N,N-二(邻硝基苯氨基乙基)甘氨酸糖酯的合成

在筛选抗植物病毒剂的研究中发现N,N-二(邻硝基苯氨基乙基)甘氨酸具有较好的抑制烟草花叶病毒(TMV)的活性,为提高其抗病毒活性,根据一些糖酯具有生理活性,而且它们的活性和药理性质都比同系物非糖酯要好,因此决定合成标题酸的酯基葡萄糖、乳糖、半乳糖和木糖酯,这些酯均为新化合物。     

N,N—二（邻硝基苯氨基乙基）甘氨酸糖酯的合成

在氢氧化钠和四丁基溴化铵存在下，将Ｎ，Ｎ－二（邻硝基苯氨基乙基）甘氨酸分别与Ｏ－乙酰基代葡萄糖，Ｏ－乙酰基溴代半乳糖，Ｏ－乙酰基溴代乳糖和Ｏ－乙酰基溴代木糖作用，制得Ｎ，Ｎ－二取代甘氨酸的对应乙酰基糖酯。由元素分析，ＩＲ，ＭＳ和Ｈ＾１Ｈ ＮＭＲ确认了４个的糖酯的结构。     

N,N-二取代甘氨酸四乙酰基葡萄糖酯的合成与表征

在碳酸钾和十六烷基三甲基溴化铵存在下, 将N-(N-乙酰基-N-芳氨基乙酰基)-N-芳氨基乙酸与全乙酰化α-溴代葡萄糖反应合成出了7个新的N,N-二取代甘氨酸四乙酰基葡萄糖酯(5a～5g), 并利用IR, 1H NMR, MS和元素分析对其结构进行了表征.     

N-茄呢基胺类糖酯化合物的合成及生理活性

在氢氧化钠和四丁基溴化铵存在下,将化合物2-N-茄呢基胺基苯甲酸(3)和N-茄呢基己二酰胺酸(6)分别与O-乙酰基溴代葡萄糖、O-乙酰基溴代半乳糖、O-乙酰基溴代乳糖和O-乙酰基溴代麦芽糖反应制得对应的糖酯4a～4d和7a～7d,由元素分析,IR,1H NMR和MS确证了8个新化合物的结构,并对其中6个化合物(4a,4d和7a～7d)在三种癌细胞模型上进行了一些初步体外生理活性的测试.     

植物用抗病毒剂的研究——含氟苯甲酸糖酯的合成

通过相转移催化反应,在氢氧化钠和相转移催化剂四丁基溴化铵存在下,将含氟苯甲酸分别与O－乙酰基溴代葡萄糖、O－乙酰基溴代半乳糖、O－乙酰基溴代乳糖和O－乙酰基溴代木糖作用,合成了14个未见文献报道的新化合物－含氟苯甲酸乙酰基糖酯。由IR,MS和^1HNMR确认了这些新的糖酯的结构及β构型。     

4－N－茄呢基氨基苯甲酸糖酯的合成

在氢氧化钠和四丁基溴化铵存在下，将化合物4－N－茄呢基氨基苯甲酸（3） 分别与O－乙酰基溴代葡萄糖、O－乙酰基溴代半乳糖、O－乙酰基溴代乳糖和O－乙 酰基溴代麦牙糖反应制得对应的糖酯4a-4d，由元素分析，IR，~1H NMR，~(13)C NMR和MS确证了四个新化合物的结构，并做了几种抗癌生理活性测试。     

Ⅷ.O-乙基N,N-二乙氨基一(或二)硫代磷酸钠的制备及其化学反应

1.本文报告以O-乙基N,N-二乙氨基硫代磷酰氯(Ⅲ)为原料,合成O-乙基N,N-二乙氨基一(或二)硫代磷酸钠(Ⅰ)、(Ⅱ)的方法。2.Ⅰ和Ⅱ分别与卤代烷反应,得到相应的酯(Ⅴ),(Ⅵ)。Ⅰ和Ⅱ在低温下用稀盐酸酸化则转化成相应的酸(Ⅶ)和(Ⅷ),后者分别与碘乙烷、重氮甲烷、环己胺等作用得到相应的酯(Ⅸ)和铵盐(Ⅺ)。3.Ⅱ与卤素(溴或碘)反应形成二硫化物(Ⅻ),后者与等量氯反应得到磷酰氯(Ⅲ)。     

