手性联萘酚的多胺缀合物的合成与表征

以N1-氨基丁基-N1,N4-二叔丁氧羰基-1,4-丁二胺和手性甲酰基联萘酚为原料,经缩合后用NaBH4还原,产物提纯后脱保护,得到目标产物S-6和R-6,所得化合物的结构均经IR、1H NMR、13C NMR和MS测试确认.     

咪唑[2，1-b]噻唑多胺缀合物的合成与表征

以2-氨基噻唑和溴乙酰基吡啶为原料合成了二个咪唑[2,1-b]噻唑的甲酰基化合物3,4,然后与N1-氨基丁基-N1,N4-二叔丁氧羰基-1,4-丁二胺经缩合后用NaBH4还原,产物提纯后脱保护得目标产物7、8,并通过IR,^1H NMR,^13C NMR,ESI-MS对目标化合物的结构进行了表征．     

N~6,N~6-二(叔丁氧羰基)-2',3'-O-异丙叉腺苷的合成

以腺苷(2)为原料,经丙酮叉保护2',3'-位羟基得2',3'-O-异丙叉腺苷(3);3经叔丁基二甲硅氯保护5'-羟基得5'-O-叔丁二甲基硅基-2',3'-O-异丙叉腺苷(4);4经二碳酸二叔丁酯保护氨基得到N~6,N~6-二(叔丁氧羰基)-2',3'-O-异丙叉基-5'-O-叔丁二甲基硅基腺苷(5);5用四丁基氟化铵脱去叔丁二甲基硅基合成了新化合物N`6,N~6-二(叔丁氧羰基)-2',3'-O-异丙叉腺苷,总收率54.3%,其结构经~1H NMR,~(13)C NMR,IR和HR-MS表征.     

含(1-芳乙酰胺基-2-叔胺基)乙烷结构的六氢-1H-1,4-二氮类新化合物的合成(Ⅰ)

合成了N,N＇-二苄基-2-甲氧羰基-六氢-1H-1,4-二氮 (3).3经还原、氯取代、胺取代、胺脱苄、单酰化及酰化反应后得到了10个带有(1-芳乙酰胺基-2-叔氨基)乙烷结构的六氢-1H-1,4-二氮类目标化合物(9a～9i和10).     

海兔毒素10关键合成子Dap的立体专一性合成

以N-丙酰基-(3R,4S)-3-甲基-4-苯基-2-羰基噁唑啉与N-(叔丁氧羰基)-S-脯氨醛为原料,经羟醛缩合反应合成了高立体专一性、具有三个手性中心的(4S,5S,2'R,3'R,2"S)-3-[3'-(N-叔丁氧羰基-2"-吡咯烷基)-3'-羟基-2'-甲基丙基)]-4-甲基-5-苯基-2-羰基噁唑烷酮(6);6脱去手性辅基,甲基化3'-羟基合成了抗肿瘤活性肽海兔毒索10的关键合成子--(2S,3S,2's)-3-(N-叔丁氧羰基-2'-吡咯烷基)-3-甲氧基-2-甲酸丙酸,其结构经1H NMR,13C NMR,m和MS表征.     

新型含七元醚环的脯氨酸衍生物的合成

以L-谷氨酸和苯甲醛为起始原料,经7步反应合成了重要中间体(2S,5R)-1-苄基-5-(2-羟乙基)吡咯烷-2-羧酸叔丁酯(1),总产率19%;1经TBDMSCl保护羟基后,用10%Pd/C催化氢解去除苄基制得游离胺(2S,5R)-5-(2-二甲基叔丁基硅氧烷基乙基)吡咯烷-2-羧酸叔丁酯(3);3与Boc-β-Cl-ala,在碱性条件下偶合得氯代烃消去产物(2S,5R)-1-[(2-叔丁氧甲酰胺基)丙烯酰基]-5-(2-二甲基叔丁基硅氧烷基乙基)吡咯烷-2-羧酸叔丁酯(4),或在中性条件下偶合得(2S,5R)-1-[(R)-2-叔丁氧甲酰胺基-3-氯丙酰基]-5-(2-二甲基叔丁基硅氧烷基乙基)吡咯烷-2-羧酸叔丁酯(5);4或5经四丁基氟化铵去除TBDMS保护并发生关环反应合成了新型的七元醚环化合物(4R,7S,9R)-4-甲基-4-叔丁氧甲酰胺基-5-羰基-3-氧杂氮杂卓[1,4]并吡咯[1,2-d]-7-羧基叔丁酯(简称6);6于室温在氯仿中静置2 d~3 d自发转换为其构象异构体(4S,7S,9R)-6(简称6’,6/6’=1/9),其结构经1H NMR,13C NMR,2D NMR和HR-ESI-MS表征。     

