Synthesis and structural characterization of new stiff rod oligomeric domains by X-ray crystallography and NMR

The monomers N,N'-dibenzylbenzene-1,4-diamine (1), N,N'-dibenzylnaphthalene-1,5-diamine (2), and N,N'-dibenzylanthracene-1,9-diamine (3) were reacted with phosgene in the presence of a base to produce the corresponding N,N'-dibenzyl-1,4-bis(chlorocarbonylamino)benzene (4), N,N'-dibenzyl-1,5-bis(chlorocarbonylamino)naphthalene (5), and N,N'-dibenzyl-9,10-bis(chlorocarbonylamino)anthracene (6). These monomers were used to create zigzag type stacks, in a stepwise fashion, of trimers and 9-mers of either 1,4-diureidobenzenes ((Phe)K(3) and (Phe)K(9)) or 1,5-diureidonaphthalenes ((Nap)K(3) and (Nap)K(9)). A byproduct in the formation of (Phe)K(9) was a cyclic hexamer (Phe)K(6). NMR gave evidence of the structure in solution while X-ray crystallographic information was obtained for 5, 6, (Nap)K(3), and the cyclic (Phe)K(6).     

Synthesis and Thermal Reaction of 1,3-Bis(alkylseleno)allenes

Reactions of Ph(2)C(3) dianion, prepared from 1,3-diphenylpropyne and n-butyllithium, with dimethyl diselenide and benzylselenocyanate yielded 1,3-bis(methylseleno)-1,3-diphenylpropadiene and 1,3-bis(benzylseleno)-1,3-diphenylpropadiene, respectively, and the reaction with a mixture of dimethyl diselenide and benzylselenocyanate gave 1-benzylseleno-3-methylseleno-1,3-diphenylpropadiene together with the symmetric products. Thermal reactions of the 1,3-bis(alkylseleno)allenes afforded (E)- and (Z)-1,3,4,6-tetraphenyl-3-hexene-1,5-diynes along with compounds derived from cyclic dimer of the allene or diselenide via radical pathway.     

含中心功能基氮支套索冠醚化合物的合成及其钠离子络合物的晶体结构

借模板法由6,9-二氧杂-3,12-二氮杂-十四烷-1,14-二醇分别与4-甲基(或氯)-2,6-二溴甲基苯甲醚在乙腈中, 以无水碳酸钠为缩合剂, 制得两种尚未见文献报道的含中心功能基氮支套索冠醚化合物: N,N'-二羟乙基-16-甲基-18-甲氧基-6,9-二氧杂-3,12-二氮杂-二环[12.3.1]十八-1(18),14,16-三烯(4a)和N,N'-二羟乙基-16-氯-18-甲氧基-6,9-二氧杂-3,12-二氮杂-二环[12.3.1]十八-1(18),14,16-三烯(4b)的钠离子络合物3a和3b。4a和4b经元素分析、红外光谱、核磁共振谱和质谱证实其组成和结构。借四圆衍射仪测定了3b的晶体结构和分子结构。     

Synthesis of 3,3-bis(2-hydroxyethyl) and 3,3,3’-tris(2-hydroxyethyl) derivatives of 1,1’-[methylenebis(oxy)]bis(triaz-1-ene 2-oxides)

Synthetic procedures to access new potential NO donors that can generate NO in living systems, 3,3-bis(2-hydroxyethyl) and 3,3,3’-tris(2-hydroxyethyl) derivatives of 1,1’-[methylenebis(oxy)]bis(3,3-dialkyltriaz-1-ene 2-oxides), were elaborated. 3,3-Bis(2-acetoxyethyl)-1(chloromethoxy)triaz-1-ene 2-oxide reacts with 1-hydroxytriaz-1-ene 2-oxide sodium salts to give a series of alkylated 3,3-bis(2-acetoxyethyl) derivatives. Deacetylation of the latter produces 3-(2-hydroxyethyl)-11,11-dialkyl-6,8-dioxa-3,4,5,9,10,11-hexaazaundeca-4,9-dien-1-ol 4,10-dioxides and 11-alkyl-3-(2-hydroxyethyl)-6,8-dioxa-3,4,5,9,10,11-hexaazatrideca-4,9-diene-1,13-diol 4,10-dioxides.     

