（E）－2－甲基－1，3－戊二烯的振动光谱及其稳定构象的研究

记录了（Ｅ）－２－二甲基－１，３－戊二烯的固、液、气态ＦＴＩＲ光谱（４００～４０００ｃｍ~（－１））和固、液态Ｒａｍａｎ光谱（５０～４０００ｃｍ~（－１）），观测了６８５及６５８ｃｍ~（－１）谱线的变温ＦＴＩＲ光谱（－７３～１０℃）．对所得谱图进行的指认分析发现，该化合物存在两种单键旋转构象异构体ｓ－ｔｒａｎｓ和ｓ－ｃｉｓ，由变温ＦＴＩＲ光谱峰强度随温度的变化得到这两种构象互变的ΔＨ~０和ΔＳ~０。     

γ－芳基取代烯丙醇菊酯的合成及杀虫活性

γ－芳基取代烯丙醇菊酯的合成及杀虫活性陈亚娟，黄润秋，马军安（南开大学元素有机化学研究所，天津，３０００７１）关键词γ－芳基取代烯丙醇，拟除虫菊酯，杀虫活性第一个人工合成除虫菊酯烯丙菊酯保留了天然除虫菊酯醇部分的环戊烯醇酮结构，至今仍广泛用作卫生杀虫...     

1－（取代异噁唑基）－1，2，4．三唑和1－（取代嘧啶基）－1，2，4－三唑的合成及生物活性

合成了１５个新的１－（取代异噁唑基）－１，２，４－三唑和１－（取代嘧啶基）－１，２，４－三唑化合物，经元素分析、ＩＲ、１ＨＮＭＲ和ＭＳ证实其结构，并对其代表化合物进行了抑菌及植物生长调节活性的初步观察     

O－烷基，O－芳基硫代磷酰取代硫脲和O－烷基硫代磷酰－双－取代硫脲的研究（Ⅱ）

用硫氰酸钾与硫代磷酰氯制备了硫代磷酰异硫氰基酯和二异硫氰基酯，并以其与不同胺反应，合成了硫代磷酰取代硫脲和硫代磷酰－双－取代硫脲两系列２０个新的有机磷化合物，经~１ＨＮＭＲ、ＩＲ及元素分析确定了它们的化学结构，测定了它们的生物活性。结果表明只有Ｏ－异丙基，Ｏ－（４－甲基－２－硝基苯基）－Ｎ＇－萘基硫代磷酰硫脲（ＰＤ－１）具有较好的杀菌活性。     

1－（取代吡唑－4－基）－1，2，4－三唑的合成及生物活性研究

合成了２３个新的１－（取代吡唑－４－基）１，２，４－三唑化合物，经ＥＡ、ＩＲ、~１ＨＮＭＲ和ＭＳ确定其组成和结构，并对其进行了抑菌及生长调节活性的初步观察。     

N－取代三氯乙酰胺合成新脲类化合物及其生物活性的研究（I）──N，N″－多亚甲基双（N＇－取代苯基）脲的合成及除草活性

Ｎ－取代三氯乙酰胺合成新脲类化合物及其生物活性的研究（Ｉ）──Ｎ,Ｎ″－多亚甲基双（Ｎ＇－取代苯基）脲的合成及除草活性郭佃顺,黄汝骐,高蓉华,吴志广（山东师范大学化学系,山东省有机合成重点实验室,济南,２５００１４）王玲秀（南开大学元素有机化学研究所...     

μ－氧代双锰（Ⅲ）卟啉氧化反应及取代基效应研究

用紫外－可见光谱对氧化剂ＰｈＩＯ、Ｈ_２Ｏ_２和空气对μ－氧代双四苯基卟吩合锰（［ＴＰＰ·Ｍｎ（Ⅲ）］_２Ｏ）的氧化过程进行监测，揭示了［ＴＰＰＭｎ（Ⅲ）］_２Ｏ在不同氧化剂作用下具有不同的反应过程。研究了８种取代μ－氧双四苯基卟吩合锰｛［ＴＸＰＰＭｎ（Ⅲ）］_２Ｏ，Ｘ＝ｐ－（ｉ－Ｐｒ），ｐ－ＣＨ_３，ｐ－Ｃｌ，ｐ－Ｆ，ｐ－ＯＣＨ_３，Ｈ，ｍ－Ｃｌ，ｏ－Ｃｌ｝与Ｈ_２Ｏ_２反应中的取代基效应和溶剂效应。结果表明：上述反应为卟啉环上的吸电子基所促进；且反应速率随着反应溶剂的亲核性能的增加而增加。     

噻吩查尔酮紫外光谱的取代基效应

噻吩查尔酮紫外光谱的取代基效应陆文兴颜朝国（扬州大学师范学院化学系江苏扬州２２５００２）朱权（扬州化工学校江苏扬州２２５００２）关键词噻吩查尔酮ＫＦ－Ａｌ２Ｏ３紫外光谱取代基效应中图分类号Ｏ６２６．１２我们曾报导查尔酮的ＫＦ－Ａｌ２Ｏ３催化合成［１］...     

