对-甲苯乙酮与芳香醛和芳香胺的Mannich反应

Mannich反应是合成新化合物的重要方法 [1] ,其对应的产物 Mannich碱常常具有广泛的生物活性 [2 ] .文献报道 ,对 -甲苯乙酮的 Mannich碱具有抑癌 [3]和麻醉拮抗 [4 ]等生物活性 ,但是文献中对 -甲苯乙酮 Mannich碱的合成却是从胺交换法 [5] 、酮交换法 [6] 、查耳酮与胺的 Michael加成[7] 、Schiff碱与酮的缩合 [8～ 14 ] 、β-内酰胺与有机锂的亲核裂解 [15] 等间接方法得到的 .即使是从直接法合成 ,一般也是甲醛参与的 Mannich反应 .虽然芳香醛和芳香胺同时参与的 Mannich反应已有报道 [16] ,但对 -甲苯乙酮与芳香醛和芳香胺直接进行…     

Low cost bifunctional initiators for bidirectional living cationic polymerization of olefins. I. isobutylene

We describe the discovery of novel low cost bifunctional initiators 2,4,7,9‐tetramethyl‐tricyclo[6.2.0.0³⁶]deca‐1(8),2,6‐triene‐4,9‐diol (bBCB‐diOH) and 4,9‐dichloro,2,4,7,9‐tetramethyl‐tricyclo[6.2.0.0³⁶]deca‐1(8),2,6‐triene (bBCB‐diCl), for living cationic bidirectional polymerization of olefins, for example, isobutylene. bBCB‐diOH was quantitatively synthesized in one step by UV radiation of commercially available diacetyl durene (DAD) and bBCB‐diCl by hydrochlorination of bBCB‐diOH. These molecules, in conjunction with TiCl₄ coinitiator, initiate the living polymerization of isobutylene. Livingness was demonstrated by linear conversion versus molecular weight (MW) plots and narrow MW distributions. Polymerizations are slower than those initiated by the universally used “hindered” bifunctional initiator 5‐tert‐butyl‐1,3‐bis(1‐chloro‐1‐methyl)benzene and are suitable for rate studies. Herein, we report the synthesis, by the use of bBCB‐diCl, of relatively low MW (M _n < 3000 g mol^?1) allyl‐telechelic polyisobutylene (PIB) used for the synthesis of PIB‐based polyurethanes and that of relatively high MW (M _n > 30,000) living PIB telechelics for the synthesis of thermoplastic elastomers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3716–3724     

Paradigms and paradoxes: analysis of the site of protonation of bifunctional organic compounds with the protonation energy/volume computation method

This study extends the empirical protonation energy/volume comparison method to the prediction of the site of protonation of multifunctional organic compounds, in particular to amino alcohols.     

Spirocyclohexadienones. 7. Three-component condensation of 1- or 2-methoxynaphthalene with isobutyraldehyde and nitriles

1-R-3,3-Dimethylbenzo[i]-2-azaspiro[4.5]deca-1,6-dien-8-ones or 1-R-3,3-dimethylbenzo[i]-2-azaspiro[4.5]deca-1,7-dien-6-ones were synthesized by three-component condensation of 1- or 2-methoxynaphthalene, isobutyraldehyde (or isobutylene oxide), and nitrile RCN in concentrated sulfuric acid.     

General equation for determining the dissociation constants of polyprotic acids and bases from additive properties. Part I. Theory

Measured additive properties of polyprotic acids and bases as functions of the pH of the solution can be used for the determination of the dissociation constants. A rigorous general equation is derived in this paper for this purpose. The equation relates the additive property of the acid or base to the dissociation constants, the limiting values and activity coefficients of the solute species, and to the pH of the solution. The equation is used to obtain the dissociation constants by fitting it to the experimental data in a nonlinear least-square fitting procedure. Overlapping dissociation constants pose no problem in this method. Applications to spectrophotometry and reversed-phase high performance liquid chromatography are presented in a following paper (Part II of this series).     

On stability and protonation of multielectron systems: The concept of proton affinity. II. Dissociative proton attachment and protonation—Deprotonation mapping

A few touches on the thematic palette “molecular protonation” directly linked to the concept of molecular stability have been accomplished. They are of different nature, of different origin, and taken from “different angles” of lighting; however, together, they definitely provide a sufficiently complete picture “The protonation interaction, as being strong enough, may break the stability of molecules subject to protonation.” © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

Chiral recognition of the Schiff bases by NMR spectroscopy in the presence of a chiral dirhodium complex. Deuterium isotope effect on 13C chemical shift of the optically active Schiff bases and their dirhodium adducts

The dirhodium method has been successfully applied in chiral recognition of the optically active Schiff bases, derivatives of ortho-hydroxyaldehydes existing in the NH-form. or at tautomeric equilibrium. The position of the equilibrium of Schiff bases as well as their adducts has been established on the basis of measurements of deuterium isotope effects on 13C chemical shifts. The presence of the proton transfer equilibrium or NH-tautomer has promoted the adduct formation. At the equilibrium state, formation of the adducts has shifted the proton transfer equilibrium towards the NH-form. The binding site was the oxygen atom of the proton donor group.     

