极化效应指数与脂肪族胺、醇和醚气相碱性的关系

脂肪族胺、醇和醚的气相质子亲合能(PA)与N, O原子所带电荷(qx)以及烷基的极化效应指数(PEI)的关系可表示为其中a、b、c为系数。回归分析结果表明, 上式较好地表达了脂肪族胺、醇和醚的气相碱性变化规律。     

脂肪族胺、醇和醚气相碱性的通用表达式

脂肪族胺、醇和醚气相质子亲合能(PA)与N、O原子所带电荷(qx)、烷基的极化效应指数(PEI)以及N、O原子的sp^3杂化轨道能量[Ex(sp^3)]的并系可以表示为：PA(kj/mol)=2383.5547-1060.3351qx+59.4247∑PEI-117.0142Ex(sp^3)。上式较好地表达了脂肪族胺、醇和醚气相碱性的共同规律。     

诱导效应指数与脂肪族胺、醇和醚的气相碱性

用烷基诱导效应指数I和RX分子中质子亲合原子X所带电荷qx及元素电负性XN与 脂肪胺，醇、醚的气相质子亲合PA进行关联，结果表明，脂肪胺，醇、醚的气相碱 性可以用下式定量描述：PA(kJ.mol^-1)-2732.0333-2457.1510∑I-1492.2351qx- 732.6277XN利用上式对64种化合物的气相碱性进行预测，平均相对误差为0．34％ ，预测值和实验值的偏差均在实验误差范围内。     

胺、醇和醚类化合物电离能的估算

脂肪族胺、醇、醚、硫醇和硫醚的第一电离能Ip与N、O、S原子的电负性X~Z^O、分子中N、O、S原子的部分电荷q~z以及烷基的极化效应指数PEI的关系可以表示为:Ip(eV)=4.4851+3.0727X~Z~O+7.1702q~z-1.3949∑PEI上式较好地表达了脂肪族胺、醇、醚、硫醇和硫醚的第一电离能变化的共同规律。     

计算脂肪族胺、醇和醚的气相碱性的经验公式

本文给出计算脂肪族胺、醇和醚气相碱性的经验公式。由公式得出的PA值与ICR实验值接近。     

脂肪族醇、醚、胺电子效应对其气相碱性的影响

有机物的气相碱性是指有机物分子在气相条件下与质子的亲合能力，通常用化合物的气相质子亲合能（PA）来表示，由于受到分子中不同取代基甚至不同空间构象的影响往往不同，因而很难测定。长期以来人们都是在溶液中测定有机物的碱性，高压质谱（HPMS）和离子回旋共振（ICR）等高新技术的发展和应用，使得人们在气相条件下测定分子本身固有的相对碱性成为可能。气相碱性比溶液中的碱性更能直接反映出化合物的分子结构特征，有利于有机化合物结构-性能／活性（QSPR／QSAR）关系的研究。     

胺、醇、醚类化合物电离能的自相关拓扑研究

原子的染色序数 fi 定义为 :fi=gi·xi,式中 gi 为原子i在分子中的序数 ,xi 为其染色系数 .基于fi 建立改进的原子序数自相关拓扑指数mF ,其中的1F对烷烃及其衍生物具有良好的结构选择性 .使用第一电离能 (Ip)与0 F ,1F的数量关系模型对 32种脂肪族胺、醇、醚进行估算、预测 ,结果令人满意     

胺、醇、醚类化合物气相碱性的CNDO/2计算

用CNDO/2方法计算了近七十种含氮及含氧化合物的气相碱性。对脂肪胺、醇和醚,羰基化合物等系列,所得结果与实验值在次序上一致。讨论了这些化合物的气相碱性与分子中的电荷分布及电离势的关系。     

分子极化效应指数与脂肪族醛酮的沸点

建立物质的定量结构—活性相关性(QSAR)和定量结构—性质相关性(QSPR)的研究一直受到化学工作者的关注。用拓扑指数研究饱和烃的各种物理化学性质已经有大量报道1 4。本文讨论了分子极化效应指数[5]与脂肪族醛酮沸点的关系,力求寻找到一个适用范围广,并且具有分子结构特征的计算脂肪族醛酮沸点的计算公式。1　分子结构参数的确定脂肪族醛酮分子中羰基的存在,使相同碳原子数的醛酮沸点比烷烃升高很多。我们以醛酮分子中的烷基极化效应指数(PEI)的差值(ΔPEI)[6]来表示羰基位置对醛酮沸点的影响:ΔPEI=PEIB,N-PEInrm,N(1)式中,…     

丹酰氯柱前衍生高效液相色谱测定痕量脂肪族仲胺

脂肪族仲胺在适宜条件下很容易形成强致癌物N-亚硝基化合物,因此研究N-亚硝基化合物及其前身物脂肪族仲胺的灵敏和准确的测定方法是研究癌变过程及其机理的前提条件。 丹酰氯作为荧光衍生试剂已广泛应用于氨基酸、生物胺和多胺的高效液相色谱分析,但应用于测定脂肪族仲胺尚未见报     

价电子均衡电负性及其应用

We take the contribution of all valence electrons into consideration and propose a new valence electrons equilibration method to calculate the equalized electronegativity including molec-ular electronegativity, group electronegativity, and atomic charge. The ionization potential of alkanes and mono-substituted alkanes, the chemical shift of ¹H NMR, and the gas phase proton affinity of aliphatic amines, alcohols, and ethers were estimated. All the expressions have good correlations. Moreover, the Sanderson method and Bratsch method were modified on the basis of the valence electrons equilibration theory. The modified Sanderson method and modified Bratsch method are more effective than their original methods to estimate these properties.     

