl-methylidene)-5(R)-[(1R)-menthyloxy]-γ-butyrolactones

Abstract

A series of enantiomerically pure (Z)-(?)-4-(1′-alkyloxy-1′-alkyloxycarbonyl-methylidene)-5(R)-[(1R)-menthyloxy]-γ-butyrolactones were synthesized and characterized in good to excellent yields via O-alkylation of (4R,5R)-(?)-4-ethoxyoxalyl-5-[(1R)-menthyloxy]-γ-butyrolactone with alkyl halides in the presence of K₂CO₃ in acetone at room temperature.     

Synthesis of (Z)-(2′R)-1-O-(2′-methoxynonadec-10′-enyl)-sn-glycerol,a new analog of bioactive ether lipids

An unsaturated 2-methoxy-substituted 1-O-alkylglycerol, (Z)-(2′R)-1-O-(2′-methoxynonadec-10′-enyl)-sn-glycerol, a new analog of bioactive ether lipids, was synthesized from oleic acid and 2,3-isopropylidene-sn-glycerol. The two key steps of this synthesis were the conversion of oleyl aldehyde to a monounsaturated epoxide using Matteson’s method followed by hydrolytic kinetic resolution and a nucleophilic epoxide opening by 2,3-isopropylidene-sn-glycerol in the presence of potassium tert-butoxide in anhydrous DMF, which appeared to be a good reagent for this purpose. Furthermore, the diol by-product of the HKR process was also easily converted back to the starting epoxide thus almost doubling the amount of target molecule.     

稀土配合物的研究(Ⅸ)——稀土元素与1,5-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)戊二酮-(1,5)配合物的合成及性质

乙醇-水混合体系中合成了15种新的稀土元素的固态配合物,通过元素分析和化学分析确定了配合物的化学组成为RE_2(BPMPPD)_3·nH_2O和Ce(BPMPPD)_2·6H_2O(BPMPPD为1,5-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)戊二酮-[1,5]),对配合物的荧光光谱等性质进行了研究。