Dialkylaminomethylated Calix[4]resorcinarenes. Reaction with Carboxylic Acids

5,11,17,23-Tetrakis(N,N-dimethylaminomethyl)-2,8,14,20-tetranonylcalix[4]resorcinolarene was found to form in solutions host-guest complexes with tartaric, phthalic, and succinic acids; the stability of the complexes depends on the degree of protonation of the host in the complex and the structure of the guest.     

Reactions of P(III)-Halides with Calix[4]Resorcinarenes

Abstract

Reactions of calix[4]resorcinarenes, bearing aliphatic radicals of different length, with P(III)-halides results in the formation of cyclic chlorophosphites and chlorophosphates.     

N-硫脲基套索杯[4]冠醚与四硫脲基杯[4]芳烃的合成

控制反应物的物质的量比, 杯式对叔丁基杯[4]-1,3-二乙酸乙酯衍生物1与5或50倍二乙烯三胺反应, 分别得到杯[4]氮杂冠醚2和开链的氮杂杯[4]芳烃衍生物3. 化合物2和3进一步与异硫氰酸苯酯反应得到首例侧链含硫脲基的套索杯[4]氮杂冠醚4和含4个硫脲基的杯[4]芳烃衍生物5, 产率为92%和87%. 新化合物的结构与构象经元素分析、红外、质谱、核磁共振谱等表征证实.     

The (Calix[4]arene)chloromolybdate(IV) anion [MoCl(Calix)](-): a convenient entry into molybdenum Calix[4]arene chemistry

The complex (HNEt(3))[MoCl(NCMe)(Calix)] (1), prepared from the reaction of [MoCl(4)(NCMe)(2)] with p-tert-butylcalix[4]arene, H(4)Calix, in the presence of triethylamine, has been used as a source of the d(2)-[Mo(NCMe)(Calix)] fragment. Complex 1 is readily oxidized with PhICl(2) to afford the molybdenum(VI) dichloro complex [MoCl(2)(Calix)] (2). Both complexes are a convenient entry point into molybdenum(VI) and molybdenum(IV) calixarene chemistry. The reaction of 1 with trimethylphosphine and pyridine in the presence of catalytic amounts [Ag(OTf)] led to the formation of neutral d(2) complexes [Mo(PMe(3))(NCMe)(Calix)] (3) and [Mo(NC(5)H(5))(NCMe)(Calix)] (4). The role of the silver salt in the reaction mixture is presumably the oxidation of the chloromolybdate anion of 1 to give a reactive molybdenum(V) species. The same reactions can also be initiated with ferrocenium cations such as [Cp(2)Fe](BF(4)). Without the presence of coordinating ligands, the dimeric complex [[Mo(NCMe)(Calix)](2)] (5) was isolated. The reaction of 1 with Ph(2)CN(2) led to the formation of a metallahydrazone complex [Mo(N(2)CPh(2))(NCMe)(Calix)] (6), in which the diphenyldiazomethane has been formally reduced by two electrons. Molybdenum(VI) complexes were also obtained from reaction of 1 with azobenzene and sodium azide in the presence of catalytic amounts of silver salt. The reaction with azobenzene led under cleavage of the nitrogen nitrogen bond to an imido complex [Mo(NPh)(NCMe)(Calix)] (7), whereas the reaction with sodium azide afforded the mononuclear molybdenum(VI) nitrido complex (HNEt(3))[MoN(Calix)] (8).     

Phosphorylation of oxyethylated resorcinol and calix[4]resorcinarene with P(III) acid amides

Abstract

Phosphorylation of 1,3-bis(2-hydroxyethoxy)benzene and octa(2-hydroxyethyl) calix[4]-resorcinarenes with P(III) acid amides and chloramides has been studied. It has been determined that the nature of phosphorous acid amides affects significantly the synthetic result of the reaction.     

Chlorination of Calix[4]arene Derivatives

New convenient method for synthesis of p-chlorinated calix[4]arenes is reported. The sulfuryl chloride was used for chlorination of unsubstituted at the lower rim calix[4]arenes. The products of this reaction were very suitable for further O-alkylation.     

Hydrophosphoryl Derivatives of Calix[4]resorcinolarenes

Russian Journal of General Chemistry -     

一些新型含氮、硫杂官能团的杯[4]芳烃衍生物的合成

以杯[4]芳烃-1,3-二溴乙氧基衍生物1为合成平台,在K2CO3/MeCN体系中分别与乙醇胺、L-亮氨醇、2-巯基苯并咪唑、巯基乙酸乙酯反应,以49%～76%的产率合成了4种新型含氮、硫杂官能团的杯[4]芳烃衍生物2,4,5和6.化合物2进一步与异硫氰酸苯酯反应,以84%的产率得到了新型树枝状杯[4]芳烃氮、硫杂衍生物3.新化合物的结构与构象经元素分析、质谱、核磁共振谱等表征证实.     

Phosphorylation of Dialkylaminomethyl-substituted Calix[4]resorcinolarenes with Hexaalkylphosphorous Triamides and Phosphorus(V) Dichlorides

A series of aminophosphino cavitands were synthesized by reactions of dialkylaminomethyl-substituted calix[4]resorcinolarenes with hexaalkylphosphorous triamides, and their properties were studied. New aminoalkylated (thio)phosphato(phosphonato) cavitands were prepared by phosphorylation of dialkylaminomethyl-substituted calix[4]resorcinolarenes with phosphorus(V) dichlorides in the presence of a base. Their reactions with electrophilic alkylating agents (methyl trifluoromethanesulfonate, methyl iodide, and triethyloxonium tetrafluoroborate) were examined.     