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。     

The Synthesis of 1－O－β－D－（5－Aryl－2－furoyl）AcetylatedSugarsbyPhaseTransferCatalysis

以相转移催化法使α－溴代乙酰基葡萄糖，α－溴代乙酰基木糖和α－溴代乙酰基葡萄糖醛酸甲酯与５－芳基－２－呋喃甲酸在水－有机相体系中反应，合成了１４个未见文献报道的糖酯类化合物，其结构经ＩＲ、１ＨＮＭＲ、ＭＳ等证实，生物活性实验正在进行之中     

13-顺-4-羰基维甲酸葡萄糖酯的合成与表征

13-顺维甲酸与溴代-2,3,4,6-四-O-乙酰基-α-D-吡喃葡萄糖在4-二甲氨基吡啶催化下合成了13-顺维甲酸葡萄糖酯(5),以二氧化锰为氧化剂,5经氧化成功地合成了新化合物13-顺-4-羰基维甲酸葡萄糖酯(6)。5和6的结构经1H NMR,13C NMR,IR和MS表征,结果表明5和6均为β-构型糖酯。     

A convenient route to N-[2-(Fmoc)aminoethyl]glycine esters and PNA oligomerization using a Bis-N-Boc nucleobase protecting group strategy

A simple and practical synthesis of the benzyl, allyl, and 4-nitrobenzyl esters of N-[2-(Fmoc)aminoethyl]glycine is described starting from the known N-(2-aminoethyl)glycine. These esters are stored as stable hydrochloride salts and were used in the synthesis of peptide nucleic acid monomers possessing bis-N-Boc-protected nucleobase moieties on the exocyclic amino groups of ethyl cytosin-1-ylacetate, ethyl adenin-9-ylacetate and ethyl (O(6)-benzylguanin-9-yl)acetate. Upon ester hydrolysis, the corresponding nucleobase acetic acids were coupled to N-[2-(Fmoc)aminoethyl]glycine benzyl ester or to N-[2-(Fmoc)aminoethyl]glycine allyl ester in order to retain the O(6) benzyl ether protecting group of guanine. The Fmoc/bis-N-Boc-protected monomers were successfully used in the Fmoc-mediated solid-phase peptide synthesis of mixed sequence 10-mer PNA oligomers and are shown to be a viable alternative to the currently most widely used Fmoc/Bhoc-protected peptide nucleic acid monomers.     

1-丁基-3-甲基咪唑磷钨酸盐的制备及其对酯化反应的催化性能

以溴化1-丁基-3-甲基咪唑盐([bmim]Br)和磷钨酸(H3PW12O40)为原料制备了1-丁基-3-甲基咪唑磷钨酸盐([bmim]3PW12O40)催化剂,并用傅里叶变换红外光谱、热重分析-差示扫描量热法、正丁胺电位滴定及元素分析等技术对催化剂进行了表征,考察了催化剂对乙醇与乙酸酯化合成乙酸乙酯反应的催化活性.结果表明,[bmim]3PW12O40中有3个结晶水,并保持有H3PW12O40的Keggin结构和酸强度,[bmim]3PW12O40的酸量明显少于H3PW12O40的酸量.在乙醇与乙酸酯化合成乙酸乙酯反应中,[bmim]3PW12O40催化剂具有较高的催化活性和较好的重复使用性能.     