手性γ-氨基酸:5-羟基-3-氨基环己基甲酸的不对称合成

以光学纯的(1S,5S)-5-叔丁氧羰基氨基-3-环己烯基甲酸为原料,经立体选择性地碘代内酯化、脱碘、醇解、水解、酯化5步反应首次合成了两个光学纯的γ-氨基酸衍生物——(1R,3S,5R)-5-羟基-3-叔丁氧羰基氨基环己基甲酸甲酯(总收率36.7%)和(1R,3S,5R)-5-羟基-3-叔丁氧羰基氨基环己基甲酸苄酯(总收率35.2%),其结构经1H NMR,13C NMR,IR和ESI-HR-MS确证。     

N-叔丁氧羰基-3-羟基-1-金刚烷基甘氨酸的合成

以金刚烷甲酸(1)为起始原料,经过酰化,取代,脱羧三步反应一锅法制得金刚烷甲基酮(2),然后氧化甲基得到1-金刚烷基乙醛酸(3),将3与盐酸羟氨反应得到1-金刚烷乙醛酸肟(4),还原4并用BOC酸酐保护氨基得到N-叔丁氧羰基-1-金刚烷基甘氨酸(5),最后经高锰酸钾氧化得到DPP-IV抑制剂沙格列汀中间体N-叔丁氧羰基-3-羟基-1-金刚烷基甘氨酸(6),总收率28%。     

硫代硫酸钠脱除氨基酸铜络合物中铜的研究

报道了用硫代硫酸钠脱去侧链保护氨基酸铜络合物中铜离子的新方法,该方法适用于合成Nδ-苄氧羰基鸟氨酸、Nδ-叔丁氧羰基鸟氨酸、Nδ-芴甲氧羰基鸟氨酸、Nδ-乙酰基鸟氨酸、Nδ-邻苯二甲酰基鸟氨酸、Nε-苄氧羰基赖氨酸、Nε-叔丁氧羰基赖氨酸、Nε-芴甲氧羰基赖氨酸、Nε-乙酰基赖氨酸、Nε-邻苯二甲酰基赖氨酸、γ-苄基谷氨酸、β-苄基天门冬氨酸.产物用元素分析法与1H NMR法进行了表征.探讨了反应温度、时间、投料比例、溶剂对脱铜反应的影响.实验结果表明,以硫代硫酸钠作为脱铜试剂,侧链保护氨基酸铜络合物与硫代硫酸钠的物质的量比为1∶1或1∶2,60℃反应1.5～2.0h,收率与产物纯度均较高.该方法简便、高效、环境友好.     

（2R，4S）-N-叔丁酰基-4-氨基-2-四氢吡咯甲酸甲酯的合成

以(2R,4S)-4-羟基-2-四氢吡咯甲酸为起始原料,经甲酰化,酰化引入叔丁氧羰基,手性反应,甲磺酰化,叠氮化及三苯基膦还原等7步反应合成了(2R,4S)-N-叔丁酰基-4-氨基-2-四氢吡咯甲酸甲酯(总收率29%),其结构经1H NMR和LC-MS表征.     

Synthesis of 1,14-diamino-5,10-diaza-N1,N14,5,10- tetrakis-/9-(β-d-ribofuranosyl)purin-6-yl/-tetradecane - a new oligonucleotide analogue with stacked base residues

The title compound 1b was obtained by reaction of 6-chloro-9-(β-D-ribofuranosyl)purine (2) with N,N′-bis-(4-aminobutyl)-1,4-diaminobutane (3).     

