(5-甲基-2-烷氧基苯基)-1-烃基胺的合成

以对甲酚(1)为起始原料,经醚化、酰化和还原氨化反应合成了5个(5-甲基-2-乙氧基苯基)-1-烃基胺;1经酯化、Fries重排、醚化和还原氨化反应合成了5个(5-甲基-2-甲氧基苯基)-1-烃基胺.其结构经1H NMR,13C NMR,IR和GC-MS表征.     

N-甲基-4-羟基-5-苯基-2-吡啶酮的合成

以丙二酸和二氯亚砜为起始原料,经氯代、环合、催化氢化及烷基化反应合成了新化合物——N-甲基-5-苯基-4-羟基-2-吡啶酮,总收率38.7％,其结构经1H NMR,IR和EI-MS表征.     

7-硝基-8-羟基喹啉的合成

以8-羟基喹啉为原料,经硝化和脱磺酸基保护两步反应合成了7-硝基-8-羟基喹啉,总收率69％,纯度高于99％.其结构经1H NMR,13C NMR和HR-MS确证.     

4,7-二苯基-1,10-菲啰啉的合成研究

以4-苯基-8-硝基喹啉为起始原料,经还原得到4-苯基-8-氨基喹啉,再以I2/KI为氧化剂,在乙酸和盐酸的存在下,用Skraup法合成了4,7-二苯基-1,10-菲啰啉.化合物结构经IR和1H NMR得到了证实.实验研究得到了最佳的合成条件为:n(3-氯苯丙酮)∶n(4-苯基-8-氨基喹啉)=1.5∶1,I2/KI用量为8%,反应温度120℃,反应时间2.5 h.产品收率可达82%.     

3,7-二甲基-7-羟基-2-辛烯-1,6-内酯和(E)-6,7-二羟基-3,7-二甲基-2-辛烯酸的全合成

以甲基庚烯酮为原料经Wittig反应、水解、环氧化和分子内环化或开环等4步反应分别以6.4%和23.7%的总收率完成了天然产物3,7-二甲基-7-羟基-2-辛烯-1,6-内酯和(E)-6,7-二羟基-3,7-二甲基-2-辛烯酸的全合成,它们的结构经1H NMR,13C NMR和ESI-MS的确证.     

2-(3-芳氧甲基-4-苯基-1,2,4-三唑-5-硫基)乙酸的微波合成及生物活性研究

在微波辐射条件下, 芳氧乙酰肼经两步反应制得4-苯基-3-芳氧甲基-1,2,4-三唑-5-硫酮衍生物, 再与氯乙酸反应得到6种尚未见文献报道的2-(3-芳氧甲基-4-苯基-1,2,4-三唑-5-硫基)乙酸衍生物. 目标化合物的结构经IR, ¹H NMR和元素分析进行了确证. 生物活性试验结果表明, 该类化合物对双子叶植物油菜具有良好的生物调节活性.     

2-烷基-6-甲氧基-1,4-苯醌的全合成

3,5-二甲氧基苯甲醛经格氏、氧化反应制到3,5-二甲氧基苯基烷基酮, 然后在微波辐射下经黄鸣龙还原和选择性脱甲基化、Teuber氧化反应制得目标化合物, 产率均在50%以上. 产物结构经IR, 1H NMR, 元素分析等进行了表征.     

2-甲基-4,5-二硝基三唑-1-氧化物的合成及其结构表征

以乙二醛、甲基肼和盐酸羟胺为起始原料,经缩合、肟化得到中间体肟基甲腙;该中间体不经分离直接加入到硫酸铜-吡啶-水体系中,经缩合环化得到2-甲基三唑-1-氧化物(MTO);随后用混酸(硝酸+硫酸)硝化得到目标产物2-甲基-4,5-二硝基三唑-1-氧化物(DNMTO);初步探讨了环化反应的机理,研究了反应温度与时间等因素对硝化反应的影响,确定了最佳硝化反应条件.与此同时,利用红外光谱、核磁共振、质谱及元素分析等分析了中间产物和DNMTO的组成和结构.结果表明,目标产物的总收率为16%,纯度为99%;最佳硝化反应温度为100℃,最佳硝化反应时间为0.5h.     

4-甲基-苯磺酸-2-氧-2-[3-(5-芳基-[1,3,4]噁二唑-2-基)-硫脲]-乙基酯的合成及生物活性研究

合成了12个未见文献报道的4-甲基-苯磺酸2-氧-2-[3-(5-芳基-[1,3,4]噁二唑-2-基)-硫脲]-乙基酯, 其结构经元素分析、¹H NMR和IR确证. 初步活性测试结果表明: 部分化合物有较好的杀菌活性.     

