1,2,4-三嗪类化合物的研究——Ⅳ.氯化N-[5′-(3′-甲硫基-6′-甲基)-1′,2′,4′-三嗪基]吡啶鎓盐的置换反应

氯化N-[5′-(3′-甲硫基-6′-甲基)-1′,2′,4′-三嗪基]吡啶?盐(Ⅱ)在吡啶中于室温通入硫化氢或与硫化氢饱和的硫氢化钠反应,均得到3-甲硫基-5-巯基-6-甲基-1,2,4-三嗪(Ⅲ);于较高温度与硫化氢反应,得3,5-二巯基-6-甲基-1,2,4-三嗪(Ⅳ).二者均可于氢氧化钠溶液中与碘甲烷反应,得到3,5-二甲硫基-6-甲基-1,2,4-三嗪(Ⅴ).Ⅱ在呲啶水溶液中与邻甲苯酚、闻甲苯酚、苯酚、间硝基苯酚、邻硝基苯酚或对硝基苯酚作用,得到相应的5-取代苯氧基化合物(Ⅶ_(a-f));与硫酚作用,得5-苯硫基化合物(Ⅷ);在吡啶中与无水乙醇作用,得5-乙氧基化合物(Ⅸ).化合物Ⅱ在吡啶水溶液中与Ⅲ作用,得S-[5′-(3′-甲硫基-6′-甲基)-1′,2′,4′-三嗪基]-3-甲硫基-5-巯基-6-甲基-1,2,4-三嗪(Ⅻ);与3-甲硫基-5-氧代-6-甲基-4,5-二氢-1,2,4-三嗪(Ⅰ)作用,得N~4_[5′-(3′-甲硫基-6′-甲基)-1′,2′,4′-三嗪基]-3-甲硫基-5-氧代-6-甲基-4,5-二氢-1,2,4-三嗪(ⅩⅧ);与3-甲硫基-5-氧代-4,5-二氢-1,2,4-三嗪(ⅪⅩ)作用,得N~4-[5′-(3′-甲硫基-6′-甲基)-1′2′4′-三嗪基]-3-甲硫基-5-氧代-4,5-二氢-1,2,4-三嗪(ⅩⅩ);与3-甲硫基-5-氧代-4,5-二氢-1,2,4-三嗪-6-羧酸乙酯(ⅩⅩⅢ)作用,得N~4_[5′-(3′-甲硫基-6′-甲基)-1′,2′,4′-三嗪基]-3-甲硫基-5-羰基-4,5-二氢-1,2,4-三嗪-6-羧酸乙酯(ⅩⅪⅤ);与喹唑酮-4(ⅩⅩⅦ)作用,得N~3_[5′-(3′-甲硫基-6′-甲基)-1′,2′,4′-三嗪基]-4-氧代-3,4-二氢喹唑啉(ⅩⅩⅧ).这些化合物的结构系通过其水解反应、胺解反应、红外吸收光谱、紫外吸收光谱或核磁共振谱等研究予以证明.3-甲硫基-5-对硝基苯氧基-6-甲基-1,2,4-三嗪(Ⅶ_f)与苯胺或对甲苯胺反应,得到3-甲硫基-5-取代苯胺基-6-甲基-1,2,4-三嗪对硝基苯酚复合物(X_(a,b).后者用碱处理,得3-甲硫基-5-取代苯胺基-6-甲基-1,2,4-三嗪(Ⅺ_(a,b)及对硝基苯酚.     

氨基糖的研究 Ⅰ.——N-(2’,4’-二硝基苯)-2-胺基-2-脱羟-D-葡萄糖的衍生物及其旋光性

在2-氨基-2-脱羟-D-葡萄糖的氮原子上引入2,4-二硝苯基后,其旋光性有显著的变化。自2-氨基-2-脱羟-D-葡萄糖(Ⅰ),我们获得一新的四乙酰-N-二硝苯基衍生物(Ⅲ), 该物经证明系属于吡喃糖α-型,但其旋光率比其β-端基差向异构体(Ⅳ)更向左旋,而与一般糖类α-与β-异构体之间的旋光率的关系不符。我们再观察N-二硝苯-2-胺基-2-脱羟-D-葡萄糖甲甙及其乙酰衍生物的α-与β-异构体的旋光率,也有相同的反常现象。 Hundson同旋律不完全适用于以上的N-二硝苯-D-胺基葡萄糖及其衍生物的原因可能由于C_(2)原子上N-二硝苯基对邻位C_(1)旋光性的影响所致。     

