氯乙酸苄酯的规模化合成

以二氯甲烷为溶剂,氯乙酰氯和苯甲醇反应,合成了氯乙酸苄酯。通过红外光谱、紫外光谱和核磁共振氢谱对氯乙酸苄酯结构进行了表征。采用单因素优选法,对反应时间、反应物比例、碱的种类和反应温度等可能影响氯乙酸苄酯收率的因素进行了讨论。结果表明,最适宜的合成条件反应温度为室温,反应时间90 min,n(氯乙酰氯)∶n(苯甲醇)=1.2∶1。氯乙酸苄酯产率为79.4%,高效液相色谱证明氯乙酸苄酯质量分数为98%。     

氯代甲酸苯氧乙基酯的合成研究

介绍了氯代甲酸苯氧乙基酯的合成方法．并重点讨论了以三光气为原料合成氯代甲酸苯氧乙基酯的方法。     

GCLE3-位硫取代产物的合成及反应动力学研究

以7-苯乙酰氨基-3-氯甲基头孢烷烯酸对甲氧基苄酯（简称GCLE）取代7-ACA,直接和三嗪环反应合成头孢曲松中间体7-苯乙酰氨基-3-三嗪环甲基头孢-4-羧酸对甲氧苄酯,通过高效液相色谱仪对反应过程进行监测。研究了该反应的动力学,确定反应为SN2历程,通过测定25℃、35℃下在不同溶剂中反应的速率常数,得出其亲核取代反应活性顺序为：乙腈〉四氢呋喃。     

氯甲酸苄酯的合成及应用

对氯甲酸苄酯的合成进行了研究 ,介绍了其在多钛合成中的应用。     

四丁基溴化铵催化合成甲酸苄酯的研究

本文以四丁基溴化铵（ＴＢＡＢ）为相转移催化剂,氯苄和甲酸钠为原料合成甲酸苄酯,从原料配比、催化剂用量、反应时间等影响因素进行了研究。结果表明该方法操作简单、原料廉价,产品质量好、产率高,无三废污染并易于工业化生产。     

ACLE盐酸盐的合成

以GCLE（7-苯乙酰氨基-3-氯甲基-3-头孢环-4-羧酸对甲氧苄酯）为原料,采用偕氯亚胺法一步合成ACLE．HCI（7-氨基-3-氯甲基-3-头孢环-4-羧酸对甲氧苄酯盐酸盐）,HPLC测定其含量97％,得率91．5％。提出了偕氯亚胺法的反应机理。主要产物和副产物结构通过MS、NMR、IR进行表征。     

水杨醛缩肼基二硫代甲酸苄酯类Schiff碱配体的合成

由水合肼、CS2与取代的溴化苄在低温条件下反应,合成肼基二硫代甲酸苄酯类化合物,再在无水乙醇体系中及高温回流条件下与取代的水杨醛进行反应,合成了一系列标题化合物,其结构经质谱、紫外光谱、红外光谱、元素分析及1H核磁共振等进行表征.     

N-苄氧羰基氨基酸的合成

以甘氨酸和氯甲酸苄酯为原料,合成N-苄氧羰基甘氨酸,通过正交实验考察工艺条件对反应的影响。结果表明,最佳工艺条件为:底物摩尔比n(甘氨酸)∶n(氯甲酸苄酯)=1∶1,反应时间2 h,反应温度20℃,反应液pH值为9,收率90.2%。此法反应条件温和,操作简单,收率良好。     

硅酸苄基三（氯乙基）酯的合成及表征

以四氯化硅、苯甲醇和环氧乙烷为原料,合成一种硅卤协同阻燃增塑剂硅酸三(氯乙基)苄酯。探讨了反应时间、反应温度以及反应物摩尔比等对产率的影响,筛选出最佳的工艺条件为:n(四氯化硅)∶n(苯甲醇)=1∶1,n(四氯化硅)∶n(环氧乙烷)=1∶3.2,反应温度40℃,反应时间2 h,在该条件下产率为98%。采用FTIR、1HNMR、极限氧指数表征了硅酸三(氯乙基)苄酯的分子结构及性能。     