Synthesis of Calix[4]resorcinarene Amide Derivatives

Three different synthetic routes were developed to introduce carbamoyloxy functional groups at the upper periphery of two calix[4]resorcinarenes. By treating activated esters 2a-b with excess corresponding amine such as 3-(dimethylamino)propylamine 3, ct-phenethylamine 4 and triethylenetetramine 5, six amide derivatives 6a-8b were obtained in high yield (Route 1). The pyridine-linked amide derivatives 9a-b were prepared by using acid chloride intermediate (Route 2).The amide derivatives 10a-b were obtained in moderate yields by direct alkylation of phenolic hydroxyl groups of la-b with N,N-dipropylchloroacetoamide in the presence of K2CO3/KI in acetone (Route 3).     

丙醛间苯二酚杯[4]芳烃烷基化衍生物的合成

以间苯二酚和丙醛为原料合成了丙醛杯[4]芳烃(1),1经不同的烷基化反应合成了新的丙醛杯[4]芳烃烷基化衍生物,其结构经1H NMR和IR表征。     

Darstellung und Struktur neuer Calix[4]aren-Titan(IV)-Imidokomplexe

Synthesis and Structure of New Calix[4]arene Titanium(IV) Imido Complexes The syntheses of the novel calix[4]arene titanium imido compounds [Cax(OMe)₂O₂Ti(NR)] ( 2 ) (R = tBu) and ( 3 ) (R = Mes = 2,4,6-trimethylphenyl) (Cax = C₄₄H₅₂) starting from [Cax(OMe)₂O₂TiCl₂] ( 1 ) and lithium amides LiNHR are described. Complexes 2 and 3 are mononuclear compounds in solution. An X-ray crystal structure analysis of the toluene adduct of 3 (Space group: P 1, lattice dimensions: a = 12.979(2) Å, b = 13.707(2) Å, c = 16.573(3) Å, α = 81.751(11)°, β = 80.555(13)°, γ = 73.541(12)°) reveals that this compound is mononuclear in the solid state. The central atom in 3 is distorted trigonal bipyramidal ligated by two ether oxygen atoms in axial positions, two phenoxide oxygen atoms in the equatorial plane, and an imido nitrogen atom in an equatorial position. The titanium nitrogen bond distance in 3 is 171.8(3) pm.     

Synthesis of Calix[4]arene Derivatives with NLO Properties

The new chromophore compounds with NLO properties were prepared by Knoevenagel condensation from forrnyl or diformyl calix[4/arene and isophorone derivatives in the presence of piperidine and acetic acid, respectively. In these chromophore calix[4]arenes, the ring locked trienes were employed as the conjugation bridge and electron acceptor in D-π-A units. The NMR spectra demonstrated that they existed in a cone conformation and consequently non-conjugated D-π-A units could be oriented at nearly the same direction.     

杯芳烃衍生物的合成和性质的研究(Ⅴ)

通过对特丁基杯[4]芳烃的酚羟基的选择性醚化制备了一系列一烃基,1,3-二烃基和四烃基醚,烃基分别含有缩醛、酰胺、氰基等活泼官能团.醚化反应的区域选择性主要取决于使用的碱的种类和反应时间的长短.     

新型正丁醛杯[4]芳烃醚衍生物的合成

以正丁醛间苯二酚杯[4]芳烃为原料,经酯化、水解、酰氯化后再与9-蒽甲醇反应,合成了蒽单取代的正丁醛间苯二酚型杯[4]芳烃醚衍生物。其结构经1H NMR和IR表征。     

新型多重氮杂杯[4]芳烃衍生物的合成

对叔丁基杯[4]芳烃-1,3-二醛基衍生物1与水杨酰肼、烟酰肼、异烟酰肼反应, 合成了具有开链结构新型杯[4]多重氮杂衍生物2a～2c, 产率分别为88%, 85%和90%. 化合物1与乙二酰肼、丙二酰肼、己二酰肼反应, 得到具有桥联结构的新型杯[4]多重氮杂衍生物3a～3c, 产率分别为86%, 89%和90%. 新化合物的结构经元素分析、质谱、核磁共振谱等表征证实, 杯[4]芳烃单元均为1,3-取代且采取锥式构象.     

新型杯[4]芳烃衍生物的合成

以对叔丁基杯[4]芳烃为起始原料,通过一步或两步取代反应合成了对叔丁基杯[4]芳烃的衍生物(1和2),其结构经FT-IR,^1H NMR,FAB-MS表征．     

Synthesis and Characterization of Calix[4]arene Functionalized Poly(ethylene glycol) Derivatives

Calix[4]arenes with both ligating and methoxy poly(ethylene glycol) groups appended have been synthesized using several approaches, involving the formation of sulfonyl ester groups on the wide rim, Schiff base derivatives on the narrow rim, and thioether groups on both the wide and narrow rims. These new derivatives have been characterized by a combination of infrared and ¹H NMR spectroscopy. Compounds 10 and 11 are insoluble in both water and aqueous poly(ethylene glycol), but the other new compounds are soluble.     

Microwave-Assisted and Thermal Synthesis of Calix[4]arene Derivatives

Russian Journal of Organic Chemistry - Some tert-butylcalix[4]arene derivatives were synthesized by thermal and microwave methods. The microwave method was conducted in two ways: (1) all the...     

Complex Formation of Some Tetraamido-type Calix[4]arene Derivatives Detected by Vibrational Spectroscopy

Abstract

Dibenzo-14-crown-4 alcohols are shown to aggregate in chloroform by the formation of hydrogen-bonded dimers. Structural variations between crown ether alcohols significantly affect the degree of dimerization. This self-association is of relevance for understanding the complexation and extractive properties of these and related macrocycles.