1-(2′-苯基-1′,2′,3′-三唑-4′-甲酰基)-4-芳基氨基硫脲及其环化产物的合成

以2-苯基-1,2,3-三唑-4甲酰肼为原料合成了几种新的1-(2′-苯基-1′,2′,3′-三唑-4′-甲酰基)-4芳基氨基硫脲,在不同条件下环化,制得一系列新的1,3,4-噻二唑、1,3,4- 二唑和1,2,4-均三唑衍生物.化合物的结构经元素分析、IR、1HMR和MS确证,并对其波谱性质进行了讨论.     

The molecular and crystal structure of N-(4-n-butyloxybenzylidene)-4′-ethylaniline (4O.2) and N-(4-n-heptyloxybenzylidene)-4′-hexylaniline (7O.6)

Abstract

The molecular and crystal structure of N-(4-n-butyloxybenzylidene)-4′-ethylaniline (4O.2) and the homologue N-(4-n-heptyloxybenzylidene)-4′-hexylaniline (7O.6) have been solved (at room temperature) by direct methods. The crystals of both compounds belong to the triclinic system with space group P1 with two molecules per unit cell. 4O.2: a = 5·531(2), b = 7·592(3), c = 19·746(7) Å, α = 86·66(2), β = 88·15(2), γ = 90·29(2)° 7O.6: a = 5·420(2), b = 8·307(3), c = 28·057(7) Å, α = 91·69(2), β = 89·76(2), γ = 108·02(2)°. The structures were refined by full-matrix least-squares calculations to R = 0·036 for 2297 observed reflections for 4O.2 and to R = 0·037 for 2150 reflections for 7O.6. The conformations in the asymmetric units of the two compounds differ considerably: The planes of the two phenyl rings of 4O.2, forming the mesogenic core of the molecule, are twisted at 61·2° to each other and the butoxy group contains a gauche conformation. In contrast the heptoxy chain of 7O.6 forms an all trans-conformation which lies almost in one plane with the two coplanar phenyl rings. The hexyl group also exists in an extended form, in a plane which is rotated against the plane of the mesogenic unit. The packing in the crystalline state of the two homologues exhibits a layered structure along c*; in 4O.2 these layers are separated, but in 7O.6 they are interdigitated. The compensation of the dipole moments of the C?O?C and C?N?C bonds occurs similarly in both structures: molecular orientations parallel to the a, c-plane in which the long axes of the molecules points in the same direction are packed in antiparallel fashion along b*.     

N-取代-N′-(2′,3′,4′,6′-四-O-乙酰基-β-D-吡喃葡萄糖基）（酰）氨基硫脲的合成

利用2,3,4,6-四-0-乙酰基-β-D-吡喃葡萄糖异硫氰酸酯(I)分别和芳酰肼(Ⅱ),2-氨基-5-烷基/芳基-1,3,4-噻二唑(Ⅲ),3-烷基/芳基-4-氨基-5-巯基-1,2,4-三唑(Ⅳ),O,O-二烷基(硫代)磷酰肼(V,Ⅵ)反应,制得了目标物1a～1c,2d～2e,3f～3i,4j～4k和51等12种新化合物,IR,1H NMR和MS分析结果证明产物为β构型.     

