新型3-氯-1-(3-氯-2-吡啶)-1H-吡唑甲酰胺类化合物的合成

2,3-二氯吡啶肼解后与马来酸二乙酯成环,再经氯代、氧化、水解制得3-氯-1-(3-氯-2-吡啶)-1H-吡唑-5-甲酸(6);6经二氯亚砜酰氯化、环胺酰胺化合成了13个新型3-氯-1-(3-氯-2-吡啶)-1H-吡唑甲酰胺类化合物,其结构经1HNMR和MS表征。     

新型吡啶衍生物的合成

以2-甲基吡啶为原料,经氧化、硝化、还原反应合成了重要中间体4-氨基-2-甲基吡啶(3); 3分别经1,4-加成反应、Heck反应及取代反应合成了11个吡啶类化合物(4~14),其中5, 6和8~14为新化合物,其结构经¹H NMR, ¹³C NMR, MS和HR-MS进行表征。     

新型2-取代氨基-3-氟-4-吡啶氟硼酸钾盐的合成

以2,3-二氟-5-氯吡啶为原料,依次经取代和还原反应制得2-取代氨基-3-氟吡啶化合物(2a~2g); 2a~2g与正丁基锂及硼酸三异丙酯经有机锂化法制得相应的硼酸化合物(3a~3g); 3a~3g分别与氟化氢钾经取代反应合成了7个新型的2-取代氨基-3-氟-4-吡啶氟硼酸钾盐,其结构经¹H NMR, ¹³C NMR, IR, ESI-MS和元素分析表征。     

1,2,4-三嗪类化合物的研究XXI.3-甲硫基-5-氧代-2.5-二氧-1,2,4-三嗪的取代苯磺铣化反应及6- 碳的亲电特性

3-甲硫基-5-氧代-2.5-二氧-1,2,4-三嗪(Ic)与取代的苯磺铣氯反应,在无水吡啶中生成N-[6-(3-甲硫基-5-负氧基)-1,2,4-三嗪基]吡啶内嗡盐(4);在NaOH-H~2O-Ch~3COCH~3中生成3-甲硫基-4-(取代苯磺铣基)-5-氧化-6-羟基-1,4,5,6-四氢- 12,4-(6);资Naoh-Ch~3O中则生成1-(对甲苯磺铣基)-3-甲硫基-6-甲氧基-1,4,5,6-四氢-三嗪(7)显示了其6-C具有不寻常的亲电特性.     

1,2,4-三嗪类化合物的研究XXI.3-甲硫基-5-氧代-2.5-二氧-1,2,4-三嗪的取代苯磺铣化反应及6- 碳的亲电特性

3-甲硫基-5-氧代-2.5-二氧-1,2,4-三嗪(Ic)与取代的苯磺铣氯反应,在无水吡啶中生成N-[6-(3-甲硫基-5-负氧基)-1,2,4-三嗪基]吡啶内嗡盐(4);在NaOH-H~2O-Ch~3COCH~3中生成3-甲硫基-4-(取代苯磺铣基)-5-氧化-6-羟基-1,4,5,6-四氢- 12,4-(6);资Naoh-Ch~3O中则生成1-(对甲苯磺铣基)-3-甲硫基-6-甲氧基-1,4,5,6-四氢-三嗪(7)显示了其6-C具有不寻常的亲电特性.     

新型N-取代苯基-9-烷基-3-咔唑磺酰脲类化合物的合成及其抗肿瘤活性

以9-烷基咔唑为原料,经磺化、氯化和氨化反应制得9-烷基咔唑-3-磺酰胺(4a和4o);取代苯胺与三光气反应制得取代苯基异氰酸酯(6a~6n,6s,6Ⅳ);4分别与6经缩合反应合成了30个新型的N-取代苯基-9-烷基-3-咔唑磺酰脲类化合物(7a~7Ⅳ),其结构经1H NMR,IR和ESI-MS表征。对7进行了Cdc25B抑制活性筛选。结果表明,在用药浓度为20μg·m L-1时,其中12个化合物对Cdc25B具有良好的抑制活性,抑制率大于90%。     

3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸的合成

以2,3-二氯吡啶为起始原料,通过水合肼亲核取代、马来酸二乙酯环合制得2-(3-氯-2-吡啶基)-5-氧-3-吡唑烷甲酸乙酯(5);5经苯磺酰氯酯化、溴化氢溴化制得3-溴-1-(3-氯-2-吡啶基)-4,5-二氢-1H-吡唑-5-甲酸乙酯(7);7经脱氢、水解合成了用于制备氯虫酰胺的关键中间体--3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸,总收率39.5%,其结构经~1H NMR和MS确证.     