Structures and redox reactivities of copper complexes of (2-pyridyl)alkylamine ligands. Effects of the alkyl linker chain length

Ligand effects on the structures and redox reactivities of copper complexes have been examined using (2-pyridyl)alkylamine derivatives as the supporting ligands, where particular attention has been focused on the effects of the alkyl linker chain length connecting the tertiary amine nitrogen atom and the pyridine nucleus: N[bond]CH(2)[bond]Py (Pym) vs N[bond]CH(2)CH(2)[bond]Py (Pye). X-ray crystallographic analysis of the copper(I) complex of tridentate ligand (Phe)L(Pym2) [N,N-di(2-pyridylmethyl)-2-phenylethylamine] (complex 1) has demonstrated that it possesses a trigonal pyramidal geometry in which a d[bond]pi interaction with an eta(1)-binding mode exists between the metal ion and one of the ortho carbons of the phenyl ring of the ligand side arm (phenethyl). The result shows sharp contrast to the d[bond]pi interaction with an eta(2)-binding mode existing in the copper(I) complex of (Phe)L(Pye2) [N,N-di[2-(2-pyridyl)ethyl]-2-phenethylamine] (complex 2). Such a d-pi interaction has been shown to affect the stability of the copper(I) complex in CH(2)Cl(2). Oxygenation of copper(I) complex 1 supported by (Phe)L(Pym2) produces a bis(mu-oxo)dicopper(III) complex, also being in sharp contrast to the case of the copper(I) complex 2 with ligand (Phe)L(Pye2), which preferentially affords a (micro-eta(2):eta(2)-peroxo)dicopper(II) complex in the reaction with O(2). Such an effect of the alkyl linker chain length of the metal binding site has also been found to operate in the RSSR (disulfide)/2RS(-) (thiolate) redox system. Namely, ligand (S2,R)L(Pym1) (di[2-[(alkyl)(2-pyridinylmethyl)amino]ethyl] disulfide) with the methylene linker group (Pym) induced the reductive disulfide bond cleavage in the reaction with copper(I) ion to give a bis(micro-thiolato)dicopper(II) complex, while the ligand with the ethylene linker group (Pye), (S2,Bn)L(Pye1) (di[2-[(benzyl)(2-(2-pyridinyl)ethyl)amino]ethyl] disulfide), gave a disulfide-dicopper(I) complex. These ligand effects in the Cu(2)[bond]O(2) and Cu(2)[bond]S(2) systems have been discussed by taking into account the difference in electron-donor ability of the pyridine nucleus between the Pym and Pye ligand systems.     

具有Gemini表面活性ATRP引发剂的合成

以2-溴异丁酰溴、N,N-二甲基乙醇胺、1,6-二溴己烷为主要原料,通过两步反应合成了一种新型具有Gemini表面活性的ATRP引发剂——N1,N6-双[2-(2-溴异丁酰氧基)乙基]-N1,N1,N6,N6-四甲基己烷-1,6-二溴化铵,总收率70%,其结构经1H NMR,IR和元素分析表征。     

Reactions of Heterocumulenes with Organometallic Reagents: IX. Synthesis and Rearrangements of N-Allyl-and N-[2-(Vinyloxy)ethyl]-3-butenethioamides and -1-(methylsulfanyl)-3-buten-1-imines

Reactions of allyl and 2-(vinyloxy)ethyl isothiocyanates with alyylmagnesium bromide (THF-Et₂O, 20-30°C, 1-3 h) after hydrolysis or alkylation of adducts afforded respectively N-allyl- and N-[2-(vinyloxy)ethyl]-3-butenethioamides or N-allyl- and N-[2-(vinyloxy)ethyl]-1-(methylmercapto)-3-buten-1-imines. The reaction carried out in ethyl ether yielded instead of Nt-allyl-3-butenethioamide its isomer N-allyl-2-butenethioamide that cleanly isomerized in the system KOH-DMSOH₂O into N-(1-propenyl)-2-butenethioamide. N-[2-(vinyloxy)ethyl]-3-butenethioamide suffers a prototropic rearrangement into N-[2-(vinyloxy)ethyl]-2-butenethioamide only in the system     

An experimental and computational study of sulfur-modified nucleophilicity in a dianionic NiN2S2 complex

The dianionic NiN2S2 complex, Ni(ema)2-, ema=N,N'-ethylenebis-2-mercaptoacetamide, known as a reasonable model of the tripeptide complex Ni(CGC)2- (C=cysteine; G=glycine) with respect to the two carboxyamido nitrogens and cis-dithiolates in a (N2S2)4- ligand scaffold as found in acetyl CoA synthase, has been explored for S-based reactivity toward oxygenation and alkylation. The isolation and structural characterization of a sulfinato species, [Et4N]2[Ni(ema).O2], prepared through a unique direct reaction of molecular O2 with crystalline [Et4N]2[Ni(ema)] is described. Reaction of [Et4N]2[Ni(ema)] with Br(CH2)3Br yields a neutral N2S2 macrocyclic complex shown by DFT computations and electrostatic-potential mapping to be opposite in electron distribution from the neutral NiN2S2 complexes in which the anionic charge is localized on sulfur.     