芳杂环腈及其聚合物XV. 不同结构芳香族腈的聚合及其聚合物结构的测定

本文研究了十二种不同取代基的芳香族腈在Lewis酸-金属体系催化下的聚合反应。结果表明, 取代基的吸电子能力越强, 聚合反应速率越快。其速率常数与Hammett方程中的取代基特性常数σ值呈线性关系, 此外, 对聚合物的结构也进行了测定。     

Synthesis,characterization, DNA interaction and cleavage activity of new mixed ligand copper(II) complexes with heterocyclic bases

Mixed ligand complexes having the formulae Cu(RPO)₂Py₂, Cu(RPO)₂Im₂ and Cu(DBO)₂Py₂ [RPO = resacetophenone oxime, DBO = 2,4-dihydroxybenzophenone oxime, Py = pyridine and Im = imidazole] have been synthesized and characterized by UV–Vis, IR, ESR, cyclic voltammetry and magnetic susceptibility methods. Absorption studies revealed that each of these octahedral complexes is an avid binder of calf thymus DNA. The apparent binding constants for mixed ligand complexes are in order of 10⁴–10⁵ M⁻¹. Based on the data obtained in the DNA binding studies a partial intercalative mode of binding is suggested for these complexes. The nucleolytic cleavage activity of the adducts was carried out on double stranded pBR322 circular plasmid DNA by using a gel electrophoresis experiment in the presence and absence of oxidant (H₂O₂). All the metal complexes cleaved supercoiled DNA by hydrolytic and oxidative paths. The oxidative path dominates the hydrolytic cleavage. The hydrolytic cleavage of DNA is evidenced from the control experiments showing discernable cleavage inhibition in the presence of the hydroxyl radical inhibitor DMSO or the singlet oxygen quencher azide ion.     

The correlation of proton affinities with atomic charges and electronegativities for the group 14 to 17 hydrides

Proton affinities for hydrides of formula $\mathrm{AH}^{-}_{n-1}$ containing the elements A from the second to the fifth period of the periodic table and groups 14 to 17 are predicted at the Hartree–Fock, MP2 and B3LYP levels of theory employing both core potential basis sets and the 3‐21G basis set. The core potential methods perform well when compared with all electron calculations using the 3‐21++G** basis set. The proton affinities of the hydrides containing elements from groups 15 and 16 of the periodic table are more accurate than those with elements from groups 14 and 17. A cancellation of errors appears to occur more completely if the protonated and nonprotonated molecules contain both bond and lone pairs before and after the protonation reaction. Proton affinities correlate nearly linearly with the atomic charges on the hydrogen atoms when these charges are determined by the generalized atomic polar tensor (GAPT) method. This tendency can be associated, in principle, with the group electronegativities as introduced by Iczkowski and Margrave. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 1119–1131, 2000     

Chiral recognition of Schiff bases by 15N NMR spectroscopy in the presence of a dirhodium complex. Deuterium isotope effect on 15N chemical shift of the optically active Schiff bases and their dirhodium tetracarboxylate adducts

Optically active Schiff bases, derivatives of ortho-hydroxyaldehydes and their adducts with dirhodium tetracarboxylate complexes have been studied by (15)N NMR spectroscopy. The position of the equilibrium of Schiff bases, as well as their adducts, has been established on the basis of measurements of deuterium isotope effects on (15)N chemical shifts. At the equilibrium state, the formation of the adducts with dirhodium complexes shifted the proton-transfer equilibrium towards the NH-form.     

微波干法催化芳香醛与绕丹宁及N-苯基绕丹宁的缩合反应

利用微波辐射和固体碱性载体试剂催化绕丹宁及N-苯基绕丹宁和芳香醛的缩合反应合成了14个绕丹宁衍生物并研究了影响反应的因素。     

微波干法催化芳香醛与绕丹宁及N－苯基绕丹宁的缩合反应

利用微波辐射和固体碱性载体试剂催化绕丹宁及Ｎ－苯基绕丹宁和芳香醛的缩合反应合成了１４个绕丹宁衍生物并研究了影响反应的因素。     

Intramolecular interactions I. The use of someMannich bases of naphthols as model compounds for intramolecular hydrogen bonding

Some model compounds for intramolecular hydrogen bonding are presented. The nmr, IR, UV and fluorescence spectra are shown to be suited for the study of such hydrogen bonds.

---

Intramolekulare Wechselwirkungen, I. Einige Mannich-Basen von Naphtholen als Modellverbindungen für intramolekulare Wasserstoffbrückenverbindung

Zusammenfassung Eine Klasse von Verbindungen zur Untersuchung von intramolekularen Wasserstoffbrücken wird vorgestellt. NMR-, IR-, UV- und Fluoreszenzspektroskopie sind bestens geeignet, derartige Wasserstoffbrücken zu studieren.