N-吡咯烷基-2-吡啶甲酰胺(NPPFA)对水溶液中苯酚的萃取行为

N-吡咯烷基-2-吡啶甲酰胺(NPPFA)对水溶液中苯酚的萃取行为;N-吡咯烷基吡啶甲酰胺(NPPFA);萃取;苯酚     

8-溴-6-甲基-2-(1-吡咯烷基羰基)咪唑并[1,2-a]吡啶的合成及晶体结构

以2-氨基-5-甲基吡啶为原料,经溴代、环合、水解及酰胺化反应合成了8-溴-6-甲基-2-(1-吡咯烷基羰基)咪唑并[1,2-a]吡啶,总收率32.82％,其结构经1H-NMR和MS确证,并用X-单晶衍射法测定了其晶体结构.结果表明:待测物块状晶体a(CCDC:2039002)属三斜晶系,空间群P-1,晶胞参数a=6....     

6-氯吡啶-3-亚甲基取代杂环化合物的合成

以2-氯-5-氯甲基吡啶、苯基哌嗪、1-苯基-3-甲基-2-吡唑酮为原料,通过3条路线合成了6个新的6-氯吡啶-3-亚甲基取代杂环化合物,其结构经1H NMR,MS和元素分析表征.     

新型2-苯并噻唑磺酰脲氨基酸及其甲酯衍生物的合成与抗肿瘤活性

以2-巯基苯并噻唑为原料,经弱氧化和氨化制得2-苯并噻唑次磺酰胺（2）; 2经高锰酸钾氧化制得2-苯并噻唑磺酰胺（3）; 3与氯甲酸乙酯反应制得2-苯并噻唑磺酰胺甲酸乙酯（4）; 4与L-氨基酸甲酯反应制得一系列2-苯并噻唑磺酰脲氨基酸甲酯（6a~6j）; 6经水解合成了10个新型的2-苯并噻唑磺酰脲氨基酸（7a~7j）,其结构经¹H NMR, IR和ESI-MS表征。并研究了6和7对Cdc25B的抑制活性。结果表明:在用药浓度为20 μg·mL^-1时,6c, 6j, 7d, 7h和7j对Cdc25B抑制活性较好,抑制率分别为78.1%, 71.2%, 65.6%, 57.2%和65.9%。     

一种新型磷酸基光控保护基的合成及其应用研究

以苯硫酚为起始原料,经脱水反应、碘代反应、Suzuki-Miyaura偶联反应和氧化反应制得4-酮基-3-苯基-4H-苯并噻喃-2-甲醛(4); 4经间氯过氧苯甲酸氧化后与对甲苯磺酰肼于室温反应制得2-甲苯磺酰腙-3-苯基-4H-磺酰基苯并噻喃(6); 6经Bamford-Stevens反应合成了一种新型磷酸基光控保护基--2-重氮基-3-苯基-4H-磺酰基苯并噻喃(7),其结构经¹H NMR, ¹³C NMR和HR-MS表征。将7应用于磷酸基团的保护和光控脱保护反应中。结果表明:保护反应可在温和条件下顺利进行。紫外光谱法和荧光光谱法对光控脱保护反应的监测结果表明:光控脱保护反应迅速(≤15 min),被保护化合物脱保护收率高(≥95％)。     

Type 2 intramolecular N-acylnitroso diels-alder reaction: stereoselective synthesis of bridged bicyclic oxazinolactams

[reaction: see text] The type 2 intramolecular N-acylnitroso Diels-Alder reaction has been employed for the synthesis of substituted bridged bicyclic oxazinolactams. Upon oxidation of hydroxamic acid 6, a 3-benzylated oxazinolactam (7) was synthesized with complete diastereoselectivity. Elaboration of cycloadduct 7 liberated a cis-3,7-disubstituted azocin-2-one (9).     

4-氧代-3（4H）-喹唑啉-5-羧酸的合成

以2-氨基-6-甲基苯甲酸为起始原料,通过合环反应生成两种4-氧代-3(4H)-喹唑啉-5-羧酸衍生物(1a, 1b), 1a, 1b分别经高锰酸钾氧化合成了4-氧代-3(4H)-喹唑啉-5-羧酸（2a, 2b）,其结构经¹H NMR, ¹³C NMR和MS表征。研究了投料比｛r［n(高锰酸钾) :n(5-甲基-3(4H)-喹唑啉-4-酮)］｝和反应温度等对收率的影响。结果表明：在最佳反应条件（r=7:1,中性高锰酸钾氧化,于90 ℃反应）下合成2总收率可达66%。     

1-氧代-1-磷杂-2, 6, 7-三氧杂双环[2.2.2]-4-含硫取代基辛烷 的合成

本文利用中间体1-氧代-1-磷杂2,6,7-三氧杂双环[2.2.2]-4-羟甲基辛烷(1)和1-氧代-1-磷杂-2,6,7-三氧杂双环[2.2.2]-4-氯甲酰基辛烷(3)分别与RSH或取代硫醇按步骤反应得到了相应的4-亚甲基硫醚(5a～f)、4-亚甲基亚砜(6a～f)、4-(氯代乙硫基)甲酰基(7)及4-(β-烷硫基)-α-硫代酯基(8a～i)的双环笼状磷酸酯新衍生物共22个。所有的化合物经元素分析、IR和^1HNMR得到了证实。     