3-(3′-芳基-5′-硫酮-1′,2′,4′-三唑-4′-基)-氨甲酰基色酮类化合物的合成

报道 3 甲酰基色酮经Jones试剂氧化后得到 3 羧基色酮 ,再与 3 芳基 4 氨基 5 硫酮 1,2 ,4 三唑在POCl3 作用下 ,得到一系列 3 (3′ 芳基 5′ 硫酮 1′ ,2′,4′ 三唑 4′ 基 ) 氨甲酰基色酮类化合物 .所有化合物的结构均经IR ,LC MS ,1HNMR ,元素分析确证     

4,5-二(2′,4′-二硝基苯硫基)-1,3-二杂环戊烯-2-酮(BNPT-DTO),4,5-二(2′,4′-二硝基苯硫基)-1,3-二杂环戊烯-2-硫酮(BNPT-DTT)分子及晶体激光倍频性质的理论研究

在ZINDO方法的基础上,按完全态求和公式编制了计算分子的二阶非线性光学系数张量元β_(ijk)的程序,并以此为基础计算了BNPT-DTO,BNPT-DTT分子二次谐波条件下的二阶非线性光学系数,从分子水平研究了其分子的光学倍频性质及分子倍频与晶体宏观倍频的关系,计算结果较好地说明了实验现象.     

3,4-双(3,′5′-二硝基苯-1′-基)氧化呋咱的合成

设计并合成了新化合物3,4-双（3′,5′-二硝基苯-1′-基）氧化呋咱（4）。以苯甲腈为起始原料,经加成、重氮化、分子间二聚得到3,4-二苯基氧化呋咱（3）,3经HNO3／H2SO。硝化合成了4,其结构经^1H NMR,IR和元素分析表征;初步考察了加成、重氮化、缩合环化、硝化等反应的主要影响因素,确定了适宜的反应条件。     

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.     

1-[2′,4′-二氟-(1,1′-联苯)-4-基苯基甲基]-咪唑的合成

以2,4-二氟联苯为起始原料,经酰化反应制得2′,4′-二氟-(1,1′-联苯)-4-基苯基甲酮(2);2经NaBH4还原得2′,4′-二氟-(1,1′-联苯)-4-基苯基甲醇(3);3经氯代得2′,4′-二氟-(1,1′-联苯)-4-基苯基氯甲烷(4);4与咪唑发生亲核取代反应合成了1-[2′,4′-二氟-(1,1′-联苯)-4-基苯基甲基]-咪唑(5). 2～5为新化合物,其结构经1H NMR, IR, MS和元素分析确证.     

Synthesis of Novel 1-Arylsulfonyl-4-(1′-N-2′, 3′, 4′, 6′-tetra-O-acetyl-β-D-glucopyranosyl)thiosemicarbazides

Some 1-arylsulfonylthiosemicarbazides have been reported as fungicides1 and bacterio-static agents2. Recently, it is well documented that thiosemicarbazide is a novel class ofnon-peptide antagonists for bradykinin B2 , which is beneficial in the symptomat…     

2-芳胺基-5-[5′-氨基-1′-(4″-氯苯基)-1′,2′,3′-三唑-4′-基]-1,3,4-噻二唑的合成~≠

1-[5’-氨基-1’-(4”-氯苯基)-1,2,3-三唑-4’-甲酰基]-4-芳基-3-氨基硫脲在浓硫酸催化下环化得到2-芳胺基-5-[5’-氨基-1’-(4”-氯苯基)-1’,2’,3’,-三唑-4’-基]-1,3,4-噻二唑2a～i,依次法合成了九个标题化合物,收率为30～74％。化合物2i的结构用X-光衍射单晶分析确证。     

1,2,4-三嗪类化合物的研究——Ⅶ.N-[5′-(3′-甲硫基-6′-乙氧羰基)-1′,2′,4′-三嗪基]-3-甲硫基-5-氧代-1,2,4-三嗪-6-羧酸乙酯的制备及其置换反应

本文报道了N-[5'-(3'-甲硫基-6'-乙氧羰基)-1',2',4'-三嗪基]-3-甲硫基-5-氧代-1,2,4-三嗪-6-羧酸乙酯(3)的制备及其与胺、酚类化合物的反应.3a 的结构经元素分析、红外光谱、质谱、核磁和紫外光谱的分析结果推定.3a 与一系列胺及酚发生置换反应,分别得到了相应的5-胺基-3-甲硫基-1,2,4-三嗪-6-羧酸乙酯(5、6、7、8)和5-芳氧基-3-甲硫基-1,2,4-三嗪-6-羧酸乙酯(12、13、14、15、16);3a 与对甲苯胺反应,除了生成5-胺基产物外,还能得到3-胺基-5-羟基-1,2,4-三嗪-6-羧酸乙酯(9)和3,5-双胺基-1,2,4-三嗪-6-羧酸乙酯(10);当3a 与水合肼(90%)反应时,则得到N,N'-双[5'-(3'-甲硫基-6-乙氧羰基)-1,2,4-三嗪基]肼(11).     