4-(7-甲氧基-2,2-二甲基-2,3-二氢苯并呋喃-5-基)-2-苄亚氨基噻唑的合成与生物活性

呋喃酚经醚化、傅克酰化、α-溴代、噻唑环化和亚胺化等反应合成了16种4-(7-甲氧基-2,2-二甲基-2,3-二氢苯并呋喃-5-基)-2-苄亚氨基噻唑新化合物.化合物的结构经1H NMR、质谱和元素分析等确证.杀虫活性实验结果表明,化合物2a和2i在500 mg/L对棉红蜘蛛死亡率分别为53.10%和67.71%,杀菌活性实验结果表明,化合物2a和2k在25 mg/L对油菜菌核病菌抑制率分别为57.9%和59.8%,除草活性实验结果表明,2l在2250 g.ai/ha浓度下对苘麻、刺苋、藜具有一定的除草活性.     

Homolytic substitutions in indolinone nitroxide radicals—II: Reaction with organic peracids

The reactions of indolinone nitroxides 7 and of the corresponding amine precursors 15 with organic peracids were studied, and were found to give substitution products at the aromatic nucleus, i.e. 5-aroyloxy- and 7-aroyloxynitroxides 8 together with N-oxides 10 and with 7-hydroxynitroxides 9. Structures were assigned on the basis of ESR and ¹H NMR spectra. A reaction scheme was proposed involving a homolytic substitution which accounts for the products obtained and is supported by an experimental proof.     

Schmidt reaction of 4-substituted adamantanones

The Schmidt reaction of various 4^a - and 4^e -substituted adamantanones has been investigated. It is shown that the direction of the nitrogen insertion is not dominated by inductive substituent influences. The main reaction pathway involves the diazoiminium ion 3 and the intermediates 4 and 5 which prefer different reactions: 4 undergoes mainly fragmentation (8 and 9) whereas 5 gives mainly water addition products (7). The recyclisation of 8 and 9 is highly regloselective. The structure determinations of the products are based on their ¹H and ¹³C NMR data.     

Synthesis and redox behavior of 1,2-dihydro-1-oxabenz[a]azulen-2-ones

Three new 1,2-dihydro-1-oxabenz[a]azulen-2-one derivatives, 1a (R¹=H, R²=Me), 1b (R¹=H, R²=Ph), and 1c (R¹=COOEt, R²=Me), have been synthesized by the reaction of 2-hydroxyazulene (2a) and its 1-ethoxycarbonyl derivative 2b with ethyl acetoacetate (3a) or ethyl benzoylacetate (3b) in the presence of aluminum chloride. To our knowledge, these are the first examples of this type of compound, although the yield of the products is low in some cases. Their electronic properties were studied in detail utilizing the analyses of 1,2-dihydro-1-oxabenz[a]azulen-2-one derivative 1a by the spectroscopic and voltammetric analyses. The analyses revealed that the fused α-pyrone system lowers both the HOMO and the LUMO energies, relative to those of parent azulene (10), but has much pronounced effect on the LUMO, consequently, leading to decrease in HOMO–LUMO gap, compared with those of 10. These results should be attracted to the development of amphoteric redox materials. Reactivity toward electrophilic reagents was also examined by bromination and Vilsmeier–Haack formylation reactions of 1a. To evaluate the scope of the reaction products we have examined Sonogashira cross-coupling reaction of the bromination products with trimethylsilylacetylene and conversion of the formylation product to dibromoolefin by the reaction with phosphorous ylide prepared with CBr₄ and Ph₃P. Effective extension of the π-electron system in the ethynyl products has been revealed by the spectroscopic analysis. These reaction products would be attracted to the application as a terminal group for electronic applications.     

温和条件下对甲基苯磺酸铝高效催化一锅法合成β-氨基酮衍生物

室温条件下, 对甲基苯磺酸铝可有效催化芳香酮、芳香醛和芳香胺的Mannich反应, 三组分“一锅法”合成了一系列β-氨基酮衍生物. 考察了溶剂及反应条件对产率的影响. 反应结束后, 催化剂经简单相分离可回收并多次重复使用, 催化活性无明显下降. 产物结构经IR, ¹H NMR, 元素分析进行表征.     