双核铜酶模型的合成及对安息香的催化氧化

为寻求更有效的仿酶模型,本文设计合成了含四个咪唑配基、两个咪唑基与铜配位的新型双核铜酶模型,并实现了在氧气存在下模型对安息香的催化氧化作用。以邻-氯苯酚为原料,经直接咪唑甲基化,醚化偶联,继与[Cu(CH~3CN)~4]CLO~4反应合成目标酶模型6-8。类似地,由对-氯苯酚合成酶模型9。以机械7为例,研究了在氧气下它们催化氧化安息香为二苯乙二酮的反应,高产率地合成目标产物,并求得催化氧化反应动力学参数。考查不同催化剂对反应的影响,发现它们的活性次序如下:7>4+[Cu(CH~3CN)~4]ClO~4>[Cu(CH~3(CN)~4]ClO~4>2+[Cu(CH~3CN)~4]ClO~4。     

Anderson型多酸基无机一有机杂化化合物的合成及催化氧化性质研究

合成了一种新的基于Anderson结构镍钼酸盐的无机-有机杂化化合物(C3 H7 NO2)2[(H2O)5 (C3 H7 NO2) Ni]2[NiMo6 H6 O24]·2H2O(C3 H7 NO2=β-丙氨酸),通过单晶X射线衍射方法确定了其晶体结构,结构分析表明,该化合物结晶于单斜空间群P21/C,晶胞参数a=1.847 25(13) nm,b=1.059 32(7) nm,c=1.224 77(7) nm,β=104.177(6)°.并对该化合物进行了红外、紫外可见和热重测试,该化合物在苯甲硫醚的催化氧化反应中作为多相催化剂,表现出好的催化活性.     

New 2-methyl-6-alkylamino-5,8-quinolinequinones and 1,2,3,4-tetrahydro derivatives

The syntheses of six new 2-methyl-6-alkylamino-5,8-quinolinequinones, three 1,2,3,4-tetrahydro-5,8-quinolinequinones, and 7-(2′,6′,10′-trimethylundecyl)-6-hydroxy-5,8-quinolinequinone are described as potential antimetabolites of coenzyme Q and as potential antimalarial agents. The six 2-methyl-6-alkylamino-5,8-quinolinequinones were prepared by a six-step synthesis. 2-Methyl-6-methoxy-8-nitroquinoline was prepared from 2-nitro-4-methoxyaniline and crotonaldehyde by a Skraup reaction. Raney nickel reduction gave 2-methyl-6-metboxy-8-aminoquinoline, which upon diazotization followed by dithionite reduction yielded 2-methyl-6-methoxy-5,8-diaminoquinoline. Subsequent dichromate oxidation gave 2-methyl-6-methoxy-5,8-quinolinequinone, which yielded the corresponding 2-methyl-6-alkylamino-5,8-quinolinequinone in good yield when treated with the appropriate alkylamine. The telrahydro-5,8-quinolinequinones were prepared by catalytic hydrogenation of the appropriate 5,8-quinolinequinones at elevated H₂ pressure followed by air oxidation of the reduction product. 7-(2′,6′,10′-Trimethylundecyl)-6-hydroxy-5,8-quinolinequinone was synthesized by radical alkylation of 6-hydroxy-5,8-quinolinequinone by thermal decomposition of di-3,7,11-trimethyldodecanoyl peroxide, which was prepared by a multistep procedure from farnesol. Of the five new 2-methyl-6-alkylamino-5,8-quinoline-quinones tested against P. berghei in mice (blood schizonticidal test), only 2-methyl-6-cycloheptylamino-5,8-quinolinequinone was active (T-C = 6.1 at 320 mg./kg.). Both 7-(2′,6′,10′-trimelhytundecyl)-6-hydroxy-5,8-quinolinequinone and the tetrahydro derivatives were inactive in this same test system.     

The Synthesis and Characterization of a Novel ( E,E )-Dioxime and its Mono- and Heterotrinuclear Complexes Containing an 18-Membered Dioxadithiadiazamacrocycle

The novel ( E , E )-dioxime, 5,6:17,18-dibenzo-11,12-(4'-nitrobenzo)-2,3-bis(hydroxyimino)-7,16-dithia-10,13-dioxa-1,4-diazacyclooctadecane) ( H 2 L ), has been synthesized from reaction of ( E , E )-dichloroglyoxime ( 1 ) with 2,3:14,15-dibenzo 8,9-(4'-nitrobenzo)-4,13-dithia-7,10-dioxa-1,16-diazahegzadecane ( 2 ). The mononuclear Co(III) complex ( 4 ) of this dioxime was prepared by oxidation of the cobalt (II) complex. The -capped Co(III) complex ( 5 ) was synthesized by using a precursor Co(III) complex and boron trifluoride dietherate. The heterotrinuclear complexes ( 6 ) and ( 7 ) were prepared by reaction of ( 5 ) with NiCl 2 ·6H 2 O and CdCl 2 ·H 2 O, respectively. In addition, the homotrinuclear Cu(II) complex ( 8 ), has also been prepared by the reaction of this dioxime with CuCl 2 ·H 2 O. The structures of the dioxime and its complexes were identified by using elemental analysis, 1 H- and 13 C-NMR, IR, and mass spectral data.