3－苯基－5－取代苯氨基－6－甲基－1，2，4－三嗪的合成

３－苯基－５－取代苯氨基－６－甲基－１，２，４－三嗪的合成陆忠娥，曾润生，席海涛（苏州大学化学系，苏州，２１５００６）关键词硫代苯甲酰胺，α－乙酰基硫代甲酰苯胺，Ｎ＇－氨基苯甲脒，３－苯基－５－取代苯氨基－６－甲基－１，２，４－三嗪１，２，４－三嗪类...     

模拟细胞色素P－450的仿生氧化反应的研究（Ⅴ）──氯合5，10，15，20－四取代苯基卟吩合铁（Ⅲ）中取代基对催化环己烷单加氧反应的影响

系统地考察了一系列氯合５，１０，１５，２０－四取代苯基卟吩合铁（Ⅲ）Ｔ（Ｒ－Ｐ）ＰＦｅ（Ⅲ）Ｃｌ（Ｒ＝ｏ，ｍ，ｐ－Ｍｅ，ＭｅＯ，Ｃｌ，Ｂｒ，Ｉ，ＮＯ２，ｏ－ｔ－Ｂｕ，ｐ－ｔ－Ｂｕ，ｏ－ＮＨ２，Ｅｔ，ｉ－ｐｒ）作模拟酶单加氧催化剂，以亚碘酰苯作供氧体对环己烷进行羟化反应时的取代基效应。环己醇产率随取代基Ｒ的拉电子性增强而提高，对位取代基常数σｐ与环己醇产率间存在Ｈａｍｍｅｔｔ线性相关式：１ｇ（ＹＲ／ＹＨ）＝３．２σｐ－０．０３。邻位取代基的立体效应也增加环己醇的产率。     

Chemiluminescence characteristics of N-(4-substituted benzyl)isoluminol

We synthesized N-(4-substituted benzyl)isoluminol which has 4-bromo-, 4-methyl-, 4-methoxy-, 4-nitrogroups. These compounds produced chemiluminescence by the reaction with the oxidizing agent, potassium hexacyanoferrate and hydrogen peroxide, in an alkaline medium. The chemiluminescence intensities of these compounds were 0.03-4.7 times that of isoluminol. We used Hamett substituent constants as a parameter for the electronic substituent effects. The relationship between the amino-H chemical shift value and the Hamett substituent constants showed a good linear correlation. The relationship between the chemiluminescence intensities and the Hamett substituent constants showed a good linear correlation. The relationship between the fluorescence intensities and the Hamett substituent constants also showed a good linear correlation. These results suggest that the change in the electron density around the amino group strongly influences the fluorescence intensities and corresponding chemiluminescence intensities of these derivatives.     

Investigation of 2,3-polymethylenequinolines

The rate of the reaction of 4-chloro-6-R-2,3-polymethylenequinolines with sodium methoxide decreases as the number of methylene groups increases; this is explained by the inductive and steric effects of the polymethylene chain. The rate constants of the reaction are in conformity with the Arrhenius equation and are found to exist in a correlation relationship with the σ_cat substituent constants for quinoline.     

A kinetic study of the mechanism of esterification of 1-arylethanols in trifluoroacetic acid

Aryl substituent effects upon the rate constants for the esterification of a series of 1-arylethanols in trifluoroacetic acid are in accordance with a reverse A_AL1 mechanism, for which the Hammett reaction constant ? = ?3.69 has been determined by correlation with σ⁺ substituent constants. The rates of reaction are ca. 50-fold faster than those for corresponding benzyl alcohols which bear an electron-donating aryl substituent and which are also believed to undergo esterification in trifluoroacetic acid by the reverse A_AL1 mechanism; the reverse A_AC2 mechanism applies to benzyl alcohols which bear an electron- withdrawing aryl substituent.     

