Synthesis of functionalized azacalix[3]aromatics from azacalix[4]pyrimidine: unexpected macrocyclic transannular reactions

The lower-rim formylated azacalix[4]pyrimidine underwent transannular Friedel–Crafts and dehydrogenative cross coupling reactions to afford, respectively, 2,4,5,7-tetraaza-9,10-dihydroacridine and -dihydroacridin-9-one containing azacalix[3]aromatics. Dihalogenation of the later compound produced resolvable inherently chiral azacalix[3]aromatics.     

25,26,27,28-羟乙氧基-杯[4]芳烃的合成

以对叔丁基苯酚为原料,经4步反应合成了新的杯[4]芳烃衍生物--25,26,27,28-羟乙氧基-杯[4]芳烃,其结构经~1H NMR和MS表征.     

苄连氮桥联双硫杂杯[4]芳烃的合成

硫杂杯[4]二醛基衍生物(1)在水合肼中肼解,合成了新化合物硫杂杯[4]二醛腙基衍生物(2);1和2在弱酸的催化下反应合成了新的具有对称结构的苄连氮双硫杂杯[4]芳烃(3);2和3的结构经1H NMR,IR,ESI-MS和元素分析表征.     

Thiocalix[4] arenes. I. Synthesis and structure of ethylthiocalix[4]arene methyl ether and the related structure of bromocalix[4]arene methyl ether

Bromocalix[4]arene methyl ether serves as a precursor in the synthesis of the title thiocalixarene via the reagent CuSEt. Ethylthiocalix[4]arene methyl ether crystallizes in the monoclinic space groupP2₁/c witha = 20.577(9),b, = 10.722(5),c = 20.315(9) Å, = 120.46(4)°, andD _c = 1.24 g cm^–3 forZ = 4. Refinement based on 1441 observed reflections led toR = 0.080. The configuration of the calixarene lies between the partial cone and the 1,3-altemate conformations. Bromocalix[4]arene methyl ether crystallizes in the triclinic space groupPI witha = 12.283(7),b = 17.658(9),c = 18.118(6) Å, = 90.25(6), = 105.95(4), = 105.11(6)°, andD _c = 1.68 g cm^–3 forZ = 4. Refinement based on 3028 observed reflections led toR = 0.083. The unit cell also contains four CHCl₃ molecules which exist pairwise enclathrated by six calixarenes. The partial cone conformation of the bromocalixarene is identical to that of ethylthiocalix[4]arene methyl ether.     

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．     

苄连氮基桥联的双杯[4]芳烃的合成

对叔丁基杯[4]芳烃-1, 3-二醛基衍生物1分别与水杨醛腙、水合肼进行“1＋2”和“2＋2”缩合反应, 方便地合成了苄连氮基取代或桥联的新型杯[4]芳烃衍生物2和双杯[4]芳烃衍生物3, 产率分别为84%和81%. 新化合物的结构与构象经元素分析、质谱、核磁共振谱和1H-1H COSY谱图等表征证实, 双杯[4]芳烃衍生物3为空间结构完全对称的具有管状三维空腔的杯式构象.     

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 Synthesis of Ester and Ketone Derivatives of Azocalix[4]arene Containing Chromogenic Groups

Azocalix[4]arenes were prepared by linking 4-ethylaniline, 4-n-butylaniline, 4-acetamide aniline and 2-aminothiazol to calix[4]arene through a diazo-coupling reaction. A new family of azocalix[4]arenes, L1–L12, have been prepared by the incorporation of acetyl, benzoyl, and methyl ketone units to azocalix[4]arene. Characterization of the synthesized compounds was carried using elemental analyses, UV–Vis, IR and ¹H NMR spectroscopic studies.     

Synthesis of Thia-calix[4]arene Hydroxamic Acids by Microwave Irradiation

Thia-calix[4]arene hydroxamic acids have been synthesized by partial reduction of nitro-thia-calix[4]arenes with hydrazine hydrate, Rn/Ni, and their coupling with benzoyl chloride under the influence of microwave irradiation with 90–95% yield and 3–6 min reaction time.     

四硫脲基杯[4]芳烃衍生物的合成

对叔丁基杯[4]-1,3-二乙酸乙酯与过量的二乙基三胺反应,生成含有游离氨基的杯芳烃酰胺衍物(2),2再与异硫氰酸苯酯反应合成了含4个硫脲基的杯[4]芳烃衍生物,其结构经1H NMR,IR,MS和元素分析表征。     

A New Efficient Synthesis of p-Nitrocalix[4]arene

A new efficient synthesis of p-nitrocalix[4]arene from calix[4]arene by using nitrogen dioxide is described.The compound is an useful intermediates for the introduction of other functional groups to obtain N containing substituted calix[4]arene.The reaction mechanism is briefly discussed.     