Synthesis of bis-3-alkyl-5-arylhydantoins and bis-3-alkyl-5-arylthiohydantoins separated by two and four carbon atoms

Synthesis of 1,2- and 1,4-bis-thiohydantoins and hydantoins employing ethylenediamine and 1,4-diaminobutane as spacers is described. Compounds containing a two carbon bridge were synthesized by alkylation of ethylenediamine with two equivalents of N-t-butyl-α-(p-toluenesulfonyloxy)phenylacetamide 3 . The phenyl isothiocyanate adduct of 3 cyclized in refluxing toluene to form 1a . Other isothiocyanate or isocyanate adducts derived from alkylation product 4 required hydrolysis to induce cyclization. Compounds 1b-1f were obtained in this way. Compounds with a four carbon bridge were obtained by reaction of two equivalents of methyl α-bromophenyl acetate and 1,4-diaminobutane to produce N,N'-bis-[(α-phenyl-α-methoxycarbonyl)methyl]butylenediamine 6 . The isothiocyanate or isocyanate adducts from 6 cyclized, without hydrolysis, to form compounds 2a-2e .     

Mass fragmentographic identification of polyamine metabolites in the urine of normal persons and cancer patients, and its relevance to the use of polyamines as tumour markers

The mass fragmentographic identification of N-(2-carboxyethyl)-4-amino-n-butyric acid, N-(3-aminopropyl)-N1-(2-carboxyethyl)-1,4-diaminobutane, N,N1-bis(2-carboxyethyl)-1,4-diaminobutane, and delta-aminovaleric acid in acid-hydrolysed urines of a normal person and two cancer patients is described. A previous study, in which the metabolic fate of intraperitoneally injected polyamines in rats was investigated, revealed that these compounds should be considered as non-alpha-amino acid metabolites of the naturally occurring polyamines. Quantification of polyamines and their non-alpha-amino acid metabolites by gas chromatography with nitrogen--phosphorus detection showed that, relative to the parent polyamines, humans normally excrete higher quantities of polyamine catabolites in urine than rats, suggesting that humans catabolize polyamines more efficiently. As illustrated by the follow-up of the concentrations of polyamines and their catabolites in the urine of a patient with high-grade non-Hodgkin lymphoma during chemotherapy, the catabolic pressure on polyamines may be considerably increased during neoplastic diseases, since an even higher proportion of oxidized polyamine metabolites was observed. It is therefore suggested that the additional measurement of the circulating concentrations of polyamine-degrading enzymes is of importance for the correct interpretation of polyamine (metabolite) determinations for oncological purposes.     

N,N'-双(苯甲酰丙酮)-1,4-丁二胺席夫碱银(I)配合物的合成及其晶体结构

以苯甲酰丙酮与1,4-丁二胺经缩合反应制得一个新的席夫碱配体——N,N'-双(苯甲酰丙酮)-1,4-丁二胺(L);L与硝酸银经配位反应合成了配合物[Ag_2(L)(NO_3)_2]_n(1),其结构经1H NMR,13C NMR,FT-IR,元素分析和X-射线单晶衍射表征。晶体结构解析表明:1(CCDC∶1 434 692)属单斜晶系,空间群P21/c,晶胞参数a=0.997 81(5)nm,b=0.778 36(4)nm,c=1.704 13(8)nm,β=106.637 0(10),V=1.261 85(11)nm3,Z=2,Dc=1.884 g·cm~(-3),R1=0.020 8,wR_2=0.054 4。1中每个银离子为扭曲四面体的配位构型,分别和相邻配体的γ-碳原子,氧原子及两个NO_3~-的氧原子配位;每个配体作为四齿配体,分别用两端的γ-碳原子,氧原子和四个银离子配位形成1D链结构,1D通过NO_3~-与银离子配位扩展形成3D网状结构。热稳定性研究结果表明:L和1的初始分解温度分别为300℃和200℃。     

Monomeric uni-ligated aluminates

The tetradentate ligand, common name Salban(But)H4 (N,N'-bis(2-hydroxy-3,5-di-tert-butylbenzyl)-1,4-diaminobutane) combines with appropriate amounts of LiAlH4 to produce the unique monomeric, uni-ligated aluminate [Salban(But)Al]Li(thf)2 (1) and the bimetallic derivative Salban(But)(AlH2Li(thf)2)2 (2).     

Preparation of Novel Side-chain Pseudopolyrotaxanes Consisting of Cucurbituril[6] and Polyamine Salts

Pseudorotaxane monomer （VBCB） containing cucurbitutil[6] （CB[6]） and N^1-（4-vinylbenzyl）-1,4-diaminobutane dihydrochloride （VBDADC） is obtained by self-assembly of cucurbituril[6] with VBDADC in water and then polymerized using potassium persulfate （KPS） as initiator to give novel water-soluble side-chain cucurbituril[6]-based pseudopolyrotaxane（PVBCB）. The chemical structures of PVBCB, VBCB and VBDADC are confirmed by ^1H NMR,^13C NMR spectra and elemental analysis. In VBCB, CB[6] is localized aliphatic group of the side chain and the molar ratio of CB[6] to VBDAC is 1：1 .     