Correlation between C and O chemical shifts and torsional strain in spiroacetals

The relationship between the ¹³C and ¹⁷O NMR chemical shifts and the dihedral energies (non-bonding interactions) of 1,4-dioxaspiro[4.4]nonane, 1,4-dioxa- and 6,10-dioxaspiro[4.5]decane, 1,4-dioxa- and 6,11-dioxaspiro[4.6]undecane, 1,5-dioxaspiro[5.5]undecane, 1,5-dioxa and 7,12-dioxaspiro[5.6]dodecane and 1,6-dioxaspiro[6.6]tridecane were analyzed. These data showed correlation of the non-bonding interactions with the chemical shift of the spiranic carbon, as well as a linear relationship between ¹³C and ¹⁷O.     

Synthesis and characterization of new copperphthalocyanine carrying mixed donor macrocyclic moieties

The new phthalocyanine peripherally substituted with a twelve-membered dioxadiaza macrocycle was synthesized by cyclotetramerization of 1,2-bis(2-{4′-[(4′-methylphenyl)-sulphonyl]-1′,7′-dioxa-4′,10′-diazacyclododecane})-4,5-dicyanobenzene (4) which was obtained from 1,2-bis(2-{4′-[(4′-methylphenyl)sulphonyl]-1′,7′-dioxa-4′,10′-diazacyclododecane})-4,5-dibromobenzene (3). Metallophthalocyanine was also prepared by the reaction of the dicyano-substituted macrocycle in the presence of anhydrous CuCN. The new compounds were characterized by a combination of elemental analysis, ¹H and ¹³C?NMR, IR, electronic and mass spectroscopies.     

Synthesis of aromatic polyethers by scholl reaction. VIII. On the polymerizability of 1,5-bis(phenoxy)pentanes and 1,5-bis(phenylthio)pentane

The synthesis and the oxidative polymerization of 1,5-bis(phenoxy)pentane, 1,5-bis(phenoxy)pentane substituted with various electron-donating groups, and 1,5-bis(phenylthio)pentane is described. The polymers derived from methyl substituted 1,5-bis(phenoxy)pentane monomers contain diphenyl methane, 1,2-diphenylethane, and benzyl chloride structural units. The mechanism for the generation of these structural units is presented. It consists of the proton transfer reactions from the cation-radical propagating species and subsequent reactions of the resulting benzyl radicals. The polymerizability of monomers with 1,5-pentanedioxy group is lower than that of the monomers with diphenyl sulfone group. This dissimilarity was attributed to the difference between both the reactivity and the concentration of the cation-radical propagating species resulted from these two classes of monomers.     

On the synthesis of siloxanes. XXIV. Nucleophilic substitution reactions of 2-functional 1,3-dioxa-2-4,7-trisilacylcloheptanes and 1,3-dioxa-2,4,8-trisilacyclooctanes

2-Hydrogen-1,3-dioxa-2,4,7-trisilacycloheptanes and 2-hydrogen-1,3-dioxa-2,4,8-trisiacyclooctanes, each as a mixture of three configurational isomers, were synthesized and halogenated with chlorine and bromine in the presence of pyridine. The stereochemical course of the halogenation reactions was studied by gas chromatography. 2-Chloro-2,4,7-trimethyl-4,7-bis(trimethyl-siloxy)-1,3-dioxa-2,4,7-trisiacycloheptanes and 2-chloro-2,4,7-trimethyl-4,7-diphenyl-1,3-dioxa-2,4,7-trisilacycloheptanes reacted with alcohols in the presence of pyridine, triethylamine, or 2,6-dimethylpyridine. Gas chromatography, and¹H NMR and²⁹Si NMR spectroscopy were used to investigate the stereochemistry of these substitution reactions. It has been found that all reactions proceed with retention of configuration and that the differences of the relative reactivities of the configurational isomers were distinctly smaller than those observed for reactions of the configurations isomers of functional cyclotrisiloxanes.     

Influence of molecular structure on the liquid-crystalline properties of 1,5-dihetero-spiro[5.5]undecane- and -dispiro[5.2.5.2]hexadecane derivatives

The synthesis and liquid-crystalline properties of 1,5-dioxa- and 1,5-dithiaspiro[5.5]undecane, 7,16-dioxa-dispiro[5.2.5.2]hexadecane and 1,5,10,14-tetraoxa-dispiro[5.2.5.2]hexadecane derivatives are described. The effects of terminal sub-stituents and molecular structure on the liquid-crystalline properties of these materials are discussed.     