     

Cyclopalladation of Schiff's bases in the ruthenocene series. The possibility of application of the asymmetric version of the reaction to metalloceneimines

p-Tolyliminoalkylruthenocenes—Schiff's bases of the ruthenocene series—react with sodium tetrachloropalladate in the presence of carboxylate anion similarly to their ferrocenyl analogs to give cyclopalladation products. The optical rotation values of the products resulting from carbonylation of palladated ferrocene and ruthenocene aldimines, prepared under conditions of asymmetric catalysis, followed by liberation of the aldehyde group were used to determine the stereochemistry and enantiomeric purity of the cyclopalladation products. Centre Nationale de Recherches Scientifiques, URA 419 4, pl. Jussieu, Bat. F, 75252 Paris, France. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1421–1424, July, 1998.     

Low cost bifunctional initiators for bidirectional living cationic polymerization of olefins. II. hyperbranched styrene–isobutylene–styrene triblocks with superior combination of properties

Both bifunctional initiators, the new low cost bBCB‐diCl [4,9‐dichloro,2,4,7,9‐tetramethyl‐tricyclo[6.2.0.0³⁶]deca‐1(8),2,6‐triene] and the universally used “hindered” HDCCl [1‐(tert‐butyl)‐3,5‐bis(2‐chloropropan‐2‐yl)benzene] induce the living bidirectional block copolymerization of isobutylene (IB) followed by styrene (St), and produce PSt‐b‐PIB‐b‐PSt (SIBS) triblocks. We discovered that the molecular weights of triblocks kept significantly increasing long after St conversion reached completion during syntheses. Results were explained by the formation of blends consisting of the expected linear SIBS plus hyperbranched SIBS, HB(SIBS)_n. The structure of high molecular weight (>10⁶ g/mol) HB(SIBS)_n was characterized by various techniques, and key properties of SIBS/HB(SIBS)_n blends were investigated. The mechanism of HB(SIBS)_n formation and the synthesis of SIBS/HB(SIBS)_n blends was elucidated. The properties of SIBS/HB(SIBS)_n blends are superior to those of SIBS. Thus, whereas SIBS exhibits ∼25 MPa tensile strength and ∼450% elongation, SIBS/HB(SIBS)_n blends exhibit 25–27 MPa tensile strength and >400% elongation; deformation under constant load of SIBS is ∼12%, whereas that of SIBS/HB(SIBS)_n is <1%; permanent set of SIBS is 1.3% whereas that of SIBS/HB(SIBS)_n is <0.5%. SIBS/HB(SIBS)_n blends also exhibit higher yield, yield strength, and toughness than SIBS. The microstructure/property relationship of HB(SIBS)_n is discussed and the reasons for enhanced properties of SIBS/HB(SIBS)_n blends are analyzed. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 705–713     

A molecular orbital study of lithium ion association with bases. I. The carbonyl bases R2CO

Ab initio SCF calculations have been performed to determine the relative lithium ion affinities of the carbonyl bases R₂CO and the structures of the complexes R₂COLi⁺. The predicted order of lithium ion affinity for the bases R₂CO with respect to R is NH₂ > CH₃ > OH> H> F. Except for (OH)₂COLi⁺ which has C_a, symmetry, the complexes R₂COLi⁺ have C_2v symmetry, with the lithium ion located on the symmetry axis near the oxygen. The major structural changes in the intramolecular coordinates of the bases which occur upon lithium ion complexation include an increase in the carbonyl C---O bond length, a decrease in the length of the bond from the carbonyl carbon to the substituent atom X, and an increase in the X---C---X angle at the carbonyl carbon. The energetic, structural, and electronic properties of the complexes indicate that the interaction between the lithium ion and a carbonyl base is predominantly an ion-dipole attraction rather than a covalent interaction.     

The thermal behaviour of some Co(II) complex combinations with schiff bases

In order to evidence the ligand influence on the thermal stability for Co(II) complex combinations, we have synthesized five complex combinations of this metal with Schiff bases obtained by condensation of ethylenediamine with acetylacetone and benzoylacetone; phenylenediamine with benzoylacetone and also anthranilic acid with benzaldehyde. This revised version was published online in July 2006 with corrections to the Cover Date.     

Carbenoid reactions of trifluoromethylelement compounds. Part 4. Reactions of trifluoromethylzinc bromide with enamines and methylene bases

The reactions of ZnBr(CF₃)·2CH₃CN with 1-morpholinocyclo-pentene and -hexene have been investigated and found to yield mixtures of two isomers of 1-morpholino-1-cyanomethyl-2-difluoromethyl-cyclopentane and -hexane, respectively. The interaction with methylene bases of nitrogen heterocycles leads to the formation of trimethinecyanine dyes. This reaction sequence includes the formation of two carbon-carbon bonds in a one-pot operation. The mechanism of the reactions is discussed.