Synthesis and structure of N,N′-bis(dihexylphosphorylmethyl)-1,4-diaminobutane

Russian Journal of General Chemistry - N,N′-Bis(dihexylphosphorylmethyl)-1,4-diaminobutane has been obtained via the Kabachnik–Fields reaction. Crystal structure of its salt with nitric...     

两个线型三核铁(Ⅱ)配合物[Fe3L2(CH3COO)2]的合成和晶体结构

The title linear trinuclear complexes, [Fe₃L₂(CH₃COO)₂](L=bis-(salicylidene)-1,3-diaminopropane (salpd) (1) and L=bis-(salicylidene)-1,4-diaminobutane (salbd) (2) were synthesized simply using solvothermal method in methanol and were characterized by X-ray single crystal diffraction. [Fe₃L₂(CH₃COO)₂](1) was obtained using salicylaldehyde, 1,3-diaminopropane and Fe(CH₃COO)₂·4H₂O via the above method with monoclinic crystal system and space group of P2₁/c, and lattice parameters of a=0.945 0(8) nm, b=1.037 0(8) nm, c=1.830 5(14) nm, β=94.357(16)°. The [Fe₃L₂(CH₃COO)₂](2) was obtained using1,4-diaminobutane instead of 1,3-diaminopropane while keeping the other conditions the same as that for synthesis of [Fe₃L₂(CH₃COO)₂] (1). The [Fe₃L₂(CH₃COO)₂](2) was in monoclinic crystal system and space group of P2₁/c, and lattice parameters of a=0.919 0(5) nm, b=1.675 6(9) nm, c=1.270 0(7) nm, β=95.126(11)°. CCDC: 754930, 1; 754931, 2.     

Vibrational Spectroscopic Studies on the Hofmann-dabn-Type Benzene Clathrates: M(1,4-diaminobutane)Ni(CN)4° 1.5C6H6 (M = Mn, Fe, Co, Ni or Cd)

IR spectra of M(1,4-diaminobutane)Ni(CN)4° 1.5C6H6 (M = Mn, Fe, or Co), and IR and Raman spectra of M(1,4-diaminobutane)Ni(CN)4° 1.5C6H6 (M = Ni or Cd) clathrates are reported. The spectral features suggest that the compounds are similar in structure to the Hofmann-dabn-type clathrates.     

Investigation of energetic materials prepared by reactions of diamines with picryl chloride

Five compounds containing picryl group(s) were synthesized from reactions of hydrazine, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane and 1,7-diaminoheptane with picryl chloride under hydrothermal conditions in methanol. Hydrazine reaction yielded N-2,4,6-trinitrophenylhydrazine which has a single picryl group, whereas the other reactants formed symmetric products with both amine groups connected to picryl groups. These compounds are N,N′-di-2,4,6-trinitrophenyl-1,2-diaminoethane, bis-N,N′-di-2,4,6-trinitrophenyl-1,3-diaminopropane, bis-N,N′-di-2,4,6-trinitrophenyl-1,4-diaminobutane and bis-N,N′-di-2,4,6-trinitrophenyl-1,7-diaminoheptane. Molecular structures of two of these compounds, N-2,4,6-trinitrophenylhydrazine and bis-N,N′-di-2,4,6-trinitrophenyl-1,3-diaminopropane, were revealed by XRD methods. All compounds were investigated by TG and DSC methods. The thermal behaviour of N-2,4,6-trinitrophenylhydrazine was explosive, undergoing a strong explosion in a very short temperature interval, 180–185 °C. In cases of the other compounds, it was found out that the carbon chain between two picryl groups reduced the explosion enthalpy. In addition, the theoretical formation enthalpy of N-2,4,6-trinitrophenylhydrazine was calculated by running CBS-4 M energy calculations under Gaussian 09 software package. From the calculated value, reaction enthalpy values for the possible explosion pathways were investigated in accordance with the experiment. The path with reaction enthalpy closest to the experimental value was proposed as the explosion mechanism.