2-氯苄基-N-琥珀酰亚胺基碳酸酯的合成研究

以2-氯苄醇和三氯甲基碳酸双酯为起始原料,以二氯乙烷为溶剂,合成了氯甲酸2-氯苄酯,并和N-羟基琥珀酰亚胺反应制备得到肽类保护剂2-氯苄基-N-琥珀酰亚胺基碳酸酯。对反应条件进行了优化,两步反应的总收率接近50%,所得产品经1H NMR确证。     

Cyanine dyes from polynitro- and poly(trifluoromethylsulphonyl)-benzenes

New monomethine and trimethine cyanine dyes with benzothiazole or indole and polynitro- or poly(trifluoromethylsulphonyl)-substituted benzene rings attached to the ends of the polymethine chain have been synthesised. Atoms of fluorine or methyl groups were introduced to the α-position of the polymethine chain. The influence of nitro and trifluoromethylsulphonyl groups on the colour of these dyes is compared. It is shown that the CF₃SO₂ group is a weaker auxochrome than the nitro group.     

The role of supporting electrolyte during the electrocatalytic hydrogenation of aromatic compounds

The electrocatalytic hydrogenation of benzene, aniline, and nitrobenzene was investigated at a Raney nickel powder cathode. The single phase electrolyte consisted of t-butanol, water, and a hydrotropic salt, either sodium or tetraethylammoniump-toluenesulphonate (TEATS). The hydrogenation of benzene was achieved only in the latter case; the only product detected was cyclohexane. The highest current efficiency (73%) was obtained at 50° C, 1.0m benzene, 2.5m TEATS, and at an apparent current density of 4.0 mA cm^–2. Aniline was electrocatalytically hydrogenated to cyclohexylamine only in the presence of a quaternary ammonium ion supporting electrolyte (containing either Br^– orp-toluenesulphonate anions), with product current efficiencies of 40%. When nitrobenzene was hydrogenated with a sodiump-toluenesulphonate supporting electrolyte, only nitro group reduction was observed. When the supporting electrolyte was TEATS, both nitro group reduction and aromatic ring hydrogenation occurred.     

1,2-二苯肼的合成工艺改进

研究了硝基苯在强碱性介质中用锌粉还原制备 1 ,2 -二苯肼的反应。探讨了锌粉用量、溶剂的醇水体积比、溶剂总量对反应的影响。最佳反应条件为 :当硝基苯的用量为 0 .2 5 mol时 ,硝基苯与锌粉的摩尔比为 1∶ 5 ;溶剂的醇水体积比为 1∶ 1 .5 ,溶剂总量为 3 2 m L,反应时间为 1 .5 h,产率为 90 %。与文献[5] 比较 ,溶剂总量减少约 2 0 m L ,反应时间缩短 1 0 h以上 ,产率提高了 9个百分点     

Synthesis and bacteriostatic properties of acylarylureas and alkylarylureas

Fatty substituted ureas (RNHCONHR’) were prepared where R is an aliphatic acyl or alkyl group and R’ is a substituted phenyl group or a thiazole group. The benzene ring was generally substituted with chlorine, nitro, hydroxy, or a combination of these groups. The compounds were ineffective against gram-negative microorganisms but a number of samples inhibited the growth ofStaphylococcus aureus at 1 ppm. Bacteriostatic activity was generally observed where the acyl or alkyl group contained 6–10 carbon atoms and where R’ is 4-nitrophenyl, 4-chloro-3-nitrophenyl or a thiazole group derived from 2-amino-5-nitrothiazole. Scattered activity at 1 ppm was observed where R’ is 3-nitrophenyl, 2,4- and 3,5-dichlorophenyl, 2-hydroxy-5-chlorophenyl, 2-hydroxy-5-nitrophenyl, 3-nitro-4-hydroxyphenyl, 3,5-dinitrophenyl and 2-nitro-4-chlorophenyl. The alkylureas appear to be more active than the acylureas.     

Crystallography and Structure–Property Relationships of 2,2″,4,4′,4″,6,6′,6″‐Octanitro‐1,1′ : 3′,1″‐Terphenyl (ONT)

An X‐ray crystallographic study of 2,2″,4,4′,4″,6,6′,6″‐octanitro‐1,1′ : 3′,1″‐terphenyl (ONT) has been carried out. The dihedral angles between benzene rings vary from 84.9° to 89.4°. Nonbinding interatomic distances of oxygen atoms inside all the nitro groups are shorter than the intermolecular contact radii for oxygen. On the basis of the DFT B3LYP/6‐31(d, p) method it was found that the difference between the X‐ray structure in the solid phase and DFT result for the gas phase is 98 kJ mol⁻¹, and the bearer of the highest initiation reactivity of the ONT molecule in the solid phase should be the nitro group at 4″‐position, in contrast to those at 4′‐ or 6′‐position that play this role in the isolated molecule. It has been stated that the nitro groups at the reaction centers of the ONT molecule are relatively well specified by their ¹⁵N NMR chemical shifts.     