Synthesis of Flavin–Calix[4]arene Conjugate Derivatives

The synthesis of two new flavin substituted calix[4]arene derivatives, 9 and 10 , is described. The first flavin substituted calix[4]arene derivative 9 was synthesized by the reaction of 3‐methylalloxazine ( 5 ) with 25,27‐bis(3‐bromopropoxy)‐26,28‐dihydroxy‐5,11,17,23‐tetra(tert‐butyl)calix[4]arene ( 4 ) in high yield (92%). The other derivative 10 was prepared from 3‐methylalloxazine‐1‐acetic acid ( 7 ) and 25,27‐bis(3‐cyanopropoxy)calix[4]arene ( 3 ). All new compounds were characterized by a combination of FT‐IR and ¹H‐NMR spectroscopy, and elemental‐analysis techniques.     

Synthesis of resorcin[4]arene bearing self-folding substituent

Thiomethylation of resorcin[4]arene using N,N-diisopropyl-2-aminoethanethiol hydrochloride and formaldehyde [1:4:4 molar ratio] carried out in methanol/acetic acid [1:1 v/v] at 60 °C produced monofunctionalized product 3 in 68% yield. The introduced substituent was intramolecularly self-included into the cavity. This self-inclusion reduced the reactivity of the aromatic rings and inhibited further functionalization.     

Isolation and X-ray crystal structure of a stable calix[4]arene monohemiketal

The formation of a stable calix[4]arene monohemiketal is described. X-ray crystallographic data provide conclusive evidence for the presence of a stabilizing hydrogen bond. Supplementary Data. Lists of H-atom parameters and bond lengths and angles involving hydrogens have been deposited with the British Library Document Supply Centre as Supplementary Publication No. SUP 82159 (5 pp.).     

Spectrophotometric study of the supramolecular complexes of [60]- and [70]Fullerenes with biscalix[6]arene and crown[4]calix[6]arene

[60]- and [70]Fullerenes have been shown to form 1:1 supramolecular complexes with bis[2-(5,11,17,23,29,35-hexa-tert-butyl-37,38,39,40,41-pentahydroxycalix[6]arenyl-oxy ethyl ether) (1) and 5,11,17,23,29,35-hexa-tert-butyl-37,38,40,41-tetra hydroxyl-39,42-(crown-4)calix[6]arene (2) in CHCl3 medium by electronic absorption spectroscopy. Formation constants (K) of the complexes of [60]- and [70]fullerenes with 1 and 2 have been determined at room temperature from which free energy of formation values of the complexes have been estimated. The very high formation constant value of [60]fullerene/1 complex (5900 dm3 mol-1) in indicative of formation of inclusion complex. Moreover, PM3 calculations reveal that intermolecular interaction between [60]fullerene and 1 proceeds through quite deep energy molecular orbital.     

含酰胺和硫脲单元的杯[4]芳烃衍生物的合成

杯[4]芳烃．1,3-二乙酸乙酯衍生物与水合肼反应生成杯[4]芳烃酰肼衍生物(2),2与异硫氰酸苯酯反应得到新型含酰胺和硫脲单元的杯[4]芳烃衍生物,总产率85％。     

单炔基桥联双杯[4]芳烃的合成与对溶剂分子的包合性能

对叔丁基杯[4]芳烃直接与1,4-二氯-2-丁炔反应,一步制备了单炔基单桥联双杯[4]芳烃和单炔基双桥联双杯[4]芳烃,并证实单桥联双杯[4]芳烃是双桥联双杯[4]芳烃的中间产物.经¹HNMR,¹³CNMR和ESI-MS分析证实了产物的结构.ESI-MS结果表明两种产物对DMF和H₂O有不同的包合能力.     

Synthesis and Characterization of Boron Complex of Calix[4]arene

IthasbeenshownthatcalixarenescanperformselectiveiontranspoFtandformneutralcomplexeswithcanonsthroughprotonlossl.Olmsteadreported'thesynthesisandXraycrystalstructuresofTitanium(IV),Iron(ill)andCobalt(II)complexesofp-tertbutylcalix[4]areneandfoundthatacompleteexchangeofallfourOHgroupsinp-lertbutylcalix[4]arenetookplacewhentreatedwithTi(NMe=).togivethearyloxocomplex[{Ti(p-lerl-butylcalix[4]arene)},]'6whichmaybeformallydescribedasacentrosymmetrictitaniumaryloxidedimerconsistingoftwoTi(P-lerl…     

Synthesis of Schiff Base Calix [4] arene Crowns

This letter reports the synthesis of Schiff base calix [4] arene crowns containing m-xylylene phenol subunit, in which calix [4] arene Schiff base crowns 2a,2b and 2c were formed by 1:1 condensation of calix [4] arene diamine 1 with dialdehydes (2,6-diformyl-4-chlorophenol 3a,2,6-diformyl-4-methylphenol 3b,2,6-diformyl-4-tert-butylphenol 3c)under high dilute condition in refluxing anhydrous ethanol in 65-70% yield.     

杯[4]芳烃四丁醚的选择性硝化

硝化反应;杯[4]芳烃四丁醚的选择性硝化