Rearrangement of O,O’-bis(2-benzylideneaminophenyl) phenylphosphonite into 1,6,7-triphenyl-3,4:9,10-dibenzo-2,11-dioxa-5,8-diaza-1-phosphatricyclo[6.3.0.01,5]undeca-3,9-diene

Keeping of O,O’-bis(2-benzylideneaminophenyl) phenylphosphonite in a CCl4 solution for 50 days resulted in its spontaneous rearrangement into 1,6,7-triphenyl-3,4:9,10-dibenzo-2,11-dioxa-5,8-diaza-1-phosphatricyclo[6.3.0.01,5]undeca-3,9-diene, a representative of spirophosphoranes with P–N bonds.     

Addition conjuguee des α, ω-bis(bromomagnesio)alcanes sur les coumarines

Reactions of 1,4-bis(bromomagnesio)bütane and 1,5-bis(bromomagnesio) pentane with coumarin and 6-methylcoumarin gave a mixture of 1-(o-hydroxystyryl)cycloalkanol and 4-alkyl-3,4-dihydrocoumarin. A large difference in product distribution was observed between the two bifunctional reagents. Annelation was favored by the use of 1,4-bis(bromomagnesio))butane, whereas conjugate addition was observed with 1,5-bis(bromomagnesio)pentane and even In the use of 4-methylcoumarin.     

Influence of molecular structure on the liquid-crystalline properties of 1,5-dihetero-spiro[5.5]undecane- and -dispiro[5.2.5.2]hexadecane derivatives

Abstract

The synthesis and liquid-crystalline properties of 1,5-dioxa- and 1,5-dithiaspiro[5.5]undecane, 7,16-dioxa-dispiro[5.2.5.2]hexadecane and 1,5,10,14-tetraoxa-dispiro[5.2.5.2]hexadecane derivatives are described. The effects of terminal sub-stituents and molecular structure on the liquid-crystalline properties of these materials are discussed.     

Macroheterocycles. 5. Synthesis of macrocyclic amido esters and amido thioesters on the basis of derivatives of α-hydroxy and α-mercapto acids

3,6-Dioxa-4-keto-, 2-benzyl-3,6-dioxa-4-keto-, and 3-oxa-6-thio-5-ketooctanedioic acids were obtained by the reaction of diglycolic acid anhydride with glycolic, β-phenyllactic, and thioglycolic acids. 2,9-Dibenzyl-3,8-dioxa-4,7-diketodecanoic acid was obtained by the reaction of succinyl chloride with β-phenyllactic acid. Eight macrocyclic amido esters and amido thioesters that are new polydentate macrocyclic ligands were synthesized by the reaction of the chlorides of the acids obtained with 3-oxa-1,5-diaminopentane, 3,6-dioxa-1,8-diaminooctane, and 1,4-diaminobutane. See [1] for communication 4. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 306–309, March, 1980.     

4-(氮杂-15-冠-5)-1,8-萘酰亚胺荧光探针的合成及性能研究

N-丁基-4-溴-1,8-萘酰亚胺与二乙醇胺反应, 合成了N-丁基-4-二(2-羟乙基)氨-1,8-萘酰亚胺, 进一步与对甲基苯磺酸二缩三乙二醇双酯反应合成了N-丁基-4-(氮杂-15-冠-5)-1,8-萘酰亚胺. 用NMR, IR, MS等表征了产物结构. 该化合物在二氯甲烷溶液中识别Li^＋和Na^＋, 识别后吸收光谱和荧光光谱蓝移.     

SYNTHESIS AND COMPLEX FORMATION OF NOVEL 12-MEMBERED MACROCYCLIC (E,E)-DIOXIMES

Abstract

Dibenzo[e,k]-2,3-bis(hydroxyimino) 1.4.7.10-tetrathia-2,3,8,9-tetrahydrocyclododecine (S₄H₂) and dibenzo-[e,k]-2,3-bis(hydroxyimino)-1,4-dithia-7,10-dioxa-2,3,8,9- tetrahydrocyclododecine (O₂S₂H₂) have been prepared from (E,E)-dichloroglyoxime, 2,3,8,9-dibenzo-1,4,7,10-tetrathiadecane (DTT) and 2,3,8,9-Dibenzo-4,7-dioxa-1,10-dithiadecane (DDD) which was synthesized by treating 1,2-bis(o-aminophenoxy)ethane with HNO₂ and potassium ethylxsanthate. The structures of these vic-dioximes have been determined as the (E,E)-forms according to ¹H-NMR and IR data. Only mononuclear complexes with a metal-ligand ratio of 1:2 have been isolated with Co(II), such as [(S₄H)₂Co(III)L′Cl] and [(O₂S₂H)₂Co(III)L′Cl]; Cu(II) forms only trinuclear complexes. Reaction of the mononuclear complexes with Pd(II) gives heterotrinuclear complexes.     