Solvent effect on the sensitized photooxygenation of cyclic and acyclic α-diimines

The reaction of singlet molecular oxygen with a series of cyclic and acyclic α-diimines was studied. Time-resolved methods were used to measure total reaction rate constants and steady-state methods were used to determine chemical reaction rate constants. GC-MS was used to tentatively assign the reaction products. 5,6-Disubstituted cyclic α-diimines are singlet oxygen quenchers, but become more effective in polar solvents. A reaction mechanism involving a perepoxide intermediate or transition state leading to a hydroperoxide seems to be a key reaction path for product formation. A replacement of the phenyl substituent for a methyl substituent opens up an additional reaction involving a perepoxide-like exciplex, which increases singlet oxygen quenching of the cyclic α-diimines. The reactivity of 5,6-disubstituted cyclic α-diimines towards singlet oxygen is highly dependent on steric interactions arising from vicinal phenyl rings and from electronic effects. 1,4-Disubstituted acyclic α-diimines are, by comparison, moderate or poor singlet oxygen quenchers. Total rate constants are scarcely dependent on solvent properties, but instead correlate with the Hildebrand parameter. These results are explained in terms of a mechanism involving a dioxetane-like exciplex that gives rise to a charged intermediate leading to products.     

Si-H键伸缩振动频率与结构关系的研究

本文研究了开链及环状硅氢化合物中硅原子上取代基的电子效应和立体效应对Si-H键伸缩振动频率的影响。     

Establishment of steric substituent constants in the adamantane system by ab initio calculations

[reaction: see text] Steric substituent constants, S(A), of both alkyl and aryl substituents were calculated in the adamantane system by both isodesmic reactions and ab initio calculations. The method provides an easy and reliable way to quantify the substituent steric effects.     

Substituent effect on exo stereoselectivity in the 1,3-Dipolar cycloaddition reaction of tulipalin A with nitrile ylides

1,3-Dipolar cycloaddition reactions of dihydro-3-methylene-2(3H)-furanone (tulipalin A) with various benzonitrile(p-X-benzylide) ylides prefer formation of exo-cycloadducts in the extent corresponding to an increasing electron donor character of the substituent X in the para-position of the benzylide phenyl ring of the 1,3-dipolar reagent. The substituent effect on diastereoselectivity of the 1,3-DC reaction is rationalized in terms of CH/pi interaction between the dipole and the dipolarophile in an exo-transition state. The determining role of such an interaction is demonstrated by the correlation of the observed diastereoselectivities with substituent Hammett sigma constants, which shows a small negative rho value. A certain contribution of CO/pi interaction between the lactone carbonyl and the substituted phenyl ring to mediation of the substituent effect is also discussed. The energy profiles of both reaction pathways were analyzed using DFT and RI-MP2 theoretical approaches. Calculated energy and structural differences between located transition states are consistent with reaction diastereoselectivities.     

取代查耳酮肟电化学氧化机理的研究

研究了７种取代查耳酮肟的电化学行为。用氢氧化钠底液热解石墨工作电极，取代查耳酮肟的电极过程为１ｅ氧化不可逆吸附电极过程。它们的氧化电位随取代基吸电子能力的增强而增高，并与它们相应的Ｈａｍｍｅｔｔ常数呈线性关系。取代查耳酮肟的电化学氧化机理为先失去一个电子生成ｉｍｉｎｏｘｙ自由基，然后由基对分子内烯键进行环化加成，脱氢后形成３，５－二聚代异恶唑。用控电位电解和紫外吸收光谱检测了部份电化学氧化产物，证     

Dediazoniations of arenediazonium ions part 25 Influence of Substituents on the Exchange of the Diazonio Group for External Molecular Nitrogen and on the N(α), N(β)-Rearrangement in the Diazonio Group

The N(α), N(β)-rearrangement of the two N-atoms which can be observed in solutions of [β-¹⁵N]-labelled p-substituted benzenediazonium ions follows dual substituent parameter treatments. The reaction yields a negative field and a positive resonance reaction constant (p_F =?3.35, p_R = 2.47). The magnitude of these constants is, within experimental error, the same as the respective reaction constants for solvolytic dediazoniation. The exchange of the diazonio group of ¹⁵N-labelled p-substituted benzenediazonium ion yields, however, field and resonance reaction constants which are close to zero. This result is attributed to cancellation of the reaction constants for the forward and reverse steps in the complex mechanism of the exchange reaction.     

The kinetic effects of substituted benzoates on the Westphalen rearrangement

The rate of the Westphalen rearrangement of 3β,6β-disubstituted 5α-cholestan-5-ols is influenced by substituted benzoates at the 6β position in a manner which can be correlated with Hammett substituent constants (σ), giving a reaction constant (ρ) of ?0·35.