Ionothermal syntheses of six three-dimensional zinc metal-organic frameworks with 1-alkyl-3-methylimidazolium bromide ionic liquids as solvents

We have performed ionothermal reactions between Zn(NO3)2 and H3BTC in 1-alkyl-3-methylimidazolium bromide ionic liquids with the alkyl group varying from ethyl to amyl. Six 3-D metal-organic frameworks (MOFs), including two isomeric compounds [Zn3(BTC)2(H2O)2] x 2H2O (1 and 2) (H3BTC = 1,3,5-benzenetricarboxylate acid), [EMI][Zn(BTC)] (3) (E = ethyl, MI = 3-methylimidazolium), [PMI][Zn(BTC)](4) (P = propyl), [BMI]2[Zn4(BTC)3(OH)(H2O)3] (5) (B = butyl), and [AMI][Zn2(BTC)(OH)Br] (6) (A = amyl), have been synthesized and structurally characterized. Compounds 1 and 2 are isomeric compounds, in which the coordination modes of Zn atoms and the BTC3- ligands are considerably different. Compounds 3-6 crystallize with the corresponding ionic liquid cations incorporated in the frameworks. Their crystal structures show various features including various coordination geometries of Zn2+ and various bridging modes of the BTC3- ligands. The incorporated cations appear to have strong interactions with the frameworks.     

An unusual electronic effect of an aromatic-F in phase-transfer catalysts derived from cinchona-alkaloid

[structure: see text] Various N-benzylcinchonidinium salts were prepared to study electronic factors in the catalytic enantioselective phase-transfer alkylation of glycine anion equivalent. An ortho-fluoro substituent on the benzyl group in the quaternary ammonium salt dramatically increased the enantioselectivity in the alkylation. O(9)-Allyl-N-2',3',4'-trifluorobenzylhydrocinchonidinium bromide (27), which gave the highest enantioselectivity of the catalysts studied, was used to prepare 12 alpha-alkylated amino acid derivatives in 94 approximately >99% ee.     

三种保护的二糖苯丙素苷的合成研究

本文采用先成苷法，从已合成的2-对烯丙氧苯乙基-4,6-O-亚苄基-β-D-葡萄糖苷(1)出发，经2位选择性乙酰化、3位引入三乙酰基保护的鼠李糖基、4，6位脱去亚苄基，得到了关键的中间体4；在化合物4的葡萄糖4、6位分别引入对位取代的肉桂酰基，便得到了保护的二糖苯丙素苷5、7、8。与后成苷法相比，路线缩短一步，收率有所提高。     

Surface-enhanced Raman spectra study of metal complexes of N-D-glucosamine beta-naphthaldehyde and glycine and their interaction with DNA

Copper(II), zinc(II), cobalt(II) and cobalt(III) complexes of N-D-glucosamine beta-naphthaldehyde (C17H19O6N, NG) and glycine were synthesized. The four novel metal complexes, Cu(II)C19H28O11N2(CuGNG), Zn(II)C19H24O9N2 (ZnGNG), Co(II)C19H28O11N2(Co(II)GNG) and Co(III)C21H29O12N2(Co(III)GNG) were characterized by means of infrared (IR), electronic absorption spectroscopy and NMR etc. The surface-enhanced Raman spectra of the four complexes and their interaction with DNA were studied. By comparison of the surface-enhanced Raman spectra (SERS), the information of the four complexes' SER active sites and adsorption orientation were obtained. Combined with fluorescence spectra of Ethidium bromide (EthBr) DNA system, we concluded that none of the four complexes intercalate into DNA and that the presence of the glycine ligand lowered the anticancer activity of NG series complexes.