Synthesis of Dialkoxydimethylsilanes and 2,2-Dimethyl-1,3-dioxa- 1-Silacyclo Compounds

In the presence of iodine, magnesium reacts with alcohols to give magnesium alkoxides, which are treated with octamethylcyclotetrasiloxane to produce dialkoxydimethylsilanes. Similarly, magnesium reacts with 1,3, 1,4 and 1,5 diols and then with octamethylcyclotetrasiloxane, producing 2, 2-dimethyl-1, 3-dioxa-2-silacyclo compounds.     

Oxidation of 2-Chloro-1-phenylethane-1,1-dithiol

Oxidation of 2-chloro-1-phenylethane-1,1-dithiol with bromine, iodine, and elemental sulfur, as well as under UV irradiation, leads to formation of 1,4-bis(chloromethyl)-1,4-diphenyl-2,3,5,6-tetrathiane in 50–95% yield. Oxidation of the same substrate with selenium dioxide gives 1,5-bis(chloromethyl)-1,5-diphenyl-2,4-dithia-3-selenapentane-1,5-dithiol. On heating to 60°C, the latter loses selenium to afford 1,4-bis-(chloromethyl)-1,4-diphenyl-2,3-dithiabutane-1,4-dithiol.     

2,3,5,6-Tetra(vinylthio)difluorobenzene in Reactions with Difunctional Nucleophiles

Reaction of 2,3,5,6-tetra(vinylthio)difluorobenzene with ethylene glycol affords 1,4-bis[2,3,5,6-tetra(vinylthio)-4-fluorophenoxy-1-ethyloxy-]-2,3,5,6-tetra(vinylthio)benzene, with diethylene glycol arises 2,3,5,6-tetra(vinylthio)-4-(4-hydroxyethoxyethyloxy)-1-fluorobenzene, with 1,5-diaminopentane forms 1,5-bis[2,3,5,6-tetra(vinylthio)-4-fluoroanilino]pentane; in reactions with 2-aminoethanethiol and 2-mercaptoethanol occurs substitution of two fluorine atoms by RS groups.     

A new route to the asymmetric cylindrical macrotricyclic ligands

New asymmeric cylindrical macrotricyclic ligands have been prepared containing two diaza-12-crown-4 units connected by diethyleneoxy or triethyleneoxy and meta- or para-xylylene bridges, 2-4 . These materials were prepared in three steps by first treating 6-tosyl-6-aza-3,9-dioxa-1,11-undecanediyl ditosylate with 3-oxa-1,5-pentanediamine or 3,6-dioxa-1,8-octanediamine to form ditosyl-substituted bis(diaza-12-crown-4)s connected by a diethyleneoxy or triethylencoxy bridge. These latter compounds were detosylated and treated with either para- or meta-α,α'-dibromoxylene to give new asymmetric cylindrical macrotricycles 2-4 . The solid state structure of one of these ligands, 3 , has been determined by X-ray diffraction methods.     

Facile synthesis of macrocyclic tetrazoles by regioselective cycloalkylation of bistetrazoles with 2,5-dimethylhexane-2,5-diol in perchloric acid

Alkylation of 1,5-bis(tetrazol-5-yl)-3-oxapentane with 2,5-dimethylhexane-2,5-diol in 65% aqueous perchloric acid was found to proceed selectively on the N2 atoms of both tetrazole rings generating a 15-membered macrocycle with tetrazol-2,5-diyl moieties incorporated (yield ca. 80%). Under analogous alkylation conditions 1,5-bis(1-methyltetrazol-5-yl)-3-oxapentane undergoes quaternization resulting in a macrocyclic tetrazolium perchlorate containing two 1-methyltetrazolium-3,5-diyl units linked by 3-oxapentane-1,5-diyl and 2,5-dimethylhexane-2,5-diyl bridges. Crystal structures of the macrocyclic compounds obtained, determined by single crystal X-ray analysis, are described.