Zinc(II) perchlorate hexahydrate catalyzed opening of epoxide ring by amines: applications to synthesis of (RS)/(R)-propranolols and (RS)/(R)/(S)-naftopidils

Commercially available zinc(II) perchlorate hexahydrate [Zn(ClO4)2.6H2O] was found to be a new and highly efficient catalyst for opening of epoxide rings by amines affording 2-amino alcohols in high yields under solvent-free conditions and with excellent chemo-, regio-, and stereoselectivities. For unsymmetrical epoxides, the regioselectivity was influenced by the electronic and steric factors associated with the epoxides and the amines. A complementarity in the regioselectivity was observed during the reaction of styrene oxide with aromatic and aliphatic amines: aromatic amines provided amino alcohols from nucleophilic attack at the benzylic carbon as major products whereas aliphatic amines resulted in formation of the amino alcohols through reaction at the terminal carbon atom of the epoxide ring as the major/sole products. Reaction of aniline with various glycidic ethers gave the amino alcohols by regioselective nucleophilic attack at the terminal carbon atom of the epoxide ring as the only/major product. Zinc(II) perchlorate hexahydrate was found to be the best catalyst compared to other metal perchlorates. The counteranion modulated the catalytic property of the various Zn(II) compounds that followed the order Zn(ClO4)2.(6)H2O>Zn(BF4)2 approximately Zn(OTf)2>ZnI2>ZnBr2>ZnCl2>Zn(OAc)2>Zn(CO3)2 in parallelism with the acidic strength of the corresponding protic acids (except for TfOH). The applicability of the methodology was demonstrated by the synthesis of cardiovascular drugs propranolol and naftopidil as racemates and optically active enantiomers.     

On molecular polarizability: 3. Relationship to the ionization potential of haloalkanes, amines, alcohols, and ethers

The relationship between the ionization potential and the parameters molecular electronegativity and molecular polarizability for haloalkanes, amines, alcohols, and ethers was investigated. There is no good linear correlation between the ionization potential Ip and molecular electronegativity chi(eq) alone for these compounds. Ip can be modeled well with three parameters: chi(eq), polarizability effect index (PEI) of an alkyl group, and atomic polarizability (P). Further, a single expression for predicting the Ip values of aldehydes, esters, nitriles, and carboxylic acids was developed: Ip(Rz)(eV) = Ip(MeZ) + 1.4544delta chi(eq) - 1.6435delta sigmaPEI(Ri). Here Ip(MeZ) is the experimental ionization potential of monosubstituted methane MeZ. Delta chi(eq) and delta sigmaPEI(Ri) are the difference in the molecular electronegativity and the difference in the polarizability effect index of alkyl groups attached to the functional group Z between molecules MeZ and RZ, respectively.     

Reaction gas chromatography/mass spectrometry. 2—the use of catalytic on-line dehydrogenation for the investigation of alcohols by gas chromatography/mass spectrometry

A method for structure determination of aliphatic alcohols within mixtures is described. It involves the use of a vapour phase dehydrogenation micro-reactor (Cu, 300°C) located between the chromatographic column and the mass spectrometer or between the injection port and the column. Since primary and secondary alcohols are converted into corresponding carbonyl compounds, they can be readily differentiated from tertiary alcohols and dialkyl ethers. An examination of the mass spectra of alcohols and carbonyl compounds permits the determination of molecular mass, the location of hydroxyl group and the determination of branching at the β-carbon atom.     

Quenching of n,pi*-excited states in the gas phase: variations in absolute reactivity and selectivity

The quenching of the n,pi*-excited azoalkane 2,3-diazabicyclo[2.2.2]oct-2-ene by 19 heteroatom-containing electron and hydrogen donors, that is, amines, sulfides, ethers, and alcohols, was investigated in the gas phase. Deuterium isotope effects were measured for 9 selectively deuterated derivatives. The data support the involvement of an excited charge-transfer complex, that is, an exciplex, for tertiary amines and sulfides, and a competitive direct hydrogen transfer from the C-H bonds of ethers or from the N-H or O-H bonds of secondary and primary amines or alcohols. The recently observed "inverted" solvent effect for the fluorescence quenching of azoalkanes by amines and sulfides in solution is supported by the observed rate constants in the gas phase, which are substantially larger than those in solution. A more pronounced inverted solvent effect for the weaker electron-donating sulfides and a presumably faster exciplex deactivation result in a switch-over in absolute reactivity relative to tertiary amines in the gas phase. Most importantly, the kinetic data demonstrate that the reactivity of the strongly dipolar O-H and N-H bonds in photoinduced hydrogen abstraction reactions shows a larger decrease upon solvation than that of the less polar C-H bonds. The azoalkane data are compared with previous studies on quenching of n,pi*-triplet-excited ketones in the gas phase.     

Rhodium‐Catalyzed Enantioselective Intermolecular Hydroalkoxylation of Allenes and Alkynes with Alcohols: Synthesis of Branched Allylic Ethers

Regio‐ and enantioselective additions of alcohols to either terminal allenes or internal alkynes provides access to allylic ethers by using a Rh^I/diphenyl phosphate catalytic system. This method provides an atom‐economic way to obtain chiral aliphatic and aryl allylic ethers in moderate to good yield with good to excellent enantioselectivities.