离子液体中的相互作用对硝基苯扩散系数的影响

应用紫外吸收光谱法和循环伏安法研究了离子液体中的相互作用及对离子液体中硝基苯的扩散系数的影响。结果表明,硝基苯的紫外光谱受离子液体EMimBF₄(1-甲基-3-乙基咪唑四氟硼酸盐)与其相互作用的影响,硝基的吸收峰红移,210 nm以下的末端吸收消失,而苯环的吸收基本不变;离子液体与硝基苯之间的作用主要发生在硝基上。在离子液体中电还原,硝基苯的扩散系数受硝基苯与离子液体、水与离子液体的相互作用的影响。同一离子液体中,随硝基苯浓度增加,扩散系数减小。相同硝基苯浓度时,不同离子液体的咪唑阳离子侧链越长扩散系数越小,但扩散系数减小得越缓慢;同一离子液体中,随着水浓度增加,硝基苯扩散系数增大;不同离子液体中,咪唑侧链越长,随着水的浓度增加,硝基苯扩散系数增加越快。     

Tests and refinements of a general structure-activity model for avian repellents

We tested the robustness of a structure-activity model for avian trigeminal chemoirritants. Fourteen benzoates and acetophenones were tested using European starlingsSturnus vulgaris as a bioassay. In general, the previously proposed model was a reasonable predictor of repellency (i.e., irritant potency). We found that the presence of a phenyl ring was critical to repellency. Basicity of the molecule is the next most critical feature influencing repellency. The presence of an acidic function within the electron-withdrawing functionality seriously detracts from repellency. The presence or absence of an electron-withdrawing or -donating group may potentiate repellent effects, but its presence is not critical, so long as the phenyl ring is electron rich. Our data suggest that there is ano-aminoacetophenone/methyl anthranilate trigeminal chemoreceptor in birds analogous to the mammalian capsaicin receptor. Both receptors contain a benzene site. However, birds seem to lack the associated thiol/hydrogen-bonding site present in mammals which is needed to activate the benzene site. Rather, birds may possess an associated exposed charged site that in turn may interact with the stimulus to activate the benzene site. These differences may explain the differential sensitivity of birds and mammals to aromatic irritants.     

2-(取代乙炔基)苯甲醛衍生物在有机合成中的应用

作为一类具有特殊结构的重要有机合成中间体，2-(取代乙炔基)苯甲醛衍生物的化学结构是由苯环、取代乙炔基和醛基三部分活性基团构成的共轭体系. 因其具有较高的反应活性，而被广泛的用于构建各种具有新颖结构的苯并碳环或苯并杂环类化合物，如苯并碳环化合物、苯并氮杂环化合物、苯并氧杂环化合物、多元苯并杂环化合物等. 本文综述了2-(取代乙炔基)苯甲醛衍生物在有机合成领域的应用，并对其发展前景进行了展望，为今后2-(取代乙炔基)苯甲醛衍生物在有机合成中的应用提供参考.     

Am1 MO Study of Benzene Nitro Derivatives

Molecular properties of benzene nitro derivatives were investigated by using semi-empirical MO calculations. As the results, the molecular structures and the rotational barrier of the nitro group calculated by AM1 showed a good agreement with the experimental values. The heats of formation in gaseous and condensed phases were obtained by considering isodesmic reactions. By this procedure, the heat of formation of hexanitrobenzene in solid phase was calculated to be +22.7 kcal/mol. The detonation parameters were also calculated by using four equations of state. The predicted detonation velocities showed a good agreement with the experimental values.     

纳米尺寸的氢化钠对硝基苯的还原反应

用纳米尺寸折氢化钠对硝基苯进行了还原，主要产物为氧化偶氮苯，收率明显优于在相同条件下使用工业氢化钠所得的结果。考察了反应参数对硝基苯转化率及产物组成的影响。