The stereochemistry of the SRN1 reaction in some cyclohexane derivatives

The substitution reactions of nitrocyclohexanes 8, 9, 12 and 23 with various nucleophiles were studied and were found to proceed by the electron-transfer initiated S_RN1 mechanism. Epimeric products were formed and the proportion of epimers under both thermodynamic and kinetic control normally reflected the bulk of the incoming nucleophile relative to the substituent which was present at the reaction site. In the reaction of 23 with relatively high concentrations of PhS^? in HMPA the reaction proceeded with high stereoretention. The results of these reactions are discussed in terms of the stability of radical configuration and the rate and mode of radical anion dissociations and associations.     

Synthesis of bacillamide 3 and its analogue

The bacillamide 1 is a new algaecide from the marine bacterium Bacillus sp. SY-1. Its analogues bacillamide 3 and alkaloid 4 were firstly synthesized effectively from d-alanine. The key step was a coupling reaction via the mixed anhydride. All structures were confirmed by ¹H NMR and ¹³C NMR. The final compounds were confirmed by ¹H NMR, ¹³C NMR and HRMS and the results are consistent with the reported natural products.     

Generation and fate of free radicals of Δ2-oxazolin-5-ones

The reaction of Δ² -oxazolin-5-ones 1a and 1b with nickel peroxide in benzene produces the corresponding 4,4-dehydrodimers 5a and 5b as the main products in yields over 75%. Under the same conditions, the 2-aryl -4-methyl - Δ²-oxazolin-5-ones 1c, 1d and 1e yield five products. In the case of 1c, the constituents of the product mixture were separated and identified as two 4,4-dehydrodimers ( meso and d] pair isomers) 5c and 5c', (40.7%), 2,4-dehydrodimer 6c (34.9%), acetylanisoylimide 8c (8.5%) and anisamide (15.9%). Adequate mechanistic schemes are discussed to account for the products formed.     

The system potassium-graphite/ methylborondibromide/ alkyne: Query about the intermediacy of methylborylene

Attempts to reproduce the reported synthesis of peralkylated 1,4-dibora-2,5-cyclohexadienes (1) using the so-called “methylborylene-generating system”, 2 C₈K/MeBBr₂, in the presence of 3-hexyne and 5-decyne were not successful. The nido-2,3,4,5-tetracarbaboranes(6) (2) contaminated with other carbaboranes and various organoboronhalides were obtained instead, irrespective of the nature of the C₈K used. Different samples of C₈K were prepared and characterized by X-ray diffraction and XPS spectra. The yields of the carbaboranes were much better when the well ordered stage 1 potassium graphite in hexane was used. In all experiments the first compounds identified from the reaction mixtures are the 1,2-haloboration products (3) and there is no indication for the intermediacy of methylborylene. Most of the organoboranes present in the reaction solution and in the final products could be readily assigned on the basis of ¹¹B- and ¹³C NMR data, supported by GC/MS analysis.     

Concise and efficient synthesis of E-stereoisomers of exo-cyclic carbohydrate enones. Aldol condensation of dihydrolevoglucosenone with five-membered aromatic aldehydes Part 1

Stereoselective synthesis of exocyclic enones 10–17 via a base-catalyzed direct aldol condensation between dihydrolevoglucosenone 1 and heterocyclic aldehydes 2–9 is described. The reaction is performed under mild conditions and is applicable to variety of heterocyclic aldehydes. E-Steroisomers of exo-cyclic enones are the only products. They are very easy to isolate and were formed in good to excellent (72–88%) yield. ¹H NMR, ¹³C NMR analyses provide the structural assignment and absolute stereochemistry of the condensation products. Single-crystal X-ray diffraction of condensation product 12, additionally supports the structural assignment.     

Vinyl carbanions derived from cis-cinnamonitrile-reactions with electrophiles and configurational stability

Vinyl carbanions derived from cis-cinnamonitrile 1 were formed by reacting it with lithium diisopropylamide (LDA) as a base in aprotic solvents at low temperatures; reaction with various electrophiles (E) resulted in the corresponding derivatives PhCHC(E)CN. The configurational stability of the vinyl carbanions derived from 1 and the geometry of the reaction products was affected by the solvating properties of the medium. Retention of configuration was achieved in a poor solvating medium-diethyl ether-hexane (4:1). Addition of a crown ether or using THF as solvent resulted in products having trans geometry. The site of deprotonation of cinnamonitrile (cis and trans) was compared to that of cinnamic esters and discussed. Determination of the geometry of the products was based on their ¹H NMR spectra.