Photophysical Properties of 4′-(p-aminophenyl)-2,2′:6′,2′′-terpyridine

Spectral and photophysical investigations of 4′-(p-aminophenyl)-2,2′:6′,2′′-terpyridine (APT) have been performed in various solvents with different polarity and hydrogen-bonding ability.The emission spectra of APT are found to exhibit dual fluorescence in polar solvents, which attributes to the local excited and intramolecular charge transfer states, respectively. The two-state model is proven out for APT in polar solvent by the time-correlated single photon counting emission decay measurement. Interestingly, the linear relationships of different emission maxima and solvent polarity parameter are found for APT in protic and aprotic solvents, because of the hydrogen bond formation between APT and alcohols at the amino nitrogen N25. Furthermore, the effects of the complexation of the metal ion with tpy group of APT and the hydrogen bond formation between APT with methanol at the terpyridinenitrogen N4—N8—N14 are also presented. The appearance of new long-wave absorption and fluorescence bands indicates that a new ground state of the complexes is formed.     

4,4′-二甲氧基-5,6,5′,6′-二次甲二氧基-2-烷氧甲酰基2′-(4-取代苄基哌嗪基-1)-甲酰基联苯的合成

在NiCl2 (PPh3 ) 2 /NaH/Zn/PPh3 作用下 ,以 2 溴 3 ,4 次甲二氧基 5 甲氧基 苯甲酸甲酯为原料进行Ullmann type偶合 ,在温和条件下以较高的收率得到中间体 4,4′ 二甲氧基 5 ,6,5′ ,6′ 二次甲二氧基联苯 2 ,2′ 二甲酸二甲酯 ,经进一步的水解、环化成酸酐、开环酯化等反应得到 4,4′ 二甲氧基 5 ,6,5′ ,6′ 二次甲二氧基联苯 2 ,2′ 二甲酸单酯 .最后再与取代苄基哌嗪在DMAP及DCC催化下缩合 ,得到 12个新的不对称联苯甲酸酯甲酰哌嗪类化合物 ,并用1 HNMR ,IR ,ESI MS等手段进行了结构确认     

Stereoselective synthesis and absolute configuration of (1′R,3R,4R)-4-acetoxy-3-(2′,2′,2′-trifluoro-1′-hydroxyethyl)azetidin-2-one

The title compound 3, an intermediate in the synthesis of fluorocarbapenems, is obtained with high stereocontrol by the condensation of (R)-(+)-ethyl 4,4,4-trifluoro-3-hydroxybutanoate with N-trimethylsilyl cinnamylidenimine. X-Ray diffraction analysis of the condensation product and chemical correlations allowed the unambiguous determination of the absolute configuration.     

N-(5-hydroxy-3′,4′-ethylenedioxyisoflavonyl-7-oxyacetyl)amino acids

For the purpose of seeking new biologically active compounds in the flavonoid series, a series of N-(5-hydroxy-3,4-ethylenedioxyisoflavonyl-7-oxyacetyl)amino acids was synthesized; their structure was confirmed by PMR spectral data.Taras Shevchenko Kiev University, Kiev 252033, Ukraine. Institute of Bioorganic Chemistry and Petrochemistry, Academy of Sciences of the Ukraine, Kiev 253660. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 482–486, April, 1998.     

4′-(二茂铁基)-2,2′∶6′,2″-三联吡啶钴(Ⅱ)配合物混合价态的电荷转移

设计合成了4′-(二茂铁基)-2,2′∶6′,2″-三联吡啶钴(Ⅱ)配合物1以及参比配合物4′-(4-甲苯基)-2,2′∶6′,2″-三联吡啶钴(Ⅱ)配合物2和2,2′∶6′,2″-三联吡啶钴(Ⅱ)配合物3,配合物1中二茂铁基给电子基团的引入使其在可见光区的吸收明显增强,并在部分氧化时呈现混合价态的电荷转移(MVCT)吸收.